CHNG 1:TNG QUAN

1.1. Tng quan v phng php sol-gel 1.1.1. Gii thiu Gia nm 1800 s quan tm phng php sol gel to gm s v knh c bt u vi Ebelman v Graham khi nghin cu v gel Silic. Nm 1950 - 1960 Roy v cc cng tc s dng phng php sol gel to ra gm s mi vi thnh phn l cc ng cht ha hc, bao gm: Si, Al, Zr.. m khng s dng c to bi phng php sol gel. Phng php sol gel l mt k thut tng hp ha keo to ra cc vt liu c hnh dng mong mun nhit thp. N c hnh thnh trn c s phn ng thy phn v phn ng ngng t t cc cht gc (alkoxide precursors) . Cng ngh sol-gel l cng ngh cho php ta trn ln cc cht quy m nguyn t v ht keo tng hp cc vt liu c sch v tnh ng nht cao. Qu trnh xy ra trong dung dch lng v cc tin cht nh cc oxyt hoc cc mui kim loi thng qua cc phn ng thy phn v ngng t, s dn n vic hnh thnh mt pha mi - l Sol. Gel l h phn tn d th, cc ht pha rn to thnh khung 3 chiu, pha lng nm khong trng ca khung 3 chiu ni trn. Bng phng php sol-gel, khng nhng tng hp c cc oxyt siu mn (nh hn 10m), c tnh ng nht cao, b mt ring ln, tinh khit ha hc cao m cn c th tng hp c cc tinh th c nanomet, cc sn phm dng mng mng, si 1.1.2. Cc khi nim c bn Mt h Sol l mt s phn tn ca cc ht rn c kch thc khong 0.1 n 1m trong mt cht lng, trong ch c chuyn ng Brown lm l lng cc ht. Kch thc ht qu nh nn lc ht l khng ng k. Lc tng tc gia cc ht l lc Val der Waals. Cc ht c chuyn ng ngu nhin Brown do trong dung dch cc ht va chm ln nhau.
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Sol c thi gian bo qun gii hn v cc ht Sol ht nhau dn n ng t cc ht keo. Mt h Gel l mt trng thi m cht lng v rn phn tn vo nhau, trong mt mng li cht rn cha cc thnh phn cht lng Precursor l nhng phn t ban u to nhng ht keo (sol). N c to thnh t cc thnh t kim loi hay kim, c bao quanh bi nhng ligand khc nhau. Cc precursor c th l cht v c kim loi hay hu c kim loi. Cng thc chung ca precursor : M(OR)X M l kim loi R l nhm alkyl c cng thc: CnH2n+1. Nhng cht hu c kim loi c s dng ph bin nht l cc alkoxysilans, nh l Tetramethoxysilan (TMOS),Tetraethoxysilan (TEOS). D nhin nhng alkoxy khc nh l cc Aluminate, Titanate, v Borat cng c s dng ph bin trong qu trnh Solgel. 1.1.3. u im v nhc im ca qu trnh Sol-Gel u im C th to ra mng ph lin kt mng mang n s dnh cht rt tt gia vt liu kim loi v mng. C th to ra mng dy cung cp cho qu trnh chng s n mn. C th d dng to hnh cc vt liu c hnh dng phc tp. C th sn sut c nhng sn phm c tinh khit cao. Kh nng thiu kt nhit thp, thng l 200 600 . C th iu khin cc cu trc vt liu. To c hp cht vi pha tp ln. khuych tn ng u cao.
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Ch to nano thay i thnh phn d. Lm vic nhit thp hiu qu, kinh t, n gin sn xut nhng mng c cht lng cao. u im ni tri nht ca phng php sol-gel l kh nng ch to c nhng vt liu mi c cu trc ng u: vt liu xp, vt liu microballoon... Nhc im S lin kt trong mng yu. C thm thu cao. Rt kh iu khin xp. D b rn nt trong qu trnh nung sy. 1.1.4. Mt s ng dng hin nay ca phng php sol-gel Phng php sol-gel c s dng rng ri trong ch to v nghin cu vt liu oxide kim loi tinh khit. Nhng nghin cu ca phng php sol-gel ch yu l ch to gel khi SiO2 (silica) v sau m rng ch to cc oxide kim loi chuyn tip khc nh TiO2 (titania), ZrO2 (zirconia), Hin nay, phng php sol gel thnh cng trong vic ch to vt liu oxide a thnh phn (multicomponent oxide: SiO2-TiO2, TiO2:SnO2) v ch to vt liu lai hu c - v c (hybrid materials). Cc nhm sn phm chnh t phng php sol-gel, c m t trong hnh 1.1 bao gm: Mng mng (thin film): ch to mng mng c cu trc ng u vi nhiu ng dng trong quang hc, in t, pin mt tri Gel khi (monolithic gel): c s dng ch to cc oxide a kim loi cc dng c quang hc: gng nng (hot mirror), gng lnh (cold mirror), thu knh v b tch tia (beam splitter) Gel kh (Aerogel): thu c bng cch sy siu ti hn gel t (wet gel). Gel kh c ng dng trong nhiu lnh vc: hp th nng lng mt tri (silica aerogel), xc tc
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(alumina (Al2O3) aerogel c pha tp kim loi), cht cch in v cch nhit (silica aerogel) Ht nano: n thnh phn v a thnh phn c kch thc ng u c th thu c bng cch to kt ta trong giai on thy phn - ngng t. Si ceramic: si quang cht lng cao v si ceramic cch nhit.

Hnh 1.1: Cc nhm sn phm ca phng php sol-gel 1.2. C s ha l ca cng ngh Sol-Gel Phng php sol-gel l mt phng php ha hc t tng hp cc phn t huyn ph dng keo rn trong cht lng v sau to thnh nguyn liu lng pha ca b khung cht rn, c cha y dung mi cho n khi xy ra qu trnh chuyn tip sol-gel.

Trong qu trnh sol-gel cc phn t trung tm tri qua 2 phn ng ha hc c bn: phn ng thy phn v phn ng ngng t (di xc tc axit hoc baz) hnh thnh mt mng li trong ton dung dch . Thc t qu trnh ny phc tp hn nhiu nhng c th a v hai qu trnh thy phn v ngng t ng thi kt qu cui cng sinh ra khung oxyt hoc hydroxyt. Tc qu trnh thy phn v ngng t nh hng n cu trc ca Gel do c vai tr quyt nh ln tnh cht ca sn phm. iu khin c tc ca hai qu trnh ny c th tng hp c vt liu dng khi, ht v mng mng nh mong mun. 1.2.1. Phn ng thy phn Phn ng thy phn thay th nhm alkoxyde (-OR) trong lin kt kim loialkoxyde bng nhm hydroxyl (-OH) to thnh lin kt kim loi-hydroxyl. Alkoxyde hay cn gi l alkolat c cng thc M(OR)n trong n l s oxy ho ca nguyn t M, OR l nhm alkoxy (gc ca mt axit hu c ROH). Theo quan im axit-bazo, c th coi cc alkoxyde l cc hp cht c to thnh bi mt bazo v mt axit rt yu (ROH) do chng rt d b thy phn theo phn ng: M(OR)n + nH2O M(OH)n + nROH C ch thy phn ca M(OR)n din bin theo s : H2O + MOR H2O:--MOR HOM-- OHR MOH + ROH (a) (a) (b) (c) (d) : AN : trng thi chuyn tip : vn chuyn proton : loi ROH. (b) (c) (d)

Trong phn t H2O, nguyn t oxy cn d hai cp electron cha tham gia lin kt, d tham gia phn ng cng vi M dng in (c ch cng i nhn AN: addition nucleophylic) to ra trng thi chuyn tip (b).
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Nguyn t M dng in ht cp electron v pha mnh, lm tng phn cc ca lin kt HO. Nguyn t H tr nn linh ng hn v di chuyn sang RO lm cho lin kt MOR yu i v kt qu cui cng ROH b loi ra khi phn t R(OH)n (c ch th i nhn SN: nucleophylic substitution). Cc qu trnh trn s thun li khi tnh i nhn ca phn t i vo (H2O), tnh i in t ca M v tnh cht i ra ca phn t b loi (ROH) l ln. Tc th i nhn cng ln khi: Trong phn t M(OR)n cha bo ha phi tr (s phi tr N > s oxy ha n). Hiu N n cng ln, nng lng hot ha ca giai on cng i nhn cng nh, tc thy phn cng ln. Kh nng vn chuyn proton trng thi chuyn tip (b) cng ln. Kh nng ny cng ln khi M cng dng in. Cc kim loi chuyn tip c orbital d s phi tr bng su thng ln hn s oxy ha ca M trong alkoxyde nn phn ng vi H2O mnh hn so vi cc alkoxyde ca silixi (N = n = 4). Cc phn ng thy phn, alcoxolation, oxolation v olation tham gia vo s bin i alkoxyde thnh khung oxyt do cu trc, hnh thi hc ca cc oxyt thu c ph thuc rt mnh vo s ng gp tng i ca mi phn ng. S ng gp ny c th ti u ha bng s iu chnh iu kin kinh nghim lin quan n: Thng s ni: bn cht ca kim loi v cc nhm alkyl, cu trc ca alkoxyde Thng s ngoi: t s thy phn h = [H2O] / [alkoxyde], xc tc, nng , dung mi, nhit

Hnh 1.2: Phn ng thy phn

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1.2.2. Phn ng ngng t Phn ng ngng t to nn lin kt kim loi - oxide - kim loi, l c s cu trc cho cc mng oxide kim loi. Hin tng ngng t din ra lin tc lm cho lin kt kim loi oxide - kim loi khng ngng tng ln cho n khi to ra mt mng li kim loioxide-kim loi trong ton dung dch. Phn ng ngng t din ra theo 2 kiu: Ngng t ru: M(OH)(OR)n-1 + M(OR)n (OR)n-1M-O-M(OR)n-1 + ROH Ngng t nc: M(OH)(OR)n-1 + M(OH)(OR)n-1 (OR)n-1M-O-M(OR)n-1 + H2O

Hnh 1.3: Phn ng ngng t Cc giai on chnh : To dung dch sol: alkoxide kim loi b thy phn v ngng t, to thnh dung dch sol gm nhng ht oxide kim loi nh (ht sol) phn tn trong dung dch sol. Dung dch c th c dng ph mng bng phng php ph quay (spin coating) hay ph nhng (dip coating). Gel ha (gelation): gia cc ht sol hnh thnh lin kt. nht ca dung dch tin ra v hn do c s hnh thnh mng li oxide kim loi (M-O-M) ba chiu trong dung dch.
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Thiu kt (sintering): y l qu trnh kt cht khi mng, c iu khin bi nng lng phn gii. Thng qua qu trnh ny gel s chuyn t pha v nh hnh sang pha tinh th di tc dng ca nhit cao. Trong ton b qu trnh, hai phn ng thu phn ngng t l hai phn ng quyt nh cu trc v tnh cht ca sn phm sau cng. Do , trong phng php solgel, vic kim sot tc phn ng thu phn - ngng t l rt quan trng. S pht trin cu trc tinh th trong qu trnh Gel ha Sol ch tn ti trong mt khong thi gian. n mt thi im nht nh th cc ht ht ln nhau tr thnh nhng phn t ln hn. Cc phn t ny tip tc pht trin n kch thc c 1nm th ty theo xc tc c mt trong dung dch m pht trin theo nhng hng khc nhau. Xc tc acid Trong cc phn ng xc tc axit, proton cng vi nc ng mt vai tr ph hy s phn cc ca lin kt tc nhn i nhn tn cng vo c d hn. Phn ng thy phn alkoxidesilane xc tc acid

Hnh 1.4 : S pht trin cu trc tinh th trong iu kin xc tc acid

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Di iu kin xc tc acid ht s pht trin thnh polymer mch nhnh ngu nhin hoc mch thng c bn, an xen vo nhau C ch xc tc baz Phn ng thy phn alkoxidesilane xc tc baz.

Hnh 1.5: S pht trin cu trc tinh th trong iu kin xc tc base Di iu kin xc tc bazo cc ht pht trin thnh cc cluster phn nhnh mc cao nhiu hn, khng xen vo nhau trc khi to thnh gel, chng th hin nh nhng cluster ring bit.

Hnh 1.6: S pht trin cu trc mng trong qu trnh sol gel
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Nh vy, vi cc loi xc tc khc nhau, chiu hng pht trin ca ht sol cng c phn khc bit. S pht trin ca cc ht trong dung dch l s ngng t, lm tng s lin kt kim loi - oxide - kim loi to thnh mt mng li trong khp dung dch. 1.3. Cc phng php phn tch ng dng trong phng php sol-gel 1.3.1. Nguyn l v ng dng ph nhiu x tia X (XRD) Nguyn l Xt mt chm tia X c bc sng chiu ti mt tinh th cht rn di gc ti . Do tinh th c tnh cht tun hon, cc mt tinh th s cch nhau nhng khong u n d, ng vai tr ging nh cc cch t nhiu x v to ra hin tng nhiu x ca cc tia X. Nu ta quan st cc chm tia tn x theo phng phn x (bng gc ti) th hiu quang trnh gia cc tia tn x trn cc mt l: L = 2.d.sin Nh vy, c cc i nhiu x th gc ti phi tha mn iu kin: L = 2.d.sin = n. n l s nguyn nhn cc gi tr 1, 2,...

Hnh 1.7: S nhiu x tia X trn mt tinh th ng dng Hin nay ang ph bin hai phng php p dng bc x in t tia X l hunh quang tia X (XRF) phn tch nh lng v nhiu x tia X (XRD) nghin cu cu trc tinh th vt cht.
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Hnh 1.8: Thit chp ph XRD 1.3.2. Nguyn l v ng dng chp ph TEM, SEM 1.3.2.1. Ph TEM Nguyn l Knh hin vi truyn qua l mt thit b nghin cu vi cu trc vt rn, s dng chm in t c nng lng cao chiu qua mu vt rn mng v s dng cc thu knh t to nh vi phng ln (c th ti hng triu ln), nh c th to ra trn mng hunh quang hay trn phim quang hc hay ghi nhn bng my chp k thut s. ng dng Nghin cu vi cu trc tinh th. Nghin cu chuyn pha, phn hy dung dch rn.

Hnh 1.9: Thit b chp TEM

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1.3.2.2. Ph SEM Nguyn l Knh hin vi in t (SEM) l mt loi knh hin vi in t c th to ra nh vi phn gii cao ca b mt mu vt bng cch s dng mt chm in t (chm cc electron) hp (c vi trm Angstrong n vi nanomet) nh h thng thu knh t, sau qut trn b mt mu nh cc cun qut tnh in. phn gii ca SEM c xc nh t kch thc chm in t hi t, m kch thc ca chm in t ny b hn ch bi quang sai, chnh v th m SEM khng th t c phn gii tt nh TEM. Vic to nh ca mu vt c thc hin thng qua vic ghi nhn v phn tch cc bc x pht ra t tng tc ca chm in t vi b mt mu vt. ng dng Nghin cu cu trc b mt vt liu mt cch chnh xc.

Hnh 1.10

Thit b chp SEM

1.4. Bt mu gm s v cng ngh sn xut bt mu theo phng php c in 1.4.1. Bt mu gm s Mu sc ca gm s, ging nh mu sc ca mi vt, l do kh nng hp ph v phn x ca men gm s i vi nh sng trong vng nhn thy. Mu ca men ng vi cc bc sng c men phn x tr li.
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Nu men gm s phn x mi bc sng nh sng, n c mu trng, nu men hp ph hon ton mi bc sng, khng phn x li bc sng no, n s c mu en. S hp th v phn x nh sng, do mu sc, ca men ph thuc vo thnh phn ho hc ca men v c bit l s phi tr ca cc cht cho cc mu khc nhau, gi l cc cht to mu men. Men gm l mt h phc tp gm nhiu xt nh Li2O, Na2O, K2O, PbO, B2O3, CaO, ZnO, MgO, Al2O3, Fe2O3, SiO2... c a vo di cc dng sau: Nguyn liu do (plastic): gm c cao lanh (kaolin), t st (clay), bt talc (steatit), betonit... Nguyn liu khng do (nonplastic) di dng khong: gm c trng thch, lmt, vi, ct... Nguyn liu khng do di dng ha cht cng nghip: BaCO3, Na2CO3, K2CO3, borax (dn gian gi l hn the), axt boric, Cr2O3, ZnO... hoc cc loi frit. xt hoc mui ca kim loi c th lm cht to mu cho men gm s. Cch ny tng t thu tinh mu nn thng to men trong c mu, cng ma tu thuc vo hm lng (%) xt gy mu a vo v bn cht men. Nhng xt mu hoc mui ca chng khi a ring vo men gm s cho mu thng thng l: CoO, Co2O3, Co3O4, Co(OH)2: cho mu xanh. NiCO3: cho mu vng bn. CuO, Cu2O: cho mu xanh khi nung trong mi trng xy ho, mu trong mi trng kh. Cr2O3: cho mu lc. Sb2O3, Sb2O5: cho mu vng. FeO, Fe2O3, Fe3O4: cho mu vang, vng v nu khi nung trong mi trng xy ho, xanh xm n xanh en trong mi trng kh. MnCO3: cho mu en, tm hoc en. SnO2: cho mu trng (men c). ZrO2: cho mu trng (men c).TiO2: cho mu vng.
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Nhm to mu ion y l nhm mu ph bin nht, cc cht to mu loi ny c mu sc ph thuc vo ha tr ca ion. V vy mi trng nung c nh hng ln n mu sc ca nhm mu ny do phn ng oxi ha kh lm bin i ha tr ca cc ion. Ta c mt s ion mang mu sau: Bng 1.1: Bng mu ca cc cht mu ion Ion gy mu Co2+ Ni2+ Mu Tm xanh Tm Xanh nu Nd3+ Ce4+ Cr3+ [CrO4]2Mn3+ Cu2+ Fe3+ Fe2++ Fe3+ Tm Vng Xanh l cy Vng Tm Xanh ng Nu vng Xanh ve chai Mn2+ c mu vng nht Cu+ khng to mu Mu rt sm khi c TiO2 Khng kh hon ton thnh Fe2+ (UO4)2Vng xanh
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Ghi ch Mu c trng ca coban Trong thy tinh can xi Trong thy tinh kim

Ce3+ khng to mu lun cng tn ti

Nhm to mu dng keo Trong trng hp ny, men c nhum mu nh cc tinh th kim loi c kch thc ht keo (ng knh ht c kch thc xp x kch thc ca bc sng nh sng ti). Cht to mu chnh l Au, Ag, Cu. Ngoi ra cc phn t Se-CdS hoc Se ( trong mi trng kh, khng c S) kch thc ht keo. Mu sc ca cht to mu ny ph thuc kch thc ht keo. Thng phi c ch nhit rt nghim ngt m bo kch thc ht theo ng yu cu. Phi nng nhit xp x Tg lu mt thi gian thch hp, ht t 10nm tr ln, thy tinh bt u c mu. Kch thc ht ln qu 100nm, tc dng mu chuyn sang c ch tn x. V d: hm lng 0,2 % Au ( a vo phi liu dng AuCl3), cc ht vng c kch thc 5 60nm cho mu ngc vng. Thy tinh c s thng phi cha 1% SnO ng vai tr cht n nh mu. Vi cc cht gy mu dng keo, mu sc s b bin i theo ch nhit do bin i s lng v kch thc ht (cc cht mu ion khng c hin tng ny). Cht mu c cu trc tinh th Oxit kim loi mang mu khng bn trong qu trnh trang tr ln b mt sn phm, nn ngi ta cho cc oxit kim loi phn ng vi nhau iu kin nhit , mi trng v thi gian nht nh to thnh cht mu tinh th (mu pigment). y l cht mu dng bt, cho nhiu mu sc khc nhau, mu p, phong ph hn men mu v tng i bn vi nhit nn c s dng rng ri trong cng nghip ceramic. V bn cht cu trc, mu pigment l cht to mu c cu trc tinh th. Cc tnh cht ca mu ph thuc vo cu trc mng tinh th mang mu. Nu tinh th mang mu l nhng tinh th bn th mu cng s bn. Khi to cc cht mu trc ht cn xc nh bn mng ca tinh th lm nhim v cht mang mu.

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Cc cht gy mu thng l cc nguyn t kim loi chuyn tip c v in t bt thng, d gy sai st trong mng tinh th to nn nhng tm hp th mu. phn loi cc cht mu pigment da vo bn cht ca tinh th mang mu. Nhng tinh th bn nhit cao c kh nng lm cht mang mu, trong thng gp nht l spinel. Mt s tinh th thng lm cht mang mu nh sau : Spinel loi 1 : ( MgO.Al2O3 ) Spinel loi 2 : ( 2ZnO.TiO2 ) Zircon Baddleyit Corund Willemit Perowskit Mulit Olivin Cht to mu bn nhit Cc cht to mu bn nhit l cc cht to mu hu nh khng tan trong men nng chy m li phn tn rt u trong men. Cht to mu bn nhit thng to mu c gi l cht to mu nhum mu men, to men trng c thng hay dng cch ny. Phng php sn xut cc cht mu ny nh sau: Phi liu to mu c trn v nghin mn trong my nghin bi t hoc kh (mu di men) hoc tch cc kt ta ca cc hn hp kim loi sau khi hon tan n vo nc (mu trn men). Nung phi liu trn n nhit thch hp cho s pht mu. Cc tng mu hnh thnh c nghin mn v ra sch. Pha thm vo cht mu 30-40% men s s c mu v di men hoc 5-10%.
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: ( ZrO2.SiO2 ) : ( ZrO2 ) : ( Al2O3 ) : ( 2ZnO.SiO2 ) : ( CaO.TiO2 ) : ( 3Al2O3.2SiO2 ) : ( CoO.SiO2 )

t st do s c mu trn men hoc pha thm cht tr chy c mu trong men. Cng thc phi liu mt s mu di men Mu lc: Al2O3.0,8CoO.0,2Cr2O3 Mu lam: SnO2.2,5CoO (xanh lam m); Al2O3.0,5CoO.0,5ZnO (xanh tri), Al2O3.0,7CoO.0,3NiO (xanh xm) Mu xanh l non: hn hp Cr2O3, CaCO3 v B2O3 Mu : c to qua vic to cht mu hng, l hn hp SnO2, SiO2, CaO, B2O3 v mt t Cr2O3. Mu tm : AuCl3 v cao lanh trn theo t l 1/9 Mu vng: ZnO.TiO2 hoc 0,8.0,2Fe2O3.TiO2 Cng thc phi liu mt s mu trn men Mu xanh nc bin: 0,25CoO.0,35ZnO.0,1B2O3.0,4PbO.0,5SiO2 Mu xanh da tri: (15-30)% hn hp (Co.Al2O3) + (85-70)% tr chy (PbO.0,5SiO2) Mu nu: 20% hn hp (Fe2O3.Cr2O3) + 80% tr chy (PbO.0,5SiO2) Mu vang: (17-20)% Fe2O3 + (83-80)% tr chy (PbO.0,5SiO2) Mu cam: 18% hn hp (Fe2O3.Al2O3) + 82% tr chy (PbO.0,78SiO2.0,24B2O3). 1.4.2. Cng ngh sn xut bt mu theo phng php c in Phng php ny c th p dng cho hu ht cc loi men gm s sng v xut pht t rt lu. Phng php ny n gin ch l nghin phi liu trong my nghin bi gin on n khi mn qua ht sng 10.000 l/cm2 (hoc cn li di 0,5%). Trong qu trnh nghin, cn khng ch mn thch hp v nu nh nghin qu mn men s b cun hoc bong men, nu men qu th s gy nhm b mt v tng nhit nung mt cch ng k.
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i vi men trng (c) v men trong hoc men cho s cch in, sau khi nghin cn thit phi a qua my kh t loi b st v xt st (c trong nguyn liu hoc do s mi mn ca my nghin). Thng thng men d b lng lm cho cc cu t trong men phn b khng u v gy li sn phm, hn ch phi dng cc bin php nh: Lm cho men c ln (hm m nh hn). Gim bt nghin mn (men khng qu mn). Thm t st, cao lanh hoc bentonit tng huyn ph v lm men c hn. Thm mt t tinh bt extrin, keo glutin, keo xenlul hoc thm vo mt t NH3, amon oxalat hoc mt axt yu... Cht mu c cu trc tinh th( pigment) Quy trnh iu ch mu pigment bao gm cc bc: Nguyn liu Thnh phm. Nghin trn Nguyn liu sau khi cn theo mt t l xc nh trc c nghin trn vi nhau. Mc ch ca qu trnh ny l t ng nht v phn tn cao lm tng hiu qu phn ng pha rn trong giai on sau. Nung L qu trnh chnh ca quy trnh ch to mu Pigment. Phi liu sau khi c nghin mn c nung trong cc l vi nhit ph thuc vo tng loi phm mu. Mc ch ca qu trnh ny l lm cho hn hp nguyn liu rn phn ng vi nhau to ra cc tinh th khong c cu trc bn vng mang mu. V d: Cc mu to thnh cc spinel nh: Co2Al2O3, Co2O3.Al2O3, MnO.Cr2O3, FeO.Cr2O3, MnO.Al2O3 thng phi nung n 14000C, cng c th gim nhit nung bng cch thm B2O3, lc ny nhit cn 13000C.
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Cn

Nghin - trn

Nung

Ra

Sy

Nghin

Ra Sau khi nung, cc sn phm c ly ra khi l, nghin v ra loi hon ton nhng hp cht tan, cc tp cht sinh ra cn li sau phn ng pha rn Nghin Sn phm sau khi ra c em sy kh, sau c nghin mn t mn mong mun. mn ca cc ht c nh hng n che ph v cng mu. Thng thng cc ht bt mu c kch thc qua ht sang 10000 l/cm2 l t mn yu cu. Nh vy, thu c mu pigment t hn hp nguyn liu rn ban u phi nung hn hp rn nhit cao cc nguyn liu rn phn ng vi nhau to ra cc khong bn mang mu. Vic nghin nguyn liu trc khi nung l mt trong cc bin php hot ha cc pha rn ban u nhm thc y phn ng gia chng xy ra d dng hn 1.5. Nguyn liu sn xut bt mu Nano t cng ngh Resinat 1.5.1. Khi nim chung v Resinat kim loi Theo mt s ti liu Resinat kim loi l sn phm ca phn ng gia hp cht hu c vi mui kim loi. Hp cht thu c v c bn l phn t hu c dng chui di m ti mt v tr no trn chui c thay th bi cc kim loi khc nhau. Resinat kim loi c ng dng rng ri v a dng, cung cp cc kim loi dng dung dch hu c, c th s dng khi b sung thm kim loi cn thit a vo cc cng thc hu c. Resinat kim loi c s dng to thnh cc lp kim loi hay oxit kim loi trn cc cht nn khc nhau. Resinat c pht ln b mt v c gia nhit n bay hi dung mi v phn hy cht hu c. iu ny c thc hin trong khng kh nhit 350C hay cao hn. Cc resinat kim loi qu phn hy thnh kim loi, cc resinat kim loi thng phn hy thnh cc oxit kim loi.
19

Mt s resinat kim loi dng dung dch c sn sut v ng dng rng ri trong nhiu lnh vc nh : Re-Al (2,65%Al), Re-Ba (11,65% Ba), Re-Bi (26,9% Bi), ReCu (6,4% Cu), Re-Au (12% - 24% - 28%), Re-Fe ( 12% Fe), Re-Ni ( 8% Ni), Re-Ti (7,2% Ti). Resinat kim loi l sn phm ca phn ng gia axit c trong nha thng vi mui kim loi. Trong H+ nhm COOH ca cc axit nha c thay th bng kim loi, cn gi l x phng kim loi nh resinat ch, resinat nhm, resinat mangan Resinat kim loi c s dng nhiu trong sn xut sn nh tham gia vo cht to mng, cht lm kh sn v ch to bt mu c cu trc siu mn. Phng php ny l mt trong cc phng php tng hp cc vt liu mu bng k thut dung dch. C s l thuyt ca phng php ny l to ra cc nguyn liu ban u l cc tin cht (precursor) c hot tnh cao, c kh nng phn ng to mu nhit thp. Vi nhng nghin cu trc y v resinat kim loi lm cht to mu trang tr thy tinh, khi nung cc resinat nhit bin mm thy tinh (<600C) to nn b mt sn phm mt lp kim loi hay oxit kim loi to mu ng sc, c s dng lm cht mu trang tr trn men. Resinat kim loi l mui c cu to gm gc hu c v ion kim loi, cc resinat kim loi c ha tan trn vi cht keo hu c thch hp ri trng ln b mt men ca sn phm cn trang tr. Khi hp li nhit 580 - 600C, gc hu c chy ri bay hi li cc ion kim loi c hot ha cao d kt hp vi nhau, to trn b mt men mt lp mng kim loi hoc kt hp vi oxy to lp oxit kim loi. Cc kim loi dng trang tr theo phng php rt phong ph. C th chia cc kim loi ny thnh hai nhm chnh: Nhm kim loi khng to mu: bn thn khng to hiu ng mu, c dng chung vi nhng resinat kim loi khc nhm tng cng mt tnh cht nht nh, bao gm mt s kim loi: Pb, Bi, Zn, Al.
20

Nhm kim loi gy mu : l nhng kim loi nh Fe, Ni, Collector, Cr, Cu, Cd, Au, Pt, Rh, U, Th nhng kim loi ny khi dng ring l to hiu qu mu c trng cho mi kim loi. 1.5.2. Cc phng php iu ch resinat kim loi C hai phng php iu ch resinat kim loi: phng php nng chy v phng php kt ta. 1.5.2.1. Phng php nng chy Resinat kim loi c ch to bng phng php nng chy l oxit kim loi hay mui kim loi c nghin mn un nng vi axit nha nhit 200 - 270C. u tin nha thng c un nh, khuy u ri cho kim loi hay oxit kim loi vo. Resinat kim loi thu c s c v phi pha long bng du Lavender hay du Turpentine vi lng nh v cho vo t t. Hainbach m t mt s phng php iu ch Resinat kim loi bng phng php nng chy nh sau: Resinat Bismuth c sn xut : 10 phn tinh th Bi(NO3), 75 phn du lavender, 30 phn nha thng. Nha thng sau khi chy mm, nhit c tng ln t t v mui nitrat c a vo tng phn nh v khuy u. Khi hn hp chuyn sang mu nu, cho du lavender vo. Hn hp c lng n khi tt c nhng phn khng tan lng xung dung dch c gn ra v dng. Resinat km c chun b bng hp phn bao gm 1 phn km acetat vi 2,5 phn nha thng v ha tan trong du lavender. Resinat ch : mt phn ch acetat nng chy vi 3 phn nha thng ha tan trong du lavender. 1.5.2.2. Phng php kt ta Khi thc hin phng php ch to Resinat kim loi kt ta u tin phi iu ch bn sn phm l x phng. Sau mun kt ta tch resinat kim loi ra khi x phng, ngi ta dng mui kim loi tan trong nc.
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Cho nha thng dng bt vo dung dch NaOH c v gia nhit cho n khi khng th ha tan nha thng c na v hn hp khng si bt th phn ng kt thc. Dung dch c pha long, un nng ri lm ngui v gn ra khi phn cn. Mui kim loi (mui clo hoc mui nitrat) c cho vo dung dch, kt ta to thnh c lc ra v sy kh. Thng thng cc resinat kim loi d b bin tnh nu a chng ra ngoi nh sng lc cn m. Khi iu ch resinat natri cn ch : lng NaOH cho v t t tng t mt. trnh kim tha qu nhiu gy phn ly x phng, duy tr keo x phng trng thi kim nh va phi, nu kim khng c th lm cho keo c qunh v ng thnh cc rt kh nu chy. Cn phn ly x phng bng mui NaCl ph trng thi nh ha ca x phng v tin hnh phn ly tp cht ra khi x phng. X phng ni ln v cc tp cht lng xung. Nhc im ca phng php ny l trong qu trnh ra ta bng nc nng tch ht Na+ ri sy kh 110 - 115C tng i lu, n hng gi nu sy nng hn v sau kh ha tan vo dung mi. T yu cu trn nn vic ra v sy rt kh khn nn ngi ta tm cch thc hin qu trnh bng tng lng. Qu trnh ch to x phng kim loi tng lng bao gm cc giai on c th nh sau: u tin phi tin hnh x phng ha nha thng bng dung dch NaOH nng 10% khong nhit 90 - 100C cho n khi dung dch ng nht trong sut tan hon ton trong nc l c, ng thi chun b ring l dung dch mui kim loi vi nng khong 10 -20 %. Trn hn hp dung dch x phng vi dung dch mui kim loi, ng thi cho thm dung mui white spirit vo (dung mi ny s ha tan x phng kt ta). Thc t cho dung mi v x phng un nng n 90C ri mi cho dung dch mui v rt t t cho kt ta to thnh tan dn trong dung mi.
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Khi cho ht dung dch mui vo ri tip tc un nng thm na gi 70 - 75C v tip tc khuy u. ngui chng ta s c hai lp: lp trn l dung dch x phng kim loi kt ta tan trong dung mi v lp di l dung dch mui ca natri. Tin hnh ra dung dch x phng kim loi, tch cc mui tan trong nc bng cch dng mt lng nc ct tng ng vi dung dch x phng trn vo nhau ri lng v tch lp nc i, nn ra 2 3 ln. 1.5.3. Cc nguyn liu dng iu ch Resinat kim loi 1.5.3.1. Nha thng Nha thng l mt cht dnh nht, khng linh ng, c mu trng, trng nu hoc trng xm. Xt theo thnh phn ha hc, nha thng l mt dung dch rn ca cc axit nha ha tan trong mt hn hp cc tecpan (tinh du thng). Thng thng nha thng c thnh phn nh sau: Cc axit nha : 71 79 %, tinh du : 14 20%, cn li l nc v cc tp cht. Nha thng ly v chng ct bng hi nc c du thng l mt loi dung mi rt tt, phn cn cn li chnh l tng hng thng (colophan thng) mu vng sng, nu c ln nhiu hp cht khc th mu s thm hn. 1.5.3.2. Colophan thng c iu ch t nha thng l mt cht rn, gin mu sng hoc thm, ha tan tt trong cc dung mi hu c c bit nhit cao. Khi nung nng ko di nhit cao 250 - 300C trong iu kin khng c mt khng kh colophan thng b phn hy to thnh cc sn phm lng gi l du colophan. Thnh phn ha hc ca colophan thng c khong 90% l nha v t hn 10% l cc hp cht trung tnh, phn khng b x phng ha ca colophan thng. Trong colophan thng c 5 loi axit nha ng phn, cng thc chung l C20H30O2, cng thc cu to gn ging nhau, u c khung phe-nan-tren. Cc axit c tnh cht gn ging nhau:
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CH3

COOH

CH3 CH(CH3)2

Axit abietic
CH3 COOH CH3 COOH CH3 COOH

CH3 C(CH3)2

CH3

CH = CH2 CH3 CH3

CH3 CH = CH2

Axit neo - abietic

Axit d-pi-ma-ric

Axit i-do-d-pi-ma-ric

Trong cc loi ng phn ca axit nha th axit abietic l cu t chim a s. Cht lng ca colophan thng c nh gi qua cc ch tiu : mu sc, tr s axit, tr s x phng ha, hm lng cht khng x phng ha, nhit chy mm, hm lng tp cht c hc, cht bc v nhit dung. Mu sc Colophan thng cht lng tt c mu vng sng, mu cng thm ti cht lng colophan thng cng km. Tr s axit Tr s ny c trng cho khi lng cc axit c trong colophan thng. Tr s axit c biu th bng s miligam KOH cn trung ha 1g mu sn phm. i vi colophan thng tr s axit nm trong khong 145 n 180. Tr s x phng ha Tr s ny c biu th bng s mg KOH cn trung ha cc axit t do lin kt c trong 1g colophan thng. Tr s x phng ha trong khong 155 n 200.
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1.5.3.3. Cc mui kim loi Cobalt Cobalt (II) clorua: CoCl2 (M = 129,85) khan l mt cht mu l ti, d = 3,35, hp th nc rt mnh to ra CoCl2.6H2O bn nhit thng, phn ng ta nhit. Nhit chy 7220C, c th thng hoa nht l trong dng clo. Tan trong ru, axeton, benzonictryl, pyridine, quinolin v piperidin. CoCl2.6H2O (M = 237,95) l nhng tinh th mu , c d = 1,84, bn nhit phng, nng chy nhit thp hn 1000C nhiu. 30 450C bt u ln hoa v bt u tr nn c. Sau khi un bn gi 45-520C hu nh chuyn ton b thnh CoCl2.4H2O. Khi un nng mui tr nn xanh l, ngui li c mu c, CoCl2.6H2O rt d tan trong ru. Cobalt (II) oxit: CoO (M = 74,93) c mu lc xm, khng tan trong H2O v kim, c th tan trong kim c, d tan trong axit. Cobalt (III) oxit: Co3O3 (M = 152,02) l cht bt mu nu sm, d = 5,18. Gn 6000C chuyn thnh Co2O4, gn 13000C phn hy tip to ra 4CoO.Co2O3 v cui cng thnh CoO. Cobalt (II) nitrat: Co(NO3)2.6H2O (M = 290,93) l nhng hnh lng tr mu , d = 1,83, chy ra ngoi khng kh m. Khi nung nng s nng chy gn 550C ri mt nc v cui cng phn hy thnh CoO. Nhm Nhm oxit Al2O3 l mt th bt trng, d = 3,5 4,1, rt ho nc. Khng kh m khi cho qua ng cha Al2O3 (200C), lc ra khi ng ch cn cha 0,003mg/l nc.
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 tan ca Al2O3 trong axit ph thuc vo nhit khi iu ch ra thnh phm: b nung mnh, n hu nh khng tan trong axit v c v ch c th c chuyn thnh dung dch bng cch nghin nh n, v nu nng chy vi KOH hay KHSO4. Nhit nng chy 20500C nhit si 29800C. Do tnh bn ca nhm oxit nn khi sn xut cht mu khng s dng n lm nguyn liu ban u m thng i t cc dng mui hydroxyt phn hy to nhm oxit. Nhm clorua AlCl3 (M = 133,351) l nhng tinh th trong sut, khng mu hnh su gc, trng lng ring bng 2,41, nng chy 1900C (ti P = 2,5 at). Ti p sut khng kh, 1830C thng hoa m khng nng chy. ngoi khng kh, n ht m, mt phn b thy phn gii phng ra HCl, tan trong H2O (to thnh AlCl3.6H2O), trong ru v ete gii phng mt lng nhit kh ln khi tan. AlCl3 (M = 241,45) l mt loi tinh bt th trng rt ho nc, tan nhiu trong nc. Khi un nng b phn hy ng thi mt nc v HCl. Nhm nitrat Al(NO3)3.9H2O (M = 375) l nhng tinh th t phng hay n t, d tan trong nc v trong ru. 700C Al(NO3)3.9H2O nng chy v chuyn thnh Al(NO3)3.6H2O 1400C, to thnh mui bazo 4Al2O3.3N2O5.14H2O v 2000C to thnh Al2O3. 1.5.3.4 Cc phng php phn tch xc nh s to mu t cc Resinat kim loi xc nh cc sn phm thu c c phi l Resinat kim loi v khong nhit to mu pigment, ta s dng mt s phng php phn tch h tr cho qu trnh nghin cu. Phng php phn tch ph hng ngoi (IR) y l mt trong s cc phng php ph nghin cu cu trc phn t. V vy ng dng phng php ny chng minh sn phm to thnh sau phn ng l cc Resinat kim loi.
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Phng php phn tch nhit vi sai Phng php phn tch nhit l mt trong nhng phng php nghin cu ng hc phn ng pha rn, ng dng trong trng hp phn ng c s thay i khi lng ng k to hiu ng r rng. S bin i v nhit ca hn hp resinat c phn tch bng phng php phn tch nhit vi sai (DTA) kt hp vi ng cong bin i trng lng (TG). Phng php phn tch nhiu x Ronghen Phng php phn tch cu trc bng tia Ronghen cng c vng chc v mt thc nghim cc quan im hnh hc v cu trc mng li khng gian ca tinh th. Khi chiu chm tia Ronghen qua tinh th, nu khng gp cc phn t cu to (nguyn t, ion) cc tia s i qua tinh th. Nu gp cc phn t cu to, chng s b phn x, s phn x c xem nh phn x ca chm tia Ronghen t cc mt mng tinh th v dng thit b thu nhng tia phn x. Dng nhiu x Ronghen chng minh ti cc hiu ng nhit xy ra qu trnh bin i v sinh ra cc sn phm g, xc nh c nhit to mu t cc Resinat kim loi.

27

CHNG 2: THC NGHIM

Ly v d t vic tng hp bt mu coban aluminat (CoAl2O4) bng phng php sol-gel. Coban aluminat (CoAl2O4) l bt mu c cu trc spinel. Phng php tng hp truyn thng s dng cc oxit hay mui cacbonat ca cc kim loi lm tc nhn ban u. Cc tc nhn dng rng (t bt oxit, bt mui cacbonat hoc hydroxit ca nhm, coban) c phi liu, nghin mn ri nung nhit 1300 1350C to bt mu. gim nhit nung, phi dng cc cht khong nh B2O3. Ty mc ch s dng c th gim nhit tng hp bt mu nhit thp bng cc k thut nh sol-gel, ng kt ta, thy nhit, thy phn alkoxit, to hp cht c kim hoc polyme ha phc cht u im ca k thut dung dch l nh vo phn ng ca cation trong dung dch dng nguyn t, phn ng tng hp cc tinh th dng bt c tinh khit cao xy ra nhit thp hn v thu c ht bt mu rt mn. 2.1. Phng php th nghim Trc tin ta tng hp cc resinat coban v resinat nhm. Sau trn u 2 resinat theo t l xc nh, nung cc nhit khc nhau. Di tc dng ca nhit , cc resinat phn hy thnh cc kim loi hoc oxit vi hot tnh rt cao d dng phn ng to hp cht mi. Dng cc phng php kim tra qu trnh nh sau : Xc nh cc resinat kim loi bng phng php phn tch ph hng ngoi IR. Theo di qu trnh bin i theo nhit bng phng php phn tch nhit vi sai DTA. Kim tra cc cht to thnh bng phng php phn tch cu trc Ronghen. Kim tra kch thc ht bng nh knh hin vi in t qut SEM. 2.2. Tng hp resinat coban v resinat nhm bng phng php x phng ha Cho nha thng ha tan trong cc dung mi hu c nhit cao khi nng nhit ti 250 - 300C khng c khng kh, nha thng phn hy to nha lng colophan.
28

Cu to phn t gc axit trong colophan thng c nhm COOH vi cc ni i, nn cc colophan thng c kh nng tham gia cc phn ng x phng ha vi NaOH. y l iu kin cn to resinat kim loi bng phn ng trao i ion. X phng ha colophan thng bng NaOH, sau cho phn ng vi dung mui kim loi CoCl2.6H2O v AlCl3.6H2O thu c cc resinat kim loi tng ng. Phn ng x phng ha: un nng chy colophan thng bng NaOH theo t l RCOOH : NaOH = 1 : 1,8. Ra kt ta bng dung dch mui NaCl bo ha nng, lc tch, thu sn phm x phng ha RCOONa : RCOOH + NaOH RCOONa +H2O

iu ch resinat coban v resinat nhm : ha tan x phng natri bng nc ct, un cch thy ti 90C. Cho cc dung dch mui vo khuy u v lu 70 - 75C cho ti khi x phng natri to kt ta. Resinat kim loi to thnh theo phn ng : nRCOONa + Men+ R(COO)nMe + nNa+

Lc kt ta v ra nhiu ln bng nc nng loi NaCl d. Sy cc sn phm nhit 100 - 150C.

Hnh 2.1 S to mu Nano

29

CHNG 3 : KT LUN
Cng ngh sol-gel l vn thi s khoa hc, ang c quan tm v pht trin nghin cu cc vin nghin cu v trng i hc. Nh trn vit, qu trnh sol-gel c bn da trn cc phn ng thu phn v ngng t. Tuy nhin cc sn phm ca qu trnh polymer ho, tc cc phn ng, hay pH v cc cht thm vo khc nhau u nh hng n qu trnh ch to. C ch thc t ca qu trnh polymer ho cha c hiu r mt cch y v c th ch c rt ra t cc kt qu thc nghim. Hin nay phng php sol-gel l k thut c s dng rng ri v t ra c u vit to ra cc vt liu khi , mng mng c cu trc nano, bt vi mn cao hoc dng si c cu trc a tinh th hay v nh hnh m cc phng php khc kh thc hin c.

30

TI LIU THAM KHO

[1] Phan Vn Tng(2007), Cc phng php tng hp vt liu gm, NXB i

hc Quc gia H Ni. [2] Ts.nguyn c Ngha(2007), Ha hc nano cng ngh nn v vt liu

ngun, NXB Khoa hc t nhin v cng ngh H Ni. [3] Ths.on Mnh Tun (2009), Gio trnh cng ngh ceramic, NXB trng

i hc Cng Nghip TP.HCM. [4] [5] C. Jeffrey Brinke, George W. Scherer (1990), Sol-gel science :The

Physics and Chemistry of Sol-Gel Processing,Academic Press. [6] Publications. [7] Trnh Thanh Thy, T Ngc Hn, L Khc Bnh, L Vit Hi(2006), Ch Lisa C.Klein, Sol-Gel Technology for thin film, fibers, preforms, electronics

and specialty shape (Materials Science and Process technology Series), Noyes

to mng mng SnO2 c cu trc nano bng phng php sol-gel, Tp ch pht trin KH&CN,11, (06), 73-78.

31

MC LC
CHNG 1:TNG QUAN ................................................................................................. 1 1.1. Tng quan v phng php sol-gel ................................................................... 1 1.1.1. Gii thiu ........................................................................................................ 1 1.1.2. Cc khi nim c bn ..................................................................................... 1 1.1.3. u im v nhc im ca qu trnh Sol-Gel .......................................... 2

1.1.4. Mt s ng dng hin nay ca phng php sol-gel ..................................... 3 1.2. C s ha l ca cng ngh Sol-Gel ................................................................. 4 1.2.1. Phn ng thy phn ........................................................................................ 5 1.2.2. Phn ng ngng t .......................................................................................... 7 1.3. Cc phng php phn tch ng dng trong phng php sol-gel ................. 10 1.3.1. Nguyn l v ng dng ph nhiu x tia X (XRD)...................................... 10 1.3.2. Nguyn l v ng dng chp ph TEM, SEM ............................................. 11 1.4. Bt mu gm s v cng ngh sn xut bt mu theo phng php c in . 12 1.4.1. Bt mu gm s ............................................................................................ 12 1.4.2. Cng ngh sn xut bt mu theo phng php c in .............................. 17 1.5. Nguyn liu sn xut bt mu Nano t cng ngh Resinat............................. 19 1.5.1. Khi nim chung v Resinat kim loi........................................................... 19 1.5.2. Cc phng php iu ch resinat kim loi ................................................. 21 1.5.3. Cc nguyn liu dng iu ch Resinat kim loi..................................... 23 CHNG 2: THC NGHIM....................................................................................... 28 2.1. Phng php th nghim.................................................................................. 28 2.2. Tng hp resinat coban v resinat nhm bng phng php x phng ha ... 28 Hnh 2.1 S to mu Nano ............................................................................................ 29
32

CHNG 3 : KT LUN ................................................................................................. 30 TI LIU THAM KHO .................................................................................................. 31 MC LC .......................................................................................................................... 32 DANH MC BNG, S , HNH ................................................................................ 34

33

DANH MC BNG, S , HNH

Hnh 1.1: Cc nhm sn phm ca phng php sol-gel .................................................... 4 Hnh 1.2: phn ng thy phn ............................................................................................. 6 Hnh 1.3: phn ng ngng t ................................................................................................ 7 Hinh 1.4 : S pht trin cu trc tinh th trong iu kin xc tc acid ................................ 8 Hnh 1.5: S pht trin cu trc tinh th trong iu kin xc tc base................................. 9 Hnh 1.6: S pht trin cu trc mng trong qu trnh sol gel ......................................... 10 Hnh 1.7: S nhiu x tia X trn mt tinh th ................................................................ 10 Hnh 1.8: Thit chp ph XRD .......................................................................................... 11 Hnh 1.9: Thit b chp TEM ............................................................................................. 11 Hnh 1.10: Thit b chp SEM ........................................................................................... 12 Bng 1.1: Bng mu ca cc cht mu ion ......................................................................... 14 Hnh 2.1: Ph hp th hng ngoi (IR) ca cc tin cht ... Error! Bookmark not defined.

34