Chng 4.

Phng php SOL-GEL Phan Vn Tng

Cc phng php tng hp vt liu gm NXB i hc quc gia H Ni 2007. Tr 34 39. T kho: Phng php SOL-GEN. si quang hc SiO2, liti niobat, LiNbO3, SnO2, (Fe1xAlx)2O3,zeolit,ferrite, Ni-Zn, corierit. 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.

Chng 4 PHNG PHP SOL-GEL ..................................................................................2 4.1 Nguyn l chung ..........................................................................................................2 4.2 Vi v d tng hp gm theo phng php sol-gel .......................................................3 4.2.1 Tng hp si quang hc SiO2 ( tinh khit 99,999%) .........................................3 4.2.2 Tng hp gm liti nibat LiNbO3 ........................................................................3 4.2.3 Tng hp SnO2 hot ho......................................................................................4 4.2.4 d) Tng hp dung dch rn (Fe1xAlx)2O3 ..........................................................4 4.2.5 Tng hp zeolit ....................................................................................................5 4.2.6 Tng hp ferrite Ni-Zn .........................................................................................7 4.2.7 Tng hp corierit bng phng php sol-gel.......................................................7

Chng 4 PHNG PHP SOL-GEL

4.1 Nguyn l chung
Phng php ny ra i t nhng nm19501960 v c pht trin kh nhanh chng do c nhiu u im nh: C th tng hp c gm di dng bt vi cp ht c micromet, nanomet. C th tng hp gm di dng mng mng, di dng si vi ng knh < 1 mm. Nhit tng hp khng cn cao. Chng ta bit rng sol l mt dng huyn ph cha cc tiu phn c ng knh khong 1100nm phn tn trong cht lng, cn gel l mt dng cht rn - na rn (solid-semi rigide) trong vn cn gi dung mi trong h cht rn di dng cht keo hoc polyme. tng hp gm theo phng php ny, trc ht cn ch to sol trong mt cht lng thch hp bng mt trong hai cch sau: Phn tn cht rn khng tan t cp ht ln chuyn sang cp ht ca sol trong cc my xay keo. Dng dung mi thu phn mt precusor cho to thnh dung dch keo. V d dng nc thu phn alcoxyt kim loi to thnh h keo oxit ca kim loi . T sol c x l hoc lu dn cho gi ho thnh gel. un nng gel cho to thnh sn phm. C th tm tt phng php sol-gel theo s sau:
Phn tn hoc thu Sol Lm nng hoc gi ho Gel Gm

nghin cu k v phng php ny nn tm c ti liu ca Lakeman [18]. Di y ch trnh by vi v d c th [8].

4.2 Vi v d tng hp gm theo phng php sol-gel

4.2.1 Tng hp si quang hc SiO2 ( tinh khit 99,999%)
Mt yu cu quan trng ca si quang hc SiO2 l phi m bo tht tinh khit, c bit l loi trit cc cation ca kim loi chuyn tip. Mun th ta khng th i t nguyn liu u l SiO2 sch m phi xut pht t ho cht siu sch nh cc loi alcoxyt ca silic Si(OR)4 vi R l CH3-, C2H5-... Tin hnh phn ng thu phn: Si(OCH3)4 + H2O SiOH(OCH3)3 + CH3OH SiOH(OCH3)3 + H2O Si(OH)2(OCH3)2 + CH3OH Si(OH)2(OCH3)2 + H2O Si(OH)3(OCH3) + CH3OH Si(OH)3(OCH3) + H2O Si(OH)4 + CH3OH Tip n l giai on ngng t axit silicxic Si(OH)4 to thnh cc lin kt:
Si O Si O Si O
OH HO Si OH 2(Si(OH)4) (HO)3 Si O Si OH OH HO Si OH (HO)3 Si (OH)3 + 6 Si(OH)4 O Si (OH)3 + H2O OH (HO)3 Si O Si (OH)3 + H2O

OH HO OH HO Si OH HO O Si O Si O Si
OH

OH OH HO Si O O Si O OH HO Si
OH

OH

Si

OH + 6H2O

OH

Khi cc tiu phn ngng t t ti mt kch thc xc nh no th hnh thnh ht keo. Dung dch sol chy tri qua mt ci khun, ti y to thnh si an cho nhau ko theo s hnh thnh gel. Lc to thnh gel th c th ko thnh si. Ru metylic v nc ti cc l gel trong qu trnh gi ho ch thi ra c mt phn, phn cn li c ui ra ht khi sy kh gel. Cui cng silic oxit c nung ln ti 1300 K lm tng mt thu tinh.

4.2.2 Tng hp gm liti nibat LiNbO3

Litinibat thuc loi gm k thut in (ferroeclectric) c s dng nh mt b phn chuyn mch quang hc.

Phng php gm truyn thng bng cch nung hn hp hai oxit Li2O + Nb2O5 khng cho php thu c sn phm ng hp thc mong mun m ch l mt hn hp a pha. Theo phng php sol-gel ngi ta ho hn hp etoxit liti LiOEt v txit nibi Nb2(OEt)10 ( y Et l C2H5-) vo ru etanol tuyt i ng theo hp thc. Thm nc dn dn vo hn hp lng ng th thc hin phn ng thu phn ng thi cho to thnh hiroxi-alcoxit. Nb2(OEt)5 + 2H2O 2Nb(OEt)4(OH) + 2EtOH Li(OEt) + H2O LiOH + EtOH Cc hiroxi-alcoxit ngng t li to thnh gel dng cao phn t cha lin kt kim loi-kim loi. un nng gel dn phn hu hp cht hu c v nc, cui cng ch ho nhit thu c litinibat.

4.2.3 Tng hp SnO2 hot ho

SnO2 l cht bn dn kiu p c cha l trng O2. dn ca gm ny tng khi thm tp cht Sb3+, Ti4+. Gm SnO2 cha tp cht c dng lm in cc trong sut nh thu tinh. Phng php sol-gel c u im l c th to thnh mt mng mng gm bao ph ln vt liu nghin cu. V d, ch to ioxit thic c cha tp cht titan theo phng php sol-gel ta tin hnh nh sau: thm dn dn butoxit titan Ti(OC4H9)4 vo dung dch SnCl2.2H2O trong etanol tuyt i. Mui thic hai b thu phn to thnh phc hiroxi ri b oxi ho dn thnh thic bn di dng sol. Gi khong 5 ngy trong bnh m s chuyn dn thnh gel. Sy gel 333 K di p sut trong thi gian khong 2 gi, ri tip tc un nng ti 600 K trong 10 pht s to thnh mng ioxit thic c ln tp cht l Ti4+.

4.2.4 d) Tng hp dung dch rn (Fe1xAlx)2O3

V thc cht l thay th mt s v tr ca ion Fe3+ trong mng tinh th Fe2O3 bng ion Al3+. Theo phng php gm truyn thng ta thc hin phn ng gia hai pha rn: (1 x)Fe2O3 + xAl2 O3 (Fe1xAlx)2O3 V phn ng ch xy ra bin gii tip xc gia hai ht oxit, do tc phn ng rt chm ngay c nhit cao v kt qu thc nghim cho thy gi tr x ch t di 0,1. Theo phng php sol-gel c th khuch tn cht phn ng trong phi liu ban u mc ion, do phn ng c th xy ra nhit thp hn v tc cao hn. Qu trnh iu ch c tin hnh nh sau: chun b dung dch hai mui ca Al3+ v Fe3+ theo t l mong mun ri thc hin phn ng thu phn thu dung dch keo ca hiroxit st v nhm. Cho dung dch sol chuyn dn thnh gel hon ton ng nht. Sy gel ri tin hnh phn hu nhit s thu c sn phm gm (Fe1xAlx)2O3.

4.2.5 Tng hp zeolit

Phng php sol-gel c s dng rng ri trong cng nghip tng hp zeolit tc l hp cht tinh th ca hirat aluminosilicat. Zeolit c b mt ring rt ln do trong cu trc ca n cha cc hc trng thng vi nhau bng cc knh dn vi kch thc xc nh (46 ). Trong cc hc trng v cc knh dn c th cha cc phn t hu c hoc v c. Bi vy zeolit c xem nh mt loi ry phn t. Cc cation kim loi trong aluminosilicat ca zeolit c th trao i d dng vi cation kim loi trong dung dch tip xc vi zeolit, c ngha l zeolit l mt loi cationit. Nhng c tnh lm cho zeolit c rt nhiu lnh vc ng dng trong nhiu ngnh cng ngh ho hc [19].
NaAl(OH)4 + Na2SiO3 + NaOH dung dch nc
25oC

[Naa(AlO2)b(SiO2)c.NaOH.H2O] gel 100oC [Nax(AlO2)x(SiO2)y].mH2O tinh th

Tng hp zeolit c th thc hin bng nhiu phng php khc nhau [4,5], y chng ti ch trnh by tm tt phng php sol-gel. V d t dung dch nc ca silicat v aluminat natri tin hnh ngng t nhit phng s to thnh gel ri kt tinh thu nhit nhit xc nh trong thi gian xc nh s to thnh tinh th zeolit. Zhdanov S.P. xc nh thnh phn pha rn v pha lng ca gel aluminosilicat natri v trnh by trn hnh 16. Trn hnh cho thy thnh phn gel tp trung trong mt khu vc hp (cc vng trn trng). T l SiO2/Al2O3 trong hn hp ban u (vng trn c ngi sao) thay i trong mt phm vi kh rng (t 0,33 n 37) nhng trong gel thu c sau khi sy kh v ui nc gia cc mixel ht ri th t l ch thay i trong mt phm vi hp thi (t 2,2 n 6,6). Na 2 O Cng trong gin cho thy trong gel c t l = 1. Al 2 O 3 iu chng t lng nhm trong gel cng nh trong khung silicat (zeolit) khng bao gi ln hn lng silic v mi ion Al3+ c mt mt ion Na+, ngha l Al3+ trong gel cng nh trong zeolit nm trong t din Al(OH) . Ta c th hnh dung qu trnh xy ra khi kt tinh zeolit nh 4 sau:

O HO Si O OH

2+ HO

OH Al OH OH

HO

O Si O O

OH Al OH

3OH + H2O

OH HO Al OH + OH HO Si OH OH O

O Si O OH + HO

OH Al OH HO OH HO

OH Al O Si OH OH O

OH Si OH O

OH Al OH OH

2+ H2O

Hnh 16. T l cc cu t (% mol) trong gel aluminosilicat natri ban u (vng trn c ngi sao), trong gel c ra ht kim d (vng trn trng) v trong pha lng (im en) [19]
O Si O Al O Si O Al O

Ri t mt xch , quy t quanh nhng ion Na+.nH2O hirat ho to nn vin gch u tin l bt din ct. T cc bt din ct ghp vi nhau li to nn nhiu mng tinh th zeolit khc nhau (hnh 17).

4.2.6 Tng hp ferrite Ni-Zn

cp ht nano v phn b trong pha nn SiO2 v nh hnh c thnh phn ng vi cng thc (Ni1xZnxFe2O4)0,2(SiO2)0,8. Ho tan nitrat Ni, Zn, Fe trong hn hp gm ba cht lng l nc (H2O), ethanol (EtOH) v tetraethoxisilane (TEOS) vi t l H2O : EtOH : TEOS l 10 : 3 : 1. Khuy trn nhit phng trong 15 pht. iu chnh pH trong khong 1,52 cho chuyn ho dn sol thnh gel. Sy kh thu c gel di dng bt ri ch ho nhit 1100oC [20].

Hnh 17. S to mm tinh th zeolit t gel hirat

4.2.7 Tng hp corierit bng phng php sol-gel

+ Trc ht iu ch gel: cho dung dch Na2SiO3.5H2O qua ct cationit dng H+ thu dung dch axit silisic. Thm dn nitrat nhm v nitrat magie vo dung dch axit silisic cho t t l Si : Al : Mg bng 5 : 2,15 : 2,25 nm trong trng kt tinh corierit.

Thm axit citric vo hn hp chnh pH t ti 2 th thu c sol. Cho sol chuyn ho dn thnh gel trong 2 ngy. + Kh nc ca gel bng cch un nng dn n 70oC trong 24 gi ri x l nhit 450oC trong 120 gi s thu c precursor. + Nung precursor v nh hnh n 1200oC trong 12 gi s thu c tinh th corierit [21].