X-Ray Diffraction

Transmission Electron Microscope

Tech. of Microstructural Analysis
Wahyuaji NP
X-Ray Diffraction
 The XRD Technique
Takes a sample of the material and places a powdered
sample which is then illuminated with x-rays of a fixed
wave-length.
The intensity of the reflected radiation is recorded using a
goniometer.
The data is analyzed for the reflection angle to calculate
the inter-atomic spacing.
The intensity is measured to discriminate the various D
spacing and the results are compared to known data to
identify possible matches.
 Powdering Samples
The samples are powdered to give a random sampling of
ALL atomic planes (crystal faces)
Statistically accurate given samples are powdered finely
AND randomly oriented on sample holder
Intensities are a reflection of d-spacing abundance

Problems arise with minerals that may preferentially

orient on sample holder
Micas and clays have special preparation techniques
X-Rays Wavelengths used for
XRD
 What is X-Ray Diffraction??
Crystalline substances (e.g.
minerals) consist of parallel
rows of atoms separated by
a unique distance
Simple Example:
Halite (Na and Cl)
 Crystalline materials are characterized by
the orderly periodic arrangements of
atoms.
The (200) planes The (220) planes
of atoms in NaCl of atoms in NaCl

The unit cell is the basic repeating unit that defines a crystal.
Parallel planes of atoms intersecting the unit cell are used to define directions
and distances in the crystal.
These crystallographic planes are identified by Miller indices.
 Crystalline substances (e.g. minerals) consist of parallel rows of atoms
separated by a unique distance
Diffraction occurs when radiation enters a crystalline substance and is
scattered
Direction and intensity of diffraction depends on orientation of crystal
lattice with radiation
 Schematic X-Ray Diffractometer

Detector

X-Ray
Source

Powdered
sample
Sample XRD Pattern
 A polycrystalline sample should contain thousands of crystallites. Therefore,
all possible diffraction peaks should be observed.

2q 2q 2q

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.
 Determine D-Spacing from XRD patterns
Braggs Law
n = 2dsin
n = reflection order (1,2,3,4,etc)
= radiation wavelength (1.54 angstroms)
d = spacing between planes of atoms (angstroms)
= angle of incidence (degrees)
 DIFFRACTION AND THE BRAGG EQUATION
Max von Laue was the first to incident reflected
beam beam
suggest that crystals might A
o
x
o
B
oo
diffract X-rays and he also d a
UNIT
(1,0,0) CELL
provided the first explanation m
o o
n
C y D
for the diffraction observed.
However, it is the explanation
(a)
provided by Bragg that is simpler
and more popular.
incident reflected
In the Bragg view crystal beam o o beam
A x B
planes act a mirrors. oo
d
Constructive interference m n UNIT
o o
is observed when the path (2,0,0)
E y F
a CELL

difference between the two O P d

reflected beams in (a) = nl.

C Z D
The path difference in (a) is
2my. Since my/d = sinq
(b)
2my = 2dsinq = nl
where d is the interplanar spacing. Fig. 11
 Braggs Law animated
In (a) above it is clear that the planes are the (1,0,0) set of planes.
If the path difference is simply one wavelength the Bragg condition
can be stated as

2d (1,0,0) sin q = l
This is a first order reflection.

If the path difference is two wave lengths the Bragg condition becomes

2d (1,0,0) sin q = 2l
and the reflection is a second order reflection.
Calculations using X-ray powder diffraction patterns.
For an orthogonal system (a = b = = 90) the relationship between
interplanar spacing (d) and the unit cell parameters is given by the
expression:

1 h2 k2 l2
2
= 2
2

d ( h, k , l ) a b c2
This is the expression for an orthorhombic crystal.
For the tetragonal system it reduces to
1 (h 2 k 2 ) l2
2
= 2

d ( h,k ,l ) a c2
and, for the cubic system, it further reduces to

1 (h 2 k 2 l 2 )
2
=
d ( h,k ,l ) a2
Pure Epsomite (orthorhombic crystal) was analyzed by XRD with an
X-ray source of MoKa = 0.7093A. The peak results are presented
above. Each diffraction has been indexed. Determine the lattice
parameter of the Epsomite crystal.
 Factors that affect XRD data
Sample not powdered fine enough
May not give all d-spacing data (not random enough)

Analysis too fast (degrees/minute)

May not give accurate peak data

Mixture of minerals??
Not crystalline glass!!
Mixture of 2 Minerals
 Intensity of Diffracted Beam
Polarization Factor
Structure Factor (F2)
Multiplicity Factor
Lorentz Factor
Absorption Factor
Temperature Factor

For most materials the peaks and their intensity are

documented
JCPDS
ICDD
Stick pattern from JCPDS

http://ww1.iucr.org/cww-top/crystal.index.html
Name and formula
Reference code: 00-001-1260
PDF index name: Nickel
Empirical formula: Ni
Chemical formula: Ni
Crystallographic parameters
Crystal system: Cubic
Space group: Fm-3m
Space group number: 225
a (): 3.5175
b (): 3.5175
c (): 3.5175
Alpha (): 90.0000
Beta (): 90.0000
Gamma (): 90.0000
Measured density (g/cm^3): 8.90
Volume of cell (10^6 pm^3): 43.52
Z: 4.00
RIR: -
Status, subfiles and quality
Status: Marked as deleted by ICDD
Subfiles: Inorganic
Quality: Blank (B)
References
Primary reference: Hanawalt et al., Anal. Chem., 10, 475, (1938)
Optical data: Data on Chem. for Cer. Use, Natl. Res. Council Bull. 107
Unit cell: The Structure of Crystals, 1st Ed.
Diffraction from a Variety of Materials

(From Elements of X-ray

Diffraction, B.D. Cullity,
Addison Wesley)
 Thin Film Specimen

qB qB
Grazing angle (very small, ~1-5)
Film or Coating

Substrate

Smaller volume i.e. less intensity of the scattered beam from the film
Grazing angle
Useful only for polycrystalline specimens
 Applications of XRD
Unknown mineral ID
Solid solution ID (e.g. feldspars, olivine)
Mixtures of minerals
Clay analyses
Zeolites
Crystallographic applications
Material Science
Transmission Electron
Microscope
(TEM)
 DASAR TEORI
Pada tahun 1931, Seorang ilmuwan dari universitas berlin yaitu Dr. Ernst Ruka
membuat miskroskop transmisi elektron pertama kali.
TEM adalah mikroskop yg dapat melakukan pembesaran objek sampai 2 juta kali,
yang menggunakan elektro statik dan magnetik untuk mengontrol pencahayaan
dan tampilan gambar serta memiliki kemampuan pembesaran objek serta resolusi
yang jauh lebih bagus.
Desain dari Transmission Electron Microspcope (TEM) analog dengan mikroskop
optic. Pada TEM yang berenergy tinggi (>100 kV) electron digunakan sebagai
pengganti dari photon dan lensa elektromaknetik menggantikan lensa gelas. Sinar
dari electron melewati electron pada sampel dan gambar yang telah dibesarkan
dibentuk oleh satu set lensa-lensa.
Gambar ini diproyeksikan ke layar fluorescent atau camera CCD.
Mengingat kegunaan dari cahaya tampak membatasi resolusi lateral dalam
mikroskop optic pada 10-1 micrometer, semakin kecil panjang gelombang dari
electron, resolusi TEM dapat mencapai 0.2 nm.
 TIPE TEM

Tergantung tujuan dari analisa dan konfigurasi dari mikroskop, TEM

dibagi menjadi:

1. Conventional transmission electron microscopy

2. High resolution electron microscopy
3. Analytical electron microscopy
4. Energy-filtering electron microscopy
5. High voltage electron microscopy
6. Dedicated scanning transmission electron microscopy
INSTRUMEN
 INSTRUMEN

Sistem Kondenser

Sistem lensa Objektif

Sistem Lensa Proyektor

Lensa Intermediet
 PRINSIP TEM
1. ILLUMINASI
Sumbernya adalah sinar dari elektron berkecepatan tinggi yang
dipercepat pada kondisi vakum, difokuskan oleh lensa kondensor
(pembelokan gelombang elektromagnetik dari sinar elektron) ke
spesimen.

2. FORMASI GAMBAR
Kehilangan dan hamburan dari elektron oleh bagian-bagian dari
spesimen. Kemunculan berkas elektron difokuskan oleh lensa
objektif. Gambar akan terbentuk pada layar fluorescent.
CARA KERJA
 CARA KERJA

Hamburan electron yang elastis

(oleh inti dari suatu atom)
untuk image contrast

Elektron yang tidak terhambur (terpancar)

Akan melewati specimen untuk
membentuk bagian electron-lucent dari
gambar.

Hamburan electron yang tidak elastis

terpusat dalam sudut hamburan yang
lebih kecil
 DATA
Data yang dihasilkan oleh

TEM:

1. Gambar tampilan mikroskop

(Imaging)

2. Gambar difraksi (SAED)

Templated Synthesis of Magnetic Nanoparticles through the Self-Assembly of Polymers and Surfactants., Vo Thu An Nguyen 1,2,3,

Mario Gauthier 3 and Olivier Sandre 1,2,*., Nanomaterials 2014, 4(3), 628-685
 CONTOH
The structure of regularly twisted poly(m-phenylene isophthalamide) (MPDI)
strands formed by slow crystallization from solution

Source: C. Kbel, D. P. Lawrence, D. C. Martin, "Super-Helically Twisted MPDI Fibers", Macromolecules,

2001, 34(26), 9053-9058.
 INTERPRETASI DATA
Dari data yang dihasilkan dari analisa material menggunakan TEM,

dapat dilihat:
1. Struktur material
Material yang dianalisis masuk dalam katagori amorf atau kristalin
Struktur material dalam ukuran yang mikro hingga nanometer,
sehingga dapat dianalisa kondisi dan kualitas material
2. Komposisi elemen dalam material
3. Morfologi material
Bentuk, ukuran, penyebaran partikel dalam sampel
 KEGUNAAN ALAT
Spesimen dari TEM
Di bidang biologi dan kedokteran

Mengambil bagian yang ingin diamati dan diletakkan pada lapisan

tipis karbon atauformvar film. Untuk partikel seperti virus harus
dibekukan pada lapisan es yang tipis.

Di bidang metalografi

Melakukan preparasi sampel untuk metalografi klasik, seperti

grinding, polishing danetching untuk memperoleh sampel yang tipis
dan tembus atau dapat dilewati electron
 KEGUNAAN ALAT
Aplikasi TEM
Life Sciences (Konvensional dan struktur Biologi)
Digunakan untuk screening diagnostic dan beberapa kebutuhan riset
seperti risetstruktur sel biologi dan riset farmasi.

Material Sciences
Digunakan untuk semua jenis material dalam riset dan produksi,
proses dan atau control kualitas, seperti : Logam dan paduannya
(Steel / Al alloys), Semikonduktor, Keramik, dan berbagai material
lain seperti komposit, polimer dan material magnetic.
 KELEBIHAN DAN KEKURANGAN

Kelebihan / keuntungan:
TEM menawarkan pembesaran dan resolusi yang tinggi
gambar yang dihasilkan memiliki kualitas detail yang tinggi
TEM memberikan informasi elemen dan komponen struktur
TEM memiliki beragam aplikasi dan dapat digunakan di berbagai disiplin
ilmu pengetahuan, pendidikan dan industrial
Resolusi Superior 0.1 0.2 nm, lebih besar dari SEM (1 3 nm)
Mampu mendapatkan informasi komposisi dan kristalografi dari bahan uji
dengan resolusi tinggi
Memungkinkan untuk mendapatkan berbagai signal dari satu lokasi yang
sama.
 KELEBIHAN DAN KEKURANGAN
Kekurangan / Kelemahan:
instrumen TEM sangat besar dan cukup mahal
dalam pengoperasian dan kemampuan menganalisa data membutuhkan
pelatihan kusus
sample yang dapat dianalisa menggunakan TEM hanya material electron
transparant
peralatan TEM membutuhkan pemeliharaan dan kondisi ruang yang khusus
data gambar yang dihasilkan tidak berwarna (hanya hitam dan putih)
Hanya meneliti area yang sangat kecil dari sampel
Perlakuan awal dari sampel cukup rumit sampai bisa mendapatkan gambar
yang baik.
Elektron dapat merusak atau meninggalkan jejak pada sampel yang diuji.