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2ND INTERNATIONAL CONFERENCE AND EXPO ON CERAMICS AND COMPOSITE MAT ERIALS

SHERATON BERLIN GRAND HOTEL ESPLANADE, 10785 BERLIN, GERMANY

NEW X-RAY DEVELOPMENTS TO CHARACTERIZE CERAMIC MATERIALS

A. DOMMANN*, O. KUZIOR, A. FLISCH, S. HARTMANN, R. KAUFMANN AND A. NEELS ,EMPA, SWISS FEDERAL LABORATORIES FOR MATERIALS SCIENCE AND TECHNOLOG Y, CENTER FOR X-RAY ANALYTICS, SWITZERLAND

MaterialsMaterials

Processing

AnalyticsSimulations

Multi-layer and system

fabrication

Materials behavior

by in-situ studies

Model simulations of

joining processes

Interfacial design of nano-

structured materials

Accelerate progress by sharing know how

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TEM/STEM HRSEMHe-SEM

FIB

ToF-SIMS

AFM

7.5 x 7.5 mm2

3D NanoChemiscope

Surface Analytics

HRXRD

X-ray Analytics: Methods & Tools

X-RAYSAbsorption

XRDHRXRD

SAXS

XPCI

Imaging: 2D, 3D

X-ray tool & methods optimisationfor materials & system studies

Low to high Energies

In-situ studies:- Temperature- Humidity- Mechanical stresses

Detectordevelopments

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X-ray Analytics: Imaging & XRD

Imaging Seeing the invisible

Atomic and Molecular StructureWhere are the atoms

SiO2

Macromolecules

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Structural properties addressed by X-ray techniques

Domain ordering

Phases

Mosaicity

Stress / Strain

Crystallite Size

Density

XRD / HRXRD

(Interface)

roughness

Layer

thickness

Texture

Defects

Nano-particle Size

Distribution

SAXS / GISAXD

Reflectivity

3D molecular structures for

new materials

Orientation

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Hard Coatings: (Al,Cr)2O3 & (Al,Hf)2O3

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THERMAL BARRIER COATINGS (TBC)

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(Al,Cr)2O3 TiCN uncoated

Thermal Stability

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Oxidation behaviour of TiCN / AlCrO at 900°C (air, 30 min)

H2 = 32 nm

Thermal stability

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Support in process development:

Hard coatings

Dedicated Design of High Temperature Corrosion Resistant PVD Oxide Coatings for Automotive Applications

Simulations Characterization:

XRD, ex- and in-situ

RBS

Mechanics

Testing

Understanding

Reactive cathodic arc evaporation (PVD)

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High Temperature Corrosion Resistant Al-Cr-O Coatings Deposited by Arc Operation

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Crystal Structure Consistency with Vegard’s law

Cr / Al ratio

4.70

4.75

4.80

4.85

4.90

4.95

5.00

0.0 0.5 1.0 1.5 2.0

13.00

13.10

13.20

13.30

13.40

13.50

13.60

13.70

13.80

4.70

4.75

4.80

4.85

4.90

4.95

5.00

0.0 0.5 1.0 1.5 2.0

13.00

13.10

13.20

13.30

13.40

13.50

13.60

13.70

13.80Measured values

(Al0.85Cr0.15)2O3(Al0.85Cr0.15)2O3

(Al0.7Cr0.3)2O3(Al0.7Cr0.3)2O3

(Al0.5Cr0.5)2O3(Al0.5Cr0.5)2O3

(Al0.25Cr0.75)2O3(Al0.25Cr0.75)2O3

latt

ice

para

mete

r a

[Å]

latt

ice

para

mete

r c

[Å]

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Cathode surface vs layer composition

Cathodes

• Phase transformation process at the cathode surface?• How this influences the deposited layer?

Layers

A. Neels, X. Maeder, A. Dommann, J. Ramm 14

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Al-Cr system:

XRD High temperature experiment

XRD Chamber at 1300°C

• Phase transformation at high temperature

• Progressive oxidation study• Stability of the coating

A. Neels, X. Maeder, A. Dommann, J. Ramm 15

Wear resistant hard coatings

Oerlikon developed a complete new deposition method:

Reactive Cathodic Arc Deposition

Need: fundamental understanding of this new deposition process

Approach: Combination of characterization, simulation and testing

Cathodic arcprocess Deposition

O2

Intermetallics + OxidesPure Al and pure Hf

O2 O2

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Post-hot isostatic pressing

Thin film multilayers: PZT

Piezoelectric materials for switches

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PZT layers by sol-gel deposition.

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J. Am. Ceram. Soc., 97, 2069–2075 (2014)

3D schematic view

The five-layer lead zirconate titanate device after patterning the three topmost electrodes:

2D schematic of the cross section

PZT multilayer systems

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Platinum

Lead Zirconium Titanium Oxide

Pt(

111)

Pt(

002)

PZ

T(0

11)

PZ

T(1

11)

PZ

T(0

01)

PZ

T(1

12)

Pt(

220)

PZ

T(0

02)

PZ

T(0

12)

Phase analysis

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PZT layers trough sputtering: Pole figures show the PZT fiber texture, the preferred orientation direction is (001). Much higher texturing compared to the sol-gel deposition process.

Texture analysis: PZT pole figures

001 011 111

002 012 112

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Only small loss in texture. Quantification trough texture index.

Texture developpement in multilayers:

J. Am. Ceram. Soc., 97, 2069–2075 (2014)

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HRXRD

Epitaxial Systems

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22.07.2016 24Center for X-ray Analytics: antonia.neels@empa.ch

Strain

Defects

Layer thickness

Lateral structure

Chemical composition

Lattice parameters

Analytical tasks to address for epitaxy films

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In-plane diffraction

Thin film X-ray Diffraction: Geometries

Out-off-plane diffraction

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Thin epitaxial films: Out-off plane BTO(002)

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BaTiO3: reflection (002) on SiOut-off-plane diffraction

d-spacing FWHM FWHM (RC)

BTO-Si 1.9975 0.45 1.401

A. Neels, M. Reinke, P. Hoffmann, A. Dommann

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22.07.2016 27Center for X-ray Analytics: antonia.neels@empa.ch

BaTiO3: asymmetric reflection (103) on Si

BTO

BaTiO3: reflection (103) on Siasymmetrical reflection

A. Neels, M. Reinke, P. Hoffmann, A. Dommann 27

22.07.2016 28Center for X-ray Analytics: antonia.neels@empa.ch

In plane diffraction:

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22.07.2016 29Center for X-ray Analytics: antonia.neels@empa.ch

BaTiO3: in-plane BTO(200) on Si and MgO

High mosaicity forBTO on MgO

BTO

BTO

MgO

Si substrate MgO substrate

A. Neels, M. Reinke, P. Hoffmann, A. Dommann 29

X-Ray Tomography

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X-RAY CT SETUPS: FAN BEAM & CONE BEAM

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source

collimator

object

detector line

manipulator

source object

detector arraymanipulator

X-ray uCT (160/220 keV)

Linac X-ray CT (4/6 MeV)

Industrial X-ray CT (450 keV)

Cone beam CT (450 keV)

High energy X-ray imaging

Insulator, region of interest (160 x 140 x 100 mm)

expoxide resign filled with aluminum oxide

pore, d = 0.7 mm

aluminum core

scan parameters:

X-ray source: 450 kV, 3 mA

Pixel size: 0.15 x 0.15 mm

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• Measurement of X-ray phase-shift and scattering instead of absorption

• Dark field imaging: sensitive to sub-micrometre structures (e.g. pores)

• Virtual Institute for New X-ray Methods in Material Science

X-RAY PHASE CONTRAST AND DARK-FIELD IMAGING

TWO XPCI SYSTEMS

G0G1G2

Add-on to µCT45 keV design energy

New, dedicated setup35 keV design energy

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BRUKER

XPCI Tomography of a tooth

enamel

caries

dentin

µ-crack

Absorption cross sections Dark-field cross sections

In c

olla

bo

rati

on

wit

hC

SEM

Discussion

XRD and in-situ XRD

support tool for layer deposition process optimization

System understanding and layer design

HRXRD For oxide materials and devices

Addressing in-plane diffraction for accessing directly in-planestructural parameters: strain, mosaicity

X-Ray Tomography For 3D information of oxide materials and devices

High sensitivity of the dark-field mode to small voids.

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Curiosity, Flexibility, Communication

Röntgenhaus

Antonia Neels, Rolf Kaufmann, Tanja Kramer, Thomas Lüthi, Alex Flisch, Felix Reifler, Olga Kuzior, Gelu Rotary, Mathieu Plamondon, Mario Beltran, Kai Zweiacker, Michele Griffa, Yu Liu, Carina Stritt, Fei Yang, Jürgen Hofmann,

Alex Dommann, Stefan Hartmann, Zoltan Balogh, Selina Kolokytha, Ramon Schmid, Kim von Allmen.

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KEYNOTE SPEAKERS (to be completed)

Jan Pieter Abraham, Basel University, Switzerland

Bob Cernik, University of Manchester, UK

Birger Dittrich, Georg-August-University Göttingen, Germany

Robert von Dreele, Argonne National Laboratory, USA

Francesca Fabbiani, Göttingen, Germany

Makoto Fujita, University of Tokyo, Japan

Sandra W. Jacob, Novartis Pharma AG, Basel, Switzerland

Sven Lidin, Lund University, Sweden

Gabor Oszlanyi, Academy of Sciences, Budapest, Hungary

Simon Parsons, University of Edinburgh, UK

Werner Paulus, Montpellier, France

Martin U. Schmidt, University of Frankfurt, Germany

Peter Schurtenberger, Lund University, Sweden

Ada Yonath Jean-Marie Lehn