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DIFFRACTION METHODS IN MATERIAL SCIENCE
PD Dr. Nikolay Zotov
Tel. 0711 689 3325
Email: [email protected]
Room 3N16
Objective: to introduce both fundamental understanding and
practical skills of the characterization
of different materials using diffraction methods
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OUTLINE OF THE COURSE
0. Introduction
1. Classification of Materials
2. Deffects in Solids
3. Basics of X-ray and neutron scattering
4. Diffraction studies of Polycrystalline Materials
5. Microstructural Analysis by Diffraction
6. Diffraction studies of Thin Films
7. Diffraction studies of Nanomaterials
8. Diffraction studies of Amorphous and Composite Materials
9. Practical Aspects
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OUTLINE OF TODAY‘S LECTURE
What is Material Science?
Brief Timeline of Materials and Material Science
Types of structural characterization methods
Types of scattering characterization methods
Brief History of X-ray and Neutron Diffraction
Role of Diffraction in Material Science
Ionization Radiation Protection
Basic recommended literature
Useful Links
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What is Material Science ?
Material Engineering
Development, processing
and testing of materials
Performance
Pharmacy
Chemistry
Metallurgy
Materials
Structure
Crystallography
Properties
Chemistry
Physics
Materials Science
Investigating the relationship between
structure and properties of materials
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What is Material Science ?
Connections between the underlying structure
of a material, its properties and what the
material can do - its performance.
New materials
New scientific
discoveries
New technologies
Future development
of societies
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Brief TimeLine of Material Science
Stone Age
(~ 35 000 Years)
Polymer Age
(~ 60 Years)
Bronse Age
(~ 1800 Years)
Iron Age
(~ 3300 Years)
Silicon Age
(~ 55 Years)
Information/
Nanotechnology Age
(~ 20 Years)
5000
4000
3000
2000
BC
1000
0
1000
1900
1960
1990
2010
AD
Discovery of X-rays
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2nd millennium BC – Bronze is used for weapons and armour
10th century BC – Glass production begins in ancient Near East
3rd century BC – Wootz steel invented in ancient India
3rd century BC – Cast iron technology developed in China (Han Dynasty )
1450s – Cristallo, a clear soda-based glass is invented by Angelo Barovier
1799 – Acid battery made from copper/zinc by Alessandro Volta
1824 – Portland cement patent issued to Joseph Aspdin
1839 – Vulcanized rubber invented by Charles Goodyear
1912 – Stainless steel invented by Harry Brearley
1931 – Nylon developed by Wallace Carothers
1954 – First Silicon solar cells made at Bell Laboratories
1985 - The first fullerene molecule discovered at Rice University
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Growth of Patents
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‚The Right Matertial for the Right Job‘
Functional Performance
↔
Property
Convertion of light
into electricity with
high efficiency
Photovoltaic effect
Conduction band
↔
Material
Silicon
(µ-crystalline Si)
Structure
Valence band
V
Space Group F d-3 m
Lattice parameter a=5.43 Å
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E. Beckerel (1836)
R. Ohl (1941)
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‚The Right Matertial for the Right Job‘
Functional Performance
High turbine efficiency
Long Lifetime
↔
Property
Material
Thermal resistance
Y2O3-doped ZrO2
Temperature
Structure
Distance
RQ ~ l k
Space Group P 42/nmc
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Application of Thermal Barrier Coatings
X-15 Aircraft
Cracks
Erosion of coating
Spallation of coating
Melting of Nozzle
Failure
TBC on the internal surface of the XLR99 rocket
engine nozzle
Hilem & Bornhorst (1969)
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Material Research in Thermal Barrier Coatings
New Composite Materials
New Structural Materials
La2Zr2O7
YZS
BC
Vaßen et al. (2009)
Pyrochlore
La2Zr2O7
Vaßen et al. (2008)
Perovskites
ABO3
Space Group P m -3 m
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Interplay between Materials –Properties-Microstructure-Functionality
Materials:
Y-stabilazed ZrO2, SrZrO3, La2Zr2O7
Preparation Techniques: Electron Beam Physical Vapor Deposition (EB-PVD)
Plasma Spraying; Spray drying + calcination
Microstructures:
Distribution of micropores
Orientation of microcracks; Compositional gradients
Properties:
Melting point, Thermal Expansion coefficient (TEC),
Thermal conductivity, Thermal resistance, Phase Stability
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Structural Characterization of Materials
Mass
Auger; EXAFS
IR
Raman
Spectroscopic methods
Atomic radius ~ 1Å
2Å
Scattering methods
Microscopic methods
45 µm
X-ray Diffraction
Neutron Diffraction
Electron Diffraction
Optical Microscopy
Scanning Electron
Microscopy (SEM)
Transmission Electron
Microscopy (TEM)
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Cu – Ge Alloy
Optical Microscopy
SEM
TEM
E. Polatidis, N. Zotov
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SCATTERING/ SPECTROSCOPIC
kf, KEf, Ef
METHODS
Detector
Source
ki, KEi, Ei
Sample
k = mv
impuls
KE = ½ mv2 kinetic energy
Ef = E i
Elastic Scattering
(Coherent)
Ef ≠ Ei Inealstic Scattering
(Incoherent)
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Comparison of Radiations
Particle
Photon
Mass (kg)
0
Charge
Spin
Magnetic Moment
0
1
0
Electron
9.109x10-31
-1
½
-1.00 µB
Neutron
1.675x10-27
0
½
-1.04x10-3 µB
Magnetic structures
Wavelengths
Photons
l (nm) = 1240/E (eV)
Cu Ka
l = 1.5418Å ; E = 8.041 keV
Electrons
l (nm) = 12.25/V1/2
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Energy of Neutrons
Distribution of velocities for thermal neutrons (produced in neutron reactors)
Cold Source
Liquid H2
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Energy of Photons
Diffraction methods
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SCATTERING METHODS
X-ray scattering/ Diffraction
X-ray photons
Electron Diffraction
Electrons
Neutron scattering/ Diffraction
Neutrons
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Brief History of X-ray and Neutron
Diffraction
Röntgen (1895, Würzburg) discovered the X-rays
(First Nobel Price in Physics in 1901)
W. Coolidge; GE (1915) First rotating anode tube
Philips (1929) First commercial rotating anode tube
(-)
(+)
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Max von Laue, Friedrich, Knipping (1912, Munich) discovered
diffraction from single crystal (Cu2SO4.5H2O)
(Nobel Price 1914)
Crystal
Collimator
Detector
Photographic Plate
X-ray tube
Laue photographs
Laue Conditions
Laue Diffractometer
Sharp diffraction spots
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Modern CCD cameras for 2D X-ray diffraction registration
MARCCD165
(Rayonix)
Primary beam
1000
800
Intensity
600
400
200
0
20
25
Diffraction Angle
30
35
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W. Bragg (1913/1914, Leeds)
(Nobel Price 1915)
Bragg law of diffraction,
first X-ray ‚Diffractometer‘
Collimator
Sample
Detector (ionization camera)
Norelco; USA (1948)
First commercial X-ray Diffractometer
Siemens (Brucker)
Phillips (X‘Pert)
Seiffert
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Invention of Powder Diffraction
P. Debye and P. Scherrer (1916/1917, Zurich)
(P. Scherrer - Nobel Price 1936)
Ag4(Sn,In)
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Hannawalt, Rinn, Frevel (1938, Dow Chemicals) First powder diffraction patterns compilation
Ce2(SO4)3 , 52-1494
Ce2(SO4)3 , 1941
ICDD Datebase
>350 000 entries
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J. Chadwick (1932) Discovery of the neutron
(Nobel Price 1935)
Schull and Woolen (1949) First neutron diffractometer
2D Detector
Schull & Brockhouse (Nobel Price 1994)
Neutron Inelastic Scattering
Sample Chamber
Neutron guide
Monochromator schielding
D1B, ILL (Grenoble, France)
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Franklin, Crick, Watson, Wilkins (1953, Cambridge) Structure of DNA
(Nobel Price 1962)
J.D. Watson
The double helix
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The Role of Diffraction in Material Science
I. Phase Analysis
(Non-destructive)
Metallurgy
Intensity (counts)
1000
800
Mineralogy
600
Ceramics
400
200
40
50
60
70
80
Pharmaceuticals
2Q (degree)
Archeology
Phases present
Quantitative phase analysis
Lattice parameters
Forensic studies
Degree of crystallinity
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II. Phase Diagrams
Hägg et al. (1926)
Ferrite (a)
Austenite (g)
Martensite
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III. Processes in the Earths Mantle and Core
Phase Diagram of Iron from
Laser-Heated Diamond Anvil
Cell XRD Experiments
Mao et al., Science (1995)
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Fe Phase Diagramme
bcc (a) – e (hcp) Transition
RT, 130 kBar (13 GPa)
Fe+NaCl Powder
No Gasket
Mo Radiation
Debye Method
1 Order Phase Transition
Takahashi and Bassett, Science (1964)
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IV. Development of New Materials
Synchrotron Radiation, Diamond, UK
Large volume change (3-5%) during
cooling down to monoclinic zirconia at RT,
which leads to cracks and failure after cycling.
Addition of oxides to stabilize the tetragonal
Zirconia at RT.
Leoni & Scardi (2000)
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V. Chemical Bonding
Electron density – type of bonding
Bond lengths
Bond Angles
Diffusion Pathways
Development of
Atomic Potentials
Molecular Dynamics Simulations
Search for new materials with specific chemical bonding
Electron Density Distribution
Experimental Electron Density Distribution
Topological Analysis of El. Density
A15-type Cr
Metal
Isolated
ion
Cr in Cr(CO6)
Cortes & Bader (2006)
Ishibashi et al. (1994)
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VI. RESIDUAL STRESSES
Origin:
Mismach of TEC, Plastic Deformation, Phase Transformations
Residual Stress Effects
● Growth of whiskers
● Fatigue
• Stress-corrosion cracking
• Crack initiation and propagation
● Undertstanding of structural failure
● Design of materials resistant to damage
● Performance of composite materials
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Residual stresses in Al-Ti alloys after shot peening
Diffraction methods for
investigation of residual
stresses are:
Non-Destructive
Phase-specific
Depth-specific
Withers et al. (2001)
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Transformation Stresses in Ni-Ti Shape Memory Thin Films
M
A
Kocker, Zotov et al. (2013)
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VII STUDIES OF MICROSTRUCTURE
(TEXTURE ANALYSIS)
Pole Figures
Diffraction methods measure the
distribution of grains with different
orientations
Texture is a critical parameter:
# Steels, Al-Ti alloys
↔
mechanical strength, formability
# Mineralogical/geological sciences
↔ texture of rocks ↔ Deformation history
# Thin Film Technology ↔ Growth modes; Strain accomodation; Physical Properties
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Ionization Radiation Protection
Alpha-particles (2P + 2N)
Beta particles (Electrons)
Gamma radiation
Neutrons
Personal protection measures
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Radiation Attenuation
Beer-Lambert Law
Io
I = Ioexp[-µ(E).x] = Ioexp[-µm(E)rx]
I
Degree of transmission(%): 100*(I/Io)
x
Degree of absorption (%): 100*(1 - (I/Io))
Alpha particles with 1 MeV energy - 100 % absorption in thin sheet of paper/polyethylene
Beta particles (electrons) with 1 MeV energy:
100% aborption in 1200 cm air
in 0.4 cm polyethylene
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Absorption of X-rays
Beer-Lambert Law
I = Ioexp[-µ(E).x] = Ioexp[-µm(E)rx]
X-rays µm ~ Z4/E3 !!!
More difficult to attenuate high
energy X-rays (gamma radiation)
http://physics.nist.gov/PhysRefData/XrayMassCoef/tab3.html
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Neutron abs. cross-section for E = 0.025 eV
(Thermal neutrons)
B, Cd, Xe, Hf
have high abs.
coefficients
The neutrons absorption cross-sections
do not depend on Z !!!
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Degree of Transmission
sA(N), cm2*
µ(N), cm-1 (µ/r)X, cm2/g*
µ(X), cm-1
Element
Z Mass Density
B
5
10.8
2.5
2x10-21
279
4.0
10.0
Ni
28 58.7
8.9
2x10-24
0.274
79.5
707.0
________________
* E = 6.868 keV; l = 1.808 Å
µ(N) = (NA/M)rsA
Degree of Transmission (%) = 100*(I/Io) = 100*exp(-µx)
x = 1 cm
Neutrons X-rays
B
0
Ni
76
0.0045
0
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Basic Recommended Literature
● Modern Diffraction Methods
Eds. E.J. Mittemeijer, U. Welzel, Wiley VCH 2013
● Fundamentals of Materials Science
E.J. Mittemeijer, Springer-Verlag, 2010
● X-ray Diffraction by Polycrystalline Materials
R. Guinebretiere
Wiley, Online Library, 2010
http://onlinelibrary.wiley.com/book/10.1002/9780470612408
● Understanding Materials Science: History, Properties, Applications.
Rolf E. Hummer
New York: Springer Verlag, 1998.
● Diffraction Methods in Material Science
Ed. J. Hasek
Nova Science Publishers, 1993
● X-ray Diffraction
W.A. Warren
Dover Publications, 1969
● X-ray Diffraction in Crystals, Imperfect Crystals and Amorphous Solids
A. Guinier
Dover Publications, 1994
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Useful Links
www.iucr.org
International Union of Crystallography
http://icsd.ill.eu/icsd/index.html
Inorganic Crystal Structure Database
http://www.icdd.com/
International Centre for Diffraction Data
http://www.nist.gov/srm/index.cfm
NIST Standard Reference Materials
http://www.ccp14.ac.uk/
Free crystallographic software database
http://www.webelements.com/
Physical/Chemical Information for all elements
http://www.cryst.ehu.es/
Bilbao Crystallographic Server
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Technical Issues
# List of participants
# Scientific Calculator; Drawing Tools necessary for the practicals
# After each lecture, a PDF file with the lecture will be uplaoded on the
Internet site of the institute
# Taking videos during the lectures not allowed
# Online registration through the LSF System before the Exam is compulsary
https://lsf.uni-stuttgart.de
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http://www.uni-stuttgart.de/mawi/aktuelles_lehrangebot/Lehrangebot.html
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Practicals
Room
Start
2P4
27.10.2016
Time
15:15 – 16:45
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