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interpretation
X-ray Powder
Diffraction
Particle size
and defects
Peak shapes
Peak relative
intensities
Background
Peak
positions
10
20
30
2
Unit cell
Symmetry
and size
Diffuse scattering,
sample holder,
matrix, amorphous
phases, etc...
40
Atomic
distribution in
the unit cell
Background
Sinyal yang
diinginkan
Noise
Epitaxy/Texture/Orientation
Crystallite Size and Microstrain
Indicated by peak broadening
Other defects (stacking faults, etc.) can be measured by analysis of peak shapes
and peak width
Phase Identification
The diffraction pattern for every phase is as unique as your
fingerprint
Phases with the same chemical composition can have drastically
different diffraction patterns.
Use the position and relative intensity of a series of peaks to match
experimental data to the reference patterns in the database
Raw data
Background substraction
Smoothing
K substraction
L
M
K1
K2
K2
K1
K2
W L1
The K1 & K2 doublet will almost always be present
Very expensive optics can remove the K2 line
K1 & K2 overlap heavily at low angles and are more
separated at high angles
Bearden
(1967)
Holzer et al.
(1997)
Cobalt
Anodes
Bearden
(1967)
Cu K1
1.54056
1.540598
Co K1
1.788965 1.789010
Cu K2
1.54439
1.544426
Co K2
1.792850 1.792900
Cu K
1.39220
1.392250
Co K
1.62079
1.620830
Cr K1
2.28970
2.289760
Cr K2
2.293606 2.293663
Molybdenum
Anodes
Chromiu
m
Anodes
Mo K1
0.709300
Mo K2
0.713590 0.713609
0.709319
Often quoted0.632288
values from0.632305
Cullity (1956)
Bearden, Rev.
Mod. Phys.2.084920
39 (1967)
and Cr
2.08487
Moare
K incorrect.
K
Holzer et al.
(1997)
Values from Bearden (1967) are reprinted in international Tables for X-Ray
Crystallography and most XRD textbooks.
Most recent values are from Hlzer et al. Phys. Rev. A 56 (1997)
Has your XRD analysis software been updated?
K
D
cos
Intensity (a.u.)
23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41
2 (deg.)
K
D
cos
K
B 2
L cos
0.94
B 2
L cos
http://prism.mit.edu/xray
sin 2 2 (h 2 k 2 l 2 )
4a
sin C (h k l )
2
dividing the above equation with the first reflection angle gives the ratio of hkl
sin 2
(h 2 k 2 l 2 )
2
2
sin 1 (h1 k12 l12 )
the ratio of hkl define the possible Miller indices: ratio = h2 + k2 + l2
if there are some possible hkl, the highest number comes first
After indexing, one of the peaks can be used to calculate the cell parameters.
As the error in measuring the diffraction angles is a systematic error, the last
reflection data will be used
sin2
ratio
Miller indices
19.213
0.0279
100
27.302
33.602
38.995
43.830
48.266
56.331
60.093
63.705
67.213
70.634
0.0557
2
3
4
5
6
8
9
10
11
12
110
111
200
210
211
220
221
310
311
222
topics
Evaluation of the intensities of X-rays
diffracted from polycrystalline samples;
Evaluating crystallinity
taking the sum total of relative intensities of
ten individual characteristic peaks1 then
taking the ratio over the corresponding
relative intensities of standard materials
E.g.:
Comparing crystallinity of flyash-based
zeolite-A using XRD and IR spectroscopy
% crystallinity =
(AD4R)/(ATO4)
72.8%
85%
98.6%
98.6%
98.6%
100%
83.2%
72.8%
92%
96.2%
93.3%
100%
(111)
00-004-0784> Gold - Au
Intensity(Counts)
8.0
(311)
(200)
6.0
(220)
4.0
(222)
2.0
(400)
3
x10
40
50
60
70
Two-Theta (deg)
80
90
100
ZnO nanorod
1 k1
2
1 ek1t
1 ek 2t N 0
1 ek 2t N 0Al
NaAlH 4 3 3 k k
Na3 AlH 6
3 k 2 k1
2
1
N Al N 0
N Na3 AlH 6
1 0
k1 k1t
e
N
ek 2t N 0
ek 2t
Na 3 AlH 6
3 NaAlH 4 k 2 k1
N NaAlH 4 N 0
NaAlH 4
ek1t
Na3AlH6
NaCl
NaAlH4
Al
dispersing the powder with alcohol onto the sample holder and then
allowing the alcohol to evaporate, often provides a nice, even coating of
powder that will adhere to the sample holder
powder may be gently sprinkled onto a piece of double-sided tape or a
thin layer of vaseline to adhere it to the sample holder
the double-sided tape will contribute to the diffraction pattern
What is polymorph?
Same Chemical formula but different crystal system
Example: phase, phase, phase
Form, Form,
These differences are very important for the
production since some phase are stable or easy to
product. Therefore originally developed company have
a patent to protect their products. Competitors
(Generic drug pharmaceutical company) should check
their product whether they are out of these patent
using XRD. Of course original drug supplier always try
to check competitors products.
xrd-6000-pharma.pp
abnormal peak
xrd-6000-pharma.pp
xrd-6000-pharma.pp
Amorphous
Crystallization
Crystal Size
Lattice Strain
Degree of Crystallization
xrd-6000-pharma.pp
It
Ic: Area of crystalline phase
It: Total area of the profile
xrd-6000-pharma.pp
Crystalinity Calculation
xrd-6000-pharma.pp
Crystallite size
D Cos
Particle size
Scherrers Formula
xrd-6000-pharma.pp
xrd-6000-pharma.pp
Acquisition concerns
Lin (Counts)
3000
2000
1000
0
15
20
30
40
50
60
70
2-Theta - Scale
QUARTZ - File: Q091506.RAW - Type: 2Th/Th unlocked - Start: 18.000 - End: 72.000 - Step: 0.030 - Step time: 0.2 s - Temp.: 25 C (Room) - Time Started: 0 s - 2-Theta: 18.000 - Theta: 0.000 Operations: Strip kAlpha2 0.514 | Background 1.000,1.000 | Import
QUARTZ OFFSET - File: 715Q-01.RAW - Type: 2Th/Th unlocked - Start: 15.000 - End: 69.990 - Step: 0.030 - Step time: 0.2 s - Temp.: 25 C (Room) - Time Started: 0 s - 2-Theta: 15.000 - Theta:
Operations: Y Scale Mul 0.712 | Strip kAlpha2 0.514 | Background 1.000,1.000 | Import
MSE715-XRD.ppt
2500
2400
2300
h<
100m
2200
2100
2000
1900
1800
1700
Illustrate
correction
process later
Lin (Counts)
1600
1500
1400
1300
1200
1100
1000
900
800
700
600
500
400
300
200
100
0
25
26
27
28
2-Theta - Scale
QUARTZ - File: Q091506.RAW - Type: 2Th/Th unlocked - Start: 18.000 - End: 72.000 - Step: 0.030 - Step time: 0.2 s - Temp.: 25 C (Room) - Time Started: 0 s - 2-Theta: 18.000 - Theta: 0.000 Operations: Strip kAlpha2 0.514 | Background 1.000,1.000 | Import
QUARTZ OFFSET - File: 715Q-01.RAW - Type: 2Th/Th unlocked - Start: 15.000 - End: 69.990 - Step: 0.030 - Step time: 0.2 s - Temp.: 25 C (Room) - Time Started: 0 s - 2-Theta: 15.000 - Theta:
Operations: Y Scale Mul 0.712 | Strip kAlpha2 0.514 | Background 1.000,1.000 | Import
MSE715-XRD.ppt
2.
X-Ray Diffraction
P123 Results
F127 Results
F127 Results
F127 Results
XRD patterns of mesostructured tin oxide displaying an Im3m derived structure. (a) after thermal
treatment at temperatures up to 250C and (b) after calcination at 400C for four hours.
F127 Results
h, k, l are
Miller indices
a, b, c are
unit cell
distances
, , are
angles
between the
lattice
directions
Complexity of
calculations is
dependent on
the symmetry
of the crystal
system.
Sin2
Rasio
Rasio x 3
(h k l)
hkil
(Sin2) /
(hcp)
(Sin21)
30
32.5
0,0667
0.0783
1
1.17
3
3
(1 1 1)
(1 1 1)
100
100
34.5
0.0879
1.32
(0 0 2)
0002
36.6
48
0.0986
0.1654
1.48
2.48
5
8
(0 2 1)
(2 0 2)
101
102
57.5
0.2277
3.41
10
(3 1 0)
1 1 2 0
65.5
69
0.2889
0.3208
4.33
4.8
12
15
( 2 1 3)
(2 3 2)
103
1 0 2 2
70.5
0.3331
15
(5 3 1)
2 0 2 1
74
0.3622
5.43
16
(0 0 4)
0004
Penentuan Struktur Kristal Kubus dan non-kubus, Sukir dkk., Tugas Matakuliah Kimia Anorganik Terapan, S2 Depag,
2010
c
a
Rule
(h k l)
hkil
(hcp)
(1 1 1)
(1 0 0)
(1 1 1)
(1 0 0)
(0 0 2)
(0 0 0 2)
(0 2 1)
(1 0 1)
(0 2 2)
(1 0 2)
10
(3 1 0)
(1 1 2 0)
12
( 2 1 3)
(1 0 3)
15
(2 3 2)
(1 0 2 2)
15
(5 3 1)
(2 0 2 1)
16
(0 0 4)
(0 0 0 4)
InP nanocrystals
Applications:
Determination of
Crystallite Size
Scherrer equation:
Bcrystallites = (k)/(L cos )
k constant ~ 1 (precision error 10%)
L average crystal size (nm)
wavelength of the X-rays used (nm)
Bragg angle (radians)
B full width at half maximum (FWHM,
radians)
Example: anatase TiO2
Cu = 0.15406 nm
L1 = 0.0061
1=25.28 B1 = 25.3 nm
L2 = 0.0061
2=37.8 B2 = 25.26 nm
K
L=
cos
where L is the dimension of the particle
is the wavelength
is the peak width
is the angle of reflection
K is a constant, can be assumed to be 1
(This is a simplified analysis)
karakterisering_2004.ppt
Example 1. Phase
identification
karakterisering_2004.ppt
karakterisering_2004.ppt
20
400
30
40
50
60
300
R: Rutile
R
R A
A R
700 C
o
A
A
R R
400
300
600 C
200
200
o
500 C
100
100
o
350 C
o
250 C
0
20
nsf.ppt
30
40
2 (degree)
50
60
23 nm (b)
o
800 C
o
750 C
o
700 C
20nm
as-deposited
12 nm (a)
R(110)
o
800 C R(101)
R(211)
R(220)
R(111)
WR
A0
0.884 AA AR
750 C
700 C
A(101)
as-deposited
A(004)
20
nsf.ppt
30
40
2 (deg.)
A(200) A(105)
A(211)
50
60
30
40
50
Intensity (arb. units)
24.5
(101)
23 nm (004)
25.0
60
25.5
26.0
26.5
Anatase (101)
23 nm
17 nm
12 nm
24.5 25.0 25.5 26.0 26.5
2 (deg.)
(200)
(105) (211)
17 nm
12 nm
20
nsf.ppt
30
40
2(deg.)
50
60
0.00 09 2
0.0 009 6
0 .0 01 00
0.001 04
Ln(AR/A0)
-1
-2
-3
-4
-5
12nm (Ea=180.28kJ/mol)
17nm (Ea=236.38kJ/mol)
23nm (Ea=298.85kJ/mol)
R=0.995
R=0.998
R=0.991
0.00092
0.00096
0.00100
-1
0.00104
1/T (K )
AR=A0Exp(-Ea/KT), A0=0.884AA+AR
Ea is anatase to rutile transformation activation energy.
The activation energy decreases with the particle size
and 12-nm sample has the lowest activation energy of 180.28 kJ/mol.
Bulk TiO2 has activation energy of 450 kJ/mol.(*)
nsf.ppt
p6mm hexagonal
symmetry
ao = 12.60 nm
ao = 12.61 nm
111
222
311
111
222
311
For every set of planes, there will be a small percentage of crystallites that
are properly oriented to diffract (the plane perpendicular bisects the incident
and diffracted beams).
Basic assumptions of powder diffraction are that for every set of planes there
is an equal number of crystallites that will diffract and that there is a
statistically relevant number of crystallites, not just one or two.
PENETAPAN PARAMETER
KRISTAL
METHOD 1:
Diffraction will occur when Bragg law is satisfied:
2d sin
The interplanar spacing d for a cubic material is given by:
d hkl
h2 k 2 l 2
d2
h k l
4 sin 2
1-92
Which gives:
Sin
h2 k 2 l 2
4a 2
2
1-93
1-94
1-96
1-97
1-98
Bravais lattice
All
None
h + k + l = even
h + k + l = odd
h, k, l = unmixed (all
even or all odd)
h, k, l = mixed
1-100
Sin 2
Rearranging gives
h2 k 2 l 2
4a 2
2
h2 k 2 l 2
a
2
4
sin
1-101
METHOD 2:
This method can be used to index the diffraction pattern from materials
with a cubic structure. From:
Sin2
h2 k 2 l 2
4a 2
2
Since 2 / 4a2 is constant for any pattern and which we will call A, we can
write:
sin 2 A h 2 k 2 l 2
1-102
2
4a
or a
2 A
1-103
1-104
Scherrers Formula
K
t
B cos B
t = thickness of crystallite
K = constant dependent on crystallite shape (0.89)
= x-ray wavelength
B = FWHM (full width at half max) or integral breadth
B = Bragg Angle
Pola difraksi sinar-X : SiO2 dan SiO2-G0SiO-G4.0. 1:SiO2 ; 2:SiO2 - G0; 3:SiO
-G0.5; 4:SiO2 -G1.0; 5:SiO2 -G1.5; 6:SiO2 -G2.0; 7:SiO2 G2.5;8:SiO2-G3.0;
9:SiO2 -G3.5; 10:SiO2 -G4.0
Daftar Pustaka :