Chng 1.

Cu trc tinh th
GS. Phm Vn Tng
Vt liu v c
NXB i hc quc gia H Ni 2007.
Tr 67 93.
T kho: Cu trc tinh th, cu trc tinh th ca cc oxit.
Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc
ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc
v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc
Chng 1 CU TRC TINH TH ...................................................................................... 2
1.1
Cc phng php m t cu trc tinh th................................................................... 2
1.1.1
M t theo kiu t bo mng li....................................................................... 2
1.1.2
M t cu trc theo kiu xp kht cc khi cu.................................................. 9
1.1.3
M t cu trc bng cch ni cc khi a din trong khng gian .................... 14
1.2
Cu trc tinh th ca cc oxit v mt s hp cht quan trng ................................. 15
1.2.1
Cu trc tinh th ca mt s oxit...................................................................... 16
1.2.2
Hp cht gia cc oxit...................................................................................... 24
1.3
Nhng nt c bit ca tinh th cng ho tr v tinh th kim loi............................ 48
1.4
Cc yu t nh hng n kiu cu trc tinh th ..................................................... 52
1.4.1
Tnh hp thc SPT ca cc nguyn t .......................................................... 52
1.4.2
nh hng ca kiu lin kt ............................................................................ 53
1.4.3
nh hng ca bn knh nguyn t, ion .......................................................... 54

Chng 1
CU TRC TINH TH
1.1

Cc phng php m t cu trc tinh th

Cu trc tinh th lin quan n mi tnh cht ca vt liu. Do tng hp c loi

vt liu c cc tnh cht mong mun phi hiu r cu trc bn trong ca n v t la chn
phng php ch to hp l.
C nhiu cch m t cu trc tinh th: Da vo kiu t bo mng, vo cch sp xp kht
khi cu, da vo cch ni cc a din trong khng gian. Trong cc gio trnh tinh th hc
u c trnh by cc phng php . y ch trnh by tm tt nhng vn lin quan n
mn vt liu hc.

1.1.1 M t theo kiu t bo mng li

Trong cht rn dng tinh th, cc tiu phn (nguyn t, ion, phn t,) c sp xp mt
cch u n, tun hon to thnh mt mng li khng gian. Gi s ta chn mt tiu phn A
bt k lm gc to , ri dng h trc to AX, AY, AZ theo 3 hng trong khng gian.
Gi gc lp bi 3 trc l , , v gi khong cch u n gia cc tiu phn theo trc
AX l a (thng s n v theo trc AX), theo trc AY l b, theo trc AZ l c. Th tch b nht
trong khng gian ABCDABCD c cha mi yu t i xng c trng cho khng gian gi
l t bo mng li.
Z
A'
B'

D'
C'

X
Hnh 1
Mng li khng gian

Ty theo cc gi tr a, b, c, , , , ngi ta phn ra thnh 7 h tinh th vi cc kiu

mng c s khc nhau, mi mng c s li phn thnh cc kiu mng li khc nhau v
c k hiu nh sau: mng c s n gin k hiu l P, nu tm ca cc mt mng c s c
cha mt tiu phn na th gi l mng li tm mt v k hiu l F, nu ch tm ca hai y
c cha thm tiu phn th gi l mng li tm y v k hiu l C, nu ti tm im ca
mng c s c cha mt tiu phn th gi l mng li tm khi v k hiu l I. Bng 1 di
y gii thiu 7 h tinh th v 14 kiu t bo mng li.

Bng 1.7
h tinh th v 14 kiu t bo mng
H
Lp phng (cubic)
Bn phng (tetragonal)
Trc thoi (orthorhombic)
Lc phng (hexagonal, trigonal)

Mt thoi (Rhombohedral)
n t (monoclinic)

Tam t (triclinic)

Cc thng s t
bomng

Yu t i xng c
trng nht

Cc kiu mng

a=b=c
o
= = = 90
a=bc
= = = 90o
abc
o
= = =90
a=bc
= = 90o,
= 120o
a=b=c
= = 90o
abc
o
= = 90 ,
o
90
abc
90o

4 trc bc ba

P. F. I

1 trc bc bn

P. I

3 trc bc hai

P. F. I. C

1 trc bc su

1 trc bc ba

1 trc bc hai

P. C

khng

H lc phng (Hexagonal) v h tam phng (Trigonal) u c thng s t bo mng

nh nhau.
Ct th 3 trong bng 1 ch a ra yu t i xng c trng nht ca mi h. Cn s yu
t i xng ca cc h th c rt nhiu. V d c nhiu yu t i xng nht l h lp phng.
H lp phng c 3 trc i xng bc 4 (3A4) l cc ng thng ni tm im ca hai mt
i din nhau, 3 ng ny trc giao vi nhau ti tm t bo, 4 trc i xng bc ba (4A3) l
cc ng thng ni hai nh i din nhau, su trc i xng bc hai (6A2) l cc ng
thng ni im gia 2 cnh i din nhau, ba mt i xng M (3M) l mt phng i qua tm
im ca 4 cnh song song vi nhau, su mt i xng M (6M) l cc mt ct khi lp
phng theo tng cp ng cho mt, mt tm i xng (C). Nh vy khi lp phng c
cc yu t i xng l:
3A4, 4A3,6A2, 3M, 6M, C
Cng vy cc yu t i xng ca h t phng l 1A4, 2A2, 2A2, M,
2M, 2M, C.
Cc yu t i xng ca h trc thoi l A2, A2, A2, M, M, M, C.
Cc yu t i xng ca h lc phng l A6, 3A2, 3A2, M, 3M, 3M, C.
Cc yu t i xng ca h mt thoi l A2, 3A2, 3M, C.
H n t c cc yu t i xng: A2, M, C.

c
b

Hnh 2
Bn t bo mng li ca h trc thoi

P: l mng li n gin

F: l mng li tm mt

C: l mng li tm y

I: l mng li tm khi

Trong mng li tinh th c rt nhiu h mt phng song song v cch u nhau. Mi

mt h mt phng song song vi nhau c c trng bng 3 ch s h k l (gi l ch s
Mile (Miller)). xc nh ch s h, k, l ca mt mt phng bt k trong mng li tinh th,
trc ht cn chn gc to O v ba trc xut pht t O l Ox, Oy, Oz. Thng s n v
theo trc Ox l a, theo Oy l b v theo Oz l c. V d mt 1 trn hnh 3 ct Ox im ng vi
1/2 thng s n v (a/2), ct Oy im ng vi mt thng s n v (b/1) ct Oz im ng
vi 1/3 thng s n v (c/3). Ly gi tr nghch o ca cc s ta c ch s h k l ca
mt 1 l 2 1 3. C mt h cc mt phng song song v cch u mt 1 , trn hnh v c ghi
mt 2. H mt phng gi l h mt 2 1 3 c mt 1 gn vi gc to nht. Hnh 4 gii
thiu ch s Mile ca mt s mt phng khc nhau.

z
b

y
a
c

c/3
0

1
o

a/2

Hnh 3
Xc nh ch s Mile hkl ca mt phng trong mng li tinh th

(a)

(b)
z

(c)
z

a
c

c
x

yc

O
a

a
b

a
b

Hnh 4
Ch s Mile ca mt s mt phng khc nhau: a(111); b(101); c(010)

Mt phng gch gch hnh 4a ct Ox, Oy, Oz im ng vi mt thng s n v a, b,

c nn gi l mt 1 1 1. Hnh 4b v mt phng ct trc Ox, Oz im ng vi mt thng s
n v v song song vi trc Oy (ct Oy ) nn gi l mt 1 0 1. Hnh 4c c cc mt c v
d song song vi nhau, ta chn mt d xc nh ch s Mile ca h mt phng ny, v mt
c i qua im gc O khng th xc nh c cc gi tr h k l. Mt d song song vi trc Ox
v Oz ct Oy mt thng s n v b nn gi l mt 0 1 0.
Thng tin quan trng nht khi kho st mng li khng gian l gi tr khong cch gia
cc mt mng dhkl. T kt qu ghi ph nhiu x tia X cho ta bit cc gi tr ca mu nghin
cu, do bit c s c mt ca cc pha rn trong mu. Mi h tinh th c mt mi lin
h gia cc gi tr dhkl vi cc thng s ca t bo mng.
Vi h lp phng ta c:
1
h 2 + k 2 + l2
=
d 2hkl
a2

(1)

v th tch t bo V = a3
Vi h t phng ta c:
1
h 2 + k 2 l2
=
+ 2
d 2hkl
a2
c

(2)

v th tch t bo
V = a2.c
Vi h trc thoi ta c:
1
h 2 k 2 l2
=
+
+
d 2hkl a 2 b 2 c 2

(3)

v th tch t bo V = a.b.c
Vi h lc phng ta c:
1
4 h 2 + kh + k 2
=

d 2hkl 3
a2

l2
+ 2
c

(4)

th tch t bo
3.a 2 .c
2
V=
= 0,866a .c
2

Vi h n t:
1
1 h 2 k 2 .sin 2 l2 2hlcos
=
+ 2
+

d 2hkl sin 2 a 2
b2
c
ac

th tch t bo

(5)

V= abc.sin
Vi h tam t ta c:
1
1
= 2 ( h 2 b 2 c 2 sin 2 + k 2 a 2 c 2 sin 2 + l 2 a 2 b 2 sin 2
2
d hkl V

(6)

+2hkabc 2 (cos .cos.cos ) + 2kla 2 bc(cos.cos .cos )

+2hlab 2 c.(cos .cos .cos))
Th tch t bo:
V=abc(1- cos2- cos2 - cos2 + 2cos.cos.cos )1/2
Di y kho st mt vi gi tr c trng ca t bo mng li kim loi. Trc ht quy
c rng mng li kim loi gm cc nguyn t xp kht nhau, nhng d hnh dung, trong
cc hnh v chng ta biu din cc nguyn t bng nhng vng trn nh.
Mng li lp phng tm khi: thng s t bo mng l a, mi t bo cha hai nguyn t,
a 3
quan h gia bn knh nguyn t v hng s mng l: r =
, t xc nh c chc c
4
C (compact).
4

a 3

2( .r 3 ) 2( .(
)3 )
th tch ca 2 nguyn t
3
3
4
C=
=
=
= 0, 68
th tch t bo
a3
a3

iu c ngha l trong t bo lp phng tm khi c 32% khong trng. Mi nguyn

a 3
t c bao quanh bng 8 nguyn t khc vi khong cch u l
, ngha l s phi tr
2
2M
(SPT) bng 8, khi lng ring d =
(M l nguyn t lng, N l s Avgar).
Na 3

T
T

Hnh 5.
T bo mng lp phng
tm khi

Hnh 6
V tr cc hc trng bt
din (hc O), k hiu

Hnh 7
V tr cc hc trng t din (hc T), k
hiu y

C hai loi hc trng l hc bt din (hc O) v hc t din (hc T).

+ Hc O:
Tm ca 6 mt u l hc O chung cho 2 t bo cnh nhau.

im gia 12 cnh u l hc O chung cho 4 t bo cnh nhau.

Do mi t bo c: (6 1/2) + (12 1/4) = 6 hc O (hnh 6).
+ Hc T: Mi mt c 4 hc T chung cho 2 t bo cnh nhau. Do mi t bo c (4 6
1/2) = 12 hc T (hnh 7).
Mng li lp phng mt tm: Thng s t bo mng l a. Mi t bo cha 4 nguyn t.
a 2
Quan h gia bn knh nguyn t v cnh l: r =
, c chc
4
4

a 2

4( .r 3 ) 2( .(
)3 )
th tch ca 4 nguyn t
3
3
4
C=
=
=
= 0,74
th tch t bo
a3
a3

Mi nguyn t c bao quanh bng 12 nguyn t khc vi khong cch bng

SPT =12, khi lng ring d =

4M
.
Na 3

Hnh 8
Mng li lp phng tm mt

Hnh 9
V tr hc O, k hiu

Hnh 10.
V tr cc hc O, k hiu x

Trong t bo lp phng mt tm c 26% khong trng l cc hc O v hc T.

+ Hc O:
Tm t bo c 1 hc O (hnh 9).

a 2
,
2

Gia cc cnh u c hc O chung cho 4 t bo (hnh 10).

Vy mi t bo c 1 + 12 1/4 = 4 hc O.
+ Hc T: Mi t bo c 8 hc T nm trong t bo cc to : (1/4, 1/4, 1/4); (3/4, 1/4,
1/4); (3/4, 3/4, 1/4); (1/4, 3/4, 1/4); (1/4, 1/4, 3/4); (3/4, 1/4, 3/4); (3/4, 3/4, 3/4); (1/4, 3/4, 3/4)
(hnh 11).
Mng li lc phng: Thng s t bo mng l a, c (hnh 12). Mi t bo c 2 nguyn
a
t. Quan h gia bn knh nguyn t v thng s t bo l r = .
2
Th tch 2 nguyn t
Th tch t bo

chc c C =

Th tch 2 nguyn t

4 a
V1 = 2 ; Th tch t bo V2 = abc
3 2

T
T
T

120o

c
A1

a
a

D1

B1

C1

B1

A1
D1

(a)
Hnh 11
V tr cc hc T

60o

A
A

C1

Hnh 12
Khi gm 3 t bo (a), t bo mng li lc phng (b)

5C
8

Hnh 13
V tr cc hc T (k hiu y)

3C
8

(b)

Hnh 14
V tr cc hc O (k hiu )

b=

Do C =

a 3
;
2

V2 =

a2 3
a
3
c; mt khc =
;
2
c 2 2

= 0,74
3 2

SPT =12; Khi lng ring d =

4M
Na 2 3c

Mi t bo c 2 hc O v 4 hc T (hnh 13 v 14).

1.1.2 M t cu trc theo kiu xp kht cc khi cu

Theo nguyn l xp kht, th khi khng c s nh hng ca lin kt, cc tiu phn to
thnh tinh th c khuynh hng sp xp sao cho khong khng gian t do c th tch b nht,
ngha l c chc c ln nht. Nu cc tiu phn to thnh tinh th u c dng qu cu vi
ng knh bng nhau th c 2 kiu xp kht gi l xp kht lc phng (kiu ABABA) v
xp kht lp phng (kiu ABCABCAB). Hnh 15 trnh by cch xp kht ca mt lp qu
cu . Trong lp xp kht ny (gi l lp A) mi mt qu cu (v d qua cu K) c bao
quanh bng 6 qu cu khc. Trong hnh b, mi qu cu ch tip xc vi 4 qu cu khc, y
khng phi l mt xp kht. Trong lp xp kht c 3 hng xp kht (XX, YY, ZZ) (hnh
15a), hnh 15b ch c 2 hng xp kht. Trong mt xp kht ny c cc dy l trng R v
dy l trng P.

10

z'
6

1
K

4
P

y'

2
R

x'

(a)

(b)

Hnh 15
Mt phng gm cc qu cu xp kht nht (a), cch xp khng kht (b)

By gi chng ta t lp xp kht th 2 (gi l lp B) ln trn lp A. Mun cho khng

gian t do c th tch b nht th phi t sao cho cc qu cu ca lp B nm ng v tr lm
gia 3 qu cu ca lp A v ngc li, cc qu cu ca lp A phi nm ng cc v tr lm
ca lp B. Mun vy th cc qu cu ca lp B hoc l phi nm vo tt c cc v tr P, hoc
l phi nm vo tt c cc v tr R ca lp A (xem hnh 15). Ta c 2 lp xp kht (hnh 16).
t lp th 3 ln lp th 2 ta c 2 cch. Nu t sao cho cc qu cu ca lp th 3
nm vo v tr S ca lp th 2 (hnh 16) th tt c cc qu cu ca lp 3 u trng vo v tr
tng ng ca lp th nht. Ngha l chu k lp li ca cc lp l 2, cc lp xp theo th t
ABABA. Kiu xp kht nh vy gi l xp kht lc phng.
A
T

S
T

Hnh 16
Hai lp xp kht A v B

A
C
B

11

Hnh 17
Ba lp xp kht ABC to thnh kiu xp kht lp phng

Nu t lp th 3 sao cho cc qu cu nm lt vo v tr T (xem hnh 16) th s hnh thnh

mt lp mi (lp C), n lp th 4 mi lp li chu k tc l lp A. Cch xp nh vy gi l
xp kht lp phng v th t lin tc ca cc lp l ABCABCAB (hnh 17). Xp kht lp
phng v xp kht lc phng l hai kiu cu trc n gin v quan trng nht. Ngoi ra
cng cn c nhiu kiu xp kht vi th t cc lp phc tp hn, v d ABCACB... hoc
ABAC to thnh nhng chu k lp li ln hn (xem cu trc tinh th ca -Al2O3 - hnh
29).
Trong 2 kiu xp kht lc phng v xp kht lp phng, mi qu cu u tip xc vi
12 qu cu khc (SPT = 12).
chc c ca c 2 kiu xp kht ny u bng nhau v bng 0,74. iu ny c ngha l
trong c hai kiu xp kht nht vn cn 26% th tch l cc khong trng. C hai loi hc
trng gi l hc trng t din (hc T) v hc trng bt din (hc O). Hc T l khong khng
gian gia 4 khi cu xp kht vo nhau. Tu thuc vo khi cu nh ca t din nm trn
hoc di m phn thnh hc T+ hoc T (hnh 18). Hc O l khong khng gian nm gia
6 qu cu xp kht ca 2 lp st nhau, su qu cu gm 4 qu cng nm trn mt mt phng
v 2 qu nm v hai pha ca mt phng .
6
2

4
1

(a)

(b)

(c)

Hnh 18
Cc hc trng trong mng li xp kht nht Hc T+ (a), Hc T- (b), Hc O (c)

Vic chn mt phng cha 4 qu cu c th ly t do theo nhiu cch. V d, cc qu

1264 hoc 2345 hoc 1356. Hnh 19 trnh by cc hc trng gia 2 lp xp kht. Mng tinh
th ca cc oxit gm cc ion O2 xp kht, cn cc cation c phn b vo cc hc T v O.
V rng trng tm ca t din gn y hn nh nn cation hc T khng ng vo v tr
chnh gia 2 lp, cn cation hc O th nm ng chnh gia 2 lp. Cc cation khi chui vo
hc T v O s lm gin n phn mng oxi.

Hc t din THc bt din O

Hc t din T+

Hnh 19
S phn b cc hc trng gia hai lp xp kht (lp cu pha trn v vng

12

m, lp cu pha di v ng chm chm)

T bo mng ca kiu gi ghm chc c lp phng (hay cn gi l lp phng tm

mt) c trnh by trn hnh 20a, cn hnh 21 trnh by t bo mng ca kiu gi ghm chc
c lc phng.

13

4
3
2

2
7

(a)

(b)

Hnh 20
T bo mng lp phng tm mt c to thnh t kiu gi ghm cc qu
cu theo kiu chc c lp phng

Kiu gi ghm chc c lp phng trng vi kiu t bo lp phng mt tm (hnh 20a).

Ni chung iu ny khng d dng thy c, v rng cc mt ca t bo lp phng khng
trng vi lp xp kht, trong mi qu cu ch tip xc vi 4 qu cu khc ch khng phi 6
qu. Trong t bo lp phng mt tm th lp xp kht l cc mt song song vi mt phng
111. thy c r hn, ta b i qu cu v tr 1 ca hnh 20a th thy ngay lp di gm
cc qu cu 2, 3, 4, 5, 6, 7 (hnh 20b) nm trn cng mt mt phng (song song vi mt 111).
T ta c th kt lun rng cu trc gi ghm chc c lp phng c 4 mt xp kht trc
giao vi ng cho ca khi lp phng.
T bo mng kiu lc phng trng vi kiu gi ghm chc c lc phng, iu ny d
thy c trn hnh 21, y cc mt c s ca mng u trng vi mt xp kht.
120o
60o

c
a
a
Hnh 21
T bo mng lc phng c to thnh t s gi ghm chc c lc phng
cc khi cu

a s cc kim loi u kt tinh theo mt trong ba kiu lp phng tm mt

(ABCABC), lc phng (ABAB) v lp phng tm khi. Bng 2 cho bit kiu t bo,
thng s t bo ca mt s kim loi.

14

Bng 2
Cu trc v thng s t bo mng li ca mt s kim loi
Lp phng tm mt
Lc phng (kiu ABAB)
Lp phng tm khi
(kiu ABCABC)
Kim loi
a ()
Kim loi
a ()
c ()
Kim loi
a ()
Cu
3,6150 Be
2,2859
3,5843 Fe
2,8664
Ag

4,0862

Mg

3,2095

5,2104

Cr

2,8839

Au

4,0786

Zn

2,6650

4,9470

Mo

3,1472

Al

4,0494

Cd

2,9793

5,6181

3,1648

Ni

3,5238

Ti

2,9500

4,6860

Ta

3,3058

Pd

3,8898

Zr

3,2320

5,1470

Ba

5,0250

Pt

3,9231

Ru

2,7058

4,2819

Pb

4,9506

Os

2,7341

4,3197

Re

2,7600

4,4580

Vic mt kim loi no kt tinh theo kiu mng li ny hay mng li khc l mt
vn cho n nay vn cha r. Trong hai kiu cu trc lp phng tm mt v lc
phng u c chc c ln (C = 0,74) cn chc c ca kiu lp phng tm khi nh
hn (C = 0,68). Kt qu tnh ton cho thy nng lng mng li ca cc kim loi c cu trc
lc phng v lp phng tm mt gn tng t nhau, do s khc nhau v cu trc c th
do s khc nhau v cu trc vng ca chng.
C mt s kim loi c bin ho th hnh, ngha l c th c cc kiu cu trc khc nhau.
V d st, tu thuc vo nhit c th c cu trc lp phng tm khi (Fe-) hoc lp
phng tm mt (Fe-); coban ngoi kiu cu trc lp phng tm mt v lc phng li cn
c th to ra cc dng khc vi chu k lp li ca cc lp xp kht phc tp hn. y l
trng hp ng vi dng a hnh c bit (polytypism) khi m s khc nhau v cu trc ca
nhng dng th hnh ch xy ra theo mt hng. Trong cc kim loi c cu trc gi ghm
chc c ca tt c cc lp nguyn t kch thc ging nhau, cn s khc nhau v cu trc ch
l cch sp xp ln nhau ca cc lp . Tuy rng ch c hai cch chnh sp xp cc lp l
ABC (lp phng tm mt) v AB (lc phng) nhng cng c th hnh thnh rt nhiu kiu
sp xp lun phin phc tp hn. l trng hp ca coban kim loi. C nhng vt liu
trong c dng th hnh vi chu k lp li gia cc lp xp kht ti vi trm lp nguyn t.
S hnh thnh nhng cu trc nh vy ang l vn cha gii thch c. V d nh c kiu
cu trc vi chu k lp li ti vi trm lp, dy ti 500. Cng c quan im cho rng chu
k lp li ln nh vy lin quan vi c ch xon c khi tinh th ln dn sinh ra bin v xon.

1.1.3 M t cu trc bng cch ni cc khi a din trong khng gian

V d tinh th mui n (NaCl) c th m t bng cch ni cc khi bt din [NaCl6]5 qua
mt cnh chung (hnh 22), mng tinh th nh vy c trnh by hnh 23.
Tuy nhin khng phi ton khi khng gian c lp y bng cc bt din, m vn cn
li cc khong trng, i vi tinh th NaCl th l cc khong trng t din nh trn hnh
23.
Kiu m t nh vy rt thun li cho cch trnh by mng tinh th ca silicat. V d mng
tinh th SiO2 c trnh by bng cch ni cc t din [SiO4]4 qua nh, mng tinh th

15

khong vt st c trnh by theo cch ni cc t din [SiO4]4 vi cc bt din [Al(OH)6]3

qua nh, mng tinh th zeolit c m t theo cch ni cc bt din ct [Si24xAlxO48]x+ qua
cc mt bn (xem phn silicat). V cc a din u c cation nm tm, anion cc nh, nn
ni cc a din qua nh, cnh hoc cc mt chung th phi lu n lc y gia cc cation,
c bit l cc cation c kch thc b v in tch ln, v d nh Si4+. Tt nhin mng li
bn nu cch ni sao cho lc y ny b nht, ngha l khong cch gia cc cation xa nht.
Hnh 24 v bng 3 cho thy khong cch gia cc cation gim dn khi ni cc a din qua
nh, cnh, mt.

Hnh 22
T bo mng NaCl c hnh thnh theo
cch ni cc bt din theo cnh chung

o
o

(a)

M
X

o
o

(b)

(c)

M
90o

M M = 2MX
(M - O, X - o)

Hnh 23
Mng tinh th NaCl c xy dng theo cch
ni cc bt din [NaCl6]5 qua cnh chung

2 MX = 1,411MX

X
M - M=

71o

M-M=

2(1 cos 71o )MX

= 1,16M
Hnh 24
Khong cch cation-cation khi ni cc bt din qua nh (a); qua cnh (b) v khi ni cc t din
qua cnh (c)
a din

Khong cch M-M khi ni 2 a din

Bng nh
Bng cnh
Bng mt
Hai t din
2MX
1,16MX
0,67MX
Hai bt din
2MX
1,41MX
1,16MX
Bng 3
Khong cch gia cc tm a din cnh nhau MX4 v MX6

1.2

Cu trc tinh th ca cc oxit v mt s hp cht quan trng

st vi i tng nghin cu vt liu v c, trong phn m t cu trc tinh th di

y s trnh by loi hp cht in hnh nht l oxit v hp cht gia cc oxit nh M2O, MO,
M2O3, MO2, AB2O4, ABO3, AB2O7,... v silicat. Cc hp cht v c khc (halogenua, sunfua,
nitrua,) s c ni n khi c cu trc tng t vi oxit.

16

1.2.1 Cu trc tinh th ca mt s oxit

1.2.1.1 Oxit c cng thc chung MO

Na+

Cl

Hnh 25
T bo mng li kiu NaCl

Oxit kim loi ho tr 2 nu c t l rM2+/rO2 nm trong khong 0,414 n 0,732 v c lin

kt ch yu l lin kt ion th c mng li tinh th thuc kiu NaCl. Ta c th biu din
mng li tinh th ny theo c 3 phng php trn. y biu din t bo mng. C th xem
t bo mng ca loi ny gm hai phn mng lp phng mt tm ca cation M2+ v ca
anion O2 lng vo nhau mt khong bng 1/2 cnh ca lp phng. Mi t bo gm 4 phn
t MO, SPT ca cation v anion u bng nhau v bng 6.
Bng 4
Mt s hp cht cu trc theo kiu NaCl
Hp cht
a ()
Hp cht
a ()
MgO
4,2130
MgS
5,2000
CaO
4,8105
CaS
5,6948
SrO
5,1600
SrS
6,0200
BaO
5,5390
BaS
6,3860
TiO
4,1770
MnS
5,2240
MnO
4,4450
SnAs
5,7248
FeO
4,3070
TiC
4,3285
CoO
4,2600
LaN
5,3000
NiO
4,1769
TiN
4,2400
CdO
4,6653

Hp cht
MgSe
CaSe
SrSe
BaSe
CaTe
BaTe
UC
ScN
UN

a ()
5,462
5,924
6,246
6,600
6,660
7,000
4,955
4,440
4,890

Hp cht c t l rcation/ranion nm gia 0,225 v 0,414 v lin kt ch yu l ion th c cu

trc kiu ZnS.
ZnS c hai dng th hnh l blend (hoc cn c tn l sphalerit) v vuazit.
Blend c t bo tinh th lp phng tm mt ca S2, ion Zn2+ nm 4 trong 8 hc t
din ca phn mng lp phng tm mt S2 (hnh 26). To ca Zn2+ l: 1/4, 1/4, 1/4;
3/4, 3/4, 1/4; 3/4, 1/4, 3/4 v 1/4, 3/4, 3/4. Hng s mng ca blend a = 5,43; d = 4,092.
Bng 5 gii thiu cc hp cht c cu trc kiu blend.

17

S
Zn

Hnh 26
T bo mng ca blend (ZnS)

Bng 5
Mt s hp cht cu trc kiu blend
Hp

4,255

BeS

4,8624

-CdS

5,818

BN

3,616

GaP

5,448

CuCl

5,416

BeSe

5,070

CdSe

6,077

BP

4,538

GaAs

5,653

-CuBr

5,690

BeTe

5,54

CdTe

6,481

BAs

4,777

GaSb

6,095

-CuI

6,051

-ZnS

5,406

HgS

5,852

AlP

5,451

InP

5,869

-AgI

6,495

ZnSe

5,667

HgSe

6,085

AlAs

5,662

InAs

6,058

-MnS

5,600

ZnTe

6,102

HgTe

6,453

AlSb

6,135

InSb

6,478

-MnSe

5,880

SiC

4,358

cht

a ()

Hp

CuF

cht

a ()

Hp

a ()

cht

a ()

Hp

Hpcht

cht

a ()

Khi un nng ti 1020oC th blend chuyn thnh vuazit. T bo mng ca vuazit c phn
mng S2 gi ghm chc c lc phng (hnh 27). Cc ion Zn2+ chim ht tt c hc t din
T+, cn cc hc t din T v hc bt din O u trng.
Hnh 27 trnh by mt t bo mng ca vuazit. C th hnh dung t bo mng ny gm
hai phn mng xp kht lc phng cation v anion lng vo nhau mt khong bng 3/8 chiu
cao. Trong thc t hai phn mng ny lng vo nhau khng ng vi gi tr 3/8 (0,375) chiu
cao, m tu theo tng loi cation gi tr dch chuyn khc nhau (gi tr u trong bng 6).
Hng s mng ca vuazit a = 3,811; c = 6,234; d = 3,98 4,08.
Mt trong nhng tnh cht c trng ca phn mng xp kht lc phng l gi tr c/a.
Trng hp l tng th t s bng 1,633. Cc gi tr trn bng 6 u khc vi 1,633,
iu ny chng t rng cc mt khng hon ton xp kht.

18

120 o

60 o

60 o
3
8

3
8

120 o

a
Hnh 27
T bo mng kiu vuazit
Bng 6
Gii thiu mt s hp cht c cu trc vuazi
Cht

a ()

c ()

c/a

Cht

a ()

c ()

ZnO

3,2495

5,2069

0,345

1,602

MnS

3,976

6,432

1,618

ZnS

3,8110

6,2340

1,636

MnSe

4,120

6,720

1,631

ZnSe

3,9800

6,5300

1,641

AlN

3,111

4,978

ZnTe

4,2700

6,9900

1,637

GaN

3,180

5,166

1,625

BeO

2,6980

4,3800

1,623

InN

3,533

5,693

1,611

CdS

4,1348

6,7490

1,632

TaN

3,050

4,940

1,620

0,378

0,385

c/a

1,600

1.2.1.2 Oxit c cng thc M2O3

l cc oxit Al2O3 (corun), Fe2O3 (hmatit), Cr2O3, Ga2O3, Ti2B3, Al2O3 c nhiu
dng th hnh. iu ny cng d hiu v t l rAl3+/rO2 = 0,42 tc l nm gia hai s phi tr l
4 v 6. Trong cc dng th hnh ch c 3 dng quan trng l , , .
Al2O3 l dng th hnh bn vng nht, loi ny cn c tn l corun, tinh th corun gm
phn mng xp kht lc phng ca ion oxi. Cation Al3+ chim 2/3 hc bt din, cn hc T+
v T u b trng.

O2-

Al3+

O2Al3+

Hnh 28
Cu trc tinh th corun Al2O3

Khong cch gia hai lp xp kht oxi bng 2,16. T bo nguyn t ca corun thuc h
mt thoi, chiu di cnh bng 5,12, gc nhn gia cc cnh bng 5o17. T bo nguyn t c
4 ion nhm v 6 ion oxi. Cc oxit c cu to ging corun gm hmatit Fe2O3, Cr2O3, Ga2O3,
Ti2O3.

19

-Al2O3. Tn gi Al2O3 ch mt nhm hp cht c cng thc M2O.nX2O3. Gi tr

ca n thay i t 8 n 11. M l cation ho tr +1 nh Cu+, Ga+, Tl+, In+, NH4+, H3O+, X l cc
cation Al3+, Ga3+, Fe3+. Quan trng nht trong cc loi hp cht ny l natri -Al2O3 (M l
Na+, X l Al3+) c bit t lu nh l mt sn phm ph khi sn xut thu tinh. Natri
-Al2O3 c hnh thnh trong ni thu tinh khi tng tc gia Na2O c trong khi nng chy
vi Al2O3 trong thnh phn gch chu la. Tn gi -Al2O3 rt d lm ngi ta nhm ln vi
mt dng th hnh ca tinh th Al2O3, nhng do thi quen dng t lu nn by gi khng
thay i na. Thc ra vai tr Na2O nh l mt tc nhn n nh cu trc tinh th ca loi hp
cht ny. Hnh 29 trnh by mng anion trong -Al2O3. Trn hnh ny cho thy c 4 lp oxi
gi ghm chc c li c mt lp ch c 1/4 ion O2 cn 3/4 v tr O2 trng. Cc ion Na+
c phn b trong lp thiu oxi . Do bn knh ion O2 rt ln hn bn knh ca Na+, mt
khc lp ny rt rng nn Na+ chuyn ng kh d dng theo mt phng ca lp ny.

B
A
C
B
A
C
A
B
C
A
B
A
C
B

Sp

Sp

Sp

A
C
Hnh 29
Cc lp oxi xp kht trong -Al2O3

Mng tinh th -Al2O3 cha cc bloc tng t spinen (Sp). Bloc Sp gm 4 lp oxi gi
ghm chc c lun phin theo th t ABCA c trng ca cu trc lp phng. Ion Al3+
chim mt s v tr t din v bt din gia hai lp oxi. Cc bloc Sp tch bit nhau bng mt
lp thiu oxi, ion Na+ nh v trong lp thiu oxi . T bo mng li lc phng c cc
thng s a = 5,60, c = 22,50. Cc lp oxi trc giao vi trc c. T bo ca -Al2O3 c cha
2 bloc Sp. Cu trc spinen y c xem nh cu trc MgAl2O4 cha khuyt tt (xem hnh
35). Trong spinen MgAl2O4 c t l ion Mg2+ v Al3+ l 1 : 2 trong khi spinen ca -Al2O3
ch c Al3+ (khng k n cc ion hp kim ho nh Li+, Na+), do cn bng in tch
trong cc bloc spinen phi c cha cc l trng Al3+.
Tinh th ca cc oxit t him c mc oxi ho +3 thng dng trong vt liu gm c cu
trc khc vi cu trc corun v bn knh Ln3+ ln hn bn knh ca Al3+. Theo Holsmit, c th
phn thnh 3 loi oxit t him: loi A c cu trc mt thoi hoc lc phng, loi B thuc h
n t, loi C thuc h lp phng. Oxit t him cng c nhiu dng th hnh.

20

Bng 7
Tnh cht ca cc dng th hnh ca Al2O3
Dng th

H tinh

hnh

th

-Al2O3

lc phng

(corun)
-Al2O3

Dng

lp
phng

(g/cm )

Bn, mt
thoi

lc phng

-Al2O3

Ch s khc

ng

np

3,99

1,786

1,76

3,33,4

1,680

1,65

Bin ho khi
nung
o
2050 C nng

chy
o
1600 C thnh

Bt din

1200 C thnh

3,6

Loi A (kiu La2O3) c La2O3, Ce2O3, Pr2O3.

Loi B c Ge2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Cd2O3, Lu2O3, Tb2O3, Dy2O3
(trn 2000oC).
Loi C (kiu Tl2O3 hoc Mn2O3) c: Sm2O3, Eu2O3, Cd2O3, Lu2O3, Tb2O3,
Dy2O3, Ho2O3, Er2O3, Tu2O3, Yb2O3.

Cc oxit Sc2O3, Y2O3, In2O3 v Tl2O3 cng c cu trc loi C nh oxit t him (thuc h
lp phng, mi t bo c 16 phn t).

1.2.1.3 Oxit c cng thc MO2

Tu thuc vo t l rcation/ranion hp cht loi ny c 3 kiu cu trc l kiu florit (CaF2),
kiu rutin (TiO2) v kiu oxit silic (SiO2).
Kiu florit: Cc anion chim hc t din trong phn mng lp phng mt tm ca
cation. Hay c th hnh dung khi phn chia mang c s lp phng mt tm ca cation
thnh 8 khi lp phng b bng nhau th cc anion nm tm ca 8 khi lp phng b .
SPT ca cation bng 8 cn ca anion bng 4. Mi t bo c 4 phn t AB2.

Oxit, sunfua, selenua kim loi ho tr mt c cu trc kiu antiflorit, ngha l vn ging
kiu florit CaF2 nhng y v tr ca ion canxi li do ion oxi chim, cn v tr ca ion flo th
cation kim loi kim chim.

Ti
O
Ca

(a)

(c)

(b)

Si
O

21

Hnh 30
T bo ca cc hp cht c cng thc AB2a) kiu florit, b) kiu rutin, c) kiu silic oxit (cristobalit)

Bng 8
Cc hp cht c cu trc florit v antiflorit
florit
Hp

a ()

cht

antiflorit
Hp

a ()

Hp

cht

a ()

Hp

cht

a ()

cht

CaF2

5,4626

PbO2

5,3490

Li2O

4,6114

K2O

6,449

SrF2

5,8000

CeO2

5,4110

Li2S

5,7100

K2 S

7,406

SrCl2

6,9767

PrO2

5,3920

Li2Se

6,0020

K2Se

7,962

BaF2

6,2001

ThO2

5,6000

Li2Te

6,5170

K2Te

8,168

BaCl2

7,3110

UO2

5,3720

Na2O

5,5550

Rb2O

6,740

CdF2

5,3895

NpO2

5,4334

Na2S

6,5390

Rb2S

7,650

HgF2

5,5373

PuO2

5,3860

Na2Se

6,823

Kiu rutin TiO2: T bo mng li thuc h t phng khi tm ca cation Ti4+ cn

anion to thnh bt din u bao quanh titan (2 ion oxi nm mt trn dc theo mt ng
cho, 2 ion oxi nm mt di cng theo hng ng cho , 2 ion oxi na nm ngay
trong t bo nhng theo hng ng cho khc). Mi t bo mng c 2 phn t TiO2. S
phi tr ca titan bng 6, cn ca oxi bng 3. To ca Ti l (0 0 0), (1/2 1/2 1/2) ca oxi l
(x x 0), ( x x 0), (1/2+x, 1/2-x, 1/2), (1/2-x, 1/2+x, 1/2). Kt qu thc nghim xc nh c x
= 0,3 (xem hnh 30b v 31).
Bng 9
Mt s hp cht c cu trc tinh th kiu rutin
Cht

a ()

c ()

Cht

a ()

c ()

TiO2

4,5937

2,9581

0,305

SnO2

4,7373

3,1864

0,307

CrO2

4,4100

2,9100

TaO2

4,7090

3,0650

GeO2

4,3950

2,8590

WO2

4,8600

2,7700

IrO2

4,4900

3,1400

CoF2

4,6951

3,1796

0,306

4,3960

2,8710

FeF2

4,6966

3,3091

0,300

MoO2

4,8600

2,7900

MgF2

4,6230

3,0520

0,303

NbO2

4,7700

2,9600

MnF2

4,8734

3,3099

0,305

OsO2

4,5100

3,1900

NiF2

4,6506

3,0836

0,302

PbO2

4,9460

3,3790

PbF2

4,9310

3,3670

RuO2

4,5100

3,1100

ZnF2

4,7034

3,1335

0,307
0,302

MnO2

0,303

C th m t cu trc mng tinh th rutin theo kiu xp kht nh hnh 31. Phn mng
anion oxi xp kht theo kiu lc phng (ABAB). Cation titan chim 1/2 s hc bt din theo
trt t: c mt dy hc bt din b trng n mt dy hc bt din b chim ht. Trt t ny
thay i lun phin theo 1/2 n v ca c.
Kiu silic oxit

22

Silic oxit (SiO2) c nhiu dng th hnh, y ni v mt trong cc dng gi l

cristobalit (hnh 30c). Cristobalit thuc h lp phng. Nguyn t Si chim cc nh, tm cc
mt v 4 trong 8 hc t din theo hai hng ng cho khc nhau (hoc c th hnh dung
chia khi hnh lp phng thnh 8 khi lp phng nh bng nhau th Si l tm ca 4 khi lp
phng nh ). Oxi l cu ni gia cc nguyn t silic. Mi t bo c 8 phn t SiO2. S
phi tr ca Si bng 4, ca oxi bng 2.
Ngoi cristobalit ra SiO2 cn rt nhiu dng hnh th khc na l: thch anh, tridimit,
cristobalit.
Mi dng chnh nh vy cn tn ti di nhiu dng ph.
Cc dng n tinh: cancedoan, m no, jat (ngc).
Dng v nh hnh: thu tinh thch anh, opal.
b
c

a
a

(b)
To cc nguyn t

Ti4+ 0, 0, 0 - 0.5, 0.5, 0.5

(a)

O2- 0, 0.3, 0.3 - 0, 0.7, 0.7

0.8, 0.2, 0.5 - 0.2, 0.8, 0.5
Hnh31
a) Cu trc rutin biu din theo mt phng xp kht ca ion oxi
b) Hnh chiu ca t bo mng rutin trn mt y

m t cu trc ca cc dng SiO2 th tt nht l dng phng php ghp cc t din

vi nhau qua nh oxi chung (hnh 32). im khc nhau ca 3 dng tinh th chnh (thch anh,
tridimit, cristobalit) l v tr tng i ca 2 t din SiO44 (hnh 33).
thch anh ta c gc lin kt Si-O-Si bng 150o, tridimit, v cristobalit th gc lin
kt Si-O-Si bng 180o. T thch anh bin thnh cristobalit ch cn nn thng gc Si-O-Si t
150o thnh 180o, trong khi chuyn thnh tridimit th ngoi vic nn thng gc ny cn
phi xoay t din SiO44 quanh trc i xng mt gc bng 180o

23

TT+
T+

TT+

TT+
T-

Hnh 32
Cch ghp cc t din SiO4 ( Si4+, { O2-)

C'

C'

A'
D

C
B

(a)

A'

) 150o

B'

B'

B'

A'

C'

C
B

(b)

C
B

(c)

Hnh 33
S t hp hai t din SiO4
a) Thch anh; b) Cristobalit ; c) Tridimit

S khc nhau ca cc dng th hnh th cp , , ch do mc khc nhau ca gc lin

kt Si-O-Si .
Qu trnh chuyn ho ca cc dng th hnh -thch anh -tridimit -cristobalit
u l qu trnh c bin, cn qu trnh chuyn ho cc dng th hnh th cp u
l qu trnh h bin.

24

tridimit
117

Thch an h
o
57 3 C
Thch anh

tridimit
o
163 C
870

tridimit

1050

1470

cristobalit
253
o

cristobalit

1728

Nng chy

Hnh 34
S biu din s chuyn ho gia cc dng th hnh ca SiO2

Trong thc t nhit chuyn ho cc dng th hnh ca SiO2 cn ph thuc vo nhiu

yu t nh s c mt ca nhiu cht khong ho, ch nng nhit v.v Trn y ch nu
ln cc dng th hnh ca SiO2 p sut kh quyn. Di p sut cao cn c cc dng th
hnh khc na (xem gin trng thi ca SiO2 hnh 92 v bng 30).

1.2.2 Hp cht gia cc oxit

1.2.2.1 Spinen
Spinen l tn gi khong vt c cng thc MgAl2O4. C th xem spinen nh l hp cht
ca hai oxit: oxit baz ca kim loi ho tr 2 v oxit lng tnh ca kim loi ha tr 3.
MgO + Al2O3 = MgAl2O4
Spinen l i din cho mt lot cc hp cht c cng thc tng qut AB2O4. Trong A
l cation ho tr 2 v B l cation ho tr 3. Mng li spinen gm cc ion oxi gi ghm chc
c lp phng mt tm, cc cation A2+ v B3+ c sp xp vo cc hc t din v bt din
(T+, T , O). Mi t bo mng gm 8 phn t AB2O4, ngha l c 8 khi lp phng b (hnh
35) trong c 32 ion oxi, 8 cation A2+ v 16 cation B3+. Ta c th tnh ton s cation, s
anion v s hc t din T, s hc bt din O khi tng tng ghp 8 khi lp phng tm mt
li vi nhau.

Hnh 35
T bo mng ca spinen

S ion oxi gm:

25

8 nh ca lp phng ln:

8 1/8 = 1

6 mt lp phng ln :

6 1/2 = 3

12 mt nh trong lp phng: 12 1

= 12

Tng s c 32 oxi

24 1/2 = 12

24 mt nh pha ngoi :

12 cnh ca lp phng ln: 12 1/4 = 3

Tm ca lp phng ln

=1

S hc T (cn gi l phn mng A). Mi lp phng nh c 8 hc t din nm trong lp

phng . T bo mng spinen c 8 lp phng nh. Nh vy mi t bo spinen c 8 8 =
64 hc T.
S hc O (cn gi l phn mng B) gm:
8 tm ca 8 lp phng b:

81 = 8

24 cnh bin ca lp phng b:

24 1/4 = 6

24 cnh gia ca 6 mt bin:

Tng s hc O l 32
24 1/2 = 12

6 cnh nm trong lp phng:

61 =6

Nh vy, mi tinh th spinen c 64 + 32 = 96 hc T v O. M s cation ch c 8 + 16 =

24 cation. Ngha l ch 1/4 s hc trng cha cation, cn 3/4 hc trng khng.
Nu 8 cation A nm trong 8 hc trng T, cn 16 cation B nm vo hc O th gi l mng
li spinen thun, k hiu A[BB]O4.
Nu 8 cation A nm trong 8 hc trng O, cn 16 cation B phn lm hai: 8 cation nm vo
hc T, 8 cation nm vo hc O th gi l spinen nghch o, k hiu B[A.B]O4.
Nu 24 cation A v B c phn b mt cch thng k vo cc hc T v hc O th gi l
spinen trung gian.
B13-+x A 2x+ A12-+x B13++x O4 vi 0 < x <1

Kt qu nghin cu cho thy cu trc lp phng tm mt ca phn mng oxi b bin

dng khi cation chui vo hc T v hc O. Th tch hc T b hn th tch hc O nn khi cation
chui vo phn mng A lm cho khng gian ca hc T tng ln bng cch ni rng c 4 ion oxi
(gin n khng gian t din). c trng cho s gin n khng gian t din ngi ta a
vo mt khi nim gi l thng s oxi. Thng s oxi c xc nh bng phng php ghi
gin nhiu x tia X hoc gin ntron. S chuyn dch ion oxi nh vy lm tng th tch
khng gian t din v gim th tch khng gian bt din, kt qu lm cho th tch ca chng
gn bng nhau.
Mi lin h gia thng s oxi (W) v kch thc hc T (rA), kch thc hc trng O (rB)
c biu din bng h thc:
rA = (W 0,25) a 3 rO

(7)

rB = (0,625 W) a rO

(8)

Trng hp mng li lp phng l tng th W = 0,375.

26

a l hng s mng li spinen (), rA v rB l bn knh khi cu nm trong khng gian t

din v khng gian bt din, rO l bn knh oxi.
S tinh th kt tinh theo mng li spinen kh ph bin trong hp cht v c. Trong cng
thc tng qut AB2O4 th A2+ c th l Cu, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, Pb, Fe, Co, Ni.
Cation B3+ c th l Al, Cr, Fe, Mn, t khi gp Ga, In, La, V, Sb, Rh. T hp cc cation li
cho thy c rt nhiu hp cht spinen. Tuy nhin cng cn phi ni thm rng khng phi tt
c cc hp cht c cng thc AB2O4 u kt tinh theo h lp phng nh spinen. V d nh
BeAl2O4, CaCr2O4 thuc h hnh thoi, cn SrAl2O4 thuc h t phng. Trong khi mt s
hp cht oxit ng vi cng thc A2BO4 (ng vi A2+, B4+), v d Mg2TiO4 li kt tinh theo h
lp phng v c sp xp vo nhm spinen. l cc hp cht nh titanat, stanat ca
coban, st(II), magi, km, Ngoi cc oxit phc tp ra, cn c cc spinen c anion l
chalcogen (S2, Se2, Te2) hoc halogen. V d Li2NiF4.
Do kh nng thay th ng hnh, ng ho tr hoc khng ng ho tr cc cation trong
spinen oxit lm cho s lng hp cht spinen tng ln rt ln.
V d t hp cc cation trong spinen oxit cho ta cc loi sau:
Spinen

MgAl2O4

Mg2TiO4

LiAlTiO4

Li0,5Al2,5O4

LiNiVO4

Na2WO4

2;3

2;4

1;3;4

1;3

1;2;5

1;6

T hp cation

Cc hp cht spinen c gi tr rt ln trong k thut. Chng c s dng lm bt mu,

vt liu chu la, vt liu k thut in t, qu, Do vn nghin cu tng hp
spinen v cc tnh cht, c, in ca chng l i tng nghin cu ca nhiu nh khoa hc.
Theo dn in, c th nh gi c cu to bn trong ca spinen. V d Fe3O4 v Mn3O4
u c cu trc spinen, nhng trong khi Mn3O4 l cht in mi (khng dn in) cn Fe3O4
li c dn in cao nh kim loi. l do Fe3O4 c cu trc spinen o:
Fe3+T[Fe2+Fe3+]OO4, cn Mn3O4 c cu trc spinen thun: Mn2+T[Mn23+]OO4. Trong mng tinh
th spinen Fe3O4, cc ion Fe2+ v Fe3+ c phn b trong cc bt din. Cc bt din ny tip
xc vi nhau theo mt cnh chung, do cation st c mc oxi ho khc nhau m gn nhau
nn trao i in tch d dng, l trng dng c th chuyn t Fe2+ sang Fe3+. Cn mng tinh
th spinen Mn3O4 th Mn3+ nm trong bt din, Mn2+ nm trong t din. Bt din v t din
ch tip xc vi nhau qua nh, ngha l cc cation Mn3+ v Mn2+ nm cch xa nhau hn so
vi khong cch Fe2+ v Fe3+ trong Fe3O4. iu ny lm cho s trao i in tch trong
Mn3O4 kh khn hn nhiu.
Bng 10
Tnh cht ca mt s spinen
Gin n

Cng thc

Tinh th

a ()

cng

d (g/cm3)

tonc

MgAl2O4

Lp

(8,09)

3,57

2135

0,593

75,3.104

5
(-10 )

R(900oC)

phng
ZnAl2O4

-nt-

(8,09)

7,5-8

4,58

1930

0,596

18,6.104

CoAl2O4

-nt-

(8,1)

>7

4,37

1960

11,7.104

NiAl2O4

-nt-

(8,04)

4,45

2020

36,4.104

CuAl2O4

-nt-

4,58

Khng tng hp

MnAl2O4

-nt-

4,12

FeCr2O4

-nt-

>7

4,392

1780

0,90

27

MgCr2O4

-nt-

(8,31)

4,429

2330

0,96

10,3.102

ZnCr2O4

-nt-

(8,31)

>7

5,393

97,2.102

FeCr2O4

-nt-

(8,34)

4,998

2180

0,85

54,7.10

CoCr2O4

-nt-

(8,31)

5,580

40,1.10

NiCr2O4

-nt-

5,160

MnCr2O4

-nt-

>7

4,870

CuFe2O4

-nt-

5,700

MgFe2O4

-nt-

(8,36)

6,65

4,560

1750

1,15

25,1

ZnFe2O4

-nt-

(8,42)

6,5

5,330

78,0

CdFe2O4

-nt-

5,800

MnFe2O4

-nt-

4,900

FeFe2O4

-nt-

(8,40)

5,210

1598

1,53

5,4(300o)

NiFe2O4

-nt-

(8,35)

5,340

CoCo2O4

-nt-

MgCo2O4

-nt-

MgV2O4

-nt-

CaV2O4

-nt-

MnV2O4

-nt-

BeAl2O4

Hnh thoi

51,3

6,073

P.hu

4,960

4,240

4,570

(8,52)

8,5

3,720

1870

0,573

(8,42)

ph
BaAl2O4

Lp

>6

3,560

1820

phng
Mg2TiO4

Lp

1,12

phng
Zn2TiO4

Lp

5,360

phng
Mn2SnO4

Lp

4,640

1850

phng

Vai tr ca s xen ph obitan d cng nh hng mnh n tnh dn in. V d spinen

LiMn2O4 v LiV2O4 u c cu trc ging nhau l Li[Mn3+Mn4+]O4, Li[V3+V4+]O4.
Trong c hai spinen, v tr bt din u cha ng thi mt loi cation c mc oxi
ho khc nhau l +3 v +4. Tuy nhin, s xen ph d trong vanai ln hn trong mangan, iu
ny c phn nh tnh cht in, LiMn2O4 l cht bn dn theo c ch nhy, cn LiV2O4
l cht dn in kiu kim loi.
Vn nghin cu tng hp spinen v nghin cu tnh cht quang, c nhit, in, t ca
chng l i tng ca nhiu nh ho hc v c. Theo dn in c th nh gi gin tip
v cu to bn trong ca spinen cng nh ca dung dch rn spinen. V dn in th c th
xp cc spinen thuc v loi hp cht bn dn v c th phn thnh 3 nhm:
Aluminat c dn in rt b (in tr ring 990oC R = 105106 m.cm),
cromit c dn in trung bnh (R 990oC t 103104 m.cm), ferit c dn
in cao (R 990oC t 10102 m.cm) ring FeFe2O4 c dn in gn bng
dn in ca kim loi.

28

Trong aluminat, tnh dn in c quyt nh bi cation ho tr 2, cn cromit v ferit (tr

hp cht FeO) li c quyt nh bi cation ho tr 3.
Mt trong cc c tnh quan trng ca spinen l d dng to thnh dung dch rn thay th
vi nhau do thng s mng ca chng gn bng nhau.
V d, cc h spinen MgAl2O4-MgCr2O4, FeCr2O4-FeFe2O4 c gin trng thi thuc
kiu tnh tan khng hn ch. Cromit cng d trn ln vi ferit. Mt s spinen c th to dung
dch rn vi nhm oxit, c bit vi -Al2O3 c mng li ging vi mng li tinh th ca
spinen. Ni chung, tnh cht ca spinen c quyt nh bi tnh cht v hm lng ca cc
oxit hp phn. Khi tng hp spinen hoc khi hnh thnh dung dch kiu spinen u c s tng
th tch ca pha tinh th. Mt nt c trng cn quan tm l phn ng thay th trong spinen, v
d cc aluminat vi oxit c 3 kiu tng tc:
1) MgO + BeAl2O4 = MgAl2O4 + BeO
2) MgO + NiAl2O4 = (Ni,Mg)O + (Mg,Ni)Al2O4
3) Cc aluminat trn ln hon ton cn cc oxit th trn ln khng hon ton. V d trong
cc h oxit km.
c tnh rt quan trng i vi k thut ca spinen l chu la cao, bn vi cc tc
nhn oxi ho cng nh tc nhn kh (xem bng 10).
Trong cc spinen trn y th FeFe2O4 c ngha quan trng nht, trong st hai mc
oxi ho l II v III. Da vo kt qu nghin cu dn in v t tnh c th kt lun c rng
FeFe2O4 thuc kiu spinen nghch o, ngha l FeII nm trong hc O cn FeIII mt na nm
trong hc O, mt na nm trong hc T.
Vi cc ferit c th biu din bng cng thc tng qut sau:

M 2x+ Fe13_+x [M12_+x Fe13++x ]O4

Trong cation nm trong hc T c t ngoi du mc, cn nm trong hc O th
trong du mc.
Khi x = 1 ta c spinen thun, x = 0 ta c spinen nghch o. Spinen trung gian th 0 < x <
1. i lng x gi l mc nghch o ca spinen cho bit lng M2+ nm trong hc T. S
ph thuc gia mc nghch o v nhit c th biu din bng h thc:
_
x(1 + x)
= e E / kT
_
2
(1 x)

(9)

k l hng s Bonzman, T l nhit tuyt i, E l bin thin nng lng t do ca

phn ng:

M 2B+ + Fe 3A+ = M 2A+ + Fe 3B+ E

trong : A, B ch phn mng A v phn mng B trong AB2O4.
Nh vy, mc nghch o lin quan n iu kin ch ho nhit ca ferit. Kt qu
nghin cu bng phng php nhiu x ntron cho thy cu trc ca spinen thun c ferit km
v ferit caimi Zn[Fe2O4], Cd[Fe2O4]. Spinen nghch o c Fe3+[Fe2+Fe3+O4], Fe3+[CoFe3+O4],
Fe3+[NiFe3+O4], Fe3+[Li0,5Fe1,5O4]. Spinen trung gian gn thun (x = 0,8) Mn0,8 Fe0,2[Mn0,2Fe1,8O4].
Spinen trung gian gn nghch (x = 0,1) Mn0,1Fe0,9[Mn0,9Fe1,1O4].

29

C ba yu t nh hng n s phn b cc cation A v B vo v tr t din, bt din.

a) Bn knh ion: Hc T c th tch b hn hc O do ch yu cc cation c kch thc
b hn c phn b vo hc T. Thng thng rA2+ ln hn rB3+ ngha l xu th ch yu l to
thnh spinen nghch o.
b) Cu hnh electron: Tu thuc vo cu hnh electron ca cation m chng thch hp vi
mt kiu phi tr nht nh. V d Zn2+, Cd2+ (c cu hnh 3d10) ch yu chim cc hc T v
to nn spinen thun, cn Fe2+ v Ni2+ (c cu hnh 3d6 v 3d8) li chim hc O v to thnh
spinen nghch o.
c) Nng lng tnh in: Nng lng tnh in ca mng spinen (nng lng Madelung)
to nn bi s gn nhau ca cc ion khi to thnh cu trc spinen. S phn b sao cho cc
cation A2+ nm vo hc T, B3+ nm vo hc O l thun li v nng lng nht.

1.2.2.2 Perpkit
Perpkit l tn gi ca khong vt c cng thc CaTiO3. Mng li ca perpkit thuc h
lp phng, cation titan nm tm lp phng, 6 ion oxi nm tm cc mt, 8 ion canxi nm
cc nh (hnh 36). Mi t bo c cha mt phn t CaTiO3.

Hnh 36
T bo mng CaTiO3

Cng c th m t t bo perpkit theo mt cch khc. V d t bo mng ca SrTiO3 nh

trn hnh 37a cho ta thy:
Ion titan nm cc nh, c to (0, 0, 0) c s phi tr bng 6; di lin kt Ti O
bng a/2 = 3,905/2 = 1,956.
Ion sronti tm t bo, c to (1/2, 1/2, 1/2). S phi tr 12, khong cch Sr O bng
2
a
= 2,76 , ion oxi nm tm cc cnh c to (0, 0, 1/2). Mi ion oxi c bao quanh
2
bng 2 ion titan (vi khong cch 1,953) v 4 ion Sr (vi khong cch 2,76). Trong cu
trc perpkit cc ion oxi khng to thnh mt phng xp kht nht, nhng cng vi ion Sr to
thnh mt phng xp kht nht. thy r iu ny nn so snh vi mng li NaCl. y
ion Cl nm gia cc cnh v tm ca t bo. Trn hnh 37b c v mt phng xp kht theo
kiu lp phng. Mt phng cha ion Sr (nh s 1) v 6 ion oxi (nh s 2, 3, 4, 5, 6, 7).
Mt phng ny song song vi mt phng 111 cha ion Ti A, B, C.

30

Trong mt xp kht ion Sr chim 1/4 nguyn t, cn 3/4 l ion oxi. Kiu cu trc perpkit
bao gm mt s ln hp cht v c cng thc tng qut ABX3, trong X c th l ion oxi
hoc halogen.
Trng hp chung A l cation c kch thc ln, B l cation c kch thc b. Cation A
cng vi X to thnh kiu gi ghm chc c lp phng mt tm, cn ion vi kch thc b
B nm tm khi lp phng . Tng in tch dng ca A v B phi bng tng in tch
m ca X. Do cc t hp c th c ca hp cht ABO3 l +1 v +5, +2 v +4, +3 v +3 vi
hp cht ABX3 (X l halogen) ch c mt trng hp duy nht l +1 v +2.
Bng 11 gii thiu mt s hp cht kt tinh theo kiu perpkit. Hp cht c cu trc
perpkit ng vai tr quan trng trong vt liu p in, vt liu bn dn. Hu ht hp cht
perpkit c cng thc ABO3 u c tnh cht xecnhet in. Theo Holsmit th gia tnh cht
xecnhet in v cu trc perpkit ABO3 c mi lin h c nh gi bng yu t tlrng (t).
t=

rA + rO
2(rB + rO )

(10)

Ti

Sr

3
4

y
5

(b)

Ti4+,

(a)

Sr2+,

O2-

Hnh 37
a) T bo mng ca SrTiO3; b) mt xp kht

Bng 11
Cc hp cht kt tinh theo kiu perpkit
in tch cation

Hp cht perpkit

+1 v +5

NaNbO3, KNbO3, AgNbO3, AgTaO3,

+2 v +4

SrTiO3, SrZrO3, SrHfO3, SrSnO3, BaTiO3, BaZrO3,

BaSnO3, BaCeO3, BaPrO3, BaThO3

+3 v +3

LaAlO3, TiTiO3, LaCrO3, LaMnO3, LaFeO3

+1 v +2

KMgF3, KNiF3, KZnF3

Yu t tlrng t ny nm trong khong 0,95 n 1 th ta c cu trc lp phng v c

tnh xecnhet in, t nh hn 0,95 th thuc loi lp phng bin dng v khng c tnh
xecnhet in.

31

y, cn lu mt iu l trong tnh ton chng ta xut pht t quan nim cho rng
lin kt trong perpkit thun tu l lin kt ion. Nh trn chng ta u bit iu ny khng
thc s ng, do khng th p dng quy tc ca Golsmit mt cch my mc c.
Trong mng li tinh th perpkit thng c l trng cation A, cn cation B th hu nh
cha gp l trng. C th xem cu trc ca WO3 thuc dng perpkit m khng c cation A.
Hp cht NaxWO4 (x = 0,3 1) c mng li n gin cu trc perpkit bin dng trong mi
gi tr ca x.
Ngi ta cng gp perpkit c l trng anion. V d titanatsronti c cng thc SrTiO2,5
ng hnh vi cu trc lp phng ca SrTiO3, trong c l trng O2.
Mt trong cc hp cht quan trng ca nhm perpkit l BaTiO3. y l cht p in u
tin thu c di dng gm v c s dng rng ri trong k thut hin i.
Bari titanat c 2 dng th hnh chnh. Trn 1460oC barititanat tn ti di dng lc
phng, khng c tnh p in; di 1460oC chuyn thnh dng lp phng v c tnh p
in. Nhng khi lm ngui xung di 1460oC dng lc phng c th cha chuyn thnh
lp phng v tn ti dng khng bn n nhit phng. Mt tnh cht l th ca dng lp
phng l bin ho mng li khi thay i nhit .
Khi lm lnh n 120oC, t bo perpkit b ko di theo mt cnh lm cho mng li t
lp phng bin thnh t phng, c/a ln hn 1. S chuyn pha lc ny km theo bin i bt
thng v in mi chng t c pht sinh s phn cc ca t bo. Lm lnh tip tc n 0oC
li xy ra bin ho th hnh th hai. S thay i cu trc lc ny c th hnh dung nh ko di
khi lp phng dc theo ng cho ca mt mt bn. nhit thp hn na (-90oC) c
s bin ho th hnh th 3, ln ny t bo b ko di theo ng cho ca khi lp phng to
thnh khi mt thoi (xem hnh 38).
tt c ba nhit hng ca momen lng cc xecnhet in u song song vi
hng ko di t bo mng. l do s chuyn dch v tr ca ion titan trong bt din oxi.
Ban u khi h nhit s hng v pha mt ion oxi, sau hng v pha gia hai ion oxi
v cui cng hng v gia ba ion oxi. Cch gii thch ny c Kay H. F. v Vonsden
a ra t nm 1949.
Cng nh spinen, cc hp cht c cu trc perpkit c th to thnh dung dch rn thay
th vi nhau trong mt gii hn rt ln. V d PbTiO3, SrTiO3, BaZrO3, BaSnO3, BaHfO3,
KNbO3, c th to thnh dy dung dch rn khng hn ch vi BaTiO3.

32

Lp phng
o

a1 = a2 = a3 = 4,009 A
a3

a2
a1

120 oC

130oC: a1 = a2 = 4,003 A
o
c = 4,022 A

T phng

0oC: a1 = a2 = 3,992 A
o
c = 4,035 A

a2
a1

0oC n t
c

Hnh thoi

a2
a1

0oC:
o
a' = 5,667 A
o
b' = 5,681 A
o
c' = 3,898 A

-90oC Mt thoi

a3

0oC: a1 = a2 = 4,012 Ao
c = 3,989 A
o
= 89 51'
o

-90oC: a1 = a2 = a3 = 3,998 A
= 89o52'

a2
a1

-90oC:
o
a' = 5,668 A
o
b' = 5,683 A
o
c' = 3,876 A

Hnh 38
Bin ho ca t bo mng BaTiO3

S thay th Ba2+, Ti4+ trong barititanat bng cc cation ho tr 2 v bng Zr4+ c th ci

thin nhiu tnh cht vt l ca gm p in bari titanat. Gm PZT l mt loi dung dch rn
nh vy. y Pb2+ thay th Ba2+ cn Zr4+ thay th Ti4+, loi gm PZT hin ti vn cn gi
vai tr trong k thut.

1.2.2.3 Pyrclo A2B2O7.

Pyrclo l tn gi ca nhm khong vt cha t him c cng thc khng n nh
(Na,Ca,)2(Nb,Ti)2O6.F.OH. Ch pyros t gc Hylp c ngha l la, cloros c ngha l
mu lc. Loi khong vt ny khi th bng phn ng ng thi th c mu lc. Thnh phn
khong vt ny rt khng n nh (bng 12).
Bng 12
Thnh phn ca mt s mu khong vt pyrclo
Cht

Hm lng

Cht

(%)

Hm lng

Cht

(%)

Nb2O5

063

Na2O

Ta2O5

077

K2O

TiO2

213

ThO2

Hm lng
(%)

(Ce,La)2O3

215,3

01,4

(Y,Er)2O3

05,1

CaO

418,1

SnO2

04,1

05

MnO

07,7

ZrO2

05,7

UO2

011,4

FeO

010

WO3

00,3

UO3

015,5

Fe2O3

09,8

H2O

06

16

Ngoi ra cn cha mt t Sb2O5, MgO, PbO, HfO2, SiO2, Al2O3, SrO, BeO, CuO, GeO2.

33

Hnh 39
Cu trc pyrclo Er2Ti2O7

Khong vt pyrclo thuc h lp phng. Mng tinh th tng t florit CaF2. Khi chuyn
t florit thnh pyrclo th v tr ca F b chim bi O2. Nhng mi t bo mng c mt ion
O2 b khuyt, 7 ion O2 cn li b chuyn dch lm cho v tr l tng ban u bin i. Trong
cng thc tng qut ca pyrclo A2B2O7 th A l cation c kch thc ln hn c bao
quanh bng 8 ion O2 to thnh mt khi lp phng bin dng. Cation nh B4+ nm trong bt
din dng BO68. Cc bt din BO6 ni vi nhau qua nh to thnh mt dy dy xch dc gn
song song vi nhau. Cc dy xch ny li ni vi nhau qua bt din BO6 lp nn dy dy
xch ngang trc giao vi dy dy xch dc (hnh 39).
V tr trung gian gia cc bt din BO6 c xp bng cc ion A. Nhm pyrclo c gi tr
nht trong vt liu mi l titanat t him c cng thc tng qut l Ln2Ti2O7. Theo tnh ton
ca nhiu tc gi th ch c nhng nguyn t t him no c bn knh tho mn h thc:
1,22 <

rLn3+
rTi4+

< 1,5

th hp cht titanat mi c cu trc pyrclo.

Bng 13 cho bit bn knh ca cc ion t him v t s

rLn3+
rTi4+

(rTi4+=0,64).

Bng 13
Bn knh ca mt s cation t him
Ion

La3+

Ce3+

Pr3+

Nd3+

Pm3+

Sm3+

Eu3+

r ()

1,061

1,034

1,013

0,995

0,979

0,964

0,050

rLn3+/rTi4+

1,660

1,610

1,580

1,550

1,530

1,500

1,480

Ion

Gd3+

Tb3+

Dy3+

Ho3+

Er3+

Tm3+

Yb3+

Lu3+

r ()

0,938

0,923

0,908

0,894

0,889

0,899

0,858

0,84

rLn3+/rTi4+

1,460

1,440

1,420

1,400

1,390

1,390

1,34

1,32

34

Nh vy l t La n Pm th cc titanat Ln2Ti2O7 kt tinh theo h n t, cn tt c cc

t him cn li (t Sm n Lu) th titanat Ln2Ti2O7 kt tinh theo h lp phng kiu pyrclo.
Trong dy ny c s ph thuc tuyn tnh gia thng s mng a v bn knh ion Ln3+.
S chuyn t cu trc florit n pyrclo lm xut hin cc vch siu cu trc trn gin
tia X, c bit trn gin ph hng ngoi chng ta thy mt cch kh r rt s chuyn pha
pyrclo khi xt h titanat v zircnat t him (RZr4+) = 0,82 (xem hnh 40).

Hnh 40.
Ph hng ngoi ca titanat v zirconat t him

i vi h titanat, cc pic c trng cho cu trc pyrclo ch c t Sm n Lu. Cn vi

h zirconat th pic c trng cho pha pyrclo li ch thy i vi La, Pr, Nd, Sm, Eu, Gd, vi
cation t him c bn knh b hn Gd th khng to thnh pha c trt t.
c tnh ca pyrclo l tnh bt hp thc. Tnh bt hp thc y l do hai nguyn nhn.
a) C s thay th mt phn Ti4+ bng cc ion t him Ln3+, lc ny s xut hin l trng
b sung trong phn mng anion.
b) C s thay th mt phn Ln3+ bng Ti4+ .
Do cng thc tng qut ca pyrclo c th vit
Ln 2 x Ti 2 x O7 x / 2
3+

1 x / 2

4+

Nu thay th 1 ion Ln vo tr Ti th thiu mt in tch dng, m bo cn bng

v in phi loi ra mt in tch m, hay ni cch khc loi ra 1/2 v tr ion oxi, do lc u
ch c mt l trng ca ion oxi by gi thm 1/2 l trng oxi v cng thc tng qut s l:
Ln2+x Ti2-x O7-x/2

1+x/2

Trong dy titanat t him c nhiu cng trnh nghin cu kh k cu trc ca

Er2Ti2O7 v Y2Ti2O7 bng cc phng php nhiu x tia X v gin ntron. T bo mng
li ca Er2Ti2O7 c cha 16 Er3+, mi ion Er3+ c bao quanh bng 8 ion oxi trong 2 ion
nm v tr i din nhau v cch nhau mt khong 2,185,cn 6 ion oxi cn li nm trn
cng mt mt phng cch nhau 2,471 (hnh 39).

35

1.2.2.4 Pha siu dn 1:2:3

Gm siu dn nhit cao (gn 100 K) l loi vt liu mi c ra i vo cui nm
1986, hin nay nhp nghin cu quanh lnh vc ny ang c pht trin vi quy m cha
tng thy. Trong vng 4, 5 nm thp k 80 ca th k XX, mi nm c ti hng nghn cng
trnh nghin cu tng hp, nghin cu cu trc v cc tnh cht ca loi vt liu ny. Ti liu
s 9 trnh by tng quan v lnh vc ny cho n nm 1988.
Cho n nay bit c nhiu loi gm c tnh siu dn nhit cao, trong loi quan
trng nht c cng thc ng vi thnh phn RBa2Cu3O7-x. y R l Y hoc Ln. Ln lt
theo th t s nguyn t ytri, bari, ng trong cng thc ny, ngi ta gi tt l pha gm
1:2:3. Gm RBa2Cu3O7-x c cu trc tinh th thuc h hnh thoi. C th xem cu trc ca pha
ny nh l dn xut ca peropkit c nhn ba gi tr trc C theo trt t Ba-Y-Ba. T bo
mng ca pha 1:2:3 gm cc lp phng peropkit c nh l nguyn t Cu, hai lp phng c
tm l bari kp gia mt lp phng c tm l ytri.
c tnh quan trng cu cu trc pha 1:2:3 l v tr ca ng khng ging nhau do s b
tr cc l khuyt oxi. Nguyn t Cu v tr 1 l tm ca mt hnh vung trong mt phng bc.
Nh vy s phi tr ca nguyn t Cu ny l 4. Nguyn t Cu v tr th 2 nm trong khi
chp c y l hnh vung. Nh vy s phi tr ca nguyn t Cu ny l 5 (xem hnh 41).
Cc hnh chp CuO5 v mt CuO4 to thnh tng lp song song vi mt ab. Hai hnh
chp CuO5 kp gia mt lp CuO4. Hai hnh chp quay nh v pha hnh vung CuO4 v ni
vi nhau qua cu oxi.
Tu theo iu kin tng hp (c bit l p sut ring phn ca oxi trong h phn ng) s
l trng oxi thay i. Do h s ca oxi trong cng thc khng xc nh (bng 7-x) v trng
thi oxi ho ca ng cng thay i lm nh hng n tnh cht in ca gm.
Cuprat lantan La2CuO4 c cu trc tinh th ca K2NiF4 l cht bn dn nhng khi ch ho
nhit p sut ring phn PO2 cao, hoc to ra cc khuyt tt cation trong cc phn mng th
c th bin thnh trng thi siu dn 40K. C th gii thch iu ny nh sau: Hp cht
cuprat khi mi iu ch c cc khuyt tt stki (xem chng sau) va c l trng cation va
c l trng anion do sn phm thu c c cng thc La2-2xCu1-xO4-4x. p sut ring
phn cao ca oxi, th oxi c th lp y cc l trng anion, do mt s cation ng (II) s
chuyn thnh cc mc oxi ho cao La2-2xCu1-xO4.
Hoc c th iu ch pha siu dn cuprat lantan bng phn ng tng hp vi t l d
CuO di p sut bnh thng ca oxi. Lc ny giai on ban u to thnh cc l trng
anion v hnh thnh hp cht trung gian La1,9Cu2+O3,85. Hp cht ny c kh nng chim ly
oxi to nn La1,9Cu2+3+O4.
Phng php th ba to thnh cuprat siu dn l hp kim ho La2CuO4 bng cc oxit
kim th. V d hp kim ho bng sronti th thu c pha tinh th La2-xSrxCuO4 vi gi tr x
t 0,15 n 0,2. C th thay th Cu bng kim loi chuyn tip 3d khc.

36

(a)

(b)

(a)

(b)

Hnh 41
Cu trc ca pha siu dn 1:2:3 (YBa2Cu3O7x )
(a) v (a) thuc h hnh thoi; (b) v (b) thuc h t phng

1.2.2.5 Silicat
Silicat l loi hp cht ph bin nht trong v Qu t cng nh trong vt liu v c.
Cu trc ca silicat c to thnh t s gi ghm chc c cc ion oxi. Trong cc hc trng
ca b khung anion c sp xp cc cation kim loi v c bit ion Si4+ chim t l ln

37

nht. Tu thuc vo kch thc ca cation m chng c xp vo cc hc trng t din, bt

din, lp phng, lc phng. Cc silicat t nhin thng thng c cc cation Si4+, Al3+, Fe3+,
Cr3+, Mg2+, Fe2+, Ca2+, Na+, K+ Khi t l rc/ra nm gia 0,41 v 0,732 th cation c SPT 6,
khi t l nm gia 0,732 v 1 th cation c SPT 8. Bng 14 gii thiu SPT ca mt s
cation ch yu trong silicat.
Bng 14
Bn knh ion v s phi tr ca vi ion quan trng trong silicat
Nguyn
t

Ion

Bn knh ion ()
(h thng Paolinh)

rc/ra

SPT

n v cu trc

Oxi

O2+

1,36

Silic

4+

Si

0,39

0,29

t din

Al3+

0,57

0,42

t din

bt din

0,59

0,59

bt din

0,83

0,63

bt din

bt din

bt din

lp phng

Nhm

3+

Fe
St

Fe2+
Magi

Mg2+

0,78

0,57

Natri

Na+

0,98

0,725

2+

1,06

0,8

lp phng

1,33

1,0

12

lc phng

Canxi
Kali

Ca
K

Trong silicat c nhiu ion c th nm trong cc n v cu trc khc nhau. V d Al va

c th nm trong t din va c th nm trong bt din. Na va c th nm trong bt din va
c th nm trong khi lp phng
C th biu din mng li silicat bng cch sp xp cc khi t din SiO4 v bt din
M(OH)6 (M c th l Al3+, Mg2+, Fe3+ ) theo mng li 3 chiu trong khng gian. S hnh
thnh cc khong vt thng xy ra s thay th cation trong mng li. Bi vy, cng thc
khong vt thng c vit di dng tng qut. V d khong vt almanin thuc nhm
grnat c cng thc l thuyt l Fe32+ Al32+ [SiO 4 ]3 . Nhng v tr nt mng ca Al3+ c th thay
th bng Fe3+, v tr ca Fe2+ thng b thay th bng Mg2+, Mn2+, Ca2+. Kh nng thay th
ph thuc vo s c mt ca cation M2+, M3+ trong qu trnh hnh thnh mng li
almanin, nhit , pH Do cng thc khong vt almanin thng c vit di dng
tng qut: (Fe2+,Mg,Mn,Ca)3(Al,Fe)2[SiO4]3, trong cng thc ny cn hiu mt phn t c
cha tng s 3 cation M2+ v hai cation M3+. Nu kt qu phn tch pha (phng php nhiu
x tia X, phng php DTA, phng php hin vi phn cc) cho bit mu ca ta ch c mt
khong vt almanin duy nht, th t kt qu phn tch ho hc ca mu ta c th vit c
cng thc chnh xc ca phn t almanin. Sau y l phng php xc nh cng thc cu
to. V d t kt qu thnh phn ho hc bng 15 ta c:
C 2,472 nguyn t oxi th c 0,615 nguyn t silic, trong phn t almanin c 12
nguyn t oxi, vy mt phn t almanin c 2,985 hoc quy trn l 3 nguyn t silic. Cng
tnh nh vy ta c s nguyn t kim loi trong mt phn t almanin ghi ct 6 ca bng 15 v
cng thc cu to ca mu nghin cu l
(Fe2+2,315Mg0,366Mn0,169Ca0,155)(Al1,961Fe3+0,038)[SiO4]3.

38

T phn trm khi lng ca cc nguyn t trong mu nghin cu v cc thng s t bo

mng, t trng (g/cm3), ta c th tnh ton s nguyn t ca mi t bo mng. V d mu ca
chng ta c t trng l d, th tch ca mt t bo l V(3) hoc V.1024(cm3). Khi lng ca
mt t bo l V.d.1024g. Thnh phn phn trm khi lng ca nguyn t kho st l Q, tng
s phn trm ca cc nguyn t l T, ta tnh c khi lng ca nguyn t trong mt t
bo l Q.V.d.1024/T.
Bng 15
Thnh phn ho hc ca mu almanin
%khi lng S pt. oxit S cation
Oxit
(3)
(4)
(2)
(1)

S ion O2
(5)

(6)

SiO2

36,96

0,615

0,615

1,230

2,985 3

Al2O3

20,65

0,205

0,406

0,609

Fe2O3

0,70

0,004

0,008

0,012

1961
1,999 2
0.038

FeO

34,30

0,477

0,477

0,477

MnO

2,45

0,035

0,035

0,035

MgO

3,17

0,077

0,077

0,077

CaO

1,81

0,032

0,032

0,032

Tng

100,04

2,315
0.169
3,005 3
0,366
0,155

2,472

Nguyn t lng ca nguyn t l A. Nu gi s nguyn t c trong T gam mu l R

(gi tr ghi trong ct 4) th s nguyn t trong mt t bo l:
Z=

Q.V.d.10

24

A.1.6602.10

24

R.V.D
(16) v Q/A = R
1,6602.T

V d almanin c t bo mng thuc h lp phng, cnh a = 11,54. T trng d = 4,22

g/cm3. Trn bng 15 c tng l 100,04. Trong 100,04 gam mu c cha 2,472 nguyn t oxi
(R = 2,472). Do s nguyn t oxi c trong mt t bo l:
(11,54 ) 3 . 4 , 22 . 2 , 472
= 96 ,51
1, 6602 .100 , 04

Kt qu thu c l s l, iu ny l do sai s khi phn tch thnh phn ho hc, khi xc

nh gi tr a, d. Nhng kt qu kho st nhm khng gian ca h tinh th grnat cho thy s
nguyn t oxi, kim loi M2+, M3+, silic trong mt t bo nguyn t ch c th l 16, 24, 32, 48,
96. Vy y ta ly gi tr l 96.
Silicat c phn thnh cc lp sau y:
_

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 4+ (v d zircon ZrSiO4), hoc bng hai cation ho tr 2+ (v
d fosterit 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.

39

4
4

-3
-

2-

-3

Hnh 42
T din

SiO

44

4+

2-

trong mng octosilicat (y Si , {O )

Hnh 43
Sorosilicat

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 grnat (Ca,Fe,Mn,Mg)3(Al,Fe,Cr)2 [SiO4]3
Nhm silicat nhm Al2[OSiO4], topaz Al2[F2SiO4], v sphen CaTi[OSiO4]
Silimanit c ba dng th hnh u c cng thc chung Al2[OSiO4] gi l silimanit,
andaluzit, disten.
2) Sorosilicat: n v cu trc gm hai t din 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 [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.
V d epiot Ca2(Al,Fe)3[O.OH.SiO4.Si2O7 ]
v ircaz Ca10(Mg,Fe)2[(OH)4(SiO4)5(Si2O7)]
Bng 16.
Mt vi khong vt thuc lp octosilicat
Khong vt

Cng thc

H tinh th

Ch s khc x

Olivin

(Mg,Fe)2[SiO4]

hnh thoi

3,3

6,57,0

Zircon

ZrSiO4

t phng

4,7

7,5

Phenacit

Be2[SiO4]

mt thoi

34

7,58,0

1,641,67

Willemit

Zn2[SiO4]

mt thoi

3,94,2

5,5

1,691,72

Pyrop

Mg3Al2[SiO4]3

lp phng

3,51

7,07,5

1,70

Almanin

Fe3Al2[SiO4]3

lp phng

4,25

7,0

1,83

Spossartit

Mn3Al2[SiO4]3

lp phng

4,18

7,07,5

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

1,671,87
1,631,83
1,921,96
1,962,02

40

Silimanit+

Al2[OSiO4]

hnh thoi

3,30

67

1,671,65

clas

AlBe[OHSiO4]

n t

3,10

7,5

1,671,65

Topaz

Al2(F,OH)2SiO4

hnh thoi

3,43,6

8,0

1,621,61

Sphen

CaTi[(OSiO4)]

n t

3,50

5,5

2,091,90

Datolit

CaB[(OH)SiO4]

n t

2,83

55,5

1,671,63

3) Xiclosilicat (silicat mch vng)

Bng 17
Mt vi khong vt thuc lp silicat vng
Tn

Cng thc

H tinh th

Ch s

Benitit

BaTi[Si3O9]

Lc phng

3,7

6,5

Catapleit

Na2Zn[Si3O9]

Lc phng

2,8

6,0

Endialit

(Na,Ca,Fe)6Zr[OH.Si3O9]

Mt thoi

3,0

5,5

Axinit

Ca2(Fe,Mn)Al2[OH.BO3 Si3O12]

Tam t

3,3

6,5-7

1,7-1,68

Beryl

Al2Be3[Si6O18]

Lc phng

2,7

7,5-8

1,6-1,58

Cordierit

Mg2Al3[AlSi5O18]

Hnh thoi

2,6

7-7,5

1,54-1,63

Mt thoi

3,5

7,5

Khc x

(Fe v Mn c th thay th Mg ti 10%

Tucmalin R+,R2+3Al6[(OH) BO3) Si6O18]

Da vo thnh phn ha hc ngi ta phn bit

1,65-1,7

Tucmalin kim (Enbaite) Na(Al,Li)3Al6[(OH)4BO3)3 Si6O18]

Tucmalin magi (Dravit) Na Mg3Al6[(OH)4BO3)3 Si6O18]
Tucmalin st (Schor) NaFe3Al6[(OH)4BO3)3 Si6O18]
Tucmalin canxi magi (uvit) CaMg3Al5 [(OH)4BO3)3 Si6O18]
Dipta

Cu6[Si6O18].6H2O

Mt thoi

3,3

1,65-1,7

n v cu trc gm 3, 4, 6 t din ni nhau qua nh oxi to thnh vng (hnh 44).

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. Bng 17 gii thiu vi khong vt thuc lp
ny.
4) Inosilicat (Silicat mch) c hai nhm:
+ Nhm pyrxen: Cc t din ni nhau bng 2 oxi. Cng thc khung anion c th vit
[SiO3]2 hoc [Si2O6]4 (hnh 45, bng 18).
-

41

[Si3O9]6-

[Si4O12]8-

[Si6O18]12-

Hnh 44
Xiclosilicat

[Si2O6]4-

Hnh 45
Nhm pyrxen
Bng 18
Mt vi khong vt nhm pyrxen
Tn

Cng thc

Tinh th

Ch s khc x
ng np

ipzit

CaMg[Si2O6]

n t

1,694-1,664

Jadeit

NaAl[Si2O6]

n t

3,4

1,667-1,665

git

Ca(MgFeAl)[Si2O6]

n t

3,5

5,5

1,711-1,686

Spodulen

LiAl[Si2O6]

n t

3,2

6,5

1,676-1,661

Enstatit

(MgFe)2[Si2O6]

hnh thoi

3,5

5,5

1,77-1,73

Mt phn MgO c th thay th bng FeO. Trong enstatit cha di 5% FeO. Nu FeO c
gi tr gia 5 n 14% th gi l bronzit, nu FeO c trn 14% th gi l hypecten.
+ 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.
6-

[Si4O11]
-

Hnh 46
Nhm amphibn

42

Bng 19. Mt vi khong vt nhm amphibn

Tn

Cng thc

Tinh th

Trmolit
Actinot
Glaocophan
Wollastonit
Rodonit

Ca2Mg5[(OH)Si4O11]2
Ca2(MgFe)5[(OH)Si4O11]2
Na2Mg3Al2[(OH.Si4O11]2
Ca3[Si3O9]
CaMn4[Si5O15]

n t
n t
n t
tam t
tam t

2,3

5-6

3,0
2,9
3,5

6-6,5
5
6

Ch s khc x
ng np
1,633 -1,60
1,634 1,61
1,63 1,61
1,634 1,62
1,76 1,72

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 cha ion OH v cc cation kim loi. Do
cng thc cu trc ca b khung anion c c 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 c kch thc ln (s phi tr 12) nm trong khi lc lng
ny.
_

Tal (Mg3[(OH)2Si4O10], mica KAl2[(OH)2AlSi3O10], bitit

v cc khong vt st thuc lp phylosilicat.

K(MgFe)3[(OH)2AlSi3O10]

[Si 4O10 ]

Hnh 47
Nhm phylosilicat

Bng 20
Mt vi khong vt thuc lp phylosilicat
Tn
Cng thc
Tinh th
Tal
Pyrofilit
Apofilit
Muscovit

Mg3[(OH)2Si4O10]
Al2[(OH)2 Si4O10]
KCa4[F.Si8O20]
KAl2[(OH.F)2 AlSi3O10]

n t
n t
t phng
n t

Ch s khc x

2,7

1,58-1,54

2,3

4,5

1,53
1,565-1,535

43

Phlogopit
Biotit
Lepidolit

KMg3[(OH.F)2 AlSi3O10]
K(MgFe)3[(OH.F)2AlSi3O10]
KLi2Al[(OH.F)2 Si4O10]

n t
n t
n t

2,9
3
3

3
3
3

1,60-1,56
1,66-1,60
1,56-1,54

Trong phylosilicat c mt nhm c bit l khong vt st. V khong vt st cn c

nhiu ng dng trong ha vt liu nn di y chng ta xt k hn.
Khong vt st

Khong vt st c cu trc lp, mi lp gm mt hoc hai l t din SiO24 v mt l bt

din Al(OH)63, hai l t din cng quay nh v l bt din. Ti cc nt chung ca t v bt
din ion OH ca bt din c thay th bng O2 ca t din. Ty theo cch xp sp ca l t
din (Te) v l bt din (Oc) m phn thnh cc nhm st sau y:
a) Nhm caolinit (Te-Oc). Caolinit l khong vt i din cho nhm ny. Mi lp caolinit
gm c mt l t din (Te) v mt l bt din (Oc) (xem hnh 48). V rng bn knh O2 v
OH u ln hn rt nhiu bn knh Si4+, Al3+, nn c th hnh dung mng tinh th caolinit
gm cc anion O2- v OH- gi ghm chc c, cn cc cation Si4+ v Al3+ c sp xp vo
cc hc trng ca phn mng anion .

Hnh 48
Cu trc tinh th caolinit

xc nh t bo mng ca caolinit, chng ta xem mt lc gic gm cc ion oxi l

y. T dng cc mt phng thng ng (theo trc c) ct ln lt qua mt oxi, mt oxi v
hiroxil v mt hiroxil (hnh 49).
Cnh a ca t bo khong 5 n 5,44, cnh b khong 9 n 9,422. Kch thc mt y
ny gn nh khng thay i vi tt c cc loi khong st. Cn chiu cao (cnh c) i vi mng
caolinit c gi tr khong 7,1 n 7,15.
Trn hnh v cho thy vi mt t bo caolinit c:
- Mt lc gic oxi gm:
- Mt hn hp gm:

- Mt hiroxil:

4 + 4/2 = 6O2
2 + 4/2 = 4Si4+
2 + 4/2 = 4O2
1 + 4/4 = 2OH
3 + 2/2 = 4Al3+
5 + 2/2 = 6OH

Nh vy cng thc ca mt t bo caolinit l Al4[Si4O10](OH)8. Vit di dng oxit l

2(Al2O3.2SiO2.2H2O). Ta c th tnh c khi lng ring ca caolinit nh sau. Mi t bo
c 2 phn t Al2O3.2SiO2.2H2O, ngha l khi lng mt t bo bng (2102) + (460) +
(418) = 516 516/6,02.1023g.

44

Th tch mt t bo l 597,1 = 319,53 = 319,5.1024cm3

Vy d = 516/(6,02.1023 319,5.1024) = 2,68g/cm3
Nt c trng ca khong vt caolinit l lin kt hir gia mt gm cc ion O2 v mt
gm cc ion OH lm cho cc lp gn vi nhau. Cp ht ca caolinit thng ln hn cc
khong vt st khc.
(b)

(a)
O

OH

1/2

1/2

O
O

1/4

O
1/2

(c)

OH
O 1/2

1/2O

1/2

OH

1/4

OH

OH

1/2

OH
OH
OH

OH
OH
OH
OH

1/2

OH
OH
OH

OH

5A

OH

OH

1/4

OH

1/4
1/2

O 1/2

9A
O

OH

Hnh 49
Cc mt ct ca t bo caolinit
a) Qua cc mt lc gic oxi;
b) Qua cc mt hn hp oxi v hiroxil
c) Qua cc mt hiroxil

b) Nhm monmorillonit (Te-Oc-Te)

S cu trc ca nhm ny gm mt l bt din nm gia hai l t din. Theo cch xc
nh trn y th mt t bo mng monmorillonit c:
- Mt lc gic oxi gm:
- Mt hn hp gm :

- Mt lc gic oxi gm:

4 + 4/2 = 6O2
4+
2 + 4/2 = 4Si
2
2 + 4/2 = 4O
1 + 4/4 = 2OH
3 + 2/2 = 4Al3
2
2 + 4/2 = 4O
1 + 4/4 =2OH
2 + 4/2 = 4Si4+
2
4 + 4/2 = 6O

Te

Oc

Te

Tng cng 2(Si4Al2O10(OH)2)

Ngha l mi t bo ng vi 2 phn t Al2O3.4SiO2..H2O. Nh vy t l SiO2/Al2O3 trong
monmorillonit ln gp 2 ln t l trong caolinit. Gia cc lp monmorillonit khng c lin
kt hiro, do cp ht thng b hn nhiu so vi caolinit.

45

O2Si4+
OHAl3+, Mg2+
Fe3+, Fe2+
Hnh 50
Mng li tinh th monmorillonit

46

O2Si4+
OHAl3+,Fe3+..
Mg2+

Hnh 51
Mng li tinh th clorit

Nt c trng monmorillonit l thng xuyn c s thay th Al3+ trong v tr bt din

bng cc ion Mg2+, Fe2+, Fe3+, Cr3+ v thay th v tr Si4+ trong t din bng Al3+. in tch
dng thiu do s thay th khng cng in tch c b tr bng cc cation trao i.
Dung tch trao i cation ca nhm khong st ny c th t t 90 150 mlg/100 gam mu.
Cc cation trao i ny thng xuyn c km theo cc phn t nc hirat.
c) Nhm hiromica (Te-Oc-Te)
Cu trc tinh th cng ging nh ca nhm monmorillonit, nhng hiromica cation b
tr ch l K+. V rng kch thc ca K+ ln hn nhiu ca Na+, Mg2+ cho nn v tr K+ c
gi kh chc khng tham gia phn ng trao i.
d) Nhm clorit (Te-Oc-Te-Oc)
51).

Gia cc lp ca monmorillonit cn c thm mt lp bt din bruxit [Mg(OH)6]4- (hnh

7) Tectosilicat (silicat vi cu trc 3 chiu)

C th hnh dung mng tinh th tectosilicat gm cc t din SiO44 ni vi nhau qua nh

oxi nh trong tinh th SiO2. Nhng y v tr ca Si4+ b thay th bng Al3+ c khi ti 50%.
S in tch dng thiu do s thay th c b tr bng cc ion dng c s phi tr ln
nh Ca2+, K+, Na+. Do lp silicat ny gi l alumosilicat. C 3 nhm tectosilicat l
phenpat, phenpatoit, zeolit.
a) Nhm phenpat: Phenpat l khong vt ph bin nht ca v qu t (chim 50% khi
lng). Cng thc ca phenpat thay i t X[AlSi3O8] n Y[Al2Si2O8] tu theo cation X v
Y ngi ta phn thnh 2 nhm:

- Phenpat kim (octoz v microlin) u c cng thc chung K[AlSi3O8] nhng octoz
thuc h n t, t trng 2,6, rn 6 c th cha mt t natri (di dng anbit), st, bari,
rubii, cn microlin thuc h tam t.

47

Anbit

(0 10%An, 90 100%Ab)

Olgoclaz

(10 30%An, 70 90% Ab)

Aesin

(30 50%An, 50 70%Ab)

Labrade

(5070%An, 30 50% Ab)

Bitonit

(7090%An, 10 30% Ab)

Anoctit

(90 100%An, 0 10%Ab)

- Phenpat kim th (plagiocla). Nhm ny gm mt dy dung dch rn lin tc ca cc

khong vt t anbit Na[AlSi3O8] n anoctit Ca[Al2Si2O8]. Cc khong vt trung gian c
phn loi theo thnh phn phn trm ca anbit (Ab) v anoctit (An).
b) Nhm phenpatoit: L loi alumosilicat natri v kali xut hin cc khi macma ngho
silic, giu kim. Trong c lxit K[AlSi2O6] thuc h t phng, c th cha mt lng rt
t natri v rubii, anaxim Na[AlSi2O6].H2O, nephelin KNa3[AlSiO4]4.
c) Nhm zeolit: Zeolit l alumosilicat natri, canxi ngm nc. Cng thc tng qut ca
zeolit l MxAyO2y.nH2O. Trong M l Na+,Ca2+; A l Si4+, Al3+. Tng s ion Si4+ v Al3+
bng y, ngha l aSi + aAl = y vi iu kin aAl < aSi.
C s cu trc ca mng tinh th zeolit l t din SiO44-. Cc t din ni vi nhau qua
c 4 nh to thnh b khung 3 chiu trong khng gian. Do s thay th Si4+ bng Al3+ nn
b khung xut hin in tch m. Cation b tr cho in tch m nm cc hc, cc
khong trng ca b khung zeolit. Do s thay th nh vy nn b khung zeolit c mch lin
kt
-Si-O-Al-O-Si-. Do tng tc tnh in nn khng th c hai t din AlO45- st nhau, iu
c ngha l trong zeolit khng c mch lin kt -O-Al-O-Al-O-. Cc t din ni vi nhau
qua nh to thnh nhng bt din ct. Hnh 52 l mt bt din ct c nh l Si4+ v Al3+.
Mi bt din ct c 24 nh do cng thc ca mt bt din ct l:
Mx Si24xAlxO48.nH2O. Mi bt din ct c 6 mt hnh vung v 8 mt lc gic u. Khi cc
bt din ct ni vi nhau qua mt hnh vung s to nn mng li khng gian thuc h lp
phng n gin, gi l zeolit A. T bo mng ca zeolit A nh vy c cha mt bt din ct.
Do l cng thc zeolit A ng bng cng thc bt din ct. Khi lng nhm t gi tr ti
a th x = 12, gi s cation trao i ch c Na+ th lng nc hp th t 27 phn t v cng
thc natri zeolit A l Na12Si12Al12O48.27H2O. Hng s mng li ca zeolit ny l 12,3.
Khong trng bn trong ca t bo mng zeolit A c ng knh 11,4(thng c gi l
hc ). Khong trng bn trong ca hc bt din ct c kch thc bng 6,6 (gi l hc ).
+

48

Hnh 52
Bt din ct, n v c s ca mng li
zeolit

Hnh 53
Zeolit A

Khi cc bt din ct ni vi nhau qua mt lc gic th to thnh mng lp phng phc

tp kiu kim cng. Zeolit thuc kiu ny c 3 loi gi l zeolit X, zeolit Y, faujazit. T bo
lp phng ny c cnh a = 25. Mi t bo c 192 t din (SiAl)O4. V d faujazit c thnh
phn: Na13Ca12Mg11(AlO2)59(SiO2)133.235H2O. Tu thuc vo phng php tng hp m thu
c sn phm c t l Si/Al khc nhau. i vi zeolit X v Y, s t din AlO4 trong mt t
bo mng lin h vi t l Si/Al theo h thc sau:
NAl =

192
1 + Si / Al

(11)

Vi zeolit X s cation Al3+ trong mt t bo nguyn t thay i t 77 n 96, trong zeolit

Y con s thay i t 48 n 76. Khi thay th Al3+ vo v tr ca Si4+, hng s mng ca
zeolit X v Y b thay i t 25 n 24,6. Breck v Flanigen kho st trn 37 mu zeolit
X v Y vi cc phng php phn tch chnh xc thnh phn Al trong tinh th v xc nh gi
tr a ca mng lp phng xc lp c h thc:
a = 0,00868 NAl + 24,191

(12)

y NAl l s ion nhm c trong mt t bo mng zeolit X hoc Y.

Zeolit c rt nhiu ng dng trong nn cng nghip hin i lm cht trao i ion, hp
th chn lc, ry phn t, cht mang xc tc v c lm cht xc tc trong k ngh ho hc, c
bit l trong cng nghip ch bin du m.

1.3

Nhng nt c bit ca tinh th cng ho tr v tinh th kim loi

Cu to tinh th v tnh cht ca cc hp cht cacbua, nitrua, borua, silixua kim loi c
nhiu nt ring bit do kiu lin kt ho hc. Khc vi cc hp cht trnh by phn trn c
lin kt ion l ch yu, trong tinh th ca cacbua, nitrua, silixua kim loi th lin kt cng ho
tr l chnh hoc lin kt hn tp gia cng ho tr ion kim loi.
Lin kt cng ho tr rt bn vng nn nhng hp cht loi ny c rn v nhit
nng chy cao, dn. Trong khi lin kt kim loi truyn cho cacbua, nitrua, borua, silixua
mt s c tnh ca kim loi nh do, c dn in cao, siu dn nhit thp.
bn v hng ca lin kt cng ho tr ph thuc vo s lng t ca in t lin kt.
V d lin kt ca cc obitan p bn hn lin kt ca obitan s. Vi kim loi chuyn tip th li

49

do lin kt ca obitan d. Mt khc hp cht gm c lin kt cng ho tr th vai tr quan trng

li l lin kt ca cc obitan lai ho. Vng xen ph ca cc obitan lai ho ln hn do loi
hp cht ny c lin kt rt bn v tnh nh hng th hin rt r rt. S phi tr ca cc
nguyn t trong tinh th c lin kt cng ho tr khng ln nh trong tinh th c lin kt ion.

Hnh 54
Cch ni cc bt ct qua mt lc gic
4+
3+
cc nh l Si hoc Al ti tm ca t din Si(Al)O4

(b)

(a )

Hnh 55
Cu trc graphit

i vi tinh th c lin kt kim loi th c mt s c tnh khc hn. l khng tun

theo quy lut ho tr, cc nt mng gn nhau v c th l cc nguyn t ca cng mt nguyn
t. Mt s loi cht dng trong vt liu gm m c lin kt kim loi (v d berilit, aluminit) c
th xem nh hp cht gia cc kim loi, hoc l hp kim c trt t.
kho st cc hp cht c lin kt cng ho tr dng trong vt liu v c chng ta nhc
li cu trc ca graphit.
Trong graphit 1 in t s v 2 in t p ca cacbon to thnh lai ho sp2. Cc obitan lai
ho ny to thnh 3 lin kt vi 3 nguyn t cacbon khc trong cng mt mt phng. in t
ho tr th t lin kt yu vi nguyn t cacbon mt khc. Do mng li graphit gm cc
lp lin kt vi nhau bng mt lc kh yu. Cc nh ca hnh lc gic trong cng mt lp
nm v pha trn hoc pha di ng tm ca hnh lc gic ca lp gia (hnh 55a v b).

50

Hnh 56
Kiu cu trc blend (ZnS), kim cng (z Zn, { S)

Hnh 57
Cu trc ca nitrua bo (z B, { N)

Do cu trc nh vy nn graphit c tnh ng hng mnh. Graphit thuc mng li lc

phng.
Kim cng gm cc nguyn t cacbon trng thi lai ho sp3. S xen ph ca cc obitan
lai ho sp3 to thnh mng li khng gian 3 chiu. S phi tr ca cacbon y bng 4. Kim
cng thuc h lp phng. Mng li ca kim cng ging mng li ca blend (hnh 56),
cng vi loi cu trc ny c cacbua silic (SiC).
Cu to tinh th ca nitrua bo cng tng t cu to graphit. im khc nhau ch ch
cch b tr gia cc lp lc gic: nitrua bo th cc nh ca lc gic nm thng hng theo
trc c, nh vy gia cc lp c mch lin kt lun phin NBNBN. Lin kt gia cc
nguyn t trong cng mt lp cng bn hn lin kt gia cc lp.
C hai kiu cu trc ca graphit v nitrua bo p sut v nhit cao u c th tr
thnh cu trc lp phng kiu blend. p sut cao hn na hp cht NB c th tr thnh
cu trc zinkit ZnO.
Cacbua, nitrua, borua, silisua ca cc nguyn t chuyn tip c cc kiu lin kt ho hc
hn tp. Nhiu hp cht trong nhm ny c cu to mng li kh n gin. Theo c tnh
cu to tinh th c th phn hp cht nhm ny thnh hai loi l pha xm nhp v pha thay
th.

51

Nu t l gia bn knh nguyn t phi kim (X) v ca kim loi (M) trong hp cht
khng ln hn 0,59 th cc nguyn t kim loi to thnh mng gi ghm chc c thng
thng nh trong mng kim loi (lp phng mt tm v lc phng), cn phn t phi kim
xm nhp vo cc khong trng. iu ny tho mn vi cacbua, nitrua v mt phn borua ca
kim loi chuyn tip. Bn knh ca nguyn t silic qu ln do silisua cu to theo kiu thay
th. Ngoi yu t hnh hc ra cu trc tinh th ca hp cht nhm ny cn ph thuc vo
thnh phn ho hc, iu kin bn ngoi (p sut, nhit ) v mt s yu t khc na.
ng v quan im vt liu gm th cacbua, nitrua c thnh phn AX c cu to kiu
NaCl, trong cc nguyn t kim loi c kiu gi ghm chc c lp phng, cn phi kim
chui vo cc hc bt din. V d tinh th TiC, ZrC, HfC, NbC, TaC, TiN, ZrN, CrN, HfN,
UN...
Cacbua ca wolfram v ca molipen c mng li tinh th ging kiu cu trc ca NiAs
(hnh 58). Trong cc cacbua ny nguyn t kim loi chim v tr ca niken, cn cacbon chim
v tr ca As. l mng li lc phng. Mi t bo mng c 6 nguyn t cacbon, 6 nguyn
t wolfram hoc molipen. S phi tr ca chng u bng 6 nhng dng a din phi tr th
khc nhau: nguyn t cacbon nm tm ca lng tr tam gic, cn cc nguyn t cacbon phi
tr quanh nguyn t kim loi th phc tp hn. Cc tinh th vi lin kt ion th cha gp kiu
cu trc ny.
Gm cacbua c cu trc chuyn tip t pha xm nhp n pha thay th. Borua l hp cht
ho hc c thnh phn rt khc nhau M1B, M2B, MB, M3B4, MB2, M2B5, MB4, MB6 v MB12.
Mng tinh th rt phc tp, trong va c lin kt cng ho tr va c lin kt kim loi.

Cr (Si)
Al (Mo)

Ni
As
Hnh 58
Cu trc tinh th nikenlin NiAs

Hnh 59
Cu trc Cr2Al

Trong gm th ph bin nht c iborua MB2, y M l Cr, Ti, Zr, Hf, Nb, Ta, W... Tt
c cc borua ny u c mng tinh th ging nhau v ging mng tinh th ca AlB2. y l
mt kiu cu trc phc tp gm cc lp nguyn t bo nh trong graphit phn b chnh xc lp
ny trn lp kia. Cc nguyn t kim loi nm tm cc lng tr lc gic ca nguyn t bo.
Nh vy l to nn cc lp lun phin: lp mt phng lc gic ca bo v lp mt phng hnh
thoi ca nguyn t kim loi. Cu trc nh vy thuc h lc phng. Mi t bo nguyn t c
mt nguyn t bo v mt nguyn t kim loi.
Bng di y gii thiu mt s loi tinh th c lin kt cng ho tr thng s dng
trong vt liu gm.

52

Bng 21.
Mt s loi tinh th c lin kt cng ho tr thng s dng trong vt liu gm
Cng thc
H
Kiu mng
Hng s mng ()
S phn t
a, b v c
trong mt t bo
Lc phng
Graphit
2,46
6,71
4
C
Lc phng
Kim cng
3,567
8
4,357
4
Lc phng
Sphalerit
_SiC
TiC
-ntNaCl
4,328
4
ZrC
-ntNaCl
4,678
4
HfC
-ntNaCl
4,487
4
NbC
-ntNaCl
4,41
4
TaC
-ntNaCl
4,454
4
MoC
Lc phng
MoC
2,901 2,768
1
WC
-ntMoC
2,903
2,833
1
TiN
-ntNaCl
4,23
4
ZrN
-ntNaCl
4,64
4
Lp phng
NaCl
4,42
4
NbN
Lc phng
ZnO
3,05
4,94
2
UN
Lp phng
NaCl
4,89
4
BN
Lc phng
BN
2,51
6,69
4
MoB2
Lc phng
AlB2
3,05
3,113
1
ZrB2
-nt_
3,03
3,22
1
TiB2
-nt_
3,03
3,23
1
NbB2
-nt_
3,09
3,31
1
2,97
3,07
1
-nt_
_CrB2
MoSi2
T phng
MoSi2
3,20
7.89
2
WSi2
-nt_
3,22
7,88
2

xt cu trc ca silixua trong gm c th kho st hp cht MoSi2. Loi hp cht ny

thng gp trong hp cht gia cc kim loi, v d Cr2Al (hnh 59). Trong tinh th MoSi2 th
Mo chim v tr ca Al, cn Si chim v tr ca Cr. Thng s t bo mng gm cnh y a v
chiu cao c. T bo gm 3 tng c cc a din phi tr phc tp.
Quanh Si c 5 nguyn t Mo, quanh Mo c 8 nguyn t Si. Mi t bo c 2 nguyn t
Mo v 4 nguyn t Si cng cu trc nh WSi2, ReSi2.. Cu trc ca mt s isilixua quan
trng khc gm lun phin nhng lp lc gic gi ghm chc c, trong cc nguyn t kim
loi chuyn tip c bao quanh bng 6 nguyn t Si, cn nguyn t Si c bao quanh bng
3 nguyn t kim loi. S lun phin khc nhau ca cc lp nh vy c th to thnh mng
li lc phng (VSi2, NbSi2, TaSi2, CrSi2) hoc hnh thoi (TiSi2).

1.4

Cc yu t nh hng n kiu cu trc tinh th

Mt cht rn tn ti di dng tinh th no c quyt nh bi nhiu yu t: kch

thc cc tiu phn (nguyn t, ion, phn t,), kiu lin kt gia cc tiu phn, cu hnh
in t ca cc nguyn t, ion,... Do vic d on cu trc mt hp cht mi l mt vic
rt phc tp, ch c th gii quyt c trong trng hp d nh trc cht ca ta tng
hp thuc v mt h tinh th no : v d tng hp mt pha mi c cu trc spinen, hoc c
cu trc perpkit,
Trong phm vi kho st cu trc ca cc loi vt liu v c chng ta ch kho st 3 yu t
sau y: Cng thc ca hp cht (tc l ni ti tnh hp thc, ho tr ca cc nguyn t), bn
cht lin kt gia cc nguyn t, kch thc tng i gia cc ion.

1.4.1 Tnh hp thc SPT ca cc nguyn t

53

C mt mi lin h gia SPT ca cc nguyn t v cng thc tng qut ca hp cht. V

d hp cht bc hai c cng thc l AxBy ta c t l:
SPT ca A y
=
SPT ca B x

(13)

Nguyn tc ny ng vi a s cc hp cht ch tr trng hp hp cht c lin kt gia

cc nguyn t cng loi (A-A, B-B), v d trong cc hp cht hu c c mch C-C th khng
p dng c.
Chng ta xt mt vi hp cht:
- Hp cht c cng thc chung AB th SPT ca A bng SPT ca B. V d trong tinh th
NaCl, SPT ca Na+ v SPT ca Cl u bng 6, trong tinh th ZnS (blend) SPT ca Zn2+ v
ca S2 u bng 4.
- Hp cht c cng thc chung AB2 th SPT ca A gp i SPT ca B. V d trong SiO2,
Si c SPT bng 4, O2 c SPT bng 2, trong TiO2, Ti4+ c SPT bng 6, O2 c SPT bng 3,
trong CaF2, Ca2+ c SPT bng 8, F c SPT bng 4.
4+

- Hp cht c cng thc AxByCz trong A v B l cation, C l anion. K hiu SPT trung
bnh ca cation l SPT cation ta c:

SPT cation =

v lin quan vi SPTanion bng h thc

x(SPTA ) + y(SPTB )
x+y

SPT cation
z
=
SPTanion x + y

t ta c h thc: x(SPTA) + y(SPTB) = z(SPTC)

V d perpkit CaTiO3, Ti4+ nm trong bt din (SPT bng 6), Ca2+ c SPT l 12, ta tnh
c SPT ca oxi bng 12 + 6 = SPT ca O nhn 3. Ngha l SPT ca O bng 6. Qu vy, xung
quanh ion O2 c 4 ion Ca2+ v 2 ion Ti4+.
Spinen MgAl2O4 c ion Mg2+ nm trong t din, ion Al3+ nm trong hc bt din vy 4
ln SPT ca O2 bng 4+26.
SPT ca O2 = 16/4 = 4
Qu vy, ion O2 trong spinen c bao quanh bng 3 ion Mg2+ v 1 ion Al3+.

1.4.2 nh hng ca kiu lin kt

Bn cht lin kt gia cc nguyn t nh hng ng k n SPT ca cc nguyn t
v do nh hng trc tip ti kiu cu trc tinh th. Hp cht lin kt ion c cu trc i
xng cao, s phi tr t gi tr cc i. Lin kt cng ho tr c c tnh nh hng, s phi
tr ph thuc vo s lin kt c th c. Do trong cu trc vi lin kt cng ho tr th SPT
ca nguyn t thng khng ln v thng b hn SPT trong cu trc vi lin kt ion tng
ng nu kch thc ca cc ion hp phn gn bng kch thc ca nguyn t c cu trc cng
ho tr .
V d, xt cu trc trong dy SrO, BaO, HgO. Cc oxit SrO, BaO c cu trc NaCl, trong
ion M2+ nm v tr bt din, ngha l c SPT bng 6, trong khi HgO c cu trc khc

54

hn. S phi tr ca thu ngn trong HgO bng 2. HgO c cu trc mch gm cc mnh OHg-O. Ta c th gii thch c iu khi lu n cu hnh in t ca Hg c lp v bn
ngoi l 4f145d106s2. trng thi kch thch nguyn t Hg c cu hnh 4f145d106s16p1. Cc
obitan lai ho sp ca Hg xen ph vi obitan ca oxi to thnh lin kt cng ho tr vi cu
hnh phn t dng ng thng.

1.4.3 nh hng ca bn knh nguyn t, ion

Khi nim bn knh nguyn t, bn knh ion tuy rng khng chnh xc v cn cn phi
bn ci nhiu na, nhng c th ni rng nu khng c thng tin v kch thc ion trong
mng li tinh th th khng th c c nhng thnh tu hin nay v ho tinh th. Cho n
nay chng ta vn dng nhng s liu v bn knh ion ca Paoling-Arenc (da trn c s tnh
ton theo c hc lng t) v ca Golsmit-Belop-Bki (da vo xc nh thc nghim theo
phng php nghin cu cu trc bng tia X). T nm 1970, Shannon v Pruit li a ra
thm mt h thng kch thc ion khc. C s ca h thng kch thc ion do Shannon v
Pruit da vo k thut hin i ca phng php nhiu x tia X xy dng bc tranh phn
b mt in t trong tinh th. Theo s liu ca Shannon v Pruit th cation c bn knh
ln hn cn anion c bn knh b hn so vi cc gi tr ca h thng Paoling cng nh ca
Golsmit a ra trc y. V d theo Paoling th bn knh ion ca Na+ v F l 0,98 v
1,36, cn theo Shannon v Pruit th bn knh ca Na+ tu thuc vo s phi tr m c cc
gi tr t 1,14 n 1,30, bn knh ca F bng 1,19. Hnh 60 v hnh 61 gii thiu bc
tranh phn b mt in t trong mt 100 ca tinh th LiF v s thay i mt in t dc
theo ng thng ni hai nhn.

Hnh 60
S phn b mt in t trong tinh th LiF
trn cc ng c ghi gi tr mt in t (e/3)

T nhng bc tranh mt in t ca cc cht rn c cu trc ch yu l lin kt ion

tng t nh hnh 60 cho php rt ra mt s nhn xt sau:

55

+ Vn c th xem ion nh ch yu c dng khi cu.

+ Ion c hai phn: phn khi cu bn trong tp trung mt cao ca in t (phn ny
tng i n nh), phn bn ngoi c mt in t kh thp v dao ng tu thuc vo s
phi tr cng nh s khc nhau v m in gia cc nguyn t trong hp cht . Nh vy,
khng th xem ion l khi cu tch in v rn chc nh quan nim trc y m khi cu
c phn ngoi n hi.
+ Khng th xc nh c chnh xc bin gii gia cc ion v rng khng c khu vc
ng vi s gim mt in t n gi tr khng. Nh vy, khng th xc nh c chnh
xc bn knh ion. Vic xc nh bn knh ion ph thuc vo phng php phn chia v tr bin
gii . V d bn knh Li+ theo Paoling l 0,60, theo Golsmit l 0,78, theo h thng ca
Shannon l 0,92. Bi vy trong vic nghin cu cu trc tinh th cn phi s dng mt h
thng n v thng nht. M- ng vi gi tr cc tiu, G v P ng vi bn knh ion Li+ theo
Golsmit v theo Paoling.
o

e/A3

0,92 0,78 0,60

M G

Li

Hnh 61
Bin thin mt in t trong LiF dc theo ng ni lin hai nhn

Kiu cu trc tinh th ph thuc rt mnh vo t l bn knh cation (Rc) v bn knh anion
(Ra) (xem bng 22)
Bng 22
T l Rc/Ra, SPT ca cation, kiu cu trc ca cc hp cht AB
Rc/Ra
S phi tr
Kiu cu trc
1> Rc/Ra > 0,732

Kiu CsCl

0,732 > Rc/Ra > 0,414

Kiu NaCl

0,414 > Rc/Ra > 0,225

Kiu blend ZnS, vuazit ZnS

Cn lu rng kh nng s dng quy tc t l bn knh ca ion on bit SPT v kiu

cu trc rt hn ch. Thc ra quy tc ny ch c ch gii thch khuynh hng chung m
thi. Gi tr tuyt i ca t l bn knh Rc/Ra ph thuc vo h n v bn knh ta s dng.
Nu s dng h n v bn knh ion ca Paoling v Golsmit (ngha l RO2 =1,40) th RRb+/RI
= 0,69, do SPT ca Rb+ bng 6 v RbI c cu trc kiu NaCl. Nu s dng h n v bn
knh ca Shannon (ngha l RO2 =1,26) th RRb+/RI = 0,8, do SPT Rb+ bng 8 v RbI c
cu trc kiu CsCl. Vi LiI cng c hai gi tr t l Rc/Ra l 0,28 v 0,46. Nu nhn l 0,28 th
SPT ca Li+ l 4. Nhng thc t SPT ca Li+ bng 6 ngha l t l phi bng 0,46.

56

Bng 23
T l Rc/Ra, SPT ca cation v kiu cu trc ca oxit c
cng thc MO2
Oxit
Rc/Ra
SPT
Kiu cu trc xc nh c
SiO2
GeO2
TiO2
SnO2
PbO2
HfO2
ThO2

0,32
0,43
0,54
0,59
0,66
0,73
0,67
0,77
0,95

4
4
6
6
6
6
6
8
8

Silic oxit (SPT 4)

Silic oxit (SPT 4)
Rutin (SPT 6)
Rutin (SPT 6)
Rutin (SPT 6)
Rutin (SPT 6)
Rutin (SPT 6)
Florit (SPT 8)
Florit (SPT 8)

Vi hp cht ca oxit hoc florua c cng thc AB2 th c ba kiu cu trc l silic oxit
(SPT 4), rutin (SPT 6) v florit (SPT 8) (xem bng 23).
Khi gi tr Rc/Ra ng vi khong bin gii chuyn kiu cu trc (0,732 hoc 0,414) th
hp cht c th tn ti di hai dng th hnh. V d vi GeO2, HfO2,
Khi kho st mng li tinh th ion ngi ta thng s dng khi nim phn in tch
ca ion hoc lc ho tr ca lin kt. V d cation Mm+ c bao quanh bng n anion Xn th
lc ho tr ca lin kt gia cation Mm+ v mt anion Xn l = m/n. in tch m ca mt
anion phi bng tng lc ho tr ca cc cation bao quanh anion , ngha l = m/n. V d
spinen MgAl2O4 gm c phn mng anion O2 xp kht kiu lp phng mt tm ABCABCA,
ion Mg2+ nm cc hc t din (SPT 4), ion Al3+ nm cc hc bt din (SPT 6), xung
quanh ion O2 c 3 cation Al3+ v mt cation Mg2+:
i vi Mg2+: phn in tch dng cho 1 ion O2 = 2/4 = 1/2
Vi Al3+: phn in tch dng cho 1 ion O2 = 3/6 = 1/2
Vy phn in tch dng ca 1 ion O2 trong MgAl2O4 l:
3Al3+ + 1Mg2+ = 31/2 + 1/2 = 2
C th chng minh rng trong cu trc silicat khng th c 3 t din SiO4 ni chung vi
nhau qua nh. V rng phn in tch dng cho mt ion O2 trong t din SiO4 l 4/4 = 1,
ngha l O2 ch chung cho 2 ion Si4+ v s c phn in tch dng tng cng l 2. Nu 3 t
din SiO4 ni chung vi nhau mt nh oxi th phn in tch dng tng cng ca oxi bng
3, l iu khng cho php.
Bng 24 gii thiu lc ho tr ca lin kt ca mt s cation. Da cc s liu trong bng
24 chng ta c th hiu c cch t hp cho php v cch t hp khng cho php khi ghp
cc a din trong mng li tinh th oxit.
Bng 24
Lc ho tr ca lin kt ca mt s cation
Lc ho tr ca
Cation
SPT
Cation
lin kt
+
Li
4; 6
1/4; 1/6 Al3+
+
Na
6; 8
1/6; 1/8 Cr3+
2+
Be
3; 4
2/3; 1/2 Si4+
2+
Mg
4; 6
1/2; 1/3 Ge4+
2+
Ca
8
1/4 Ti4+
2+
Zn
4
1/2 Th4+

SPT
4; 6
6
4
4; 6
6
8

Lc ho tr
ca lin kt
3/4; 1/2
1/2
1
1; 2/3
2/3
1/2

57

Cho n by gi chng ta vn gi thit rng trong mng tinh th ion ch c thun tu l

lin kt ion, bn cht lc lin kt trong mng li ch thun tu l lc ht tnh in gia cc
ion tch in ngc du. iu ny khng ng vi thc t, v d trong mng tinh th ca KCl,
in tch xc nh c ca cc ion khng phi bng 1 m l 0,76. iu ny c ngha l
gia ion kali v ion clo c 24% l lin kt cng ho tr, lin kt ion ch chim 76%.
Bng 25
Cch ni cho php v cch ni khng c php ca cc a din oxi qua nh chung
Cho php
V d pha rn
Khng c php
2SiO4 (T)
1MgO4 (T) + 3AlO6 (O)
1 SiO4(T) + 3 MgO6 (O)

oxit silic
spinen
olivin

>2SiO4 (T)
3AlO4 (T)
1 SiO4(T) +3AlO4 (T)

xc nh mc lin kt cng ho tr trong mng li tinh th ion, Sanderson a

ra mt phng php mi. Phng php ny da trn c s thang in m ca cc nguyn
t do ng xy dng. Theo ng th m in l o sc ht gia in tch dng hiu dng
ca ht nhn nguyn t ca nguyn t vi in t ngoi cng, ngha l m in lin
quan n mc chc c ca nguyn t. nh gi m in S ng s dng cng thc:

S=

D
Da

(14)

trong D: mt in t trong nguyn t c xc nh bng t l gia nguyn t s v

th tch nguyn t, Da: l mt in t khi ngoi suy tuyn tnh t gi tr D ca nguyn t
khi tr thnh kh tr. Bng 26 gii thiu thang in m ca Sanderson.
Khi cc nguyn t c m in khc nhau lin kt vi nhau to thnh hp cht ho
hc th c s san bng m in cc nguyn t trong hp cht u c gi tr m
in trung bnh ( S ) bng nhau.
V d vi NaF c S = SNa .SF = 2,006
vi BaI2 c S = 3 SBa .S2I = 2, 26 .
S cn bng m in c ngha l trong lin kt gia cc nguyn t khc nhau th cc
in t lin kt b lch v pha nguyn t c m in ln hn, lm cho nguyn t d
in tch m, cn nguyn t c m in b hn th d in tch dng. Phn in tch d
() bng t l bin thin m in ca nguyn t (S) vi gi tr ( S c ) khi gi thit
in t lin kt i hn v pha nguyn t c m in cao to thnh ion c mt n v
din tch 1.
=

S
Sc

(15)

trong :
S = S S , cn S C = 2,08 S

(16)

58

Bng 26
m in v kch thc nguyn t ca mt s nguyn t
B (i vi trng thi
Bn knh cng ho tr
Nguyn t
S
rn)
Rc ()
H
3,55
0,32
Li
0,74
1,34
0,812
Be
1,99
0,91
0,330
B
2,93
0,82
C
3,79
0,77
N
4,49
0,74
O
5,21
0,70
4,401
F
5,75
0,68
0,925
Na
0,70
1,54
0,763
Mg
1,56
1,38
0,349
Al
2,22
1,26
Si
2,84
1,17
P
3,43
1,10
S
4,12
1,04
0,657
Cl
4,93
0,99
1,191
K
0,42
1,96
0,956
Ca
1,22
1,74
0,550
Zn
2,98
Ga
3,28
Ge
3,59
1,22
As
3,90
1,19
Se
4,21
1,16
0,665
Br
4,53
1,14
1,242
Rb
0,36
2,16
1,039
Sr
1,06
1,91
0,429
Ag
2,59
1,50
0,208
Cd
2,84
1,46
0,132
Sn
3,09
1,40
Sb
3,34
1,38
Te
3,59
1,35
0,693
I
3,84
1,33
1,384
Cs
0,28
2,35
0,963
Ba
0,78
1,98
0,348
Hg
2,93
Tl
3,02
1,48
Pb
3,08
1,47
Bi
3,16
1,46

SC
3,92
1,77
2,93
2,56
4,05
4,41
4,75
4,99
1,74
2,60
3,10
3,51
3,85
4,22
4,62
1,35
2,30
3,58
3,77
3,94
4,11
4,27
4,43
1,25
2,14
3,35
3,16-3,66
3,80
3,94
4,08
1,10
1,93
3,59
2,85
3,21-3,69
3,74

ri ()
0,53
0,58

1,10
1,61
0,78
1,03

1,70
2,18
1,00
1,19

1,83
2,38
1,12
1,18
1,29
1,33

2,04
2,71
1,39
1,63

Khi xc nh c ta tnh c phn lin kt cng ho tr trong hp cht, ng thi tnh

c bn knh nguyn t ca cc nguyn t tham gia lin kt.
Paoling v Sanderson a ra cng thc kinh nghim xc nh bn knh nguyn t nh
sau:
r = rc B

(17)

trong : rc l bn knh cng ho tr, l phn in tch d ca n

B l hng s ca nguyn t cho trong bng 26
Xt vi v d:
Xc nh phn lin kt cng ho tr trong BaI2 v di ca lin kt BaI.
in m trung bnh ca Ba v I trong BaI2.

59

S = 3 0,78.3,842 = 2, 26

SBa = 2,26 0,78 =1,48

vy

SI = 3,84 2,26 =1,58

Sc ca Ba = 1,93; ca I = 4,08

Do
Ba = 1,48/1,93 = 0,78; I = 1,58/4,08 = 0,39

Vy trong lin kt BaI c 39% l lin kt ion v 61% l lin kt cng ho tr.
Bn knh nguyn t bari rBa = 1,98 0,348 0,78 = 1,71
Bn knh nguyn t it rI = 1,33 + 1,384 0,39 = 1,87
Khong cch hai nguyn t trong hp cht (dng tinh th) bng 1,71 + 1,87 = 3,58, thc
nghim xc nh c l 3,59.
Bng 27
in tch phn v bn knh ca clo trong mt s tinh th
clorua
Hp cht
Hp
rCl()
rCl()
Cl
Cl
cht
CdCl2
0,21
1,24 BeCl2
0,28
1,26
CuCl
0,29
1,34 AgCl
0,30
1,35
MgCl2
0,34
1,39 CaCl2
0,40
1,47
SrCl2
0,43
1,50 BaCl2
0,49
1,57
LiCl
0,65
1,76 NaCl
0,67
1,79
KCl
0,76
1,90 RbCl
0,78
1,92
CsCl
0,81
1,95
Bng 28
in tch phn oxi trong mt s tinh th oxit
Hp cht
Hp cht
O
-O
Cu2O
Ag2O
Li2O
Na2O
K2O
Rb2O
Cs2O

0,41
0,41
0,80
0,81
0,89
0,92
0,94

HgO
ZnO
CdO
CuO
BeO
PbO
SnO
FeO
CoO
NiO
MnO
MgO
CaO
SrO
BaO

0,27
0,29
0,32
0,32
0,36
0,36
0,37
0,40
0,40
0,40
0,41
0,50
0,56
0,60
0,68

Hp cht
Ga2O3
Tl2O3
In2O3
B2O3
Al2O3
Fe2O3
Cr2O3
Sc2O3
Y2O3
La2O3

O
0,19
0,21
0,23
0,24
0,31
0,33
0,37
0,47
0,52
0,56

Hp cht
CO2
GeO2
SnO2
PbO2
SiO2
MnO2
TiO2
ZrO2
HfO2

O
0,11
0,13
0,17
0,18
0,23
0,29
0,39
0,44
0,45

S dng phng php Sanderson xc nh c in tch phn () v bn knh nguyn

t ca nhiu hp cht. Bng 27 gii thiu in tch phn v bn knh nguyn t ca clo
trong cc clorua kim loi ho tr 1 v kim loi ho tr 2. Bng 28 gii thiu in tch phn ca
oxi trong cc tinh th oxit.

60

T cc s liu trong bng 27 cho thy in tch ca ion clo thay i t 0,21 (trong
CdCl2) n 0,81 (trong CsCl), cn bn knh nguyn t clo thay i t 1,24 n 1,95. So
snh cc gi tr vi bn knh cng ho tr ca clo l 0,99 v bn knh ca ion clo l 2,18
ta thy sai lch qu ln. Tt c cc hp cht trong bng 27 chng ta vn xem nh c mng
li ion v quy cho ion clo c in tch khng i l 1, qu l khng ng thc t.
Cc s liu trong bng 28 cho thy in tch phn ca ion oxi ch thay i trong khong
t 0 n 1. Cc tnh ton cho thy t trc ti nay ta vn xem trong cc oxit c cha ion oxi
l 2, th m thc t in tch ca ion oxi khng vt qu 1 v trong hu ht trng hp cn
nh hn 1.

Cu hi v bi tp
1.

Mt mt phng chn 3 trc ca tinh th ti cc im ng vi thng s n v l

3/2.1.1. Hy cho bit ch s Miller (h, k, l) ca n.

2.

Chng minh rng trong t bo lp phng th:

a. Mt [111] vung gc vi ng (111);
b. Mt [100] vung gc vi ng (100).

3.

Xc nh kiu cu trc ca cc t bo mng li c to ca cc nguyn t nh

sau:
a. MX:
X

1/2 0 0 ,

000,

b. MX:
X
c. MX:

1/2 1/2 0 ,
000,

0 1/2 0 ,

0 0 1/2,

1/2 0 1/2,
1/2 1/2 0 ,

0 1/2 1/2

1/2 0 1/2,

1/4 1/4 1/4 , 3/4 1/4 3/4 , 3/4 3/4 1/4,

1/2 1/2 1/2

0 1/2 1/2

1/4 3/4 3/4

M 0 0 0

X 1/2 1/2 1/2

4.

Xc nh chc c, s hc trng bt din, s hc trng t din ca t bo

mng li lp phng khi tm, lp phng mt tm, gi ghm chc c lc
phng.

5.

Na2O c cu trc kiu antiflorit vi hng s mng a = 5,55, xc nh di

lin kt NaO, khong cch OO, NaNa, khi lng ring (g/cm3). Cng cu
hi i vi CeO2 c cu trc florit a = 5,41.

6.

M t cu trc peropkit ABO3. SrTiO3 c cu trc perpkit vi hng s mng a

= 3,905. Tnh di lin kt SrO, TiO. Xc nh s phi tr ca oxi trong
SrTiO3.

7.

Xc nh s phi tr ca oxi trong spinen MgAl2O4. Cho bit thng s mng ca

n bng 8,09, xc nh t trng (g/cm3). Xc nh thng s oxi ca spinen
MgAl2O4, cho bit bn knh ca ion Mg2+ bng 0,74, bn knh ca O2 bng
1,36.

8.

Gi s phn mng ion O2 trong spinen AB2O4 gi ghm chc c lp phng

mt tm l tng. T tnh ton spinen ca cc kim loi ho tr 2 v kim loi
ho tr 3 no c thng s oxi l tng (W = 0,375).

61

9.

9. Ti sao ZnS c t l Rc/Ra = 0,63 nhng t bo mng li li khng theo kiu

NaCl m theo kiu blend.