X

Powder X-Ray Diffraction

(PXRD)

hjinping@shnu.edu.cn

XRD QQ:221323865


X


X

1901 Wil hel mConral Ront gen X
1914 Max von Laue X
. Henry Bragg
1915 X
. Lawrence Bragg.
1917 Charl es Gl over Barkl a X
1924 . Karl Manne Georg Si egbahn X
Cl i nt on J oseph Davi sson
1937
George Paget Thomson
1954 Li nus Carl Panl i ng
J ohn Charl es Kendrew
1962
Max Ferdi nand Perut z
Franci s H. C. Cri ckJ AMES d. Wat son
1962 DNA
Mauri ce h. f . Wil ki ns
1964 Dorot hy Crowf oot Hodgki n B12
Herbert Haupt man
1985
J erome Karl e
E. Ruska
1986 G. Bi nni g
H. Rohrer
B. N. Brockhouse
1994
C. G. Shul l
X

1.
2.
3.
4.
5.
6.
7.
8.


2 X

3 X

4 X

5 X
 1
1.

; ; ; ;


2.

NaCl Cl- Na+

Na+ Cl-




Lattice
NaCl

Unit Cell

a b c
Cell/Lattice Parameter


[uvw]








a)
m n p a b c
b) 1/m 1/n 1/p
hkl 1/m 1/n 1/p=h k l hkl
hkl
 L
Z

HKL X Y
Z
OH=2a
OK=3b
K
OL=6c Oc
a b Y
H

X Y Z X
OH=2a OK=3b OL=6c

1/21/31/6
321
(321)

hkl
dhkl d

d 100 = a d 200 =
a/2


(h k
l)

 Selected crystallographic directions in the lattice with ===90o

Families of (213) crystallographic planes

Families of (110) and (111) crystallographic planes

 [001]
[101] [011]

[010]

[100] [110]

[111]

[111]

[111]
 d h k l

1 1 2 2 2 2
2
2
[h b c sin k 2 a 2 c 2 sin 2 l 2 a 2b 2 sin 2hkabc 2 (cos cos cos )
d V
2kla 2bc(cos cos cos ) 2hlab 2 c(cos cos cos )

V abc(1 2 cos cos cos cos 2 cos 2 cos 2 )1/ 2

 2 2 2
1 h k l 2 2 2
1 h k l
2 2 2 2 2
d a2 d a b c

1 4 h 2 hk 2 k 2 l 2
1 h k l 2 2 2
2
2 d 2
3 a 2
c
d a2 c2

1 (h 2 k 2 l 2 ) sin 2 2(hk kl hl )(cos 2 cos )

2
d a 2 (1 3 cos 2 2 cos 3 )

1 1 h 2 k 2 sin 2 l 2 2hl cos

( 2 2 )
d 2
sin a
2
b 2
c ac


14
14 Bravais 14

 Cubic
14
Cubic

Orthorhombic
Tetragonal

(14

Bravais

hexagonal
Rhombohedra

Monoclinic
Triclinic


ab c; 90o
2 ab c; = = 90o
2 a b c; = = = 90o
3 a=b = c; = = 90o
4 a=b c; = = = 90o
6 a=b c; = = 90o;=120o
3 a=b =c; = = = 90o



32 14 Bravais

230


= *

14

32 http://metafysica.nl/derivation_32.html




1,2,3,4,6
( = = )

32 32

Simple symmetry operations. From left to right : rotation, inversion, reflection, and translation
 Schnflies
Cn: n

Cnh: n

Cnv: n n

Dn: n n

Sn: n
T: 4 3 4 2
O: 3 4 ,4 3 6 2
32
1. (C=cyclic)

C1,C2, C3, C4, C6; 1,2,3,4,6

2.

C1h=Cs, C2h,C3h,C4h,C6h; m,2/m,3/m ( ) ,4/m,6/m

3.

C2v,C3v,C4v,C6v; mm2,3m,4mm,6mm

4.

S2= Ci, S4,S6=C3d; -1,-4,-3

32
5. (n) n

D2,D3,D4,D6; 222,32,422,622

6. (n) n

D2h,D3h,D4h,D6h;mmm,3/mm,4/mm,6/mmm

7. D D2d,D3d; -42m,-3m

8. (T=tetrahedral O=octahedral)

T, Th, O, Td, Oh; 23,m3,432,-43m,m3m



1,`1 1 `1
2,m,2/m Y 2,m,2/m
2m X 2m Y 2m Z 222,mm2,mmm
4,`4 4/ Z 2 X 4,`4 4/m 42
m m 2m 2 4mm, `42m,
4/mmm
3,`3 Z 2 X 3,`3, 32,3m, `3m
m
6,`6, 6/m Z 2 X 6,`6, 6/m,622,
m 2m 6mm, `62m,
6/mmm
2,m,4, `4 X 3,`3 23,m3,432, `43m,
2m m`3m
32 Schnflies

1. 15
2. 10
3. 20 (432
)
4. 18

 (Space Group)

( )
( )
230
( )
230 14 Bravais 32

http://asdp.bio.bnl.gov/asda/Libraries/sgtable.html

Schnflies

1.
P I F C A B
2.
3. ( Pm
P1m1)
*
P21/c, a
P21/a; P21/n


b [010]
a [100] b [010] c [001]
c [001] a [100]/[010] a+b [110]
c [001] a [100]/[010] 2a+b [120]

(R) a+b+c [111] a-b [1 1 0]

a [100]/[010]/ a+b+c [111] a+b [110]

[001]

2 3 3 ( Ia3, Pm3m, Fd3m)

1 4, 4 , 41, 42 43 ( P41212, I4/m, P4/mcc)

1 6, 6 , 61, 62, 63, 64 65 ( P6mm, P63/mcm)

1 3, 3 31 32 ( P31m, R3, R3c, P312)

2 2
( Pnma, Cmc21, Pnc2

2
/ ( Cc P2 P21/n)

1 (- 1)
X-
2 X

h
X h 6.626 10 34 J s
mv

390 770 nm

X 0.001 10 nm

X 0.05 0.25 nm

X 0.005 0.1 nm
 X

103 10 10 10 310 5 10 7 10 9 10 10
1 11 13
cm

1 nm = 10-9 m = 10-7 cm= 10

 X

1 X 99

1.

2.

3.
 X X

2. X
 3 W
20KV 50KV
X
X
X X

0
X
0
X

hc e 4.803 10 10
eV h max h 6.626 10 34 J s
0


50 X

X
 X
X

20.1KV
20.1KV
X
X

X

 X
X X
J/cm 2.s.
X I hv n ,
I=nhv. X 1.5 0, 0



X



L M N
K 2 L
8 M 18

5 X


X

K L M N


L K K M
K K M K
L K K
K LK
MK K K

L K K
L M N
L L
 K



K K 20%
K
K
1 600 K
K
 X
Z X
Moseley
1
k(Z ) K

K

X X

K 3-5 I /I

X

X






X

X
I0

X

X

A.H.Compton

X



X X

X


X a
X
= a cos -
cos

n

=0 =


D
D

= 2dsin

2d hkl sin
= n
X


X

d

X



X





2dsin = n

sin =(n )/2d

1
n=1( 1 )

/2d

X
d /2
 :-Fe
2.02 1.43 1.01 0.90
0.83 0.76,

k=1.5418 Cu
k/2=0.77



1

2 ,
X

X




 X

X X
X

I 0 e 4 3 2 2 M 1 cos 2
2
I JF e AV ( 2 )
32 m c Ru
2 4 2
sin cos



3 X

3.1

Bragg-Branteno (B-B)

X
X
1.X
2.
3.
4.
5.



.

ON
( )O

Bragg-Brantano ,

X
O

F O G




H
O

O
O D

1 2

 X X

Soller W. S1 S2

0.05mm 0.5mm DS X
RS
SS

X F X S1 DS
SS S2 RS
D
1/8 8
2 165 20
0.01 185mm

3 X

1.




325
1m
1 5m


 2.

1/30 1/12 1/6 1/2 1 4
0.05 0.1 0.2 0.4 2.0mm







8 00 12 00 1 30 5

30

18101879958


/

SBA-15 1 0.5~5o 0.5 o /min 40KV 20mA 1/6 o 10mm 1/6 o

2 10~80o 4 o /min 40KV 30mA 1o 10mm 1 o

3 3~40o 4 o /min 40KV 30mA 1o 10mm 1 o

/MOF
4 30~90o 4 o /min 40KV 30mA 1o 10mm 1 o
nanoparticles
/MCM 5 1~10o 0.5 o /min 40KV 30mA 1/6 o 10mm 1/6 o

/ 6 1~30o 0.5 o /min 40KV 30mA 1 o 10mm 1 o

4 X

1.
2.
3.
4.
5.
6.
7.
8.
9.
 2 2 2
1 h k l 2 2 2
1 h k l
2 2 2 2 2
d a2 d a b c

1 h 2
k 2
l 2 1 4 h 2 hk 2 k 2 l 2
2 2
2
2
d 2
a 2
c d 3 a c

1 (h 2 k 2 l 2 ) sin 2 2(hk kl hl )(cos 2 cos )

2
d a 2 (1 3 cos 2 2 cos 3 )

1 1 h 2 k 2 sin 2 l 2 2hl cos

( 2 2 )
d 2
sin a
2
b 2
c ac

2d hkl sin
 1.








d

d
d d
I/I1


International Centre for Diffraction
Data ICDD Joint Commitee of Powder Diffraction
Standard JCPDS
PDF Powder Diffraction File)


ICDD (PDF2, PDF4)

http://www.icdd.com
ICSD ( ):
http://www.fiz-karlsruhe.de/icsd_.html
CRYSTMET
http://www.tothcanada.com
CSD ( )
http://www.ccdc.cam.ac.uk/
PDB (Protein Data Bank)
http://www.pdb.bnl.gov/
 PDF
PDF-2 PDF
2003 157048
133370 25609 92011
56614
PDF-4

d

32




d I
PDF-4
350000
348516
300000
140000
65000
230000
46000000
600000
1800

d I

EVA Jade Graphics&Identify,

Bede, Highscore(Plus), Powder
Suite
 X PDF#08-0490
SrWO4
 P25 X PDF#73-1764 Anatase TiO2
PDF#75-1749 Rutile TiO2
JADE 6.5
2.
2.
 2.
100

90

80

Relative Weight ( % )
70
DTA (uV)

60

50

40

30

20
100 200 300 400 500 600 700 800 900 1000
o
Temperature ( C )

Figure 4. TG-DTA curves of the Figure5.InsituvariabletemperaturepowderXray

Pd/Y-MOF in air diffractionpatternsofPd/YMOF.

3.

3-2 VN Wt%

Formula VO2

Wt 57 12 6 730 35 93 0 2204


SrFe12O19 -Fe2O3

99.73 0.27 sig=1.35
4.
Scherrer

K
Crystallite Size =
FW(S) Cos( )
4.

WO3

XRD patterns of silica with the structure of short-distance order


x
Ic
100%
I I
c a
5.
 002

Preferential growth along c-axis of hydroxyapatite

6.X
 6.X

Fig 6 lattice parameters vary with x values Fig 7 refinements results

6.X



CdS1-xSex CdS-CdSe

7.X

7.X
7.X

Fig. 2 Y2O3 atomic coordination parameters

XRD Eu
Y2 Eu1
Eu3+ Y2

8.
8.
8.
8.
8.
5 X

1.

X
X


 2.
X

X


(X ) X

-




X



3. X

,

,
Single crystal or Powder : that is the question !


(0.1-1mm) ---- ------

------ --

+ (+Rietveld
)
 <->

No : continue

Yes : The "last chance" method!



, ->
, -> ,

, -> ?
, -> ?


1.
2.
3.

.
4. NMR

25003 200



EXPO2000: A.Altomare , Mont
Carlo
Endeavour H. Putz , Rwp
DASH WIF David K. Shankland SA
ESPOIR Armel LeBail Mont Carlo SA
EAGER Kenneth D.M.Harris GA
PSSP P.W. Stephens SA
PowderSolve G.E. Engel SA


Patterson

Rietveld

Structure of Cr2[BP3O12] and Fe2[BP3O12]



1 K2
2
3
4
5
6
7
8
 100

90

DTA
TG
80

70

0 200 400 600 800 1000 1200

0
Temperture ( C)

Fig.2. TG -DTA curves

 Table 1 Phase evolution of various annealing temperatures
300C 450C 600C 750C 900C 1100C
Y6W2O15
NaY(WO4)2 NaY(WO4)2 NaY(WO4)2 Y6W2O15
Y6W2O15 Y2WO6
Na2(W2O7) Y2WO6 Y6W2O15 WO3
WO3
 Y2WO6

Figure 1. The Bragg positions of the diffraction lines and the Rietveld refinement result. Red dots
represent the observed data, black lines the calculated data, and ticks the peak position of Y2WO6
(above) and Y2O3 (below). The bottom line in blue shows the difference observed-calculated data.
 Index Le Bail refinement Systematic absences Establish
structure model
of Y2WO6
ITO
TREOR
Fullprof Chekcell
DICVOL
McMaille

Tetragonal
Impure phases: space group
a=5.262
Y22O33 (JCPDS No. 43-1036) P4/nmm (No. 129)
c=8.421
P4/n (No. 85)
(Rp=0.105, WO2.92
2.92
(JCPDS No.301387).
FOM=382.76)
Extinction conditions
hk0 : h + k = 2n

h00: h = 2n
Establish the structure model of Y2WO6

Sir2008: direct methods The partial structure model

ESPOIR :Monte Carlo and pseudo simulated annealing code

P4/nmm (No. 129)

O1 is obvious on a Fourier map at special position 8j.

O2 is suggested at x=1/4, y=0.008, z=0.555 half occupied at special position 8i
leading to [WO6] and [YO6] trigonal prisms connected by an edge
others [YO8] form cubes
 Table 2 refinements results

Fig. 5 YO6,WO6 structure

Table1.CrystallographicparametersofY2WO6fromRietveldrefinement

atom site x y z Biso(2) Occ

Y1 2c 0.25 0.25 0.3348(7) 3.11 1
Y2 2a 0.25 0.75 0 1.71 1
W 2c 0.25 0.25 0.7242(2) 0.73 1
O1 8j 0.0003(6) 0.0003(6) 0.8258(8) 2.15 1
O2b 8i 0.25 0.0007(7) 0.5597(9) 1.33 0.5

Xraydiffractionpattern:145reflections,Rp=17.7%,Rwp=22.4%,RBragg=10.9%,
RF=8.38%.SpacegroupP4/nmm(No.129),a=5.2596(2),c=8.4158(4),Z=2,
calculateddensity=5.2596g/cm3bHalfoccupiedsite.
Table2.Selectedinteratomicdistancesfound Table3.Calculatedbondvalenceand
inY2WO6 atomiccoordinationnumbers(CN)
forY2WO6
Atom1 Atom2 Distance()
Y1 O2 2.2496 BVSum
Atom CN
Y1 O1 2.3003 ()
Y2 O1 2.3679 Y1 6 2.79(5)
W O2 1.9105 Y2 8 3.11(2)
W O1 2.0437 W 6 4.88(5)
O1 4 1.95(3)
O2 2 1.49(1)

Valence=exp(Rod)/B
B=0.37,R0(Y3+O2)=2.019andR0(W6+O2)=1.917
 The occupancy of each site ( n) is given as a product of the
population parameter ( g) and site multiplicity (m) divided
by the multiplicity of the general site position (M

The fractional population parameter,

g, varies from 1 (fully occupied site)
to 0 (completely unoccupied site).

(PDF)

Rietveld

Rietveld GSAS
PDF PDFgetX2 PDFgui
Li Eu(WO4)2
I41 /a No.88
Na Eu(WO4)2

KEu(WO4)2 C2/c (No. 15)



AEu(WO4)2 (A = Li, Na, K) Eu3+

(CaWO4)
Eu3+
0.5 Ca2+
Eu3+ LiEu(WO4)2
NaEu(WO4)2 I41/a (No.
88) KEu(WO4)2 C2/c (No. 15)

Rietveld
(PDF)

Rietveld
Bragg
Debye-
Waller
PDF
Bragg


 XRD

Rietveld Bragg-Brentano (Rigaku

D/Max-2000) XRD 2
= 9~130 0.02 2
40s/step GSAS
PDF PDF G exp(r)
S(Q) Fourier S(Q)
I(Q) Compton

X (Rigaku D/Max-
2000 Mo K = 0.717 07 2 = 5~105
0.01 (2) 10 s/step Qmax = 13.4
1) PDFgetX2 PDFgui
PDF
 1. X Rietveld
(a) LiEu(WO4)2,
(b) NaEu(WO4)2,
(c) KEu(WO4)2
(d )
(e)
(f)
 LiEu(WO 4) 2 NaEu(WO 4) 2 KEu(WO 4) 2

Structure Tetragonal Tetragonal Monoclinic

Space group I41/a (88) I41/a (88) C2/c (15)
a 5.2115(3) 5.25997(3) 10.7043(2)
b 5.2115(3) 5.25997(3) 10.4730(2)
c 11.2823(4) 11.4030(1) 7.6082(2)
90.00 90.00 90.00
90.00 90.00 130.78(1)
90.00 90.00 90.00

Z 4 4 4
Volume of the unit cell 306.43(4) 315.49(1) 645.87(3)

R p(%) 6.65 6.70 9.74

R wp(%) 9.22 10.3 13.7

R F(%) 4.23 3.56 4.34

 Bond type CN Bond distance
Bond type CN Bond distance ()
()
Na|Eu-O1 4 2.4543(2)
Li|Eu-O1 4 2.4465(2)
Na|Eu-O2 4 2.4876(2)
Li|Eu-O2 4 2.4532(2)
W-O 4 1.7866(1)
W-O 4 1.7602(3)

Bond type CN Bond Bond CN Bond distance

distance() type ()
W-O1 1 1.7974(2) Eu-O1 2 2.2779(2)
W-O2 1 1.9963(2) Eu-O2 2 2.3187(2)
W-O2 1 2.1046(1) Eu-O3 2 2.3285(2)
W-O3 1 1.8343(3) K-O1 2 2.9588(1)
W-O4 1 1.7814(3) K-O4 2 2.7752(2)
W-O4 1 2.3576(3) K-O4 2 2.8476(2)
 Figure 4 4f4f
4f

270 nm W6+O2 Eu3+O2 CT

KEu(WO4)2 CT LiEu(WO4)2 NaEu(WO4)2
Dexter

180
90 ( ) Van Uitert
Eu3+
LiEu(WO4)2
NaEu(WO4)2 WOEu 143 KEu(WO4)2
WOEu 176
KEu(WO4)2 LiEu(WO4)2 NaEu(WO4)2
 When excited, the lattice vibration results in a deviation of the
metalligand distance ( R) from that of the ground state ( R 0). For
KEu(WO4)2, the presence of K+ ions with a larger radius affords softer
surroundings around the luminescence center, which results in a larger
deviation (R), thus producing a larger Stokes shift and a broader optical
bands. In addition, the lower crystal symmetry of KEu(WO 4)2 may also
contribute to the large Stokes shift and broader optical bands of
KEu(WO4)2.

Rietveld PDF
LiEu(WO4)2, NaEu(WO4)2 KEu(WO4)2
LiEu(WO4)2 NaEu(WO4)2 PDF
Eu3+
LiEu(WO4)2 NaEu(WO4)2 KEu(WO4)2
CT Stokes
PDF
- Rietveld
PDF
Rietveld
PDF


X


Vitalij K. Pecharsky Peter Y. Zavalij.
Fundamentals of PowderDiffraction and Structural
Characterization of Materials.

X




TiO2 WO3
.





X
X BET