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Chuyn mc cng loi Kinh t Lut Ngoi ng Xy dng - Kin trc S phm Khoa hc t nhin Khoa hc x hi Vn ha ngh thut Y Dc Nng Lm nghip Thy sn Giao thng vn ti Tng hp Ti liu ting nc ngoi

Vt liu polyme v c

Like v Send chia s ti liu ny! Lun vn, n, bo co > K thut - Cng ngh > K thut vt liu xy dng Loi file: pdf, docx | | S trang: 83 | Trnh : i hc | Chuyn mc: K thut vt liu xy dng Thnh vin chia s: tanlocvnn | Sa i ln cui: 07/02/2012 Ti file pdf | Ti file docx Click vo y xem hng dn khc phc nu b li font ch Vi vt liu polyme v c thuc loi hp cht c khi lng phn t ln hay gi l hp cht cao phn t v thuc h polyme ni chung nhng c hp thnh t cc hp cht hay n cht c phn t b v gi l monome a t hay ngng t thnh hp cht phn t ln gi l polyme. Polyme v c c chia lm 3 nhm: - Polyme rn vi lin kt dng ion. - Cc hp cht kim loi, bn kim loi v kim loi tr. - Hp cht c tnh cht keo lin kt theo kiu cng ha tr ca cc nguyn t. Dng ny tn ti ph bin dng lng. Cng c 1 s tc gi quan nim rng polyme v c ch nn chia lm 2 nhm: - Polyme ng nht c hnh thnh t mt nguyn t do lin kt cng ha tr ca cc nguyn t thnh nhiu nguyn t c phn t lng cao gi l polyme v c d ngun gc ca nguyn t c th l nguyn t v c hay kim loi hay phi kim loi. Kt cu ti: Chng 1: Vt liu polyme v c Chng 2 :C s ha l ch to polyme Chng 3: ng dng v trin vng ca vt liu polyme v c Tag

Vt liu

Phn bn di ch hin th mt s trang ngu nhin trong ti liu. Bn ti v xem y tt c cc trang trong ti liu.

PHN I: TNG QUAN NGHIN CU CHNG 1: VT LIU POLYME V C. Trong cc ngnh khoa hc v cng ngh hin nay i hi ngy cng nhiu loi vt liu vi cc tnh cht khc nhau phc v cho cc yu cu a dng ca vt liu. Trong cc loi vt liu c vt liu polyme v c l loi vt liu c nhiu tnh cht c trng cho nhu cu ca vt liu bn nhit v bn ha. Vi hi vng trong nhng nm ti y ca th k 21 s c nhiu loi vt liu polyme v c p ng c nhu cu a dng ca vt liu. 1.1 Khi nim v vt liu polyme v c.

Vi vt liu polyme v c thuc loi hp cht c khi lng phn t ln hay gi l hp cht cao phn t v thuc h polyme ni chung nhng c hp thnh t cc hp cht hay n cht c phn t b v gi l monome a t hay ngng t thnh hp cht phn t ln gi l polyme. Polyme v c c chia lm 3 nhm: Polyme rn vi lin kt dng ion. Cc hp cht kim loi, bn kim loi v kim loi tr. Hp cht c tnh cht keo lin kt theo kiu cng ha tr ca cc

nguyn t. Dng ny tn ti ph bin dng lng. Cng c 1 s tc gi quan nim rng polyme v c ch nn chia lm 2 nhm: Polyme ng nht c hnh thnh t mt nguyn t do lin kt cng ha tr ca cc nguyn t thnh nhiu nguyn t c phn t lng cao gi l polyme v c d ngun gc ca nguyn t c th l nguyn t v c hay kim loi hay phi kim loi. Polyme khng ng nht chng c to thnh t cc hp cht phn t lung nh thnh hp cht phn t lng ln ( t monome thnh polyme). Loi ny c th tn ti dng cc mui rn nh cc mui poly sunphat, poly photphat hay dng lng di dng dung dch keo ca cc hydroxit kim loi, photphat kim loi ha tr cao hay silicat kim loi ha tr thp v cao.

Nh vy vt liu polyme v c c th c hnh thnh t nhiu nguyn t trong bng h thng tun hon Mendelev. Cc nguyn t v tr gn nguyn t Ccbon trong bng h thng tun hon Mendelev nh: B, H, Si, S, P, Ge, As, Se, Sr, Sb, Te, Bi Nng lng lin kt ca polyme ng nht c nng lng lin kt c gi tr khong 80 kcal/ mol so vi nng lng lin kt C - C trong polyme hu c. Cn polyme v c khng ng nht c nng lng lin kt kh cao hn nng lng lin kt C-C. V d nh polyme khng ng nht cha Bo v Nit c lin kt B - N vi nng lng 104,3kcal/mol. 1.1 Tnh cht ca polyme v c.

Trong polyme v c ty thuc tng loi polyme ng nht hay khng ng nht, dng rn hay dng lng m cu trc polyme c th tn ti di cc dng sau: 1.1.1 S lin kt trong vt liu polyme v c.

Cc nguyn t trong monome lin kt theo kiu lin kt cng ha tr to polyme hnh thnh mch ni cc monome vi nhau to mch thng hay mch nhnh. V d Lu hynh do c to thnh t cc nguyn t S vi mc polyme ha t 25. 000 nguyn t S to thnh mch ca polyme S mm, cn lu hunh cng ch c mc polyme ha bng 8 nguyn t lu hunh Hiro polysunfua cng to cu trc mch thng (H-S-S) Vi Oxi th nguyn t lu hunh c th to polyme khng ng nht cha oxi mng c bn v c lp li bi cc nhm S O hay S O to polyme khng ng
2 3 22 7 2-

nht c cu trc mng. Trong polyme v c c th to lin kt phi tr v lin kt cng ha tr do mt s polyme v c c th tn ti dng hp cht phc di dng cc tinh th, chng hp thnh mch c gii hn hoc khng gii hn. Do vy polyme v c cng c tnh do v n hi nh S dng do, trong to phn t ln vi mc polyme ha 25000 nguyn t S to mch di c gii hn, do Polyme ca S c dng (S) v c tnh
n

do , n cng ln tnh do cng cao. Kt lun ny do

Spekkler a ra khi nghin cu Polyme ca S . Khi n cng b tc mc polyme ha thp, tnh do ca Polyme km . V vy mun tng mc de ca Polyme v c cn tng mc Polyme ha tc tng khi lng phn t ca Polyme . Hai kim loi Selen v Tanlua v ng trng hp 2 nguyn t cng to hp cht cao phn t, ngay c oxit ca chng cng to hp cht cao phn t dng (SeO ) v (TeO ) . i vi
2 n 2 n

polyme v c th hp cht cao phn t c th tn ti dng cation hay anion dng mch thng hay mch vng. V d S c th kt hp vi Nit to polyme mch vng hay mch thng , tng t nh vy S c th tc dng vi kim loi Se hoc Te to polyme sunfua kim loi . Cc hp cht cao phn t ca anion c khi lng phn t thay i rt rng, ty thuc vo axit ca mi trng mng dao ng t 1500 - 14000 monome , cao nht c th t 120000 monome. Vi dung dch vonframmat natri khi polyme ha mi trng axit c th to phn t lng ca cc ion di dng [H O(KO )(HKO . H O) (H O) ] hay c th
3 4 4 3 2 2 3 6-

vit [ (HK O ) . x H O] hay [(HW O ). xH O] . yH WO (y = n-1). Ty thuc vo gi

6 11 52 n 4 22 2 52 4

tr pH ca mi trng. y c th c gi tr t 3-70.

Khi phn hy thy phn photphat vonframmat axit bng kim s thu c hp cht cao phn t, hp cht ny ha tan trong axeton cho sn phm dng lng v keo, trong dung dch nc s tch ra v kt tinh dng thy tinh c thnh phn ha hc nh sau (6-7)Na O. P O (22-24)WO (45-60)H O. Tt c cc nguyn t ha tr 5 u c
2 2 5 4 2

kh nng to polyme. i vi photpho v cc nguyn t ha tr 5 u to hp cht cao phn t tng t dng mch thng. Tuy nhin cng c 1 s nguyn t ha tr 5 to c c mch thng v mch vng nh cc mui poly photphat, poly acxemat, poly cloacxemat, c bit photpho nitril clorit c th to mch di v do nh cao su lu ha thp. Vi nguyn t ha tr 4 c th to polyme v c nh hp cht Silic poly silosan, hp cht hu c silic. Ngoi ra cn hp cht ca poly octo titanic axit cng thuc hp cht cao phn t chu nhit c tnh c v bn dn khi to polyme t hp cht ny . c trng lin kt ca hp cht Titan l qua cu Oxi ch khng lin kt trc tip vi nguyn t Titan trong hp cht polyme. V d khi nghin cu qu trnh Polyme ha trong dung dch Garmenat Titan to c hp cht cao phn t ca Titan . Nh vy thy r cc

polyme v c c th thc hin c s lin kt gia kim loi kim loi , kim kim, hoc kim kim loi to cc monome Se-Se, B-As, B-N, S - S vi cc nguyn t ca nhm 2 bng h thng tun hon Mendelev cng c th to cc polyme khc nhau : xi mng soren MgCl . nMgO. mH O.
2 2

i vi cc nguyn t nhm 1 bng h thng tun hon Mendelev v phn nhm th nht bng h thng tun hon Mendelev cng to c hp cht cao phn t theo kiu lin kt phi tr dng cation hoc amit. Nh vy c th khng nh a s cc nguyn t trong bng h thng tun hon Mendelev t nhm 1 n 7 u c th to c hp cht cao phn t di dng hp cht lin kt phi tr hoc lin kt cng ha tr c mc polyme ha khc nhau to ra sn phm polyme ha dng rn, lng, hay dung dch . 1.2.2. Tnh cht do ca vt liu polyme v c . Mt trong nhng c tnh khc bit ca polyme v c v hu c l tnh cht do . Vi polyme hu c c tnh do cao hn do d ch to mng mng, cn polyme v c tnh cht do thng km v ph thuc vo cu trc , mch cu trc v bn cht ca polyme.

Di y trnh by 1 trong cc polyme v c c tnh do l hp cht cao phn t ca 1 s vt liu polyme v c. Tnh bin dng do ca polyme v c ty thuc vo bn cht ca cc cht v s lin kt ca cc nguyn t trong t chc cu trc. Mt trong nhng polyme v c c tnh do gn nh cao su l S do, dng thy tinh ca Selen, photpho nitril clorit thng gp trong qu trnh ch to polyme, hp cht cao phn t ca polyphotphat nitril clorit c gi l cao su v c. V c s l thuyt do trong polyme v c: Khi nghin cu cu trc polyme v c cho thy tnh cht do cao ca polyme v c ph thuc bn cht cc cht to polyme v cu to mch lin kt gia cc nguyn t di v mc chuyn ng ni ti cc nguyn t c trong mch cu trc. nghin cu cc cht c do khc nhau thng dng phng php tnh da trn l thuyt ng hc phn t do Vonlise a ra u tin. Chng ta quan st si cao su ban u c di l khi ko dn ra c th c di l, trc khi b t c
o

di l . Khi ko cc phn t b tch ring bit khi nhau ca cc phn t c

max

cu trc dng hp c bin i t trng thi tn ti xc sut thp sang trng thi tn ti xc sut cao. S khc bit bi cao su l khi ko si dy thp s gy ra bin i ni nng ca cc ht, bin i ny khng lm thay i v tr cc ht trong cu trc m ch lm trt khi h th nng cc tiu so vi v tr tng i cc ht trong mng tinh th. i vi cc hp cht c s quay tng i ca cc phn t to ra mch tng t nh cao su th chng u c do nht nh th khi dng l thuyt ca Kun c th xc nh, nh gi nh lng c bng biu thc phn nh s thay i ca Entropi khi ko dn mc xc inh. i vi cht c cu to cao su l tng th c th dng quan h lc tc dng vo vt liu gy ra bin dng do vi khi lng phn t cc ht to ra mch ( cc nguyn t to ra mch). Quan h ny ch ph hp vi trng hp khi xem xt tng phn t l tng c cu trc dng khi( hp). Khi ny khng xem xt ti s tng tc ca phn t. S ph thuc gia Moun do ca polyme cao su l tng vo khi lng phn t c biu din bng cng thc sau: E= Trong : - Khi lng phn t cht kho st. - Khi lng ring ca cht th nghim (1)

a- H s thc nghim kh xc nh chnh xc. Theo Kun th coi a= 3 i vi polyme cu trc dng li nh polystyrene ( thc nghim a=1,3). R Hng s kh. T Nhit th. Trong c s khc bit v s a gia cc s liu thc nghim, nhng a s cc nh nghin cu cho rng nu poyme c cu trc dng li th h s a bng 3 cho nhiu cht polyme dng li. C th s dng cng thc (1) xc nh khi lng phn t ca cc polyme m bo tin cy. i vi S do th khi t nng khong 160 C quan st thy
0

nht tng t ngt, iu gii thch do s chuyn i ca mch S trong phn t

8

trng thi rt di. iu ny c thc nghim xc nh bng cc yu t: - nht rt cao ca S lng c trng cho cu trc polyme v phn t ca n gm c mch rt di v phn t lng rt cao. - Lu hunh lng c cu trc nht. - Hn hp sau lm lnh nhanh S chy lng c th ko thnh si do c dn gp 6 - 8 ln di ban u. Khi phn tch Rnghen tm thy c cu trc si. Tuy vy hin ti cha th xc nh c hay khng c cc ui t do trong mch ca phn t khi ko v mt phng bt k. Vn t ra i vi S do bao gm: - C bao nhiu phn trm S dng cao phn t khi chy lng. - Chiu di mch polyme ca S nh th no v trng lng phn t bng bao nhiu. Theo mt s thc nghim gn y cho rng khog 80% ng lng S khng ha tan trong Sunphua Cacbon, chng t 80% S to thnh polyme, cn 20% S ho tan trong Sunphua Cacbon l S khng to polyme. Paoem dng phng trnh trng thi cn bng v phng trnh Phlori c lin quan gia nht v khi lng phn t tnh c khi lng phn t ca S do dng polyme . Tnh tan cho thy rng phn t mch thng ca S do cha t 1,00010. 000 nguyn t S. Tuy nhin xut hin vn c th hay khng xc nh khi lng

phn t khi nht thay i phc tp khi nu chy. gii thch hin tng ny tin hnh th nghim gii thch da trn c s do ca S polyme sau khi c lm lnh nhanh S chy lng. Mt s tc gi nghin cu tnh cht do ca S polyme u cho rng gia S do v cao su cha lu ha c tnh tng t ( so snh trng thi ko v trng thi bin dng). Modun do trng hp tng qut theo Kun c th vit: E=E .e
01 -t/

+E .e
02

-t/

Trong :

E , E l gi tr c bn ca Modun do thnh phn do c ch dnh kt

01 02

ca phn t cht kho st. v thi gian lay ng ca phn t l i lng ni ln tc do s thay i v ph thuc nhit . Trong khi Modun do ca cc hp phn ph thuc nhit rt t. V vy gi tr quyt nh ca cao phn t l hay phn b E theo . Nu
0

>> v E >> E th do tng ng vi trng hp khi m gi tr o tin hnh

1 01 02

trong khong thi gian kho st.

>> t > > . Nu

1

v khc nhau cng nhiu v ph thuc

1

nhit th khong nhit o cng rng vn c th quan st c do ca cht Ni chung gi tr ca lin quan n do cc hp phn E ca cao su v
01

tng t nh ca cao su khng ln. V d ca cao su th E = 1. 10 . E = 2. 10 m/ cm th = 10 sec, = .

01 11 01 6 2 1 -5 2

Theo thuyt dng hc phn t ca kun th khi bin dng cc cht cao phn t th mt mt bin i v tr ca tng nguyn t so vi cc nguyn t cnh n, do vy bit c v tr c ng sut do, mt khc s bin i v tr tng mch ca khi lon trong phn t v theo l thuyt thng k s gy ra ng sut loi 1 d cn bng v cn pht trin th trng n nh ca polyme. phc hi trng thi cn bng tnh gia cc khi i hi phi c thi gian tng i lu, do qu trnh din bin cn c v tr rng ( khong din tch) khi phc. kun cho rng l s chuyn ng Brao trng thi v m v vi m. Do vy cn c 2 loi ng sut th hin l Bin dng do c xc nh bng t l s tng tnh bin dng do ( tc tng tng t i vi vi chuyn ng. / / v

v l hm ca nhit vi 1

lot cc hp cht ca S vi . Khi c nh hm lng photpho (P) th khi nhit tng ). Theo Kun ti vng tng nhit do thi gian chuyn ng lay ng gim () s chuyn ng Brao cng c hin tng

Ti vng nhit trung bnh, khi hm lng P nh th s bin dng rt t c gii thch do ng sut loi 1 tr nn rt yu, cn chuyn ng Brao v m cng cha ng vai tr chnh. Khi tip tc tng nhit do chuyn ng Brao v

m nhn thy thi gian lay ng b gim mnh. Khi tng hm lng P trong S
2

th khu vc chy mm ca S chuyn dch v pha nhit cao. iu ny gii thch do c ch ng mch (khu mch trong polyme) loi 1 ( ng vi thi gian lay ng )
1

xy ra rt mnh v tng khi tng thm hm lng P trong S. Khi ny do km khu vc chy mm. C khi thi gian lay ng v ngy cng gn nhau. S ph thuc
1 2

i lng bin dng ca hp cht S lng cha P v hm lng P khi ti trng t vo. Polyme v c phn t ln. ( Cao phn t v c). Thng thng cc hp cht phn t ln thuc v nhm ha hu c, tuy nhin hin nay khi nim khng ng bi v cc hp cht v c cng c th to hp cht phn t ln nh cc hp cht hu c. Cc hp cht v c phn t ln cng thuc nhm polyme v c, polyme v c ngy nay c nhiu ng dng trong k thut nh trong thy tinh silicat. Cc hp cht v c ni chung v hp cht v c phn t ln c tnh cht in hnh nhng t c ch ngay c trong cc gio trnh v ha bc i hc. V mt cu trc cc hp cht cao phn t hu c thng c cu trc mch dng li, cn cc cu trc cao phn t v c c cu trc a dng: dng li, dng mng, dng phng, dng khng gian v c lin kt cc nguyn t cng a dng: lin kt cng ha tr, lin kt phi tr to cu trc khng gian rt rng. Ngai ra cc hp cht v c cn c c tnh l cc ion ha tr khc nhau ngoi cc in t lp s v p cn c cc in t lp d v f. Do vy tnh cht phc tp ca cc hp cht cao phn t v c tng nhiu so vi cc hp cht hu c, do lin kt ha hc trong cc hp cht v c rt phc tp kh c th vit hon thin cho tt c cc dng hp cht. Cc c vo nhiu hin tng c th trong ha hc cc nh nghin cu a ra 4 loi mi lin kt trong ha hc: lin kt phn cc ng hnh. Lin kt phn cc d hnh ( hay lin kt dng mui). Lin kt kiu kim loi. Lin kt vandecvan (tnh in).

Ngoi ra cn c lin kt ion.

Ni chung cc hp cht cao phn t v c c cc dng lin kt khc nhau ty thuc vo bn cht tham gia to hp cht dng kt tinh hay v nh hnh. V d cc hp cht kt tinh th s lin kt ca cc nguyn t trong l lin kt phn cc ng hnh ca kim loi hay bn kim loi. 1.1 Cc dng polyme v c.

1. 3. 1 Polyme v c dng rn: Chng ta bit nguyn t Nit v oxy so vi nguyn t Ccbon u c kh nng to cu hnh t din bi v trong cc nguyn t c in t lp p c kh nng tham gia to mi lin kt c 2 u ca 1 nguyn t. Trong hp cht polyme v c kt tinh dng bn kim loi cng vi cc lin kt chnh bn phn t ln cn tn ti cc mi lin kt khc hng v pha ngc chiu vi lin kt chnh. Nh vy xut hin h lin kt cng hng lm tng kh nng phn ng ca cc phn t lm cho trng thi gi n nh km bn c th to pha v nh hnh. V vy polyme v c dng rn c th c cu trc tinh th v cu trc v nh hnh ca kim loi hoc bn kim loi. 1. 3. 2 polyme v c dng bn kim loi. Polyme v c dng bn kim loi cng tng t nh cc polyme hu c u c to thnh do phn ng polyme ha. Hi ca nguyn t Se bao gm cc vng (Se) , khi
6

lm lnh hi Selen trn b mt lnh s to ra dng Selen thy tinh ( c cu trc v nh hnh), khi ny cc vng Selen b ph v xy ra qu trnh polyme ha mch thng tuy khng phi l to mch m l c s polyme ha to polyme v c dng mch vng. Kh nng to mch vng c th xy ra khi Selen v nh hnh tn ti dng chy lng v ng rn ca Selen. Qu trnh to mch ca Selen do s phn ly nhit v khuych tn ca cc vng. Cc nh hu c gii thch rng mch to thnh iu kin khng c dng khi m dng cu trc song song nhiu hay t, do vy bc tip theo c th l to vng ln Selen v nh hnh c tnh cht chun mc ca cc polyme dng rn. Do nng lng lin kt gia 2 nguyn t mt v nh hnh rt nh, chng b polyme ha v chuyn i nhm to polyme kt tinh. Chuyn t polyme v nh hnh v dng tinh th bt u 70 C. Ban u c th cn tn ti a s polyme v nh hnh, sau
0

mi chuyn thnh polyme tinh

th trong polyme. Pht trin theo chiu di nm song song mi mng hnh xon c.

u t do ca mch trn b mt tinh th tr thnh km bo ha nu nh tp cht khng lm t mch. Nh vy trong Se c cu trc mng c s tn ti khng phi trong mch m ko di theo cc mch ca mch cu trc. Polyme v c dng lng. 1.1.1 Gii thiu chung.

Polyme v c dng lng thng l polyme khng ng nht c hnh thnh t cc nguyn t khc nhau to monome sau tng hp thnh polyme. Do vy polyme v c c th bao gm cc hp cht sau: - Poly sunphua: X- S - S - S - - S - S - X Trong X l nguyn t halogen.

- Hp cht cao phn t mt s Crom amit

- Photpho nitril clorit:

Flo bezylat:

Poly photphat:

Poly Silicat

Nh vy cc hp cht cao phn t v c rt a dng v c hp thnh t cc cht khc nhau to ra cc polyme rt a dng khng ch loi mch thng m cn c c loi mch nhnh, mch vng, cu to phng, cu to khng gian do s lin kt ca cc nguyn t trong hp cht cao phn t v c ( hay gi l polyme v c), tn ti cc polyme c th trng thi kt tinh, trng thi thy tinh (v nh hnh). Do polyme v c dng lng cng rt rng, di y ch gii thiu 2 loi polyme v c dng lng l silict v photphat. 1.1.1 cc dng tn ti ca cc cao phn t v c.

Cc tinh th ca hu ht cc hp cht ion u c phn t lng rt ln. V d nh NaCl iu kin chun ch tn ti dng kt tinh vi lng rt ln cc nguynt to cu trc mng. Cn trong dung dch chng ch tn ti dng hp cht ion c phn t khng ln, bi v khi ha tan cc phn t b tan c s chuyn dch ln hay nh ca cc ion. i vi mui Kali phtphat li c th to hp cht phn t ln l Kali poly

photphat, trong nc mui ny phn ly thnh ion (K ) vaf ion poly photphat. Khi ny
+

anion poly photphat l mt mch cao phn t bao gm cc nhm t din PO mang
34

in tch m. Cc anion ny to tinh th hnh kim, cng c cc ion cao phn t trong dung dch vn gi c dng tn ti nu pH c nhit gn vi gi tr pH ca nc.

cc mui KH PO 300 C, cha cc ion trong c cc mi lin kt P-O-P2 4 0

gia cc phn t tin a t rt vng chc. Nn xc sut to tin a t tng ( nh trong cc axit hay photphat) th hp cht to cu trc dng li.

Dng cu trc dng li ca Photphat. Trong cc trng hp ny th bn vng ca cc hp cht b gim dn t oxit photphoric n mui photphat, do chng d b thy phn. Nh vy bn thn H PO b a t khi nhit rt cao khi khng c nc. n
3 4

nh ca cc polyphotphat c to thnh cn bng rt nhy cm vi nc c mt

trong h. Nh vy c 2 loi mui photphat c th to polyme, mt loi khng cn nc, mt loi phi c nc, hai loi na c s khc nhau v c trng lin kt. Hin nay c bit giac poly axit photphoric v monome octo photphoric axit trong nc khng c cn bng. Tuy nhin v tr cc ion b thay i, nu trong dung dch tn ti khng ch bn thn axit photphoric m l cc dn xut ca n. i vi dn xut clo anhyric photphoric nhit thng c thit lp cn bng polyme dng:

cc cu t tn ti v hnh thnh s lin kt keo. Thi gian keo ha cng di cht keo c th c hnh thnh khng ch l hp cht polyme v c hay b polyme ha khi ha tan. Axit poly photphat cha cc mc phn t ln. Mch t din photphat c kt hp vi mch vng phn t thp ca 3 n 8 meta photphat. Dung dch nht polyme v c c th c hnh thnh v ch to bng cch ha tan: photphoric. i vi cc nguyn t c mc oxy ha khc nhau c th to ra keo cation a nhn, cc phc hydroxyl hoc cc keo anion nu mc oxy ha thp. Qu trnh polyme ha c s tham gia ca phn ng oxy ha kh cho php ch to nhn v c. Ngoi ra c th s dng cc nhm c trng trong dung dch c mui Ha tan polyme rn hay thy tinh t bn ha ( Ha tan polyme rn nhn Ha tan cc cht c xu th polyme ha theo cation hay anion s cho Ha tan cc oxit, hydroxit hay cc mi trng cht lng phn cc to hay tng hp nh ct thch anh trong kim hay ha tan cc cht in ly a ha tr). keo axit hay keo kim. to thnh polyme do phn ng tng tc axit- kim ca dung dch photphat trong axit

v c c d dng to cc tinh th ngm nc t cc tp hp ht v s chuyn nhm bin i. Mun vy c th: - Ha tan cc tinh th hydrat ti nng gn bo ha. - Ha tan cc hydrat ngm nc v kt tinh c bit trong nc s tng bn ca keo v c cn phi c s phn pha to ra pha mi ha tan ca keo khi polyme ha, do vy cn phi c c ch chuyn i t cht c ha tan b bng cc gii php sau: + a vo dung dch cht ng rn lm gim ha tan ca cc cht d tan lm thy phn ca h c ion tham gia polyme ha to hp cht km tan. ( V d hp cht Silicat kim loi kim cho thm ion Ca bin thnh cht khng
2+

pic hp ph tng ng vi dao ng ca lin kt Si - O v phc tn s hn tp v quan st thy khung cc anion hn tp t cc t din SiO v AlO .
4 4

Trong dung dch cha bo ha ca alumonat kim khi pH cao l s chuyn i ion aluminat n nhn Al(OH) , [Al(OH) . 2H O] . [AlO(OH) ] . Cc dng ny c th
4 4 2 2 -

tn ti trong dung dch v d: Al(OH) [AlO(OH) ] + H O AlO + H O

3 2 2 2 2

V chuyn dch cn bng v pha phi khi t tng v nng tng. Trong dung
0

dch long v pH 13 s tn ti ime [Al O(OH) ] (OH)

2 6 2-

(m+2)-

. Trong dung dch c th

khi pH > 13 li to cc monome. S khc nhau gia Kali v natri trong dung dch ny khng nhn thy. Trong dung dch c s tng tc lp v ngoi ca ion aluminat vi cc cation, trong ion tch in cao [Al(OH) ](OH)
4 2 (m+2)-

c kh nng phn ly anion

phn t vi in tch ca cation. Khi tng nng aluminat v cc i ion gia Al(OH) v ion Natri khi thy phn. Vn tn ti cc anion polyme khi nng cao
4

trong dung dch v gi tr pH ln ang l i tng nghin cu ca nhiu tc gi. Theo s liu quang ph lin hp tn x (CRP) th trong dung dch aluminat Natri quan st oc cc monome Al(OH) vi cc nhm i xng t din AlO v ime
4 4

[(OH) .AlOAl(OH) ] , trong ime to ra trong dung dch c. Cn trong dung dch
3 3 2-

long th cc mui tn ti cc phc a nhn [Al (OH) ] . Cc polyme anion cng c

5 20 4+

th to ra t cc poly ocxo ion ca cc nguyn t nhm d- bng h thng tun hon. S bn vng ca cc poly ocxo ion tng ng vi bn c cao ca cc vt liu c th ch to t hp cht ca ng Cu . Vic hnh thnh cu trc v tnh cht ca dung dch
2+

cha cc poly ocxo ion ng vai tr rt ln ca lin kt hydro.

Trong dung dch c ca anion photpho c s lin kt ca mi lin kt hydro, cn trong dung dch long th nht gim lm yu mi lin kt hydro ca H O trong
2

mng anion. Phn t H O phi tr vi cation v lin kt trc tip gia mi lin kt
2

hydro vi cc anion trong h. 2. 3 Thnh phn v cu to dung dch cha polyme v c.

c im chuyn dung dch v trng thi 2 pha. Khi nng dung dch cao th trong dung dch bt u c s to ra cac mixen (tm to ht) c s chuyn i h v trng thi keo. Khi ny bt u c hin tng tp hp cc cht in ly mnh to ht mang in tch Mixen ( cha ti 50- 100 phn t) khi ny nu tng lc ion ca dung dch th khi lng dung dch biu kin tng. Hin tng bin dung dch thnh 2 pha c tc gi (49) nghin cu. S to gel xy ra qua vic hnh thnh cc phc a nhn ca Al v ph thuc nng Al , bn cht cc
3+ 3+

anion, t l [OH ]/ [Al ] = x. Khi nghin cu cng hng t ht nhn ca Al cho php
3+

theo di ring cc bc xy ra to gel bi cc phc [Al(OH) ] , [Al (OH) (H O) ] ,

2 6+ 2 2 2 6 4+

[Al O (OH) ] (k hiu Al , Al , Al )

13 4 24 7+ 1 2 3

S ion trung bnh Al trong phc a nhn hydroxo khoarng 6-13, khi lng
3+

phn t trung bnh 1000-1400. Dung dch cha Al nh dung dch thc, cn qu trnh
13

a t i qua tp hp phc hydroxo gin on ch khng phi ng tng lin tc. Khi Al > 1M to gel tp hp phc sau: Al
3+ 1

Al , Al + Al
2 1

Al , Al
p

30C

To kt ta bao gm cc giai on sau: Monome -> imer -> phc a nhn hydroxo - >ht s cp (h gel khng trt t) -> tp hp c trt t. Trong qu trnh a t cc ion kim loi hot tnh s tp hp gii hn ht phc a nhn hydroxo, khi ny gi tr quyt nh l phc a nhn hydroxo t to ht s cp. C th iu chnh phc a nhn hydroxo v thnh phn nh dng phc a nhn hydroxo. Quan im l thuyt khi kt tinh hydroxo dng v nh hnh khng bng con ng ha tan m bng con ng thay i cc polyme va chm ca cc ht s cp. Trong khi xut hin cc ht s cp trong khu vc ca cc ht c trt t pht trin ln mt mt duy nht ca cc ht bn cnh. l cc vi tp hp hay cc ht tin kt tinh v tr thnh trng tm kt tinh ca cc ht, pht trin cc ht th

cp thc hin c bng nhiu cch khc nhau. Tukanop l ngi nghin cu cc vn ng hc kt tinh ht th cp. Trong

cao. S bm dnh phn cc ca cc nhm hot ng trong polyme lm cho s bm dnh ca cc vt liu tt hn c 2 pha b mt ca vt rn vi lp keo ng rn. Cc polyme trong dung dch nc u c mi lin kt hydro- l nguyn nhn to ra lc kt dnh ng mch ca nc ( sc cng b mt ln) nn chng d c kh nng thm t cc vt rn. S lin kt thm t do c mi lin kt hydro gia cc phn t nc vi nguyn t Oxy ca vt rn. V vy cn s c mt ca oxit a vo polyme v c. Cc s liu v s thm t ca cc cht cng cho bit vai tr quan trng cc tng tc ca cht in ly phn cc khi hp ph. Nhit thm t t l thun vi ng sut trung bnh in trng trn b mt v rt gn vi phn t momen lng cc ca cc nguyn t. S cn bng phn b cc ht trn b mt cng thay i, mt phn cc cation c th dch chuyn vo trong vt rn, cn b mt mang in tch. Nh vy theo tnh cht ca ha tinh th vt cht c dnh li vi nhau (cc ht cht kt dnh, cht n, cht mi to ra) v cu to in t cc cation cng nh hng, tc thm t v tnh kt dnh ca h keo. Vi cc nhn nhn nh vy cho thy s nng cao phn cc ca vt liu cng s nng cao c bm dnh. Do vy c th coi bm dnh ban u ca cc polyme v c c thy bng bn bm dnh cui cng. Mt s tc gi cho rng s to hp cht ha hc pht trin theo 2 chiu ca b mt s c nng lng b mt thp do to hp cht b mt khng bn. Cn phn tch nhit ng cho thy s tht ng, s hnh thnh pha 2 chiu trn b mt c ghi nhn bi thc nghim khi xem xt 2 oxit. Nhiu trng hp cc qu trnh kt dnh c gii thch bng hin tng tch in ca lp in tch kp v s to ra s khc bit v in th. L lun kt dnh theo thuyt tng tc phn cc c Epphremevo t nn mng bng m hnh cu to theo lp- lp kt dnh vi nhau nh cc lp hp ph i xng trn b mt hot ng ca lp kt dnh mang c tnh ca ion phn cc . L lun ny c cng c thm khi c s tng tc tp hp ca cc phn t phn cc trong lp kt dnh b mt i xng. Cn khi cu trc nc bin i lp b mt v tnh cht mng ca gel s bin i n hiu ng phn cc cn thit ca nc v ca phn t phn cc sn phm ngng t. Khong cch nh hng ca b mt vt rn c chuyn thnh gii hn ca lp s tng khi c mt ca H O v ng vai tr quan trng n s to thnh lp
2

gii hn. Trong qu trnh ng c ca keo lm tng s tng tc i

kh nng cho- nhn in t ( donor). Nu cc qu o ca nguyn t l vng ha tr th s l cc anion, cc qu o anion ny xut hin trn trng thi b mt cng c tnh cht cho nhn in t. Nh vy trng thi kch ng c th mang tnh cht axit hay kim ti trung tm tip xc. Ngha l c tnh cht cho- nhn in t trng thi ion b mt tip xc pha. i khi cng c th xut hin ng thi cc tnh cht cho v nhn in t lp b mt tip xc ca nguyn t. Tnh cht ny ph thuc iu kin tin hnh, cc nguyn t cng dn in th hin tnh cht cho- nhn mnh hn cc nguyn t bn dn. Mi nguyn t c th tn ti cc trng thi b mt khc nhau: V d nh Silic c 3 trng thi b mt: - Trng thi vi nng lng max to lin kt. - 2 trng thi cn li lin kt cc nguyn t b mt. i vi cc tinh th vi lin kt hn hp th tn ti trng thi b mt ca ion hay ca dng lin kt cng ha tr: trng thi ion. B mt rt gn vng dn v vng ha tr tng t nh cc nguyn t trng thi ha tr c lin kt (mi ni) t do. Khi ng rn keo phe to ra c lin kt ion v lin kt cng ha tr, chng c trng bng trng thi kch ng b mt v trng thi to mi lin kt dng khng cp i in t trn b mt cc nguyn t vi s phi tr thp ( tng t nh cc nhm chc v c kh nng phn ng cao). Tt c tnh cht xut hin trong qu trnh tng tc b mt ( hp ph, phn ng phn ly) i vi cht hp ph cng nh i vi pha tch ra vi cht n hay vi kim loi. Cc nguyn t bn cnh khng bao bc hon ton cc nguyn t b mt ( gim phi tr), s thay i cc nguyn t b mt gy ra s gim trng lc, tc dng trn cc nguyn t b mt. Kt qu thay i tnh cht ng ca b mt mnh to ra cc hiu ng b mt: ph proton v bnh phng bin , tc dao ng nguyn t, Cc hin tng ny ch ra trn cc hin tng sau: khuych tn b mt, thm t, chy mm nhit dung, dn nhit, phn tn dng in trn b mt. S yu lin kt ha hc trn b mt dn n tng bin dao ng ca cc nguyn t trn b mt. Do vy i vi cc phn ng b mt i hi nng lng hot ha t hn. Mt trong nhng tng tc b mt l s hp ph. Hin tng hp

lng KNH m vi 4 ng lng ca n, do vy ocxoamit tch ra tng

2

tc trc tip vi lng KNH cn li cha phn ng to mui amit, mui ny khng
2

b tch m t phn ly ra NH v mui amit.

3

[UO (NO ) ]K + 4KNH UO (NH ) K + 3KNO

2 3 3 2 2 2 4 2

UO (NH ) K 1/ n [UO (NH ) K ] + 2NH

2 2 4 2 2 2 2 2 n

Cc mui v nh hnh ny v cao phn t ca amit khi t nng li tip tc thot ra NH to mui ocxoamit v nh hnh v cao phn t:
3

3[UO (NH ) K ] 3 [(UO )N K ] + 2nNH

2 2 4 2 n 2 4 6 n

Mui ocxo amit Uran tng t nh mt bazo khi phn ng n vi amon Iodua. Khi ny cc ocxo amit b ha tan trong NH lng to mui km theo s ct
3

cc cu ni gn hay xa ion trung tm theo c ch sau: 1/ n[UO (NH ) ] + 2NH I UO (NH ) I + 2 NH

2 2 2 n 4 2 3 2 2 4 + 3

Ion NH c th ct cc cu ni tip tc n ht to:

u tin to ion tatra amin Uranil dng XXI, ion ny d cho i 2 phn t NH , khi to mui kt ta Uranil diamin Iodua dng XXII. Ocxoamit dng XV mi
3

u c lin kt phi tr gn nguyn t trung tm oxy, nhng trong NH lng cng

3

tng t nh cc amit kim loi ha tr 3 ca Crom, Titan, Coban u thuc h mui amoni. Khi thay th mt nhm amin bng hydroxyl OH trong amit kim loi ha tr 3
-

s thu c hp cht mi monohydroxo amit kim loi: V d Coban c hp cht Co. OH(NH ) - monohydroxo amit Coban.
2 2

Vi cc hp cht monohydroxo amit ca kim loi ha tr 3 c th to c bng 2 cch khc nhau:

Nu khong cch gia cc nguyn t ti b mt ln hn 0. 5-0. 6 nanomet th tip xc s c cu trc

v bn ca mi tip xc thp. i vi thu tinh lng hay t gel SiO c th c ion Silic chuyn ra b mt v tip xc trn c s
2

v bn rt cao. Tuy nhin do s ri khi ca Silic khi cng gm cc ion oxy mt t din (SiO ), nng oxy trn b mt s cao. S hydrat amino thc hin bng cch nh mi
4

lin kt hydro. Do vy tn ti vai tr tip xc s thuc dng:

bn mi lin kt hydro ca cc anion s tng theo dy cc cht sau: SO ,

4 2-

PO , SiO . Kt qu ny tng ng vi kt lun. S dnh kt trn c s sunphat km

4 34 4-

hn cht kt dnh trn c s photphat v silict. Thng trong qu trnh ng rn xy ra cc giai on: ng t v ng rn. i vi giai an ng t c trng bng bin dng i hi thun nghch cao. Khi khng c s chy nht - nh c lin kt bn gia cc ht. Ngoi ra cn do un n hi ca phn t ln v kh nng bin i ca n khi ng t . Khi c phn ng trao i ( gia Magi sunphat hay sunphitbari, sunphatbari v nh hnh bt u ng t to gel n h. S ng rn ca keo c th thc hin nh a thm vo keo cht in ly lin kt vi cc mi lin kt ngang to thnh v khng nht thit phi c bn cht ho hc ging nhau, bi v khi xut hin ng t trong trng hp t nng s bin thnh cht chy nht. Rt nhiu loi keo ng rn khi t nng. c th din ra cc phn ng thu

phn dn n hnh thnh cht rn, bi v hng s cn bng ca phn ng tng khi tng nhit s tng theo. Khi thu phn c th kt ta cc hydoxit, hydroxitoxit v oxit kim loi. V d Nitrat st c th dn n nng v pH n gi tr t c th kt ta Fe(OH) nhit 80 - 120 C v dng
3 0

Bng phng php tn x nh sang v nhiu x tia X gc nh cho bit s to ra cu trc (to gel t gel) trong qu trnh hidro gel SiO to thnh t dung dch Silicat
2

natri di dng hidro gel SiO v hidro gel alumosilicat. Ht s cp ca gel c kch
2

thc trung bnh1, 5.10 cm s to gel thc hin c nh s t tp cc ht xp to ra.

-7

Theo Phuronop- ngng t cc nhm silan b mt khng phi do pht trin tp hp bng cch tch silic t dung dch . Tc tp hp n khi hnh thnh gel trong hidro gel 1 cao hn hidro gel 2(gel to ra t Na SiO v gel to ra t Alumo silicat). Ti
2 3

mt thi im mt linh ng ca h kch thc trung bnh cc ht 6, 58, 5.10 cm

-6

cn trong gel 1 t 46. 10 cm, trong gel 2 nng chng t 21, 5.10 g/ cm . Mt
-6 -2 3

s tc gi cho rng cu trc keo t ca keo SiO ch xy ra trong lp hp ph b mt

2

vi cc cation c bn cht khc nhau . i vi cu trc a phn tn ca keo SiO c

2

xc sut phn gi thp trc khi tip xc pha. S ng rn ca keo axit dng hidroxoclorit c lin quan n s dch chuyn cn bng thy phn v pha ngng t cc cation thy phn v kt qu cui cng h l cc hidroxit: ZnO.HCl+ H O
2

Zn(OH) +HCl. Khi dng cc mui hydroxoclorit quan st thy s tng tc khc nhau
2

v ph thuc c tnh ca bt thch anh v nhn c kt dnh cao cn bt magietit bm dnh km hn do tng tc ha hc. c bit khi dng polyme v c d chy ca nguyn t S trng thi lng sau khi nng chy mi c tnh cht polyme (tng t nh kim loi hn). bm trng thi lng sau chuyn thnh rn khi lm lnh. Kt qu qu trnh nng chy v lm lnh cht lng ng rn v chuyn v dng v nh hnh hoc tinh th c bin dng do c bit Vi cc cht v keo c s dn n khc nhau khi ; m lnh trong keo xut hin ng sut d, do c th lm gim tnh cht bn ca mi ni. 3.2. Trin vng pht trin ca polyme mi. V mt l lun ch to polyme v c , ngi c ng gp u tin l Strep. Ngy nay cc tng ny c p dng v nghin cu pht trin i vi cht dnh kt cn phi c nng cao, mc ngng t dn n to cc pha hidrat (nh trong xi

mng). Do vy ch to polyme v c mi l lm xut hin kh nng dnh kt da trn c s pht trin ca hp cht .

Nh vy trin vng nghin cu cc hp cht c kh nng cho tnh cht keo phi c tnh cht: - Tnh quy lut ca s xut hin tnh dnh kt. - C kh nng polyme ha thy phn khi ha tan. - C kh nng to polyme dng anion bng cch a t. Vi t lng nh vy cn da trn c s bng h thng tun hon Mendelev trong c s ph thuc vo nhit chy lng, bn knh ion, th ion ha, nng lng hydrat ha ca cc ion ph thuc s th t mang tnh chu k ti cc i v cc tiu. S c mt ca pha hydrat- hp cht phc (tinh th ngm nc) l iu kin cn xut hin tnh dnh kt. V vy trn c s pht trin phi da vo kh nng to tinh th ngm nc nh hp cht phc. Bc u phn tch mt vi vn d lm xut hin tnh dnh kt theo quan im h keo. Cc ion trong thnh phn ca n c cc nhm OH hay cc nguyn t oxy, mt vi
-

nguyn t kim loi hay kim l cc polyoco ion: Be (OH) , ZnOH , Cr O ,

3 3+ 3 3+ 2 7 2-

ThOOHTh .
3+

Polyocxo c hnh thnh vi nhiu kim loi c mc oxy ha t + _2 n +4. Poly ocxo anion to ra ch yu bi cc kim vi mc oxy ha + 3 n +6. Cc a ion c 1 phn lin kt cng ha tr khi bn cao hn khi khng c dng lin kt ny. S xut hin 1 phn lin kt cng ha tr dng s lm gim hiu ng tch in trn cc nguyn t v gim s tng tc tnh in. Do vy a ion c lin kt hn hp bn hn lin kt n l. Theo lc ko th s gim tng tc c b tng bng s xut hin lin kt cng ha tr, cn s gim lc y khng c g b tng. Do vy c lc hn hp trong cc a ion c li. Khi c mt 1 phn lin kt cng ha tr s dn n a t thy phn polyme ca cc cation Cd , cn khi khng c lin kt cng ha tr ca ion Cd .
2+ 2+

Khi khng c mt ca cc c ion Mg v Tl c lin quan n s c mt ca s lai ha

2+ 2+

qu o in t sp v ds-orbitan. bn ln ca cc ion polyme Ca so vi cc

2+

nguyn t cnh n c lin quan n hiu qu ca trng lc do lin kt bn v i xng vi gc. Tro polyme khi thy phn c lin quan n s gim nng lng t do Gips v gim Entropi. V vy khi

t nng qu trnh xy ra v pha kh polyme. Khi tng lc ion ca dung dch cn bng s dch chuyn v pha to phc polyocxo cation, cn poly anion to ra bi c trng cc nguyn t c tnh cht kim. Poly anion c to ra t cc nguyn t oxy v ion trung tm trong cc trng hp sau: - Nu khc nhau v bn lin kt M - O v M = O nh (i vi Si= 0,01; C= 0,11; N=0,13) - Mc oxy ha cng thp ca nguyn t trung tm cng thp cng khng c kh nng to polyanion. - Nu trong dung dch to cc ht trung ha in tch v khng phn ly ca axit( vi axit c mc phn ly anion yu)

Gim nhit v tng lc ion ca dung dch lm thay i cn bng v pha to poly cation. Bit cu trc ca polyme Metyl silicat ( SiO ), oxy anion kim loi vi mc oxy ha thp
3 2-

(BeO , AlO , ZnO , SnO ) khng c kh nng vit bng s d ha tr v trng thi
2 23 322 2 2-

rn my ha tr ca. Cc nhm hydroxo v phn t nuc phi tr quanh ion l cc in t i vi my ha tr ca nguyn t trung tm :

Mc oxy ha cc nguyn t dng oxy anion nh hn s nhm c ha tr cha bo ha v 1 phn in t ha tr khng b li ko vo lin kt ha hc. V d my ha tr ion CrO Zn
3 3-

c 3 in t khng lin kt, s dng cc anion ny cn bit chng v

4 23 333 3 23 23 3

tng t polyme vi: CrO . M , KO , V, SiO , SnO , PbO , GaO , Ti, Zr, Al, Ga,

 bn mi lin kt O - H v X - O - H cng yu nu th ion cc nguyn t X ln, khi ny xy ra chuyn dch cc in t lin kt v pha nguyn t X v keo chng khi nguyn t hidro, do lc axit tc ng, lc axit cng cao mc oxy

ha cng ln trong anion. Trong cng nhm th oxi ha gim t trn xung di (kch thc nguyn t tng), tch in ion hnh thnh khng thay di- t l tch in ion/ bn knh ion b gim. Hin tng ny s t mi lin kt O-H. Khi chuyn cc nhm chu k t tri qua phi tch in tng, cn kch thc nguyen t gim, axit cha oxy c kh nng phn ly mnh cc nguyn t nhm 7. Do vy c th polyme anion Silicat,phtphat, sunphat. Cc polyme cation c th c cc nguyn t : Be , Al , S ,
2+ 3+ 4+

Zr , Cr , Fe , Ca Cc nguyn t nhm f c mc chuyn tip Ga , Sn

4+ 3+ 3+ 2+ 3+

2+,3+,4+

, Sb ,
5+

Bi to polyme cation.
3+

Cc polyme v c thng chy nht trong dung dch do hin tng dn n trng thi thy tinh d dng v cn phi tnh n khi nghin cu kh nng to polyme mi. i vi cc oxit c s tng quan gia thy tinh ha v loi keo v c c trng bng hiu m in. Cc cht n phn hay phc tp u c lin kt cng ha tr hay lin kt hn hp, trong cc iu kin xc nh u c kh nng a n cc phn t cha bo ha v tn ti trng thi thy tinh. Trng thi thy tinh c trng bng chiu di thc ca ni lin kt v gc to ra lin kt. V vy thy tinh khng c th to ra t cc hp cht ch c thun ty lin kt cng ha tr, i vi cc cht ny c c trng bng di mi ni v gc quay khng i. Cc cht ch thun ty c lin kt dng ion hay dng kim loi khng cho trng thi thy tinh. Do vy trng thi thy tinh to ra cc cht c lin kt hn hp: ion - cng ha tr (SiO , B O ), cng ha tr - Vandecvan (hp cht hu c) trong
2 2 3

lin kt cng ha tr dng cu trc mch v lc Vandecvan gia cc nhm mch. Nng lng mi lin kt M - O trong mc xc nh l ch s thy tinh ha. Nng lng chy nht i vi hp cht chy lng SiO , B O c gi tr khong (25- 30)
2 2 3

RT . Tuy nhin cha bo ha mi lin kt ca cc tp cht v qu trnh xy ra trn l

ch

mt phn cha pha c th gim thp thm nng lng kt tinh. Vai tr quan trng khi thy tinh ha l bn lin kt. Vi thy tinh khi cho cht c bn mi lin kt M - O cao (335500Kj/mol) th d to trng thi thy tinh.

Tilo cho rng cn bng polyme ha c thit lp trong dung dch nc nn nng monome khng phn ly cao. V vy dung dch axit hay kim mnh hm lng polyme khng phn ly thp v khng phi l s quan tm ca cc nh nghin cu polyme bi s hnh thnh cc cht c ngng t trong mi trng khng phi nc. Theo Tilo s ngng t cc hydroxit xy ra cng d nu bn knh ion trung tm cng ln ngha l s ngng t c lin quan n mc ion ha. Bn knh nguyn t trung tm cng ln th khong cch gia cc nguyn t cng ln, lc y cng yu trong nhm X-O-X. Khi thay i dng lin kt trong nhiu ion cho thy gy ra s thay i s phi tr. Khi r r = 0, 12-0, 26 k mui c kh nng to dung dch keo. Theo ha tinh th
c/ a

c vng to cu trc thng phng hay chuyn thnh cc khi t din. Khi tng t l r / r th s phi tr tng v c s thay i dng cu trc v c s thay i dng cu
c a

trc v nng cao mc khng bo ha mi lin kt. Vng c s phi tr 4 - 6 l vng to kh nng hnh thnh phc v xut hin tnh cht dnh kt ca h tng t nh xi mng. Khi tip tc tng s phi tr v s chuyn cu trc v dng cu trc c hn th mi lin kt tr thnh ba ha hn v lm mt kh nng phn tn ca h, kt qu dn n s xut hin ng rn theo s ng rn trong keo ( tch pha rn t t). Trn bin chuyn i ca loi cu trc xem xt th bn ng rn c gi tr cc tr cao. ngha s phi tr c lin quan ti cu trc lp in t ca cc nguyn t. V d nh sp ,
3

d s qu o lai ha tng ng vi cu trc t din, dsp cu trc phng, d sp cu trc 8

3 3 2 2

mt, dp v sp cu trc thng. do qu o lai ha ca t din s dn n to cu trc thng v phng ca cc phn t v nhiu kh nng ch to keo dng dung dch, cn t din a n ng rn theo c ch to pha rn t t ( xi mng). i vi cc hp cht km tan v ngng t cao c th dn n qua dung dch mui, cc mui ny tn ti trong mi trng axit hay kim. Mc polyme ha cc tiu h c dch chuyn rt cao do c mt nhm H O , OH v cc yu t khc. i vi cc h km tan v a t tt
3 + -

c th thng qua dung dch mui i vi cc hp cht km tan v ngng t cao c th dn n dung dch mui, cc mui ny tn ti trong mi trng axit hay kim.

i vi cc hp cht c ha tan nh hn th thi im tch pha c phn tn cc i do c dng keo ln nht. Vi phng din xem xt 1 lot cc hp cht ha hc: mui trung tnh- kim tnh, mui hydroxit th c th da vo to ra nhiu keo mi. v d dung dch hydroxo mui c kh nng to phc a nhn trong

dung dch, cc hp cht ny thuc nhm polyme phi tr. Ty thuc vo gi tr pH ca dung dch nng , nhit c th to ra mui trung tnh M A ti hydroxit [ M(OH) ]
x y p n

mt dy lin tc cc polyme mui thay i thnh phn R[M (OH) ]

x p

p-x

v c s dng

nh cc cht kt dnh v c. Cc nguyn t c tnh cht nh vy gm c Al cho php th hin dng s v to ng i cho ch to cht keo v c.

Nh vy cng c thm s v cc cht axit yu kim ngng t trong dung dch nc n kh nng bin i to ra cc keo v c dng dung dch nc theo s H1 ca mt nguyn t c th tn ti nhiu dng keo khc nhau dng n l hay phi hp vi cc nguyn t khc to keo phc tp da trn cc nguyn tc: - chuyn cc mui axit v mui trung tnh - Chuyn mui trung tnh v kim v dng hydroxit. i vi cc hp cht a d th thuc nhm 4 v 5 bng h thng tun hon c bit cc ion cha nhiu in tch (+) v c bn knh ion nh. Khi bn knh ion tng kh nng to hp cht d th km. Cc axit d th v mui ca chng ha tan tt trong nc, trong r axeton. Khi kt tinh chugns to dng ngm nc, do cho sn phm dng lm nguyn liu ch to keo v c. Cho rng cc hp cht d th trong dung dch nc s to cc phn t ca phn t v vt m ra trin vng ch to keo t chng. Tuy nhin cc hp cht d th bn trong mi trng axit v khi tng nng s xy ra hin tng polyme ha v to keo axit. V vy keo axit c th pht trin t hydroxo Nitrat, hydroxo

clorit Zr, Cr, Ce, Ti, . Ngoi keo axit cn c keo kim. Trong loi keo kim gm c cc mui hydroxo ca Al, Si, Cr, Sn, Be, zn, Nb, Ge, Sb, Ta, V bng con ng ngng t anion trong dung dch cc mui hydroxo ca cc nguyn t trn chuyn chng vdng polyme ca cc hydroxit. Hin tng ny cng cho php c s dng nh mt phng php chuyn i keo v trng thi a phn tn. Burop chia cc ion theo kh nng polyme thy phn thnh 3 nhm:

Nhm 1: Cc ion ca S nguyn t kim loi khng to ra phc a nhn ( kim loi kim v kim th nng). - Nhm 2: Cc ion to anion polyme ca cc phc hydroxo ( p, d- nguyn t: B, Si, Ge, P, As, S, Se, Te, Nb, Mo, W, Tc, Os) - Nhm 3: Ion to phc a nhn ( s, p, d, f nguyn t) Nguyn nhn khc nhau v kh nng to phc ca cc nguyn t l do c tnh lin kt ca cc nguyn t trong dung dch vi ligan ( oxy, H O, OH , O ). Theo gi tr khc nhau ca m in cc nguyn t x, gia cc nguyn t v Oxy tr thnh r rng hn do s khc nhau mc lin kt ion ca - O. Cc loai keo v c c th m rng bng cch bin i dng ca cc keo c. V duj bin dng keo axit photphat nhm mt lng Crom, cng c th bin dng theo anion i vi keo photphat nhm da vo keo hp cht MoO , V O . Keo kim th dung dch kim ca hydroxyl vi a nguyn dng ion Al - O - Si cng c dng ph bin. V d dung dch alumo silicat kim to cc Silicat khng ha tna khi thay i pH mi trng, do vy c th dng keo dng. Khi ny c th coi s c mt ca cc phc anion silicat trong thy tinh lng ( alumo silicat, titanoslicat, kim silicat) s lm thay i tnh cht ca keo. C th cng tn ti dung dch kim cc phc dng nu trn c xc nh bng cc yu t sau: - c vng pH gii hn ca dung dch m trong vng pH c s tn ti c 2 loiaj phc. - Khng c s tng tc ha dn n hnh thnh hp cht ngng t khng tan trong vng pH . - Bn trong vng pH nhm ha cc polyme trong dung dch vi gi tr nng xc nh.
2 23 2 5

V mt l lun cc iu kin nh vy tha mn cha cc dung dch Natri Silicat c cha cc phc hydroxoanion dng: [Al(OH) ] , [Al(OH) (H O) ] , [Co(OH) ] , [Zn(OH) ] , [Cr(OH) (H O)] , [Sn(OH) ] hoc dng anion loi FeO , MnO , CrO , Cr O , PO , SO , NO . Cc ion loi trn trtreenmooi trng kim cao c th hay tn ti trng thi t do hay mui ca n (alumosilicat Natri). Nh vy bin dng thy tinh ha tan c th khng phi ch bng cch a thm aluminat Natri vo m cn c th thay th 1 phn titan, cromat, manganat
4 4 2 2 24 26 35 2 26 24 24 224 2 7 234 4 23 -

cng to ra keo bin dng ca thy tinh lng cho rng khng c th tn ti cc dung dch silicat v aluminat natri khi nng ca chng vn tn ti bn vng. Cc nguyn t nhm 5 v 6 xut hin kh nng to thnh cc axit ngng t khi gim gi tr pH ca dung dch c cha cc anion n gin ca cc nguyn t . Vi nguyn t Photpho ca nhm 5 to vi oxy cc t din PO c s tham gia ca lin kt
4

-p

iu kin c s qu o p cc i. Do phn ng ngng t s to ra cc

polyaxit hay axit d thng- cc photphat ngng t, cc acxenat, cc anion axit ca phn nhm ph kim loi: V, Cr, Mo.

 bn cc polyme thng, vng, meta v poly photphat cho php ch to cc keo trn c s cc polyme ca chng. Dung dch alumo photphat cha ch yu phc anion [Al(HPO )] . Ngoi ra cn c th tn ti trong keo alumophotphat cc phn t polyme
4 3-

mch nhnh v khng gian. thit lp rng cn bng trong c dung dch axit photphoric ng vai tr v bn cht v tnh cht ca cc phn t kim loi c lin kt vi nguyn t anion trung tm. S hnh thnh keo photphat c ngha rt ln v nht ca bn thn axit, c xc nh qua lin kt hydro. Trong nhiu mui ca cc cation khc nhau lc lin kt hydro tng khi tng m in ca kim loi. Do vy hot tnh kt dnh v bm dnh ca keo photphat trong dy kim loi: Mg - Zn - Al - Cr s tng. i vi keo silicat v aluminat cn phi ch ra s khc nhau v m in ca nguyn t trung tm ( ca Silan hn Al)- lm tng lin kt ion ca Si - O so vi Al-O. Cc hp cht Silic c kh nng polyma ha l do s c mt ca cc qu o t do 3d-ord, cc qu o ny c kh nng mang tnh cht cho in t v do c mi lin kt . Qu trnh polyme ha theo anion th nng lng kj c tnh n s phi tr ln ca Si so vi C v c lin quan n s gim Entanpi khi phn ng 2SiO khc Si O c
2 2

li cho polyme ha ca cc phn t s, p v c bit Si c coi tng ng vi gi tr nng lng lm t mi lin kt n, i v ba.

E lin kt n (Kj) E lin kt i (Kj) SiSi PP SS 222 176 205 318 377 427

E lin kt ba (Kj) 377 286 -

S chuyn t lin kt i, ba v lin kt n bi s polyme ha th nguyn t Silic d dng hn. Ticatovi [51] nhn mnh rng s gim Entanpi l iu kin dch chuyn cn bng v pha qu trnh polyme ha. c trng nh lng ca lin kt O l gi tr in tch ring phn trn oxy trong cc oxit tham gia tip xc vi s thy phn ca phc cht.

Ch to polyme v c theo quan im cu trc ha hc c Beravonic Casakin [107] xut v xem xt. Khi ha tan mt phn nhng ch trng c cc ion in y vo ( cc phn t phn ly) lm cho cu trc ca n bn vng. Hin tng ny cho php xem xt cc qu trnh ch to dung dch polyme v c theo quan im ha tinh th ( xt c, s phi tr, bn knh nguyn t v ion) th Bokia l ngi quan tm nhiu [112]. Cc chng c cho php phn tch ha tan, tnh quy lut xut hin ca tnh kt dnh v l nguyn tc ch to keo mi. Ch to keo km theo s chuyn i t cu trc biu kin sang cu trc chc c trong c s trt t nht nh ca cu trc. Cc cht chy lng c trng thi rn xp cu trc s lm tng s phi tr, do lm tng mt khi ca n. Tng t nh vy khi ch to v s dng cht dnh kt tng s phi tr v dn n s hnh thnh cu trc chc c hn lm tng c tnh dnh kt ca vt liu. Khong cch ngn nht quan st c phc t din ca phc ng. S nh gi khong cch gia cc ion phc tp v ch c th th hin n qua khong cch - O trong oxit. Cng c th ch to keo khi t cu trc chc c vi khong cch - O cc tiu. Khi ha tan cc cht gn ging nhau theo thnh phn nhng khng nh nhau v cu trc cng to cc tnh cht dung dch khc nhau c bit khi c 1 dng cu trc c lp cc ion. V d dung dch Na CO cn c dung dch khc lp ion nh
2 3

Na SiO . l keo Silicat truyn thng. Cc phc ca borat cha cc nhm

2 3

polyme khc nhau: dng octo borat:

V dng meta borat:

Khi pha long dung dch keo borat th cc polyme borat b phn hy lm gim tnh dnh kt do lm thay i cu trc axit boric to ra khi thy phn. Trong axit boric

n v cu trc c nht l B(OH) lin kt gia chng bng lin kt hydro v to ra

3

lp phn b ring phn bn cnh, do khng cho php thu c lin kt bn cao. Khi ha tan Al(OH) ch to keo th polyme ha km theo tng s phi tr khi
3

ch to keo nhm t Al(OH) . Vi cc nguyn t nhm d phc c cha bn cao do

3

phc c cu trc 8 mt bao xung quanh cc phi t ( d sp qu o lai ha), cn phc 4

2 3

mt bn km hn (sp ). Chun s xc nh hng pht trin keo l kh nng tao

3

phc v bn lin kt trong . Cc nguyn t nhm p 3 kt hp vi nc cho mi lin kt cho- nhn mnh hn phn cc ca n v d to ra cc phi t lin kt vi hydro. c bit nguyn t nhm 3 l nhm. Ion Al lin kt cht vi H O v c th gii
3+ 2

thch do bn knh ion ca n nh v phn cc nh ca cc nhm in t sp . Trn

6

c s mui nhm c th gia cng thnh keo nhm. Nng lng mi lin kt c phn ng gp nhiu ca thnh phn ha tr th polyoxyion cc bn Bi s to ra - keo do
3+

s in y qu o. Do vy trn c s ca mui hydroxo ca cc kim loi trn c th c dung dch nht, dung dch ny c th dng lm keo c [80]. Tng hp cc keo c th da trn c s m rng nng dung dch c ln ca cc dung dch mui hydroxo ca cc nguyn t phn nhm Scandi.

Mt lot cc nguyn t nhm 3d nh Se - Zn u tng s in t qu o khng lin kt. Do s khng hon thin trn 3d gy ra s gim mnh bn knh ion lp 4s- orbitan khi chuyn t Ca n Zn. Do c th dng m hnh ion khi xem xt tnh cht dnh kt ca cc keo trn c s nguyn t 3d. i vi Gali tng t nh Al u xut hin tnh cht v nh hnh ca cc hydroxit ca n v c tnh axit mnh hn hydroxit nhm. Trong dung dch kim Gali kim loi c kh nng polyme ha dng a ngng t. Theo [104] polyme ha trong dung dch qu bo ha ca Galat kim c th tin hnh theo s sau:

Khi to Ga(OH) s ng vai tr pha lng ng khng m bo tnh cht kt dnh

4

tt, do vy mong mun tnh cht keo bng cch a thm vo h ion Ca , nh s
2+

to tinh th ngm nc Ganat Canxi [104] Trn c s keo axit thu c t cc mui polyme kim trong c mui nhm. T loi hp cht ha hc kiu ny to keo dng dung dch ca cc mui kim Ti, Cr, Fe, Zr, Ca cng c th s dng cc dung dch nh trn lm keo nh [45, 117] ch ra. Bit ha cht t nhin ca cc polyme ca mui Crom, do cng c th ngh dung dch mui Crom kim cng c tnh cht keo v c. Cui cng cho rng cc nghin cu c trin vng to ra cc keo dung dch mi l hng ch to keo i vi cc hp cht Fe, Nb, V, Mo. K, Se. trin vng nhiu hn l cc nguyn t t him, keo trn c s cc nguyn t dt him c nhiu tnh cht qu cng cng nh bin tnh cc keo c v u khng cp n keo hn hp v chu c v chng c nhiu nhm cha khc nhau v rt a dng v chng loi.

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