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Lý Thuyết Về Sol Gel
Lý Thuyết Về Sol Gel
C ch xc tc ca Baz:
Phn ng thu phn trong xc tc Baz xut pht chm hn nhiu so vi
phn ng thu phn xc tc acid ti c ng mt nng cht xc tc t ng ng.
Nhng oxi alkoxy c bn c khuynh hng y
-
OH. Tuy nhin mt khi phn ng
thu phn ban u xut hin, nhng phn ng tip theo xy ra nh bc thang, vi
mi nhm alkoxy tip theo loi b mt cch d d ng hn t Monomer v cng l
nhm u tin. Qu trnh thu phn ca nhng polymer to thnh th b gy cn tr
khng gian nhiu hn i vi qu trnh thu phn ca mt monomer. Mc d qu
trnh thu phn trong cc mi tr ng kim xy ra chm, nhng n vn c khuynh
hng xy ra mt cch hon ton theo chiu thun.
C ch xc tc acid:
Trong iu kin acid, c kh nng mt nhm Alkoxide b proton ho trong
bc u tin rt nhanh. Mt Electron b rt ra khi nguy n t kim loi, lm
cho n c i lc vi in t nhiu hn v d b nh hng hn bi s tn cng
ca nc. V iu ny dn n s to thnh trng thi trung gian. Trng thi
chuyn i ph v bi s tch ra mt alcohol v s o ngc ca khi t
din silicon.
Trong iu kin bnh thng, phn ng thu phn c pht hin l bc
nht trong mi trng Baz. Tuy nhin khi nng Prescusor tng l n th phn
ng chuyn t phn ng bc nht n gin sang phn ng bc hai phc tp hn.
Vi nhng Baz yu hn ammonium hydroxide v pyridine t c d c th o
lng ca phn ng oc sinh ra ch khi tn ti nng ln. V vy so snh vi
iu kin acid, ng lc phn ng thu phn xc tc baz chu nh hng mnh
m hn bi bn cht dung mi.
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 l n cho n khi to ra mt
mng li kim loi oxide kim loi trong khp dung dch. Phn ng ngng t
c thc hin theo m hnh hnh 7 v phng trnh phn ng sau
Hnh 7: Qu trnh ngng t.
MOR + MOH M-O-M + ROH
MOH + MOH M-O-M + H
2
O
Trong iu kin thch hp, s ngng t xy ra lin tc v ph hu polimer,
ti to thnh nhng ht keo ln, t to thnh cc polime ln hn.
Cc thng s nh hng ch yu n qu tr nh ngng t: pH, bn cht
v nng ca cht xc tc, nhit , dung mi, t s H
2
O/M
Cc thng s nh hng n phn ng ngng t
a, nh hng ca pH
Qu trnh trng hp to nn cc ni Siloxan sinh ra hoc do phn ng
ngng t hnh thnh nc hoc do phn ng ngng t to ru. Mt chui cc sn
phm in hnh ca phn ng ngng t l monomer, dimer, trimer mch thng, cc
tetramer tun hon, cc vng c bc cao hn. Chui ngng t ny ph thuc vo
c Depolymerization v s c mt ca cc monome, ci m trong dung dch cn
bng vi dng oligomeric c sinh ra bi qu trnh Depolymerization.
Tc ca qu trnh trng hp m vng ny v cc phn ng thm vo
monomer ph thuc vo pH ca mi trng. Trong nhng phn ng tr ng hp m
pH<2 th tc ngng t t l vi nng [H
+
]. Bi v tnh tan ca Silica yu cu
pH<2. S to thnh v s kt khi ca nhng ht silicat c bn xut hin cung
nhau v ng gp phn no i vi pht trin sau khi cc ht c ung knh
vt qu 2 nm. Thm vo s pht trin ca mng l i Gel bao gm nhng ht
c bn nh qu mc.
Vi 2< pH<6 th tc phn ng ngng t t l vi nng [
-
OH]. Tnh
tan ca cc silicat gim tr li v s pht trin ca cc ht dng li khi cc ht tin
ti ng knh 2-4 nm.
Khi pH>7 th qu trnh t rng hp xut hin ging nh 2<pH <6. Tuy
nhin, trong phm vi pH ny kiu c c b ion ho v kt qu l gy lc y ln
nhau. S pht trin xut hin c bn thng qua s thm vo ca monomers c
c nhng ht ng c cao hn. Cc ht pht trin v kch thc v gim v s
lng. Trn hnh 8 l tc ha tan v thi gian gel ha theo s thay i pH
Hnh 8 : Tc ha tan v thi gian gel ha trong iu kin pH
b, nh hng ca xc tc
Phn ng ngng t thng thng vi cht xc tc l HCl, HNO
3
, CH
3
COOH
C ch xc tc acid:
C ch phn ng ngng t di xc tc acid lin quan n mt silano c
thm proton. S c thm proton ca silanol lm cho silicon c i l c vi in t
nhiu hn v thm vo d b tn cng bi i nhn. Kiu silanol c bn nht
c ch i nht c c thm mt proton. Kt qu l , cc phn ng ngng t
c th xy ra mt cch u tin gia nhng loi trung tnh v nhng silanol nhn
thm mt proton nm trn cc monomer, cc nhm u mt ca chui.
C ch xc tc baz:
C ch c chp nhn mt cch rng r i nht i vi phn ng ngng t
xc tc baz lin quan n s tn cng ca mt silanol i nhn l n mt acid sililic
trung tnh
c, nh hng ca dung mi :
i vi dung mi phn cc vi xc tc l baz s lm cho phn ng xy ra
chm, nu xc tc l axit th lm phn ng xy ra nhanh hn
Thm mt s cht ph gia lm gel kh nhanh m khng b t gy, ph gia
thng l cc loi axit hu c axit oxalic, axit acetic, axit polycrylic, axit stearic
IV. Qu trnh ng hc v s pht trin cu trc
1, Chuyn ng ngu nhin Brown:
L s chuyn ng hn lon ca cc ht keo c kch thc nh (~ nm) trong
dung dch v cng chuyn ng khng b suy gim theo thi gian, l tng hp
kt qu ca s va chm theo cc hng ca cc phn t mi trng phn tn vi
ht keo. Chuyn ng ca ht keo n y c biu hin ca chuyn ng nhit v v
th cng c cc tnh cht ng hc nh : thm thu, khuch tn .
1. Ht keo hnh cu c kch thc ln hn phn t nn dung dch n b cc
phn t nc do chuyn ng nhit va p t khp cc h ng khc nhau.
2. Cc ht c kch thc > 5m coi nh ng im: do cc va p ng thi t
cc hng c th b tr ht cho nhau (v thnh phn lc).
3. Cc ht c kch thc nh hn 5 m chuyn ng ngu nhin Brown: do s
va p t cc pha l t hn nn c kh nng khng b tr ht cho nhau lm
ht b y v 1 hng .V cc phn t nc chuyn ng hn lon nn
chng lun thay i hng va p, do cc ht keo cng b thay i
hng chuyn ng.
2, Qu trnh ng hc v cc thng s:
Trong phn ng thu phn v ngng t, cc thng s nh hng n ng
hc Sol-Gel l cc hng s tc phn ng:
K
h
: hng s tc thu phn
K
cw
: hng s tc ngng t nc
K
ca
: hng s tc ngng t ru
M-O-R + H
2
O M-OH + R-OH (hydrolysis)
M-OH + HO-M M-O-M + H
2
O (water condensation)
M-O-R + HO-M M-O-M + R-OH (alcohol condensation)
(M = Si, Zr, Ti )
Trong thc t,s thu phn v ngng t xy ra song song nhng nhm chc gn
nht.
Nu K
h
>> K
wc
v K
h
>> K
ac
: thu phn hon ton, khng ngng t nn mt
nhm OR gim nhanh.
Khi tc gim OR nh hn tc ngng t th thu phn v ngng t cng xy
ra.
Tc ngng t:
dt
MOM d ] [
= K
wc
[M(OH)]
2
+ K
ac
[M(OH)][M(OR)]
K
wc
> K
ac
: tc ngng t nc t l vi [M(OH)]
2
K
wc
< K
ac
: tc ngng t ru t l vi [M(OH)][M(OR)]
Hai phn ng ngng t ru v nc xc nh chnh xc ng hc ca phn ng.
3. S pht trin cu trc
nh hng ca axit v baz n s pht trin cu trc:
Sol tn ti trong dung dch 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 1 nm th tu theo xc tc c mt trong ung dch m pht trin theo
nhng hng khc nhau. Nh vy, vi cc loi xc tc khc nhau, chiu h ng
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.
Hnh 9 : S pht trin cu trc mng trong qu tr nh sol-gel
4. Cc lai pht trin cu trc:
C 3 loi pht trin cu trc : monomer -monomer, monomer-cluster,
cluster-cluster, tuy nhin cu trc monomer-monomer l khng ng k.
a, S pht trin monomer-cluster
Cc monomer lin kt vi nhau to thnh cc oligomer, bn cnh , cc
monomer cng lin kt vi oligomer va to thnh, nhng v tr tu gn u
mch hay nhnh. Cc nhnh ca oligomer to khng gian cn tr s li n kt ca
monomer v cc gc bn trong ca oligomer, lm cho phn ng to lin kt ngng
li. y chnh l iu kin gii hn phn ng hay kh nng khuch tn monomer
lp y l trng trong mng, khin cho cu trc mng kt cht hn. Tuy nhin
vn cn nhng v tr alkoxide khng b thu phn hay thy phn khng ho n ton
nn khng th ngng t.
b, S pht trin cluster-cluster
Vi xc tc acide v t s r (H
2
O:M) thp (r<2), phn ng thu phn cha
hon ton th xy ra ngng t. Cc monomer va b thu phn tng phn va
ngng t pht trin cu trc, to ra oligomer c khi l ng phn t thp cho
n khi ht nc v M(OH)
x
th ngng li.
Khi chm thm nc, nhng v tr alkoxide cn li tip tc thy phn v
ngng t xy ra lin tip gia nhng oligomer va to th nh.Vi xc tc acide v
t s r ln , giai on u phn ng thu phn xy ra ho n ton, cc monomer
nhanh chng lin kt thnh cc dimer v oligomer (cluster) lm pht tri n cu trc
cluster-cluster.
c, S pht trin monomer monomer.
Qu trnh ny xy ra rt t, khng ng k
V. Cc phng php ph mng Sol gel:
iu kin tin quyt i vi qu trnh ph mng Solgel l: phng th nghi m phi
sch, dung dch ph mng c lc v thu tinh cng mt s thit b phi c
ra sch. Mt s phng php ph mng Sol gel l: ph nhng (dip coating),
ph quay (spin coating), ph phun (spray coating), ph cun (roll coating),
capillary coating
Hnh 10 l 3 phng php ph thng dng cc phng th nghim.
Hnh 1. 1: Mt s phng php ph mng Solgel.
1, Phng php ph nhng (dip coating):
y l phng php c dng rt nhiu b mn Vt l ng dng tr ng
H KHTN. thu tinh dng ph mng c a xung v c nhng hon
ton trong cht lng vi 1 vn tc nht nh d i s iu khin ca nhit v p
sut kh quyn. Sau mng c ko ln vi cng 1 vn tc .
Hnh 11 : Qu trnh dipcoating.
Nhng vo bn trong dung dch ph.
Hnh thnh lp mng m khi ko ln.
Qu trnh gel xy ra bi s bay hi dung mi.
dy mng: c tnh bng phng trnh LaudauLevich:
2 / 1 6 / 1
3 / 2
) . (
) . (
. 94 . 0
g
h
LV
=
(1)
Vi:
h : dy mng.
: nht ca cht lng.
LV
: p lc b mt cht lng kh.
: t trong, khi lng ring ca cht lng.
g : trng lng.
v : vn tc ko mng.
T ta c th thy dy ca mng ph thuc vo cc yu t nh: vn
tc ko mng ln, cht rn cha trong dung dch v nht ca cht lng. Vic
chn tc ko mng v nht 1 cch thch hp c kh nng tng d y t
20nm n 50m trong khi tnh cht quang ca mng khng thay i.
2, Phng php ph quay (spin coating):
c t trn mt b mt phng quay quanh 1 trc vung gc vi mt
t. Dung dch c a ln v tin hnh quay (ly tm), tn mng mng v bay
hi dung dch d.
Hnh 12 : Cc bc ca qu trnh spincoating.
Ph quay l phng php to mng kh n gin v t tn km, mng c
to kh ng nht v c dy tng i ln.
dy mng: Meyerhofer m t s ph thuc ca dy mng cui cng
ph thuc vo vn tc gc, nht v tc bay hi ca dung mi bng cng
thc bn thc nghim sau:
1/3
2
1 3 .
.
2 .
A
Ao Ao
m
h
/ \/ \
=
' 1' 1
\ \
(2)
Vi:
h : dy cui cng.
A
v
Ao
: khi lng v khi lng hiu dng ca
dung mi d bay hi trn 1 n v th tch.
: nht.
: vn tc gc.
m : tc bay hi ca dung mi.
Khi m c xc nh bng thc nghim, ph ng trnh c
n gin thnh:
.
B
h A
= (3)
Vi A v B l cc hnng s xc nh bng thc nghim. Lai,
Chen v Weill bng thc nghim s dng nhiu vn tc gc
khc nhau, v kt qu thu c l rt khp vi phng trnh
(3). H s B c xc nh trong khong 0.4 0.7.
3, Phng php ph phun v ph dng chy
Phng php ny thng c dng trong cng nghi p sn du, vic kim sot
tnh ton dng phun suy ra dy mng tng i kh khn, v th phng
php ny t c dng trong cng ngh ch to mng mng nano
4, Qu trnh x l nhit
Tng nhit : cung cp nhit l ng loi b dung mi cn st li trong
mng va to thnh, qu trinh tng nhit v x l nhit trong nhng mi trng
khc nhau nh hng ng k n cht l ng mng. Nung kh bng cch bay hi
iu kin bnh thng ta thu c sn phm gi l gel kh, nung iu kin ti
hn th sn phm nhn c it b co hn v gi l gel kh
VI. To mng bng phng php solgel c tng cng plasma
Plasma l mt trong nhng k thut hin i c s dng lm bin i
tnh cht b mt vt liu nh : kim loi,hp kim, gm s,mng mng, polymer.
nhm phc v cho nhng mc dch s dng khc nhau ca cc loi vt liu n y.
Plasma to thnh khi mt cht kh hoc mt hn hp kh c t trong in
trng thch hp.Mi trng Plasma cha cc phn t b kch thch bi in
trng nh cc nguyn t, phn t, cc ion,in t, cc gc t do v c th pht ra
nh sng vi bc sng ngn nm trong vng t ngoi.
Cc phn t kch thch ny c th tc ng vo vt liu (substrate) t
trong mi trng Plasma v lm bin i b mt ca n, cc tc ng n y c th l
cc tc ng vt l hay tc ng ho hc hoc ng thi c vt l v ho hc.
Thit k h thng c x l bng Plasma:
Hi dung dch
DUNG DCH PH
Mng c t ln b trong thit b Plasma sao cho b mt hot ng
ca mng tip xc vi mi trng Plasma. Thit b c rt chn khng ti p
sut nh hn 0.3 torr.Sau kh Argon c dn vo thit b vi tc dng thch
hp cho ti khi t ti p sut xc nh. ng mch in to ra mt in tr ng
gia hai in cc. Plasma xut hin v b mt mng b tc ng bi cc phn t
kch thch trong mi trng Plasma.
C ch tc ng ca Plasma c to ra trong mi trng kh Argon trong
cc iu kin thc nghim sau :
Trong vng Plasma, di tc dng ca in tr ng, kh Argon b ion ho,
cc ion Ar
+
i v pha Catot v cc in t i v pha Anod. Va chm gia cc
in t v cc nguyn t Argon sinh ra cc ion Ar
+
ng thi to thnh cc in t
th cp c nng lng cao, cc in t ny s tc ng vo b mt mng v gy ra
nhng bin i v cu trc ca b mt.
Quan st qua knh hi n vi in t qut (SEM) hoc qua php phn tch ph
hng ngoi bin i Furie (FTIR) pht hin s thay i v mt ho hc ca
mng. So snh vi lc u cha tng cng Plasma.
VII. ng dng phng php Sol gel:
To mng bo v v mng c tnh cht quang hc.
To mng chng phn x.
B nh quang.
To knh giao thoa.
Mang a l p tao vi i en t
VIII. u v nhc im phng php Sol gel:
u im Nhc im
- C th to ra mng ph lin kt mng
mang n s dnh cht rt tt gia
vt kim loi v mng.
- C th to mng dy cung cp cho qu
trnh chng s n mn.
- C th phun ph ln cc hnh dng
phc tp.
- C th sn xut c nhng sn phm
c tinh khit cao.
- L phng php hiu qu, kinh t, n
gin sn xut mng c cht lng
cao.
- C th to mng nhit bnh
thng.
- S lin kt trong mng yu.
- chng mi mn yu.
- Rt kh iu khin
xp.
- D b rn nt khi x l nhit
cao.
- Chi ph cao i vi nhng vt
liu th.
- Hao ht nhiu trong qu trnh
to mng.