B GIO DC V O TO

TRNG I HC BCH KHOA H NI

--------------------

BI QUC HUY

Tng hp cht mu trn c s h km silicat pha tp bi

Niken hay Coba

Chuyn ngnh : Cng ngh cc cht v c

LUN VN THC S KHOA HC :

Ngnh: Cng ngh cc cht v c

NGI HNG DN KHOA HC :

L XUN THNH

H Ni, 2010
 LI CAM OAN

Ti xin cam oan y l cng trnh nghin cu ca ti, cc s liu trong lun vn l
trung thc, c cc ng tc gi cho php s dng v khng sao chp bt c mt
ti liu khoa hc no.
Bi Quc Huy

1
 LI CM N

Ti xin by t lng bit n su sc n PGS.TS L Xun Thnh, ngi

tn tnh hng dn, ch bo cho ti trong sut qu trnh nghin cu, thc nghim
hon thnh lun vn cao hc ny.
Ti xin chn thnh cm n cc thy c gio cng cc bn ng nghip Khoa
Cng ngh Ho hc & Mi trng Trng i hc S phm k thut Hng Yn
gip ti trong sut qu trnh hc tp v thc hin lun vn.
Ti xin cm n hai sinh vin: Nguyn Trng Hng v Phm Vn Tng
cng tc thc hin lun vn ny.
Xin chn thnh cm n.

Bi Quc Huy

2
LI CAM OAN ......................................................................................................1
LI CM N............................................................................................................2
DANH MC CC BNG ........................................................................................5
DANH MC CC HNH V, TH ..................................................................6
M U ....................................................................................................................8
CHNG I : TNG QUAN CHT MU CHO GM........................................9
1.1 L thuyt v cht mu [1,2,11,12,13] ...............................................................9
1.1.1 Bc x in t ...........................................................................................9
1.1.2 Tnh ht ca nh sng ..............................................................................10
1.1.3 Tng tc gia nh sng v vt rn ........................................................10
1.1.4 Cc nguyn t gy mu ............................................................................13
1.2 Cht mu cho gm [3,4,]................................................................................14
1.2.1 Cc loi tinh th nn dng tng hp cht mu cho gm s: ..............15
1.2.2. Gii thiu mt s tinh th nn s dng trong tng hp cht mu gm ..15
1.2.3 Cc phng php s dng cht mu gm: ..............................................19
1.2.4. K thut tng hp cht mu [5,6]............................................................21
1.3. Gii thiu v km silicat ...............................................................................23
1.3.1. Cc silicat: ..............................................................................................23
1.3.2. Phn loi silicat: .....................................................................................25
CHNG II: PHNG PHP NGHIN CU .................................................29
2.1. Cc thit b v ho cht cn thit: ..................................................................29
2.2. Phng php thc nghim .............................................................................29
2.2.1.Tng hp cht mu theo phng php sol gel bin tnh.......................29
2.2.2. Tng hp cht mu theo phng php ng kt ta: ............................30
2.3. Cc phng php phn tch [7]:.....................................................................31
2.3.1. Phng php phn tch nhit:.................................................................31
2.3.2. Phng php nhiu x tia X (XRD):.......................................................32
2.3.3. Phng php qut hin vi in t (SEM): ..............................................34
2.3.4. Phng php hin vi in t truyn qua TEM........................................35
CHNG 3: KT QU V THO LUN.........................................................39
3.1. Tng hp km silicat pha tp bi niken theo phng php sol gel bin tnh:
...............................................................................................................................39
3.1.1.iu ch cc tin cht km silicat pha tp bi niken...............................39
3.1.2. Kho st thnh phn pha ca cc mu theo nhit nung ....................39
3.2. Tng hp km silicat pha tp bi coban theo phng php ng kt ta .....45
3.2.1. iu ch tin cht km silicat pha tp bi coban ...................................45
3.2.2. Kho st s bin i ca mu tin cht P6 theo nhit ......................46
S bin i ca mu tin cht P6 theo nhit c ch ra hnh 3.7................46
3.2.3. Kho st thnh phn pha ca cc mu sau nung ...................................47
3.2.4. Mt s c tnh ca sn phm ................................................................51
Hnh thi v c ht............................................................................................51
hp th mu.................................................................................................52
3.3. Kho st kh nng to mu cho men..............................................................55

3
KT LUN ..............................................................................................................58
TI LIU THAM KHO ......................................................................................59
Ting Vit..............................................................................................................59
Ting Anh..............................................................................................................59

4
 DANH MC CC BNG

STT TN NI DUNG
TRANG
1 Bng 1.1 Mu ca cc cht theo bc sng nh sng b hp
13
th
2 Bng 1.2 Cc khong silicat 26
3 Bng 3.1 Ch to mu km silicat pha tp niken 39
4 Bng 3.2 Thnh phn phi liu khi iu ch cc mu tin
46
cht theo phng php ng kt ta
5 Bng 3.3 Cc thng s cng pic v d 2 theta 34,1 50
6 Bng 3.4 nh hng mc pha tp n hp th nh
55
sng ca mu
7 Bng 3.5 Thnh phn ha hc ca t st H long 56

5
 DANH MC CC HNH V, TH

STT TN NI DUNG TRANG

1 Hnh 1.1 Sng nh sng 9
2 Hnh 1.2 Di bc x in t 10
3 Hnh 1.3 C ch tng tc ca proton vi cht rn 11
Hnh 1.4 Phng php gm truyn thng sn xut vt
4 21
liu mu

5 Hnh 1.5 T din SiO 44 trong mng octosilicat 25

6 Hnh 1.6 Nhm pyroxen 27

7 Hnh 2.1 S tng hp theo phng php ng kt ta 30
8 Hnh 2.2 S nhiu x tia X trn b mt tinh th 33
9 Hnh 3.1 Gin XRD mu 1.1 40
10 Hnh 3.2 Gin XRD mu 1.2- pha tp 5% niken 41
11 Hnh 3.3 Gin XRD mu 1.3- pha tp 10% niken 42
12 Hnh 3.4 Gin XRD mu 1.4- pha tp 20% niken 43
Hnh 3.5 Gin XRD mu 1.4- pha tp 20% niken nung
13 44
1h 12000C
14 Hnh 3.6 nh SEM ca mu Zn1,8Ni0,2SiO4 45
15 Hnh 3.7 Gin phn tch nhit mu 1.5 46
16 Hnh 3.8 Gin XRD mu P7.2 (x=0,2) 47
17 Hnh 3.9 Gin XRD mu P8.2 (x=0,4) 49
18 Hnh 3.10 Gin XRD mu P9.2 (x=0,6) 48
19 Hnh 3.11 Gin XRD mu P10.2 (x=0,8) 49
20 Hnh 3.12 Gin XRD mu P11.2 (x=1.0) 49
21 Hnh 3.13 nh TEM mu P8.2 Zn1,6Co0,4SiO4 51
22 Hnh 3.14 Ph hp th UV-Vis mu P7.2 (x=0,2) 52

6
23 Hnh 3.15 Ph hp th UV-Vis mu P8.2 (x=0,4) 52
24 Hnh 3.16 Ph hp th UV-Vis mu P9.2 (x=0,6) 53
25 Hnh 3.17 Ph hp th UV-Vis mu P10.2 (x=0,8) 53
26 Hnh 3.18 Ph hp th UV-Vis mu P11.2 (x=1,0) 54
27 Hnh 3.19 Gin XRD t st H long 56
28 Hnh 3.20 Mu th nghim trn gm 57

7
 M U

Sn xut cht mu l mt ngnh cng nghip em li li ch kinh t to ln.

Tuy nhin nc ta hin cha c mt c s no sn xut v cung cp ra th trng
cc sn phm cht mu thng mi vi qui m cng nghip. Trong khi nhu cu
s dng cht mu ti Vit Nam ngy cng ln vi nhng yu cu ngy cng kht
khe v cht lng, mu m, chng loi. V vy cn c chnh sch pht trin ngnh
cng nghip cht mu ti Vit Nam t nghin cu phng th nghim cho n trin
khai cng nghip. Cc cht mu trn c s mng km silicat bn nhit, bn ha hc
c th dng lm cht mu cho nhiu lnh vc cng nghip v i sng. Do vy
ti Nghin cu tng hp cht mu trn c s h km silicat pha tp bi niken hay
coban r rng c ngha khoa hc v thc tin quan trng.
Mc ch ca ti:
Tng hp thnh cng cht mu trn c s h km silicat pha tp bi niken hay
coban.
Ni dung ca ti:
- Tng hp cht mu trn c s h km silicat pha tp bi niken hay coban.
- nh gi c tnh sn phm thu c
- Thm d kh nng ng dng

8
CHNG I : TNG QUAN CHT MU CHO GM

1.1 L thuyt v cht mu [1,2,11,12,13]

1.1.1 Bc x in t
Bc x in t l s pht v truyn nng lng di dng sng in t. Mi
sng gm hai thnh phn in trng v t trng vung gc vi nhau v vung
gc vi phng truyn.

Hnh 1.1: Sng nh sng

Ph ca bc x in t tri rng t tia (do cc cht phng x pht ra) c

bc sng c 10-12m, qua tia Rntghen, tia t ngoi, nh sng nhn thy, tia hng
ngoi v cui cng l sng raio (sng v tuyn in) vi bc sng di 105m. nh
sng nhn thy nm trong mt vng hp ca ph vi bc sng t 0,4m n
0,7m.

9
 Hnh 1.2: Di bc x in t

1.1.2 Tnh ht ca nh sng

nh sng l mt ti lun thu ht c s quan tm ca cc nh khoa hc
trn th gii. n nay l thuyt v nh sng c lm sng t v c dng lm
c s gii thch rt nhiu hin tng t nhin. Theo quan im lng t, bc x
in t l cc ht lng t hay photon. Mi photon mang mt nng lng c
xc nh bi phng trnh:

c
= h = h
(1.1)
Trong : h- l hng s Plng, c gi tr 6,63.10-34 J.s
Nh vy, nng lng photon t l thun vi tn s v t l nghch vi bc sng ca
nh sng.

1.1.3 Tng tc gia nh sng v vt rn

Khi chm photon chiu vo mt cht rn, s tng tc din ra, iu ny lin
quan n l thuyt lng t. Theo nguyn l tn x bc x in t ca Huygen, khi
cc photon n gn tip xc vi mt cht rn, cc vect in trng v t trng
ca cc photon ti cp i vi cc vect in trng v t trng ca cc electron
trong cc nguyn t ca cht rn. Tng tc ny gm 4 thnh phn, c th l:

10
R - bc x c phn x,
A - bc x c hp th,
T - bc x c truyn qua
S - bc x c tn x.
C ch ny c minh ha hnh 1.2 nh sau:

Hnh 1.3: C ch tng tc ca photon vi cht rn

Ta c Io = IR + IA + IT + IS vi:
+ Io l cng nh sng ti
+ IR, IA, IT, IS l cng nh sng c phn x, hp th, truyn qua v tn x
Trong trng hp hp th, nng lng ca photon lm thay i nng lng ca
nguyn t hoc phn t trong cht rn, dn n lm nng ln v tr hp th.. Khi
photon truyn qua cht rn (coi nh cht rn l trong sut i vi chiu di sng
photon), khng c tng tc no xy ra. Khi phn x (tn x), photon c th va
chm n hi hoc khng n hi vi cc nguyn t cht rn. trng hp va
chm n hi bc sng khng thay i, cn va chm khng n hi lm thay i
bc sng ca cc photon. iu ny c ngha l mt phn nng lng hp th to ra
trng thi kch thch, electron c chuyn ln vng nng lng cao hn.

11
Trng hp bc sng photon pht ra khng b thay i, photon c gi l tn
x v s phn x l mt va chm n hi.
Cc cng thc c th p dng i vi cc tnh cht quang hc ca cht rn nh sau:
- hp th:
A = log 1 /T = log Io /I (1.2)
Trong : I: l cng nh sng o c
Io: l cng nh sng ti
- truyn qua:
T = I / Io (1.3)
- Cng :
Cng I c nh ngha l nng lng trn mt n v din tch ca mt chm
photon, tc l bc x in t.
Mt phn cng ban u Io c hp th, phn khc c truyn qua,
phn khc c tn x v mt phn khc na c phn x. Cc thnh phn, S v
T, l cc qu trnh khng ph thuc vo bc sng ca photon ti, trong khi R v A
ch yu l ph thuc vo bc sng.
Trng hp s hp th l rt nh so vi s tn x, cht m c mu trng.
Trng hp s hp th l cao hn nhiu so vi s tn x trong vng nh sng nhn
thy, cht mu c mu en. cc cht mu c mu khc, s hp thu l chn lc
(ph thuc bc sng). Chng hn, mt cht c mu lc khi chng ch cho tia mu
lc i qua hoc n hp th tia mu v cho tt c cc tia khc i qua . Bng 1.1
sau ch ra mu ca cc cht theo bc sng nh sng b hp th

12
Bng 1.1: Mu ca cc cht theo bc sng nh sng b hp th

Bc sng ca Mu ca nh
Nng lng kj/mol Mu ca cht
vch hp th (nm) sng b hp th
<400 >299 Tia t ngoi Khng mu
400 435 299 274 Tm Lc Vng
435 480 274 249 Lam Vng
480 490 249 244 Lam Lc nht Cam
490 500 244 238 Lc Lam nht
500 560 238 214 Lc ta
560 580 214 206 Lc Vng Tm
580 595 206 200 Vng Xanh bin (blue)
595 605 200 198 Cam Xanh bin Lc nht
605 750 198 149 Lc Xanh bin nht
>750 <149 Tia hng ngoi Khng mu

1.1.4 Cc nguyn t gy mu
Cc nguyn t gy mu cc cht rn thng l cc ion kim loi chuyn tip
trng thi oxy ha khc nhau. Nguyn t kim loi chuyn tip l cc nguyn t m
phn lp d hoc f cha c in y cc electron. Trong bng h thng tun
hon cc nguyn t chuyn tip bt u t chu k 4 n chu k 7, cc nhm B. Cc
nguyn t chuyn tip c dng tng qut (n-1)d1-10ns1-2, h lantan v h
actini c cu hnh in t tng qut dng (n-2)f1-14 (n-1)d0-1 ns2. Cc dng oxy
ha khc nhau ca cc nguyn t chuyn tip c hnh thnh bng cch mt i
electron lp ngoi cng. Di tc dng ca trng tinh th c s phn tch mc
nng lng ca cc ion kim loi chuyn tip v do vy chng c kh nng hp th
nh sng trong vng nhn thy v do vy chng c mu.

13
Trong tng hp cht mu, cc ion kim loi chuyn tip c a vo phi liu di
dng cc oxit hoc mui c kh nng phn hy nhit to thnh oxit nhit cao
trong qu trnh nung phi liu mu.

1.2 Cht mu cho gm [3,4,7]

Cht mu cho gm s v bn cht ch l nhng khong vt t nhin hoc
nhn to c mu, bn mu i tc ng ca nhit cao.
Mc d trong t nhin c rt nhiu khong cht c mu v c kh nng bn mu
nhit cao (th d nh nhng xit hoc nhng mui ca kim loi chuyn tip),
nhng chng thng c hm lng khong mu khng cao, c ln nhiu tp cht
khng c li cho trang tr mu cho gm s v thnh phn ca cc khong gy mu
trong t nhin thng khng n nh, dn ti mu sc ca sn phm trang tr cng
khng n nh trong qu trnh gia cng.
Ngy nay, nhng cht mu s dng cho gm s thng l nhng cht mu
tng hp bn nhit. Cc cht mu vi yu cu va c tnh trang tr, va i hi phi
chu tc ng khc nghit ca nhit , tc nhn ha hc, mi trng
Cht mu cho gm s ch yu thuc h dung dch rn (dung dch rn xm nhp hay
dung dch rn thay th), thng c tng hp da trn c s a mt s ion kim
loi chuyn tip hoc t him vo mng li tinh th ca cht nn khi nung nhit
cao to nhng khong bn, hoc c th ch l mt thnh phn ca dung dch
rn ca cu trc khong bn . Nh vy cu trc ca cc cht mu l khng hon
chnh, ngha l c s bin i v cu trc. Mt khc, bin dng khng phi ch xy
ra mt di in t nht nh m c cc di ln cn dn n kh nng hp th nh
sng khng phi mt bc sng c trng m l c mt di nhiu bc sng. V
vy, mu nhn thy khng thun khit hay ni cch khc l c nhiu tng mu.
Trong sn xut cht mu cho gm s th iu kin cng ngh ch yu l nhit
nung, mi trng khi nung mu. l cc yu t quyt nh kh nng to mu,
bn mu ca cht mu khi s dng.
Cht mu cho gm s phi tha mn cc iu kin c bn sau:

14
 + Phi bn vng vi tc ng ca nhit cao, bn vi cc tc nhn ha hc
trong qu trnh a mu vo sn phm gm s.
+ Khng b bin i mu di tc ng ca men nng chy nhit cao
+ D dng trang tr ln sn phm.
+ C tnh kinh t.

1.2.1 Cc loi tinh th nn dng tng hp cht mu cho gm s:

Cht mu c tng hp trn c s mng li tinh th ca cht nn. Nhng
mng li phi t mt s tnh cht nh bn nhit cao, bn vi tc dng ca
mi trng xm thc, ha tan c trong men hoc cht chy.
Cc tinh th nn thng khng c mu, to mu cho chng cn phi a
vo trong cu trc tinh th nn, iu ny thng c thc hin bng phn ng gia
nhng pha rn gia cc oxit. Ion sinh mu trong tinh th nn di dng dung dch
rn xm nhp (nm cc hc trong mng tinh th nn) hoc dung dch rn thay th
(thay th cc ion trong nt mng tinh th nn). Di tc ng ca trng tinh th,
cu trc lp v in t ca cc ion sinh mu d bin dng, s suy bin v mc nng
lng mt s phn lp in t ca ion gim so vi trng thi ca ion t do. y
chnh l nguyn nhn cc ion ny c kh nng hp th mt cch chn lc bc x
in t v chng chnh l tc nhn gy mu trong tinh th nn.

1.2.2. Gii thiu mt s tinh th nn s dng trong tng hp cht mu gm

1.2.2.1.Tng hp cht mu trn c s mng li spinen AB2O4.
Cht mu ny c bn nhit cao, nhit nng chy khong trn 17000C.
c tnh quan trng l kh nng thay th ng hnh cc cation trong mng li
spinen. Nguyn liu loi ny c th i t cc oxit, hoc cc mui phn hy cho oxit.
h nhit phn ng c th chun b phi liu theo phng php ng kt ta,
hoc ng to phc Cht khong dng vi cht mu loi ny l axit boric
(khong 2% khi lng phi liu). Khi tng lng axit boric s tng lng spinen
trong sn phm, tng cng mu v bn ha hc. H mu spinen c: mu

15
xanh l cy (CoAl2O4), mu xanh thm (Ni.Al2O3), lc thm (CoO.Cr2O3), lc xm
(MnO. Al2O3), vng xm (CuO.Fe2O3).
1.2.2.2. Cht mu trn c s mng zircon
y l loi cht mu hin nay ang c s dng nhiu nht. c tnh qu
gi ca cht mu ny l bn nhit, bn ha, bn vi tc dng ca cht chy. Bn
thn mng li zircon (ZrSiO4) khng c mu, mun t c mng zircon c mu
phi a vo cht sinh mu nh vanadi, st, v mt s nguyn t t him khc.
Cht khong thng dng trong tng hp cht mu trn c s mng li zircon l
NaF, Na2SiF6, Na3AlF6. Cc cht mu trn c s zircon c mu xanh da tri vi
nguyn t sinh mu l vanadi (dng oxit) nung trong kh quyn oxi ha. Mu hng
trn c s zircon c cha ion Fe3+. Mu vng trn c s zircon c cha ion Pr3+
1.2.2.3. Cht mu trn c s ipzit CaO.MgO.2SiO2
ipzit thuc nhm pyroxene c cc t din SiO44 ni vi nhau theo hai
nhm O2
to thnh mch di. Gia cc mch c phn b cc cation Ca2+,
Mg2+, cc ion ny c th thay th ng hnh bi nhng cation to mu nh Co2+,
Ni2+, Cr3+, V3+, Fe3+ Phn ng to mu trn c s mng ipzit c tin hnh
nhit tng i thp v khng nht thit phi s dng cht khong ha. Nguyn
liu ban u c th dng cc khong cht t nhin c cha cc oxit cn thit (CaO,
MgO,). Nhit tng hp ty theo thnh phn phi liu v nm trong khong
1150o n 1300oC. Khi thay th MgO bng CoO th thu c cht mu t hng n
tm. Cng trn c s mu ny m thay th mt phn SiO2 bng Al2O3 th c mu
lam thm, nu thay th hon ton th c mu xanh lam tm. Thay th MgO bng
NiO s cho sn phm t xanh lc ti dn thm
1.2.2.4. Mu trn c s vilemit
Vilemit c cu trc mng tinh th gm cc t din ring r SiO44 -, cation kim
loi nm gia nhng t din . Cng thc ca vilemit l 2ZnO.SiO2. Khi thay th
mt phn ZnO bng CoO th c mu xanh lam sng. Nh vo cht khong ha
(oxit kim loi kim, axit boric) c th gim nhit tng hp xung 1000oC . Khi

16
thay th mt phn hoc ton b SiO2 bng P2O5 c th c c nhiu mu khc
nhau trang tr thy tinh, gm.
1.2.2.5. Cht mu trn c s phsterit (2MgO.SiO2)
Phsterit c cu trc ring r SiO44- , ion Mg2+ c phn b u gia cc t
din , cc ion O2- trong phsterit to thnh cu trc gi gm lc phng. Trong
cc cu trc phsterit ion Mg2+ c th thay th hon ton bng ion Fe2+ to thnh
dy cc dung dch rn lien tc(Mg,Fe)2SiO4 gi l olivine. Tc dng nhum mu
ca st ph thuc vo trng thi cn bng oxi ha kh, c th ng thi tn ti c 2
ion Fe2+ v Fe3+ ty thuc vo kh quyn nung. Vic thay th MgO bng oxit st
lm tng mnh kh nng kt khi ca sn phm mu, mc kt khi tng khi bn
knh cation tng
1.2.2.6. Cht mu trn c s mng li augite Ca(MgFeAl)[Si2O6].
Augite thuc nhm khong vt pyroxene. Do nhit nng chy thp nn
khi tng hp khong vt ny khng cn dng cht khong ha. Trong cng thc ca
augite Si4+ ca b khung silicat c th thay th bng Al3+, cn cc cation gia cc
mch pyroxene c th thay th ng hnh to thnh mt dy cc dung dch rn gm
cc nguyn t Co2+, Ni2+, Cr3+, V3+, Fe3+, Ti3+ tng hp cc cht mu nhm
ny c th i t nguyn liu l cc oxit, cacbonat, thch anh, sau khi nghin tht
mn ri tin hnh nung trong kh quyn oxi ha nhit 800 n 1200oC. Cht
mu augite s dng lm mu trn men cho s

1.2.2.7. Cht mu thuc nhm grenat

Grenat t nhin c mu sng thuc nhm octosilicat. Cng thc chung ca
grenat l (Ca,Fe,Mn,Mg)3(Al,Fe,Cr)2(SiO4). Grenat c mng li lp phng. Mi
t bo c cha 8 phn t 3MO.N2O3.3SiO2. Grenat nhum mu c th xp vo loi
tng i qu. V d nh almadin (3FeO.Al2O3.SiO2) mu anh o,
pyrop(3MgO. .Al2O3.SiO2) la. Trong cc loi grenat cht khong ha dng
trong tng hp l axit boric.
1.2.2.8. Cht mu nhm Sphen v xeian

17
 Sphen l khong vt thuc lp octosilicat c cng thc CaTi[OSiO4] mng
tinh th thuc h n t. Khi cho Cr3+ khuch tn vo mng li ny s c mt
lot cht mu t hng n thm. tng hp cht mu ny ta trn cc phi liu
t phn CaCO3, SnO2, SiO2, bicromat v cht chy l borac ri nung trong kh
quyn ooxxi ha n 1300oC.
tng hp cht mu trn c s mng xezian (BaO.Al2O3.3SiO2)c th dng cht
khong ha l axit boric, cht sinh mu l Cr2O3 v V2O5
1.2.2.9. Cht mu trn c s mng li cordierrit, mullit.
Cordierrit c cng thc 2MgO.2Al2O3.5SiO2 nng chy nhit 1550oC
c h s dn n nhit thp. Khi thay th magie bng coban s to c mu xanh.
Tng hp nhm ny khong 1320oC vi s c mt ca cht khong ha l axit
boric. Cng c th tng hp cht mu trn c s mng li cordierrit bng cch
thay th Al3+ bng Cr3+ .
Mullit c cng thc 3Al2O3.2SiO2 nhit nng chy cao, v l thnh phn chnh
trong gm
1.2.2.10. Cht mu trn c s t him
Ion t him a vo cht mu v c s lm tng cng mu, c bit l
lm n nh mu. Ngoi ra cc oxit ca neeodim, xri, parazeodim, terbi thm
vo cht mu s to ra nhiu mu c bit. Cc mc electron cha c lp y c
bn tng i thp, d hp th nng lng trong vng quang ph nhn thy lm
cho n c mu. Cn c vo vic chuyn electron trn cc phn mc ngi ta phn
thnh cht sinh mu loi mt (do cc ion ca nguyn t chuyn tip) v cht sinh
mu loi hai (do cc ion nguyn t t him). V d dng cht sinh mu Nd2O3 s
thu c cht mu tm du c th dng lm mu trn men, hoc cht to mu trong
thy tinh pha l. S dng oxit prazeodim lm cht sinh mu c th thu c dy
mu kh rng. xit xeerri cho mu gch sng, sc mu ca cht ny ph thuc vo
mc oxi ha ca xeerri, Ce4+ cho mu ooliu, Ce3+ cho mu thm hn.

18
1.2.3 Cc phng php s dng cht mu gm:
Theo c tnh s dng, cc cht mu gm x c chia thnh hai loi: cht
mu nh la v cht mu nng la. Xt v kh nng chu nhit, mu trong xng s
v cht mu di men chu nhit cao nht, tip n l mu trong men v sau cng l
mu trang tr trn men. L do l v nhit thu kt xng s cao hn nhiu nhiu
chy ca men v nhit chy ca men cao hn nhit chy ca mu trang tr
trn men, chnh v vy m sn phm c nung mt ln, hai ln hoc ba ln theo
th t nhit nung ln sau thp hn ln trc.
1.2.3.1. Mu trong xng
Yu cu ca loi mu ny l phi chu nhit cao (v xng s phi nung
nhit cao mi t kt khi p ng cc ch tiu quy nh). Cht mu c
nghin trn vi xng s to hn hp ng nht, v d: gm s m ngh, gm s
dn dng hoc gch granit nhn to. Sau nung thu kt nhit cao t 1190oC
1400oC ty theo loi sn phm. Do nung nhit cao, nn chng loi mu trong
xng rt hn ch, nhiu cht mu d b bin i mu sc khi nung nhit cao.
1.2.3.2. Mu trong men
Mu trong men thng c tao ra bng cch a trc tip mt s hp cht
gy mu hoc cht mu tng hp bn nhit vo men. Ty theo kh nng chu nhit
ca mi kim loi mu dng men c nhit nung chy thch hp. Cht mu cho
gm s vn c th phn ng mt phn vi cc oxit trong men, v vy ngi ta phi
lu s ph hp ca h cht mu vi thnh phn ca men. mn ca mu c nh
hng ti cng mu, cng nh s ng u mu men. C th, mu c c ht
cng mn cho mu men c cng cng cao v kh nng ng u mu cng cao.
S phn b mu trong men c phn thnh hai c ch da trn bn cht ca chng
nh sau:
- S to mu trong men bng cc phn t mu:
Cc phn t mu c to ra t cc oxit khc nhau ca st, coban, niken, mangan,
crom, ng, vanadi ha tan c trong men nng chy. Mu men trong trng
hp ny rt d thay i v mu sc bi d tng tc ha hc phc tp chnh cc oxit

19
gy mu vi thnh phn men di tc ng ca nhit nung , mi trng nung,
cng nh s ph thuc vo s phi tr ca oxit gy mu tn ti trong men.
- S to mu trong men bng cc cht mu khng tan trong men: chnh l
nhng cht mu c cu trc bn nhit, khng b tan trong men nng chy m ch
phn b u trong men. Cc cht mu ny c th l nhng cht mu tng hp bn
nhit hoc cc khong thin nhin bn c mu. Trng hp ny mu trong men s
n nh hn v bn hn vi cc tc nhn ha hc, nh sng, kh quyn
1.2.3.3. Mu trang tr:
- Mu trn men: Mu ny dng trang tr (v th cng, in n hoc dn giy
) ln sn phm gm trng men v nung chin ri, sau nung li nhit
thp hn (khong 600oC n 900oC), thng gi l men thp. Thng thng nhit
nung kt ca loi mu ny l khong 700oC 850oC. Mu trn men gm hn hp
cht mu vi cht tr dung (dng frit nhit chy thp c cha nhiu cht chy
nh ch, bo ), cht pha long (cao lanh, silica, oxit nhm, ) v du hu c, hoc
vi nc th c thm ph gia hu c do v chng lng. Cht tr dung c nhit
chy thp hn nhit chy ca men, c tc dng lm cho mu v ln sn phm
chng kh cng, sau khi nung mu c bm chc vo men, ng thi l tng
nh ca mu. Chng loi ca cht mu trn men rt phong ph. Mu trn men th c
cng bng rt p v tng mu rt sng, nhng v mt ha hc th chng km
bn hn so vi cht mu di men, do hnh v ni bt kn mt s d b xc
mn.
- Mu di men: mu ny dng trang tr (v th cng hoc in n) ln sn
phm mc sy kh hoc ch nung s b, sau mi trng men, ri tin hnh
nung chn nhit t 1300oC 1400oC ty theo loi sn phm. Nh vy mu
di men va tip xc vi xng mc va tip xc vi lp men do i hi tnh
cht khc nghit hn so vi loi mu trn men, sn phm khng b rn nt th h
s dn n nhit khng chnh lch nhiu so vi xng s v men. Mu di men c
cht tr dung t hn v nhit chy cao hn mu trn men. Nh c mt lp men
bng v trong sut che ph trn lp cht mu nn cc cht mu ny bm rt cht

20
trn b mt sn phm v c mu rt p, c nh, sng cao v rt bn. Do nung
nhit cao, nn chng loi mu di men rt hn ch, nhiu cht mu d b bin
i mu sc khi a ln nhit cao. Trong chng loi cc cht mu di men cho
gm nung nhit 1160oC 1200oC khng c c cc tng mu rc r. Cn
chng loi cht mu di men cho s nung ti nhit 1400oC cho ti ny th ch
c mt t cht mu. Song cc cht mu ny vi c tnh thm m v bn vng rt
cao tr ln qu gi, v vy m rng v pht trin chng loi cht mu di men
ang l mt nhim v quan trng trong lnh vc tng hp cht mu gm s hin
nay.

1.2.4. K thut tng hp cht mu [5,6]

1.2.4.1 Phng php gm
y l phng php truyn thng, c th m t phng php theo dng s
khi di y:

Chun b Nghin, p vin Nung

phi liu trn (3) (4)
(1) (2)

Sn phm
(5)

Hnh 1.4: Phng php gm truyn thng sn xut vt liu mu

21
 Phi liu to mu thng c nghin trn k n mt mn thch hp
trong my nghin bi t hoc kh. Phi liu trn thng bao gm:
- Cc oxit hoc hidroxit, cc mui c kh nng phn hy nhit cao to ra oxit
- Cc cht khong ha: y l cc cht gip thc y nhanh qu trnh tng hp cht
mu, h bt nhit nung cn thit. Cc cht chy thng l cc hp cht ca bo
(H3BO3, Na2B4O7.10H2O) hoc cc mui ca cc kim loi kim (ch yu l cc
mui cacbonat).
Hn hp nghin c kim tra k v mn qua cc sang thch hp, nu
nghin t th phi sy kh. Phi liu mu thng c nung khong nhit
900oC 1400oC, trong nhng khong thi gian khc nhau ty theo tng loi mu.
Hn hp c nghin v ra bng nc ngm chit vi axit HCl 5% loi b cht
chy, cc hp phn cha sch. Cui cng c em nghin mn ti c ht 1-3m.
Vic khng ch c ht rt quan trng v chi ca mu s gim vi c ht th.
Nu nghin qu mn, cht mu s d b ha tan trong pha thy tinh lng.
1.2.4.2. Phng php ng kt ta
y l phng php ang c s dng rng ri tng hp vt liu.
Phng php ny cho php khuch tn cc cht tham gia phn ng kh tt, tng
ng k b mt tip xc ca cc cht phn ng do c th iu ch c sn phm
mong mun nhit nung to sn phm thp.
Mt iu quan trng nh hng ti cht lng sn phm l thnh phn ca vt liu,
do khi tin hnh phn ng ng kt ta. Phi lm sao thu c pha kt ta c
thnh phn mong mun.
Phng php ng kt ta c cc thun li sau:
+ Cho sn phm tinh khit v qu trnh s dng cc phn t tin cht khng
phi l cc khi vt liu ln.
+ Tnh ng nht ca sn phm cao, d iu khin t l ha hc. Qu trnh
cho php ly nhng lng cht u chnh xc trn vi nhau theo t l ha hc ca
sn phm t c nh mong mun. iu ny c bit quan trng trong tng hp
vt liu cao cp, i hi t l chnh xc cao ca cc cu t.

22
 + iu chnh tnh cht thng qua iu chnh cc yu t iu kin ca phn
ng nh: pH, nhit , nng , tc ca s thy phn, s kt tinh nh hng ca
hnh thi hc, ln v tnh cht ca cc ht sn phm cui cng.
+ Tng hp nhit thp v sn phm ng nht v kch thc ht nh hn
phng php gm do d ln ln ca tinh th c th xy ra nhit thp
1.2.4.3. Phng php sol-gel
Trong phng php ny qu trnh u tin din ra l qu trnh ng t tin
cht hnh thnh dng sol, dng ng nht ca cc ht oxit siu nh trong cht
lng. Giai on ny c th iu chnh bng s thay i pH, nhit v thi gian
phn ng, xc tc, nng tc nhn, t l nc
Cc ht sol ln ln v ng t thnh mng polime lin tc hay gel cha cc by
dung mi. Phng php lm kh s xc nh cc tnh cht ca sn phm cui cng:
gel c th c nung nng loi tr cc tc nhn dung mi, gy p lc ln mao
qun v lm xp mng gel, hoc lm kh siu ti hn cho php loi b cc phn
t dung mi m khng sp mng gel. Sn phm cui cng thu c t phng
php lm kh c em nung to sn phm.
Phng php sol-gel c quan tm nhiu v n thnh cng trong lnh vc tng hp
vt liu cp ht nano

1.3. Gii thiu v km silicat

1.3.1. Cc silicat:
Ngay trc khi pht minh ra tia X, ngi ta ch nhiu ti bn cht ho
hc ca silicat. Cc nh bc hc nh Vecnaski, Trecmac, Clack, Grot ... nghin
cu silicat.
Mun gii quyt vn ny, ngi ta phi nghin cu t m cc tnh cht
vt l v ho hc ca khong vt v cc cht tng hp trong phng th nghim, c
bit nhng sn phm ph hu, do tm c mt s qui lut thc nghim.
Trn c s quan nim cu to phn t, cc silicat c coi l mui ca nhiu
axit gi thit. Trn quan nim , trong cc silicate, ngi ta phn ra:
(1) Octosilicat l mui ca axit H4SiO4

23
 (2) Metasilicat l mui ca axit H2SiO3
(3) Pyrosilicat l mui ca axit H6Si2O7
Nu nh vi loi hp cht kiu th nht, ta thy c nhiu tnh cht, trong
c c kin trc ca mng tinh th, tng t nh cc photphat, sunfat th trong hai
loi sau, nht l trong nhng hp cht giu silic cc du hiu trn gim i nhiu.
Cc loi hp cht cui cng ny gi v tr trung gian gia cc mui in hnh v cc
oxit (nht l SiO2).
V c im kin trc ca silicat, s nghin cu bng tia X a ti cc
kt lun sau;
- Trong tt c cc silicat nghin cu, mi ion Si4+ bao gi cng nm gia 4
ion O2- b tr cc gc ca mt t din. Mi lin kt gia cc ion oxi vi silic mnh
hn nhiu mi lin kt vi cc kim loi ng vai tr cation trong kin trc tinh th
ca silicat. Kch thc ca cc t din SiO4 khng thay i bao gi. Khong
cch Si-O ch khong 1,6Ao. iu v cc ti liu nghin cu bng tia X khc cho
bit mi lin kt Si-O l mi lin kt cng ho tr. Nh vy, t din [SiO4]4- l n
v kin trc c s ca tt c cc silicat.
- Trong kin trc tinh th ca silicat, cc nhm SiO4 c th thnh nhng n v
ring l, c th khp li vi nhau theo nhiu cch, to nn nhng gc anion phc
tp. Cc nhm SiO4 ch c th gn lin nhau bi cc gc ch khng qua cc cnh,
cc mt c. Trng hp y nht l tt c cc gc ca nhm t din SiO4 u
chung cho 4 t din SiO4 na xung quanh. l trng hp ca thch anh, c
cng thc SiO2. Do , t s O:Si trong anion phc tp c th thay i trong gii
hn 4:1 ti 2:1.
- Tu theo cch thc cc t din SiO4 khp vi nhau nh th no, chng ta s c
cc dng anion phc tp khc nhau:
+ Anion phc tp l nhng t din [SiO4]4- ring l, ng vng trong kin
trc nh cc cation ca cc kim loi khc.
+ Anion phc tp gm nhng nhm ring l [Si2O7]6- gm c hai t din
SiO4 gn lin nhau vi mt gc chung.

24
 + Anion phc tp gm 3, 4, 6 t din SiO4 khp vi nhau bi hai gc chung
thnh mt vng kn trn mt mt phng. Cc anion phc tp s l: [Si3O9]6-,
[Si4O12]8- v [Si6O18]12-.
+ Anion phc tp gm c mt mch lin tip cc t din SiO4 lin kt vi
nhau theo mt chiu.

1.3.2. Phn loi silicat:

Ngy nay nh nhng kt qu to ln ca s nghin cu bng tia X, s phn
loi cc silicat tt nhin khng phi ch xy dng trn c s thnh phn ho hc m
cn phi theo kiu kin trc tinh th.
Cc cch thc lin kt cc t din [SiO4] vi nhau hon ton c nh hng
ti cng thc ho hc v c im hnh thi ca tinh th, cng nh vi nhiu tnh
cht vt l khc.

Hnh 1.5: T din SiO 44 trong mng octosilicat

1. Octosilicat: (cn gi l nezosilicat), gm cc t din ring l SiO 44 . Bn ho

tr d c bo ho bng mt cation ho tr 2+ (v d fosoerit Mg2SiO4 faialit
Fe2SiO4). Cc cation Fe2+ v Mg2+ c kch thc gn bng nhau do c th thay
th ln nhau trong fosterit v trong faialit to thnh mt dy dung dch rn lin
tc c tn gi l olivin (hoc cn gi l periot) vi cng thc (Mg,Fe)2SiO4.

25
 Octosilicat thng kt tinh trong h tinh th i xng cao, c rn cao, ch s
khc x cao. i khi c cha ion O2- khng lin kt trc tip vi silic. Lp silicat
ny c cc nhm sau:
Nhm olivin (Mg,Fe)2[SiO4]
Nhm grenat (Ca,Fe,Mn,Mg)3(Al,Fe,Cr)2[SiO4]3
Nhm silicat nhm Al2[OSiO4], topaz Al2[F2SiO4] v sphen CaTi[OSiO4]
Bng 1.2 cc khong silicat

Khong vt Cng thc H tinh th d H Ch s khc x

1,67-1,87
Olivin (Mg,Fe)2[SiO4] Hnh thoi 3,3 6,5-7,0
1,63-1,83
1,92-1,96
Zircon ZrSiO4 T phng 4,7 7,5
1,96-2,02
Phenacit Be2[SiO4] Mt thoi 3-4 7,5-8,0 1,64-1,67
Willemit Zn2[SiO4] Mt thoi 3,9-4,2 5,5 1,69-1,72
Pyrop Mg3Al2[SiO4]3 Lp phng 3,51 7,0-7,5 1,7
Almanin Fe3Al2[SiO4]3 Lp phng 4,25 7,0 1,83
Spossartit Mn3Al2[SiO4]3 Lp phng 4,18 7,0-7,5 1,80
Grossulair Ca3Al2[SiO4]3 Lp phng 3,53 6,5 1,73
Andradit Ca3Fe2[SiO4]3 Lp phng 3,75 7,0 1,89
Uvarovit Ca3Cr2[SiO4]3 Lp phng 3,77 7,0 1,86
Siliimanit+ Al2[OSiO4] Hnh thoi 3,30 6-7 1,67-1,65
clas AlBe[OHSiO4] n t 3,10 7,5 1,67-1,65
Topaz Al2(F,OH)2SiO4 Hnh thoi 3,4-3,6 8,0 1,62-1,61
Sphen CaTi[(OSiO4)] n t 3,50 5,5 2,09-1,90
Datolit CaB[(OH)SiO4] n t 2,8-3 5-5,5 1,67-1,63

2. Sorosilicat: n v cu trc gm hai t din c mt c mt oxi chung. Nh vy

trong n v cu trc c 6 ho tr cha bo ho v cng thc ca b khung anion l

26
[Si2O7]6-. V d khong vt llilit Ca2Mg[Si2O7]. Anion OH- c th kt hp vi
nhm anion ny.V d khi kt hp thm 2 anion OH- th c ion phc
[Si2O7(OH)2]8- nh khong vt laosonit CaAl2[Si2O7(OH)2].2H2O. Mng li ca
lp ny c khi c mt t din c lp.
3. Xiclosilicat (silicat mch vng)
n v cu trc gm 3, 4, 6 t din ni nhau qua nh oxi to thnh vng
(hnh 1.8). Nhng vng c th c lp hoc chng ln nhau to thnh khng gian
trng cha cc cation c kch thc ln hn (Ca, K) chim.
4. Inosilicat: (Silicat mch) c hai nhm:

Hnh 1.6: Nhm pyrxen

+ Nhm pyrxen: Cc t din ni nhau bng 2 oxi. Cng thc khung anion
c th vit [SiO3]2- hoc [Si2O6]4- (hnh 1.9)
+ Nhm amphibn: Cng thc ca b khung anion l [Si4O11]6-. Tm ca
mi lc gic c th c nhm OH- lc cng thc ca b khung anion l
[(OH)Si4O11] 7-.

5. Phylosilicat (silicat lp): Cc mch pyroxen hoc amphibn kt hp li vi

nhau to thnh mt phng ln v hn. Nu xt mt n v nh nht c trng cho
c lp, th trong cu trc ny mi t din ch cn mt oxi cha bo ho ho tr. Do
cng thc ca b khung anion c th vit di dng [Si4O10]4-. Nhng lp phng

ny chng ln nhau v cng quay nh t din SiO 44 vo nhau. Gia hai lp c

27
cha ion OH- v cc cation kim loi. Do cng thc cu trc ca b khung anion
c c b nhm OH-, v d [Si4O10(OH2)]6-.
Silic trong t din c th b thay th bng nhm n 50% nguyn t. Su

nh ca 6 t din SiO 44 to thnh cc mt lc gic, ion OH- nm tm ca lc

gic . Pha y cc t din cng c nhng mt lc gic. Khi hai mt y chng
ln nhau s to nn cc khong trng dng khi lc lng. Cc cation kim loi kch
ln (s phi tr 12) nm trong khi lc lng ny.

28
 CHNG II: PHNG PHP NGHIN CU

2.1. Cc thit b v ho cht cn thit:

Thit b:
Mt s thit b chnh:
- L nung Nebertherm, c.
- T sy
- Cn Precisa chnh xc 0,1mg.
- Cc thit b chp phn tch nhit, chp SEM, XRD, TEM, UV Vis.
Ho cht:
- CoCl2.6 H2O c M = 237,93 g/mol (Merck)
- Ni(AC)2.4H2O , M = 248,86 g/mol (Merck)
- Zn(AC)2.2 H2O, M = 219,39 g/mol (Trung quc)
- NH3 dung dch 25% , d = 0,88 g/ml, M = 17,03 g/mol.
- t st H Long
- Nc ct v mt s ho cht khc.
2.2. Phng php thc nghim
2.2.1.Tng hp cht mu theo phng php sol gel bin tnh
Cc mui Zn(AC)2.2H2O, Ni(AC)2.4H2O (hoc CoCl2.6 H2O) v SiO2 c
ly vi t l mol theo ng thnh phn ca cht cn iu ch Zn2-xNixSiO4 (vi x
thay i). Ha tan chng trong nc ct v t ln my khuy t khong 20 pht
sau thm NH3 vi s mol kt ta hon ton Zn2+ v Ni2+/Co2+ . y cc
bng mt knh ng h v gia nhit c khuy 70oC trong 6h. M np, c cn c
khuy v sy mu nhit 1200C trong 2h, mang cn ri em nung cc nhit
nung khc nhau v thu sn phm.

29
2.2.2. Tng hp cht mu theo phng php ng kt ta:

Zn(CH3COO)2 CoCl2 1M H2O

1M

Dung dch dd
A Na2SiO3
1M

dd
Cc phn ng Dung dch NH3 2M
B

H2O
Lc ra kt ta

Sy

Nghin

Nung

Sn phm

Hnh 2.1: S tng hp theo phng php ng kt ta

30
Chun b dung dch A gm c km axetat 1M, coban clorua 1M v nc.
Chun b dung dch B gm c natri silicat 1M, dung dch NH3 2M v nc.
Ty theo t l pha tp ca coban m thnh phn dung dch A c th thay i nhng
thnh phn dung dch B khng i.
Trn dung dch A v dung dch B theo mt t l tnh ton trc ng vi thnh
phn cht cn iu ch Zn2-x CoxSiO4 sau t ln my khuy t trong khong 30
pht. Lc v ra kt ta, sau sy kh 1200C trong 2h v nung cc nhit
khc nhau thu c sn phm.

2.3. Cc phng php phn tch [7]:

2.3.1. Phng php phn tch nhit:

- Nguyn tc:
Khi t nng mu th thng trong mu s xy ra nhng bin i v khi
lng, thnh phn, cu trc v c th xy ra mt hay nhiu phn ng ho hc gia
cc thnh phn, cc nguyn t trong mu mt nhit no . Khi nhng bin i
xy ra thng km theo cc hiu ng thu nhit hay to nhit. Tt c nhng hiu
ng trn c xc nh v ghi trn cc gin . Kt qu ghi trn gin nhit cng
vi cc phng php phn tch, kho st khc s gip ta rt ra c nhng kt lun
b ch v s bin i ca mu theo nhit t nng chng.
Trong php phn tch nhit, ngi ta thng s dng hai phng php l
phng php phn tch nhit vi sai DTA hoc DSC v phng php phn tch nhit
trong lng TGA.
- Phng php phn tch nhit vi sai
Khi t nng mt mu, vic xut hin cc hiu ng nhit rt nh s kh hoc
khng pht hin c bng cc k thut o thng thng. V vy, phi dng
phng php DTA hoc DSC.
Phng php DTA v DSC s dng mt cp pin nhit in v mt in k
o s chnh lch nhit gia hai vt khi t nng chng. Trong hai vt , mt
vt l vt liu cn nghin cu v vt kia c tnh tr v nhit. Nu mu b t nng

31
c bin i th bao gi cng km theo cc hiu ng nhit v lc trn ng DTA
hoc ng DSC s xut hin cc nh (pic) ti im m mu c s bin i.
Phng php ny cho ta bit s b v cc hiu ng nhit xy ra, nh tnh v
s b v nh lng cc hp phn c trong mu m chng ta kho st.
- Phng php phn tch nhit trng lng (TGA)
Phng php ny da vo s thay i trng lng ca mu cn nghin cu
khi ta em nung nng mu . Khi mu c t nng, trng lng ca mu b thay
i l do mu b phn hu nhit to ra kh thot ra nh hi nc, kh CO2 (phn hu
hp phn cacbonat,...), SO2 (phn hu cc hp phn sunfua) hay do mu b mt
nc vt l (m hp ph), nc cu trc (nc hirat nc kt tinh trong tinh
th mu). Nu cn lin tc mt mu b t nng, ta c th bit s thay i v trng
lng ca mu ng vi s thay i v nhit .
Kt hp hai phng php DTA v TGA cho php xc nh s bin thin trng
lng, hiu ng nhit tng ng theo nhit t nng. y l nhng thng s cho
php ta xc nh c lng nc hyrat cng nh xc lp cc phn ng phn hu
nhit c th c cng nh d on cc thnh phn sau tng giai on tng nhit .
Ch phn tch nhit thng chn nh sau:
+ Tc t nng 10oC/ pht
+ Nng nhit t 25oC ti 1200oC
+ Mi trng khng kh

2.3.2. Phng php nhiu x tia X (XRD):

- Nguyn tc:
Theo l thuyt cu to tinh th, mng tinh th c xy dng t cc nguyn
t hay ion phn b u n trong khng gian theo mt quy lut xc nh. Khi chm
tia Rnghen ti b mt tinh th v i vo bn trong mng li tinh th th mng li
ny ng vai tr nh mt cu t nhiu x c bit. Cc nguyn t, ion b kch thch
bi chm tia X ti s to thnh cc tm pht ra cc tia phn x. Mt khc, cc
nguyn t, ion ny c phn b trn cc mt phng song song. Do , hiu quang

32
trnh ca hai tia phn x bt k trn hai mt phng song song cnh nhau c tnh
nh sau:
= BC +CD = 2dsin
Trong :
d: l di khong cch gia hai mt phng song song.
: l gc gia chm tia X v mt phng phn x.

Hnh 2.2: S nhiu x tia X trn b mt tinh th

Theo iu kin giao thoa, cc sng phn x trn hai mt phng cng pha
th hiu quang trnh phi bng s nguyn ln di bc sng. Do :
2dsin = n (2.1)
Trong : - l bc sng ca tia X.
n =1,2,3,...
y l h thc Vufl- Bragg, l phng trnh c bn nghin cu cu trc
mng tinh th. Cn c vo cc cc i nhiu x trn gin , tm c 2. T
suy ra d theo h thc Vufl- Bragg. So snh gi tr d tm c vi d chun s xc
nh c thnh phn cu trc mng tinh th ca cht cn nghin cu. V vy,
phng php ny c s dng rng ri trong nghin cu cu trc tinh th ca vt
cht.

33
 Ngoi ra, phng php nhiu x tia X cn s dng tnh ton kch thc
gn ng ca tinh th. Da vo kt qu ch ra gin nhiu x tia X, ta c th tnh
c c ht tinh th theo phng trnh Scherrer:
k .
D=
. cos (2.2)
Trong :
D : kch thc tinh th trung bnh vi gc nhiu x 2
k: l h s hnh hc c chn l 0,9
: bc sng tia X, =0.154nm
: rng ti v tr na pic, radian

: gc theo phng trnh Vufl- Bragg

Cc mu sn phm c ghi gin nhiu x tia X trn my SIEMENS D5005 ca
c ti trung tm Ha hc vt liu, khoa Ha Hc trng i Hc Khoa Hc T
Nhin. Cc ch ghi gin nh sau:
+ Gc quay 2 t 2080o
+ Anot Cu vi Cu = 1,54056 10-10 m
+ Kch thc ht tinh th trung bnh tnh theo phng trnh Scherre

2.3.3. Phng php qut hin vi in t (SEM):

- Nguyn tc:
Hin vi in s dng chm tia in t to nh mu nghin cu, nh khi
n mn hunh quang c th t phng i theo yu cu.
Chm tia in t c to ra t catot qua hai t quang s c hi t ln mu
nghin cu. Khi chm in t p vo mu, trn b mt mu pht ra cc chm tia
in t th cp. Mi in t pht x ny qua in th gia tc vo phn thu s bin
i thnh mt tn hiu nh sng. Tn hiu c khuch i, a vo mng li iu
khin to sng trn mn hnh dng b mt mu nghin cu.
Hin vi in t qut thng c s dng nghin cu b mt, kch thc, hnh
dng vi tinh th do kh nng phng i v to nh rt r nt v chi tit.

34
My chp nh SEM vi thit b v ch chp nh sau
+ Knh hin vi in t qut S-4800, s hiu HI- 9022 0003
+ Kiu nh JPG
+ phng i t 30 ti 120000 ln

2.3.4. Phng php hin vi in t truyn qua TEM

Sng phng in t

Cu to ca sng phng in t.
Trong TEM, in t c s dng thay cho nh sng (trong knh hin vi quang
hc). in t c pht ra t sng phng in t. C hai cch to ra chm in
t:

S dng ngun pht x nhit in t: in t c pht ra t mt catt c t

nng (nng lng nhit do t nng s cung cp cho in tng nng thot ra
khi lin kt vi kim loi. Do b t nng nn sng pht x nhit thng c tui th
khng cao v n sc ca chm in t thng km. Nhng u im ca n l
rt r tin v khng i hi chn khng siu cao. Cc cht ph bin dng lm catt
l W, Pt, LaB6...

S dng sng pht x trng (Field Emission Gun, cc TEM s dng nguyn l
ny thng c vit l FEG TEM): in t pht ra t catt nh mt in th ln
t vo v th ngun pht in t c tui th rt cao, cng chm in t ln v
n sc rt cao, nhng c nhc im l rt t tin v i hi mi trng chn
khng siu cao.

35
Sau khi thot ra khi catt, in t di truyn n ant rng v c tng tc di
th tng tc V (mt thng s quan trng ca TEM). Lc , in t s thu c
mt ng nng:

V xung lng p s c cho bi cng thc:

Nguyn l hot ng ca mt thu knh t trong TEM

Nh vy, bc sng ca in t quan h vi th tng tc V theo cng thc:

Vi th tng tc V = 100 kV, ta c bc sng in t l 0,00386 nm. Nhng vi th

tng tc c 200 kV tr nn, vn tc ca in t tr nn ng k so vi vn tc nh
sng, v khi lng ca in t thay i ng k, do phi tnh theo cng thc
tng qut (c hiu ng tng i tnh):

36
Cc h thu knh v lng knh
V trong TEM s dng chm tia in t thay cho nh sng kh kin nn vic iu
khin s to nh khng cn l thu knh thy tinh na m thay vo l cc thu
knh t. Thu knh t thc cht l mt nam chm in c cu trc l mt cun dy
cun trn li lm bng vt liu t mm. T trng sinh ra khe t s c tnh ton
c s phn b sao cho chm tia in t truyn qua s c lch thch hp vi
tng loi thu knh. Tiu c ca thu knh c iu chnh thng qua t trng
khe t, c ngha l iu khin cng dng in chy qua cun dy. V c dng
in chy qua, cun dy s b nng ln do cn c lm lnh bng nc
hoc nit lng. Trong TEM, c nhiu thu knh c vai tr khc nhau:

H knh hi t v to chm tia song song (Condensed lens)

y l h thu knh c tc dng tp trung chm in t va pht ra khi sng phng
v iu khin kch thc cng nh hi t ca chm tia. H hi t C1 c vai tr
iu khin chm tia va pht ra khi h pht in t c tp trung vo qu o ca
trc quang hc. Khi truyn n h C2, chm tia s c iu khin sao cho to
thnh chm song song (cho cc CTEM) hoc thnh chm hi t hp (cho cc
STEM, hoc nhiu x in t chm tia hi t) nh vic iu khin dng qua thu
knh hoc iu khin ln ca khu hi t C2.

Vt knh (Objective lens)

Nguyn l ghi nh trng sng v trng ti trong TEM

37
L thu knh ghi nhn chm in t u tin t mu vt v lun c iu khin sao
cho vt s v tr c kh nng ly nt khi phng i ca h c thay i. Vt
knh c vai tr to nh, vic iu chnh ly nt c thc hin bng cch thay i
dng in chy qua cun dy, qua lm thay i tiu cc ca thu knh.

Thu knh nhiu x (Diffraction lens)

C vai tr hi t chm tia nhiu x t cc gc khc nhau v to ra nh nhiu x in
t trn mt phng tiu ca thu knh.

Thu knh Lorentz (Lorentz lens, twin lens)

c s dng trong knh hin vi Lorentz ghi nh cu trc t ca vt rn. Thu
knh Lorentz khc vt knh thng thng vic n c tiu c ln hn v v tr ly
nt (in focus) l v tr m cc chm tia in t truyn qua hi t ti mt phng
tiu sau, trng vi mt phng khu vt knh. Thu knh Lorentz thng b t xa
kh nng ghi gc lch do t tnh (vn rt nh).

Thu knh phng i (Magnifying lens, intermediate lens)

L h thu knh sau vt knh, v phng i ca h c thay i bng cch thay
i tiu c ca thu knh.
Ngoi ra, trong TEM cn c cc h lng knh c tc dng b ng i ca in t
lt nh hoc iu khin vic ghi nhn in t trong cc php phn tch khc
nhau.

38
 CHNG 3: KT QU V THO LUN

3.1. Tng hp km silicat pha tp bi niken theo phng php sol gel bin tnh:

3.1.1.iu ch cc tin cht km silicat pha tp bi niken

Ch to cc mu Zn2-xNixSiO4 theo phng php nh nu 2.2.1. vi gi tr x
thay i. Mu ca cc mu tin cht v ca mu sau khi nung 1h 10000C c ch
ra bng 3.1. Da vo cc kt qu ch ra bng 3.1, ta thy cc mu sau nung c
mu xanh lc m dn theo hm lng ca niken pha tp.

Bng 3.1: Ch to cc mu km silicat pha tp niken

Mu 1.1 1.2 1.3 1.4

x 0 0.05 0.10 0.20
Mu ca cc Trng Trng xanh Xanh nht Xanh m
mu tin cht
Mu cc mu Trng Xanh lc m dn
sau nung

3.1.2. Kho st thnh phn pha ca cc mu theo nhit nung

Gin nhiu x tia X ca cc mu 1.1 1.4 nung 1h 10000C c ch ra cc
hnh 3.2 3.5

39
 Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau B1
2000

1900

1800

1700

d=2.632
d=2.831
1600

1500 d=3.483

1400

1300

1200
Lin (Cps)

1100

1000

900

d=2.316
800

700

d=1.858
d=4.020

600

d=1.420
500
d=2.474

400
d=4.089

d=1.365
d=1.550
d=1.932
d=2.602

d=1.598
d=2.010

300

d=1.520
d=1.625
d=1.688
d=3.148

d=1.641

d=1.476
d=3.257

d=2.142

d=1.909

d=1.378
d=4.339

d=1.394
d=2.281

d=1.723
d=2.071

d=1.964
d=2.920

d=2.048
d=3.855

d=2.214

200
d=2.722

d=1.824
d=1.804

d=1.446
d=2.377

d=2.112

d=1.777
100

20 30 40 50 60 7

2-Theta - Scale
File: Dung BK mau B1.raw - Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.0
01-070-2551 (C) - Zincite, syn - ZnO - Y: 16.20 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 3.24900 - b 3.24900 - c 5.20700 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P63mc (186) - 2 - 47.6
01-079-2005 (C) - Zinc Silicate - Zn2SiO4 - Y: 52.12 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 13.94800 - b 13.94800 - c 9.31500 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3 (148)

Hnh 3.1: Gin XRD mu 1.1

Nhn xt: Trong sn phm thu c khi nung 1h 10000C ngoi thnh phn chnh
l pha km silicat mong mun cn xut hin thm pha km oxit. iu ny chng t
phn ng xy ra khng hon ton, tuy nhin cng ch ra c l c th tng hp
cht nn km silicat theo phng php sol gel bin tnh kho st.

40
 Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau 1-5%Ni nung
1500

1400

1300

d=2.635
d=2.838
1200

d=3.488
1100

d=2.476
1000

900
Lin (Cps)

800

d=2.812
700

d=2.317
600
d=4.024

d=2.600
500

d=1.860
400

d=1.421
d=6.978

d=1.626

d=1.477
d=4.087

300

d=1.911

d=1.379
d=1.366
d=1.552
d=1.598
d=1.934
d=2.011

d=1.359
d=1.641

d=1.520
200

d=1.689
d=3.146
d=4.349

d=2.142
d=3.258

d=2.102

d=1.393
d=1.725
d=5.074

d=2.286

d=2.074

d=1.967
d=3.855

d=1.824
d=2.214

d=2.047

d=1.446
100

10 20 30 40 50 60 7

2-Theta - Scale
File: Quan mau 1 5%Ni nung.raw - Type: Locked Coupled - Start: 10.000 - End: 70.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 12 s - 2-Theta: 10.000 - Theta: 5.000 - Chi
01-079-2005 (C) - Zinc Silicate - Zn2SiO4 - Y: 63.02 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 13.94800 - b 13.94800 - c 9.31500 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3 (148)
01-089-1397 (C) - Zinc Oxide - ZnO - Y: 61.24 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 3.25300 - b 3.25300 - c 5.21300 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P63mc (186) - 2 - 47.77

Hnh 3.2: Gan XRD mu 1.2 - pha tp 5% niken

Nhn xt: Trong mu tin cht c niken, tuy nhin hnh 3.2 ch thy xut hin cc
pic ca Zn2SiO4 v ZnO. iu ny chng t niken i vo mng li ca cht nn
km silicat. V do vy c th kt lun l tng hp c km silicat pha tp bi
niken theo phng php kho st.

41
 Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau 2-10%Ni nung
1500

1400

1300

1200

d=2.633
1100

d=2.834
d=3.486
1000

900
Lin (Cps)

800

700

d=2.318
600

500

d=1.859
d=4.016

400

d=1.421
d=2.476
d=6.993

300
d=4.087

d=1.365
d=1.551
d=2.597

d=1.933

d=1.599
d=2.010

d=1.520
d=1.626
200

d=2.100

d=1.688
d=3.153

d=1.478
d=1.641
d=1.910
d=3.263

d=2.142
d=4.354

d=1.393
d=1.378
d=2.757

d=2.284

d=1.968

d=1.826
d=2.214

d=1.779

d=1.447
d=1.803
d=5.111

100

10 20 30 40 50 60 7

2-Theta - Scale
File: Quan mau M2-10%Ni nung.raw - Type: Locked Coupled - Start: 10.000 - End: 70.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 13 s - 2-Theta: 10.000 - Theta: 5.000 -
01-079-2005 (C) - Zinc Silicate - Zn2SiO4 - Y: 40.31 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 13.94800 - b 13.94800 - c 9.31500 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3 (148)
01-089-1397 (C) - Zinc Oxide - ZnO - Y: 13.03 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 3.25300 - b 3.25300 - c 5.21300 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P63mc (186) - 2 - 47.77

Hnh 3.3: Gin XRD mu 1.3 - pha tp 10% niken

Nhn xt: Khng xut hin pha ca Niken chng t niken vn c th pha tp hn
vo trong mng km silicat. hon thin tinh th ca km silicat l 40,31% nh
hn so vi mu pha tp 5% niken( 63,02%) iu ny chng t lng niken vo thay
th km trong mng tinh th km silicat l nhiu hn.

42
 Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau B3

1400

d=2.623
1300

d=2.823
1200

d=3.463
1100

1000

900
Lin (Cps)

800

d=2.308
700

600

d=1.854
d=4.002

d=1.418
500
d=2.085

400
d=2.408

d=1.362
300
d=4.059

d=1.549
d=1.594
d=2.003

d=1.477
d=1.516
d=1.927

d=1.637
d=1.684
d=3.131

200
d=2.135
d=4.314

d=1.390
d=3.243

d=2.275
d=2.704

d=1.958
d=2.204
d=2.516

d=1.775

d=1.721
d=1.801

100

20 30 40 50 60 7

2-Theta - Scale
File: Dung BK mau B3.raw- Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C(Room) - Time Started: 10 s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.0
00-037-1485 (*) - Willemite, syn - Zn2SiO4 - Y: 54.41 %- d x by: 0.9975 - WL: 1.5406 - Rhombo.H.axes - a 13.93810 - b 13.93810 - c 9.31000 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3
00-004-0835 (D) - Bunsenite, syn - NiO - Y: 12.84 %- d x by: 1. - WL: 1.5406 - Cubic - a 4.17690 - b 4.17690 - c 4.17690 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fm-3m(225) - 4 - 72

Hnh 3.4: Gin u XRD mu 1.4 pha tp 20% niken

Nhn xt: Xut hin pha niken oxit, iu ny c ngha l bng phng php
ny kh nng pha tp ti a l 20% khi nung 10000C trong 1h.

43
Gin nhiu x tia X ca cc mu 1.4 nung 1h 12000C c ch ra cc hnh
3.6
Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau C5,4

700

d=2.636
600

d=2.839
500
d=3.490
Lin (Cps)

400

d=2.321

300

d=1.861

d=1.422
200
d=4.028

d=1.553

d=1.366
d=1.600
d=4.096

d=2.010

d=1.935

d=1.522
d=3.149

d=1.641
100
d=1.965
d=2.147

d=1.688

d=1.395
d=2.075
d=4.345

d=2.728

20 30 40 50 60 7

2-Theta - Scale
File: Huy BK mau P5,4.raw- Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 17 s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.0
01-079-2005 (C) - Zinc Silicate - Zn2SiO4 - Y: 43.43 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 13.94800 - b 13.94800 - c 9.31500 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3 (148)

Hnh 3.5: Gin XRD mu 1.4 nung 1h 12000C

Nhn xt: Mu thu c ch cha mt pha duy nht l km silicat. iu ny cho
php kt lun iu kin kho st iu ch thnh cng cht mu km silicat pha
tp bi niken c thnh phn Zn1.8Ni0.2SiO4 . Mu thu c bao gm cc ht kh
ng nht vi c ht khong 200nm nh c ch ra nh SEM di y.

44
 Hnh 3.6 : nh SEM ca mu Zn1.8Ni0.2SiO4 (1.4 nung 1h 12000C)
Tm li c th iu ch km silicat pha tp bi niken theo phng php sol gel bin
tnh. Khi nung 1h 10000 C phn ng cha xy ra hon ton, kh nng pha tp
niken ti a l 20% mol so vi tng s mol cc cation kim loi. Tuy nhin vi mc
pha tp ny, phn ng xy ra hon ton khi nung 1h 12000C.

3.2. Tng hp km silicat pha tp bi coban theo phng php ng kt ta

3.2.1. iu ch tin cht km silicat pha tp bi coban

Ch to cc mu tin cht Zn2-xCoxSiO4 theo phng php ng kt ta nh nu
2.2.2. vi gi tr x thay i. Th tch dung dch A cn dng gm Zn(CH3COO)2 v
CoCl2 v nc trong cc th nghim l 80 ml. Thnh phn ca cc phi liu cn
thit khi iu ch cc mu tin cht c ch ra bng 3.2.
Bng 3.2: Thnh phn ca cc phi liu khi iu ch cc mu tin cht theo
phng php ng kt ta
Mu tin cht P6 P7 P8 P9 P10 P11
x 0 0.2 0.4 0.6 0.8 1.0
Zn(CH3COO)21M (ml) 20 18 16 14 12 10
CoCl2 1M (ml) 0 2 4 6 8 10
H2O (ml) 60 60 60 60 60 60
dd B (Na2SiO3 1M + 20 20 20 20 20 20
NH3 2M) (ml)

45
3.2.2. Kho st s bin i ca mu tin cht P6 theo nhit

S bin i ca mu tin cht P6 theo nhit c ch ra hnh 3.7

Hnh 3.7: Gin phn tch nhit mu P6

Theo hnh 3.7 ng DTG c ba hiu ng thay i khi lng 95,5oC,

704oC v 1136oC. Kt hp vi ng DTA v ng TG hiu ng 95,5oC l thu
nhit ng vi gim khi lng 13% c gn cho s mt nc kt tinh v nc
cu trc ca tin cht. Cc hiu ng thay i khi lng 704oC v 1136oC khng
thy xut hin cc hiu ng tng ng ng DTA c l do c hiu ng nhit
khng ng k. Kt hp vi ng TG cc hiu ng ny c gim khi lng
tng ng l 1,84 v 1,79 % ng vi s mt nc cu trc cn li. S xut hin pic
to nhit nh nhit khong 900oC trn ng DTA chng t c s to km
silicat. Da trn gim khi lng, thnh phn gn ng ca mu tin cht P6 c
dng Zn(OH)2.ZnSiO3.H2O. Trn c s s bin i ca mu tin cht P7 theo nhit
, chng ti chn nhit nung iu ch cc cht mu km silicat pha tp bi
coban l 10000C.

46
3.2.3. Kho st thnh phn pha ca cc mu sau nung
Gin nhiu x tia X ca cc mu tin cht km silicat pha tp bi coban ( cc
mu P7 - P11) nung 1h 10000C (k hiu tng ng l P7.2 P11.2) c ch ra
cc hnh sau:
Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau P7,2
700

600

d=2.640
d=2.840

500
d=3.491

400
Lin (Cps)

d=2.320

300

d=1.862

d=1.422
200
d=4.035

d=1.367
d=1.553
d=1.601
d=1.936

d=1.521
d=2.014
d=4.096

d=1.690
100
d=3.152

d=1.642

d=1.395
d=3.264

d=2.148

d=2.074

d=1.970
d=2.533

d=1.724
d=4.337

d=1.446
d=1.490
0

20 30 40 50 60 7

2-Theta - Scale
File: Huy BK mau P7,2.raw - Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 17 s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.0
01-079-2005 (C) - Zinc Silicate - Zn2SiO4 - Y: 49.75 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 13.94800 - b 13.94800 - c 9.31500 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitiv e - R-3 (148)

Hnh 3.8: Gin XRD ca mu P7.2 (x=0,2)

47
 Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau P8,2
80 0

70 0

d=2.637
d=2.840
60 0

d=3.493
50 0
Lin (Cps)

40 0

d=2.322

d=1.862
30 0

d=1.422
d=4.040

20 0

d=1.366
d=1.600

d=1.553
d=2.012
d=4.096

d=1.933
d=2.145

d=1.521
d=1.690

d=1.644
d=3.153

d=1.395
10 0
d=4.345

d=1.726
d=2.286

d=1.464
d=3.263

d=2.217

d=2.075
0

20 30 40 50 60 7

2-Theta - Scale
File : Huy B K m au P 8,2 .ra w - T yp e : L o cked Co up le d - Star t: 2 0 .0 0 0 - E nd : 70 .01 0 - Ste p: 0 .03 0 - Step time : 1. s - Te mp .: 25 C (Ro om ) - Ti me Sta rte d: 11 s - 2 -Th eta : 2 0 .00 0 - Th eta : 10 .00 0 - C hi: 0 .0
01 -0 79 -2 0 05 (C) - Zinc Sil ica te - Zn 2SiO 4 - Y: 6 2.6 3 % - d x by: 1. - W L : 1.5 40 6 - Rho mb o .H .a xe s - a 1 3.9 4 80 0 - b 13 .94 8 00 - c 9.3 1 50 0 - a lp ha 90 .00 0 - be ta 9 0.0 00 - g am ma 12 0.0 00 - P rim itiv e - R- 3 ( 14 8)

Hnh 3.9: Gin XRD ca mu P8.2 (x=0,4)

F a culty o f C he m istry, H US , VN U, D8 A DV A NC E-Bru ke r - M au P9 ,2

60 0

50 0
d=2.638
d=2.841

40 0
Lin (Cps)

d=3.489

30 0
d=2.321

d=1.861

20 0
d=1.422
d=4.035

d=1.368
d=1.554
d=2.013

d=1.600

d=1.523

10 0
d=1.936

d=1.689
d=2.144
d=4.089

d=1.394
d=1.644
d=2.220
d=3.144

d=2.721

d=2.079
d=2.046
d=3.256

d=1.724

d=1.488
d=1.825

d=1.781

20 30 40 50 60 7

2-Theta - Sc ale
F ile : H uy B K m au P 9,2 .ra w - T yp e : L o ck ed C o up le d - S tar t: 2 0 .0 0 0 - E nd : 70 .01 0 - Ste p: 0 .03 0 - S tep tim e : 1. s - T e mp .: 25 C (R o om ) - Ti me Sta rte d: 16 s - 2 -Th eta : 2 0 .00 0 - T h eta : 10 .00 0 - C hi: 0 .0
01 -0 79 -2 0 05 (C ) - Z inc S il ica te - Z n 2S iO 4 - Y: 3 5.5 5 % - d x by: 1. - W L : 1.5 40 6 - Rho mb o .H .a x e s - a 1 3.9 4 80 0 - b 13 .94 8 00 - c 9.3 1 50 0 - a lp ha 90 .00 0 - be ta 9 0.0 00 - g am m a 12 0.0 00 - P rim itiv e - R - 3 ( 14 8)

Hnh 3.10: Gin XRD ca mu P9.2 (x=0,6)

48
 Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau P10.2
400

d=2.836

d=2.630
300

d=3.478
Lin (Cps)

200

d=2.316

d=1.860

d=1.421
d=4.015

100

d=1.555
d=2.009

d=1.366
d=1.596
d=2.146

d=1.394
d=1.933

d=1.520
d=1.960

d=1.689
d=4.089

d=3.134

d=1.642
d=2.469

d=2.065
d=3.249

d=1.723
d=2.221
0

20 30 40 50 60 7

2-Theta - Scale
File: Huy BK mau P10,2.raw - Type: Locked C oupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 8 s - 2-Theta: 20.000 - Theta: 10.000 - C hi: 0.0
01-079-2005 (C) - Zinc Silicate - Zn2SiO4 - Y: 42.36 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 13.94800 - b 13.94800 - c 9.31500 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitiv e - R-3 (148)

Hnh 3.11: Gin XRD ca mu P10.2 (x=0,8)

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau P11,2

250

240

230

220

210

200

190

180

170
d=1.422
d=2.625

160
d=1.366

150
d=1.858

d=1.519
d=2.829

140
Lin (Cps)

130
d=3.467

d=1.790
d=2.314

120

110
d=2.209

100
d=4.003

90

80

70

60

50

40

30

20

10

20 30 40 50 60 7

2-Theta - Scale
File: Huy BK mau P11,2.raw - Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.
01-079-2005 (C) - Zinc Silicate - Zn2SiO4 - Y: 71.38 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 13.94800 - b 13.94800 - c 9.31500 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3 (148)

Hnh 3.12: Gin XRD ca mu P11.2 (x=1,0)

49
Nhn xt: Gin XRD ca tt c cc mu t P7.2 P11.2 u cha duy nht mt
pha km silicat Zn2SiO4 (01-079-2005) cu trc trc thoi. iu ny chng t tt c
coban khi pha tp u i vo thnh phn cht nn. V do vy ta c th kt lun
tng hp thnh cng cc cht mu km silicat pha tp bi coban c thnh phn l
Zn2-xCoxSiO4 vi gi tr ca x l 0,2; 0,4; 0,6; 0,8 v 1,0. Theo c im ca gin
nhiu x tia X, pic c cng cng cao, c tnh tinh th ca mu cng ln. Cc
thng s v mng c s; cng pic v gi tr d ng vi pic 2 theta 34,1
ca cc mu trn c ch ra bng di y.

Bng 3.3: Cc thng s v cng pic v d 2 theta 34,1

Mu Mc mng c s cao Gi tr () C ht
(a)
pha tp pic (cps) d D(b)
(nm)
P7.2 x=0,2 a=13,94800 550 2,640 0,5 16,5
P8.2 x=0,4 b=13,94800 620 2,637 0,4 20,6
P9.2 x=0,6 c=9,31500 400 2,636 0,35 23,5
P10.2 x=0,8 alpha=90,beta=90 280 2,630 0,25 33,0
P11.2 x=1,0 gamma=120 140 2,625 0,85 9,7
(a)
d l khong cch gia hai mt phng tinh th
(b)
D l c ht tinh th trung bnh gn ng tnh theo phng trnh Schrrer nh
c ch ra phng trnh 2.2
Theo bng 3.3 c tnh tinh th ca mu tng khi chuyn t mu P7.2 sang mu
P8.2 v sau gim dn khi chuyn t mu P8.2 sang mu P11.2. Mu P11.2 c
c im tinh th km nht. S pha tp coban tng dn vo mng li tinh th cht
nn silicat lm gim gi tr ca d gim dn. Ngoi ra ln c ht trung bnh D tnh
theo Schrrer tng khi tng mc pha tp mu c x=0,2 n 0,8. Ring mu P11.2
vi x=1.0 c c im tinh th km th ln c ht trung bnh l nh hn c.

50
3.2.4. Mt s c tnh ca sn phm
Cc c im v hnh thi v c ht ca mu c xc nh theo phng php chp
nh hin vi in t truyn qua (TEM). Tnh cht mu sc ca sn phm c nh
gi khi o ph hp th UV- Vis.

Hnh thi v c ht
Mu 8.2 - Zn1,6Co0,4SiO4 c tinh th ln nht c xc nh hnh thi v c ht
theo phng php chp nh hin vi in t truyn qua (TEM). Kt qu c ch ra
hnh di y

Hnh 3.13: nh TEM mu P8.2 Zn1,6Co0,4SiO4

Nhn xt:
Mu thu c bao gm cc ht hnh cu c kch thc thay i t khong 16nm n
30nm. Cc gi tr thu c y l kh ph hp vi gi tr tnh ton Schrrer ch ra
bng 3.3 trn.

51
 hp th mu

0,7

hp th
0,6

0,5

0,4

0,3

0,2

0,1

0
200 400 600 800 1000
-0,1
Bc sng (nm)

Hnh 3.14 : Ph hp th UV Vis mu P7.2 (x=0,2)

0,8
hp th

0,7
0,6

0,5
0,4
0,3

0,2
0,1
0
200 400 600 800 1000
Bc sng (nm )

Hnh 3.15: Ph hp th UV Vis mu P8.2 (x=0,4)

52
 1

hp th
0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0
200 300 400 500 600 700 800
bc sng(nm)

Hnh 3.16: Ph hp th UV Vis mu P9.2 (x=0,6)

1
hp th

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0
200 300 400 500 600 700 800

bc sng (nm )

Hnh 3.17: Ph hp th UV Vis mu P10.2 (x=0,8)

53
 1

hp th
0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0
200 300 400 500 600 700 800
bc sng (nm )

Hnh 3.18: Ph hp th UV Vis mu P11.2 (x=1,0)

Nhn xt:
ng cong hp th l tng t nhau v hnh dng chng t cc mu tng
hp c c bn cht ging nhau. Ph hp th UV Vis ca cc mu trn c 2 pic
c trng. Mt pic nm trong vng t ngoi c bc sng khong 215nm v mt
pick hp th rng nm trong vng nhn thy vi cc cc i 540nm; 580nm;
635nm. Do vy mu c mu xanh nc bin (blue). Do c kh nng hp th tia t
ngoi nn cht mu thu c c kh nng bo v chng tia t ngoi khi a vo sn
hay nha. nh hng ca mc pha tp n hp th nh sng ca mu c
ch ra bng 3.4.

54
Bng 3.4: nh hng ca mc pha tp n hp th nh sng ca mu
Mu T l pha tp Pic vng t ngoi Pic vng nhn thy
(nm) Abs (nm) Abs
P7.2 x=0,2 205 0,48 635 0,60
P8.2 x=0,4 205 0,51 635 0,71
P9.2 x=0.6 215 0,59 635 0,86
P10.2 x=0.8 215 0,61 635 0,91
P11.2 x=1.0 215 0,62 635 0,93

Theo bng 3.4 vi cc mu pha tp x=0,2 v x=0,4 pic vng t ngoi c cc i

bc sng l 205nm. Vi cc mu cn li c cc i 215nm. Tuy nhin cc i
pic nm trong vng nhn thy khng thay i theo x. C 2 dng pic nm trong vng
t ngoi v vng nhn thy u c hp ph tng theo gi tr ca x v thc t mu
ca cc mu thu c l xanh m dn.

3.3. Kho st kh nng to mu cho men

Cc cht mu km silicat pha tp bi coban c tng hp thnh cng theo phng
php ng kt ta vi mc pha tp x=0,2 n x=1.0. Do vy chng ti chn mu
c thnh phn l Zn1,6Co0,4SiO4 trong vic to mu cho men gm.
Da trn vic o ph tn x nng lng ( EDS ) v gin nhiu x tia X
mu t st H long c thnh phn chnh l silic, nhm di dng oxit hay nhm
silicat, di dng cc khong quartz, alumium silicat l thch hp cho vic ch
to gm thnh phn cc nguyn t ha hc v thnh phn pha c ch ra bng
3.5 v hnh 3.19 di y.

55
 Bng 3.5 Thnh phn ha hc mu t st H long

Element Weight% Atomic%

OK 59.61 72.54
Mg K 0.45 0.36
Al K 9.09 6.56
Si K 27.61 19.14
KK 1.69 0.84
Ti K 0.24 0.10
Fe K 1.31 0.46
Totals 100.00

H U T - P C M -B r u ke r D 8 A d va n c e d -3 2 # 2 0 0 8 -t.T h a nh -S1
33 0
32 0
d=3,34871

31 0
30 0
29 0
28 0
27 0
26 0
25 0
24 0
23 0
22 0
21 0
20 0
Lin (Counts)

19 0
18 0
17 0
16 0
15 0
14 0
13 0
12 0
d=4,25871

11 0
10 0
90
d=3,20741

80
d=3,57752
d=7,19075

d=1,81827

70
d=2,45865

d=2,12840

d=1,37337
d=1,54219

60
d=1,97933
d=2,28244

d=1,38121

50
40
30
20
10
0

10 20 30 40 50 60 70 80

2 -Th eta - Sca le

H U T-P CM -Bruk er D 8 Adv anced -32#200 8-t.Th an h-S1 - F ile: S1.raw - T y pe: 2T h/T h lock ed - Start: 1 0.00 0 - End: 79.990 - Step: 0.03 0 - Step tim e: 0.3 s - T em p.: 25 C (Room ) - Ti me Started: 12 086635 52 s - 2-T heta:
Operat ions: Sm ooth 0.15 0 | Im port
79 -1910 (C) - Qu artz - Si O2 - Y: 1 00.00 % - d x b y: 1. - W L: 1.5 406 - H exagonal - a 4. 91400 - b 4.91400 - c 5 .406 00 - alpha 9 0.00 0 - beta 9 0.00 0 - gamm a 12 0.000 - Primi tiv e - P 3121 (152) - 3 - 11 3.05 2 - I/Ic PD F 3.1 - S-
89 -0888 (C) - S illim an ite - Al2(SiO4 )O - Y: 12.50 % - d x by : 1. - W L: 1 .5406 - Orthorhom bic - a 7.1 5250 - b 7.5 3990 - c 5.91850 - al pha 90 .000 - b et a 90 .000 - g am m a 90.000 - Prim itive - Pbnm ( 62) - 4 - 319. 180 - I/Ic PD F
89 -0890 (C) - Alu minu m Silic ate - Al2(SiO4)O - Y: 14.58 % - d x by : 1 . - W L: 1.5406 - Orthorhomb ic - a 3.41 900 - b 9.390 00 - c 9.22200 - alph a 90. 000 - bet a 90.000 - gam ma 90.0 00 - Base-c entred - C m cm (63 ) - 4 - 296.
80 -0886 (C) - K aolin ite - Al2(Si2 O5)(OH) 4 - Y: 14 .58 % - d x by : 1. - W L : 1 .540 6 - Tr iclin ic - a 5.157 70 - b 8.941 70 - c 7.3 9670 - alph a 91. 672 - bet a 104.860 - gam ma 89.898 - Prim iti ve - P1 (1) - 2 - 329.571 - I/Ic PD F 1.1 -

Hnh 3.19: XRD mu t st H long

56
 Vi mc ch to ra cc mu gm c khi lng ring ln, bn nhit
cao, cc mu gm c to ra khi phi liu mu t st H Long nung 1100oC
vi t st cha nung v nc theo t l khi lng tng ng l 7:3:2. v p thnh
cc vin c ng knh 1.0cm.
Men gm s dng h men Frits c nhit nng chy 1100oC c thnh
phn nh sau (theo t l mol)
0,69 CaO 0,37Al2O3 2,17SiO2
0,19 Na2O 1,16 B2O3 0,12 K2O
Tin hnh trn men trn vi 5% cht mu trn, 10% cao lanh v 2% thy
tinh lng sau ph ln gm ri nung nhit 1100oC trong 1h. Sn phm thu
c c mu xanh v phn tn kh u trong men nh c ch ra hnh di y.

Hnh 3.20 : Mu th nghim trn gm

57
 KT LUN

Da trn kt qu nghin cu, c th rt ra mt s kt lun chnh nh sau:

1. tng hp thnh cng cht mu km silicat pha tp bi niken c thnh
phn Zn1.8Ni0.2SiO4 khi nung 1h 12000C, i t SiO2 km axetat v niken
axetat theo phng php sol gel bin tnh. Mu thu c bao gm cc ht
kh ng nht vi c ht khong 200nm.
2. tng hp thnh cng cht mu km silicat pha tp bi coban c thnh phn
Zn2-x CoxSiO4 c x thay i t 0,2 n 1.0 theo phng php ng kt ta. Tt c
cc mu tng hp c u n pha, c cu trc trc thoi v c kch thc ht
khong nh hn 50nm. Bng phng php phn tch ph UV- Vis ta c c
hp th tng dn khi tng t l pha tp x= 0,2 n 1,0.
3. Bc u kho st cht mu Zn1,6Co0,4SiO4 khi to mu cho gm trn h men
Frits thu c thnh cng v trin vng c th p dng vo thc t.

58
TI LIU THAM KHO

Ting Vit
1. La Vn Bnh (2000), Khoa hc v cng ngh vt liu, i hc Bch Khoa,
H Ni.
2. Hong Ngc Cang, Hong Nhm (1990), Ha hc v c, NXB i hc v
Trung hc chuyn nghip H Ni.
3. L Cng Dng (1997), Vt liu hc, NXB Khoa hc v k thut H Ni.
4. Quan Hn Khang, Trnh Hn, L Nguyn Sc (1979), Tinh th hc i
cng, NXB i hc v Trung hc chuyn nghip H Ni.
5. Trn Vn Hng, Kho st nh hng ca phng php khuch tn n tnh
cht ca vt liu pht quang Stronti Tetraborat, Lun vn Thc s khoa
hc, i hc Hu.
6. Trn Th Lin, nh hng ca tp cht ln cu trc tinh th v c tnh in
hunh quang ca ZnS: Cu, Lun vn Thc s khoa hc, i hc Bch
Khoa, H Ni.
7. T Vn Mc (2003), Phn tch ha l v phng php ph nghim nghin
cu cu trc phn t, NXB Khoa hc v k thut H Ni.
8. o nh Thc (1980), Cu trc phn t v lin kt ho hc, NXB i hc
v Trung hc chuyn nghip H Ni.
9. Phan Vn Tng (2005), Vt liu v c, H Ni.
10. Nguyn Vn Xuyn (2004), Cu to phn t v lin kt ho hc, NXB
Khoa hc v k thut, H Ni.

Ting Anh

11. A. F. Wells (1975), Structural Inorganic Chemistry, Clarendon Press,

Oxford.
12. Akos Kiss, Peter Kleinschmit and Giinter Halbritter (1988), Process for
producing luminous material based on manganese activated zinc
silicate, Patent number: 4767567.

59
13. Antoinette Morell and Nathalie Goumard (1997), Phosphor material based
on manganese-doped zinc silicate and method for obtaining such a
material, Patent number: 5645761.
14. A. Roy, S. Polarz and S. Rabe (2004), First preparation of nanocrystalline
zinc silicate by chemical vapor synthesis using an organometallic
single-source precursor.
15. Burtrand I. Lee and Song Wei Lu (2000), Synthesis of nanoparticles via
surface modification for electronic applications, Journal of Ceramic
Processing Research, Vol.1 (1), pp.20-26.
16. Chapman and Hall (1993), Solid state chemistry, Boundary Row, London.
17. Fuhai Su, Baoshan Ma and Kun Ding (2005), Luminescence temperature
and pressure studies of Zn2SiO4 phosphors doped with Mn2+ and Eu3+
ions.
18. Ha-Kyun Jung, Bu Young Sung and Hee Dong Park (2004), Preparing
green phosphor based on zinc orthosilicate, Patent number: US
6716369.
19. Hideki Hoshino and Satoshi Ito (2004), Zinc silicate system phosphor,
method for producing the same, zinc silicate system phosphor paste, and
display device, Patent number: US 0075386.
20. Kai Su, T. Tilley and Michael J. Sailor (1996), Molecular and Polymer
Precursor Routes To Manganese - Doped Zinc Orthosilicate
Phosphors", Journal of the American Chemistry Society, Vol. 118 (14),
pp. 3459 - 3468.
21. Karl A. Franz (1996), Luminescent materials from Ullmann s
Encyclopedia of Industrial Chemistry, Vol. A15, pp. 519-557.
22. Morell Antoinette, Marx Annie and Manouvrier Olivier (1993), Zn2SiO4:
Mn phosphor powder and methods for making same.
23. Rimantas Glemza and Gordon James Turner (1968), Method of preparing a
zinc silicate phosphor, Patent number: 1190544.

60
24. Robert M. Rose, Lawrence A. Shepard, John Wultt (1977), The Structure
and Properties of Materials, John Wiley & Sons, Inc, London.
25. Xiong Liangming and Shi Jianlin (2005), Method for preparing
manganese-doped zinc silicate green luminescent powder by low
temperature solid state reaction.
26. X. W. Sun and H. S. Kwok (1999), Pulsed laser deposition of silicate
phosphor thin films.

61