XRD applications and

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

c
b

Diffuse scattering,
sample holder,
matrix, amorphous
phases, etc...

40

Atomic
distribution in
the unit cell

ANATOMI DIFRAKTOGRAM XRD

Background
Sinyal yang diinginkan

Noise

X-Ray Powder Diffraction (XRPD) uses information about

the position, intensity, width, and shape of diffraction peaks
in a pattern from a polycrystalline sample.

The x-axis, 2theta, corresponds to the angular position of the detector

that rotates around the sample.

You can use XRD to determine

Crystalline phase and sample identification

Phase Composition of a Sample
Quantitative Phase Analysis: determine the relative amounts of phases in a
mixture by referencing the relative peak intensities

Unit cell lattice parameters and Bravais lattice symmetry

Index peak positions
Lattice parameters can vary as a function of, and therefore give you information
about, alloying, doping, solid solutions, strains, etc.

Residual Strain (macrostrain)

Crystal Structure
By Rietveld refinement of the entire diffraction pattern

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

in-situ studies (evaluate all properties above as a function of time,

temperature, and gas environment)

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

Databases such as the Powder Diffraction File (PDF)

contain d-I lists for thousands of crystalline phases.
The PDF contains over 200,000 diffraction patterns.
Modern computer programs can help you determine what phases are
present in your sample by quickly comparing your diffraction data to
all of the patterns in the database database XRD pattern matching
The PDF card for an entry contains a lot of useful information,
including literature references.

XRD patterns of furnace materials and reference patterns of identified phases

Pengolahan data XRD

Raw data
Background substraction
Smoothing
K substraction

The wavelength of X rays is determined by the

anode of the X-ray source.

Electrons from the filament strike the target anode, producing

characteristic radiation via the photoelectric effect.
The anode material determines the wavelengths of characteristic radiation.
While we would prefer a monochromatic source, the X-ray beam actually
consists of several characteristic wavelengths of X rays.

K
L
M

Spectral Contamination in Diffraction Patterns

K1

K1

K2
K2

K1

K2

Kb

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

W lines form as the tube ages: the W filament

contaminates the target anode and becomes a new Xray source
W and Kb lines can be removed with optics

Wavelengths for X-Radiation are Sometimes Updated

Copper
Anodes

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 Kb

1.39220

1.392250

Co Kb

1.62079

1.620830

Cr K1

2.28970

2.289760

Molybdenum
Anodes

Chromium
Anodes

Mo K1

0.709300

Mo K2

0.713590 0.713609

Cr K2

2.293606 2.293663

Mo Kb

0.632288 0.632305

Cr Kb

2.08487

0.709319

2.084920

Often quoted values from Cullity (1956) and Bearden, Rev. Mod. Phys. 39 (1967)
are incorrect.

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?

Crystallite Size and Microstrain

Crystallites smaller than ~120nm create broadening of diffraction peaks

this peak broadening can be used to quantify the average crystallite size of
nanoparticles using the Scherrer equation
must know the contribution of peak width from the instrument by using a
calibration curve

microstrain may also create peak broadening

analyzing the peak widths over a long range of 2theta using a Williamson-Hull
plot can let you separate microstrain and crystallite size
00-043-1002> Cerianite- - CeO
2

K
D
b 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
b cos

The Scherrer Constant, K

K
B2
L cos

0.94
B2
L cos

The constant of proportionality, K (the Scherrer constant)

depends on the how the width is determined, the shape of the
crystal, and the size distribution
the most common values for K are:
0.94 for FWHM of spherical crystals with cubic symmetry
0.89 for integral breadth of spherical crystals w/ cubic symmetry
1, because 0.94 and 0.89 both round up to 1
K actually varies from 0.62 to 2.08

For an excellent discussion of K, refer to JI Langford and AJC

Wilson, Scherrer after sixty years: A survey and some new
results in the determination of crystallite size, J. Appl. Cryst. 11
(1978) p102-113.

Center for Materials Science and Engineering

http://prism.mit.edu/xray

Different crystallite sizes

With high quality data, you can determine

how much of each phase is present
must meet the constant volume assumption
(see later slides)

The ratio of peak intensities varies linearly

as a function of weight fractions for any two
phases in a mixture
need to know the constant of proportionality

RIR method is fast and gives semiquantitative results

Whole pattern fitting/Rietveld refinement is
a more accurate but more complicated
analysis

I(phase a)/I(phase b)

..

Quantitative Phase Analysis

60
50
40
30
20
10
0
0

0,2

0,4

0,6

X(phase a)/X(phase b)

0,8

Unit Cell Lattice Parameter Refinement

By accurately measuring peak positions over a long
range of 2theta, you can determine the unit cell lattice
parameters of the phases in your sample
alloying, substitutional doping, temperature and pressure, etc
can create changes in lattice parameters that you may want to
quantify
use many peaks over a long range of 2theta so that you can
identify and correct for systematic errors such as specimen
displacement and zero shift
measure peak positions with a peak search algorithm or profile
fitting
profile fitting is more accurate but more time consuming

then numerically refine the lattice parameters

determination and refinement of

lattice parameters (indexing)
relationship between Miller indices and diffraction angles

sin
2

2
4a

(h k l )
2

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

exercise 1: indexing XRD data (cubic)

2
19.213

sin2
0.0279

ratio
1

Miller indices
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

1. define the Miller

indices
2. calculate the
lattice
parameters
Answer:
ao = 4.6138

lattice type and systematic absences

on cubic system
destructive interferences occurring
between the diffracted waves intensity
cancels out
eg:

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

1CURRENT

SCIENCE, VOL. 89, NO. 12, 25 DECEMBER 2005

% crystallinity = (IR sample)/(IR standard)

% crystallinity =
(AD4R)/(ATO4)

72.8%

85%

98.6%
98.6%

98.6%

100%

83.2%
72.8%

92%

96.2%

93.3%

100%

Crystallinity = (A ratio of 560 over 464 cm-1 bands of sample/reference) x 100%

Preferred Orientation (texture)

Preferred orientation of crystallites can create a
systematic variation in diffraction peak intensities
can qualitatively analyze using a 1D diffraction pattern
a pole figure maps the intensity of a single peak as a function of
tilt and rotation of the sample
this can be used to quantify the texture
10.0

00-004-0784> Gold - Au

(111)

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

 For example MoO3 crystallizes in thin plates (like sheets

of paper) these crystals will pack with the flat surfaces
in a parallel orientation.
Comparing the intensity between a randomly oriented
diffraction pattern and a preferred oriented diffraction
pattern can look entirely different.
Quantitative analysis depend on intensity ratios which
are greatly distorted by preferred orientation.
Careful sample preparation is most important to deal
with preferred orientation samples

The following illustrations show the Mo O3 spectra's

collected by using transmission , Debye-Scherrer
capillary and reflection mode.

ZnO nanorod

In-situ XRD can yield quantitative analysis to study reaction

pathways, rate constants, activation energy, and phase
equilibria
2 1 k

1 k1

2
1 ek1t
1 ek 2t N 0
1 ek 2t N 0Al

NaAlH 4 3 3 k k
Na 3 AlH 6
3 k 2 k1

2
1

N Al N 0

N Na 3 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

Ways to prepare a powder sample

Top-loading a bulk powder into a well
deposit powder in a shallow well of a sample holder. Use a
slightly rough flat surface to press down on the powder, packing
it into the well.
using a slightly rough surface to pack the powder can help minimize
preferred orientation
mixing the sample with a filler such as flour or glass powder may
also help minimize preferred orientation
powder may need to be mixed with a binder to prevent it from falling
out of the sample holder
alternatively, the well of the sample holder can be coated with a
thin layer of vaseline

 Dispersing a thin powder layer on a smooth surface

a smooth surface such as a glass slide or a zero background holder
(ZBH) may be used to hold a thin layer of powder
glass will contribute an amorphous hump to the diffraction pattern
the ZBH avoids this problem by using an off-axis cut single crystal

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

these methods are necessary for mounting small amounts of powder

these methods help alleviate problems with preferred orientation
the constant volume assumption is not valid for this type of sample, and
so quantitative and Rietveld analysis will require extra work and may not
be possible

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.ppt

Most popular way for polymorph identification

Comparison of raw data profiles

Compare raw data profiles with standard sample data using Multi Plot
function whether abnormal appear or disappear.

abnormal peak

xrd-6000-pharma.ppt

Polymorph Identification(Search/Match Method)

xrd-6000-pharma.ppt

Some Meanings of Diffraction Pattern

Half Height width

Amorphous

Crystallization
Crystal Size
Lattice Strain

Degree of Crystallization

xrd-6000-pharma.ppt

Crystalinity calculation in XRD

In a X-ray diffraction method, total intensity from certain
volume of the sample are always fixed by their combination of
the atoms even they are amorphous phase or crystalline
phase. Sharpe profile are detected from the crystal phase
are and broad peak profile from the amorphous phase area.
So crystalinity degree is determined by the calculation of
the ratio of these area.

Ic
CrystalinityXc=K
It
Ic: Area of crystalline phase
It: Total area of the profile

xrd-6000-pharma.ppt

Crystalinity Calculation

xrd-6000-pharma.ppt

What is Crystallite size?

Crystallite size

Particle size

DCos

Scherrers Formula

xrd-6000-pharma.ppt

Application of the Crystallite size

xrd-6000-pharma.ppt

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
2200

h < 100mm

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

Interpretasi data XRD

1.

Identifikasi keteraturan pori struktur meso

2.
Identifikasi indeks kristal heksagonal

Pore Structure Characterization

X-Ray Diffraction

Small angle XRD

0.6 to 3.0 degrees 2

Peaks in XRD pattern show d-spacing between micelles

(pores) in parallel planes.

Transmission Electron Microscopy (TEM)

Example of silica XRD pattern

indicating mesostructure

Self-assembled mesoporous metal oxide thin films , Heidi Springer, Purdue University MSE REU, August 5, 2004

P123 Results

Counts Per Second (CPS)

P123 Surfactant Concentration

16000
14000
12000
10000

1.2g P123

8000

1.5g P123

6000

1.8g P123

4000
2000
0
0.6

1.1

1.6

2.1

2.6

Degrees 2-theta

Best mesostructure observed at 1.8g P123.

(EO):Sn molar ratio of 0.6.
Self-assembled mesoporous metal oxide thin films , Heidi Springer, Purdue University MSE REU, August 5, 2004

F127 Results
Lowest Concentrations F127
18000

Counts Per Second (CPS)

16000
14000
12000
10000

.75g F127

8000
6000

1.0g F127

4000
2000
0
1

Degrees 2-theta

No XRD peaks observed at lowest concentrations.

Self-assembled mesoporous metal oxide thin films , Heidi Springer, Purdue University MSE REU, August 5, 2004

F127 Results
Low Angle XRD at 1.25g F127
Counts Per Second (CPS)

16000
14000
12000
10000
8000
6000
4000
2000
0
1

Degrees 2-theta

Unresolved peaks, indicating poor

mesostructure begin to appear at 1.25g F127.
Self-assembled mesoporous metal oxide thin films , Heidi Springer, Purdue University MSE REU, August 5, 2004

F127 Results

Best structure is observed at 1.75g F127.

(EO):Sn molar ratio of 1.4.

Self-assembled mesoporous metal oxide thin films , Heidi Springer, Purdue University MSE REU, August 5, 2004

Courtesy of Vikrant Urade

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

Courtesy of Vikrant Urade

Self-assembled mesoporous metal oxide thin films , Heidi Springer, Purdue University MSE REU, August 5, 2004

Menentukan nilai a dan c heksagonal

1d2 = 43((h2 + hk + k2)a2) + l2c2
100
a = 2d3
110
a = 2d
200
a = 4d3
210
a = 2d53
300
a = 2d3
Dengan trial and error jika pada harga d berbeda, a
tetap itulah a. Panjang c dicari dari persamaan dg
variasi hkl yang harga l tidak nol. Harga d sudah
diketahui dari tabel.
Penentuan Struktur Kristal Kubus dan non-kubus, Sukir dkk., Tugas Matakuliah Kimia Anorganik Terapan, S2 Depag, 2010

 h, k, l are
Miller indices
a, b, c are
unit cell
distances
, b, are
angles
between the
lattice
directions

Complexity of
calculations is
dependent on
the symmetry
of the crystal
system.

Selection Rules for Observing X-ray Peaks

FCC :
even

(h k l) must all be either odd or

BCC : sum h + k + l must be even

(Otherwise, an in between plane will

cancel the reflection)

CARA PERHITUNGAN DENGAN MODEL BERDASARKAN

HARGA h k l KUBUS
Sudut 2

Rasio

Rasio x 3

(h k l)

hkil

(derajat)

Sin2

(Sin2) / (Sin21)

(bil. bulat) (ccp)

(hcp)

30

0,0667

(1 1 1)

100

32.5

0.0783

1.17

(1 1 1)

100

34.5

0.0879

1.32

(0 0 2)

0002

36.6

0.0986

1.48

(0 2 1)

101

48

0.1654

2.48

(2 0 2)

102

57.5

0.2277

3.41

10

(3 1 0)

1 1 2 0

65.5

0.2889

4.33

12

( 2 1 3)

103

69

0.3208

4.8

15

(2 3 2)

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

CUBIC IN HEXAGONAL MODEL, CREATED BY SECOND GROUP, MARCH 2010

Hubungan hkl kubus dengan hkil hcp

(h k l)

hkil

(bil.

(ccp)

(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)

bulat)

Rule

Rasio x 3

Tentukan hkl sistem kubus

jika salah satu dari h atau k pada hkl ccp = 1 atau
0, maka cenderung nilai a1 = 1.
Jika baik h maupun k pada ccp 1, maka a1 = 12.
Ingat , (h + k + i) = 0.
Jika l pada hkil adalah 0 maka bidang akan tegak
pada sisi heksagonal.
Kubus bisa diputar.

InP nanocrystals

Guzelian et al., J. Phys. Chem., 100, 7212 (1996)

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

Particle size measurement

Diffraction line of a perfect, infinite crystal = narrow
spike
Smaller particles = line broadening
Scherrer formula used to calculate particle size:

K
L=
cos
where L is the dimension of the particle
is the wavelength
b 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

Example 2. Supported metal

particles

karakterisering_2004.ppt

XRD of TiO2 Nanoparticles as a Function of

Deposition Temperature
20

400

30

40

50

A: Anatase
R: Rutile

Intensity (arb. units)

R
300

60

R A
o
A
700 C

A
A

400

R R

300

600 C
200

200
o

500 C
100

100

350 C
o

250 C
0

20

nsf.ppt

30

40

2 (degree)

50

60

TiO2 Phase Transformation: Effect of Particle

size

Intensity (arb. units)

23 nm (b)
o

800 C

XRD patterns from asdeposited

samples and samples annealed
at 700, 750, and 800 oC.
The phase compositions were
calculated based on formula

750 C
o

700 C
20nm

as-deposited

12 nm (a)

R(110)
o

Intensity (arb. units)

800 C

R(101)

R(211)
R(220)

R(111)

AR
AR

A0 0.884 AA AR

750 C

Particle sizes were calculated.

o

700 C

(*)

A(101)

A. A. Gribb and J. F. Banfield, Am.

Mineral. 82, 717 (1997).

as-deposited
A(004)

20

nsf.ppt

WR

30

40

2 (deg.)

A(200) A(105)
A(211)

50

60

X-ray Diffraction Patterns for TiO2 with

Different Particle Sizes
20

30

40

50
Intensity (arb. units)

24.5

Intensity (arb. units)

(101)

23 nm (004)

25.0

60
25.5

26.0

26.5

Effect of O2 gas flow rate on

particle size.

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

All peaks belong to the anatase

phase and no other phase is
detected within the X-ray
detection limit
The measured average particle
sizes were 12 2, 17 2, and
23 2 nm for the three samples.

Activation Energy Calculation

0

0.00092

0.00096

0.00100

0.00104

0.00100

0.00104

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

-1

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.(*)
(*) H. Zhang and J. F. Banfield, Am. Mineral. 84, 528 (1999).

nsf.ppt

Karakterisasi Struktur Meso

XRD sudut kecil:
1. struktur heksagonal
2. struktur kubus
3. struktur lamellar

MCM-41, fasa heksagonal

presents a typical 4-peak pattern:
a very strong at low angle (d100) and
3 weaker peaks at a higher angle (d110 , d200,
d210)

can be indexed on a hexagonal unit cell (ao

= 2d100/3 )
wall thickness, t = ao pore diameter
periodic array of mesopores gives a
crystalline character

Guo et al., Chem. Mater., 2003, 15, 2295

p6mm hexagonal
symmetry
ao = 12.60 nm

ao = 12.61 nm

MCM-48, fasa kubus

MCM-50, fasa lamellar

Its a single crystal

200
220

111

222
311

At 27.42 2, Braggs law

fulfilled for the (111) planes,
producing a diffraction peak.

The (200) planes would diffract at 31.82

2; however, they are not properly
aligned to produce a diffraction peak

The (222) planes are parallel to the

(111) planes.

A random polycrystalline sample that contains thousands of

crystallites should exhibit all possible diffraction peaks
200
220

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.

Hubungan antara tekstur tekanan pada padatan

dengan pola difraktogram XRD

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:

dhkl

h2 k 2 l 2

Combining the above equations results in:

d2

a
h k l
2

2
4 sin 2

1-92

 Which gives:

Sin2

h2 k 2 l 2
4a 2
2

Since 2 / 4a2 is constant, sin 2 is proportional to (h2 + k2 + l2),

As increases, planes with higher Miller indices will diffract.
Writing the above equation for two different planes and diving by the
minimum plane, we get:

sin 2 1
sin 2
2

h12 k12 l12

h22 k 22 l 22

1-93

Example: indexing of Aluminium diffraction pattern by method 1

1-94

Example: indexing of Aluminium diffraction pattern by method 1

1.

Identify the peaks

2.

Determine sin2

3.

Calculate the ratio sin2 / sin2min and multiply by the appropriate

integers (1, 2, or 3)
4.

Select the result from step (3) that yields h2 + k2 + l2 as an integer

5.

Compare results with the sequences of h2 + k2 + l2 values to

identify the Bravais lattice

6.

Calculate lattice parameter.

1-95

1-96

1-97

1-98

 The bravais lattice can be identified by noting the systematic

presence (or absence) of reflections in the diffraction pattern.

The Table below illustrates the selection rules for cubic lattices.
According to these rules, the (h2 + k2 + l2) values for the different
cubic lattices follow the sequence:
Simple cubic
BCC
FCC

:
:
:

1,2,3,4,5,6,8,9,10,11,12,13,14,16,.
2,4,6,8,10,12,14,16,18,...
3,4,8,11,12,16,19,20,24,27,32,

1-99

Bravais lattice

Reflections present for

Reflections absent for

Primitive (simple cubic)

All

None

Body Centered Cubic

(BCC)

h + k + l = even

h + k + l = odd

Face Centered Cubic

(FCC)

h, k, l = unmixed (all
even or all odd)

h, k, l = mixed

1-100

CALCULATION OF THE LATTICE

PARAMETER
The lattice parameter,a, can be calculated from:

Sin2

h2 k 2 l 2
4a 2
2

Rearranging gives

2 2
h k2 l2
a
2
4 sin
2

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

 In a cubic system, the possible (h2 + k2 + l2) values are: 1, 2, 3, 4,

5, 6, 8, . (even though all may not be present in every type of
cubic lattice).
The observed sin2 values for all peaks in the pattern are therefore
divided by the integers 1, 2, 3, 4, 5, 6, 8, to obtain a common
quotient, which is the value of A, corresponding to (h2 + k2 + l2) =1.
We can then calculate the lattice parameter from the value of A
using the relationship:

2
4a

or a

2 A
1-103

Note that 0.1448 is also common in 1, 2, 3, 4, 5, 6, BUT absent in 8

It can only be FCC

1-104

Smaller Crystals Produce Broader XRD Peaks

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

Contoh 1. Modifikasi silika dilakukan dengan mensintesis

ester dan amino dengan polimer silika gel (Qu, et al., 2006)

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

 Dari pola difraksi sinar-X menunjukkan hasil

modifikasi bersifat amorph dan secara umum puncakpuncak difraksi SiO2 dan SiO2-G0- SiO2-G4.0
disekitar 24o. Puncak lebar pada sudut 2 antara 1535o merupakan puncak yang karakteristik dari
senyawa amorph.
Dalam senyawa amorph penyusunan atom terjadi
secara acak atau dengan derajat keteraturan rendah.
Puncak lebar pada sudut 22o merupakan sifat amorph
dari silika (Kalaphaty, 1998).

Contoh 2. Modifikasi MCM-41oleh 5-merkapto-1-metiltetrazol

(Perez-Quintanilla, et al., 2007)

Pola difraksi sinar-X a) MCM-41 dan MTTZ-MCM-41 (modifikasi MCM41oleh 5-merkapto-1-metiltetrazol )

MCM-41 sebelum dimodifikasi menunjukkan harga 2 yang

rendah dengan sangat tajam (100) pada puncak difraksi 2,24o dan
ditambah dua puncak lain, yaitu (110) pada 3,88o dan (200) pada
4,65o. Sistem ini menunjukkan kisi suatu heksagonal dengan
ketebalan kristal (d) berturut-turut : 39,31; 22,47 dan 18,97.
Parameter unit kristal ao = 45,39 ; yang diperoleh dari persamaan
:
ao = 2d100/3
Penurunan puncak 2 = 2,25o pada pola difraksi sinar-X (100)
dalam MTTZ-MCM41 memberikan fakta bahwa terjadi grafting
(pencangkokan) di dalam celah mesopori. Adanya gugus
fungsional oganik di dalam celah mesopori cenderung mengurangi
daya hamburan dari lapisan silika mesopori. Hal ini juga didukung
oleh tingkat struktural dari sintesis material yang dipertahankan
setelah fungsionalisasi (Tabel 2)

Tabel 2. Data karakterisasi MCM-41 dan MTTZ-MCM-41

Daftar Pustaka :

Cullity, B.D., 1967, Element of X- Ray Diffraction, Addison-Wisley

Publishing Company Inc, New York.
Imelik, B., dan Vedrine, J.C., 1994, Catalyst Charactherization : Physical
Tehnique for Solid Materials, Plenum Press, New York.
Jenkins, R. dan Snyder, R.L., 1996, Introduction to X-ray Powder
Diffractometry, John Wiley and Sons Inc, New York.
Kalaphaty, U., Proctor, A., and Shultz, J., 2002, An Improved Method for
Production of Silica from Rice Hull Ash, Bioresource, 85 : 285-289.
Niemantsverdriet J.W., 2000, Spectroscopy in Catalysis, Wiley-VCH,
Weinheim.
Perez-Quintanilla, D., Hierro I.D., Fajardo M., dan Sierra I, 2006, 2Mercaptotiazoline modified mesoporous silica for mercury removal
fromaqueuos media, Journal Hazardous Materials, B134 : 245-256.
Qu R., Niu Y., Sun C, Ji C., Wang C., dan Cheng G., 2006, Syntheses,
characterization, and adsorption properties for metal ions of silica-gel
functionalized by ester-and amino-terminated dendrimer-like
polyamidoamine polymer, Microporous and Mesoporous Materials, 97 : 5865.