DIFFRACTION METHODS IN MATERIAL SCIENCE

PD Dr. Nikolay Zotov

Tel. 0711 689 3325

Email: zotov@imw.uni-stuttagrt.de

Room 3N16

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 TODAYS 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 (-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

E. Beckerel (1836)

R. Ohl (1941)

11

Functional Performance Property Material

High turbine efficiency Thermal resistance Y2O3-doped ZrO2Long Lifetime

Temperature

Distance

Space Group P 42/nmc

RQ ~ 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

Vaen et al. (2008)

New Structural Materials

Material Research in Thermal Barrier Coatings

New Composite Materials

La2Zr2O7

YZS

BC

Vaen et al. (2009)

14

Pyrochlore

La2Zr2O7Perovskites

ABO3Space 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 ~ 1

Scattering methods

Microscopic methods

2

45 m

16

Mass

Auger; EXAFS

IR

Raman

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

SCATTERING/ SPECTROSCOPIC METHODS

Source

Sample

Detector

ki, KEi, Ei

kf, KEf, Ef

k = mv impuls

KE = 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 -1.00 B

Neutron 1.675x10-27 0 -1.04x10-3 B

Wavelengths

Photons

l (nm) = 1240/E (eV) Cu Ka l = 1.5418 ; E = 8.041 keV

Electrons

l (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

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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

Rntgen (1895, Wrzburg) 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 (XPert)

Seiffert

first X-ray Diffractometer

26

Detector (ionization camera)SampleCollimator

Invention of Powder Diffraction

P. Debye and P. Scherrer (1916/1917, Zurich)

(P. Scherrer - Nobel Price 1936)

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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

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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)

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Franklin, Crick, Watson, Wilkins (1953, Cambridge) Structure of DNA

(Nobel Price 1962)

30

J.D. WatsonThe 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

)

2Q (degree)

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Phases present

Quantitative phase analysis

Lattice parameters

Degree of crystallinity

II. Phase Diagrams

Ferrite (a) Austenite (g) Martensite

Hgg 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

3434

Fe Phase Diagramme

Takahashi and Bassett, Science (1964)

Fe+NaCl Powder

No Gasket

Mo Radiation

Debye Method

bcc (a) e (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.

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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

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Electron Density Distribution

Metal

Isolatedion

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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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

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Transformation Stresses in Ni-Ti Shape Memory Thin Films

Kocker, Zotov et al. (2013)

M

A

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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

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Alpha-particles (2P + 2N)

Beta particles (Electrons)

Gamma radiation

Neutrons

Personal protection measures

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Radiation Attenuation

Beer-Lambert Law

I = Ioexp[-(E).x] = Ioexp[-m(E)rx]

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[-(E).x] = Ioexp[-m(E)rx]

X-rays m ~ Z4/E3 !!!

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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

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The neutrons absorption cross-sections

do not depend on Z !!!

Element Z Mass Density sA(N), cm2* (N), cm-1 (/r)X, cm

2/g* (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; l = 1.808

(N) = (NA/M)rsA

Degree of Transmission (%) = 100*(I/Io) = 100*exp(-x)

x = 1 cm

Neutrons X-rays

B 0 0.0045

Ni 76 0

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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, 199446

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

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Useful Links

http://www.iucr.org/http://icsd.ill.eu/icsd/index.htmlhttp://www.icdd.com/http://www.nist.gov/srm/index.cfmhttp://www.ccp14.ac.uk/http://www.webelements.com/http://www.cryst.ehu.es/

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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 2P4

Start 27.10.2016

Time 15:15 16:45