Analisis Difraksi Sinar-X

(X-Ray Diffraction Analysis)

Crystal Structure
LATTICE = Kisi susunan titik dalam ruang yang memiliki lingkungan identik antara
satu dengan lainnya


CRYSTAL STRUCTURE = Susunan atom (kelompok atom) yang berulang .
It can be described by associating with each lattice point
a group of atoms called the MOTIF (BASIS)

Primitive Cell: simplest cell, contain one lattice point
Not necessary have the crystal symmetry
UNIT CELL = The smallest component of the crystal, which when
stacked together with pure translational repetition reproduces the
whole crystal
5 Kisi Bravais dalam 2D
P P NP
Definition:
Bravais Lattice: an infinite array of discrete points with an
arrangement and orientation that appears exactly the same from
whichever of the points the array is viewed.

Name


Number of Bravais lattices


Conditions

Triclinic

1 (P)


a
1
= a
2
= a
3

o = | =

Monoclinic

2 (P, C)


a
1
= a
2
= a
3

o = | = 90 =

Orthorhombic

4 (P, F, I, A)


a
1
= a
2
= a
3

o = | = = 90

Tetragonal

2 (P, I)


a
1
= a
2
= a
3

o = | = = 90

Cubic

3 (P, F, I)


a
1
= a
2
= a
3

o = | = = 90

Trigonal

1 (P)


a
1
= a
2
= a
3

o = | = < 120 = 90

Hexagonal

1 (P)


a
1
= a
2
= a
3

o = | = 90
= 120

3D: 14 Bravais Lattice, 7 Crystal System
Kisi FCC
Logam Cu memiliki
kisi face-centered
cubic

Atom-atom identik
terletak pada sudut
dan pada bagian
muka kisi
Jenis Kisi adalah
type F

also Ag, Au, Al, Ni...
BCC Lattice
o-Fe merupakan sebuah
kisi body-centered
cubic

Atom-atom Identik
terletak pada sudut dan
body center (nothing at
face centers)

Lattice type I

Also Nb, Ta, Ba, Mo...
FCC Lattices
Sodium Chloride
(NaCl) - Na is much
smaller than Cs

Face Centered Cubic

Rocksalt structure

Lattice type F

Also NaF, KBr, MgO.
Unit cell contents
Counting the number of atoms within the unit cell
Many atoms are shared between unit cells
Atoms Shared Between: Each atom counts:
corner 8 cells 1/8
face center 2 cells 1/2
body center 1 cell 1
edge center 4 cells 1/4
lattice type cell contents
P 1 [=8 x 1/8]
I 2 [=(8 x 1/8) + (1 x 1)]
F 4 [=(8 x 1/8) + (6 x 1/2)]
C
2 [=(8 x 1/8) + (2 x 1/2)]
e.g. NaCl
Na at corners: (8 1/8) = 1 Na at face centres (6 1/2) = 3
Cl at edge centres (12 1/4) = 3 Cl at body centre = 1

Unit cell contents are 4(Na
+
Cl
-
)

CRYSTAL STRUCTURE
DETERMINATION
BY X-RAY DIFRACTION (XRD)





















































Bravais lattices
Crystals possess a regular, repetitive
internal structure. The concept of symmetry
describes the repetition of structural features.
Symmetries are most frequently used to classify the
different crystal structures. In general one can generate 14
basic crystal structures through symmetries. These are called
Bravais lattices. Any crystal structures can be reduced to one
of these 14 Bravias lattices.




























































CRYSTAL STRUCTURE DETERMINATION

The determination of an unknown structure
proceeds in three major steps:
1. The shape and size of the unit cell are deduced
from the angular positions of the diffraction
lines.
2. The number of atoms per unit cell is then
computed from the shape and size of the unit cell,
the chemical composition of the specimen, and
its measured density.
3. Finally, the position of the atoms within the unit
cell are deduced from the relative intensities of
the diffraction



Size and Shape of the Unit Cell
This step is same as the indexing of power diffraction pattern.
It involves:

The accurate determination of peak positions.
Determination of the unit cell parameters from the peak
positions.
Braggs Law
Interplanar d-spacing
Systematic Absences








Bragg's Law

When x-rays are scattered from a crystal lattice, peaks of
scattered intensity are observed which correspond to the
following conditions:

1. The angle of incidence = angle of scattering.

2. The pathlength difference is equal to an integer number of
wavelengths.

The condition for maximum intensity contained in Bragg's
law above allow us to calculate details about the crystal
structure, or if the crystal structure is known, to determine
the wavelength of the x-rays incident upon the crystal.


























































































- Indexing Tetragonal system:
2
2
2
2 2
2
1
c
l
a
k h
d
hkl
+
+
= hkl
d 2 / sin u =
2 2 2
2
2
2
2 2 2
2
2
) (
4 2
sin Cl k h A
c
l
a
k h
d
hkl
+ + =
|
|
.
|

\
|
+
+
=
|
|
.
|

\
|
=

u
2 2 2 2
4 / ; 4 / c C a A = =
The value of A is obtained from hk0 lines.
When l = 0,
Possible values for h
2
+ k
2
are 1, 2, 4, 5, 8, 9, 10,
The rest of lines are
Possible values for l
2
are 1, 4, 9, 16,
- Indexing Hexagonal system:
2
2
2
2 2
2
3
4 1
c
l
a
k hk h
d
hkl
+
+ +
=
2 2 2
2
2 2
2
2 2 2
2
) (
4 3
sin Cl k hk h A
c
l
a
k hk h
+ + + = +
|
|
.
|

\
|
+ +
=

u
2 2 2 2
4 / ; 3 / c C a A = =
Possible values for h
2
+ hk + k
2
are 1, 3, 4, 7, 9, 12,

The rest of lines are
Possible values for l
2
are 1, 4, 9, 16,
2 2 2 2
2 2 2 2
) ( sin
) ( sin
Cl k hk h A
atau
Cl k hk h A
+ + + =
= + +
u
u
y C x A Cl k hk h A = = + + + =
2 2 2 2
) ( sin u
l
h,k
0,0 1,0 1,1 2,0 2,1 2,2 3,0 3,1
0 0 x 3x 4x 7x 12x 9x 13x
1 y x + y 3x + y 4x + y 7x + y 12x + y 9x + y 13x + y
2 4y x + 4y 3x + 4y 4x + 4y 7x + 4y 12x + 4y 9x + 4y 13x + 4y
3 9y x + 9y 3x + 9y 4x + 9y 7x + 9y 12x + 9y 9x + 9y 13x + 9y
4 16y x + 16y 3x + 16y 4x + 16y 7x + 16y 12x + 16y 9x + 16y 13x + 16y
h,k
1,0 1,1 2,0 2,1 2,2 3,0 3,1
Sin
2
u Sin
2
u
/3
Sin
2
u
/4
Sin
2
u /7 Sin
2
u /12 Sin
2
u /9 Sin
2
u /13
1 0,097 0,032 0,024

2 0,112 0,037 0,028

3 0,136 0,045 0,034

4 0,209 0,070 0,052

5 0,332 0,111 0,083

6 0,390 0,130 0,098
7 0,434 0,145 0,109
8 0,472 0,157 0,118
9 0,547 0,182 0,137
10 0,668 0,223 0,167
11 0,722 0,241 0,180
A = 0,112
Example:
sin
2
u sin
2
u/3 sin
2
u/4 sin
2
u/7
0.097 0.032

0.112 0.037

0.136 0.045

0.209 0.070

0.332 0.111

0.390 0.130

0.434 0.145

0.472 0.157

0.547 0.182

0.668 0.223

0.722 0.241
0.024

0.028

0.034

0.052

0.083

0.098

0.109

0.118

0.137

0.167

0.180
0.014

0.016

0.019

0.030

0.047

0.056

0.062

0.067

0.078

0.095

0.103
100
110
Lets say A = 0.112
1

2

3

4

5

6

7

8

9

10

11
sin
2
u sin
2
u-A sin
2
u-3A
0.097

0.112

0.136

0.209

0.332

0.390

0.434

0.472

0.547

0.668

0.722
0.806
0.879

0

0.024

0.097

0.220

0.278

0.322

0.360

0.435

0.556

0.610
0.694
0.767









0.054

0.098

0.136

0.211

0.332

0.386
0.470
0.543
0.097 belongs to Cl
2
.
What is the l?
There are two lines
between 100 and 110.
Probably, 10l
1
and
10l
2

0.024 and 0.097
are different ls.
0.097/0.024 ~ 4
0.220/0.024 ~ 9
0.390/0.024 ~ 16
C = 0.02441
1

2

3

4

5

6

7

8

9

10

11
12
13
100
110
101
102
002
112
0 2 4 6 8 10 12 14 16 18
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40


C
l
2
l
2
Slope = C = 0.02441
- Indexing orthorhombic system:
2 2 2
2
2
2
2
2
2 2
2
4
sin Cl Bk Ah
c
l
b
k
a
h
+ + =
|
|
.
|

\
|
+ + =

u
More difficult! Consider any two lines having indices
hk0 and hkl Cl
2
; get a guesses value C then put it back
and get A and B. If the guess is right, the number will be
consistent. If not try another guesses value of C.
- Indexing Monoclinic and Triclinic system:
Even more complex, 6 variables, must have enough
diffraction lines for the computer to indexing.
+ Effect of Cell distortion on the powder Pattern:
+ Determination of the number of atoms in a unit cell:
- After establishing shape and size we find the number
of atoms in that unit cell.
M
N V
n
C 0

=
V
C
: unit cell volume; : density
N
0
: Avogodros number;
M: molecular weight;
n: number of molecules in a unit cell
We need to index the powder pattern in order to obtain
the unit cell parameters unit cell volume
66054 . 1
) 10 022 . 6 ( ) ( ) 10 (
23
0
3
3 3 8

C
C
V
N
cm
g
cm V nM = =

in
3
in g/cm
3

A





MENENTUKAN INTENSITAS PUNCAK
DIFRAKSI SINAR X


Multiplicity factor
Lattice Index Multiplicity Planes
Cubic
(with highest
symmetry)
(100) 6 [(100) (010) (001)] ( 2 for negatives)
(110) 12 [(110) (101) (011), (110) (101) (011)] ( 2 for negatives)
(111) 12 [(111) (111) (111) (111)] ( 2 for negatives)
(210) 24
*
(210) 3! Ways, (210) 3! Ways,
(210) 3! Ways, (210) 3! Ways
(211) 24
(211) 3 ways, (211) 3! ways,
(211) 3 ways
(321) 48
*

Tetragonal
(with highest
symmetry)
(100) 4 [(100) (010)] ( 2 for negatives)
(110) 4 [(110) (110)] ( 2 for negatives)
(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)
(210) 8
*

(210) = 2 Ways, (210) = 2 Ways,
(210) = 2 Ways, (210) = 2 Ways
(211) 16 [Same as for (210) = 8] 2 (as l can be +1 or 1)
(321) 16
*
Same as above (as last digit is anyhow not permuted)
* Altered in crystals with lower symmetry
Cubic
hkl hhl hk0 hh0 hhh h00
48
*
24 24
*
12 8 6
Hexagonal
hk.l hh.l h0.l hk.0 hh.0 h0.0 00.l
24
*
12
*
12
*
12
*
6 6 2
Tetragonal
hkl hhl h0l hk0 hh0 h00 00l
16
*
8 8 8
*
4 4 2
Orthorhombic
hkl hk0 h0l 0kl h00 0k0 00l
8 4 4 4 2 2 2
Monoclinic
hkl h0l 0k0
4 2 2
Triclinic
hkl
2
* Altered in crystals with lower symmetry (of the same crystal class)
Multiplicity factor





If atom B is different from atom A the amplitudes must be weighed by the
respective atomic scattering factors (f)
The resultant amplitude of all the waves scattered by all the atoms in the UC gives
the scattering factor for the unit cell
The unit cell scattering factor is called the Structure Factor (F)
Scattering by an unit cell = f(position of the atoms, atomic scattering factors)
electron an by scattered wave of Amplitude
uc in atoms all by scattered wave of Amplitude
Factor Structure F = =
[2 ( )] i i h x k y l z
E Ae fe
t ' ' ' + +
= =
2 ( ) h x k y l z t
' ' '
= + +
In complex notation
2
F I
[2 ( )]
1 1
j j j j
n n
i i h x k y l z
hkl
n j j
j j
F f e f e
t ' ' ' + +
= =
= =

Structure factor is independent of the shape and size of the unit cell
For n atoms in the UC
If the UC distorts so do the planes in it!!
n ni
e ) 1 ( =
t
) (
2
u
u u
Cos
e e
i i
=
+

Structure factor calculations
A Atom at (0,0,0) and equivalent positions
[2 ( )]
j j j j
i i h x k y l z
j j
F f e f e
t ' ' ' + +
= =
[2 ( 0 0 0)] 0 i h k l
F f e f e f
t + +
= = =
2 2
f F =
F is independent of the scattering plane (h k l)
t t ni ni
e e

=
Simple Cubic
1
) (
=
t i n odd
e
1
) (
+ =
t i n even
e
B Atom at (0,0,0) & (, , 0) and equivalent positions
[2 ( )]
j j j j
i i h x k y l z
j j
F f e f e
t ' ' ' + +
= =
1 1
[2 ( 0)]
[2 ( 0 0 0)]
2 2
[ 2 ( )]
0 ( )
2
[1 ]
i h k l
i h k l
h k
i
i h k
F f e f e
f e f e f e
t
t
t
t
+ +
+ +
+
+
= +
= + = +
F is independent of the l index
C- centred Orthorhombic
Real
] 1 [
) ( k h i
e f F
+
+ =
t
f F 2 =
0 = F
2 2
4 f F =
0
2
= F
e.g. (001), (110), (112); (021), (022), (023)
e.g. (100), (101), (102); (031), (032), (033)




































































































X-Ray Fluorescence Analysis



Analisis X-ray Fluoresensi
Pendahuluan
Prinsip Kerja
Skema Cara Kerja Alat
Preparasi Sampel
Instrumen XRF
Contoh spektra
Radiasi Elektromagnetik
1Hz - 1kHz 1kHz - 1014Hz
1014Hz - 1015Hz
1015Hz - 1021Hz
Extra-Low
Frequency
(ELF)
Radio Microwave Infrared
Visible Light
X-Rays,
Gamma Rays
Low energy High energy
Pendahuluan
Teknik fluoresensi sinar x (XRF) merupakan
suatu teknik analisis yang dapat menganalisa
unsur-unsur yang membangun suatu material,
dengan dasar interaksi sinar-X dengan materi
analit.
Teknik ini juga dapat digunakan untuk
menentukan konsentrasi unsur berdasarkan
pada panjang gelombang dan jumlah sinar x
yang dipancarkan kembali setelah suatu
material ditembaki sinar X.
Fitur XRF
Akurasi yang relative tinggi
Dapat menentukan unsur dalam material tanpa
adanya standar (bandingkan dg. AAS)
Dapat menentukan kandungan mineral dalam
bahan biologis maupun dalam tubuh secara
langsung.
Kelebihan
tidak dapat mengetahui senyawa apa yang
dibentuk oleh unsur-unsur yang terkandung
dalam material yang akan kita teliti.
tidak dapat menentukan struktur dari atom
yang membentuk material itu.
Kelemahan
Prinsip Kerja
Menembakkan radiasi
foton elektromagnetik
ke material yang
diteliti.
Radiasi
elektromagnetik yang
dipancarkan akan
berinteraksi dengan
elektron yang berada
di kulit K suatu unsur.
Elektron yang berada
di kulit K akan
memiliki energi kinetik
yang cukup untuk
melepaskan diri dari
ikatan inti, sehingga
elektron itu akan
terpental keluar.
Peristiwa pada tabung sinar-X.
Prinsip Kerja XRF
Pada teknik XRF,
dienggunakan sinar-X dari tabung pembangkit
sinar-X untuk mengeluarkan electron dari kulit
bagian dalam untuk menghasilkan sinar-X
baru dari sample yang di analisis.
Prinsip Kerja XRF
Untuk setiap atom di dalam sample,
intensitas dari sinar-X karakteristik tersebut
sebanding dengan jumlah (konsentrasi)
atom di dalam sample.
Intensitas sinarX karakteristik dari setiap
unsur, dibandingkan dengan suatu standar
yang diketahui konsentrasinya, sehingga
konsentrasi unsur dalam sample bisa
ditentukan.
Skema Cara Kerja Alat
Instrumen XRF
Instrumen XRF terdiri
dari :
Sumber cahaya
Optik
Detektor

Syarat Sampel
Serbuk
Ukuran serbuk < 4 00 mesh
Padatan
Permukaan yang dilapisi akan meminimalisir efek
penghamburan
Sampel harus datar untuk menghasilkan analisis kuantitatif
yang optimal
Cairan
Sampel harus segar ketika dianalisis dan analisis dilakukan
secara cepat jika sampel mudah menguap
Sampel tidak boleh mengandung endapan

Sumber Cahaya
Tabung Sinar X
End Window
Side Window
Radioisotop
Tabung sinar x
End Window

Side Window
Be W indow
Silicone Insulation
Glass En v elope
Filament
Electron beam
Target (Ti, Ag,
Rh, etc.)
Copper Anode
H V Lead
Radioisotop
Isotope

Fe-5 5

Cm-244

Cd-109

Am-241

Co-57

Energy (keV)

5.9

14.3, 18.3

22, 88

59.5

122

Elements (K-
lines)

Al V

Ti-Br

Fe-Mo

Ru-Er

Ba - U

Elements (L-
lines)

Br-I

I- Pb

Yb-Pu

None

none

Optik
Source
Detector
Filter

Detector
X-Ray
Source
Source Filter
Contoh Spektra
Contoh Spektra
Detektor
Si(L i)
P N Diode
Silicon Drift Detectors
Proportional Counters
Scintillation Detectors

Si ( Li) Detektor

WIndow
Si(Li)
crystal
Dewar
filled with
LN 2
Super-Cooled Cryostat
Cooling: LN
2
or Peltier
Window: Beryllium or Polymer
Counts Rates: 3,000 50,000 cps
Resolution: 120-170 eV at Mn K-alpha
FET
Pre-Amplifier
PIN Diode






Cooling: Thermoelectrically cooled (Peltier)
Window: Beryllium
Count Rates: 3,000 20,000 cps
Resolution: 170-240 eV at Mn k-alpha
Silicon Drift Detector

Packaging: Similar to PIN Detector
Cooling: Peltier
Count Rates; 10,000 300,000 cps
Resolution: 140-180 eV at Mn K-alpha
Proportional Counter

Anode Filament
Fill Gases: Neon, Argon, Xenon, Krypton
Pressure: 0.5- 2 ATM
Windows: Be or Polymer
Sealed or Gas Flow Versions
Count Rates EDX: 10,000-40,000 cps WDX: 1,000,000+
Resolution: 500-1000+ eV
Window

Scintillation Detector
PMT (Photo-multiplier tube)
Sodium Iodide Disk
Electronics
Connector
Window: Be or Al
Count Rates: 10,000 to 1,000,000+ cps
Resolution: >1000 eV

(0,0,0)
(0, , )
(, , 0)
(, 0, )
Fractional Coordinates
Cs (0,0,0)
Cl (, , )
Density
Calculation
A C
N V
nA
=
n: number of atoms/unit cell
A: atomic mass
V
C
: volume of the unit cell
N
A
: Avogadros number
(6.023x10
23
atoms/mole)
Calculate the density of copper.
R
Cu
=0.128nm, Crystal structure: FCC, A
Cu
= 63.5 g/mole
n = 4 atoms/cell,
3 3 3
2 16 ) 2 2 ( R R a V
C
= = =
3
23 3 8
/ 89 . 8
] 10 023 . 6 ) 10 28 . 1 ( 2 16 [
) 5 . 63 )( 4 (
cm g =

=
8.94 g/cm
3
in the literature
(100) (111)
(200)
(110)
2
2 2 2
2
1
a
l k h
d
hkl
+ +
=
For cubic system
Lattice spacing
Braggs Law
For cubic system:
But no all planes have the
diffraction !!!
u
u u

sin 2
sin sin
hkl
hkl hkl
d
d d
QT SQ n
=
+ =
+ =
2 2 2
l k h
a
d
hkl
+ +
=
X-ray diffraction from a crystal: Braggs Law
u sin 2 =
hkl
d n
2 2 2
l k h
a
d
hkl
+ +
=
X-Ray Diffraction
n: order of
diffraction peak
d
hkl
: interplanar
spacing
(hkl): Miller
indices of plane
Crystal Structures [OGN 21.2]
Body-centered
cubic (BCC)
(200)
(211)
Powder diffraction
X-Ray
Phase purity.
In a mixture of compounds each crystalline phase present will contribute to
the overall powder X-ray diffraction pattern. In preparative materials
chemistry this may be used to identify the level of reaction and purity of the
product. The reaction between two solids Al
2
O
3
and MgO to form MgAl
2
O
4

may be monitored by powder X-ray diffraction.
At the start of the reaction a mixture of Al
2
O
3
and MgO will produce an X-
ray pattern combining those of the pure phases. As the reaction proceeds,
patterns (a) and (b), a new set of reflections corresponding to the product
MgAl
2
O
4
, emerges and grows in intensity at the expense of the reflection
from Al
2
O
3
and MgO. On completion of the reaction the powder diffraction
pattern will be that of pure MgAl
2
O
4
.
A materials chemist will often use PXRD to monitor the progress of a
reaction.
The PXRD method is widely employed to identify impurities in materials
whether it be residual reactant in a product, or an undesired by-product.
However the impurity must be crystalline.

Observable diffraction
peaks
2 2 2
l k h + +
Ratio
Simple
cubic
SC: 1,2,3,4,5,6,8,9,10,11,12..

BCC: 2,4,6,8,10, 12.

FCC: 3,4,8,11,12,16,24.
2 2 2
l k h
a
d
hkl
+ +
=
u n d = sin 2







Ex: An element, BCC or FCC, shows diffraction peaks
at 2u: 40, 58, 73, 86.8,100.4 and 114.7.
Determine:(a) Crystal structure?(b) Lattice constant?
(c) What is the element?
2theta theta (hkl)
40 20 0.117 1 (110)
58 29 0.235 2 (200)
73 36.5 0.3538 3 (211)
86.8 43.4 0.4721 4 (220)
100.4 50.2 0.5903 5 (310)
114.7 57.35 0.7090 6 (222)
u
2
sin
2 2 2
l k h + +
a =3.18 A, BCC, W










































































0
5
10
15
20
25
30
0 20 40 60 80
Bragg Angle (u, degrees)
L
o
r
e
n
t
z
-
P
o
l
a
r
i
z
a
t
i
o
n

f
a
c
t
o
r
Polarization factor
Lorentz factor
( )
|
.
|

\
|
|
.
|

\
|
=
u
u
u 2
1
2
1

Sin
Cos
Sin
factor Lorentz
( ) ( ) u 2 1
2
Cos I
P
+ =
( )
|
|
.
|

\
| +
=
u u
u
Cos Sin
Cos
factor on Polarizati Lorentz
2
2
2 1

Intensity of powder pattern lines (ignoring Temperature & Absorption factors)
|
|
.
|

\
|
+
=
u u
u
Cos Sin
Cos
p F I
2
2
2 2 1
Valid for Debye-Scherrer geometry
I Relative Integrated Intensity
F Structure factor
p Multiplicity factor
POINTS
As one is interested in relative (integrated) intensities of the lines constant
factors are omitted
- Volume of specimen - m
e
, e - (1/dectector radius)
Random orientation of crystals in a with Texture intensities are
modified
I is really diffracted energy (as Intensity is Energy/area/time)
Ignoring Temperature & Absorption factors valid for lines close-by in
pattern