AT0200480

216 GT48 P. Ramminger et al.

15" International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 4

Application of High Temperature X-Ray Diffraction as a tool for

material characterisation and product optimisation

P. Ramminger*, R. Tessadri*, R. Krismer**, P. Wilhartitz**

* Institute of Mineralogy and Petrography, University of Innsbruck, Austria

** Plansee AG., Reutte, Austria

Summary

X-ray Diffraction (XRD) combined with insitu high temperature experiments is

a very powerful tool for the characterisation of structural parameters of
industrial materials. Although this method has been known for some decades,
new instrumental developments such as flexible diffracting geometries
(Theta-theta movement), high temperature XRD chambers with
homogeneous temperature distribution and parallel beam optics provide
much better application to a wide range of specimen. Parallel to the progress
in instrumental developments, data processing and evaluation of XRD data
also underwent significant changes due to the development of new
mathematical algorithms and new software packages which allow to gather
more precise sample dependent information.

In addition to the qualitative identification of crystalline phases, XRD patterns

contain a lot of additional information such as crystallite size distribution,
texture, lattice parameters and residual stress.
Insitu thermal observations with the high temperature XRD equipment provide
additional unique information such as temperature-dependent phase
transformations, the thermal changes of structural parameters and changes
of the real structure parameters. Furthermore, insitu cycled thermal exposure
simulates relevant changes in the physical properties similar to industrial
processes.
For optimal data quality, the calibration of the high temperature XRD chamber
and the setup routines have to be established prior to gathering all sample-
related information available.
Industrial-relevant examples for the use of this method will be shown.
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Keywords

X-ray Diffraction, high temperature; parallel beam optics, crystallite size,

microstrain

Introduction

X-ray Diffraction (XRD) is a traditional tool for industrial applications (steel-

and cement industries) and has been mainly applied for qualitative and semi-
quantitative analysis. During recent years the extraction of advanced sample-
dependent parameters and the behaviour of industrial samples during non-
ambient conditions has become of widespread interest, not only for
fundamental research but also for manufacturing processes and quality
control.

Major changes in the construction of X-ray equipment were made; i.e. theta -
theta movement of the goniometer and changes of the X-ray beam path like
parallel beam optics which provides flexibility of sample properties, pin-hole
and glass fibre collimators, position sensitive - and 2-D detection systems for
large 2-theta coverage and fast data acquisition.
For simulations of physical operations or phase reaction studies, non-ambient
chambers have been developed for insitu sample characterisation.
Construction of new high temperature (HT) and Low temperature (LT)
chambers with good temperature homogeneity provide the basis for accurate
measurements under non-ambient conditions.

Software developments like advanced profile description methods (Direct

Convolution Approach, Fundamental Parameter Approach) implemented into
user friendly profile fitting- and Rietveld structure refinement software gathers
most of the sample related information accessible. Additional specific
software provides the evaluation of mechanical and/or thermal-induced
impacts due to residual stress of a sample.

The aim of this contribution is to provide information about the setup and
calibration procedure of a modern high temperature X-ray Diffraction system
as well as the measurement and evaluation of HT-data. The procedure
described in this paper is aimed to industrial research on thin film hard
coatings and shows the capabilities of modern XRD analysis in respect to
regular quality control and industrial research.
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15" International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 4

1. Experimental setup

For the characterisation of hard coatings thin films, a standard laboratory X-

ray diffractometer (Siemens D5005) equipped with parallel beam optics and a
high temperature XRD-chamber (Paar HTK-1200) which can be used for
temperatures up to 1200°C. In combination to the HT-appliance, a high
vacuum (up to 5 E-6 mbar) and gas supply station for reaction- and inert
gases has been installed to provide the flexibility of different well defined gas
atmospheres in the chamber in order to prevent uncontrolled reactions such
as oxidation and/or reduction.

Powder diffractometer Siemens D5005

8 / 8 goniometer, Scintillation Counter
with attached high temperature Chamber
(Paar HTK-1200)

X-ray tube /settings fine focus Cu anode; 40kV 40mA

Primary Goebel mirror
parallel beam optics 2nd generation, 2° Soller slit
Secondary Soller slit
parallel beam optics 0.4 mm
Primary slits 1; 0.6 mm
Secondary slit 2 mm

Table 1: Experimental setup used for HT-characterisation

The experimental setup described above has been chosen for maximum
resolution and flexibility in respect to the sample material for the following
reasons:

• In order to achieve high intensity and fast data acquisition the X-ray
optics and additionally attached equipments have to be perfectly
aligned and adjusted. This is important, because the installation of the
HTK-1200 into the beam path reduces the intensity of the diffracted X-
ray by approximately 40% due to the X-ray windows of the chamber.
The window material used in this study is made of a flexible capton -
aluminium composite and withstands internal temperatures in the
chamber of up to 1000°C. For temperatures up to 1200°C a
combination of thin capton - graphite layers is used.
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The disadvantage of the second setup is the low oxidation resistance of

graphite at temperatures above 500°C. In order to avoid graphite
erosion, inert gases such as helium or argon have to be constantly
supplied during application.

• The use of gas-atmospheres in the chamber, may result in significant

intensity losses due to the absorbance of heavy gas molecules. For
example the use of argon reduces the diffracted X-ray intensity by
approx. 95%. Depending on the chemistry of the sample alternatives
like high vacuum (5 E-6 mbar) or helium should be considered.

2. Calibration of the high temperature chamber

The HT-calibration of the XRD chamber is necessary because of the

uncertainties of the heat transfer between the heating coil, the thermocouple
and the chamber itself.
Additional factors such as the oxidation of the coil and/or the thermocouple,
the gas pressure in the chamber, the gas atmosphere, etc. influence the
precision of the temperature measurement.
To guarantee a thermal equilibrium between the HT-chamber and the sample
as well as a homogeneous temperature distribution through out the sample,
low heating-rates should be preferred in general.
Consideration of the thermal response of the applied thermocouple is also
important for the evaluation of the calibration results. The S-type Pt/Pt90-
Rh10 thermocouple used in this study responds linear in the temperature
range from approx. 350°C up to 1200°C.

Three different kinds of calibrations are commonly used: [1.] measurement of

the linear expansion of well characterised substances, [2.] temperature-
dependent polymorphic phase transformations. [3.] observation of well-
defined melting points.
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2.1 Temperature calibration due to linear expansion of cubic

materials

This calibration method is based on the isotropic thermal expansion of the

lattice parameter of cubic structured materials during temperature treatment.
The calibration experiments of this study were carried using a platinum disc
(Merck Pt 99,997%, diameter 17mm, 0.1 mm thickness), because of the well
known linear expansion coefficient of platinum and its good high temperature
and oxidation resistance (1). During the high resolution measurements
temperatures where increased in 100°C steps, ranging from 100°C to 1000°C
(heating-rate 0.1 °C/min).
The results of the obtained lattice spacing of platinum fit well to the reference
values of Touloukian et al. (1) are shown in figure 1. The thermal expansion
of the lattice of platinum shows a linear thermal behaviour of the chamber
during firing.

3.9650

3.9600

3.9550

i
Calibration Experiment 2%
lattice spac ing [Angstöm)

R2 = 0.9997 JS
3.9S00

3.9450

3.9400
n ^ Reference datasets by Touloukian
y^- R2 = 0.9988
3.9350

3.9300

3.9250 <?
3.9200
100 200 300 400 500 600 700 800 900 1000 1100

Temperature [°C]

Figure 1: Comparison of the lattice parameter of Platinum: reference values (triangular) and calibration
experiment (circles) on Pt 99.
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15'" International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 4

2.2 Temperature calibration due to polymorphic phase

transformations

This calibration method is based on isochemical phase transformation of well

known substances such as SiO2 (Alpha -Beta transformation at 573°C) or
BaCO3 (803°C) at 1 bar. These calibration experiments show the displacive
structural change from the LT- to the HT-modification (2).

Quarz at 573"C; t
A

Breakdown of (1 0 2)
indices at 572° + 2°C

650°C

A
Intensity
572°C
Temperature

t-r,
A
2 Theta
soo'c

Figure 2: Alpha - Beta Quartz transition experiment:

The breakdown of the (1 0 2) of the trigonal Quartz modification was detected at 572°C + 2"C, shown as
surface-plot (Intensity - 2Theta - temperature) and as XRD-overlay plot (Intensity vs. 2Theta).

2.3 Temperature calibration due to melting reactions

This calibration method is based on the melting-point determination of well

characterised substances such as Au at 1064°C, NaCI at 804°C (2). The
exact point of melting is described by the breakdown of Bragg-reflections.
This calibration has not been carried out in this work.
222 GT48 P. Ramminger et al.
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15 International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 4

3. Application of HT-XRD for investigations on chemical reactions

The use of HT-XRD in industrial laboratories is traditionally used for studying

iso- or allochemical phase reactions. This has important implications for
studying certain questions of reaction kinetics, such as thus a reactions
proceed continuously or discontinuously, or thus a reaction proceeds directly
form reactant to products or forms stable or meta-stable intermediate product-
phases. The final goal is to establish the stability field in dependence of
temperature (T), sample chemistry (X) and fugacity (F) of the gas phase
present in the chamber.

An example of a reaction involving solid and gaseous phases is the reaction

of Zr + O2 => ZrO2 Baddeleyite

MO

£00
Lin i

•> I 600°C
•

r 1 520°C

o
1 i 450°C
i

2-Thela - Scale

Figure 3: Oxidation experiment of an zirconium-sheet shown as overlay-plot ranging from 450°C - 600°C,
temp-steps 10°C; The formation of Baddeleyite was established at 520°C ± 10°C in this experiment.
P. Ramminger et al. GT48 223^
15" International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 4

4. Determination of real-structure and crystallographic data

The study of chemical reactions and phase transformations as shown in

figure 3 is capable to provide a lot more information than transformation-
temperatures since comprehensive treatment of XRD-data provides real-
structure information (crystallite size, microstrain, residual stress) and
information about the crystallographic parameters of the specimen during HT-
treatment (i.e. observation of the recrystallisation process during heating
and/or cooling).
The extraction of lattice parameters (i.e. figure 1; determination of the thermal
induced expansion of platinum) from XRD-patterns can be carried out easily
using various software packages. Even more sophisticated information (i.e.
structural refinement of atomic coordinates) can be calculated from the XRD-
data-sets by using Rietveld-based algorithms (3).
However, in order to determine real-structure parameters like size of the
crystallites and the microstrain of a crystalline sample, a close description of
the obtained peak shapes and the instrumental contribution of the observed
pattern is necessary.
Although there are a lot of software packages, which are capable to describe
the sample dependent information sufficiently, the new profile fitting software
module TOPAS (Bruker-AXS) is an exciting development for industrial
research, since it is based on a powerful mathematical algorithm and has the
advantage of an easy to learn and intuitive handling.

4.1. Theoretical background

The enduring development of X-ray diffractometers allows to evaluate the

sample specific information on a very high level of precision. To maintain this
grade of performance, new advanced mathematical methods are necessary
to describe each observed peak shape as close as possible. These methods
define an instrumental function which is used to derive the instrumental
contribution to the peak profile of an unknown substance. Based on the
determination of the instrumental contribution, sample contributions like
crystallite size, strain, microstrain can be extracted.
224 GT48 P. Ramminger et al,
15* International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 4

4.2 Parametrisation of the instrumental contribution

The description of the instrumental function is important regardless of the

profile fitting methods applied. This instrumental contribution can be
calculated in the case of Bragg-Brentano geometries and fundamental
convolution based approach for the individual instrument (4).
The basis for this approach is the strict separation of the instrumental
contribution, the contribution caused by the X-ray source and the sample.
This is performed by using a pool of well defined aberrational functions for the
description of the instrument. These aberrational functions are included in
Fundamental Parameter Approach (FPA) based Software modules like
TOPAS.
Due to the widespread use of new X-ray geometries (parallel beam optics as
used in this study), this convolution based profile fitting method has to be
adapted.
In order to derive a unique instrumental function for non-Bragg-Brentano
geometries, CeO2, LaB6 and Y2O3 were used as experimental standards,
because they do not contribute any crystallite size, strain and microstrain to
the observed peak profile. Thus the experimentally gathered XRD-pattern
reflect the contribution caused by the instrument and the X-ray source.
In a second step the aberrational functions provided by TOPAS are
convoluted over the peak profile of these idealized specimen profiles to obtain
the instrumental function.
In addition, the obtained function strongly depends on the X-ray optics and
wavelength characteristics used and has to be adopted whenever one of the
components is changed.
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4.3. Preparation of reference samples

For determination of the instrumental contributions, well described

substances are needed which are nearly perfectly crystallized. Such an ideal
substance does not introduce any additional contributions to the instrumental
profile function such as domain size broadening caused by crystallite size,
strain, microstrain and lattice defects to the peak profile. Three substances,
cerium oxide (CeO2), Yttrium Oxide (Y2O3) and lanthanum hexaboride (LaB6)
which meet the requirements for a accurate determination of the instrumental
breadth were used in the present study .

substance Formula approx. crystallite size approx. crystallite size approx. strain
[ran] [nm]
Lorenzian Value Gaussian Value

Lanthanum LaB6 -1000 -300 -0,001

Hexaboride
Cerium Oxide CeO2 -1000 -1000-2000 -0,001

Yttrium Oxide Y2O3 -1000 -400 -0,001

Table 2: Reference substances used for parametrisation of the instrumental function

In order to minimize microstrain and the number of lattice defects (crystallite

size), Cerium Oxide and Yttrium Oxide were annealed at 1600°C for 7 days in
a platinum (Pt95Pd5) crucible using a muffel furnace. To suppress the
introduction of strain as a result of cooling after the heat treatment, a cooling
ramp of TC/min was applied to decrease temperature from 1600°C to 300°C.
After reaching a temperature of 300°C, the crucible was removed from the
furnace and stored in a desiccator for further cooling-down to room
temperature. As a result of the heat treatment, Y2O3 and CeO2 sintered to
form lumps. This required subsequent grinding in a agate-mortar with
minimum pressure applied, to prevent the introduction of additional strain.
226 GT48 P. Ramminger et al.
15" International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 4

4.4 Evaluation of the parametrisation procedure

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S0Ü0O
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65 000 /
80 000
75 000
70 000- t
65 000
v
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60 000
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SOOOO i ' 1\ —
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Figure 4: The XRD-pattern show the profile description of LaB6 (left peak), CeO2 (middle peak) and Y2O3
(right peak) by the obtained instrumental function. The close fit to the observed peak profile is documented
by the small difference plot (x-axes).

As shown in figure 4 (detail-B) the LaB6 -reflex at 30.44 °2Theta; (1) marks
the observed peak profile. The calculated fit-profile (2) indicates a severely
misfit due to a wrong instrumental function. This clearly shows that a correct
parametrisation is necessary for a full describtion of the peak-profile, when
using non-Bragg-Brentano geometries and the fundamental parameter
approach.
P. Ramminger et al. GT48 227
15" International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 4

4.5 Application of the instrumental function for the evaluation of

real-structure parameters

2-Theta - Scale

Figure 5: This HT-experiment shows the recrystaliisation of hard coatings during temperature treatment. The
decrease of peak-broadening with increasing temperature indicates the changes of real-structure parameters
with temperature, (for example detail A: increase of crystallite size ranging from 6 nm at 300°C up to 22 nm
at 800°C).

5. Conclusion

Using modern X-ray powder diffractometers with high Temperature

equipment, unique information can be achieved by insitu thermal observation.
This combination enables the determination of thermal changes in
crystallographic expansion, real structure parameters and phase kinetics.
Furthermore, insitu cycled thermal exposure simulates relevant changes in
physical properties during the production and application.

To achieve high quality results in routine analysis, an exact temperature

calibration of the HT-chamber has to be performed. Furthermore, the
knowledge of the precise instrumental contributions is fundamental for the
extraction of crystallographic and real-structure data.
228 GT 48 P. Ramminger et al.
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This work has shown, that the new possibilities of HT-diffraction are
interesting improvements for industrial research. The integration of this
method into the analytical routine of process- and quality control, makes it
necessary to adopt certain aspects for quick and easy data-evaluation.
Nevertheless, the results prove that the experimental setup used is capable
of resolving slight structural differences, which allows to apply this method of
characterisation in a wide range of industrial and scientific tasks.

References:

(1) Touloukian et al.: "Thermal expansion metallic elements and alloys"

Thermophysical properties of matter, IFI/Plenum, New York -
Washington, 1975, pp. 1348

(2) Kern A.: "Hochtemperatur Rietveld Analysen: Möglichkeiten und

Grenzen", (Heidelberger Geowiss. Abh., Heidelberg, 1998), pp. 57-102

(3) Young, R.A.: "Introduction to the Rietveld Method", (IUCR Book Series,
Oxford University Press, 1993) pp. 289

(4) Cheary, R.W. & Coelho, A.A., "A fundamental parameters approach of
X-ray line profile fitting, (Journal of Applied Crystallography 1992), Vol
25, pp. 109-121