diffraction methods in material science - … · la 2 zr 2 o 7 perovskites abo 3 ... diffraction...
TRANSCRIPT
Objective: to introduce both fundamental understanding and
practical skills of the characterization
of different materials using diffraction methods
2
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
3
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
4
Materials
Properties
Structure
Performance
Materials Science
Investigating the relationship between
structure and properties of materials
Material Engineering
Development, processing
and testing of materials
5
Crystallography
Pharmacy
Chemistry
Metallurgy
What is Material Science ?
Physics
Chemistry
6
Connections between the underlying structure
of a material, its properties and what the
material can do - its performance.
What is Material Science ?
New materials
New scientific
discoveries New technologies
Future development
of societies
5000 4000 3000 2000 1000 0 1000 1900 1960 1990 2010
BC AD
Stone Age
(~ 35 000 Years)
Bronse Age
(~ 1800 Years)
Iron Age
(~ 3300 Years)
Polymer Age
(~ 60 Years)
Silicon Age
(~ 55 Years)
Information/
Nanotechnology Age
(~ 20 Years)
Brief TimeLine of Material Science
Discovery of X-rays
7
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
8
9
Growth of Patents
Functional Performance ↔ Property ↔ Material
Convertion of light Photovoltaic effect Silicon
into electricity with (µ-crystalline Si)
high efficiency
Conduction band
Valence band
V
‚The Right Matertial for the Right Job‘
10
Structure
Space Group F d-3 m
Lattice parameter a=5.43 Å
E. Beckerel (1836)
R. Ohl (1941)
11
Functional Performance ↔ Property Material
High turbine efficiency Thermal resistance Y2O3-doped ZrO2
Long Lifetime
Temperature
Distance
Space Group P 42/nmc
R ~ l k
12
Structure
‚The Right Matertial for the Right Job‘
X-15 Aircraft
TBC on the internal surface of the XLR99 rocket
engine nozzle
Hilem & Bornhorst (1969)
13
Cracks
Erosion of coating
Spallation of coating
Melting of Nozzle
Failure
Application of Thermal Barrier Coatings
Vaßen et al. (2008)
New Structural Materials
Material Research in Thermal Barrier Coatings
New Composite Materials
La2Zr2O7
YZS
BC
Vaßen et al. (2009)
14
Pyrochlore
La2Zr2O7 Perovskites
ABO3
Space Group P m -3 m
15
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
Structural Characterization of Materials
Spectroscopic methods
Atomic radius ~ 1Å
Scattering methods
Microscopic methods
2 Å
45 µm
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Mass
Auger; EXAFS
IR
Raman
X-ray Diffraction
Neutron Diffraction
Electron Diffraction
Optical Microscopy
Scanning Electron
Microscopy (SEM)
Transmission Electron
Microscopy (TEM)
17
Cu – Ge Alloy
Optical Microscopy
SEM
TEM
E. Polatidis, N. Zotov
SCATTERING/ SPECTROSCOPIC METHODS
Source
Sample
Detector
ki, KEi, Ei
kf, KEf, Ef
k = mv impuls
KE = ½ mv2 kinetic energy
Ef = Ei Elastic Scattering
(Coherent)
Ef ≠ Ei Inealstic Scattering
(Incoherent)
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Particle Mass (kg) Charge Spin Magnetic Moment
Photon 0 0 1 0
Electron 9.109x10-31 -1 ½ -1.00 µB
Neutron 1.675x10-27 0 ½ -1.04x10-3 µB
Wavelengths
Photons
(nm) = 1240/E (eV) Cu K = 1.5418Å ; E = 8.041 keV
Electrons
(nm) = 12.25/V1/2
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Magnetic structures
Comparison of Radiations
Distribution of velocities for thermal neutrons (produced in neutron reactors)
Cold Source
Liquid H2 20
Energy of Neutrons
Energy of Photons
21
Diffraction methods
SCATTERING METHODS
X-ray scattering/ Diffraction
X-ray photons
Electron Diffraction
Electrons
Neutron scattering/ Diffraction
Neutrons
22
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
(-)
(+)
23
Max von Laue, Friedrich, Knipping (1912, Munich) discovered
diffraction from single crystal (Cu2SO4.5H2O)
(Nobel Price 1914)
X-ray tube
Collimator
Crystal Detector
Photographic Plate
24
Laue photographs
Laue Conditions
Laue Diffractometer
Sharp diffraction spots
25
Modern CCD cameras for 2D X-ray diffraction registration
MARCCD165
(Rayonix)
20 25 30 35
0
200
400
600
800
1000
Inte
nsity
Diffraction Angle
Primary beam
W. Bragg (1913/1914, Leeds) Bragg law of diffraction,
(Nobel Price 1915)
Norelco; USA (1948)
First commercial X-ray Diffractometer
Siemens (Brucker)
Phillips (X‘Pert)
Seiffert
first X-ray ‚Diffractometer‘
26
Detector (ionization camera) Sample Collimator
Invention of Powder Diffraction
P. Debye and P. Scherrer (1916/1917, Zurich)
(P. Scherrer - Nobel Price 1936)
27
Ag4(Sn,In)
Hannawalt, Rinn, Frevel (1938, Dow Chemicals) First powder diffraction patterns compilation
Ce2(SO4)3 , 1941
Ce2(SO4)3 , 52-1494
>350 000 entries
28
ICDD Datebase
Schull and Woolen (1949) First neutron diffractometer
Schull & Brockhouse (Nobel Price 1994)
Neutron Inelastic Scattering
D1B, ILL (Grenoble, France)
Monochromator schielding
Neutron guide
Sample Chamber
2D Detector
J. Chadwick (1932) Discovery of the neutron
(Nobel Price 1935)
29
Franklin, Crick, Watson, Wilkins (1953, Cambridge) Structure of DNA
(Nobel Price 1962)
30
J.D. Watson The double helix
The Role of Diffraction in Material Science
I. Phase Analysis
(Non-destructive)
Metallurgy
Mineralogy
Ceramics
Pharmaceuticals
Archeology
Forensic studies
40 50 60 70 80
200
400
600
800
1000
Inte
nsi
ty (
cou
nts
)
2 (degree)
31
Phases present
Quantitative phase analysis
Lattice parameters
Degree of crystallinity
II. Phase Diagrams
Ferrite ( ) Austenite ( ) Martensite
Hägg et al. (1926)
32
Mao et al., Science (1995)
33
Phase Diagram of Iron from
Laser-Heated Diamond Anvil
Cell XRD Experiments
III. Processes in the Earths Mantle and Core
34 34
Fe Phase Diagramme
Takahashi and Bassett, Science (1964)
Fe+NaCl Powder
No Gasket
Mo Radiation
Debye Method
bcc ( ) – (hcp) Transition
RT, 130 kBar (13 GPa)
1 Order Phase Transition
Leoni & Scardi (2000)
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.
35
IV. Development of New Materials
V. Chemical Bonding
A15-type Cr
Ishibashi et al. (1994)
Experimental Electron Density Distribution Topological Analysis of El. Density
Cr in Cr(CO6)
Cortes & Bader (2006)
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
36
Electron Density Distribution
Metal
Isolated ion
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
37
VI. RESIDUAL STRESSES
Withers et al. (2001)
Residual stresses in Al-Ti alloys after shot peening
Diffraction methods for
investigation of residual
stresses are:
Non-Destructive
Phase-specific
Depth-specific
38
Transformation Stresses in Ni-Ti Shape Memory Thin Films
Kocker, Zotov et al. (2013)
M
A
39
40
VII STUDIES OF MICROSTRUCTURE
(TEXTURE ANALYSIS)
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
Diffraction methods measure the
distribution of grains with different
orientations
Pole Figures
Ionization Radiation Protection
41
Alpha-particles (2P + 2N)
Beta particles (Electrons)
Gamma radiation
Neutrons
Personal protection measures
42
Radiation Attenuation
Beer-Lambert Law
I = Ioexp[-µ(E).x] = Ioexp[-µm(E) x]
Degree of transmission(%): 100*(I/Io)
Degree of absorption (%): 100*(1 - (I/Io))
x
Io I
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
http://physics.nist.gov/PhysRefData/XrayMassCoef/tab3.html
Beer-Lambert Law
I = Ioexp[-µ(E).x] = Ioexp[-µm(E) x]
X-rays µm ~ Z4/E3 !!!
43
More difficult to attenuate high
energy X-rays (gamma radiation)
Absorption of X-rays
Neutron abs. cross-section for E = 0.025 eV
(Thermal neutrons)
B, Cd, Xe, Hf
have high abs.
coefficients
44
The neutrons absorption cross-sections
do not depend on Z !!!
Element Z Mass Density A(N), cm2* µ(N), cm-1 (µ/ )X, cm2/g* µ(X), cm-1
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; = 1.808 Å
µ(N) = (NA/M) A
Degree of Transmission (%) = 100*(I/Io) = 100*exp(-µx)
x = 1 cm
Neutrons X-rays
B 0 0.0045
Ni 76 0
45
Degree of Transmission
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 46
Basic Recommended Literature
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
47
Useful Links
48
Technical Issues
# List of participants
# Scientific Calculator; Drawing Tools necessary for the practicals
# After each lecture, a PDF file with the lecture will be uploaded 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
49
http://www.uni-stuttgart.de/mawi/aktuelles_lehrangebot/Lehrangebot.html
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Practicals
Compulsery!
Room 2P4
Start 26.10.2017
Time 15:15 – 16:45