Vt liu v c (Phn l thuyt c s) GS.

Phan Vn Tng
NXB i hc quc gia H Ni 2007, 190 Tr. T kho: Cu trc tinh th, cu trc tinh th ca cc oxit, cc kiu khuyt tt mng tinh th, stki, frenken, tm mu, l trng, nguyn t xm nhp, o cu trc, mt trt, lch mng, dung dch rn, gin pha, h mt cu t, h hai cu t, h ba cu t, tnh cht vt l ca vt liu v c, dn in, dn nhit, dn electron, pht quang, laze . Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc

Chng 1 CU TRC TINH TH ...................................................................................... 7 1.1 Cc phng php m t cu trc tinh th ................................................................... 7 1.1.1 M t theo kiu t bo mng li....................................................................... 7 1.1.2 M t cu trc theo kiu xp kht cc khi cu................................................ 14 1.1.3 M t cu trc bng cch ni cc khi a din trong khng gian .................... 19 1.2 Cu trc tinh th ca cc oxit v mt s hp cht quan trng ................................. 20 1.2.1 Cu trc tinh th ca mt s oxit...................................................................... 21 1.2.2 Hp cht gia cc oxit...................................................................................... 29 1.3 Nhng nt c bit ca tinh th cng ho tr v tinh th kim loi............................ 53 1.4 Cc yu t nh hng n kiu cu trc tinh th ..................................................... 57 1.4.1 Tnh hp thc SPT ca cc nguyn t .......................................................... 57 1.4.2 nh hng ca kiu lin kt ............................................................................ 58 1.4.3 nh hng ca bn knh nguyn t, ion .......................................................... 59 Chng 2 TINH TH THC - CC KIU KHUYT TT - DUNG DCH RN ...... 67 2.1 Cc kiu khuyt tt................................................................................................... 67 2.1.1 Khuyt tt Stki................................................................................................ 67 2.1.2 Khuyt tt Frenken ........................................................................................... 68 2.1.3 Nhit ng hc ca s hnh thnh khuyt tt ................................................... 69

2.1.4 Tm mu........................................................................................................... 73 2.1.5 L trng v nguyn t xm nhp trong tinh th bt hp thc.......................... 74 2.1.6 Khuyt tt o cu trc..................................................................................... 77 2.1.7 Cc khuyt tt ko di - Mt trt ................................................................... 78 2.1.8 Lch mng l loi khuyt tt ph bin trong tinh th ....................................... 80 2.2 Dung dch rn ........................................................................................................... 81 2.2.1 Dung dch rn thay th ..................................................................................... 82 2.2.2 Dung dch rn xm nhp .................................................................................. 83 2.2.3 Nhng c ch phc tp trong s hnh thnh dung dch rn thay th................ 84 2.2.4 Nhng nhn xt tng qut v cc iu kin hnh thnh dung dch rn ............ 87 2.2.5 Cc phng php nghin cu dung dch rn.................................................... 88 Chng 3 GII THCH GIN PHA........................................................................... 94 3.1 M u ..................................................................................................................... 94 3.2 H mt cu t (h bc 1) .......................................................................................... 97 3.3 bc hai (K = 2).......................................................................................................... 99 3.3.1 Trng hp to thnh tecti n gin.............................................................. 99 3.3.2 Trng hp c to thnh hp cht mi .......................................................... 101 3.3.3 H bc hai trng hp c to thnh dung dch rn ........................................ 104 3.4 H bc ba (K = 3) ................................................................................................... 107 3.4.1 H bc ba to thnh tecti n gin ............................................................... 108 3.4.2 H bc ba trng hp c to thnh hp cht ho hc .................................... 110 3.4.3 H bc ba trng hp to thnh dung dch rn .............................................. 113 3.5 H tng tc bc ba................................................................................................ 116 Chng 4 MT S TNH CHT VT L QUAN TRNG CA VT LIU V C ............................................................................................................... 123 4.1 Nhm tnh cht in ............................................................................................... 123 4.1.1 Cht dn in ion, cht in li rn.................................................................. 123 4.1.2 Cht dn electron............................................................................................ 143 4.1.3 Cc tnh cht in khc .................................................................................. 151 4.2 Nhm tnh cht t ................................................................................................... 163 4.2.1 Phn l thuyt.................................................................................................. 164 4.2.2 V d mt s vt liu t, cu trc v tnh cht................................................ 169 4.3 Cc tnh cht quang, vt liu pht quang v laze ................................................... 179 4.3.1 S pht quang v cht pht quang.................................................................. 179 4.3.2 Laze ................................................................................................................ 185

Li m u
Vt liu V c c mt ni dung kh rng, kh lng trnh by ht trong mt cun gio trnh. Khc vi cun gio trnh c nh my v pht nhn bn cho sinh vin nm 1998, ln ny chng ti chia thnh 3 phn l: Phn l thuyt c s Phn k thut tng hp Phn gii thiu tng loi vt liu

Ba phn tuy ni dung khc nhau nhng c mi lin h mt thit vi nhau v b sung cho nhau. Cun gio trnh ny ch trnh by phn l thuyt c s nhm vo i tng chnh l sinh vin v hc vin cao hc i v lnh vc vt liu v c ni ring v ho hc cht rn ni chung. hc vin c th t kim tra kin thc ca mnh, chng ti c a ra mt s cu hi v bi tp sau mi chng. Xin chn thnh cm n i hc Quc gia H Ni, trng i hc Khoa hc T nhin, khoa Ho hc v b mn V c gip chng ti c iu kin xut bn cun gio trnh ny. Cm n Thc s V Hng Sinh nhit tnh gip trong vic hon thin ch bn bn tho.
TC GI

M u
1. Vai tr ca vt liu i vi s pht trin khoa hc k thut Lch s ca loi ngi gn lin vi lch s pht minh v s dng ca tng loi vt liu chnh. Ni v cc thi i trc, ngi ta thng phn chia ra thnh: thi i , thi i ng v thi i st thp. T gia th k XX n nay, s xut hin ca nhiu loi vt liu khc nhau c cc c tnh vt c st thp v ang thay th dn st thp trong nhiu lnh vc lm cho ngi ta a ra nhiu tn gi v thi i: thi i nhm v hp kim nhm, thi i gm thu tinh, thi i ca cht do v thi i compozit, Gia th k XX vt liu bng hp kim nhm ng vai tr quan trng trong nhiu lnh vc khc nhau. Nh c tnh nh, cng v bn i vi mi trng nn hp kim nhm ang gi mt v tr quan trng trong cng ngh sn xut cc phng tin giao thng vn ti. Hp kim nhm gp phn quan trng trong vic gii quyt cc vn v nng lng ca k nguyn ny. Mt chic xe t du lch c ch to bng hp kim nhm nh hn khi c lm bng st thp 600 kg, do tnh ht thi gian s dng tit kim c khong 10.000 lt xng. Hp kim nhm cho php ch to c cc loi my bay phn lc siu thanh t c tc khong 3000 km/gi. Cc loi tn la, tu v tr u ch to bng hp kim nhm. Nh c bn cao vi mi trng khc nghit nn hp kim nhm c s dng xy dng nh my in thu triu khai thc nng lng ca i dng. Trong i sng hng ngy chng ta tip xc vi nhiu dng bng nhm, thi gian gn y hp kim nhm c s dng ph bin trong xy dng Gm l loi vt liu c v tr c bit i vi lch s loi ngi c i, cn i, ng i v chc chn l trong th k XXI, vt liu gm cn a li nhiu iu k diu na i vi khoa hc k thut. S ra i ca gm mi c nh hng dn ti cuc cch mng trong ngnh in t ni ring v trong khoa hc k thut ni chung. Thnh tu trong lnh vc tng hp gm mi a ngnh in t hc t th h th nht (s dng bng n in t chn khng) sang th h th hai (s dng bng bn dn - tranzito) v sang th h th ba (s dng cc vi mch hay cn gi l mch t hp). Nh m c th thu nh cc thit b, my mc cng knh thnh nhng my mc gn nh, b nh hn, rt thun li trong s dng v c bit l tit kim c trit nng lng trong i sng hng ngy, trong sn xut cng nh trong nghin cu khoa hc. Cng ngh gm mi cn to ra c cc vt liu siu cng, chu c nhit rt cao, vt liu siu dn, iu c bit l nguyn liu sn xut cc loi gm mi hu ht u i t cc nguyn t ph bin nht trong t nhin nh oxi, nit, cacbon, silic. Cng ngh hin i i hi nhng loi vt liu c cc tnh cht c bit nh: rn cao, chu mi mn va p, nh, bn nhit, bn i vi mi mi trng n mn khc nghit, Compozit l loi vt liu t hp gia kim loi gm polime p ng c nhng i hi . Trong t nhin ngi ta bit c nhiu loi compozit nh vy. V d g gm cc si xenlulo do v dai c bao bc bng loi vt liu cng l lignhin. Xng ng vt l compozit ca colagen protein dai nhng mm v apatite cng nhng gin. Hoc mt s loi

vt liu compozit m t xa ngi ta ch to c nh thp peclit c rn cao nhng do l do s t hp gia pha xementit (Fe3C) rt rn nhng gin vi pha ferrite (dung dch rn xm nhp ca cacbon trong -Fe) mm v do. Phi hp gia ct thp, rm, ct v pha nn l xi mng pooclng hirat ho cho ta vt liu b tng ct thp c cc tnh cht c bit p ng yu cu ca cng ngh xy dng Nhng loi vt liu compozit do kt qu ca cc cng trnh nghin cu l thuyt c a ra sn xut quy m cng ngh u tin l compozit bnh kp gm polyeste - si thu tinh - kim loi nh ch to my bay tng hnh Mosquito do ngi M cng b t 1940. T n nay vt liu compozit xm nhp vo rt nhiu ngnh cng nghip khc nhau: - Cng nghip quc phng - ch to cc loi my bay qun s, tn la, cc loi qun trang, qun dng. - Giao thng vn ti - sn xut cc phng tin giao thng nh cc loi my bay dn dng, v v khung xe hi, tu thu, tu ha - Cng ngh xy dng - sn xut cc loi tm lp, vt liu cch m cch nhit, cc loi vt liu xy dng c bit - Y hc - sn xut xng gi, rng gi, da - Cng ngh sn xut cc dng c sinh hot, dng c th thao nh xe p ua, giy th thao, vt tennis, thuyn, cc loi dng trong gia nh. Trong lnh vc ch to vt liu mi i hi s hiu bit su sc v cu to, tnh nng v c bit l cng ngh sn xut ca tng loi vt liu. Trong hai thnh phn ca gi thnh sn phm l gi nguyn liu v gi tr tu, th gi tr tu ngy cng tng ln, cn gi nguyn liu ngy cng gim i mt cch nhanh chng. Hin nay c nhiu sn phm gi tr tu chim trn 80% gi thnh. C th ni th k XXI l th k ca tr tu, nc no bit khai thc tt tr tu th s tr nn giu mnh. iu ny ng cho mi lnh vc, c bit l trong lnh vc pht trin khoa hc cng ngh vt liu. 2. Phn loi vt liu Theo quan im ho hc c th phn thnh cc nhm vt liu v c l: a) Vt liu kim loi v hp kim b) Vt liu gm (gm sinh hot, gm xy dng, gm m ngh, gm k in, quang) ch yu di dng tinh th. c) Vt liu thy tinh ch yu di dng v nh hnh d) Vt liu kt dnh: Xi mng v cc cht kt dnh khc. e) Vt liu t hp (compozit) Theo c tnh k thut li phn thnh 5 nhm vt liu l: a) Vt liu kim loi: c trng ca loi vt liu ny l c cc electron chuyn ng t do trong mng tinh th. iu ny lm cho loi vt liu ny c cc tnh cht nh dn nhit v thut nhit, c,

dn in tt, khng trong sut, khi c mi nhn th c b mt rt bng, rt bn nhng li d bin dng, d dt mng, d ko si, b) Vt liu gm: l hp cht gia kim loi v phi kim, thng thng l cc oxit, cacbua, borua, nitrua, silixua. y l nhm vt liu a dng nht gm cc loi: gm, xi mng, thu tinh. c tnh chung ca nhm vt liu ny l cch in, cch nhit, bn nhit cao v bn vi mi mi trng khc nghit hn so vi nhm vt liu kim loi cng nh vt liu polime. Gm c rn cao nhng rt dn. c) Polime: Gm cc cht do v cao su, ch yu l hp cht hu c c cu trc phn t ln. c tnh chung ca loi vt liu ny l nh, do v d to hnh. d) Compozit: Bao gm nhiu kiu vt liu t hp vi nhau. V d si thu tinh kt hp vi vt liu polime va c c tnh bn ca thu tinh va c tnh do ca polime. Ni chung phn ln cc vt liu mi thuc nhm ny. e) Vt liu bn dn: L nhm vt liu c tnh cht trung gian gia cht dn in v cht cch in v c bit nht l tnh cht in ca loi vt liu ny rt nhy cm vi s c mt ca tp cht nng cc nh. Tnh cht bn dn ca nhm vt liu ny a ti cuc cch mng v in t hc v cng ngh my tnh. Gio trnh ny gii thiu nhng kin thc c s ca vt liu v c nh: cu trc tinh th, cc loi khuyt tt, dung dch rn, gin cn bng pha, mt s tnh cht vt l quan trng. L thuyt v phn ng gia cc pha rn c trnh by trong cun cc phng php tng hp vt liu gm (*) .

(*)

Phan Vn Tng: Cc phng php tng hp vt liu gm, NXB i hc Quc gia H Ni 2006.

Chng 1 CU TRC TINH TH

1.1 Cc phng php m t cu trc tinh th

Cu trc tinh th lin quan n mi tnh cht ca vt liu. Do tng hp c loi vt liu c cc tnh cht mong mun phi hiu r cu trc bn trong ca n v t la chn phng php ch to hp l. C nhiu cch m t cu trc tinh th: Da vo kiu t bo mng, vo cch sp xp kht khi cu, da vo cch ni cc a din trong khng gian. Trong cc gio trnh tinh th hc u c trnh by cc phng php . y ch trnh by tm tt nhng vn lin quan n mn vt liu hc.

1.1.1 M t theo kiu t bo mng li

Trong cht rn dng tinh th, cc tiu phn (nguyn t, ion, phn t,) c sp xp mt cch u n, tun hon to thnh mt mng li khng gian. Gi s ta chn mt tiu phn A bt k lm gc to , ri dng h trc to AX, AY, AZ theo 3 hng trong khng gian. Gi gc lp bi 3 trc l , , v gi khong cch u n gia cc tiu phn theo trc AX l a (thng s n v theo trc AX), theo trc AY l b, theo trc AZ l c. Th tch b nht trong khng gian ABCDABCD c cha mi yu t i xng c trng cho khng gian gi l t bo mng li.
Z A' B' a C C' A B X
Hnh 1 Mng li khng gian

D'

Ty theo cc gi tr a, b, c, , , , ngi ta phn ra thnh 7 h tinh th vi cc kiu mng c s khc nhau, mi mng c s li phn thnh cc kiu mng li khc nhau v c k hiu nh sau: mng c s n gin k hiu l P, nu tm ca cc mt mng c s c cha mt tiu phn na th gi l mng li tm mt v k hiu l F, nu ch tm ca hai y c cha thm tiu phn th gi l mng li tm y v k hiu l C, nu ti tm im ca

mng c s c cha mt tiu phn th gi l mng li tm khi v k hiu l I. Bng 1 di y gii thiu 7 h tinh th v 14 kiu t bo mng li.
Bng 1.7 h tinh th v 14 kiu t bo mng H Lp phng (cubic) Bn phng (tetragonal) Trc thoi (orthorhombic) Lc phng (hexagonal, trigonal) Cc thng s t bomng a=b=c = = = 90o a=bc = = = 90o abc o = = =90 a=bc o = = 90 , o = 120 a=b=c = = 90o abc = = 90o, o 90 abc 90o Yu t i xng c trng nht 4 trc bc ba 1 trc bc bn 3 trc bc hai 1 trc bc su Cc kiu mng P. F. I P. I P. F. I. C P

Mt thoi (Rhombohedral) n t (monoclinic)

1 trc bc ba 1 trc bc hai

P P. C

Tam t (triclinic)

khng

H lc phng (Hexagonal) v h tam phng (Trigonal) u c thng s t bo mng nh nhau. Ct th 3 trong bng 1 ch a ra yu t i xng c trng nht ca mi h. Cn s yu t i xng ca cc h th c rt nhiu. V d c nhiu yu t i xng nht l h lp phng. H lp phng c 3 trc i xng bc 4 (3A4) l cc ng thng ni tm im ca hai mt i din nhau, 3 ng ny trc giao vi nhau ti tm t bo, 4 trc i xng bc ba (4A3) l cc ng thng ni hai nh i din nhau, su trc i xng bc hai (6A2) l cc ng thng ni im gia 2 cnh i din nhau, ba mt i xng M (3M) l mt phng i qua tm im ca 4 cnh song song vi nhau, su mt i xng M (6M) l cc mt ct khi lp phng theo tng cp ng cho mt, mt tm i xng (C). Nh vy khi lp phng c cc yu t i xng l: 3A4, 4A3,6A2, 3M, 6M, C Cng vy cc yu t i xng ca h t phng l 1A4, 2A2, 2A2, M, 2M, 2M, C. Cc yu t i xng ca h trc thoi l A2, A2, A2, M, M, M, C. Cc yu t i xng ca h lc phng l A6, 3A2, 3A2, M, 3M, 3M, C. Cc yu t i xng ca h mt thoi l A2, 3A2, 3M, C. H n t c cc yu t i xng: A2, M, C.

c a P b a

c b C a

c b I a

c b F

Hnh 2 Bn t bo mng li ca h trc thoi

P: l mng li n gin C: l mng li tm y

F: l mng li tm mt I: l mng li tm khi

Trong mng li tinh th c rt nhiu h mt phng song song v cch u nhau. Mi mt h mt phng song song vi nhau c c trng bng 3 ch s h k l (gi l ch s Mile (Miller)). xc nh ch s h, k, l ca mt mt phng bt k trong mng li tinh th, trc ht cn chn gc to O v ba trc xut pht t O l Ox, Oy, Oz. Thng s n v theo trc Ox l a, theo Oy l b v theo Oz l c. V d mt 1 trn hnh 3 ct Ox im ng vi 1/2 thng s n v (a/2), ct Oy im ng vi mt thng s n v (b/1) ct Oz im ng vi 1/3 thng s n v (c/3). Ly gi tr nghch o ca cc s ta c ch s h k l ca mt 1 l 2 1 3. C mt h cc mt phng song song v cch u mt 1 , trn hnh v c ghi mt 2. H mt phng gi l h mt 2 1 3 c mt 1 gn vi gc to nht. Hnh 4 gii thiu ch s Mile ca mt s mt phng khc nhau.

z b a c c/3 0 1 o a/2 2 b x y

Hnh 3 Xc nh ch s Mile hkl ca mt phng trong mng li tinh th

(a)
z a c c x a o b b a

(b)
z

(c)
z

yc
x

O a b

1 a

c O

2 a

10

Hnh 4 Ch s Mile ca mt s mt phng khc nhau: a(111); b(101); c(010)

Mt phng gch gch hnh 4a ct Ox, Oy, Oz im ng vi mt thng s n v a, b, c nn gi l mt 1 1 1. Hnh 4b v mt phng ct trc Ox, Oz im ng vi mt thng s n v v song song vi trc Oy (ct Oy ) nn gi l mt 1 0 1. Hnh 4c c cc mt v song song vi nhau, ta chn mt xc nh ch s Mile ca h mt phng ny, v mt i qua im gc O khng th xc nh c cc gi tr h k l. Mt song song vi trc Ox v Oz ct Oy mt thng s n v b nn gi l mt 0 1 0. Thng tin quan trng nht khi kho st mng li khng gian l gi tr khong cch gia cc mt mng dhkl. T kt qu ghi ph nhiu x tia X cho ta bit cc gi tr ca mu nghin cu, do bit c s c mt ca cc pha rn trong mu. Mi h tinh th c mt mi lin h gia cc gi tr dhkl vi cc thng s ca t bo mng. Vi h lp phng ta c:
1 h 2 + k 2 + l2 = d2 a2 hkl

(1)

v th tch t bo V = a3 Vi h t phng ta c:
1 h 2 + k 2 l2 = + 2 d2 a2 c hkl

(2)

v th tch t bo V = a2.c Vi h trc thoi ta c:

1 h 2 k 2 l2 = + + d2 a 2 b2 c2 hkl

(3)

v th tch t bo V = a.b.c Vi h lc phng ta c:

1 4 h 2 + kh + k 2 = 3 d2 a2 hkl l2 + 2 c

(4)

th tch t bo
3.a 2 .c 2 V= 2 = 0,866a .c

Vi h n t:
1 1 h 2 k 2 .sin 2 l2 2hlcos = + 2 + d2 sin 2 a 2 b2 c ac hkl

(5)

th tch t bo

11

V= abc.sin Vi h tam t ta c:
1 1 = 2 ( h 2 b 2 c 2 sin 2 + k 2 a 2 c 2 sin 2 + l 2 a 2 b 2 sin 2 2 d hkl V

(6)

+2hkabc 2 (cos .cos .cos ) + 2kla 2 bc(cos .cos .cos ) +2hlab 2 c.(cos .cos .cos ))
Th tch t bo: V=abc(1- cos2- cos2 - cos2 + 2cos.cos.cos )1/2 Di y kho st mt vi gi tr c trng ca t bo mng li kim loi. Trc ht quy c rng mng li kim loi gm cc nguyn t xp kht nhau, nhng d hnh dung, trong cc hnh v chng ta biu din cc nguyn t bng nhng vng trn nh.
Mng li lp phng tm khi: thng s t bo mng l a, mi t bo cha hai nguyn t, a 3 , t xc nh c chc c quan h gia bn knh nguyn t v hng s mng l: r = 4 C (compact).
2( .r 3 ) 2( .( )3 ) th tch ca 2 nguyn t 3 3 4 C= = = = 0, 68 th tch t bo a3 a3 4 4 a 3

iu c ngha l trong t bo lp phng tm khi c 32% khong trng. Mi nguyn a 3 , ngha l s phi tr t c bao quanh bng 8 nguyn t khc vi khong cch u l 2 2M (SPT) bng 8, khi lng ring d = (M l nguyn t lng, N l s Avgar). Na 3

T T T

Hnh 5. T bo mng lp phng tm khi

Hnh 6 V tr cc hc trng bt din (hc O), k hiu

Hnh 7 V tr cc hc trng t din (hc T), k hiu

C hai loi hc trng l hc bt din (hc O) v hc t din (hc T). + Hc O: Tm ca 6 mt u l hc O chung cho 2 t bo cnh nhau.

12

im gia 12 cnh u l hc O chung cho 4 t bo cnh nhau. Do mi t bo c: (6 1/2) + (12 1/4) = 6 hc O (hnh 6). + Hc T: Mi mt c 4 hc T chung cho 2 t bo cnh nhau. Do mi t bo c (4 6 1/2) = 12 hc T (hnh 7).
Mng li lp phng mt tm: Thng s t bo mng l a. Mi t bo cha 4 nguyn t. a 2 , c chc Quan h gia bn knh nguyn t v cnh l: r = 4
4( .r 3 ) 2( .( )3 ) th tch ca 4 nguyn t 3 3 4 C= = = = 0,74 th tch t bo a3 a3 4 4 a 2

Mi nguyn t c bao quanh bng 12 nguyn t khc vi khong cch bng SPT =12, khi lng ring d =
4M . Na 3

a 2 , 2

Hnh 8 Mng li lp phng tm mt

Hnh 9 V tr hc O, k hiu

Hnh 10. V tr cc hc O, k hiu x

Trong t bo lp phng mt tm c 26% khong trng l cc hc O v hc T. + Hc O: Tm t bo c 1 hc O (hnh 9).

13

Gia cc cnh u c hc O chung cho 4 t bo (hnh 10). Vy mi t bo c 1 + 12 1/4 = 4 hc O. + Hc T: Mi t bo c 8 hc T nm trong t bo cc to : (1/4, 1/4, 1/4); (3/4, 1/4, 1/4); (3/4, 3/4, 1/4); (1/4, 3/4, 1/4); (1/4, 1/4, 3/4); (3/4, 1/4, 3/4); (3/4, 3/4, 3/4); (1/4, 3/4, 3/4) (hnh 11).
Mng li lc phng: Thng s t bo mng l a, c (hnh 12). Mi t bo c 2 nguyn a t. Quan h gia bn knh nguyn t v thng s t bo l r = . 2

chc c C = Th tch 2 nguyn t

Th tch 2 nguyn t Th tch t bo

3

4 a V1 = 2 ; Th tch t bo V2 = abc 3 2
A
A B D C

T T T T T T

60o

B C

120o

c
A1

a a
B1

D1 C1

A1 D1

B1 C1
(b)

(a) Hnh 11 V tr cc hc T

Hnh 12 Khi gm 3 t bo (a), t bo mng li lc phng (b)

5C 8

3C 8

Hnh 13 V tr cc hc T (k hiu )

14

Hnh 14 V tr cc hc O (k hiu )

b=

a 3 ; 2

V2 =

a2 3 a 3 c; mt khc = ; 2 c 2 2

Do C =

= 0,74 3 2 4M Na 2 3c

SPT =12; Khi lng ring d =

Mi t bo c 2 hc O v 4 hc T (hnh 13 v 14).

1.1.2 M t cu trc theo kiu xp kht cc khi cu

Theo nguyn l xp kht, th khi khng c s nh hng ca lin kt, cc tiu phn to thnh tinh th c khuynh hng sp xp sao cho khong khng gian t do c th tch b nht, ngha l c chc c ln nht. Nu cc tiu phn to thnh tinh th u c dng qu cu vi ng knh bng nhau th c 2 kiu xp kht gi l xp kht lc phng (kiu ABABA) v xp kht lp phng (kiu ABCABCAB). Hnh 15 trnh by cch xp kht ca mt lp qu cu . Trong lp xp kht ny (gi l lp A) mi mt qu cu (v d qua cu K) c bao quanh bng 6 qu cu khc. Trong hnh b, mi qu cu ch tip xc vi 4 qu cu khc, y khng phi l mt xp kht. Trong lp xp kht c 3 hng xp kht (XX, YY, ZZ) (hnh 15a), hnh 15b ch c 2 hng xp kht. Trong mt xp kht ny c cc dy l trng R v dy l trng P.

15

x
6 1
K

z'

5 4
P

2 3
p
P

y'
R p

(a)

x'

(b)

Hnh 15 Mt phng gm cc qu cu xp kht nht (a), cch xp khng kht (b)

By gi chng ta t lp xp kht th 2 (gi l lp B) ln trn lp A. Mun cho khng gian t do c th tch b nht th phi t sao cho cc qu cu ca lp B nm ng v tr lm gia 3 qu cu ca lp A v ngc li, cc qu cu ca lp A phi nm ng cc v tr lm ca lp B. Mun vy th cc qu cu ca lp B hoc l phi nm vo tt c cc v tr P, hoc l phi nm vo tt c cc v tr R ca lp A (xem hnh 15). Ta c 2 lp xp kht (hnh 16). t lp th 3 ln lp th 2 ta c 2 cch. Nu t sao cho cc qu cu ca lp th 3 nm vo v tr S ca lp th 2 (hnh 16) th tt c cc qu cu ca lp 3 u trng vo v tr tng ng ca lp th nht. Ngha l chu k lp li ca cc lp l 2, cc lp xp theo th t ABABA. Kiu xp kht nh vy gi l xp kht lc phng.
A
T T T

S
T T

S
T

S
T

Hnh 16 Hai lp xp kht A v B

A C B

16

Hnh 17 Ba lp xp kht ABC to thnh kiu xp kht lp phng

Nu t lp th 3 sao cho cc qu cu nm lt vo v tr T (xem hnh 16) th s hnh thnh mt lp mi (lp C), n lp th 4 mi lp li chu k tc l lp A. Cch xp nh vy gi l xp kht lp phng v th t lin tc ca cc lp l ABCABCAB (hnh 17). Xp kht lp phng v xp kht lc phng l hai kiu cu trc n gin v quan trng nht. Ngoi ra cng cn c nhiu kiu xp kht vi th t cc lp phc tp hn, v d ABCACB... hoc ABAC to thnh nhng chu k lp li ln hn (xem cu trc tinh th ca -Al2O3 - hnh 29). Trong 2 kiu xp kht lc phng v xp kht lp phng, mi qu cu u tip xc vi 12 qu cu khc (SPT = 12). chc c ca c 2 kiu xp kht ny u bng nhau v bng 0,74. iu ny c ngha l trong c hai kiu xp kht nht vn cn 26% th tch l cc khong trng. C hai loi hc trng gi l hc trng t din (hc T) v hc trng bt din (hc O). Hc T l khong khng gian gia 4 khi cu xp kht vo nhau. Tu thuc vo khi cu nh ca t din nm trn hoc di m phn thnh hc T+ hoc T (hnh 18). Hc O l khong khng gian nm gia 6 qu cu xp kht ca 2 lp st nhau, su qu cu gm 4 qu cng nm trn mt mt phng v 2 qu nm v hai pha ca mt phng .
6 2 3

5 1

(a)

(b)

(c)

Hnh 18 Cc hc trng trong mng li xp kht nht Hc T+ (a), Hc T- (b), Hc O (c)

Vic chn mt phng cha 4 qu cu c th ly t do theo nhiu cch. V d, cc qu 1264 hoc 2345 hoc 1356. Hnh 19 trnh by cc hc trng gia 2 lp xp kht. Mng tinh th ca cc oxit gm cc ion O2 xp kht, cn cc cation c phn b vo cc hc T v O. V rng trng tm ca t din gn y hn nh nn cation hc T khng ng vo v tr chnh gia 2 lp, cn cation hc O th nm ng chnh gia 2 lp. Cc cation khi chui vo hc T v O s lm gin n phn mng oxi.

Hc t din THc bt din O Hc t din T+

Hnh 19 S phn b cc hc trng gia hai lp xp kht (lp cu pha trn v vng

17

m, lp cu pha di v ng chm chm)

T bo mng ca kiu gi ghm chc c lp phng (hay cn gi l lp phng tm mt) c trnh by trn hnh 20a, cn hnh 21 trnh by t bo mng ca kiu gi ghm chc c lc phng.

18

4 3 2 1

4 3 2

7 5

6 5

(a)

(b)

Hnh 20 T bo mng lp phng tm mt c to thnh t kiu gi ghm cc qu cu theo kiu chc c lp phng

Kiu gi ghm chc c lp phng trng vi kiu t bo lp phng mt tm (hnh 20a). Ni chung iu ny khng d dng thy c, v rng cc mt ca t bo lp phng khng trng vi lp xp kht, trong mi qu cu ch tip xc vi 4 qu cu khc ch khng phi 6 qu. Trong t bo lp phng mt tm th lp xp kht l cc mt song song vi mt phng 111. thy c r hn, ta b i qu cu v tr 1 ca hnh 20a th thy ngay lp di gm cc qu cu 2, 3, 4, 5, 6, 7 (hnh 20b) nm trn cng mt mt phng (song song vi mt 111). T ta c th kt lun rng cu trc gi ghm chc c lp phng c 4 mt xp kht trc giao vi ng cho ca khi lp phng. T bo mng kiu lc phng trng vi kiu gi ghm chc c lc phng, iu ny d thy c trn hnh 21, y cc mt c s ca mng u trng vi mt xp kht.
120o 60o

c a a
Hnh 21 T bo mng lc phng c to thnh t s gi ghm chc c lc phng cc khi cu

a s cc kim loi u kt tinh theo mt trong ba kiu lp phng tm mt (ABCABC), lc phng (ABAB) v lp phng tm khi. Bng 2 cho bit kiu t bo, thng s t bo ca mt s kim loi.

19

Bng 2 Cu trc v thng s t bo mng li ca mt s kim loi Lp phng tm mt Lc phng (kiu ABAB) Lp phng tm khi (kiu ABCABC) Kim loi a () Kim loi a () c () Kim loi a () Cu 3,6150 Be 2,2859 3,5843 Fe 2,8664 Ag Au Al Ni Pd Pt Pb 4,0862 4,0786 4,0494 3,5238 3,8898 3,9231 4,9506 Mg Zn Cd Ti Zr Ru Os Re 3,2095 2,6650 2,9793 2,9500 3,2320 2,7058 2,7341 2,7600 5,2104 4,9470 5,6181 4,6860 5,1470 4,2819 4,3197 4,4580 Cr Mo W Ta Ba 2,8839 3,1472 3,1648 3,3058 5,0250

Vic mt kim loi no kt tinh theo kiu mng li ny hay mng li khc l mt vn cho n nay vn cha r. Trong hai kiu cu trc lp phng tm mt v lc phng u c chc c ln (C = 0,74) cn chc c ca kiu lp phng tm khi nh hn (C = 0,68). Kt qu tnh ton cho thy nng lng mng li ca cc kim loi c cu trc lc phng v lp phng tm mt gn tng t nhau, do s khc nhau v cu trc c th do s khc nhau v cu trc vng ca chng. C mt s kim loi c bin ho th hnh, ngha l c th c cc kiu cu trc khc nhau. V d st, tu thuc vo nhit c th c cu trc lp phng tm khi (Fe-) hoc lp phng tm mt (Fe-); coban ngoi kiu cu trc lp phng tm mt v lc phng li cn c th to ra cc dng khc vi chu k lp li ca cc lp xp kht phc tp hn. y l trng hp ng vi dng a hnh c bit (polytypism) khi m s khc nhau v cu trc ca nhng dng th hnh ch xy ra theo mt hng. Trong cc kim loi c cu trc gi ghm chc c ca tt c cc lp nguyn t kch thc ging nhau, cn s khc nhau v cu trc ch l cch sp xp ln nhau ca cc lp . Tuy rng ch c hai cch chnh sp xp cc lp l ABC (lp phng tm mt) v AB (lc phng) nhng cng c th hnh thnh rt nhiu kiu sp xp lun phin phc tp hn. l trng hp ca coban kim loi. C nhng vt liu trong c dng th hnh vi chu k lp li gia cc lp xp kht ti vi trm lp nguyn t. S hnh thnh nhng cu trc nh vy ang l vn cha gii thch c. V d nh c kiu cu trc vi chu k lp li ti vi trm lp, dy ti 500. Cng c quan im cho rng chu k lp li ln nh vy lin quan vi c ch xon c khi tinh th ln dn sinh ra bin v xon.

1.1.3 M t cu trc bng cch ni cc khi a din trong khng gian

V d tinh th mui n (NaCl) c th m t bng cch ni cc khi bt din [NaCl6]5 qua mt cnh chung (hnh 22), mng tinh th nh vy c trnh by hnh 23. Tuy nhin khng phi ton khi khng gian c lp y bng cc bt din, m vn cn li cc khong trng, i vi tinh th NaCl th l cc khong trng t din nh trn hnh 23. Kiu m t nh vy rt thun li cho cch trnh by mng tinh th ca silicat. V d mng tinh th SiO2 c trnh by bng cch ni cc t din [SiO4]4 qua nh, mng tinh th

20

khong vt st c trnh by theo cch ni cc t din [SiO4]4 vi cc bt din [Al(OH)6]3 qua nh, mng tinh th zeolit c m t theo cch ni cc bt din ct [Si24xAlxO48]x+ qua cc mt bn (xem phn silicat). V cc a din u c cation nm tm, anion cc nh, nn ni cc a din qua nh, cnh hoc cc mt chung th phi lu n lc y gia cc cation, c bit l cc cation c kch thc b v in tch ln, v d nh Si4+. Tt nhin mng li bn nu cch ni sao cho lc y ny b nht, ngha l khong cch gia cc cation xa nht. Hnh 24 v bng 3 cho thy khong cch gia cc cation gim dn khi ni cc a din qua nh, cnh, mt.

Hnh 22 T bo mng NaCl c hnh thnh theo cch ni cc bt din theo cnh chung

Hnh 23 Mng tinh th NaCl c xy dng theo cch ni cc bt din [NaCl6]5 qua cnh chung

o o M o o

(a) o M X o

o o o o
M - M=

(b)
X M
90o

(c)
X
M

71o

X
M-M=

M M = 2MX (M - O, X - o)

2 MX = 1,411MX

2(1 cos 71o )MX

= 1,16M Hnh 24 Khong cch cation-cation khi ni cc bt din qua nh (a); qua cnh (b) v khi ni cc t din qua cnh (c) a din Khong cch M-M khi ni 2 a din

Bng nh Bng cnh Bng mt Hai t din 2MX 1,16MX 0,67MX Hai bt din 2MX 1,41MX 1,16MX Bng 3 Khong cch gia cc tm a din cnh nhau MX4 v MX6

1.2

Cu trc tinh th ca cc oxit v mt s hp cht quan trng

st vi i tng nghin cu vt liu v c, trong phn m t cu trc tinh th di y s trnh by loi hp cht in hnh nht l oxit v hp cht gia cc oxit nh M2O, MO, M2O3, MO2, AB2O4, ABO3, AB2O7,... v silicat. Cc hp cht v c khc (halogenua, sunfua, nitrua,) s c ni n khi c cu trc tng t vi oxit.

21

1.2.1 Cu trc tinh th ca mt s oxit

1.2.1.1 Oxit c cng thc chung MO

Na+

Cl

Hnh 25 T bo mng li kiu NaCl

Oxit kim loi ho tr 2 nu c t l rM2+/rO2 nm trong khong 0,414 n 0,732 v c lin kt ch yu l lin kt ion th c mng li tinh th thuc kiu NaCl. Ta c th biu din mng li tinh th ny theo c 3 phng php trn. y biu din t bo mng. C th xem t bo mng ca loi ny gm hai phn mng lp phng mt tm ca cation M2+ v ca anion O2 lng vo nhau mt khong bng 1/2 cnh ca lp phng. Mi t bo gm 4 phn t MO, SPT ca cation v anion u bng nhau v bng 6.
Bng 4 Mt s hp cht cu trc theo kiu NaCl Hp cht a () Hp cht a () MgO 4,2130 MgS 5,2000 CaO 4,8105 CaS 5,6948 SrO 5,1600 SrS 6,0200 BaO 5,5390 BaS 6,3860 TiO 4,1770 MnS 5,2240 MnO 4,4450 SnAs 5,7248 FeO 4,3070 TiC 4,3285 CoO 4,2600 LaN 5,3000 NiO 4,1769 TiN 4,2400 CdO 4,6653 Hp cht MgSe CaSe SrSe BaSe CaTe BaTe UC ScN UN a () 5,462 5,924 6,246 6,600 6,660 7,000 4,955 4,440 4,890

Hp cht c t l rcation/ranion nm gia 0,225 v 0,414 v lin kt ch yu l ion th c cu trc kiu ZnS. ZnS c hai dng th hnh l blend (hoc cn c tn l sphalerit) v vuazit. Blend c t bo tinh th lp phng tm mt ca S2, ion Zn2+ nm 4 trong 8 hc t din ca phn mng lp phng tm mt S2 (hnh 26). To ca Zn2+ l: 1/4, 1/4, 1/4; 3/4, 3/4, 1/4; 3/4, 1/4, 3/4 v 1/4, 3/4, 3/4. Hng s mng ca blend a = 5,43; d = 4,092. Bng 5 gii thiu cc hp cht c cu trc kiu blend.

22

S Zn

Hnh 26 T bo mng ca blend (ZnS)

Bng 5 Mt s hp cht cu trc kiu blend Hpcht CuF CuCl -CuBr -CuI -AgI -MnS -MnSe a () 4,255 5,416 5,690 6,051 6,495 5,600 5,880 Hp cht BeS BeSe BeTe -ZnS ZnSe ZnTe SiC a () 4,8624 5,070 5,54 5,406 5,667 6,102 4,358 Hp cht -CdS CdSe CdTe HgS HgSe HgTe a () 5,818 6,077 6,481 5,852 6,085 6,453 Hp cht BN BP BAs AlP AlAs AlSb a () 3,616 4,538 4,777 5,451 5,662 6,135 Hp cht GaP GaAs GaSb InP InAs InSb a () 5,448 5,653 6,095 5,869 6,058 6,478

Khi un nng ti 1020oC th blend chuyn thnh vuazit. T bo mng ca vuazit c phn mng S2 gi ghm chc c lc phng (hnh 27). Cc ion Zn2+ chim ht tt c hc t din T+, cn cc hc t din T v hc bt din O u trng. Hnh 27 trnh by mt t bo mng ca vuazit. C th hnh dung t bo mng ny gm hai phn mng xp kht lc phng cation v anion lng vo nhau mt khong bng 3/8 chiu cao. Trong thc t hai phn mng ny lng vo nhau khng ng vi gi tr 3/8 (0,375) chiu cao, m tu theo tng loi cation gi tr dch chuyn khc nhau (gi tr u trong bng 6). Hng s mng ca vuazit a = 3,811; c = 6,234; d = 3,98 4,08. Mt trong nhng tnh cht c trng ca phn mng xp kht lc phng l gi tr c/a. Trng hp l tng th t s bng 1,633. Cc gi tr trn bng 6 u khc vi 1,633, iu ny chng t rng cc mt khng hon ton xp kht.

23

120 o 60 o 3 8

60 o 3 8

120 o

c
a

a
Hnh 27 T bo mng kiu vuazit Bng 6 Gii thiu mt s hp cht c cu trc vuazi Cht ZnO ZnS ZnSe ZnTe BeO CdS a () 3,2495 3,8110 3,9800 4,2700 2,6980 4,1348 c () 5,2069 6,2340 6,5300 6,9900 4,3800 6,7490 0,378 u 0,345 c/a 1,602 1,636 1,641 1,637 1,623 1,632 Cht MnS MnSe AlN GaN InN TaN

a () 3,976 4,120 3,111 3,180 3,533 3,050

c () 6,432 6,720 4,978 5,166 5,693 4,940

c/a 1,618 1,631

0,385

1,600 1,625 1,611 1,620

1.2.1.2 Oxit c cng thc M2O3

l cc oxit Al2O3 (corun), Fe2O3 (hmatit), Cr2O3, Ga2O3, Ti2B3, Al2O3 c nhiu dng th hnh. iu ny cng d hiu v t l rAl3+/rO2 = 0,42 tc l nm gia hai s phi tr l 4 v 6. Trong cc dng th hnh ch c 3 dng quan trng l , , .
Al2O3 l dng th hnh bn vng nht, loi ny cn c tn l corun, tinh th corun gm phn mng xp kht lc phng ca ion oxi. Cation Al3+ chim 2/3 hc bt din, cn hc T+ v T u b trng.

O2-

Al3+

O2Al3+

Hnh 28 Cu trc tinh th corun Al2O3

Khong cch gia hai lp xp kht oxi bng 2,16. T bo nguyn t ca corun thuc h mt thoi, chiu di cnh bng 5,12, gc nhn gia cc cnh bng 5o17. T bo nguyn t c 4 ion nhm v 6 ion oxi. Cc oxit c cu to ging corun gm hmatit Fe2O3, Cr2O3, Ga2O3, Ti2O3.

24

-Al2O3. Tn gi Al2O3 ch mt nhm hp cht c cng thc M2O.nX2O3. Gi tr ca n thay i t 8 n 11. M l cation ho tr +1 nh Cu+, Ga+, Tl+, In+, NH4+, H3O+, X l cc cation Al3+, Ga3+, Fe3+. Quan trng nht trong cc loi hp cht ny l natri -Al2O3 (M l Na+, X l Al3+) c bit t lu nh l mt sn phm ph khi sn xut thu tinh. Natri -Al2O3 c hnh thnh trong ni thu tinh khi tng tc gia Na2O c trong khi nng chy vi Al2O3 trong thnh phn gch chu la. Tn gi -Al2O3 rt d lm ngi ta nhm ln vi mt dng th hnh ca tinh th Al2O3, nhng do thi quen dng t lu nn by gi khng thay i na. Thc ra vai tr Na2O nh l mt tc nhn n nh cu trc tinh th ca loi hp cht ny. Hnh 29 trnh by mng anion trong -Al2O3. Trn hnh ny cho thy c 4 lp oxi gi ghm chc c li c mt lp ch c 1/4 ion O2 cn 3/4 v tr O2 trng. Cc ion Na+ c phn b trong lp thiu oxi . Do bn knh ion O2 rt ln hn bn knh ca Na+, mt khc lp ny rt rng nn Na+ chuyn ng kh d dng theo mt phng ca lp ny.

B A C B A C A B C A B A C B A C
Hnh 29 Cc lp oxi xp kht trong -Al2O3

Sp

Sp

Sp

Mng tinh th -Al2O3 cha cc bloc tng t spinen (Sp). Bloc Sp gm 4 lp oxi gi ghm chc c lun phin theo th t ABCA c trng ca cu trc lp phng. Ion Al3+ chim mt s v tr t din v bt din gia hai lp oxi. Cc bloc Sp tch bit nhau bng mt lp thiu oxi, ion Na+ nh v trong lp thiu oxi . T bo mng li lc phng c cc thng s a = 5,60, c = 22,50. Cc lp oxi trc giao vi trc c. T bo ca -Al2O3 c cha 2 bloc Sp. Cu trc spinen y c xem nh cu trc MgAl2O4 cha khuyt tt (xem hnh 35). Trong spinen MgAl2O4 c t l ion Mg2+ v Al3+ l 1 : 2 trong khi spinen ca -Al2O3 ch c Al3+ (khng k n cc ion hp kim ho nh Li+, Na+), do cn bng in tch trong cc bloc spinen phi c cha cc l trng Al3+. Tinh th ca cc oxit t him c mc oxi ho +3 thng dng trong vt liu gm c cu trc khc vi cu trc corun v bn knh Ln3+ ln hn bn knh ca Al3+. Theo Holsmit, c th phn thnh 3 loi oxit t him: loi A c cu trc mt thoi hoc lc phng, loi B thuc h n t, loi C thuc h lp phng. Oxit t him cng c nhiu dng th hnh.

25

Bng 7 Tnh cht ca cc dng th hnh ca Al2O3 Dng th hnh -Al2O3 (corun) -Al2O3 -Al2O3 H tinh th Dng D (g/cm )
3

Ch s khc x ng 1,786 np 1,76

Bin ho khi nung

o 2050 C nng

lc phng

Bn, mt thoi

3,99 3,33,4

chy
o 1600 C thnh

lc phng lp phng

1,680

1,65

1200 C thnh
o

Bt din

3,6

Loi A (kiu La2O3) c La2O3, Ce2O3, Pr2O3. Loi B c Ge2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Cd2O3, Lu2O3, Tb2O3, Dy2O3 (trn 2000oC). Loi C (kiu Tl2O3 hoc Mn2O3) c: Sm2O3, Eu2O3, Cd2O3, Lu2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tu2O3, Yb2O3.

Cc oxit Sc2O3, Y2O3, In2O3 v Tl2O3 cng c cu trc loi C nh oxit t him (thuc h lp phng, mi t bo c 16 phn t).

1.2.1.3 Oxit c cng thc MO2

Tu thuc vo t l rcation/ranion hp cht loi ny c 3 kiu cu trc l kiu florit (CaF2), kiu rutin (TiO2) v kiu oxit silic (SiO2).
Kiu florit: Cc anion chim hc t din trong phn mng lp phng mt tm ca cation. Hay c th hnh dung khi phn chia mang c s lp phng mt tm ca cation thnh 8 khi lp phng b bng nhau th cc anion nm tm ca 8 khi lp phng b . SPT ca cation bng 8 cn ca anion bng 4. Mi t bo c 4 phn t AB2.

Oxit, sunfua, selenua kim loi ho tr mt c cu trc kiu antiflorit, ngha l vn ging kiu florit CaF2 nhng y v tr ca ion canxi li do ion oxi chim, cn v tr ca ion flo th cation kim loi kim chim.

Ti O
Ca (a) F

(c)

Si O

(b)

26

Hnh 30 T bo ca cc hp cht c cng thc AB2a) kiu florit, b) kiu rutin, c) kiu silic oxit (cristobalit)

Bng 8 Cc hp cht c cu trc florit v antiflorit florit Hp cht CaF2 SrF2 SrCl2 BaF2 BaCl2 CdF2 HgF2 5,4626 5,8000 6,9767 6,2001 7,3110 5,3895 5,5373 a () Hp cht PbO2 CeO2 PrO2 ThO2 UO2 NpO2 PuO2 5,3490 5,4110 5,3920 5,6000 5,3720 5,4334 5,3860 a () Hp cht Li2O Li2S Li2Se Li2Te Na2O Na2S Na2Se 4,6114 5,7100 6,0020 6,5170 5,5550 6,5390 6,823 antiflorit a () Hp cht K2O K2 S K2Se K2Te Rb2O Rb2S 6,449 7,406 7,962 8,168 6,740 7,650 a ()

Kiu rutin TiO2: T bo mng li thuc h t phng khi tm ca cation Ti4+ cn anion to thnh bt din u bao quanh titan (2 ion oxi nm mt trn dc theo mt ng cho, 2 ion oxi nm mt di cng theo hng ng cho , 2 ion oxi na nm ngay trong t bo nhng theo hng ng cho khc). Mi t bo mng c 2 phn t TiO2. S phi tr ca titan bng 6, cn ca oxi bng 3. To ca Ti l (0 0 0), (1/2 1/2 1/2) ca oxi l (x x 0), ( x x 0), (1/2+x, 1/2-x, 1/2), (1/2-x, 1/2+x, 1/2). Kt qu thc nghim xc nh c x = 0,3 (xem hnh 30b v 31).
Bng 9 Mt s hp cht c cu trc tinh th kiu rutin Cht TiO2 CrO2 GeO2 IrO2 MnO2 MoO2 NbO2 OsO2 PbO2 RuO2 4,8600 4,7700 4,5100 4,9460 4,5100 2,7900 2,9600 3,1900 3,3790 3,1100 MgF2 MnF2 NiF2 PbF2 ZnF2 4,6230 4,8734 4,6506 4,9310 4,7034 3,0520 3,3099 3,0836 3,3670 3,1335 0,303 0,303 0,305 0,302 a () 4,5937 4,4100 4,3950 4,4900 4,3960 c () 2,9581 2,9100 2,8590 3,1400 2,8710 0,302 0,307 x 0,305 Cht SnO2 TaO2 WO2 CoF2 FeF2 a () 4,7373 4,7090 4,8600 4,6951 4,6966 c () 3,1864 3,0650 2,7700 3,1796 3,3091 0,306 0,300 x 0,307

C th m t cu trc mng tinh th rutin theo kiu xp kht nh hnh 31. Phn mng anion oxi xp kht theo kiu lc phng (ABAB). Cation titan chim 1/2 s hc bt din theo trt t: c mt dy hc bt din b trng n mt dy hc bt din b chim ht. Trt t ny thay i lun phin theo 1/2 n v ca c. Kiu silic oxit

27

Silic oxit (SiO2) c nhiu dng th hnh, y ni v mt trong cc dng gi l cristobalit (hnh 30c). Cristobalit thuc h lp phng. Nguyn t Si chim cc nh, tm cc mt v 4 trong 8 hc t din theo hai hng ng cho khc nhau (hoc c th hnh dung chia khi hnh lp phng thnh 8 khi lp phng nh bng nhau th Si l tm ca 4 khi lp phng nh ). Oxi l cu ni gia cc nguyn t silic. Mi t bo c 8 phn t SiO2. S phi tr ca Si bng 4, ca oxi bng 2. Ngoi cristobalit ra SiO2 cn rt nhiu dng hnh th khc na l: thch anh, tridimit, cristobalit. Mi dng chnh nh vy cn tn ti di nhiu dng ph.
Cc dng n tinh: cancedoan, m no, jat (ngc). Dng v nh hnh: thu tinh thch anh, opal.
b
c a

(b) To cc nguyn t

Ti4+ 0, 0, 0 - 0.5, 0.5, 0.5

(a)

O2- 0, 0.3, 0.3 - 0, 0.7, 0.7 0.8, 0.2, 0.5 - 0.2, 0.8, 0.5
Hnh31 a) Cu trc rutin biu din theo mt phng xp kht ca ion oxi b) Hnh chiu ca t bo mng rutin trn mt y

m t cu trc ca cc dng SiO2 th tt nht l dng phng php ghp cc t din vi nhau qua nh oxi chung (hnh 32). im khc nhau ca 3 dng tinh th chnh (thch anh, tridimit, cristobalit) l v tr tng i ca 2 t din SiO44 (hnh 33). thch anh ta c gc lin kt Si-O-Si bng 150o, tridimit, v cristobalit th gc lin kt Si-O-Si bng 180o. T thch anh bin thnh cristobalit ch cn nn thng gc Si-O-Si t 150o thnh 180o, trong khi chuyn thnh tridimit th ngoi vic nn thng gc ny cn phi xoay t din SiO44 quanh trc i xng mt gc bng 180o

28

TT+ TT+ T+ TT+ T-

Hnh 32 Cch ghp cc t din SiO4 ( Si4+, O2-)

C'

B' A' C'

B' A' A'

B' C'

) 150o
C B A B

A B

(a)

(b)

(c)

Hnh 33 S t hp hai t din SiO4 a) Thch anh; b) Cristobalit ; c) Tridimit

S khc nhau ca cc dng th hnh th cp , , ch do mc khc nhau ca gc lin kt Si-O-Si . Qu trnh chuyn ho ca cc dng th hnh -thch anh -tridimit -cristobalit u l qu trnh c bin, cn qu trnh chuyn ho cc dng th hnh th cp u l qu trnh h bin.

29

tridimit
117 o

C cristobalit
253 o o

Thch an h o 57 3 C Thch anh

870 o

tridimit o 163 C C tridimit

o 1470

C
1728 o

cristobalit

Nng chy

1050

Hnh 34 S biu din s chuyn ho gia cc dng th hnh ca SiO2

Trong thc t nhit chuyn ho cc dng th hnh ca SiO2 cn ph thuc vo nhiu yu t nh s c mt ca nhiu cht khong ho, ch nng nhit v.v Trn y ch nu ln cc dng th hnh ca SiO2 p sut kh quyn. Di p sut cao cn c cc dng th hnh khc na (xem gin trng thi ca SiO2 hnh 92 v bng 30).

1.2.2 Hp cht gia cc oxit

1.2.2.1 Spinen
Spinen l tn gi khong vt c cng thc MgAl2O4. C th xem spinen nh l hp cht ca hai oxit: oxit baz ca kim loi ho tr 2 v oxit lng tnh ca kim loi ha tr 3. MgO + Al2O3 = MgAl2O4 Spinen l i din cho mt lot cc hp cht c cng thc tng qut AB2O4. Trong A l cation ho tr 2 v B l cation ho tr 3. Mng li spinen gm cc ion oxi gi ghm chc c lp phng mt tm, cc cation A2+ v B3+ c sp xp vo cc hc t din v bt din (T+, T , O). Mi t bo mng gm 8 phn t AB2O4, ngha l c 8 khi lp phng b (hnh 35) trong c 32 ion oxi, 8 cation A2+ v 16 cation B3+. Ta c th tnh ton s cation, s anion v s hc t din T, s hc bt din O khi tng tng ghp 8 khi lp phng tm mt li vi nhau.

Hnh 35 T bo mng ca spinen

S ion oxi gm:

30

8 nh ca lp phng ln: 6 mt lp phng ln : 24 mt nh pha ngoi : Tm ca lp phng ln

8 1/8 = 1 6 1/2 = 3 = 12 Tng s c 32 oxi 24 1/2 = 12 =1

12 mt nh trong lp phng: 12 1

12 cnh ca lp phng ln: 12 1/4 = 3 S hc T (cn gi l phn mng A). Mi lp phng nh c 8 hc t din nm trong lp phng . T bo mng spinen c 8 lp phng nh. Nh vy mi t bo spinen c 8 8 = 64 hc T. S hc O (cn gi l phn mng B) gm: 8 tm ca 8 lp phng b: 24 cnh bin ca lp phng b: 24 cnh gia ca 6 mt bin: 6 cnh nm trong lp phng: 81 = 8 24 1/4 = 6
Tng s hc O l 32 24 1/2 = 12

61 =6

Nh vy, mi tinh th spinen c 64 + 32 = 96 hc T v O. M s cation ch c 8 + 16 = 24 cation. Ngha l ch 1/4 s hc trng cha cation, cn 3/4 hc trng khng. Nu 8 cation A nm trong 8 hc trng T, cn 16 cation B nm vo hc O th gi l mng li spinen thun, k hiu A[BB]O4. Nu 8 cation A nm trong 8 hc trng O, cn 16 cation B phn lm hai: 8 cation nm vo hc T, 8 cation nm vo hc O th gi l spinen nghch o, k hiu B[A.B]O4. Nu 24 cation A v B c phn b mt cch thng k vo cc hc T v hc O th gi l spinen trung gian.
3+ 2+ 2+ 3+ B1 - x A x A 1- x B1+ x O4 vi 0 < x <1

Kt qu nghin cu cho thy cu trc lp phng tm mt ca phn mng oxi b bin dng khi cation chui vo hc T v hc O. Th tch hc T b hn th tch hc O nn khi cation chui vo phn mng A lm cho khng gian ca hc T tng ln bng cch ni rng c 4 ion oxi (gin n khng gian t din). c trng cho s gin n khng gian t din ngi ta a vo mt khi nim gi l thng s oxi. Thng s oxi c xc nh bng phng php ghi gin nhiu x tia X hoc gin ntron. S chuyn dch ion oxi nh vy lm tng th tch khng gian t din v gim th tch khng gian bt din, kt qu lm cho th tch ca chng gn bng nhau. Mi lin h gia thng s oxi (W) v kch thc hc T (rA), kch thc hc trng O (rB) c biu din bng h thc: rA = (W 0,25) a 3 rO rB = (0,625 W) a rO Trng hp mng li lp phng l tng th W = 0,375. (7) (8)

31

a l hng s mng li spinen (), rA v rB l bn knh khi cu nm trong khng gian t din v khng gian bt din, rO l bn knh oxi. S tinh th kt tinh theo mng li spinen kh ph bin trong hp cht v c. Trong cng thc tng qut AB2O4 th A2+ c th l Cu, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, Pb, Fe, Co, Ni. Cation B3+ c th l Al, Cr, Fe, Mn, t khi gp Ga, In, La, V, Sb, Rh. T hp cc cation li cho thy c rt nhiu hp cht spinen. Tuy nhin cng cn phi ni thm rng khng phi tt c cc hp cht c cng thc AB2O4 u kt tinh theo h lp phng nh spinen. V d nh BeAl2O4, CaCr2O4 thuc h hnh thoi, cn SrAl2O4 thuc h t phng. Trong khi mt s hp cht oxit ng vi cng thc A2BO4 (ng vi A2+, B4+), v d Mg2TiO4 li kt tinh theo h lp phng v c sp xp vo nhm spinen. l cc hp cht nh titanat, stanat ca coban, st(II), magi, km, Ngoi cc oxit phc tp ra, cn c cc spinen c anion l chalcogen (S2, Se2, Te2) hoc halogen. V d Li2NiF4. Do kh nng thay th ng hnh, ng ho tr hoc khng ng ho tr cc cation trong spinen oxit lm cho s lng hp cht spinen tng ln rt ln. V d t hp cc cation trong spinen oxit cho ta cc loi sau:
Spinen T hp cation MgAl2O4 2;3 Mg2TiO4 2;4 LiAlTiO4 1;3;4 Li0,5Al2,5O4 1;3 LiNiVO4 1;2;5 Na2WO4 1;6

Cc hp cht spinen c gi tr rt ln trong k thut. Chng c s dng lm bt mu, vt liu chu la, vt liu k thut in t, qu, Do vn nghin cu tng hp spinen v cc tnh cht, c, in ca chng l i tng nghin cu ca nhiu nh khoa hc. Theo dn in, c th nh gi c cu to bn trong ca spinen. V d Fe3O4 v Mn3O4 u c cu trc spinen, nhng trong khi Mn3O4 l cht in mi (khng dn in) cn Fe3O4 li c dn in cao nh kim loi. l do Fe3O4 c cu trc spinen o: Fe3+T[Fe2+Fe3+]OO4, cn Mn3O4 c cu trc spinen thun: Mn2+T[Mn23+]OO4. Trong mng tinh th spinen Fe3O4, cc ion Fe2+ v Fe3+ c phn b trong cc bt din. Cc bt din ny tip xc vi nhau theo mt cnh chung, do cation st c mc oxi ho khc nhau m gn nhau nn trao i in tch d dng, l trng dng c th chuyn t Fe2+ sang Fe3+. Cn mng tinh th spinen Mn3O4 th Mn3+ nm trong bt din, Mn2+ nm trong t din. Bt din v t din ch tip xc vi nhau qua nh, ngha l cc cation Mn3+ v Mn2+ nm cch xa nhau hn so vi khong cch Fe2+ v Fe3+ trong Fe3O4. iu ny lm cho s trao i in tch trong Mn3O4 kh khn hn nhiu.
Bng 10 Tnh cht ca mt s spinen Cng thc MgAl2O4 ZnAl2O4 CoAl2O4 NiAl2O4 CuAl2O4 MnAl2O4 FeCr2O4 Tinh th Lp phng -nt-nt-nt-nt-nt-nt(8,09) (8,1) (8,04) 7,5-8 >7 >7 4,58 4,37 4,45 4,58 4,12 4,392 1930 1960 2020 1780 0,596 0,90 18,6.104 11,7.104 36,4.104 a () (8,09) cng 8 d (g/cm3) 3,57 tonc 2135 Gin n
5 (-10 )

R(900oC) 75,3.104

0,593

Khng tng hp

32

MgCr2O4 ZnCr2O4 FeCr2O4 CoCr2O4 NiCr2O4 MnCr2O4 CuFe2O4 MgFe2O4 ZnFe2O4 CdFe2O4 MnFe2O4 FeFe2O4 NiFe2O4 CoCo2O4 MgCo2O4 MgV2O4 CaV2O4 MnV2O4 BeAl2O4 BaAl2O4 Mg2TiO4 Zn2TiO4 Mn2SnO4

-nt-nt-nt-nt-nt-nt-nt-nt-nt-nt-nt-nt-nt-nt-nt-nt-nt-ntHnh thoi Lp phng Lp phng Lp phng Lp phng

(8,31) (8,31) (8,34) (8,31)

6 >7 >7 -

4,429 5,393 4,998 5,580 5,160 4,870 5,700 4,560 5,330 5,800 4,900 5,210 5,340 6,073

2330 2180 1750 1598 P.hu 1870 ph 1820

0,96 + 0,85 1,15 1,53 0,573

10,3.102 97,2.102 54,7.10 40,1.10 25,1 78,0 5,4(300o) 51,3 -

(8,36) (8,42)

6,65 6,5 6

(8,40) (8,35) -

6 5 -

4,960 4,240 4,570 3,720 3,560 5,360 4,640

(8,42) (8,52) -

8,5 8 >6

1,12

1850

Vai tr ca s xen ph obitan d cng nh hng mnh n tnh dn in. V d spinen LiMn2O4 v LiV2O4 u c cu trc ging nhau l Li[Mn3+Mn4+]O4, Li[V3+V4+]O4. Trong c hai spinen, v tr bt din u cha ng thi mt loi cation c mc oxi ho khc nhau l +3 v +4. Tuy nhin, s xen ph d trong vanai ln hn trong mangan, iu ny c phn nh tnh cht in, LiMn2O4 l cht bn dn theo c ch nhy, cn LiV2O4 l cht dn in kiu kim loi. Vn nghin cu tng hp spinen v nghin cu tnh cht quang, c nhit, in, t ca chng l i tng ca nhiu nh ho hc v c. Theo dn in c th nh gi gin tip v cu to bn trong ca spinen cng nh ca dung dch rn spinen. V dn in th c th xp cc spinen thuc v loi hp cht bn dn v c th phn thnh 3 nhm:
Aluminat c dn in rt b (in tr ring 990oC R = 105106 m.cm), cromit c dn in trung bnh (R 990oC t 103104 m.cm), ferit c dn in cao (R 990oC t 10102 m.cm) ring FeFe2O4 c dn in gn bng dn in ca kim loi.

33

Trong aluminat, tnh dn in c quyt nh bi cation ho tr 2, cn cromit v ferit (tr hp cht FeO) li c quyt nh bi cation ho tr 3. Mt trong cc c tnh quan trng ca spinen l d dng to thnh dung dch rn thay th vi nhau do thng s mng ca chng gn bng nhau. V d, cc h spinen MgAl2O4-MgCr2O4, FeCr2O4-FeFe2O4 c gin trng thi thuc kiu tnh tan khng hn ch. Cromit cng d trn ln vi ferit. Mt s spinen c th to dung dch rn vi nhm oxit, c bit vi -Al2O3 c mng li ging vi mng li tinh th ca spinen. Ni chung, tnh cht ca spinen c quyt nh bi tnh cht v hm lng ca cc oxit hp phn. Khi tng hp spinen hoc khi hnh thnh dung dch kiu spinen u c s tng th tch ca pha tinh th. Mt nt c trng cn quan tm l phn ng thay th trong spinen, v d cc aluminat vi oxit c 3 kiu tng tc: 1) MgO + BeAl2O4 = MgAl2O4 + BeO 2) MgO + NiAl2O4 = (Ni,Mg)O + (Mg,Ni)Al2O4 3) Cc aluminat trn ln hon ton cn cc oxit th trn ln khng hon ton. V d trong cc h oxit km. c tnh rt quan trng i vi k thut ca spinen l chu la cao, bn vi cc tc nhn oxi ho cng nh tc nhn kh (xem bng 10). Trong cc spinen trn y th FeFe2O4 c ngha quan trng nht, trong st hai mc oxi ho l II v III. Da vo kt qu nghin cu dn in v t tnh c th kt lun c rng FeFe2O4 thuc kiu spinen nghch o, ngha l FeII nm trong hc O cn FeIII mt na nm trong hc O, mt na nm trong hc T. Vi cc ferit c th biu din bng cng thc tng qut sau:
+ 3+ 2+ 3+ M2 x Fe1_ x [M1_ x Fe1+ x ]O4

Trong cation nm trong hc T c t ngoi du mc, cn nm trong hc O th trong du mc. Khi x = 1 ta c spinen thun, x = 0 ta c spinen nghch o. Spinen trung gian th 0 < x < 1. i lng x gi l mc nghch o ca spinen cho bit lng M2+ nm trong hc T. S ph thuc gia mc nghch o v nhit c th biu din bng h thc:
_ x(1 + x) = e E / kT _ 2 (1 x)

(9)

k l hng s Bonzman, T l nhit tuyt i, E l bin thin nng lng t do ca phn ng:
+ 3+ 2+ 3+ M2 B + Fe A = M A + Fe B E

trong : A, B ch phn mng A v phn mng B trong AB2O4. Nh vy, mc nghch o lin quan n iu kin ch ho nhit ca ferit. Kt qu nghin cu bng phng php nhiu x ntron cho thy cu trc ca spinen thun c ferit km v ferit caimi Zn[Fe2O4], Cd[Fe2O4]. Spinen nghch o c Fe3+[Fe2+Fe3+O4], Fe3+[CoFe3+O4], Fe3+[NiFe3+O4], Fe3+[Li0,5Fe1,5O4]. Spinen trung gian gn thun (x = 0,8) Mn0,8 Fe0,2[Mn0,2Fe1,8O4]. Spinen trung gian gn nghch (x = 0,1) Mn0,1Fe0,9[Mn0,9Fe1,1O4].

34

C ba yu t nh hng n s phn b cc cation A v B vo v tr t din, bt din. a) Bn knh ion: Hc T c th tch b hn hc O do ch yu cc cation c kch thc b hn c phn b vo hc T. Thng thng rA2+ ln hn rB3+ ngha l xu th ch yu l to thnh spinen nghch o. b) Cu hnh electron: Tu thuc vo cu hnh electron ca cation m chng thch hp vi mt kiu phi tr nht nh. V d Zn2+, Cd2+ (c cu hnh 3d10) ch yu chim cc hc T v to nn spinen thun, cn Fe2+ v Ni2+ (c cu hnh 3d6 v 3d8) li chim hc O v to thnh spinen nghch o. c) Nng lng tnh in: Nng lng tnh in ca mng spinen (nng lng Madelung) to nn bi s gn nhau ca cc ion khi to thnh cu trc spinen. S phn b sao cho cc cation A2+ nm vo hc T, B3+ nm vo hc O l thun li v nng lng nht.

1.2.2.2 Perpkit
Perpkit l tn gi ca khong vt c cng thc CaTiO3. Mng li ca perpkit thuc h lp phng, cation titan nm tm lp phng, 6 ion oxi nm tm cc mt, 8 ion canxi nm cc nh (hnh 36). Mi t bo c cha mt phn t CaTiO3.

Hnh 36 T bo mng CaTiO3

Cng c th m t t bo perpkit theo mt cch khc. V d t bo mng ca SrTiO3 nh trn hnh 37a cho ta thy: Ion titan nm cc nh, c to (0, 0, 0) c s phi tr bng 6; di lin kt Ti O bng a/2 = 3,905/2 = 1,956. Ion sronti tm t bo, c to (1/2, 1/2, 1/2). S phi tr 12, khong cch Sr O bng 2 = 2,76 , ion oxi nm tm cc cnh c to (0, 0, 1/2). Mi ion oxi c bao quanh a 2 bng 2 ion titan (vi khong cch 1,953) v 4 ion Sr (vi khong cch 2,76). Trong cu trc perpkit cc ion oxi khng to thnh mt phng xp kht nht, nhng cng vi ion Sr to thnh mt phng xp kht nht. thy r iu ny nn so snh vi mng li NaCl. y ion Cl nm gia cc cnh v tm ca t bo. Trn hnh 37b c v mt phng xp kht theo kiu lp phng. Mt phng cha ion Sr (nh s 1) v 6 ion oxi (nh s 2, 3, 4, 5, 6, 7). Mt phng ny song song vi mt phng 111 cha ion Ti A, B, C.

35

Trong mt xp kht ion Sr chim 1/4 nguyn t, cn 3/4 l ion oxi. Kiu cu trc perpkit bao gm mt s ln hp cht v c cng thc tng qut ABX3, trong X c th l ion oxi hoc halogen. Trng hp chung A l cation c kch thc ln, B l cation c kch thc b. Cation A cng vi X to thnh kiu gi ghm chc c lp phng mt tm, cn ion vi kch thc b B nm tm khi lp phng . Tng in tch dng ca A v B phi bng tng in tch m ca X. Do cc t hp c th c ca hp cht ABO3 l +1 v +5, +2 v +4, +3 v +3 vi hp cht ABX3 (X l halogen) ch c mt trng hp duy nht l +1 v +2. Bng 11 gii thiu mt s hp cht kt tinh theo kiu perpkit. Hp cht c cu trc perpkit ng vai tr quan trng trong vt liu p in, vt liu bn dn. Hu ht hp cht perpkit c cng thc ABO3 u c tnh cht xecnhet in. Theo Holsmit th gia tnh cht xecnhet in v cu trc perpkit ABO3 c mi lin h c nh gi bng yu t tlrng (t).
t=
z

rA + rO 2(rB + rO )

(10)

Ti
4

2 7 6 1

3 4 5

Sr
y
5

(b)

(a)

Ti4+,

Sr2+,

O2-

Hnh 37 a) T bo mng ca SrTiO3; b) mt xp kht

Bng 11 Cc hp cht kt tinh theo kiu perpkit in tch cation +1 v +5 +2 v +4 Hp cht perpkit NaNbO3, KNbO3, AgNbO3, AgTaO3, SrTiO3, SrZrO3, SrHfO3, SrSnO3, BaTiO3, BaZrO3, BaSnO3, BaCeO3, BaPrO3, BaThO3 LaAlO3, TiTiO3, LaCrO3, LaMnO3, LaFeO3 KMgF3, KNiF3, KZnF3

+3 v +3 +1 v +2

Yu t tlrng t ny nm trong khong 0,95 n 1 th ta c cu trc lp phng v c tnh xecnhet in, t nh hn 0,95 th thuc loi lp phng bin dng v khng c tnh xecnhet in.

36

y, cn lu mt iu l trong tnh ton chng ta xut pht t quan nim cho rng lin kt trong perpkit thun tu l lin kt ion. Nh trn chng ta u bit iu ny khng thc s ng, do khng th p dng quy tc ca Golsmit mt cch my mc c. Trong mng li tinh th perpkit thng c l trng cation A, cn cation B th hu nh cha gp l trng. C th xem cu trc ca WO3 thuc dng perpkit m khng c cation A. Hp cht NaxWO4 (x = 0,3 1) c mng li n gin cu trc perpkit bin dng trong mi gi tr ca x. Ngi ta cng gp perpkit c l trng anion. V d titanatsronti c cng thc SrTiO2,5 ng hnh vi cu trc lp phng ca SrTiO3, trong c l trng O2. Mt trong cc hp cht quan trng ca nhm perpkit l BaTiO3. y l cht p in u tin thu c di dng gm v c s dng rng ri trong k thut hin i. Bari titanat c 2 dng th hnh chnh. Trn 1460oC barititanat tn ti di dng lc phng, khng c tnh p in; di 1460oC chuyn thnh dng lp phng v c tnh p in. Nhng khi lm ngui xung di 1460oC dng lc phng c th cha chuyn thnh lp phng v tn ti dng khng bn n nhit phng. Mt tnh cht l th ca dng lp phng l bin ho mng li khi thay i nhit . Khi lm lnh n 120oC, t bo perpkit b ko di theo mt cnh lm cho mng li t lp phng bin thnh t phng, c/a ln hn 1. S chuyn pha lc ny km theo bin i bt thng v in mi chng t c pht sinh s phn cc ca t bo. Lm lnh tip tc n 0oC li xy ra bin ho th hnh th hai. S thay i cu trc lc ny c th hnh dung nh ko di khi lp phng dc theo ng cho ca mt mt bn. nhit thp hn na (-90oC) c s bin ho th hnh th 3, ln ny t bo b ko di theo ng cho ca khi lp phng to thnh khi mt thoi (xem hnh 38). tt c ba nhit hng ca momen lng cc xecnhet in u song song vi hng ko di t bo mng. l do s chuyn dch v tr ca ion titan trong bt din oxi. Ban u khi h nhit s hng v pha mt ion oxi, sau hng v pha gia hai ion oxi v cui cng hng v gia ba ion oxi. Cch gii thch ny c Kay H. F. v Vonsden a ra t nm 1949. Cng nh spinen, cc hp cht c cu trc perpkit c th to thnh dung dch rn thay th vi nhau trong mt gii hn rt ln. V d PbTiO3, SrTiO3, BaZrO3, BaSnO3, BaHfO3, KNbO3, c th to thnh dy dung dch rn khng hn ch vi BaTiO3.

37

Lp phng
a1 = a2 = a3 = 4,009 A a3 a2 a1 120 oC 130oC: a1 = a2 = 4,003 A o c = 4,022 A c a2 a1 0oC: a1 = a2 = 3,992 A o c = 4,035 A 0oC: a1 = a2 = 4,012 A o c = 3,989 A o = 89 51' -90oC: a1 = a2 = a3 = 3,998 A = 89o52'
o o o o o

T phng

0oC n t c

Hnh thoi

a2 a1

-90oC Mt thoi

0oC: o a' = 5,667 A o b' = 5,681 A o c' = 3,898 A

a3

a2 a1

-90oC: o a' = 5,668 A o b' = 5,683 A o c' = 3,876 A

Hnh 38 Bin ho ca t bo mng BaTiO3

S thay th Ba2+, Ti4+ trong barititanat bng cc cation ho tr 2 v bng Zr4+ c th ci thin nhiu tnh cht vt l ca gm p in bari titanat. Gm PZT l mt loi dung dch rn nh vy. y Pb2+ thay th Ba2+ cn Zr4+ thay th Ti4+, loi gm PZT hin ti vn cn gi vai tr trong k thut.

1.2.2.3 Pyrclo A2B2O7.

Pyrclo l tn gi ca nhm khong vt cha t him c cng thc khng n nh (Na,Ca,)2(Nb,Ti)2O6.F.OH. Ch pyros t gc Hylp c ngha l la, cloros c ngha l mu lc. Loi khong vt ny khi th bng phn ng ng thi th c mu lc. Thnh phn khong vt ny rt khng n nh (bng 12).
Bng 12 Thnh phn ca mt s mu khong vt pyrclo Cht Nb2O5 Ta2O5 TiO2 ThO2 UO2 UO3 Hm lng (%) 063 077 213 05 011,4 015,5 Na2O K2O CaO MnO FeO Fe2O3 Cht Hm lng (%) 16 01,4 418,1 07,7 010 09,8 (Ce,La)2O3 (Y,Er)2O3 SnO2 ZrO2 WO3 H2O Cht Hm lng (%) 215,3 05,1 04,1 05,7 00,3 06

Ngoi ra cn cha mt t Sb2O5, MgO, PbO, HfO2, SiO2, Al2O3, SrO, BeO, CuO, GeO2.

38

Hnh 39 Cu trc pyrclo Er2Ti2O7

Khong vt pyrclo thuc h lp phng. Mng tinh th tng t florit CaF2. Khi chuyn t florit thnh pyrclo th v tr ca F b chim bi O2. Nhng mi t bo mng c mt ion O2 b khuyt, 7 ion O2 cn li b chuyn dch lm cho v tr l tng ban u bin i. Trong cng thc tng qut ca pyrclo A2B2O7 th A l cation c kch thc ln hn c bao quanh bng 8 ion O2 to thnh mt khi lp phng bin dng. Cation nh B4+ nm trong bt din dng BO68. Cc bt din BO6 ni vi nhau qua nh to thnh mt dy dy xch dc gn song song vi nhau. Cc dy xch ny li ni vi nhau qua bt din BO6 lp nn dy dy xch ngang trc giao vi dy dy xch dc (hnh 39). V tr trung gian gia cc bt din BO6 c xp bng cc ion A. Nhm pyrclo c gi tr nht trong vt liu mi l titanat t him c cng thc tng qut l Ln2Ti2O7. Theo tnh ton ca nhiu tc gi th ch c nhng nguyn t t him no c bn knh tho mn h thc:
1,22 < rLn3+ rTi4+ < 1,5

th hp cht titanat mi c cu trc pyrclo. Bng 13 cho bit bn knh ca cc ion t him v t s
Bng 13 Bn knh ca mt s cation t him Ion r () rLn3+/rTi4+ Ion r () rLn3+/rTi4+ La3+ 1,061 1,660 Gd3+ 0,938 1,460 Ce3+ 1,034 1,610 Tb3+ 0,923 1,440 Pr3+ 1,013 1,580 Dy3+ 0,908 1,420 Nd3+ 0,995 1,550 Ho3+ 0,894 1,400 Pm3+ 0,979 1,530 Er3+ 0,889 1,390 Sm3+ 0,964 1,500 Tm3+ 0,899 1,390 Eu3+ 0,050 1,480 Yb3+ 0,858 1,34 Lu3+ 0,84 1,32

rLn3+ rTi4+

(rTi4+=0,64).

39

Nh vy l t La n Pm th cc titanat Ln2Ti2O7 kt tinh theo h n t, cn tt c cc t him cn li (t Sm n Lu) th titanat Ln2Ti2O7 kt tinh theo h lp phng kiu pyrclo. Trong dy ny c s ph thuc tuyn tnh gia thng s mng a v bn knh ion Ln3+. S chuyn t cu trc florit n pyrclo lm xut hin cc vch siu cu trc trn gin tia X, c bit trn gin ph hng ngoi chng ta thy mt cch kh r rt s chuyn pha pyrclo khi xt h titanat v zircnat t him (RZr4+) = 0,82 (xem hnh 40).

Hnh 40. Ph hng ngoi ca titanat v zirconat t him

i vi h titanat, cc pic c trng cho cu trc pyrclo ch c t Sm n Lu. Cn vi h zirconat th pic c trng cho pha pyrclo li ch thy i vi La, Pr, Nd, Sm, Eu, Gd, vi cation t him c bn knh b hn Gd th khng to thnh pha c trt t. c tnh ca pyrclo l tnh bt hp thc. Tnh bt hp thc y l do hai nguyn nhn. a) C s thay th mt phn Ti4+ bng cc ion t him Ln3+, lc ny s xut hin l trng b sung trong phn mng anion. b) C s thay th mt phn Ln3+ bng Ti4+ . Do cng thc tng qut ca pyrclo c th vit
Ln 2 x Ti 2 x O7 x / 2
3+ 4+
1 x / 2

Nu thay th 1 ion Ln vo tr Ti th thiu mt in tch dng, m bo cn bng v in phi loi ra mt in tch m, hay ni cch khc loi ra 1/2 v tr ion oxi, do lc u ch c mt l trng ca ion oxi by gi thm 1/2 l trng oxi v cng thc tng qut s l: Ln2+x Ti2-x O7-x/2
1+x/2

Trong dy titanat t him c nhiu cng trnh nghin cu kh k cu trc ca Er2Ti2O7 v Y2Ti2O7 bng cc phng php nhiu x tia X v gin ntron. T bo mng li ca Er2Ti2O7 c cha 16 Er3+, mi ion Er3+ c bao quanh bng 8 ion oxi trong 2 ion nm v tr i din nhau v cch nhau mt khong 2,185,cn 6 ion oxi cn li nm trn cng mt mt phng cch nhau 2,471 (hnh 39).

40

1.2.2.4 Pha siu dn 1:2:3

Gm siu dn nhit cao (gn 100 K) l loi vt liu mi c ra i vo cui nm 1986, hin nay nhp nghin cu quanh lnh vc ny ang c pht trin vi quy m cha tng thy. Trong vng 4, 5 nm thp k 80 ca th k XX, mi nm c ti hng nghn cng trnh nghin cu tng hp, nghin cu cu trc v cc tnh cht ca loi vt liu ny. Ti liu s 9 trnh by tng quan v lnh vc ny cho n nm 1988. Cho n nay bit c nhiu loi gm c tnh siu dn nhit cao, trong loi quan trng nht c cng thc ng vi thnh phn RBa2Cu3O7-x. y R l Y hoc Ln. Ln lt theo th t s nguyn t ytri, bari, ng trong cng thc ny, ngi ta gi tt l pha gm 1:2:3. Gm RBa2Cu3O7-x c cu trc tinh th thuc h hnh thoi. C th xem cu trc ca pha ny nh l dn xut ca peropkit c nhn ba gi tr trc C theo trt t Ba-Y-Ba. T bo mng ca pha 1:2:3 gm cc lp phng peropkit c nh l nguyn t Cu, hai lp phng c tm l bari kp gia mt lp phng c tm l ytri. c tnh quan trng cu cu trc pha 1:2:3 l v tr ca ng khng ging nhau do s b tr cc l khuyt oxi. Nguyn t Cu v tr 1 l tm ca mt hnh vung trong mt phng bc. Nh vy s phi tr ca nguyn t Cu ny l 4. Nguyn t Cu v tr th 2 nm trong khi chp c y l hnh vung. Nh vy s phi tr ca nguyn t Cu ny l 5 (xem hnh 41). Cc hnh chp CuO5 v mt CuO4 to thnh tng lp song song vi mt ab. Hai hnh chp CuO5 kp gia mt lp CuO4. Hai hnh chp quay nh v pha hnh vung CuO4 v ni vi nhau qua cu oxi. Tu theo iu kin tng hp (c bit l p sut ring phn ca oxi trong h phn ng) s l trng oxi thay i. Do h s ca oxi trong cng thc khng xc nh (bng 7-x) v trng thi oxi ho ca ng cng thay i lm nh hng n tnh cht in ca gm. Cuprat lantan La2CuO4 c cu trc tinh th ca K2NiF4 l cht bn dn nhng khi ch ho nhit p sut ring phn PO2 cao, hoc to ra cc khuyt tt cation trong cc phn mng th c th bin thnh trng thi siu dn 40K. C th gii thch iu ny nh sau: Hp cht cuprat khi mi iu ch c cc khuyt tt stki (xem chng sau) va c l trng cation va c l trng anion do sn phm thu c c cng thc La2-2xCu1-xO4-4x. p sut ring phn cao ca oxi, th oxi c th lp y cc l trng anion, do mt s cation ng (II) s chuyn thnh cc mc oxi ho cao La2-2xCu1-xO4. Hoc c th iu ch pha siu dn cuprat lantan bng phn ng tng hp vi t l d CuO di p sut bnh thng ca oxi. Lc ny giai on ban u to thnh cc l trng anion v hnh thnh hp cht trung gian La1,9Cu2+O3,85. Hp cht ny c kh nng chim ly oxi to nn La1,9Cu2+3+O4. Phng php th ba to thnh cuprat siu dn l hp kim ho La2CuO4 bng cc oxit kim th. V d hp kim ho bng sronti th thu c pha tinh th La2-xSrxCuO4 vi gi tr x t 0,15 n 0,2. C th thay th Cu bng kim loi chuyn tip 3d khc.

41

(a)

(b)

(a)

(b)

Hnh 41 Cu trc ca pha siu dn 1:2:3 (YBa2Cu3O7x ) (a) v (a) thuc h hnh thoi; (b) v (b) thuc h t phng

1.2.2.5 Silicat
Silicat l loi hp cht ph bin nht trong v Qu t cng nh trong vt liu v c. Cu trc ca silicat c to thnh t s gi ghm chc c cc ion oxi. Trong cc hc trng ca b khung anion c sp xp cc cation kim loi v c bit ion Si4+ chim t l ln

42

nht. Tu thuc vo kch thc ca cation m chng c xp vo cc hc trng t din, bt din, lp phng, lc phng. Cc silicat t nhin thng thng c cc cation Si4+, Al3+, Fe3+, Cr3+, Mg2+, Fe2+, Ca2+, Na+, K+ Khi t l rc/ra nm gia 0,41 v 0,732 th cation c SPT 6, khi t l nm gia 0,732 v 1 th cation c SPT 8. Bng 14 gii thiu SPT ca mt s cation ch yu trong silicat.
Bng 14 Bn knh ion v s phi tr ca vi ion quan trng trong silicat Nguyn t Oxi Silic Nhm Ion O2+ Si
4+

Bn knh ion () (h thng Paolinh) 1,36 0,39 0,57 0,59 0,83 0,78 0,98 1,06 1,33

rc/ra 0,29 0,42 0,59 0,63 0,57 0,725 0,8 1,0

SPT 4 4 6 6 6 6 6 8 8 12

n v cu trc t din t din bt din bt din bt din bt din bt din lp phng lp phng lc phng

Al3+ Fe
3+

St Fe2+ Magi Natri Canxi Kali Mg2+ Na+ Ca K

2+

Trong silicat c nhiu ion c th nm trong cc n v cu trc khc nhau. V d Al va c th nm trong t din va c th nm trong bt din. Na va c th nm trong bt din va c th nm trong khi lp phng C th biu din mng li silicat bng cch sp xp cc khi t din SiO4 v bt din M(OH)6 (M c th l Al3+, Mg2+, Fe3+ ) theo mng li 3 chiu trong khng gian. S hnh thnh cc khong vt thng xy ra s thay th cation trong mng li. Bi vy, cng thc khong vt thng c vit di dng tng qut. V d khong vt almanin thuc nhm 2+ + . Nhng v tr nt mng ca Al3+ c th thay grnat c cng thc l thuyt l Fe3 Al3 2 [SiO 4 ]3 th bng Fe3+, v tr ca Fe2+ thng b thay th bng Mg2+, Mn2+, Ca2+. Kh nng thay th ph thuc vo s c mt ca cation M2+, M3+ trong qu trnh hnh thnh mng li almanin, nhit , pH Do cng thc khong vt almanin thng c vit di dng tng qut: (Fe2+,Mg,Mn,Ca)3(Al,Fe)2[SiO4]3, trong cng thc ny cn hiu mt phn t c cha tng s 3 cation M2+ v hai cation M3+. Nu kt qu phn tch pha (phng php nhiu x tia X, phng php DTA, phng php hin vi phn cc) cho bit mu ca ta ch c mt khong vt almanin duy nht, th t kt qu phn tch ho hc ca mu ta c th vit c cng thc chnh xc ca phn t almanin. Sau y l phng php xc nh cng thc cu to. V d t kt qu thnh phn ho hc bng 15 ta c: C 2,472 nguyn t oxi th c 0,615 nguyn t silic, trong phn t almanin c 12 nguyn t oxi, vy mt phn t almanin c 2,985 hoc quy trn l 3 nguyn t silic. Cng tnh nh vy ta c s nguyn t kim loi trong mt phn t almanin ghi ct 6 ca bng 15 v cng thc cu to ca mu nghin cu l (Fe2+2,315Mg0,366Mn0,169Ca0,155)(Al1,961Fe3+0,038)[SiO4]3.

43

T phn trm khi lng ca cc nguyn t trong mu nghin cu v cc thng s t bo mng, t trng (g/cm3), ta c th tnh ton s nguyn t ca mi t bo mng. V d mu ca chng ta c t trng l d, th tch ca mt t bo l V(3) hoc V.1024(cm3). Khi lng ca mt t bo l V.d.1024g. Thnh phn phn trm khi lng ca nguyn t kho st l Q, tng s phn trm ca cc nguyn t l T, ta tnh c khi lng ca nguyn t trong mt t bo l Q.V.d.1024/T.
Bng 15 Thnh phn ho hc ca mu almanin %khi lng S pt. oxit S cation Oxit (3) (4) (2) (1) SiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Tng 36,96 20,65 0,70 34,30 2,45 3,17 1,81 100,04 0,615 0,205 0,004 0,477 0,035 0,077 0,032 0,615 0,406 0,008 0,477 0,035 0,077 0,032 S ion O2 (5) 1,230 0,609 0,012 0,477 0,035 0,077 0,032 2,472

(6) 2,985 3

1961 1,999 2 0.038

2,315 0.169 3,005 3 0,366 0,155

Nguyn t lng ca nguyn t l A. Nu gi s nguyn t c trong T gam mu l R (gi tr ghi trong ct 4) th s nguyn t trong mt t bo l: Z=
Q.V.d.10
_

24
_

A.1.6602.10

24

R.V.D (16) v Q/A = R 1,6602.T

V d almanin c t bo mng thuc h lp phng, cnh a = 11,54. T trng d = 4,22 g/cm3. Trn bng 15 c tng l 100,04. Trong 100,04 gam mu c cha 2,472 nguyn t oxi (R = 2,472). Do s nguyn t oxi c trong mt t bo l:
(11,54 ) 3 . 4 , 22 . 2 , 472 = 96 ,51 1, 6602 .100 , 04

Kt qu thu c l s l, iu ny l do sai s khi phn tch thnh phn ho hc, khi xc nh gi tr a, d. Nhng kt qu kho st nhm khng gian ca h tinh th grnat cho thy s nguyn t oxi, kim loi M2+, M3+, silic trong mt t bo nguyn t ch c th l 16, 24, 32, 48, 96. Vy y ta ly gi tr l 96. Silicat c phn thnh cc lp sau y: 1) Octosilicat: (cn gi l nezosilicat), gm cc t din ring l SiO 4 4 . Bn ho tr d c bo ho bng mt cation ho tr 4+ (v d zircon ZrSiO4), hoc bng hai cation ho tr 2+ (v d fosterit Mg2SiO4, faialit Fe2SiO4). Cc cation Fe2+ v Mg2+ c kch thc gn bng nhau do c th thay th ln nhau trong fosterit v trong faialit to thnh mt dy dung dch rn lin tc c tn gi l olivin (hoc cn gi l periot) vi cng thc (Mg,Fe)2SiO4.
_

44

-3 -

24+

-3
2-

Hnh 42 T din

SiO

44

trong mng octosilicat ( Si , O )

Hnh 43 Sorosilicat

Octosilicat thng kt tinh trong h tinh th i xng cao, c rn cao, ch s khc x cao. i khi c cha ion O2 khng lin kt trc tip vi silic. Lp silicat ny c cc nhm sau: Nhm olivin (Mg,Fe)2 [SiO4] Nhm grnat (Ca,Fe,Mn,Mg)3(Al,Fe,Cr)2 [SiO4]3 Nhm silicat nhm Al2[OSiO4], topaz Al2[F2SiO4], v sphen CaTi[OSiO4] Silimanit c ba dng th hnh u c cng thc chung Al2[OSiO4] gi l silimanit, andaluzit, disten. 2) Sorosilicat: n v cu trc gm hai t din c mt oxi chung. Nh vy trong n v cu trc c 6 ho tr cha bo ho v cng thc ca b khung anion l [Si2O7]6. V d khong vt llilit Ca2Mg[Si2O7]. Anion OH c th kt hp vi nhm anion ny. V d khi kt hp thm 2 anion OH th c ion phc [Si2O7(OH)2]8 nh khong vt laosonit CaAl2[Si2O7 (OH)2].2H2O. Mng li ca lp ny c khi c mt t din c lp. V d epiot Ca2(Al,Fe)3[O.OH.SiO4.Si2O7 ] v ircaz Ca10(Mg,Fe)2[(OH)4(SiO4)5(Si2O7)]
Bng 16. Mt vi khong vt thuc lp octosilicat Khong vt Olivin Cng thc (Mg,Fe)2[SiO4] H tinh th hnh thoi d 3,3 H 6,57,0 Ch s khc x 1,671,87 1,631,83 1,921,96 1,962,02 1,641,67 1,691,72 1,70 1,83 1,80 1,73 1,89 1,86

Zircon Phenacit Willemit Pyrop Almanin Spossartit Grossulair Andradit Uvarovit

ZrSiO4 Be2[SiO4] Zn2[SiO4] Mg3Al2[SiO4]3 Fe3Al2[SiO4]3 Mn3Al2[SiO4]3 Ca3Al2[SiO4]3 Ca3Fe2[SiO4]3 Ca3Cr2[SiO4]3

t phng mt thoi mt thoi lp phng lp phng lp phng lp phng lp phng lp phng

4,7 34 3,94,2 3,51 4,25 4,18 3,53 3,75 3,77

7,5 7,58,0 5,5 7,07,5 7,0 7,07,5 6,5 7,0 7,0

45

Silimanit+ clas Topaz Sphen Datolit

Al2[OSiO4] AlBe[OHSiO4] Al2(F,OH)2SiO4 CaTi[(OSiO4)] CaB[(OH)SiO4]

hnh thoi n t hnh thoi n t n t

3,30 3,10 3,43,6 3,50 2,83

67 7,5 8,0 5,5 55,5

1,671,65 1,671,65 1,621,61 2,091,90 1,671,63

3) Xiclosilicat (silicat mch vng)

Bng 17 Mt vi khong vt thuc lp silicat vng Tn Benitit Catapleit Endialit Axinit Beryl Cordierit Cng thc BaTi[Si3O9] Na2Zn[Si3O9] (Na,Ca,Fe)6Zr[OH.Si3O9] Ca2(Fe,Mn)Al2[OH.BO3 Si3O12] Al2Be3[Si6O18] Mg2Al3[AlSi5O18] H tinh th Lc phng Lc phng Mt thoi Tam t Lc phng Hnh thoi Mt thoi d 3,7 2,8 3,0 3,3 2,7 2,6 3,5 H 6,5 6,0 5,5 6,5-7 7,5-8 7-7,5 7,5 1,65-1,7 1,7-1,68 1,6-1,58 1,54-1,63 Ch s Khc x

(Fe v Mn c th thay th Mg ti 10% Tucmalin R+,R2+3Al6[(OH) BO3) Si6O18] Da vo thnh phn ha hc ngi ta phn bit Tucmalin kim (Enbaite) Na(Al,Li)3Al6[(OH)4BO3)3 Si6O18] Tucmalin magi (Dravit) Na Mg3Al6[(OH)4BO3)3 Si6O18] Tucmalin st (Schor) NaFe3Al6[(OH)4BO3)3 Si6O18] Tucmalin canxi magi (uvit) CaMg3Al5 [(OH)4BO3)3 Si6O18] Dipta Cu6[Si6O18].6H2O Mt thoi 3,3 5 1,65-1,7

n v cu trc gm 3, 4, 6 t din ni nhau qua nh oxi to thnh vng (hnh 44). Nhng vng c th c lp hoc chng ln nhau to thnh khng gian trng cha cc cation c kch thc ln hn (Ca, K...) chim. Bng 17 gii thiu vi khong vt thuc lp ny. 4) Inosilicat (Silicat mch) c hai nhm: + Nhm pyrxen: Cc t din ni nhau bng 2 oxi. Cng thc khung anion c th vit [SiO3]2 hoc [Si2O6]4 (hnh 45, bng 18).
-

46

[Si3O9]6Hnh 44 Xiclosilicat

[Si4O12]8-

[Si6O18]12-

[Si2O6]4Hnh 45 Nhm pyrxen Bng 18 Mt vi khong vt nhm pyrxen Tn ipzit Jadeit git Spodulen Enstatit Cng thc CaMg[Si2O6] NaAl[Si2O6] Ca(MgFeAl)[Si2O6] LiAl[Si2O6] (MgFe)2[Si2O6] Tinh th n t n t n t n t hnh thoi d 3 3,4 3,5 3,2 3,5 H 5 7 5,5 6,5 5,5 Ch s khc x ng np 1,694-1,664 1,667-1,665 1,711-1,686 1,676-1,661 1,77-1,73

Mt phn MgO c th thay th bng FeO. Trong enstatit cha di 5% FeO. Nu FeO c gi tr gia 5 n 14% th gi l bronzit, nu FeO c trn 14% th gi l hypecten. + Nhm amphibn: Cng thc ca b khung anion l [Si4O11]6. Tm ca mi lc gic c th c nhm OH lc cng thc ca b khung anion l [(OH)Si4O11]7.
[Si4O11] 6-

Hnh 46 Nhm amphibn

47

Bng 19. Mt vi khong vt nhm amphibn Tn Trmolit Actinot Glaocophan Wollastonit Rodonit Cng thc Ca2Mg5[(OH)Si4O11]2 Ca2(MgFe)5[(OH)Si4O11]2 Na2Mg3Al2[(OH.Si4O11]2 Ca3[Si3O9] CaMn4[Si5O15] Tinh th n t n t n t tam t tam t d 2,3 3,0 2,9 3,5 H 5-6 6-6,5 5 6 Ch s khc x ng np 1,633 -1,60 1,634 1,61 1,63 1,61 1,634 1,62 1,76 1,72

5) Phylosilicat (silicat lp): Cc mch pyroxen hoc amphibn kt hp li vi nhau to thnh mt phng ln v hn. Nu xt mt n v nh nht c trng cho c lp th trong cu trc ny mi t din ch cn mt oxi cha bo ho ho tr. Do cng thc ca b khung anion c th vit di dng [Si4O10]4. Nhng lp phng ny chng ln nhau v cng quay _ nh t din SiO 4 4 vo nhau. Gia hai lp c cha ion OH v cc cation kim loi. Do cng thc cu trc ca b khung anion c c nhm OH v d [Si4O10(OH2)]6. Silic trong t din c th b thay th bng nhm n 50% nguyn t. Su nh ca 6 t
din SiO 4 4 to thnh cc mt lc gic, ion OH nm tm ca lc gic . Pha y cc t din cng c nhng mt lc gic. Khi hai mt y chng ln nhau s to nn cc khong trng dng khi lc lng. Cc cation kim loi c kch thc ln (s phi tr 12) nm trong khi lc lng ny.
_

Tal (Mg3[(OH)2Si4O10], mica KAl2[(OH)2AlSi3O10], bitit v cc khong vt st thuc lp phylosilicat.

K(MgFe)3[(OH)2AlSi3O10]

[Si 4O10 ]
Hnh 47 Nhm phylosilicat

Bng 20 Mt vi khong vt thuc lp phylosilicat Tn Cng thc Tinh th Tal Pyrofilit Apofilit Muscovit Mg3[(OH)2Si4O10] Al2[(OH)2 Si4O10] KCa4[F.Si8O20] KAl2[(OH.F)2 AlSi3O10] n t n t t phng n t

d 2,7 2,3

H 1 4,5

Ch s khc x 1,58-1,54 1,53 1,565-1,535

48

Phlogopit Biotit Lepidolit

KMg3[(OH.F)2 AlSi3O10] K(MgFe)3[(OH.F)2AlSi3O10] KLi2Al[(OH.F)2 Si4O10]

n t n t n t

2,9 3 3

3 3 3

1,60-1,56 1,66-1,60 1,56-1,54

Trong phylosilicat c mt nhm c bit l khong vt st. V khong vt st cn c nhiu ng dng trong ha vt liu nn di y chng ta xt k hn.
Khong vt st

Khong vt st c cu trc lp, mi lp gm mt hoc hai l t din SiO24 v mt l bt din Al(OH)63, hai l t din cng quay nh v l bt din. Ti cc nt chung ca t v bt din ion OH ca bt din c thay th bng O2 ca t din. Ty theo cch xp sp ca l t din (Te) v l bt din (Oc) m phn thnh cc nhm st sau y:
a) Nhm caolinit (Te-Oc). Caolinit l khong vt i din cho nhm ny. Mi lp caolinit gm c mt l t din (Te) v mt l bt din (Oc) (xem hnh 48). V rng bn knh O2 v OH u ln hn rt nhiu bn knh Si4+, Al3+, nn c th hnh dung mng tinh th caolinit gm cc anion O2- v OH- gi ghm chc c, cn cc cation Si4+ v Al3+ c sp xp vo cc hc trng ca phn mng anion .

Hnh 48 Cu trc tinh th caolinit

xc nh t bo mng ca caolinit, chng ta xem mt lc gic gm cc ion oxi l y. T dng cc mt phng thng ng (theo trc c) ct ln lt qua mt oxi, mt oxi v hiroxil v mt hiroxil (hnh 49). Cnh a ca t bo khong 5 n 5,44, cnh b khong 9 n 9,422. Kch thc mt y ny gn nh khng thay i vi tt c cc loi khong st. Cn chiu cao (cnh c) i vi mng caolinit c gi tr khong 7,1 n 7,15. Trn hnh v cho thy vi mt t bo caolinit c:
- Mt lc gic oxi gm: - Mt hn hp gm: 4 + 4/2 = 6O2 2 + 4/2 = 4Si4+ 2 + 4/2 = 4O2 1 + 4/4 = 2OH 3 + 2/2 = 4Al3+ 5 + 2/2 = 6OH

- Mt hiroxil:

Nh vy cng thc ca mt t bo caolinit l Al4[Si4O10](OH)8. Vit di dng oxit l 2(Al2O3.2SiO2.2H2O). Ta c th tnh c khi lng ring ca caolinit nh sau. Mi t bo c 2 phn t Al2O3.2SiO2.2H2O, ngha l khi lng mt t bo bng (2102) + (460) + (418) = 516 516/6,02.1023g.

49

Th tch mt t bo l 597,1 = 319,53 = 319,5.1024cm3 Vy d = 516/(6,02.1023 319,5.1024) = 2,68g/cm3 Nt c trng ca khong vt caolinit l lin kt hir gia mt gm cc ion O2 v mt gm cc ion OH lm cho cc lp gn vi nhau. Cp ht ca caolinit thng ln hn cc khong vt st khc.
(b) O OH
O
1/2

(a) O
1/2

(c)
OH

OH OH OH OH OH
1/2 1/2

OH OH OH OH OH OH OH OH

O
1/2

O O O 9A
o

1/4

O OH

1/4 1/2

O 1/2 O 1/2
1/4

O O

OH

O O
1/2O

1/2

O
1/4

OH
5A
o

OH O

OH

Hnh 49 Cc mt ct ca t bo caolinit a) Qua cc mt lc gic oxi; b) Qua cc mt hn hp oxi v hiroxil c) Qua cc mt hiroxil

b) Nhm monmorillonit (Te-Oc-Te) S cu trc ca nhm ny gm mt l bt din nm gia hai l t din. Theo cch xc nh trn y th mt t bo mng monmorillonit c:
- Mt lc gic oxi gm: - Mt hn hp gm : 4 + 4/2 = 6O2 4+ 2 + 4/2 = 4Si 2 2 + 4/2 = 4O 1 + 4/4 = 2OH 3 + 2/2 = 4Al3 2 2 + 4/2 = 4O 1 + 4/4 =2OH 2 + 4/2 = 4Si4+ 2 4 + 4/2 = 6O Te

Oc

- Mt lc gic oxi gm:

Te

Tng cng 2(Si4Al2O10(OH)2) Ngha l mi t bo ng vi 2 phn t Al2O3.4SiO2..H2O. Nh vy t l SiO2/Al2O3 trong monmorillonit ln gp 2 ln t l trong caolinit. Gia cc lp monmorillonit khng c lin kt hiro, do cp ht thng b hn nhiu so vi caolinit.

50

O2Si4+ OHAl3+, Mg2+ Fe3+, Fe2+

Hnh 50 Mng li tinh th monmorillonit

51

O2Si4+ OHAl3+,Fe3+.. Mg
2+

Hnh 51 Mng li tinh th clorit

Nt c trng monmorillonit l thng xuyn c s thay th Al3+ trong v tr bt din bng cc ion Mg2+, Fe2+, Fe3+, Cr3+ v thay th v tr Si4+ trong t din bng Al3+. in tch dng thiu do s thay th khng cng in tch c b tr bng cc cation trao i. Dung tch trao i cation ca nhm khong st ny c th t t 90 150 mlg/100 gam mu. Cc cation trao i ny thng xuyn c km theo cc phn t nc hirat. c) Nhm hiromica (Te-Oc-Te) Cu trc tinh th cng ging nh ca nhm monmorillonit, nhng hiromica cation b tr ch l K+. V rng kch thc ca K+ ln hn nhiu ca Na+, Mg2+ cho nn v tr K+ c gi kh chc khng tham gia phn ng trao i. d) Nhm clorit (Te-Oc-Te-Oc) 51). Gia cc lp ca monmorillonit cn c thm mt lp bt din bruxit [Mg(OH)6]4- (hnh 7) Tectosilicat (silicat vi cu trc 3 chiu) C th hnh dung mng tinh th tectosilicat gm cc t din SiO44 ni vi nhau qua nh oxi nh trong tinh th SiO2. Nhng y v tr ca Si4+ b thay th bng Al3+ c khi ti 50%. S in tch dng thiu do s thay th c b tr bng cc ion dng c s phi tr ln nh Ca2+, K+, Na+. Do lp silicat ny gi l alumosilicat. C 3 nhm tectosilicat l phenpat, phenpatoit, zeolit.
a) Nhm phenpat: Phenpat l khong vt ph bin nht ca v qu t (chim 50% khi lng). Cng thc ca phenpat thay i t X[AlSi3O8] n Y[Al2Si2O8] tu theo cation X v Y ngi ta phn thnh 2 nhm:

- Phenpat kim (octoz v microlin) u c cng thc chung K[AlSi3O8] nhng octoz thuc h n t, t trng 2,6, rn 6 c th cha mt t natri (di dng anbit), st, bari, rubii, cn microlin thuc h tam t.

52

Anbit Olgoclaz Aesin Labrade Bitonit Anoctit

(0 10%An, 90 100%Ab) (10 30%An, 70 90% Ab) (30 50%An, 50 70%Ab) (5070%An, 30 50% Ab) (7090%An, 10 30% Ab) (90 100%An, 0 10%Ab)

- Phenpat kim th (plagiocla). Nhm ny gm mt dy dung dch rn lin tc ca cc khong vt t anbit Na[AlSi3O8] n anoctit Ca[Al2Si2O8]. Cc khong vt trung gian c phn loi theo thnh phn phn trm ca anbit (Ab) v anoctit (An). b) Nhm phenpatoit: L loi alumosilicat natri v kali xut hin cc khi macma ngho silic, giu kim. Trong c lxit K[AlSi2O6] thuc h t phng, c th cha mt lng rt t natri v rubii, anaxim Na[AlSi2O6].H2O, nephelin KNa3[AlSiO4]4. c) Nhm zeolit: Zeolit l alumosilicat natri, canxi ngm nc. Cng thc tng qut ca zeolit l MxAyO2y.nH2O. Trong M l Na+,Ca2+; A l Si4+, Al3+. Tng s ion Si4+ v Al3+ bng y, ngha l aSi + aAl = y vi iu kin aAl < aSi. C s cu trc ca mng tinh th zeolit l t din SiO44-. Cc t din ni vi nhau qua c 4 nh to thnh b khung 3 chiu trong khng gian. Do s thay th Si4+ bng Al3+ nn b khung xut hin in tch m. Cation b tr cho in tch m nm cc hc, cc khong trng ca b khung zeolit. Do s thay th nh vy nn b khung zeolit c mch lin kt -Si-O-Al-O-Si-. Do tng tc tnh in nn khng th c hai t din AlO45- st nhau, iu c ngha l trong zeolit khng c mch lin kt -O-Al-O-Al-O-. Cc t din ni vi nhau qua nh to thnh nhng bt din ct. Hnh 52 l mt bt din ct c nh l Si4+ v Al3+. Mi bt din ct c 24 nh do cng thc ca mt bt din ct l: Mx Si24xAlxO48.nH2O. Mi bt din ct c 6 mt hnh vung v 8 mt lc gic u. Khi cc bt din ct ni vi nhau qua mt hnh vung s to nn mng li khng gian thuc h lp phng n gin, gi l zeolit A. T bo mng ca zeolit A nh vy c cha mt bt din ct. Do l cng thc zeolit A ng bng cng thc bt din ct. Khi lng nhm t gi tr ti a th x = 12, gi s cation trao i ch c Na+ th lng nc hp th t 27 phn t v cng thc natri zeolit A l Na12Si12Al12O48.27H2O. Hng s mng li ca zeolit ny l 12,3. Khong trng bn trong ca t bo mng zeolit A c ng knh 11,4(thng c gi l hc ). Khong trng bn trong ca hc bt din ct c kch thc bng 6,6 (gi l hc ).
+

53

Hnh 52 Bt din ct, n v c s ca mng li zeolit

Hnh 53 Zeolit A

Khi cc bt din ct ni vi nhau qua mt lc gic th to thnh mng lp phng phc tp kiu kim cng. Zeolit thuc kiu ny c 3 loi gi l zeolit X, zeolit Y, faujazit. T bo lp phng ny c cnh a = 25. Mi t bo c 192 t din (SiAl)O4. V d faujazit c thnh phn: Na13Ca12Mg11(AlO2)59(SiO2)133.235H2O. Tu thuc vo phng php tng hp m thu c sn phm c t l Si/Al khc nhau. i vi zeolit X v Y, s t din AlO4 trong mt t bo mng lin h vi t l Si/Al theo h thc sau: NAl =
192 1 + Si / Al

(11)

Vi zeolit X s cation Al3+ trong mt t bo nguyn t thay i t 77 n 96, trong zeolit Y con s thay i t 48 n 76. Khi thay th Al3+ vo v tr ca Si4+, hng s mng ca zeolit X v Y b thay i t 25 n 24,6. Breck v Flanigen kho st trn 37 mu zeolit X v Y vi cc phng php phn tch chnh xc thnh phn Al trong tinh th v xc nh gi tr a ca mng lp phng xc lp c h thc: a = 0,00868 NAl + 24,191 (12) y NAl l s ion nhm c trong mt t bo mng zeolit X hoc Y. Zeolit c rt nhiu ng dng trong nn cng nghip hin i lm cht trao i ion, hp th chn lc, ry phn t, cht mang xc tc v c lm cht xc tc trong k ngh ho hc, c bit l trong cng nghip ch bin du m.

1.3

Nhng nt c bit ca tinh th cng ho tr v tinh th kim loi

Cu to tinh th v tnh cht ca cc hp cht cacbua, nitrua, borua, silixua kim loi c nhiu nt ring bit do kiu lin kt ho hc. Khc vi cc hp cht trnh by phn trn c lin kt ion l ch yu, trong tinh th ca cacbua, nitrua, silixua kim loi th lin kt cng ho tr l chnh hoc lin kt hn tp gia cng ho tr ion kim loi. Lin kt cng ho tr rt bn vng nn nhng hp cht loi ny c rn v nhit nng chy cao, dn. Trong khi lin kt kim loi truyn cho cacbua, nitrua, borua, silixua mt s c tnh ca kim loi nh do, c dn in cao, siu dn nhit thp. bn v hng ca lin kt cng ho tr ph thuc vo s lng t ca in t lin kt. V d lin kt ca cc obitan p bn hn lin kt ca obitan s. Vi kim loi chuyn tip th li

54

do lin kt ca obitan d. Mt khc hp cht gm c lin kt cng ho tr th vai tr quan trng li l lin kt ca cc obitan lai ho. Vng xen ph ca cc obitan lai ho ln hn do loi hp cht ny c lin kt rt bn v tnh nh hng th hin rt r rt. S phi tr ca cc nguyn t trong tinh th c lin kt cng ho tr khng ln nh trong tinh th c lin kt ion.

Hnh 54 Cch ni cc bt ct qua mt lc gic 4+ 3+ cc nh l Si hoc Al ti tm ca t din Si(Al)O4

(b)

(a )

Hnh 55 Cu trc graphit

i vi tinh th c lin kt kim loi th c mt s c tnh khc hn. l khng tun theo quy lut ho tr, cc nt mng gn nhau v c th l cc nguyn t ca cng mt nguyn t. Mt s loi cht dng trong vt liu gm m c lin kt kim loi (v d berilit, aluminit) c th xem nh hp cht gia cc kim loi, hoc l hp kim c trt t. kho st cc hp cht c lin kt cng ho tr dng trong vt liu v c chng ta nhc li cu trc ca graphit. Trong graphit 1 in t s v 2 in t p ca cacbon to thnh lai ho sp2. Cc obitan lai ho ny to thnh 3 lin kt vi 3 nguyn t cacbon khc trong cng mt mt phng. in t ho tr th t lin kt yu vi nguyn t cacbon mt khc. Do mng li graphit gm cc lp lin kt vi nhau bng mt lc kh yu. Cc nh ca hnh lc gic trong cng mt lp nm v pha trn hoc pha di ng tm ca hnh lc gic ca lp gia (hnh 55a v b).

55

Hnh 56 Kiu cu trc blend (ZnS), kim cng ( Zn, S)

Hnh 57 Cu trc ca nitrua bo ( B, N)

Do cu trc nh vy nn graphit c tnh ng hng mnh. Graphit thuc mng li lc phng. Kim cng gm cc nguyn t cacbon trng thi lai ho sp3. S xen ph ca cc obitan lai ho sp3 to thnh mng li khng gian 3 chiu. S phi tr ca cacbon y bng 4. Kim cng thuc h lp phng. Mng li ca kim cng ging mng li ca blend (hnh 56), cng vi loi cu trc ny c cacbua silic (SiC). Cu to tinh th ca nitrua bo cng tng t cu to graphit. im khc nhau ch ch cch b tr gia cc lp lc gic: nitrua bo th cc nh ca lc gic nm thng hng theo trc c, nh vy gia cc lp c mch lin kt lun phin NBNBN. Lin kt gia cc nguyn t trong cng mt lp cng bn hn lin kt gia cc lp. C hai kiu cu trc ca graphit v nitrua bo p sut v nhit cao u c th tr thnh cu trc lp phng kiu blend. p sut cao hn na hp cht NB c th tr thnh cu trc zinkit ZnO. Cacbua, nitrua, borua, silisua ca cc nguyn t chuyn tip c cc kiu lin kt ho hc hn tp. Nhiu hp cht trong nhm ny c cu to mng li kh n gin. Theo c tnh cu to tinh th c th phn hp cht nhm ny thnh hai loi l pha xm nhp v pha thay th.

56

Nu t l gia bn knh nguyn t phi kim (X) v ca kim loi (M) trong hp cht khng ln hn 0,59 th cc nguyn t kim loi to thnh mng gi ghm chc c thng thng nh trong mng kim loi (lp phng mt tm v lc phng), cn phn t phi kim xm nhp vo cc khong trng. iu ny tho mn vi cacbua, nitrua v mt phn borua ca kim loi chuyn tip. Bn knh ca nguyn t silic qu ln do silisua cu to theo kiu thay th. Ngoi yu t hnh hc ra cu trc tinh th ca hp cht nhm ny cn ph thuc vo thnh phn ho hc, iu kin bn ngoi (p sut, nhit ) v mt s yu t khc na. ng v quan im vt liu gm th cacbua, nitrua c thnh phn AX c cu to kiu NaCl, trong cc nguyn t kim loi c kiu gi ghm chc c lp phng, cn phi kim chui vo cc hc bt din. V d tinh th TiC, ZrC, HfC, NbC, TaC, TiN, ZrN, CrN, HfN, UN... Cacbua ca wolfram v ca molipen c mng li tinh th ging kiu cu trc ca NiAs (hnh 58). Trong cc cacbua ny nguyn t kim loi chim v tr ca niken, cn cacbon chim v tr ca As. l mng li lc phng. Mi t bo mng c 6 nguyn t cacbon, 6 nguyn t wolfram hoc molipen. S phi tr ca chng u bng 6 nhng dng a din phi tr th khc nhau: nguyn t cacbon nm tm ca lng tr tam gic, cn cc nguyn t cacbon phi tr quanh nguyn t kim loi th phc tp hn. Cc tinh th vi lin kt ion th cha gp kiu cu trc ny. Gm cacbua c cu trc chuyn tip t pha xm nhp n pha thay th. Borua l hp cht ho hc c thnh phn rt khc nhau M1B, M2B, MB, M3B4, MB2, M2B5, MB4, MB6 v MB12. Mng tinh th rt phc tp, trong va c lin kt cng ho tr va c lin kt kim loi.

Cr (Si)

Al (Mo)

Ni As
Hnh 58 Cu trc tinh th nikenlin NiAs Hnh 59 Cu trc Cr2Al

Trong gm th ph bin nht c iborua MB2, y M l Cr, Ti, Zr, Hf, Nb, Ta, W... Tt c cc borua ny u c mng tinh th ging nhau v ging mng tinh th ca AlB2. y l mt kiu cu trc phc tp gm cc lp nguyn t bo nh trong graphit phn b chnh xc lp ny trn lp kia. Cc nguyn t kim loi nm tm cc lng tr lc gic ca nguyn t bo. Nh vy l to nn cc lp lun phin: lp mt phng lc gic ca bo v lp mt phng hnh thoi ca nguyn t kim loi. Cu trc nh vy thuc h lc phng. Mi t bo nguyn t c mt nguyn t bo v mt nguyn t kim loi. Bng di y gii thiu mt s loi tinh th c lin kt cng ho tr thng s dng trong vt liu gm.

57

Bng 21. Mt s loi tinh th c lin kt cng ho tr thng s dng trong vt liu gm Cng thc H Kiu mng Hng s mng () S phn t a, b v c trong mt t bo Lc phng Graphit 2,46 6,71 4 C Lc phng Kim cng 3,567 8 4,357 4 Lc phng Sphalerit _SiC TiC -ntNaCl 4,328 4 ZrC -ntNaCl 4,678 4 HfC -ntNaCl 4,487 4 NbC -ntNaCl 4,41 4 TaC -ntNaCl 4,454 4 MoC Lc phng MoC 2,901 2,768 1 WC -ntMoC 2,903 2,833 1 TiN -ntNaCl 4,23 4 ZrN -ntNaCl 4,64 4 Lp phng NaCl 4,42 4 NbN Lc phng ZnO 3,05 4,94 2 UN Lp phng NaCl 4,89 4 BN Lc phng BN 2,51 6,69 4 MoB2 Lc phng AlB2 3,05 3,113 1 ZrB2 -nt_ 3,03 3,22 1 TiB2 -nt_ 3,03 3,23 1 NbB2 -nt_ 3,09 3,31 1 2,97 3,07 1 -nt_ _CrB2 MoSi2 T phng MoSi2 3,20 7.89 2 WSi2 -nt_ 3,22 7,88 2

xt cu trc ca silixua trong gm c th kho st hp cht MoSi2. Loi hp cht ny thng gp trong hp cht gia cc kim loi, v d Cr2Al (hnh 59). Trong tinh th MoSi2 th Mo chim v tr ca Al, cn Si chim v tr ca Cr. Thng s t bo mng gm cnh y a v chiu cao c. T bo gm 3 tng c cc a din phi tr phc tp. Quanh Si c 5 nguyn t Mo, quanh Mo c 8 nguyn t Si. Mi t bo c 2 nguyn t Mo v 4 nguyn t Si cng cu trc nh WSi2, ReSi2.. Cu trc ca mt s isilixua quan trng khc gm lun phin nhng lp lc gic gi ghm chc c, trong cc nguyn t kim loi chuyn tip c bao quanh bng 6 nguyn t Si, cn nguyn t Si c bao quanh bng 3 nguyn t kim loi. S lun phin khc nhau ca cc lp nh vy c th to thnh mng li lc phng (VSi2, NbSi2, TaSi2, CrSi2) hoc hnh thoi (TiSi2).

1.4

Cc yu t nh hng n kiu cu trc tinh th

Mt cht rn tn ti di dng tinh th no c quyt nh bi nhiu yu t: kch thc cc tiu phn (nguyn t, ion, phn t,), kiu lin kt gia cc tiu phn, cu hnh in t ca cc nguyn t, ion,... Do vic d on cu trc mt hp cht mi l mt vic rt phc tp, ch c th gii quyt c trong trng hp d nh trc cht ca ta tng hp thuc v mt h tinh th no : v d tng hp mt pha mi c cu trc spinen, hoc c cu trc perpkit, Trong phm vi kho st cu trc ca cc loi vt liu v c chng ta ch kho st 3 yu t sau y: Cng thc ca hp cht (tc l ni ti tnh hp thc, ho tr ca cc nguyn t), bn cht lin kt gia cc nguyn t, kch thc tng i gia cc ion.

1.4.1 Tnh hp thc SPT ca cc nguyn t

58

C mt mi lin h gia SPT ca cc nguyn t v cng thc tng qut ca hp cht. V d hp cht bc hai c cng thc l AxBy ta c t l:
SPT ca A y = SPT ca B x

(13)

Nguyn tc ny ng vi a s cc hp cht ch tr trng hp hp cht c lin kt gia cc nguyn t cng loi (A-A, B-B), v d trong cc hp cht hu c c mch C-C th khng p dng c. Chng ta xt mt vi hp cht: - Hp cht c cng thc chung AB th SPT ca A bng SPT ca B. V d trong tinh th NaCl, SPT ca Na+ v SPT ca Cl u bng 6, trong tinh th ZnS (blend) SPT ca Zn2+ v ca S2 u bng 4. - Hp cht c cng thc chung AB2 th SPT ca A gp i SPT ca B. V d trong SiO2, Si c SPT bng 4, O2 c SPT bng 2, trong TiO2, Ti4+ c SPT bng 6, O2 c SPT bng 3, trong CaF2, Ca2+ c SPT bng 8, F c SPT bng 4.
4+

- Hp cht c cng thc AxByCz trong A v B l cation, C l anion. K hiu SPT trung bnh ca cation l SPT cation ta c:

SPT cation =

x(SPTA ) + y(SPTB ) x+y

v lin quan vi SPTanion bng h thc

SPT cation z = SPTanion x + y

t ta c h thc: x(SPTA) + y(SPTB) = z(SPTC) V d perpkit CaTiO3, Ti4+ nm trong bt din (SPT bng 6), Ca2+ c SPT l 12, ta tnh c SPT ca oxi bng 12 + 6 = SPT ca O nhn 3. Ngha l SPT ca O bng 6. Qu vy, xung quanh ion O2 c 4 ion Ca2+ v 2 ion Ti4+. Spinen MgAl2O4 c ion Mg2+ nm trong t din, ion Al3+ nm trong hc bt din vy 4 ln SPT ca O2 bng 4+26. SPT ca O2 = 16/4 = 4 Qu vy, ion O2 trong spinen c bao quanh bng 3 ion Mg2+ v 1 ion Al3+.

1.4.2 nh hng ca kiu lin kt

Bn cht lin kt gia cc nguyn t nh hng ng k n SPT ca cc nguyn t v do nh hng trc tip ti kiu cu trc tinh th. Hp cht lin kt ion c cu trc i xng cao, s phi tr t gi tr cc i. Lin kt cng ho tr c c tnh nh hng, s phi tr ph thuc vo s lin kt c th c. Do trong cu trc vi lin kt cng ho tr th SPT ca nguyn t thng khng ln v thng b hn SPT trong cu trc vi lin kt ion tng ng nu kch thc ca cc ion hp phn gn bng kch thc ca nguyn t c cu trc cng ho tr . V d, xt cu trc trong dy SrO, BaO, HgO. Cc oxit SrO, BaO c cu trc NaCl, trong ion M2+ nm v tr bt din, ngha l c SPT bng 6, trong khi HgO c cu trc khc

59

hn. S phi tr ca thu ngn trong HgO bng 2. HgO c cu trc mch gm cc mnh OHg-O. Ta c th gii thch c iu khi lu n cu hnh in t ca Hg c lp v bn ngoi l 4f145d106s2. trng thi kch thch nguyn t Hg c cu hnh 4f145d106s16p1. Cc obitan lai ho sp ca Hg xen ph vi obitan ca oxi to thnh lin kt cng ho tr vi cu hnh phn t dng ng thng.

1.4.3 nh hng ca bn knh nguyn t, ion

Khi nim bn knh nguyn t, bn knh ion tuy rng khng chnh xc v cn cn phi bn ci nhiu na, nhng c th ni rng nu khng c thng tin v kch thc ion trong mng li tinh th th khng th c c nhng thnh tu hin nay v ho tinh th. Cho n nay chng ta vn dng nhng s liu v bn knh ion ca Paoling-Arenc (da trn c s tnh ton theo c hc lng t) v ca Golsmit-Belop-Bki (da vo xc nh thc nghim theo phng php nghin cu cu trc bng tia X). T nm 1970, Shannon v Pruit li a ra thm mt h thng kch thc ion khc. C s ca h thng kch thc ion do Shannon v Pruit da vo k thut hin i ca phng php nhiu x tia X xy dng bc tranh phn b mt in t trong tinh th. Theo s liu ca Shannon v Pruit th cation c bn knh ln hn cn anion c bn knh b hn so vi cc gi tr ca h thng Paoling cng nh ca Golsmit a ra trc y. V d theo Paoling th bn knh ion ca Na+ v F l 0,98 v 1,36, cn theo Shannon v Pruit th bn knh ca Na+ tu thuc vo s phi tr m c cc gi tr t 1,14 n 1,30, bn knh ca F bng 1,19. Hnh 60 v hnh 61 gii thiu bc tranh phn b mt in t trong mt 100 ca tinh th LiF v s thay i mt in t dc theo ng thng ni hai nhn.

Hnh 60 S phn b mt in t trong tinh th LiF trn cc ng c ghi gi tr mt in t (e/3)

T nhng bc tranh mt in t ca cc cht rn c cu trc ch yu l lin kt ion tng t nh hnh 60 cho php rt ra mt s nhn xt sau:

60

+ Vn c th xem ion nh ch yu c dng khi cu. + Ion c hai phn: phn khi cu bn trong tp trung mt cao ca in t (phn ny tng i n nh), phn bn ngoi c mt in t kh thp v dao ng tu thuc vo s phi tr cng nh s khc nhau v m in gia cc nguyn t trong hp cht . Nh vy, khng th xem ion l khi cu tch in v rn chc nh quan nim trc y m khi cu c phn ngoi n hi. + Khng th xc nh c chnh xc bin gii gia cc ion v rng khng c khu vc ng vi s gim mt in t n gi tr khng. Nh vy, khng th xc nh c chnh xc bn knh ion. Vic xc nh bn knh ion ph thuc vo phng php phn chia v tr bin gii . V d bn knh Li+ theo Paoling l 0,60, theo Golsmit l 0,78, theo h thng ca Shannon l 0,92. Bi vy trong vic nghin cu cu trc tinh th cn phi s dng mt h thng n v thng nht. M- ng vi gi tr cc tiu, G v P ng vi bn knh ion Li+ theo Golsmit v theo Paoling.
4

e/A3

0,92 0,78 0,60

M G

Li

Hnh 61 Bin thin mt in t trong LiF dc theo ng ni lin hai nhn

Kiu cu trc tinh th ph thuc rt mnh vo t l bn knh cation (Rc) v bn knh anion (Ra) (xem bng 22)
Bng 22 T l Rc/Ra, SPT ca cation, kiu cu trc ca cc hp cht AB Rc/Ra S phi tr Kiu cu trc 1> Rc/Ra > 0,732 0,732 > Rc/Ra > 0,414 0,414 > Rc/Ra > 0,225 8 6 4 Kiu CsCl Kiu NaCl Kiu blend ZnS, vuazit ZnS

Cn lu rng kh nng s dng quy tc t l bn knh ca ion on bit SPT v kiu cu trc rt hn ch. Thc ra quy tc ny ch c ch gii thch khuynh hng chung m thi. Gi tr tuyt i ca t l bn knh Rc/Ra ph thuc vo h n v bn knh ta s dng. Nu s dng h n v bn knh ion ca Paoling v Golsmit (ngha l RO2 =1,40) th RRb+/RI = 0,69, do SPT ca Rb+ bng 6 v RbI c cu trc kiu NaCl. Nu s dng h n v bn knh ca Shannon (ngha l RO2 =1,26) th RRb+/RI = 0,8, do SPT Rb+ bng 8 v RbI c cu trc kiu CsCl. Vi LiI cng c hai gi tr t l Rc/Ra l 0,28 v 0,46. Nu nhn l 0,28 th SPT ca Li+ l 4. Nhng thc t SPT ca Li+ bng 6 ngha l t l phi bng 0,46.

61

Bng 23 T l Rc/Ra, SPT ca cation v kiu cu trc ca oxit c cng thc MO2 Oxit Rc/Ra SPT Kiu cu trc xc nh c SiO2 GeO2 TiO2 SnO2 PbO2 HfO2 ThO2 0,32 0,43 0,54 0,59 0,66 0,73 0,67 0,77 0,95 4 4 6 6 6 6 6 8 8 Silic oxit (SPT 4) Silic oxit (SPT 4) Rutin (SPT 6) Rutin (SPT 6) Rutin (SPT 6) Rutin (SPT 6) Rutin (SPT 6) Florit (SPT 8) Florit (SPT 8)

Vi hp cht ca oxit hoc florua c cng thc AB2 th c ba kiu cu trc l silic oxit (SPT 4), rutin (SPT 6) v florit (SPT 8) (xem bng 23). Khi gi tr Rc/Ra ng vi khong bin gii chuyn kiu cu trc (0,732 hoc 0,414) th hp cht c th tn ti di hai dng th hnh. V d vi GeO2, HfO2, Khi kho st mng li tinh th ion ngi ta thng s dng khi nim phn in tch ca ion hoc lc ho tr ca lin kt. V d cation Mm+ c bao quanh bng n anion Xn th lc ho tr ca lin kt gia cation Mm+ v mt anion Xn l = m/n. in tch m ca mt anion phi bng tng lc ho tr ca cc cation bao quanh anion , ngha l = m/n. V d spinen MgAl2O4 gm c phn mng anion O2 xp kht kiu lp phng mt tm ABCABCA, ion Mg2+ nm cc hc t din (SPT 4), ion Al3+ nm cc hc bt din (SPT 6), xung quanh ion O2 c 3 cation Al3+ v mt cation Mg2+: i vi Mg2+: phn in tch dng cho 1 ion O2 = 2/4 = 1/2 Vi Al3+: phn in tch dng cho 1 ion O2 = 3/6 = 1/2 Vy phn in tch dng ca 1 ion O2 trong MgAl2O4 l: 3Al3+ + 1Mg2+ = 31/2 + 1/2 = 2 C th chng minh rng trong cu trc silicat khng th c 3 t din SiO4 ni chung vi nhau qua nh. V rng phn in tch dng cho mt ion O2 trong t din SiO4 l 4/4 = 1, ngha l O2 ch chung cho 2 ion Si4+ v s c phn in tch dng tng cng l 2. Nu 3 t din SiO4 ni chung vi nhau mt nh oxi th phn in tch dng tng cng ca oxi bng 3, l iu khng cho php. Bng 24 gii thiu lc ho tr ca lin kt ca mt s cation. Da cc s liu trong bng 24 chng ta c th hiu c cch t hp cho php v cch t hp khng cho php khi ghp cc a din trong mng li tinh th oxit.
Bng 24 Lc ho tr ca lin kt ca mt s cation Lc ho tr ca Cation SPT Cation lin kt + Li 4; 6 1/4; 1/6 Al3+ + Na 6; 8 1/6; 1/8 Cr3+ 2+ Be 3; 4 2/3; 1/2 Si4+ 2+ Mg 4; 6 1/2; 1/3 Ge4+ 2+ Ca 8 1/4 Ti4+ 2+ Zn 4 1/2 Th4+ Lc ho tr ca lin kt 3/4; 1/2 1/2 1 1; 2/3 2/3 1/2

SPT 4; 6 6 4 4; 6 6 8

62

Cho n by gi chng ta vn gi thit rng trong mng tinh th ion ch c thun tu l lin kt ion, bn cht lc lin kt trong mng li ch thun tu l lc ht tnh in gia cc ion tch in ngc du. iu ny khng ng vi thc t, v d trong mng tinh th ca KCl, in tch xc nh c ca cc ion khng phi bng 1 m l 0,76. iu ny c ngha l gia ion kali v ion clo c 24% l lin kt cng ho tr, lin kt ion ch chim 76%.
Bng 25 Cch ni cho php v cch ni khng c php ca cc a din oxi qua nh chung Cho php V d pha rn Khng c php 2SiO4 (T) 1MgO4 (T) + 3AlO6 (O) 1 SiO4(T) + 3 MgO6 (O) oxit silic spinen olivin >2SiO4 (T) 3AlO4 (T) 1 SiO4(T) +3AlO4 (T)

xc nh mc lin kt cng ho tr trong mng li tinh th ion, Sanderson a ra mt phng php mi. Phng php ny da trn c s thang in m ca cc nguyn t do ng xy dng. Theo ng th m in l o sc ht gia in tch dng hiu dng ca ht nhn nguyn t ca nguyn t vi in t ngoi cng, ngha l m in lin quan n mc chc c ca nguyn t. nh gi m in S ng s dng cng thc:

S=

D Da

(14)

trong D: mt in t trong nguyn t c xc nh bng t l gia nguyn t s v th tch nguyn t, Da: l mt in t khi ngoi suy tuyn tnh t gi tr D ca nguyn t khi tr thnh kh tr. Bng 26 gii thiu thang in m ca Sanderson. Khi cc nguyn t c m in khc nhau lin kt vi nhau to thnh hp cht ho hc th c s san bng m in cc nguyn t trong hp cht u c gi tr m in trung bnh ( S ) bng nhau. V d vi NaF c S = SNa .SF = 2,006 vi BaI2 c S = 3 SBa .S2 I = 2, 26 . S cn bng m in c ngha l trong lin kt gia cc nguyn t khc nhau th cc in t lin kt b lch v pha nguyn t c m in ln hn, lm cho nguyn t d in tch m, cn nguyn t c m in b hn th d in tch dng. Phn in tch d () bng t l bin thin m in ca nguyn t (S) vi gi tr ( S c ) khi gi thit in t lin kt i hn v pha nguyn t c m in cao to thnh ion c mt n v din tch 1.
= S Sc

(15)

trong :
S = S S , cn S C = 2,08 S

(16)

63

Bng 26 m in v kch thc nguyn t ca mt s nguyn t B (i vi trng thi Bn knh cng ho tr Nguyn t S rn) Rc () H 3,55 0,32 Li 0,74 1,34 0,812 Be 1,99 0,91 0,330 B 2,93 0,82 C 3,79 0,77 N 4,49 0,74 O 5,21 0,70 4,401 F 5,75 0,68 0,925 Na 0,70 1,54 0,763 Mg 1,56 1,38 0,349 Al 2,22 1,26 Si 2,84 1,17 P 3,43 1,10 S 4,12 1,04 0,657 Cl 4,93 0,99 1,191 K 0,42 1,96 0,956 Ca 1,22 1,74 0,550 Zn 2,98 Ga 3,28 Ge 3,59 1,22 As 3,90 1,19 Se 4,21 1,16 0,665 Br 4,53 1,14 1,242 Rb 0,36 2,16 1,039 Sr 1,06 1,91 0,429 Ag 2,59 1,50 0,208 Cd 2,84 1,46 0,132 Sn 3,09 1,40 Sb 3,34 1,38 Te 3,59 1,35 0,693 I 3,84 1,33 1,384 Cs 0,28 2,35 0,963 Ba 0,78 1,98 0,348 Hg 2,93 Tl 3,02 1,48 Pb 3,08 1,47 Bi 3,16 1,46

SC 3,92 1,77 2,93 2,56 4,05 4,41 4,75 4,99 1,74 2,60 3,10 3,51 3,85 4,22 4,62 1,35 2,30 3,58 3,77 3,94 4,11 4,27 4,43 1,25 2,14 3,35 3,16-3,66 3,80 3,94 4,08 1,10 1,93 3,59 2,85 3,21-3,69 3,74

ri () 0,53 0,58

1,10 1,61 0,78 1,03

1,70 2,18 1,00 1,19

1,83 2,38 1,12 1,18 1,29 1,33

2,04 2,71 1,39 1,63

Khi xc nh c ta tnh c phn lin kt cng ho tr trong hp cht, ng thi tnh c bn knh nguyn t ca cc nguyn t tham gia lin kt. Paoling v Sanderson a ra cng thc kinh nghim xc nh bn knh nguyn t nh sau: r = rc B (17) trong : rc l bn knh cng ho tr, l phn in tch d ca n B l hng s ca nguyn t cho trong bng 26 Xt vi v d: Xc nh phn lin kt cng ho tr trong BaI2 v di ca lin kt BaI. in m trung bnh ca Ba v I trong BaI2.

64

S = 3 0,78.3,842 = 2, 26

vy
Sc ca Ba = 1,93; ca I = 4,08

SBa = 2,26 0,78 =1,48 SI = 3,84 2,26 =1,58

Do
Ba = 1,48/1,93 = 0,78; I = 1,58/4,08 = 0,39

Vy trong lin kt BaI c 39% l lin kt ion v 61% l lin kt cng ho tr. Bn knh nguyn t bari rBa = 1,98 0,348 0,78 = 1,71 Bn knh nguyn t it rI = 1,33 + 1,384 0,39 = 1,87 Khong cch hai nguyn t trong hp cht (dng tinh th) bng 1,71 + 1,87 = 3,58, thc nghim xc nh c l 3,59.
Bng 27 in tch phn v bn knh ca clo trong mt s tinh th clorua Hp cht Hp rCl() rCl() Cl Cl cht CdCl2 0,21 1,24 BeCl2 0,28 1,26 CuCl 0,29 1,34 AgCl 0,30 1,35 MgCl2 0,34 1,39 CaCl2 0,40 1,47 SrCl2 0,43 1,50 BaCl2 0,49 1,57 LiCl 0,65 1,76 NaCl 0,67 1,79 KCl 0,76 1,90 RbCl 0,78 1,92 CsCl 0,81 1,95 Bng 28 in tch phn oxi trong mt s tinh th oxit Hp cht Hp cht O -O Cu2O Ag2O Li2O Na2O K2O Rb2O Cs2O 0,41 0,41 0,80 0,81 0,89 0,92 0,94 HgO ZnO CdO CuO BeO PbO SnO FeO CoO NiO MnO MgO CaO SrO BaO 0,27 0,29 0,32 0,32 0,36 0,36 0,37 0,40 0,40 0,40 0,41 0,50 0,56 0,60 0,68

Hp cht Ga2O3 Tl2O3 In2O3 B2O3 Al2O3 Fe2O3 Cr2O3 Sc2O3 Y2O3 La2O3

O 0,19 0,21 0,23 0,24 0,31 0,33 0,37 0,47 0,52 0,56

Hp cht CO2 GeO2 SnO2 PbO2 SiO2 MnO2 TiO2 ZrO2 HfO2

O 0,11 0,13 0,17 0,18 0,23 0,29 0,39 0,44 0,45

S dng phng php Sanderson xc nh c in tch phn () v bn knh nguyn t ca nhiu hp cht. Bng 27 gii thiu in tch phn v bn knh nguyn t ca clo trong cc clorua kim loi ho tr 1 v kim loi ho tr 2. Bng 28 gii thiu in tch phn ca oxi trong cc tinh th oxit.

65

T cc s liu trong bng 27 cho thy in tch ca ion clo thay i t 0,21 (trong CdCl2) n 0,81 (trong CsCl), cn bn knh nguyn t clo thay i t 1,24 n 1,95. So snh cc gi tr vi bn knh cng ho tr ca clo l 0,99 v bn knh ca ion clo l 2,18 ta thy sai lch qu ln. Tt c cc hp cht trong bng 27 chng ta vn xem nh c mng li ion v quy cho ion clo c in tch khng i l 1, qu l khng ng thc t. Cc s liu trong bng 28 cho thy in tch phn ca ion oxi ch thay i trong khong t 0 n 1. Cc tnh ton cho thy t trc ti nay ta vn xem trong cc oxit c cha ion oxi l 2, th m thc t in tch ca ion oxi khng vt qu 1 v trong hu ht trng hp cn nh hn 1.

Cu hi v bi tp
1. 2. Mt mt phng chn 3 trc ca tinh th ti cc im ng vi thng s n v l 3/2.1.1. Hy cho bit ch s Miller (h, k, l) ca n. Chng minh rng trong t bo lp phng th: a. Mt [111] vung gc vi ng (111); b. Mt [100] vung gc vi ng (100). 3. Xc nh kiu cu trc ca cc t bo mng li c to ca cc nguyn t nh sau: a. MX: X b. MX: X c. MX: 4. M 000, M 1/2 0 0 , 1/2 1/2 0 , 000, 0 1/2 0 , 1/2 0 1/2, 1/2 1/2 0 , 0 0 1/2, 0 1/2 1/2 0 1/2 1/2 1/4 3/4 3/4 1/2 0 1/2, 1/2 1/2 1/2

1/4 1/4 1/4 , 3/4 1/4 3/4 , 3/4 3/4 1/4, M 0 0 0

X 1/2 1/2 1/2 Xc nh chc c, s hc trng bt din, s hc trng t din ca t bo mng li lp phng khi tm, lp phng mt tm, gi ghm chc c lc phng. Na2O c cu trc kiu antiflorit vi hng s mng a = 5,55, xc nh di lin kt NaO, khong cch OO, NaNa, khi lng ring (g/cm3). Cng cu hi i vi CeO2 c cu trc florit a = 5,41. M t cu trc peropkit ABO3. SrTiO3 c cu trc perpkit vi hng s mng a = 3,905. Tnh di lin kt SrO, TiO. Xc nh s phi tr ca oxi trong SrTiO3. Xc nh s phi tr ca oxi trong spinen MgAl2O4. Cho bit thng s mng ca n bng 8,09, xc nh t trng (g/cm3). Xc nh thng s oxi ca spinen MgAl2O4, cho bit bn knh ca ion Mg2+ bng 0,74, bn knh ca O2 bng 1,36. Gi s phn mng ion O2 trong spinen AB2O4 gi ghm chc c lp phng mt tm l tng. T tnh ton spinen ca cc kim loi ho tr 2 v kim loi ho tr 3 no c thng s oxi l tng (W = 0,375).

5.

6.

7.

8.

66

9.

9. Ti sao ZnS c t l Rc/Ra = 0,63 nhng t bo mng li li khng theo kiu NaCl m theo kiu blend.

67

Chng 2 TINH TH THC - CC KIU KHUYT TT DUNG DCH RN

Tinh th hon thin l tinh th m trong cc tiu phn (nguyn t, ion...) c phn b vo ng v tr nt mng li ca n mt cch hon ton c trt t. Tinh th hon thin nh vy ch l trng hp l tng v 0 K. Khi nhit tng ln th cc tiu phn cc mng li dao ng mnh dn v c th ri khi v tr ca n i vo cc hc trng gia cc nt mng, cn v tr nt mng ca n th tr thnh l trng. Mng li lc ny s c ch mt trt t. C th ni tt c cc tinh th thc u l mng li khng hon thin v c cha cc loi khuyt tt khc nhau. Ngay nh n tinh th kim cng c gi l hon thin nht cng c cha khuyt tt tuy vi nng rt nh (<1%). Phn ln cc tinh th thc c nng khuyt tt ti trn 1%.

2.1

Cc kiu khuyt tt

C nhiu cch phn loi khuyt tt. Da theo thnh phn ho hc ngi ta phn thnh khuyt tt hp thc (khng lm thay i thnh phn ho hc ca tinh th) v khuyt tt khng hp thc (lm thay i thnh phn ho hc ca tinh th). Da theo o hnh hc ca khu vc khuyt tt trong mng li ngi ta phn thnh khuyt tt im (khng c o), khuyt tt ng (c 1 o), khuyt tt mt (c 2 o), khuyt tt vng hay l khuyt tt khi (3 o). C s l thuyt c xut pht t khuyt tt im do Stki v Frenken a ra t nm 1930, nhng hin nay cn ang tranh ci v s tn ti c lp ca nhng khuyt tt im nh vy. Khuyt tt ni ti (intrinsic) ch khuyt tt ca cht nguyn cht v khuyt tt ngoi lai (extrinsic) l khuyt tt do c mt ca tp cht.

2.1.1 Khuyt tt Stki

Khuyt tt Stki l loi khuyt tt hp thc ca cc tinh th ion. y l s xut hin cp l trng cation v l trng anion. m bo trung ho v in th s l trng cation phi bng s l trng anion. Khuyt tt Stki l khuyt tt ch yu ca tinh th halogenua kim (tr Cs). Cc l trng c th phn b hn lon trong mng tinh th hoc c th hnh thnh tng cp trong mng li. Trong mng tinh th NaCl, s c mt cc in tch dng cha b tr ca 6 ion natri (hnh 62) l trng clo to nn mt in tch hiu dng +1, cn s c mt cc in tch m cha b tr ca 6 ion clo to ln mt in tch hiu dng 1. Cc in tch hiu dng ngc du ca cc l trng c th ht nhau to thnh cp l trng. ph v cc cp l trng nh vy cn cung cp mt nng lng c gi tr bng H kt hp, i vi NaCl

68

bng 1,3 eV (120 kJ/mol). Nng khuyt tt Stki trong tinh th NaCl nhit phng c gi tr khong 1 l trng trong 1015 v tr nt mng. Nu tnh mt ht mui c khi lng 1 mg (gm 1019 ion) th c 104 khuyt tt Stki. Con s khng phi l nh. Chnh khuyt tt ny quyt nh nhiu c tnh quang, in ca tinh th NaCl. Cl Cl Na Cl Na
Na Cl
Hnh 62 Khuyt tt Stki

Na Cl Na Cl Na Na Cl Na Cl Cl Na Cl Na Cl Cl Na Na
+

Na Cl

Na Cl

Na Cl

Na Cl Na Cl

2.1.2 Khuyt tt Frenken

Khuyt tt Frenken cng thuc loi khuyt tt hp thc. N c hnh thnh khi mt ion chuyn t v tr bnh thng vo khong trng gia cc nt mng. V d bc clorua th cation bc chui vo khong trng gia cc nt. Bao quanh Ag+ gia cc nt c s phi tr 8 gm 4 ion Cl nm nh t din v 4 ion Ag+ cng vi khong cch nh vy (xem hnh 63). Tng tc tnh in gia Ag+ (gia cc nt) v 4 ion Cl c tc dng lm n nh khuyt tt Frenken. V rng ion Na+ t b bin dng hn ion Ag+ do khuyt tt Frenken t xy ra i vi tinh th NaCl. Tinh th CaF2 th khuyt tt ch yu l Frenken, nhng ion chui vo v tr gia cc nt li l F . Tinh th ZrO2 vi cu trc florit th ion xm nhp l O2, cn Na2O c cu trc antiflorit th Na+ li l ion xm nhp.

Cng nh khuyt tt Stki, l trng v ion xm nhp ca Frenken tch in ngc du, nn c lc ht to thnh cp. Cc cp Frenken v Stki u l nhng lng cc. Khi nhng lng cc ny ht nhau to nn nhng tch t ln hn gm mt tp hp cc khuyt tt c gi l claster. Cc claster nh vy c th lm mm cho nhng pha mi trong tinh th bt hp thc.

69

Ag Cl Cl Ag Ag Ag Cl Cl Ag Ag Cl

Cl Ag Cl Ag Cl

Ag Cl Cl Ag Ag

Ag Cl Cl Cl

Ag Ag
Ag

Cl

Cl Ag Cl

Ag

Cl

Ag

Cl Ag

Ag Cl

(a)
Hnh 63

(b)

Khuyt tt Frenken

2.1.3 Nhit ng hc ca s hnh thnh khuyt tt

V mt nhit ng hc, s hnh thnh khuyt tt mt nng no l thun li v nng lng. Gi s chng ta kho st s hnh thnh khuyt tt trong mt tinh th hon thin, v d to thnh l trng cation. to ra l trng cation i hi phi tiu th mt nng lng H, nhng do vic lm mt trt t ca h nn li tng S ln. Gi tr S ny lin quan n xc sut to l trng. V nguyn tc c mt s rt ln v tr c th hnh thnh l trng. V d mu tinh th ca ta c cha mt mol cation. Nh vy, to ra mt l trng cation, c th c ti 1023 v tr. S tng entropi lin quan n xc sut to thnh mt l trng S = klnW (W l 1023 i vi mt mol, k l hng s Bonzman). Mt khc, do lc tng tc gia cc tiu phn trong mng li tinh th trng hp hon chnh ng vi trng thi cn bng, khi xut hin mt l trng cation s lm cho cc tiu phn quanh l trng mt trt t. iu ny cng lm tng entropi ca h. Gi tr tng cng ca s tng dn ti h qu l mc du qu trnh c lm tng H nhng nng lng t do G ca h (G = H TS) vn gim so vi cu trc hon chnh l tng. By gi, mt tinh th ban u c mt lng tng i nhiu khuyt tt (v d 10%) th s hnh thnh thm khuyt tt mi ch lm tng S khng ng k na, v rng xc sut hnh thnh khuyt tt ngy cng gim. Hnh 64 cho bit bin thin G ph thuc vo nng khuyt tt trong mng li. Gi tr cc tiu ca G ng vi nng khuyt tt trong mng li trng thi cn bng nhit ng. Qua hnh 64 chng ta thy mi loi tinh th u c cha mt nng khuyt tt nht nh. Nng cn bng khuyt tt tng khi tng nhit . Ngay c khi gi thit H, S khng ph thuc vo nhit nhng khi tng nhit th gi tr TS tng nn cc tiu ca G s chuyn dch v pha tng nng khuyt tt. ng cong trn hnh 64 c th xy dng i vi mi loi khuyt tt (Stki, Frenken, l trng cation, l trng anion). i vi mi loi tinh th nht nh th khuyt tt ch yu l khuyt tt d hnh thnh nht, ngha l ng vi gi tr H nh nht. V d trong tinh th NaCl th d hnh thnh l

70

trng nht (khuyt tt Stki), do khuyt tt ch yu l khuyt tt Stki, cn tinh th AgCl th d to thnh cation xm nhp Ag+ ngha l khuyt tt Frenken.

nng lng G =H TS

S nng khuyt tt
Hnh 64 Bin thin G ph thuc vo nng khuyt tt trong tinh th

Bng 29 Kiu khuyt tt ch yu trong tinh th Tinh th Kiu cu trc Halogenua kim (tr Cs) Oxit kim th AgCl, AgBr Halogenua Cs, TiCl BeO Florua kim th CeO2, ThO2 NaCl NaCl NaCl CsCl Vuazit Florit (CaF2)

Kiu khuyt tt Stki Stki Khuyt tt cation (Frenken) Khuyt tt Stki Stki Khuyt tt anion (Frenken)

Thng thng nng khuyt tt thc t c trong tinh th cao hn l nng khuyt tt cn bng nhit ng. iu ny c th do trong qu trnh tng hp cht rn thng phi chu tc ng mt trt t nhit cao lm tng phn gp entropi TS trong phng trnh tnh G. Nh vy, nhit tng hp cng cao th nng khuyt tt c trng cng ln. Khi lm ngui lnh n nhit phng th mt phn khuyt tt c th b hu theo cc c ch khc nhau. Tuy nhin, ngay c khi lm ngui lnh vi tc rt chm i na vn cn li mt lng ng k khuyt tt pht sinh khi nhit cao cn c gi li d tha so vi nng khuyt tt cn bng nhit thp. S d tha nng khuyt tt cn c th to ra bng cch dng mt chm tiu phn c nng lng cao bn ph vo tinh th loi b mt s nguyn t ra khi v tr bnh thng ca n trong mng li. m t trng thi cn bng ca khuyt tt im c th s dng hai phng php. + Phng php nhit ng hc thng k da trn c s thnh lp mt hm y ca s phn b nng lng i vi mt mu khuyt tt. T hm s thu c biu thc xc nh G. Gi tr cc tiu ca G l iu kin cn bng. Phng php ny cng c th s dng m t trng thi cn bng ca khuyt tt khng hp thc. + Phng php th hai m t trng thi cn bng ca khuyt tt Stki v Frenken l s dng nh lut tc dng khi lng. y nng khuyt tt c biu din di dng lu

71

tha vo nhit . Sau y trnh by mt v d ca phng php ny m t cn bng trong tinh th hp thc. V d trng thi cn bng ca phn ng hnh thnh khuyt tt Stki trong tinh th NaCl. Na+ + Cl + VNabm + VClbm (bm l b mt, V l l trng ) Hng s cn bng
[V ][V ][Na + bm ][Cl bm ] K = Na + Cl _ bm bm [Na ][Cl ][VNa ][ClCl ]
_

VNa +VCl + Na+bm + Clbm

(18)

(19)

Vi mt b mt tng cng nht nh th s nt trn b mt l mt con s khng i v do khng nh ngay c s ion Na+, Cl chim cc nt trn b mt . Khi hnh thnh khuyt tt Stki, cc ion Na+, Cl i t trong tinh th ln b mt v chim mt s v tr trn nhng ng thi li to ra mt lng nh vy v tr b mt mi (ni mt cch nghim ngt th vic hnh thnh khuyt tt Stki din tch b mt tng cng c tng ln cht t nhng c th b qua _ bm bm ] v [Cl bm ] = [VCl ] v h thc trn y c th hiu ng ). Nh vy th [ Na + bm ] = [VNa vit:
K= [VNa ][VCl ] _ [Na + ][Cl ]

(20)

Gi s N l tng s nt ca mi mt dng, NV l s l trng ca mi dng, ngha l khuyt tt Stki. Mt khc s nt b chim ca mi dng bng N NV, vy ta c:

(N V ) 2 K= (N N V ) 2
Nu nng khuyt tt rt b th N N NV

(21)

K=

(N V ) 2 , t N V = N K (N) 2

(22)

Hng s K ph thuc lu tha vo nhit v rng G = RTlnK K= eG/RT eH/RT.eS/R v K= const.eH/RT (23)
G l nng lng t do, H l entanpi, S l entropi ca vic hnh thnh mt mol khuyt tt trong th tch ln v cng ca tinh th. Do :

NV = N.const.eH/2RT

(24)

i vi khuyt tt ca tinh th cht n cht, v d kim loi cng thu c kt qu tng t. S khc nhau ch ch do c mt ch mt loi l trng nn phng trnh (21) v (22) c th vit n gin NV = N.K (25) Do bin mt s nhn 2 trong phn s lu tha ca phng trnh (24). Cn bng ca khuyt tt Frenken (v d tinh th AgCl) c th biu din bng phn ng: Ag+ + Vi Agi+ + VAg (26)

72

y Vi v Agi+ l v tr gia cc nt trng v c cation.

K=

[Ag i ] + [VAg ] [Ag + ] + [Vi ]

[VAg] = [Ag+] = N, [Ag+] = N Ni

(27)

N l s nt ca mng li tinh th hon thin, Ni l s hc trng gia cc nt. Vy:

i vi a s cu trc tinh th c trt t, s khong trng gia cc nt t l vi s nt ca mng, [Vi] = N.

Ag Cl Ag Cl Ag Cl Ag Cl Ag Hnh 65 V tr hc T quanh Ag+ hc bt din

Vi AgCl th = 2 v rng mi mt nt bt din b chim bi Ag+ c 2 khong trng t din gia cc nt (hnh 65). Cu trc gi ghm chc c lp phng kiu NaCl i vi AgCl th s hc T gp i s hc O. Ta c i vi phng trnh 26 l:
K= N i2 N2 = i2 (N N i )N N

(28)

Theo phng trnh Arrenius th nng khuyt tt Frenken ph thuc vo nhit : [VAg] = [Agi+] =Ni = N eG/2RT [VAg] = const.N.eH/2RT (29) (30)

Trong mu s ca phn lu tha cc biu thc (24) v (30) c s nhn 2 l do khuyt tt Stki v Frenken to thnh 2 nt khuyt tt ca mng li (khuyt tt Stki gm 2 l trng, cn khuyt tt Frenken th mt l trng v mt ion xm nhp). Nh vy, trong hai trng hp entanpi ca qu trnh to khuyt tt c th xem nh gm hai hp phn. Kt qu xc nh thc nghim s khuyt tt Frenken trong AgCl c trnh by trn hnh 66. Ly logarit phng trnh (29) v (30) ta c:
lg Ni H lg e = lg(const) N 2RT

(31)
H lg e . 2R

th s ph thuc lg(Ni/N) vo 1/T l ng thng c h s gc l

Kt qu thc nghim thu c i vi AgCl tng i ph hp vi s ph thuc Arrenius, tuy rng nhit cao cng c sai lch phn no vi tuyn tnh. Ngoi suy t s ph thuc nhit cho thy rng n 450oC (gn nhit nng chy ca AgCl, Tnc ca AgCl = 456oC) cho ta nh gi c nng cn bng khuyt tt nhit

73

vo khong 0,6%, ngha l 1 trong 200 ion Ag+ ca mng li hon chnh chuyn t nt bt din sang hc t din. Entanpi ca s hnh thnh khuyt tt Frenken ca AgCl khong 1,35eV (130 kJ/mol), cn entanpi ca s hnh thnh khuyt tt Stki trong NaCl khong 2,3 eV (220 kJ/mol). Cc gi tr hon ton in hnh vi tinh th ion.
300 -4 200

ToC

lgN i/N -5 -6 1,6 1,8 2,0 2,2

-1 1000/T (K )
Hnh 66 Phn khuyt tt Frenken trong AgCl ph thuc vo nhit

2.1.4 Tm mu
Tm mu (cn gi l tm F ly ra t ch c Farbenzentre c ngha l tm mu) l l trng anion gi ly electron (hnh 67). Tm mu c th c to thnh trong tinh th halogenua kim bng cc phng php khc nhau, v d un nng NaCl trong hi kim loi natri. Tinh th mui n gi ly nguyn t Na lm cho cng thc sai lch vi hp thc Na1+xCl (x rt nh hn 1) v tr nn c mu vng lc. Qu trnh ny xy ra qua giai on hp th nguyn t natri, ri ion ho n trn b mt tinh th cn electron th khuch tn vo trong ri b gi li l trng anion. m bo trung ho v in trong ton khi tinh th th mt lng tng ng ion Cl phi i khi khi tinh th ln b mt. L trng gi electron nh vy l mt v d c in v electron trong hp th. Electron ny c mt dy mc nng lng, cn nng lng cn thit chuyn electron t mc ny sang mc khc nm trong vng quang ph thy c. Do tinh th c mu. V tr ca cc mc nng lng v mu pht sinh ra c quyt nh bi tnh cht ca tinh th ch khng ph thuc vo dng nguyn t cho electron. Nh nung NaCl trong hi kali cng c mu vng rm nh nung trong hi natri. Nhng khi dng tinh th KCl trong hi kali th c mu tm.
Cl Na Cl Na Na Cl Na Cl Cl Na e Na Na Cl Na Cl Cl Na e Na Hnh 67 Tm mu Cl Na Cl Na Cl

Mt phng php khc to ra tm mu l dng bc x chiu vo tinh th. V d dng tia X chiu vo tinh th NaCl trong 30 pht th tinh th NaCl c mu vng rm. Tm mu pht sinh lc ny cng l l trng anion gi electron nhng khng lin quan n tha Na so vi hp thc. Hnh nh n pht sinh ra trong tinh th bng cch lm bt ra mt electron ca anion clo no trong tinh th.

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V rng tm mu to ra do kt qu chp ly mt electron duy nht, ngha l c spin l nn c tnh thun t. Do phng php cng hng t electron cho nhng thng tin tt nht khi nghin cu i tng ny. Nh phng php ny ngi ta xc lp c trng thi bt nh v ca electron b chim bi cc hc bt din v lm sng r tc dng tng h rt tinh t gia momen spin electron vi momen t ca ion Na+ bao quanh electron . Ngoi tm F, trong halogenua kim cn c nhng tm mu kiu khc na. V d tm H v tm V (hnh 68).
Cl Na Cl Na Cl Na Cl Na Cl Na Cl Na ClNa Cl Na Cl Na Cl Na Cl Cl Na e Na Cl (a) Hnh 68 Tm H(a) v tm V(b) Cl Na Cl Na Cl Na Cl Na Cl Na Cl Na Cl Na Cl Na Cl Na Cl Na Cl Na Cl Na Cl (b)

C hai tm ny u gm ion phn t Cl nh hng dc theo mt [101] nhng tm H th ion phn t chim mt v tr nt mng, cn tm V chim hai v tr nt mng. Tm V pht sinh khi dng tia X bc x tinh th NaCl, s hnh thnh tm V xy ra qua giai on bin ho ion Cl thnh clo nguyn t, sau nguyn t ny lin kt cng ho tr vi ion clo bn cnh. Tng tc cc khuyt tt vi nhau c th dn ti s hu dit chng. V d tng tc ng thi tm F v tm H trong cng mt tinh th s to thnh khu vc khng c khuyt tt.

2.1.5 L trng v nguyn t xm nhp trong tinh th bt hp thc

Mt s tm mu trn y v bn cht l khuyt tt bt hp thc ca tinh th. Loi khuyt tt ny c th iu ch bng con ng hp kim ho (a vo lng tp cht rt t) tinh th nguyn cht bng tp cht khc ho tr. V d a CaCl2 vo tinh th NaCl to thnh tinh th bt hp thc c thnh phn Na1-2xCaxVNa(x)Cl. Trong tinh th ny ion clo vn nm trong phn mng gi ghm chc c lp phng cn cc ion Na+ v Ca2+ v l trng (V) chim cc nt bt din cation. y l trng xut hin do a tp cht vo nn gi l khuyt tt tp cht, khc vi khuyt tt c trng c ngun gc nhit. m t trng thi cn bng trong tinh th khi nng khuyt tt t (<<1%) c th s dng nh lut tc dng khi lng. T phng trnh (21) ta thy hng s cn bng K trong qu trnh to thnh khuyt tt Stki t l vi tch s nng l trng cation v nng l trng anion. K [VNa][VCl] Gi s thm mt lng nh tp cht nh Ca2+ khng nh hng n gi tr K th c th i ti kt lun rng tng dn nng tp cht s lm tng VNa do VCl gim. S hnh thnh khuyt tt trong tinh th l mt vn c nghin cu si ni trong ho hc cht rn. Khi nghin cu chi tit trng thi ca khuyt tt bng cc phng php hin i nh chp nh bng knh hin vi in t c phn gii cao c th xc lp c khuyt tt im (l trng v nguyn t xm nhp) thng to thnh mt tp hp nhiu khuyt tt c kch thc ln gi l claster. Trc ht chng ta kho st nguyn t xm nhp trong tinh th kim loi lp phng tm mt. Gi thit mng li khng thay i khi to thnh khuyt tt, th nguyn t xm nhp c th chim hai v tr gia cc nt (t hoc bt din). Kt qu nghin cu gn y cho thy nguyn t xm nhp c lm sai lch mng li ban u, c bit khu vc gn n nht. V d kim loi platin c cha mt nguyn t Pt xm nhp vo hc O c tm l trong hnh 69. Nhng n khng nm tm bt din m dch chuyn i mt on cch

75

khong 1 gn vo nguyn t tm ca mt. Do lm cho nguyn t tm ca mt cng b dch chuyn mt cch tng ng theo hng [1 0 0]. Nh vy, khuyt tt by gi gm hai nguyn t (xem hnh 69). Trong kim loi lp phng tm khi, v d Fe cng c khuyt tt nh vy (hnh 70). V tr l tng ca nguyn t xm nhp ng ra l tm ca mt ( ) nhng n li dch chuyn v gn mt nh v nh vy lm cho nguyn t nh cng b dch i mt khong tng ng theo mt [1 1 0].

1 2 3

Hnh 69 Cc nguyn t xm nhp ghp i trong t bo lp phng tm mt 1- Nguyn t xm nhp; 2- V tr nt bnh thng; 3- V tr bt din

Hnh 70 Cc nguyn t xm nhp ghp i trong tinh th lp phng khi tm

Trong tinh th ca halogenua kim cng c ion xm nhp, nhng s ion b hn rt nhiu s khuyt tt ch yu ca Stki. Cu trc chi tit ca loi khuyt tt ny hin nay cha r. Kt qu tnh ton cho thy rng trong mt s vt liu th t ra thun li chim v tr gia cc nt l tng (khng b sai lch), cn trong mt s vt liu khc th li c s sai lch nh trn. Tt nhin nhng kt lun ny cn phi tin hnh nghin cu nhiu hn na. Do c mt l trng nn gy ra hin tng ni lng cu trc tinh th vng xung quanh. Tuy nhin, trong kim loi v trong tinh th ion hin tng ni lng khc nhau v bn cht. Trong kim loi, cc nguyn t quanh l trng b chuyn v v hng tm l trng cho nn kch thc l trng gim i vi phn trm, cn trong tinh th ion th xy ra mt cch ngc li, do lc tnh in khng c b tr nn cc ion quanh l trng chuyn v ra xa tm l trng. Lc ht tng h ca cc l trng tch in ngc du trong tinh th ion dn ti hnh thnh claster. Loi claster c kch thc nh nht l cp l trng cation l trng anion v cp tp cht khc ho tr l trng cation. Nhng cp nh vy v ton b trung ho in v l mt lng cc nn c th ht cc cp khc to thnh claster c kch thc ln hn. Mt trong cc cht c cu trc khuyt tt c nghin cu nhiu nht l Fe1-xO (0 x 0,1). FeO hp thc, kt tinh theo kiu NaCl vi ion Fe2+ trong cc nt bt din. Kt qu xc nh t trng chng t rng trong cu trc khng hp thc Fe1-xO c cc l trng ca st, ch khng d oxi so vi cng thc FeO. Da trn c s quan nim n gin v khuyt tt im c th gi thit rng trong oxit st II khng hp thc Fe1-xO c khuyt tt biu din 2+ 3+ 2+ Fe3+ v l trng cation phn b mt cch theo h thc Fe1-3x 2x Vx O. Trong cc ion Fe , Fe khng c trt t trong nt bt din ca mng tinh th gi ghm chc c lp phng mt tm ca phn mng ion O2. Tuy nhin, kt qu nghin cu bng phng php nhiu x ntron v phng php tia X cho thy cu trc thc t ca oxit st II khng hp thc khc vi gi thit . Cc ion Fe3+ nm cc nt t din, hnh nh trong cu trc c cc claster. Hnh 71 l cu trc claster do Kokha gi thit v c gi l claster Kokha. Claster ny bao gm tt c cc nt cation c trong t bo gi ghm chc c lp phng tm mt kiu NaCl. Mi hai nt bt din nm gia cc cnh v mt nt bt din nm tm khi u khng b chim, cn bn

76

trong tm v tr t din th b chim bi ion Fe3+. Claster nh vy c in tch m tng cng l 14 (in tch ca 13 l trng bt din 213= 26, in tch ca 4 ion Fe3+ l 3 4= +12 vy 12 26 = 14). bo m trung ho in tch, cc ion Fe2+ khc c phn b cc nt bt din xung quanh claster. Claster Kokha to thnh tinh th vurtit Fe1-xO vi cc gi tr x khc nhau. S claster tng khi tng x v lm gim khong cch trung bnh gia cc claster. Uran ioxit c cha mt lng d oxi cng c cu trc claster nh vy. Thnh phn ca cht bt hp thc l UO2+x (0 < x 0,25). UO2 hp thc c cu trc kiu florit. Trong cu trc ca florit UO2+x nguyn t oxi b sung khng nm tm m lch v mt cnh theo hng [1 1 0]. iu ny lm cho hai ion oxi gn b dch ra theo hng [1 1 1]. Nh vy l thay cho vic mt ion oxi chim v tr gia cc nt to thnh claster gm 3 oxi gia cc nt v 2 l trng oxi.

1 2 3

Hnh 71 Cu trc gi thit claster Kokha trong vurtit Fe1-xO 3+ 1 - Ion oxi; 2- Hc bt din ; 3- Ion Fe trong hc t din

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1 2 3 4

Hnh 72 Claster ca khuyt tt xm nhp trong UO2+x. Trn hnh khng v v tr U tm ca mi lp phng th hai 1 - Ion oxi; 2 - V tr l tng gia cc nt; 3 - Oxi gia cc nt; 4 - L trng oxi

2.1.6 Khuyt tt o cu trc

Mt s loi vt liu tinh th c s trao i v tr ca cc ion v nguyn t lm xut hin khuyt tt o cu trc (antistructure). Thuc loi vt liu ny gm h hai hoc nhiu cu t, trong cc loi nguyn t khc nhau chim cc phn mng khc nhau. Mt s hp cht ion cng c kiu mt trt t nh vy. Nu s khuyt tt o cu trc ln v c bit l khi tng nhit th c th xy ra s chuyn ho trt t thnh mt trt t. Gii hn ca s trt t l s cp nguyn t thay i v tr ca nhau nhiu n ni khng th xc nh c v tr tri hn ca tng loi nguyn t. y c th hnh dung nh loi dung dch rn thay th. Dung dch rn thay th c th c trt t hoc khng c trt t. Trng hp nguyn t khc nhau chim cc h nt khc nhau th gi l dung dch rn thay th c trt t. Dung dch rn thay th c trt t thng xy ra hin tng to thnh siu cu trc, iu ny pht hin c do da vo s xut hin cc phn x ph trn gin nhiu x tia X. Zn hoc Cu

Hnh 73 Trt t trong t bo mng lp phng n gin ca ng thau

ng thau CuZn trt t siu cu trc quan st c 450oC nh trn hnh v bn cnh. trng thi trt t th ng thau c cu trc tng t nh cu trc CsCl: nguyn t ng nm tm ca lp phng c cc nh l Zn. Hp kim khng c trt t cng c thnh phn nh vy c gi l ng thau trong Cu v Zn phn b hn lon cc nh v tm ca t bo lp phng. Mt v d na v khuyt tt o cu trc ca spinen AB2O4. MgAl2O4 cc ion O2 c mng li gi ghm chc c lp phng tm mt, ion Mg2+ chim

78

cc hc t din, ion Al3+ chim cc hc bt din. Kiu cu trc nh vy c biu din theo 2+ v 1/2 v tr B3+ to thnh cng thc A te B0 2 O 4 gi l spinen thun. Khi thay i cc v tr A spinen o hon ton. V tr spinen o nh magie titanat Mg2TiO4 hoc vit theo cng thc cu trc Mgte[MgTi]oO4. Nu s phn b cc cation mt cch thng k trung gian gia spinen o v spinen thun th gi l spinen trung gian.

2.1.7 Cc khuyt tt ko di - Mt trt

a) Cu trc ca mt trt tinh th Mt trt tinh th gi tt l mt trt v k hiu l M.T. mt thi gian di ngi ta cho rng cc oxit khng hp thc ca mt s kim loi chuyn tip, v d WO3-x, MoO3-x, TiO2-x c mt khu vc ng th kh rng. Tuy nhin cc cng trnh ca Magnen chng minh rng mi oxit trong mt khong thnh phn c xem l ng th cng c nhng dy pha c thnh phn khc nhau cht t tuy cu trc th hu nh ging nhau. V d trong oxit thiu oxi TiO2-x gm mt dy cc ng ng c cng thc chung l TinO2n-1 (vi n = 4, 5, 610). Mi thnh vin trong dy ng ng ny v d khi n = 8 ta c Ti8O15 (hoc TiO1,875), n = 9 ta c Ti9O17 (hoc TiO1,889), c cu trc kh trt t. m t cu trc ca pha nh vy Magnen v Uorsli a ra khi nim mt trt tinh th (M.T) v cho l mt khuyt tt mi. Cu trc tinh th ca rutin thiu oxi gm cc khu vc rutin hp thc ng vi cu trc l tng tch bit nhau bng cc M.T l nhng lp mng c thnh phn khc v trt t cu trc cng khc. Oxi b thiu tp trung ti cc M.T . Khi thc hin phn ng kh, lng oxi gim dn lm tng s M.T v gim vng khng khuyt tt ca tinh th. V d khi kh TiO2, giai on u oxi gim dn lm xut hin l trng oxi, ng thi Ti4+ bin thnh Ti3+, Ti2+ Cc l trng oxi khng phi phn b mt cch hn lon m c tp trung vo mt s mt. Sau khi tch t mt s ng k l trng oxi, s xy ra s dn nn cu trc v loi b l trng lm xut hin M.T. khu vc cha c phn ng kh, cu trc tinh th cn hon chnh th cc bt din TiO6 tip xc vi nhau qua cnh chung, khu vc xy ra phn ng kh do thiu oxi v c s dn nn cu trc nn cc bt din TiO6 li tip xc vi nhau qua mt chung v xut hin M.T. d dng hnh dung, ta xt qu trnh kh MoO3. Mng li MoO3 c th m t bng cch ghp cc bt din MoO6 li vi nhau qua nh, to thnh mt khung pht trin ra 3 chiu trong khng gian (hnh 74a). Khi b kh thnh MonO3n-1 (v d n = 8 ta c Mo8O23) mt s bt din dch li gn nhau hn to thnh mt mt trong cc bt din ni vi nhau qua cnh chung. Trong mt c tng nhm bt din nm st nhau (hnh 74b). Qua tng khong u n, bc tranh cu trc MnO3n-1 (n = 8, M l Mo), c lp li theo hng v ng chm chm. Thnh phn ca mi dy ng ng lin quan n tng khong xc nh gia cc M.T cnh nhau. Khi kh tip tc (ngha l gim gi tr n trong cng thc chung ca dy) th khong cch gia cc M.T cng nh dn. Khi chuyn t nhm ng ng ny sang nhm ng ng khc, khong cch gia cc M.T thay i mt cch t ngt. Mi mt pha trong dy ng ng c th xem nh ng thng, ngha l c thnh phn khng i. Hai pha cnh nhau trong dy ng ng c ngn cch bng mt mt mng cha hai pha. nhit cao, mi mt pha c th c s mt trt t v tn ti trong mt khong thnh phn no .

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(a) Hnh 74 Mt trt tinh th trong dy ng ng ca oxit

(b)

Trong mt s trng hp, v d CeO2-x; s khc nhau gia cc pha ng ng bin mt v trn mt nhit ti hn no s to thnh mt dy dung dch rn lin tc. C th gii thch s chuyn pha nh vy theo nhiu cch. Cc M.T vn cn tn ti dung dch rn nhng phn b mt cch hn lon. S phn b hn lon cc M.T gi l khuyt tt Uorsli. Kt qu nghin cu cho thy khi kh rutin to thnh hai dy ng ng ca cc hp cht ng vi cng thc tng qut TinO2n-1. Hp cht ca dy ng ng th nht ng vi gi tr 3 n 10, hp cht ca dy ng ng th hai ng vi gi tr 16 n 36. Khi chuyn t mt dy ng ng ny sang dy ng ng khc hng ca M.T thay i mt gc quay bng 11053. iu ng lu l hp cht ng vi gi tr 10 n 14 s nh hng ca M.T thay i mt cch t t trong khong thnh phn , mi mt thnh phn ng vi mt gc lch ca M.T. Cng nh trong hai dy ng ng trn cc M.T y cng phn b c trt t. Cc dy ng ng ca cc hp cht oxit vanai b kh VnO2n-1 (vi n nm gia 4 v 8) v oxit hn hp crom - titan Cr2Tin-2O2n-1 (vi n gia 6 v 11) to ra mt h M.T ng cu trc ging nh cc sn phm ca phn ng kh rutin. Cc v d chng ta xt trn y, trong cc tinh th c cha mt b M.T song song v cch u nhau. Khu vc xy ra phn ng kh l M.T cn khu vc cha xy ra phn ng kh l lp b kp gia cc M.T cnh nhau. Trong Nb2O5 v cc oxit hn hp niobi-titan, niobiwolfram b kh mt phn, cu trc ca cc M.T li to thnh mt b M.T trc giao vi nhau. Do ti khu vc cha xy ra phn ng kh, cu trc cn hon thin khng phi gm nhng lp v tn m l nhng bloc v tn. Cu trc bloc nh vy c gi l cu trc M.T kp. Chiu di, rng v phng php ghp bloc vn gi nguyn c trng cho cu trc cha kh ca ReO3. Mc phc tp ca cc pha bloc cn tng ln, khi trong cu to thay v bloc mt kch thc bng bloc hai kch thc khc nhau t hp vi nhau theo mt trt t nht nh. V d cc pha ca Nb25O62, Nb47O116, W4Nb26O77 v Nb65O161F3 b) Bin gii bloc- min o pha (xem hnh 75)

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Cc min o pha

bin gii o pha

nguyn t A nguyn t B

(a) (b) Hnh 75 Cu trc min ca n tinh th (a), min o pha v min bin gii o pha trong tinh th hon chnh AB (b)

Ngay trong n tinh th cng c cc t chc min (men), chnh s c mt t chc min l mt dng khng hon thin ca tinh th. Trong tng min ring bit (kch thc ti 10.000) cu trc tinh th hon thin, nhng bin gii cc min th cu trc khng trng nhau. Hng khc nhau ca cc min c th t mt n vi . Khu vc bin gii cc min c gi l bin gii bloc, ti y xut hin mt o pha. V d trong hnh 75b l bin gii o pha ca tinh th AB. Ti cc nguyn t cng loi c phn b cnh nhau. Tnh lin tc A B A B A theo chiu dc vn gi nguyn trong khi theo chiu ngang th thay i ti min o pha nh c phn chiu qua gng.

2.1.8 Lch mng l loi khuyt tt ph bin trong tinh th

C hai loi lch mng l lch mng bin v lch mng xon.
Lch mng bin c hnh thnh khi mt phn ca tinh th dch chuyn i vi phn khc sao cho s phn t ca hai phn khc nhau mt n v. Tm ca lch mng nm trong mt phng trt ti ch mng li b xo trn mnh nht (hnh 76). Bin gii gia phn tinh th b trt v phn tinh th khng b trt gi l ng lch mng. Lch mng bin ko di trong mt phng trt v dc theo ng trc giao vi mt phng trt.

Lch mng xon (hnh 77) y bin gii gia phn chuyn dch v phn khng chuyn dch ca tinh th phn b song song vi hng trt. C th tng tng s hnh thnh lch mng xon nh sau: ct mt nht vo tinh th t AB n EF ri y mt bn xung di. ng thng ng EF l ng lch mng xy ra s bin dng ln nht. lch mng xon cc nguyn t trong phn t phn b theo ng xon c, c mi vng quay quanh ng lch mng li c mt bc chuyn dch.

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Hnh 76 Lch mng bin

Hnh 77 Lch mng xon

Lch mng thng pht sinh ra trong qu trnh hnh thnh tinh th hoc khi tinh th chu tc dng bin dng n hi. S c mt ca lch mng nh hung nhiu n cc tnh cht vt l ca tinh th: tnh cht c, in v c bit l kh nng phn ng ca cht rn. C th gii thch nh hng ca lch mng n tnh cht in ca tinh th nh sau: - Khi c mt lch mng s lm gim th nng ca tinh th. Cc tp cht ca tinh th c xu hng khuch tn vo khu vc mt trt t nht ca mng li, ngha l tp trung xung quanh vng lch mng. - u mt ca nhng mt phng lch c mt dy nguyn t cn mt lin kt cha c bo ho. Dy nguyn t ny to ra mt mc nng lng ph, nh v trong quang ph nng lng ca tinh th. Phn ln mc nng lng ny nm ngay pha di vng dn v cch vng dn mt gi tr bng 0,2 eV. S c mt lch mng trong tinh th nh hng n qu trnh khuch tn v ti t hp cc phn t mang in trong tinh th.

2.2

Dung dch rn

S hnh thnh dung dch rn l qu trnh rt ph bin trong vt liu tinh th. Do nt c trng ca dung dch rn l kh nng thay i thnh phn, nn thng thng iu ch cc vt liu c tnh cht mong mun ( dn in, t tnh) th cn li dng s hnh thnh dung dch rn. C hai kiu dung dch rn ch yu l: + Dung dch rn thay th, trong nguyn t hoc ion ca cht tan thay th vo v tr ca nguyn t hoc ion ca dung mi. + Dung dch rn xm nhp, trong cc phn t nh ca cht tan xm nhp vo cc hc trng ca mng tinh th dung mi (thng l hc T v hc O) ch khng y nguyn t hoc ion ra khi mng li tinh th ca chng. Xut pht t hai kiu c bn c th hnh thnh hng lot loi dung dch rn khc vi c ch phc tp hn.

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2.2.1 Dung dch rn thay th

V d xt dung dch rn gia Al2O3 v Cr2O3 nhit cao. C hai cu t ny ca dung dch rn u c cu trc corun vi mng li gi ghm chc c lc phng ca cc anion O2, cn cation Al3+ hoc Cr3+ chim 2/3 v tr hc bt din. Cng thc ca dung dch rn ny l Al2-xCrxO3 (0 x 2). cc gi tr trung gian ca x, cc cation Al3+, Cr3+ c phn b mt cch trt t vo cc hc bt din. to thnh dung dch rn thay th, cc cu t phi tho mn mt s iu kin. Cc ion thay th phi c in tch bng nhau nu khng th s to thnh l trng hoc ion xm nhp. Kch thc ca cc ion phi gn bng nhau. i vi kim loi (s hnh thnh hp kim) to thnh dung dch rn thay th th bn knh cc nguyn t kim loi khng c khc nhau qu 15%. Vi cc h khng phi l kim loi th kh nh gi c gii hn ny (v ngay c bn knh ion cng khng c s thng nht gia cc s liu thc nghim ca cc tc gi). Tuy nhin s liu thc t cho thy s khc nhau c th ln hn 15%. V d theo Paoling th bn knh cation kim loi kim (n v ) l Li+ 0,60; Na+ 0,95; K+ 1,33; Rb+ 1,48; Cs+ 1,69. S khc nhau v kch thc ion gia K+ v Rb+ cng nh gia Rb+ v Cs+ nh hn 15%, do cc mui ca chng u c th hnh thnh dung dch rn. Tuy nhin, gia kali v natri cng c lc to thnh dung dch rn (v d nhit cao i vi KCl-NaCl) mc du bn knh ca K+ v Na+ khc nhau ti 40%. Ngay c Li+ v Na+ c bn knh khc nhau ti 60% m trong nhiu trng hp chng c th thay th ln nhau to thnh dung dch rn. Cn Li+ v K+ th bn knh khc nhau qu ln nn cc mui ca chng khng th ho tan vo nhau c. to thnh dy dung dch rn lin tc th cc cu t hp phn phi c cu trc tinh th nh nhau. iu ny khng th pht biu ngc li c, ngha l c cu trc tinh th ging nhau th c th to dung dch rn lin tc vi nhau. V d LiF v CaO u c mng li tinh th kiu NaCl nhng trng thi tinh th chng khng ho tan hon ton vo nhau. Nu nh vic to thnh dung dch rn khng hn ch ch xy ra trong mt s iu kin thun li, v d h Al2O3-Cr2O3 nhit cao, th vic hnh thnh dung dch rn hn ch li xy ra thng xuyn. Vi dung dch rn hn ch th khng nht thit cc cu t hp phn phi c cu trc tinh th ging nhau. V d fosterit Mg2SiO4 (c cu trc olivin) v villemit Zn2SiO4 c th ho tan vo nhau mt phn mc du cu trc ca chng rt khc nhau. Olivin c phn mng oxi gn vi gi ghm chc c lc phng, trong khi villemit khng c lp oxi gi ghm chc c. Cu trc ca hai loi khong vt ny u gm cc t din SiO44 nhng trong olivin Mg nm trong bt din, cn trong villemit Zn2+ nm trong t din. Tuy nhin, c hai cation khng phi ch i hi bao quanh cng mt kiu m c th khi th kiu ny khi th kiu khc. Trong dung dch rn trn c s villemit (Zn2-xMgxSiO4), Mg2+ thay th Zn2+ trong v tr t din. Tri li, trong dung dch rn trn c s fosterit Mg2-xZnxSiO4, Zn2+ thay th v tr bt din ca Mg2+.
2+

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Hnh 78 Gin trng thi h Mg2SiO4 (fosterit)-Zn2SiO4 (villemit) 1- Hn hp gia hai dung dch rn; 2- Dung dch rn trn c s villemit 3- Pha lng; 4- Dung dch rn trn c s fosterit

Trong cc oxit phc tp, ion Mg2+ thng v tr bt din cn Zn2+ li v tr t din l do bn knh Mg2+ ln hn bn knh Zn2+ (thc ra Zn2+ v tr t din cn lin quan n phn no lin kt cng ho tr vi oxi). Ion Al3+ trong cc hp cht oxit c th c s phi tr 4 hoc 6. V d trong h LiAlO2LiCrO2. Trn c s LiCrO2 to thnh dung dch rn Li(Cr1-xAlx)O2 (vi 0 x 0,6) trong Al3+ v Cr3+ u chim cc v tr bt din. Tuy nhin, trong LiAlO2 th Al3+ li nm trong v tr t din, iu ny khng thch hp vi Cr3+. Do khng th to thnh dung dch rn trn c s LiAlO2. Trong nhng trng hp khi cc ion thay th nhau c kch thc rt khc nhau th thng thy c s thay th mt phn ion ln bng mt phn ion b, cn trong trng hp ngc li th thy t xy ra. V d trong Na2SiO3, ion Na+ c th thay th bng ion Li+ to thnh dung dch rn (Na2-xLix)SiO3 nhng Li2SiO3 ch di 10% Li+ b thay th bng Na+. Rt nhiu dng nguyn t v ion thay th c ln nhau tr thnh dung dch rn thay th. Cc silicat v germanat thng l ng hnh vi nhau v to thnh dung dch rn vi s thay th Si4+, Ge4+. Cc lantanoit do kch thc rt gn nhau nn dng oxit c khuynh hng to thnh dung dch rn vi nhau. cng l mt trong cc nguyn nhn kh tch ring r cc nguyn t t him. Cc dung dch rn c th hnh thnh khi thay th anion (v d trong h AgCl-AgBr). Tuy nhin, dung dch nh th t ph bin so vi trng hp thay th cation. l do cc anion c kch thc khc nhau nhiu v kiu lin kt cng nh s phi tr thng l khc nhau.

2.2.2 Dung dch rn xm nhp

Cc nguyn t c kch thc b nh hiro, cacbon, bo, nit, c th chui vo cc hc trng trong mng li kim loi. c bit palai kim loi c th hp th mt th tch rt ln kh hiro to thnh cc hirua PdHx, l dung dch rn xm nhp trn c s cu trc lp phng mt tm ca palai. Hin nay vn cha gii thch c hc trng no (t din hoc

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bt din) cha hiro trong cu trc . Thp austenit l mt v d c th nht ca dung dch rn xm nhp gia st v cacbon.

2.2.3 Nhng c ch phc tp trong s hnh thnh dung dch rn thay th

Chng ta kho st nhng iu g xy ra khi thay th cation c in tch khc nhau. Cc trng hp c th xy ra: l trng cation - Thay th bng cation c in tch ln hn anion xm nhp l trng anion - Thay th bng cation c in tch b hn
a) To thnh l trng cation

cation xm nhp

Nu cation ca cu trc ban u c in tch b hn in tch ca cation thay th th xy ra s thay i ph v cu trc sao cho bo m tnh trung ho in. Mt trong cc cch l to ra l trng cation. V d, khi ho tan mt lng nh CaCl2 vo NaCl th mt mi ion Ca2+ thay th hai ion Na+, do c mt v tr ca Na+ b b trng, thnh phn dung dch rn c th vit Na1-2xCaxVxCl ( 600oC 0 x 0,16), V y l l trng cation.
o
2800

2200

C 2

2600

2000

2400

1800

2200 2030 2000

2135

2 3 1
80

1600

1
1400

MgAl2O4

MgO

20

40

60

% khi lng

Al2O3

MgAl2O 4

60

70

80

90

% mol

Al2O 3

Hnh 79 Gin trng thi h MgO-Al2O3 1- corun + dung dch rn spinen; 2- lng; 3- dung dch rn spinen

nhit cao, spinen MgAl2O4 to thnh mt khu vc dung dch rn vi Al2O3 trong ion Al3+ thay th ion Mg2+ phn b trong cc nt t din theo t l 2/3. Cng thc dung dch rn c vit Mg1-3xAl2+2xVxO4. S hnh thnh dung dch rn ny xut hin x l trng cation. Rt nhiu hp cht ca kim loi chuyn tip u thuc v loi hp cht bt hp thc do 2+ 3+ cc ion ca chng nhiu mc oxi ho khc nhau. V d vurtit Fe1-3x Fe2x O ng vi cng thc Fe1-xO (0 x 1) c th xem nh mt loi dung dch rn. Quan nim v cu trc vurtit nh hp cht gm cc ion Fe3+, Fe2+ v cc l trng cation phn b khng trt t trong mng

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bt din kiu NaCl l qu n gin v khng ng vi thc t, thc ra y to thnh cc claster khuyt tt. b) C ch anion xm nhp Mt c ch khc v s thay th cation c in tch b bng cation c in tch ln l to thnh dung dch rn anion xm nhp. V d ytri florua ho tan vo florua canxi. Mc lp y phn mng cation khng thay i, do pht sinh ra s xm nhp ca ion F v cng thc dung dch rn s l (Ca1-xYx)F2+x. Anion xm nhp F c phn b vo hc trng c kch thc ln gia cc nt ca cu trc florit v c phi tr xung quanh bng 8 ion F khc (tc l tm ca lp phng trong hnh 30a). ioxit urani cng c cu trc kiu florit. Khi oxi ho n to thnh dung dch rn UO2+x cng tng t nh khi dng YF3 hp kim ho CaF2. Trong UO2+x in tch ca ion xm nhp O2 b tr cho in tch ca ion urani b oxi ho ln U6+ v cng thc ca hp cht s thnh
( U1 x U x )O2 + x .
4+ 6+

c) To thnh l trng anion Khi cation ca cu trc ban u c in tch cao hn in tch ca cation thay th th tnh trung ho in c th t c bng cch xut hin cc l trng anion, hoc c cation xm nhp. ioxit zircon (c cu trc florit) c lm bn ho bng canxi oxit (Zr1-xCax)O2-x (0,1 x 0,2). Khi to thnh dung dch rn CaO trong ZrO2 th tng s nt cation vn gi nguyn, cn vic thay th Zr4+ bng Ca2+ lm xut hin cc l trng O2. Dung dch rn loi ny c s dng trong vt liu chu la, cht in li rn c cht dn l O2. d) C ch cation xm nhp Khi thay th bng cation c in tch nh hn cn c th dng c ch xm nhp cation. Khi bin ho cu trc SiO2 ( mt trong cc dng th hnh nh thch anh, triimit, cristobalit) vi s thay th Si4+ bng Al3+ s to thnh alumosilicat, trong cation kim chui vo v tr gia cc nt m trc y trong SiO2 ban u cn b trng. Thnh phn nh vy ng vi cng thc Lix(Si1-xAlx)O2 vi 0 x 0,5. Hnh 80 cho thy khu vc dung dch rn kh rng trn c s hp cht LiAlSiO4 (x = 0,5) gi l evcriptit v LiAlSi2O6 (x = 0,33) gi l spoumen.

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Hnh 80 Mt phn ca gin trng thi h SiO2-LiAlO2

1. 2. 3. 4. 5. 6.

SiO2 dung dch rn trn c s spoumen Dung dch rn trn c s spoumen Dung dch rn trn c s evcriptit Hn hp hai dung dch rn Lng SiO2 lng

Spoumen l loi vt liu kh l th v h s gin n nhit gn bng khng, thm tr c gi tr m. Tnh cht bt thng ny lm cho gm c cha -spoumen l thnh phn ch yu, c kch thc c nh, chng li cc xung nhit, nn c s dng nhit cao. Khong trng gia cc nt trong cu trc thch anh rt nh do ch c th a vo cation liti. T trng ca triimit v cristobalit nh hn t trng ca thch anh, bi vy kch thc khong trng gia cc nt ca chng cng ln. Tng t nh thch anh, triimit v cristobalit cng to thnh dung dch rn nhng y cation xm nhp, khc vi thch anh, c th l Na+, K+. e) Thay th kp C ch ny l trng hp thay th ng thi c hai phn mng. V d s hnh thnh dung dch rn trn c s ovilin tng hp. Cc ion Mg2+ c th b thay th bng cc ion Fe2+, ng thi ion Si4+ b thay th bng Ge4+ cho dung dch rn c cng thc: (Mg2-xFex)(Si1-yGey)O4. Bc bromua v natri clorua c th to thnh dy dung dch rn trong c s thay th xy ra c hai phn mng cho cng thc sau: (Ag1-xNax)(Br1-yCly) (0 < x, y < 1) Cc ion thay th c th c in tch khc nhau, nhng vn quan trng l phi m bo tnh trung ho in ca tinh th. Nh anoctit CaAl2Si2O8 v anbit NaAlSi3O8 to thnh dy

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dung dch rn (plagioclaz) c cng thc: (Ca1-xNax) (Al2-xSi2+x)O8 vi (0 < x < 1). iu ny cho thy rng s thay th Na Ca v Al Si phi thc hin ng thi mc bng nhau. Theo c ch thay kp c s hnh thnh SiAlON tc l mt dung dch rn trong h Si-AlO-N trn c s cu trc Si3N4. Nitrua silic c cc t din SiN4 ni vi nhau qua nh to thnh b khung 3 chiu. Trong dung dch rn ca cu trc SiAlON, Si4+ b thay th mt phn bng Al3+ cn nit b thay th bng oxi vi t l sao cho bo m trung ho in. n v cu trc ca dung dch rn ny l t din (SiAl)(O,N)4, cng thc c th vit di dng (Si3xAlx)(N4-xOx). Vt liu gm trn c s nitrua silic c trin vng to ln trong vic s dng ch to cc thit b lm vic nhit cao. Nhng cng trnh gn y v tng hp SiAlON v tin ti sn xut vt liu ny m ra mt trang mi trong ho tinh th v m rng phm vi s dng gm trn c s nitrua.

2.2.4 Nhng nhn xt tng qut v cc iu kin hnh thnh dung dch rn
Hin nay ch mi bit c mt cch nh tnh v nh hng ca cc yu t quyt nh s hnh thnh dung dch rn c bit, l loi dung dch rn phc tp. i vi mt h c th kh lng d on c s to thnh dung dch rn hay khng, v gii hn ca dung dch rn . tr li cc cu hi ny thng l phi bng con ng thc nghim. Nhng min dung dch rn bn trn gin trng thi ch c hnh thnh trong trng hp khi chng c gi tr G thp hn tng G ca cc pha hp phn. Cn trong nhng iu kin khng cn bng khi s dng cc phng php ho hc mm hoc cc th thut ch ho khc, thng thu c cc dung dch rn trong mt khong thnh phn rng hn. Th thut nh vy c th thy trong k thut iu ch -Al2O3 (cng thc tng qut Na2O.nAl2O3). Cc ion Na+ trong Na2O.nAl2O3 (vi n = 8) c th thay th mt phn hoc thay th hon ton bng phng php trao i ion vi dy cation ho tr 1 (Li+, K+, Ag+, Cs+) mc du rt nhiu loi -Al2O3 vi cc cation u khng bn v nhit ng (c bit -Al2O3 dng liti). V vai tr kch thc ion khi hnh thnh dung dch rn thay th hoc dung dch rn xm nhp ni trn, trng hp xy ra s thay th ion khng ng ho tr th trc ht phi bo m s cn bng in tch. Nhng ngay c khi tho mn cc iu kin cn bng in tch v kch thc ion, vn c nhng c ch khc nhau v s hnh thnh dung dch rn vi ion khc in tch. V d tc ng ca hai c ch ngc nhau trong qu trnh hnh thnh dung dch rn trn c s Li2TiO3. Hp cht ny nhit cao c cu trc tinh th kiu NaCl, trong Li+ v Ti4+ c phn b khng c trt t vo cc nt bt din ca mng O2 gi ghm chc c. Khi tha Li2O (trng hp a) hoc TiO2 (trng hp b) s to thnh hai dy dung dch rn: Li2+4xTi1-xO3 Li2-4xTi1+xO3 0 < x 0,08 0 < x 0,19 (a) (b)

S hnh thnh dung dch rn ca c hai kiu u km theo phn ng trao i ca cation in tch +1 v cation in tch +4 dn ti qu trnh xm nhp Li+ (trng hp a) hoc xut hin l trng Li+ (trng hp b). S khc nhau rt ln v in tch Li+ v Ti4+ khng cn tr vic hnh thnh dung dch rn, d nhin iu ny cn nh vo vai tr kch thc ion. C hai ion Li+ v Ti4+ u c kch thc gn ging nhau v thch hp vi v tr bt din c khong cch kim loi - oxi 1,9 2,2.

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C th a nhiu v d v trng hp cc ion c kch thc rt gn nhau nhng in tch rt khc nhau m vn thay th cho nhau to thnh dung dch rn. V d: trn c s LiNbO3 vi cu trc tng t imenhit, to thnh dung dch rn bng s trao i cc v tr bt din 5Li+ Nb5+ (hnh 81).
o

C lng

1200 1000 800 600 400 45 50 55 60

ddch rn ca LiNbO3

Li3NbO4
+

ddch rn LiNbO 3

ddch rn LiNbO3 + LiNb3O8

% mol

Nb2O5

Hnh 81 Mt phn ca gin trng thi h Li2O-Nb2O5

Hnh 81 l mt phn ca gin trng thi h bc hai Li2O-Nb2O5 gn vng dung dch rn trn c s mng tinh th LiNbO3. nhit cao (~1150oC) hp cht LiNbO3 ho tan thm cc cu t hp phn l Li2O v Nb2O5 to thnh mt vng dung dch rn. Hm lng Nb2O5 trong vng thay i t 49% n 55% mol Nb2O5.. nhit thp hn (~600oC) rng ca dung dch rn b thu hp li t 49,5% n 51% mol Nb2O5. Trong cu trc lp phng bn ca ZrO2, ion Zr4+ nm v tr bt din (bao quanh bng 6 ion O2) c th thay th bng Ca2+ v Y3+. V d thay th Zr4+ bng Y3+ theo c ch l trng anion O2 c dung dch rn c cng thc phn t l Zr1-xYxO2-x/2.

2.2.5 Cc phng php nghin cu dung dch rn

a) Ghi gin nhiu x tia X theo phng php bt Phng php bt ghi gin nhiu x tia X c nhiu mc ch. Trc ht l xc nh thnh phn nh tnh ca cc pha trong mu nghin cu. Mc ch ny khng i hi phi o tht chnh xc v tr v cng ca cc vch phn x. Vic xc nh nh lng thnh phn dung dch rn cng da vo cc thng tin chnh xc v v tr v cng ca cc vch phn x trn gin nhiu x tia X. Thng thng, khi thay i thnh phn ca dy dung dch rn s lm cho cc thng s mng ca t bo nguyn t co li hoc gin ra. xc nh thnh phn dung dch rn c th cn c vo s ph thuc khong cch gia cc mt mng hoc th tch t bo mng vo thnh phn di dng mt th chun. V d kt qu phn tch nh tnh thnh phn pha theo phng php nhiu x tia X cho bit i vi h MgAl2O4-Al2O3 (hnh 79) nhit 1800oC, thnh phn gii hn ca dung dch rn spinen ln hn rt nhiu so vi nhit 1000oC. Nu ly mu c 65% Al2O3, 35% MgO theo gin ta thy trn 1550oC trong iu kin cn bng ch c mt pha rn ng th l dung dch rn spinen.

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Di 1550oC hnh thnh hai pha l corun v dung dch rn spinen c < 65% Al2O3. Thnh phn ca Al2O3 trong dung dch rn ny c xc nh theo v tr ca ng bo ho dung dch rn. V d 1200oC ch c 55% Al2O3. T l khi lng ca hai pha rn (dung dch rn v corun) c xc nh theo quy tc n by. xc nh thnh phn dung dch rn th vic xc nh khong cch gia cc mt mng cn phi o tht chnh xc. Thng th t bo mng s tng kch thc khi thay th ion c bn knh b bng ion c bn knh ln, nu ngc li kch thc t bo s gim. Theo nh lut Vunfa-Brega th khi tng kch thc t bo mng s tng gi tr d. Kt qu lm dch chuyn tt c cc pic phn x v pha gc 2 b. Nhng s dch chuyn nh vy i vi cc pic khc nhau l khc nhau. Trong cc tinh th khng thuc h lp phng th vic co hay gin t bo mng khi thay i thnh phn c th khc nhau theo c 3 hng. Trong mt s trng hp th vic co dc theo mt hng ny lm gin n theo hng khc. Theo quy tc Vegard th thng s t bo mng thay i tuyn tnh theo thnh phn. Tuy nhin quy tc ny ch gn ng thi, khi o lng chnh xc s pht hin ra sai lch so vi quy tc Vegard. Cn phi xem quy tc Vegard nh l mt quy tc khng nghim ngt i vi dung dch rn to thnh bng cch thay th khng trt t cc ion. Vi h Al2O3-Cr2O3 trong khong 2100oC n 950oC to thnh dy dung dch rn khng hn ch. Di 950oC c mt vng phn lp thnh hai pha tinh th. V d trong iu kin cn bng th dung dch rn t l 50 : 50 trn 950oC s phn thnh hai pha: mt pha giu Al2O3 cn pha kia giu Cr2O3. Trong thc t, vic phn hu dung dch rn thnh hai pha nhit 800 900oC xy ra vi tc rt chm, tuy rng c th thc nhanh bng k thut ch ho thu nhit hoc di tc dng ca p sut cao. Do m dung dch chun b 1300oC c th gi c n tn nhit phng vi mi thnh phn. Gin nhiu x tia X chp mu bt ca cc dung dch rn cho php xc nh c s ph thuc ca cc thng s a v c ca t bo mng lc phng vo thnh phn. Trn hnh 81 cho thy s ph thuc c sai lch dng vi quy tc cng tnh ca Vegard. iu ny c th do cc ion Al3+ v Cr3+ khng phi c phn b mt cch ln xn m to thnh s tp trung cc ion cng loi, lm pht sinh ra nhng vng vi cu trc ca hai kiu: giu Al2O3 v giu Cr2O3 tuy rng mc v m cm thy dung dch l ng th. S tch t (segregation) cc ion cng tn trong dung dch rn lm tng thng s t bo mng so vi gi tr khi gi thit cc ion khng tng tc c phn b mt cch hn lon. S c mt ng cong sai lch dng so vi quy tc Vegard xy ra ng thi vi s phn lp t vi ca dung dch rn cn pht hin c trong nhiu h na.

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2200

nhit (o C)

2000 1800 1000 800 600

1 2

Al2O3 20

40

60

80

Cr2O3

% mol
Hnh 82 Gin trng thi h Al2O3-Cr2O3 1. Hai dung dch rn; 2. Dung dch rn; 3. Lng

gi tr hng s mng (A)

13.4 13,2 13,0

4,8 4,7

Al2O 3

% mol

Cr2O 3

Hnh 83 S ph thuc ca thng s t bo mng vo thnh phn dung dch rn trong h Al2O3-Cr2O3

i vi h khng kim loi cng c khi thu c ng cong sai lch m vi quy tc Vegard. C th l do lc ht gia cc ion khc tn (v d trong h A-B th tng tc gia A v B c th mnh hn tng tc gia A-A hoc gia B-B). Do tng tc kh mnh gia A v B nn c th dch chuyn dn cc nguyn t lm cho s sp xp tr thnh c trt t hn (v d s sp xp trt t cc nguyn t ng v km trong ng thau CuZn). Siu cu trc thng quan st thy mt s t l c bit gia cc cu t (v d 1:1) cc thnh phn khc do tng tc A-B khng mnh. Do trt t cation c th ch xy ra mt khong cch rt nh (c vi ng knh nguyn t) v dung dch rn lc vn mt trt t. Tc dng trt t cc ngn nh vy (trt t gn) kh lng pht hin bng thc nghim, do hin nay ch bng cch so snh nh tnh v s sai lch m vi quy tc Vegard vi trt t cation. Cho n by gi chng ta ch mi xt s sai lch vi quy tc Vegard mt cch n iu. Tuy nhin, khi thay i tnh i xng ca dung dch rn hoc thay i c ch s to thnh dung dch rn c th dn ti s thay i t ngt hoc c th lm gin on s ph thuc .

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V d khi kho st dung dch rn hn ch gia Li4SiO4 v Zn2SiO4. Gia hai cu t ny c hnh thnh hp cht t l 1 : 1, ngha l ng vi thnh phn -Li2ZnSiO4. Hp cht ny c th ho tan thm cu t hp phn v c 2 pha. Dung dch rn ny c mng tinh th hnh thoi vi 3 thng s a, b, c. Khi to thnh dung dch rn th thng s c vn gi yn 5,1 cn gi tr a v b thay i theo cc lch khc nhau (hnh 84). l do s khc nhau v c ch to thnh dung dch rn. Gi s i v pha giu km, theo c ch thay i cation km theo hnh thnh l trng cation ng vi cng thc dung dch (Li2-2xZn1+x)SiO4 (0 < x 0,5). Trong khi v pha giu liti th theo c ch thay th cation km theo s to thnh ion xm nhp Li+ ng vi cng thc (Li2+2xZn1-x)SiO4 (0 < x 0,5). Cu trc -Li2ZnSiO4 kh phc tp, trong b khung anion O2 c gi ghm chc c trung gian gia lc phng v t phng. Cc cation trong hp cht ny phn b vo cc hc t din theo cc kiu khc nhau. b) o t trng i lc c th da vo vic xc nh t trng v xc nh th tch t bo mng kt lun s hnh thnh dung dch rn. V tng th c th tin chc rng s hnh thnh dung dch rn xm nhp s lm tng t trng, cn s hnh thnh dung dch rn c l trng ion th lm gim t trng. V d dung dch rn trn c s ZrO2 c cha 10 n 25% CaO. C th gi thit theo hai c ch:
Tng s O2 khng i do Ca2+ thay th Zr4+ phi km theo s xm nhp Ca2+ vo khong gia cc nt v cng thc dung dch l (Zr1-xCa2x)O2. Tng s cation khng i nh vy th Ca2+ thay th vo Zr4+ s to thnh l trng O2 v cng thc dung dch l (Zr1-xCax)O2-x.

Thng s mng 6,6

6,4 a

10,8 10,6 10,4 Li4SiO4 20 40 60 % mol

80Zn2SiO4

Hnh 84 o S ph thuc thng s mng dung dch rn Li2ZnSiO4 vo thnh phn 700 C

Theo c ch th nht th mt ion Zr4+ c thay th bng hai ion Ca2+ (vi gi thit thay i x t 0 n 1) s lm gim phn t lng i 11. Theo c ch th hai th mt ion Zr4+ v mt ion O2 thay th bng mt ion Ca2+ s lm gim phn t lng i 67 (khi thay i x t 0 n 1). Nu th tch t bo khng thay i theo thnh phn (iu ny khng thc s nghim ngt) th c ch th hai, khi x tng t trng gim mnh hn c ch th nht. S liu thc nghim thu c chng t c ch th hai ng (t nht cng nhit 1600oC). V l thuyt c th cn c c ch khc na phc tp hn, v d nu khi tng s cation Zr4+ khng i th c th gi thit s xm nhp ng thi Ca2+, O2. Tuy nhin thng l c ch n gin.

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Kt qu xc nh t trng ca cc dung dch rn trong h CaF2-YF3 trnh by trn hnh 86 cho thy c ch c s xm nhp F l ng hn c ch l trng cation. D nhin, khi o t trng khng bit g chi tit v cu trc khuyt tt (l trng hoc nguyn t xm nhp) m ch chng minh gin tip cho c ch no ng hn. nghin cu cc khuyt tt cn phi s dng phng php thc nghim khc, c bit l phng php khuch tn ntron. Nhng kt qu nghin cu tht chi tit cng nhiu h th cng tin chc rng cc khuyt tt im (l trng hoc nguyn t xm nhp) l khng tn ti m thay vo l s ni rng cu trc tinh th quanh khu vc khuyt tt im to thnh claster. c) Phng php DTA C th ni mi bin ho ho hc v vt l xy ra trong pha rn u km theo hiu ng nhit (H). Phng php DTA l phng php tt nht xc nh hiu ng nhit . Do phng php DTA c mt phm vi s dng rt rng ri trong nghin cu ho hc nh nghin cu phn ng gia cc pha rn, xc nh thnh phn pha, xy dng gin trng thi Trong lnh vc nghin cu s hnh thnh dung dch rn phng php DTA nhiu lc cho nhng thng tin quan trng. Nhit nng chy cng nh nhit bin ho th hnh ca cht rn l mt gi tr hng nh, c th dng nh gi mc nguyn cht ca cht nghin cu. Nhng c s ho tan cht l vo hnh thnh dung dch rn th nhit nng chy cng nh nhit bin ho th hnh gim xung r rt. V d st nguyn cht th nhit bin ho dng l 910oC, nhng ch ho tan 0,02% cacbon (to thnh dung dch rn xm nhp) h nhit chuyn pha xung 723oC (gim i 187oC). Barititanat (BaTiO3) nguyn cht c nhit curi 120oC nhng thay th Ba2+ hoc Ti4+ bng cc ion khc s lm thay i nhit curi. Phng php DTA cho php xc nh nhit curi . Bin ho th hnh -SiO2 -SiO2 xy ra 573oC. y l qu trnh xy ra vi tc rt ln. Tu theo nhit thnh to v mi trng thnh to m c s ho tan cc ion l vo mng tinh th SiO2 t nhin hnh thnh dung dch rn. Tu vo bn cht cht tan v lng cht tan lm cho bin ho th hnh xy ra vi tc chm hn (dng ng DTA v tr hiu ng chuyn pha tr nn t hn) nhit thp hn.

Cu hi v bi tp
1. Nu ln im khc nhau gia khuyt tt Stki v Frenken. Chng minh rng s hnh thnh khuyt tt l thun li v mt nhit ng hc, nhit tng th nng khuyt tt ng vi cn bng nhit ng tng. Trnh by khi nim v claster, m t bng hnh v. Cc kiu c ch c th c khi hnh thnh dung dch rn bng cch thay th cation khng ng ho tr. Tnh d (g/cm3) ca dung dch rn khi cho YF3 khi ho tan vo CaF2 ph thuc vo thnh phn ca cht tan theo kiu c ch l trng cation, theo kiu c ch anion F xm nhp, gi s hng s mng khng thay i. Vit cng thc cu to ca BaTiO3:

2. 3. 4.

5.

7% Ba2+ b thay th bng Pb2+ v 5% Ti4+ b th bng Zr4+ 3% Ba2+ b thay th bng Pb2+ v 2% Ti4+ b th bng Zr4+

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6.

Tinh th FeO c cu trc kiu NaCl vi gi tr a = 4,299, xc nh d (g/cm3) theo l thuyt. Trong thc t mu FeO tng hp c c d = 5,57 g/cm3. Gii thch s sai lch . Vit cng thc ng ca oxit . Vit cng thc ca oxit st II c 2% v tr nt mng ca Fe2+ l l trng. a ra nhng cng thc cu to c th c i vi dung dch rn thay th sau y: KCl c ln mt lng nh MnCl2, CaF2 c tp cht l YF3. Titan monooxit c cu trc kiu NaCl, kt qu kho st gin nhiu x tia X cho bit hng s mng a = 4,18,kt qu xc nh t trng c d = 4,92 g/cm3. T kt qu cho bit mu ca chng ta c khuyt tt g? Trong mng li tinh th c l trng hoc nguyn t xm nhp.

7. 8. 9.

10. Tinh th vanai monooxit c d tnh theo l thuyt l 6,49 g/cm3, thc nghim o c 5,92 g/cm3. Gii thch s sai khc . 11. Oxit zircon ZrO2 c cu trc kiu florit. Hy m t t bo mng ca n. Tnh t trng ca n theo l thuyt cho bit hng s mng a = 5,06. n nh mng li tinh th oxit zircon ngi ta thm vo 12% mol CaO cho to thnh dung dch rn theo c ch l trng anion. Vit cng thc phn t ca dung dch rn thu c. Tnh t trng ca dung dch rn (g/cm3). 12. Trong bng 11 c a ra thng s mng li ca mt lot oxit c cu trc kiu NaCl. Trc ht nhn gi tr bn knh rO2 = 1,26 ri sau ly gi tr bn knh rO2 = 1,4 hy tnh: a) b) Hai gi tr bn knh cation rM2+, Hai gi tr t l bn knh rM2+/ rO2.

Hy kim tra trong v d ny c cho php s dng quy lut t l bn knh d on phi tr bt din ca cation M2+ trong cc oxit c khng? Cng vi bi tnh hy xt hai oxit c cu trc vuazit.

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Chng 3 GII THCH GIN PHA

3.1 M u
Gin pha l cc thng tin cho bit s ph thuc gia nhit , p sut, tnh cht ca h cn bng nhit ng theo thnh phn c trnh by di dng gin . Gin pha cho bit khu vc nhit , p sut, thnh phn m mt pha no , hoc mt hn hp nhiu pha tn ti trng thi cn bng nhit ng. Da vo gin cho bit phng hng tng hp mt cht rn, gii thch mi bin ho xy ra trong qu trnh tng hp mt vt liu c th. C th ni gin pha vi k thut tng hp vt rn nh ci la bn i vi ngi i bin. Chng ny ch trnh by gii thch gin pha v ng dng thc t ca n, ch khng cp n cc l thuyt nhit ng v gin pha, cng nh cc phng php thc nghim xy dng gin pha. C s l thuyt ca gin pha l quy tc pha. H c K cu t c lp v F pha trng thi cn bng nhit ng, nu ta ch quan tm n hai yu t vt l l nhit v p sut, th s bc t do V ca h c xc nh theo h thc V = K + 2 F. Trc ht, chng ta lm quen vi cc khi nim: cu t c lp, pha v trng thi cn bng nhit ng, s bc t do. S cu t c lp: l s nh nht hp phn ca h cn thit biu din thnh phn tt c cc pha trong h . Xt vi v d c th.

H ch c MgO l h c mt cu t c lp (K = 1) v gi l h bc 1 v rng ngay n nhit nng chy th trong h cng ch c mt cht l MgO. H gm c MgO v Al2O3 l h c hai cu t c lp v gi l h bc 2 mc d nhit v thnh phn xc nh, trong h cn sinh ra mt pha rn mi gi l spinen MgAl2O4, nhng ta cng ch cn bit thnh phn ca hai cu t l c th biu din thnh phn ca mi pha trong h. H CaO v SiO2 c th to thnh nhiu pha rn khc nhau nh: 3CaO.SiO2 (k hiu l C3S), 2CaO.SiO2 (C2S), 3CaO.2SiO2 (C3S2), CaO.SiO2 (CS ), nhng vn gi l h bc 2 v l mt mt ct ca gin trng thi h bc ba Ca-Si-O (hnh 87). Thnh phn FeO l mt phn ca h bc 2 st v oxi v rng vurtit ch l mt pha khng hp thc Fe1-xO do thiu st, ng thi xut hin Fe3+ (xem chng trc). Thnh phn hp thc FeO thc t l hn hp cn bng gia 2 pha Fe1-xO v st kim loi.

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Si

SiO

SiO2 C3S2 CS C 3S C2S Ca CaO O

Hnh 87 Mt ct CaO-SiO2 trong h bc ba Ca-Si-O

S bc t do V l thng s trng thi c lp gm nhit , p sut, thnh phn cc cu t c trng cho trng thi cn bng ca h. Xt vi v d:

Nc trng thi si (ngha l cn bng nc lng v hi nc) c thnh phn khng i ng vi cng thc H2O. xc nh y trng thi cn bng ny ch cn bit mt gi tr thng s trng thi l nhit hoc p sut. Theo quy tc, y ta c K = 1, F = 2 do V = 1. H c mt s bc t do cn gi l h nht bin. Nu ta chn t do nhit th p sut hon ton c xc nh. V d chn nhit l 100oC th p sut phi l 760mmHg. nhng vng cao nh Mexico-city c p sut kh quyn ch 560mmHg th nc si 92oC.

H gm cc oxit kim loi ngay nhit cao, gi tr p sut hi trn pha rn cng nh pha lng u v cng nh so vi p sut kh quyn, bi vy ta c th b qua nh hng ca p sut n cc h cn bng gia pha lng v pha rn (gi l h ngng kt). i vi cc h ngng kt c th p dng quy tc pha V = K + 1 F.
Pha: l tp hp tt c cc phn ng th ca h, ng nht v thnh phn ho hc v mi tnh cht vt l, nhng phn ng th ny ngn cch vi phn ng th khc bng b mt phn chia qua c s bin i nhy vt cc tnh cht ho l. Cn phi ni thm rng, phn ca h ni y c kch thc ln c th p dng vo cc khi nim nhit , p sut. Nh vy th dung dch keo, dung dch cht tan c kch thc cao phn t vn gi l mt pha. Xt vi v d, mt cc nc c nc v trn b mt c hi nc l h c 3 pha: Pha rn l nc , pha lng l nc, pha hi l hi nc. Dung dch bo ho KCl v K2SO4 v di y c mui KCl v K2SO4, trn mt dung dch c hi nc bo ho l h cn bng c 4 pha: pha hi l hi nc, pha lng l dung dch bo ho hai mui v hai pha rn KCl, K2SO4. un nng mt mu st nguyn cht ln 910oC s xy ra qu trnh bin ho th hnh Fe (thuc h lp phng tm khi) thnh Fe (thuc h lp phng tm mt). Khi gi nhit th h c hai pha cng nm cn bng vi nhau. trn hoc di 910oC th h ch c mt pha. Khi gi yn nhit mt thi gian ri lm lnh nhanh xung nhit phng cho Fe khng kp tr v Fe th h vn c mt 2 pha nhng khng phi trng thi cn bng. V rng Fe vn ang chuyn ho thnh Fe tuy vi mt tc v cng b. Trng thi cn bng nhit ng l trng thi m h khng thc hin mt cng no vi mi trng hoc ngc li mi trng ngoi cng hon ton khng tc dng mt cng no

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i vi h. Trong thc t tht kh lng bit c h trng thi cn bng hay cha. tr li cho cu hi ny tu tng tnh hung ring bit c th tin hnh nh sau: 1) Gi yn mi thng s trng thi (T, P, thnh phn) bng phng php thc nghim no theo di s pha ca h c thay i theo thi gian khng? Nu s pha cn thay i th h cha t trng thi cn bng. Nu s pha vn gi nguyn khng i theo thi gian th h t trng thi cn bng. y cn lu n phng din ng hc ca qu trnh l iu quy tc pha khng nhc n. V d, trn gin bc hai CaO-SiO2 cho thy tu theo t l vi v ct, chng c th tng tc vi nhau cho nhiu hp cht C3S, C2S, C3S2, nhng khi ta trn vi v ct tht lu di th chng cng khng tng tc vi nhau. i vi nhng h s tng tc c th xy ra vi tc quan st th tt nht l bng thc nghim xc nh trng thi cn bng khi i t hai hng: un nng dn n nhit kho st, mt khc t nhit tng i cao lm ngui lnh dn n nhit kho st ri cng xc nh s pha trong hai mu thc nghim. V d cu hi t ra trong h CaO-SiO2 1100oC c mt pha C3S trong trng thi cn bng hay khng? Hay cu hi t ra mt cch khc l: Ti sao khi trn CaO v SiO2 theo t l 3 : 1 ri a nhit ln 1300oC thu c sn phm C3S, nhng cng t hp a ln 1100oC th khng thu c C3S? Phi chng 1100oC phn ng c th xy ra nhng vi tc qu chm? gii quyt vn ny ta phi tin hnh thc nghim theo 2 hng: un nng ln 1300oC, gi mt thi gian cho phn ng kt thc, thu c mt pha rn C3S sau lm lnh C3S t 1300oC n 1100oC v xc nh thnh phn pha thu c CaO v C2S. Hng th hai l un nng hn hp CaO v SiO2 c t l 3 : 1, nh vy t nhit phng n 1100oC gi lu mt thi gian, xc nh thnh phn pha cng thu c hai pha l CaO v C2S. Hp cht C3S khi ngui lnh t t n 1250oC b phn hu thnh CaO v C2S cn khi un nng CaO v SiO2 n 1100oC ch c pha mi l C2S (xem hnh 102, trang 138) Mt phng php khc kim tra trng thi cn bng bn ca mt pha l s dng cc cht phn ng ban u khc nhau xt tnh ng nht thu c. V d Na2Si2O5 c phi l mt pha bn nhit ng khng. un nng hn hp Na2CO3 v SiO2 ly theo t l mol 1 : 2 n khong 700 750oC v gi trong vi ngy nhit . Trn ln dung dch nc ca mui natri vi hp cht oxit silic tan trong nc (v d este etylic ca axit octosilisic) sau sy kh dung dch cho n to thnh gel, ri cui cng nung gel khong 700oC. Phng php th ba l lm ngui nhanh mt hn hp nng chy cc cht ban u (to thu tinh) ri nung nng vi gi 700oC gy nn s kt tinh thu tinh.

2)

3)

Ta tin hnh tng hp pha bng nhiu phng php khc nhau:

V rng c ba phng php u thu c silicat natri Na2Si2O5 do ta c th kt lun y l mt pha bn v nhit ng. S dng cc phng php tng hp khc nhau c ngha rt ln trong vic kim tra tnh cn bng ca kt qu thu c. S tng tc ca cc pha tinh th hoc s kt tinh cc pha thu tinh thng xy ra theo vi giai on v s i gn n trng thi cn bng giai on cui cng c th rt chm. Bi vy, chng minh tnh cn bng ca sn phm cui cng cn s dng nhiu cch tng hp.

97

G Trng thi khng bn

Trng thi gi bn Trng thi bn

Hnh 88. Biu din bng th v tr tng i ca trng thi gi bn, trng thi khng bn v trng thi bn
trng thi cn bng ca h c nng lng t do thp nht (hnh 88). Vn cn xt h t cn bng hay cha, cn phi lu n l ngoi cc tiu ca nng lng t do cn v tr cc tiu khc ca nng lng t do nhng khng thp bng so vi trng thi cn bng. cao ca hng ro th nng khi chuyn t trng thi gi bn sang trng thi bn c nhng lc ln n ni khng th thc hin c s chuyn . Trng thi gi bn ca kim cng nhit phng so vi than ch c th v nguyn nhn nh vy. Hng ro nng lng (hoc gi l nng lng hot ho) ca qu trnh bin ho kim cng thnh than ch ln n ni nhit phng kim cng c to thnh t cc iu kin khc nhau vn bn vng mc du l trng thi gi bn v nhit ng. ngha nhit ng ca trng thi gi bn hnh 88 c th hiu nh sau: qu cu nm trn nh g c th ri xung bn ny hoc bn kia khi c mt s dch chuyn nh. L d nhin vic chuyn t trng thi khng bn sang trng thi bn hoc gi bn u khng cn nng lng hot ho. V d v trng thi khng bn rt him (v n l khng bn) nhng cng c khi gp. Nh sau ny s thy khu vc ca hai cht lng khng trn ln to thnh mt hnh thi vm (gi l spinoal). Trong mi vm spinoal cht lng ng th l khng bn v t phn hu thnh hai cht lng khc (qu trnh ny c gi l qu trnh phn hu spinoal).

3.2 H mt cu t (h bc 1)
K = 1 do V = 3 F H c mt pha l h nh bin, c trng trng thi cn bng ca h ta cn bit hai thng s l nhit T v p sut P, ngha l h c biu din bng mt vng c T, P thay i c lp vi nhau. H c hai pha l h nht bin, c trng trng thi cn bng gia hai pha ch cn bit mt thng s (hoc T hoc P), thng s kia hon ton ph thuc vo thng s chn. Nh vy trng thi cn bng gia hai pha ca h bc mt c biu din trn mt ng xc nh. Phng trnh Claperon-Clauziut biu din ng cn bng nht bin .
dp Q =T V dt

(32)

Q l nhit chuyn pha, V l bin thin th tch khi chuyn pha. H cn bng gia ba pha c s bc t do bng 0, ngha l trng thi cn bng gia ba pha ca h bc mt hon ton

98

c xc nh bng mt im. V d trng thi cn bng gia nc lng, nc v hi nc c biu din bng im A trn hnh 89 ng vi p sut hi nc 4,6 mmHg v 0,0098oC. Tt c cc im trn ng AC u c trng cho trng thi cn bng gia hai pha nc lng v hi nc. Cn bng gia nc v nc lng c biu din bng cc im trn ng AD. Cc im trn ng AB biu din trng thi cn bng gia nc v hi nc. Hnh 90 l gin trng thi ca lu hunh. Lu hunh tn ti di hai dng th hnh l S t phng bn nhit thp, S n t bn nhit cao hn. Trn gin c gii thiu cc min ng vi cn bng nh bin, ng ng vi cn bng nht bin, im ng vi trng thi cn bng v bin. V d im A c trng cho cn bng gia 3 pha l S t phng S n t v hi lu hunh. P D C P E
1510o

Nc lng Nc
A B
Hnh 89 Gin trng thi ca nc

S t phng

Hi nc
T B

S n t C H 125o A Hi
T

Hnh 90 Gin trng thi ca lu hunh

Trn gin cn trnh by cc min c trng cho trng thi gi bn, v d lu hunh lng c th tn ti trng thi gi bn trong khu vc CHE. Lu hunh t phng c th tn ti trng thi gi bn trong min AHE. Hnh 91 v 92 l gin trng thi ca C v ca SiO2. Trong SiO2 l thnh phn ch yu ca nhiu loi vt liu xy dng cng nh cc vt liu k thut khc, hn na n l oxit ph bin th hai trong v Qu t (ch thua H2O), nn ta xt k hn gin ny. Silic oxit c nhiu dng th hnh (xem chng trn) di p sut kh quyn c s bin ha lin tc:
573 C 870 C Thch anh Tridimit Thch anh
o o

bar Tng p sut ln s xy ra cc bin ho nh sau (hnh 92): + Min triimit hp li dn v khong 900 atm th mt hn + Min cristobalit bin mt trn 1600 atm + T trn 1600 atm pha bn duy nht ch cn thch anh

1710 C 1470 C Cristobalit Lng

o o

99

Bar
500 400 300 200 100 500 1500

Thch anh Thch anh

SiO2 lng

Kim cng

Lng

1000

Than ch
1000 2000 3000 4000

oC

Tridimit
500 1000

1500

Hnh 91 Gin trng thi ca C

Hnh 92 Gin trng thi ca SiO2

Cristobalit

oC

Khi tng p sut ln lm bin mt triimit v cristobalit, iu ny ph hp vi gi tr t trng ca thch anh cao hn t trng ca cc pha triimit cng nh ca cristobalit (bng 30).
Bng 30 T trng ca cc dng th hnh SiO2 Dng th hnh T trng (g/cm3) Triimit Cristobalit Thch anh 2,298 2,334 2,467 Dng th hnh Coezit Stisovit T trng (g/cm3) 2,90 4,28

Tng p sut s to thnh cc dng th hnh c th tch ring b hn, theo nguyn tc , p sut rt cao, trn 20.000 40.000 atm (tu thuc vo nhit ) thch anh c th bin thnh dng th hnh khc nhau nh ceozit v trn 90.000 120.000 atm cn c mt dng th hnh bn na l stisovit.

3.3 bc hai (K = 2)
Trong trng hp tng qut V = 2 + 2 F = 4 F. Nh vy, trng hp n gin nht l F = 1 c s bc t do bng 3. biu din trng thi y ca cc h nh vy phi s dng gin khng gian: mt trc biu din p sut, mt trc biu din nhit , mt trc biu din thnh phn. i tng ca ho vt liu ch yu ch quan tm n cn bng pha trng thi rn, do ta c th b qua nh hng ca yu t p sut, kho st h cn bng di p sut kh quyn. Di y ta ch trnh by gin trng thi h bc hai trn mt phng, trong mt trc biu din nhit cn mt trc biu din thnh phn ca h.

3.3.1 Trng hp to thnh tecti n gin

trng thi lng cc cu t ho tan hon ton vo nhau, trng thi rn cc cu t hon ton khng ho tan vo nhau, ngha l ch kt tinh ra cc cht nguyn cht khng to thnh dung dch rn, ta c gin tecti n gin (hnh 93). Min lng l khu vc nm trong vng pha trn ng KEH.

100

Min KEM c trng cho trng thi cn bng gia hai pha l pha RA v pha lng l dung dch bo ho tinh th RA. Min HEN c trng cho trng thi cn bng gia hai pha l rn B v dung dch lng bo ho B. V d h c im biu din l C gm hai pha nm cn bng vi nhau l pha rn c im biu din R, pha lng c im biu din L, t l khi lng ca hai pha c xc nh theo quy tc n by.
K Lo L1 L M E A C F K H R P R' N B M E A L N

H
H

M D E

N I B

(a)

(b)

B A

(c)

Hnh 93 H bc hai trng hp to thnh tecti n gin (a), cu t A c hai dng th hnh, nhit chuyn ho gia chng ng vi im P (b), cu t B c hai dng th hnh, nhit ca chng ng vi im R v im I (c).

h C ta c:
L ng pha lng CR = L ng pha rn CL

Min nm di ng MN biu din h ch c hai pha rn l RA v RB. Tt c cc im nm ngay trn ng KE biu din trng thi ca h ch gm mt pha lng bo ho RA hay cn gi l ng kt tinh rn RA. Cng nh vy ng kt tinh RB l HE. im E gi l im tecti biu din dung dch lng bo ho ng thi RA v RB. Chng ta xt qu trnh ngui lnh dung dch lng c im biu din L0 (hnh 93a). Khi ngui lnh im biu din ca h t ti L1 th bt u bo ho rn B. T tr i vic lm ngui lnh tip tc h s c hai pha cng nm cn bng vi nhau l tinh th rn B v dung dch bo ho rn B. Gi s lm ngui lnh h cho n im C (C l im biu din thnh phn ca h ton b c rn ln lng) th im biu din thnh phn pha lng t ti L, cn im biu din thnh phn pha rn R. Khi ngui lnh im biu din ton b ti F, th im biu din pha lng ti E, im biu din pha rn ti N. Pha lng E bo ho ng thi RA v RB, nn t tr i h c 3 pha l rn A, rn B v lng E. Theo quy tc pha i vi h ngng kt (khng ch ti nh hng ca p sut P) lc ny h v bin (h bc 2 nn K = 2, c mt 3 pha: F = 3 do V = 0). Ngha l RA+ RB nhit ca h khng thay trong qu trnh kt tinh ng thi hai pha rn: lng E i na mc du ta vn tip tc lm lnh. Trn hnh 93 pha nhit thp nht (st cnh AB) c trnh by hnh thi pha rn thu c khi lm lnh cc h lng khc nhau. Nu pha lng c thnh phn ng vi thnh phn tecti th lc t nhit ng vi im E s bt u kt tinh ng thi c hai pha rn, do cc tinh th RA v RB thu c u c ht rt mn. Pha rn thu c sau khi mi nhn bng v xem trn knh hin vi thy mt tp hp cc ht rt nh kch thc kh u nhau, trong khi nu lm lnh hn hp lng giu A hoc giu B hn so vi thnh phn tecti s thu c hn hp rn c cha cc tinh th A hoc tinh th B kh ln nm trong mt tp hp cc ht mn ca pha rn tecti. Trn hnh 93b ng vi trng hp cu t A trng thi rn c hai dng th hnh, nhit chuyn ho gia chng ng vi im P, cn hnh 93c th pha rn B c hai dng th hnh, mt dng c nhit chuyn ho ng vi im R (cao hn nhit tecti), mt dng khc c nhit chuyn ho thp hn nhit tecti (ng vi im I).

101

321o 271o

lng

144o

Cd

20

40

60

80

Bi

Hnh 94 Gin trng thi h bc 2 Cd-Bi

% khi lng

3.3.2 Trng hp c to thnh hp cht mi

Gin c dng nh trn hnh 95 v 96. Thnh phn hp cht mi trn hai gin ny u biu din im S. Hai gin ny khc nhau ch: trn gin 95 hp cht S c cc i r rt l M, l im cc i trn ng cong kt tinh hp cht S (ng E1ME2), cn gin 96 ng kt tinh hp cht S ch c mt on E1P khng c im cc i. Qu trnh tng hp cht S hai trng hp ny khc nhau. Hp cht S trn hnh 95 gi l hp cht nng chy tng hp, cn hp cht S trn hnh 96 gi l hp cht nng chy khng tng hp. Khi ly cc cht A v B theo ng t l trong hp cht S nu nng chy (ng vi im Lo) ri kt tinh hp cht S. trng hp hnh 95 khi nhit t ti im M th bt u kt tinh hp cht S, qu trnh kt tinh din ra cho ti khi tt c cc pha lng ht. Sn phm thu c l hp cht S nguyn cht vi tinh th hon chnh. Cn trng hp hnh 96 khi lm lnh h n im L (trn ng kt tinh B) s xy ra qu trnh kt tinh B. Qu trnh kt tinh B tip tc th im biu din h ton b chy t L n G, im biu din pha lng cn li (bo ho B) chy t L n P, im biu din pha rn chy t R1 n R (cc im ny u biu din B nguyn cht nhng nhit khc nhau). Khi im biu din pha lng n P (nm trn ng kt tinh S l E1P) s bt u kt tinh hp cht S. Lc ny trong h xy ra phn ng: dung dch lng P + rn B = hp cht S. Nu thnh phn ban u ly A v B theo ng t l ca chng trong hp cht S th phn ng ny kt thc khi ng thi ht rn B v dung dch lng P. Nu thnh phn ban u ly tha B th phn ng kt thc khi tiu th ht dung dch lng P v cui cng thu c hai pha rn l S v B. Nu thnh phn ban u ly tha A th phn ng kt thc khi tiu th ht cht rn B v qu trnh ngui lnh s tip tc kt tinh cht rn S thnh phn pha lng chy t P n E1, thnh phn pha rn chy t G n H. T dung dch E1, s kt tinh ng thi rn S v rn A. Cui cng thu c hn hp hai pha rn A v S.

102

Lo TA M E2 E1

TB TA

Lo L P E1 G H

TB

R1 R

Hnh 95 H bc hai to thnh hp cht nng chy tng hp

Hnh 96 H bc hai to hp cht nng chy khng tng hp

Trong thc t, qu trnh ho tan rn B vo lng P kt tinh hp cht S khng xy ra ng nh l thuyt chng ta va trnh by. V rng rt c th nhng tinh th rn B cha tan ht th b bao ph bi cc tinh th hp cht S nn khng tip xc vi dung dch lng P c. Do , qu trnh xy ra gn ng vi l thuyt trnh by trn gin chng ta phi m bo mt iu kin k thut sao cho tc ho tan rn B ph hp vi tc kt tinh hp cht S v m bo tinh th rn B thng xuyn tip xc vi dung dch P. Di y trnh by mt s gin trng thi h bc hai c to thnh hp cht ho hc lin quan n cc loi vt liu v c.

Hnh 97 H SiO2-Cr2O3

Hnh 98 H Na2O-SiO3

V d ta xt gin trng thi ca h CaO-SiO2 hnh 102. Hai oxit ny c th phn ng vi nhau to thnh 4 hp cht. Hp cht CaO.SiO2 (vit tt l CS) nng chy tng hp gn 1600oC, hp cht C3S2 nng chy khng tng hp 1464oC phn hu thnh C2S v pha lng. Hp cht C2S nng chy tng hp khong 2100oC. Hp cht C2S tn ti di hai dng th hnh: trn 1450oC gi l -C2S, di 1450oC chuyn thnh dng -C2S. Hp cht C3S nng chy khng tng hp 2150oC thnh CaO v pha lng. Hp cht C3S khi lm ngui lnh n 1250oC th phn hu thnh CaO v C2S.

103

2500 2300 2100 1900 1700 1500

2300 2100 1900 1700

2 pha lng

1500

Sc2SiO5
20

Sc2Si2O7
80

C3A
1300

CA2
40

Sc2O3

40 1:1 60 1:2

SiO2

CaO

20

Hnh 99 H Sc2O3-SiO2

% mol

C12A7

60 CA 80 CA6

Al2O3

Hnh 100 H CaO-Al2O3

t oC
2400

1890

1800 1600 1400 1200

2 lng
1557 1543

2200

2150
2050

1850

2000 1800 1600 1400 1200

C3S

C2S
1464

2 Lng
1680 1544 1470 1436 1175

C3S +'C2S 1450

1250

CS
+

1460

SiO2

20

40

MS 60 M2S 80

MgO

1000

C2S3 CS
+

'C2S
20

C2S3 CS 30 2 C3S 2 CS
60 70

870 80 90

% mol

CaO

10

SiO2

C 3S

Hnh 101 H SiO2-MgO

Hnh 102 H CaO-SiO2

Trn cc hnh 103 c vng phn lp gia hai pha lng gi l vng cupl phn lp hoc mi vm spinal. Trong vng mi vm spinal, cht lng ng th l trng thi khng bn v nhit ng s t phn hu thnh hai pha lng. Trng hp ny kh ph bin trong cc h silicat v borat. Kho st kiu gin ny c ngha ln i vi k thut silicat v k thut gm cng nh nghin cu cc qu trnh a cht.

104

TB T A T A M

TB N T A

TB

E A

(a)

(b)

(c)

Hnh 103 H bc hai trng hp c s phn lp gia hai pha lng

S phn lp thnh hai pha lng c th xy ra trong mt khong nhit xc nh. Trn hnh 103a cupl phn lp nm ngay trong vng lng, cn hnh 103b th cupl phn lp xy ra nhit thp hn nm trn ng kt tinh rn B, chia ng kt tinh B thnh hai phn v vng phn lp to thnh vm spinal. im M v N u ng vi trng thi cn bng v bin v lc h c 3 pha: 2 pha lng v 1 pha rn. Khi lm ngui lnh vi tc nhanh v cu trc tinh th ca B phc tp kh kt tinh, th vng phn lp ca pha lng c th i vo khu vc gi bn pha di ng MN ca hnh 103b. Hnh 103c ng vi trng hp vng phn lp hai pha lng nm trong khu vc gi bn pha di nhit tecti.

3.3.3 H bc hai trng hp c to thnh dung dch rn

a) H to thnh dung dch rn khng hn ch: c 3 kiu gin nh trn hnh 104.
Lo L M H P R N

TB

TB TA M

M TB TA

TA Q

x2

x (a)

x1 x1 B

x (b)

(c)

Hnh 104 H bc hai trng hp to thnh dung dch rn khng hn ch

Kiu th nht (a) ng vi trng hp khi tng nng mt cu t s lm tng (hoc gim) nhit bt u kt tinh ca h mt cch u n. Kiu th hai (b) ng vi trng hp khi tng nng ca bt k mt cu t no cng lm gim nhit bt u kt tinh ca h v kiu th ba (c) l khi tng nng ca mt trong hai cu t u lm tng nhit bt u kt tinh ca h. Chng ta xt qu trnh xy ra khi lm ngui lnh hn hp L0 (hnh 104a), L0 nm trong khu vc lng hon ton. Khi lm ngui lnh im biu din trng thi ca h thay i t L0 n L. n L h bt u kt tinh. Tinh th pha rn u tin c im biu din l R giu B hn so vi dung dch lng ban u L0. Lc ny h c hai pha: dung dch lng v dung dch rn. Trong qu trnh ngui lnh tip tc im biu din ca h tng cng chy t L n P, im biu din pha lng chy t L n Q, im biu din pha rn chy t R n P. V d khi im

105

biu din ton b t ti H th im biu din pha lng t ti M v im biu din pha rn t ti N. Theo quy tc n by ta c: Ti H:

Khi l ng pha lng cn l i HN = Khi l ng pha r n kt tinh HM

Khi im biu din h ton b t ti P th lng cht lng ht. Hnh 105 trnh by mt s gin trng thi ca h bc hai to thnh dung dch rn khng hn ch.

2600 2400 2200 2000

2800 2400 2000 1600

NiO

(1)

MgO

FeO
1580

(2)

MgO

1500 1400 1300 1200 1100

1540 1500 1460 1420 1380

(CaAl2Si2O8)

anoctit

(3)

(NaAlSi3O8)

anbit

gelemit

(CaAl2Si2O8)

(4)

okemanit
(NaAlSi3O8)

Hnh 105 Gin trng thi ca h bc hai to thnh dy dung dch rn khng hn ch

Qu trnh xy ra khi lm ngui lnh khi nng chy L0 nh trnh by trn y phi thc hin tc lm lnh rt chm v u n lm sao bo m lun lun gi trng thi cn bng gia pha lng cn li v pha rn kt tinh. iu ngha l m bo s khuch tn ca cc tiu phn trong pha rn cng nh trong pha lng vi tc sao cho gi c trng thi cn bng. iu ny rt kh thc hin. Do qu trnh kt tinh i vi cc h c gin to thnh dung dch rn thng to ra sn phm khng cn bng, hoc l sn phm gi bn. V rng khng th to c tc ngui lnh tht ng u v tht chm cho php gi trng thi cn bng tng nhit mt. V d tinh th tch ra u tin khi lm ngui lnh khi nng chy L0 c thnh phn l X1, nu khng thi gian thit lp cn bng mi ca cc tinh th vi cht lng th thc t c th xem nh nhng tinh th mt khi h v nh vy tinh th tch ra tip theo s giu A hn so vi l thuyt. Kt qu pha rn tch ra khng ng nht: Phn trung tm l tinh th tch ra u tin c thnh phn X1, nhng theo mc cng xa tm th cng giu cu t A. S hnh thnh cu trc nh vy pht trin xung quanh tm ca mm thng xuyn xy ra khi kt tinh khi lng nng chy (hnh 106).

106

Nhn tinh th kt tinh u tin

a3 a4 a2 a1

Hnh 106 S khng ng nht v thnh phn khi kt tinh dung dch rn t khi nng chy

S kt tinh sai lch nh vy thng gp trong cc khong cht. V d trong plagiocla (mt dng ca phenpat) l dung dch rn gia anoctit v anbit (hnh 105-3). ni la c cha plagiocla c hnh thnh khi ngui lnh macma nng chy mt cch chm chp, tuy nhin trong khi plagiocla vn thy s khng ng nht v thnh phn, trung tm thng giu canxi cn pha ngoi th giu natri hn. b) H to thnh dung dch rn hn ch y l trng hp ph bin nht. V nguyn tc c th phn thnh hai kiu gin nh trn hnh 107.
a TA E H A (1) M N K B
S P

a
TB

b Lo
L D

c TB
R

N K B

Q E

TA A

V (2)

Hnh 107 H bc hai to thnh dung dch rn hn ch Kiu tecti (1), kiu peritecti (2)

Kiu tecti (1) c dng tng t nh gin h bc hai to thnh tecti n gin (hnh 93a) ch c iu khc l ng kt tinh TAE khng kt tinh A nguyn cht m kt tinh dung dch rn B ho tan vo A gi l dung dch rn , cng vy ng TBE kt tinh dung dch rn: A ho tan vo mng li tinh th ca B gi l dung dch rn . Cc ng HMTA, KNTB cho bit tnh tan thay i theo nhit . nhit tecti tan l ln nht. Phn hnh v nh pha trn hnh 107-2 cho thy kiu peritecti l s t hp ca gin to thnh dung dch rn khng hn ch (a) v gin c s phn lp trong khu vc dung dch rn (b). V d xt qu trnh ngui lnh pha lng Lo, khi im biu din ca h t ti L th bt u kt tinh dung dch rn c im biu din l R, lm ngui lnh tip tc im biu din h ton b chy t L v D, im biu din pha lng chy t L v P, im biu din pha rn chy t R v N. Khi im biu din h ton b t ti im D th im biu din pha lng t ti im P, im biu din pha rn N v: D:
Lng pha rn tch ra PD = Lng pha lng P cn li DN

107

Lc ny h c 3 pha: pha rn c im biu din l N v pha rn mi bt u kt tinh c im biu din l M, pha lng P. Do h v bin ngha l nhit cng nh thnh phn cc pha khng thay i na trong qu trnh lm lnh. Thc ra lc ny c phn ng: pha rn tan vo dung dch lng P kt tinh pha rn . R + Lng P
TB K E2
H E
K

R
a b c d

M TA H M E1 N

TA

TB
Q P

(1)

(2)

Hnh 108 Gin trng thi bc hai trng hp c to thnh hp cht nng chy tng hp (1), v hp cht nng chy khng tng hp (2) cc cu t hp phn cng nh hp cht mi c th to thnh dung dch rn hn ch

Tu theo v tr im biu din dung dch ban u nm v pha phi hay pha tri im M, qu trnh v bin s kt thc bng cch s bin mt pha lng P (nu thnh phn ban u nm pha phi im M) hoc tan ht pha rn (nu thnh phn ban u nm pha tri im M nh trng hp ang xt). trng hp ang xt khi tinh th cui cng tan ht, h ch cn pha lng P v pha rn . Lm lnh tip tc im biu din h ton b chy t D n Q, im biu din pha lng chy t P n S, im biu din pha rn chy t M n Q. Khi im biu din h ton b n Q th git cht lng cui cng S bin mt. H ch cn mt pha rn . Khi nhit h n im V th pha rn bt u phn hu thnh pha rn v h gm hai pha. Hnh 108 l gin trng thi h bc hai, trng hp c to thnh hp cht mi v hp cht mi c kh nng to thnh dung dch rn vi cu t hp phn. Dung dch rn ca hp cht mi vi cc cu t hp phn gi l dung dch rn . hnh dung gin to thnh dung dch rn ca hp cht nng chy khng tng hp (hnh108-2), pha trn hnh v c trnh by mt lot cc hnh nh t trng hp (a) cht S khng ho tan cc cu t hp phn v cc cu t cng kt tinh ra dng nguyn cht; n trng hp (b), hp cht S c to thnh dung dch ; trng hp (c) c to thnh dung dch v dung dch ; trng hp (d) c to thnh dung dch ; dung dch v dung dch . Trong phn trn, khi trnh by v dung dch rn ta gp cc gin trng thi hnh 78, 79, 81, 82, di y gii thiu thm mt s gin thuc kiu ny. Trn gin 79 v 111 cho thy tinh th spinen MgAl2O4 v FeAl2O4 ch ho tan thm Al2O3 ch khng ho tan MgO v FeO hay ni cch khc, cc cation Al3+ c th i vo hc trng ca phn mng anion O2 ca tinh th spinen, cn cc cation Ca2+, Fe2+ khng th i vo cc hc trng .

3.4 H bc ba (K = 3)
Trng hp tng qut

108

V=3+2F=5F Nh vy, trng hp n gin nht khi h ch c mt pha th s bc t do bng 4, ngha l biu din trng thi ca h cn 4 thng s v ta phi s dng khng gian nhiu chiu. Nh phn trn ta ni khi nghin cu trng thi ngng kt (ch c cn bng pha lng v pha rn) c th b qua s c mt ca pha hi. Vy quy tc pha i vi trng hp ny s l V = 3 + 1 F = 4 F. Lc h c mt pha s bc t do bng 3, ta dng mt trc biu din nhit , hai trc biu din hai thnh phn ca hai cu t, cn thnh phn ca cu t th 3 c th suy ra mt cch d dng t hai thnh phn ca 2 cu t kia.
o

2600

1400 1350

2400

1300 1250 1200

+ lng
olivin Ca-Fe

olivin Ca-Fe + lng

2200

2000

1150

CaO

20

40

60

CaZrO3

80

ZrO2

Ca2SiO4

20

40

60

80

Fe2SiO4

Hnh 109 H CaO-ZrO2

o

Hnh 110 H CaO.SiO2-2FeO.SiO2

o

C sp + lng

2100 1900 1700 1500 1300

1500 1450 1400

sp Al2O3 + sp
20 40

1350 1300 1250

olivin Ca-Fe

FeO

Spinen FeAl2O4

60

80

Al2O3

nefelin

20

40

60

80

anoctit

Hnh 111 H FeO - Al2O3

Hnh 112 H hflin anoctitNa2Al2Si2O8- Ca Al2Si2O8

3.4.1 H bc ba to thnh tecti n gin

Hnh 113 gii thiu gin trng thi h A-B-C hnh thnh tecti n gin. Khi dng cc mt phng ng nhit ct gin khng gian ri chiu trc giao ln tam gic thnh phn ta s thu c gin mt phng c ghi cc ng ng nhit nh hnh 114 l gin trng thi h Zn-Cd-Sn. Chng ta xt qu trnh ngui lnh hn hp nng chy thnh phn 30% Cd, 30% Sn v 40% Zn. Hnh chiu ca im biu din h ny trong khng gian ln tam gic y ng vi im L. Nh trn hnh v cho thy, khi lm lnh n gn 280oC th dung dch bt u bo ho Zn, lm lnh tip tc s tch ra cc tinh th Zn. im biu din ton b ca h lun lun nm

109

L, im biu din thnh phn pha lng cn li chy t L n K (K l giao im gia ng thng k t Zn qua L v ng E3-E l ng bo ho ng thi Zn-Cd), im biu din thnh phn pha rn nm Zn. Khi im biu din pha lng t ti K th bt u bo ho ng thi Zn v Cd nn Zn v Cd cng kt tinh. Lm lnh tip tc s kt tinh ng thi Zn v Cd, im biu din thnh phn pha lng chy t K v E, im biu din pha rn chy t Zn ti R (R l giao im ca cnh Zn-Cd v ng thng k t E qua L). Khi im biu din thnh phn pha lng ti E, im biu din thnh phn pha rn t ti R lc ny ta c:
L ng pha r n kt tinh LE = LR L ng pha lng E cn l i

Trong pha rn th:

L ng r n Zn Cd R = L ng r n Cd Zn_ R
_

Pha lng E bo ho ng thi Zn, Cd, Sn, do bt u kt tinh ng thi Zn, Cd, Sn v h c 4 pha (lng E, rn Zn, rn Cd, rn Sn) ngha l s bc t do bng khng. Lm lnh tip tc nhit ca h vn gi nguyn nhit tecti, thnh phn pha lng vn gi nguyn E cn thnh phn pha rn chy t R v L. Khi thnh phn pha rn n L th lng cht lng ht.
T A P T1

t'1

TB E'1

T C E'3 TE E' E'2

E1

t1
E3 E E2

C Hnh 113 Gin trng thi h bc ba trng hp to thnh tecti

110

Zn (419)
380 360 340 320

300

260 240 220

30% Cd 30% Sn

280

E3 K
180 200 220 240 260 300

E1

180

200

Sn (232)

E2

(321)Cd

Hnh 114 Gin trng thi h Zn-Cd-Sn c cc ng ngin

3.4.2 H bc ba trng hp c to thnh hp cht ho hc

Hnh 115 l hnh chiu trn tam gic thnh phn ca gin trng thi h bc ba, trong 2 cu t B v C c to thnh hp cht nng chy tng hp. C th xem tam gic ABC hnh 115a gm hai tam gic nh ABS v ASC ng vi h bc ba kiu tecti n gin nh xt trn hnh 114. iu cn xt y l v tr im yn nga K. y l im tecti ca h bc hai A-S. im K chim v tr thp nht trn ng AS nhng li chim v tr cao nht trn ng bin gii E1KE2. Cn hnh 115b phc tp hn, y hp cht S cng nng chy tng hp nhng qu trnh kt tinh ca mt s khi lng bc ba xy ra kh phc tp. Chng ta thy trn hnh 115b c ba min: kt tinh A (min Ae1PEe4), kt tinh B (min Be1Pe2), kt tinh S (min e2PEe3) gp nhau P. Ngha l dung dch bo ho ng thi A, B v S nhng nm ngoi tam gic ABS. Ni P vi B ct AS M ta c Lng P + Rn B = Rn A + Rn S. Vy P l im v bin khng tng hp, trong khi E1, E2 (trn hnh 115a) v E (trn hnh 115b) l im v bin tng hp, ngha l dung dch lng kt tinh ng thi 3 pha rn. Ta xt qu trnh xy ra khi lm ngui lnh hn hp lng c im biu din l L. V rng L nm trong min kt tinh A do trc ht kt tinh rn A, im biu din thnh phn pha lng cn li chy t L v K (K l giao im ca ng AL ko di ct ng e1P), im biu din pha rn nm A. Khi im biu din pha lng t ti K th bt u bo ho B, ngha l kt tinh ng thi c A v B, im biu din pha lng chy trn ng KP, im biu din pha rn chy t A n R (R l giao im ca on thng PL vi on thng AB). Khi im biu din thnh phn pha lng t ti P th im biu din thnh phn pha rn t ti R. V lng bo ho ng thi 3 pha rn A, B, S do bt u xy ra qu trnh v bin khng tng hp ho tan B kt tinh A v S. Trong khi xy ra qu trnh ny th im biu din thnh phn pha lng nm nguyn P, cn im biu din thnh phn pha rn chy t R n L. Khi im biu din thnh phn pha rn n L th pha lng kh ht.

111

A
R

e1
E1

e1
K E2

e4

L K M P E

e4

e2

(a)

e3

e2 S

(b)

e3

Hnh 115 Hnh chiu trc giao ln tam gic thnh phn ca gin trng thi h bc ba c to thnh hp cht bc hai nng chy tng hp (a)

Lng E1 Lng E2

rn A + rn B + rn S rn A + rn C + rn S

Hnh 116 l hnh chiu ln tam gic thnh phn ca gin khng gian h bc ba c to thnh hp cht bc hai S nng chy khng tng hp.
A
A

L1

e1
E

e4

S2

P
L2

e2

e3 S

S1

Hnh 116 H bc ba to thnh hp cht bc hai nng chy khng tng hp

Hnh 117 Phng php phn chia gin bc ba thnh nhng tam gic nh

Xt hnh 116: im E biu din thnh phn pha lng bo ho ng thi A, B v S. V rng E nm trong tam gic ABS nn y xy ra qu trnh v bin tng hp. Lng E1 rn A + rn B + rn S. Trong khi lng P bo ho ng thi rn A, rn C v rn S nhng nm ngoi tam gic ASC nn ti y xy ra qu trnh v bin khng tng hp. Lng P + rn C rn A + rn S. Vic xt qu trnh kt tinh khi lm ngui lnh khi nng chy c thnh phn nm trong tam gic ABC cng tng t nh trng hp ta xt trn hnh 115b. y ch cn lu mt im quan trng l tu theo v tr im biu din thnh phn pha lng ban u nm trong tam gic no (ABS hoc ASC) ta s bit c thnh phn pha rn thu c cui qu trnh s ch gm 3 pha rn ng vi tam gic , cng nh pha lng cui cng ca qu trnh l E hoc P. V d nu im biu din thnh phn pha lng ban u L1 nm trong tam gic ASC th pha lng cui cng ca qu trnh l P v khi kt thc qu trnh

112

kt tinh ch thu c hn hp 3 pha rn l A, C, S. Nu im biu din pha lng ban u l L2 nm trong tam gic ABS th pha lng cui cng ca qu trnh kt tinh s ng vi im E v khi kt thc qu trnh kt tinh s thu c hn hp 3 pha rn l A, B v S. i vi nhng h bc 3 to thnh nhiu hp cht th vic phn chia gin thnh cc tam gic nh (gi l php tam gic c), l mt vn rt quan trng v l thuyt cng nh thc t cng nghip. V d h chng ta c to thnh hai hp cht bc hai l S1 (hp cht gia B v C) v S2 (hp cht gia A v C) nh trn hnh 117. T cc im A, B, S1, C, S2 c th dng thnh 3 tam gic nh. Trong ta d dng thy c cch ni S1 vi S2 to thnh tam gic S1CS2. Cn phn hnh thang ABS1S2 th c th phn chia theo hai cch: ni B vi S2 hoc ni A vi S1. Mun bit cch phn chia no ng ta phi bit hai pha rn no cng tn ti bn vi nhau. iu ny phi gii quyt bng con ng thc nghim. V d chun b hn hp hai pha rn B v S2 un nng chy ri lm ngui lnh n nhit phng. Tin hnh ghi gin nhiu x tia X xc nh thnh phn pha. Nu trong thnh phn pha vn thu c cc pha rn ban u (B v S2) ngha l hai pha rn tn ti bn vi nhau th ta c th k c BS2 chia phn cn li thnh hai tam gic nh l ABS2 v BS2S1. Nu khi nung chy hn hp thu c hai pha rn mi l A v S1 th c ngha B v S2 khng tn ti bn vi nhau. Trong trng hp nh vy ta ni A v S1 phn thnh hai tam gic nh AS1B v AS2S1.
ZrO2 ZrTiO4
1590 1580 1610

56,08

TiO2

Al2O 3 Al2TiO5 Al O (% khi lng 2 3 )

Hnh 118 Gin trng thi h ZrO2-TiO2-Al2O3

Hnh 118 l gin trng thi h ZrO2-TiO2-Al2O3. Trong h ny c to thnh hai hp cht bc hai l titanat nhm nng chy tng hp v titanat zirconi nng chy khng tng hp. Trong gin ny c 3 h bc 3 l oxit zirconi, oxit nhm v titanat nhm (c im tecti 1610oC); oxit zirconi, titanat nhm v titanat zirconi (c im tecti 1590oC); oxit titan, titanat nhm v titanat zirconi (c im tecti 1580oC). Cc h bc ba gm 3 oxit thng c gin trng thi kh phc tp. V d h MgOAl2O3-SiO2 c gin trng thi trn hnh 119. Trong to thnh 4 hp cht bc hai l mulit (3Al2O3.2SiO2 vit tt l A3S2), spinen (MgO.Al2O3 vit tt l MA), octosilicat magie cn gi l fosterit, (2MgO.SiO2 vit tt l M2S), metasilicat magie cn gi l clinoenstatit (MgO.SiO2 vit tt l MS) v hai hp cht bc ba l corierit (2MgO.2Al2O3.5SiO2 vit tt l M2A2S5), saphirin (4MgO.5Al2O3.2SiO2 vit tt l M4A5S2). Tam gic thnh phn c chia ra thnh 9 tam gic nh ng vi 9 sn phm rn thu c khi lm ngui lnh cc hn hp lng c thnh phn ban u nm trong cc tam gic, l: hn hp rn M, MA, M2S; hn hp rn MA, M2S, M2A2S5; hn hp cc pha rn M2A2S5, MA, M4A5S2; hn hp cc pha rn MA, M4A5S2, A3S2; hn hp cc pha M2A2S5, S, MS; hn hp MS, M2A2S5, M2S.

113

Ta xt mt v d sau. Xc nh lng pha rn v hng pha lng cn li khi kt tinh pha lng c thnh phn MgO 38%, Al2O3 46%, SiO216% n nhit ng vi im tecti 4. T thnh phn pha lng ta tm c im biu din trn gin l L (hnh 119). L nm trong tam gic nguyn t MA-M2S-M2A2S5 nn khi kt thc qu trnh kt tinh ng vi pha lng cui cng nm giao im ca 3 min ngha l im 4. Trong qu trnh kt tinh, im biu din thnh phn pha lng chy theo L-b-c-d-4 dc trn ng bin gii ca hai min M2S v MA. Mun xc nh lng pha rn kt tinh (%) tng giai on chng ta k cc on thng bL, cL, dL, 4L v ko di ct ng M2SMA MA, c, d, 4. Khi im biu din thnh phn pha lng chy t L (1850o) n b (1670o) ch kt tinh rn MA. Khi im biu din thnh phn pha lng n b th lng MA kt tinh l: P = bL 100%
bMA

SiO2

MgO.SiO2 (MS)
2 MgO.SiO

1
1500o 4 5

(M2S)

M2A2S5
3 7

b
6

1600o 9 1700o 1800o

(A3S2) 3 Al2O3. 2 SiO2

1900o

M
MgO

4'd'

c'

M4A5S2 MA MgO.Al2O3

A
Al2O3

Hnh 119 Gin trng thi h MgO-Al2O3-SiO2 (min 5-9-3 kt tinh M4A5S2, min 1-2-9-5-4 kt tinh M2A2S5)

Khi im biu din pha lng n c (1600o) th pha rn l hn hp M2S v MA vi t l khi lng l:

M 2S MA _ c' = _ MA c' M 2S
v lng pha rn kt tinh l: P =
cL .100% cc'

Khi im biu din thnh phn pha lng t ti 4 lc pha lng bt u bo ho M2A2S5 v pha rn ang l hn hp M2S, MA. Lng pha rn tch ra l: P=
4L .100% 4 4'

3.4.3 H bc ba trng hp to thnh dung dch rn

114

S hnh thnh dung dch rn trong h bc ba lm cho gin trng thi tr nn rt phc tp. Sau y ch trnh by mt vi nt quan trng nht trong cn bng gia cc pha rn ca cc h n gin. Hnh 120a l gin trng thi h ABC trong B v C to thnh dy dung dch rn lin tc, do bt k thnh phn no ca h, s pha cng tn ti cng khng qu hai (rn A v dung dch rn BC). T A c th k v s tia n cnh BC, mi mt tia u ng vi cn bng gia hai pha. Hnh 120b biu din s to thnh dung dch rn gia hp cht bc hai AB2 v mt pha khng tn ti AC2, thnh phn ca dung dch rn c th biu din bng cng thc AB2-xCx. Dung dch rn ny c th cng tn ti vi A to thnh mt khu vc hai pha tng ng. y c th k hnh tam gic ba pha (A + C + dung dch rn thnh phn n). Vic tam gic c phn gin cn li, trong cng tn ti B, C v dung dch rn trn c s AB2 phi tu theo tng h c th. C hai kh nng c trnh by trn hnh 120b v 120c. Cc dung dch rn trn c s AB2 trong c khong thnh phn cng tn ti vi pha B (hnh 120c) vi pha C (khng biu din trn hnh v) hoc cng tn ti vi pha B trong mt khong thnh phn, cn vi pha C trong mt khong thnh phn khc (120b). S ng n ca php tam gic c ch c th da vo thc nghim.
A
A
A

a A + dung dch BC

b AB2

c
3

3 2 3

n
3

AB2

Hnh 120 H bc ba c to thnh cc dung dch rn bc hai

S to thnh dung dch rn lm cho vic xt qu trnh xy ra khi ngui lnh hn hp nng chy tr nn phc tp hn. Hnh 121 l hnh chiu trc giao ca gin khng gian h A-B-C kiu trn gin 120a. Cnh AB v AC ca h ny c dng tecti n gin, cn cnh BC ng vi h to thnh dy dung dch rn lin tc nh hnh 104a, ngha l cc ng cong lng v ng cong rn u khng c cc tr. H bc ba ny khng c cc im v bin m ch c ng nht bin XY phn chia thnh min kt tinh bc nht v min dung dch rn BC, nhit gim dn theo hng t X n Y. Mi mt thnh phn pha lng nm cn bng vi mt thnh phn xc nh ca dung dch rn. Cc ng ni pha rn A v dung dch lng cn bng vi A trn ng lng XY u xut pht t A, cn cc ng ni im biu din dung dch rn BC vi pha lng cn bng vi n li tn ra, thay i lch dn dn t cc im trn ng XY v cc im trn ng BC. V d dung dch lng c thnh phn y cng tn ti cn bng vi dung dch BC thnh phn x.

115

(b) lng

oC

(a)
A X

B y

dung dch rn BC

%C
Y

a
X

r s t

dung dch rn BC
B

m n p

Hnh 121 Cn bng khi kt tinh trong h A-B-C c to thnh dung dch rn BC (a) v gin h bc hai B-C (b)

Hnh 122 Con ng kt tinh trong h bc ba c to thnh dung dch rn bc hai

Kho st qu trnh xy ra khi lm ngui lnh h lng c thnh phn a (hnh 122). H ny khi ngui lnh hon ton c hai pha rn cng tn ti l rn A v dung dch rn BC c thnh phn p. Khi ngui lnh, cht lng bt u kt tinh rn A, thnh phn pha lng cn li chuyn dch t a n r (dc theo on thng A-r). Khi thnh phn pha lng t ti r nm trn ng nht bin th bt u thot ra tinh th dung dch rn c thnh phn m. Ngui lnh tip tc, thnh phn pha lng chy trn ng XY theo hng r s t, thnh phn dung dch rn thay i mt cch lin tc (lng s ng vi dung dch rn n) lng tinh th ca hai pha (A v dung dch rn BC) cng ngy cng tng. Qu trnh kt tinh tip tc cho n khi thnh phn pha lng v pha rn t ti im t v im p. Lc ny git cht lng cui cng mt, ch cn hai pha rn A v dung dch BC. Mc du tin hnh ngui lnh mt cch rt chm, nhng qu trnh va trnh by trn y thng thng cui cng vn dn ti trng thi khng cn bng v khng trnh khi hin tng kt tinh phn on. Nh tinh th dung dch rn c thnh phn m mi tch ra u tin khng t c trng thi cn bng vi pha lng nhit thp th lc c th xem nh b tch ra khi h. Nu iu ny xy ra trong qu trnh kt tinh th cui cng thu c sn phm kt tinh c cu trc lp, thnh phn thay i t m cho ti dung dch giu C hn, im p. Phn gia cc tinh th khng ng nht nh vy s giu B, cn phn bn ngoi giu C. Qu trnh kt tinh c phn phc tp hn khi tinh th tch ra ban u li l dung dch rn BC (xem hnh 123). Khi chuyn dch im biu din pha lng xung di theo b mt lng, t kt tinh ra dung dch rn cng ngy cng giu C, cn nhng tinh th tch ra trc phi thng xuyn nm cn bng vi pha lng th cng giu C. Cui cng, khi h nhit thnh phn pha lng i theo ng cong b c d e cn thnh phn dung dch rn th theo ng p g r s. Cc ng ni pha lng v pha rn cng cn bng, quay quanh im b. Mi mt thnh phn lng nm trn ng ni s e khi ngui lnh s xy ra theo con ng ring ca mnh, nhng tt c cc con ng u ni vi nhau ti im chung e ca ng nht bin XY cho n khi no kh ht phn lng cui cng (vi dung dch c thnh phn lng b ta ang xt qu trnh xy ra im f). Cui cng thu c hn hp gm rn A vi dung dch rn t.

116

e f d c b

pg rs t

Hnh 123 ng kt tinh h ABC c dung dch rn BC

Vic kho st y mt h nh trn y i hi phi hon thnh mt khi lng thc nghim rt ln. Do hin nay loi gin ny c cng b khng nhiu lm.

3.5 H tng tc bc ba
H gm hai mui khng c ion chung AX v BY l h bn cu t, v gia hai mui c phn ng trao i to thnh hai mui khc: AX + BY AY + BX nhng s cu t c lp ch c ba, v c mt phng trnh lin h gia thnh phn ca bn cu t (hng s cn bng ca phn ng trao i). Do h hai mui khng c ion chung l h bc ba, phn bit vi h gm ba mui c ion chung y ta gi l h bc ba tng tc. Thnh phn ca h bc ba tng tc thng c biu din theo phn trm ng lng cation v phn trm ng lng anion.
b
AX 40% M %X
-

BX

70%

AY

%B

BY

Hnh 124 Cch biu din thnh phn ca h bc ba tng tc

V d h chng ta c: ng lng B+ l 40% (ng lng A+ l 60%), ng lng X l 70% (ng lng Y l 30%). Cch tm im biu din nh sau: T cnh AX-AY ly v pha cnh BX-BY mt on b = 40% ri k mt ng thng song song vi BX-BY. T cnh AY-BY ly v pha cnh AX-BX mt on x = 70% v k mt ng thng song song vi AX-BX. Hai ng thng ct nhau M l im cn tm. Hnh 125 l gin trng thi ca h bc ba tng tc AX + BY trng hp trong h khng to thnh hp cht ho hc mi, khng to thnh dung dch rn gia cc cu t m ch to thnh cc im tecti bc hai v tecti bc ba.

117

TBX e'4 TAX e'1 M' e'2 e1 E1 e2 Hnh 125 Gin trng thi ca h AX + BY AY + BX BX M E2 e4 TAY e'3

TBY

BY e3

Thng thng ngi ta chiu trc giao cc im trong gin khng gian xung hnh vung y v di y chng ta s xt cc gin mt phng hnh chiu trc giao ln hnh vung y nh vy. i lc c th biu din thnh phn ca h bc ba tng tc ln tam gic u nh sau. Gi tng ng lng ca 3 ion bt k l 100 v thnh phn ca h biu din theo phn trm ng lng ca 3 ion . Trn hnh 126 thnh phn ca h c biu din theo phn trm ng lng ca 3 ion X , A+, B+ . V rng cnh y A+B+ c 0% X, do ti y tt c A+, B+ kt hp vi Y, ngha l nh A+ chnh l AY nguyn cht, nh B+ chnh l BY nguyn cht. Ti im gia hai cnh bn c thnh phn 50% X v 50% A+ (pha cnh A+X) v 50% X vi 50% B+ (pha cnh kia). Do im biu din mui AX nguyn cht nm chnh gia cnh A+X, cn im biu din BX nguyn cht nm chnh gia cnh kia, phn tam gic nh pha trn khng c ngha.

xy dng gin khng gian chng ta tin hnh nh trn hnh 125. Trn hnh 126 c v hnh chiu trc giao cc mt kt tinh ca gin khng gian nh hnh 125.
X-

AX e2 E1

e1

BX e4

E2 A+ B+ e 3 (AY) (BY) Hnh 126 Tam gic thnh phn ca h tng tc bc ba AX-BY

118

By gi chng ta xt cc trng hp c th ca h tng tc bc ba trn hnh chiu trc giao xung hnh vung thnh phn. Trng hp n gin nht l h kt tinh di dng cu t nguyn cht, khng to thnh dung dch rn. Hnh 127 l hnh chiu trc giao ln hnh vung y. Hnh 127a ng vi trng hp chiu phn ng l: BX + AY AX + BY y ta c hai h bc ba to thnh tecti n gin l AX-AY-BY v AX-BY-BX. ng cho bn l AX-BY. Cn trng hp hnh 127b th phn ng theo chiu ngc li AX + BY AY + BX Cho bn BX-AY chia hnh vung thnh hai h bc ba l AX-BX-AY v AY-BX-BY. Cng nh trng hp trn y, vic xt qu trnh xy ra khi lm ngui lnh h t trng thi lng ta cn quan tm n v tr im biu din h ban u. V d im biu din h ban u l K (hnh 127a) nm trong tam gic AX-BX-BY th kt thc qu trnh ngui lnh s xy ra qu trnh v bin: lng E2 = rn AX + rn BX + rn BY v cui cng ta thu c sn phm cha 3 pha rn . Ta c th trnh by tm tt qu trnh ngui lnh h lng ng vi im K nh sau. Trc ht xy ra qu trnh kt tinh rn BY im biu din thnh phn pha lng cn li chy t K n L, tip l qu trnh kt tinh ng thi rn AX v rn BY im biu din thnh phn pha lng cn li chy trn ng ME2 (t L n E2) im biu din pha rn chy t BY n R. Khi im biu din thnh phn pha lng n E2 th im biu din thnh phn pha rn n R, t xy ra qu trnh v bin kt tinh ng thi 3 pha rn BY, AX, BX v im biu din thnh phn pha rn chuyn t R n K l kt thc qu trnh.
AX e4 BX AX E1 e3 K R e2 BY AY e2 e1 M e3 E1 AY E2 e4 BX

L M e1

E2

(a)

(b)

BY

Hnh 127 Hnh chiu trc giao ca gin trng thi h bc ba tng tc AX-BY

Hnh 128 ng vi trng hp h bc ba tng tc thun nghch, y khng c cho bn. Ta ly hai mui v mt v phng trnh phn ng vi bt k mt t l thnh phn no, khi lm ngui lnh cng thu c mt pha rn ca mui th ba. Nh vy phn ng y l phn ng thun nghch.

119

AX

e4

BX

P e1 E AY e2

e3

BY

Hnh 128 H bc 3 tng tc thun nghch

AX + BY

AY+ BX

hnh ny im E l tecti bc ba, ti xy ra qu trnh kt tinh ng thi 3 mui: Lng E rn AX + rn AY + rn BY

Cn im P l im peritecti, ho tan rn BX vo lng P kt tinh rn AX v rn BY: Lng P + rn BX rn AX + rn BY

Theo nhit ng ta c th d on vi mt h bc ba tng tc gin s c cho bn ng vi cp mui c tng sinh nhit (Ho298) ln hn. iu c ngha l phn ng trao i xy ra theo chiu to nhit. iu ny c N. Beketop v I.A. Kablucop kim tra bng thc nghim i vi nhiu h. Nhng thc ra chiu hng ca phn ng c quyt nh bi gi tr Go ch khng phi bng gi tr Ho, do vic d on hng ca cho bn phi bit c gi tr Go ca phn ng v s ph thuc ca Go vo nhit na. Hnh 129 l gin h clorua v sulfat natri v tali vi cho bn l clorua tali-sulfat natri, ngha l phn ng xy ra theo chiu to thnh cp mui . H bc ba tng tc i lc kh phc tp. Hnh 130 l gin trng thi h K+, Mg2+, Cl, SO42. Trong h ny ngoi mui n cn to thnh mui kp nh K2Mg(SO4)2, KMgCl3, KMgClSO4. 2NaCl
(800)
650

Na2SO4

(884)

552 410 358

2TlCl
(429)

Tl2SO4

Hnh 129 + + 2 H Na , Ti , Cl, SO4

120

K2SO4
1076
1000 900 800 700 650

750

875 1185

K2Mg(SO4)2
1000

MgSO4
K2SO4
KMgClSO4

1000

MgSO4 800
700

870

K2Cl3 600
800

700

K2Cl3 K2SO4 M g Cl2 K2Cl2

700 600 500

K2Cl2

778

425

495

769

MgCl2

Hnh 130 + 2+ 2 Gin trng thi h K , Mg , Cl, SO4

Vi h K+, Cs+, Cl, SO42 th ch to thnh 2 vng dung dch rn lin tc ca clorua kalixezi v sulfat kali-xezi nh trn hnh 131.
K2Cl2 (778) 750
700 650

690

K2SO4

(1076)

1050 1000 950

600

550 750 700

800

900

850

Cs 2Cl2
(632)

574

Cs 2SO4
(860)

Hnh 131 Gin trng thi h K+, Cs+, Cl, SO42

Cu hi v bi tp
1. 2. 3. 4. nh ngha v minh ho cc khi nim pha, cu t, s bc t do ca h cn bng. Chng minh rng i vi cc h c t hai cu t tr ln th thnh phn ca cu t trong 3 pha khng th bng nhau c. Xc nh s bc t do ca qu trnh phn hu nhit hirat. Dng gin trng thi ca h Al2O3-SiO2 theo cc s liu sau y: Al2O3 nng chy 2060oC, ca SiO2 1720oC, chng to thnh hp cht Al6Si2O13 nng chy tng hp 1850oC. Trong h c cc tecti 1595oC (5% mol Al2O3) v 1840oC (67% mol Al2O3). So snh gin vi gin trong gio trnh.

121

5. 6.

Lp cng thc bin i thnh phn % mol sang % khi lng ca gin trng thi h bc hai (c th dng phng php ton ). Xy dng gin pha ca h A-B theo cc thng tin sau y: trong h to thnh 3 hp cht A2B, AB, AB2. Trong A2B v AB2 nng chy tng hp, cn AB nng chy khng tng hp to thnh A2B v pha lng. Pha lng c thnh phn 40% khi lng Sn v 60% khi lng Pb lm ngui lnh n nhit no th bt u kt tinh, xc nh thnh phn pha rn bt u kt tinh. Lm ngui lnh chm chp n 150oC ri gi yn mt thi gian cho n nh trng thi cn bng. Xc nh thnh phn nh tnh v nh lng ca cc pha trong hp kim (xem hnh di y).
327oC 300 232oC 200 183oC

7.

61,9
100

Pb

20

40

60

80

Sn

% khi lng Sn

Gin trng thi h Pb-Sn

8.

Gii thch ngha cc ng, vng trong gin trng thi ca cc h Mg2SiO4-Zn2SiO4 (hnh 78), MgO-Al2O3 (hnh 79), SiO2-LiAlO2 (hnh 80), Cr2O3-SiO2 (hnh 97), CaO-ZrO2 (hnh 109). Xem gin trng thi h Al2O3-Cr2O3 (hnh 82), trnh by kh nng ho tan ln nhau ca hai oxit ny. Khi lm lnh mt h lng cha 60% oxit nhm, 40% oxit crm n nhit phng thu c h rn c thnh phn pha nh th no trong trng hp lm ngui lnh nhanh, lm ngui lnh t t.

9.

10. Xc nh nhit nng chy ca hp kim c thnh phn khi lng l 70%Zn, 10%Cd, 20%Sn. Mun h nhit nng chy ca hp kim xung 30oC th phi thm bao nhiu Sn v Cd vo 100g hp kim (xem h Zn-Cd-Sn hnh 114). 11. Thm 25g ZrO2 vo 75g Al2TiO5 ri nung cho nng chy hon ton, xt qu trnh xy ra khi lm lnh hn hp lng n lc thnh phn pha lng t ng cong bin gii. Tnh lng pha rn tch ra v lng pha lng cn li (h ZrO2-TiO2-Al2O3 hnh 118). 12. Lp bng qu trnh kt tinh ca hn hp lng nm trong cc hnh tam gic a) b) c) A3S2-MA-M4A5S2 A3S2-M2A2S5-M4A5S2 M2S-M2A2S5-MS (H MgO-SiO2-Al2O3 hnh 119). 13. Hnh di y l mt gc ca gin trng thi h CaO-SiO2-Al2O3. Xt qu trnh kt tinh hn hp lng ng vi im K.

122

14. Cng vi hnh di y xt qu trnh kt tinh hn hp lng c thnh phn 8% Al2O3, 8% SiO2, 84% CaO. Tnh thnh phn phn trm ca pha lng v pha rn tch ra khi im biu din ca h t ng bin gii.
C2S
30 3

P C3S
20

K' K" K K"'

C2S

F' CaO
10

C3S
34

33

C3A CaO b
10

ad

20

30

ec

C3A H

123

Chng 4 MT S TNH CHT VT L QUAN TRNG CA VT LIU V C

C rt nhiu tnh cht vt l lin quan n vic s dng vt liu v c, trong chng ny ch gii thiu nhng nt c bn ca ba nhm tnh cht quan trng nht. l nhm tnh cht lin quan n kh nng dn in, lin quan n t tnh v lin quan n s pht quang.

4.1

Nhm tnh cht in

Da vo kh nng dn in ngi ta phn thnh: cht dn in, cht cch in v cht bn dn in. Da vo phn t mang in trong qu trnh dn in ngi ta phn thnh: cht dn in ion (i vi cht rn th gi l cht in li rn) v cht dn in electron. Ngoi ra da vo mi tng quan gia c v in cn c cht p in, mi tng quan gia nhit v in cn c cht ho in, hin tng nhit in, da vo kh nng phn cc ca cc t bo mng li cn c loi cht xenhet in.

4.1.1 Cht dn in ion, cht in li rn

Tnh dn in ca cc vt th rn c thc hin bng s dch chuyn electron hoc ion trong khong cch ln. Thng thng, ch mt trong cc phn t mang in chim u th, nhng cng c mt s vt liu v c th hin ng thi dn in ion v dn in electron. c trng cho kh nng dn in ca vt liu rn ngi ta dng khi nim dn in ring , tc l dn in ca mt th tch cht rn c tit din cng nh chiu di bng mt n v. dn in ring thng c biu din bng m1. cm1; m1.m1, CM.m1 (CM c l cimen c gi tr bng 1 m1). dn in ring ca mt vt bt k khng ph thuc vo bn cht cht mang in v c xc nh bng phng trnh.
=

n e
i i i

(33)

ni l nng cht mang in tch loi i, ei v i l in tch v linh ng ca cht mang in tch . i vi electron v ion c in tch 1 th e = 1,6.1019C (in tch electron). Bng 31 gii thiu gi tr dn in ring ca mt s loi vt liu Thng thng, dn in ph thuc vo nhit , khi tng nhit th dn in tng (tr kim loi). Vi kim loi th ngc li, dn in c gi tr cc i khi nhit thp, c mt s kim loi gn khng tuyt i c tnh siu dn.

124

.
Bng 31 Gi tr dn in ring ca mt s loi vt liu Phn t dn in Ion Vt liu Tinh th ion Cht in li rn Cht in li mnh (lng) Kim loi Bn dn Cch in (m1. cm1) <1018104 103101 103101 10105 105102 <1012

Electron

Trong iu kin thng thng, a s cht rn c lin kt ion v lin kt cng ho tr (cc oxit, halogenua) th s dch chuyn ca cc ion l khng ng k. Cc ion thng c phn b ti cc nt xc nh ca mng li, s chuyn ch ca chng ch xy ra khi c mt khuyt tt trong mng tinh th. Ch nhit cao, khi m nng khuyt tt ln, cc ion c nng lng nhit ng k th mi o c gi tr ca dn in. V d dn in ca NaCl gn 800oC (ngha l gn nhit nng chy ca NaCl) bng 103 m1.cm1, cn nhit phng NaCl nguyn cht l cht cch in. Tuy nhin, c mt nhm cht rn, trong cc ion ca mt phn mng c th chuyn ng vi tc kh nhanh. l cht dn in ion, cht dn in siu ion. dn in ca cc vt liu ny l do tnh cht c bit ca cu trc tinh th ca chng, chnh l s c mt cc khe rnh trong mng li. Gi tr dn in ca vt liu ny cng tng ng vi dn in ca dung dch cc cht in li mnh. V d: dn in ca -Al2O3 25oC l do s dch chuyn ca ion Na+ v bng 103 m1.cm1. Hin nay ngi ta ch nhiu n vic nghin cu tnh cht ca cc cht in li rn, tm kim cc cht in li rn mi v m rng lnh vc s dng chng. Trc ht, chng ta kho st cc hp cht bc hai nh NaCl, AgCl. Tuy rng vic nghin cu tnh dn in ca cc tinh th ny thng c xt trong cc gio trnh vt l cht rn, nhng s hiu bit cc hin tng lin quan n n cng rt cn thit i vi lnh vc ho hc vt liu v c.
4.1.1.1 S khuch tn ion trong cc tinh th in hnh

Xt vi v d c th: a. V d tinh th NaCl Thng thng cation linh ng hn anion. Gi s tinh th c cha mt nt trng Na+, di tc dng ca in trng, ion Na+ dch li l trng bn cnh, dng li v li l trng pha sau. Ion Na+ th hai dch n l trng mi iu ny cho ta thy hin tng dch chuyn l trng cation. Trong tinh th NaCl cng c l trng anion nhng linh ng ca chng b hn nhiu. Gi tr dn in ion ca tinh th NaCl l do s c mt ca l trng cation. S l trng cation li ph thuc vo nguyn cht ho hc v k thut ch ho nhit ca mu NaCl. C hai cch lm tng s l trng cation. Khi t nng tinh th s l trng cn bng nhit ng ca tinh th nguyn cht tng ln theo cp s lu tha (Nv = N.const.eH/2RT). Trong khi vic a tp cht l c ho tr khc cng lm pht sinh ra l trng. V d thm mt t MnCl2 to thnh dung dch rn Na1-2xMnxVxCl. Ngha l mi ion Mn2+ s lm xut hin mt l trng Na+. Loi l trng ny gi l l trng tp cht.

125

Cl Na Cl Na Cl

Na Cl Na Cl Na

Cl Na Cl

Na Cl
1

Cl
2

Na Cl Na Cl Na

Na Cl Na Cl

Na Cl

Cl

Na

Hnh 132 S dch chuyn l trng cation trong tinh th NaCl

nhit thp, nng l trng c ngun gc nhit cn rt b m ch yu l l trng tp cht. Do dn in tp cht l quyt nh. Khi nhit tng c th chuyn dn tp cht n dn ring. dn in ion ph thuc vo nhit theo phng trnh Arrenius.
= A.e E/RT

(34)

E l nng lng hot ho, R l hng s kh, T l nhit tuyt i. Gi tr A bao gm nhiu hng s, trong c tn s dao ng ca cc ion linh ng. S ph thuc ca ln() vo 1/T l ng thng c h s gc l E/R. vng nhit thp th s l trng do nng tp cht quyt nh. ng vi mt nng tp cht c mt gi tr s l trng nht nh. Bi vy, trn hnh 133 vng dn tp cht c nhng ng song song ng vi tng nng tp cht. Trong khu vc ny ph thuc vo T l do s ph thuc ca linh ng cation vo nhit quyt nh.
= o.eEdc/RT (35)

Edc l nng lng hot ho ca s dch chuyn l trng cation.

lg
3 2 1

1/T
Hnh 133 S ph thuc dn ion ca NaCl vo nhit . Nhng ng song song trong khu vc tp cht ng vi tng nng khc nhau ca tp cht 1 - Tng lng tp cht; 2 - dn tp cht Edc; 3 - dn ring Edc + Eht/2

126

Cl
1

Na Na

Cl

Cl Na

2,82A

Cl

Hnh 134 Con ng dch chuyn ca ion Na+ trong tinh th NaCl

hiu c bn cht ca nng lng hot ho dch chuyn, chng ta hy kho st cc con ng c th cho php ion Na+ chuyn t nt mng sang l trng cnh . Hnh 134 biu din mt mnh ca cu trc tinh th NaCl (1/8 t bo) c cha mt l trng Na+. Mt trong ba ion Na+ c th nhy vo l trng . S nhy trc tip (theo ng chm chm) khng th xy ra c, v rng cc ion Cl (1) v (2) nu nh khng hon ton tip xc vi nhau th cng rt gn nhau, khng cho php Na+ lt qua c. Bi vy Na+ phi nhy qua v tr tm ca t din gm bn ion Cl (1,2,3,4). Mun th Na+ phi i qua hai ca s tam gic clo (1,2,3) v (1,2,4). Cn phi tnh ton kch thc cc ca s ny hnh dung c mc kh khn ca vic chuyn dch ion Na+. Thng s t bo mng NaCl l a = 5,64 di lin kt Na-Cl bng a/2 = 2,82 bn knh ion Na+ = 0,95, ca Cl l 1,85. di Na-Cl t cc bn knh c gi tr khong 2,82.
3

r'
1

30 o 2

Hnh 135 + Ca s tam gic m ion Na phi i qua trong tinh , th NaCl, r bn knh ca s, cc vng trn 1, 2, 3 l ion Cl c bn knh x/2

Trong cu trc gi ghm chc c nh NaCl th cc anion hoc tip xc vi nhau, hoc rt gn nhau. Cc ion 1, 2, 3 to thnh mt mnh ca lp xp kht v khong cch Cl(1) v
a 2 a 2 Cl(2) cng nh Cl(1) v Cl(3) bng: + = 3,99. Ngha l 0,3 ln hn 2rCl , 2 2 do cc ion Cl cnh nhau khng tip xc vi nhau.
1/ 2

Bn knh ca s r trong tam gic Cl(1), Cl(2), Cl(3) c th xc nh nh sau: cos(30o) = (rCl+r)=
x/2 1,995 = y rCl + r'

1,995 =2,30 cos 30 0

127

Nu rCl = 1,85 th r=0,45. Cng tng t nh vy c th xc nh bn knh r ca l trng ti tm lp phng. di ng cho khi lp phng bng (2rCl + 2r), ngha l:
a 2 a 2 a 2 2(rCl+r) = + + 2 2 2
1/ 2

= 4,88

T r= 0,59 Nh vy, s chuyn dch Na+ trong mng li NaCl rt kh khn. Ban u Na+ phi len qua mt l tam gic nh vi bn knh ca vng l 0,45, sau ri vo l trng t din c bn knh khi cu trng l 0,59. Thi gian Na+ lu li y rt ngn, t gi v tr Na+ phi len qua l tam gic th hai vi r= 0,45 ri mi ri vo l bt din. S tnh ton trn y ch l l tng v rng gn v tr l trng (khuyt tt) th no cng c sai lch v cu trc (ni rng ra) lm cho gi tr cc khong cch hi khc, nhng d sao s tnh ton cng cho thy vic chuyn dch Na+ phi vt qua mt hng ro nng lng hot ho ng k. Nh vy trong khu vc tp cht, dn ph thuc vo nng l trng, vo linh ng v c biu din bng h thc:
= n.e.o.eEht/2RT

(36)

nhit cao, trong khu vc dn in ring th nng l trng c ngun gc nhit vt nng l trng do tp cht. By gi Nv ph thuc vo nhit theo phng trnh Arrenius: Nv = N.const.eEht/2RT (37)

Phng trnh ny c dng ging phng trnh (24) trong Eht l nng lng hot ho ca s hnh thnh mt mol l trng cation, ngha l 1/2 nng lng cn thit hnh thnh mt mol khuyt tt Stki. linh ng ca l trng tnh theo phng trnh (35). Nh vy, v ton b dn in trong khu vc dn in ring tun theo phng trnh:
= N.const.e.o.eEdc/RT.o.eEht/2RT = A.e(Edc+Eht/2)/RT

(38) (39)

Hnh 133 biu din s ph thuc dn in ca tinh th NaCl cc mc nguyn cht khc nhau. Mt dy cc ng song song trong vng tp cht l dn ng vi tng nng tp cht nht nh, trong khi ch c mt ng duy nht ng vi khu vc dn ring. iu ny chng t dn ring khng ph thuc vo tp cht. Thc ra iu ch ng vi trng hp nng tp cht rt b (nh hn 1%), mc tp cht nh vy s khng nh hng n Edc l trng cation. lch ca s ph thuc dn in ring ln hn lch ca dn in tp cht. Xc nh hai gi tr lch cho php tnh c Edc v Eht. Nhng s liu thu c i vi tinh th NaCl (hnh 136) cho thy s ph thuc ca dn in vo nng tp cht nh trn s hnh 133 ch l l tng. Trong thc t c phn phc tp hn. Cc phn I v II ng vi cc vng dn ring v vng tp cht trong s n gin (hnh 133). ng chm chm l ng ngoi suy ca ng I v ng II cho thy s sai lch gia l thuyt v thc nghim. S xut hin phn I gn nhit nng chy (Tnc = 802oC) c th do hai nguyn nhn:

128

Nguyn nhn th nht do l trng anion tr nn linh ng hn nn thm mt phn gp vo . Nguyn nhn th hai l khi tng nng l trng nhit cao th tng tc bai-Hucken gia cc l trng cation v l trng anion cng th hin r rt. iu ny cng tng t nh tng tc gia cc ion trong dung dch. Lc pht sinh ra lc ht lm b tr mt phn nng lng to thnh l trng. Do s hnh thnh l trng tr nn d hn v nng ca n tng ln lm tng dn. Vn cn li cha r l i vi NaCl th nguyn nhn no l chnh.
Lg(m 1.cm 1.K) I'
1 2 3 4 5

I II III -1 1,4 1,6 1000/T (K )

1,2

Hnh 136 S ph thuc dn in ion trong tinh th NaCl nguyn cht

Phn III ( di 390oC) l sai lch m so vi ng l tng vng tp cht. iu ny lin quan ti s hnh thnh phc hp khuyt tt nh cp l trng cation-l trng anion hoc l trng cation v cation tp cht. Phc hp khuyt tt pht sinh khi tng tc gia cc khuyt tt n gin cnh nhau. Tng tc gia cc khuyt tt cnh nhau y khc vi tng tc bai-Hucken ni trn, lin quan n vic gi tnh trung ho in. cho l trng cation trong phc hp c th chuyn ng cn cung cp cho n mt nng lng phn li phc hp, do nng lng hot ho trn phn III ln hn Edc phn II.
Bng 32 dn in ca tinh th NaCl Qu trnh Dch chuyn ion Na+ (Edc) Dch chuyn ion Cl To cp Stki Phn li cp l trng Phn li cp l trng cation-ion Mn2+ Nng lng hot ho (eV) 0,65 0,85 0,90 1,10 2,18 2,38 Khong 1,3 0,27 0,50

Mc du dn ca tinh th NaCl c nhiu tc gi nghin cu nhiu phng th nghim khc nhau nhng cc gi tr thu c cng khng ph hp nhau. Gi tr Edc ca Na+ nm trong khong 0,65 0,85 eV (60 80 kJ/mol).

129

Ag Cl Ag Cl Ag

Cl Ag
1

Ag Cl

Cl Ag

Ag Cl Ag Cl Ag

Ag Cl Ag Ag Cl Ag (b) Cl

Cl

Cl Ag Cl 2 Ag Ag Cl Ag Ag Cl Ag Cl (a)

Ag

Hnh 137 Dch chuyn ion Ag+ gia cc nt

a) b) b.

bng cch chuyn trc tip gia cc nt (1), bng cch y Ag+ nm gia cc nt bnh thng ra gia cc nt (2). cc hng c th c ca vic y Ag+ vo v tr gia cc nt.

Tinh th AgCl

Vi clorua bc th khuyt tt in hnh l khuyt tt Frenken. Ngha l ion Ag+ xm nhp gia cc nt v cc l trng cation. Thc nghim chng t rng Ag+ gia cc nt (gi l Ag+ xm nhp) linh ng hn l trng Ag+. C hai kiu c ch dch chuyn Ag+ gia cc nt.

Dch chuyn trc tip qua cc nt (hnh 137a, 1). Dch chuyn gin tip bng cch y mt ion Ag+ ra khi nt ca n, ri ion Ag+ gia cc nt chim v tr nt (hnh 137a, 2).

Bng phng php dng ng v phng x Ag+ ri xc nh con ng dch chuyn ion bc nh du xc nh c ch gin tip hay cn gi l c ch y l ng. C ch l trng ca s dch chuyn ion Na+ trong tinh th NaCl v c ch y trong tinh th AgCl khc nhau. V c bn c hai u c cu trc kiu NaCl. Trong c ch l trng, ion Na+ dch chuyn t nh lp phng sang mt nh khc qua v tr gia cc nt l tm ca lp phng. Cn c ch y th Ag+ chuyn t v tr gia cc nt (tm ca lp phng) ti mt v tr gia cc nt khc (tm ca lp phng bn cnh) sau khi y mt ion Ag+ ra khi nh. nh hng ca tp cht cation, c ho tr khc nhau n dn in ca NaCl v AgCl l khc nhau. V d c mt Cd2+ trong trng hp NaCl s lm tng l trng cation, nhng trong trng hp AgCl v tch s nng Ag+ gia cc nt v nng l trng cation l khng i, nn tng l trng cation th s gim Ag+ gia cc nt, ngha l gim s phn t linh ng do s gim dn in (xem hnh 138).

130

Lg (m 1.cm 1.K)
+2

AgCl/Cd

1/T (K )
Hnh 138 S ph thuc dn in ca AgCl (c pha tp cht Cd2+) vo nhit

4.1.1.2 Cht in li rn

a s cc cht tinh th nh NaCl, MgO u c dn in ion thp v rng cc ion tuy c dao ng nhit nhng thng thng khng ri khi v tr nt mng. Trng hp ngoi l l mt s cht rn m trong mng li tinh th c mt hp phn cu trc (cation hoc anion) khng b gn cht vo nt mng li c th chuyn ng t do trong ton mng. Nhng cht nh vy c gi l cht dn in ion hay cht in li rn. Nh vy, cht in li rn chim v tr trung gian v cu trc cng nh v tnh cht gia mt bn l cht rn cu trc tinh th bnh thng, mt bn l cht in li lng. Trong cht rn c cu trc bnh thng cc ion b gn cht ti cc nt mng khng gian, cn cc cht in li lng th cc tiu phn hp phn khng c cu trc trt t gm cc ion chuyn ng linh ng.
Tng nng khuyt tt Cht trng thi tinh th bnh thng Chuyn pha Cht in li rn Cht in li lng

tC

131

x
546 o

C DTA

600 500 400 300 200 100

T
600

825

DTA
400 300

T
170

159

(a)
oC

200 100

(b)

856

x
577

(c)
Hnh 139 Gin nhit AgI (a), Ag2S (b), Li2SO4 (c)ng dn in k hiu x

nhit bin ho th hnh cc ion trong tinh th ca nhiu cht rn tr nn rt linh ng, do lm tng mnh dn in. Gin nhit ca AgI, Ag2S, Li2SO4 trn hnh 139 cho thy cc nhit bin ho th hnh (vi AgI l 159oC, vi Ag2S l 170oC, vi Li2SO4 l 577oC) ng dn in tng ln mt cch t ngt, t gi tr ti a cho ti nhit nng chy hon ton cng khng tng na. dn in ca cht in li rn c th tng ln do tng dn nng khuyt tt nhit cao. V d trn 600oC nng l trng anion ln n ni lm cho tinh th ZrO2 tr thnh cht dn anion O2 kh tt. Thc ra lc ny khng phi ZrO2 nguyn cht tuyt i m do s c mt ca tp cht c in tch khc vi Zr4+, l CaO, Y2O3, Sc2O3... V l thuyt cng nh thc nghim xc nh c rt nhiu cht in li rn c dn in t ti 0,1 10 1cm1. Gi tr ny ng vi trng thi khi phn ln cc ion trong tinh th ng thi chuyn ng. Nhiu tc gi ngh gi nhng cht nh vy l nhng cht dn in siu ion hay cht dn ion nhanh. Vic phn loi cc cht in li rn nh l cht trung gian gia cc tinh th ion thng thng v cht in li lng c khng nh bng s so snh S nng chy. Lc nng chy xy ra s mt trt t ng thi ca cation v anion. i vi cc cht mt in tch (hp cht A+B), v d NaCl c S nng chy bng 24 J/mol.K. Khi chuyn dng th hnh ca AgI 159oC c gi tr S bng 14,5 J/mol.K c th xem nh s gi nng chy ca phn mng cation Ag+, n khi nng chy AgI th xy ra s mt trt t ca phn mng I, do S nng chy tt nhin l b hn S nng chy ca cc cht mt in tch khc v ch bng 11,3 J/mol.K. Tng entropi bin ho th hnh v entropi nng chy gn bng entropi nng chy NaCl. iu ny cng thy c nhiu florua ca kim loi ha tr 2. V d PbF2, S nng chy ch bng 16,4 J/mol.K trong khi MgF2 hp cht ion in hnh c dn in thp th S nng chy bng 35 J/mol.K. Hnh nh khi un nng PbF2 ban u xy ra s mt trt t ca F ( trn 500oC ), gi tr entropi nng chy ch ng vi s mt trt t ca ion Pb2+. Hnh 140 trnh by dn in ring ca mt s cht in li rn di dng s ph thuc vo nhit theo phng trnh Arrenius.

132

lg (m 10 1 cm ) 1 2 3 4 5
ZrO2 CaF2 1

-AgI

H2SO4

RbAg4I5 NaAl2O3

NaZr2PSi2O12 AgCl 2

-AgI 3 4 1000/T(K)

Hnh 140 dn in ion ca mt s cht cin li rn

Di y chng ta kho st mt s cht in li rn quan trng.

a) -Al2O3
A C B A C B A C B A C B A C B A sp sp A B A C B A C A B C A B A C B A sp sp mt phn chiu gng

sp

sp

'' C C Hnh 141 Tnh lin tc ca cc lp Oxi trong cu trc v -Al2O3 +

Na

O2sp: bloc spinen

chng 1 gii thiu cu trc ca -Al2O3. y ni v cht in li rn ng vi cng thc Na2O.nAl2O3. Tinh th ca loi hp cht ny gm phn mng anion O2 c cu trc lp nh hnh 29, trong c bn lp O2 xp kht theo kiu spinen (gi l bloc sp) li n mt lp ch c 1/4 s ion O2, 3/4 s ion cn li l cc khong trng. Ion Al3+ c phn b c nh ti cc v tr t din gia hai lp O2 xp kht, ion Na+ nm lp c khong trng, do c th dch chuyn d dng di nh hng ca in trng.

133

-Al2O3 c hai dng th hnh v khc nhau th t sp xp cc lp (hnh 141). Dng cha hm lng kim ln (n = 5 7) cn dng b c n t 8 11. C hai dng u cha cc bloc tng t spinen MgAl2O4. Bloc spinen gm bn lp O2 xp kht lun phin theo th t ABCA c trng ca cu trc lp phng. Cc bloc sp tch bit nhau bng mt lp thiu oxi (gi l mt dn), ion Na+ c nh v trong mt . T bo mng lc phng c cc thng s a = 5,60; c = 22,5 (dng ) v a = 5,60, c = 33,8 (dng ), cc lp oxi trc giao vi trc c. T bo mng ca -Al2O3 c cha 2 bloc spinen, cn ca -Al2O3 c cha 3 bloc spinen.
m A m br B abr m A br A A C A A m B abr m br A C A m A
Na+ Na+ Na+ Na+

C A

m
(b)

(a)
A C

Na+

Hnh 142 Mt dn trong -Al2O3 a) O2- trong lp dn; b) Na+ chuyn dch trong lp dn

Cu trc spinen y c xem nh cu trc MgAl2O4 cha khuyt tt, trong spinen MgAl2O4 c t l ion Mg2+ v Al3+ l 1 : 2, trong khi spinen ca b v b" ch c Al3+ (nu khng k n cc ion l Li+, Mg2+), do cn bng in tch trong cc bloc spinen phi c cha cc l trng Al3+. Cu trc ca mt dn trong -Al2O3 l i tng nghin cu ca rt nhiu nh khoa hc, nhng cho n nay vn cn nhiu chi tit cha r. Hnh 142 biu din lp chc c ca oxi (k hiu A, B) nm ngay st di mt dn. Oxi gch sc l ca lp dn. Hnh v cho thy lp ny ch chim 1/4 v tr c oxi, c mi oxi C th c 3 v tr b trng, k hiu m. Trong -Al2O3 mt dn l phn x gng (xem hnh 141) do lp oxi gi ghm chc c pha di cng nh pha trn, ngha l trn lp dn C c mt lp oxi nm ng cc v tr AB nh lp di. Trong -Al2O3 mt dn khng phi l mt gng, lp oxi nm v hai pha lp dn lch v tr nhau. Ion Na+ trong -Al2O3 c th chim 3 v tr khc nhau:

V tr gia cc oxi (m). SFT6 V tr Biversa - Rosa (br). SFT6 V tr i Biversa - Rosa (abr).

Kt qu nghin cu cu trc cho thy Na+ ch yu v tr br v m, nhng cch chuyn dch no cng phi i qua abr. Trong v tr br cng nh m c kch thc ln, ion oxi c phi tr 6: (3 oxi lp di, 3 oxi lp trn). di lin kt Na-O trong v tr ny tng ln ( 2,4). V tr abr c kch thc b hn do hai oxi lp trn v lp di xp gn nhau. Khong cch Na-O ch = 2,3. Cc cation ho tr 1 khc nhau trong -Al2O3 u chim v tr br v m. Tr trng hp Ag+, Tl+ li chim v tr abr. iu ny l do xu hng to thnh lin kt cng ho tr vi c trng s phi tr thp.

134

C hai pha -Al2O3 v -Al2O3 u thuc hp cht bt hp thc c th tn ti trong mt khong thnh phn. Tuy nhin, c ch ca s pht sinh ra bt hp thc khc nhau. Thng thng ngi ta cho rng cu trc l tng ca -Al2O3 ng vi cng thc Na2O.11Al2O3 (hoc NaAl11O17). Tuy nhin, thc t -Al2O3 cha natri nhiu hn thnh phn . Ban u kt qu nghin cu cu trc -Al2O3 ca Biversa v Rosa cho thy mi t bo mng ca NaAl11O17 ch c mt ion Na+ trong mt dn nm v tr br. Sau kt qu nghin cu vi nhng mu c thnh phn gn Na2O.8Al2O3 li thy rng mi t bo c cha 11/3 ion Na+ phn b gia cc v tr br v m, tnh trung ho in lc ny t c do c b sung ion O2 chim mt s v tr m. Nh vy, so vi cu trc ca cc NaAl11O17 th -Al2O3 giu kim c cha ion Na+ xm nhp. Trong -Al2O3 c hp cht in hnh l Na2O.6,6Al2O3. Mi t bo c 1,2/3 ion Na+ nm trong mt dn. in tch ca ion Na+ b sung (2/3) khng c b tr bng cch xm nhp ion O2 vo mt dn m c l trng Al3+ trong bloc spinen. Vic m t c ch hnh thnh pha khng hp thc v cn phc tp hn na khi a thm Li2O, MgO vo. C hai oxit ny xm nhp vo bloc spinen v Li+, Mg2+ thay th v tr ca Al3+.
+ Tnh dn in v c ch tnh dn in.

Cht dn in rn c cu trc -Al2O3 thuc loi cht dn hai phng. Cc ion kim c kh nng chuyn ng dc theo mt dn nhng khng th i xuyn qua bloc spinen (xem hnh 142b).
lg (m-1 2 cm-1. 1 K) 0 1 2 3 4 5 6
2 4

Tl

K (0,36)
6 8

Na Ag (0,16) (0,30) (0,17) 10 12 1000/T(K)

Hnh 143 dn ca n tinh th -Al2O3 khi thay th bng cc cation khc nhau S liu trong ngoc l nng lng hot ho bng eV

dn ca -Al2O3 ln hn dn in ca -Al2O3 n 2 hoc 3 ln, nhng trc y vic iu ch -Al2O3 cha th tin hnh c, do cc s liu dn in ch kho st vi -Al2O3. Hnh 143 trnh by s ph thuc vo nhit ca dn in -Al2O3 khi thay th Na+ bng cation khc nhau. Gi tr cc i ca dn, v ng thi nng lng cc tiu ca s hot ho xc nh c Na+, Ag+ -Al2O3. Tng bn knh ion, dn km hn i, v rng cation ln K+, Tl+ kh lng dch chuyn d dng trong mt dn. Ion Na+ v Ag+ c kch thc thch hp, trong khi Li+-Al2O3 (trn hnh khng c) li c nng lng hot ho cao v dn b hn so vi Na+ -Al2O3 v Ag+ -Al2O3. iu ny c th do kch thc Li+ qu b, c kh nng phn cc ln nn khng thch hp nm trong hc c s phi tr cao, v bt buc phi nm p v mt trong cc lp oxi pha trn hoc pha di mt dn.

135

S ph thuc dn ca -Al2O3 vo nhit kh ph hp vi phng trnh Arrenius. Cho n tn 1000oC ng biu din vn thng v dn tng ln ti 107 ln. Trong khi dn in ca tinh th NaCl (hnh 136) ch trong khong nhit khng ln m ng biu din thay i hai, ba ln: l iu c bit ca cht in li rn. Mt iu c bit na ca cht in li rn l: khc vi cc cht dn ion nh NaCl, AgCl dn in ca cht in li rn c tnh cht lp li cao, ngha l mc du c iu ch bng phng php khc nhau cc phng th nghim khc nhau, gi tr dn in vn khng thay i ng k. iu ny chng t tnh dn in ca loi cht ny hu nh khng ph thuc vo s c mt ca nhiu tp cht. V d nng lng hot ha ca tnh dn Al2O3 thu c ca nhiu phng th nghim khc nhau u c tnh cht lp li v bng 0,16 0,01 eV. T kt qu kho st tnh dn in ca -Al2O3 cho thy khng th xem pha rn ny c trng thi cn bng ca khuyt tt, khng th p dng nh lut tc dng khi lng y. iu th nht l phng trnh xc lp nng khuyt tt Frenken, Stki ch p dng vi trng hp nng khuyt tt rt b (nh hn 0,1% v tr nt l khuyt tt), trong khi Al2O3 c mt lng ln (nu khng ni l tt c) ion Na+ linh ng. iu th hai l dn in ca -Al2O3 b nh hng khng ng k vi s c mt ca tp cht. Lng ion Na+ linh ng, ln n ni cn phi xem chng khng phi nh khuyt tt m nh nhng nt mng bnh thng ca cu trc. V d khi thm mt t MnCl2 vo n tinh th NaCl lm tng dn mt cch t ngt, nhng vi lng tp cht nh vy th nh hng khng ng k ti dn in ca -Al2O3. C ch tnh dn in ca -Al2O3 c th hnh dung qua hnh 144. Ion Na+ dch chuyn theo cc v tr br m abr br m. Nng lng hot ho ca tnh dn in bng 0,16 eV l tng hng ro nng lng m Na+ phi vt t v tr br ny ti v tr br bn cnh. Kt qu xc nh bng thc nghim cng nh t tnh ton cho thy tnh dn trong -Al2O3 theo c ch y ca cation gia cc nt. V d tinh th ban u ng vi cng thc NaAl11O17, ion Na+ chim cc v tr br, cn cc v tr m v v tr abr u b trng. Ion Na+ v tr br phi vt qua mt khe nh v tr m chui vo v tr abr ri t y li i qua v tr m ly ion Na+ v tr br bn cnh
m m br m br

m m m m m abr abr abr m m m br br br m m m m m m abr abr m m

Hnh 144 Con ng dn trong -Al2O3

Mt trong cc hng c nghin cu hin nay l tng dn ca gm -Al2O3. Trong hng c lu nhiu l tng hp -Al2O3 v thm mt lng nh Li2O v MgO vo tng dn. b) AgI v cc cht in li rn dn Ag+
+ AgI.

Cu trc: AgI c 3 dng th hnh theo nhit tng dn l , v . Trong -AgI c cu trc kiu blend ZnS (hnh 145). T bo mng gm phn mng anion kiu lp phng mt

136

tm ca I, trong khi lp phng c cha 4 cation Ag+ nm tm ca 4/8 lp phng nh. S phi tr l 4-4.

Hnh 145 T bo mng kiu blend O : I; : Ag+

-AgI c cu trc kiu vuazit (hnh 27). Phn mng anion gm cc ion I gi ghm chc c lc phng. Cation Ag+ nm cc hc t din. S phi tr l 4-4. -AgI c phn mng anion I kiu lp phng tm khi. Mi t bo mng c 12 hc t din, nhng ch c 4 cation Ag+. Cc ion I thc t khng linh ng, trong khi ion Ag+ c th dch chuyn t do t v tr hc t in ny n hc t din khc nh trong cht lng. Trng thi khng trt t ca Ag+ v kh nng chuyn ng nhanh ca n xc nh bn cht lin kt gia AgI. Cation Ag+ do c lp v ngoi cng l 4d nn c kh nng phn cc cao v hiu ng chn in tch ht nhn khng ln, cn I th d b phn cc. Nh vy gia it v bc c lin kt cng ho tr. Khi tham gia dn in, Ag+ chuyn ng t do t hc t din ny n hc t din khc qua v tr trung gian c phi tr tam gic ( v tr phi tr tam gic ny s phi tr ca bc ch l 3). Lin kt cng ho tr cc v tr trung gian ny c tc dng lm bn vng ho v lm gim nng lng ho ca dn.
+ RbAg4I5.
oC
600 500 400 300 200 100 0 5
8

1
6

1- RbI + lng 2 - RbI + Rb2AgI3 3 - Rb2AgI3 + AgI 4 - Rb2AgI3 + RbAg4I5 5 - Rb2AgI3 + lng 6 - AgI + lng 7 - Lng 8 - RbAg4I5 + lng 9 - RbAg4I5 + AgI

27o C 3

RbI

Rb2AgI3

RbAg4I5 % mol AgI

AgI

Hnh 146 Gin trng thi h RbIAgI

Cc nh lm n nh pha nhit cao ca -AgI l hng ch yu trong nghin cu ca cht dn ion AgI. thc hin hng ny ngi ta tin hnh thay th ion ca cc phn mng. Thnh tu ng k nht l thay th mt phn Ag+ bng Rb+ khi tng hp RbAg4I5. V mc dn ion th vt liu ny vt xa tt c cc cht in li rn tinh th khc. nhit phng (25oC) dn ca n l 0,25 m1cm1, nng lng hot ha dn l 0,07 eV, trong khi mc dn electron cc nh c th b qua 109 m1cm1. Hnh 146 l gin trng thi

137

ca h AgI-RbI cho thy to thnh hai hp cht nng chy khng tng hp l Rb2AgI3 v RbAg4I5. di 27oC hp cht RbAg4I5 phn hu theo phn ng:
RbAg 4 I5 AgI + Rb 2 AgI3

Tuy rng v ng hc, phn ng ny xy ra rt chm, nhng nu c mt m hoc hi it th c th xy ra vi tc rt nhanh. c th xc nh dn ca RbAg4I5 nhit phng th phi lm lnh rt thn trng trong kh quyn kh v khng c hi it. iu ch RbAg4I5, c th un trong chn khng mt hn hp RbIAgI theo t l mol 1 : 4 n nhit nng chy (500oC) ri lm lnh nhanh n nhit phng. Khi ngui lnh khi nng chy kt tinh to thnh vt th rn ng nht bao gm nhng tinh th nh khng hon chnh. Sau khi nhit khong 165oC trong 10 gi s to thnh nhng tinh th RbAg4I5 hon chnh. Cng c th khng cn a ln nhit nng chy bng cch thc hin phn ng trc tip gia cc pha rn AgI v RbI trong khong 100200oC. Phn ng c th xy ra vi tc ng k khi chun b hn hp ng th ca hai cht rn c phn tn tht cao v nn p sut cao. Cu trc RbAg4I5 khc vi cu trc ca AgI. Nhng trong RbAg4I5 cng c s phn b thng k cc ion Ag+ trong cc hc t din ca phn mng anion I . Cng nh trong cu trc ca -AgI, mng li tinh th ca RbAg4I5 c s hc t din rt nhiu so vi s cation Ag+. Ion Rb+ b gi cht cc hc bt din ca I. Khc vi ng s ph thuc dn vo nhit di dng ng thng theo phng trnh ca Arrenius, ng dn ca RbAg4I5 vo nhit l mt ng cong u n.
+ Cc cht in li rn khc dn xut ca AgI.

Cu trc khng trt t nh AgI c th n nh n nhit thp bng cch thay th cc cation c kch thc ln: NH + 4 , cation hu c. V d mt s loi hp cht c dn khong 1 1 o 0,02 n 0,2 m cm 25 C nh [(CH)3N]2Ag13I15, (C5H5NH)+Ag5I6 v NH4Ag4I5. Cng c th thay th mt phn I cho nhng pha c dn ion cao nh Ag3SI, Ag7I4PO4, Ag6I4WO4. c bit hp cht Ag6I4WO4 kh bn nhit v khng b nh hng ca m cng nh hi it. Mt hng l th l tng hp cc cht in li rn dng thu tinh bng cch ti nhanh n nhit phng cc hn hp nng chy gm AgI vi mt trong cc hn hp sau: Ag2SeO4, Ag3AsO4, Ag2Cr2O7.
c) Cht dn anion halogen

V d PbF2 c cu trc kiu florit nhit phng l tinh th ion in hnh c dn ion rt b, nhng trn 500oC c dn ion t ti 5 m1cm1. iu c bit ng quan tm l ng dn ph thuc vo nhit khng thay i t ngt do thay i cu trc tinh th nh trng hp AgI (hnh 139) m tng u t ti gi tr cc i 500oC, trn nhit tng khng ng k na, cn khi nng chy, thm ch dn cn hi gim (822oC). Tng t PbF2, hp cht SrCl2 c dn ion cao 700oC cho ti nhit nng chy (873oC). Cn CaF2 ch n nhit nng chy (1418oC) mi t dn ion ng k. C ch dn ion ca cc halogenua c cu trc florit hin nay cha r. y cn quan tm trong cu trc florit l khong trng ca tm t bo c bao quanh bng 6 ion Ca2+ v 8 ion F c kch thc kh ln, phi chng iu ny thun li cho s chuyn dch ion.

138

lg (m-1 cm-1) 1
2 3 4

Tnc

1
Hnh 147 dn ca PbF2

-1 1000/T(K )

d) Cht dn anion O2

ZrO2 nhit cao c dng th hnh lp phng kiu florit, dng ny c th tn ti bn nhit phng to dung dch rn vi CaO, Y2O3 v.v Oxit zirconi c bn ho nh vy nhit cao c tnh dn ion O2. C th iu ny do tch lu nhiu l trng O2 khi to dung dch rn vi ion dng thiu in tch. Thnh phn dung dch rn c th vit (CaxZr1-x)O2-x vi 0,1 < x < 0,2. Ngha l c a vo mt ion Ca2+ th lm xut hin mt l trng O2. dn ca ZrO2 khi bn ho bng 15% mol CaO, 1000oC l 5.102 m1cm1 v nng lng hot ho dn bng 1,3 eV. Vt liu ny nhit thp c dn ion rt b.
4.1.1.3 Vn nghin cu tm kim cc cht in li rn mi

C th tm tt cc iu kin c bn i vi cht in li rn l: 1. 2. 3. C nng ion linh ng cao (ngha l gi tr n trong phng trnh = n.e.m phi ln). C nhiu v tr cn trng cho ion linh ng. Nng lng ca v tr b chim v ca v tr cn b trng khng khc nhau lm, hng ro hot ha nh khi chuyn ion t v tr ny n v tr khc bn cnh. S c mt mt s ln v tr b trng c th l v ch nu nh ion vn chuyn khng th ri vo v nng lng hot ho cao. C mt cc knh, rnh m dch chuyn cc ion linh ng trong cu trc. Phn mng anion d b phn cc.

4. 5.

Trong -Al2O3 v ZrO2 bn vng ho, p ng 4 iu kin u cn trong cht dn Ag+ tho mn c 5 iu kin. Cc vt liu m tnh dn ion thp v cn thiu mt trong cc iu kin trn. V d nhiu silicat c cu trc khung nhng linh ng ca cation trong km v hng ro nng lng qu cao. Vic tm kim cht in li rn mi cho php pht hin c mt s hp cht c cu trc khung v linh ng cao ca cation. Mt trong cc hp cht kh l th l Na3Zr2PSi2O12 do cc tc gi Hong, Kafalac, Gudenaph tm ra v ngh gi l NASICON (t ting Anh Na+ Superionic Conductor). Cu trc khung ca NASICON gm cc bt din ZrO6 v cc t din (P,Si)O4 t hp vi nhau qua nh. Trong cu trc c mt h thng rnh to thnh li

139

khng gian, trong cc rnh c cha Na+ linh ng. dn Na+ ca NASICON cng tng ng vi -Al2O3. Zeolit c cu trc khung v cc hc trng vi ng knh ln cng c th lm cht in li rn. Tuy nhin thc t dn ion thp. Cc cation nm trong cu trc zeolit thng b hirat ho v d trao i nhng linh ng khng cao. Khi kh hirat ca zeolit c th lm cho cc rnh tr nn qu rng dn n vic cc cation np vo cc vch rnh, tng t nh Li+-Al2O3, do kch thc qu b ca Li+ nn chng nm p vo cc vch rnh lm cho dn ca Li+-Al2O3 b hn nhiu so vi dn ca -Al2O3. Nhu cu vt liu c dn Li+ kh ln do ngun in vi dng cc liti c sc in ng cao hn ngun in tng t nhng dng cc l Na+. Li2SO4 c nhit chuyn pha 572oC, dn Li+ ca pha nhit cao c gi tr khong 1 m1cm1 nhng nhit thp dn gim hn. Vic nghin cu thm tp cht lm n nh pha nhit cao cng ch h n 400oC. Li4SiO4, Li4GeO4 c dn Li+ trung bnh (khong 104 m1cm1) cu trc ca cc cht ny l cht nn thun li thm cc ph gia khc nhau. Cc hp cht ny gm cc t din ring l SiO4 v GeO4 to thnh cc mng li gm khong trng a din c mt chung, Li+ nm trong . C th tin hnh cc phn ng thay th. Li+ + Si4+ Si4+ 2Li+ P5+ Zn2+ (trong Li4SiO4) (trong Li4GeO4) Al3+ + Li+ (trong Li4SiO4)

S thay th nh vy c tc dng lm tng dn ion ca cht nn ln vi bc khong nhit khng cao lm (2030oC). Cht dn tt nht trong khong nhit trung bnh l Li14ZnGe4O16 (gi l LISICON) 300oC c = 101 m1cm1. Cht dn nhit phng th c Li3,5V0,5GeO0,5O4 c = 105 m1cm1. Mt pht hin bt thng khi nghin cu hn hp LiI v Al2O3. Trong hn hp ny khng c du hiu g chng t c phn ng ho hc nhng dn ca hn hp ng phn t gam cao hn vi bc so vi dn ca LiI nguyn cht (Al2O3 nguyn cht l cht cch in) v bng 105 m1. Nguyn nhn ca hin tng ny cha c gii thch nhng c th c lin quan n tnh dn b mt dc theo bin gii cc ht LiI v Al2O3.
lg (m-1 cm-1) 1
2 3 4
5 6 7 1000 500 300 100 25

Li Al2O3

Li2SO4 Li3,4Si0,4V0,6O4 Li4SiO4

0 1,0 Hnh 148 + dn ca vi cht dn Li

2,0

3,0

4,0

140

C nhiu cng trnh nghin cu tm kim cht dn proton. Hin bit c c hai cht l H3O+-Al2O3 v axit uranin photphat HUO2PO4.4H2O 25oC c dn 4.10 2 m1.cm1.
4.1.1.4 ng dng cht in li rn

1) Nguyn l lm vic ca pin in ho bng cht in li rn Trn c s cht in li rn c th ch to c cc loi pin in ho dng gii quyt cc nhim v khoa hc k thut khc nhau, chnh iu ny l nguyn nhn thc y vic nghin cu cc loi vt liu c dn ion. Hnh 149 trnh by s mt pin in ho lm bng cht in li rn. A1 v A2 l khng gian in cc c th l pha lng, pha rn, hoc pha kh vi bn cht ho hc ging nhau hoc khc nhau. V d A1 v A2 u l oxi nhng vi p sut ring phn khc nhau, hoc A1 l natri, A2 l lu hunh.

A1

cht in li rn

A2

Hnh 149 Pin in ho bng cht in li rn

S (E)

Sc in ng (S) pht sinh ra trong pin c tnh theo phng trnh Nest: E = Eo + RT ln [oxi ho]
nF [kh]

(40)

Ti mi bin gii in cc cht in li thit lp mt th oxi ho - kh. V d trn ant c qu trnh oxi ho M = M+ + e. ng vi th oxi ho kh:
E1 = E o + M / M+ RT [M + ] ln F [M]

o trong E M / M + l th oxi ho kh tiu chun ca phn ng , [M+] v [M] l nng

cc tiu phn, F l hng s Faraay (96500 C). Ion M+ pht sinh ra ant chuyn ng qua cht in li rn sang phn ng vi anion X bn catt l sn phm ca phn ng X + e = X ng vi th oxi ho kh:
+ E2 = Eo X / X RT [X] ln _ F [X ]

Tng i s E1 v E2 l sc in ng (S) ca mch, lin quan n gi tr th ng p G ca phn ng xy ra trong pin X + M MX theo h thc: G = nEF (41)

141

Pin in ho vi cht in li rn c th p dng nghin cu nhit ng hc xc nh gi tr G ca nhiu phn ng trong pha rn. V d pin Ag(r)AgI(r)Ag2S(r), Slng, C(r) c s dng xc nh gi tr G ca phn ng xy ra trong pin 2Ag + S Ag2S. V Ag v S u trng thi tiu chun nn G o Ag S = 2EF.
2

Bng thc nghim xc nh c s ph thuc ca sc in ng (S) vo nhit ta c th tnh c entropi, entanpi ca phn ng. 2) Ch to cc ngun in Trn c s cht in li rn c th ch to ra cc ngun in. Trong cc pin s dng cht in li rn quan trng i vi k thut c l l pin S Na trong s dng cht in li rn l Na+-Al2O3. y l loi acquy c in dung ring ln (tnh theo n v khi lng) v c cng sut cao. Acquy lu hunh natri u tin c dng cho xe in v h thng cn bng cng sut cc nh my in, hin nay nhiu nc tin hnh ci tin hon thin loi acquy ny. y l loi acquy kh n gin, c th m t nh trn hnh 150. Cht in li rn -Al2O3 ngn cch natri lng (ant) v lu hunh lng (catt). Cht in li rn c lm thnh mt ng rng bt kn mt u, pha trong cha natri lng, pha ngoi l lu hunh lng (c th t ngc li). V lu hunh lng l cht c lin kt cng ho tr khng dn in nn catt c ch to bng pht graphit tm lu hunh. V ngoi ca acquy lm bng thp khng r ng vai tr cc gp. Khi phng in trong pin xy ra phn ng: 2Na + xS Na2Sx
natri cht cch in Al2 O3 cht in li rn Al2 O3 lu hunh (trng thi tch in) hoc sunfua natri (tch in)

Hnh 150 Pin lu hunh natri vi cht in li rn -Al2O3

Phn ng: 2Na + 5S

Na2S5 (2,08 V)

giai on u phng in x c gi tr bng 5, ng vi cng thc sunfua giu lu hunh nht Na2S5. Theo qu trnh phng in gi tr x gim. Hnh 151 l gin trng thi ca h Na S. Pin ny vn hnh 300 350oC. Gin cho thy l ngng nhit thp nht gi trng thi lng ca sn phm phng in (cc hp cht sunfua natri) trong mt khong thnh phn kh rng. Trong qu trnh phng in gi tr x 3 (ng vi 60% S, 40% Na) th c kh nng bt u xut hin tinh th Na2S2, nu phng in tip s lm khi catt ho rn dn. in p cc i khi lm vic 300oC t 2,08 V. Khi phng in t gi tr x = 3 in p gim n 1,8 V. Gi tr l thuyt v in dung ca acquy ny t 750 W.gi/kg nhng trn thc t ch t c 100 200 W.gi/kg.

142

C
+

500

Na2S lng

lng
Na2S5 + lng

400

Na2S
300

Na2S2

Na S Na2S2 + 2 4 lng + lng

hai pha lng

200

Na2S2
+

Na2S5

lng

100

Na2S4

Na2S5 + S
60 80 90

Na Na2S2

Na2S4

Na2S5

Hnh 151 Gin trng thi h Na S

Cc loi pin lm bng cht in li rn khc c u vit l to c ngun in vi kch thc rt b. Cc ngun in ny c s dng cung cp cho ng h in t v mt s thit b cho mc ch qun s. Trong s cc h in ho lm vic tt i vi mc ch ny thng s dng hai loi pin sau: AgRbAg4I5I2 LiLiII2
E khng kh
O
2-

(0,65 V) (2,80 V)
1/2O2 + 2e O2ZrO 2 (CaO) O
2-

1/2O2 + 2e

P' O

P'' O2 (khng kh)

(a)

P' O

P'' O

(b)

cht in li rn cc in cc xp 2e Hnh 152 Pin nng oxi vi cht in ly rn bng ioxit zirconi n nh
2e

Thng ngi ta s dng cc phc ca it nh (CH3)4NI hoc phc c cha anion poliiotit v phc chuyn dch in tch (poli-2-vinyl pyriin) thay th it. Pin LiI2 rt thun tin s dng trong cardiosti-mulator 37oC, mt dng 110 microampe/cm2, nng lng ring t 0,8 W.gi/cm3 c th s dng trn 10 nm. 3) Cc cm bin v pin nng oxi Pin in ho vi cht in li rn c th s dng o p sut ring phn ca kh hoc nng kh tan trong cc cht lng. Hnh 152 trnh by s mt pin nng bng cht in li rn l ZrO2 (CaO). Thit b gm mt ng bt kn di, trong ng c kh bit p sut ring phn oxi (v d khng kh). Bn ngoi v ng c ph bng kim loi xp dng lm in cc v c th cho oxi khuch

143

tn ra vo. Hnh 152b l s dch chuyn ion oxi qua cht in li rn v cc phn ng in cc xy ra khi PO2 < PO2. S ca pin lin quan n thng s p sut ca oxi.
'' RT PO 2 E= ln ' 4F PO 2

(42)

V rng ZrO2 n nh bng CaO c dn ion tt ch nhit cao nn loi pin ny c kh nng lm vic trong khong nhit 500 1000oC, lc c th o c p sut ring phn ca oxi ti 1016 atm. Cht in li rn trn c s ThO2 n nh c th o c p sut ring phn ca oxi b hn na. Pin nng oxi cng tng t nh loi u d ZrO2 (CaO) c nhiu ng dng rng ri, c bit trong phn tch kh thi, o lng s hp th oxi khi th, nghin cu nhng cn bng kh v oxit kim loi (CO/CO2, H2/H2O) v o hot ca oxi ho tan trong kim loi nng chy.
4) Pin nhin liu

Oxit zirconi n nh lm di dng hnh ng hoc dng a c s dng trong cu to pin nhin liu lm vic nhit cao. Trong c mt khng gian in cc cha oxi hoc khng kh, cn khng gian in cc kia cha kh chy, v d H2 hoc CO. Bn ngoi cht in li rn y cng ph cc in cc kim loi xp. Trn b mt cc in cc xy ra cc phn ng: H2 + 1/2O2 H2O hoc CO +1/2O2 CO2 u vit ca pin nhin liu l khng bao gi c s phn cc ho in cc v c th cung cp mt dng cao (0,5 A/cm2), nng lng ring cao (0,5 W/cm2). Tuy nhin, khi s dng cc pin nhin liu cn quan st ch hm nng chm chp n nhit lm vic. V cu trc ang i hi phi gii quyt nhiu vn . Qu trnh xy ra trong pin nhin liu l thun nghch: thay i hng ca dng li c th phn hy hi nc thnh oxi v hiro. S in phn nhit cao nh th c th s dng tch tr in nng di dng ho hc. Trong nhng trng hp khc c th s dng phn ng loi ny y oxi ra khi CO2 s dng trong cc con tu v tr hoc ui oxi ra khi kim loi lng

4.1.2 Cht dn electron

Cc vt liu dn in vi cht mang in tch l electron gm kim loi, cht bn dn (nu tnh n dn rt b ca cht in mi th c th xp c cht in mi vo loi ny). Nhng phn sau s thy khi gii thch c ch dn in ca cht bn dn ngi ta phn thnh cht bn dn loi n (dn electron) v bn dn loi p (dn l trng dng). Cht bn dn loi n th khng phi bn ci na v cht mang in y l electron, cn cht bn dn loi p v thc cht cng do s dch chuyn electron theo chiu ngc li. Do y chng ta xp vo loi vt liu dn electron. Trong bng 31 chng ta thy, da vo dn in ngi ta quy c gi cht dn in kim loi l cht c dn cao ( = 102 106 m1cm1), cht in mi (hay cn gi l cht cch in) l cht c dn rt b (<1012 m1cm1 ), cht bn dn c gi tr dn trung gian (khong 105 102 m1cm1). im khc nhau c bn trong c ch dn in ca loi vt liu ny l s ph thuc ca dn in vo nhit . Cht bn dn cng nh cht in mi c dn in tng khi tng

144

nhit , trong khi kim loi th dn in gim khi tng nhit . V rng dn in c xc nh theo h thc (33) = n.e.. Do s ph thuc ca dn in vo nhit c quyt nh bi s ph thuc ca ba thng s n, e, , vo nhit . Vi tt c cc cht dn electron th e l gi tr khng i v khng ph thuc vo T. Do ch cn xt n s ph thuc vo T ca n v . Ni chung, khi tng nhit th linh ng ca cht mang in gim v tng cng va chm gia electron vi phonon (do s tn x electron trong h nt giao ng ca mng li tinh th). Bi vy, s khc nhau gia kim loi v cht bn dn ch yu lin quan n s ph thuc n vo nhit . Kim loi c nng cht dn in rt ln v khng thay i khi thay i nhit T. i lng duy nht lm thay i ch l . V gim khi tng nhit nn ca kim loi gim khi tng nhit . Vi cht bn dn v cht in mi th khi tng nhit n tng rt nhanh theo cp s lu tha, do tuy c hi gim nhng vn tng nhanh. Vi ngha ny cht in mi c th xem nh l trng hp gii hn, v rng nhit thp gi tr n rt b. nhit cao n tng ln lm cho dn in ca mt s cht in mi c th t gi tr dn in ca cht bn dn, ngc li nhit thp mt s cht bn dn c th tr thnh cht in mi. Trong phn ny chng ta kho st cc cht bn dn.
4.1.2.1 Thuyt vng nng lng ca vt liu rn

Theo phng php obitan phn t chng ta c th hnh dung s to thnh cc vng nng lng trong mng li tinh th nh sau: cc nguyn t ring l (khi chng xa nhau nh trong pha kh) th electron chim cc mc nng lng hon ton xc nh. S chnh lch gia hai mc nng lng E1 v E2 ng vi mt bc x c tn s xc nh trong vch quang ph E2 E1 = h (trong h l hng s Plank, l tn s bc x). Khi cc nguyn t dch li gn nhau nh trong mng li tinh th th cc obitan nguyn t s b phn tch ra. V d t hp 2 obitan nguyn t 1s to thnh hai obitan phn t lk v plk vi nng lng khc nhau l Elk < Es < Eplk. Nu t hp n nguyn t s to thnh N mc nng lng khc nhau ca N obitan phn t. V d vi 1 cm3 kim loi th gi tr N t ti khong 1022 n 1023 nguyn t. Do N mc nng lng ny to thnh mt vng nng lng lin tc. S sai khc ca cc mc nng lng trong vng ny ch khong 1022 eV. Theo nguyn l Paoli th mi obitan phn t cng nh obitan nguyn t ch c ti a hai electron. Do s electron cc i trong cc vng nng lng to thnh khi t hp cc obitan nguyn t s, p, d, f s l 2N (vng s), 6N (vng p), 10N (vng d), 14N (vng f). Vng nng lng c lp y cc electron, gi l vng ho tr, cc electron y gi vai tr lin kt trong mng li tinh th. Vng nng lng cn trng (cao hn vng ho tr) gi l vng dn. Nu trong vng ny c mt electron th chnh nhng electron ny s l cht mang in tch trong qu trnh dn in. Ty thuc vo cu trc nguyn t v mc i xng ca tinh th m vng ho tr v vng dn c th xen ph nhau (hnh 154), hoc khng xen ph nhau (hnh 155). Trong trng hp khng xen ph nhau th vng ho tr v vng dn cch nhau mt khong nng lng gi l vng cm Eg. Ty theo gi tr vng cm ngi ta phn ra thnh cc cht cch in (Eg > 3eV), cht bn dn (Eg < 3eV). Cht dn in kim loi th khng c vng cm (Eg = 0).

145

Mc nng lng E

16

S nguyn t
Hnh 153 S hnh thnh vng nng lng khi cc nguyn t dch li gn nhau trong mng li tinh th

V d hnh 154 trnh by s cu trc vng nng lng ca kim loi natri. Trn hnh v cho thy rng ca cc vng nng lng ph thuc vo khong cch gia cc nguyn t natri trong mng li tinh th. khong cch ro (gi tr o c bng thc nghim), cc obitan 3s v 3p ca cc nguyn t cnh nhau trong tinh th xen ph vo nhau to thnh mt vng nng lng lin tc kh rng. khong cch cc obitan 1s, 2s, 2p ca cc nguyn t cnh nhau khng xen ph vo nhau m vn nh v cc mc nng lng hon ton xc nh thuc v tng nguyn t ring r. iu ny c ngha rng trong tinh th natri, electron 3s c chuyn ng trong vng nng lng lin tc (vng xen ph 3s v 3p) trong ton b tinh th. Cn cc electron 1s, 2s, 2p th nh v hon ton ph thuc v tng nguyn t ti cc nt mng. Nu nh tng tng khi nn tinh th natri vi mt p lc ln cho khong cch gia cc nguyn t dch gn li n v tr r th cc obitan 2s v 2p s xen ph vi nhau to thnh vng nng lng lin tc (vng 2s v 2p) v lc cc electron ny khng nh v na m c th chuyn ng trong khp mng li, ngha l tham gia vo lin kt, nhng khong cch gi thit cc electron 1s vn nh v mc hon ton xc nh thuc v tng nguyn t ring bit. Gi thit ny cng c th t ra i vi vic nn cc n cht khc. V d t s tnh ton cho thy khi nn vi p lc 106 atm c th to thnh hiro kim loi. nng lng 3p 3s 2p 2s 1s r' ro

Hnh154 nh hng ca khong cch gia cc nguyn t ln v tr cc mc nng lng v vng nng lng trong tinh th natri kim loi

Cu trc vng nng lng ca cc nguyn t thuc phn nhm chnh nhm IV trong bng h thng tun hon c m t theo cch khc. Trong khi natri kim loi c mng li lp

146

phng tm khi (s phi tr l 8) th C, Si, Ge, Sn (xm) c mng li tinh th kiu kim cng, mi nguyn t u nm v tr tm ca t din ngha l c bao quanh bi 4 nguyn t khc. 3N OA 3p Min cm N OA 3s 2N obitan phn lin kt cn trng
Eg

2N obitan lin kt bo ho electron

Hnh 155 M hnh vng nng lng trong tinh th silic

V d Si c cu hnh electron ca lp v ngoi cng l 3s2 3p2. Bn electron ny u nm trn obitan nguyn t lai ho sp3. Khi cc nguyn t Si gn li nhau trong mng li tinh th th mt obitan nguyn t lai ho sp3 ca nguyn t ny t hp vi obitan nguyn t lai ho sp3 ca nguyn t bn cnh to thnh hai obitan phn t: obitan lin kt (c nng lng thp hn nng lng ca obitan nguyn t lai ha sp3) v obtan phn lin kt * (c nng lng cao hn nng lng ca obitan nguyn t lai ho sp3). Hai vng nng lng: vng gm cc obitan lin kt (vng ho tr) v vng gm cc obitan phn lin kt (vng dn) cch nhau mt khong nng lng (gi l vng cm). i vi tinh th Si th vng ho tr c lp y electron, vng dn cn trng. rng ca vng cm c gi tr 1,1 eV.
e- eevng dn e-

vng cm
+ + + +

vng ho tr
Hnh 156 Hng chuyn dch ca cht mang in trong bn dn

Bng 33 rng vng cm ca cc nguyn t nhm IV Nguyn t Kiu mng SPT li Cacbon (C) Kim cng Silic (Si) Kim cng Gecmani (Ge) Kim cng Thic xm (Sn) Kim cng Thic trng (Sn) T phng Ch (Pb) Lp phng mt tm

4 4 4 4 6 12

rng vng cm (eV) 6,0 1,1 0,7 0,1 0 0

c tnh Cch in Bn dn Bn dn Bn dn Kim loi Kim loi

Di tc dng kch thch bn ngoi (nhit , nh sng,) electron vng ho tr c th nhn c nng lng nhy sang vng dn. Khi nm trong in trng, electron trong vng dn chuyn ng v in cc dng, cn vng ho tr im c mt electron nhy sang vng dn s tr thnh l trng dng. Do tc dng ca in trng ngoi, electron ca

147

nt mng bn cnh v pha cc m nhy sang l trng dng. Do dng in chuyn dch trong vng ho tr c th dng nh cc l trng dng chuyn dch v pha in cc m (hnh 156).
4.1.2.2 Cc loi cht bn dn

Cht bn dn c th phn thnh hai loi:

a) Cht bn dn l nguyn t nguyn cht nh Si, Ge, thic xm. Cc cht bn dn loi ny c s electron trong vng dn hon ton xc nh bi rng ca vng cm v nhit . Nu gi nE l lng tng i electron c nng lng E, nng lng Fermi-Dirac ta c:
nE = 1 E Ef +I e kT
_

(43)

Khi EEf >> kT th hm phn b Fermi-Dirac tr thnh hm b Boltzmann n gin hn:

n E = e( EEf ) / kT

(44)

Vi cht bn dn l nguyn t nguyn cht th s electron trong vng dn bng s l trng dng trong vng ho tr, mc Fermi nm gia vng cm. Nng lng cn thit chuyn electron vo vng dn ch bng Eg/2, v lng electron chuyn vo vng dn s l:

n = A.e

E g / 2 kT

2mkT 2 2 h

3/ 2

.e E / 2kT

(45)

y m l khi lng electron, h l hng s Plank. Di tc dng ca in trng ngoi electron trong vng dn chuyn v dng cc, l trng dng trong vng dn i v m cc. Gi tr dn ring theo electron() t l vi nng cht mang dng v linh ng ca chng.

= e.(ne + ph)

(46)

y e l in tch electron, n l lng electron chuyn ng trong 1cm3, p l lng l trng dng, e, h l linh ng ca electron v ca l trng dng (vi cht bn dn l nguyn t nguyn cht th n = p). linh ng ca cht mang dng ch lin quan n s phn b cc loi khuyt tt trong mng tinh th.
b) Cht bn dn tp cht l cht bn dn trn nhng c a thm tp cht vo ( d hiu chng ta gi l cht bn dn do a tp cht vo). Chng ta kho st cc vng nng lng thay i ra sao khi a tp cht vo Si nguyn cht. V d a mt lng rt t Ga vo tinh th Si to thnh dung dch rn thay th. V rng Ga ch c 3 electron ho tr, do trong t din GaSi4 ch c 3 lin kt cng ho tr bnh thng, cn mt lin kt GaSi gi l lin kt thiu electron. Theo thuyt vng nng lng th lin kt mt electron ng vi mc nng lng khng nm trong vng ho tr ca silic, m to thnh mt mc nng lng ring bit hi cao hn mc nng lng cao nht ca vng ho tr (ngha l nm ngay st pha trn ca vng ho tr). Mc nng lng ny gi l mc nhn cch vng ho tr khong 0,1 eV. Do , ch vi s kch thch nhit rt b l electron t vng ho tr s nhy vo li l trng dng trong vng ho tr. Nu nng Ga t hn th mc nhn phn tn v e y khng tham gia vo phn gp ca dn in. Di nh hng ca in trng ngoi, l

148

trng dng trong vng ho tr i v pha cc m. Nh vy, thm tp cht Ga vo th Si tr thnh cht bn dn loi p.
(a) Si
X O

Si
O X

(b) Si
X O
X O

Si
O X thiu mt electron X O

(c) Si
X O

Si
O X mt electron d X O

Si
X O

Ga
X O

As
X O

Si
1,1eV

Si

Si

Si
e

Si

Si

vng dn e
0,1eV

vng dn
0,1eV

vng dn e e e vng ho tr

mc cho

e mc nhn

vng ho tr

vng ho tr

Hnh 157 Tnh dn in ca Si nguyn cht

(a) Si nguyn cht; (b) Si c tp cht Ga - l cht bn dn loi p; (c) Si c tp cht As - l cht bn dn loi n. Nu tp cht thuc nhm V, v d As vo Si th As cng thay th mt v tr ca Si trong t din. By gi trong t din AsSi4 c mt electron d nguyn t As. Electron d ny c mc nng lng xc nh nm trong vng cm ngay st pha di vng dn v cch vng dn mt khong bng 0,1 eV. Mc nng lng ny gi l mc nng lng cho v ch cn kch thch nhit khng ln l electron mc ny s nhy vo vng dn v tham gia dn in, to thnh cht dn loi n. Chng ta c th phn bit cht bn dn nguyn cht v cht bn dn a tp cht vo nh sau:

dn in ca cht bn dn tp cht ( nhit phng) cao hn dn in ca cht bn dn nguyn cht. V d 25oC Si nguyn cht c dn in khong 102 m1cm1, khi thm tp cht vo dn in tng ln vi bc. dn in ca cht bn dn tp cht c th xc nh chnh xc bng nng tp cht a vo. iu ny c s dng khi tng hp cc vt liu xc nh. Cn dn ca cht bn dn nguyn cht th ph thuc vo nhit v tp cht ngu nhin.

149

lg(n)
3 2 1

lg() (a)
3 2

(b)
1

T1

Hnh 158 S ph thuc vo nhit ca nng cht mang in (a) v dn (b) trong cc cht bn dn 1 - Vng dn tp cht; 2 - Vng bo ho; 3 - Vng dn ca cht nguyn cht

dn ca vt liu bn dn phi km nhy vi s thay i nhit (vng 2). cho vng bo ho 2 tht rng phi dng hai phng php: 1) Chn vt liu c vng cm rng. 2) a vo cht bn dn nhng tp cht to ra vng nhn (hoc vng cho) nm gn mp vng ho tr (hoc vng dn). Trong hai trng hp ny vng 1 chuyn v pha nhit thp, cn vng 3 chuyn v pha nhit cao.
4.1.2.3 Nguyn tc tng hp gm bn dn

Ngoi cc loi bn dn trn y cn c th k thm mt s loi vt liu bn dn khc nh:

Hp cht gia nguyn t nhm III v nhm V (gi l hp cht AIIIBV) (v d GaAs, InSb); hp cht gia nguyn t nhm II v nhm VI (gi l hp cht AIIBVI) (v d CdTe, ZnS, ZnTe). Gm oxit v gm hp cht gia cc oxit.

Ni chung tnh bn dn ca cc cht rn v c c quyt nh bi cc khuyt tt trong mng tinh th do a tp cht vo, hoc bi s sai khc vi thnh phn hp thc do to thnh cc nt mng trng trong mng... Phng php tng hp gm bn dn c da trn c s iu chnh cc khuyt tt ca mng li tinh th. iu ch cc vt liu ny c th s dng cc oxit kim loi chuyn tip t Sc n Ni. l cc nguyn t c phn mc 3d cha c lp y. Trong c th k n Cr2O3, MnO, Fe2O3, CoO, NiO v cc hp cht gia cc oxit nh ZnFe2O4, MgCr2O4, LaMnO3 iu ch gm bn dn c th s dng 3 phng php l phng php iu chnh ho tr, phng php iu ch hp cht bt hp thc, phng php pha long. + Phng php iu chnh ho tr l a cc ion l vo mng tinh th ca oxit kim loi c ho tr thay i. Cc loi gm bn dn iu ch theo phng php ny da vo hp cht cc h NiOLi2O, NiOCr2O3, Li2OZnO.

150

Ni2+ O2 Ni2+ O2 Ni2+ Ni2+ O2 Ni2+ O2 Ni2+ Ni2+ O2 Ni2+ O2 Ni2+ 22+ 2 2+ 2 2 2+ 2 3+ 2 2 2+ 2 3+ 2 O Ni O Ni O O Ni O Ni O O Ni O Ni O 2+ 2 2+ 2 2+ 2+ 2 2 2+ 2+ 2 + 2 2+ O Ni Ni O Ni O Ni Ni O Ni O Li O Ni 2 2+ 22+ 2 2 3+ 2 2+ 2 2 2+ 2 2+ 2 Ni O Ni O Ni O Ni O O Ni O Ni O O O ( a) (b) (c) Hnh 159 Mng li niken oxit: hon chnh (a); tha oxi (b); thm tp cht Li+ (c )

V d i t oxit niken (NiO) tinh khit l cht rn mu xanh nht v l cht cch in. Mu ca n l do s dch chuyn d d trong Ni2+ v tr phi tr bt din. Khi oxi ho nh NiO trong khng kh, v d 1000oC th niken oxit tr thnh mu en v dn in tng ln 2+ 3+ ng k. Sn phm oxi ho c th biu din theo cng thc: Ni1 3x Ni 2x Vx O (hnh 159b). Khi oxi ho th oxi t pha kh i ti b mt tinh th, mt phn Ni2+ khuch tn t trong ln b mt cn bng in tch d v c s xut hin ng thi vi l trng cng vi ion Ni2+ bin thnh Ni3+. Oxit niken en dn in l do electron i t Ni2+ ti Ni3+: Ni2+ Ni3++ e Ni3+ Ni2+ + p S dch chuyn electron nh vy c th xem nh s dch chuyn ca Ni3+, do niken oxit l cht bn dn loi p. Tnh dn in ca niken oxit c c ch nhy. V s trao i electron trong h Ni2+/Ni3+ l do qu trnh kch ng nhit, nn s trao i ph thuc vo nhit . Theo quan im ca thuyt vng nng lng c th gii thch rng cc obitan d ca niken xen ph yu vo nhau, do hnh thnh mt vng nng lng d tng i hp. Tuy nhin, cht bn dn niken oxit thng khng c s dng v rng kh iu chnh tnh bn dn in. Tnh dn in ca n va ph thuc vo nhit li va ph thuc vo p sut ring phn ca kh quyn oxi ho NiO. trnh iu ny c th a vo y mt tp cht iu chnh ho tr, v d a ion Li+ vo v tr ca ion Ni2+ n nh v tr Ni3+ khc (hnh 159c). Oxit liti tham gia to dung dch rn vi oxit niken cho thnh phn ng vi cng thc 3+ +2 +3 Li x Ni1 (v do dn) ch ph 2x Ni x O . Trong dung dch rn nh vy, nng ca Ni + thuc vo nng tp cht Li m khng ph thuc vo p sut ring phn ca oxi na. 25oC dn thay i rt mnh khi thay i thnh phn. Khi x = 0 c dn vo khong 1010 1 cm1, khi x = 0,1 dn t 0,1 1cm1 (hnh 160) . Theo phng php ny c th iu ch c nhiu cht bn dn. V d: (Sr1-xLax) (Ti1-xFex)O3 Zn(TixFe2-2xFex)O4 Tix(Fe2-2xFex)O3 (SbxSn1-2xSnx)O2 (cu trc kiu perpskit) (cu trc spinen) (cu trc hematit) (cu trc rutin)

+ Theo phng php iu ch hp cht bt hp thc, ngi ta p mt mu bt oxit kim loi ri nung trong mi trng oxi ho hoc mi trng kh. Ph bin nht l nung trong kh quyn ca kim loi . V d mu TiO2 nung trong hi Ti, mu ZnO nung trong hi Zn, mu FeO nung trong hi Fe

151

2+ 3+ Thnh phn ca vt liu bn dn thu c khc vi hp thc. V d Fe1 3x Fe 2x y l l trng. Gi tr ca x = 0,1.

x)O.

dn 10 ring m-1cm-1 1
10-1 10-2
-3 10 35

9,05% 2,4%
0,1 %Li2O

0,01 %Li2O
30 25 20

1/T

Hnh 160 S ph thuc ca dn niken oxit vo lng tp cht + Li Ni2+ O2 Ni2+ O2 O2 Ni3+ O2 Ni2+ 2+ O2 O2 Ni 2 2+ 2 Ni O Al3+ O Hnh 161 a Al2O3 vo NiO

dn in ca loi bn dn ny l do s c mt ca l trng. + Ni dung ca phng php pha long l trn ln cht dn in, cht bn dn vi cht khng dn in to thnh dung dch rn. V d cht bn dn hnh 159c, by gi thay th mt v tr Li+ v mt v tr Ni2+ bng ion Al3+ s lm xut hin thm mt l trng (hnh 161).

4.1.3 Cc tnh cht in khc

4.1.3.1 Hin tng nhit in v pin nhit in

Khi cho hai kim loi (hoc hp kim) khc nhau tip xc vi nhau th ti ch tip xc xut hin mt sc in ng E. Sc in ng ny ph thuc vo bn cht ca kim loi v vo nhit ca ch tip xc. S d c sc in ng ch tip xc l v mi kim loi (hoc hp kim) c mt nng electron ho tr bnh qun khc nhau. Bn c nng electron cao c th chuyn electron v bn c nng electron thp. Nhng kh nng chuyn electron nh vy cn ph thuc vo nhit ch tip xc.
V d: Ta cho ba si dy A, B, C hn tip xc vi nhau nh hnh 162. Gi s nhit T1 v T2 khc nhau th trong mch kn CABC s pht sinh ra mt dng in lm quay in k D. Sc in ng pht sinh ra trong mch CABC l E = VAB + VBC + VCA.

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T2 T1 A B T2
Hnh 162 S mch nhit in

C D C

Mt khc theo Pencher th sc in ng pht sinh ra mt mi hn ca hai si dy AB l: VAB = VB VA +

kT n 0 A ln e n 0B

(47)

y k l hng s Boltzmann, e l in tch electron, T l nhit ti ni tip xc hai si dy, n0A v n0B l nng electron bnh qun ca mi si dy. Vy trong mch kn CABC ta c: VAB = VB VA + kT1/e.ln.(n0A/n0B) VCA = VA VC + kT2/e.ln.(n0C/n0A) VBC = VC VB + kT2/e.ln.(n0B/n0C) E = VAB + VCA + VBC =
kT1 n 0 A kT2 + ln e n 0B e
n 0B

ln

n 0C n + ln 0 B n 0A n 0C

kT n E = kT1 ln n 0 A + 2 ln 0 B
e

n 0A

E=

n k1 (T1 T2 )ln 0A e n 0B

(48)

Ngha l sc in ng ca mch CABC ch ph thuc vo bn cht ca hai kim loi A v B, hiu s gia T1 v T2. i vi mt cp dy nht nh, khi gi nhit T2 c nh th sc in ng nhit E pht sinh ra trong mch ch ph thuc vo nhit T1. l nguyn tc ca vic s dng pin nhit in o nhit . Thng thng nhit T2 c gi 0oC (hn hp nc v nc ). Yu cu i vi mt cp nhit in l: Sc in ng nhit ln v thay i tuyn tnh theo nhit T1; Bn i vi mi trng oxi ho kh, khng b n mn (c bit nhit cao). nh gi sc in ng nhit ca cc kim loi v hp kim, ngi ta thng xc nh gi tr E ca pin nhit in c mt dy l kim loi hoc hp kim mun o, cn mt dy l platin nguyn cht, nhit T2 gi 0oC cn nhit T1 gi 100oC. Nu k hiu kim loi so snh l S, ta c:
T2 T2 T ET = ET ET (S / B ) 1 (A / B) 1 (A / S)
2 1

(49)

Ta c th da vo h thc tnh sc in ng nhit ca mt pin nhit in bt k khi nhit T2 l 0oC cn nhit T1 l 100oC.

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V d tnh sc in ng nhit ca pin cromen alumen trong iu kin T2 l 100oC, T1 l 0oC. Ecromen alumen = Ecromen Pt Ealumen Pt = + 2,95 (1,2) = 4,15 (mV). Sc in ng nhit ca Cu-constantan cng trong iu kin nh trn l: ECu-constantan = ECu Pt Econstantan - Pt = + 0,75 (3,4) = 4,15 (mV). Theo quy c (c bit thun li khi lp rp cc pin nhit in) th tn gi ca mt cp nhit in cn gi theo th t in cc dng trc, in cc m sau. V d, cn gi cp nhit in cromen alumen, cp nhit in ng constantan, cp platin (ri) platin
Bng 34 Sc in ng nhit ca kim loi v hp kim trong cp nhit in vi Pt nhit T2 o bng 0 C Sc in ng Gii hn trn ca T (oC) Kim loi hoc hp kim nhit 100oC (mV) Gi lu o nhanh Antimoan (Sb) +4,86 550 Cromen (89%Ni; 9,8%Cr; 1%Fe; 0,2%Mn) +2,95 1000 1250 Nicrom (80%Ni, 20%Cr) +2,00 1000 1100 St (Fe) +1,80 600 800 Molipen (Mo) +1,31 2000 2500 Vng (Au) +0,80 Volfram (W) +0,79 2000 2500 ng (Cu) +0,75 350 500 Bc (Ag) +0,72 600 700 Platin (Roi) (90%Pt, 10%Rh) +0,62 1300 1600 Platin (Pt) +0,00 1300 1600 Alumen (94%Ni; 0,5% Fe; 2% Al; 2,5%Mn; 1%Si) 1000 1250 1,20 Vng Palai (60%Au; 40%Pd) 1100 1200 1,47 Niken (Ni) 1000 1100 1,52 1300 1200 Vng Platin Palai (60% Au, 30%Pd; 10%Pt) 1,91 Bc Palai (30%Ag, 70%Pd) 1100 1200 2,47 1200 1100 Vng Palai (40% Au, 60%Pd) 2,78 Au Ag Pd (10%Au, 30%Ag, 60% Pd) 1200 1300 3,11 Constantan (60%Cu, 40%Ni) 600 800 3,40 Copen (56%Cu, 44%Ni) 600 800 4,00 Bitmut (Bi) 200 7,34

Mun xc nh sc in ng nhit ca pin nhit in nhit bt k ti T1 th phi bit s ph thuc gi tr E theo nhit . S ph thuc ca E theo nhit T1 thng c biu din di dng bng trong cc ti liu chuyn v phn tch nhit. Trong bng 35 cho bit gi tr sc in ng nhit ca mt s pin nhit in ph bin trong cc phng th nghim mt vi gi tr nhit T1 trong iu kin nhit T2 c gi 0oC. Nu nhit T2 khng gi c 0oC (v d nhit phng chng hn) th cn hiu chnh li gi tr E theo h thc: E (T1/0oC)= ET1/T + ET/0oC T1 l nhit u mi hn AB hnh 160, t l nhit T1 khi o. ng dng ca pin nhit in ch yu xc nh nhit , ngoi ra cn lp rp nhiu thit b nghin cu khoa hc khc nhau trong cc thit b phn tch nhit. Khi ghp ni tip n cp nhit in s thu c mt acquy c sc in ng nhit ln gp n ln sc in ng nhit ca mt cp. Nhng ngun acquy nh vy c s dng khai thc nng lng mt tri, cn trong thin vn th dng o nhit cc ngi sao

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Bng 35 Sc in ng nhit ca mt s cp nhit in (n v l milivn) ph thuc vo nhit T1 (khi gi T2 o 0 C) Nhit T1(oC) 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 Pt+10/Rh v Pt 0,00 0,64 1,44 2,31 3,25 4,22 5,22 6,26 7,33 8,43 9,57 10,74 11,92 13,12 14,31 15,50 17,84 Cromen alumen 0,00 4,10 8,13 12,21 16.39 20,64 24,90 29,14 33,31 37,36 41,31 45,14 48,85 52,41 53,81 St constantan 0,00 5,40 10,90 16,56 22,07 27,58 33,27 39,30 45,72 52,29 58,22 Cromen copen 0,00 6,95 14,65 22,90 31,48 40,15 49,60 57,75 66,40 St copen 0,00 5,75 5,75 18,10 24,55 30,90 37,40 44,10 51,15 ng constantan 0,00 4,16 4,16 14,13 20,04 26,19 -

4.1.3.2 Cht in mi

Danh t cht in mi (dielectric material) do Faraay ln u tin a ra ch cc cht khng dn in. Trong thc t th d nhiu hoc t, cht no cng c dn in. Do cht gi l in mi cng c gi tr dn tuy rt b (khong nh hn 1012 m1cm1). Tuy nhin, trong cht in mi th qu trnh chuyn dch cc in tch v s mt mt nng lng lin quan n qu trnh ny chim u th so hn vi qu trnh dn. C th xem mt cch gn ng l trong cht in mi hu nh khng c cc in tch t do c th b in trng ngoi chuyn dch i mt khong cch ln. Cht in mi c cu to t cc nguyn t hoc phn t trung ho in, hoc t cc ion dng v ion m (tinh th ion) c gn cht cc v tr cn bng trong mng tinh th. Di tc dng ca in trng ngoi, cc in tch trong cht in mi b ri lon trong phm vi phn t, nguyn t, hoc t bo mng. Khi khng c in trng th lng cc in ca mt th tch nguyn t bt k trong cht in mi u c gi tr bng khng. Khi c mt in trng th cc in tch c du khc nhau chuyn dch theo hng chuyn ngc nhau lm cho mmen in ca th tch nguyn t s khc khng v lc cht in mi b phn cc. Tnh cht ca cht in mi c xc nh bng mt loi t in phng (hnh 163). Nu gia hai bn in cc l chn khng th in dung Co ca t l: Co = eo.A/d (50) eo l thm in mi ca chn khng bng 8,854.1012 F/m, A l din tch ca bn in cc, d l khong cch gia hai bn in cc. in dung ca t in nh vy ch ph thuc vo kch thc hnh hc. Nu t mt in p V gia hai bn in cc th t in s tch lu c mt in tch. Qo = Co.V (51)

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bn cc dng
++++++++++++++++

cht in mi
+++++++++++++++

bn cc m
Hnh 163 T in phng

By gi ta t cht in mi vo gia hai bn in cc v vn gi mt in p bng V nh vy th in tch t in tch lu c s tng ln Q1, cn in dung tng ln n gi tr C1. Ngi ta gi thm in mi ca cht in mi l v c xc nh bng t l:

= C1/Co

(52)

ph thuc vo phn cc, hoc s dch chuyn in tch trong cht in mi. Vi khng kh = 1, vi a s cc cht rn lin kt ion c t 5 10, cn i vi cht xenhet in (v d BaTiO3) = 103 104.
phn cc ca cht in mi l h s lin quan n mmen lng cc P v in trng cc b E. P = .E phn cc bao gm nhiu hp phn (53) (54)

= e+ i + d + s

e l phn cc electron do s chuyn dch cc m my in t i vi ht nhn nguyn t. Tt c cc cht u c kiu phn cc ny. i l phn cc ion, c trng cho kh nng dch chuyn tng i ca cation v anion i vi v tr cn bng ti cc nt ca mng li tinh th. d l phn cc lng cc (cn gi l phn cc tch thot) c trng cho cc phn t phn cc (v d HCl, H2O). Khi khng c in trng ngoi th cc phn t phn cc c phn b mt cch hn lon, n ch tham gia vo chuyn ng nhit v c nng lng t l thun vi nhit (kT). Khi nm trong mt in trng th cc lng cc c mt nh hng u tin dc theo hng ca in trng ngoi, cht in mi b phn cc. d ph thuc rt mnh vo nhit ( nhit thp c th xem nh cc lng cc b ng cng li). s l hp phn in tch th tch c trng cho cc vt liu khng c tnh cht in mi tt, v n c kh nng dch chuyn cc cht mang in tch trong mt khong cch tng i ln. V d tinh th NaCl, Na+ c th dch chuyn theo l trng dng hng n cc m lm xut hin lp in kp gia bin gii tinh th NaCl v bn in cc (thc ra loi cht rn ny phi xp vo cht in li rn ng hn l xp vo cht in mi). thm in mi ca cc cht ny gi l thm in mi biu kin v c gi tr khong 106 107. Nh vy gi tr ny khng c trng i vi cht in mi. Gi tr phn cc gim dn theo th t s > d > i > e.

156

Gi tr v thm in mi c th xc nh bng thc nghim bng cch o in dung, o microvon v o tnh cht quang hc trong mt khong kh rng ca tn s ca dng xoay chiu (hnh 164). Khi tn s thp (103 hz) c th c mt c 4 hp phn trong , tn s sng v tuyn (106 hz) th hp phn trong s in tch th tch khng kp to thnh trong a s vt liu dn ion, do khng c nh hng n gi tr tch thot. Trong dy sng ngn (109 hz) c th dng s nh hng ca cc lng cc vnh cu, v rng lng cc khng theo kp s thay i ca in trng ngoi. Thi gian tch thot i vi s phn cc ion (i) bin mt cc tn s ln hn vng ph hng ngoi (1012 hz). Tip tc tng tn s ln na th ch cn hp phn e o c trong vng cc tm. Khi t mt in p xoay chiu vo cht in mi th xy ra s mt mt nng lng lin quan n cc qu trnh phn cc. S mt mt nng lng trong cht in mi c biu din bng h thc: W = V2.G.C.tg (55) G = 2/f, f l tn s ca in p xoay chiu, C l in dung ca mu nghin cu, V l phn hiu dng ca in p, tg l t s gia dng thc hin (active) trong cht in mi v dng h khng (reactive), thng gi l tang ca gc tn tht ca cht in mi. Trong k thut ngi ta khng dng gi tr tuyt i ca s mt mt nng lng m dng gi tr tang ca gc tn tht (tg).
thm in mi ' 106
105 104 10 3 102 10 1

e + i + d + s e + i + d o ' '
10 3 106 10 9

e + i e
1012

Hnh 164 Hin tng phn cc trong cht in mi

tn s f

i vi cht in mi ng nht thuc loi phn cc electron (e) v phn cc ion (i) th tg thay i t l nghch vi tn s ca in p v tng khi tng nhit . Cc loi s cch in, in p dng c tn s 50 hz 20oC, tg nm trong khong 0,0025 0,035. Vi cc loi cht in mi tt th tg c th t ti 105. Mt i lng quan trng na ca cht in mi l in p nh thng. Ta c th hiu mt cch gn ng khi nim in p nh thng l vi mt dy xc nh ca cht in mi, khi t gia mt in p bng bao nhiu s xy ra hin tng phng in. VEt = UEt/h (56) VEt l tr s trung bnh ca in p nh thng (kV/mm hoc kV/cm); UEt l in p nh thng (kV), h l dy ca cht in mi im b nh thng (mm hoc cm).

157

nh thng l mt hin tng kh phc tp. i vi cht in mi kh th in p nh thng l in p ion ho kh. Tt nhin gi tr lin quan vi nng lng lin kt ca cc obitan ho tr ca cc cht kh . V d i vi khng kh p sut kh quyn trong trng ng nht th VEt = 30 kV/cm. C ch s nh thng ca cht in mi lng (v d vi cc loi du bin th) ph thuc vo sch v mc loi ht kh c trong cht in mi. Khi trong cht lng cha hp cht dn in tt th gia cc cc trc khi b nh thng c mt cu ni bng cc tp cht . Dng in qua cht lng c tng dn lm tng s to nhit v nhit cht in mi quanh vng cu ni tng dn n im si. Lc ny to ra mt rnh kh v bt u phng in. in p nh thng cc cht in mi lng cha c sch v cha ui ht kh c gi tr nm trong khong 1 10 kV/cm. Khi lm sch tht cn thn th gi tr ny c th t ti 1000 kV/cm. S nh thng cc cht lng nguyn cht l do cc electron p ln cc phn t cht lng lm ion ho n. Nh vy, c ch s nh thng ca cht lng nguyn cht cng tng t nh c ch s nh thng ca cht kh. in p nh thng ca cht in mi rn cao hn nhiu in p nh thng ca cht in mi kh cng nh cht in mi lng. C mt s cht in mi rn c VEt t ti 10.000 kV/cm. Vi cht in mi rn c th phn thnh hai dng nh thng: nh thng v nhit v nh thng v in. nh thng v nhit c th gii thch nh sau: Khi tng cng ca dng i qua cht in mi th lng nhit sinh ra tng ln. Mt khc, nhit tng li lm tng dn in ca n v nh vy li lm tng cng dng v do lm tng nhit trong lng cht in mi. Cui cng trong cht in mi t ti nhit lm phn hu nhit cht rn. bn in ca cht in mi rn khi b nh thng v nhit c gi tr khong 10 100 kV/cm. nh thng v nhit ph thuc vo thi gian chu tc dng ca nhit v in p. Khi hai gi tr tng ln th gi tr in p nh thng v nhit gim xung. nh thng v in l do qu trnh tng s lng electron trong cht in mi di nh hng ca in trng mnh. Cc qu trnh ny gm: s ion ho do va p electron ln nguyn t hoc ion trong mng li, s t pht x electron t catt. nh thng v in khng ph thuc vo thi gian tc dng ca in p v nhit . Tnh ng nht ca vt liu hnh dng ca in trng v.v cng c nh hng n in p nh thng ca cht in mi rn. Khi dy ca mu th tng s lm gim tnh ng nht ca mu.
4.1.3.3 Cht xenhet in

Cng nh cht in mi, di tc dng ca in trng ngoi cht xenhet in b phn cc, nhng khc vi cht in mi hai im l:

Cht xenhet in c thm in mi rt cao. Khi ngt in trng ngoi trong vt liu xenhet in vn cn gi li tnh phn cc.

Khi tng in p bn ngoi (V) vi cht in mi thng thng th tc phn cc cm ng tng mt cch u n v do in tch cm ng cng tng u n theo h thc Q = C.V. Vi cht xenhet in th khng phi n gin nh vy. Mi quan h gia phn cc cm ng P vi in p V c hin tng tr, ngha l ng biu din s ph thuc gia P v V khi tng V khng lp li nh khi gim V. Cht xenhet in c c trng bng s c mt phn cc bo ho Ps khi tng in p (v d 23oC vi BaTiO3 c Ps = 0,26 C/cm2), v phn cc tn d Pr (ngha l phn cc vn cn li sau khi ngt in trng ngoi). gim phn cc n gi tr 0 th cn phi t mt in trng ngoi ngc chiu vi in trng ban u (gi l trng khng t). Bng 36 gii thiu mt s cht xenhet. Tt c cc cht u c cc cu trc m trong c mt cation (v d Ti4+ trong BaTiO3) c th chuyn dch (khong 0,1 ) trong vng phi tr anion ca mnh, chnh s chuyn dch lm pht sinh ra

158

lng cc v do thm in mi ca cht xenhet in c gi tr ln. T bo mng li ca perpkit (hnh 36 v 37) cho thy ion Ti4+ nm trong v tr bt din TiO6. T kch thc Ti4+ v O2 cho ta bit c Ti4+ c th dch chuyn t do trong mt gii hn no ca bt din TiO6. Hnh 38 cho thy trn 120oC t bo mng ca BaTiO3 thuc h lp phng bn vng khng c mmen lng cc ring, v tt c cc in tch u c phn b mt cch i xng. Do trn 120oC BaTiO3 ch l mt cht in mi thng thng, tuy rng c thm in mi cao.
P (C/m2) PS Pr Ec

V(v/m)

Hnh 165 Vng in tr ca cht xenhet in in hnh

ng chm chm i qua gc to biu din c tnh ca cht in mi thng thng

Bng 36 Nhit Curie ca mt s vt liu xenhet in Cht xenhet in Nhit Curie (Tc, o C) Barititanat BaTiO3 120 Mui xenhet KNaC4H4O6.4H2O T 18 n +24 Kali niobat KNbO3 434 Kaliihirophotphat KH2PO4 150 Ch titanat PbTiO3 490 Liti niobat LiNbO3 1210 Bimut titanat Bi4Ti3O12 675 Galini molipat Gd2(MoO4)3 159 Zirconat titanat ch (PZT) Ph thuc vo gi tr Pb(ZrxTi1-x)O3 x

Di 120oC mng tinh th BaTiO3 b sai lch, bt din TiO6 mt tnh i xng (xem hnh 38), ion Ti4+ b x dch trong bt din theo mt hng xc nh no (dch gn v mt O2 hoc gia hai ion O2, hoc gia ba ion O2). Nu s dch chuyn xy ra trong tt c cc bt din TiO6 th trong vt liu pht sinh ra phn cc t nhin. Trong cht xenhet in BaTiO3, mi mt bt din TiO6 b phn cc di nh hng ca in trng ngoi dn ti s nh hng cng bc ca tt c cc lng cc. Sau khi xp t tt c cc lng cc theo mt hng nht nh th vt liu t trng thi bo ho Ps. T gi tr Ps o c trong thc nghim ngi ta xc nh c khong cch m ion Ti4+ ri khi tm bt din TiO6 hng v mt trong cc ion oxi l 0,1 , gi tr ny kh ph hp vi kt qu xc nh c bng phng php ghi gin nhiu x tia X. Nu so vi di lin kt

159

Ti O trong bt din (1,95 ) th khong chuyn dch cng b hn. Hnh 166 cho bit s nh hng ca cc lng cc, y mi mi tn ng vi mt bt din bin dng TiO6. Trong cc xenhet in tng t BaTiO3 c cu trc men do cc lng cc TiO6 cnh nhau t sp t mt cch song song vi nhau (hnh 167). Kch thc ca cc men khc nhau thng t ti (theo mt ct ngang) hng chc n hng trm angstron. Trong gii hn ca mt men, cc lng cc phn cc theo mt hng tinh th. phn cc ca mt mu xenhet in bng tng vect ca phn cc cc men.
Hnh 166 S biu din s nh hng ca cc lng cc trong: cht xenhet in (a), cht antixenhet in (b), cht xenheti in (c) (a)

(b) (c)

x Khi t vo in trng s lm thay i phn cc ring ca mu xenhet in, nguyn nhn ca s thay i c th l cc qu trnh sau:

Thay i hng phn cc ca men. iu ny xy ra nu tt c cc lng cc TiO6 trong gii hn kho st u thay i hng ca mnh, v d tt c cc lng cc trong men 2 thay i hng song song vi lng cc ca men 1 (xem hnh 167). Lm tng s phn cc trong gii hn ca mi men, iu ny c th xy ra nu trc khi t in trng th cc lng cc c s nh hng khng trt t. Chuyn ng ca cc thnh men lm cho kch thc ca cc men nh hng dc theo trng tng ln do gim cc men c hng khng thun li. V d trn hnh 167 men 1 c th tng ln khi chuyn dch mt bc sang phi, thc hin s chuyn ng th cc lng cc trn bin gii men 2 phi chp nhn s nh hng theo mi tn chm chm.

Hnh 167 Cc men xenhet in b ngn cch bi thnh men

160

Trng thi xenhet in thng thy khi nhit thp, v rng s chuyn ng nhit tng ln khi tng nhit s ph v cu trc men c trng thch hp ca s chuyn dch cc bt din cnh nhau do ph v cu trc men. Nhit m bt u xy ra s ph v gi l im Curie (Tc). Trn Tc th vt liu tr thnh paraelectric (ngha l khng xenhet in na), thm in mi ca n vn c gi tr cao nh trc (hnh 168), nhng phn cc tn d khi khng c trng ngoi th khng thy na. Trn nhit Tc i lng tun theo nh lut Curie Weiss.

= C/(T q )

( 57)

C l hng s Curie, q l nhit Curie Weiss. Thng thng Tc v q trng nhau hoc ch khc nhau vi . S chuyn t trng thi xenhet in sang trng thi paraelectric Tc l mt v d s chuyn pha trt t thnh khng trt t (v d trong ng thau) khng xy ra s chuyn dch khuch tn ion trong mt khong cch ln. Di nhit Tc tnh trt t c thc hin bng cch sai lch u tin hoc lch mt cch phi hp vi nhau ca cc a din, ngha l mt s chuyn pha di ch. pha paraelectric nhit cao s sai lch v s lch cc a din nu c xy ra th cng ch mang tnh cch ngu nhin. iu kin cn thit ca s phn cc t pht v tnh cht xenhet in trong tinh th l tinh th phi thuc nhm khng gian khng c tm i xng. Pha paraelectric bn trn Tc thng l i xng tm cn tnh trt t xy ra khi lm lnh li gim i xng n nhm khng gian khng c i xng tm na.
10000 8000 6000 4000 2000 40 80 120 160

'

Tc

Hnh 168 Gin cho bit thm in mi ca gm BaTiO3 ph thuc nhit

Hin nay bit n hng trm vt liu xenhet in trong c mt nhm kh ln l hp cht oxit c cu trc perpkit bin dng (khng phi dng lp phng). Nhng hp cht c cha cc cation c b tr thun li trong phi tr bt din bin dng Ti, Ni, Ta. Tnh khng ng u ca cc lin kt trong cc bt din bin dng l nguyn nhn pht sinh ra s phn cc v mmen lng cc. Khng phi tt c cc perpkit u l xenhet in. V d khc vi BaTiO3 v PbTiO3, canxititanat khng c tnh xenhet in, hnh nh lin quan n s khc nhau v kch thc ca cation ho tr 2. Bn knh ln ca ion Ba2+ cng nh Pb2+ c nh hng lm gin n t bo mng li so vi ion Ca2+, iu ny lm ko di lin kt Ti O trong BaTiO3 (cng nh trong PbTiO3) v lm chuyn dch mnh Ti4+ trong bt din TiO6. Trong thnh phn ca cc oxit khc nhau c tnh xenhet in c cha cation m lin kt gia cation vi oxi khng ng u v c cp electron t do trn lp v ngoi cng. iu ny c th xy ra vi cation ca nguyn t p nng c hai n v ho tr thp hn ho tr gii hn ca nhm nh Sn2+, Pb2+, Bi3+...

161

Cc oxit xenhet in c s dng lm cc t in c thm in mi ln, c bit gn nhit Tc (hnh 168). Bi vy, trong iu ch vt liu ang theo ui mt mc ch tng , ngha l to ra vt liu c Tc gn vi nhit phng. c bit, nhit Curie ca BaTiO3 (120oC, hnh 168) c th gim i ng k v khong nhit chuyn cng c m rng ra khi thay th mt phn Ba2+ hoc Ti4+ bng cc cation khc: thay th Ba2+ bng Sr2+ gy ra hin tng co t bo mng li li v gim Tc, thay th Ti4+ (hot ng) bng cation in tch 4 khc (khng hot ng), c bit Zr4+, Sn4+ cng gim mnh Tc. Trong cc cht antixenhet in cng c s phn cc t pht v bn cht ging nh s phn cc ca cht xenhet in. Cc lng cc c th ca cht antixenhet in c sp xp trt t vi nhau sao cho mi mt lng cc nm gia hai lng cc i song song hai bn (hnh 166b). Kt qu phn cc t pht ca vt liu bng khng. Trn im Curie antixenhet in, vt liu tr nn paraelectric bnh thng. Ch zirconat PbZrO3 (233oC), natri niobat NaNbO3 (638oC), amoni ihirophotphat NH4H2PO4 (125oC) l v d cc cht antixenhet in (s trong ngoc l im Curie). Tnh cht in ca antixenhet in v xenhet in rt khc nhau. V rng trong trng thi antixenhet in, s phn cc t pht khng c nn khng thy c vng t tr trong in trng xoay chiu, tuy rng i vi cc cht cng c thm in cao gn im Tc (vi PbZrO3 c 100 200oC v 3000 230oC). i khi s sp xp trt t i song ca cc lng cc trong cht antixenhet in v song song trong vt liu xenhet in c bn rt gn nhau. Trong nhng trng hp nh vy th mt s thay i nh ca iu kin bn ngoi c th dn ti s chuyn pha. V d, di tc dng ca in trng ngoi PbZrO3 c th chuyn t trng thi antixenhet sang trng thi xenhet in. in trng gy nn s chuyn ph thuc vo nhit . Tng ng vi trng hp c s bin ho phn cc nh c m t trong hnh 169. in trng thp khng c t tr v rng PbZrO3 trong iu kin l cht antixenhet in, cn khi in trng mnh hn (c hai pha) PbZrO3 tr thnh trng thi xenhet v pht sinh vng t tr. Ngi ta cn bit c c mt dng khc ca hin tng phn cc na, l cu trc antixenhet ch pht sinh ra trong mt hng no . Cu trc men ca dng nh vy c ch trn hnh 166c, s phn cc ring bng khng theo hng x, nh trong cht antixenhet, nhng theo hng Z li khng bng khng. V d cht Bi4Ti3O12, monohirat ca tactrat liti v amoni (nhng cht nh vy gi l cht xenhetielectric).
E(kV/cm)
P

(a)
30 20 10

(b)

xenhet antixenhet in paraelectric oC

E

220

225

230

235

Hnh 169 S ph thuc gia nhit chuyn trng thi antixenhet-xenhet trong PbZrO3 vo in trng (a) v tnh phn cc trong qu trnh chuyn (b)

4.1.3.4 Cht ha in (pyroelectric)

162

Cc tinh th ho in cng c ngun gc vi cht xenhet in ngha l chng u khng c tm i xng v c s phn cc t pht. Tuy nhin, khc vi cht xenhet in ch hng Ps khng c th thay i bng in trng bn ngoi. phn cc ca cht ho in ph thuc vo nhit .

PS = .T

(58)

l h s ho in. S pht sinh ra phn cc ho in c gii thch nh sau, khi un nng s lm gin mng li tinh th do lm thay i di ca lng cc. V d tinh th ho in nh km oxit ZnO c cu trc vuazit. Hp cht ny gm cc lp ion O2 gi ghm chc c lc phng v cc ion Zn2+ chim mt kiu hc t din, v d T+. Tt c cc t din ZnO46 u nh hng theo mt hng v v rng mi t din l mt lng cc, nn v ton b tinh th phn cc. Trn cc mt i din ca tinh th ZnO theo ch s 001 ch c th c mt loi ion O2 hoc Zn2+. Tuy nhin, trn b mt ca tinh th thng hp th cc phn t ca tp cht nn che ph mt in tch. Do hiu ng ho in ca tinh th thng khng pht hin c khi nghin cu nhit thng m ch pht hin khi un nng.
400 300 200 100 1 0,2 2

C
3

PbZrO3

0,4

0,6

0,8 PbTiO3

Hnh 170 Gin pha h PZT 1- Pha antixenhet; 2- Pha mt thoi (xenhet in ); 3- Perpkit lp phng (paraelectric); 4- Pha t phng (xenhet in ).

4.1.3.5 Cht p in (piezoelectric)

Trong tinh th ca cht p in, s phn cc v in tch cc mt i din pht sinh khi t ln mt ng sut c hc. Cng nh cc cht xenhet in v cht ho in, tinh th ca cht p in phi thuc h khng c tm i xng. S xut hin hiu ng p in ngoi vic ph thuc vo cu trc tinh th cn ph thuc vo hng ca ng lc t vo. V d vi tinh th thch anh, hiu ng p in ch xut hin di p lc ca lc nn vung gc v song song vi trc i xng bc hai. S ph thuc gia phn cc (P) v ng lc () theo h thc: P = d d l h s p in. Rt nhiu tinh th m trong cu trc c cha cc mnh t din (v d ZnO, ZnS) u c tnh p in. V rng khi t mt ng sut trt ln th lm sai lch t din. PZT l mt trong cc nhm cht in p quan trng nht. l dung dch rn gia zircronat v titanat ch (PbZrO3, PbTiO3). Trn gin hnh 170 cho thy cc khu vc ca thnh phn pha rn c tnh cht xenhet in v tnh cht antixenhet in. Tnh cht p in tt nht ng vi thnh phn cu t ng phn t gam. (59)

163

Cc tnh cht xenhet, p in, ho in u c chung mt nguyn nhn l s pht sinh cc vng phn cc trong tinh th, do gia cc vt liu ny phi c tnh cht chung. Tt c cc vt liu u thuc v nhm cht in mi, do trc ht l nh hng ca in trng ln tnh cht in ca chng. Cc cht p in thuc vo phn nhm cht in mi m khi t ng sut c hc ln th pht sinh ra in tch, cn khi nm trong in trng th n li sinh ra ng sut c hc. Cc cht ho in to thnh phn nhm vi cht p in, trong cc vt liu c s phn cc t pht, v c mmen lng cc tng cng. Mt s cht ho in cng c tnh cht xenhet c th l hng phn cc t pht, trong c th quay ngc tr li di tc dng in trng ngoi. Do theo nh ngha th cc vt liu xenhet in cng l vt liu p in v vt liu ho in, nhng ni ngc li th cha chc, ngha l khng phi tt c cc cht p in c tnh cht ho in.
X1

X1

X2

X3

X1

+ +

X2

X3

X1

Hnh 171 S pht sinh lng cc khi nn tinh th thch anh theo hng vung gc v song song vi trc i xng bc hai

4.2

Nhm tnh cht t

Ngoi tnh nghch t c trng cho tt c cc hp cht v c, c mt s cht rn v c c tnh cht c bit, lin quan n s c mt nhng electron cha ghp i. Cc electron cha ghp i nh v trn cc cation kim loi. Bi vy nhng tnh cht t s ni n trong phn ny c trng ch yu i vi cc kim loi chuyn tip, cc lantanoit v rng cc hp cht phn ln c cc electron d v f cha ghp i. C th phn loi cc vt liu t nh sau:

Vt liu thun t l vt liu m trong spin ca cc electron cha ghp i c th nh hng mt cch ngu nhin. Vt liu st t l vt liu m tt c cc spin ca cc electron cha ghp i c nh hng song song vi nhau, do c mmen t ln. Vt liu phn st t khi spin ca cc electron c thn cc v tr i song song v lng cc spin theo hai chiu ngc nhau bng nhau do mmen t tng cng bng khng. Loi vt liu ny cn gi l vt liu antiferomagnhetic. Khi lng spin

164

theo hai chiu ngc nhau khng bng nhau th mmen t tng cng khc khng v gi l vt liu ferimagnhetic.

Nh vy l c mt mi tng quan gia tnh cht t v tnh cht in, c bit l tnh cht xenhet in. S khc nhau duy nht ch ch cc vt liu t khng c mt in tch t duy nht (n cc, monopole) tng t nh in tch in ngha l in tch ca ion, ca electron. Vt liu t trn c s oxit, v d ferrit (MgFe2O4), hin nay c s dng rng ri sn xut cc li bin th, cc thit b ghi t, gi cc thng tin. L thuyt v t kh phc tp, trong s dng nhiu danh t, k hiu, n v o rt d nhm ln nhau. Tnh trng cn rc ri hn na do trong thc t s dng c hai phng php nh gi mmen t ca cc ion c electron c thn (hai phng trnh ny c khi cn mu thun vi nhau). Trong phn ny ch trnh by mt s kin thc ti thiu cn thit c kh nng hnh dung cc kiu vt liu t khc nhau v gii thch mi lin h vi cu trc tinh th.

4.2.1 Phn l thuyt

4.2.1.1 Cht trong t trng

Nu t mt cht trong t trng c cng H th mt ng sc trong mu (gi l cm ng t) bng tng s cng t trng H v mt phn gp no ca chnh mu na. B = H + 4I I l cng t ho ca mt n v th tch mu.
Bng 37 cm t ca cc cht khc nhau Gi tr x in Bin thin x khi Cht hnh tng T Nghch t 1.106 khng Thun t 0 102 gim 2 St t 10 106 gim Phn st t 0 102 tng

(60)

Ph thuc vo cng t trng Khng Khng Ph thuc Ph thuc

t thm P v cm t c xc nh theo h thc sau:

P = B/H = I + 4 x; x = I/H cm t mol c xc nh theo h thc:

(61)

= x F/d
F l khi lng mol ca mu, d l t trng.

(62)

Cc vt liu t khc nhau l do s khc nhau ca cc gi tr P, , x v cc i lng ph thuc vo nhit nh th no. Cht nghch t c c trng bng gi tr m, b ca , x v P < I. Cht thun t th cc i lng dng (P > I, v x dng). Nu t trong t trng th s ng sc i qua cht thun t ln hn so vi s ng sc i qua chn khng, nhng s ng sc i qua cht nghch t th c phn gim i (hnh 172). Do cht thun t b t trng ht, cn cht nghch t b t trng y nh.

165

(a) H

(a) H

nghch t

nghch t

Hnh 172 Cht thun t v cht nghch t trong t trng

Cht st t c c trng bng gi tr v x ln, cn P >> I v do b t trng ht rt mnh. cht phn st t P > I cn v x cng c cc gi tr dng v gn vi cht thun t.
4.2.1.2 nh hng ca nhit . nh lut Curie Weiss
-1 nh lut Curie -Weiss nh lut Curie

lch = C -1
Hnh 173
1 S ph thuc = f(T) theo nh lut Curie v Curie Weiss

T (K )

cm t ca vt liu t khc nhau, khc nhau v s ph thuc vo nhit v ngay c gi tr cu chng. Nhiu cht thun t tun theo nh lut n gin ca Curie (c bit khu vc nhit cao) ngha l cm t t l nghch vi nhit .

= C/T

(63)

C l hng s Curie. Tuy nhin ph hp tt hn vi cc d kin thc nghim l nh lut Curie Weiss.

= C/(T+q)
1

(64)

q l hng s Weiss. Hnh 174 gii thiu hai kiu ph thuc ca cm t theo nhit = f(T). Vi cht st t v cht phn st t th s ph thuc vo nhit ca khng tun theo nh lut Curie v nh lut Curie Weiss (hnh 174). nhit thp, cht st t c cm t rt ln, khi tng nhit th gim mnh (hnh 174b). Trn nhit Curie (Tc) th mt tnh st t v bin thnh cht thun t v li tun theo nh lut Curie Weiss. cm t ca cht phn st t tng khi tng nhit (hnh 174c). Nhit m cm t c gi tr cc i gi l nhit neli TN. Trn TN vt liu tr thnh thun t. (a) Thun t x
Tc Thun t (b) St t
(c) Phn st t Thun t

TN

166

Hnh 174 th biu din s ph thuc ca cm t vo nhit : (a) cht thun t; (b) cht st t; (c) cht phn st t

i lng ca cc vt liu khc nhau v s ph thuc ca n vo nhit c gii thch nh sau: cm t ca cht thun t c gi tr dng l do trong cht thun t c cc electron c thn ng thi spin ca chng c khuynh hng xp xp theo hng ca t trng. Trong vt liu st t, spin ca cc electron c sp xp song song v c tng tc t hp cc spin ca nhng ion cnh nhau trong mng li tinh th. Gi tr ln l do s sp xp song song ca spin trong cht ngay c khi nhit thp v t trng mnh. Trong cc cht phn st t, cc spin electron c sp xp i song song v b tr ln nhau. Do loi vt liu ny c th c gi tr khng ln. Gi tr cn li lin quan n s mt trt t trong vic phn b spin. Vt liu no th khi tng nhit cng lm tng s chuyn ng ca cc ion v electron. Do iu ng nhin l khi tng nhit th khuynh hng ch yu l tng s mt trt t ca cu trc. Trong cc vt liu thun t th nng lng nhit ca electron v ca ion c kh nng b tr mt phn tnh trt t pht sinh ra di tc dng ca t trng ngoi. Thc t ngay t khi mt t trng ngoi th s nh hng ca cc spin electron li tr nn mt trt t. Do khi tng nhit th cm t ca cht thun t gim theo nh lut Curie v Curie Weiss. Vt liu st t v phn st t th khi tng nhit s lm tng tnh mt trt t ca s phn b sn c trt t ca cc spin song song v i song song. Vi cht st t th iu ny c tc dng lm gim khi tng nhit. Vi cht phn st t th vic gim mc trt t i song song li lm tng . Thng thng, c trng cho tnh t ca vt liu ngi ta dng gi tr mmen t m, v rng thng s ny lin quan trc tip vi s electron c thn. S ph thuc gia v l:
= N.2.2/3kT = 2,83 .T

(65) (66)

N l s avgar, b manheton Bohr, k l hng s Boltzmann v

cm t, mmen t ca mt cht c xc nh bng php cn t. Mu c t gia cc cc ca in t ri cn khi lng mu tu thuc vo cng ca t trng. Electron c thn trong cc cht thun t b t trng ht nn khi lng tng ln khi ngt nam chm in. Ngoi suy gi tr thu c ca cm t v cn tnh n cc yu t khc nhau, c bit l tnh nghch t ca mu v gi ng mu.
4.2.1.3 Tnh ton i lng mmen t

Hai nguyn nhn c bn pht sinh ra mmen t l spin ca electron v chuyn ng obitan ca electron. Phn gp ln nht cho mmen t tng cng l spin ca electron. C th m t mt cch th thin electron nh l mt in tch im m v t quay xung quanh trc ca n. Gi tr mmen spin trong mu theo cch m t nh vy bng 1,73 manheton Bohr (B) Trong :

167

1B = eh/4mc

(67)

y e l in tch electron, h l hng s Planck, m l khi lng electron, c l tc nh sng. tnh mmen spin ca mt electron th s dng cng thc:
s = g s(s + 1) (68)

y s = 1/2 l s lng t spin, g 2,00 tha s Lander, thay cc gi tr vo ta c s =1,73B. Vi nguyn t hoc ion c s electron c thn ln hn 1 th mmen spin tng cng bng:
S = g S(S + 1)

(69)

y S l tng s s lng t spin ca cc electron c thn. Nh i vi ion st cao spin Fe3+ c 5 electron c thn S = 5/2 cn = 5,92. Bng 38 gii thiu gi tr s ca mt s ion. Trong mt s cht, s chuyn ng ca electron quanh ht nhn cng dn ti s pht sinh mmen obitan, a mt phn gp vo mmen tng cng. i vi nhng cht nh vy, mmen tng cng bng:
S+L =
4S(S + 1) + L( L + 1)

(70)

L l s lng t obitan ca electron. Cc phng trnh (67) v (69) s dng tnh mmen t ca cc nguyn t cng nh cc ion c lp. i vi cht rn th phng trnh (69) khng s dng c, v rng cc mmen obitan b trit tiu hon ton hoc mt phn. iu ny l do in trng ca cc nguyn t xung quanh (hoc ion xung quanh) hn ch s chuyn ng obitan ca electron. Cc s liu thc nghim thu c v mmen t ca cc ion trn bng 38 v trong cn a thm nhng gi tr tnh ton theo phng trnh (69) v (70). a s trng hp gi tr thc nghim gn bng hoc c phn no hi ln hn gi tr tnh ton khi xut pht ch c mmen spin.
Bng 38 Gi tr thc nghim v l thuyt mmen t ca cc ion ca kim loi chuyn tip Ion S electron c thn S (tnh c) s+L (tnh c) thc nghim V4+ 1 1,73 3,00 ~1,8 V3+ 2 2,83 4,47 ~2,8 Cr3+ 3 3,87 5,20 ~3,8 Mn2+ 5 (trng thi cao spin) 5,92 5,92 ~5,9 Fe3+ 5 (trng thi cao spin) 5,92 5,92 ~5,9 Fe2+ 4 (trng thi cao spin) 4,90 5,48 5,1 5,5 Co3+ 4 (trng thi cao spin) 4,90 5,48 ~5,4 Co2+ 3 (trng thi cao spin) 3,87 5,20 4,1 5,2 Ni2+ 2 2,83 4,47 2,8 4,0 Cu2+ 1 1,73 3,00 1,7 2,2

Cc phng trnh va trnh by tnh mmen t da trn c s ca c hc lng t. Vic kho st mt cch chi tit ca phng php ny rt kh khn v b my tnh ton kh phc tp. S ph hp gia tnh ton v thc nghim ni chung l khng tt (xem bng 38). Thng thng, cc nh chuyn mn nghin cu v s dng cc cht st t cng nh phn st t dng mt phng php khc n gin hn nhiu tnh ton mmen t. Trong khun kh

168

ca phng php ny ngi ta chp nhn rng mmen t ca mt electron cha ghp i bng 1mB. Nh vy th mmen t ca ion c n electron c thn bng nB. V d c hai ion cao spin Mn2+ v Fe3+ u c mmen t bng 5B. H thc chnh xc hn tnh ton mmen t c dng:
= gS

(71)

y g = 2 cn S = n/2 l trng thi spin ca electron. Gi tr mmen t s tnh theo phng php phn no thp hn gi tr thc nghim trong bng 38, du sao phng php ny cng c ch tnh . cho phng trnh (71) ph hp tt vi thc nghim phi thay i gi tr g, xem n nh mt thng s iu chnh. Phng trnh (71) ch tnh mmen t spin. Nu chp nhn rng g c th ln hn 2 th iu ny ng vi vic a vo s b chnh c mt mmen obitan. V d vi Ni2+ ngi ta chp nhn l g = 2,2 2,3.
4.2.1.4 C ch trt t st t v phn st t tng tc trao i

Trong cc cht thun t, mmen t ca cc ion ring r c cha electron c thn, nh hng mt cch ngu nhin. Trt t ho chng ch xy ra di tc dng ca t trng ngoi. Nng lng tng tc gia t trng v lng cc c th tnh ton d dng. Trong phn ny khng nu chi tit ca vic tnh ton, nhng v ton b c th ni rng i lng nng lng ln hn nng lng nhit ca ion hoc ca lng cc v bng kT. Trong cc cht st t v phn st t th trt t nh hng ca mmen t xy ra mt cch t nhin. Bi vy, trt t cn phi c trng bng mt nng lng dng no ca s tng tc gia cc spin cnh nhau c sp xp song song hoc i song song. S ghp i ca cc spin hoc tng tc tp th ca chng c bn cht c hc lng t. Hin tng xy ra c th hnh dung mt cch nh tnh, tuy nhin bc tranh r rng v dt im ca st t, v d nh st, coban cho n nay vn cha bit c. Tng tc ca cc spin xy ra trong cht phn st t gi l tng tc trao i. Qu trnh i vi niken oxit c trnh by trn s hnh 175. Ion Ni2+ c 8 electron d. Nu Ni2+ nm v tr bt din ca cc ion oxi th 2 trong 8 electron c phn b trong cc obitan eg (dz2 v dx2 y2). Nhng obitan nh hng song song vi trc ca t bo mng do chng nh theo hng ca cc ion oxi bn cnh. Nhng electron c thn ca obitan eg ca Ni2+ c th tng tc vi cc obitan p ca ion O2. Kt qu ca tng tc lm pht sinh ra mt trng thi kch ng lm chuyn electron t obitan eg ca Ni2+ ln obitan p ca ion oxi. Trn mi obitan p ca O2 c 2 electron ghp i i song song. Do trong trng hp nu ion Ni2+ v O2 nm gn nhau n ni tng tc electron c th xy ra th trong ton b tinh th s to thnh mt mch cc electron tng tc. Kt qu spin ca tt c cc ion Ni2+ bn cnh b ion O2 tch ra v nh hng i song song.
o b ita n p z o b ita n d 2 z

Ni2

O2

Ni

2+

Hnh 175 Tng tc spin ca cc electron d ca Ni qua obitan p

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ca ion oxi lm pht sinh tnh phn st t

4.2.1.5 Mt s khc nim khc

Vt liu st t c cu trc min tng t nh cu trc min ca cht xenhet in (cu trc men). Trong mi men nh vy tt c spin nh hng song song. Tuy nhin, mc du trong vt liu v ton b l bo ho t nhng cc men khc nhau vn c nh hng khc nhau. Di tc dng ca t trng ngoi, trong cc cht st t xy ra hin tng tng t nh hin tng trong cht xenhet in nm trong in trng. ng cong ph thuc t ho M hoc cm ng t B vo cng t trng H cng c vng t tr (ging nh vng t tr trong cht xenhet in hnh 165). Khi gi tr cng t ln s t bo ho t, lc spin ca tt c men nh hng song song vi nhau. S t ho v kh t ca vt liu trong t trng theo hng ngc nhau th xy ra s tn nng lng, thng thng thot ra di dng nhit. Gi tr nng lng t mt mt trong mt chu k (t ho - kh t) t l vi din tch ca vng t tr. l gi tr tn tht t trong vng t tr. i vi mt s lnh vc dng vt liu st t th yu cu cn thit l tn tht t trong vng t tr phi rt nh. iu c ngha l din tch vng t tr cng b cng tt. Vt liu c lc khng t Hc nh gi l vt liu t mm. Lc khng t l cng ca t trng ngc chiu cn thit t vo kh t hon ton trong vt liu . Vt liu t mm c c trng bng t thm thp, do nn vng t tr hp v din tch b. Vt liu t cng c c trng bng lc khng t cao t ho cn li Mr ln. Vt liu t cng rt kh kh t bi vy c s dng lm nam chm vnh cu. Trong tinh th vt liu st t, mmen t hp thnh c phn b dc theo mt s hng u tin. V d st hng song song vi cc trc ca t bo lp phng. Nhng trc nh vy gi l trc d t ho (hnh 176a). Nhiu vt liu t c tnh t gio, ngha l c th bin dng khi t ho. V d Ni v Co b co li theo hng t ho v gin ra theo hng trc giao. Trong t trng yu th st c c tnh ngc li, cn trong t trng mnh th dng ca st cng thay i nh Ni v Co. Mc thay i ny khng ln lm. H s t gio c xc nh bng t l s = L/Lo. Ni chung, s thay i kch thc di tc dng ca t trng cng ch tng ng vi s thay i kch thc khi un nng mu vi .

4.2.2 V d mt s vt liu t, cu trc v tnh cht

4.2.2.1 Kim loi v hp kim

Nm kim loi chuyn tip Cr, Mn, Fe, Co, Ni v a s cc lantanit u c tnh st t v phn st t. Rt nhiu hp kim v hp cht gia kim loi cng c c trng bng mt mc trt t t no . Hnh 176 gii thiu cc cht st t Fe, Co, Ni.

170

a c
60 o

c a b Ni, TC = 631 K Co, TC = 1404 K -Fe, Tc = 1043 K Hnh 176 Trt t st t trong cu trc Fe (lp phng tm khi),Ni (lp phng tm mt) v Co (chc c lc phng)

Spin trong Fe nh hng theo hng 100 song song vi mt cnh ca t bo mng. Spin trong Ni nh hng theo hng 111 ngha l song song vi ng cho khi ca lp phng. Spin ca Co nh hng song song vi trc c ca t bo mng. Nhng v d ny chng t s tn ti tnh st t khng lin quan g n cu trc ca tinh th. Cr v Mn nhit thp l cht phn st t. Nhit Neli TN ca Mn v Cr bng 95 K v 313 K. Mng li tinh th ca mangan rt phc tp cn ca Cr th c mng li lp phng khi tm nh Fe. Trong mng li Cr cc spin nh hng i song song vi mt trong cc trc ca t bo mng. Mt s c trng ca vt liu st t c trnh by trn hnh 177. Hnh a cho bit s ph thuc cm t (hoc mmen t) theo nhit . Trn trc tung t gi tr ca t ho bo ho ca st ng vi gi tr cc i ( 0 K), trc honh t t l nhit thc vi nhit Curie (gi l nhit quy i). Bi vy im Curie nhit qui i bng n v (T/TC = 1). S dng ta ny cho php so snh vt liu c nhit Curie khc nhau v mmen t khc nhau. Hnh a cho thy t tnh ca st v niken rt ging nhau, cc gi tr T/TC thp t ho bo ho ca kim loi khng thay i v bt u gim rt nhanh khi T gn ti TC. Trn nhit Curie th Fe, Ni, Co u l thun t. Gn nhit TC ng biu din khng tuyt tnh na. S sai lch lin quan n vic tn ti gn ca trt t spin. Trt t xa c trong trng thi st t (di TC) b bin mt, cn trt t gn vn gi c mt phn no trn TC. Bi vy nhit (hng s Weiss) hi khc TC.
t ho bo ho
0,8 0,6 0,4 0,2 0,2 0,4 0,6 0,8 1,0 T/Tc

-1

Cp (J/mol)

(a) Ni, Fe

8.10 6.10 4.10 2.10

4

(b)
60

(c) Fe
40 20

Ni
Tc
400 600 800

T(oC)

200 400 600 800 1000 T (K)

Hnh 177 Mt s tnh cht ca vt liu st t

a) S ph thuc ca t ho bo ho i vi t ho bo ho 0 K vo nhit quy i; b) S ph thuc gia gi tr nghch o cm t vo nhit (gn TC c sai lch vi s ph thuc tuyn tnh); c) Nhit dung ca Fe nh l mt hm i vi nhit . Vic chuyn t trng thi st t sang trng thi thun t nhit TC c m t bng nhng thng s nh l mt s chuyn pha loi hai bt k (hoc chuyn pha dng ). l

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mt v d ca s chuyn pha t trt t thnh khng trt t. Trng thi trt t tuyt i ch tn ti 0 K. bt k nhit no th cng xy ra qu trnh mt trt t, nhit cng tng th s mt trt t cng tng. S ph thuc ca nhit dung vo nhit i qua cc i TC (hnh 177c). Cc lantanit cng c mt cu trc t trt t do s c mt ca electron c thn 4f (tr nguyn t 4f0 l La v 4f14 l Yb v Lu). nhit thp hn nhit phng th a s cc lantanit u l phn st t. C mt s lantanit (ch yu cui dy) c th l st t hay phn st t tu thuc vo nhit . Khi gim nhit th cc nguyn t ny c bin ho sau: Thun t Phn st t St t Bng 39 gii thiu TC v TN ca mt s nguyn t.
Bng 39. Nhit TN (bin ho phn st t) v TC (bin ho st t) ca cc lantanit Nguyn t Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm TN (K) 12,5 25,0 19,0 14,8 90 229 179 131 84 56 TC (K)

293 222 85 20 20 25

4.2.2.2 Oxit ca kim loi chuyn tip

S thay i tnh cht t ca cc oxit ny cng lin quan n s thay i tnh cht in ni trong phn trc. Ba oxit thuc chu k 4 ca nhm ny l TiO, VO, CrO l cc cht nghch t. Trong cc electron d khng nh v tng ion M2+ ring bit m chuyn dch trong ton mng li, chng lp mt phn vng t2g. Hnh nh mmen t ca cc electron khng nh v khng tng tc vi nhau. Do cc cht ny nghch t v c dn in cao. Oxit ca cc nguyn t chuyn tip (MnO, FeO, CoO, NiO) nhit cao th thun t, cn nhit thp c c trng bng cu trc t c trt t, cc electron d nh v ti cc ion M2+ ring bit. Chnh s nh v ca cc electron c thn l nguyn nhn ca tnh t v khng c tnh dn. Cc oxit MnO, FeO, CoO, NiO nhit thp th phn st t, nhit cao th thun t. Nhit TN ca cc oxit l MnO - 153oC, FeO - 75oC, CoO - 2oC, NiO + 250oC. Cu trc tinh th ca tt c cc oxit trng thi phn st t cng nh trng thi thun t u ging nhau. nhit cao chng c cu trc kiu NaCl. C th tng tng v m t cu trc ny theo nhiu phng khc nhau. y tin nht l xem cu trc tinh th theo mt trong bn hng 1 1 1, ngha l song song vi ng cho ca t bo lp phng mt tm. V d cu trc tinh th NiO gm cc ion Ni2+ v O2 lun phin. Di 250oC cu trc tinh th chu s bin i thnh mt thoi sai lch, dc theo trc bc ba song song vi hng 1 1 1 mng li hi b co li. Trong MnO cng c th xy ra s co tng t nh vy. Ngc li, trong cu trc FeO dc theo trc ny c phn b gin ra. i xng ca cu trc gim, v rng tt c cc trc bc bn v ba trong s cc trc bc ba tr thnh khng i xng na. Ch cn mt yu t i xng l trc bc ba. Mc sai lch ca mng li lp phng khng ln lm do trn gin nhiu x tia X cha chc thy c.

172

Nguyn nhn ca s sai lch mt thoi ca mng tinh th NiO lin quan n s trt t ho phn st t ca ion Ni2+. Trong gii hn ca mt lp cation, spin ca tt c cc ion Ni2+ nh hng song song vi nhau nhng i song song vi spin cc ion Ni2+ ca lp bn cnh (hnh 178). Siu cu trc t nh vy ch c nghin cu bng phng php th ntron. Lc s khuch tn ntron s xy ra trn ht nhn nguyn t cng nh trn cc electron c thn. Kiu khuch tn trn ht nhn cho ta bc tranh nhiu x tng t nh bc tranh nhiu x ca tia X. Cng ca cc pic trn gin ntron v trn gin tia X hi khc nhau. Cu trc phn st t (kiu khuch tn th hai) th hin di dng cc vch ph trn gin ntron ca mu bt. C th c hai nguyn nhn lm xut hin cc vch ny l: a) Tng tc tp th ca cc electron c thn c th dn ti xut hin siu cu trc.

173

Hnh 178. Cu trc phn st t ca MnO, FeO, NiO biu din t bo mng gi lp phng (khng v v tr ca ion oxi)

b) Ntron khuch tn trn cc electron c thn, trong khi tia X khng b khuch tn. Hnh 179 gii thiu gin nhiu x ntron ca MnO ghi trn v di nhit TN v gin nhiu x tia X ca mu bt MnO nhit phng.
Cng Nhiu x ntron 80K o a=8,85A
111* 311* 400 331* 511* 440 622

222

(a)

Nhiu x ntron 293K o a=4,43A

111 311 200 220

(b)

200

th rngen 293K o a=4,43A

20

111

220 311 40 60

(c)

80

Hnh 179. Gin nhiu x ntron v gin nhiu x tia X mu bt MnO ( = 1,542 )cc vch u c ch s Mille i vi t bo lp phng

So snh hai bc tranh nhiu x thu c trn TN (b v c) cho thy v tr cc vch tng t nhau nhng rt khc nhau cng . Cu trc kiu NaCl th cc gi tr hkl phi chn hoc l. Do 4 vch u tin trn hai gin nhiu x c cc ch s 111, 200, 220, 311 nhng trn gin nhiu ntron cc vch 200, 220 li c cng rt b. iu ny l do khuch tn ntron trn ion Mn2+ v O2 ngc nhau v du, t khc nhau v i lng. Bc tranh hon ton khc khi quan st gin nhiu x tia X, cc vch 200 v 220 c cng cao v rng tia X b khuch tn bng cc ion Mn2+ v O2 lan truyn cng pha. So snh cc hnh 179a v 179b cho thy di nhit TN trn gin nhiu x xut hin cc vch b sung (c nh du sao). Cc vch b sung l ca pha siu cu trc phn st t. Nh ni trn, i xng thc ca pha phn st t l mt thoi nhng mt cch gn ng c th xem nh lp phng vi thng s mng gp i. 80 K (<TN) a = 8,85 cn 293 K (>TN) a = 4,43 (hnh 178). Th tch ca cc t bo nguyn t t l vi nhau nh 8 : 1. Cc vch ph trn gin nhiu x

174

ntron ca pha phn st t c th ghi cc k hiu nh trn hnh 179a. Tt c cc gi tr hkl u l.

4.2.2.3 Spinen

V cu trc ca spinen c trnh by chng 2. Trong phn ny ch quan tm n phng din t tnh do s bn n cc spinen c cng thc MFe2O4. y M l cation ho tr 2 (Fe2+, Ni2+, Cu2+, Mg2+ ). Cc ferit thng thng l spinen o hon ton hoc o mt phn. V rng ion Fe3+ c 5 electron theo thuyt trng tinh th th khng thch hp vi v tr bt din. iu l th l cu trc t ca ferit c th l st t hoc cng c th l phn st t. iu ny do cc ion nm trong v tr t din c spin t nh hng i song song vi cc spin t ca cc ion nm trong v tr bt din (xem hnh 180). Trong hnh 180 khng v cc ion O2. Vic tnh ton mmen t ca cc spinen khc nhau c s dng h thc (71). V d tnh mmen t ca ZnFe2O4 nhit thp nht c cu trc spin o. [Fe3+]Te[Zn 2+, Fe3+]OcO4 V rng mt na s ion Fe3+ nm trong v tr t din, cn mt na khc th nm v tr bt din, spin ca chng i song song nn mmen tng cng ca ion Fe3+ bng khng, ion Zn2+ c mmen t bng khng. Vy y l cht phn st t. Kt qu thc nghim khng nh iu l ng (TN = 9,5K).
V tr 8a (t din) V tr 16d (bt din)

z y x

Hnh 180. Cu trc t ca spinen st t v spinen phn st t V tr 8a (t din), v tr 16d (bt din)

Vi ferit magie MgFe2O4 cng thu c kt qu nh vy. Tuy nhin thc t y l cht st t, ngha l c mt gi tr mmen t no . C th gii thch hin tng ny theo hai cch. Th nht l c th ferit c cu trc mt phn trn ln, trong mt phn ln Fe3+ nm trong hc bt din, cn mt phn nh Fe3+ nm trong hc t din. Nh vy, cc spin i song song ch b tr nhau c mt phn thi. Th hai c th l mmen t hiu dng ca ion Fe3+ cc v tr khc nhau khng ging nhau. Kt qu nghin cu thc nghim khng nh quan im th nht. nhit cao MgFe2O4 dn dn c cu trc spinen thun. Mc o ca spinen nhit phng ph thuc rt mnh vo ch ho nhit ban u. Quan trng nht l tc ngui lnh. Nh trong cc mu ti nhanh th mc o ca spinen s nh v mmen t ca nhng cht nh vy cao hn nhng mu lm ngui lnh chm n nhit phng. Ferit mangan l spinen trn ln, mc o ca n khong 20%. V rng c hai ion Mn2+ v Fe3+ u c cu hnh electron d5 nn mmen t chung khng ph thuc vo mc o v cch ch ho nhit. C th ch i rng MnFe2O4 l cht st t v mmen t chung ca n bng 5B. Thc nghim cng chng t iu .

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ngha to ln nht v s phn b cation vo cc hc khc nhau c th ly v d ferit c thnh phn M1-xZnxFe2O4, y M l Mg, Ni, Co, Fe, Mn. Khi x = 0 th c cu trc spinen o, ngha l [Fe3+]Te[Fe3+,M2+]OcO4. Nu spinen o hon ton th c th tnh c mmen t ca cc ferit khc nhau c cc gi tr l: M = Mg, = 0; M = Ni, = 2; M = Co, = 3; M = Fe, = 4; M = Mn, = 5. Cc gi tr tm c bng thc nghim c phn no cao hn (hnh 181). Ferit km nguyn cht (x = 1) nhit phng c cu trc spinen thun. Tuy nhin spin ca ion Fe3+ nm trong hc bt din, nh hng mt cch ngu nhin v hon ton khng c trt t dc theo mt hng no c. Bi vy ZnFe2O4 thun t t ho bo ho bng khng. Khi hnh thnh spinen hn hp bng cch thay th mt phn Zn2+ vo v tr M2+ s xy ra s chuyn dn dn t cu trc spinen o ti cu trc spinen thun. Vic a ion Zn2+ vo hc t din li dn ti s y Fe3+ t hc t din vo hc bt din ngha l 3+ 2+ 3+ [Fe1-x Zn 2+ x ]Te [M1-x Fe1+x ]O c O 4 . Nu dung dch rn vn cn phn st t (MFe2O4 khi x = 0) th mmen t phi tng tuyn tnh theo x v khi x = 1 (ZnFe2O4) phi bng 10B. Tuy nhin rt lu trc khi t thnh phn x = 1 tng tc phn st t ca spin cc ion v tr t din v bt din b ph v v i lng t ho bt u gim. cc gi tr nh ca x i lng t ho bo ho thu c t thc nghim cn tng dn ph hp vi gi thit phn st t. Khi x = 0,4 0,5, s ph thuc t ho bo ho vo thnh phn dung dch rn i qua cc i.
t ho bo ho B
10 9 8 7 6 5 4 3 2 1

M1 -xZnxFe2O4 Mn Fe Co Ni

Mg
0,2 0,4 0,6 0,8 1,0

Hnh 181. S ph thuc mc t ho bo ho vo thnh phn dung dch rn

3+ 2+ 3+ [Fe1-x Zn 2+ x ]Te [M1-x Fe1+x ]O c O 4

T tnh ca cc ferit v s bin i ca chng c xc nh khng nhng ch bng gi tr ca mmen t ca chng m cn bng nhiu thng s khc. Trong c t ho bo ho Mbh, hng s t gio s, t thm P, hng s bt i xng tinh th hc v t K1. Tu theo mc ch thc t ngi ta c th chn cc ferit c nhng tnh cht thch hp. S thay i cc thng s t c th t c bng cch to thnh cc ferit hn hp dung dch ca hai hay nhiu ferit nguyn cht. V d, khi thay th ion Mn2+ bng ion Fe2+ trong MnFe2O4 c th to 2+ 3+ Fe 2+ thnh dung dch rn Mn1-x x Fe 2 O 4 vi thng s bt ng hng t bng khng. Thng s ny c trng cho s d dng ti nh hng mmen t ca cht trong t trng ngoi. S gim tnh cht bt ng hng t lm tng thm t l mt iu rt quan trng i vi ng dng thc t.
4.2.2.4 Granat

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Mt s granat l vt liu t quan trng. Cng thc chung granat c th biu din di dng A3B2X3O12. A l ion c bn knh ln ( 1 ) v s phi tr 8. Trong tinh th granat th ion A nm trong tm lp phng bin dng. B v X l cc ion c kch thc b chim cc v tr t din v bt din tng ng. Trong granat c tnh cht t quan trng nht l: A = Y hoc l t him (Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), B v X l Fe3+. Mt trong s cc i din quan trng nht ca granat l granat ytri Y3Fe5O12. C th c cc t hp A B X khc na, v d:

177

A Grossula Uvarvit Pirp Andradit Ca3 Ca3 Mg3 Ca3 Ca3 Ca3 Na2Ca NaCa2

B Cr2 Al2 Al2 Fe2 CaZr Te2 Ti2 Zn2

X Si3 Si3 Si3 Si3 Ge3 Zn3 Ge3 V3

O O12 O12 O12 O12 O12 O12 O12 O12

Granat st ytri v tt c cc granat nguyn t t him u c nhit Curie t 548 n 578 K. nh gi mmen t ca cc granat cn phi tnh mmen t ca c ba kiu ion nm trong cc hc lp phng bin dng (s phi tr 8 k hiu 24c), hc t din (k hiu 24d) v bt din (k hiu 16a). Hnh nh spin ca cc ion nm trong cc nt 24d nh hng i song song vi spin ca nhng ion cc nt 24c v 16a. Mmen t ca cc ion Fe3+ chim hai v tr khc nhau thng b tr cho nhau, do c mt n v cng thc M3Fe5O12 ch cn mmen t ca mt ion Fe3+ cha bo ho. V rng ion Y3+ c cu hnh electron l d0 nn mmen t ca Y3+ bng khng. Vy mmen t ca granat st ytri phi bng 5B, thc nghim chng t iu ny. Mmen t ca granat t him c th tnh theo cng thc (3M 5)B. y M l mmen t ca ion v tr 24c. Ion Gd3+ c 7 electron f do Gd = 7B.Vy mmen t tng cng ca granat st gaoli phi bng 16B. Gi tr ny kh ph hp vi gi tr thc nghim. Vi ion Lu3+ (cu hnh f14) c Lu = 0. Do mmen t tng cng bng 5B, ph hp vi thc nghim. Mmen obitan ca cc ion t Tb n Yb c l khng b nn hon ton, bi vy gi tr M phn no cao hn gi tr tnh theo cng thc (69) l cng thc ch tnh n mmen t ca spin. Hnh 182 so snh cc gi tr thc nghim v tnh ton. Cc gi tr thc nghim u nm gia hai ng l thuyt, iu chng t rng mmen obitan ch b nn mt phn thi.

B
25 20 15 10 5 0 -5
Hnh 182. Mmen t granat t him 0 K 1- Tnh theo phng trnh (70); 2- Tnh theo phng trnh (69); 3- Gi tr thc nghim

1
Tb Cd Dy Ho

3
Er Tm Yb Lu

Mmen t ca granat t him ph thuc vo nhit c dng c bit. Mmen t granat t him 0 K gim khi tng nhit v nhit b tr th bng 0. Sau li tng nhng c du ngc li. n nhit Curie li gim n 0 (hnh 183). Nguyn nhn ca s ph thuc l do spin ca cc ion trong phn mng t him b mt trt t nhanh hn spin ca cc ion trong phn mng st.

178

Cc cation trong thnh phn granat d dng thay i bng nhng cation khc v do thay i mt cch h thng tnh cht t ca loi vt liu ny. V d ion ca nguyn t ho tr 3 c bn knh ln nm v tr 24c c th thay th mt phn bng cc ion Ca2+ v m bo tnh trung ho in th mt phn ion Fe3+ v tr t din li b thay th bng V5+, cng thc ca loi granat nh vy c th vit di dng:
3+ 3+ 3+ 5+ [Y3-2x Ca 2+ 2x ]Fe 2 [Fe3-x Vx ]O12

4.2.2.5 Imenhit v perpkit

Imenhit l tn gi ca mt nhm cht c cng thc ABO3, trong A l Fe, Co, Ni, Cd, Mg; B l Ti, Rh, Mn. Chng c cu trc tng t Cr2O3, hematit -Fe2O3 v corun -Al2O3. Imenhit c mng li mt thoi (a = 5,538, = 54o41) nhng tin nht xem n nh mng lc phng c kch thc ln (a = 5,048, c =14,026). C th tng tng mt cch n gin cu trc tinh th gm phn mng gi ghm chc c lc phng ca ion O2, cation chim 2/3 v tr bt din. Cu trc tinh th ca imenhit cng c th hnh dung l dn xut ca mng li NiAs trong 1/3 v tr bt din trng.
Mmen t B
18 16 14 12 10 8 6 4 2 100 -2

Dy3Fe5O12

nhit b tr nhit Curi

200 300 400 500 600

T (K)

Hnh 183. S t ho t nhin ca granat st-dydim ph thuc vo nhit

Cu trc perpkit trnh by kh k trong chng 2. Mt s oxit c cha Fe3+, Mn3+,4+ c cu trc perpkit l nhng cht st t. V d hn hp La3+Mn3+O3 v A2+Mn3+,4+O3 to thnh dung dch rn thay th bc hai.
3+ 3+ 4+ [La1-x A 2+ x ] [Mn1-x Mn x ]O3

Trong ion c kch thc ln La3+ v A2+ nm v tr c s phi tr 12 cn ion Mn3+,4+ nm hc bt din. A2+ c th l Ca2+, Sr2+, Ba2+, Cd2+, Pb2+. Kt qu nghin cu chi tit cc h ny cho thy gin trng thi ca chng, tnh cht t c trng tinh th ca chng rt phc tp.
4.2.2.6 Magnhetplmbit

l khong vt c cng thc PbFe12O19. Hp cht cng c cu trc nh vy nhng trong ch b thay th bng bari BaFe12O19 c tn gi l hexaferit bari l mt cu t quan trng ca nam chm vnh cu. Cu trc ca magnhetplmbit cng ging nh cu trc ca Al2O3 (cng thc NaAl11O17 xem hnh 29, 141, 142). Hnh 141 cho thy -Al2O3 c cu trc gm cc lp oxi gi ghm chc c. Mi chu k c 5 lp. C mi lp c 4 oxi trong t bo mng, nhng n lp th nm th ch c mt ion oxi; do mi mt tng c (4 4) + 1 = 17 ion oxi. Trong -Al2O3 th ion Na+ c phn b cc v tr trong ca lp th nm. Cn trong

179

magnhetplmbit th lp th nm ch c 3 ion oxi (ngha l ch cn thiu 1 ion), v tr cn trng c ion kch thc ln Pb2+ hoc Ba2+ chim. Do mt tng ca magnhetplmbit c (4 4) + 3 = 19 ion v mt ion Ba2+ (hoc Pb2+). Hexaferit bari c cu trc t rt phc tp, v rng ion Fe3+ chim 5 v tr khc nhau trong tinh th. Tuy nhin mmen t tng cng ca BaFe12O19 bao gm mmen t ca 8 ion Fe3+ nh hng cng chiu v mmen t ca 4 ion Fe3+ nh hng theo chiu ngc li. Do mmen t tng cng bng 20B.

4.3

Cc tnh cht quang, vt liu pht quang v laze

4.3.1 S pht quang v cht pht quang

4.3.1.1 nh ngha v nhn xt m u
Pht quang l tn gi chung ca hin tng pht ra nh sng ca cht sau khi hp th nng lng bn ngoi. C nhiu ngun bc x kch thch khc nhau. Nh quang pht quang l s pht quang do tc dng ca phtn nh sng. in pht quang l pht quang do tc dng ca nng lng in, cn pht quang tia m cc l dng tia m cc hoc chm electron c nng lng ln gy ra s pht quang, nu s pht sng ch ko di c 108 giy sau khi ngng kch thch th gi l s pht hunh quang. Nh vy, s pht hunh quang dng li hn ngay sau khi ly ngun kch thch. Nu sau khi ly ngun kch thch m s pht sng cn ko di tip tc (hng giy, hng pht, hng gi) th gi l hin tng pht ln quang.

Vt liu pht quang c cha hai thnh phn chnh: cht tinh th ng vai tr nn (v d ZnS, CaWO4, Zn2SiO4), cht hot ho thm vo tinh th nn mt lng rt t (v d cation Mn2+, Sn2+, Eu2+) i khi cn c thm mt lng cht ph gia th hai gi l cht ph gia tng nhy. C ch ca s pht bc x nh sng ca cht pht quang v c c trnh by trong hnh 184. Ni chung nng lng ca cht pht ra b hn nng lng ca tia kch hot, ngha l s pht sng ca cht rn thng thng chuyn dch v pha sng di so vi tia kch hot. Trong cc n hunh quang (lnh vc quan trng nht trong vic s dng cht pht quang v c) th bc x kch hot l nh sng cc tm (ngun bc x thu ngn).
S kch H hot H H H H H H H H H H H A H H (a) H H H H H H H pht tia H H H
S kch H hot H H H H H H H H H H H H truyn nng lng H S A H H H H H (b) H H H H pht tia

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Hnh 184. C ch s pht quang a) Mng tinh th nn l H, a thm cht hot ho A vo b) Mng tinh th nn l H, a thm cht hot ho A v cht tng nhy S.

Hnh 185 gii thiu s mt bng n hunh quang: gm mt ng thu tinh bn trong ph cht hunh quang. Trong ng c lp y hi thu ngn v argon. Khi phng in qua bng n cc electron va p vo nguyn t Hg trng thi kch ng, cc electron chuyn sang mc nng lng cao hn. Khi chuyn tr li trng thi c bn chng s gii phng ra cc tia cc tm c di sng 2540 v 1850. Cc tia ny va p ln lp cht hunh quang ph mt bn trong ng lm pht nh sng trng.
ng thu tinh
-

ph cht hunh quang

1850

Hg

2540

nh sng trng
Hnh 185. S n hunh quang

Hnh 186 l quang ph bc x ca cc cht hunh quang trn c s nn ZnS c hot ho bng cc cht khc nhau. Mi cht hot ho ng vi mt quang ph c trng lm cho nn tinh th ZnS c mt nh sng nht nh. Trong qu trnh pht quang, cc ion cht hot ho u trng thi kch ng.
c ng bc x Co Mn Ag
xanh da tri l cy
4000 5000

vng
6000

Hnh 186. Quang ph hunh quang ca cht pht quang trn nn ZnS c cha cc cht hot ho khc nhau, khi bc x bng nh sng cc tm Ion Ag+ Sb3+ Eu
2+

di bc sng ()

Trng thi c bn 4d10 4d105s2 4f7

Trng thi kch thch 4d95p1 4d105s15p1 4f65d1

Cht nn dng iu ch tinh th pht ln quang gm hai nhm:

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Cht in mi c trng bng kiu lin kt ion. V d Cd2B2O5, Zn2SiO4, apatit 3Ca3(PO4)2.Ca(Cl,F)2, khi a cht hot ho vo tinh th nn ny s pht sinh ra mt dy mc nng lng gin on. V tr ca cc mc nng lng c bin i bng s bao quanh tng khu vc ca mng tinh th cht nn. m t tnh cht pht quang trong cc hp cht ion ny ngi ta dng to hnh th (configuration). Cc sunfua bn dn vi lin kt cng ho tr, v d ZnS. Trong cu trc vng ch yu c bin ho bng cch thm cc mc nng lng nh v do a thm ion kch hot vo.

4.3.1.2 Mu to hnh th (configuration coordinate)

Biu din th s ph thuc th nng ca trng thi c bn v trng thi kch thch ca electron tm cht pht quang vo to tng qut (thng l khong cch gia cc nguyn t). Hnh 187 trnh by s ph thuc ca trng thi c bn. ng cong th nng cho php nh gi nh tnh s thay i th nng ph thuc khong cch gia cc nguyn t. ng cong i qua cc tiu ng vi i lng cn bng no ca di lin kt re. Trong trng thi c bn ca electron ch c th c nhng trng thi dao ng gin on khc nhau ca ion ng vi cc mc nng lng V0, V1 ng cong th nng trn hnh 187 tng ng vi mi trng thi electron ca tm pht quang.
Th nng

re

V2 V1 V0

Khong cch cc nguyn t

Hnh 187. S thay i th nng ca trng thi c bn ca tm pht quang ph thuc vo khong cch gia cc nguyn t trong tinh th ion

Hnh 188 m t v tr in hnh cc ng cong th nng ca trng thi c bn v ca trng thi kch. S dng hnh 188 gii thch mt s nt c bit ca cht pht quang. Trc ht, qu trnh kch thch l chuyn tm hot ng t mc nng lng A ca trng thi c bn ln mt trong cc mc dao ng cao hn. V d mc B ca trng thi kch thch. Sau trong qu trnh tch thot (relaxation) nhanh trng thi kch thch s chuyn v mc nng lng thp C v xy ra s tch ly mt phn nng lng. Nng lng mt i di dng nhit. Cui cng tm hot ng quay v trng thi c bn ca mnh (ln mc A, hoc mc D) v pht ra nh sng. V rng nng lng kch hot chuyn t A n B cao hn nng lng pht ra khi chuyn t C n D, nn bc x pht ra c c trng bng sng di hn so vi bc x kch hot. Hnh 188 c th gii thch hin tng tt nhit xy ra khi mt nhit cao no th s pht sng ca cht pht quang gim i r rt.

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Hnh 188 cho thy im E ng cong th nng ca trng thi c bn v ng cong th nng ca trng thi kch thch giao nhau. Nh vy, im ny ion trng thi kch thch c th chuyn v trng thi c bn cng mc nng lng. Nh vy im E l im di chuyn c bit. Nu ion chuyn vo trng thi kch thch c nng lng v t im E th n c th ri ln mt trong nhng mc dao ng ca trng thi c bn. Nu iu ny xy ra th tt c nng lng tch ra c thot ra di dng nng lng dao ng v khng c s pht sng. Bi vy nng lng ng vi im E c gi l nng lng ti hn. Mc ti hn nh vy ca nng lng c th t c bng cch un nng v rng khi nng lng nhit ca ion tng ln v kh nng chuyn ln mc dao ng cao hn.

183

Hnh 188. S thay i th nng ca trng thi c bn v trng thi kch thch ca tm cht cht pht quang ph thuc vo khong cch gia cc nguyn t

iu trnh by trn y gii thch hin tng tt nhit kiu chuyn tc l mt trong cc v d ca s chuyn khng bc x. Trong nhng qu trnh chuyn nh vy ion kch thch mt nng lng d ca mnh bng cch truyn nng lng dao ng ra xung quanh trong mng li ca tinh th nn. trng hp ny, ion kch thch c th quay li mc nng lng thp m khng pht ra bc x in (ngha l nh sng).
chuyn nng lng th nng Kch thch bc x

Trng thi c bn ca cht tng nhy

Trng thi c bn ca cht hot ho

Hnh 189. Chuyn nng lng khng bc x trong cht hunh quang c cha cht tng nhy

Mt kiu khc ca s chuyn khng bc x lin quan n trng hp cht pht quang cha cht tng nhy gi l s chuyn nng lng khng bc x (hnh 189). S chuyn nng lng khng bc x c thc hin nu: + Mc nng lng ca cht hot ho v cht tng nhy trng thi kch thch gn nhau. + Ion cht hot ho v cht tng nhy chim v tr gn nhau trong mng li tinh th nn. Trong trng hp nh vy, di tc dng ca chiu sng kch thch, trc ht chuyn tt c cc ion ca cht tng nhy ln trng thi kch thch. Sau mi xy ra s chuyn nng lng ln ion ca cht hot ho bn cnh. Lc ny qu trnh chuyn khng xy ra s mt nng lng (hoc ch mt mt phn nng lng khng ng k), cn ion ca cht tng nhy li chuyn v trng thi c bn. Cui cng cc ion hot ho chuyn sang trng thi c bn v pht ra nh sng. S chuyn khng bc x nng lng l c s ca tc dng nhim c do mt s tp cht. C ch ca tc dng nhim c l vic chuyn nng lng t cht tng nhy hoc cht hot ho sang nguyn t tp cht. Lc ny nng lng khuch tn trong mng li tinh th ca cht nn chuyn thnh nng lng dao ng. Khi iu ch cc tinh th ln quang cn phi loi

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ht cc ion c khuynh hng gy ra s chuyn khng bc x v trng thi c bn (v d Co2+, Fe2+, Ni2+).
4.3.1.3 Mt s vt liu pht ln quang

Hin nay nghin cu thc nghim rt nhiu h kiu nn-cht hot ho vi mc ch xc nh cc c tnh ch yu ca chng nh l nhng cht pht ln quang. Trong c nhiu h t ra c trin vng s dng thc t. Tuy nhin, cc tin b trong vic to ra nhiu vt liu pht quang mi u lin quan n vic gii thch mt cch l thuyt mi quan h gia cu trc tinh th v v tr mc nng lng ca cc ion tp cht. Di y a ra vi v d ca vic s dng cht pht quang. Trong cc bng n hunh quang s dng rng ri cht pht quang trn nn apatit vi cc ph gia l ion Mn2+ v Sb3+. Fluoapatit c cng thc Ca5(PO4)3F, a thm Sb3+ th s pht ra mu vng da cam, ng thi a c hai ion Mn2+ v Sb3+ s cho mt ph pht x kh rng ca vt liu pht quang bao gm ton vng pht nh sng trng. Thay th mt phn F trong fluoapatit bng ion Cl c th thay i s phn b di sng ca ph bc x. Hiu ng ny c gii thch nh sau: thay th Cl vo v tr F lm thay i v tr mc nng lng ca cc ion hot ho v do lm thay i di sng bc x. Nh vy, s thay i thnh phn ho hc ca cht pht sng l mt bin php c hiu qu t mu mong mun khi chiu sng.
Bng 40. Mt s cht pht quang s dng trong n hunh quang Cht pht quang Hot ho Mu Villemit Zn2SiO4 Mn 2+ Xanh da tri Y2O3 Eu3+ iopzit CaMg(SiO3)2 Ti Xanh Vollastnit CaSiO3 Pb, Mn Xanh (Sr,Zn)3(PO4)2 Sn Da cam Fluoapatit Ca5(PO4)3(F,Cl) Sn, Mn Trng

Ion hot ho l Eu3+ c gi tr quan trng nht. Khi a n vo cht pht quang s cho nh sng mu , iu ny c s dng cho mn nh v tuyn mu. Trong cht pht quang YVO4:Eu3+, nhm [VO4]3 hp th nng lng tia m cc trong ng pht electron, ion Eu3+ l mit (cc pht) pht nng lng. Vic chuyn in tch t nhm VO43 cho Eu3+ hnh nh l qu trnh khng pht x xy ra theo c ch trao i qua ion O2. S pht sinh trt t phn st t ca cc ion Ni2+ trong NiO cng gii thch bng c ch ca s tng tc trao i nh vy. S chuyn nng lng trong cc cht pht quang theo c ch trao i c bit c hiu qu nu lin kt ho hc kim loi oxi kim loi dc theo mt ng. Chnh trong trng lc mi t c s xen ph cc i cc obitan nguyn t. Trong cht pht quang YVO4:Eu3+ gc gia cc lin kt vanai oxi ropi bng 170o, do vic chuyn nng lng c thc hin mt cch nhanh chng. Khi dng cht hot ho l ion Eu3+ th v nguyn tc c th thc hin s chuyn nng lng ln cc mc f khc nhau. Nhng s chuyn khc nhau nh vy c th quan st c v rng mu ca cc cht pht quang ph thuc vo cu trc ca tinh th nn, c bit l vo v tr i xng m ion Eu3+ chim. Nu Eu3+ nm tm i xng (v d khi hot ho cc tinh th NaLuO2 v Ba2GdNbO6 bng Eu3+) th xc sut ln nht l kiu chuyn 5D07F1. Kt qu cht pht quang ny pht ra nh sng mu da cam. Nu Eu3+ khng nm tm i xng (nh trng hp NaGdO2-Eu3+) th xc sut ln nht l kiu chuyn 5D07F2 v nh sng l mu . Nh vy cu trc tinh th nn c gi tr bc nht i vi mu ca cht pht quang.

185

chun b lm mn hnh ca cc v tuyn mu ngi ta s dng cc cht pht quang m cc c ba mu: (thng thng l YVO4-Eu3+) Xanh (ZnS:Ag+) Da tri (ZnS:Cu+).

chun b lm mn hnh ca v tuyn en trng, s dng hn hp xanh (ZnS Ag+) v vng ((Zn, Cd)S:Ag+) lm cht pht m cc.
4.3.1.4 Cht pht quang phn tch tr
(a) Giai on kch thch th hai Giai on kch thch th nht
Kch thch (b)

Pht quang

Pht quang

Hnh 190. S ca qu trnh xy ra trong cht pht quang phn tch tr (a) v trong cht pht quang thng (b)

Trng thi c bn

Trng thi c bn

Cht pht quang phn tch tr l mt loi cht pht sng gn y ang c lu nhiu. Nt khc bit ca loi cht ny l n pht ra mt dng photon c nng lng ln (bc sng ngn) hn nng lng kch thch ban u. ng dng ca cht pht quang phn tch tr l cho php bin i bc x hng ngoi thnh bc x in t c nng lng ln hn (thnh nh sng thy c). D nhin y nh lut bo ton nng lng vn khng b vi phm. y qu trnh kch thch xy ra hai hoc nhiu giai on. Hin nay nghin cu kh k cc cht pht quang phn tch tr trn c s YF3, NaLa(WO4)2 v -NaYF4 vi cht tng nhy l Yb3+, cht hot ho l Er3+. Khi chiu nh sng vo cc cht pht quang bng nh sng hng ngoi th n pht quang mu xanh da tri. Trong thc hin chuyn 2 phtn b Yb3+ hp th trong qu trnh chiu sng vt liu bng tia hng ngoi ln ion Er3+ bn cnh. Sau hai giai on kch thch cht hot ho bt u pht ra sng in t trong vng thy c.

4.3.2 Laze
Laze rn lm vic da trn c s s dng cc cht pht quang phi tho mn mt s i hi c bit. Tn gi laze c rt ra t cc ch u tin ca Ligh Amplification by Stimulated Emission of Radiction (c ngha l khuch i nh sng bng bc x do kch thch ca s pht x). Qu trnh kch thch bao gm s chuyn cc tm hot ho sang trng thi kch thch (gi l qu trnh bm np), c th lu li trng thi ny mt thi gian kh lu. Trng thi c c trng bng phn ln cc tm hot ng u b kch thch c gi l trng thi kch o. Trong laze s pht mt photon nh sng bng mt tm hot ng s kch thch s pht sng bng nhiu tm hot ng khc, v tt c cc sng in t pht ra u cng pha. Do pht sinh ra mt chm rt mnh hoc mt xung bc x kt hp. Nm 1960 Meiman ln u tin ch to ra laze rubi. Hin nay lnh vc ny tr thnh mt mn khoa hc k thut c lp lin quan n vic s dng laze trong nhiu lnh vc khc

186

nhau nh: chp nh, gii phu, cc phng tin lin lc, o lng chnh xc Ngi ta ch to thnh cng rt nhiu kiu laze, c th phn tch thnh 3 kiu: laze kh, laze trn cc thuc mu s dng sng di v laze rn. y ch ni n laze rn.
4.3.2.1 Laze rubi

Laze rubi l my pht lng t quang hc u tin. n nay trn na th k qua ri m vn ang c s dng rng ri. Quan trng nht ca laze rubi l n tinh th Al2O3 c cha khong 0,05% khi lng Cr3+. Ion Cr3+ thay th Al3+ trong cc bt din bin dng ca tinh th corun lm cho corun c mu hng (t Cr3+) hoc xanh da tri (nhiu Cr3+). Hnh 191 biu din v tr mc nng lng ca ion Cr3+ trong rubi. Vic bm np laze c thc hin nh ngun nh sng mnh, v d bng n xenon. Khi electron d ca Cr3+ c th chuyn t trng thi c bn 4A2 sang trng thi cao hn 4F2, 4F1. Sau xy ra s chuyn khng bc x n mc 2E. Thi gian lu electron li trng thi kch thch 2E kh lu khong 5.103 giy. iu c ngha l kp to nn mt trng thi kch o. Bc x laze pht ra khi chuyn electron t trng thi kch thch 2E v trng thi c bn. S chuyn ny kch thch ng thi nhiu ion v bc x in t pht ra cng truyn theo mt pha.
Nng lng 103 cm-1
30
4

F1 F2

Chuyn khng bc x

20

2 10

hp th
4

E bc x lade 6934

A2

Hnh 191. Mc nng lng ca Cr3+ v bc x laze trong tinh th rubi

Hnh 192 biu din s thit b laze rubi. Phn chnh ca thit b ny l mt thi rubi di vi centimet, ng knh 1 2 cm. Thi rubi c bao quanh bng cc bng n pht xung. Mt u thi rubi c t gng phn chiu cc xung i vo ng rubi. u kia thi rubi t mt thit b c bit gi l chuyn mch Q. Ci chuyn mch Q ny c pht ra tia lade, hoc phn chiu tr li to mt chu k mi. Chuyn mch Q c th l mt gng quay. Cu trc nh vy cho php t c bc x c cng ti u, v rng cc xung nh sng pht ra c phn x t gng trc ra sau qua thi rubi lm tng cng ln.

Hnh 192. S thit b o laze rubi

4.3.2.2 Laze neodim

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Nng lng103 cm-1

20 4

F3/2 hp th 8800 bc x laz e 10600

4

10

I11/ 2

I9/2

Hnh 193. Mc nng lng ca ion Nd3+ trong laze neodim

Cht pht quang s dng ch yu trong laze ny thng lm bng thu tinh hoc granat nhm-ytri: Y3Al5O12. Tm hot ng trong vt liu ny l Nd3+. Hnh 193 c ch v tr cc mc nng lng v s chuyn nng lng khi laze lm vic. Bc x kch thch l mt bng n mnh. Khi hp th nng lng c th chuyn tip ln mt vi mc sau thc hin s chuyn khng bc x v mc kch thch 4F3/2, t 4F3/2 nhy v trng thi 4I11/2 km theo s pht tia laze c bc sng 10600 (vi thu tinh neodim) hoc 10640 (vi Y3Al5O12; Nd3+), thi gian lu li 4F3/2 kh ln v ph thuc vo nng Nd3+.
Cu hi v bi tp 1. Cc tp cht sau y: a) KCl; b) NaBr; c) CaCl2; d) AgCl; e) Na2O c nh hng n dn in ca tinh th NaCl khng? Nu c th nh hng nh th no? 2. Cng cu hi nh trn nu nh hng ca cc tp cht sau y n dn in ca tinh th AgCl? a) AgBr; b) ZnCl2; c) Ag2O. 3. Da vo gin trng thi hnh 151 gii thch ti sao ch lm vic v kh nng lm vic ca acquy lu hunh natri 200oC v 300oC li khc nhau? 4. Cu hnh in t ca canxi l 1s2 2s2 2p6 3s2 3p6 4s2. Gii thch ti sao canxi li c tnh dn in kim loi. 5. V m hnh vng nng lng ca silic (Si) vi rng vng cm l 1,1 eV. Nguyn t no c th a vo Si c vt liu bn dn loi p? V m hnh nng lng ca vt liu thu c khi mc nhn phn b cao hn mc ho tr l 0,01 eV. 6. Tinh th no ca cc cht sau y c tnh p in: NaCl, CaF2, CsCl, ZnS, NiAs, TiO2. Gii thch. 7. Nguyn tc s dng cn t xc nh vt liu thun t, st t, phn st t. 8. Gii thch t tnh ca cc spinen sau y:

a) b) c)

ZnFe2O4 phn st t; MgFe2O4 st t v mmen t tng khi tng nhit ; MnFe2O4 st t v mmen t khng ph thuc vo nhit .

9. Tnh dn in ca CaTiO3 v PbTiO3 thuc vo nhit khc nhau nh th no. 10. Thnh phn ch yu ca vt liu pht quang v chc nng ca tng hp phn . 11. Ti sao cht pht quang tch tr li c th pht ra nh sng c di bc sng ngn hn di bc sng ca bc x kch hot? iu ny c mu thun vi nh lut bo ton nng lng khng?

188

12. Yu cu chung ca cc vt liu rn s dng trong laze.

Ph lc

Mt s gi tr c trng ca kim loi

Tn Antimoan Bc Bari Berili Caimi Canxi Ch Coban Crm ixprozi ng Ecbi Galini Gali Gecmani Hafni Honmi Ini Irii Kali Km K hiu Sb Ag Ba Be Cd Ca Pb Co Cr Dy Cu Er Gd Ga Ge Hf Ho In Ir K Zn Tnc 630 961 710 1280 321 850 327 1492 1900 1500 1083 1525 1320 30 958 2000 1500 156 2443 63 419 RA 1,61 1,44 2,24 1,12 1,52 1,97 1,75 1,25 2,885 1,77 1,28 1,75 1,79 1,53 1,39 1,59 1,76 1,67 1,36 2,35 1,37 moxh 3,5 1 (2) 2 2 2 2 2,4 2,3 3,6 3 (4) 1,2 3 3 (1) 3 (2) 4 4 3 (1) 3 3,4 (6) 1 2 2,07(2) 2,70(8) 2,76(6) 3,00(12) 1,57(3) 1,67(4) 2,19(4) 2,35(6) 2,40(6) 2,47(8) 2,34(4) Pb2+ 4+ 2,18(6) Pb 2,052,14(6) 1,932,01(6) 2,02(6)Cr3+ 6+ 1,70(4)Cr 2,31(6) 1,86(2) 1,972,66(6) 2,29 (6) 2,44(7) 1,87(4) 2,00(6) 1,79(4) 1,94(6) 2,11(6) 2,23(8) 2,30(6) 2,42(8) 2,18(6) 2,32(8) 2,13(6) 2,03(6) 2,78(6) 3,00(12) 2,00(4) 2,15(12) dM-O T bo mng li rob 4,5067 o 57 6 lfmt4,0875 lfkt5,019 clf2,2856 3,5832 clf2,9788 5,6167 lfmt5,582 lfmt4,9502 clf2,507 4,069 lftk2,8846 clf3,5923 5,6545 lftm3,6147 clf3,559 5,592 clf3,6315 5,777 octhob 4,52 7,661 4,526 blend 5,6575 clf3,1946 5,0511 clf3,5761 5,6174 tetr3,2512 4,9467 lfmt3,8389 lfkt 5,32 clf2,6649 4,9468 d (g/cm3) 6,62 10,05 3,5 1,83 8,65 1,55 11,4 8,90 7,19 8,54 8,96 9,05 7,89 5,91 5,32 13,1 8,08 7,31 22,5 0,86 7,14

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Lantan Liti Lutexi Magi Mangan Molipen Natri Neoim Niken Niobi Nhm rpi Osmi Palai Platin Poloni Prazeoim Rni Roi Rubii Ruteni St Samari Scani Selen Sronti

La Li Lu Mg Mn Mo Na Nd Ni Nb Al Eu Os Pd Pt Po Pr Re Rh Rb Ru Fe Sm Sc Se Sr

920 180 1700 650 1250 2620 98 1024 1453 2420 660 900 2700 1552 1769 254 935 3170 1960 39 2400 1539 1052 1400 217 770

1,88 1,55 1,72 1,60 1,37 1,40 1,91 1,82 1,25 1,47 1,43 2,06 1,35 1,37 1,39 1,76 1,82 1,37 1,34 2,54 1,34 1,26 1,80 1,64 1,40 2,15

3 1 3 2 2,3,4,7 (3,4,5) 6 1 3 (4) 2 (3) (4) 5 3 2,3 4 (6) 8 2 (4) 4 (6) 2,4 3 (4) 3,4.5.7 3 (4,6) 1 4 (6) 8 2,3 (4,6) (2) 3 3 (2) 4,6 2

2,46(6) 2,68(10) 1,99(4) 2,14(6) 2,25(6) 2,37(8) 1,89(4) 2,12(6) 2,10(6) 1,66(4) 1,82(4) 2,00(6) 2,39(4) 2,72(9) 2,40(4) 2,52(8) 2,10(6) 1,98(6) 2,04(6) 2,06(7) 1,79(4) 1,93(6) 2,35(6) 2,43(7) 2,03(6) 2,04(4) 2,02(6) 2,03(6) 2,50(8) 2,41(6) 2,39(8) 2,03(6) 1,97(6) 2,07(6) 2,02(6) 2,89(6) 3,13(12) 2,08(6) 2,02(6) 2,18(6) 1,86(4) 2,36(6) 2,49(8) 2,13(6) 2,27(8) 1,69(4) 2,56(6)

ABAC3,770 12,131 lfkt3,5092 clf3,5050 5,5486 clf3,2094 5,2105 lfkt 8,914 lfkt3,1469 lfkt4,2906 ABAC3,6582 11,802 lfmt3,524 lfkt3,006 lfmt4,0495 lfkt4,578 clf2,7353 4,3191 lfmt3,8907 lfmt3,9239 cub 3,345 ABAC3,6702 11,828 clf2,760 4,458 lfmt3,8044 lfmt 5,70 clf2,7058 4,2816 lfkt2,8664 rob 8,996 23o13 clf3,3080 5,2653 ABAC4,3655 4,9590 lfmt6,0849

6,17 0,53 9,84 1,74 7,43 10,0 0,97 7,0 8,90 8,40 2,70 5,26 22,6 12,0 21,4 (9,2) 6,77 21,0 12,4 1,53 12,2 7,86 7,54 3,0 4,79 2,6

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2,84(12) Tantan Tali Thic Thu ngn Tecnexi Terbi Thori Titan Tuli Ta Tl Sn Hg Tc Tb Th Ti Tm 3000 304 232 -39 2700 1450 1700 1680 1600 1,47 1,71 1,56 1,55 1,35 1,77 1,82 1,47 1,74 (3,4) 5 1 (3) 2,4 1,2 (3)4(5,6)7 3,4 3,4 (2) 4 (2) 3 2,07(6) 2,04(6) 2,90(6) 3,16(12) 2,62(8) 2,09(6) 2,37(3) 2,09(2) 2,04(6) 2,32(6) 2,28(8) 2,40(6) 2,49(9) 2,26(6) 2,01(6) 2,27(6) 2,39(8) 2,45(9) 1,88(4) 2,1 (4) 2,19(6) 1,76(4) 1,81(4) 1,98(6) 2,26(6) 2,38(9) 2,29(6) 2,50(9) 2,12(6) 2,24(8) lfkt3,3026 clf3,4566 5,5248 tetr5,8315 3,1814 rob 3,005 70o32 clf2,735 4,388 clf3,599 5,696 lfkt5,0843 clf2,9506 4,6788 clf 3,5372 5,5619 octhob2,854 5,869 4,955 lfmt 4,0783 lfkt 3,028 lfkt 3,1650 lfmt 5,481 clf 3,6451 5,7305 clf 3,2312 5,1477 16,6 11,85 7,3 13,6 11,5 8,28 11,7 4,51 9,33

Urani Vng Vanai Vonfram Ytecbi Ytri Ziriconi

U Au V W Yb Y Zr

1133 1063 1920 3380 824 1500 1850

1,56 1,44 1,35 1,41 1,94 1,82 1,60

(3) 4(5) 6 (1), (3) 2-5 (4) 2,3 3 4

19,07 19,3 6,1 19,3 6,98 4,47 6,49

K hiu trong bng:

RA: l bn knh nguyn t () moxh: l mc oxi ho chnh (s ghi trong ngoc l mc oxi ho khng bn). Tnc: l nhit nng chy (oC) dM-O: l di lin kt trong mng li tinh th oxit () (s ghi trong ngoc l s phi tr ca kim loi trong mng tinh th ). T bo mng li c ghi hng s mng (): lfmt (lp phng mt tm a); lfkt (lp phng khi tm a); cdlf (chc c lc phng a, c); octhob (trc thoi a, b, c); rob (mt thoi a, ); tetr (t phng a, c); blend (tng t ZnS, a); ABAC (lc phng a, c); ABAB (lc phng a, c). d (g/cm3): t trng.