In-situ X-ray Diffraction

Instruments & Applications

Christian Resch
Anton Paar GmbH, Graz

www.anton-paar.com

Contents

1. Short Intro to X-ray Techniques and Laboratory © Wikipedia

Instrumentation for Structure Analysis

2. Sample Stages for In-situ X-ray Diffraction under

Non-ambient Sample Conditions

3. Application Examples

4. Small Angle X-Ray Scattering

Intensity [a.u.]

0.1

0.01

0 1 2 3 4 5 6 7
q [1/nm]

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 X-ray Techniques for Structure Analysis

Single Crystal
(SCD)

X-ray diffraction Powder diffraction

(XRD) (PXRD)
Pole figures
2D-Diffraction Reflectivity

Grazing incidence
Tomography (3D)

Nano-particles
in solution
Small Angle X-ray Scattering
(SAXS) Grazing incidence
SAXS (GI-SAXS)

Powder and 2D XRD

Powder XRD
 Standard analytical tool at universities and in the industry
 “Simple” diffractometers with only two mechanical “circles” to rotate either source
and detector (θ-θ) or sample and detector (θ-2θ)
 Measurements are quick and data evaluation straight forward
 Many materials are produced/used as powders or polycrystalline material:
pharmaceuticals, ceramics, metals, building materials (cement,…), catalysts,
polymers, …

2D XRD
 Mainly for materials preferred orientation of crystals and layered structures
o Texture
o Internal stress
o Layer propertries: thickness, interface roughness, stress, particle orientation, …

 Diffractometers and measurements more complicated:

o 2D detectors
o More mechanical circles (up to 5)

2
 Typical Laboratory Diffractometers

Bruker D2 Phaser
Bruker D8 Discover Benchtop diffractometer
PANalytical Empyrean
 no special supplies required
 very limited variability

Other Suppliers:
STOE&Cie
GE Inspection Technologies
Inel
….
Rigaku Smartlab

Why in-situ analysis ?

PhaseEquilibria Reaction Kinetics

Crystal Oxidation,
Fundamental Description
Structure Reduction,
of the
Analysis Corrosion
Material System

Anisotropic Phase
Thermal Expansion Transformations
Quantitative Analysis
Optimize Thermal Processing
Crystallization from
Glasses /Liquids
for
Polycrystalline
Improved Material
Texture
Performance
Crystallite Growth
Solid Solution &
Composition Microstrain
Source: S. Misture; Materials Science & Engineering, Alfred University, NY, USA
Denver X-ray Conference 2008

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 Non-ambient Sample Stages - Oberview

Commercially available non-ambient sample stages for laboratory X-ray

instruments:
 Heating and cooling –260 to +2400 °C
 Relative humidity (climate chambers) 5 – 95 %rF up to 60 °C
 Variable gas pressure <110-4 mbar to 100 bar
 Reactive and explosive gases
 Mechanical tension and compression
 Pressure cells up to several GPa
 Flow cells to study reactions, crystal growth and agglomeration
 Battery cells for electrical load

Temperature Stages for PXRD

Furnace Strip Heater Direct Heating+Cooling

1 2 1 1
2
3+4 4
4

1 2
3

1 … temperature controlled housing

2 ... X-ray window
3 … heating/cooling device
4 … sample carrier
Gas Flow
Cooler+Heater Oxford Cryosystems

4
 Sample Stages for 2D-diffraction
Temperature stage
2
3 1
1. Air-cooled housing
2. Heater = sample carrier
3. X-ray window (dome)
Comparison of Temperature Stages
Furnace heater
+ Good temperature homogeneity
+ most reliable sample
temperature measurement
+ Easy sample exchange
+ sample  sample holder
reactions unlikely
+ Sample spinning possible
– heating only
– max. 1670 K
– slower heating/cooling than
direct heaters
– temperature control not so
good at T < 650 K
– sample holder expansion
– residual oxygen
10
Tensile stage
Load cells
Direct heater/cooler
+ Very high/low temperatures
possible
+ Very fast heating/cooling
+ Temperature control less
dependent on the atmosphere
inside the sample stage
+ Simpler instrument design,
cheaper instrument
– sample preparation difficult
(strip heater)
– sample temperature
uniformity not so good
– sample temperature deviation
– sample  sample holder
reactions (strip heater)
Diamond Anvil Cell
(High pressure)
~ 100 GPa
Source: Pamela C. Burnley,
University of Nevada, Las Vegas
Gas flow heater/cooler
+ only option for single crystals
and cooling of capillaries
+ transmission geometry
+ small background from
sample holder (glass)
+ sample spinning
+ no sample displacement
– limited to low and medium
high temperatures
– sample temperature
uniformity difficult (capillaries)
– accurate temperature
measurement difficult
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 Synthesis of Semiconducting
Nanoparticles & Particle Growth

 ZnS and ZnO belong to the group of II-VI

semiconductors.
 Materials for many possible applications
(solar cells, infrared windows, lasers,
displays, …).
 Optical and optoelectronic properties of
nanoparticles are size-dependent
 control of the crystallite size required.
 Various synthesis methods established,
but low-cost, time-saving synthesis
methods are still under investigation.

 Established synthesis method [1] for ZnS from cheap precursors, followed
by an oxidation in air to ZnO.

[1] Lu, H.-Y.; Chu, S.-Y.; Tan, S.-S. Journal of Crystal Growth (2004), 269, 385-391

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Semiconducting Nanoparticles
Experimental
Formation of ZnS nanoparticles
 In N2 at 1 bar rel.
 Studied Parameters:

Sample heating stage for

 Reactive gases
 Temperature up to 900 °C
Oxidation to ZnO nanoparticles
 Gas pressure up to 10 bar
 ZnS samples oxidized in air at 600°C.
 Heating ramp: 100°C/min
 Sample of ZnS (100°C; 50°C/min) used to evaluate the
conversion time Study done by A. Pein
Anton Paar GmbH
 For other ZnO samples: Time for conversion 15 min
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 Semiconducting Nanoparticles
Formation of ZnS

Scherrer Equation
d …particle size
K …form factor
(2θ) …peak FWHM
θ …peak angle

Final ZnS particles

broader peaks ≡ smaller nanoparticles

Crystallite sizes depending on

formation conditions

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Semiconducting Nanoparticles
Formation of ZnO

Oxidation of ZnS to ZnO nanoparticles Resulting ZnO – nanoparticles

(Scans stacked)

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7
 Semiconducting Nanoparticles
Results
Formation of ZnS Formation of ZnO

 Formation of Cubic ZnS (Sphalerite)  Formation of Hexagonal ZnO (Wurtzite)

 Size range: 1.4 – 4.2 nm  Size range: 12.7 – 23.6 nm

(Scherrer equation)
 Conversion time:
 Influence of temperature: o after 10 minutes at 600°C no ZnS
o bigger crystallite size at higher T reflections left
 Influence of reaction time: o formation of ZnO has nearly finished
o bigger particles at prolonged
 ZnS particles synthesized at 100°C and
reaction time
300°C give similar sized ZnO nano-
 Influence of heating ramp: crystallites (20.5 to 23.7 nm)
o no clear trend concerning the size
 ZnS particles from 200°C give significantly
o relative and absolute growth rate
smaller ZnO crystallites (around 13 nm)
increased at lower ramp speed

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Hydrogen Storage Materials

Hydrogen as energy carrier

The ideal solid state H2 storage material
 light
 high H2 content
 reversible absorption and desorption
 abs/des @ T<180°C, p<50 bar
 rapid kinetics

Hydrogen storage
 Gas tanks  200-700 bar
 Liquid H2 tanks  -253 °C
 Solid state matrix
Source: Sandia Nat. Labs
Source: M.Sommariva, PANalytical B.V. Almelo, NL

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8
 H2 Storage in LaNi5

LaNi5+H2 as a model system for H2 storage

 H2 Storage capability of LaNi5 long known

 Properties of LaNi5:
o Stable in air
o Adsorption/desorption reversible and under moderate conditions
o Storage capacity low (1 wt% of H2)

Adsoprtion/Desorption mechanism

 LaNi5 + 3H2 ↔ LaNi5H6

 1st adsorption and desorption slow
 Subsequent adsorption and desorption fast

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H2 Storage in LaNi5 - Experimental

 1st absorption @ 100C and 65 bar H2

 desorption @ 50C in vacuum

 absorption @ 50°C and 5 bars H2

 des @ 50°C in vacuum

HPC 900 High-Pressure chamber

on X’Pert Pro diffractometer

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9
 H2 Storage in LaNi5 - Result

Data collection  quick scans over characteristic peaks for good time resolution

1st desorption Cycles of adsorption

and desorption
Data analysis  peak area of characteristic peaks

M. Sommariva
PANalytical B.V. Almelo, NL
C. Resch
Anton Paar GmbH

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Small Angle X-ray Scattering

A long scientific tradition in Graz

1957 Kratky Small-Angle X-ray Scattering Camera

 Prof. Otto Kratky, Univ. of Graz
 first SAXS instrument worldwide
 first scientific instrument produced by Anton
Paar GmbH
 > 600 systems sold worldwide

2003 SAXSess system

 jointly developped by Prof. Otto Glatter, successor of
Prof. Kratky, and Anton Paar GmbH
 with X-ray mirror, wide-angle capability, point
collimation, …
 Since 2005 sold directly by Anton Paar as a
complete X-ray instrument

2012 New SAXSpace system

 developped by Anton Paar GmbH
 with large sample chamber, auto-alignment, new
instrument control software, …

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10
 Small Angle X-ray Scattering (SAXS)

(1) SAXS informs about:

a) Particle Shape and Size OR Particle-Size Distribution
b) Surface-To-Volume Ratio
c) Molecular weight OR Particle Density

Size / size Shape Internal Porosity Degree of Moleculare

distribution Structure Crystallinity Weight

(2) SAXS investigates structures indirectly

(3) SAXS delivers averaged numbers

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The Purpose of SAXS

A method to investigate
o Morphologies
o Structures Microscopy  Optical lens Visible image

o Particle Architectures
Scattering Reconstruction

just as microscopy does … Object

Detector
BUT….

Light Source

Picture
SAXS  Fourier Mathematical
transformation reconstruction
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11
 Microscopy and Scattering

Microscopy Scattering

Small Details &

Easily detected. Are lost.
Local Structure

Average values Hard to obtain. Are always obtained.

Preparation
Hard to prevent. Are rare.
artefacts

Unique but with bad Ambiguous but with

Results are:
statistics. good statistics.

(1) The methods are complementary.

(2) You need both methods to get the complete picture !

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SAXS Ingredients

Small-Angle (SAXS): 0.1 – 10 deg

Wide-Angle (WAXS, XRD): 10 – 170 deg

Scattering
2
Angle

Detector
X-Ray Collimation Beam +
Source System Sample Stop Software

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12
 Investigating Nano-particles: SAXS
Measurement gives scattering pattern

Scattered intensity is recorded by a detector

and is processed mathematically

Scattering Reconstruction

Object Detector Software

Light Source

There are no x-ray lenses in SAXS instruments

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SAXSess
Simultaneous small- and wide angle scattering

Crystalline particles, strong interaction

WAXS: crystalline peaks

Large d-spacing

SAXS peaks
SAXS WAXS

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 SAXSess
Simultaneous small- and wide angle scattering

Crystalline particles, strong interaction

WAXS: crystalline peaks

Small d-spacing

WAXS peaks
SAXS WAXS

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Collimation Systems

Point Collimation: Line Collimation:

X-Ray Source X-Ray Source

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14
 Microfibril angle (MFA) in Natural Fibres

The microfibril angle (MFA) of the cellulose fibers is directly

proportional to the magnitude of the applied strain1).
45
°

38
°

Coir fibre
mounted on tensile stage 2D diffraction pattern
of coir fibre while
straining the sample.
X-rays
Azimuthal integration along
the 200 reflections.
The position of the maximum
is shifted to the center for
the strained fiber.

1) K. J. Martinschitz, P. Boesecke, C. J. Garvey, W. Change of MFA upon

Gindl, J. Keckes; J. Mater. Sci. 43 (2008) 350.
cyclic straining
Samples provided by Dr. Jozef Keckes, University of
Leoben, Austria
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Non-ambient XRD – Summary

In-situ X-ray diffraction and scattering provides unique information about important
material properties under controllable non-ambient conditions
 changes in crystal structure / crystal phase transformations
 transitions from amorphous to crystalline state and vice versa
 lattice parameters and expansion/contraction of the crystal structure
 recrystallization and crystallite growth
 chemical reactions
 internal stress
 layer and layer interface properties of layered structures
 nano-particle size and shape
 structural properties of nano-porous materials
 agglomeration
 and more …
averaged over a representative amount of material and with little sample preparation.

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