CHNG 4: CU TRC CA KIM LOI & HP KIM

4.1. Cu trc kim loi

Trong cc kim loi, cc kiu mng tinh th c trng v thng gp nht l:
- Lp phng tm khi: Bcc: Body centered cubic.
- Lp phng tm mt: Fcc: Face - centered cubic.
- Lc gic xp cht: Hcp: Hexagonal close packed.
4.1.1. Lp phng tm khi: Bcc

a. c s
Hnh lp phng cnh a, 8 nguyn t 8 gc, 1 nguyn t tm khi.
b. S nguyn t trong c s, n
Nguyn t gc l chung ca 8 c s 1 c 1/8 nguyn t 8 gc c 8 x
1/8 nguyn t.
Nguyn t tm hon ton thuc mt .
n = 1/8 x 8 + 1 = 2 nguyn t.
c. S sp xp K (S lng cc nt bao quanh gn nht (BQGN) hay s phi tr)
Mi nguyn t c BQGN bi 8 nguyn t vi khong cch

a 3
2

K = 8 (xt

cho c nguyn t nh v tm).

Mi nguyn t cn c bao quanh bi 6 nguyn t khc vi khong cch a c
th xem K = 8 + 6.
d. Khong cch hai nguyn t gn nht:

a 3
2

e. Hnh chiu c s trn mt phng ngang

(0,1)

Biu din hnh chiu c s xung mt

phng ngang xoy theo gi tr x, y v ghi
ta z bn cnh cc nt mng.

O
1/2

f. Mt xp
Do cc nguyn t c xem l hnh cu hoc gn nh hnh cu nn gia chng s
c khe h. nh gi mc st cht dng mt xp ca mt M s v mt xp
th tch Mv. l t s % din tch (th tch) ca tt c cc nguyn t trn 1 vng cho
trc v din tch (th tch) ca vng .
Ms =

n s r
x 100%
S
2

4
n. r 3
Mv = 3
x 100%
V

ns: S nguyn t trn din tch S ca mt cho.

n: S nguyn t / c s,
r: Bn knh nguyn t.
V: Th tch c s.
i vi Bcc: cc nguyn t ch tip xc nhau theo phng < 111>
z

a 3
4
4
a 3 3
2x x(
)
3
4
Mv =
x 100% = 68%
a3
4r = a 3 r =

[111]
y

Mt c mt xp ln nht l {110} cha phng

<111>

2
r

S = a2 2

r
r

[110]

r=

a 3
4

S nguyn t trn mt S
1
x 4 + 1 = 2 nguyn t
4
a 3 2
2..(
)
4
M s{110} =
.100% = 83,3 %
a2 2
ns =

g. Mt thng, mt phng, lp li
Mt thng (linear density): LD = s nguyn t trn on thng /chiu di on
thng (ngtu/cm)
Mt phng (planar density): PD = s nguyn t trn mt phng S /din tch mt
phng S (ngtu/cm2)
lp li (Repetition spacing) theo mt phng: khong cch gia cc nguyn t
trn phng .

h. Khi lng ring (g/cm3)

2

d = m /V =

M
AN = n.M
V
AN.V

trong

m: khi lng 1 c s, V: th tch 1 c s

n: s nguyn t /1 c s
M: khi lng nguyn t (g/mol)
AN (s Avogadro): s nguyn t /1 mol = 6,02. 1023 (ngtu/mol)
i. Cc kim loi c kiu mng Bcc l Fe, Cr, W, Mo, V, Li, Na, K
4.1.2. Lp phng tm mt: Fcc
a. c s
Hnh lp phng cnh a, 8 nguyn t 8 gc, 6 nguyn t gia cc mt.
b. S nguyn t / c s
1 nguyn t gc l ca 8 1 c 1/8 nguyn t, 8 gc c 1/8 x 8 nguyn t.
1 nguyn t mt l ca 2 1 c 1/2 nguyn t, 6 mt c 1/2 x 6 nguyn t.
n=

1
1
x8+ x 6 =4
8
2

nguyn t.

c. S sp xp K
Mi nguyn t c BQGN bi 12 nguyn t vi khong cch

a 2
2

K = 12

nh: cch u 4 tm ca 3 mt qua n.

Tm: cch u 4 nh v 8 tm ca 2 c s k nhau.
d. Khong cch 2 nguyn t gn nht:

2
2

e. Hnh chiu c s
(0,1)

1/2

(0,1)

r
a

r
r
x

f. Mt xp
Cc nguyn t ch xp st cht nhau trn {111} v tip xc nhau theo phng
<110> nm trn {111}. Do 4r = a 2 v r = a 2 /4

4
a 2 3
4x x(
)
3
4
Mv =
x 100% = 74%
a3

a 3
1 a2 3
xa 2x =
2
2
2
1
1
n s (111) = x 3 + x 3 = 2
6
2
a 2 2
2(
)
4
M s (111) =
x 100% = 91%
a2 3
2

S(111) =

g.

Cch sp xp nguyn t trong Fcc

Trong Fcc, thc cht l cc lp (111) xp st ln nhau.
Lp I: K hiu A.
Lp II: K hiu B xp vo khe lm lp I.
Khong cch 2 khe cnh nhau < 2r.
Khong cch 2 khe cch nhau = 2r.
Lp III: K hiu C: xp vo khe lm lp II, tng ng vi khe cn cha trng lp
I.
Lp IV: lp li nh lp I.
K hiu trt t sp xp ca Fcc l ABCABC.

h. Kim loi c kiu mng Fcc l Fe, Cu, Ni, Al, Pb

4.1.3. Lc gic xp cht: Hcp
a. c s:
Hnh lng tr 6 cnh c chiu cao c, y lc gic u cnh a. C 12 nguyn t
gc, 2 nguyn t tm 2 mt y v 3 nguyn t tm ca 3 khi lng tr tam gic
cch nhau.
b. S nguyn t / c s:
n=

1
1
x 12 + x 2 + 3 = 6
6
2

nguyn t.

c. Mt xp
Cc nguyn t xp st nhau theo mt {0001} v tip xc nhau theo 2 phng.
< 2 1 1 0 > : trc x1 2r = a r =

a
2

1 1 1

G ( 3 , 3 , 2 ) OG < 2 203 >

IG =

2
IL
3

2a 3 a 3
=
3 2
3

OG = 2 r = a
IO =

c
2

c2
a 3 2
+(
) = a2
4
3
c2
1
2
8
= a 2 (1 ) = a 2 c 2 = a 2
4
3
3
3
2
c
c = 2a
1,633
3
a

IO2 + IG2 = OG2

G
I

Nh vy iu kin xp cht cc lp {0001} l

c
1,633 . Thc
a

t cc lp c th xp khng

hon ton st cht nhau

c
a

c th khc 1,633

do nguyn t c th dng ellip.

Qui c
V d:

c
=1,57 1,64
a

Kim loi
Be
Mg
Ca
Zn
Cd

Mng xp cht.
c/a
1,57 xp cht
1,62
1,64
1,86 khng xp cht
1,89

n=6

6a 2 3
6a 2 3 2 2
V=
.c =
.a
= 3a 3 2
4
4
3

a a 3 a2 3
6a 2 3
x
=
S( 0001) =
2
2
4
4
a 2
3 x ( )
2 x 100% = 91%
M ( 0001) =
2
a 3
6
4

S1 =

4 a
6 x .( ) 3
3 2 x 100% = 74%
Mv =
3a 3 2
1
a
ns = x 6 +1 = 3
r=
3
2

d. Cch sp xp nguyn t trong Hcp

Thc cht l cc lp (0001) xp st ln
nhau.
Lp I: k hiu A.
Lp II: k hiu B: xp vo khe lm
lp I.
Lp III: lp li lp I.
Trt t sp xp l ABAB.
Ch : Nu lp III xp vo khe lm lp
II nhng khng trng vi lp I Kiu
ABCABC Fcc.
x3
(0,1)
1/2
(0,1)

Fcc

x2

x1

Hcp

e. Hnh chiu trn mt phng ngang

f. S sp xp
Mi nguyn t bao quanh gn nht bi 12 nguyn t vi khong cch a K = 12.
(Nguyn t tm y c 6 nguyn t xung quanh, 3 nguyn t trn, 3 nguyn t
di).
Nu

c
1,633 th khong cch n 3 nguyn t pha trn v pha di s khc
a

khong cch n cc nguyn t xung quanh nn K = 6 + 6.

g. Kim loi c kiu mng Hcp l Ca,Mg, Be, Co, Ti, Zn, Cd.

4.1.4. L hng trong cu trc

C hai loi l hng trong cu trc: L hng khi 8 mt (octahedral site) to bi
6 nguyn t v l hng khi 4 mt (tetrahedral site) to bi 4 nguyn t. K hiu vng
trn mu trng l tm cc l hng, vng trn mu en l tm cc nguyn t.
L hng khi 8 mt

Cu
trc
Bcc
Fcc
Hcp

Fcc

Bcc
L hng khi 4 mt

Hcp

Fcc

Bcc

Hcp

L hng khi 4 mt
rl / rnguyn t
0,291
0,225
0,225

L hng khi 8 mt
rl / rnguyn t
0,155
0,414
0,414

S l khi S l khi
4 mt /
8 mt /
12
6
8
4
12
6

4.2. Cu trc hp kim

Khi cho cc kim loi trng thi lng ha tan vo nhau hoc vi mt vi kim
nh: C, H, B, N, sau lm ngui tr v trng thi rn ta s thu c hp kim. Mi
kim loi gi l mt nguyn, v d hp kim hai nguyn Pb Sn, hp kim ba nguyn Ag
Au Cu.
Ty thuc vo bn cht cc nguyn t v nhng iu kin bn ngoi m hp kim
c th to ra hai loi pha khc nhau: dung dch rn v pha trung gian.
4.2.1. Dung dch rn
4.2.1.1. Tnh cht chung
Trong dung dch rn, nguyn t c lng cha nhiu hn gi l nguyn t dung
mi, cc nguyn t khc l nguyn t ha tan.
B ha tan trong A th k hiu l A(B) hoc dng , ,
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 Mng tinh th ca dung dch rn ging vi kiu mng ca nguyn t dung mi.
S sp xp ca B trong A ni chung l khng c quy lut, trong mt s iu kin
nht nh, s sp xp ny tr nn c quy lut to dung dch rn c trt t.
Mi lin kt trong dung dch rn l lin kt kim loi nh trong nguyn t dung mi.
4.2.1.2. Phn loi:
Dung dch rn xen k: nguyn t ca nguyn t ha tan chen vo nm cc l hng
4 mt hoc 8 mt trong mng tinh th ca nguyn t dung mi.
Dung dch rn thay th: nguyn t ca nguyn t ha tan thay th nguyn t ca
nguyn t dung mi cc nt mng.

4.2.1.3. Mc ha tan:
Dung dch rn ha tan v hn: B ha tan trong A vi lng bt k.
Dung dch rn ha tan c hn: B ch ha tan trong A n mt gii hn.
4.2.1.4. Dung dch rn xen k
Ni chung to dung dch rn xen k th nguyn t ca nguyn t ha tan phi
nh hn ng k nguyn t ca nguyn t dung mi (v ng knh). Ngoi ra kch
thc ca nguyn t ha tan phi nh hn hoc bng kch thc l hng trong mng
tinh th ca dung mi. Tuy nhin do nguyn t khng phi l mt hnh cu nh gi
thit, nn trong mt s trng hp, dung dch rn xen k vn c to thnh d kch
thc nguyn t ha tan ln hn kch thc l hng.
V d bn knh r(C) = 0,077 nm v r(Fe) = 0,124 nm trong cu trc Bcc.
T s r(C) / r(Fe) = 0,077 / 0,124 = 0,62. Tuy nhin t s gia kch thc l hng
v bn knh nguyn t trong mng Bcc l k /r 0,155 i vi l hng 8 mt v k / r
0,291 i vi l hng 4 mt. Nh vy theo l thuyt th cacbon khng th to dung
dch rn xen k vi Fe c v c kch thc ln hn kch thc l hng. iu ny tri
vi thc t (s tn ti ca gang, thp), l do trong l thuyt chng ta gi s cc
nguyn t c dng cu.
Khi to dung dch rn xen k th s nguyn t / c s s tng ln nhng kiu
mng tinh th ca dung mi khng thay i.
S lng cc l hng trong mng l c gii hn, v vy dung dch rn xen k lun
lun l dung dch rn ha tan c hn.
4.2.1.5. Dung dch rn thay th
Theo quy tc Hume Rothery, to dung dch rn thay th th cc iu kin sau
y phi c tha mn:
a. Chnh lch ng knh gia nguyn t dung mi v nguyn t ha tan phi < 15%.
b. m in ca hai nguyn t phi xp x nhau.
c. Ha tr ca hai nguyn t phi ging nhau.
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d. Cu trc tinh th ca hai nguyn t phi ging nhau.

iu kin d ch p dng khi mun to dung dch rn ha tan v hn. iu kin
ny c th b qua khi to dung dch rn long (hm lng nguyn t ha tan rt nh).
V d: r (Ni) = 0,128 nm, r (Cu) = 0,125 nm, d= 2,4%. Ngoi ra m in ca
Cu l 1,9 v ca Ni l 1,8. Ha tr ca Cu l +1, +2, cn ca Ni l +2. C Cu v Ni u
c cu trc Fcc. C 4 iu kin u tha nn Cu Ni c th to dung dch rn thay th
ha tan v hn.
4.2.2. Pha trung gian
Mng tinh th ca pha trung gian khc vi mng tinh th cc nguyn t to
thnh. Cu trc ca cc pha trung gian ph thuc vo kch thc nguyn t, ha tr v
v tr ca nguyn t trong bng phn loi tun hon.
4.2.2.1. Hp cht ha hc ha tr thng
To thnh gia cc nguyn t khc loi theo mt t l nht nh vi dng lin kt
ch yu l ion hoc cng ha tr.
V d: Mg2Cu: lin kt cng ha tr: pha c c tnh kim loi.
MgCl2: lin kt ion:

pha c c tnh mt mui.

Trong tinh th ca hp cht ha hc, cc nguyn t khc loi sp xp xen ln

nhau theo mt trt t nht nh to thnh mng tinh th ring ca hp cht ha hc.
V d: Mg2Pb c kiu mng CaF2 nhng MgS c kiu mng ca NaCl.
4.2.2.2. Pha xen k
Cc kim nh: C, H, B, N khi to hp kim vi cc kim loi chuyn tip c th
to dung dch rn xen k, nhng cng c th to ra cc pha trung gian c kiu mng
tinh th khc vi kiu mng ca dung mi (kim loi).
Khi d( kim) / d(kim loi) < 0,59 th cc kim s nm trong l hng ca mng
tinh th kim loi, v vy pha trung gian c gi l pha xen k v c cng thc ph
bin l MX, MX2.
V d r c cu trc Bcc nhng ZrH, ZrH2 c cu trc Fcc.
Mc d % kim tng i ln, nhng cc pha xen k u mang tnh kim loi (c
nh kim, dn in, nhit tt), c nhit nng chy v cng cao.
4.2.2.3. Pha in t
a. Nng in t: s e- ha tr tnh cho mt nguyn t, k hiu Cdt
Kim loi nguyn cht: Cdt = ha tr kim loi
Hp cht
: Cdt = i xi
(i: Ha tr nguyn t i, xi: phn nguyn t nguyn t i)
b. Pha in t:
Khi Cu, Ag, Au to hp kim 2 nguyn vi kim loi khc s to ra cc pha c kiu
mng nht nh khi tng thnh phn cu t th hai.
Trong h Cu- Zn, ngi ta thy khi % Zn tng ln s to cc pha khc nhau
Pha (< 50% Zn)
to dung dch rn thay th c kiu mng ca Cu
Pha (50% Zn)
to pha CuZn
Pha (61% Zn)
to pha Cu5Zn8
Pha (75% Zn)
to pha CuZn3
9

Xem Cu c ha tr 1, Zn c ha tr 2 th nng in t
1x1 + 2 x1 3
=
2
2
1x1 + 2 x 3 7
C dt (CuZn 3 ) =
=
4
4
C dt (CuZn ) =

C dt (Cu 5 Zn 8 ) =

1x 5 + 2 x8 21
=
13
13

Khi nghin cu cc pha to thnh trong hng lot h khc, ngi ta thy rng
chng cng tn ti vi cc C dt 3/2, 21/13, 7/4 v c kiu mng ca pha , , nh
trong h Cu-Zn. S tn ti cc pha ny c lin quan n tr s nng in t nn
c gi l pha in t. Cc pha in t cn c to thnh trong h kim loi chuyn
tip nu xem cc kim loi ny c ha tr = 0.

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