11/9/2013

CC NI DUNG CHNH
Gii thiu tia X
An ton bc x
Qu trnh to tia X
nh lut Bragg (Braggs law)
Cc phng php phn tch bt (powder

difraction)
Phng php nh danh cc pha tinh th
1

CC NI DUNG CHNH
Cc phn mm thng dng trong nghin cu

tia X.

Phn mm origin 8.0

Tnh kch thc tinh th (origin 8.0)

Tnh thng s mng ( Unicell)

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KHI NIM TIA X

William Rontgen, tm ra tia X vo ngy 8 thng

11 nm 1895, nh vt l u tin nhn gii Nobel vt

l vo nm 1901.
Tia X l loi sng in t c bc sng ngn.
Bc sng: 10-8m 10-11m
Nng lng: 200eV 1MeV
Bc sng ca tia X s dng trong phn tch cu

trc: khong 1 (10-10m).

11/9/2013

KHI NIM TIA X (tt)

Cc tnh cht ca tia X:

Tia X truyn theo ng thng.

Tia X b hp th theo t l hm m theo khi lng
ca cht hp th.
C kh nng xuyn qua 1 s tm chn thng
thng, lm en phim nh.
Kh nng gy hin tng pht quang (ph hunh
quang tia X).
Gy s ion ha cht kh.
Tc dng mnh ln c th sng, gy hi cho sc
khe.

KHI NIM TIA X (tt)

Tia X pht ra t cc ng pht l cc bc x lin tc

gm nhiu bc sng khc nhau (do cc in t mt

nng lng trong cc va chm vi cc nguyn t
anode).
Mi electron mt nng lng theo cc cch khc

nhau nn ph tia X thu c l lin tc.

11/9/2013

KHI NIM TIA X (tt)

Bc sng ca tia X c trng cho tng kim loi lm
anode c xc nh bi nh lut Moseley:
1/ = R(Z-1)(1-1/n2)
: bc sng;
R = 109678 cm-1, hng s Rydberg;
Z: s hiu nguyn t;
n l mt s nguyn, n = 2, 3 i vi vch K v K
tng ng
7

Cac phng phap phn tich bng tia X

Nhiu x tia X

Phn tch cu
trc ca cht
rn

Hunh quang tia X

Xc nh hm lng
nguyn t c trong mu

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Lng bc x v cc khi nim

Khi

lm vic ni phn tch tia X:

Nhn

thc v s nguy him tim tng lin quan n s tip

xc lin tc hoc cp tnh vi bc x tia X.

Cn

phi hiu bit cc nguy c v tun th nghim ngt

cc quy nh bo v ngi vn hnh thit b phn tch
tia X v nhn vin lm vic gn ngun pht ra tia X.

10

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Lng bc x v cc khi nim

Kh

nng mt photon s hon ton xuyn qua mt mi

trng ph thuc vo rt nhiu yu t:

Nng lng ca tia X

dy ca mi trng.

Nng

lng ca qu trnh bc x ion ha khi tng tc vi

vt cht c th dn n vic ph v cc lin kt ha hc.

Nu

chiu x vo m sng, c th lm thay i cu trc

hoc chc nng ca t bo.

11

Lng bc x v cc khi nim

liu lng hp th tng ln, cc kh nng xy ra ung
th hoc nh hng di truyn cng tng.

Khi

Tuy nhin, khi liu lng hp th cao, th thi im

cng khng chc chn rng ung th hoc gy tn hi di
truyn s xy ra.
c bt k ngng no m di n l chc chn
rng mt tc ng bt li khng th xy ra.

Khng

: chm tia X (phn tch cu trc) thng c s

dng vi cng rt cao.

Ch

12

11/9/2013

nh hng sinh hc
Tip

xc vi bc x khng ch t cc chm tia chnh m

cn t cc tia phn tn (hoc nhiu x) v bc x th cp
t mu hoc cc vt liu cch ly.

Thng

c gi l tia X mm v n d dng b cch ly

(~mm ch).
X c bit nguy him v chng c hp th ngay c
bi cc m mm.

Tia

13

nh hng sinh hc
Tip

xc di hn vi mc tng i thp:

C kh nng bt u gy ung th

Hoc gy tn hi di truyn.

Tip

xc ngn hn vi mc tng i cao (tip

xc cp tnh), c kh nng nh:

Ban

Rng tc

Lot

Ung th.
14

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Cac tiu chun kim soat

Yu

cu i vi thit b

Thit b ngt tia: lm cho chm tia phi dng li

L chn: cng vo ca ngun c trang b mt l chn m

khng th c m ra tr khi mt ng chun trc hoc khp ni
c kt ni vi u ng .

H thng kho lin ng bo v: Mi ng tia X c trang b

vi mt kho lin ng tt ng nu ng c ly ra t cc khung bo
v.

V bc cch ly

n cnh bo: X-RAY ON

Ghi nhn

15

Cac tiu chun kim soat

Yu

cu i vi s hot ng, vn hnh

Tun th cc quy nh v an ton

KHNG b qua thit b an ton

KHNG thay i thnh phn h thng

My pht hin phng x cho nhn vin

o to v cc vn lin quan n bc x v vn
hnh thit b.

16

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17

PHN LOI NGUN TO RA TIA X

Tia X c to thnh t 2 phng php:

Phng php 1: pht ra t ng tia X (s tng tc ca

cc electron nng lng cao vi tm kim loi).

Phng php th 2: tia X c to ra t thit b c

gi l Synchrotron s dng cc in t c nng lng
cao chuyn ng thnh qu o trong h thng kn v
c nh hng trung tm ca vng trn v pht ra
bc x in trng.

18

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TO RA TIA X T NG PHT
Cc b phn chnh pht tia X:

ng pht: Anode (v cathode) t trong ng thy

tinh bng thch anh, p sut (10-6- 10-7 mmHg).

Cathode K (Vonfram) pht ra chm in t khi

c t nng.
Anode (Vonfram, Cu, Ni, Mo, Cr). in th p t
vo anode ~ 100kV.

19

TO RA TIA X T NG PHT
Tia X c to ra trong ng tia X (X-ray tube) l qu trnh
bn ph ca mt chm tia electron (trong electron
c to ra bi dng in 30-45kV, thm ch 100kV) vo
bia kim loi (metallic target).

Beam of electrons

Target

X-rays

20

10

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TO RA TIA X T NG PHT
Chm tia in t t cathode c gia tc do in
p ln cathode s bay v pha anode vi vn tc
ln. Cc in t ny c ng nng ln, nn khi va
p vo anode phn ln bin thnh nhit nng.
Hu ht nng lng ca electron b hp th bi kim
loi v <1% nng lng tia electron pht ra tia X.

21

NGUN TO RA TIA X

22

11

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TO RA TIA X T NG PHT
Chm tia X sinh ra thot ra ngoi qua cc ca s

bng beryllium.
Chiu dy ca Be lm ca s c kch thc ~0,25mm.

Be (t hp th tia X nht trong cc loi vt liu) cho

php tia X i qua, ng thi chu c p sut c

chn khng khong 10-7 mmHg.

23

Qu trnh to tia X ca anode ng

Chm electron ca tia ti c
nng lng ln lm bt 1
electron ca lp K (1s). Kt
qu l lm nguyn t ca Cu
(Copper target) b kch thch
v to 1 l trng.

24

12

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Qu trnh to tia X ca anode ng

Khi l trng lp K (1s) c in y bi mt electron

lp L, M, th thu c dy vch K, K,

V d: (i vi kim loi Cu)

K =0.15418 nm
K =0.13922 nm

25

Qu trnh to tia X ca anode ng

Cc

vch L, L xut hin l do s chuyn dch

electron t lp M (n=3), N(n=4) v lp L (n=2)

Bc x ca tia K mnh hn K, L .
Trong nghin cu nhiu x tia X thng s dng tia K

ca ca cc kim loi khc nhau (c bit l kim loi

Cu). V vch K c nng lng ln, khng b hp th
bi vt liu nghin cu, n sc cao.

26

13

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Qu trnh to tia X ca anode ng

Qu trnh m 1 electron orbital lp ngoi (2p hoc

3p) in vo l trng orbital 1s th 1 photon tia X c

to ra.
Nng lng ca photon pht ra c gi tr bng hiu

ca 2 mc nng lng .
Nng lng ca photon pht ra c trng cho tng kim

loi.
Tm li: Qu trnh 1electron orbital 2p hoc 3p in

vo l trng orbital 1s pht ra nng lng v to ph

tia X.
27

Qu trnh to tia X ca anode ng

28

14

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Qu trnh to tia X ca anode ng

Chiu di sng pht ra tia X

ph thuc vo tng loi
nguyn t lm bia (ph
thuc vo in tch ht
nhn).

R(Z - 1)2 (1 -

1
2

)
29

Qu trnh to tia X ca anode ng

Cn phi dng knh lc

loi b bc x tng
v bc x K.

30

15

11/9/2013

Qu trnh to tia X ca anode ng

Bc

x K l bc x kp: K1=0.154051nm,
K2=0.154433 nm. S d gi tr K1 khc K2 l v s
khc nhau v gi tr spin ca 2 electron 2p.

Trong nhiu trng hp c bit, bc x yu K2 c th

loi b. Tuy nhin, hu ht cc my phn tch tia X (Xray diffractometers ) khng tch ri 2 tia bc x ny.

31

Cc c trng ca VL lm Anode
Nguyn
t

K1 (nm)

K2 (nm)

Ngng
V

Cr

24 0,229361

0,228970

0,208487

5950

Fe

26 0,193736

0,193998

0,193604

7100

Co

27 0,179026

0,179285

0,178897

7700

Ni

28 0,1662

0,1658

0,1500

8300

Cu

29 0,154051

0,154433

0,13922

9000

Mo

42 0,071073

0,071359

0,070930

20000

Ag

47 0,0564

0,0559

0,0497

25600

32

16

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TIA X N SC
Trong phng php phn tch nhiu x tia X ngi ta

ch s dng cc bc x n sc.
Thng thng ngi ta chn vch K v lc loi b cc

vch khc, c bit l vch K bng cch cho chm tia

X (sinh ra t ngun pht) i qua mt l mng ca kim
loi c bin hp th thch hp hp th bc x K v
cho bc x K i qua

V d: Ni s hp thu vch K ca i catod bng ng,

Nb hp th vch K ca molybden

33

TIA X N SC
Trong nghin cu nhiu x tia X thng s dng
tia K ca ca cc kim loi ng (Cu) v knh lc
l Niken kim loi lc tia K.

34

17

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B LC TIA TNG NG VI CC ANODE

35

36

18

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NH LUT BRAGG
nh lut Vulf-Bragg c a ra nm 1913 th hin

mi lin h gia bc sng tia X v khong cch gia

mt phng nguyn t.
Tia nhiu x c coi l tia phn x
nh lut Vulf-Bragg gi thit rng mi mt phng

nguyn t phn x sng ti nh gng phn x v

mt phng nguyn t c coi l mt phn x.

37

NH LUT BRAGG
1

Gi thit hai tia ti n sc, song song v cng pha vi

bc sng , cng gc ti .

38

19

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NH LUT BRAGG

Gi s c hai mt phng song song AA v BB c cng

ch s Miller h, k, l, v cch nhau bi khong cch gia
cc mt phng nguyn t dhkl.
Hai tia 1 v 2 b tn x bi nguyn t O, P cho 2 tia phn
x song song 1 v 2, c cng gc so vi mt phng A,
B.

39

NH LUT BRAGG
iu kin nhiu
x: n = 2dsin
l bc sng tia
ti.
d l khong cch
gia cc mt phng
phn x.
l gc phn x.
n l bc phn x.
40

20

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NH LUT BRAGG
n = 2dsin
Trong hu ht cc trng hp, bc phn x th nht
(n = 1) c s dng, v nh lut Bragg c vit:

= 2dsin

41

CNG NHIU X
Cng tia X tn x bi ht nhn l rt nh, b qua.
Sng tn x ton phn ca nguyn t bng tng cc sng tn x

ca cc electron trong nguyn t .

Sng tn x ca mi nguyn t c trng bi 2 i lng l:

cng v gc tn x (2).

Cng tn x tng cng ph thuc vo hng tn x (do cc

sng thnh phn c cc pha khc nhau).
Tha s tn x nguyn t f ( c s dng m t hiu sut tn

x ca nguyn t theo 1 hng xc nh):

bin sng tn x bi mt nguyn t

f =
bin sng tn x bi mt electron
42

21

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CNG NHIU X
v . f t l thun
vi s Z, f gim khi tng v gim.

Gi tr f ph thuc v

30

th f l mt hm ca (sin)/, i vi

Cu, f gim t 29 khi (sin)/ tng.

fCu
20

Gi tr ca f c cho App. 8 (B.D.

Cullity, Elements of X-ray diffraction,

1956,
Addison-Wesley
Publishing
company, Inc, pp475-476).

fO

ln ca cc sng tn x thnh phn

ca cc nguyn t, k hiu: fj. fj t l

thun vi s hiu nguyn t, t l nghch
vi gc Bragg ().

fAl

10

10

sin
nm-1

43

CNG NHIU X
Tha s tn x

sin/
()-1

44

22

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CNG NHIU X
i vi nguyn t j (trong mng c s-unit cell), ln
sng nhiu x l fj v c pha (gc) j, sng nhiu x c
biu din:
Fj=fj (cosj + isin j)
Fj=fj eij

Hoc

F: tha s cu trc (structure factor).

45

CNG NHIU X
Cng thc:
eix=cosx + isinx
Aei=A (cos + isin )
Aei 2=A2

46

23

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CNG NHIU X
Cng nhiu x:
I Qfj2

Hng s cu trc ( ln cu trc) Fhkl i vi mt

phng nhiu x hkl:
N

Fhkl ( f j [cos j i sin j )]

j 1

47

CNG NHIU X
lch pha gia hai sng tn x bi hai nguyn t gc
ta (A(0,0,0)) v nguyn t B (u, v, w) i vi mt
phng phn x (hkl) l:

= 2(hu+kv+lw)
N

Fhkl f j exp[ 2i (hu j kv j lw j )]

j 1

48

24

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CNG NHIU X
Fj2=fj2 (cos2j + sin2j)
Ihkl QFhkl2
Fhkl

Cng tia nhiu x t l thun vi |F(hkl)|2.

j 1

j 1

( f j cos j ) 2 ( f j sin j ) 2

Cc phn x c F = 0 s c cng bng 0.

Phng trnh trn p dng cho mi mng tinh th.

Cho php xc nh nhng phn x (hkl) no mc d

tha mn iu kin Bragg nhng khng quan st
c.
49

CNG NHIU X
A. Mng lp phng n gin (Simple Cubic)
Xt c s ch gm mt nguyn t
v tr (0,0,0).

F f j ei f j ei 2 ( hu kv lw)
F f ei 2 ( h0 k 0l 0) f e0 f
F2 f 2

F is independent of the scattering plane (h k l)

50

25

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CNG NHIU X
A. Mng lp phng n gin (Simple Cubic)
F khng ph thuc vo h, k, l; mi phn x (tha mn

iu kin Bragg) u xut hin trn gin nhiu x.

Cc phn x l:

(100), (110), (111), (200), (210), (211), (220), (300), (221), (310),

51

CNG NHIU X
B. Mng lp phng tm khi (Body Centred Cubic)
Xt mt c s gm: mt nguyn t v
tr (0,0,0) & mt nguyn t (1/2,1/2,1/2)

F f je
F fe

i j

f je

i 2 ( hu kv lw) j

i 2 ( h 0 k 0 l 0 )

fe

1 1 1
i 2 ( h k l )
2 2 2

f e 0 fe i ( h k l ) f [1 ei ( h k l ) ]
52

26

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CNG NHIU X
B. Mng lp phng tm khi (Body Centred Cubic)
Nu (h+k+l) l s chn: F = 2f
Nu (h+k+l) l s l th F = 0

quan st c

khng quan st c

Cc phn x quan st c:

(100), (110), (111), (200), (210), (211), (220), (300), (221), (310),

53

CNG NHIU X
C. Mng trc thoi tm y (C-Centred Orthorhombic)
Xt mt c s gm: mt nguyn t v
tr (0,0,0) & mt nguyn t (1/2,1/2,0).

F f e

i 2 ( h 0 k 0 l 0 )

fe

1
1
i 2 ( h k l 0 )
2
2

f e 0 fe i ( h k ) f [1 ei ( h k ) ]

(ab c)
===90o

54

27

11/9/2013

CNG NHIU X
C. Mng trc thoi tm y (C-Centred Orthorhombic)
Nu (h+k) chn (even):(both even or both odd)
e.g. (001), (110), (112); (021), (022), (023)

F = 2f quan st c
Nu (h+k) l (odd): (mixture of odd or even)
e.g. (100), (211); (210), (032), (033)

F = 0 khng quan st c

55

CNG NHIU X
D. Mng lp phng tm mt (Face centered Cubic):
Xt bn nguyn t v tr (0,0,0), (1/2,1/2,0),
(0,1/2,1/2), (1/2,0,1/2)
hk
k l
l h
i [ 2 (
)]
i[ 2 (
)]
i [ 2 (
)]

2
2
2
F f ei[ 2 ( 0)] e
e
e

i ( h k )
i ( k l )
i ( l h )
f [1 e
e
e
]

(, , 0), (, 0, ), (0, , )

56

28

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CNG NHIU X
D. Mng lp phng tm mt (Face centered Cubic):
Nu h, k, l cng chn hoc cng l (unmix):
e.g. (111), (200), (220), (333), (420)

Nu h, k, l l hn hp (mixed):
e.g. (100), (211); (210), (032), (033)

57

CNG NHIU X
Unmixed

CASE h

odd

odd

odd

even

even

even

CASE A : [1 ei (e) ei (e) ei (e) ] [1 1 1 1] 4

CASE B: [1 ei (e) ei ( e) ei ( e) ] [1 1 1 1] 4

F 4f
Quan st c

F 2 16 f 2

e.g. (111), (200), (220), (333), (420)

58

29

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CNG NHIU X
Mixed indices

CASE

odd

odd

even

odd

even

even

CASE A : [1 ei (e) ei (o) ei (o) ] [1 1 1 1] 0

CASE B: [1 ei (o) ei ( e) ei ( o) ] [1 1 1 1] 0

F 0

F2 0

Khng quan st c
e.g. (100), (211); (210), (032), (033)

59

CNG NHIU X
E. Mng kim cng:
Xt tm nguyn t v tr:

(0,0,0), (0,1/2,1/2), (1/2,0,1/2), (1/2,0,0), (1/4,1/4,1/4),

(1/4,3/4,3/4), (3/4,1/4,3/4), (3/4,3/4,1/4)
Tnh F:

60

30

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CNG NHIU X
E. Mng kim cng:
F = f.[1+ ei..(h+k) + ei..(k+l) + ei.2.(h+l) + ei..(h+k+l)/2 +
ei..(h+3k+3l)/2 + ei.2.(3h+3k+l)/2 + ei.2.(3h+3k+l)/2]
Cc phn x khng quan st c:

(100), (110), (111), (200), (210), (211), (220), (300), (221), (310),

61

CNG NHIU X
F. Mng NaCl (Face Centred Cubic)
Na+ at (0,0,0), (, , 0), (, 0, ), (0, , )
Cl- at (, 0, 0), (0, , 0), (0, 0, ), (, , )

Tnh F:
hk
k l
l h
i [ 2 (
)]
i [ 2 (
)]
i [ 2 (
)]

2
2
2
F f Na ei[ 2 ( 0)] e
e
e

h
k
l
h k l
i[ 2 ( )]
i[ 2 ( )]
i [ 2 (
)]
i[ 2 ( 2 )]
2
2
2
f Cl e
e
e
e

62

31

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CNG NHIU X
F. Mng NaCl ( Face Centred Cubic)
F f Na [1 ei ( h k ) ei ( k l ) ei (l h ) ]
f Cl [ei ( h ) ei ( k ) ei (l ) ei ( h k l ) ]
F f Na [1 ei ( h k ) ei ( k l ) ei (l h ) ]
f Cl ei ( h k l ) [ei ( k l ) ei ( l h ) ei ( h k ) 1]
F f Na [1 ei ( h k ) ei ( k l ) ei (l h ) ]
f Cl ei ( h k l ) [ei ( k l ) ei ( l h ) ei ( h k ) 1]
63

CNG NHIU X
F. Mng NaCl ( Face Centred Cubic)
F [ f Na f Cl ei ( hk l ) ][1 ei ( h k ) ei ( k l ) ei (l h) ]
Mixed indices

CASE

odd

odd

even

odd

even

even

CASE A : [1 ei (e) ei (o) ei (o) ] [1 1 1 1] 0

CASE B : [1 ei (o) ei (e) ei (o) ] [1 1 1 1] 0

F 0

F2 0
64

32

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CNG NHIU X
Unmixed

CASE h

odd

odd

odd

even

even

even

NaCl:
Face Centred Cubic

CASE C : [1 ei (e) ei (e) ei (e) ] [1 1 1 1] 4

CASE D : [1 ei (e) ei (e) ei (e) ] [1 1 1 1] 4

F 4[ f Na f Cl ei ( h k l ) ]
If (h + k + l) is even

e.g. (111), (222); (133), (244)

F 4[ f Na f Cl ]

e.g. (222),(244)

If (h + k + l) is odd
e.g. (111), (133)

F 4[ f Na f Cl ]

F 2 16[ f Na f Cl ]2
F 2 16[ f Na f Cl ]2
65

CNG NHIU X
F. Mng NaCl (Face Centred Cubic)
h, k, l cng chn th F = 4(fNa + fCl)
h, k, l cng l th F = 4|fNa fCl|
h, k, l l hn hp th F = 0

khng quan st c

66

33

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CNG NHIU X
Loi tinh th

Mng Bravais

Phn x quan st c

Phn x b cm

n gin

n gin

h, k, l bt k

Khng c

Tm khi

Tm khi

h + k + l chn

h + k + l l

Tm mt

Tm mt

h, k, l cng chn hoc l

h, k, l hn hp

NaCl

Lptm

h, k, l cng chn hoc l

h, k, l hn hp

Kim cng

Lptm

Nh lptm, nhng nu tt
c cng chn v h + k + l
4N th khng c

h, k, l hn hp v
cng chn nhng h
+ k + l 4N

Tm y

Tm y

h v k chn hoc c hai

cng l

h v k hn hp

Lc phng
cht kht

Lc phng

h + 2k = 3N vi l chn
h + 2k = 3N + 1 vi l l
h + 2k = 3N + 1 vi l l

h + 2k = 3N vi l l

67

h2 + k2 + l2

SC

100

110

111

111

200

200

210

211

FCC

BCC

DC

110
111
200
211

7
8

220

220

300, 221

10

310

11

311

311

12

222

222

13

320

14

321

220

220

310
311
222
321

15
16

400

17

410, 322

18

411, 330

19

331

400

400

400

411, 330
331

331

68

34

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CNG NHIU X
V d:
CaF2, c cu trc fluorite vi v tr ca cc
nguyn t trong mng (lp phng tm din).
a=5.464, =1.5418 (Cu K)
Ca

(0,0,0)

(, , 0)

(, 0, )

(0,, )

( , , ) ( , , )

(, , )

(, , )

(, , )

(, , )

(, , )

(, , )

Tnh F202
69

70

35

11/9/2013

71

72

36

11/9/2013

Tnh F202
a=5.464 d202=1.929
=2dsin(202), =1.5418
sin(202)=0.4 202 = 23.6o.
[sin(202)]/=0.259
T Fig.5.36(b) fCa=12.65, fF=5.8
F202=4fCa+8fF=97
73

74

37

11/9/2013

PHNG PHP BT
(POWDER DIFFRACTION)
Phng php bt c s dng hu ht trong nghin

cu nhiu x. Mc d tn gi l phng php bt,

nhng mu dng tinh th th hon ton c th s
dng cho phng php bt.
V bt gm v s vi tinh th nh hng hn lon cho

nn khi chiu mt tia n sc vo mu a tinh th, lun

c th tm c c nhng mt (hkl) (vi d(hkl) tng
ng) nm v tr thch hp, tho mn iu kin VulfBargg 2dhklsin=n v cho tia nhiu x.

75

PHNG PHP BT
Nguyn tc ca phng php bt:
S dng tia X n sc
Mu: dng bt hoc dng vin nn.

76

38

11/9/2013

PHNG PHP BT
A few useful experimental tips are listed as follows:
The powder should be ground, preferably to the size

of 1 10 m. If the particle size is too large, the

sample can not provide every crystal plane with
equal probability. The particle sample taken right
after high temperature heat treatment is not
adequate for XRD diffraction pattern, since the
particles generally developed certain preferred
crystal plane.

If the particle size is too small, the reflection peak

shall be broadened. The peak width can be used to

study the particle size. But for a standard reflection
pattern, the broadening is an undesirable side effect.
77

PHNG PHP BT
It will be nice if the ground powder sample is

sieved to ensure the particle size.

Sometimes the ground and polished ceramic

surface can be used for XRD diffraction pattern, if

you are sure that there is no preferential crystal
growth in the ceramic sample. It is convenient for
some ceramic studies. Again the surface has to
be ground and polished so that the preferential
growth is eliminated.

78

39

11/9/2013

PHNG PHP BT

Hai phng php thu kt qu nhiu x tia X t

phng php bt:

Phng php Debye-Sherrer.

Phng php diffractometer.

79

Phng php CHP FILM

Debye - Scherrer
Thit b: Phim c lt st vo
thnh trong ca mt hp kim loi
hnh tr - gi l camera. Camera
c bn knh xc nh.
Mu c t trn mt gi
nm trc trung tm ca
camera.
Kt qu: trn phim c nhng
cung trn i xng qua vt trung
tm.
Yu cu ca phng php l
vch nhiu x phi mnh, c
en u, nn phim phi sng
c c cc vch yu.
80

40

11/9/2013

Phng php CHP FILM

Debye - Scherrer
Sample

Phim c ra, ct v tri

phng.
o khong cch tng i
gia cc vch, tnh gc phn
x, t xc nh c cc
c trng ca tinh th nghin
cu.
Phim

81

Phng php CHP FILM

Debye - Scherrer

C th t mt tm phim pha
trc hoc sau mu hng
cc chm tia nhiu x.
Trn phim l cc vt trn ng
tm.
Cch ny c hiu qu i vi cc nhiu x c gc nh hoc gn 180o
82

41

11/9/2013

Phng php CHP FILM

Debye - Scherrer

S1
2W

Hoc

S2
1
2 W

83

Phng php CHP FILM

Debye - Scherrer
Phng php xc nh:

T nhng kt qu ghi nhn c, c th xc nh

cu trc v thng s mng ca vt liu, bng cch:

Xc nh khong cch S1 t mt vch nhiu x n

tm ca l en (to bi chm tia ti).

i vi chm tia phn chiu (ngha l khi 2 > 90)

ta c th dng cc khong cch S2.

84

42

11/9/2013

Phng php CHP FILM

Debye - Scherrer
Khong cch S1 tng ng vi gc nhiu x 2.
Gc gia chm tia nhiu x v chm tia ti lun lun l

2.
Khong cch W gia cc chm en trn phim ng vi

gc nhiu x =.

Gc c tnh nh sau:

S1
2W

hoc

S
(1 2 )
2
W
85

Phng php CHP FILM

Debye - Scherrer
Theo nh lut Bragg n = 2dsin v khong cch d gia
cc mt trong cng mt h mt phng hkl c cho bi
cng thc:

d hkl

a
2
h k2 l2

sin 2

2
4a

(h 2 k 2 l 2 )

T cc kt qu o S1 sin2 tng ng (lp bng).

Gi s cu trc ca vt liu (v d SC, BCC, FCC) tnh cc
gi tr (h2+k2+l2).
T tm hng s mng a v chn cu trc vt liu.
C th o c cng tng i ca mt vt bng cch so snh
en ca n (I) vi en ca vt c cng mnh nht (Io) trn phim.
Cng tng i ca mt vt c tnh bng: I/Io
86

43

11/9/2013

Phng php CHP FILM

Debye - Scherrer
V d:
Mt vt liu c cu trc lp phng c phn tch X-ray
bng cch chp phim Debey, kt qu S1 (mm) c gi tr
nh sau: 17, 19.5, 28, 33, 34.5, 40, 43.5, 45.
Cho bit bn knh bung Debey l 57.35mm, tia X c bc
sng =0.71069.
Xc nh:
Cu trc lp phng ca vt liu.
Thng s mng a () ca vt liu.
87

Phng php CHP FILM

Debye - Scherrer

W
S1

sin
sin2
SC
K
a2
BCC
K
a2
FCC
K
a2

0.71069
180.5378
17

Ao
mm
19.5

57.35

mm

28

33

34.5

40

43.5

45

10

12

14

16

11

12

16

19

20

aTB

88

44

11/9/2013

Phng php CHP FILM

Debye - Scherrer

W
S1

0.71069
180.5378
17

8.4746795 9.720956 13.9583 16.45085 17.19861 19.94042 21.68521

sin
sin2
SC
K
a2
BCC
K
a2
FCC
K
a2

Ao
mm
19.5

28

57.35

mm

33

34.5

40

0.147
0.169
0.241
0.283
0.296
0.02
0.03
0.06
0.08
0.09
1
2
3
4
5
46.043 70.150 51.559 49.876 57.189
5.814
8.858
6.510
6.298
7.221
2
4
6
8
10
92.087 140.300 103.119 99.753 114.377
11.628 17.716 13.021 12.596 14.442
3
4
8
11
12
138.130 140.300 137.492 137.160 137.253
17.442 17.716 17.361 17.319 17.331

0.341
0.12
6
51.586
6.514
12
103.172
13.028
16
137.563
17.370

43.5

0.370
0.14
8
58.593
7.398
14
102.537
12.947
19
139.157
17.571

45
22.4329
8
0.382
0.15
aTB
9
61.804 2.650
7.804
16
109.874 3.689
13.874
20
137.343 4.175
17.342

89

DIFRACTOMETER

ewfref

My o nhiu x tia X, D8 Bruker.

90

45

11/9/2013

DIFRACTOMETER
Cu to ca my m nhiu x bt gm c nhng b phn
chnh sau y:
ng pht tia X

B lc n sc: Thng dng n tinh th n sc

ho chm tia (chm tia ch cn mt bc sng duy nht, v
d K).
Gi mu: gm curvet cha mu bt hoc mu khi
mng (vin dp). Gi mu cng vi mu c th quay
quanh v tr cc mt phng tinh th u ri vo gc
nhiu x.
91

DIFRACTOMETER
ng m: dng ghi cng tia nhiu x da trn
nguyn l in ho cht kh cha trong ng m bi chm
tia X nhiu x.
ng m quay t gc 0o (v tr ca chm tia xuyn qua)
n 180o ghi li tt c cc nhiu x t mu (nhiu x t
cc h (hkl)) di dng ph.

92

46

11/9/2013

DIFRACTOMETER
u d (detector) c
kt ni vi gi ng
mu bng mt h thng
c kh chnh xc v
chuyn ng trn cung
trn ABC. Gc c
o chnh xc v c
bc nhy (step size)
khong 0,03o.

B
C

My m

My phng tia X

Gi

A
Vng gic k

Kt qu: gin nhiu x ( th hin mi quan h gia

cng v gc 2 () ).
93

DIFRACTOMETER
Bao gm cc peak c cng khc nhau. Mi peak
tng ng vi mt phn x ca h mt (HKL).
Hai yu t chnh quyt nh n hnh dng ca gin
nhiu x tia X:
(a) Kch thc v hnh dng ca mng n v (unit
cell)
(b) S nguyn t v v tr cc nguyn t trong n v.

94

47

11/9/2013

Cc Thng Tin Cung Cp T

PH TIA X
V tr cc peak ph
V tr cc peak cung cp cc thng tin v hnh dng

v kch thc mng.

T c th xc nh tn ca khong cht, hp

cht, phada trn cc ph chun JCPDS.

95

Cc Thng Tin Cung Cp T

PH TIA X
Cng cc peak ph:
C th xc nh c v tr ca cc nguyn t trong
mng thng qua cc phn mm (.

96

48

11/9/2013

Cc Thng Tin Cung Cp T

PH TIA X
Hnh dng v b rng peak
B rng v hnh dng cc peak c th cung cp

thng tin v s sai lch so vi tinh th hon ho

(sai khuyt trong tinh th)
Ngoi ra, t cc thng tin v b rng v cng

cc peak c th xc nh kch thc tinh th.

97

V d:
PH NHIU X TIA X ca NaCl

98

49

11/9/2013

D LIU NHIU X CA PH CHUN

Nm 1941, ASTM cng b d liu nhiu x ln
u tin di dng cc ming ba c kch thc
35 ca khong 1300 cht khc nhau.
Trc nm 1955, d liu ln ti 5900 cht.

Hu ht trong s cc cht ny l cc nguyn t v

hp cht v c.

99

D LIU NHIU X CA PH CHUN

K hiu mi tm ba bao gm mt dy 5 ch s: x-xxxx. K

hiu x trc du gch ni l s ch khu vc v 4 s sau cng l

ch s trong tm ba ca cht i vi tng khu vc.

3.

V d: 3-0167 l s th t 167 trong tm ba i vi khu vc

100

50

11/9/2013

JCPDS CARD

To identify a unknown compound, there is a file of x-ray

powder diffraction patterns which are collected from the

literature, reviewed by a committee (Joint Committee on
Powder Diffraction Standards, USA). We call it the
JCPDS file. It is a handy tool for anyone who is
interested in the crystal study.
An JCPDS file example is shown in Fig.14-1 (B D Cullity,

Elements of X-ray Diffraction), we shall understand the

information contain in this card.

101

102

51

11/9/2013

JCPDS CARD

The old version of JCPDS file is in form of cards or

books. Nowadays, a CD-ROM disk contains all the

cards of JCPDS file.
The position and the intensity of reflection are the most

important information in one entry.

103

JCPDS CARD

Cht lng:

: tt

c: tnh ton

o: tin cy thp
i: kh tin cy

104

52

11/9/2013

JCPDS CARD

The position can be expressed in two theta or d-spacing.

The d-spacing is directly related to the crystal structure,
thus it is more informative.

The value of two theta appears to be directly related to

the reflection data, but you must be aware that these two
theta values change with the radiation wavelength, and
the wavelength of JCPDS card is generally different from
the one you use.

105

JCPDS CARD

106

53

11/9/2013

Cc ng Dng Ca Phng Php

BT NHIU X TIA X
Xc nh cc vt liu cha bit
Kim tra s hin din ca cc pha, tinh khit.
Xc nh cu trc tinh th.
Xc nh kch thc tinh th.
Nghin cu s bit i cu trc ca vt liu (v d
nh hng ca nhit ).
Phn tch nh lng.

107

PHN TCH PHA NH TNH

Qu trnh phn tch nh tnh c bt u bng
vic chun b mu i vi cc cht cha bit.

Thu thp d liu bng phng php: chp phim

debye-scherrer hoc nhiu x k.

108

54

11/9/2013

PHN TCH PHA NH TNH

Cc d liu nhiu xa ca cht chun c th c tm
thy trc tip t ba d liu.

Thng s dng nhng cun s ch dn i km

Mi cun thng gm 2 phn:

(1) Danh mc c sp xp theo th t alphabet i
vi tn ca cc cht.
(2) Danh mc c sp xp theo s th t.

109

PHN TCH PHA NH TNH

Nguyn tc c bn:
Lit

k tt c cc gi tr d v I ca cc vch nhiu

x thu c t kt qu phn tch.

Sp
So

xp theo chiu gim dn gi tr d.

snh s liu thc t ca mu vi c s d

liu c sn.

110

55

11/9/2013

PHN TCH PHA NH TNH

Phng php Hanawalt:

Da vo gi tr d trn gin , chn 3 vch c

cng cao nht (d1- I1 =100%,d2- vch ln
th 2, d3-vch ln th 3). C th chuyn i gi
tr - d tm d1, d2, d3 tng ng bng cch
tra bng (hoc tnh t cng thc = 2dsin ).

111

PHN TCH PHA NH TNH

Phng php Hanawalt:

So snh 3 vch cao nht (d-I) vi cc vch

trong ngn hng d liu xc nh c pha
tinh th ca mu:

Khi tm c d1 , tm tip gi tr gn nht i vi d2

(sai s 0.01A), tng t i vi vch th 3 (d3).

Sau khi tm ra gi tr gn ng nht ca d1,d2 v d3.

So snh cng ca chng vi gi tr trong ngn
hng ph chun.
112

56

11/9/2013

PHN TCH PHA NH TNH

Phng php Hanawalt:
Sau khi xc nh s b c pha tinh th, cn

so snh tt c cc peak cn li m bo s
chc chn.
i vi vt liu a tinh th, vic xc nh phc

tp hn.

113

Bng 14-1- Ba d liu nhiu x tiu chun ca ASTM dnh

cho molybdenum carbide (molypdem carbua) (ngun t ASTM).

114114

57

11/9/2013

PHN TCH PHA NH TNH

Bng 14-1. S liu thc nghim nh d hay I/I1.

115

PHN TCH PHA NH TNH

V du: (Bng 14.1)
Cac gi tr ca d1, d2 v d3 ca cht cha bit ln lt l
2.27, 1.50 v 1.34.

ln ca cc vch ln nht ri vo khong t 2.29

2.25 (gi tr d1).
Gi tr d2 :1.49 1.51.
Gi tr d3 :1.33 1.35.
So snh vi bng 14.2 Pha cn tm l Mo2C.

116

58

11/9/2013

PHN TCH PHA NH TNH

117

PHN TCH PHA NH TNH

Cch 2:
xc nh c pha tinh th mt cch nhanh chng
v chnh xc, cn:
Xc nh ngun gc hnh thnh mu (nguyn liu,

iu kin iu ch, thnh phn ha)

D on cc pha tinh th c th tn ti trong mu.
Ghp cc ph cn phn tch vi cc ph chun

d on (s dng origin 8.0 software ghp

ph).
So snh vi cc ph chun xc nh pha tinh

th.
118

59

11/9/2013

V D
Nghin cu
s hnh thnh
MgAl2O4 (t
phn
ng
gia Al2O3 v
MgO).

119

PHN TCH PHA NH TNH

Hng dn s dng phn mm Origin 8.0.

120

60

11/9/2013

121

122

61

11/9/2013

Kim tra
S PHN NG GIA CC CHT
Nghin cu phn ng gia electrolyte LDMW82
(La1.8Dy0.2Mo1.6W0.409) v cathode LSCF6482
(La0.6Sr0.4Co0.8Fe0.2O3).

123

Kim tra
S PHN NG GIA CC CHT

124

62

11/9/2013

XC NH KCH THC TINH TH

Mt s hiu ng c th lm thay i b rng ca pc nhiu
x, l: kch thc tinh th, s xen ph ca cc pic gn
nhau
Nhiu x tia X theo phng php bt ch xc nh kch
thc tinh th, khng xc nh c kch thc ht

1 ht = mt tinh th

1 ht = nm tinh th nh

125

XC NH KCH THC TINH TH

c c cc peak nhn trong gin
nhiu x tia X th tinh th phi c c
kch thc ln m bo cc phn
x sai lch so vi gc 2 s khng giao
thoa tng cng to thnh tia nhiu
x.
nh hng ca kch thc tinh th n
b rng ca vch nhiu x trong
phng php bt.

126

63

11/9/2013

XC NH KCH THC TINH TH

127

XC NH KCH THC TINH TH

Hng dn s dng phn mm Origin lab 8.0
xc nh crystalize size.
Ghi ch: Cc phn mm nghin cu cu trc trong
phng php XRD.

Phn tch pha tinh th nh tnh EVA, WINPROFILE

Xc nh kch thc tinh th WINCRYSIZE,

WINMETRIC

Xc nh ch s mng WININDEX

Tnh ton, m phng cu trc tinh th WINRIETVELD

128

64

11/9/2013

PHN TCH NH LNG

Cch 1: Phng php thm 1 cht vo hn hp mu
Thm 1 lng xc nh pha a (Ya) vo hn hp (a+b)

c nng Xa, Xb.

Mu cn xc nh: Xa
Chun b nhiu mu c hm lng Ya thay i v xc

nh t l

Ia
t gin tia X.
Ib

Ia
k(X a Ya )
Ib

129

PHN TCH NH LNG

Cch 1: Phng php thm 1 cht vo hn hp mu (tt)

V th s ph thuc I a vo Ya ta c ng thng
Ib
c h s gc k.

Ia
k(X a Ya )
Ib
ng thng ct trc honh ti
XA

130

65

11/9/2013

PHN TCH NH LNG

Cch 2: Phng php chun ni
tch pha nh lng da trn c s: cng ca tia
nhiu x ph thuc vo nng ca pha tng ng trong
hn hp.

Phn

snh cng hai tia nhiu x ca hai pha A v B ca

cng mt mu:

So

Ia
X
k a
Ib
Xb

131

PHN TCH NH LNG

Cch 2: Phng php chun ni (tt)
Vi

Trong :

A( a )N a
A( b )N b

I: cng ca tia nhiu x

Io : cng tia ti
A(): tha s hp th, ph thuc vo c im
hnh hc php o, hnh dng mu
N: tha s hp th, ph thuc vo bn cht ca
pha
Xa :hm lng ca pha a cha bit(%)
Xb :hm lng ca pha b bit(%)
132

66

11/9/2013

PHN TCH NH LNG

Cch 2: Phng php chun ni (tt)
X

Phn tch nhiu x tia X vi nhiu mu c t l a thay

Xb
i.
X
V th s ph thuc I a vo a ta c ng thng
Xb
Ib
c h s gc k.

Xa

Trn c s th va xy dng, xc nh c t l X
da trn t l

Ia
ca mu t kt qu tia X, tnh c Xa.
Ib

133

CCH TNH TON CHO

H LP PHNG
Cubic crystal

2dSin
2

4a 2 sin 2
h2 k 2 l 2

d Cubic

a
h k2 l2
2

(h 2 k 2 l 2 )

4a 2

sin 2

sin

2 const , ( 1 / K)
2
2
h k l
4a
2

sin 2 1
sin 2 2

... const
(h 2 k 2 l 2 )1 (h 2 k 2 l 2 ) 2
134

67

11/9/2013

CCH TNH TON CHO

H Diffraction
LP PHNG
Angles
2d sin

cubic:
Lp phng
d2

d
2 sin

h2 k 2 l 2

a2

sin 2

2
4a 2

k2 l2

orthorhombic

Trc giao

hexagonal
Lc
phng
1

4 h 2 hk k 2 l 2

c2
d 2 3
a2

h2
a

sin 2

h 2 hk k 2 l 2

sin 2 2
4c 2
3a 2

k2
b

l2
c2

h
k 2 l 2

a2 b2 c2

Hnh thoi
rhombohedral
1
d2

sin 2

k 2 l 2 sin 2 2hk kl hl cos2 cos

a 2 1 3 cos2 2 cos3

2 h 2 k 2 l 2 sin 2 2hk kl hl cos2 cos

4
a 2 1 3 cos2 2 cos3

135

XC NH CU TRC TINH TH
Bao gm cc bc sau:
Tin hnh phn tch nhiu x tia X.
Xc nh v tr cc peak 2.
Tnh gi tr d.
Tnh cc hng s mng a
Tnh sai s ca a (a)

136

68

11/9/2013

XC NH CU TRC TINH TH
S th t

10

LPG
(SC)

H2

L2

1
100

2
110

3
111

4
200

5
210

6
211

8
220

9
300
221

10
310

11
311

LPTK
(BCC)

H2 + K2 + L2
HKL

2
110

4
200

6
211

8
220

10
310

12
222

14
321

16
400

18
411
330

20
420

LPTM
(FCC)

H2 + K2 + L2
HKL

3
111

4
200

8
220

11
311

12
222

16
400

19
331

20
420

24
422

27
333
511

K2

+
+
HKL

137

XC NH CU TRC TINH TH
V d 1:
Mt vt liu dng bt kt tinh theo cu trc BCC (a =
10 10-10 m) c chiu x bi cc tia pht ra t mt
ng pht tia X vn hnh di th V. Di gi tr th V
bao nhiu th khng c bc x no pht ra t ng pht
tia X c kh nng gy nn nhiu x.
Trong cu trc BCC, h mt {110} gy nn gc nhiu
x nh nht, t tnh c d110

138

69

11/9/2013

Bi gii

Cc bc x c > 14,14.10-10 m khng c kh nng

gy nhiu x trn h mt {110}.
(V<848 Volts)

139

V d 2:
Tnh v tr gc ca peak nhiu x u tin ( nh nht)
ca Cr khi dng bc x CuK ( = 1,542).
Cr c cu trc BCC vi r = 1,30. 1010 m
Cu trc BCC: 3a2=(4r)2 a = 3.00 x 10-10 m
Cu trc BCC, peak u tin ng vi mt {110}.
d110 = 2.12 x 10-10 m
= 2dsin sin1 = /2d110 = 0.3634

1 = 21.3o

140

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Radiation: Cu K, = 1.54056

420

422

400

331

311
222

200

220

111

Powder diffraction pattern from Al

141
X-Ray Diffraction: A Practical Approach, C. Suryanarayana & M. Grant Norton, Plenum Press, New York (1998)

Determination of Crystal Structure from 2 versus Intensity Data

n

Sin

Sin2

ratio

Index

a (nm)

38.52

19.26

0.33

0.11

111

0.40448

44.76

22.38

0.38

0.14

200

0.40457

65.14

32.57

0.54

0.29

220

0.40471

78.26

39.13

0.63

0.40

11

311

0.40480

5*

82.47

41.235

0.66

0.43

12

222

0.40480

6*

99.11

49.555

0.76

0.58

16

400

0.40485

7*

112.03

56.015

0.83

0.69

19

331

0.40491

8*

116.60

58.3

0.85

0.72

20

420

0.40491

9*

137.47

68.735

0.93

0.87

24

422

0.40494

* 1 , 2 peaks are resolved (1 peaks are listed)

142

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V d 3
Mt mu vt liu M c cc d kin phn tch tia X nh
sau:
Tnh thng s mng, a ()
ca vt liu.
Cho bit
(K)=1.54184

2
18.85
21.80
28.97
31.02
34.79
36.55
38.24
39.86
42.96

I (%) hkl
5.02
211
2.56
220
3.13
321
32.88
40 0
100.00
420
3.41
332
20.22
422
10.18
431
15.97
521
143

STT
2
I(%)

Sin
(Sin2
h
k
l

1.54184()
1
2
18.85 21.8
5.02 2.56
9.425 10.9
0.1638 0.1891
0.0268 0.0358
2
2
1
2
1
0

h2+k2+l2
d
a

3
4
5
28.97 31.02 34.79
3.13 32.88
100
14.485 15.51 17.395
0.2501 0.2674 0.2990
0.0626 0.0715 0.0894
3
4
4
2
0
2
1
0
0
14

16

20

6
36.55
3.41
18.275
0.3136
0.0983
3
3
2
22

7
8
38.24 39.86
20.22 10.18
19.12 19.93
0.3275 0.3409
0.1073 0.1162
4
4
2
3
2
1
24

26

11.5315

144

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V d 7:
NaCl c cu trc FCC. V tr
ca cc nguyn t Na v Cl
mng c s nh sau:

Xc nh F2 ng vi cc mt
phng nhiu x 111, 220,
311?
145

146

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Cc phn mm phn tch pha nh lng:

Phn

tch pha tinh th nh tnh EVA, WINPROFILE

nh kch thc tinh th WINCRYSIZE,

WINMETRIC
Xc

Xc

nh ch s mng WININDEX

Tnh

ton, m phng cu trc tinh th WINRIETVELD

147

148

74