Guidelines For Methods of Testing and Research in High Temperature Corrosion (1995)

European Federation of Corrosion
Publications
NUMBER 14
A Working Party Report on
Guidelines for Methods of

Testing and Research in
High Temperature Corrosion
Edited by
AND D. B. MEADOWCROFT
H. J. GRABKE
Published for the European Federation of Corrosion

by The Institute of Materials
THE INSTITUTE OF MATERIALS

1995
Book Number 604
Published in 1995 by The Institute of Materials
1 Carlton House Terrace, London SWlY 5DB
01995 The Institute of Materials
All rights reserved
British Libray Cataloguing in Publication Data

Available on application
ISBN 0-901716-78-2
Neither the EFC nor The Institute of Materials

is responsible for any views expressed
which are the sole responsibility of the authors
Design and production by

PicA Publishing Services,
Drayton, Nr Abingdon, Oxon
Made and printed in Great Britain

Contents
Series Introduction ........................................................................................................... vii
Introduction ....................................................................................................................... ix
List of Abbreviations ......................................................................................................... xi
1 Guidelines for Plant Measurements of High Temperature .............................. 1

Corrosion
D. B. MEADOWCROFT A N D J. E . OAKEY
2 Discontinuous Measurements of High Temperature Corrosion...................11

J. R. NICHOLLS
3 In Situ Measurement Techniques ....................................................................... 37

M . I. BENNETT
4 Thermogravimetry ............................................................................................... 52
H . 1. GRABKE
5 Definition and Preparation of Gas Atmospheres ............................................ 62

H . J. GRABKE
6 Corrosion in the Presence of Melts and Solids ................................................. 85

S. R. J. SAUNDERS
7 Simultaneous Corrosion and Mechanical or Thermal Stresses ...................104

M. SCHUTZE,V . GUTTMANN,
M . F. STROOSNIJDER
8 Corrosion and Wear or Erosion ....................................................................... 121

F. H . STOTT
9 Oxidation/Corrosion of Advanced Ceramics: A Review of the .................136

Progress Towards Test Method Standardisation
D. J. BAXTER
10 Metallography, Electron Microprobe and X-Ray Structure ......................... 147

Analysis
A. RAHMEL AND V . KOLARK
vi Contents
11 Surface Microsurgery Preparation Procedures for High .............................. 158
Temperature Corrosion Characterisation
M. 1. BENNETT
12 The Application of Transmission Electron Microscopy in the .................... 177

Analysis of High Temperature Corrosion
M. R U H L E A N D E . SCHUMANN
13 The Application of Surface Analysis Techniques in High ........................... 189

Temperature Corrosion Research
W.J. QUADAKKERS A N D H. VIEFHAUS
lndex ................................................................................................................................. 218

Introduction
High temperature oxidation and corrosion cause great problems in power plants,
petrochemical and chemical industries and in engines. In recent years new problems
have arisen in energy recovery from chemical processes and waste incineration and
also in special technologies, e.g. high temperature fuel cells, space craft components,
aircraft engines, etc. Thus, there is a great need for materials testing for such
applications. New materials are mostly developed to exhibit mechanical strength and
reliability at high temperatures and the corrosion resistance is often only a secondary
consideration. However, new materials should also be tested in the environments of
their applications from the beginning of their development.
The great need for testing is obvious, both in the research and development
laboratories as well as in industrial and application environments. But it must be
admitted that, at present, there are no standards or even guidelines for material
testing for high temperature corrosion, in contrast, for example, to the situation in wet
corrosion and mechanical testing. As yet, the laboratories of material producers and
users and research institutions have conducted testing and research according to their
own methods and ideas. This certainly leads to mistakes in the performance and
errors in the evaluation, as are reflected in the wide range of results on oxidation
constants and corrosion resistance.
The working party ‘Corrosionby Hot Gases and Combustion Products’ of the EFC
decided to tackle the task to develop guidelines and standards for high temperature
corrosion research and testing. One milestone in this approach was a workshop in
January 1994 in Frankfurt, at which eleven presentations provided information on
methods of corrosion measurement and testing and on the investigation of corroded
specimens and corrosion products. In most cases the presentations were the outcome
of joint efforts of many colleagues from numerous laboratories concerned with high
temperature corrosion. Most work was done by the coordinators of each topic, who
had corresponded and discussed with the other experts, put together the most
important points to be considered and presented the outcome in oral presentations
at the workshop. These contributions form the basis of the guidelines published in
this book, and take into account the discussions and comments at the workshop.
Great efforts were made by the authors to compile their papers which provide
much information and advice. The editors are extremely grateful to the coordinators
of the workshop and authors of the chapters. Furthermore, all scientists and engineers
concerned with the problems of high temperature corrosion should be very grateful
for the efforts made by the authors.
Following the organisation of the workshop, this book may now be considered as
a second milestone on the way to codes of practice and standards in high temperature
corrosion research and testing. Further effort is necessary for progress in
standardisation and in fact projects are under way for developing the codes of
practice for discontinuous exposures and the definitions of gas atmospheres. But
X Introduction
these developments will take some years and just now the present guidelines will, it
is hoped, be useful to many colleagues already active or just starting in high
temperature corrosion testing and research, and should help them to avoid mistakes
and to obtain reliable relevant data.
H. J.Grabke
Chairman of EFC Working Party on
Corrosion by Hot Gases and Combustion Products
European Federation of Corrosion Publications
Series Introduction
The EFC, incorporated in Belgium, was founded in 1955 with the purpose of
promoting European co-operation in the fields of research into corrosion and corro-
sion prevention.
Membership is based upon participation by corrosion societies and commit-
tees in technical Working Parties. Member societies appoint delegates to Working
Parties, whose membership is expanded by personal corresponding membership.
The activities of the Working Parties cover corrosion topics associated with
inhibition, education, reinforcement in concrete, microbial effects, hot gases and
combustion products, environment sensitive fracture, marine environments, surface
science, physico-chemical methods of measurement, the nuclear industry, computer
based information systems, corrosion in the oil and gas industry, and coatings.
Working Parties on other topics are established as required.
The Working Parties function in various ways, e.g. by preparing reports,
organising symposia, conducting intensive courses and producing instructional
material, including films. The activities of the Working Parties are co-ordinated,
through a Science and Technology Advisory Committee, by the Scientific Secretary.
The administration of the EFC is handled by three Secretariats: DECHEMA
e. V. in Germany, the Societe de Chimie Industrielle in France, and The Institute of
Materials in the United Kingdom. These three Secretariats meet at the Board of
Administrators of the EFC. There is an annual General Assembly at which delegates
from all member societies meet to determine and approve EFC policy. News of EFC
activities, forthcoming conferences, courses etc. is published in a range of accredited
corrosion and certain other journals throughout Europe. More detailed descriptions
of activities are given in a Newsletter prepared by the Scientific Secretary.
The output of the EFC takes various forms. Papers on particular topics, for
example, reviews or results of experimental work, may be published in scientific and
technical journals in one or more countries in Europe. Conference proceedings are
often published by the organisation responsible for the conference.
In 1987 the, then, Institute of Metals was appointed as the official EFC
publisher. Although the arrangement is non-exclusive and other routes for publica-
tion are still available, it is expected that the Working Parties of the EFC will use The
Institute of Materials for publication of reports, proceedings etc. wherever possible.
The name of The Institute of Metals was changed to The Institute of Materials
with effect from 1January 1992.
A. D. Mercer
EFC Scientific Secretary,
The Institute of Materials, London, UK
...
Vlll Series Introduction
EFC Secretariats are located at:
Dr J A Catterall
European Federation of Corrosion, The Institute of Materials, 1 Carlton House
Terrace, London, SWlY 5DB, UK
Mr R Mas
Federation Europeene de la Corrosion, Societe de Chimie Industrielle, 28 rue Saint-
Dominique, F-75007 Paris, FRANCE
Professor Dr G Kreysa
Europaische Foderation Korrosion, DECHEMA e. V., Theodor-Heuss-Allee 25,
D-60486, Frankfurt, GERMANY
1
Guidelines for Plant Measurements of High
Temperature Corrosion
D. B. MEADOWCROFT and J. E. OAKEY*

ERA Technology, Ltd, Cleeve Road, Leatherhead, KT22 7SA, UK
*BritishCoal, Coal Technology Development Division, PO Box 199, Stoke Orchard, GL52 4ZG, UK
ABSTRACT
This paper gives broad guidelinesfor the procedures to be followed when carrying out
plant measurements of high temperature corrosion. It covers the selection of exposure
conditions, the design of metal loss probes and component inserts, the measurements
of metal loss and other post-exposureanalyses,experimentaldesign, and other methods
of predicting metal loss including high temperature corrosion monitors.
1. Introduction
The aim of this document is to bring together best practices for the effective determi-
nation of the high temperature corrosion behaviour of operational plant. The pur-
poses of such measurements are therefore always ultimately directed towards
optimising the operation of the plant, either by improved lifetime prediction for the
materials of construction, or towards recommending a replacement material. Re-
quired lifetime predictions are generally measured in tens of thousands of hours if
not years. Mechanistic arguments can, and should, be used to aid these predictions,
but are never the purpose of the work. For instance, it is necessary to establish whether
the observed corrosion kinetics are a long term value or are an incubation rate prior
to an accelerated propagation rate. Even if the corrosion kinetics are established,
extrapolation of measurements by even one order of magnitude must be made with
caution, and should be based on a series of measurements made over different time
intervals (e.g. data at a range of times up to 10 000 h for 100 000 h lifetime predic-
tions). It must also be emphasised that, even more so than in mechanistic laboratory
experiments, the basic requirement is rate of metal loss, not 'mass gain', and due
allowance must be made for sub-surface penetrations such as internal oxidation or
carburisation. Other points of general concern in plant measurements are that it is
usually the maximum corrosion rate which defines the component lifetime, and that
frequently the components of interest are cooled relative to the hot gas.
The entire subject should include specifications for measurements made directly
on standard plant components as well as on component inserts, probes or corrosion
monitors exposed in the plant specifically for lifetime prediction purposes. There
2 High Temperature Corrosion Research and Testing
are, remarkably, few published standards even for measurements on standard tubes
(for instance, in the UK the CEGB published general guidelines many years ago -
’The Control of Fireside Corrosion’ [l]based on repeated ultrasonic tube wall meas-
urements). However, it is not the intention to pursue measurements of standard
components in this paper, although the issues discussed and methods described in
this paper are often applicable. This present paper addresses those cases where com-
ponent inserts, probes or corrosion monitors are used as sensors to assess lifetimes.
The difference between probes and monitors is that probes are samples of materials
exposed, cooled if appropriate, in the process gas stream, and subsequently ana-
lysed by changes in mass, dimensions, and metallography, whilst monitors are able
to give an on-line indication of metal wastage, again as a function of temperature if
required.
The primary purpose of the document is therefore to cover pre- and post-expo-
sure mensuration techniques, and the associated metallurgical examinations from
which extrapolations about future rates of material loss can be made. The selection
of appropriate designs of inserts and probes is an integral part of such studies, as is
characterisation of the environment. In addition, the development in the past few
years of novel high temperature corrosion probes, specifically electrochemical and
resistance probes, will widen the scope of plant measurements as these techniques
become established. It is proposed that independent assessment of these techniques
is required.
The document therefore, in turn, considers the factors related to the selection of
exposure conditions, the design of metal loss probes and component inserts, the
measurements of metal loss and other post-exposure analyses, experimental design,
and other methods of predicting metal loss including high temperature corrosion
monitors. Most of the considerations relate equally to other forms of surface wast-
age such as erosion and wear, but for clarity only corrosion processes will be consid-
ered explicitly.
2. Selection of Exposure Conditions

2.1. Physical Location of Measurement Positions
The criteria to consider include:
(a) That the positions should be near where the maximum corrosion rate is, or is
expected to be experienced. Unless attack in very localised areas is under
investigation, e.g. near burners, unique or atypical positions should be
avoided. Preferably the measurements should be made where the environ-
ment is known or can readily be measured.
(b) A probe should not significantly affect the gas flows normally present. How-
ever, in complex gas atmospheres, free flowing gas or stagnant conditions
can give the most aggressive conditions in different cases, and both extremes
must be considered.
Guidelines for Plant Measurements of High Temperature Corrosion 3
(c) Unless it is actually corrosion of a wall which is being studied, probes should
be positioned away from walls because of the associated thermal boundary
layer and flow considerations.
(d) It is essential that the inserts or probes operate at the same temperatures as
the plant components: in many cases this will mean the inserts or probes be-
ing cooled to the appropriate temperatures. To improve lifetime predictions
exposure temperatures of the inserts or probes need to be adjustable in order
to encompass the range which might occur in plant even under fault or ex-
treme design (‘upset’) conditions.
2.2. Characterisationof the Environment

There are several ways in which the environment can be characterised:
(a) Detailed gas analysis, including minor components, particularly sulphur, car-
bon, chlorine, and alkali metal species. Sampling of such acidic gases must be
carried out with care, particularly if water vapour is present, to avoid con-
densation of the species of interest in the sample lines. Reaction of trace ele-
ment species with high temperature sample pipelines can also invalidate meas-
urements, and condensable species can take a long time to reach an equilib-
rium concentration along a sample line. Many man years of effort have been
devoted to measuring the alkali salt concentration in the combustion gas from
a pressurised fluidised bed combustor, before reproducible results have been
achieved [2].
(b) Determination of particulate flows, compositions and size ranges, in order to

aid the interpretation of deposition, erosion, and erosion-corrosion processes.
(c) Analysis of surface deposits after removal of the specimens. It is necessary

both to ensure that deposits are taken from representative locations and that
they are handled and analysed without altering their composition. Whilst
corrosion so serious that perforation of a tube or wall has occurred is obvi-
ously of concern, care must be taken in selecting the deposits for analysis.
The ingress of the gas composition from the other side of the perforation can
cause very great changes in the local environment and in the local corrosion
rate, such that the local deposits are no longer typical of the corrosion process
which caused the initial perforation. For instance, if a combustion gas perfo-
rates a wall to ambient air allowing ingress of the cold air, local cooling of the
internal gas may cause condensation of acidic species and catastrophic rates
of dew point corrosion. Care is required in the interpretation of the corrosion
process if deposits are ’contaminated’ by such changes, or have seen long
start-up/shut-down periods.
(d) Exposure of reference elements and compounds in order to determine the

effective partial pressure of oxygen, sulphur and chlorine (PO,,pS,, pC1). This
has been developed and used very successfully by Norton [3]to characterise
uncooled coal gasification atmospheres. A range of elements and compounds
are exposed in the gas, and the equilibrium phases after exposure are ana-
lysed by X-Ray diffraction. From the changes which are observed, ranges for
the effective PO, and pS, values in the atmosphere have been determined.
Only uncooled samples have been exposed to date, so that the effective non-
equilibrium conditions on cooled samples have not yet been determined by
this method. In complex gas atmospheres such as those in coal gasification
plants, the differencesbetween the thermodynamic conditions in the uncooled
gas and those local to cooled components can be very significant and cannot
be ignored [4].
3. Design of Probes and Component Inserts

3.1. Uncooled Corrosion Specimens
The simplest arrangement is where uncooled specimens are being tested. In this
case the specimens are generally discs or rectangular coupons, and critical aspects
are their size and shape to avoid atypical corners, etc, and how they are supported in
the hot gas. The specimens can be welded to the structure of the plant or to a flange,
a composite bar of the materials can project into the gas stream, or a specimen holder
is required. The latter has to be either a much more resistant alloy than that being
tested (why is that material not under test itself?), or made of a ceramic, and high
purity alumina is generally the preferred choice. Ceramics avoid the possibility of
cross contamination at the points of contact. The position of the specimens must be
typical for the application as discussed in Section 2.1., and the design of the speci-
men holder must not prevent ready gas access to the specimens, unless stagnant gas
conditions are deliberately required. In some applications, for instance where the
aerodynamics of deposition are critical, the shape of the specimens must mirror the
profile of the actual component, or models must exist to correlate the results with
real component shapes.
3.2. Cooled Corrosion Specimens

Many applications involve heat transfer and the material of the real component will
operate at a lower temperature than the gas. It is then essential that the material is
tested cooled to the appropriate temperature - preferably so that a range of tem-
peratures can be investigated about the nominal plant operating temperature. Sev-
eral techniques have been employed, generally using air and/or water or steam
cooling. In some applications it is desired that the temperature varies along the probe
to give a range of exposure conditions; in other cases that the temperature is kept
constant. Air cooling, with its limited thermal capacity, is generally utilised when a
temperature gradient is needed or permissible (Fig. l),or only a small specimen area
is being exposed in a probe. To avoid blockages in the valves and small flow paths,
cleaned "instrument quality air" should always be specified as a requirement. Steam
Guidelines for Plant Measurements of High Temperature Corrosion 5
AIR
FLANGE
IN I
/ SAMPLES
h i
Fig. 1 A schematic of an air cooled probe (courtesy of British Coal). The tube samples are either
spigoted or, preferably, welded together. The thermocouples are threaded along a hole bored centrally
in the wall along the length of each tube sample, to provide a continuous path along the probe, so
that the thermocouples can be positioned in the mid-wall of selected samples.
cooling can similarly be used, particularly where steam supplies are available, and
can give a closer simulation of the heat fluxes occurring in boiler plant, for instance.
Water cooling alone generally gives too low an associated metal temperature, but
its high thermal capacity allows nearly constant conditions along a probe. There-
fore, for closely controlled temperature conditions along a probe, combined water
and air cooling can be utilised, such as shown in Fig. 2.
Obviously if the corrosion specimen is an identical replacement insert into a com-
ponent (e.g. a boiler tube), the cooling is automatically typical of the application. In
this case, if a temperature gradient is desired along the surface of a tube, one tech-
nique which has been developed [6] is to use a tube with tapered wall thickness (Fig.
3). A variable thickness plate would be the equivalent in a plane application.
I/'
'/I
/I
,-I
,I
-
Fig, 2 A schematic of a probe utilising air and water cooling to give a reasonably constant
temperature along the length of the probe [51.
Fig. 3 A schematic of a tube insert with variable wall thickness to give a range of metal
temparatures. Temperatures obtained in a specific application are shown [61.
4. Material Finish
Material finish is important in all corrosion experiments and is considered in many

of the sections of this volume on oxidation measurement techniques. In many plant
trials commercial finishes are desirable in order to reproduce production surfaces,
but this frequently reduces the precision of measurable metal losses, and requires
longer exposures to obtain statistically significant results. The effect of appropriate
surface finishes such as shot peening or pre-oxidation should be included if these
are, or could be, used in practice. Recently certain plant programmes (e.g.pressurised
fluidised bed combustion(PFBC))at Grimethorpe [7]) have used machined samples
in order to provide accurately measured surfaces before exposure so that significant
losses could be measured after the shortest possible time - because of the huge
expense of running a 30 MW pilot plant. This approach must be considered with
care, and is probably not acceptable for alloys which behave differently after
machining. As already stressed, the basic criterion in plant trials is to simulate the
practical behaviour of commercial materials. Very accurate metrology (see Section
5 ) , can obviate the need for precisely machined surfaces, but surface roughness must
be avoided as it leads to measurement errors.
5. Mensuration of Specimens
As has already been stated, metal loss rather than mass loss is usually the required
parameter. For racks of uncooled specimens, the results have frequently been re-
ported in the past as mass gains, but these have limited value for lifetime prediction.
In general, both for uncooled specimens, and for cooled probes and inserts, pre- and
post-mensuration techniques are preferred, as it is generally metal loss rate which is
required. (Metallography must not be ignored to aid the interpretation and extrapo-
lation of results - see Section 6). The techniques utilised depend on the loss rates
involved and the exposure times available between measurements. The options must
be divided into pre- and post-exposure measurements. Pre-exposure techniques in-
clude:
Guidelinesfor Plant Measurements of High Temperature Corrosion 7
(a) Vernier callipers or micrometers - the standard in the past and often ad-
equate, particularly where metal losses greater than 100 microns are expected.
Care must be taken to ensure parallel orientation of the instrument to the
measurement plane.
(b) Ultrasonic thickness measurements can be used, not only for measurements
of standard plant components as mentioned earlier, but for precise probe meas-
urements, particularly by using the very accurate instruments now available.
These readily allow measurements to 10 pm and potentially to 1pm. Difficul-
ties can occur with accurate measurements of materials with large grain sizes
since a thin walled material cannot then be assumed to be isotropic.
(c) The use of co-ordinate machines to accurately map profiles of a specimen

before exposure has recently been used, particularly by British Coal [8] in the
later Grimethorpe programmes.
In all cases it is essential to calibrate the instrument used, and with ultrasonic and
coordinate measuring techniques calibration must be with samples of the materials
being assessed. Repeat measurements of reference samples at regular intervals dur-
ing a measurement campaign are also recommended to determine repeatability/
reproducibility. These reference samples would then be remeasured using the se-
lected post-exposure technique to define any required calibration corrections.
Post-exposure techniques include:
(i) Vernier callipers or micrometers can be used to give an indication of wastage

if gross corrosion has occurred (or if the wastage is erosive or abrasive with-
out oxide formation), but any corrosion product present on the surfaces will
reduce the measured wastage, and any internal damage will be overlooked.
Care must be taken to allow for the fact that wastage may not be uniform, and
if both sides of the specimen are corroding (e.g. a tube or a flat coupon), the
measurement only gives an indication of the average loss.
(ii) Ultrasonic thickness techniques can be used, as are generally utilised for rou-
tine plant measurements. Surface scale must be removed, internal oxide can
give uncertainties in the thickness measured, and again, internal damage will
be overlooked.
(iii) Accurate post-exposure metrology can be carried out. This involves either
mounting the specimen so that the pre-measured profile lies in the surface of
the mount, or by stripping the scale in a molten salt. The latter was popular
many years ago, but as a complete measurement involves measuring sub-
surface degradation as well as surface recession, measurements on
metallographically mounted specimens have become the norm. Recently, sys-
tems using a microscope with an accurate stepping stage (typically pm
steps) connected to a video camera or image analyser have been developed to
partially automate the measurement process. These can include measurements
of deposit/ scale thickness and sub-surface penetrations. With accurate cut-
ting and mounting of the specimen so that measurements are made along a
pre-measured profile it is possible to build up a co-ordinate map of the cor-
roded profile. The pre- and post-exposure data can then be analysed to give
probability plots of wastage. This is a powerful method of analysis particu-
larly for complex profiles such as turbine aerofoils [8]. While the set up costs
are likely to make it available only at specialised laboratories, once estab-
lished the cost of use per sample is little more than conventional metallography.
6. Other Post-Exposure Analyses
Whilst the basic aim of plant measurements is metal loss rates, it is nearly always
required to extrapolate the data to predict long term values for life prediction. It is
essential that as much mechanistic information as possible is collected to aid such
predictions, particularly in interpreting whether breakdown of the protective scale
is probable, and the contribution of sub-surface degradation such as internal oxida-
tion or carburisation. These analytical techniques, such as scanning electron
microscopy, energy and wavelength dispersive elemental analyses, X-Ray diffrac-
tion, are standard for both plant and laboratory studies and are covered in detail in
the other papers in this volume. The lack of close control of the environment in a
plant trial can make such long term predictions even more difficult than from labo-
ratory tests. The results from controlled laboratory tests have to be utilised in inter-
preting the mode of degradation of the plant samples.
7. Experimental Design
It is essential that consideration is given to the design of the overall programme to

ensure that the results are statistically significant and appropriate to the assessment
being undertaken. Included under this heading are the accuracy and statistical va-
lidity of the results which themselves can define which of the techniques described
above are used. The range of temperatures to be investigated, number of materials,
extent of corrosion rates expected, all influence the scale of the programme. Suffi-
cient results must be obtained to be able to demonstrate the statistical validity of the
work, not only between samples, but also the variations within a sample. The accu-
rate coordinate machine pre-measurements supported by accurate post exposure
measurements, described above, readily allow a large number of data to be collected
to give a statistically reliable analysis of the results from a sample.
8. Other Methods of Predicting Metal Loss
One of the disadvantages of direct metal loss measurements, even with the accurate
Guidelinesfor Plant Measurements of High Temperature Corrosion 9
mensuration techniques outlined above on machined samples, or the use of coordi-
nate measuring systems, is that for materials with corrosion rates which are com-
mercially viable, exposure periods of 1000 h or more are required to provide a sig-
nificant loss measurement. This has the added disadvantage that the effects of plant
changes - e.g. fuel, operating conditions - during the exposure cannot be distin-
guished. Two techniques have been developed in the last few years which enable
effects to be monitored over much shorter intervals. Both require independent veri-
fication before they can become standard techniques.
8.1. Electrochemical Techniques

High temperature corrosion involving surface deposits which play an active role in
the corrosion process can be followed by using electrochemical responses. CAPCIS
MARCH in the UK (now CML Ltd) have pioneered such techniques including im-
pedance, zero resistance ammetry, and potential and current noise measured on a
cylindrical or flat-faced probe [9]. In appropriate environments these techniques give
responses which enable wastage rate and type of corrosion (general or pitting) to be
estimated over a matter of hours, and hence once properly validated will be invalu-
able for determining the effects of operating conditions on corrosion in an opera-
tional plant. Parallel coupon studies are recommended to provide correlations for
life prediction purposes.
8.2. Electrical Resistance Probes

A standard low temperature technique is to measure the electrical resistance of a
metal electrode as it corrodes. Because the resistance of a metal changes with tem-
perature, the difference in resistance from a reference electrode protected from the
environment but at the same temperature is generally determined to provide a cali-
bration. The technique is currently being developed for high temperature applica-
tions [10,11]; an additional complication for such purposes is that the probe must be
cooled, and the manufacturers are using different methods of dealing with this re-
quirement. This technique is more direct than the eletrochemical probe, but the lat-
ter can potentially obtain indications of rate more rapidly in suitable environments.
9. Conclusions
1. The prime variables are rate of metal loss at the appropriate temperature. The
latter will frequently mean the use of cooled probes or inserts. Usually air is used, or
air and water.
2. Very accurate pre- and post-mensuration techniques are now available. The post
mensuration measurements also allow an assessment of the metallurgical condition.
3. Atmosphere characterisation is very important in enabling sensible lifetime pre-

dictions to be made. Gas composition and the use of reference materials to bracket
the thermodynamic condition are important measurements.
4.Metal loss measurements generally must be made over periods of 1000 h or more.
Electrochemical and electrical resistance probes have recently been developed which
enable wastage rates to be deduced over much shorter times.
10. Acknowledgements
This paper is published by permission of ERA Technology and British Coal. The
views presented are those of the authors and not necessarily those of these organisa-
tions. The authors gratefully acknowledge the contributions made by many col-
leagues, both in writing and at the Frankfurt workshop in January 1994.
11. References
1. D. W. C. Baker et al., ‘The Control of High Temperature Fireside Corrosion, 2nd Edn, Central
Electricity Generating Board, London, 1975.
2. I. R. Fantum, ’Measurement and control of alkali vapours in coal derived gases’,in Gas
Cleaning at High Temperatures (Eds R. Clift and J. P. K. Seville), Blackie, Glasgow, 1993.
3. J. E. Oakey, T. M .Lowe, N. J. Simms and J. F. Norton, ’Materials experience in British Coal’s
spouted bed gasifier’, Materials at High Temperatures, 1993,11,90-93.
4. W. T. Bakker, ’Effect of gasifier environment on materials performance’, Materials at High
Temperatures, 1993,11,90-93.
5. E. Haggblom, ’Materials for Waste Fired Boilers’, Project 4.S.1 in COST 501 Round I1 Work
Package 13, Final Report pp. 207-243. European Commision Report EUCO/MCS/10/93.
6. P. L. F. Rademakers, ’Corrosion Erosion behaviour of FBC heat exchanger materials’, Project
4NL.1in COST 501 Round I1 Work Package 13, Final Report pp. 113-156. European Commision
Report EUCO /MCS / 10/ 93.
7. D. B. Meadowcroft, E. D. Montrone, J. E. Oakey and J. Stott, ’Experiencesof combating tube
bank wastage in the Grimethorpe PFBC’, in FBC Technology and the Environmental Challenge,
Adam Hilger, Bristol, UK, 1991, pp. 105-114.
8. N. J. Simms and J. E. Oakey, ’Valid Measurements of Metal Wastage: Application in Opera-
tional Plants’, presented at UK Corrosion and Eurocorr ’94,2 November 1994, The Institute of
Materials, London, UK.
9. G. A. Whitlow, W. Y. Mok, W. M. Cox, P. J. Gallagher, S. Y. Lee and P. Elliott, ’On-line mate-
rials surveillance for improved reliability in power generation systems’, Paper No. 254, Cor-
rosion ’91, NACE, Houston, TX,1991.
10.D. M. Farrell, M. Higginbottom, G. Rocchini and A. Colombo, Application of an electrical
resistance probe for monitoring superheater corrosion in a coal fired boiler’, pp. 110-119, in
Volume 2, UK Corrosion and Eurocorr ’94, Vol. 2 , pp. 110-119,2 November 1994, The Institute
of Materials, London, UK.
11.R. D. Townsend, et al.,’On-line Monitoring for Condition Assessment of Boiler Tubing’, in
Proc. Conf. on Life Assessment of Industrial Components and Structures, Cambridge, 30 Septem-
ber-1 October 1993, ERA Technology, Leatherhead, UK.
2
Discontinuous Measurements of High

Temperature Corrosion
J. R. NICHOLLS
Cranfield University, Cranfield, Bedford MK43 OAL, UK
ABSTRACT
Discontinuous thermogravimetric measurements are widely used to assess reaction ki-
netics in oxidation and high temperature corrosion studies. Exposure times may be
from several hundreds of hours to tens of thousands of hours. Despite the importance
of such measurements in assessing high temperature materials performance, there has
been surprisingly little effort in the past aimed at developing appropriate guidelines
and standards that permits best practice to be agreed.
This paper aims to address this omission and presents the results of a survey of 25
laboratories throughout Europe. Based on the results of this survey, guidelines for the
discontinuous measurement of high temperature corrosion have been prepared. Adop-
tion of such guidelines are considered the first step in the establishment of an interna-
tional standard on high temperature corrosion measurement methods.
1. Introduction
High temperature oxidation/corrosion has been an important technological subject

for over 70 years, and is a major life limiting factor for most equipment that operates
at high temperature. Resistance of a material to corrosion degradation at high tem-
peratures depends on the formation of a protective oxide scale and maintenance of
its integrity throughout the service life. Thermogravimetric methods are widely used
to monitor these oxidation and corrosion processes, from which kinetics of oxide
growth, the onset of breakaway corrosion and the loss of protection due to oxide
spallation are often determined. Such thermogravimetric studies may be either 'con-
tinuous' or 'discontinuous' in nature. The former are widely used to determine oxi-
dation kinetics over relatively short times and have been the subject of a recent re-
view [l]which forms the basis of Chapter 4 of this present volume. The latter, dis-
continuous measurements of oxidation and corrosion, are the subject of this current
paper.
Discontinuous thermogravimetric measurements are widely used to assess the
reaction kinetics, especially over long term exposures of several hundreds to tens of
thousands of hours. For such studies, the specimen is weighed and measured and
then exposed to the high temperature corrosive environment for known times. Dur-
ing this exposure the specimen may be cooled to room temperature at regular or
preset time intervals, removed and reweighed. Thus, this technique imposes a ther-
mal cycle on the specimen at each removal and provides only discrete data points
for the evaluation of corrosion kinetics. However, many specimens of several differ-
ent materials may be exposed at the same time, the technique is very simple and can
be used for studies in corrosive gases and mixed oxidants, for studies at pressure or
where specimens are exposed within plant under service conditions.
Surprisingly for such a scientific and industrially relevant topic, there have been
no significant efforts, in the past, to develop standards and guidelines that permit
best practice to be agreed. This paper aims to address this omission and presents the
results of a survey of 25 laboratories throughout Europe, with 54 questionnaires on
the 'discontinuous measurement of oxidation and corrosion' returned for evalua-
tion.
2. Testing Methods for the Discontinuous Measurement of Oxidation

and Corrosion Processes
Numerous test methodologies have been proposed in the literature to assess oxida-
tion/corrosion kinetics.These have encompassed continuous thermogravimetry, dis-
continuous thermogravimetric methods, burner and combustion rigs, component
oriented test methods, through to pilot plant and in plant studies. A review of all of
these methods is beyond the scope of a single paper. Recommended practices for
continuous thermogravimetry was the first paper published with aim of establish-
ing best practice [l]. The influence of superimposed stress [2], corrosion deposits [3,
41, erosion and wear [5] are considered elsewhere in this monograph. As is the appli-
cation of burner/combustion rig test procedures [3] to simulate plant performance.
Methods for measuring the corrosion rates within plant [6] are also reviewed else-
where in this monograph. This current review will be restricted to the use of furnace
exposure test procedures to the study of discontinuous measurement of high tem-
perature corrosion processes.
2.1. Scope of this Study

The furnace exposure methodologies reviewed will encompass (a) isothermal oxi-
dation, (b) cyclic oxidation, (c) gas phase corrosion, and (d) hot corrosion test meth-
ods.
Discontinuous measurement methods involve the interruption of the corro-
sion processes, usually by cooling the specimen to room temperature, then speci-
men removal for corrosion rate assessment.Specimensmay be periodically removed,
without replacement; replaced with new specimens; or periodically removed, as-
sessed and then reinserted into the furnace for further exposure. Assessment meth-
ods may include weight change, section loss measurements, measurements of oxide
thickness, internal oxidation and oxide spallation. Each of these aspects will be dis-
cussed later in the paper together with recommendations for a standardised test
procedure.
To aid in the determination of best practice, and hence the formulation of guide-
Discontinuous Measurements of High Temperature Corrosion 13
lines, questionnaires were circulated to 25 laboratories throughout Europe (the labo-
ratories that returned the completed questionnaire are acknowledged at the end of
this paper). Based on the analysis of these results recommendation for the choice of
test apparatus, test piece geometry, test procedure, methods of assessing corrosion
damage and the reporting and presentation of result are made.
3. Furnace Exposure Test Procedures
High temperature oxidation of metals and alloys generally leads to a mass increase
due to the growth of an external oxide scale, together with the possible formation of
internal oxidation products. These observations are more generally valid and apply
to high temperature corrosion in mixed oxidant and under salt deposit conditions,
where external and/or internal sulphide, carbide, nitride and chloride formation
may occur. Thermogravimetric methods are the most widely used to monitor the
kinetics of these high temperature oxidation reactions.
Continuous thermogravimetry permits the automatic recording of weight change
on a single material. Such methods are widely used to monitor oxidation processes
[l]and can be used to monitor corrosion processes even in very hostile environ-
ments [7]. Generally exposure times are relatively short, from under 1h up to 100 h,
although longer term continuous thermogravimetric studies have been reported ([8,
91). Guidelines for continuous thermogravimetry have already been published [ 11.
Discontinuous thermogavimetric methods are more widely used, when attempt-
ing to simulate industrial service. This is especially true when monitoring corrosion
in complex gas atmospheres, under salt deposits or for long term (100-10 000 h +)
oxidation and corrosion studies. Although discontinuous methods, give only dis-
crete mass gain data per specimen and impose a thermal shock on the specimen
each time the samples are removed for measurement, simplicity of experiment, the
ability to handle complex atmospheres, and possibility of including a wide variety
of alloys in a single test have led to its wide adoption for long term oxidation and
corrosion studies.
Table 1summarises the preferred uses of discrete furnace exposure methods, the
temperature ranges and exposure times that are generally applied and shows that
discrete thermogravimetric methods are most widely used for isothermal oxidation
and gas phase corrosion studies, usually for exposure times in excess of 100 h. Re-
sults out to 22 000 h have been reported under oxidising conditions [ll]but such
long term exposures are rare. The preferred maximum exposure times are usually
between 2000 and 5000 h. Below 100 h exposure, continuous thermogravimetric
methods are preferred.
Specimen removal times are generally related to the overall exposure time. Cited
time intervals vary from removing specimens hourly for short duration studies to
removing specimens every 1000 h for long exposure tests. Generally specimen re-
moval at intervals that are 10% of the total exposure are acceptable, although to
permit comparison between data and micrographs from various laboratories some
preferred removal intervals should be adopted. Table 2 summarises the specimen
Table 1. Summary offurnace exposure test methods reported
Usage Proportion Temp. Range of Preferred Preferred

of Replies Range Exposure Temp. Maximum
(OO/ ) ("C) time (h) (OC) Exposure
(A) Isothermal 34 400-1500 100-50 000 650-1000 2000,5000

Oxidation
(i) in air 19
(ii) in oxygen 10
(iii) under reduced PO, 5
(B)Cyclic Oxidation 10 250-1500 100-50 000 900-1150 2000,5000
( C ) GasPhase 32 250-1500 100-10,000 650-900 1000,5000

Corrosion
(D) Hot Salt Corrosion 24 500-1100 100-2000 600, 650, 500+

(i) Crucible test 8 700+,800,
(ii) Salt coat test 8 900'
(iii) Burner rig tests 8
removal time adopted by the laboratories returning questionnaires, together with

the number of citations made to each specimen removal interval.
It is clear from this table that no standard removal intervals have been adopted,
although some preferred removal intervals are evident, namely 1h, 5 h, daily (20-30
h), 50 h, 100 h, 250-300 h, 500 h, 1000 h and 5000 h. On this basis it is recommended
that some form of logarithmic scale be adopted, for example 1, 3/10! 30, 100, 300,
1000,3000h ... or alternatively 1,2,5,10,20,50,100,200,500,1000,2000,5000 h. The
latter is preferred because, in conjunction with a maximum cycle interval of 10% of
the total exposure, such a removal strategy will provide four specimens for
metallographic examination (one at lo%, 20-25%, 40-50% and the end of test, de-
pending on the test duration).
The distribution in temperatures used either for isothermal oxidation, cyclic oxi-
dation and gas phase corrosion are broadly Gaussian, and cover a very wide range
(250-15OO0C), with no clear preferred temperatures evident from the replies received
to the survey.
Only in the area of hot salt corrosion testing have preferred test temperatures
been adopted, for example 700 and 900°C for the evaluation of type 2 and type 1hot
corrosion.
These recognised preferred test temperatures reflect the work undertaken under
a VAMAS initiative to establish guidelines for hot salt corrosion testing in dynamic
burner rigs [3], [lo].
Table 3 summarises the range of gas mixtures and salt mixtures used to generate
the test environments, as reported within this survey. It is beyond the scope of this
Table 2. Specimen removal times
Specimen Removed at Number of Citations Preferred Removal Times

(h) (h)
1 3 l h
5 5 5h
10 1
20 4
24 5 20-30 h
25 5
30 7
40 1
50 12 50 h
75 5
100 26 100 h
168 1
250 14 250 or 300 h
300 11
500 18 500 h
750 7
1000 16 1000 h
1500 7
2000 7
2500 2
3000 7
4000 7
5000 9
paper to discuss the choice of each environment or the selection of preferred test
environments. These aspects and the selection of preferred test environments is cov-
ered in a companion paper elsewhere in this monograph [ 121, However, some points
from the survey on the conduction gas phase corrosion test are worthy of particular
note. Apart from the most simple of gas mixes it is recommended that premixed gas
be used. Gas flow rates should be in the range 20-200 mL min-l, with 100 mL min-'
the preferred flow rate in this survey.Where possible duplicate specimens should be
used. Care should be taken over the positioning of specimens and in particular the
possibility of catalyticeffectsbetween multiple specimens of different alloys, whereby
volatile corrosion products from one sample may trigger corrosion on a neighbour.
To minimise this possibility, duplicate sample positions should be randomised in
the autoclave, avoiding like specimen configurations.
An area of concern, must be the procedures adopted for test start up, following
each shutdown procedure. Current practice includes:
(i) the use of an inert gas purge and heating to temperature in the inert gas be-
fore introducing the corroding gas species.
Table 3. Gus phased corrosion studies - reported test environments
Furnace Exposure Test Environment
(A) Isothermal Oxidation (i) Air

(ii) Oxygen
(iii) 0, t H,O
(iv) H,/H,O
(VI co/co,
(B) Cyclic Oxidation (i) Air
(ii) Oxygen
(iii) 0, + H,O
(C) Gas Phase Corrosion Oxidising/high PO, Reducing/low PO,
(i) O,+SO, (xi) H, t H,S

(ii) Air + SO, (xii) Ar t H, + H,S
(iii) Air t SO,/SO, (xiii) H, + H,O + H,S
(iv) Air + SO2 t HC1 (xiv) H, t H 2 0 t H,S + CO
(v) Air t SO, + HCl + Na2S0, (xv) H,+ H20 + H2S + CO + CO,
(vapour) (xvi) N, t H2 + H 2 0 t H2S t CO
(vi) N2 t CO + H 2 0 t SO, t HCI (xvii) H, t H20 t HC1
(vii) Air t HC1 (xviii)H2+ CH,
(viii) Air t C1,
(ix) A r t 0,t CI2
(x) co + co, t so,
(xi) CO + CO, t COS
(D)Hot Corrosion (i) Na2S04

(ii) Na,S04 t NaCl
(iii) Na2S04 t K2S0,
(iv) Na.V.V.*+ Na2S04
(v) NaV03 t Na2S04
(vi) sea salt
*Sodium vanadyl vanadate (Na.V.V.)
(ii) heating to temperature once the corrosion gas environment has been estab-
lished, or
(iii) establishing the corrosive gas environment, then bringing the specimens to
temperature using a moveable preheated furnace.
The problem with the first of these procedures is in the definition of an inert gas.
For example, Ar may be inert for studies under oxidising conditions, but it contains
trace oxygen contaminants at the 1 ppm level and thus cannot be considered inert
when operating in low PO,environments. The latter two procedures are therefore to
be preferred.
A further recommendation is that heating rates should be between 5 and 300°C
min-* and preferably faster than 100°C min-' to minimise corrosion occurring dur-
ing this heat up period. This is best achieved by establishing the environment and
then moving a preheated furnace over the specimens to be corroded.
3.1. Furnace Design

Both horizontal and vertical furnace geometries are widely used, with horizontal
furnaces preferred for isothermal oxidation studies and vertical furnace geometries
preferred for gas phase corrosion studies (see Table 4). In the replies received, fur-
nace hardware was fabricated from alumina, mullite, silica or various high tem-
perature alloys, the exact choice depending on test temperature and the exact corro-
sion environment to be employed. Alumina is the preferred material for the con-
struction of furnace hardware, (some 60% of replies used alumina) with silica widely
used when test temperatures were below 1000°C for isothermal oxidation, cyclic
oxidation and gas phase corrosion tests. Silica has the advantage of better thermal
shock resistance when compared with alumina, although at temperatures above 900°C
or under low oxygen partial pressures volatile Si0 species can form and may be
deposited onto the specimen surface.
Table 4. Test apparatus -furnace design"
Isothermal Cyclic Gas Phase Hot

Oxidation 3xidation Corrosion Corrosion
(i)Furnace Orientation
- Horizontal 80% 67% 44% 40%
- Vertical 50% 50% 56% 40'/o
(ii)Hurdwure
- Mullite 20O/" 20%
- Alumina 60% 67% 44% 20%
- Silica 30%t 33% 44%t 20%
- HTAlloys 25% 22% 20%
Number of Replies 20 6 18 10
*The percentages in each column represent the proportional usage of each furnace geometry/hardware,
based on the number of replies received under each column heading. Some laboratories need more than
one furnace geometry.
1Half the replies in each of these categories only recommended using Silica (Quartz) below 1000°C: above
1000°C use Alumina.
High temperature alloys (for example 310 stainless steel, Fecralloy) have been
used for isothermal oxidation, gas phase corrosion and hot corrosion tests, particu-
larly if tests under pressure are undertaken [13].One must however, be wary of the
fact that these metal autoclaves will also oxidise/corrode and hence may modify the
local gas environment seen by the specimens under test.
Figure 1illustrates a particularly good design of vertical exposure furnace used at
the JRC Petten for gas phase corrosion studies [14]. It has a furnace tube and speci-
men support tube made from alumina. Specimens are retained in individual alumina
crucibles. The double furnace tube arrangement provides a containment for corro-
sive gases; an inner active gas system, surrounded by an inert shield gas. The fur-
nace is three zone, with individual control thermocouples for each zone plus over
temperature protection.
An important aspect of all furnace exposure studies is the precision and repro-
ducibility of the thermometry, as this dictates the actual temperatures achieved dur-
ing the oxidation or corrosion study. The type of thermocouple used, type K, R or S,
is dependent on the temperature of the test. Although many operators installed cali-
ERT GAS OUT
COOL WATER OUT -7aOL WATER OUT
coo1 66rWATER OUT

INERT
IhTRT
I I.
Fig,1 Schematic diagram of the corrosion test autoclaves used for testing with H,-based gas
mixtures.
brated thermocouples when setting up a new facility or replacing failed thermocou-
ples, few regularly checked this calibration. For example, under isothermal oxida-
tion conditions some 80% of replies reported that new thermocouples would be Cali-
brated prior to installation (see Table 4). However, only 5% recalibrate these thermo-
couples at 500 h and 15%recalibrated the thermocouples after 3 months (-2200 h).
Equally, no preferred policy on thermocouple replacement was evident, even
though a poorly calibrated thermocouple, or more seriously a failed thermocouple
could ruin many thousands of hours of oxidation/corrosion exposure. This survey
would suggest that some 17%of researchers replace thermocouples at 3 months (2200
h), with 39% replacing them within a year. It was more likely that thermocouples
were replaced early (within 3 months) under gas phase corrosion conditions than
under isothermal oxidation. Thus, over 50% of all oxidation or corrosion studies
reported are undertaken with uncalibrated thermocouples of indeterminate age.
Clearly if this paper achieves one thing, that is a more consistent approach to the
monitoring, control and calibration of thermocouples during high temperature oxi-
dation and corrosion studies, then it will have been worthwhile. Recommended pro-
cedures for undertaking discontinuous oxidation/corrosion are given later in this
paper.
3.2. Specimen Support Hardware

Many geometries have been reported in the literature to support specimens. These
include specimens in individual crucibles, multiple specimens per crucible and the
support of individual specimens using metallic or silica hooks. The results of this
survey (Table 5) showed that individual alumina crucibles are preferred for isother-
mal and cyclic oxidation, gas phase corrosion and hot corrosion test procedures.
Some 30% of researchers, use alumina lids on the crucibles to retain any spall. How-
ever, if there is likely to be an effect of gas flow rate on the oxidation/corrosion
processes then the use of lidded crucibles should be avoided to ensure a good flow
of gas around the specimen. Provided spalling is not a problem, then the preferred
test procedure for such flow rate sensitive tests would be to hang specimens from
hook supports. Hook supports based on silica, platinum and Fecralloy steel have
been reported. Platinum wires are most often used, but these will loose platinum by
evaporation above 1000°C and may contaminate sample surfaces during exposure
above this temperature. At these elevated temperatures alumina forming wires (e.g.
Fecralloy or Kanthal) are to be recommended.
Using current specimen support architectures between 4 and 50 specimens may
be exposed at one time. Generally the vertical furnace architecture permits more
specimens to be tested at one time. For example, in the furnace design illustrated in
Fig. 1,40 samples can be exposed at one time. The exposure of multiple specimens is
efficient, especially when long exposures (> 1000h) are involved. However, one must
undertake such tests with caution particularly under gas phase and hot salt corro-
sion conditions. Particularly under hot corrosion conditions it has been noted by
many workers that volatile by-products from one material may influence the rate of
corrosion measured on neighbouring samples (e.g. Ref. [15]).Thus when undertak-
20 High Temperature Corrosion Research and Tcsting
Table 5.T est apparatus - specimen geometry. Percentage of replies per column heading*
Isothermal Cyclic Gas Hot

Oxidation Oxidation Phase Corrosion
Corrosion
(i) Individual Crucibles

- Silica (max. 1000°C) 10% 17%
- Alumina 90% 83%
- plus lids 30% 33%
(ii) Multiple Specimens

per Crucible
- Silica (max. 1000°C)
- Alumina 25% 17%
- plus lids 10% 17%
(iii) Hook Supports

- Silica
- Pt 17%
- Pt/Rh 17%
- Fecralloy 17%
(iv) Number of Specimens

per Test
- Horizontal furnace 4 to 15 4 to 11 5 to 15 5 to 40
- Vertical furnace 4 to 30 4 to 50 1 to 50 1 to 24
Numbers of replies 20 6 18 10
‘See Table 4 footnote.
ing multiple alloy corrosion tests, inclusion of materials that may form volatile cor-
rosion products should be avoided.
3.3. Specimen Geometry and Surface Preparation

It is widely agreed (see Section 4 on assessment methods) that weight change/unit
surface area provides an acceptable, and often sufficient, method of monitoring cor-
rosion processes provided breakaway corrosion phenomena, or severe internal at-
tack are not observed. It is equally accepted that corrosion rates at corner and edges
may be significantly greater than on flat surfaces. It is surprising, therefore, that
there has been little attempt to standardise specimen geometries.
In the 54 questionnairesanalysed, 31 different specimen geometries were reported.
These are summarised in Table 6 and can be broadly separated into four classes: (i)
rectangular flat plates, (ii) disc, (iii) arc-shaped samples, and (iv) rod or tube
geometries.
Rectangular, flat plate samples were the preferred geometry (52% of replies) and
Table 6. Specimen geometry (dimensionsin mm)
qectangular Disc I Arc Rodflube
l x wxt dxt l x wxt lxd

50x 4 x 3 * 25 x ? 30 x 20 x 5 50 x 6.25
30 x 20 x 5 20 x 5 30 x 20 x 2 25 x 10
30 x20 x 2 20 x 2 20 x 10 x 5 15 x 10
20 x 10 x 5 12 x 3 20 x 10 x 2
20xlOx2 12 x ?
20 x 10 x 0.5 10 x 5
30 x 10 x ? 10 x 2
15 x 10 x 1.5 7.3 x 3
15 x 10 x ?
12 x 10 x 2
10xlOx2
10 x 10 x 1.5
10 x 10 x 1
10 x 10 x ?
lox 8x6
are recommended for sheet materials. Preferred sizes were either 20 x 10 mm or 10 x

10 mm, with the thickness dependent on the available sheet material, but usually in
the range 0.5-5 mm. For tube stock, arc samples cut through thickness from tube
wall of similar geometry to the flat plate samples have been used (e.g. Ref. [16]).
Rod and disc samples are the preferred specimen geometries for cast materials,
although no standard specimen geometry has been adopted. A cylindrical geometry
of 8 mm 0 x 15 mm long, or a disc geometry of 16 mm 0 x 2 mm thick, have similar
surface areas to a rectangular specimen 20 mm x 10 mm x 2 mm. All have a surface
area of 5 cm2,within + 5%. Thus, these three geometries may form the basis of a set
of recommended specimen sizes with similar surface area. Disc samples can also be
manufactured from sheet material by EDM (electro discharge machining), thus a
disc shaped specimen offers the possibility of one standard specimen geometry ap-
plicable to cast or wrought alloys in rod form and to rolled sheet materials. This
geometry would also limit the likelihood of breakaway corrosion from comers and
would minimise the fraction of sample edge per unit sample cross section area.
Surface preparation also plays a vital role. In order to compare corrosion per-
formancebetween laboratories it would be necessary to adopted a preferred surface
finish. One possibility is to finish all surfaces to 600 grit, using Sic papers. To mini-
mise the possibility of preferential attack at edges or comers, edges should be rounded
off slightly, using a 600 grit Sic paper, prior to corrosion testing. Finally, before expo-
sure all samples should be rigorously cleaned. One possibility is to ultrasonically
clean in 1:1:1inhibited trichloroethane followed by a hot wash and vapour clean in
Analar isopropyl alcohol.
4. Specimen Evaluation
The second part of the questionnaire concentrated on the methods used to assess the
extent of corrosion damage, and encompassed measurement of corrosion rate and
kinetics, assessment of the corrosion morphology and identification of corrosion
products. The use of mechanical tests to assess the extent of corrosion damage was
also briefly addressed, although this is covered in more detail in a separate paper in
this monograph [2].
Firstly, researchers were asked how they select samples for evaluation. The op-
tions considered included:
(i) Periodic removal of specimens. Using this procedure samples would be re-
moved from the furnace after a predefined exposure, usually weighed, then the ex-
tent of corrosion would be assessed metallographically.Some researchers adopted a
procedure of introducing a further specimen to replace the one removed and so
maximised the use of the corrosion test to produce specimen with different periods
of corrosion for metallographic assessment.
Others removed specimens leaving an empty crucible (or location) for the remain-
der of the test.
Specimen removal and the introduction of replacement samples is generally more
efficient. For example to undertake a 500 h test with samples removed every 100 h;
the first approach would use 3 locations within the autoclave, namely (1 x 500 h),
(1 x 100 h + 1 x 400 h) and (1x 200 h + 1 x 300 h); while the second would use 5
locations, one for each 100 h exposure.
(ii) Periodic assessment, then replacement.Using this procedure samples would
be removed, weighed, visually inspected and then reinserted into the furnace for a
further period of exposure. This approach is widely adopted for cyclic oxidation
studies and has been used for isothermal oxidation and hot corrosion studies (it is
particularly suitable for the salt coat test procedure [17,18] and assessment of burner
rig test pins [3,10]).For studies in contaminant gases, particularly those containing
low partial pressures of oxygen, the periodic removal of specimens for weighing etc.
may modify the subsequent corrosion process either due to spallation of corrosion
product during the cool down cycle or due to the effects of repeated start up proce-
dures. Thus under gas phase corrosion conditions only periodic specimen removal
is recommended.
(iii) Both procedures. This is a combination of the above two. Specimens would,
for example, be cycled to room temperature weighed and visually inspected every
20 h, with samples removed say at 100,200,500 and 1000 h for metallographicevalu-
ation.
Table 7.Specimen evaluation -sampling methods*
Test Method
I Furnace
Exposure I Burner Rig
I In-Plant
Exposure
(a) Periodic Removal 29% 20% 40%

(b) Periodic Assessment/Replace 21% 20% 0%
(c) Both Procedures 50% 60% 20%
(d) Not stated 0% 0% 40%
Number of replies 28 5 5
*See Table 4 footnote.

Table 7 summarises the procedures adopted as determined from the results of the
questionnaire. For furnace exposure and burner rig test, over 50% of research labo-
ratories adopt a procedure based on both periodic assessment (usually mass gain)
and the replacement of samples for further exposure, followed by the removal of
samples at predefined time intervals for metallographic evaluation. If this combined
procedure is not adopted, then periodic removal of samples after predefined expo-
sures is preferred. This is particularly so for in-plant studies where specimen re-
moval can be timed to coincide with plant shutdowns.
4.1. Measurements of Corrosion Rate

Everyone replying to the questionnaire undertook some form of corrosion rate as-
sessment. In its simplest form this was an assessment of specimen mass change,
after cooling samples from the exposure temperature to room temperature. 86% of
laboratories undertaking furnace exposure tests assessed corrosion rates from mass
change. Sixty percent of laboratories involved in burner rig test and 20% of laborato-
ries involved in plant exposure studies routinely used mass change to assess corro-
sion rates. Table 8 summaries these results together with other metallographic meth-
ods used to assess the degree and extent of corrosion. Figures 2 and 3 show typical
examples of discontinuous oxidation measurement.
Figure 2 is an example of breakaway oxidation for two Oxide Dispersion Strength-
ened (ODS) alloys, MA956 and ODM751 [19] and demonstrates that the time to
breakaway for these alloys increases with increase in wall thickness. The point at
which a rapid mass change is observed is indicative of non protective oxidation. The
use of frequent shutdown periods (i.e. procedures (ii) or (iii) in Section 4) improves
the precision with which the onset of breakaway can be detected. Figure 3 is an
example of cyclic oxidation (1h cycles) for CoCrAlY coatings [20], where the oxida-
tion performance reflects a balance between mass gain due to new oxide formation
and mass loss due to spallation. The data can generally be fitted to an equation of the
form:
Table 8. Evaluation of corrosion rate*
Test Method
Furnace Burner Rig In-plant
Exposure Exposure
Corrosion Rate Assessment 100% 100% 100%
(a) mass change 86% 60%
(b) Spallation 71%

(i) Visual 25%
(ii) Lidded crucible (weigh sample t crucible) 46%
(c) Section Loss 61% 100% 60%

(i) Mean 61% 100% 60%
(ii) Maximum 57% 100% 60%
- Deepest penetration 25% 20% 20%
- Smallest of 4 diameters 7% 20% 0%
- 20 4% 0% 20%
- Extreme Value Analysis 7% 40% 20%
(d) Oxide Thickness 96% 80%
(e) Internal Penetration I 100% 100% 40%
(f) Depletion of Scale Forming Elements 71% 60%
Number of Replies 5 5
a
oJ7 rn
-1-
4:
-.a- xdl Wcknsro $
-12 1 , . , . ,
'Zi-
. 1
1I I
(b)
*
0 m 4 c a ~ s c o o l o o o o l :
Time h Time h
Fig. 2 Mass change data for (a) MA956 (batch BDY) and (b) ODM 751 (batch CCC) during
oxidation at 1200°C showing effect of specimen thickness on breakaway oxidation.
Fig. 3 Specific mass change vs time for four Co-Cr-A1 alloy samples of 1200°C for 200 I h
heating cycles. Vector (solid line). Based on paralinear constants (see e9n (1)) [291.
where k, represents an oxide growth rate constant analagous to parabolic oxidation

and k, is an oxide spalling constant.
Assessment of oxide/scale spallation was undertaken routinely by some 70% of
those laboratories using furnace exposure test methods (isothermal oxidation, cyclic
oxidation, gas phase corrosion).This was either assessed visually (25%)or by weigh-
ing the quantity of spa11 (46%). Assessment of spallation as part of burner rig studies
or in-plant tests, were not reported in replies to this questionnaire, although the use
of thin layer activation (TLA) has been proposed for the assessment of spallation
problems [21,22].
Metallographic methods included the measurement of section loss, oxide thick-
ness, internal corrosion penetration and the depletion profile of scale-forming ele-
ments. Every laboratory now involved in burner rig testing routinely measures sample
section loss. Such standardisation probably reflects the ongoing work under VAMAS
r, = Original surface
rc = Metalkoating interface
rm = Remaining metal after corrosion
ri = Remaining sound metal
rg= Grain boundary attack
Fig.4 Diagram showing metrology of likely corrosion.
on ‘Guidelines for hot corrosion assessment using dynamic burner rigs’ (see Refs [3]
and [lo]). Figure 4 illustrates the corrosion measurements to be recorded on each
corrosion section [MI. The section loss measurements recommended in the VAMAS
guidelines are as follows:
Measurement of Section Loss

Twenty-four measurements of corrosion (as specified below) should be made on
each section. Assuming a pin or cylindrical specimen the measurements would con-
sist of:
(a) loss of section (original radius less remaining radius);
(b) general internal attack (originalradius less radius to the onset of internal oxi-
dation/ sulphidation);
(c) grain boundary attack (original radius less radius to local grain boundary
corrosion);
(d) position of maximum attack, depth of attack and angular displacement rela-
tive to a reference mark (the leading edge of the pin for burner rig tests).
In addition, for coated samples:
(e) the radius of the coating/substrate interface should be recorded, from which a
measure of the remaining coating may be determined.
Further sections may also be taken as necessary, e.g. through areas of extreme
corrosion as evident from visual analysis.
The precision of radial (or diametrical) measurements should be as accurate as
possible, f 0.2 pm repeatability is achievable with modern measurement systems.
An accuracy of +_ 5 pm is considered the minimum, allowing for all sources of error
in the measurement system and sample preparation. For flat or sheet specimen ref-
erence to specimen radius in the above specification can be replaced with ’half the
specimen thickness’.
Measurement of corrosion loss as outlined above allows statistical methods to be
used in assessing corrosion performance. It is recommended that probability analy-
sis of section/corrosion loss be used to minimise the effects of uncontrolled vari-
ables within corrosion tests and to maximise available corrosion loss data. (Exam-
ples of this approach are given in Refs [18] and [23].)Adoption of such measure-
ments is recommended for all oxidation and corrosion studies and would unify the
procedures for metallographic corrosion loss assessment.
In other areas reviewed, laboratory furnace exposure tests and in-plant studies,
some 60% of laboratories routinely measure section losses. Of the laboratories meas-
uring section loss, all quote a mean metal loss rate and over 90% also report some
measure of maximum attack. It is in the assessment of maximum attack that there is
widest discrepancy. The most popular measurement is ’the deepest penetration meas-
ure on the particular section examined’ (43% of replies assessing maximum attack),
others include ‘the smallest of four diameters’, ’the evaluation of a standard devia-
tion’ and the use of ’extreme value statistics’. The author believes that the last is the
most rigorous, as it uses well proven statistical methods to predict the most prob-
able maximum corrosion rate to be expected [23-251 and this method is recommended
in the guidelines outlined in Section 5. The ’deepest penetration’ only provides a
single point estimator of maximum attack. The ’smallest of four diameter’s offers a
marginal improvement over the ’deepest penetration’. Tthe use of a standard devia-
tion (+ 20) implies that maximum corrosion follows a Gaussian distribution. This
has been shown not to be the case [23], although (pf 20) is a reasonable approxima-
tion of the most probable extreme value [23,25].
In addition to section loss, oxide thickness (96%), internal penetration (100%)and
depletion of scale forming elements (71%)are routinely measured during furnace
exposure studies.
4.2. Scale Characterisation

For completeness, methods used to assess the corrosion morphology (Table 9) and
to identify the corrosion products formed (Table 10)were also addressed in the ques-
tionnaire. The response would imply that under laboratory conditions some 90% of
corrosion/oxidation studies routinely assessed the corrosion morphologies pro-
duced.
However, following ’in-plant trials’ only 40% of the respondents would under-
take studies to characterisethe corrosionmorphologies and these studies in the main
would be limited to the scanning electron microscope (SEM).
Table 9. Scale characterisation - corrosion morphology*
Test Method
Exposure Exposure
Corrosion Morphology Assessed 89% 100% 40%

(a) Optical 39% 100% 20%
(b) SEM 89% 100% 40%
(c) EPMA 14% 60% 0%
(d) TEM 18% 0% 0%
Number of replies 28 I 5 1 5 I
Even within laboratory studies, many researchers would go straight to the SEM
to evaluate the morphology of attack, thus missing out the valuable information
available optically. Discussion of the methods to be adopted for the assessment of
corrosion morphologies is outside the scope of this paper, reference is made to the
excellent review by Rahmel[26], published as part of this monograph.
For the identification of corrosion products (Table lo), X-ray diffraction (XRD),
SEM/EDX and electron probe microanalysis (EPMA)are most widely used.
SecondaryIon Mass Spectrometry (SIMS),X-ray PhotoelectronSpectroscopy(XPS),
Auger Electron Spectroscopy (AES)and Laser Raman Spectroscopy (LRS)are mainly
restricted to laboratory studies of corrosion. Their use in burner rig studies and for
the evaluation of plant exposed specimens was not reported within this survey, and
may therefore be assumed to be small, restricted to specific needs.
Table 10. Scale characterisation - corrosion product identification*
Furnace Burner Rig In-plant

Exposure Exposure
Corrosion Product Identification 89% 80% 40%

(a) X-ray Diffraction 64% 80% 40%
(b) SEM/EDX or EPMA 89% 80% 40%
(c) SIMS 18% 0% 0Yo
(d) XPS 29% 0% 0Yo
(e) AES 7% 0% 0%
(f) LRS 4% 0% 0%
Number of replies 28 I 5 1 5 I
4.3. Evaluation of Specimen Mechanical Properties
A review of 'Simultaneous Corrosion and Mechanical or Thermal Stress' is presented
elsewhere in this monograph [2], where the most commonly used test methods for
assessing the role of external stress include:
Creep or creep rupture,
constant strain or extension rate tests, and
fatigue tests and crack growth rate tests.
In this study, respondents were asked to comment on alternative methods (other
than mass change, section loss, scale characterisation)used to assess corrosion dam-
age. 29% of researcher undertaking furnace exposure studies and 20% of those in-
volved in burner rig testing reported the evaluation of specimen mechanical proper-
ties (see Table 11).Creep rupture, hardness and modulus of rupture (MOR) were
used equally to assess the mechanical properties of corroded test pieces.
For operating procedures and evaluation methods to determine specimen me-
chanical properties under corrosion condition reference is made to the paper by
Schutze et al. [2] in this monograph.
5. Recommended Guidelines for 'The Discontinuous Measurement of

High Temperature Corrosion'
5.1. Definition
Discontinuousmeasurement methods involve the interruption of the corrosion proc-
esses to remove specimens for corrosion assessment.
5.2. Scope
(a) Isothermal oxidation;
Table 11. Evaluation methods mechanical properties*
Test Method
Furnace I BurnerRig I In-plant
I Exposure I I Exposure
Mechanical Property Evaluation 29% 20% -

(a) Creep rupture 21% - -
(b) Post exposure ductility 4% - -
(c) Hardness 21% - -
(d)MOR 21% - -
Number of replies 28 5 5
~~

(b) Cyclic oxidation;
(c) Gas phase corrosion;
(d) Hot corrosion - crucible tests, and
(e) Hot corrosion - salt coat tests.
5.3. Test Apparatus

(1) Either a vertical or horizontal furnace geometry may be used. The vertical
geometry permits more materials to be evaluated at one time.
(2) The furnace hot zone should be controlled to within [2]:

+
3°C from room temperature to 600°C
f 4°C from 600 to 800°C
*
5°C from 800 to 1000°C
k 8°C from 1000 to 1500°C
f 10°C for temperatures greater than 1500°C.
(3) Furnace hardware in contact with the environment should ideally be made
from 'alumina'. Below lOOO"C, 'silica' or 'high temperature alloys' may be
used. Any reaction of the furnace hardware with the corrosive environment
must not modify the composition of the environment within the corrosion
cell.
(4) Specimens should be retained in individual alumina crucibles. Lids may be

used to retain possible spallation products, provided there is no effect of gas
flow rate on the oxidation/corrosion process. When the corrosion process is
flow rate dependent, crucibles should be avoided (unless severe spallation is
anticipated) and specimens may be suspended from hooks within the corro-
sion cell. Hook supports may be made from silica, platinum or alumina form-
ing steel wire. Platinum use is restricted to temperatures below 1000°C. At
temperatures above lOOO"C, alumina forming wires are to be recommended
(Kanthal or Fecralloy steel).
( 5 ) Thermocouples: Type K, R or S thermocouples may be used depending on

the test temperature range. Thermocouples should be calibrated as new.
Recalibration at three month periods is recommended. Thermocouples should
be accurate to within f 2°C throughout their life.
(6) Thermocouples should be replaced at least every 12 months, or if they no

longer remain within a f 2°C calibration accuracy.
(7) Measurement thermocouples should be placed adjacent to the test sample,

embedded in an equivalent thermal mass.
5.4. Test Piece Geometry and Surf ace Preparation
(1) Rod or disc samples are preferred for cast materials. Rectangular or disc sam-
ples are preferred for sheet materials.Arc samples for materials from tube stock.
(2) Samples should have a surface area between 4 and 6 cm2.Preferred sizes are:
(a) Sheet materials: Rectangular 20 mm x 10 mm x sheet thickness
Disc 16 mm 0 x sheet thickness
(b) Tube materials: Arc 20 mm x 10 mm x wall thickness
(c) Cast materials: Rod 8mm 0 15 mm long

Disc 16mm 0 x 2 mm thick
(3) Surfaces should be finished to 1.0 pm RJ0.1 mm R, (equivalent to a 600 grit

Sic ground finish),where R, = a measure of the peak to trough roughness and
R, = centre line average roughness.
(4) Specimen edges should be slightly rounded, to avoid breakaway corrosion at

comers or edges.
(5) All specimens should be ultrasonically cleaned in a proprietary degreasant

(for example, inhibited 1:l:l trichloroethane), then hot washed and vapour
degreased using clean Analar isopropyl alcohol. Samples susceptible to cavi-
tation damage when cleaned in an ultrasonic bath (e.g. aluminium alloys)
should not be ultrasonically cleaned.
5.5. Test Procedure

(1) Load specimens into individual crucibles (or on individual hooks) ensuring
each specimen is vertical.
(2) Use duplicate specimenswhere possible, and randomise the position of speci-
mens in the corrosion cell to minimise near neighbour interactions (e.g. the
transfer of volatile corrosion products).
( 3 ) For gas corrosion studies:

(a) use premixed gases where possible.
(b) purge the corrosion cell with the corrosive gas prior to heating to tempera-
ture, to establish the corrosion test environment.
(4) Heat to the test temperature at 100°C min-l or faster. This is best achieved
using a moveable, preheated furnace to achieve the heating rates.
(5) Hold the isothermal test temperature within the following limits:
(a) +_ 3°C for temperatures up to 600°C
(b) f 4°C for temperatures from 600-800°C
(c) k 5°C for temperatures from 800-1000°C
(d) f 8°C for temperatures from 1000-1500°C and
(e) f 10°C for temperatures greater than 1500°C.
(6) Preferred test temperatures and maximum exposure times are summarised
in Table 1.
(7) Samples should be cooled to room temperature and examined (mass change
and visual examination) at time intervals that are, at maximum, 10% of the
total exposure time. Specimens may be replaced for further exposure.
(8) Samples should be removed for metallographic evaluation etc. at one of the
following preferred exposure times. 1,2,5,10,20,50,100,200,500,1000,2000,
and 5000 h. Using a 10% of total exposure for the cycle period, these times
will give at least four metallographic samples per material per test (e.g. for a
500 h exposure, samples would be removed at 50,100,200 and 500 h), from
which to assess the progression of corrosion damage metallographically.
(9) At test completion, or during any thermal cycle, the furnace should be cooled
at 100°C min-l.
(10) For gas phase corrosion tests, cool down should be in the corrosive gas. The
system should only be purged with an inert gas once cool (below 200°C).
5.6. Assessment of Corrosion Damage

5.6.1. Mass change
Mass change is determined from the difference in successive weighings of a speci-
men + crucible after a period of further exposure and is presented as Aw cm-2.
All weighings should be made on a five figure balance (a semi microbalance)
with sensitivity o f f 0.01 mg and a repeatability o f f 0.02 mg. It is important that the
balance calibration be checked prior to each weighing, using a standard mass. The
following procedure is recommended:
(1)Weigh the standard mass and recalibrate if necessary.

(2) Weigh the specimen plus crucible.
(3) Remove the specimen and reweigh the crucible.
(4) Recheck the weight of the standard specimen.
It is recommended that the above procedure be repeated three times. This will
allow the repeatability of the balance to be verified. The change in weight of the
crucible plus specimen, since test commencement, gives the total mass change.
The change in weight of the crucible with specimen removed, since test com-
mencement, gives the accumulated mass of spa11 collected. The difference in speci-
men mass may also be calculated, where a rapid increase in mass indicates breaka-
way corrosion and a rapid decrease in mass is indicative of extensive spallation or
volatile corrosion products.
5.6.2. Section loss, oxide thickness, internal penetration. depletion of scale forming ele-
ments
1.Prepare a metallographic section, ensuring the specimen is mounted vertically.
The procedure adopted for the statistical evaluation of corrosion loss [24], has
been described in detail elsewhere [MI. A specialist mounting jig is used that con-
tains two reference pins (see Fig. 5 ) .These are used to retain the specimen such that
the reference pins and specimen are parallel and in contact. The reference pins are
used with a custom fixture to ensure that the section taken is perpendicular to the
specimen length. The reference pins have a secondary function, they provide a method
of correcting for any angularity during polishing. This is evident as an ellipsoidal
section for each reference pin. Measurements of the major and minor axes of these
ellipses permits the orientation of cut to be calculated. The precision of measure-
ments should be as accurate as possible, & 0.2 pm is achievable with modern meas-
urement systems. An accuracy of k 5 pm is considered the minimum, allowing for
all sources of error in both the measurement system and sample preparation.
I -- KNIFE EDGE
\
W MOULD BASE
LOCATING PINS
TEST PIECE MOULD SIDE ELEVATION
SPRING
I Y
Fig. 5 Specimen mounting fixture.

2. Measure on each metallographic section, at a minimum of 24 random locations
(typically every 15" if circular), the following:
(i) Loss in section. This is half of (the original thickness less the remaining thick-
ness) at the point of measurement for flat samples. The original radius less the re-
maining radius for rod samples.
There is always a problem in identifying the original sample surface, or knowing
the original sample dimensions. If precision machined samples are used, then a ref-
erence sample can be taken from a batch and this may be considered to be repre-
sentative. Checks made using a precision, digital, micrometer (+ 2 pm) on all speci-
mens before corrosion can be used to validate this assumption. This procedure is
discussed in reference [18].
(ii) Oxide Thickness.
(iii) Internal penetratiodgrain boundary attack. Depending on the mode of at-

tack either internal penetration of oxides/sulphides or the depth of grain boundary
attack should be recorded.
(iv)Depth of depletion of scale forming elements. This may be visible as a change

in microstructure, but more normally it is expected that an SEM, with EDX, or an
EPMA will have to be used. Cross correlation with previous optical measurements
is possible by re-measuring one of the above mentioned micrographic features on
the SEM or EPMA.
5.6.3. Presentation of section loss. oxide thickness and other corrosion metrology
To complete the analysis, the following should be recorded as a minimum for each
metallographic section measured.
(i) An optical micrograph of the corrosion morphology. Where possible stand-

ard magnifications should be adopted.
(ii) An SEM micrograph, plus elemental maps, of the corrosion morphology.
(iii) An analysis of the corrosion products formed, using X-ray diffraction and
EPMA (or SEM/EDX).SIMS, XPS, AES, LRS and other analytical tools may be used
where necessary to further characterise the corrosion products.
6 . Concluding Remarks
This paper has attempted to formulate guidelines for the discontinuous measure-
ment of high temperature corrosion.The draft guidelines presented are based on the
analysis of 54 questionnaires, returned from 25 laboratories throughout Europe.
The guidelines, as summarised in this paper, are only the first step.
Comparison between laboratories have to be made to provide a proficiency evalu-
ation on an international basis. Systematic prenormative research is required across
laboratories to validate some of the recommendations and to check corrosion sensi-
tivities to such aspects as surface finish, start up conditions and use of crucibles
(specimen containment). Reference gases need to be defined for gas phase corrosion
tests. Most importantly the procedures recommended must be widely adopted.
Hence, much work has still to be done before a formal standard can be intro-
duced.
7. Acknowledgements
The authors wishes to thank the following for returning questionnaires or providing
information incorporated in this manuscript.
A. Atkinson AEA Technology, UK

D. Baxter JRC Petten, Netherlands
M. J. Bennett AEA Technology, UK
G. Borchardt Technische Universitat Clausthal, Germany
R. Cope Rolls Royce, UK
P. K. Datta University of Northumbria, UK
H. E. Evans University of Birmingham, UK
H. J. Grabke Max-Planck-Institute fur Eisenforchung, Germany
P. Greenfield E.G.T., UK
M. G. Hocking Imperial College, UK
A. M. Huntz Universitie Paris-XI. France
J. Jedlinski Staszic University, Poland
D. B. Meadowcroft ERA Technology, UK
G. E. Moores University of Leeds, UK
J. E Norton JRC Petten, Netherlands
J. E. Oakey British Coal, UK
W. J. Quadakkers KFA Julich, Germany
A. G. Rahmel Dechama, Germany
S. R. J. Saunders National Physical Laboratory, UK
M. Schiitze Dechema, Germany
F. H. Stott UMIST, UK
M. E Stroosnijder JRC, Ispra, Italy
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S. Mrowec, J. F. Norton, W. J. Quadakkers, S. R. J. Saunders and Z. Zurek, Werksfofle und
Korros., 1993,44,345-350.
36 High TemperafureCorrosion Research and Testing
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136-146,1995.
5. F. H. Stott, ’Corrosion and wear of erosion’, this volume, pp. 121-135,1995.
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ume, pp.147-157,1995.
3
In Situ Measurement Techniques

M. J. BENNETT"
Materials Technology Department, AEA Technology, Harwell, Didcot, Oxon OX11 ORA, UK
ABSTRACT
In situ experimental methods either measure or observe directly high temperature cor-
rosion processes, as they happen in real time. A summary is presented of the techniques
in current use, their main limitations and scope for development. The methods are de-
scribed in the context of six topic areas for which they may be used, namely, measuring
or following the extent/kinetics of attack, the chemical reaction sequence,the scale physi-
cal structure/topography, the scale mechanical failure (by cracking and spallation), the
stress state within the scale and finally, the scale mechanical properties. Future tech-
nique requirements and developments are identified in the light of mechanistic ques-
tions needing to be addressed.
1. Introduction
In studying the corrosion behaviour of metallic and ceramic materials at high tem-
peratures the foremost requirement is to monitor the extent and kinetics of attack. To
obtain a complete mechanistic understanding such data have to be augmented by
precise details of all the processes involved, starting with the chemical reaction se-
quence leading to the formation of gaseous products and of solid products at the
reacting surface. The development, and failure, of protective surface scales crucially
governs the resistance of most materials in aggressive environments at elevated tem-
peratures. So, knowledge is essential also on the changes throughout the exposures
of the scale chemical composition, physical structure (including topography), stress
state and mechanical properties, as well as on the scale failure sequence, e.g. by
cracking and spallation.
All these processes involved in high temperature corrosion are dynamic. There-
fore, to obtain unambiguous informationthe main experimentalapproach in research
should be based on in situ methods [l].These can be defined as being techniques
which either measure or observe directly high temperature corrosion processes, as
they happen, in real time. Although numerous in situ methods have been devel-
oped, to date, with several notable exceptions, the most important being controlled
atmosphere thermogravimetry [2], the deployment of these techniques often has
been limited. This may be attributed largely to experimental difficulty and also to
*Now a Materials Research Consultant, Three Chimneys, South Moreton, Nr Didcot, Oxon OX11 9AH,
UK
the lack of suitable equipment. Current understanding of the chemical and physical
characteristics, the stress state and mechanical properties of corrosion scales, largely
derives from post corrosion investigations. In fact certain detailed aspects, e.g. vari-
ations in mechanical properties and microstructure through scales, can be revealed
only by post corrosion studies. The two main experimental approaches, i.e. in situ
and post corrosion, are not mutually exclusive, as they both complement and aug-
ment each other. Nevertheless, at the current state of mechanistic knowledge of high
temperature corrosion further understanding of many critical facets, e.g. the break-
down of protective oxide scales, will be revealed only by real time experimentation.
These requirements, taken in conjunction with recent advances in both commercial
experimental equipment design/capabilities and in data storage/processing, make
it imperative that all researchers in this field should be fully aware of the available in
situ experimental test methods.
The purpose of this paper is to provide an overall summary of the real time tech-
niques in current use, their main limitations and scope for development, For ease of
presentation these will be described in the context of six key topic areas in which
they may be used, namely, extent/kinetics of attack, chemical reaction sequences,
scale physical structureltopography, scale mechanical failure (cracking and
spallation), stress state within scale and scale mechanical properties. The paper will
not describe either the detailed methodology of any technique or the complete re-
sults of any specific study using any such technique. Such information should be
obtainable from the references given to published papers. Finally, future technique
requirements and developments are identified in the light of mechanistic questions
needing to be addressed and conclusions are drawn as to the role of in situ methods
in high temperature corrosion research.
This paper is based on the twenty four replies received to a questionnaire distrib-
uted in October 1993 to about 30 active High Temperature Corrosion researchers in
Europe and in North America. It also includes comments from the discussion fol-
lowing a presentation on this topic at the EFC Workshop on ’Methodsand Testing in
High Temperature Corrosion’ held at DECHEMA eV, Frankfurt on 20 and 21 Janu-
ary 1994.
2. In Situ Techniques for High Temperature Corrosion Studies

2.1. Techniques for Measurement of the Extents and Kinetics of Attack
Five main groups of techniques are used to measure the extents and kinetics of at-
tack by monitoring respectively mass gain, gas consumption, product formation,
electrochemical properties and metal loss.
The most widely used method is continuous thermogravimetry and the points to
consider in using this technique are detailed in a recent paper [2] originating from a
European Federation of Corrosion Action. The majority of high temperature corro-
sion research laboratories worldwide are equipped with automatic recording micro
balances, for which there are several commercial manufacturers. Most models can
be operated as closed gas systems enabling corrosion monitoring in defined gas
In Situ Measurement Techniques 39
mixtures, at pressures up to atmospheric and also in zlucuo. Micro balances on the
market often have a greater sensitivity than is required for corrosion kinetics meas-
urement but a limitation can be imposed by the balance total load carrying ability,
usually I 2 5 g. Such a problem can be overcome readily with a thermal balance in
which the sample is suspended from a recording laboratory balance into a reaction
chamber within a furnace. Such a facility can have a greater capacity, e.g. I 2 5 0 g yet
retain an adequate sensitivity, e.g. f 0.02 mg. Thermobalancescan be used easily for
oxidation in air (e.g. [2,3]), but require secondary containment for monitoring corro-
sion in other environments. Maintenance of constant balance temperature and gas
flow rate through the reaction system are essential prerequisites for balance stability.
Micro and thermal balances have now largely replaced spring balances (e.g. [4]),
in which the extension of the spring, usually silica, monitored by either a cathetometer
or a transducer, provides a measurement of mass change. However, spring balances
are still being employed to follow corrosion in hostile environments [5] and with an
appropriate containment vessel can be used for gas pressures in excess of 1 atm 16,
71. Thermal insulation becomes a problem for pressures above 20 atm due to the
increased thermal conductivity of oxygen. Water cooling of the exterior vessel shell
is essential at pressures greater than 40 atm [7].
Continuous assessment of the extent and kinetics of attack by measurement of
the consumption of gas may be carried out by monitoring the fall in either pressure
in a constant volume system [8-lo], the manometric method, or that of volume at
constant pressure, the volumetric method [ l l ] . An interesting variant of the later
approach is based on a solid-state zirconia electrolyte. This maintains a constant
oxygen partial pressure and at the same time measures the rate of oxygen uptake
[12, 131. Advantages of these methods include first, a superior sensitivity to a
microbalance in that the uptake of less than a monolayer coverage can be detected at
a pressure of torr, and second, the ability to examine the influence of gas pres-
sure. Disadvantages are that the methods are only applicable in pure gases, since
consumption of one component of a mixture would alter the composition and con-
sequently affect the rates of attack. Care has to be exercised in the choice of chamber
size in the manometric method to avoid appreciable oxidant pressure variation, as
this could affect the reaction rate. Both methods are particularly sensitive to fluctua-
tions in room temperature and ambient pressure. Corrosion measurement in envi-
ronments containingmixed gaseous species can be followed by an evolved gas analy-
sis technique 114,151. This is based on the use of gas chromatography to monitor the
relative change in the concentrations of the reactive species in the gas, which in turn
is a direct measure of the gas-metal reactions occurring.
The third group of techniques monitor the formation, and subsequent develop-
ment of each of the scale constituents by a range of surface analytical techniques,
including X-ray diffraction. (XRD) [16], laser Raman spectroscopy (LRS) [17]. reflec-
tion high energy electron diffraction (RHED) [ 181,Auger electron spectroscopy (AES),
X-ray photoelectron spectroscopy (XI'S) and secondary electron mass spectrometry
(SIMS)[19,20]. As will be discussed in Section 2.2., the main role of these techniques
is to establish the chemical reaction sequence. Nevertheless, if the spectral informa-
tion can be quantified, these data also can provide the extent and kinetics of attack.
These techniques are often limited to following the early stages of corrosion, and to
probing reactions at low gas pressures. A powerful adjunct to SIMS can be combina-
tion with isotopic labelling of gas components [20]. This group of techniques also
can encompass the use of optical methods [21,22], in particular ellipsometry, which
have been deployed effectively to measure oxide film thickness. These procedures
are based on reflecting polarised light from the oxidised metal surface and measur-
ing the state of polarisation. Again the procedures are usually limited to thin films,
typically less than 200 nm, but these could be halides, sulphides, nitrides, as well as
oxides.
The fourth group of techniques are based on the measurement of electrochemical
properties. Hot corrosion processes, involving molten salt phases or the formation
of scales with a high ionic transport number, may be monitored successfully using
three a.c. or d.c. electrochemical techniques, namely zero resistance ammetry (ZRA),
electrochemical potential noise (EPN)and electrochemical current noise (ECN) [23-
251. These techniques cannot be used to follow oxidation, sulphidation or combus-
tion, as the scales formed are electronic conductors.
The final procedure for monitoring the extents/kinetics of attack is the electrical
resistance technique, which directly measures the loss of metal thickness [23, 261.
The characteristicsof the scale and/or surface deposits do not affect the accuracy of
measurement.
2.2. Techniques for Following Chemical Reaction Sequences

The real time experimental techniques for following the sequence of the chemical
reactions at oxidising surfaces may be collated into two groups, the first based on
analysis of the environment and the second based on analysis of the formation and
development of the surface products.
Various monitoring procedures of the gaseous environment have been employed.
These range from simply measuring gas evolution as an increase in pressure (e.g.
associated with hydrogen production from reaction with steam [27]) or involving
analytical techniques, such as mass spectrometry [28] and gas chromatography [ 14,
291. These follow either the consumption or the release of gaseous components dur-
ing oxidation in mixed reactants (e.g. in H,O/H, [28], SO,/O, [14], SO,/H,O/H,
[29]). The additional use of labelled oxidants can be advantageous for elucidation of
reaction mechanisms (e.g. [28]). Similar analysis procedures have been used also to
follow the evolution of gaseous products formed by the oxidation of ceramics such
as Sic and Si3N, [30,31].
Several surface analytical techniques have been deployed for in situ studies of the
formation and development of products at reacting surfaces. The early stages of
oxidation of metals and alloys have been followed by interfacial/near surface ana-
lytical techniques (XPS, AES, SIMS), either alone [19, 321 or in combination with
LEED (low energy electron diffraction) [33]. RHEED has been used also for such
studies [18, 341. Diffraction ring patterns of the nucleation and growth of the first
oxide phases also can be obtained during in situ TEM investigations [35, 361, to-
gether with microstructural information, as described in Section 2.3. A further im-
portant recent use of interfacial analysis techniques has been to examine the chemis-
try and particularly the concentration of non-metallic segregates at a scale-alloy in-
terface. This has involved the development of an in situ scratch technique to remove
the oxide scale and expose that interface in ultra high vacuum within a scanning
Auger microscope (SAM) [37,38].
In the majority of the studies so far described in this section the specimen was
oxidised and/or examined within the surface analytical instrument due to operat-
ing pressure restrictions. The availability of environmental cells, fitted with speci-
men hot-stages, capable of operation either in uacuu or with controlled gas composi-
tions up to 1 atm pressure, at temperatures at least up to 1000°C (and with recent
commercial models up to higher temperatures) has facilitated in situ studies involv-
ing oxidation within the cell and examination from outside the cell. Environmental
cells with a radiatio-n transparent beryllium window can be attached to a
diffractometer (as shown in Fig. 1) to enable the chemical sequence at the reacting
surface to be followed by X-ray diffraction (e.g. during the oxidation of uranium
Fig.2 A high temperature environmentalcellfitted with a transparent beryllium window attached

to an APEX goniometer at the Harwell Laboratory of AEA Technology.
dioxide [39] and of steels [16] in air).X-ray diffraction can be carried out either in the
normal or glancing angle [40] mode, thereby ensuring maximum sensitivity over
scale thicknesses ranging between 0.5 and 10 pn.In addition to followingthe chemical
reaction sequence this technique is used also to provide measurements of stress within
the scale and substrate, as described in Section 2.5.
Laser Raman spectroscopy (LRS)can also provide compositional information, with
an advantage over XRD of a smaller spatial resolution, as the probe diameter is 1-2
pm. As a consequenceit becomes possible to examine variations across surfaces, for
example, to compare the behaviour of different alloy phases within an alloy and
within alloy grains and over emerging alloy grain boundaries [41].The LRS penetra-
tion depth depends on the material but can be up to 1 pm. Another environmental
cell variant is fitted with a quartz optical window (an example is shown in Fig. 2)
and is used extensively in conjunction with optical microscopy (as described in Sec-
tion 2.3.).As a consequence this type of cell can be attached to a laser Raman micro-
scope. However, use of in situ LRS to follow chemical reaction sequences so far has
been limited [42], although this technique has been employed for this purpose in a
number of ex situ studies (e.g. [43]).There remains considerable scope for the exploi-
tation of in situ LRS. As with XRD, LRS can provide stress information, as will be
described in section 2.5.
Fig. 2 A high temperatue environmental cellfitted with an optical quartz window for in situ
optical microscopy and laser Raman spectroscopy studies.
2.3. Techniques for Following Microstructural and Topographical Changes
Three techniques, optical microscopy, scanning electron microscopy, and transmis-
sion electron microscopy have been used to follow microstructural, and in particu-
lar mainly topographical, changes during corrosion: Optical microscopy may be car-
ried out in conjunction with the type of environmental hot-cell shown in Fig. 2. The
reacting surface is viewed with an optical microscope and topographical changes
have been recorded either with time lapse cine-photography [44] or more recently
by video recording [45].Studies have concentrated on the early stage nucleation and
growth of surface products in mixed gas environments [45,46], spallation of scales
from an alloy surface [44] and of reactions [39, 471, including disintegration [39],
occurring at ceramic surfaces. The maximum magnification achievable with in situ
optical microscopy is x 320. Other limitations on the technique can be imposed by
depth of focus problems, which increase as the surface topography changes due to
non-uniform outward growth of scale constituents or to surface disintegration. In
addition the evolution of volatile reaction products can cloud the viewing window.
Nevertheless, the technique offers substantial potential for further exploitation.
To improve depth resolution and increase magnification capability up to 20 000 x
modifications have been made [48-521 to scanning electron microscopes (SEM),in-
volving the insertion of specimen hot stages capable of operation up to 1000°C.Pro-
vision was made also for the entry of non-condensable reactive gases, at a low pres-
sure, typically between 10-6-10-3 atm, to the specimen chamber through a capillary
leak. Resultant studies followed the evolution of product phase morphologies dur-
ing the initial oxidation of several metals, including iron [48,49,51], and copper [50]
and other metals [52]. Considerable problems had to be surmounted with the re-
quired engineering modifications to the microscopes and also with temperature/
gas pressure calibration.These, taken together with the limited type of investigation
which could be carried out, slowed down the subsequent use of in situ SEM in high
temperature oxidation studies. However, this situation has now been changed with
the development, about five years ago, of a commercial environmental scanning
electron microscope (ESEM)incorporating either a hot-stage and/or a mechanical-
strain jig, capable of operation with aggressive atmospheres, at near ambient pres-
sures, at temperatures up to 1000°C.The availability of this microscope has opened
up new possibilities for in situ SEM [53]. Work in progress at M.I.T.,hasshown that
this equipment can be deployed not only to follow the early oxidation stages of
metals, important though that is, but the ESEM also has much wider applications,
such as surface morphological studies of the behaviour of materials in mixed gase-
ous reactants, of cracking and spallation of scales and of the pest type oxidation of
intermetallics.
Ultimate resolution implies transmission electron microscopy (TEM)and gas-re-
action cells [35,54,55], have been developed for a High Voltage Electron Microscope
(HVEM).This technique has been employed for the investigation of the early stages
of oxidation, at low gas pressures, of a Ni-Cr alloy, with and without a thoria disper-
sion [54], of Fe-Cr-Ni-Zr alloys [55] and of titanium aluminium alloys [35]. As with
all TEM work, the technique requires the preparation of thinned electron transpar-
ent specimens,for oxidation and examination.Aresulting problem, in many instances,
has been that specimensunderwent 'block' type oxidation, whereby the thinnest foil
section completely oxidised and the oxidation front subsequently moved rapidly
through the remaining foil section. It proved necessary, therefore to limit the oxida-
tion rate by reducing substantially either temperature and/or gas pressure, so that
surface reactions only occurred. In view of these experimental difficulties and the
current limited HVEM availability worldwide, little further work using this tech-
nique seems likely. The role of high resolution microscopy in the future will prob-
ably involve scanning tunnelling microscopy [56].
2.4. Techniques for Following the Mechanical Failure of Oxide Scales

Mechanical failure of oxide scales during both thermal cycling and under conditions
of applied load involve scale cracking, which can be followed by scale spallation. In
situ techniques are used, some quite widely, to establish the conditions for the onset
of both modes of failure and their continuing extents.
Cracking can be studied by three in situ techniques, thermogravimetry, resonant
frequency and acoustic emission. In cyclic thermogravimetric exposures, with con-
trolled cooling, cracking of a scale, with a thickness above a threshold value, can
occur on a critical temperature drop. Providing rapid oxidation then occurs over a
sufficiently large area of the substrate exposed, cracking can be manifest by a weight
increase [57]. However, often this can be masked, as further cooling occurs, by a
more extensive weight loss due to spallation. The resonant frequency technique [58-
601 is particularly suited to the determination of the first crack in the scale as oxide
cracking modifies the effective stiffness of the composite system, which can be de-
tected as an instantaneous drop in the resonant frequency. However, continuing spa11
formation, following the initial cracking will produce little further change in fre-
quency. The third technique used is acoustic emission (AE) and especially with the
availability of commercial equipment, it has found wide usage in monitoring crack-
ing during thermal cycling [61-671 and during superimposed stress [68]. Three ex-
perimental arrangements are employed. In the first [61,62], with component type
specimens (i.e.bars or tubes), their ends extend to outside the furnace.At these ends
AE transducers are attached and spatial discrimination is applied to exclude noise
not arising from the processes of interest in the furnace centre. Besides the AE counts
and events the amplitude distribution can be used for interpretation of scale dam-
age. In the second experimental arrangement [63-681 specimens are attached to a
platinum wire, which acts as a wave guide to an AE transducer located outside the
furnace. In the third, a most recently developed experimental arrangement [66,67],
the acoustic emission detection system is coupled to a controlled atmosphere
microbalance. This provides the significant advantage of being able to measure si-
multaneously two parameters, mass change and AE, describing the formation and
mechanical failure of oxide scales. Although the use of an external platinum wave
guide in the later two experimental modes does not impede monitoring of the number
AE counts and events, it could result in loss of ability to resolve AE spectral differ-
ences, as these could be masked by the more complex experimentalAE transfer func-
tion. Although, as stated, AE monitoring is now widely employed, there are strong
arguments that the technique should be used like thermogravimetry, almost on a
routine basis in most high temperature corrosion studies, where scale failure is an
important parameter.
The commonest technique employed universally for the continuous measurement
of scale spallation is thermogravimetry(e.g. [2,57,66,67,69-711). The potential for a
second technique, thin layer-activation (TLA),to monitor spallation has been dem-
onstrated [70,71] and is beginning to find further applications in high temperature
corrosion studies [72]. TLA is now a well established in situ technique for the meas-
urement of material loss resulting from wear, erosion and aqueous corrosion [73-
761. The underlying principles of the TLA.method for monitoring material loss in
high temperature corrosionprocesses are shown schematically in Fig. 3. TLA is based
on the production, by a high energy ion beam of trace quantities of hard gamma
emitting radioisotope atoms (1 part in lo6 atoms) within a thin surface layer. For
Fig.3 Schematic representation of principles underlying monitoring high temperaturecorrosion/

erosion processes by thin layer activation.
high temperature applications, where solid state diffusion processes are expected,
the radio tracer atoms chosen need to participate in the formation of the corrosion
scale. For the studies undertaken on scale spallation from the 20Cr-25Ni-Nb stain-
less steel [70, 711, activation was arranged to produce radioisotopes 51Cr,52Mnand
54Mnof scale constituents, as well as 56C0,57C0and 5 8 c ~non-scale
, constituents.
Measurement of the total activity of the surface then monitors activity loss, which
can be translated into material loss. Assessment of the respective behaviour of the
individual radioisotopes also provided valuable chemical information about the scale
failure process [70,71]. Although the use of this technique does necessitate radioac-
tive safeguards, these fall within normal laboratory arrangements and do not im-
pose any unreasonable restrictions. It is anticipated therefore, that TLA will find
increasing applications in the future for monitoring material loss from high tem-
perature corrosion/ erosion processes.
2.5. Techniques for Measurement of Scale Stresses

In providing mechanistic understanding of scale failure, and in particular the ability
to model processes by fracture mechanics, detailed information is required on the
changes in stress state within the scale. This stress will include growth stresses, ther-
mally induced stresses and directly applied (tensile,compressive or bending) stresses.
Three methods, X-ray diffraction, laser Raman spectroscopy, and bending beam,
have been employed to determine the internal or growth stresseswithin oxide scales.
The X-ray technique is the most widely used and in situ high temperature measure-
ment can be made with a range of commercial environmental cells, an example is
shown in Fig. 1.The determination of stresses is based on the measurement of lattice
strains in a set of lattice planes of known orientation and then correlating these lat-
tice strains with the strain calculated from elastic theory [77-811. This approach is
known as the sin2q method. Recent studies have included measurement of stress
changes during the oxidation of chromium [I, 801 nickel [80,81] and Ni-Cr alloys
[80]. Only a single investigation [42] has been undertaken using Raman microscopy
to determine the stress distributions within thin oxide scales formed on the 20Cr-
25Ni-Nb stainless steel. The improved spatial resolution of LRS over XRD proved to
be advantageous and enabled stress mapping over the scale surface. LRS, therefore,
offers considerable potential for wider usage.
The third technique for stress determination is by direct deflection measurements
of a thin beam at temperature [82-841. The thin metallic strip under test is only per-
mitted to oxidise on one side by coating the second, usually with silica. Oxidation
causes the strip to bend with the degree of deflection providing a measure of the
stress generated within the scale. The technique is restricted to a maximum tem-
perature of -1100°C by the lack of barrier coatings for higher temperatures. Amodi-
fied two sided oxidation bending method has been developed recently [85], offering
advantages over the one-side method.
Currently there is critical need for much more stress information including stress
maps, on a variety of oxide scales and most especially for alumina scales. The latter
will necessitate the development of new equipment capable of operation in corro-
sion environments at temperatures up to -14OO0C, without risk of generating impu-
rity contaminants, e.g. oxides of platinum.
2.6. Techniques for Measurement of Scale Mechanical Properties

The vibration technique currently is the only method available for in situ measure-
ment of oxide scale mechanical properties, such as the elastic modulus and the frac-
ture stress [60, 861. Recent technique developments have resulted in a fully auto-
mated procedure allowing automatic tracking of the specimen frequency during
heating, cooling and isothermal exposure. A depth sensing submicron indentation
technique has proved effective in measuring room temperature micromechanical/
elastic modulus, hardness etc. properties of oxide scales [87]. A nano-indenter for in
situ high temperature measurementsis currently under development at the Oak Ridge
National Laboratory in the United States.
3. Future Technique Requirements and Developments
An immediate development would be to extend the approach of combining two

techniques, as demonstrated successfully from the use of thermogravimetry in com-
bination with thin layer activation [70] and with acoustic emission monitoring [66].
Obvious possibilities for this approach would be to link laser Raman spectroscopy
to optical hot-stage microscopy to follow concurrently changes in surface chemistry
and topography.Another relatively simple development would be to combine acous-
tic emission monitoring with thin layer activation to establish further the relation-
ship between cracking and spallation. Several new test methods, which need to be
developed, can be clearly identified. Above all there is an urgent requirement for
further direct observations of the protective oxide scale failure by cracking and
spallation. This should be possible by innovative modifications to existing optical
and/or scanning electron microscopy techniques. Again it would be highly desir-
able to combine such direct physical observations with acoustic emission monitor-
ing. Another area where critical information is lacking is scale mechanical properties
at temperature. In situ indentation at elevated temperatures is under development
but major problems have to be overcome before this procedure becomes a reality.
Among other methods which could be pursued, would be infra-red Fourier trans-
formed techniques, particularly in a reflectance mode, which would seem to offer
potential for following chemical reaction sequences, especially those involving wa-
ter vapour, which again is an area of current concern.
There is a need to ensure that all techniques, including those that are well estab-
lished, can be deployed to study every type of high temperature corrosion problem.
For this purpose it could be necessary to extend the capabilities of techniques to
operate in all relevant gas environments, i.e. containing S- and C1-bearing gases and
other highly corrosive constituents and also in the presence of deposits, e.g. in hot
corrosion etc.
Although the test methods have been described in this paper in the context of
laboratory research studies, it should always be realised that there is a continuing
need for procedures to monitor corrosion in industrial plant. As a consequence due
consideration needs to be given constantly to the possibility of developing labora-
tory in situ methods for on line in-plant applications. Several techniques, including
electrochemical and variable temperature electrical resistance probes, are in use [23].
Thin layer activation, which has been used extensively in the oil industry and aque-
ous systems for monitoring metal wastage, has obvious potential applications for
high temperature process plant. In fact, the procedure is being assessed currently in
industrial trials to monitor erosion rates in coal-burning boilers [88].
4. Conclusions
Future high temperature corrosion R&D will continue to be based on the comple-
mentary use of both post corrosion and real time experimental methods. However,
the deployment of in situ techniques should be increased and in certain critical areas
is essential for providing vital mechanistic understanding.
Amongst the existing in situ methods, most European Laboratories employ con-
trolled atmosphere thermogravimetry to establish the extent and kinetics of attack,
while several also use X-ray diffraction for stress/strain measurement and/or acoustic
emission for monitoring cracking. Guidelines, at least, should be drawn up for the
use of all three of these techniques. There are also strong arguments for a European
standards programme of round-robin tests to provide a cross check of the results
obtained by the different laboratories.
Real time techniques are based on a substantial capital investment in equipment
and also in human professional resources, often with a specialised skill base. It has
to be recognised also that certain techniques have unique applications. As a conse-
quence existing laboratory facilities and scientific skills throughout Europe should
be used to the fullest advantage within both CEC and national collaborative R&D
programmes. To enable all researchers throughout Europe to be fully aware of the
facilities available within Universities, Research Institutes and Industry, there is an
urgent need for the compilation of a directory of relevant equipment, and responsi-
ble staff. A similar compendium of all active researchers in the high temperature
corrosion field would also be of inestimable value.
5. Acknowledgements
This paper would not have been possible without the contributions provided by the
respondents to my questionnaires and by participants at the European Federation of
Corrosion Workshop in January 1994, I am most grateful for their help and trust that
the paper adequately reflects their views. I wish also to acknowledge the help from
colleagues at AEA Technology in the production of this review.
In Situ Measuvemenf Techniques 49
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54. H. M. Flower, 1.Microsc., 1972,97, 1971.
55. H. M. Flower and B. A. Wilcox, Corros. Sci., 1977,17,253.
56. V. Maurice, H. Talah and I? Marcus, Microscopy of Oxidation - 2 (Eds S. B. Newcomb and
M. J. Bennett), The Institute of Materials, London, 1993,99.
57. R. C. Lobb, Thermochem. Acta, 1984,82,191.
58. D. Bruce and P. Hancock, 1,Inst. Metals, 1969,97,140-148 and 148-155.
59. P. Hancock, Werk. und Korros., 1970,21,1002.
60. P. Hancock, Stress Eflects and the Oxidation ofMetals, (Ed. J. V. Cathcart), AIME, New York,
1978,155.
61. C. Coddet, G. Beranger and J. F. Chretien, Materials and Coatings to Resist High Temperature
Corrosion, Applied Science, London, 1978,175.
62. W. Christl, A. Rahmel and M. Schutze, Oxid. Met., 1989,31,1.
63. S. Becker, M. Schiitze and A. Rahmel, Oxid. Met., 1993,39,93.
64. A. S. Khanna, B. B. Jho and 8. Raj, Oxid. Met., 1985,23,159.
65. Y. Zheng and D. A. Shores, Oxid. Met., 1993,40,529.
66. M. J. Bennett, D. J. Buttle, P. D. Colledge, J. B. Price, C. B. Scruby and K. A. Stacey, Mat. Sci.
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Europ. Con5 in Life Assessment of Industrial Components, ERA Technology Ltd, 1993,47.
Thermogravimetry
H. J. GRABKE
Max-Planck-Institut fur Eisenforschung GmbH, Max-Planck-Str. 1,40237 Dusseldorf, Germany
ABSTRACT
Continuous thermogravimetry is a common method used to test materials in gaseous
corrosive environments at high temperatures, and to elucidate kinetics and mechanisms
of high temperature corrosion.Recommendationson how to conduct thermogravimetric
tests are collected here, together with the considerations surrounding sample size and
form, surface preparation, reaction chamber, starting procedure, sensitive measurements,
gas supply and dosing.
1. Introduction
High temperature oxidation of metals and alloys generally leads to a mass increase
of the materials by growth of an external oxide layer and possibly internal oxida-
tion. This is valid more generally for high temperature corrosion where external and
internal sulphide, carbide, nitride and chloride formation may also occur.The method
most widely used to follow the kinetics of high temperature oxidation and corrosion
is to measure the mass change at temperature: thermogravirnetry. In the case of forma-
tion of only one well-defined oxide the measured mass increase can be easily con-
verted into a rate of oxide growth and metal loss, but often a range of corrosion
products are formed and analyses of the corroded sample are needed to give addi-
tional information on the corrosion processes.
Sometimes discontinuous gravimetry is applied to assess the reaction kinetics,
especially in long-term exposures and technologically related studies. The specimen
is weighed and measured and it is then exposed to the conditions of high tempera-
ture corrosion for measured times, being regularly removed and reweighed. This
technique yields only discrete points per specimen and imposes a thermal cycle on
the specimen each time. However, many specimens, possibly including several dif-
ferent alloys can be exposed simultaneously and the technique and the apparatus
are very simple. This procedure is described in Chapter 2 of this publication.
In the present chapter, the continuous thermogravimetric techniques are to be
described, such as are applied in many laboratories all over the world and which
mainly use automatic recording microbalances. In earlier years spring balances were
used in which the specimen was suspended from a sensitive spring whose extension
is measured. Such balances are still used in cases of very hostile environments [l]
but they generally need continuous monitoring by cathetometer observation, unless
a remote monitoring transducer such as a linear voltage differentialtransducer (LVDT)
Thermogravimetry 53
can be used by hanging a metal pick-up (encased in silica) from the spring
(Meadowcroft,private communication).
Continuous monitoring is possible of the oxidation of a sample suspended from a
recording balance in the reaction chamber within a furnace. Oxidation in air can be
measured easily using a laboratory balance with a hole in the bottom through which
the suspension wire is directed. For corrosion in defined gas mixtures, closed
systems are necessary and microbalances are available which also can be used un-
der vacuum conditions (Fig. 1)[2]. Several models are on the market, usually having
high sensitivities,e.g. 1yg with a load carrying ability of up to 25 g. This sensitivity
in many cases is not necessary to follow the corrosion kinetics and the researcher is
well advised to use lower sensitivity ranges if possible, where errors by buoyancy
and temperature effects are less (see Section 5).
The most recent systems for thermogravimetry equipment with improved
versatility and precision of the measurement include temperature controlled enclo-
sure and antivibration mounting for the balance, temperature measurement with
high sensitivity, gas handling system with precise pressure control and regulation,
->
I Balance shiela
- 1
Bnlnnce shield gos e x i t
Norrow-bore t u b e
suspensior,
Furnace pas in1
Thermocouple
1
Specimen
Furnace
Fig. 1 Experimental arrangementfor use with an automatic recording balance [21

power controller with wide range of sample heating and cooling facilities and versa-
tile software for control and evaluation, e.g. buoyancy correction.
2. Sample Shape and Suspension
In the following, mechanistic studies, in which fundamental data on mechanism

and kinetics of the corrosion process are to be obtained, are distinguished from de-
sign data studies, i.e. data on materials consumption or for a ranking of different
alloys, as may be most important for design engineers.
For mechanistic studies the samples should be flat discs with rounded edges to
avoid effects of corners and edges as far as possible. The samples should be large
and thin, e.g. 15 mm dia., 1mm thick with the edges chamfered. For suspending, a
small hole may be drilled in the sample, but hanging in a basket made of Pt wire or
silica filaments is also possible. Inserting the sample in a crucible of alumina or silica,
allows spalled corrosion products to be collected. However, a crucible can alter the
kinetics, if the atmosphere in the crucible becomes atypical of the bulk atmosphere.
Small slots in the crucible can minimise the effects of uneven gas flow.
For suspension, Pt wire or quartz filaments are used. Pt-Rh wires have better
mechanical strength than Pt. At high temperatures (> 9OOOC) and high PO,Pt is to be
avoided because of volatile PtO, formation; at high temperatures and at low oxygen
pressures SiO, filaments cannot be used, since volatile Si0 is formed (see also Sec-
tion 4 -reaction chamber). Preoxidised wires of Kanthal (Fe-Cr-Al) Fecralloy-steel
or ODs-alloys can be used. Suspension of specimens at very high temperatures is
best achieved by using a sapphire suspension hook. The mass gain must be related
to the surface area of the specimen - in the case of fast corrosion the decrease of
surface area caused by the materials consumption must be considered [3-51.
In studies for determination of engineering design data the specimens should
have a geometry as similar as in industrial application as possible - the effects of
corners and edges certainly must be considered.
3. Sample Preparation
Cleaning is important to remove the Sic left from grinding and the polishing parti-
cles, alumina or diamond powder, which may affect the structure of scales [6]. Ultra-
sonic cleaning therefore is important. The solutes differ: water with detergent, alco-
hol, acetone, ethyl ether... but alcohol or methanol appear to be usual.
Instead of mechanical grinding and polishing, electropolishing may be used which
leads to a very even surface without any asperities. However, electropolishing may
cause enrichment of certain alloying components in the surface and formation of a
passive layer, and the results may be irreproducible. One should realise also that
electropolishing removes any near-surface deformation whereas grinding and me-
chanical polishing introduce some cold working of the surface. This difference can
strongly affect the formation of protective scales on alloys (e.g. the formation of a
Thermogravimetry 55
chromia scale on Alloy 800 at intermediate temperatures is favoured by cold work-
ing and virtually suppressed by electropolishing [7]). Further means to favour for-
mation of protective scales include the following.
Cold working, such as provided by sandblasting or rolling; whereas annealing at
high temperature (in H2)and electropolishing adversely affect the selective oxida-
tion of the element which should form the protective scale. Surface deformation and
small grains favour outward diffusion of the protective element (Cr,A1...) by provid-
ing fast diffusion paths, whereas recrystallisation and electropolishing remove these
easy diffusion paths. Recrystallisation and electropolishing thus sensitise alloys for
attack by multiple oxidants, e.g. metal dusting is readily observed after such treat-
ment [81.
To obtain design data the material should be tested in the condition in which it is
to be used, delivered after machining or still covered with a skin from hot rolling.
The oxidation and corrosion behaviour of weldments, i.e. welding material and heat
affected zone should also be studied: often great differences occur in comparison
with the base material!
4. Furnace and Reaction Chamber
The reaction tube in which the sample is hanging can be of silica or alumina.
Silica tubes cannot be used with reducing atmospheres at high temperatures, since
SiO(g)is formed (in sulphidising atmospheres volatile SiS) and Si is transferred onto
and into the specimen. The critical temperature and PO, ranges can be established
from Fig. 2. Generally it can be said that temperatures > 900°C and 'dry hydrogen'
are critical. Furthermore, a conditioning of silica tubes appears to be necessary for
all atmospheres; with fresh silica tubes peculiar results have been obtained, the re-
sults changing upon repeating under the same conditions 191.
Alumina tubes are appropriate for most conditions, joining is difficult, but ground
surfaces on the tubes with O-ring seals give good gas sealing.
Electrostatic fields are to be avoided by the use of metal coatings on the cold parts
of the tubes - difficulties from magnetic fields can be avoided by bifilar winding of
the furnace.
Correct temperature measurement is important; uncertainties in temperature
appear to be one of the most important reasons for differences in results of different
authors. Ni-NiCr thermoelements should not be used (their characteristics depend
on the temperature gradients in the legs and thermal history), but only Pt-PtRh ele-
ments. The calibration of the thermoelements must be checked at regular intervals
(4-6 weeks). The thermoelement should be situated as near as possible to the speci-
men -placed in a thin thermowell of quartz or alumina. The temperature profile of
the furnace must be measured to determine the constant temperature region; the
radial gradient of temperature should also be measured in experiments with high
gas flow rates. A certain span of temperature control is allowed, depending on the
temperature range, below 1000°C_+ 3"C, above k 6°C and above 1500°C k 10°C.
Checks must be made to ensure that the gas is preheated sufficiently when it
Fig. 2 Equilibrium pressures of SiO(g) in dependence on the oxygen pressure, calculated for
different temperatures.
reaches the sample so that the sample is not blown cold. If fast flow rates have to be
used (see Section 5), special constructions of the reaction chamber are necessary. For
heating a flowing gas, maximum contact with the hot walls is important, therefore
thin tubes are favoured, e.g. a spiral coil before or in the reaction chamber. The heat
transfer can be calculated and the approach of gas temperature to the desired reac-
tion temperature can be assessed from the experience in chemical engineering (e.g.
[101).
In a wide reaction chamber with a slow gas flow, some demixing of gases by
thermodiffusion is possible, especially in the case of gases with very different densi-
ties, when the lighter gas enriches in the hotter regions.
There are different ways to protect the balance against aggressive gases, either by
a flow of inert gas which can be directed in different ways (see Fig. 3), or by a liquid
seal. Balances are available commercially which incorporate a magnetic coupling in
the suspension to allow a complete separation of the balance and reaction chamber.
The magnetic coupling is established by a magnet hanging at the balance, and a
suspended magnet carrying the sample. Electronic control keeps the distance of both
the magnets constant.
5. Experiment
There are four different ways of starting a thermogravimetric experiment:

Thermogravimetry 57
L inert gas
r
a1
t I I onlygases
harmless
rotating
Pump
d)
Fig. 3 Different ways of leading the gas flowsthrough reaction chamber and balance (a)-(c) at
atmospheric pressure, and (d) at a reduced pressure, established in the reaction chamber by
pumping via regulating values.
(a) moving the hot furnace over the sample which is in the reaction gas;
(b) lowering the sample into the hot reaction gas within the hot furnace;
(c) heating up the sample in vacuum or in an inert gas atmosphere and abruptly
changing to the reaction gas; and
(d) heating of the sample in the reaction gas within the furnace.
It must be realised that changes in the method are related to how the transient
state in oxidation or corrosion is passed through. In the transient state all those com-
pounds may be formed whose formation pressures are exceeded until the compounds
that are stable in equilibrium with the gas atmosphere have overgrown these which
are then replaced by the most stable phases, which are in equilibrium with the
substrate metal phase.
For mechanistic studies the procedures (a) and (b) are recommended - in both
cases the experiment is started with a clean uncorroded surface. Method (b) is ad-
vantageous since the thermal equilibrium is established faster because of the smaller
change of thermal capacity. Its experimental realisation is difficult but ways and
means have been described [ll,121. In respect of method (c), vacuum or gases such
as Ar, He, N, are not sufficiently inert since most high temperature alloying ele-
ments are oxidised by traces of 0,, H,O, CO,. . . present in such conditions. Heating
in very 'dry' hydrogen may leave the metal or alloy surfaces clean and bright if the
alloy is a chromia-forming alloy (dew point < 50°C) but not an alumina-forming
alloy. In H,, however, processes such as decarburisation, desulphurisation .. . and
evaporation of the most volatile alloying components: Mn, Cr... occur. In the case of
alumina-forming alloys there is no inert environment (except UHV) and method d)
which is most simple can be used anyway. Certain ramping rates should be attained,
e.g. 10°C m i d . Method (d) is generally applied when conditions of industrial ap-
plication are to be simulated. To obtain design data, heating may be conducted in
the reaction gas, or in air, steam, feed gas etc., as is most appropriate for the indus-
trial process. It should be noted that in many processes special conditions for heat-
ing may be used.
6. High Sensitivity Measurements
On very oxidation resistant materials, i.e. chromia-, alumina- or silica-formingma-

terials, the oxidation rates are rather low under usual conditions and high sensitiv-
ity measurements are necessary to record the mass increase. In such cases effects of
buoyancy and friction in the flowing gas atmosphere play a great role. The best way
to avoid such effects is to keep the conditions which affect buoyancy and friction as
constant as possible, i.e. density, temperature, pressure, flow rate and viscosity of
the gas. Ambient temperature and ambient pressure also play a role, since the gas
exit normally is directly to the surrounding atmosphere; atmospheric pressure
changes can thus play a role in sensitive measurements [13],since they affect the gas
density and buoyancy effect in the reaction chamber (Fig.4). To avoid such effects, it
would be necessary to keep the pressure constant at the gas exit! Another possible
method is to establish a well-controlled reduced pressure in the balance and reac-
tion chamber, by pumping the corrosive atmosphere through the system which must
then be enclosed by two adjustable valves. The pressure is to be measured continu-
ously and pressure fluctuations can be compensated by adjusting the valves. Meas-
urements at reduced pressure < 0.1 bar are of advantage anyway, since the friction in
the gas flow is significantly decreased, vibrations of the sample caused by friction
being effectively suppressed.
Thermogravimetry 59
0 100 200 300 400 5 00

reaction time [ h l
Fig. 4 Extremely sensitive measurement of mass changes; (a) errors caused by fluctuations of
atmospheric pressure - leading to changes of buoyancy in an open balance system; (b) very
sensitive, reliable measurement of the oxidation of two Ti-alloys at 650 “c measured at reduced
pressure (see Fig. 3(d)).
7. Gas
Before starting an experiment, the reaction chamber must be flushed using a suffi-
cient volume of reaction gas - at least 5 times the volume of the reaction chamber
(dead ends of the apparatus must be avoided as it takes very long periods to ex-
change the atmosphere in these regions). The gas flow rate should be sufficient to
avoid depletion of the reactant, the gas supply rate should be much higher (> factor
10) than the consumption rate, which easily can be calculated. Depletion can be a
problem especially in mixtures with small concentrations of the reactant, e.g. H,-
H,O, H,-H,S.. . .
Furthermore, diffusion from the gas flow to the sample surface must be adequate.
In most cases the gas flow will be laminar and a diffusion boundary layer is estab-
lished over^ the sample. Its thickness, and thus the diffusion transport through this
boundary layer, depends on the flow rate zj being proportional to zj,’l [lo]. To avoid
control by diffusion in the gas, in doubtful cases a check must be made to determine
whether the reaction rate depends on flow rate.
To reduce the vibration caused by friction and buoyancy effects it may be recom-
mended to use mixtures with high contents of light gases, based on H, or He (in-
stead of Ar or N2), Reduction of pressure also helps to avoid such effects and to
increase the sensitivity - this can be achieved by enclosing the reaction chamber
between two leak valves and pumping the gas flow through the system, as already
described (Fig. 3(d)). By adjusting the valves any reduced pressure can be estab-
lished in the reaction chamber.
The preparation, establishment, and control of the gas mixtures for conducting
thermogravimetric measurements is presented in Chapter 5.
8. Acknowledgement
Many valuable contributions to this topic have been supplied by W. Auer, M. J.

Bennett, E Bregani, F. Gesmundo, D. B. Meadowcroft, S. Mrowec, J. E Norton, W. J.
Quadakkers, S. R. J, Saunders, and Z. Zurek; I would like to thank them sincerely for
their help in preparing the publication in Werkstofle und Korros., 1993, 44, 345-350,
which is the basis of this chapter.
References
1. S. Mrowec and A. Stoklosa, J. Thermal Anal., 1970,2,13.
2. N. Birks and G. H. Meier, Introduction to High Temperature Oxidation ofMetals, Edward Arnold,
London, 1983.
3. J. Romanski, Corros. Sci.,1968, 8,67, 89.
4. S. Mrowec and A. Stoklosa, Werkstofle und Korros., 1970,21,934.
5. S. Mrowec and A. Stoklosa, Oxid. Met., 1974, 8,379.
6. I. Wolf, H. J. Grabke and H.-I? Schmidt, Oxid. Met., 1988,29,289.
7. S. Leistikow, I. Wolf and H. J. Grabke, Werkstofle undKorros., 1987,38,556.
8. H. J. Grabke, R. Krajak and E.M. Muller-Lorenz, Werkstofie u,Korros.,l993,44,89.
9. J. E. Rhoades-Brown and S. R. J. Saunders, Corros. Sci., 1980,20,457.
10. R. Bird, W. E. Stewart and E. N. Lightfoot, Transport Phenomena, John Wiley & Sons Inc.,
NY, 1960; E. R. G. Eckert and R. M. Drake, Heat and Mass Transfer, McGraw Hill, NY, 1959.
Thermogravimetry 61
11.W. C. Tripp, R. W. Vest and N. M. Tallan, Vacuum Microbalance Techniques, Vol. 6,
Plenum Press, NY, 1967, pp 63-73.
12. H. C. Graham, W. C. Tripp and H. J. Davis, in Progress in Vacuum Microbalance Techniques
- I (Eds T. Tast and E. Robins), Heyden & Sons Ltd., London 1972, pp. 125-143.
13. W. Auer, unpublished results.
5
Definition and Preparation of Gas Atmospheres

H. J. GRABKE
Max-Planck-Institut fur Eisenforschung GmbH, Max-Planck-Str. 1,40237 Dusseldorf, Germany
ABSTRACT
A short introduction to the kinetics of oxidation and similar corrosion processes is
given; the kinetics in special gas mixtures causing oxidation, sulphidation, carburisation
and chloridation are then described. Recommendations are given for the compositions
of reference atmospheres, simulating certain industrial environments, with a discussion
of the questions concerning accelerated testing, non-equilibrium mixtures and
equilibration, and equilibrium calculations. Furthermore, some helpful hints are given
for the preparation, purification and handling of gases and mixed atmospheres.
1. Introduction
Before discussing the special features of gases and gas mixtures that play a role in
high temperature corrosion, a short introduction to the kinetics of oxidation and
similar corrosion processes will be given. The kinetics may be controlled by different
steps:
(i) transport by the gas flow and diffusion of molecules bearing the corrosive
element X to the surface of the corroding material,
(ii) surface reaction, i.e. a dissociation reaction of molecules in which the atoms
or ions of X are liberated and incorporated into the reaction product,
(iii) growth of the scale by solid state diffusion, in most cases of cations and/or
anions, and
(iv) the transfer of metal atoms into the scale.
In textbooks [l,21 it is mainly the diffusion controlled kinetics that are described
and discussed; this is valid only when step (i), gas transport, is fast and when the
surface and interface reactions (ii) and (iv) are rapid and in equilibrium. In that case
the growth rate of the scale is inversely proportional to its thickness x and the 'para-
bolic law' results
dx/dt = k / x X' = 2 kt
Generally, thermogravimetric measurements are conducted and the mass increase

per unit area Am/A is determined for which follows
(Am/A)2 = k, . t
Definition and Preparation of G a s Atmospheres 63
a) lime
Fig. 1 Schematic drawings illustrating the transition from linear kinetics to parabolic kinetics
(ai plot of the mass gain vs time, the lower rate is rate determining, thus in the beginning the
process is described by a linear rate law and later on described by a parabolic rate law (diffusion
control). (b) behauiour of the activity of the corroding species X, in the beginning for a thin scale
the activity drop is highest at the sutface, there is only a small gradient in the scale, later on for
a thick scale the main gradient for activity is in the scale and the scalegrowth is diffusion controlled.
in the case of a solid state diffusion controlled mechanism where kp is the ’parabolic
rate constant’. However, in the beginning of any scale formation the parabolic law
cannot apply, since for x 3 0 the rate would be infinitely high, and some mechanism
with ‘linear time dependence’ will be rate controlling (Fig. l(a)),i.e.
( A m l A )= k, . t
where k, is a linear rate constant’. In most cases, the initial rate-controlling step is a
surface reaction, e.g. the dissociation of CO, or H,O for oxidation by these gases or
the dissociation of H,S for reactions involving sulphidation. (The kinetics are dis-
cussed in more detail in the second part of this chapter.) During the initial ’transient
state’ of scale growth, there is an approximate equilibrium between metal and scale,
but not between scale and atmosphere (Fig. l(b)).The activity of the corrosive ele-
ment ax is only a little lower at the metal-scale interface MeX, than at the surface,
and also the metal activity aMehas not decreased much on the surface of the corro-
sion product. However, with increasing time and thickness of the scale, ax increases
on the surface and aMe decreases (Fig. l(c)), until the equilibrium between the gas
phase and scale is (almost) established on the surface. After this, concentration gra-
dients in the scale are at a maximum and the reaction is diffusion controlled. This
transition from surface reaction to diffusion control is a gradual one, during which
the activities on the surface of the corrosion product are changing, these facts must
be taken into consideration from both the kinetic and thermodynamic viewpoints.
In recent years, the use of thermodynamic stability (ts) diagrams has become very
popular in high temperature corrosion science.These diagrams give the phase fields
where certain compounds are stable as a dependence on activities in the gas atmos-
phere, (PO,,pS,, ac etc.) e.g. oxides, sulphides, thiospinels and sulphates for one
metal or more than one metal in an alloy (Fig. 2). In this way, the composition of an
atmosphere is represented by one point in the diagram, indicating the phase@)in
equilibrium with that atmosphere. The construction of such t.s. diagrams has been
simply described [3, 41 and extended into 3D perspective diagrams in the case of
more complex environments having 3 reactants [5]. However, it must be empha-
sised that these diagrams show only the phase which is in equilibrium with the gas
atmosphere, i.e. the phase which should be present on the surface of the scale when
the situation in Fig. l(c) is reached and it should be noted, especially during the
’transient state’ that any compound for which the formation pressure is exceeded,
can be formed on the metal surface. Under (near) equilibrium conditions all phases
in the scale should lie on a line (diffusion path) drawn from the point representing
the gas atmosphere to the metal phase. However, this is only valid if there is equilib-
rium between all layers of the scale, down to the metal and if there is no scale
spallation.
Surface reaction control may prevail for long times up to layer thicknesses of sev-
eral tens of ym in C0,-CO, H,O-H,, H,S-H, mixtures and the transition to diffu-
sion control is gradual. The rate is never exactly linear in this case but decreases with
time, due to the increase of the activity ax on the scale surface. During chloridation,
in particular, transport control generally plays a role. These facts are emphasised
here since they are mostly neglected in the textbooks. More details specifically con-
cerned with the kinetics in special gas mixtures are given in the following section.
2. Thermodynamic and Kinetic Considerations of Gas Mixtures

2.1. Oxidation
Oxidation studies are often conducted in air, sometimes in oxygen at different pres-
sures ranging from high vacuum (HV) conditions -loT7 mbar 0, up to 1bar 0, and
also occasionally in mixtures of inert gases (Ar, He) with 0, In air, not only oxidation
may occur but also nitridation, especially of alloys containing A1 and/or Cr. The
content of H,O in the ambient atmosphere may play a great role in oxidation -
further details are discussed in the second part of this chapter. Oxidation under HV-
conditions may be controlled by the amount of molecules impinging on the surface
which is given by an equation from gas kinetics
j [mol s-l cm-,] = p/(2 5-t MRT)’’,
where p is the partial pressure and M the molecular mass of the gas, R the gas con-
Definition and Preparation of Gas Atmospheres 65
-30 -25 -20

log PO, Ibar)
--c log Pol Ilmrl

Fig.2 Examples of thermochemical stability diagrams. (ai Phases in the systems Cr-0-S,
Fe-0-S and Mn-0-S at 700°C. (b)Phases in the systems Cr-0-Cl, Fe-0-Cl and Ni-0-Cl at
727°C.
stant and T the temperature. The number of molecules interacting with the surface
may be considerably lower; this fact is generally described by a sticking coefficient a
5 1 (introduced as a factor at the right hand side of the equation). For experiments in
vacuum, it is necessary to check whether the number of moles impinging and inter-
acting with the oxidised surface is in fact much higher than the amount necessary
for the oxidation rate observed, otherwise control by gas phase transport is to be
expected. A similar problem may arise in flowing mixtures, such as Ar-0,, where,
again, it is important and a check must be made by calculation that the amount of 0,
provided during the experiment is much higher than the amount consumed in the
oxidation reaction; also if laminar gas flow prevails and possible control by diffu-
sion in the stagnant boundary layer around the specimen must be excluded. Experi-
mentally, this can be done by varying the gas flow rate V , in the case of control by
diffusion in the boundary layer the rate is proportional to v1I2 and becomes inde-
pendent of v at high flow rates.
Oxidation in low PO, atmospheres may be of interest for different reasons, for
example to obtain only Cr,O, on alloys such as Fe-Cr, Ni-Cr, or Fe-Ni-Cr. Such low
oxygen pressures can be established using H,O-H, or CO,-CO mixtures. The oxy-
gen pressure in a C0,-CO mixture is given by the equilibrium value for the disso-
ciation reaction
2 CO,(g) = 2 CO(g) + O,(g) (1)
po, = K , (pco,lpco)2
K, can be derived from thermodynamic data, in principle from the standard Gibbs'
free energy change AGO for the reaction (1)according to In K = - AG"/RT.
Using similar principles, the oxygen pressure in a H,O-H, mixture is given by the
equilibrium value for the dissociation reaction
PO, = K, (pH,01pH,)2
The values for PO, from the equilibria are in the range 10-15-10-30 for convenient
mixtures of C0,-CO or H,O-H, in the temperature range 700-1000°C. Accordingly,
it is easy to establish mixtures for obtaining the different phases Fe, FeO and Fe30,
in the system Fe-0 (Fig. 3(a)).It is possible also to attain the stability ranges of Fe-
Cr, Cr203,FeCr,O, in the system Fe-Cr-O using H,O-H, gas mixtures although the
dewpoint must be very low to ensure metal phase stability (e.g. for reduction at
lOOO"C, dew point < 45°C). There would be problems in using CO,-CO mixtures,
however, since these mixtures are also carburising and chromium carbides would
be formed even at rather low carbon activities ac.
It must be emphasised that the oxygen transfer from C0,-CO or H,O-H, to the
oxidised solid is not achieved directly by the very few oxygen molecules present in
these gas mixtures, even at high temperatures, but via the oxygen transfer reactions
H,O(g) = OH(ad) + H(ad)

OH(ad) = O(ad) + H(ad)
2 H W = H,(g)
The kinetics of these reactions are described by

Definitionand Preparation of Gus Atmospheres 67
vl = k, . a~"pC0,[l- a. / ( K:/2pC0, / pCO)]
as was derived from studies, mainly on FeO, using isotope exchange and resistance-
relaxation methods [6-lo]. Here k, and k, are rate constants, and a. is the oxygen
activity at the surface of the solid to which the oxygen is transferred (in case of oxi-
dation of an oxide surface).The exponents rn and n are numbers < 1 and express a
retardation of oxidation with increasing oxygen activity on the solid surface (Fig.
3(b) overleaf).(The effect is caused by participation of electrons from the oxide in the
oxygen transfer and, at lower temperatures also by a coverage with adsorbed oxy-
gen, increasing with a. [ll])During surface reaction controlled kinetics k, is con-
stant, since a. is determined by the equilibrium with the metal, this retardation with
increasing a. becomes effective during the transition from linear to parabolic kinet-
ics [12,13].
These equations can be used to describe the situation in a flowing C0,-CO-H,O-
H, mixture. If such a mixture is in equilibrium
i.e. the oxygen pressure is the same for both dissociation equilibria (1)and (2).
In the case of a non-equilibrium mixture for which the oxygen pressure from re-
action (1)would be higher than the value from reaction (2) the situation, depicted in
Fig. 4(a) results [14, 151. A steady state is established for the oxygen activity at an
activity where the rate of oxygen transfer due to reaction (1)is equal to the rate of
oxygen removal by reaction (2). Since k, >> k, [7,10], the steady state is nearer to the
oxygen activity corresponding to the equilibrium of reaction (2) than to the value
corresponding to the equilibrium of reaction (l),(for the precondition that the par-
tial pressures of the gases involved are comparable).If experiments are conducted in
C0,-H, mixtures, as some authors have, the steady state value of oxygen activity
would be expected to be much lower than the value expected for equilibrium, due to
the fast kinetics of reaction (2)!
The question may arise as to whether CO,-CO and H,O-H, gas mixtures must be
equilibrated with respect to their 0, content in order to obtain relevant oxidation
data? For the CO,-CO mixture the reactions to be considered are:
Data for reaction (3'), the oxygen transfer from molecular oxygen into solid ox-
ides, were obtained from resistance-relaxation measurements on Cu,O and NiO.
a)
Fig. 3 Studies of oxygen transfer in C0,-CO and H,O-H, mixtures. (a) Equilibria in the system
Fe-FeO-Fe,O, in dependence on the C0,-CO ratio and the H20-H2 ratio. (b)Measurements of
the oxygen transfer in C0,-CO and H,O-H, mixtures at different temperatures plotted us the
C0,-CO resp. H,O-H, ratio.
The rate constants are relatively high compared with the values for k, and k, [ 9 ] .
However, due to the very low equilibrium pressure, p 0 , = 10-20-10-30bar, in a C0,-
CO mixture the rate of oxygen transfer would be negligible in an equilibrated mix-
VI = k, 00" pco, ( 1 - -O-

D 1
\ K :I2 P,,(P,
0 is
111
&-- surface oxygen
OCtlVlt 0
4 pco,~pco
Fig. 4 Schematic drawings, demonstrating the attainment of steady-state at the surface of a

solid, (a)for the oxygen activity in aflowing C02-CO-H20-H2-mixture, i.e. for the water-gas
shift reaction C O , + H2 = C O + H 2 0 , and (bifov the carbon activity in ajlowing mixture of
CH4-H2-H,0, i.e.for the conversion of methane: C H , + H,O = C O + 3H,
ture. In the non-equilibrium mixture, CO,-CO without 0,, reaction (3) would occur
only in the reverse direction. However, due also to the very low equilibrium pres-
sure PO, characteristic of the oxide surface, the oxygen desorption rate would be
negligible [16]. Accordingly, C0,-CO and H,O-H, mixtures need not be equilibrated
for oxidation studies, in which the equilibrium oxygen activity on the oxide surface
can be assumed -there is even less reservation using H,O-H, since the kinetics for
oxygen transfer from H,O are much faster than from CO,.
It must be emphasised again that oxidation in CO,-CO or H,O-H, may be broadly
controlled by surface reaction kinetics, i.e. oxygen transfer is described by the rate
equations for u1 and u2 already given, in a wide range of time, temperatures and gas
compositions. Although a number of authors have assumed solid state diffusion
controlled kinetics for oxidation in C0,-CO or H,O-H,, in reality, in these gas mix-
tures surface reaction control and ’linear kinetics’ can prevail for long periods in-
volving thick oxide layers. The ‘linear kinetics’ are not exactly linear, but due to the
effect of increasing a. on the oxide surface the oxidation rate gradually decreases
[12,13].The rate decreases until the oxygen activity at the surface corresponds closely
to that in the gas atmosphere, following which the reaction is controlled solely by
diffusion in the oxide layer. This transition from surface reaction controlled ’linear
kinetics’ to diffusion controlled parabolic kinetics is faster for H,O-H, than for C0,-
CO mixtures, due to the faster kinetics of oxygen transfer by H,O. These facts must
be always kept in mind when using C0,-CO or H,O-H, mixtures for oxidation.
Effects due to surface reaction control are quite self-evident and natural and must
not be complicated by assuming special effects due to dissolution or adsorption of C
or H from these gas mixtures [17].
In general, for oxidation by 0,, surface reaction control need not be considered,
since the adsorption and dissociation of 0, appears to be a fast process on most
oxides [9]. However, this simple statement should not be taken as absolute, since on
insulating oxides such as A1,0, the ionisation of O(ad) may be retarded.
2.2. Sulphidation
Sulphidation of metals has frequently been studied in sulphur vapour S,(g), and
because of its high aggressivity quartz spring balances have so far been used [18,
191. Sulphidation at lower sulphur pressures pS, is of great interest since in many
industrial processes, e.g. coal and residuals gasification, H,S and COS can occur in
concentrations up to about 1 vel.%. For sulphidation in H,S-H, mixtures the sul-
phur partial pressure results from the dissociation reaction
Since pS, in many processes is in a range of pressures about < atm, both
sulphur transfer reactions must be considered (in contrast to the C0,-CO and H,O-
H, mixtures) from H,S and S,
Definition and Preparation of Gus Atmospheres 71
It is particularly important to realise that if equilibria are to be studied, the
desorption of S, from the specimen would falsify the state of the solid [16] since the
steady state may correspond to a lower sulphur activity in non-equilibrated H,S-H,
than in an equilibrated mixture.
Concerning kinetics, in H,S-H, mixtures the surface reaction will be rate control-
ling anyway over a wide range of conditions and for long periods and thick sul-
phide layers [20-231, since the surface reaction rate (Le. the H,S dissociation) is slow
and the diffusion in most sulphides is fast. For sulphidation of iron with formation
of FeS the following kinetic equation has been found [23]
This equation indicates a strong retardation of sulphidation with increasing sul-

phur activity as on the surface of the growing sulphide. The decrease of the ’linear’
rate with increasing reaction time, sulphide thickness and sulphur activity on its
surface may be misinterpreted as a ’parabolic behaviour’. In fact, (in some cases)
sulphidation measurements on iron have been misinterpreted and parabolic con-
stants k have been calculated from experiments in which the preconditions for para-
bolic diffusion-controlled kinetics were obviously not fulfilled [24].
Corrosion under combined oxidation and sulphidation conditions has been in-
vestigated in COST 501 research programmes on materials for coal gasifiers. In these
early programmes H,-H,O-H,S mixtures have been used [25]. For such mixtures
PO, is fixed by the H,O/H, ratio according to eqn (2) and the pS, by the H,S/H,
ratio according to eqn (4). The resulting values of PO, and pS, lay in an area of the
thermochemical stability diagram where formation of a protective Cr,O, might have
been expected (Fig. 3). However, if the chromia-forming alloys were exposed to the
H,-H,O-H,S mixtures, simultaneous growth of oxides, Cr,O, and spinels, and of
sulphides (Fe,Cr)S,Cr,S, etc. was observed [25-301. With increase in pH,O with re-
spect to PO, the sulphide growth was gradually suppressed. In the literature a ‘ki-
netic boundary’ was delineated, a line in the thermochemical stability diagram, cor-
responding to the oxygen pressures necessary to suppress sulphidation. This kinetic
boundary is generally situated at oxygen pressures 2-3 orders of magnitude higher
than the thermodynamic boundaries between Cr,O, and the Cr-sulphides. There
has been much discussion concerning this kinetic boundary, but the explanation is
obvious. The simultaneous growth of oxides and sulphides on a blank metal surface
is to be expected. Since this situation is far from being in equilibrium with the at-
mosphere (transient state) all oxides and sulphides for which the formation pressure
is exceeded can grow. The sulphides can grow to considerable thicknesses (due to
their high concentration of defects and diffusivities) before the metal activity at their
surface decreases to a value at which further sulphide formation cannot take place
and only oxide formation is possible. At this stage the sulphide becomes overgrown
[26]. During simultaneous growth, the ratio of oxide to sulphide formation depends
on the ratio of oxygen transfer from H,O to sulphur transfer from H,S. Thus, with
increasing H,O/H,S ratio the amount of sulphide in the scale diminishes and even-
tually becomes negligible - at the kinetic boundary [29,30].
Since it is difficult to suppress sulphide growth when starting with a blank metal-
lic surface, many oxidation and sulphidation studies have been conducted on
preoxidised samples. Even after preoxidation, however, scale failure was observed
to occur by two mechanisms:
1. Internal sulphide formation by sulphur transport through the scale and,
2. External sulphide growth by outward diffusion of cations (Fe2+,Mn2+ N i2+)

I
through the chromia and spinel scale [29,31,32].
Thus, the consequence was that no conventional commercial high temperature

alloy is sufficiently resistant to oxidation-sulphidation at high temperatures > 600°C
and consequently the heat exchangers of coal gasification plants are generally oper-
ated now at < 400°C using low alloy steels.
In SO,-containing atmospheres the equilibrium sulphur partial pressure is given
by the reaction
In pure SO, or mixtures of SO, and inert gases oxidation as well as sulphidation is
possible, as a result of the above equilibrium, and in several studies the simultane-
ous growth of oxides and sulphides has been observed [33,34]. If SO, diffuses through
defective oxide scales and reaches the oxide/metal interface, then the PO, corre-
sponds to the equilibrium value at that interface which may be very low, leading to
very high pS, values. Accordingly, in flue gases containing SO, strong internal
sulphidation has been seen with sulphides observed which should not have formed
during exposure to the oxidising atmosphere. Another reaction equilibrium is of
importance for flue gases
because the formation of SO, is of critical importance in corrosion by molten sul-

phates (hot corrosion).In studies where sulphates can form or are present as depos-
its it is very important to equilibrate gas mixtures containing 0, + SO, by a Pt cata-
lyst, to obtain the right thermodynamic conditions.
2.3. Carburisation
Carburisation without oxidation can be studied in CH,-H, mixtures. Oxidation of
chromia-forming alloys can be avoided, if the gases are sufficiently dry, but this is
not possible for alumina-forming alloys where oxidation will occur. The carbon ac-
tivity of a CH4-H, mixture results from
The carbon activity is generally defined by a, = 1 for equilibrium with graphite,

i.e. at higher values ac > 1 carbon deposition is possible. At lower values ac < 1
carbon is dissolved into the metal matrix and internal carbide formation occurs. For
Cr containing alloys the carbides M,3C, and M,C, are formed in successive layers
and, in higher Cr-containing alloys, Cr3C2may also form. The internal carbide for-
mation should be diffusion controlled and can be described by
where x is the penetration depth, D, and cc the diffusivity and solubility of carbon
and cM the concentration of the alloying elements forming the carbides MC, [35,36].
However, due to the sluggish kinetics of CH, decomposition which is slow even at
metal surfaces at about lOOO"C, control by surface reaction kinetics occurs, for the
initial period of carburisation [36]. The slow kinetics of reaction (7) also leads to
incorrect carbon activities, if the gases are not sufficiently dry. The interplay of car-
burisation
and decarburisation by H 2 0
yields a steady state where a, << ( Q ) (i.e. the carbon activity calculated for overall
equilibrium) [37] even at some ppm H 2 0in the flowing CH4-H,-H,O mixture (Fig.
4@), p.69).
Carburisation also has been investigated in the 'pack carburisation test'. The sam-
ples are packed with active charcoal in a steel box, and heated to the testing tem-
perature. The air in the free space of the pack reacts with carbon to produce CO and
CO, and the carburisation occurs by the Boudouard reaction
2 CO(g) = CO,(g) + c (8)
However, the C0,-CO mixture is also oxidising and most materials are oxidised
so that the test, in fact, assesses the protectivity of the oxide layer, which in most
cases is a spinel or chromia layer. At temperatures of about 1050-1100°C the ratio
CO,/CO, i.e. the oxygen activity in the pack decreases to values at which Cr,03 is
converted to carbides Cr,C2 or Cr,C3 (Fig. 5 ) and the protective oxide layer is de-
stroyed [35]. Consequently, at a testing temperature of 1100°C the carbon ingress is
L,
950 1000 1050 1100 OC
Fig. 5 Change of the C0,-CO ratio in pack carburisation with increasing temperature, at about
1050-21OO0C and 1 bar total pressure, the line of equilibrium is crossed for the conversion of
Cr,O, in the carbides Cr,C, and Cr,C,.
mainly controlled by diffusion and the internal carbide formation is governed by

the product Dccc as given above. The results of such a test at 1000°C reflect the
dependence of this product on the Fe and Ni content of the metal matrix, remaining
after precipitation of the chromium carbides [35,38]. Only in cases where the alloys
tested contain 1.5-2% Si is it possible for an inner SiO, layer to form beneath the
Cr,O, layer thereby conferring continued protection, even at temperatures > 1050-
1100°C [39]. Researchers using the pack carburisation test should realise which ac-
tual information they obtain from this test!
Carburisation can also be investigated in CO-H,-H,O mixtures, in this case the
carbon activity results from
uC = & pC0. pH, /pH,O
The kinetics of this reaction are very fast [40-42] so there are generally no prob-
lems with rate controlling surface reaction kinetics. The gas mixture is oxidising and
chromia- or alumina-forming alloys will be oxidised in a wide range of conditions.
In CO-H,-H,O mixtures with ac > 1the corrosion phenomenon 'metal dusting' can
easily be generated [43-47]. This phenomenon is observed in a temperature range
between 350 and 800°C on Fe-, Ni- or Co-base materials, which are converted into a
carbon dust containing finely dispersed metal particles.
The atmospheres in which metal dusting was observed, have carbon activities of
up to lo3 at low temperatures if calculated for the equilibrium of reaction (9). These
carbon activitieswith ac >> 1are in fact thermodynamic values calculated for a non-
equilibrium atmosphere indicating the tendency to dump carbon, to solid solution
in metals or as graphite. Such values, indicating the oversaturation of the atmos-
pheres, are much higher than oversaturations in other cases, e.g. aqueous solutions,
but in principle they are corresponding to such data.
An oversaturation of lo3 may be difficult to envisage but the gaseous atmosphere
is indeed oversaturated with regard to solid graphite, which nucleates with diffi-
culty, even at solid surfaces and much less in the homogeneous gas. Carbon is rap-
idly transferred into alloys from such atmospheres, if their surface is not protected
by oxide scales, the carbon transfer leading to formation of unstable carbides in the
Fe-base alloys and graphite precipitation in Ni-base alloys. The decomposition of
the unstable carbides leads to metal dusting in the case of Fe-base alloys and the
graphite growth causes a similar disintegration of Ni-base alloys.
Chromia-forming steels are sensitised to attack by metal dusting after annealing
at high temperature in H, and electropolishing [45].Such pretreatments lead to large
grained alloys free of near-surfacedeformation,and thus without fast diffusionpaths
for Cr. If no protective Cr203is formed, metal dusting starts immediately on the
whole surface, otherwise it commences only at defects of the scale where pits are
formed.
2.4. Chloridation
The sources of chlorine in coal or waste incineration are resp. minerals in the coal
and HC1 formed from chlorine containing polymers (PVC) in waste combustion.
The chlorides can react directly with oxide scales, e.g.
The hydrogen chloride can dissociate
which leads to relatively low pC1, in reducing atmospheres or it may react with oxy-
gen
which may give very high C1, pressures in oxidising atmospheres [48,49].
The latter reaction is catalysed by oxides and takes place at the surface of oxide
scales. The chlorine generated by the reactions (10) and (12) at the scale surface very
easily penetrates to the oxide/metal interface, where at low oxygen activity metal
chlorides are formed [50-531.Chloridation has several special aspects: the corrosion
products, i.e. the chlorides have a relatively low melting point and a high volatility.
Volatile chlorides can be formed at any chlorine pressure, because in contrast to the
formation of solid corrosion products no formation pressure must be exceeded. The
equilibrium pressures of the chlorides formed depend upon the pC1, in the case of
the reaction of a metal
Me(s) + x/2 Cl,(g) = MeCl,(g) (13)
and on pC1, and PO, in the case of the reaction with an oxide
MeOy(s)+ x / 2 Cl,(g) = MeCl,(g) + y/2 0, (14)

Diagrams of these equilibria are given in Fig. 6.
If the formation pressure of a condensed chloride MeC1, is exceeded, liquid or
solid chloride is formed, as described above, often at the oxide/metal interface. In-
ternal chloride formation does not occur since chlorine does not dissolve in metals,
but attack of carbides along grain boundaries is observed. The chlorides at the ox-
ide/metal interface continuously evaporate and the evaporating chloride, mainly
FeCl,, is oxidised on its way to the surface thereby liberating C1, again. Thus, chlo-
rine catalyses an ’active corrosion’ which leads to loose non-protective oxide scales
[50-521.
The kinetics of chloridation in most cases are controlled by transport, either by
diffusion of C1, or HC1 through the diffusion boundary layer to the reacting oxide or
metal, or by outward diffusion of the volatile corrosion product [51].The latter case
is often valid, also for the ’active corrosion’ where the outward diffusion of the metal
chloride (mostly FeC1,) through the porous scale is rate determining. The diffusion
is described by Fick’s first law
where D iis the diffusivity of the chloride, pi” its pressure at the interface and p i its
pressure in the atmosphere ( p i E 0), 6 is the diffusion path and E a labyrinth factor
which considers the reduction of free surface by oxide in the case of ’active oxida-
tion’. The pressure p/may be a saturation vapour pressure, in the case of presence of
a condensed chloride, or it can be an equilibrium pressure in the case of formation of
a volatile chloride according to reaction (13)or (14).
Formation of a solid chloride and its continuous evaporation leads to the so-called
Tedmon kinetics or paralinear rate law [54]
0)
- 15 -10 -5
Iq pn2 latml -
0
Fig. 6 Thermodynamic diagrams demonstrating the partial pressures of volatile chlorides MeCl,
in dependence on chlorine pressure. (a)for the reaction of metals with chlorine, (b)for the reaction
of oxides with chlorine at 1000 K and PO, = 0.2 bar.
describing the diffusion controlled parabolic growth of the solid chloride and the
linearly time dependent evaporation. The scale grows to a constant thickness, at
which time the growth rate and evaporation rate are equal (see Fig. 7), then the mass
of the sample starts to decrease. Such kinetics are also observed in simultaneous
oxidation and chloridation, when a protective oxide layer is growing and simulta-
neously volatile chloride is formed at the oxide surface [53].
v metal recession
time -
moss change
Fig. 7 Paralinear kinetics (Tedmon kinetics), i.e. the simultaneous growth of the scale and
evaporation of a volatile chloride.
3. Reference Atmospheres
In research studies simple gas mixtures have generally been used to elucidate the
mechanisms of corrosion involving single reactions, e.g. oxidation, sulphidation,
carburisation etc., or of simultaneous reactions, e.g. sulphidation or carburisation
which are affected by the presence of oxidising components. In testing of materials
for specific applications, laboratories have often tried to closely simulate the indus-
trial atmospheres by including all components. Here, another approach is proposed
in which a selection of reference gases (reported in Table 1)is identified for testing
materials under conditions which are closely related to certain environments. The
gas mixtures are simplified and standardised in order to allow interlaboratory com-
parisons. Producers of materials are particularly interested in such reference atmos-
pheres in order to test their products for certain applications and to have the possi-
bility for a materials-ranking. The reference gases presented in the table do not cor-
respond exactly with the application environments, but are intended to produce
similar corrosion phenomena and rates.
Some comments are necessary as an explanation and in order to justify these sim-
plified compositions.
In atmospheres (A),( B ) and (C), in which the main component is air, the ratio O,/
N, has no great influence on the oxidising or nitriding power. H,O should be added
since it is present in all applications and has a distinct influence on the morphology
of scales and oxidation kinetics of steels. The presence of H,O is important, less so its
partial pressure, and therefore it is convenient to use 2-3% H,O which corresponds
to the saturation pressure at room temperature. Thus it is not necessary to heat the
Table 1. Set of recommended testing atmospheres and temperatures
Environment Composition Temperature

A. Air air, 2.5% H,O 450-1200°C
B. Fluegas air, 2.5% H,O, O.l-l%SO, 400-1000°C
C. Waste incineration air, 2.5% H,O, O.l-l%SO,, 0.05-0.1%HC1 400-850°C
D. Sulphidising environment 0.1-1% H,S, balance H, 300-600°C
E. Carburising environment 1%CH,, balance H,, dew point 4 5 ° C 800-1100°C
F. Nitriding environment 90% N,, 10% H,, dew point 45°C 800-1300°C
G. Metal dusting environment 25%co,73% H,, 2% H,O 350-750°C
H. Coal gasification (wet) 0.1-lo/~H,S, 5% CO, 2.5% H,O, bal. H, 400-700°C
I. Coal gasification (dry) 0.1-1Yo H,S, 70% CO, 2.5% H20, 25% H, 400-700°C
J. Waste gasification (pyrolysis) 90% H,O, 5% H,, 5% CO, 0.1% HCl, 0.05% H,S 400-700°C
supply lines which conduct the gas to the reaction chamber. In these atmospheres
carburisation is no problem and the addition of CO, is superfluous. Waste incinera-
tion atmospheres generally contain also traces of HF, NO, and CO, but these can be
omitted from the model atmospheres, since no significant effects of them have ever
been reported (at high temperatures!). However, it must be emphasised that corro-
sion below deposits (fly ash) is decisive in heat exchangers of waste incineration
plants - ranking tests should therefore be conducted in such atmospheres but be-
low deposits collected from the waste incineration plants.
The following reducing sulphidising and carburising environments ( D ) and (E),
occur in the chemical and petrochemical industry, the nitriding conditions ( F ) occur-
ring in industrial furnaces with protective atmospheres. Sulphidation cannot be sup-
pressed in low PO, atmospheres, thus it is necessary to fix the H,O-content not at 2-
3% H,O but according to the actual conditions. The atmospheres (E) and (F) are
carburising and nitriding respectively without retardation by an oxide scale -thus
the conditions are very critical and the approach is somewhat questionable. The
following atmosphere, (G), has been used in testing the resistance of alloys against
metal dusting [4347], a catastrophic form of carburisation. The gas mixture is not
oxidising to low alloy steels but is to chromia-formingsteels. However, the latter can
be sensitised by annealing in H, and electropolishing so that the chromia formation
is widely suppressed. Metal dusting is mainly a problem in synthesis gas produced
by methane reforming. Such atmospheres mostly contain CO, which can be omitted
or compensated for by somewhat raising the H,O content of the testing gas. In any
case, the rate of metal wastage by metal dusting is independent of the gas composi-
tion anyway [46], the only precondition for the occurrence of this process is that ac >
1,only the amount of carbon dumped in the corrosion product depending upon the
gas composition.
Atmosphere (H) was conceived to simulate the corrosion in gases from coal gasi-
fication using steam. However, nowadays dry gasification with oxygen or air is gen-
erally applied and this process leads to an atmosphere which is mainly sulphidising
and may be represented by the gas mixture (I) where the inert component, N,, has
been omitted. Pyrolysis of waste is not a technology which is widely applied as yet.
However a representative composition is given as gas mixture u) -it may be noted
that the corrosion in such a mixture is not very severe.
Some general remarks are necessary concerning accelerated testing and non-equi-
librium conditions with regard to the application and testing with these atmos-
pheres.
It must be emphasised that, generally, there is no value in accelerated testing. It is
suggested that the concentrations of the most aggressive components should be set
to average values in order to allow better comparison of laboratory data with plant
data and thereby provide greater confidence in the extrapolation of laboratory tests.
With this in mind, no H,S, SO, and HC1 levels should be used in testing which ex-
ceed those occurring in practice. Also, the temperatures of testing should not be
raised above those which are of practical interest.
Process atmospheres, in coal gasification or waste incineration plants are often
generated at high temperatures and are therefore not in equilibrium when passed
over the heat exchangers, which are at much lower temperature. In practice, at the
high gas flow rates and with relatively cool metal and scale surfaces there is not
much interaction between the gas components and the high temperature composi-
tion can be considered as ‘frozen in’. On the tube walls steady state conditions will
be established (see Section 2 of this chapter) regarding oxygen and sulphur activities
etc. and it serves no purpose to try to equilibrate the gas mixtures. In addition, many
atmospheres will not be in equilibrium with regard to the carbon containing compo-
nents. CH, is virtually inert and does not react, either by homogeneous reaction in
the atmosphere below 1000°Cor by heterogeneous catalysis at surfaces below 700°C.
CO should decompose with decreasing temperature and rising ac - although this
does not usually occur on oxide surfaces and in the absence of metallic surfaces
(then metal dusting occurs!).
Since such ‘frozen in‘ atmospheres are not in equilibrium at the temperatures
where they meet the walls of heat exchangers, it is of no great value to calculate the
overall equilibrium!Although there are excellent computer programs available nowa-
days which make it easy to calculate the equilibrium composition for any atmos-
phere, it is more reasonable to consider partial equilibria of the fastest reactions. For
example, the oxygen activity will be closer to the value established by the H,O/H,
than to the value corresponding to the CO,/CO ratio (as explained in Section 2 of
this chapter).The carbon activity will be established mainly by the reaction (9) of CO
+ H,, since the Boudouard reaction (8) and the carburisation by methane (7) are
negligible at moderate temperatures.
A good technique for determining steady state activities in flowing atmospheres
was proposed by Norton [ 5 ] ,in which certain metals or oxides are inserted, along
with the test materials, so that after a given exposure time the various phases formed
by interaction with the atmosphere under actual conditions can be established. One
may try to measure steady state activities, e.g. the oxygen activity by using a solid
electrolyte cell -however, the Pt electrodes of such cells catalyse equilibration reac-
tions and therefore the measured value forao will not be representative of the steady
state on the corroding tube walls.
The limitations inherent in theoretical applications of thermochemical stability
diagrams must be clearly appreciated - they are of no great use in many cases in
industrial environments where non-equilibrium conditions arise - this relates not
only to non-equilibrium in the gas phase but also to non-equilibrium at the surface
of the corrosion products. For example, under conditions of surface reaction control-
led linear kinetics, simple thermochemical stability diagrams are insufficient - see
the case of the ’kinetic boundary’.
4. Preparation of Gas Atmospheres
Most laboratories use flow apparatus, in which the gas components are passed
through cleaning devices and then through flow meters, after which the gases are
combined and the mixture is conducted to the reaction chamber for thermogravimetry
or exposures.A mixing chamber is not necessary because diffusivitiesin gases are so
high that complete mixing is attained immediately in the joint flow. Capillary flow
meters are being used (Fig. 8) which can easily be calibrated with a soap bubble flow
meter, i.e. a burette through which a soap bubble is carried by the gas flow. Nowa-
days, electronic mass flow meters are available for control and measurement of gas
flows. Several laboratories use premixed gases which can be obtained from external
suppliers. However, it is necessary to control these mixtures, since incomplete mix-
ing is possible and also adsorption and reaction of components such as H,S and HC1
on the steel walls of the tanks can occur.
electronic
m i c r o balance
exhaust J
---
resistance
furnace
;ilica or
ilumina t u b e
Fig. 8 Schematic drawing of an experimental set comprising a flow apparatus for mixing two
gases over capillaryflow meters and an electronic microbalance for measuring the mass increase
by corrosion.
Generally, the companies delivering gases offer very pure qualities, however, for
certain experiments and tests, additional cleaning is necessary. The O,-content in
inert gases and H, can be reduced by passing the gas through Oxisorb* (CrO,), over
active copper catalyst in a ’copper-tower’or even more effectively over Ti-sponge at
elevated temperature. For having an inert or ’reducing’ atmosphere it is necessary
also to remove the H,O content, which can be done by drying agents ranked accord-
ing to their effectiveness in Table 2.
It must be noted that acid gases (H,S, CO,) cannot be dried using basic drying
agents, neither can basic gases (NH,) with acid drying agents. A very effective way
of drying is to pass the gas through a trap cooled with liquid N,, filled with glass
beads or silicagel grains in order to avoid the ‘snowstorm’effect, i.e. avoid ice crys-
tals being carried through the trap by the gas flow. A special situation exists for CO
which must be cleaned of iron carbonyl formed by reaction with steel surfaces, it is
easily adsorbed in a trap with silica gel.
Water vapour is usually added to the gas flow by passing one partial flow or the
complete gas mixture through a temperature-controlled humidifier. In order to at-
tain the saturation pressure it is necessary to bubble the gas through a frit which
produces very fine bubbles which pass a sufficiently long distance through the wa-
ter bath. The humidifier must have two additional volumes, before and after the
bubbler, in order to prevent water flowing back and to trap droplets. To obtain rather
low, well defined water vapour pressures, it is possible to pass the gas over ice in a
cryostat or to pass H, over a metal/oxide mixture, but also saturation over oxalic
acid dihydrate gives very exact low pH,O values [55].
H,S dosing at low concentrations can be done by mixing two-component gas flows,
e.g. H, + 1%H,S with a higher gas flow of H,. Passing H, over mixtures of a metal
and its lowest sulphide, e.g. Fe + FeS or Cr + CrS also gives very precise H,S/H,
ratios which can be calculated from the thermodynamics of the respective system.
The dosing of HC1 can be done by bubbling a partial or total gas flow through hy-
drochloric acid. The water vapour also taken up can be removed afterwards by dry-
ing, for example with P,O,. Diagrams of the dependence of pHCl of hydrochloric
acid on concentration and temperature are available, however, it has been suggested
that for some reason the exact dosing is not possible and must be checked and con-
trolled.
Control of the exit gases may be necessary in several cases so as to check the level
of dosing with small amounts of SO,, H,S, HC1 etc. and also to measure the con-
sumption of the corroding gases which should not be too high, if depletion and
concentration differences over the specimen are to be avoided. Analyses are possible
by wet chemical determination after absorbing the critical component at the outlet
P,O, Mg(ClO,), KOH A1,0, H,SO,(conc.) CaO CaCl,
3.10-5 7.104 3.10-3 4.10-3 4.10-3 0.3 2

of the reaction chamber in an appropriate solution for some time. Continuous con-
trol is possible using a gas chromatograph or other physical methods of gas analysis.
5. Acknowledgement
I would like to thank F. Gesmundo, J. Klower, D. B. Meadowcroft, J. E Norton, W. J.

Quadakkers, H. P. Schmidt, and Z. Zurek for many valuable contributions to this
topic.
I am especially grateful to J. E Norton and E Gesmundo, who have carefully read
the manuscript and made many corrections and important improvements.
References
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London, 1983.
2. P. Kofstad, High Temperature Corrosion, Elsevier Applied Science, London & New York, 1988.
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8. A. Gala and H. J. Grabke, Arch. Eisenhutt., 1972,43,463.
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20. S. Wegge and H. J. Grabke, Werkstofle u. Korros., 1992,43,437.
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28. D. S. Williams, R. Moller and H. J. Grabke, Oxid. Metals, 1981,16,253.
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31. R. E. Lobnig, H. J. Grabke, H.-P. Schmidt and K. Hennesen, Oxid. Met., 1993,39,353.
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38. S. K. Bose and H. J. Grabke, Z. Metallkde., 1978,69,8.
39. W. Steinkusch, Werkstoffe u. Korros., 1979,30,837
40. H. J. Grabke and G. Tauber, Arch. Eisenkuttenwes., 1975,46,215.
41. H. J. Grabke, Arch. Eisenhuttenwes., 1975,46,75.
42. S. Shatynski and H. J. Grabke, Arch. Eisenhuttenwes., 1978,49,129.
43. J. C. Nava Paz and H. J. Grabke, Oxid. Metals, 1993,39,437.
44. H. J. Grabke, R. Krajak and J. C. Nava Paz, Corros. Sci., 1993,35,1141.
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46. H. J. Grabke, C. B. Bracho-Troconis and E. M. Muller-Lorenz,Werkstoffe u. Korros.,1994,45,
215.
47. H. J. Grabke, Corrosion NACE, in press, 1995.
48. P. L. Daniel and R. A. Rapp, 'Halogen corrosion of metals', Adv. Corros. Sci. Technol. 1976,5,
55.
49. H. J. Grabke, Fundamental mechanisms of the attack of chlorine, HC1 and chlorides on
steels and high temperature alloys, in Incinerating Municipal and lndustrial Waste (Ed. R. W.
Bryers), Hemisphere Publ. Corp. 1991, p. 161-177.
50. D. Bramhoff, H. J. Grabke, E. Reese and H. P. Schmidt, Werkstoffe u. Korros., 1990,41,303.
51. E. Reese and H. J. Grabke, Werkstofe u. Korros., 1992,43,547.
52. E. Reese and H. J. Grabke, Werkstofe u. Korros., 1993,44,41.
53. D. Bramhoff, H. J. Grabke and H. P. Schmidt, Werkstofe u. Korros., 1989,40,642.
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Corrosion in the Presence of Melts and Solids
S. R. J. SAUNDERS
Division of Materials Metrology, National Physical Laboratory, Queens Road, Teddington,
Middlesex, Twll OLW, UK
ABSTRACT
Test methods for deposit-induced corrosion by either molten or solid materials are dis-
cussed. While very little work has been carried out to develop standardised tests for
these conditions, some progress has been made for the case of gas turbine hot-salt cor-
rosion. The results of a round-robin test on the evaluation of burner rig testing for the
assessment of hot-salt corrosion resistance are reported. It is concluded that where tests
are conducted in burner rigs of different design, control of contaminant flux through
the rig is an important parameter to achieve some degree of reproducibility between
the different test facilities. Deposit-induced corrosion in power station boilers, fluidised
bed combustors and ethylene crackers is also reviewed and the progress toward stand-
ardisation of test methods considered. It is concluded that simulation of the deposit
structure, composition and deposition rate are essential features of tests, and other pa-
rameters such as heat flux, gas atmospheres control, equilibration and catalytic effects
are also important. Guidelines for test design are proposed, but it is considered prema-
ture for standardisation for many procedures without carrying out some prenormative
research.
1. Introduction
High temperature corrosion under conditions where deposits form is a common

feature of many industrial plants, particularly where fossil fuels are burnt or in the
petrochemical industry. Depending on the operating conditions, the deposits that
form may be solid or molten, and generally the latter results in much more severe
attack. Because of the industrial importance of this form of corrosion, it has been the
subject of intensive research over a period of cu. 50 years. While this has resulted in
considerable advances in our understanding of the mechanism of this phenomenon,
it is perhaps surprising that there remain considerable difficulties in establishing
tests that find general acceptance. However, as will be demonstrated, when one con-
siders the complexity of the corrosive environments, it is perhaps less of a puzzle.
Deposit-induced corrosion occurs in coal- or oil-fired power stationsboilers, waste
incineration plant, gas turbine and diesel engines, coal gasification plants, fluidised
bed combustors, glass recuperators and petrochemical plants (ethylene crackers, for
example).Gas turbine and power station boiler corrosion have been the most exten-
sively studied, and, for the former, significant attempts have been made to develop
acceptable test procedures and recent progress is described below. Also, this paper
will consider some of the other industrial applications, describing, briefly, the corro-
sive environment and the currently understood mechanism of attack so that some
guidance can be given about the parameters that must be considered when design-
ing test procedures for deposit-induced attack. Thus the paper is considered in two
parts, the first gives a detailed account of work to establish guidelines for hot-salt
corrosion testing relevant to the hot stage of gas turbines, and the second part con-
siders some other typical forms of deposit-induced attack and draws together some
common strands to establish guidelines for testing.
2. Hot-Salt Corrosion Testing
Hot-salt corrosion is a phenomenon that results when materials are exposed to com-
bustion gases contaminated with sulphur and alkali metal salts. These contaminants
combine in the gas phase to form alkali metal sulphates, so if a component is ex-
posed at a temperature below the dew point of the alkali metal sulphate vapours
and above their melting point, molten deposits of the sulphates form on the compo-
nent. These circumstances are common for gas turbine engines. In the gas turbine
two forms of attack have been identified both of which involve dissolution (fluxing)
of the normally protective oxide scale by the molten sulphatic deposit. Type 1corro-
sion involves general broad front attack with internal sulphidation which occurs at
temperatures above cu. 8OO"C, and Yype 2 corrosion results in pitting attack where
sulphides are found within the pitted area and this form of attack occurs around
700°C. The two forms of corrosion are associated with different basicities of the mol-
ten sulphate deposit which are controlled by the gas composition -principally the
partial pressure of sulphur trioxide, pS0,. At high temperatures, above cu. 8OO"C,
where p S 0 , is relatively low, basic fluxing occurs, and at low temperatures, cu. 700"C,
where p S 0 , is relatively high, acid fluxing takes place [ 1,2].
Various tests have been used to assess corrosion resistance which include:
(i) a simple furnace test where a simulated deposit is placed on the sample and
replenished [3,4], and the gas atmosphere is either air, or, better, a controlled
partial pressure of SO,/SO,;
(ii) a Dean test, in which Na,SO, is heated to above cu. 1100°C to establish an
appropriate vapour pressure and the sample is maintained at a temperature
below the dew point where condensation occurs and again the partial pres-
sure of SO,/SO, in the furnace atmosphere should be controlled [5];
(iii) electrochemical tests involving immersion in the molten salt while monitor-
ing electrochemical parameters [6-81; and
(iv) burner rigs in which fuels are burnt to closely simulate operating conditions
[9-111.
There have been various attempts to compare the different test methods used,
and the earliest of these was a round-robin test initiated by the ASTM in 1970 [12], in
which six uncoated alloys were exposed between 884-1079°C for 100 h in burner
Corrosion in the Presence of Melts and Solids 87
rigs of different design in a set of conditions largely selected by the operator. The
relative ranking of alloy performance was generally in agreement, although there
were some notable exceptions. Of more concern was that there was at least an order
of magnitude range in the measured corrosion rates; a summary of the results of this
work is given in Ref. [9].The ASTM round-robin did not attempt to relate the corro-
sion product morphology to service experience. This deficiency was addressed in
the COST 50 programme on materials for gas turbines [9]. Generally good simula-
tion of the corrosion product morphology on gas turbine blades taken from service
was found with samples exposed in burner rigs and some furnace tests. Work by
Hancock [lo] suggested that the contaminant flux rate (CFR) through the gas tur-
bine controlled the overall corrosion rate. Saunders et al. [9] proposed that a more
important factor was the deposition rate which was related to the CFR, but it was
acknowledged that this is difficult to control in practice. An initial study comparing
the low and high velocity rigs supported this premise that corrosion rates would be
similar at similar CFRs [ll].Thus the VAMAS project* attempted to build on this
work to test the thesis that burner rig testing at the same CFR would yield similar
corrosion rates. In outline, a round-robin test was arranged with both coated and
uncoated materials at two temperatures to allow both Type 1 and Type 2 hot-salt
corrosion to be studied for tests lasting 500 h. A special issue of the journal High
Temperature Technology outlined the VAMAS work and reviewed the topic of hot-salt
corrosion testing [13]. This issue provided a good springboard for the round-robin
undertaken by the VAMAS participants.
2.1. Round-robin Procedures
2.1.1. Materials
Two alloys were used; IN 738LC and Rene 80, with both materials produced from a
single cast, and pins 3 and 6 mm in diameter obtained in their normal heat treated
condition. Two coatings systems were studied, IN 738LC/RT22, a platinum aluminide
diffusion coating, and Rene 80/ATD2B, an overlay Co-21Cr-lOA1-0.3Y coating, were
supplied by Chromalloy UK Ltd, and Electron Beam Vacuum Coatings Inc., respec-
tively. After coating, the specimens were given a recovery heat treatment.
2.1.2. Test Method

The nominal test conditions were for tests at two temperatures (700 and 900OC) for
500 h with thermal cycles once every 10 h to room temperature. The CFR was to be 4
mg cm-2 h-l of Na added as artificial seawater (ASTM D1171-75)-this condition is
most likely for gas turbines operating in a marine environment. A 1wt% S fuel was
specified at an air: fuel ratio of between 30: 1 and 40: 1to achieve 200-300 vpm S (as
SO, and SO,) in the combustion gas. All materials were to be tested in triplicate.
“The VAMAS (Versailles agreement on Advanced Materials And Standards) organisation was set up a
number of years ago to promote adoption of international standards by encouraging international
prenormative research.
Deposition rates were to be monitored using inert specimens (Pt and A1,0, were
recommended) by determining the mass change and from chemical analysis.
Three cross-sections were to be taken from each sample, and 24 radial measure-
ments from each cross-section in which the loss of section due to external scale for-
mation, loss of section including grain boundary attack and internal sulphidation
was to be recorded. The maximum attack on the circumference of the cross-section is
the original radius minus the radius of completely unattacked alloy. In the case of
coatings the thickness of remaining coating was also measured. These data would
enable a full statistical analysis of the tests as recommended by Nicholls and Hancock
~41.
2.2. Participants
Initially 22 participants had been identified; 11in Europe, 4 in Japan and 7 in North
America, but difficulties in funding the work were encountered by some of the po-
tential participants so that finally only 10 organisations produced results (3 in Eu-
rope, 4 in Japan and 3 in North America), and in many cases the conditions sug-
gested were not adhered to. Table 1 lists the nominal conditions used in the tests;
errors in determining these values were not quoted.
2.3. Results
The main emphasis in the analysis of data from the round-robin was concerned with
a comparison of the maximum attack found on each material. All results were plot-
ted using probability paper for the three cross-sections taken from a single sample
(Fig. 1).These plots were used to identify the mean of the maximum attack on the
three cross-sections from triplicate samples (mean maximum) (i.e. the average of all
values of maximum metal loss found on the triplicate samples) and the extreme
2000, 7 200
1750 -
1500 - 150
5 1250 - E
a
m'
1000 -
n'
s 2 1co
-
d
,E
750 - L
0
500 - 0
50
250
01
t tL 0
O h
1 10 30 50 70 90 99 1 10 30 50 70 90
(4 Probability X (b) Probability
Fig. 1 Probability plots of metal loss for (a) IN 738 LC and (b) IN 738LC coated with RT22
exposed at 900°C in a burner rig for 500 h, showing the results for the three sections takenfrom
a single sample.
Corrosion i n the Presence of Melts and Solids 89
maximum attack (Le. the largest single value found anywhere on the triplicate sam-
ples). In some cases only one cross-section was measured, and also fewer than 24
radial measurements were recorded. These deviations would underestimate the ex-
treme maximum attack but may not seriously affect the mean maximum value.
Table 1indicates that not all participants used the recommended conditions, thus
section loss data was linearly normalised with respect to time and CFR to the stand-
ard condition. This procedure, although far from ideal, does have some justification,
since in some ranges of CFR there is a linear relationship between CFR (or more
E
Table I(a). Participants' operating conditions at 700°C
Organisation Time Velocity Rig Type Na CFR Deposition Rate

(h) (ms-l) (mg Em-* h-l) (pg h-9
500.0 0.1 Ducted 4.0 100.0
50.0 301.0 Ducted 40.0 32.0
105.0 165.0 Ducted 4.0 48.9
100.0 static -
500.0 I 170.0 I ?
300.0 I 184.9 I Unducted 4.0 28.0
%alt replenishment test, 20 mg cm-* 10 h-I (85%V,O,, 15%Na2S0, - 10 x 10 h).
Table 1(b). Participants' operating conditions at 900°C
Salt replenishment test, 20 mg cm-, 10 h-I (90'/0 Na,SO,, 10% NaCl - 10 x 10 h).
* RT22 and ATDZB coatings were exposed for 1000 and 2000 h, respectively
exactly deposition rate) and corrosion rate, although overall it is sigmoid. For exam-
ple, with high and low velocity rigs a linear relationship was observed for IN 713
and IN 100 for Na CFR between and 2 mg cm-2 h-l at 750 and 850"C, but was
parabolic for IN 738LC and IN 939 [HI. If parabolic, linear normalisation would
overestimate corrosion rates for lower than the specified CFR and vice versa. The
normalisation procedure ignores any incubation of corrosion, but in the presence of
HC1 the incubation period was observed to be less than 25 h [15] and hence should
have only a small effect for 300 and 500 h tests.
The data obtained in this way was analysed to show the mean maximum and the
extreme maximum attack on any set of three identical samples. Figures 2-5 present
these data as a series of histograms for each material type at the two test tempera-
tures, and for comparison with the ASTM round-robin, Fig. 6 is a histogram show-
ing the maximum (i.e. the extreme maximum as defined in the VAMAS work) metal
loss data obtained during that work. Taking the mean of the normalised data the
results show that:
(i) at 900"C, the two uncoated alloys had similar corrosion resistance, but that
ATD2B was superior to RT22;
(ii) at 700"C, IN 738LC had better corrosion resistance than Rene 80, but in this
case RT22 was superior to ATD2B;
(iii) the two uncoated alloys had higher corrosion rates at 900°C compared with
700°C;
(iv) ATD2B had a higher rate at 700°C than at 900°C; and
(v) RT22 had similar rates at the two temperatures.
1400 2000 , I
: 200
1000
800
600
1000
E, 500
E,
yi yi
S 400 B
-
i J
<
1
300
500
200
100
0
Q R S T V Y Q R S T U V W X Y Z
Fig, 2 Histogram showing the normalised extreme (dark shading) and mean (light shading)
maximum metal loss on IN 738LC exposed at (a) 700°C and (b) 900°C.
3000
1600
1200 2000
800
5 400
u;
0
-0
A
-
0
I
200
0
Q R S T V Y S T U X Y z
Porticipont
Fig. 3 Histogram showing the normalised extreme (dark shading) and mean (light shading)
maximum metal loss on Rene 80 exposed at (a) 700°C and (b) 900°C.
600 2000
500 1500
400
303 1000
500
200 350
300
E,. 150
5
Lo A 250
b s
-
J J
200
;
I
100
150
50 100
50
Porticiponts Porticlponts
(a) (b)
Fig. 4 Histogram showing the norrnalised extreme (dark shading) and mean (light shading)
maximum meal loss on IN 738LCIRT22 exposed at (a) 700°C and (b) 900°C.
2.4. Discussion
2.4.1. 900°C data - Type 1 corrosion

The ASTM round-robin results indicates that for burner rig tests carried out at a
similar temperature (884°C) the metal loss data for the uncoated alloys varied by as
much as a factor of 16 for U-500 and a factor of 11for IN 738LC (Fig. 6 -participants
A, B, C, D, G, I, J, L, M, N, 0).Comparison with the VAMAS study shows that a
much tighter data set was achieved for both the uncoated alloys at a similar tem-
92 High Temperature Corrosion Research and Tesfing
1500 1000 I
1000
500
400:
7 300
s
-
2
2 200
u
I
100
DorltcNpan! ?crt,ciponrs
(a) (b)
Fig. 5 Histogram showing the normalised extreme (dark shading) and mean (light shading)
maximum metal loss on Rene 80/ATD2B exposed at (a) 700T and (b) 900OC.
aor
.
d 406oln
to
nll 1
(b)
A B C D E F G H I J K L M N O
Por I i c i o o n ¶
Fig.6ASTM round-robin resultsfor (a) U 500, and (b)IN 738LC, showing the extreme maximum
metal loss.
perature, particularly if only the high velocity rigs are considered (Table 2 and see
for example Figs 2(b) and 3(b), participants R, S, V, X and Y), but this difference in
behaviour was not apparent for the two coated samples. A possible explanation of
this effect may be that the thickness of the deposit in the low velocity rigs was greater
than in the high velocity rigs due to the effect of the high gas velocity removing
deposit. That this effect was not observed in the case of the coated samples may be
related to the difficulty sometimes observed in interpreting the microstructure of the
Table 2. Metal loss data range for VAMAS tests
Material Temperature Factor Covering Range of Extreme of

"C Maximum Loss
high velocity low velocity all rigs
IN 738LC 900 2.2 2.3 6.7
Rene 80 900 1.6 >3.9 9.3
IN 738LC /RT22 900 9.8 2.8 11.1
Rene 80/ATD2B 900 8.9 3.6 8.9
IN 738LC 700 13.0 - 56.6
Rene 80 700 25.8 - 25.8
IN 738LC /RT22 700 11.1 - 11.1
Rene 80/ATD2B 700 22.2 - 22.2
coatings, so that these figures may be less reliable. An example of this difficulty was
the behaviour of the ATD2B coatings, where, after a relatively short exposure, the
entire thickness of the coating was often penetrated by internal oxide particles, but it
is widely believed that most of the coating life remains. Some observers of this micro-
structure may interpret the microstructure as being fully penetrated, while others
realise that little coating life has been used and therefore may have ignored this
change in the microstructure. This latter hypothesis finds some support in the much
larger ranges of values reported for the coated samples. In any future work it would
be important to specify in detail the assessment criteria for each coating type, rather
than as was done in this case to give general criteria.
2.4.2. 700°C data - Type 2 corrosion

The previous ASTM round-robin did not study this temperature regime, in part be-
cause at that time the significance of this type of corrosion had not been fully appre-
ciated. Figures 2(a)-5(a) clearly shows, however, that the data was much more scat-
tered even though the data set was more limited. An incubation period may well be
observed in Type 2 corrosion and inspection of the data indicates that the tests in the
low velocity rig and those with the shorter durations had lower material losses. Thus,
it would seem that the linear normalisation of the results has contributed to the large
scatter. Previous work by Nicholls and Saunders [ll]had suggested that the low
velocity rig may not be able to accurately simulate Type 2 corrosion because of the
lack of particle impaction which can mechanically damage the scale and initiate at-
tack, whereas this can occur in the high velocity rigs due to carbon shedding from
the combustor. Another important factor affecting the behaviour in all rigs is the
p S 0 , level. Luthra [16] pointed out that because of the difference in pressure be-
tween an operating gas turbine and an atmospheric pressure burner rig, the $30,
should be raised to produce the equivalent value to that in the turbine. This would
involve using fuels containing as much as 20-30'/0 sulphur.
2.4.3. Deposition rates
It is important to realise that rigs having the same CFR may not necessarily achieve
the same deposition rate at the sample. This can occur because of a variety of factors,
but probably the most important are differences in residence time between the point
of combustion and the sample and the temperature profile of the gas path, so that a
significant fraction of the salt loading can deposit on parts of the ductwork before
reaching the sample. It was for that reason that the guidelines requested measure-
ment of deposition rates as the only parameter that could be reliably be used when
attempting to compare rigs of very different design. Luthra [ 161 suggested that con-
trol of deposition rates can be achieved by determining the equivalent sodium and
sulphur partial pressures, but this can only be done by adjusting input of contami-
nants.
In attempting to normalise the data a linear extrapolation was used. This is not
satisfactory since when excessive amounts of deposit are present, either a shielding
effect can occur, or a critical level can be reached such that no further increase in
corrosion rate is observed with increasing deposit thickness. This behaviour has been
noted in ash recoat procedures [4]. It is not known with any certainty at what CFRs
these critical deposition rates would occur, but the data listed in Table l(b) show
that, for example, participants R and S, and V and X both have similar deposition
rates while the CFRs differed by a factor of ca. 10 and 3.5, respectively. Deposition
rates were often not as might be predicted from simple dew point consideration, for
example, participants R and S had higher deposition rates at 900°C than at 700°C,
and participant R operated their rig at ten times the standard CFR but obtained
relatively low deposition rates. These results suggest that the procedures recom-
mended would need to be improved if deposition rate data is to be used in the cor-
relation of measured corrosion rates.
2.5. Conclusions and Future Work

1. Attempts to use CFR as a controlling parameter in burner rig testing have had
some measure of success in allowing rigs of different designs to produce compara-
ble corrosion rates. However, generally higher rates were observed in the low veloc-
ity rigs at 900"C, and this was attributed to a thicker deposit being present on sam-
ples compared to those exposed in the high velocity rigs. Deposition rates were
measured, but this was not successful; it would seem that quantitative agreement
between rigs of different design will only be possible when deposition rates can be
controlled.
2. The scatter in the data for coated samples was greater than for the uncoated al-
loys. Part of the problem was assessing the coating microstructures, with different
observers making subjective judgements about the extent of attack. Equally, of course,
there may be a large variability in the coating quality. All samples should be meas-
ured by a single experimenter to determine whether this scatter was if fact due to
measurement errors or coating variability. An omission in this work was that no
reference samples were examined by each experimenter to determine measurement
errors.
3. Corrosion rate data was more scattered at 700°C than at 900"C, and in this case
there was no differencebetween coated and uncoated materials. Unfortunately,only
a limited data set was available at 700°C; four from high velocity rigs, one from a
low velocity rig, and one from an ash test, furthermore, three of the burner rigs tests
were of shorter durations than specified. The attempt to linearly normalise the re-
sults was clearly inadequate because of the effects of incubation periods.
4. An important conclusion which came out of planning this work was that it is
essential to increase sulphur levels in fuels when conducting laboratory burner rigs
at atmospheric pressure, particularly for tests in the Type 2 temperature regime.
This arises out of the fact that in a gas turbine the partial pressures of active species
such as SO, is increased by a factor equivalent to the operating pressure in the tur-
bine, Burner rig testing therefore needs to be modified to take account of this impor-
tant effect.
3. Other Forms of Deposit Induced Attack
While it is not possible to discuss at great length all the various forms of deposit-
induced attack in this paper, at attempt will be made to summarise the main forms
encountered in industrial applications covering power station boilers, fluidised bed
combustors, and petrochemical plant. Each of these forms of attack illustrate the
various different aspects of deposit-induced attack that can occur in industrial plant
and, therefore, can be considered as representative. Thus these processes, together
with the experience of gas turbine testing discussed above, will be used to deter-
mine the main parameters that govern the corrosion reaction in operating plant, and
thereby identify key parameters that must be controlled in any attempt to simulate
the mechanism of attack in a laboratory test.
3.1. Power Station Boilers - Superheater Corrosion

Fireside corrosion of power station superheaters is, in many ways, similar to the
molten sulphate attack found in gas turbines, since the combustion products of coal
contain both sulphurous gases and alkali metal salts, and, in the case of fuel oil com-
bustion, vanadium compounds may also form which are molten at relatively low
temperatures. Three major differences can be distinguished, however, for the case of
coal combustion where potassium and chlorine compounds are present in larger
amounts in the combustion gas mixture compared with the gas turbine environ-
ment described above, and as will be shown the effect of heat flux plays an impor-
tant role in determining the course of the reaction. Figure 7 is a schematic diagram of
the corrosion product and deposit layers and the corresponding temperature re-
gimes for superheater corrosion.Amaximum corrosion rate is observed at ca. 680°C.
A molten deposit of (NaK),Fe(SO,), forms, which fluxes the protective oxide scale
(iron and chromium oxides) to form, for example, Fe,(SO,),, but because of the tem-
perature gradient across the tube wall and the instability of the molten sulphates
with increasing temperature, the oxide re-precipitates at the melt/deposit interface
Bulk
gas
\O5O0C
Ou&r wall Molten sulphates
Fig. 7 Schematic diagram showing cross-section through a superheater tube, corrosion product
and deposit. The temperature profile through the system is also shown (after 1171).
as a solid non-protective porous oxide scale [17]. This process sustains a concentra-
tion gradient in the melt so that continued fluxing can occur. This is very similar to
the Rapp Goto criteria [18] for sustained fluxing in gas turbine hot-salt corrosion,
expect that, in that case, the driving force for re-precipitation of the oxide is the
altered partial pressure of SO,/SO, at the melt/atmosphere interface. Plant data
show that there is a direct and linear relationship between coal chlorine content and
the corrosion rate. The current understanding is that HC1 is generated during com-
bustion of the coal and that this promotes release of sodium and potassium salts
from the coal ash [19].
Attempts at simulating this form of corrosion in the laboratory have had only
moderate success [20]. Electrochemical tests showed that there was only a minor
increase in the corrosion rate as the HC1 content of the atmosphere increased. How-
ever, in burner rig tests with cooled metal samples a much stronger increase in cor-
rosion rate with increasing HC1 content of the atmosphere was observed. The in-
crease in corrosion rate with HC1 content was related to an increased deposition rate
of a potassium and sodium sulphate deposit. In fact no potassium was added to the
combustion gas mixture, but was released from the burner rig refractory lining by
the action of HC1. It is postulated, therefore, that HC1 derived from the combustion
of coal promotes release of alkali metals from the coal ash thereby causing an in-
crease in the corrosion rate.
3.2. Power Station Boilers - Evaporator Corrosion

Evaporator or furnace wall corrosion is another form of fireside corrosion in power
station boilers. In this case, because the metal temperatures are much lower (maxi-
mum ca. 350OC) than for the superheaters, no molten phases form. Instead a thick
outer solid ash layer develops which can sinter at the high temperature in the com-
bustion gas 12OO0C).This sintering process prevents oxygen access so that reducing
conditions can exist within the deposit. This condition is aggravated if unburnt coal
particles are trapped in the ash layer which continue to smoulder and release HC1,
carbon monoxide, sulphurous gases and volatile alkali metal compounds as indi-
cated in Fig. 8 [17]. Thus, in practice low corrosion rates of evaporator tubes are
observed if oxidising conditions can be maintained within the deposit and high cor-
rosion rates where reducing conditions are created by the unburnt coal particles.
Generally large boilers experience low corrosion rates, but where the clearance be-
tween the burners and the furnace wall is small, coal impingement can occur and
high rates are observed. Again corrosion rates increase linearly with increasing coal
chlorine content [ 191.
The mechanism proposed above suggests that a microclimate is created within
the ash deposit that controls the corrosion process; the atmosphere is very similar to
that found in coal gasifiers. Laboratory testing to simulate this form of attack has
1200O c
Internol
scale
Furnace
1
90s
>
1650' C
Steam I wa ter
flow
Inner c er
wall $ .I
Intergranular Fa s iornelloe
'1
I .Islands of FeS
I* Furnace
gas
Tube
metal
1
1
$- '
Spheres of '
unburnt coal
particles
Protective- oxide scole formed in Nm-protective fast -growing SColeS

oxidising condihons caused by reducing condrions
Fig. 8 Schematic diagram showing a cross-section through an evaporator tube, corrosion product
and deposit. The temperature profile through the system is also shown (after [271).
been the subject of an extensive investigationwhich has been summarised by Latham
et al. [19],in which the importance of the use of H2S-containinggas is stressed. How-
ever, despite extensive testing it has not been possible to reproduce all aspects of the
corrosion of evaporator tubes in the laboratory. Further work proposes testing in
heat flux conditions and also possibly examining the influence of free radicals which
would be present in the very hot combustion gas (-1650°C).
3.3. Fluidised Bed Combustors (FBC)

Conditions within a fluidised bed combustor burning coal are in many ways similar
to the superheater and evaporator corrosion described above, where both metal tem-
perature regimes can be experienced. Heat-flux is, of course, present as are coal ash
deposit, but because of the low gas temperatures in the FBC (-900°C) molten depos-
its do not form even at superheater metal temperatures. Also, limestone is usually
added to the FBC to aid sulphur capture, so that in addition to coal ash, the deposit
contains a mixture of calcium sulphate and calcium oxide. A feature of bubbling
beds is that the p 0 , has been shown to fluctuate between values representative of air
(2 x lo4 Pa) and Pa. Sulphidation of tubes exposed at temperatures above ca.
650°Chas been observed in operating plant, while the lower temperature tubes have
often suffered extensive erosive damage. Sulphidation was observed to be strongly
dependent upon the type of coal (compositionand ash fusion temperature) and the
FBC design.
Simulation of both sulphidation and erosion damage has been attempted in labo-
ratory tests. Sulphidation has not been reported by workers who have attempted to
carry out tests in gas atmospheres which simulate the CaO/CaSO, equilibrium be-
low 900°C but without the presence of the solid. Thus it would appear that direct
interaction with the solid is an essential component of the reaction, and indeed evi-
dence for solid/solid reaction has been observed [21]. A number of experimenters
have observed sulphidation at temperatures of ca. 800°C and above by using a vari-
ety of tests involving solid deposits of mixtures of loosely packed CaO/CaS04 with
additions of carbon [22] or slurries of the CaO/CaSO, for tests carried out in air, or
loosely packed CaO/CaSO, in controlled gas mixtures with PO, and p S 0 , values
equivalent to the CaO/CaSO, equilibrium. Sulphidation at lower temperatures has
been observed for loose CaO/CaSO, mixtures containing chlorides or alkali metal
salts (where sintering of the deposits was observed after the test), or with a cold
pressed compacted CaO/CaSO, mixture both exposed in controlled low PO, atmos-
phere [23,24].These results suggest that sulphidation of the type found in FBCs was
related to solid/solid interactions, control of deposit porosity and possibly the pres-
ence of small amounts of impurity such as chloride or alkali metal salts. Clearly the
creation of the correct microclimate within the deposit was an essential feature of
simulating this form of attack.
While not directly the topic of this paper the occurrence of erosion in FBCs has
provoked considerable interest, and many attempts to simulate this form of attack
have been carried out in laboratory tests. To date, none have been satisfactory,but it
has been suggested that, even in this case, it is important to carry out tests in heat
flux conditions. Some work has been carried out to prove this hypothesis and, al-
though not completely satisfactory, a better simulation of erosion was obtained when
tests were carried out under heat flux conditions.
3.4. Petrochemical Plant - Ethylene Crackers

Carbonaceous deposits are often found in petrochemical plants. As an example, the
case of ethylene furnaces is considered. Ethylene is normally produced by decom-
position of a relatively high molecular weight hydrocarbon, naptha is usually used,
by heating the hydrocarbon with some steam at a process temperature of ca. 800-
900°C. During the reaction to form ethylene, a carbonaceous deposit (coke)forms on
the bore of the externally heated tube. The presence of this deposit impedes heat
transfer, so that in order to achieve the desired process gas temperature, the metal
temperature is raised to as much as 1150°C.The presence of the deposit and the high
metal temperature then causes carburisation of the tube material. There comes a
point in the process where the coke deposit must be removed by an oxidising cycle
in a steam air mixture. Thus the tube material experiences alternating oxidising and
carburising atmospheres.
Traditional methods of test for materials for this applicationhave used either pack
carburisation or continuous gas carburisation tests, but there is no established corre-
lation between the results from these test procedures and plant experience. Work at
NPL in conjunction with an alloy manufacturer investigated [25, 261 the effect of
imposing thermal cycles, alternating oxidising and carburising cycles and operating
in a gas mixture where carbon formation occurred (carbon activity > 1)and at a PO,
below which a protective chromium oxide was thermodynamically unstable. The
results of this investigation demonstrated that the performance of material exposed
in tests incorporating these features was in good agreement with plant experience.
Other workers have expressed concern that the gas composition does not allow chro-
mium oxide formation, and suggest that, since Cr,O, is observed on alloys exposed
in these environments, a higher PO, should be used [27]. It was recently observed
[28] that even the nature of the oxidising cycle during the simulation of the decoking
procedure altered alloy ranking. Generally a procedure that involved use of steam
which more closely simulates industrial practice led to more severe carburisation.
Another feature of this work was the demonstration of the importance of catalytic
effects in promoting carbon formation. Some alloy surfaces were free from carbon
deposition even though the carbon activity was greater than unity. It is clear, there-
fore, that the simple pack carburisation tests would give misleading information in
these cases.
4. Guidelines for Testing

4.1. Purpose of Testing
Before consideringthe guidelines to be adopted when planning tests involving solid
or molten deposits, it is important to understand the purpose of the test. Three types
of test can be considered. Firstly, tests designed to improve our understanding of the
mechanism of the reaction. Secondly, tests used to generate data for a life prediction
model, and finally, a complete simulation of the industrial environment in order to
obtain reliable quantitative data. Each of these constraints will be considered briefly
below.
In mechanistic studies it is important to understand the controllingparameters in
the corrosion process. This can be done by introducing different parameters, and
examining their effect on the corrosion process having particular regard to the corro-
sion product morphology and comparing this with that observed in practice. Tests
carried out with this purpose, therefore, have a relatively wide scope and it is clearly
not appropriate to attempt to standardise test procedures.
The second type of test where data is required either to validate life prediction
models or to provide a framework for the model should be carried out with much
more care. An important issue here is the relevance of accelerated testing, that is
tests aimed at obtaining long-term data in the short-term by altering test parameters
such as temperature or composition of the gaseous environment. It is clearly desir-
able to be able to accelerate testing in order to validate the long-term predictions of
a model, but it is also clear that such procedures are fraught with difficulties. How
can one be certain, for example, that by increasing the temperature or the concentra-
tion of active species in the environment that this has not caused a change in the
mechanism of the reaction?Knowledge of activation energies derived from Arrhenius
plots can be useful here to ensure that operating in a higher temperature regime
does not change the process.Accelerationby changes to the composition of the envi-
ronment are more problematical, and it is suggested that only when the corrosion
product morphology can be related to that found in the long-term is it safe to use the
accelerated procedure. This implies, of course, that long-term data are available, so
that such a procedure should not be used when predicting the life of components to
be used in new or modified industrial processes. Having decided that it is appropri-
ate to use an accelerated test one must deduce the acceleration factor. If temperature
is the accelerant, then this can be simply derived from the Arrhenius plot, while for
acceleration due to changes in the composition of the environment, the acceleration
factor can only be derived empirically by reference to the long-term behaviour.
The final test method designed to give accurate quantitative data may be appro-
priate for standardisation. It is evident that the test conditions should be such that
the development of the corrosion product morphology should parallel that found in
the plant. This may not necessarily mean a complete simulation of all the process
conditions, but extreme care should be taken when attempting to simplify proce-
dures. An expedient often used in laboratory testing is to carry out tests at atmos-
pheric pressure while attempting to simulate process conditions at high pressures. It
is generally believed that provided the partial pressures of the active species are
appropriately adjusted the chemical activity of the test environment is accurately
replicated. It should not be overlooked, however, that pressure per se may be a con-
trolling parameter. Finally when carrying out tests to produce such quantitative data
it must be emphasised that all data should be obtained only from traceably cali-
brated equipment.
Corrosion in the Presence ofMelts and Solids 101
4.2. Guidelines for Corrosion Testing
This paper has discussed five different cases of deposit-induced attack where either
molten or solid material act to accelerate the corrosion process. It is believed that
these five cases are representative of most of the industrial situations, so that the
insights gained from their consideration are summarised in Table 3 and represent
guidelines that should be adopted when designing tests for deposit-induced corro-
sion. It is not possible to detail the precise conditions to be used in every case, so that
the guidelines listed below briefly discuss the different test parameters that must be
considered and their appropriateness for inclusion in the test. Further prenormative
research is required before the standardisation process can proceed.
5. Conclusions
A review of test procedures designed to simulate deposit-induced corrosion has

shown that there are a number of key parameters that control the overall corrosion
rate. These are deposit composition, deposit structure, deposition rate (contaminant
flux rate), gas velocity test facility aerodynamics, gas and metal temperature, gas
composition, total pressure, catalytic activity of the test surface, test time and ther-
mal cycles. There have been very few attempts to conduct tests to an agreed guide-
lines. One such round-robin was recently carried out in conditions relevant to gas
turbine operation. This exercise showed that many laboratories were not able to
complete the test as required, and in addition, evaluation of the samples after testing
suggested that different criteria were used to assess specimen damage. Any future
work to develop standard tests or guidelines should take care to include reference
samples so that measurement accuracy can be assessed, and it was evident that im-
proved procedures are needed to measure deposition rates.
The current initiative of the EFC is to be welcomed and further much needed
work is to be encouraged so that standardisation of hot corrosion testing can be put
on a firm basis.
6. Acknowledgements
The author gratefully acknowledges the input of the participants in the VAMAS
round-robin for the many helpful discussions, and especially Prof. J R Nicholls for
his guidance during the VAMAS project. The contributions of delegates to the EFC
Workshop held at DECHEMA on 20 January 1994 are also acknowledged. Drs D. B.
Meadowcroft, R. Rahmel, H.-J. Ratze-Scheibe, C. A. C. Sequeira, H.-P. Martinz, G. P.
De Gaudenzi, F. Umberti and F. Gesmundo are thanked for their specific contribu-
tion to this paper. The research reported in this paper was partly funded by the
Measurement and Testing programme of the European Commission and as part of
the ‘Environmental Degradation of Materials Programme’, a programme of under-
pinning research financed by the UK Department of Trade and Industry.
Table 3. Parameters to be considered i n test design
Test Parameter Comments
Deposit It is necessary to have the deposit present as a solid or molten phase

composition since there is evidence to indicate that in many cases direct reaction
between the melt or solid plays an important role in the corrosion
process. The composition of the deposit should accurately reflect
that found in practice. Exceptionally,where the microclimate created
by the deposit can be accurately simulated in the gas phase, the
deposit may not be necessary.
Deposit structure In the case of solid deposits there is evidence that the porosity of
the deposit controls the microclimate, thus a good simulation of
the pore structure may be necessary.
Deposition rate In most industrial plant continuous deposition occurs which acts
to replenish ageing deposits. It is helpful to work at similar
contaminant flux rates to that found in industrial plant.
Replenishment of deposits in static tests can be effective in
simulating the dynamic test.
Aerodynamics /Gas Deposition is controlled by the gas flow over the component. At
velocity high velocities erosion can occur when solids are present, while
with deposition from the vapour phase the detailed component
shape will influence preferred deposition sites.
Gas atmosphere The stability of the deposit is determined by the surrounding

control atmosphere. Both equilibrium and non-equilibrium situations occur
in industrial plant. The occurrence of cyclic conditions in operation
shouldbe noted and replicated in the test.
Gas and metal Generally these are different, so that the effects of heat flux can be
temperatures important by, for example, altering the solubility or stability of the
deposit or altering oxide stability in the deposit.
Catalytic effects Deposition is often controlled by the catalytic activity of the surface.
It is important to ensure, therefore, that relevant surface preparation
procedures are used.
Time Many corrosion processes require an incubation period to initiate

reaction, likewise at longer times transitions to high rates
(breakaway) can occur. It is important to allow for these effects in
the design of the experiment.
Thermal cycles Thermal cycling rates control mechanical stability of both the
protective oxide scale and the deposit. Care should be taken to
correctly simulate these rates in the test.
Corrosion i n the Presence of Melts and Solids 103
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7
Simultaneous Corrosion and Mechanical or

Thermal Stresses
M. SCHUTZE, V. GUTTMANN* and M. E STROOSNIJDERt
Karl-Winnacker-Institutder DECHEMA e.V.,P.O. Box 15 0104, D-60061 Frankfurt, Germany
*Institute for Advanced Materials, Joint Research Centre of the European Commission,
Petten, The Netherlands
+Institutefor Advanced Materials, Joint Research Centre of the European Commission,
Ispra, Italy
ABSTRACT
Under practical conditions mechanically or thermally induced stresses, which natu-
rally can affect the extent and appearance of high temperature corrosion, are always
present in high temperature components. Therefore, stress-free corrosion testing may
yield valuable information. However, particularly when aiming at obtaining data to
characterise suitability for use under service conditions, the effects of stresses on corro-
sion cannot be ignored. Therefore, in accordance with the two main sources of stresses,
test techniques have been developed to investigate corrosion under the influence of
temperature changes (thermally induced stresses) and externally applied stresses (me-
chanically induced stresses). These techniques are discussed with regard to the differ-
ent types that exist, their performance and limitations and to the first steps towards
standardisation in order to make the results obtained in different laboratories compat-
ible. Recommendations for the different test procedures are given, but it also becomes
evident that more work still has to be done before standardised tests can be defined in
this field.
1. Introduction
In almost all technical high temperature applications mechanically or thermally-in-
duced stresses can be expected for the components. There may be stress-free opera-
tion conditions at high temperatures, but certainly in the subsequent cooling period
stresses will build up in the metallic substrate and in the corrosion/oxidation prod-
ucts formed on top of the metal due to the different thermal expansion coefficients
and constraints imposed by the structural situation of the component. Stresses at
operating temperatures can arise from gravity, centrifugal forces, component creep
and fatigue or other types of operation-induced forces.
Mechanical or thermal stresses can influence the course and type of high tem-
perature corrosion to a significant extent. This was illustrated in several reviews,
conference proceedings and data compilations [1-51. Therefore, isothermal stress-
free high temperature corrosion testing, as commonly practised in most laborato-
ries, may yield valuable information on materials resistance. However, when aim-
Simultaneous Corrosion and Mechanical or Thermal Stresses 105
ing at obtaining data to characterise suitability for use under practical conditions,
the effects of stresses on corrosion should not be ignored. This emphasises the need
for relevant testing methods.
The various effects that may occur due to the interaction of mechanical stresses
and high temperature corrosion are:
cracking and healing of the protective oxide scales;

increased depletion of such elements that form the protective scale in the sub-
surface zone of the alloy;
increased internal corrosion if scale cracks cannot heal or if subsurface zone
depletion no longer allows the formation of protective oxide; and
subsurface zone crack initiation and growth assisted by internal corrosion.
The mechanisms can be regarded as fairly well understood from a scientific point
of view [6, 71. However, there is still a considerable lack of quantitative data, i.e.
there is a strong need for validated testing under relevant test conditions.
Several testing methods have been developed for the investigation of simultane-
ous corrosion and mechanical or thermal stresses. Tests under thermal cycling con-
ditions (i.e. thermal stresses) were the earliest among these tests and are still the
most widely used. Nevertheless, no efforts have yet been made to standardise these
tests, i.e. the data have to be considered qualitatively and, therefore, caution is ad-
visable when comparing data from different laboratories. This is also valid for
mechanical tests under corrosion conditions even if most were derived from stand-
ardised mechanical test procedures developed for tests without corrosion. The im-
portant high temperature mechanical tests are creep rupture tests, low constant strain
rate (or extension rate) tests, fatigue tests and crack growth tests (high temperature
fracture mechanics). In combination with superimposed corrosion, the creep rup-
ture test is most frequently used and, as a first step, this test deserves some efforts on
standardisation. Crack growth tests are not yet very common and the general proce-
dure is described in some detail elsewhere [8,9]. Fatigue tests are more frequently
used, but, with few exceptions [lo, 111,mainly to compare the behaviour in air with
that in argon or vacuum. Standards exist for fatigue testing as a mechanical test [12,
131. These can also be used for tests with superimposed corrosion if the recommen-
dations for combined mechanical-corrosiontests made in the present paper are ob-
served. Low constant strain rate tests can be regarded as a special type of creep test.
Thus, in the end it seems to be most appropriate to focus on creep testing when
trying to formulate general recommendations for testing under simultaneous corro-
sion and mechanical stresses.
As a general remark it should be mentioned that many of the recommendations
given for high temperature corrosion testing without superimposed stresses also
apply to the types of tests discussed in this paper. These are summarised to a great
extent in the associated papers in this monograph ‘Points to be considered in
thermogravimetry’ [ 141, ‘Discontinuous measurements of high temperature corro-
sion’ [15], and ’Definition and preparation of gas atmospheres’ [16].Recommenda-
tions presented in these papers are not repeated in detail in the present paper, but
should be referred to for testing under mechanical or thermally induced stresses as
well.
2. Materials Characterisation Before the Experiments
Prior to any type of test considered here, it is most important to provide as complete
as possible a characterisation of the material. This should include:
the chemical composition of the material;

data on possible thermomechanical pretreatment;
data on the grain structure (size, shape);
data on the precipitates (type, size, shape, number or distribution density,
position at grain boundaries or in the grains);
data on the specimen surface (surfaceroughness, surface finishing technique);
and
data on the preoxidation or precorrosion, if applicable.
All these data are necessary for a correct interpretation of the test results and for
comparison with results from other investigations. In particular the behaviour of
materials under the effect of corrosion combined with mechanical stresses is very
much influenced by the parameters listed above (cf. [17]).
3. Thermal Cycling Tests
In all cases a proportional-integral-differential-controlled(PID) furnace is recom-

mended with either the furnace or the specimen being moved in the cooling periods
of the thermal cycles. The specimens should be encapsulated in a reaction chamber
in order to allow testing with different gases. Silica and alumina are recommended
for the chamber materials. At very low oxygen partial pressures volatile Si0 species
can, however, be formed and deposited on the specimen surface. In this respect
alumina should be the material of choice, but it has the disadvantage of having less
thermal shock resistance.
3.1. Types of Tests

Table 1 shows a compilation of the types of tests found in the literature. The most
widely used tests are those with small specimens (coupons) in a crucible or vessel or
attached to a wire. Component testing or burner rig tests require greater technical
effort and are thus limited mainly to the simulation of practical situations (heat-
exchanger tubes, turbine blades, etc.) when the added complexity is necessary to
obtain reliable data on the use of materials. Cruciblesor vessels (preferably alumina)
are mainly used when the specimens are to be embedded in ashes. If an effect of the
gas flow rate on oxidation is expected, this type of test should be avoided and the
Table 1. Spectrum of existing tests (thermally induced stresses)
Specimen in a crucible or vessel

- temperature change by moving crucible
- temperature change by moving the furnace
Specimen attached to a wire (hooked, spot-welded, cage system, etc.)

- temperature change by moving the specimen
-temperature change by moving the furnace
Component testing
-temperature change by moving the furnace
Burner-rig tests
- temperature change by moving specimens into and out of the flame
second type of test in Table 1 preferred. Connecting the specimen to the wire by a
hook or by a cage system should be preferable to spot-welding, since oxidation or
corrosion may preferentially attack under the weld and thus separate the specimen
from the wire during the test. In some cases, low melting eutectics may form be-
tween the wire material and the specimen (a eutectic between Pt and TiSi, melts at
830°C),which makes the specimen drop from the wire. Pt wires, which are most
often used, start to evaporate at temperatures of 1000°Cand above at a considerable
rate which is of importance when combining thermal cycling with thermogravimetric
measurements. Instead of Pt wires alumina-forming alloys can be recommended as
a wire material. Ceramic hangdowns are also possible. Cage systems can, for exam-
ple, be built from metal wires inserted into small silica tubes and arranged as a te-
tragonal cage connected to a wire. The specimen is placed on the basal plane. It may
be helpful to place a spall collector below the specimen in order to catch the spalled
corrosion products for weighing and to obtain a better interpretation of the experi-
mental results.
Figure 1 shows the schematic of a test arrangement which has proved to work
well [18] and which can be recommended as a standard rig with room for testing 4
specimens at the same time. A spall collector below the specimens permits one to
weigh and further analyse the spalled material and can, thus, facilitate a more de-
tailed interpretation of the experimental results. In the case shown, tests were com-
bined with acoustic emission measurements in order to record spalling of the oxide
during cooling. The rig can, however, also be used for thermogravimetric measure-
ments (only one specimen) in combination with a balance above the furnace (Fig. 2).
Table 2 summarises the parameters measured in thermal cycling tests. The most
commonly used parameter is mass change as a function of test cycles or of testing
time. A rather simple set-up uses a multi-specimen tray system with several speci-
mens attached to it. After defined test intervals the specimens are removed during
the cold period, the mass is determined, the specimens are inserted again and the
test is continued with the same specimens (discontinuous mass change measure-
Pre-amplifier Computer
Fatube
AE-transducer
Gas inlet
Tube furnace
Sample
Control thermocouple1
I
Gas outlet
3
Fig. 1 Schematic of the set-up for cyclic oxidation testing combined with acoustic emission
measurements.
ments, cf. recommendations in Ref. [15]).It should, however, be pointed out that, in
most cases, mass change measurements only provide global information. This is
due to the fact that mass change results from various processes, e.g. mass gain by
ordinary corrosion, mass loss by (localised)spallation or (if significant)by evapora-
tion of corrosion products and mass gain by reformation of oxide in spalled areas
(possibly with different composition and kinetics). Specimen geometry, e.g. edge
effects, will further complicate the interpretation of the data.
A more detailed understanding can be obtained by determining materials degra-
dation from metallographic cross-sectionsand recommendations for metallographic
preparation procedure are given in Ref. [15]. Obviously this is far more elaborate
than mass measurements, however, in order to get a more complete idea, cross-sec-
tional examinations have at least to be performed at the end of the tests. A possible
approach is first to obtain the mass change curves and then to decide in which test
periods additional samples should be taken for further cross-sectional examination
~91.
acoustic decoupler
AE-transducer
polymer seal
thermocouple
c
- testing gas
furnace
(movable)
i'
quartz tube
Fig. 2 Set-upforcontinuous thermogravimetric measuremenfsunder thermal cycling conditions

combined with acoustic emission measurements.
Table 2. Parameters to be measured and techniques (thermally induced stresses)

~~ ~
Mass change
- discontinuously by weighing specimens after cooling at room temperature
- continuously by thermogravimetry
Metal loss
- by post-experiment metallography
-by thin layer activation
Oxide scale spalling

-by in situ acoustic emission measurements
Another way of measuring material loss is by using Thin Layer Activation (TVA).
The principal basis of TLA is the creation of radionucleides in a surface layer by
exposure to a high energy particle beam from, for example, a cyclotron. The nucleides
disintegrate under simultaneous emission of nucleide specific y-radiation. Any loss
of the activated material due to a material degradation process will result in a loss in
y-activity of the activated component. This reduction in signals can be directly re-
lated to mass or depth loss. Due to its need for specialised facilities and, to some
extent, also to nuclear safety aspects, the application of TLA for cyclic corrosion
testing is at present only performed at the Institute for Advanced Materials of the
European Commission on a day to day basis. In the TLA application as applied in
Ref. [20], the activated material sample is exposed to a cyclic corrosion test. The
detached material is accumulated in a spa11 collector which is removed at various
intervals to determine its radioactivity as a function of y-energy. The y-intensity for
specific radionucleides, corrected for their natural decay, can then be used as a quan-
titative indication of the material loss. The benefits of this application include the
direct relation to material loss, sensitivity, accuracy, area selectivity and the speed of
analysis.
Another technique that can be used in cyclic corrosion testing is that of acoustic
emission (AE) measurements [21-251. During cracking and spallation, part of the
released energy is emitted as acoustic wave packets which can be detected with
piezoelectric sensors. It can, for example, also be used under simultaneous measure-
ment of mass changes [23,25] (Fig.2). In most cases AE is only used as a qualitative
indication of the processes occurring, especially the onset of cracking. However, fur-
ther analysis, i.e. frequency spectrum, energy and amplitude distribution might re-
veal far more details of the processes going on (cf [21-24,261).
3.2. Specimens
Except for component-like specimens, in most cases coupons or small cylindrical
specimens are used. Cylindrical specimens have advantages when the cyclic oxida-
tion behaviour of overlay coatings is to be tested. A common type which can be
recommended when it is possible to apply overlay coatings has a diameter of 8-10
mm and a length of 15-20 mm. These specimens have a further advantage in that
they have no corners and a low edge to surface ratio which prevents overestimating
corrosion due to edge or corner effects. Disc-shaped specimens are less desirable
from this point of view and rectangular coupons are even worse. A more detailed
discussion of specimen geometry is given in Ref. [15]. Generally, edges should be
rounded off slightly. Surface preparation plays a vital role. In order to make a com-
parison of results from different experiments, possibly as a finishing step, grinding
with 600 grade Sic paper should be agreed upon. Before the experiments, the speci-
mens should be cleaned in an ultrasonic ethanol bath. Recommended cleaning stages
for a more thorough cleaning procedure are 'inhibisol' (inhibited 1,1,1trichloroethane)
and isopropyl alcohol.
3.3. Experimental Procedure
Before the tests, a temperature calibration of the test procedure is absolutely neces-
sary. Appropriately a calibration thermocouple is inserted into a hole in a dummy
specimen (thermocoupled calibration specimen) and the course of the temperature
during the test is adjusted to the required values [15]. Parallel to this another ther-
mocouple has to be placed close to the specimen(s)by which the course of the tem-
perature in the calibration temperature cycle is recorded and which serves as the
reference thermocouple in the actual tests. It is assumed that the relation between
the values of the calibration thermocouple and the reference thermocouple remains
relatively constant within the test. From time to time, however, the calibration pro-
cedure has to be repeated (every 3 months is recommended). The maximum tem-
perature chosen in the tests depends on the relevant practical background informa-
tion and material. Ideally the minimum temperature in the cooling period should be
close to room temperature in order to allow for compatibility with other test results.
The minimum temperature value very much determines the degree of oxide spalling.
For example, it has been observed with Ni-base single-crystal superalloys that cool-
ing from 1000 to 90°C leads only to very little spalling, while spalling is extensive
when cooling further down to room temperature [27]. The cooling rate should be
above a minimum value in order to prevent relaxation processes by creep in the
metal substrate. A value of 30°C per min and higher seems to be practical for most
equipment, The isothermal hold times between cooling periods have a significant
influence on the course of corrosion.A long hold time can mean a long time in which
a protective scale prevents increased corrosion. For tests with the background of jet
engine applications, isothermal periods of 1 h seem to be reasonable as a reference
basis. For long-term applications isothermal periods of 24 h or 100 h are recom-
mended.
3.4. Data to be Measured

The data which are most easily accessible are mass change vs time or number of
cycles. For continuous measurements by thermogravimetry the testing times do not
usually exceed 1000 h. In discontinuous tests it is recommended to record the mass
change at least after approx. 30, 100, 300, 1000, 3000 h etc. [15], which has proved
useful in particular for a logarithmic plot of the data. Measurements at shorter inter-
vals are, however, advisable, especially in the case of irregular behaviour of the ma-
terial. The recording intervals can be increased with total test time, e.g. every cycle
up to 20 cycles, after which the test is measured up to 100 cycles at intervals of 5
cycles, after which the test is continued with measurements every 20 cycles. Addi-
tional information is provided by determining the mass of the collected spalled ma-
terial, for which the same remarks concerning measurement intervals can be made.
Figure 3 shows a typical example of discontinuous measurements. Measurement at
short intervals, e.g. every 20 cycles, or continuous measurements might enable a
rather more precise determination to be made of the number of cycles at which the
mass change rapidly increases, which would provide an indication of non-protec-
tive corrosion.This can be used as a qualitative parameter of materials behaviour (cf
Number of cycle
Fig. 3 Weight change curves from discontinuous measurements in thermal cycling tests (cooling
from 1000°C to room temperature, isothermal period 1 h).
[ 191). Metallographic cross-sectional examination should be performed at least at

the end of the test period. More complete information would be obtained if this was
also performed at regular intervals, e.g. after approximately 30,100,300,1000,3000
h, etc. As mentioned above, a more efficient approach might be first to obtain the
mass change curves and then to decide in which test periods additional samples
should be taken for further cross-sectionalexamination [ 191.Additional information
is provided by the mass of spall as a function of time which reveals discontinuities in
the mass change vs time plots. The spall collector should be in the cold part of the
test rig so that it can be removed during the tests. From the engineering point of
view the loss of the metal cross-section is the most important parameter. Another
important parameter for technical use is the time to the beginning of a strongly in-
creased mass change or to the beginning of non-protective oxidation (corrosion),i.e.
the time from which the deterioration rate of the material increases. Both param-
eters can be measured by the procedures described.
4. Mechanical Tests
Test rigs for plain mechanical testing are commercially available in the form of ten-
sile testing machines (mechanical or servohydraulic systems) or creep testing ma-
chines. It is recommended to use commercial testing machines since they are de-
signed according to current standards [28-331 and, thus, fulfil the requirements for
load frame stiffness, constancy of load parameters, reproducibility, etc. These testing
machines have to be modified for tests in aggressive environments by installing an
appropriate reaction chamber. Further requirements are pull-rods of a sufficiently
high temperature strength and corrosion resistance which lead into the reaction cham-
ber through gas tight flange and bellows systems. The principles of a test set-up for
creep testing under high temperature corrosion conditions are shown in Fig. 4 and
can also be applied to other types of mechanical tests. It should be mentioned here
that, in principle, every high temperature mechanical test includes corrosion whether
in air (oxidation), 'inert' gas (e.g. alumina formation in Ar of commercial purity) or
vacuum (e.g. decarburisation or selective metal evaporation at high temperatures).
4.1. Types of Tests

Table 3 summarises the common mechanical tests which have been used under con-
ditions of high temperature corrosion up till now. The most widely used is the creep
test under constant load. Nevertheless, this type of test has some disadvantages.
Firstly, the creep rate changes during the test according to the different creep stages.
The course of corrosion is, however, dependent on the creep rate [7]. Secondly, the
influence of corrosive attack on the creep rate is more marked for specimens of small
diameter than for those with larger ones, as illustrated by the example in Fig. 5 . This
is simply because the smaller the specimen diameter, the greater the cross-section
m- zs
Fig.4 Modified creep rig for testing in corrosive gas environments.

Table 3. Spectrum of existing tests (extevnal stresses)
Creep or creep rupture test under constant load or stress
Constant strain or extension rate test
Fatigue test
Crack growth test

- under static load
- under cyclic load
Time, h
Fig. 5 Creep curves for various specimens diameters of CrMoV steel tested in air at 675OC
1441.
ratio of the corroded material and the original will be. In other words, creep or creep
rupture data can only be compared if the tests have been performed with specimens
of equal diameter. As the present understanding of the interaction of corrosion and
deformation shows, the course of corrosion can be best related to strain, time and
strain rate values under these conditions [I, 7,34-371.
Therefore, if these mechanisms are to be investigated in detail, rather than obtain-
ing technological data the constant strain rate, or constant extension rate technique
[38] is recommended which is better suited to this purpose. The main disadvantage
of this technique, however, concerns the fact that strain rates below lov9s-l cannot
be achieved in a reproducible manner.
Fatigue or cyclic creep tests are less frequent, but still relatively often used since
many practical applications include cyclic loading conditions. For these tests, and
Siinultaneous Corrosion and Mechanical or Thermal Stresses 115
also for crack growth tests (static or cyclic), most of the remarks made with respect
to creep or creep rupture testing also apply.
For all mechanical tests it is imperative that the temperature along the gauge length
is kept only within a very narrow band since high temperature strength may de-
pend on temperature to a great extent [39]. The limits set by present standards [40,
411 are shown in Table 4 and should be observed under all circumstances. Usually
this is possible with a 3-zone resistance furnace with 3 separate control units. The
reaction chamber may be fabricated from a metallic alloy (310 stainless steel, alloys
800 H, 600 and MA 956 have often been used), quartz or alumina, according to the
test atmospheres. In atmospheres of high sulphur activity and low oxygen partial
pressure alloy MA 956 has proved to be a good choice [42]. Quartz tubes have been
used successfully for chlorine-containing atmospheres at 800°C [43]. Under condi-
tions of low oxygen partial pressures again alumina should be preferred to quartz.
The pull-rod system and the connection to the specimen must exhibit high creep
strength and sufficient corrosion resistance. Materials in use are Nimonic 90, Nimonic
105 and alloy MA 956, but again the choice must be related to the environment. For
extremely corrosive conditions alumina is recommended [43]. If relatively low cor-
rosion rates are expected (for the test material as well as for the connecting devices
between pull-rods and specimen) a thread system can be used combined with round
tensile test specimens. For high corrosion rates and when using a ceramic pull-rod
system a bolt connection is recommended [43].The reaction chamber must be sealed
from the pullrods by bellows. In some cases PTFE bellows have been used which,
however, allow gas penetration, at least with a low rate. Therefore, metal bellows
(stainless steel) should be preferred which, furthermore, can tolerate higher tem-
peratures without failure. For strain measurements extension rods made of metal,
quartz or alumina can be attached to the ends of the specimen gauge length (clamp-
ing or screwing). In the case of metal it must be ensured that creep does not occur in
the extension rods. Quartz rods may recrystallise at temperatures around 1000°C
and above, leading to changes in rod length, but alumina rods are regarded as the
best choice. The extension rods lead out of the hot zones in the furnace to strain
measurement devices (usually capacitance or inductive transducers). These devices
should be placed in a cold part of the reaction chamber (Fig. 4), or outside the cham-
Table 4. Allowable temperature deviation in thegauge length (EN 10 002-5: 1991)

- ~
k 3°C for T < 600°C
& 4°C for 600°C < T < 800°C
k 5°C for 800°C < T < 1000°C
k 8°C for T > 1000°C (DIN 50118)
T measuring device < k 2°C

ber. In the latter case, however, complex sealing systems using very soft bellows
become necessary. The strain measuring system should be kept under constant tem-
perature conditions, using a thermostat for the transducers if necessary. Generally,
for tests with tensile testing machines (constant strain or extension rate testing) tem-
perature changes in the room with the testing machines should be kept to a mini-
mum (preferably less than kl°C) since changes in thelength of the load frame, caused
by temperature changes, strongly affect the strain rates, particularly for all tests at
very low strain rates. In constant extension rate tests deformation rates below
must be regarded as critical and should be avoided.
4.2. Specimens
The shape of the specimens depends on the type of test and should be chosen ac-
cording to the recommendations in the standards for the respective mechanical test.
In creep rupture tests, creep curves and life-time of the specimen may be strongly
influenced by the specimen diameter, as becomes evident from the example in Fig. 5.
In order to create test data which are compatible it is recommended to generally
agree on round tensile test specimens with a gauge diameter of 8 mm. The literature
contains a large number of results based on specimens of this diameter which can be
compared with one’s own results in such a case. If, however, data for component
design is the objective creep rupture tests should be performed with specimens of a
diameter that is close to the planned wall thickness of the component. It may some-
times be useful, especially for component data, to take flat strip specimens. The re-
sults of this specimen geometry may, however, be influenced by edge effects so round
specimens are preferable.
The specimens will usually be prepared by lathe turning and grinding and the
finishing step should be gauge length polishing with 600 grit. Before the tests the
specimens should be cleaned in an ultrasonic ethanol bath and the characteristic
geometrical parameters of the gauge length should be carefully determined (prefer-
ably by a profile projector or any other type of measuring microscope). The speci-
mens should show absolute axial symmetry in order to avoid any additional bend-
ing stresses in the tests. The same applies to the specimen grips and the pull-rod
system since bending stresses would influence the interaction between deformation
and corrosion to a significant extent.
4.3. Experimental Procedure

Temperature calibration of the heating system is most important. Although in three-
zone furnaces controlled by modern control units the temperature in the actual test-
ing zone can be kept constant within narrow limits, it is recommended to check the
temperature distribution. For this a dummy specimen with a longitudinal slot is
used into which a hook-shaped thermocouple is inserted. In the calibration proce-
dure the heating system is adjusted so that, when moving the thermocouple in mil-
limetre stages along the slot, the temperature remains constant at the desired value
within the limits given in Table 4.During the calibration procedure the thermocou-
ple should remain in each position for at least 10 min. Close to the specimen one or
three (in a line) thermocouples should be installed to control the temperature during
the test. Heating prior to the test should occur under a certain low preload (max.
10% of the test load) in order to avoid misalignment of the specimen/pull-rod sys-
tem. Pre-heating may be performed in the test atmosphere although the activities of
the different corrosive species in complex atmospheres vary with temperature. If
this is regarded as a problem pre-heating in argon is recommended. However, it
should be kept in mind that oxygen impurities in argon may be sufficient to form the
more stable oxides like alumina which may influence further materials behaviour. It
is recommended to start the test 1h after the temperature has reached the nominal
value in order to avoid too much pre-corrosion before the load is applied. Strain
recording should begin immediately before the load is increased to test level. The
full load should be added slowly and relatively continuously (e.g. by a hydraulic
device).
Corrosion-deformation interaction is very much a function of the applied strain
rate. Therefore, it appears to be necessary to define a strain rate range within which
the tests should be performed, which implies the choice of an appropriate load level
in constant load tests. For long-term applications of the materials, data should be
used which have been measured in a strain rate range of 10-10-104 s-l. In the case of
short-term applications the data should cover a strain rate range of 10-7-10-3 s-l. As
already mentioned before, difficulties may arise to achieve constant strain rates be-
low about s-l in the constant strain rate test. For such low strain rates the creep
test seems to be more suitable. Apart from a short period of primary creep the creep
rate can be fairly constant for a relatively long time of the test provided the corrosion
rate and, thus, the rate of cross-sectional decrease is not too fast. At the end of the
test the load should be removed and cooling should occur under load-free condi-
tions quite rapidly in order to preserve possible oxide scale cracks, which might
otherwise heal again by oxidation in the cooling period, for post-experimental in-
vestigations. The specimen should be removed from the specimen grip system very
carefully in order to avoid any further damage, in particular to the corrosion layer,
which might spoil the results of post-experimental investigations.
4.4. Data to be Measured

The data depend on the type of test. In creep tests under constant load, strain re-
corded as a function of time is plotted in the form of creep curves which yield the
characteristic creep data like minimum creep rate or time to reach a certain strain
value (e.g. 0.2 or 1%).Furthermore, in the context of the influence of corrosion on
mechanical behaviour, the time to rupture, the elongation to fracture, the reduction
in area and the complete creep curves may be of interest. It is recommended to ter-
minate the tests after approx. 30,100,300,1000,3000 h and to take the specimens to
the post-experimental investigations (SEM, metallography, etc.). By this means the
course of corrosion under load can be re-examined (scale thickness, depth of inter-
nal corrosion, depth of surface cracks, subsurface zone depletion, etc.) and these
data compared with those obtained under load-free conditions. This will reveal the
influence of stress on the course of corrosion, while a comparison of the data men-
tioned above with those obtained under corrosion-free conditions gives the influ-
ence of corrosion on the strength of materials.
It has already been mentioned that the constant load creep test may have some
disadvantages which can be overcome by using the constant strain rate or constant
extension rate test. In general these tests enable one to define exactly the correlation
between applied strain, strain rate and corrosive attack, which permit the establish-
ment of corrosion-deformation interaction diagrams [34,45] which are independent
of specimen or wall thickness. Such diagrams can be used to assess the behaviour of
materials even under constant load or stress conditions with superimposed corro-
sive attack [46]. The potential of this procedure is promising, but it needs further
experimental verification before it can be used more extensively and, thus, cannot
be a subject for standardising recommendations at present.
In fatigue tests life-time, cyclic yield curves, etc. (curves according to the descrip-
tion in the respective standards) are also determined in the tests under superim-
posed corrosion. The necessary parameters to be measured for this are stress and/or
strain (amplitude) as a function of time and number of cycles. Crack growth tests
both under static and under cyclic conditions aim at crack growth rates, which are
usually measured by the potential drop technique (cf. [9,43]).Just as in tests without
corrosion, in combined corrosion-deformation tests crack length is recorded as a
function of crack-opening displacement, time or cycle number and load or load
amplitude. As a result static or cyclic crack growth rates are plotted vs a suitable
load parameter. It is also recommended to terminate these tests after the times al-
ready mentioned and to use the specimens for post-experimental investigations on
the course of corrosion and damage.
5. Concluding Remarks
This paper is a first attempt to formulate recommendations for testing under simul-
taneous high temperature corrosion and the effect of stresses/deformation which,
to some extent, can be a basis for standards. Therefore, several details, which may be
important in specific modifications of the tests described (e.g. including acoustic
emission measurements), have been omitted. It was rather the intention to provide a
basis by which the results obtained in different laboratories will be comparable pro-
vided these guidelines are followed by the investigator. The authors are aware that
this can only be regarded as a first step and that much more work has to be done in
this context before a formal standard can be introduced. This includes systematic
pre-normative research on the role of the various test parameters.
6. Acknowledgement
We are grateful to D. B. Meadowcroft, K. Dohle and J. R. Nicholls for the careful

reading of the manuscripts and for valuable additions, corrections and comments.
References
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Temperature Alloys in Aggressive Environments (Eds I. Kirman et al.), The Metals Society, Lon-
don, 1980, p. 869.
2. V.Guttmann and M. Merz (Eds), Corrosion and Mechanical Stress at High Temperature, Ap-
plied Science, London, 1981.
3. V.Guttmann and M. Schiitze, in High Temperature Alloysfor Gas Turbines and Other Applica-
tions - 1(Eds W. Betz et al.), D. Reidel Publishing Company, Dordrecht, 1986, p. 293.
4. C. A. Barrett, R. G. Garlick and C. E. Lowell, High Temperature Cyclic Oxidation Data -Part
I , NASA Report TM-83665, NASA-Lewis Research Centre, Cleveland, OH, 1989.
5. C. A. Barrett and R. G. Garlick, High Temperature Cyclic Oxidation Data - Part 11, NASA
Report TM-101468, NASA-Lewis Research Centre, Cleveland, OH, 1989.
6. I? Hancock and J. R. Nicholls, Mat. Sci. Technol., 1988,4,398.
7. M. Schutze, in Corrosion-Deformation Interactions (Eds T. Magnin and J. M. Gras), Les Edi-
tions de Physique, Les Ulis 1993, p. 703.
8. M. Welker, A. Rahmel and M. Schiitze, Metall. Trans., 1989,20A, 1541.
9. M. Welker, A. Rahmel and M. Schiitze, Metall. Trans., 1989,20A, 1553.
10. K.-T. Rie and H. Klingelhoffer, Ref. [7], p. 493.
11. P. Hancock, Corros. Sci., 1989, 29, 657.
12. ASTM Designation E606-92, Standard Practice for Strain-Controlled Fatigue Testing.
13. ASTM Designation E647-93, Measurement of Fatigue Crack Growth Rates.
14. H. J. Grabke, W.Auer,M. J. Bennett, F. Bregani, F. Gesmundo, D. J. Hal1,D. B. Meadowcroft,
S. Mrowec, J. F. Norton, W. J. Quadakkers, S. R. J. Saunders and Z. Zurek, Werkst. und Korros.,
1993,44,345.
15. J. R. Nicholls et al., Discontinuous measurements of high temperature corrosion, this vol-
ume, pp. 11-36.
16. H. J. Grabke et al., Definition and preparation of gas atmospheres, this volume, pp.62-84.
17. J. Barbehon, A. Rahmel and M. Schiitze, in Ref. [3], p. 1267.
18. M. Gobel, A. Rahmel and M. Schiitze, Oxid. Metals, 1994,41,273.
19. M. F. Stroosnijder, R. Hofmann, F. Lanza, A. Gil, N. Zheng and W. J. Quadakkers, to be
publ. in Corros. Sci.
20. M. F. Stroosnijder, in Application of Particle and Laser Beams in Materials Technology (Ed. P.
Misaelides), Plenum Press, New York, 1994.
21. W. Christl, A. Rahmel and M. Schutze, Oxid. Metals, 1989,31, 1.
22. W. Christl, A. Rahmel and M. Schutze, Oxid. Metals, 1989, 31, 35.
23. M. Walter, M. Schutze and A. Rahmel, Oxid. Metals, 1993, 39, 389.
24. M. Walter, M. Schiitze, A. Rahmel, Oxid. Metals, 1993, 40, 37.
25. H. J. Schmutzler and H. J. Grabke, Oxid. Metals, 1993, 39,15.
26. Y. Zhang and D. Shores, Oxid. Metals, 1993, 40,529.
27. M. Gobel, Karl-Winnacker-Institut der DECHEMA e.V., Frankfurt. M., unpublished re-
sults.
28. DIN Standard 51 220, Material Testing Machines: General Directions.
29. DIN Standard 51 221, Material Testing Machines: Tensile Testing Machines.
30. DIN Standard 51 223, Material Testing Machines: Compression Testing Machines.
31. DIN Standard 51 226, Material Testing Machines: Long Period Creep Testing Machines for
Tensile Stress of Metals.
32. DIN Standard 51 227, Material Testing Machines: Bending-Test Machines.
33. DIN Standard 51 228, Material Testing Machines: Fatigue Testing Machines.
34. M. Schiitze, Mat. Sci. Eng.,1989, A121,563.
35. M. Schutze, Die Korrosionsschutzwirkung oxidischer Deckschichten unter thermisch-
chemisch-mechanischer Werkstoffbeanspruchung, Gebr. Borntraeger Verlag, Berlin, 1991.
36. W. Hartnagel, R. Bauer and H. W. Griinling, in Ref. [2], p. 257.
37. M. F. Stroosnijder, V. Guttmann, R. J. N. Gommans and J. H. W. de Wit, Mat. Sci. Eng., 1989,
A121,581.
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KEMA, Arnhem, 1986.
39. K. H. Kloos, J. Granacher, A. Scholz and R. Tscheuschner, Z . Materialpriifing, 1988,30,5.
40. EN Standard 10 002.
41. DIN Standard 50 118Creep Rupture Test.
42. V. Guttmann and J. Timm, Werkst. und Korros. 1988,39,322.
43. B. Glaser, EinfluiS chlorhaltiger Atmospharen auf das KriechriiSwachstum warmfester
Legierungen. Dissertation, RWTH, Aachen, 1994.
44. B. J. Cane and R. D. Townsend in Flow and Fracture at Elevated Temperatures (Ed. R. Raj),
ASM, Materials Park, 1983, p. 279.
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46. S. Osgerby, in Ref. [7], p. 553.
Corrosion and Wear or Erosion
E H. STOTT
Corrosion and Protection Centre, University of Manchester Institute of Science and Technology,
Manchester. UK
ABSTRACT
Studies of the damage sustained by metal surfaces during sliding wear or erosive wear
by impacting particles under high-temperature corrosion conditions have not been very
extensive to date. Most laboratory test rigs have been based on those built for room
temperature wear, and used either to provide data and give information on damage
mechanisms or to simulate, to some extent, particular industrial processes. Some of the
features of such facilities are described and the main methods of measuring wear dam-
age are considered. It is concluded that there is no universal method of presenting wear
data under corrosion conditions since wear damage is very dependent on a range of
interacting parameters. Nonetheless, some discussion is given of the usefulness of the
various wear measurement methods.
1. Introduction
Wear can be defined as the progressive loss of material from the operating surface of
a body occurring as a result of relative motion at that surface. This loss of material
has enormous economic consequences. Unfortunately, there is no reliable way of
predicting wear, given the nature of the contacting surfaces and the conditions of
interaction at those surfaces. Thus, it is generally agreed that the only safe method of
selecting materials for a particular application is on the basis of tests, initially, realis-
tic laboratory tests and then field tests [l].
There are various types of wear that can cause damage to components in service,
such as:
sliding wear - which occurs when two solid surfaces slide in contact with
each other under an applied load, and
erosive wear -which occurs when fast-moving hard particles impact onto a
solid surface at various angles.
These phenomena have been studied extensively at room temperature, since there
are numerous industrial processes in which such wear damage can be extensive,
with implications for efficiency, safety and maintenance. However, wear can also
occur at high temperatures, where corrosion/oxidation can influence significantly
the damage process. Indeed, the synergistic interactions of corrosion and wear can
be very complex. Under certain conditions, oxides may form on the component sur-
face and be removed by the mechanical wear process, often resulting in faster rates
of damage than in the absence of oxidation. Under other conditions, oxides may
form and be retained on the surface, giving protection against wear damage.
Although there are various types of wear-corrosion interactions, this paper is con-
cerned with the two most important ones in terms of high-temperature environ-
ments, namely sliding wear in the presence of gaseous corrosion and erosion by
hard particles in the presence of gaseous corrosion. It should be appreciated that
most laboratory facilities to study such phenomena have been built as 'one-offs',
usually to provide information and data relating to one particular process. There are
few, if any, standard high-temperature sliding wear or erosion test rigs, making cross-
correlation and comparison between data from different machines difficult. Many of
the methods for examining and analysing specimens from high temperature wear
tests are similar to those for examining specimens from other high temperature proc-
esses, so they will not be considered further. Rather, emphasis is placed on wear test
facilities and methods of measuring damage.
2. Wear Test Methods
There are two main approaches to the use of laboratory wear-test facilities, namely
to design and build a rig to study a specific wear situation or to use one or more
standard systems. The main advantage of the former is that it permits a closer simu-
lation of the required service conditions than a standard rig while its main disad-
vantage is that it is restricted in the range of situations that can be simulated. How-
ever, it is widely recognised that the reliability and relevance of results from a test
increase with increasing simulation of the real service conditions. If a test condition
differs significantly from that in service, it is important that there is no change in the
nature of the wear process between the two situations, otherwise the test results
would be almost worthless. Thus, it is essential that, when materials are to be classi-
fied with respect to their high-temperature wear resistance, the utmost care must be
taken to ensure that the test rig is constructed such that the practical service condi-
tions are approximated as closely as possible. This particularly applies to tempera-
ture, load, sliding speed and environment since these can modify considerably the
nature of the contacting surfaces, such as the extent of oxide retained on them. Hence,
the applicability of standard rigs for studying the interaction of wear and high-tem-
perature corrosion is very limited since the usual methods of accelerating the rate of
damage, such as increased temperature, increased load or increased speed, are also
likely to alter the wear process.
2.1. Sliding Wear-Corrosion

There are numerous test rigs that are used to measure wear damage at room tem-
perature. These are designed to allow two surfaces in contact to move relative to
each other under carefully-controlled conditions of applied load, sliding speed and
Corrosion and Wear or Erosion 123
specimen size and configuration. There are various ways in which contact between
the specimens can be attained. Figures l(a) and (b) show examples where the speci-
mens are symmetrically disposed and the wear rates for both (if of the same mate-
rial) should be the same. Here, contact is along a line (Fig. l(a))or a face (Fig. l(b)).
Asymmetrical systems are more common. These include pin-on-disc, either on the
flat face (Fig. 2(a))or on the rim (Fig. 2(b)),block-on-ring (Fig. 2(c)) and pin-on-flat
(Fig. 2(d)).In these cases, contact may initially be over an extended nominal contact
area (e.g. flat-ended pin on a flat disc) or only a point or line contact (e.g. round-
ended pin on a flat disc) (Fig. 3). In asymmetrical systems, one component (usually
the pin or block) is treated as the specimen and is the component for which wear is
measured, while the other is the counterface (which may be the same material as the
specimen or may be any other material, such as a harder surface or an abradable
surface). Motion between the components can be unidirectional or reciprocating,
depending on the system. For room-temperature sliding, various standards apply,
e.g. for pin-on-disc (ASTM G99),for rotating pin-on-flat (ASTMG98) and for sphere-
on-disc (DIN 50324).
However, for studying sliding wear at high temperatures, where formation of
oxides on the contacting surfaces can influence significantly the rate of wear dam-
age, such standard machines are of less use in evaluating materials performance for
specific applications. It is more usual to design and build a system that simulates as
Fig.1 Geometries of specimens used in sliding-wear tests, where the specimens are symmetrically
disposed Ill.
(a)
( C) 6(d14.i!p
i
Fig. 2 Geometries of specimens used in sliding-wear tests, where the specimens are asymmetrically
disposed 111.
Fig. 3 Geometries of (a) conformal contact and (b) counterformal contact.
closely as possible a particular process, in terms of sliding and corrosion conditions,

rather than use a standard, all-purpose system. Nonetheless, most high-tempera-
ture sliding wear rigs are based on similar principles as those for studying room-
temperature wear. Such rigs have almost always been designed for use in oxidising
gases, so components in the hot zone have typically been made from nickel-or iron-
base high-temperature alloys. Most rigs use the round-ended pin-on-disc configura-
tion, in either unidirectional or reciprocating motion. A typical rig to study wear of
turbine alloys is shown in Fig. 4 [2] Here, a round-ended pin is in contact with a flat
disc specimen that moves in a reciprocating motion. The system can operate under
well-defined oxidising gases at temperatures to 900°C; parameters such as load,
amplitude of motion and speed can be fixed and controlled at desired values to
simulate appropriate sliding processes. A similar rig is shown in Fig. 5 [3].
Button specimen
Fig. 4 Schematic diagram of a high-temperature reciprocating sliding-wear apparatus f21.

Heater
Sliding
\ \
......e...
r
c"r,
6
-,.
Linear R ec ipr ocat ing 'Fr ic t ion
bear t ngs shaft transducer
Sliding I ; : , steei ,Sliding

sleeve
/sleeve
+lZ4
Front
View
flat
specimen
- Cross
32-
- Section
Fig. 5 (a) Schematic diagram of a high-temperature sliding-wear apparatus 131. (b) Specimen
design [31.
2.2. Erosion-Corrosion
In erosion, several forces of different origins may act on a particle as it comes into
contact with a solid surface [l](Fig. 6 ) . Neighbouring particles may exert contact
forces and a flowing medium, if present, may cause drag. However, the main force is
usually the contact force exerted by the surface; this is largely responsible for decel-
erating the particle from its original impact velocity. The impacting particles may
cause damage to the surface, with the extent depending on their number and mass,
the impact velocity and the angle of impact.
There have been many studies of room-temperature erosion wear but it is only in
the past few years that systematic investigations of the interactions of high-tempera-
ture corrosion and erosion have been carried out. This is perhaps surprising since
erosion-corrosion involving impact by hard particles in a flowing gaseous medium
is potentially a serious damage mechanism in various high-temperature industrial
processes, such as those with gas turbines where very fast-moving small particles at
low concentrations can impact onto blade or other component surfaces or fluidised-
bed coal combustors where slow-moving large particles at high concentrations can
impact onto heat exchanger or other component surfaces. It is often difficult to pre-
dict such damage since it can be a relatively random phenomenon and, for instance,
may be influenced by the systems that are designed to filter out or deflect the parti-
cles from vulnerable components in the plant or process.
Fluid
Surface flow lp.
__
contact
force
Inter-particle contact forces
j. Weight
Fig. 6 Forces acting on an erosion particle in contact with a sutface 111.
In order to study erosion-corrosion processes, it is necessary to have closely-de-

fined conditions of particle impact velocity, particle flux, impact angle, environment
and temperature. There are two main methods available to achieve these conditions:
(a) particles are accelerated in a gas stream, and

(b) circular motion is used to achieve the relative impact velocity.
Figure 7 shows schematic diagrams of four types of systems that involve these
methods. In (a), particles are accelerated in a gas stream along a nozzle under a
pressure drop and impact onto a stationary specimen at a given angle. Velocities in
such systems can achieve up to 200-300 m s-l, e.g. as may occur in gas turbines. In
(b), a two-phase flow of particles plus gas is driven around a pipework loop; this
recirculating loop system is useful for studies of erosion-corrosion of pipework com-
ponents, but has problems of particle disintegration. In (c), a centrifugal accelerator
system uses circular motion to generate a continuous steam of particles. This is
achieved by feeding particles into the centre of a rotating arm; these leave the tube at
a speed determined by the peripheral speed of the arm and impact onto stationary
specimens located around the rim. In (d), two specimens are held at the ends of a
(a)
-
A-
Gas
(C)
Fig, 7 Schematic diagram showing various methods of exposing specimens to erosive wear in the
laboratory 111.
balanced rotor arm and move through a slowly falling stream of particles at a speed
determined by the rotational speed of the arm and an angle determined by their
orientation (a whirling-arm tester).
Figure 8 shows a diagram of a jet-impingement rig where particles are fed into an
air stream by a screw feeder and accelerated and impacted on to a stationary speci-
men held at a well-defined angle to the particle flow in a controlled-temperature
environment 141. An example of a whirling-arm rig is illustrated in Fig. 9. Here, the
specimens are rotated through a stream of particles, carried in nitrogen, and mixed
with a controlled, essentially reducing gas mixture (such as hydrogen/hydrogen
sulphide) at high temperature. This enables erosion-corrosion in coal-conversion
type environments to be investigated [5].
One area of particular interest in recent years has been erosion-corrosion in fluid-
ised-bed combustion conditions. Several groups have independently designed and
built rigs to examine the interactions of erosion and oxidation under such condi-
tions. These involve moving specimens through a bed of fluidised particles to obtain
the required relative speeds between the two. In one case, they are vibrated rapidly
in a vertical mode in the bed (Fig. 10, on p.129) 161, in another, they are rotated hori-
zontally within the bed (Fig. 11 (p.130))[7] and, in a third, they are rotated vertically,
in and out of the bed (Fig. 12 (p.130))[8].However, despite these differences, similar
trends in terms of erosion damage as a function of temperature have been obtained.
€rodent panicles
Scre
Specimen location Specimen circulating

assembly pumps
Fig, 8 Schematic diagram of a high-temperature erosion-oxidation jet-impingement rig f41.

W D i r e c t i c n of gas flow
1 I
Fig. 9 Schematic diagram of a high-temperature controlled-environment whirling-arm, erosion-

corrosion test facility r51.
3. Measurement of Wear Damage
Wear damage can be defined in at least two ways which may not always be consist-
ent with each other. These are:
(i) actual loss or removal of material, and

(ii) displacement of material from its original position.
The former is often measured in terms of mass loss while the latter is character-
ised by a change in surface topography which may not be accompanied by a corre-
sponding change in mass. Displacement changes are of particular importance to the
design engineer while loss of material is usually the main concern to the materials
engineer. For most purposes, it is usual to equate material loss (mass loss or thick-
ness loss) with wear damage.
3.1. Sliding Wear-Corrosion

In sliding wear, the specimen is usually removed after a certain time of sliding and
weighed or measured to determine the loss of material. However, mass changes are
less reliable for high-temperature wear, due to the need to compensate for mass
gains due to oxidation of the non-contacting parts of the specimen.For counterformal
contact, such as a hemisphere-on-flat configuration, measurement of the area of the
Solenoru Valve
near Dlsulaeemenl
Actuation Rod
ProWs
Air Inlet
-20 cm
Fig. 20 Schematic diagram of afluidised-bed erosion-corrosion rig 161.
wear scar on the former enables the volume of material lost to be calculated.
Profilometry techniques can also be used to provide three-dimensional representa-
tions of the wear scar and measurements of material loss or material displacement.
The problems of interrupted tests for high-temperature wear tests are similar to those
for high-temperature corrosion tests, in terms of the possibility of scale damage due
to differential thermal contraction/expansion effects. It is usual to stop the sliding
motion prior to cooling the specimens and not re-start it until the specimens have
reattained the test temperature.However, there is the possibility that any wear-formed
oxides on the contacting surfaces may undergo mechanical or even chemical changes
during the cooling and heating cycles. An additional difficulty is in ensuring that
the two specimens are relocated in exactly the same positions and relative orienta-
tion in the rig. This can be helped by measuring the wear damage without removing
the specimens from the specimen holder (e.g. the wear-scar dimensions can be ob-
tained in situ, although not the mass changes). In some test rigs, it is possible to
obtain continuous wear data, e.g. by measuring the position of the specimen con-
Air 1
Cooling
Frame
Gearbox
_ _ Bearing
Column Contrnl
Reductinn
’Gearhox Unit
Drive
Motor
Fluidized
I I I I I I l l 1 I
Rotors
Heater
Elements
Distrihutor
Fig. 11 Schematic diagram of a fluidised-bed erosion-corrosion rig 171.
-2 -Baffles
Drive motor
1
speci m‘on
holder
t Fluidized bed of particles
‘
-4 i
-y‘
j Preheater
Fig. 12 Schematic diagram of a fluidised-bed erosion-corrosion rig 181.

tinuously with an electrical or mechanical transducer and determining the wear
damage from changes in specimen dimensions (usually height). However, this is
often not a very sensitive technique and gives information on the wear of both speci-
mens together, rather than on the wear of each specimen separately.
In addition to wear data, sliding wear tests can also generate two other sets of
data that can often be very useful in terms of providing information on the condition
of the contacting surfaces, particularly when oxidation or corrosion is playing a sig-
nificant role. The coefficient of friction can be determined continuously by measur-
ing the tangential force on the specimen or the torque on a rotating counterface.
Such data can allow changes in sliding behaviour to be observed almost instantane-
ously. For instance, a change from an irregular high coefficient of friction to a lower
value and a much smoother frictional trace can indicate a change from metal-metal
contact to oxide-oxide contact, as often occurs during sliding at high temperature in
an oxidising environment (Fig. 13) [9]. Similarly, continuous measurements of the
contact resistance between the sliding surfaces can indicate when the contact changes
from metal-metal and an oxide scale develops at the points of contact, as shown in
Fig. 13. In some cases, the data can be used to estimate the thickness of such a scale.
Often, such information can be more useful than measurements of the absolute wear
values.
3.2. Erosion-Corrosion
Accurate information on erosion-corrosion damage is also difficult to obtain and,
almost always, involves intermittent measurements, of either mass change or thick-
ness change. Mass-change data can be useful under certain circumstances but, es-
. '
I I I
1.5
Jethete
r
Cor icient of friction
I
-106 5
c 0
- d
.Q
U
.li 1. -lo5
L C
"--Friction peaks -'-Smooth sliding- n
c
0
I -lo4 5u
c
1 f!
C
.s.-r 05 -
x
u Contact resistance
I I
Time, 5
Fig.13 Plots ofcoeflicient ofpiction and contact resistance us time during like-on-like sliding of
an iron-12% chromium alloy in air at 400°C [91.
sentially, give only summations of mass loss due to erosion, mass gain due to oxida-
tion of the non-exposed surfaces and possible mass gain due to embedment of erodent
particles. However, the extent of erosion damage is rarely uniform over a surface. It
is very dependent on impact angle, particle loading and relative speed of impact
with the particles [lo]. This is illustrated in Fig. 14 which shows schematically the
extent of damage to a rod specimen from a fluidised-bed rig in which the specimen
was rotated horizontally. The relative angles of impact, speeds of impact and parti-
cle loadings vary along and around the specimen, producing the damage profiles
shown. In a jet-impingement rig, flat specimens can be inclined to produce a con-
stant angle of impact over the surface but, even so, there is usually a change of par-
ticle loading from the centre to the edge of the particle stream (and, hence, in the
corresponding damage to the specimen surface).
Thickness-change data can accommodate some of these difficulties. They can be
obtained in a non-destructive manner by using micrometer or more sophisticated
surface profiling methods, as illustrated in Fig. 15 [HI. These can give accurately-
located data, although the latter do not always correlate with metal loss, particularly
if there is significant scale on the eroded surfaces. Metal loss is usually determined
by the normal destructive methods of mounting and examining metallographically-
prepared cross sections and comparing residual metal thicknesses with those of
mounted standards.
3.3. Presentation of Wear Data
3.3.1. Sliding wear-corrosion

In room-temperature sliding, it is often found that, after an initial running-in period,
the wear rate becomes relatively constant with time and follows a relationship of the
type:
V=kW
where Vis volume of material removed per unit distance, W is applied normal load,
and k is the wear coefficient. The value of k is often used as a measure of wear resist-
Rouh
Fig.14 Schematic diagram of erosion damage to a cylindrical specimen after exposure in afluidised-
bed erosion-corrosion rig 1101.
Fig. 25 Jigfor measuring surface profiles of cylindrical erosion-corrosion specimens 1121.
ance. It represents the volume of material removed by wear per unit distance of
sliding per unit normal load on the contact. The units are usually mm3 (Nm)-l or
m2N-l .
Although this approach is used successfully for many applications, it is less use-
ful under high-temperature conditions where the formation of oxides may, eventu-
ally, eliminate metal-metal contact, causing a change in wear mechanism and, thus,
wear rate. Figure 16 shows typical wear volume versus time plots for sliding at vari-
ous temperatures [12]. At 200°C and above, the wear rate decreases to almost zero
after some time of sliding, due to the establishment of wear-protective oxides on the
load-bearing surfaces. The time to attain this transition and the effectiveness of the
oxides in reducing wear are very dependent on sliding conditions, e.g. applied load,
sliding speed, temperature, environment, etc., making it difficult to use a universal
relationship to describe the wear rate. Nonetheless, wear rates pertinent to the initial
stages of sliding, prior to establishment of the wear-protective oxides, and to the
later stages, after establishment of the oxides, are often quoted in terms of either
mm3m-* or mg m-l for a given load or mm3(Nm)-*.This is acceptable provided there
is no significant change in surface condition during such periods.
3.3.2. Erosion-corrosion
In room-temperature erosion, there is often a linear relationship between the amount
of material removed and the total mass of erosion particles impacting the surface;
this gives a simple universal relationship:
mass of material removed

E=
mass of erosion particles striking the surface
where E is a dimensionless parameter, or

Time Is)
Fig.16 Wear volume versus time plots during like-on-like sliding of Nimonic 108 at temperatures
of20" to 600°Cin a high-temperature reciprocating sliding-wear rig f121.
volume of material removed

E=
mass of erosion particles striking the surface
where E has units of mm3 8-l.

However, at high temperatures, where oxidation plays a much larger role, such
parameters are less useful as they take no account of particle flux. An important
factor in erosion-corrosion is the time between impacts at a particular location since
this will determine the thickness of oxide that is impacted by the next particle. The
reaction of the oxide, in terms of susceptibility to damage, is influenced by its thick-
ness. Hence, a universal method of expressing erosion rate is not particularly useful
under erosion-corrosion conditions. The damage rates measured under a given set
of conditions of impact angle, particle velocity, particle size and shape, particle flux,
temperature and environment are likely to be pertinent to those conditions only. A
change in only one of those parameters could cause a change in the mechanism of
damage. Indeed, as for sliding wear, a change in mechanism can occur as a function
of time, particularly if oxides are retained and grow on the surfaces during the ero-
sion-corrosion process.
4. Conclusions
1. Studies of the interactions of high-temperature corrosion with sliding wear or

erosive wear by impacting particles have mainly involved laboratory test facilities
designed to simulate as closely as possible the conditions of particular processes.
Standard machines are not generally available and, in view of the synergism be-
tween mechanical wear and chemical corrosion, are unlikely to provide universal
data of general applicability.
Corrosion and W e a r or Erosion 135
2. Measurements of damage usually involve intermittent thickness-change or mass-
change data; the former have the disadvantage of giving average values for the whole
specimen, including non-contacting as well as contacting surfaces, while the latter
can be more specific to the contacting surfaces.
3. Continuous measurements of friction and contact resistance can provide useful

information under sliding-wear conditions, particularly on changes in the surface
condition during sliding.
References
1.I. M. Hutchings, Tribology: Friction and Wear of Engineering Materials, Edward Arnold, Lon-
don, 1992.
2. E H. Stott and G. C. Wood, Tribology, 1978,11,211.
3. J. Skinner, CEGB Report RD/B/5220N81,1981.
4. E H.Stott, G. C. Wood, P. Jordan and S. Casey, unpublished work.
5. E H. Stott, G. C. Wood and P. Jordan, unpublished work.
6. S. S. MacAdam and J. Stringer, Corrosion, 1993,49,156.
7. I. M. Hutchings, J. A. Little and A. J. Ninham, Corrosion-Erosion - Wear of Materials at El-
evated Temperatures (Ed. A. Levi), NACE, Houston, TX, 1991.
8. F. H. Stott, S. W. Green and G. C. Wood, Mat. Sci. Engng, 1989, A121,611.
9. J. Glascott, E H. Stott and G. C. Wood, Wear, 1984,97,155.
10. A. J. Ninham, M. J. Entwistle, I. M. Hutchings and J. A. Little, Proc. 20th Int. Conf. on Fluid-
ized-Bed Combustion, San Francisco (Ed. A. M. Manaker), ASME, New York, 1989, p.583.
11.D. J. Hall and S. R. J. Saunders, High Temperature Materialsfor Power Engineering- 2, Kluwer
Acad. Pub., 1990, p.157.
12. D. S. Lin, E H. Stott and G. C. Wood, ASLE Trans., 1973,17,251.
Oxidation/Corrosion of Advanced Ceramics: A
Review of the Progress Towards Test Method
Standardisation
D. J. BAXTER
Institute for Advanced Materials, JRC Petten, 1755 ZG Petten, The Netherlands
ABSTRACT
The last five years have seen a progressive increase in attention paid to the develop-
ment of standard test methods for a range of properties important in the engineering
application of structural materials. For ceramics, the efforts have resulted in a number
of physical and mechanical property standards being published in the three major eco-
nomic areas of the world, Japan, North America and Europe. The first advanced ceram-
ics oxidation standard was published in Japan in 1990. This standard is analysed and
the work towards an oxidation standard in Europe is described. The situation regard-
ing corrosion of ceramics is similar to that for metals. The initial approach is to develop
guidelines for the assessment of corrosion damage with the manner by which corrosion
tests are done covered by codes of practice. Details of the development of corrosion
standards are discussed.
1. Introduction
The class of monolithic and composite ceramic materials termed engineering, tech-
nical or advanced ceramics exhibits a n attractive range of properties relative to me-
tallic counterparts commonly used in a number of high temperature applications. In
particular, retention of mechanical properties to temperatures in excess of 1200°C
present the opportunity to plant designers to increase operating temperatures, im-
prove process efficiencies and reduce the levels of emitted pollutants. Lower densi-
ties of ceramic materials than competing metallic counterparts permit the achieve-
ment of higher specific strength and thus increased pay loads and reduced energy
consumption. Advanced ceramics are thus attractive candidate structural materials
for use in energy production and conversion and in engines. Continued progress to
actual adoption in commercial installations has been hindered mainly by poor me-
chanical reliability and uncompetitive costs of production. Advances in manufac-
turing technology are yielding improvements in mechanical performance and gradu-
ally reducing the cost of production. While the financial systems for determining
cost are well developed and understood, the judgement of component reliability is
dependent on the availability of a solid base of valid materials test data. Past experi-
ence has shown time and again that sound materials performance databases only
OxidationlCorrosion of Advanced Ceramics:A Review 137
result from well planned and coordinated test programmes using agreed test meth-
odologies. In essence, a range of standards is a core part of a materials development
programme. The absence of standard test procedures, precise guidelines or agreed
codes of practice precludes effective comparison of test data. The consequence is
that a considerable amount of the effort expended in obtaining test data is wasted.
Even worse, the exploitation of a promising material may be delayed or missed if
reliable performance data are not produced.
In the last ten years, work has been focused on formulating standard tests for
physical and mechanical property determination in various parts of the world. Oxi-
dation and corrosion are relatively new additions to the agendas of the standards
committees. In principle, oxidation testing ought to be relatively straightforward
and so existing test methodologies should be readily amenable to standardisation.
The main question to be addressed is the level to which the standard is targeted, i.e.
how much and how detailed should be the data generated by the test? How simple
can a simple test be without the risk of obtaining misleading results, and how com-
plex can a test be made without making it prohibitively expensive to carry out? A
simple standard oxidation test methodology has recently been published. The re-
lease of the Japanese Industrial Standard, JIS-R-1609, for non-oxide advanced ce-
ramics in 1990 has had the effect of stimulating greater international action on the
subject of oxidation/corrosion, particularly in Europe. The Comite Europeen de
Normalisation (CEN)technical committee for advanced ceramics is involved in evalu-
ating the Japanese standard and considering the way forward for corrosion stand-
ards. This article describes the organisation of ceramics standards activities around
the world. The Japanese oxidation standard is described in detail and philosophies
for the approach to corrosion standards are discussed.
2. Summary of Ceramics Standards Activities
Standardisation of test procedures for advanced ceramics is being conducted in the

three major economic zones of the world, Japan, North America and Europe. While
direct contact between the respective standards organisations (TIS,ASTM and CEN)
is somewhat limited, there exist other bodies, particularly the VAMAS (Versailles
Project on Advanced Materials and Standards) that facilitate collaboration and re-
duce duplication of effort. The IS0 (International Standards Organisation) has only
recently started an activity on ceramics (TechnicalCommittee TC206) and is expected
in the future to enhance unification of standards at a world level. In order to provide
a perspective of the scope and direction of activities, a summary of the work of each
zone or major body is given.
2.1. Japan
Since 1983ceramics standardisation work has been contracted out to the Japan Fine
Ceramics Association (JFCA).In 1988 the work has been organised within four ex-
pert committees; thermal and mechanical; electrical, magnetic and optic; powder,
process and chemical; field of artificial materials for organisms. To date, sixteen stand-
ards have been published:
JIS R 1600 Glossary of terms

JIS R 1601 Flexural strength at room temperature
JIS R 1602 Elastic modulus at room temperature
JIS R 1603 Chemical analysis of S$N, powder
JIS R 1604 Flexural strength at elevated temperature
JIS R 1605 Elastic modulus at elevated temperature
JIS R 1606 Tensile strength at room and elevated temperatures
JIS R 1607 Fracture toughness
JIS R 1608 Compressive strength
JIS R 1609 Oxidation of non-oxide ceramics
JIS R 1610 Room temperature Vickers hardness
JIS R 1611 Thermal diffusivity, specific heat and thermal conductivity
JIS R 1612 Bending creep
JIS R 1613 Wear resistance by the ball-on-disc method
JIS R 1614 Corrosion in acid and alkaline solutions
JIS R 1615 Adaptation assessment under high temperature and pressure.
Additionally, work is continuing on producing a classification system, as well as

standards for a range of other physical and mechanical properties and high tem-
perature corrosion [l].
2.2. North America

Substantial work is being directed towards the development of ceramics for heat
engines and heat exchange applications. Some of the vast experience gained on mili-
tary research and development, partly evident through the well known Military
Handbooks, is now being put to civil use. The ASTM committee C28 is the prime
coordinator of national standards activities on advanced ceramics with sub-com-
mittees focusing on: properties and performance; design and evaluation; wear /
tribology; rheology, machining and thermal processing; processing and characteri-
sation; ceramic matrix composites; nomenclature. The National Institute of Stand-
ards and Technology (NIST)is involved in the development and distribution of evalu-
ated data bases for ceramic properties. The committee, E49 is working on general
materials databases.
To support accurate and reproducible testing, a number of Standard Reference
Materials (SRMs) is available through the NIST. A summary of the American stand-
ards work has been published recently [2].
2.3. VAMAS
VAMAS was established in 1982 by the seven countries of the Economic Summit
OxidationlCoruosion of Advanced Ceramics:A Review 139
(USA, Canada, J, D, F, I, UK as well as the European Commission) in order to pro-
mote a concerted effort on advanced technology that would contribute to stimulat-
ing economic growth, trade and international collaboration. Included in the VAMAS
portfolio are nineteen Technical Work Areas (TWAs)spanning metals, polymers, ce-
ramics and composites. Three of the TWAs relate to ceramics corrosion:
TWA 3: Ceramics. The work is concerned with the mechanical properties, crack
growth in alumina and Si,N,, hardness of alumina and thermal shock and fracture
toughness of Sic and ZrO,.
TWA 8: Hot salt corrosion resistance. Though not originally planned to include
ceramics, the methodology developed should in principle be adaptable to the corro-
sion testing of ceramics. Guidelines for the hot corrosion testing of superalloys in
burner rigs have been published [3] and subjected to a round-robin test campaign.
The final report of the round-robin is expected in 1995, after which any changes to
the methodology will be made.
TWA 14: Classification system. The results of an extensive industrial survey [3]
showed a definite need for a system of terminology and classification. The issues
involved in forming the system are contained in the proceedings of a 1991 VAMAS
workshop [4]. The collaboration between participants from Europe, Japan and the
USA has resulted in unification of effort, thereby avoiding the parallel development
of different systems. For Europe, the VAMAS classification system is being adopted
by CEN.
2.4. The International Energy Agency

The IEA programme has two main themes in its work on high temperature ceram-
ics, ceramics for automotive engines and ceramics for advanced engines and other
conservation applications. Starting in 1986 with the USA, Germany and Sweden
participating (and later Japan), the main stated objectives of the work are to avoid
unnecessary duplication of effort and to formulate standards for testing and charac-
terisation of ceramics. As with NIST (in the USA) data bases are to be used for effi-
cient compilation of reference data, enabling a better correlation between mechani-
cal test results and engineering application for selected ceramics.
2.5. Europe
While a number of national initiatives have been launched in the last ten years, for
example in Germany, France and the UK, the main thrust for standardisation of ce-
ramics testing comes from the European standards committee, CEN. Following a
review of the status of standardisation [ 5 ] ,the Technical Committee, TC184 was set
up in 1989 specifically to address advanced ceramics. Ten of the eighteen members
of the European Union and EFTA take part in TC184 activities, which had five Work-
ing Groups in the first three-year programme (1990-1992):
WG 1 Classification and terminology (convenor -Netherlands). Work being done
in conjunction with VAMAS TWA14.
WG2 Methods of test for ceramic powders (convenor - France). Including impu-
rity determination, powder size distribution, specific area, bulk density and
compaction properties.
WG3 Methods of test for monolithic ceramics (convenor - UK).
WG4 Methods of test for ceramic composites and reinforcements (convenor -

France). In essence this work runs in parallel with that for monolithic ce-
ramics in WG3.
WG5 Methods of test for ceramic coatings (convenor - Germany).
A summary of the progress made by the TC in its first 3-year programme has
been published [6].
3. Related Testing Standards
A survey of existing standards, mostly in the field of aqueous corrosion of metals

[7], revealed a number of test methods with some relevance to the oxidation/corro-
sion of advanced ceramics. Most corrosion related standards refer to test methods
for metals under aqueous conditions, with few applicable to high temperature cor-
rosion. The following is a brief list which gives an indication of the state of standards
development.
JIS R 1609 Oxidation resistance of non-oxide high performance ceramics
JIS R 1614 Corrosion of high performance ceramics in acid and alkaline

solutions
ASTM (2863-83 Oxidation resistance of Sic refractories at elevated temperatures
IS0 8044 Glossary of terms for corrosion of metals and alloys
IS0 9223 Classification of corrosivity of atmospheres (discussion docu-

ment)
IS0 9226 Determination of corrosion rate of standard specimens for the

evaluation of corrosivity(discussion document)
ASTM G1-90 Preparing, cleaning and evaluating corrosion test specimens

OxidationlCorrosionof Advanced Ceramics:A Review 141
ASTM G46-76 Examination and evaluating of pitting corrosion
ASTM G54-84 Simple static oxidation test (metals)
ASTM G79-83 Evaluation of metals exposed to carburisation environments
ASTM G107 Formats for collection/compilation of corrosion data for metals

for computerised data base input.
The Japanese Oxidation Standard:]IS-R-1609 (1990)

The official English translation of this, the only published advanced ceramic stand-
ard [8] is summarised below. This is done section by section, with comments/criti-
cisms originating from a working group convened to develop corrosion standards
for ceramics [9].
3.1. Scope
Test method for the oxidation resistance at high temperature of non-oxide, high per-
formance ceramic sintered bodies such as S$N, Sic and SiAlON.
(Comment:Could also include particulate ceramic composite materials, other oxides and
nitride and borides.)
3.2. Definition
Oxidation resistance: The resistance against lowering of strength and collapse by
oxidation of material surface due to reaction with oxygen in air.
3.3. Test Apparatus and Appliances

3.3.1. High temperaturefurnace
Vertical or horizontal tubular furnace or box-type resistance heated furnace with
temperature capability of 1500°C (k 5°C) and equipped with air supply to avoid
oxygen depletion.
3.3.2. Specimen support

Material of support to avoid reaction and adhesion and allow point or line contact
with test specimen in a vertical position.
(Note: For testing Si,N, or SiAlON support material should be Si,Np or alumina in
combination with platinum wire. For Sic the support material should be Sic or alumina.)
In addition, an oven (105 to 120°C) for drying specimens, a bend tester to JIS-R-
1601requirements [lo], a micrometer, dial gauge, vernier callipers and chemical bal-
ance are defined in the standard.
(Comments: Should specih alumina furnace work tube and hot zone furnace furniture
and programmable heating and cooling rates capability ( e g . 5°C m i d ) . Platinum and silica
should not be used in thefurnace hot zone.)
3.4. Test Piece
3.4.1. Ceramic
For determination of strength in the as-received condition and of oxidation behav-
iour a minimum of 10 test pieces, 3 mm x 4 mm x a minimum of 36 mm should be
used. The surface roughness should be not more than R, = 0.2 pm, and the corners
rounded or chamfered.
3.4.2. Reference material

High purity electrolytic nickel, the same dimensions as the ceramic test piece.
(Comments: There should be an option to enable the collection of oxidation kinetic data, in
which case a different test piecegeometry would be preferred; i.e. a disc, typically 20mm diu.
and 2 mm thick. The adoption of the European standard for room temperatureflexural test-
ing, EN843/1 [Zl], would permit a choicefrom three different, well defined methods of speci-
men manufacture and surfacefinish to be made.)
3.5. Test Method

(i) Oxidation test: After measuring dimensions of the test pieces, wash, dry and
desiccate before weighing. Place test pieces in uniform hot zone of furnace
with adequate spaces between for air circulation. Flow air at 0-10 cm and
raise temperature to 1300°C for Si,N, or SiAlON or 1400°C for.SiC, for 100 h
in each case. Desiccate test pieces after exposure and record mass change.
(ii) Measure bend strength of as-received and oxidised material at room tem-
perature using JIS-R-1601.
(iii) Expose the nickel reference material at 1200°C for 24 h, otherwise under the
same conditions and record mass change.
(Comments: A wider test temperature range (800°C -1400°C) should be encouraged /
specified and times up to 500 h with the possibility of thermal cycling (after every 20 h ?).
Discontinuous or continuous mass change measurement should be supported. A better refer-
ence material than nickel would be Sic. The measurement of strength should be at room and
elevated temperature and the injluence of annealing (as apart from oxidation) needs to be
established via a third batch of material annealed in an 'inert'atmosphere.)
3.6. Reporting Results

(i) Determine mass change per unit area and report average and standard devia-
tion.
(ii) Determine bend strength according to JIS-R-1601, using the original dimen-
sions before oxidation (Le. not the dimensions of ceramic plus surface oxida-
tion product) and report average and standard deviation. Report Weibull
modulus if the number of test pieces is at least 30.
OxidationlCourosionof Advanced Ceramics:A Review 143
The composition and preparation history of the test material, precise test condi-
tions (air flow, humidity, support material, mass change of reference material), type
and construction of furnace and number of test pieces, in addition to thickness and
composition (with SEM micrograph) of the oxide layer must also be reported.
(Comment:Damage assessment should also include change in dimensions, suYface rough-
ness, change in hardness and indication offracture origin.)
4. Development of a European Oxidation Standard
The approach to any standard must first address the question of the need that the
standard has to meet. Should the standard be a simple proof test, as is the case of the
Japanese standard, or something providing wider technical (performance) data? At
the present time, this issue has not yet been resolved. However, it is likely that the
first European standard for oxidation will follow the theme of the Japanese stand-
ard. Initially, it is necessary to establish whether JIS-R-1609 is valid on technical
grounds. From the comments made at the 1993 Petten workshop [9] and the devel-
oping opinions within CEN TC184/WG3, the Japanese standard must clearly be
used as a model. The use of strength change as the main measure of oxidation in-
duced damage in JIS-R-1609is widely supported in Europe, but the Japanese stand-
ard is considered inadequate mainly in the areas of specification and use of test ap-
paratus and the range of conditions covered by the recommended test parameters.
The main objections to JIS-R-1609 are included in the previous section and in more
detail in a discussion document [12] submitted to the CEN working group. The first
draft European oxidation standard was issued near the end of 1994, [13].
5. Work Towards European Oxidation Standard
Most industrial process or engine systems obviously do not operate with what can
be termed simple oxidising environments. Additional standards must therefore be
written in order to serve materials testing in environments that are not simply oxi-
dising. The problem facing the standards writers is clearly; what kind of test meth-
odology can possibly serve this complex area of materials performance?
Currently, the task is being approached on two fronts. The first is to identify proc-
esses where a specific test (which may include a limited range of temperatures, or
pressures or similar parameters) could be adopted. The second is a broader, more
general approach by which the methods for assessing corrosion damage are being
developed for use as guidelines (or codes of practice) which would be applied after
corrosion testing under whatever conditions may be chosen by a particular pro-
duced/user, The first such guidelines of this type appear to originate in a draft 1987
British Standards document on determination of resistance to chemical corrosion,
which has subsequently been submitted as a discussion document to CEN [14].This
document states the following criteria as being important in defining corrosion dam-
age:
- depth of penetration of corrosion
- change of mass
- change of cross section
- change of strength
- change of surface hardness
The guidelines do not, however, venture far in providing the person carrying out
the corrosion test with assistance in avoiding the production of erroneous data. The
criticisms of the Japanese oxidation standard strongly suggest that unless very close
attention is paid to experimental details, the test results will almost certainly not
truly reflect the planned conditions of exposure. Hence, the publication of guide-
lines alone for corrosion assessment cannot be considered adequate. Moreover, for
corrosion guidelines themselves to make a significant contribution to promoting
comparison of data, they must necessarily be detailed to the extent of fixing such
parameters as test piece geometry, dimensions and surface finish. With these param-
eters fixed (maybe 2 or maximum 3 geometries permissible), constraints are then
placed on the method of test in terms of test piece support and size of the test zone
and so the demand is placed back on the writers of the original guidelines to greatly
expand their scope of effort. After completion of the needs for reporting results,
which must be in a format amenable for data base entry, the only component of the
'standard' left to be tackled is the specification of the actual corrosion test (corrosion
atmosphere). It is certainly appropriate to develop some existing test methods (e.g.
burner rig) that do strictly define the corrosion atmosphere, but the structure and
layout of standards must be carefully planned from the outset to ensure maximum
possible compatibility.An uncoordinated, unstructured collection of standards, each
with its own format and philosophy, will only serve to alienate the potential user
and therefore put to waste the considerable costs of making the standards. There
will always be the need to permit freedom in the selection of test atmosphere while
encouraging the use of assured codes of practice.
6. Summary
The first oxidation standard for advanced ceramics was published in Japan in 1990
and work is progressing in Europe to produce a similar EN standard. As far as corro-
sion is concerned, the argument over whether a standard should be specific or whether
guidelines (or codes of practice) can be issued has not been completely resolved.
Current work is adopting a modular approach in which specific parts of a standard
are being addressed. For example, sections on setting the geometry and preparation
of test pieces and methods of corrosion assessment are currently being developed. It
seems possible that an EN standard on methods of corrosion assessment could be
drafted in the foreseeable future. At the same time specific (stand alone) methodolo-
gies for tests such as burner rig hot-salt corrosion are being evaluated.
While numerous oxidation and corrosion standards, mainly for metallic materi-
als have been published in the past, the most important consideration is whether
Oxidation/Corrosion of Advanced Ceramics:A Review 145
anyone uses them. ASTM C863 is often applied for testing of refractory Sic and JIS-
R-1609 is being used increasingly by manufacturers and users of ceramics in Japan.
On the other hand, alloy producers rarely refer to standards in material certification
tests and in research and development standards are hardly ever used (and as a
consequence useful comparison of data quoted in the literature is often impossible).
So why is such limited use made of oxidation/corrosion standards? In some respects
the old standards are too basic and are not well targeted at industrial needs. Regard-
less of the problems of the past, the financial pressures of the increasingly interna-
tional nature of the world economy demand far more efficient use of resources. This
means, above all, the virtual elimination of duplication of effort and closer collabo-
ration of those working in a given field. For this to happen, common methods of
testing (standards) are needed. A major driving force for standardisation is the in-
creasing adoption of business and manufacturing quality systems (i.e. IS0 9000) in
which reproducibility and traceability are entwined in the operating culture. Stand-
ard laboratory testing systems (e.g.EN 45000) are similar in their demand of the use
of standards. With these changes in the ‘way of doing business’ there can be little
doubt as to whether material testing standards need to be developed!
7. Acknowledgements
The author wishes in particular to thank the many individuals involved in the ce-
ramics corrosion working group that met in Petten in October 1993 who have par-
ticipated in reviews and discussions on ceramics corrosion test standardisation and
in so doing have contributed invaluably to the content of this paper.
References
1.K. Matsuhiro and M. Matsui, ’Present status of standardisation for fine ceramics in Japan’,
in lnternational Gas Turbine and Aeroengine Congress and Exposition, ASME, New York, 1993.
2. S. J. Dapkunas, lnt. Confi on the Promotion of Standards for Fine Ceramics, ABTT-FC, Nagoya,
Japan, 1992, pp. 3249-3259.
3. International Survey on the Classification of Advanced Ceramics (Ed. S. Schneider), VAMAS
Report No. 5, ISSN 1016-2186,1991.
4. Classification of Advanced Ceramics - Development of the First International System for
Producer and User Industries, in Proc. VAMAS Workshop (Ed. K. W. Reynard), Ceramics In-
ternational, 19, 1993, Elsevier Applied Science, New York.
5. R. Morrell, ‘Standards for test methods for advanced ceramics’, NPL Report DMA (D)729,
July 1989.
6. J. J. Kublerand R. Morrell, ’European standardisation activities for advanced technical ce-
ramics’, in lnt. Gas Turbine and Aeroengine Congr. and Exposition, ASME, New York, 1993.
7. Corrosion Standards: European and lnternational Developments (Eds P. McIntyre and A. D. Mer-
cer), The Institute of Metals, 1991.
8. Japanese Industrial Standard, JIS R 1609, ’Testing methods for oxidation resistance of non-
oxide high performance ceramics’, F S I , 1990.
9. Ceramics Corrosion Working Group, First Workshop, Petten, 26 October, 1993.
10. Japanese Industrial Standard, JIS R 1601, ’Testing method for flexural strength (modulus
of rupture) of high performance ceramics’, ]GI, 1981.
11. European Standard, EN 843/1, ’Methods of testing advanced technical ceramics: flexural
tests at ambient temperature’.
12. CEN discussion document, CEN TC184/WG3/N209,1993.
10
Metallography, Electron Microprobe and X-Ray
Structure Analysis
A. RAHMEL and V. KOLARIK*
Karl-Winnacker-Institut der DECHEMA e.V., P.O. Box 15 0104, D-60061 Frankfurt am Main, Germany
*Fraunhofer-Institut fur Chemische Technologie, Joseph von Fraunhofer-Str. 7, D-76327 Pfinztal, Germany
ABSTRACT
The metallographic investigation of specimens covered with corrosion products can be
improved by special procedures. A Ni coat of 30-80 Fm thickness, deposited by electro-
plating, can significantly reduce the danger of scale spallation during the preparation
of metallographic cross-sections. Interference layer metallography can be helpful in the
development of the microstructure of scale and subsurface zone, because the various
phases, in particular sulphides, carbides and nitrides, can be identified by their charac-
teristic colour.
Electron probe microanalysis is a useful tool for a quantitative analysis of a volume
of cu. 1-3 pm3. Together with X-ray structure analysis it enables the characterisation of
composition and phase structure of corrosion products. Modern methods of in situ X-
ray diffraction allow not only a phase analysis at the reaction temperature, but can also
be used to follow the growth kinetics of very thin surface layers.
1. Metallography
Metallography is one of the most important post-oxidation or more general post-

treatment methods because it gives the best information on the microstructure of
scale and subsurface zone. No other method gives such a detailed ‘picture’ of the
microstructure, in particular that of the subsurface zone. The investigation of the
subsurface zone 1s at least as important as that of the scale. Practically all metallic
materials used in technical plants are alloys that can suffer intensive internal corro-
sion. There are several cases where damage to the material by internal corrosion
exceeds that by external corrosion.
Metallography involves preparation of a cross-section, in general perpendicular
to the surface. In exceptional cases a taper section may be useful, e.g. if only a very
thin scale has been formed. The length of the taper section depends on the taper
angle (see Fig. 1 [l]).It should be kept in mind that a taper section is not a real
magnification of the scale. Because only one direction of the scale becomes extended,
distortions cannot be excluded.
One major problem in the preparation of cross-sections of metallic specimens cov-
ered with a scale is the tendency of the brittle scale to spall. Spallation can already
occur during cooling of the specimen, but also during the preparation of the cross-
section.
Polishing
position
1 micron
thick
oxide
scale
/
Alloy
5'44"
100
1000 3"
2000 1 '*
Fig. 2 Scheme oftaper section fZ1.
No generally applicable method exists to avoid spallation during cooling. One

possibility is to press the specimen into a bath of a liquid metal with comparable
temperature and cool this system rapidly in order to avoid a reaction between scale
and liquid metal or to keep this reaction low. Very often the scale does not spall
completely, so small areas with adherent scale can be found for investigations. If the
spall consists of rather large particles, these particles can be used in addition to the
metal specimen for preparation of cross-sections and investigations. By applying
such techniques in combination with others, e.g. X-ray diffraction investigations of
the spall, realistic figures of scale and subscale can be obtained in spite of scale
spallation.
One rather successful method to avoid -or to reduce significantly - the danger
of scale spallation during the procedure of cross-section preparation is to coat the
specimen with a 50-80 pm thick Ni coating before starting the procedure of cross-
section preparation. At Karl-Winnacker-Institut of DECHEMA e.V. the following
procedure is applied to practically all specimens: in a first step a thin gold layer is
sputtered on the specimen in order to make the scale surface electrically conductive.
In a second step a 50-100 pm thick Ni layer is deposited electrolytically.The deposi-
tion occurs at room temperature in a bath containing 130 g nickel sulphamate, 31 g
NiC1, 6 H,O and 31 g H,BO, dissolved in 1 L water. The pH of the bath is kept
between 5-6. The deposition requires a period of 4-6 h at a current density of 25-30
mA cm-2. Round robin tests in Germany have shown that Ni coatings formed by
electrolytic plating show better adherence to the scale than those formed by chemi-
cal plating [2] so the danger of a gap forming between scale and coating is signifi-
cantly reduced in the first case. Ni-plated specimens have the following advantages:
The danger of scale spallation is reduced.

The marginal sharpness of the cross-section is improved ( the Ni coating is
rather hard ) [2].
In EPMA investigations there is less danger of the beam hitting the plastic
mount which would result in a negative charging of the mount and a deflec-
tion of the beam.
Metallography, Electron Microprobe and X-Ray Structure Analysis 149
For better handling the specimens are generally mounted in a resin after Ni-plat-
ing. The subsequent preparation of the cross-section is more or less the same as in
the case of a metal without a scale.
Another problem is the development of the microstructure of the scale and sub-
surface zone, which is certainly more difficult and not as well developed -or known
- as for metals. Metal etching agents often contain acids and, therefore, the danger
exists that corrosion products will dissolve, e.g. sulphides. At DECHEMA ‘interfer-
ence layer metallography’ is successfully applied. For the fundamentals of this tech-
nique (see Refs [3,4]).A coating with the capability of interference put on a polished
surface can strongly increase the black/white contrast as well as the colour contrast.
Examples of colour contrast cannot be given here (see Refs [3,4]). For optimal selec-
tion of the coating material a knowledge of the optical properties, in particular ab-
sorption coefficient and refractory index, of the metal and/or the corrosion products
is necessary [3,4]. Such data have been determined for sulphides [5], carbides [6],
nitrides [6] and oxides [7] in recent years. The black/white contrast can additionally
be increased by applying light of an optimal wave length. Examples are given in
Figs 2 4 . Interference layer metallography offers the following possibilities and ad-
vantages:
The surface of the cross-section is not attacked by the coating (contrary to

etching).
It permits a qualitative identification of various phases of the microstructure
which would look identical without the interference layer.
The investigation of a series of cross-sections of the same material or of vari-
ous materials under the same corrosion conditions is facilitated because the
various phases can easily be identified by their different colours.
In general a new or unknown phase can easily be identified by the appear-
ance of particles with a new colour.
It is often a prerequisite for automatic image analysis and thus opens ways
up for a quantitative characterisation of the microstructure.
Two kinds of coating preparation exist, evaporation of the coating material with
condensation on the specimen surface and gas ion etching [4]. At DECHEMA the
evaporation method is applied. Examples of suitable coating materials for sulphides,
carbides and nitrides are ZnSe or ZnS. The limits of this technique are often reached
with oxides because the enhancement of the contrast by the coating is unsatisfac-
tory. The gas ion etching method is successfully used at Research Centre Julich, In-
stitute for Materials in Energy Systems.
A differentiation of various phases of base metal and scale is also possible in the
back scattered electron (BSE) image of a scanning electron microscope (SEM)or elec-
tron microprobe. Assuming that chemical analysis is not the objective of the investi-
gation, in the authors’ opinion interference layer metallography has advantages over
BSE images, such as:
No expensive equipment is needed.

Fig.2 Intensified blacklwhite contrast between Cr-rich carbides and nitrides in HK 40 by coat-
ing the cross-section with ZnSe with an interference colour rangingfrom purple to violet. Car-
bides have been converted into nitrides due to internal nitridation during long term exposure in
air at 1000°C. Dark = Cr-rich carbides (red), grey = Cr-rich nitrides (blue), white = oxides.
Photograph taken at A = 545 nm.
Fig. 3 Intensified blacklwhite contrast of intermetallic TiAl with a two-phase microstructure,

oxidised at 1100°C in air, by coating the cross-section with ZnSe with a yellow interference
colour. Selective oxidation of the yTiAl phase (dark grey). The large dark inclusion consists of
Ti-rick nitrides. The preferential nitridation of Ti has converted the cl2-Ti81 (bright grey) phase
intoTiA1, (bright zone) and yTiA1. The selective oxidation of AI to Al,O, (white) has lead to AI
depletion and subsequently to formation of &-Ti,Al. Photograph taken at A = 545 nm.
Metallography, Electron Microprobe and X-Ray Structure A n a l y s i s 151
Fig. 4 Another area of the same specimen as in Fig. 3, showing that the inner part of the scale is
growing by inward difliision of oxygen. Thisfollowsfrom the fact that the Al,O? plates, formed
by internal oxidation, are partly embedded in the scale. Cross-section coated with ZnSe with a
yellow interference colour. Photograph taken at A = 545 nm.
Changing specimens is easy.

The identification of phases according to their colour is much easier than ac-
cording to their grey level in BSE images. Furthermore, two phases of differ-
ent colour in interference layer metallography can show the same grey level
in the BSE image if the phases consist of elements with similar atomic num-
bers.
Other methods for the development of the microstructure can, of course, be ap-
plied and each laboratory will have its own experience or will have to acquire it.
Chlorides (or halides) cause a special problem as corrosion products because prac-
tically all chlorides dissolve in water or become hydrolysed by water. Many chlo-
rides also have significant solubility in methanol and ethanol. If chlorides are ana-
lysed in an electron-probe microanalyser, water and even alcohol must be avoided
in the preparation of cross-sections. One example of a suitable agent is carefully
dried petroleum ether [8].
2. Electron Probe Microanalysis
Electron probe microanalysis (EPMA)is a commonly used analytical technique which

permits a quantitative analysis of the elements from boron to the transuranium ele-
ments in a volume of ca. 1 ym. It can be applied to a wide range of materials in bulk
form.
The analysis is carried out by means of an electron beam striking the specimen
and characterisation of the X-rays subsequently emitted. The incident electrons eject
an electron from the K, L or M shell. X-ray emission occurs when an electron from a
higher energy shell replaces the electron emitted from the lower energy shell.
The X-rays can be detected according to their energy by use of an energy disper-
sive detector (EDX) or according to their wave length by wavelength dispersive
spectrometers (WDX).EDX detectors are commonly attached to a SEM while WDX
systems are decisive parts of the electron probe microanalyser. Details of the funda-
mental principles and means of carrying out qualitative and quantitative analysis
can be found in several text books [9]. A CEN (Comite Europeen Normalisation)
paper which describes electron probe microanalysis of advanced technical ceramics
in detail is also very helpful [lo]. Therefore, it appears unnecessary to develop a
similar guideline for EPMA of high temperature corrosion specimens because in
both cases the technique is practically identical. High temperature corrosion prod-
ucts are ceramics or very similar to ceramics. There is, however, one aspect which is
not considered in the CEN paper and that is analysis of internal corrosion products,
because in general technical ceramics do not suffer internal corrosion. The analysis
of internal corrosion products is, however, very similar to that of multilayer coatings
which is described in the CEN paper. This means it must be guaranteed that the X-
rays ejected are only generated by the precipitate and not partly by the surrounding
matrix. This can be checked by analysing a greater number of precipitates of the
same kind. If such analysis results in a large scatter band, it is very probable, that the
particles are too small for analysis by EPMA.
Three modes of analysis can be performed:
Element distribution maps,

qualitative or quantitative analysis along a line (line scan), and
quantitative analysis of a volume of about one pm3.
An example of EPMA of a scale formed on the intermetallic TiSi, during 1000 h

oxidation in air at 1400°C is given in the Figs 5 and 6. The X-ray maps in Fig. 5 show
the distribution of the elements Ti, Si, A1 and 0 in the scale. A1 is incorporated into
the scale as an impurity. From Fig. 5 it follows that the scale consists of three phases.
A quantitative analysis of these three phases is given in Table 1.From these data it
follows that the dark phase is SiO, with small amounts of Ti and traces of Al, the
white phase is TiO, and the grey phase is SiO, with noticeable amounts of A1 and Ti.
Qualitative line scans of these four elements along the white line in the BSE pic-
ture are presented in Fig. 6. They confirm the distribution of the elements shown in
Fig. 5.
3. X-Ray Diffraction Structure Analysis
An X-ray diffraction structure analysis can be performed under two general condi-
tions:
Phase Ti Si A1 0 (at.%)
SiO, (dark) 0.8 33.0 0.1 66.1
TiO, (bright) 32.7 < 0.1 0.5 66.7
A1 content (grey) 2.6 25.0 3.8 68.7
Fig. 5 X-ray maps of Ti, Si, A1 and 0, showing the distribution of these elements in the scale
formed on TiSi, during 1000 h oxidation in air at 1400°C. Dark = SiO,, grey = AI-containing
SiO,, bright = TiO,.
Fig. 6 Qualitative line scans of Ti, Si, AI and 0 along the white line in the B S E picture. The
scans run across the SiO, phase (dark), the AI-containing phase (grey)and TiO, (bright).
(a) E x situ X-ray diffraction analysis of the samples after exposure in the corro-
sive medium (post-oxidation-method),and
(b) In situ X-ray diffraction analysis during oxidation (time and temperature re-
solved X-ray diffractometry).
X-ray diffraction is a frequently used method of a post-oxidation analysis. The

crystalline phases and their modifications are identified and their amounts can be
Fig. 7 Series of diffvaction patterns showing theformation of NiO on Ni during heating up.
Fig. 8 Diffraction geometry with grazing incidence.
determined by quantitative phase analysis [ 111,The crystalline structure of unknown

corrosion products can be determined. Details of the basic principles and means of
carrying out X-ray diffraction measurements are described in several texts [ 12-14].
Concerning the performance of X-ray diffraction measurements, no general stand-
ards are available comparable with that for EPMA measurements on ceramics [lo].
The most reliable information on 'standards' is contained in the Guidelinesfor Grant-
in-Aid Proposals for measurements of diffraction data which should be included in
the ICDD data bank ofthe International Centrefor Difiaction Data (ICDD) [15].
The parameters and conditions for performing X-ray diffraction measurements
are characterised by the technical data of the equipment which is used. As a refer-
ence, all components should be described:
Diffraction geometry ( Bragg-Bretano,Guinier, grazing incidence, micro beam,
etc.);
Diffractometer (producer, type, model);
X-ray source;
Monochromator;
Detector (producer, type, model); and
Sample holder.
For the investigations into high temperature oxidation, however, time and tem-
perature resolved X-ray diffractometry is of particular interest. This in situ method
yields information about the oxide scale at each stage of the oxidation process and
allows one to observe the behaviour of each oxide individually [16,17]. The oxides
can be identified in situ, the kinetic parameters can be determined for each oxide
individually, preferred crystallographic orientation can be observed [18], and the
thermal dilatation can be detected for all oxides and the substrate simultaneously.
Figure 7 shows an example of a series of diffraction patterns of Ni/NiO recorded
during stepwise heating. A detailed description of the time and temperature resolved
X-ray diffractometry can be found in Chapter 2 of this volume.
X-ray diffraction with grazing incidence is worth mentioning as a special means
of investigating thin scales. It can be performed ex situ as well as in situ [19]. The
incident beam is maintained constantly at a very low angle CD(< lo).With this geom-
etry the X-ray beam penetrates the thin scale along a significantly longer path (Fig.
8). Scales with thicknesses in the range of nm can be detected.
An example of the application of X-ray diffraction measurements combined with
EPMA investigations for identifying the phases formed on the Ni-base superalloys
IN 939 and IN 738 LC can be found in Ref. [20].
References
1. M. J. Bennett, 'High Temperature Corrosion Characterisation by the Combined Use of Sur-
face Microsurgery and Surface Analysis', paper presented at ECASIA '93, Catania, October
1993.
2. B. Kolsch, A. Rahmel, M. Schorr, I? Schwab and E. Wallura, Praktiscke Metallogvapkie,
Sonderband, 1989,20,89-99.
3. H.-E. Buhler and H.-P. Hougardy, 'Atlas of Interference Layer Metallography', Deutsche
Gesellschaft fur Materialkunde, Oberursel, 1980. Also available at the American Society of
Metals and the Metals Society.
4. K. Schmidt, H. Hoven, K. Koizlik, J. Linke and H. Nickel, 'Gefugeanalyse metallischer
Werkstoffe -Interferenzschichtenmetallographie und automatische Bildanalyse', Carl Hanser
Verlag, Miinchen und Wien, 1985.
5. W. T. Wu, J. Aydin and H.-E. Buhler, Praktiscke Metallogr., 1982,19,322-346.
6. J. Aydin, H.-E. Biihler and A. Rahmel, Microstruct. Sci., 1981,9,55-63.
7. W. T. Wu, H.-E. Biihler and A. Rahmel, Metallogr., 1983,20,479-494.
8. B. Glaser, K. Rahts, M. Schorr and M. Schiitze, Sonderband der Pvaktiscken Metallograpkie,
1994,25,75-84.
9. See V. D. Scott and G. Love, Quantitative Electron Microprobe Analysis, Ellis Horwood, Chich-
ester, 1983.
10. CEN/TC 184/WG 5: Advanced technical ceramics: Methods of test for ceramic coatings.
ENV draft 38: Determination of chemical composition; Electron probe microanalysis (EPMA).
11.J. Fiala, Mat. Sci. Forum, 1991, 79-82,27-34.
12. H. P. Klug and L. E. Alexander, X-Ray Diffraction Procedures for Polycrystalline and Amor-
phous Materials, Wiley, New York, 1974.
13. D. L. Bish and J. E. Post (Eds), ‘Modern Powder Diffraction’, Review in Mineralogy, Vol. 20,
Mineralogical SOC.of America, 1989.
14. J. Urlaub, ’Rontgenanalyse’, Siemens AG, IBSN 3-8009-1193-0.
15. ’Guidlines for Grant-in-Aid Proposals’, International Centre for Diffraction Data (ICDD),
Newtown Square Corporate Campus, 12 Campus Boulevard, Newtown Square, PA, 19073-
3273 USA.
16. V. Kolarik, M. Juez-Lorenzo, N. Eisenreich and W. Engel, ’High Temperature Corrosion
Kinetics by a Fast X-Ray Diffraction Methods Applied to Nickel’, 3rd Int. Symp. on High Tem-
perature Corrosion, J. Phys., 1992, IV, Colloque C9,3,447-452.
17. V. Kolarik, W. Engel and N. Eisenreich, ’Kinetics of Growing Oxide Layers Studied by
means of X-Ray Diffraction’, Proc. 2nd Europ. Powder Diffraction Conf. EPDIC2; Mat. Sci.
Forum, 1993,133-136,563-568.
18. V. Kolarik, M. Juez-Lorenzo, N. Eisenreich and W. Engel, ‘In situ Study of the Formation of
Orientations during the High Temperature Oxidation of Copper’, Proc. 3rd Europ. Powder Dif-
fraction Conf. EPDIC3, Wien, 1993.
19. V. Kolarik, M. Juez-Lorenzo, W. Engel and N. Eisenreich, ’Kinetics of the a-Fe,O, Forma-
tion on Fe,O, between 400 and 570°C by means of X-Ray Diffraction with Grazing Incidence’,
Fresenius J. Anal. Ckem., 1993,246,252-254.
20. J. Litz, A. Rahmel, M. Schorr and J. Weiss, Oxid. Metals, 1989,32,167-184.
11
Surface Microsurgery Preparation Procedures for
High Temperature Corrosion Characterisation
M. J. BENNETT*
AEA Technology, Materials Technology Department, 552 Harwell, Didcot, Oxon OX11 O R A , UK
ABSTRACT
Mechanistic understanding of the behaviour of metallic and ceramic materials, includ-
ing coatings, in aggressive environments at high temperatures is crucially dependent
upon the characterisation of both the chemical and physical nature of the interactions at
the reacting interfaces. This can be achieved post exposure by the use of defined surface
analytical techniques but is reliant upon the development of appropriate surface micro-
surgery procedures, such as metallography, fractography, taper section polishing, se-
lective etching, complete metal dissolution etc., for the preparation of the surfaces to be
analysed. Recent studies, undertaken at the Harwell Laboratory of AEA Technology, to
improve the precision and the effectiveness of surface microsurgery procedures are re-
viewed. The underlying objective was to ensure the optimum exploitation of the capa-
bilities of surface analytical techniques, especially those in more common usage, such
as scanning electron microsurgery, electron probe microanalysis, laser Raman
spectroscopy, secondary ion mass spectrometry etc. Although most of the examples
presented on the combined use of surface microsurgery and surface analysis are for the
characterisation of thick (> 1 pm) corrosion scales and of internal attack resulting from
high temperature corrosion, several of the surface microsurgery procedures have rel-
evance to the analysis of sub-micron layers.
1. Introduction
The surface behaviour of metallic and ceramic materials, including coatings, in ag-
gressive chemical environments, at elevated temperatures, experienced in service is
a dominating, and often life limiting factor in many technologies (Le. power genera-
tion, automotive, petrochemical, aerospace etc.). Corrosion leads to the formation of
an external scale and additionally, in some instances, to internal attack, with the
formation of intrusions, precipitation of second phase particulates etc. With coat-
ings, in addition to external corrosion, further degradation can ensue also from in-
terfacial interaction with the underlying substrate. Chemical characterisationof these
reactions is crucial, therefore, both to mechanistic understanding of the behaviour of
high temperature materials and to component life-time predictions.
*Now a Materials Research Consultant, ’Three Chimneys’, South Moreton, Nr Didcot, Oxon OX11 9AH,
UK
Surface Microsurge y Preparation Procedures 159
One of the main features of surface science during the last two decades, or so, has
been the explosion in surface analytical technique development, with each succes-
sive generation of instruments providing ever increasing capability and precision. A
comprehensive range of what maybe termed, conventional techniques, such as scan-
ning electron microscopy (SEM),secondary ion mass spectrometry (SIMS),electron
probe microanalysis (EPMA),Laser Raman spectroscopy (LRS),etc., are now widely
available for the characterisation of the microstructure and composition of surface
layers. In certain instances, e.g. SEM examination of surface topography and SIMS
depth profiling of a surface layer, the techniques may be deployed directly. How-
ever, in the majority of applications utilisation of these techniques, and in particular
realisation of their full potential, is dependent upon the ability to prepare speci-
mens, such that the features required are revealed satisfactorily for examination.
Numerous preparation procedures have been used and on account of the critical
role of this branch of surface science it has been described by a general title, surface
microsurgery [ 11. Most of the basic experimental approaches, which include
metallographic mounting and polishing, taper section polishing, selective etching,
complete metal dissolution and fractography, have been used by scientists in the
corrosion and coatings fields over many years. With the possible exception of
metallography,each laboratory has adopted its own empirical and often, ad hoc way
of carrying out surface microsurgery procedures.
During the last six years work has been undertaken at the Harwell Laboratory of
AEA Technology, which has aimed at improving the precision, and thereby, the ef-
fectiveness of these surface microsurgery procedures [ 1-31. A subsidiary objective
was to ensure optimum utilisation of the capabilities of the surface analytical tech-
niques. From the outset three main principles were adopted in this programme.
The first was to remove all material not required, in order to facilitate the expo-
sure of the region to be analysed. This was achieved either by controlled mechanical
lapping or by chemical etching. The second principle was to optimise the effective-
ness of the surface microsurgery procedure by exercising maximum care and preci-
sion at every stage through the procedure, including the initial cutting of the speci-
men being examined. These principles were accomplished by the development of
numerous and relatively simple, pieces of equipment for carrying out the various
operations. The third principle was to protect and to delineate as a point of refer-
ence, wherever possible, what had been the outer gas interface. This was achieved
by coating the surface prior to surface microsurgery.
The purpose of this paper is to provide an overview of these recent studies at the
Harwell Laboratory on the combined use of surface microsurgery procedures and
surface analytical techniques in the characterisation of chemical interactions at in-
terfaces at elevated temperatures. Although substantial work was undertaken also
on the development of surface microsurgery procedures for the production of trans-
verse through interface sections for transmissionlscanning transmission electron
microscopy [5,6], this review will concentrate on the major aspects of this programme,
which focused on procedure developments for use with surface analytical techniques
in more common use. The developments undertaken for each surface microsurgery
procedure are described separately.Although most of the examples presented are of
thick (> 1 pm) corrosion scales and internal attack, several of the surface microsur-
gery procedures have relevance to the analysis of sub-micron layers.
2. Development of Surface Microsurgery Procedures

2.1. Metallography
This is the most universally employed surface microsurgery procedure to produce a
polished transverse section through material for examination by conventional sur-
face analytical techniques. With the availability of commercial preparative equip-
ment it can almost be considered a routine procedure. Nevertheless, improvements
are possible both in the surface microsurgery and in the surface analysis of mounted
specimens. With regard to the form there are advantages in coating specimens with
a metallic overlayer, such as nickel or gold, prior to metallographical mounting to
retain and delineate the outer surface. Turning to surface analytical techniques opti-
cal microscopy can be even more revealing when accompanied by the deployment
of phase contrast techniques, such as Nomarski. Examination of metallographically
mounted specimens in an SEM enables higher magnification than is possible in an
optical microscope and can be augmented by semi-quantitative elemental analysis
by EDAX. Metallography is also the main surface microsurgery procedure for the
preparation of specimens for quantitative elemental analysis by EPMA.
Microcompositional information can be derived using a laser Raman microprobe [ 61
having a 2 pm spot size and a 1-2 pm probe depth. Figure 1shows the Raman spec-
tra obtained at the positions indicated on the optical micrograph across the pitting
attack of 20Cr/25Ni/Nb stainless steel after 3061 h oxidation in a CO, based envi-
ronment at 900°C. These established that the outermost layer comprised spinels whose
composition varied with depth but at least to 12 pm were predominantly MnCr20,
and (Fe Ni),O,. In a transition region, 18 pm deep, the spinel Fe2-xCrx0,was present
with Cr203,which at greater depths was the sole component of the lowest continu-
ous layer. The reflective region in the optical micrograph was nickel, which does not
give a Raman scattered spectrum.
2.2. Fractography
A major disadvantage of examining a metallographically polished transverse sec-
tion is that only a two dimensional image is obtained of a three dimensional struc-
ture. This further imposes limitations on the microstructural and microchemical in-
formation that can be derived. To overcome such deficiencies another surface micro-
surgery procedure, fractography, has been employed in some studies (e.g. [7,8]) to
produce a transverse cross-section for subsequent SEM examination. The experi-
mental procedure was simply to bend a corroded metal specimen following cooling
in liquid nitrogen. This rather basic approach is at best ‘hit and miss’ and does not
work for materials having a ductile-brittle temperature below 78°K. As a consequence
improvements to this surface microsurgery procedure were instigated to ensure frac-
ture of all materials within a defined specimen region, better retention of the corro-
sion layers, delineation of the gas interface and the ability, if required, of being able
Surface Microsurgery Preparation Procedures 161
f
Pitting
attack
20125lN b
stainless
steel I
(FeNi)30, Depth from 'osi t i on
intensity
surface(pm:
(CPS)
2 a
6 b
12 C
18 d
22 e
(Scalelsteel
interface)
I 1 I I I I I 1
200 400 600 800
Wavenumbers shift (cm-')
Fig. 2 Raman spectra obtained at the positions shown in the optical micrograph across the pitting
attack of 20/25/Nb stainless steel after 3061 h oxidation in a CO, based environment at 900°C.
to examine the corresponding aspects of both fracture faces. The principal innova-
tions [2] were to produce simple, suitable,equipment to produce miniature H-shaped
tensile specimens of the oxidised metallic alloy and to fracture these specimens in a
controlled manner.
The miniature tensile specimens were produced using a fixture designed to fit
onto a Beuhler Isomet low-speed saw. This fixture consisted of a movable platform
whose movement was controlled in both the x and y directions by micrometers linked
to the stage. Mounted on top of the platform was a clamping arrangement capable
of accommodating and securing a small section (1.5 cm long 3 5 mm wide) of the
oxidised alloy. The section was held only at the ends to ensure that no damage was
caused to the oxide scale over the main specimen body, which was formed into the
gauge length. The diamond slitting wheel normally used on the machine was re-
placed by a silicon carbide wheel (100 mm dia. 3 3 mm width) with a hemispherical
end face. This arrangement transformed the machine, from its normal role for slit-
ting small samples of material, to that of a profile grinder. The micrometers were
used to control the surface grinding process using distilled water as a lubricant, the
specimen was profiled on one side, then was reversed and a similar section was cut
from the opposite side to produce a 7 mm 3 3 mm wide gauge length. After cleaning
the small H-shaped tensile specimen was sputter coated with a 3 pm thick gold layer
to delineate the outer oxide surface.
Fracture was undertaken using a modified machine vice (Fig. 2). This had a lead
screw, which consisted in part of left-hand and in part of right-hand thread; thus,
both jaws could open and close simultaneously when the lead screw was turned.
The jaws moved on two stout guide rails, which ensured that rigidity was main-
tained during the course of travel. The specimens were loaded through slits in oppo-
site ends of a PTFE reservoir so that the gauge length was centralised within the
reservoir and the specimen ends protruded from it. The reservoir was then fitted
between specimen clamps, consisting of stainless steel plates mounted on top of the
respective vice jaws and secured by fixing screws. A simple clamping arrangement
at the centre of each plate enabled the specimens to be gripped at both ends. The
design varied with the particular specimen, e.g. 20Cr/25Ni/Nb stainless steel fuel
cans were held by their protruding rib sections [2], while flat ferritic oxide disper-
sion strengthened (ODS) alloy specimens were held by a spigot on the underside of
the clamp, which located into holes drilled through the specimen end sections [ 9 ] .
Liquid nitrogen was poured into the reservoir to ensure the sample temperature
was reduced to -78K. The lead screw of the vice was turned slowly in an anticlock-
wise direction, causing the vice jaws to open and a tensile load to be applied to the
specimen until fracture occurred.
For examination by SEM, the sections were mounted vertically with fracture faces
uppermost in a special holder. Thus the fractured faces could be placed close to-
gether to facilitate identification of common surface features, where required.
This surface microsurgery procedure has been used extensively at Harwell, most
notably for a detailed characterisation of the corrosion attack of the 20/25/Nb stain-
less steel in carbon dioxide at 1000°C [2] and also to establish the microstructure of
the alumina scales formed on ODS ferritic alloys, with the general composition
Fe + 16-20%Cr + 5%A1+ 0.5%Y20, such as ODM751 [9]. Scanning electron micro-
graphs of the respective scales formed on this alloy in air at temperatures between
1200 and 1400°C (Fig.3) indicated that the grain size increased with temperature. At
1200°C (Fig. 3(a)) the alumina scale structure was columnar with grains 1pm wide
Surface Microsurgery Preparaf ion Procedures 163
Fig. 2 Modified machine vice to fracture oxidised metal tensile specimens.
and in some areas with a single grain extending across the scale thickness. The corre-
sponding alumina grain structure formed at 1400°C (Fig. 3(d)) was equiaxed, with
grains up to 15 pm wide, so that the scale thickness comprised two, or at most three,
such grains. Also present at the outer gas interface of all alumina scales were dis-
crete smaller Ti, Y, Al, Fe and Cr bearing grains, whose composition and size varied
with temperature.
2.3. Precision Taper Section Preparation

The principal attraction of this procedure lies in its ability to enlarge a transverse
cross-section through any surface region. Theoretically magnifications in excess 1000
times should be possible (Fig. 4) and have been achieved now following the devel-
Fig. 3 Fracture cross sections of alumina scales formed on ODM751 after oxidation in air f o r
(ai 200 k at 1200°C; (b) 197 k at 1300°C; ( c ) 200 k a t 1350°C; and ( d ) 200 k a t 1400°C.
opment of relatively simple equipment to improve procedure precision [l].Other
advantages of this procedure are its versatility and ability to reveal regions, e.g. thin
interlayers, not readily accessible directly by any other procedure, with the result
that precision taper sectioning has been deployed in a variety of applications [l].
The experimental procedure involved the use of a watchmakers lathe, modified
into a precision lapping facility (Fig.5) and a specimen mounting mandrel assembly.
The mandrel, fabricated from stainless steel, had a two arc unit goniometer head to
provide precise, independent, movement in two dimensions. A small stainless steel
platform, with a series of 0.5 mm wide open ended slots at right angles, was screwed
onto the outermost arc for mounting specimens by means of wax, with a low melt-
ing point. The specimens were a small representative section, typically 3 mm 3 5 -
Polishing
position
,
201251Nb
stainless steel
i
1 Taper sectton I
I Taper angle
'
length iY1 6
microns
,b",o
2000 I
3L',
3"
1"
I
Fig. 4 Angle of taper polishing required to magnify an exposed through scale section.
Fig. 5 Precision lapping machine for surface microsurgery.

mm 3 5 mm, cut dry from the bulk material using a 0.5 mm wide silicon carbide
wheel. The grinding procedure has been described in detail [l].Throughout process-
ing the mandrel was positioned horizontally on two wear resistant phosphor bronze
bearing surfaces, within a cradle located on the cross-slide of the lathe. The bearings
also enabled mandrel movement laterally and about its own axis. For grinding op-
erations boxwood laps were specially constructed, which were screwed successively
into the lathe head stock. The laps had a series of 0.5 mm dia. 3 0.5 mm deep holes
to permit retention on their surfaces of water soluble diamond paste. Initial lapping
used 3 pm dia. diamond grains. Glycerol was applied to the surfaces to act as a
lubricant and to reduce friction. After lapping and examination in an optical micro-
scope the goniometer arcs were altered carefully to produce, on further lapping, and
successive reiteration of the process a uniform, parallel taper section across the en-
tire specimen width. At this stage consideration of the taper angle was possible by
using the upper arc only as a means of control. Choice of the angular displacement
was dependent on several factors relating to the material and the required extent of
depth investigation beneath its surface. Controlled precise and fine adjustment of
the goniometer arc to obtain progressively shallower taper angles on successive lap-
ping operations was achieved using a clock gauge attached to a stand, into which
the mandrel was positioned. Having obtained the required taper, its surface finish
was improved by lapping firstly, on 1pm diamond using a second boxwood lap and
secondly, on 0.5 pm diamond employing a cast iron lap and a TEXMET polishing
cloth. After each lapping stage thorough cleaning with distilled water ensured re-
moval of all traces of the diamond paste previously used. The specimen was re-
leased from the platform, immersed in acetone to dissolve any residual wax and
then mounted in an appropriate holder for the required surface analysis.
Three examples will be described to illustrate the use of this surface microsurgery
procedure for the analysis of coatings and corrosion attack. The first was the charac-
terisation of a TiON interfacial layer within a composite TiN-SiO, coating, produced
by plasma-assisted chemical vapour deposition (PACVD) [ 101.To achieve optimum
duplex coating performance, particular attention was directed towards maximising
adhesion at both the substrate-TiN and the TiN-SiO, interfaces. This involved pro-
ducing a gradual compositional transition over these regions, which was under-
taken readily using the flexible PACVD coating procedure. To ensure that this gradu-
ation actually was achieved, the composition of the thin (0.5 pm thick) TiON graded
interfacial layer between the 2 pm inner TiN and the 10 pm thick outer silica coating
on a nickel based superalloy IN639 was characterised. The only way by which the
interlayer could be exposed readily was by precision taper sectioning a cross-section
through the coating and the IN939 substrate. By this procedure the interlayer was
clearly revealed and magnified by over a factor of 25 (Fig. 6(a)).This enabled EPMA
of the TiN-SiO, interface, which established the smooth graduations, concurrently
in opposite directions, of the oxygen and nitrogen concentrations within the TiON
interlayer (Fig. 6(b)).
The second illustration concerns the analysis of chromia scales formed on chro-
mium to establish the transport mechanism during scale growth [ll].The experi-
mental technique employed by most researchers for this purpose is based on se-
lbl Distance (pm)
Fig.6 Scanning electron micrograph of a taper section through a silica TiON-TiN multilayered
coating on IN939 (a), and elemental distributions across the interlayers as measured by EPMA (b).
quential exposure to oxidants containing different l80isotope concentrations (usu-
ally normal, 0.2% and then enriched, > 97%). This then followed by analysis of the
isotopic distributions through the scale, from which the transport mechanisms of
diffusing species can be deduced. Most studies have measured the depth profiles of
the respective average isotopic concentration, with data being obtained by either
nuclear reaction or SIMS analysis. However, greater mechanistic insight is provided
by two-dimensional spatial information of the isotopic distributions, which can be
achieved by SIMS image analysis. Here, precision taper sectioning has proved to be
the indispensable preparation technique. The oxide scales produced are usually a
few (typically 1-5) pm thick and although these are magnified only slightly to achieve
optimum instrumental resolution, the main advantages of the taper sectioning pro-
cedure lie in its ability to produce clearly defined, parallel, flat, polished transverse
sections through the oxide scale and the metallic substrate. This has ensured high
quality image data acquisition with maximum efficiency. Preparation of scale cross
sections by this surface microsurgery procedure has proved to be superior to those
produced by other methods, e.g. ball-cratering, or the pit sides resulting from SIMS
depth profiling.
SIMS elemental images of a transverse section of a chromia scale formed on chro-
mium during sequential oxidation in I6O2and then I8O2,at 950°C [ll],are shown in
Fig. 7. The secondary electron and 52Crimages (Figs. 7(a) and (b)) delineated the
scale. Comparison of the l60and the l8O ion images (Figs. 7(c) and (d)) indicated
that the latter lay above the former, so that the principal transport mechanism was
outward Cr3+movement. The two dimensional images also revealed other informa-
tion that would not be so clearly apparent from basic depth profiles. This was the
occurrence of l80and l60l8Ostreaks into the scale formed in 1602,at a decreasing
intensity with increasing depth from the Cr2l6O3-Cr2I 8 0 , interface (Fig. 7(d)). The
streaks occurred at a distance of separation probably consistent with the oxide scale
grain size. This would suggest that outward Cr3+diffusion was accompanied by
limited anion transport into, and exchange along, the oxide grain boundaries.
The third example is described in the next Section 2.4.
2.4. Selective Etching and Complete Dissolution

The combination of appropriate mechanical abrasion with chemical and electrolytic
etching techniques can provide complete flexibility for the characterisation of corro-
sion and in particular, internal attack [ 3 ] .Abrasion was carried out with the modi-
fied precision lapping machine. In addition to the mandrels with a goniometer mount-
ing for taper sectioning, two other mandrels were employed for polishing, with dif-
ferent mounting arrangements for similar sized (typically 3.5 mm long 3 2.5 mm
wide) specimens depending on the ultimate thickness required. When this was >
100 pm specimens were mounted with low melting point wax on a porous ceramic
optical flat forming part of the mandrel head. Grinding was started on a 600 grit Sic
lap and was continued with successively finer diamond laps. For thickness reduc-
tion below 100 pm the specimen had to be secured more firmly and was supported
on a stainless steel ring (4 mm o.d., 2.8 mm id., 0.25 mm thick) having lapped/
Fig. 7 SIMS elemental images of a transzlerse section of a chromia scale formed on chromium during
oxidation at 960°C for 45.75 h in I6O2and then for 20.25 h in I8O2;(a) secondary electron image;
(b) j2Cr+ion image; (cl l6O- ion image; ( d ) 150- image (Log).
polish surfaces. The specimen was placed in the centre of the ring and welded at the
four corners using a micro-tweezer welder. For continued lapping of the specimen
the ring was attached onto the third type of mandrel, having a spigot mounting to
support the specimen. Further reduction of specimen thickness could then be con-
tinued, down to 10 pm if required, with intermittent checking with an optical micro-
scope.
Metal grains surrounding oxidised regions were dissolved chemically by several
procedures. If desired, only a small portion of the exposed surface could be etched
by carefully masking the remainder with 'Lacomet' lacquer. For electropolishing,
since constant monitoring was necessary, a special unit was constructed for this pur-
pose. This consisted of a PTFE base block into which two small reservoirs were lo-
cated, one to contain an electrolyte, e.g. Lenoirs solution (78 g CrO,, 310 mL H,PO,,
67 mL, H,SO, and 120 mL H,O) and the other, distilled water. A vertical PTFE col-
umn was also mounted onto the block with a moveable head through which was
fitted a retractable arm attached to platinum tipped tweezers to hold the specimen
for insertion into the electrolyte a t an angle of about 30" to its surface. The tweezer
arm allowed specimen movement also from one bath to the other. The reservoir
containing the electrolyte was fitted with a platinum electrode screwed to the base
block through which electrical contact was made. Power was supplied by a
POLIPOWER unit. Since the electrolyte was partially opaque the specimen had to
be held just beneath the surface so that visibility was unimpaired and this could be
controlled with the tweezer arm. The etching process was carried out at 3 V, with a
50 mA current, typically for -45 s and could be observed directly with a low power,
optical microscope.At the completion of etching the specimen was transferred quickly
to the distilled water bath. The masking lacquer was removed with acetone and the
specimen was cleaned finally in distilled water and methylated spirits.
For SEM examination of the ring assembly a standard aluminium alloy stub was
adapted to avoid the use of colloidal graphite normally employed for both fixing a
specimen and providing electrical contact. For this purpose a recess was machined
in the stub centre to accommodate the ring. The recess depth ensured that the upper-
most surface stood proud of that of the stub. The ring was secured by two small
screws and washers into the stub, one on either side of the ring.
Complete dissolution of metal to expose internal precipitates was effected using
an iodine-methanol solution. The main problem was the small mass of the precipi-
tates and the necessity of containing them within a small and defined volume. This
was achieved with the apparatus shown in Fig. 8. The oxidised specimen, from which
the outer scale and any oxide intrusions on both major faces had been removed by
mechanical abrasion, was placed in the small inner PTFE vessel having a row of
small drainage holes beneath the top rim. This vessel had a spigot protruding from
its underside for location within a larger PTFE vessel with bottom drainage holes
and this in turn was loaded into a glass vessel fitted with a drainage cock. The glass
and PTFE vessels were filled with iodine-methanol solution. After 24 h the solution
was drained and depending on whether or not metal dissolution was complete, io-
Iodine methanol - , ,-Glass vessel
Outer PTFE-- Inner PTFE

vessel vessel
Drainage holes - Specimen
Drain cock
Fig. 8 Apparatus for the extraction of internal precipitatesfollowing complete metal dissolution in
iodine-methanol.
dine-methanol solution was replenished or residual iodine was removed by flush-
ing a number of times with methanol. After cleaning, the precipitates were trans-
ferred using a fine paintbrush to a silicon wafer for XRD, these being held in posi-
tion by a drop of cyclo-hexane and for SEM to a standard stub covered with a self-
adhesive label with the adhesive side uppermost.
All these surface microsurgery procedures were deployed to study the internal
attack of the 20Cr/25Ni/Nb stainless steel, which also contained O.6%Siand 0.75O/0Mn,
following oxidation in CO, based environments at 900-1000°C. Optical microscopy
and fractography [2] had revealed that the attack consisted of an external scale com-
prising of an outer FeCrMn bearing spinel layer and an inner Cr,O, layer, beneath
which there were silica intergranular intrusions into the steel and often internal pre-
cipitates, as is shown schematically in Fig. 9. More detailed characterisation was
required of the microstructure and composition of (a) the underside of the scale and
the intrusions; (b) the intrusions throughout their entire length, (c) the distribution
of internal precipitates through the alloy and (d) the morphology and composition
of the internal precipitates.
OUTER SCALE
INTRUSIONS
INTERNAL
PRECIPITATES
@ - SCALE UNDERSIDE
(J - INTRUSION CHARACTERISATION
B
Q - PRECIPITATE DISTRIBUTION
(J - PRECIPITATE CHARACTER1SATION
D
Fig. 9 Specific aspects of the microstructure and composition of the attack of 20/25/Nb stainless steel
in CO, based environments at 900-1000°C to be revealed.
For examination of the underside of the outer scale the oxidised 20Cr/25Ni/Nb
stainless steel was first abraded from one major face to just above the silica intru-
sions on the face to be examined. This was achieved using the support of a stainless
steel ring. Only a small area of the specimen was electrochemically etched in Lenoirs
solution, so that the surrounding unattacked steel supported the oxide scale win-
dow exposed. A scanning electron micrograph of this region (Fig. 10) shows at the
top left-hand corner the edge of unetched steel. The intrusions of silica, proved to be
platelets, which grew from the bottom-most layer of the external scale having a globu-
lar structure. Energy dispersive X-ray analysis suggested these could be essentially
coated articles consisting of silica overlaying chromia.
Fig, 10 Scanning electron micrograph of the underside of the scale formed on 20/25/Nb stainless steel
following 120 h oxidation in C0,at 1000°C.
It was possible that a finer and more fragile structure at the intrusion extremities
could have been detached during electrochemical etching. To facilitate examination
of the intrusion structure throughout its depth, the thickness of this region was mag-
nified by the preparation of a taper section.A short electropolish removed sufficient
steel at the intrusion interface to reveal the feather-like structure of their extremities
(Fig. 11).The small white particles revealed were Nb rich and probably NbC.
The distribution of the internal precipitates was exposed by etching in aquaregia
a transverse cross-section of the oxidised steel. A scanning electron micrograph of a
region from the base of the silica intrusions is shown in Fig. 12. Small Nb rich parti-
Fig. 11 Silica intrusionsformed at 20/25/Nb stainless steel grain boundaries during 120 h oxidation
i n CO, at ZOOO°C.
Fig. 12 Distribution of carbide precipitates in 20/25/Nb stainless steel beneath the silica intriisions
following 8094 h oxidation in a CO, based environment at 900 "C.
cles, varying in size, were apparent in the steel grains at about the same density
across the section. Larger Cr rich particles formed a continuous network in the grain
boundaries of the steel underlying the silica intrusions.
Extraction of the internal precipitates was achieved firstly by abrasion from both
specimen faces of the external scale and metal to the depth of the silica intrusions,
followed by complete dissolution of the remaining steel in iodine-methanol. The X-
ray diffraction pattern of the particles indicated that they were Cr2& and NbC. A
scanning electron micrograph (Fig. 13)revealed that the former had an angular and
often well defined crystalline structure, with smaller NbC particles attached to the
outer surfaces.
The microstructural evidence suggested that under these oxidation conditions
internal attack, with the formation of silica intrusions and carbide precipitates, in-
volved inward movement of the oxidant, CO,, in addition to outward transport of
cations. A probable mechanism for what was essentially a crevice type corrosion
was developed [3].
3. Conclusions
The satisfactory preparation of specimens by surface microsurgery procedures is
an essential prerequisite for effective surface analysis. The more precise is specimen
preparation the more detail that can be revealed as to the composition and structure
of chemical interactions at interfaces. Thus in turn provides the opportunity also for
the fullest possible exploitation of the capabilities of conventional surface analytical
techniques, such as SEM, EPMA, SIMS etc.
Su $ace Microsurgery Preparation Procedures 175
Fig. 13 Scanning electron micrograph ofCr,,C, and NbC particles formed intergranularly 20/25/Nb
stainless steel during 8094 k oxidation in a CO, based environment at 900°C.
All researchers need to review frequently their own surface microsurgery proce-
dures. The experimental procedures described in this review can be adapted to suit
available equipment and requirements. There remains considerable scope for the
innovative development of new surface microsurgery procedures, details of which
should be made available rapidly to other researchers.
4. Acknowledgements
The development of these surface microsurgery techniques would not have been
possible without the enthusiasm and technical skills of J. A. Desport. I am most grate-
ful also to my colleagues, G. Angood, B. A. Bellamy, H. E. Bishop, M. D. Fones, P.
Graves and D. M. Poole, in the Materials Characterisation Service, AEA Technology,
for carrying out the surface analyses involved in these studies.
References
1.J. A. Desport and M. J. Bennett, J. Pkys. IV, Colloque C9, (suppl. J. Phys. 111), 1993, 3,453.
2. J. A. Desport and M. J. Bennett, Oxid. Met., 2988, 29,327.
3. J. A. Desport and M. J. Bennett, in Microscopy of Oxidation (Eds M. J. Bennett and G. W.
Lorimer), The Institute of Metals, London, 1991, pp.356-361.
4. J. A. Desport, UKAEA, Harwell Laboratory Report, AERE-R11266,1984.
5. D. P. Moon, UKAEA Harwell Laboratory Report, AERE-R11579,1985.
6. M. J. Bennett, P. R. Graves and R. W. M. Hawes, in High Temperature Alloys-Tkeiu Exploitable
Potential (Ed. J. B. Marriott), Elsevier, 1988, pp.205-215.
7. D. Caplan and G. I. Sproule, Oxid. Met., 1975, 2,459.
8. P Kofstad, Oxid. Met., 1985,24,265.
9. M. J. Bennett, H. Romary and J. B. Price, in Heat Resistant Materials (Eds K. Natesan and D.
J. Tillack), ASM International, 1991, pp. 95-102.
10. M. J. Bennett, C. E Knights, C. E Ayres, A. T. Tuson, J. A. Desport, D. S. Rickerby, S. R. J.
Saunders and K. S. Coley, Mat. Sci. Eng., 1992, A139,91.
11.M. J. Bennett, A. T. Tuson, D. P. Moon, J. M. Titchmarsh, P. Gould and H. M. Flower, I. Surf.
Coatings Tecknol., 1992, 51,65.
12
The Application of Transmission Electron
Microscopy in the Analysis of High Temperature
Corrosion
M. RUHLE and E. SCHUMANN
Max-Planck-Institut fur Metallforschung, Institut fur Werkstoffwissenschaft, Seestr. 92,70174 Stuttgart,
Germany
ABSTRACT
The application of transmission electron microscopy to the study of high temperature
oxidation has received increasing interest recently. The adhesion of the oxide scale de-
pends on the microstructure and is strongly influenced by impurities and dopants. To-
day’s electron microscopy techniques, conventional, analytical and high-resolution trans-
mission electron microscopy, are capable of investigating the structure and chemistry
on a nanometer level. The usefulness of these different methods for studying high tem-
perature corrosion processes will be presented in this paper. In particular, the applica-
tion of transmission electron microscopy to the oxidation of the intermetallic alloys
NiAl and Ni3Al will be demonstrated.
1. Introduction
A main problem in high temperature corrosion is the adhesion of corrosion scales

under cyclic as well as under isothermal conditions. The adhesion is influenced by
different factors, such as the mechanical properties of the metal and the scale, scale
thickness, the interfacial bond strength, defects (e.g. misfit dislocations, voids) and
segregation phenomena. In order to understand the influence of these factors, it is
necessary to study the structure and chemistry of the scale, the metal and the metal/
scale interface at the nanometer level. Modern electron microscopic techniques are a
useful tool to study structure and composition of materials near the atomic scale.
The techniques of transmission electron microscopy (TEM) can be divided into
three areas: conventional transmission electron microscopy (CTEM), analytical trans-
mission electron microscopy (AEM) a n d high resolution transmission electron
microscopy (HREM). A schematic overview is given in Fig. 1.
CTEM techniques include bright field imaging (BF), dark field imaging (DF) and
selected area electron diffraction (SAD). These methods can be used to identify reac-
tion products and to characterise the microstructure of the scale and the metal/scale
interface. Defects, such as dislocations, voids, and microcracks, which play a n im-
portant role for the growth and adhesion of the scale, can also be detected. With
electron diffraction techniques, it is possible to determine the crystal structure and
Transmission Electron Microscopy (TEM)
A EM
113s. EELS, IiLNES
cliemical atiillysis
li gratlienrs
* segregation
* cheniical
bonding
Fig. 1 Schematic overview of the different techniques of transmission electron microscopy.
the relative orientation relationship between the metal and the scale.
The second area is analytical transmission electron microscopy (AEM).The dis-
tribution of impurities and dopants as well as chemical profiles and compositional
gradients can be determined with AEM techniques. AEM techniques include energy
dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS).
A review and a comparison between EDS and EELS was presented by Mullejans
and Bruley [l]. The highest spatial resolution (0.4 nm) and smallest probe size
(< 1nm) can be reached if these analytical methods are combined with a dedicated
scanning transmission electron microscope (STEM),such as a VG-HB501 STEM.
EELS can provide information about the chemical bonding at interfaces. For ex-
ample, the oxidation states of metals can be investigated as has been demonstrated
for Nb/cc-Al,O, interfaces [2].It is possible by analysing the energy-loss-near-edge-
structure (ELNES) of EELS spectra to determine the coordination and distance of
atoms at interfaces. A line scan across the interface can provide information about
the chemical width of the interfacial region.
The third area of TEM is high resolution transmission electron microscopy (HREM).
Using HREM the crystal lattice can be imaged and the atomistic structure of materi-
als can be investigated. The point-to-point resolution [3] of conventional HREM in-
struments (400 kV) is about 1.7f\ (0.17 nm). However the new generation of HREM
instruments operates at 1250 kV with a point-to-point resolution of 1 A (0.10 nm).
With this resolution the structure of many different interfaces and defects in materi-
als can be investigated.
However, HREM can only be applied if special conditions are fulfilled. The thick-
ness of the TEM sample has to be smaller than 10 nm. This means very high quality
of sample preparation is required. Lattice images of heterophase boundaries or grain
boundaries are only possible if both crystals adjacent to the interface are oriented
The Application of TEM in the Analysis of High Temperature Corrosion 179
parallel to low-indexed Laue zones. The interface itself has to be parallel to the in-
coming electron beam, since small tilts away can change the lattice image and make
interpretation difficult.
The interpretation of HREM micrographs is not possible on a naive basis owing
to phase shifts introduced by lens aberrations, defocus values, sample composition
and thickness. Therefore, computer calculations are necessary to simulate images of
model structures of crystals and defects (e.g.interfaces)for comparison with experi-
mental images [3].
2. TEM Sample Preparation
The preparation of thin, electron transparent specimen, is a key point for the TEM
analysis. There are two types of TEM specimens, which are useful in the study of
high temperature corrosion problems: parallel sections and cross-sections. Parallel-
sections through the corrosion scale are prepared by back-thinning, where the metal
is removed by electropolishing or by ion milling. The phases in the scale can be
investigated with electron diffraction and analytical methods from parallel-sections.
The use of parallel-sectionshas been demonstrated by Doychak et al. [4]in the study
of oxidation of NiA1. However, it is not possible to study the metal/scale interface
with parallel-sections.
The complementary type of TEM specimen is the cross-section through the scale
and the metal. Cross-sections are useful for the investigation of the microstructure of
the metal, the scale and the interface and local chemistry at interfaces and grain
boundaries. Segregation of dopants at interfaces and grain boundaries can be de-
tected using analytical methods. However the preparation of thin cross-sectional
specimens is difficult because of the roughness of the oxide scale, the brittleness of
the materials and different thinning rates of the metal and the oxide. Another prob-
lem, which is important concerning high temperature corrosion, is that cross-sec-
tional TEM is restricted to adherent scales.
There are several examples where cross-sectionshave been successfullyused. TEM
cross-sections have been used to study the oxidation of Ni [ 5 , 6 ] ,of Fe and FeCrNi
[7] and of NiAl and Ni3A1[SI.
In the following paragraphs (see Fig. 2) a standard method for TEM cross-section
preparation will be explained [9].After characterisationof the specimen surface with
optical microscopy and scanning electron microscopy (SEM) two pieces of the metal
carrying the corrosion scale are glued together as a sandwich (Fig. 2 (a)).The sand-
wich is glued within a brass tube, with an outer diameter of 3 mm (Fig.2 (b, c)). Thin
discs are cut from this tube and ground with Sic paper to a thickness of about 200
pm (Fig. 2 (d)).The discs are dimpled from both sides with 3 pm diamond resulting
in a residual thickness of 10 pm.
The final step in thinning is ion milling. The samples are ion thinned with a low
angle of incidence (4")from both sides with a BalTec ion mill. This method produces
cross-sectional samples with high efficiency (80%). The details of the preparation
method will differbetween different systems in order to obtain the optimal sample.
brass
Omm0
- T
10mm =>
matrix
brass tube
3.0 mm 0
it,, mm
=>
Fig.2 Schematic summary of the TEM cross-section preparation technique (see text
for explanation).
3. Application of TEM in Oxidation Studies
In this section, the application of TEM techniques to investigate high temperature

corrosion, specifically, oxidation of Ni3A1and NiA1, will be presented. It was possi-
ble to obtain cross-sectional samples for CTEM, AEM and HREM investigations by
using the TEM preparation method described in the previous section.
3.1. Oxidation of Ni,A1

As a first example, results from the oxidation of Ni3A1will be presented. Ni3A1has
been oxidised under low (LOP)and high oxygen partial pressure (HOP). TEM cross-
sections have been prepared after different oxidation stages. The oxidation was con-
ducted under LOP conditions in a H,/H,O atmosphere (PO,= 4 x Pa) as well
as under HOP (air) conditions. The oxidation temperature was 1223 K. The oxida-
tion periods ranged between 1 min and 50 h.
Under LOP conditions A1,03 is the only thermodynamically stable oxide, which
means selective oxidation can be studied. Figure 3 shows a SEM micrograph of the
Fig. 3 SEM micrographfrom Ni,Al oxidised under LOP conditions showing Ni

particles on the surface.
Ni3A1oxidised under LOP conditions for 1min. EDS revealed the existence of small
Ni particles on top of the oxidised surface. TEM cross-sections have been prepared
from the same samples. The TEM bright field image (Fig. 4)shows that the Ni parti-
cles are connected with the Ni3A1single crystal by a metallic channel. The diameter
of this channel is about 10 nm.
A cube-on-cube orientation relationship between the Ni particle and Ni,A1 was
determined by selected area electron diffraction. The thin oxide layer consists of
cubic y-Al,O,, which is a metastable phase. Protrusions of y-Al,O, into the metal can
be seen. The average wavelength of the protrusions is 30 nm. After further oxida-
tion, the metal/oxide interface flattens and the outward flow of Ni stops.
Theoretical analysis of the morphology of the oxide growth on Ni,A1 [ 101 and the
outward flow of Ni in the early stage oxidation of Ni3A1 [ l l ] has been performed by
Bobeth et al. It could be shown that growth stresses are the driving force for the
extrusion of Ni. The compressive stresses necessary for the diffusion of Ni are in the
range of 1 GPa.
After longer oxidation periods (50 h), the oxide scale thickens and it transforms
into a-Al,O,, which is the thermodynamically stable configuration of A1,0,. This
example demonstrates, that the microstructural development can be analysed using
cross-sectional TEM. A more detailed description of the oxidation of Ni3A1 under
LOP conditions can be found in [ 121.
In the next example, the oxidation of Ni3A1 in air (HOP) will be considered [13].
Figure 5 shows a TEM cross-section after 2 h oxidation at 1223 K. The oxide layer
consists of 3 different sublayers: an outer layer of NiO (800 nm), an intermediate
182 High Temperatwe Corrosion Research and Testing
Fig.4 TEM cross-sectionfrom Ni,Al (LOP)showing Ni particle connected to the

underlying metal by a channel.
layer consisting of y-Al,O,, NiO and NiA1,0, (400 nm) and an inner layer of y-Al,O,
(500 nm). In the metal beneath the oxide scale an additional layer (1.1pm) Ni-A1, i.e.
a solid solution of Ni and A1 is present. A cube-on-cube orientation relationship
between the cubic y-Al,O, and the metal was determined by electron diffraction.
Because of this low index crystallographic orientation relationship, it was possible
to apply HREM to the interface between y-Al,O, and Ni-A1 [14]. Figure 6 shows a
HREM micrograph from the metal/ y-Al,O, interface. The original micrograph has
been Fourier-filtered. The lattices of Ni-A1 and cubic y-Al,O, are resolved. The inter-
face is semicoherent consisting of coherent regions and misfit dislocations. The mis-
fit dislocations relieve strains caused by a misfit of about 11%between Ni-A1 and y-
A1,0,. The distance between neighbouring misfit dislocations varies from 7 to 10
lattice planes.
3.2. Oxidation of NiAl

The oxidation of NiAl has also been studied by CTEM, AEM, and HREM techniques.
Under all exposure conditions, NiAl forms exclusively an external A1,0, scale. There-
fore, NiAl is an excellent model system to study the so-called reactive element effect.
It has been known for some time that alloy additions of rare earth elements like Y
and Zr improve the oxide scale adhesion; different models are under discussion (see
Fig.5 TEM cross-section from Ni,Al oxidised under HOP conditions showing oxide
scale with three different sublayers.
[15]).The present example demonstrates how the distribution of reactive elements

can be investigated by AEM with high spatial resolution.
There are several methods used to add reactive elements, such as ion implanta-
tion, oxide dispersions and alloying. First, the influence of Y ion implantation on the
oxidation will be considered. Single crystals of NiAl were cut, oriented parallel to
(100) and ion implantation performed with a dose of 5 x 1OI6 Y ions/cm2 and an
energy of 70 keV. The oxidation temperature was 1223 K. Figure 7 is a BF image of a
TEM cross-section after 50 h oxidation in air. Three different layers in the oxide scale
can be distinguished. The outer part of the oxide scale consists of monoclinic 8-A120,
platelets. The intermediate layer, 200 nm thick, consists of nanocrystalline y-Al,O,.
A concentration of 6 at.% Y could be measured within the intermediate layer with
EDS. Between the Y-rich layer and the metal a third A120, sublayer, 30 nm thick, was
found. This layer was too thin to determine the structure by selected area electron
diffraction.
Oxidation for longer times (Le. 100,200 h) showed that Y is concentrated only in
a small layer within the oxide scale. Thus, ion implantation of Y is not an effective
Fig. 6 HREM imagefvom the Ni (Al)/yAl,O, interface after oxidation of Ni,Al

(HOP).
Fig. 7 TEM cross-sectionfrom Y implanted NiAl after 50 h oxidation at 1223 K

(HOP).
method to dope the newly grown oxide. This results in a limited effect of implanted
Y on the scale adhesion.
In another experiment, polycrystalline NiAl alloyed with 0.1 wt% Zr was oxi-
dised at 1473K in oxygen. Under these conditions the oxide scale consists entirely of
a-Al,O,. TEM cross sections were prepared. The distribution of Zr has been deter-
mined with EDS in the STEM. Figure 8 shows a TEM cross-section of the Zr-doped
sample. The interface between NiAl and a-Al,O, is imaged. No precipitations or
interfacial phases are present at the metal/oxide interface. The concentration of Zr
as a function of distance from the interface has been measured with EDS in the STEM
(Fig. 9). Segregation of Zr at the NiAl/a-Al,O, interface clearly can be seen. This
example shows that with analytical electron microscopy the distribution of dopants
and impurities can be determined. Similar analysis can be applied to the grain
boundaries within the oxide scale. Figure 10 is an EDS measurement across an a-
A1,0, grain boundary. Segregation at the grain boundaries can clearly be seen.
For more detailed studies single crystals of NiAl have been oxidised. The oxida-
tion has been performed for 50 h at 1223 K. Figure 11 (p.187) shows a CTEM micro-
graph from a cross section of the oxidised single crystal. The oxide scale consists of
cubic y-Al,O,. The interface is faceted along (100)and (110). Between the cubic NiAl
and the cubic y-Al,O, well-defined orientation relationships could be detected with
electron diffraction. Because of these crystallographic orientation relationships it was
possible to apply HREM to the interface. However, it is not possible to image the
lattice spacing of d,,, = 0.139 nm in y-Al,O, in a conventional HREM instrument
(400 kV). Figure 12 (p.187) is a HREM micrograph taken in a HREM instrument
Fig. 8 NiAl/a-AI,O, interface after 200 h oxidation at 1473 K.

-30 -20 -10 0 10 20 30

Dlstance (nm)
Fig. 9 EDS measurement showing segregation of Zr at the NiAl/a-Al,O, interface.
z 0.064 I
'-t
-30 -20 -10 0 10 20 30
Dlstance (nm)
Fig. 10 EDS measurement showing segregation of Zr at an a-Al,O, grain bound-

ary.
operating at 1250 kV (JEOLARM 1250).The image shows the metal/oxide interface
at the (110) facet of NiA1. The following orientation relationship was determined
between the crystal lattices:
The metal/oxide interface is atomically flat and sharp. No misfit dislocations can
be seen within the image. However, to make any conclusion about the coherency of
the interface another crystallographic direction of the interface has to be investi-
The Application of T E M i n the Analysis of High Temperature Corrosion 187
Fig. 11 T E M cross-section f r o m N i A l oxidised 50 h at 1223 K.
Fig. 12 H R E M imagefrom the NiAl/yAI,O, interface ut a (110)-facet.

gated. Furthermore, computer simulations have to be performed to interpret the
contrast of the image. It may be feasible to determine the structure of the interface by
comparison with simulated images of proposed crystal structures. The results can
be compared with analytical measurements, which give indications of the terminat-
ing layers of interfaces.
4. Summary
It has been shown that electron microscopical techniques like CTEM, AEM and HREM
can be combined to study the growth of oxide scales and to understand the relations
between structure and chemistry. Although the effort for TEM sample preparations
of the relevant systems is very high, electron microscopy yields important
informationin the investigation of high temperature corrosion, as has been demon-
strated with oxidation studies of NiAl and Ni3A1.
5. Acknowledgement
The authors want to thank Prof. H. J. Grabke for providing excellent single crystal
material of NiAl and Prof. M. Graham for cooperation during the study of Y- and
Zr-doped NiA1. The authors thank Dr J. C. Yang (NSF Grant INT 9301705) for col-
laboration in STEM and HREM investigations. The work was funded by the Deutsche
Forschungsgemeinschaft (AZ Ru 342/6-4).
References
1.H. Mullejans and J. Bruley, J. Phys. IV, 1993,3,2083.
2. J. Bruley, Ii. Brydson, H. Miillejans, J. Mayer, G. Gutekunst, W. Mader, D. KnauB and M.
Ruhle, J. Mat. Res., in press, 1995.
3. J. C. H. Spence, Experimental High-Resolution Microscopy, 2nd Edn, Oxford University Press,
Oxford, 1988.
4. J. Doychak, J. L. Smialek and T. E. Mitchell, Met. Trans. A, 1989,20A, 499.
5. M. T. Tinker and P. A. Labun, Oxid. Met., 1982,18,27.
6. H. T. Sawhill and L. W. Hobbs, Proc. 9th lnt. Con$ Met. Corros., 1984,1,21.
7. S. B. Newcomb and W. M. Stobbs, J. Micuosc., 1985,140,209.
8. J. Doychak and M. Riihle, Oxid. Met., 1989,31,431.
9. A. Strecker, U. Salzberger and J. Mayer, Practical Metallogr., 1993,30,482.
10. M. Bobeth, W. Pompe, M. Rockstroh and E. Schumann, Acta Metall. Mater., 1994,42,579.
11.M. Bobeth, W. Pompe, E. Schumann and M. Ruhle, Acta Metall. Mater., 1992,40,2669.
12. E. Schumann, G. Schnotz, K.P. Trumble and M. Ruhle, Acta Metall. Mater., 1992,40,1311.
13. E. Schumann and M. Ruhle, Acta Metall. Mater., 1994,42,1481.
14 . M. Ruhle, U. Salzberger and E. Schumann, Proc. 2nd. lnt. Conf. on Microscopy of Oxidation,
1993,3.
15. J. Jedlinski, Solid State Phenom., 1992,Zl & 22,335.
13
The Application of Surface Analysis Techniques
in High Temperature Corrosion Research
W. J. QUADAKKERS and H. VIEFHAUS"
KFA Julich, Institute for Materials in Energy Systems (IWE), P.O. Box 1913,52425 Julich, Germany
'Max-Planck-Institut fur Eisenforschung GmbH, Max-Planck-Str. 1,40237 Dusseldorf, Germany
ABSTRACT
The responses to a questionnaire concerning the application of surface analytical meth-
ods to high temperature corrosion research are summarised here; these were obtained
from numerous researchers in the field of surface analysis. The most frequently used
surface analytical methods: AES, XPS, SIMS, SNMS, GDOES and RBS are briefly de-
scribed and discussed with respect to their application possibilitiesand limitations. The
main intention is to give guidelines to researchers who apply or are going to apply
those surface analysis methods in high temperature corrosion research.
1. Introduction
In spite of the fact that during the recent years a large number of publications on the
application of surface analytical methods have appeared in literature [l-151 a more
thorough study of those articles reveals that in most cases it appears difficult or
sometimes even impossible to compare the results of surface analytical studies on
corrosion scales obtained in different laboratories even if the same surface analytical
method is applied. One important reason for this fact is that at present no standards
or guidelines for the application of surface analytical methods to high temperature
corrosion problems exist. Although several round robin tests for different surface
analytical methods have shown that even on standard samples, comparability of the
results can be difficult, it seems nevertheless recommended to derive proposals and
guidelines for the application of surface analytical methods in high temperature cor-
rosion research.
This article summarises the responses to a questionnaire concerning the applica-
tion of surface analysis methods to high temperature corrosion research The ques-
tionnaire was drawn up by the present authors, and send to the contributors listed
at the end of the chapter. It was restricted to six frequently used surface analysis
methods: SIMS, SNMS, RBS, AES, XPS, GDOES (full titles follow in the text). Due to
this large number of experimental techniques, this paper cannot give an extensive
description of the application of the various methods, but is a first attempt to de-
scribe the possibilities and limitations of the various techniques, based on the an-
swers to the questionnaire. The paper should give guidelines to researchers which
apply the mentioned surface analysis methods in high temperature corrosion re-
search.
In the following, the characteristics of the six mentioned surface analysis meth-
ods will briefly be compared. Then, some general recommendations will be given
concerning the preparation of specimens which are to be analysed by surface analy-
sis techniques. Subsequently,the main part of the paper will summarise the responses
of the various contributors to the questionnaire concerning the applicability and
limitations of the various methods.
2. Comparison of the Various Techniques
A schematic model of a typical oxide layer formed during high temperature corro-
sion is shown in Fig. 1. The scale may consist of several phases, i.e. different oxides
and/ or occasionally carbides, sulphides and nitrides, in planar or columnar struc-
tures. Inclusions of other phases may be present within the oxide scale and/or within
the alloy.
The protective oxide scales formed on commercial high temperature alloys can
have a thickness ranging from < 1-100 pm. In many cases, the required information
concerning composition and microstructure of the scale can be obtained by chemical
analysis, optical metallography, scanning electron microscopy, energy dispersive X-
ray analysis, X-ray diffraction and electron microprobe analysis. But if laterally re-
solved analysis and in-depth resolution is required, these methods have only a lim-
ited applicability. Surface analytical methods possess the capacity to obtain detailed
information on the composition and structure of thick as well as very thin layers.
The individual properties, advantages and disadvantages of the six surface ana-
lytical methods discussed in this paper are summarised in Table l.
2.1. Samples and Sample Preparation

As ultra high vacuum (uhv) is a precondition for the application of most of the sur-
face analytical methods (Table 1)some general remarks and limits for samples and
sample preparation are necessary.
---- 1 contamination layer
2 oxide 1
---- 3 oxide 2
4 a l l o y matrix
Fig. 1 Schematic illustration of typical features in corrosion scales on high temperature alloy.
Research Application of Surface Analysis Techniques 191
Table 1. Comparison of the six surface analysis methods discussed
AES I XPS GDOES I SIMS SNMS RBS

Excitation e- I hu ions ions ions ci
Detection hu ions neutrals a
Elements all all all (1)
Isotopes 0.5-5
~ 0.5-10 no Yes Yes
Information 10-103 <1 <1
depth (nm)
Detection < 0.1 1 <1 10-100 103
limit (YOof
a monolayer
(PPm)
Lateral - 0.05 several <1 (3) 1000
resolution
(mm)
Chemical no no
information
Imaging (4) no
Vacuum uhv 10" bar

conditions
Destructive no
"1 Depending on specimen to be analysed (high Z-elements preferred)

Depth resolution: 10 nm.
f3) Plasma SNMS: 1 mm for DB mode, > 100 pm for separate bombardment; e-beam/laser: 1 pm.
Plasma mode: no; e-beam/laser: yes.
Sample sizes quite often depend on the type of instrument used for the analysis,
or may sometimes also be a question of the experience of the operator or the labora-
tory specialisation. A lot of commercial or self-made sample holders designed for
bulk specimens, fracture specimens, fibres or powders exist, which may be heated
or cooled. Nevertheless, some general guidelines concerning suitable sample sizes
can be given: for most instruments an ideal sample will have the dimensions of 1cm
x 1 cm area and about 1- 2 mm thickness. The maximum dimension will be in the
order of 30 mm in any direction (except for GDOES). The thickness is quite often
more critical, as for example for electron energy analysers, where there may exist
only a limited range of Z-movement to get the sample surface in focus with the focal
point (maximum intensity) of the analyser. This is quite critical for Auger systems
equipped with a cylindrical mirror analyser (CMA) and of less importance for HSA
equipped systems.
Often it may be necessary to reduce large samples in size to make them suitable
for the surface analytical investigations. Reducing of sample size may be performed
by:
(a) Breaking the sample, if it is sufficiently brittle, using clean lint-free paper for
holding the sample during fracture; or
(b) Cutting the sample (using different kinds of saws). Care should be taken to
preserve the original surface e.g. invert the sample during cutting in order to
avoid particles being deposited on the surface (no fluids should be used for
cutting).
The procedure to be applied for sample cleaning strongly depends on the history
of the sample. The only method to produce a completely clean surface is to prepare
the surface within the system for analysis under uhv-conditions. For samples which
were exposed to air or other corrosive environments, cleaning by solvents is not
recommended because any cleaning procedure will affect the surface condition and
can introduce contaminants. All samples exposed to air will have adventitious car-
bon on the surface. This can be removed by ion etching within the instrument (AES,
ESCA, SIMS, SNMS).The same procedure should be used for native oxides on metal
samples.
A sample which was exposed to an organic or greasy type of environment may be
washed by using acetone or ethanol (chlorinated solvents should be avoided). Speci-
mens exposed to inorganic environments, both aqueous and non-aqueous are best
cleaned in ultra-clean water. However it should be noted that aggressive species
causing corrosion can be removed by this process and to clean or not to clean those
samples depends on the information to be required from the following analysis.
3. Discussion of the Various Methods

3.1. Secondary Ion Mass Spectrometry (SIMS)
In secondary ion mass spectrometry (SIMS) the specimen to be analysed is bom-
barded by a beam of ions of energy 3-12 keV. The particles which are eroded from
the surface by the bombardment leave the surface in form of neutrals or ions [16].
Analysis of the secondary ions by a mass spectrometer allows a chemical analysis of
the specimen (corrosionscale) laterally and as a function of sputtering time, i.e. eroded
depth (depth profiling by dynamic SIMS).
SIMS is a suitable method for the depth profiling of laterally uniform scales of 50
nm-10 pm thickness. For thinner scales AES/XPS might be more suitable whereas
for thicker scales conventional or tapered cross sections should be used. With mod-
ern ion sources, scales of up to several micrometers thickness can be analysed within
one hour. Compared to other surface analysis methods, SIMS is very suitable to
measure trace elements because it can theoretically detect all elements and their iso-
topes, most of them down to concentrations in the ppb-range, however the sensitiv-
ity differs for the various elements and in practice, nitrogen for example, appears to
be difficult to measure.
The analysis of oxide scales can be hampered by the fact that the sputtering proc-
ess induces charging of the specimen surface. Charging affects the primary ion beam
and, more important, alters the part of the energy distribution contributing to the
detected signal. For thin films this can be overcome by a gold coating (10-20 nm) of
the specimen but in most cases, especially for thicker scales, charge neutralisation
by electron bombardment of the specimen is required.
A problem in the analysis by SIMS is the occurrence of mass interferences. In
some cases this can be overcome by high mass resolution using magnetic sector-
field mass spectrometers or time of flight (T0F)-SIMS,whereas in quadrupole-based
SIMS, energy filtering can be a remedy. However all these methods reduce the de-
tection sensitivity.
Depending on the actual analysis problem the primary ions can be Ar, Xe, 0, Cs,
Ga. Oxygen primary ions facilitate charge compensation and are suitable for meas-
uring positive ions of metallic species, whereas Cs has the advantage of high sput-
tering yields and is preferred for the detection of non-metallic elements. With Ar the
ion yields are relatively small, however positive ion yields are generally high during
analysis of oxide scales due to the presence of oxygen. Generally it can be said that
all reactive primary ions such as 0 and Cs have the advantage of increasing the ion
yield. By using a liquid metal Ga source, analyses with high spatial submicron (50
nm) resolution is possible, however the ion yields are small, making depth profiling
difficult.
Current density and crater size depend on the actual analysis problem. Typical
crater sizes are 200400 pm square with 0 and 100 x 150 ym with a Ga source. If the
crater size is too small, crater edge effects can become significant.They can be avoided
by applying a suitable gating. The preferred primary ion current depends on the
actual problem to be analysed. To ensure a sufficiently high erosion rate, the crater
size has to be reduced as far as possible. Primary currents of some 10 nA and crater
sizes of 100 ym2 should be a suitable parameter set. High current densities lead to
high sputter rates and are recommended in analysis of trace elements. However,
high current densities often increase charging of the sample and also decrease the
depth resolution. In analysis of naturally grown corrosion scales, this last mentioned
factor is mostly not a problem: the depth resolution is generally determined by the
intrinsic roughness of surfaces and interfaces of the oxide scale, i.e. the irregularities
of the interfaces in naturally grown corrosion scales are larger than the variation in
depth resolution of the SIMS analysis.
Quantification of the measured SIMS depth profiles is time consuming in most
cases, and sometimes impossible. The reason is, that the ion yields and sputter rates
strongly differ in various phases (matrix-effect). If the oxide scale is single phase,
quantification is sometimes possible by using relative sensitivity factors (RSFs) de-
termined from a standard composition which should be very similar in composition
to the scale to be analysed. Implanted elements are often recommended as internal
standard, however, it has to be born in mind, that lattice defects caused by implanta-
tion might lead to changes in sputter rate. Apart from that, the use of standards does
not solve the problem of quantification near interfaces. In some cases, the matrix
effect can largely be eliminated by relating the elements to be analysed to the main
100
OXIDE SCALE -- tALLOY -1
b~ 60
- 5JCrlBO+
!
fI
3 A = '+OC~'~O+(X~OO
40 o = ' 4 " ~ e' * o + ( x ~ o o )
20
0 10 20 30 40 50 60
Sputter Time , min
Fig. 2 SIMS profile of oxide scale, around 1 mm thickness, on Fe-250, in wt%, coated with 4
nm CeO,,after two-stageoxidationin 160/180, (1 kl2 k), at ZZOOOC 1271.
alloy or oxide component. As the total number of detected secondary particles is

related to the sputter rate, this value can sometimes be used to recalculate the time
axis to depth [16].
For the analysis of oxidised samples some researchers prefer the use of cluster
ions rather than the single atomic species (Fig. 2). However, other researchers claim
that the use of clusters can cause misleading results. Probably it depends on the
actual problem to be analysed whether single- or polyatomic species are more suit-
able to obtain the correct analysis result.
Recent studies [18,19] have shown, that the matrix effect can strongly be reduced
by using MCs+-SIMS.In this technique the oxidised specimen is bombarded by Cs+-
ions whereas the positive molecule cluster ions of the elements (M) with Cs are be-
ing analysed. Although the mechanisms of the molecule formation at the specimen
surface are not yet completely understood, a number of recent studies seem to con-
firm the suitability of this technique for quantitative scale analysis, provided the
impact angle is larger than around 65" (depending on material and sputter yield).
Figure 3 shows an example of the reduced matrix effect during analysis of an alumina
scale formed on an FeCrAl-alloy. It can be seen, that a good approximation of the
real concentration profiles is obtained by using relative sensitivity factors (RSFs)for
the various elements (same RSFs for oxide and alloy) which lie in the same order of
magnitude, in contrast to conventional SIMS, where the sensitivity factors for the
various elements can differ by several orders of magnitude. Figure 3 illustrates that
MCs+-SIMSis capable of measuring concentrations as high as 60 at.% and as low as
0.01% simultaneously in one depth profile. If the RSFs are constant throughout the
depth profile, they provide the possibility to derive the relative sputter yields dur-
ing the depth profiling. Combined with an absolute measurement of the crater depth,
\ I
>
.-U
+
C
a
L
-C
lE.011 I
-
-
-
I
--
-
0 100 200 300
Sputter time / rnin
1E+02,
_ _ _ ^ - _ _ _ _ _ _ - - - - - -
0 100 200 H)
Sp,Jtter time / rnin
Fig. 3 MCs'-analysis of alumina scale on Fe-20Cr-5Al ODs-alloy, composition in wt%, after

215 h oxidation at 1100°C SIMS-parameter, 50 nA, 5.5 K e y scanning area 150 x150 m, charge
compensation by electron gun; (a) Non-corrected intensities of main elements €e, Cr, AI, 0;
(b)Intensities after isotope correction, multiplication with sensitivity factors, AI = 1, Cr = 0.85,
Fe = 0.9, 0 = 6.5, and normalisation to total corrected intensity 1181.
a depth scale can than be derived. Further studies are necessary to prove the suit-
ability of the MCs+-SIMStechnique.
If the oxide scale composition is not laterally homogeneous, depth profiles can
only give limited information of the real element distribution in the scale because
they give an average value over the analysed area. In such cases the good lateral
resolution which is achieved by SIMS imaging can be used for scale characterisa-
tion. The achievable lateral resolution depends on a number of experimental factors.
Generally it can be said, that Ar- and 0-primary ion beams are more difficult to
focus than Ga or Cs, so that the lateral resolution is around 2 pm if Ar- or 0-primary
ions are being used. With Cs-ions however, a lateral resolution of 0.2-1 pm can be
achieved whereas a Ga-beam [9] can even be focussed to around 50 nm (see Section
3.3.),however, this will be associated with a lower sensitivity. The lateral resolution
during imaging not only depends on the primary beam. With quadrupole systems
the poor transmission is a limiting factor in high resolution imaging.
In imaging, even by using the MCs+-SIMStechnique, the matrix effect can make
the mapping result difficult to interpret, because differences in sputter rates and/or
ion yields of different phases in the oxide scale can indicate different concentrations
of the various elements which in reality do not exist. Therefore, in multi-phase scales
the intensities at every measured pixel of the image should be corrected to account
for the differences in sputter rate and ion yield for obtaining the real element distri-
butions. This obviously requires significant computer capacity, however in using
MCs+-SIMS,promising results have been obtained.
3.2. Secondary Neutral Mass Spectrometry (SNMS)

Whereas in SIMS, part of the particles which are eroded from the surface are trans-
ferred to ions which then are used for analysis, in secondary neutral mass
spectrometry (SNMS)the ionisation process is decoupled from the sputtering proc-
ess [20], Two fundamentally different SNMS concepts are currently being applied:
(i) the surface sputtering is carried out in a similar manner as in SIMS, mostly
with Ar+ions, whereas the sputtered neutrals, which are the vast majority of
the eroded particles, are post-ionised e.g. by an electron or laser beam; and
(ii) the sputtering is accomplished by ions which are attracted from an Ar-plasma
to the surface of the specimen due to a direct or alternating (high frequency)
voltage between specimen and plasma. The sputtered neutrals are then ion-
ised in the plasma.
Charging induced by sputtering only affects the intensity of the primary ion beam
but not that of the neutrals (in SIMS, charging additionally alters the part of the
energy distribution contributing to the detected signal). Oxide scales up to 10 pm
thickness can therefore often be analysed without significant charging problems.
Mass interferences are significantly less than with SIMS because only few molecule
clusters are being formed.
Because the neutrals can not be directed towards the spectrometers, a significant
amount of the eroded material is lost and therefore the sensitivity of SNMS for most
elements is sometimes a factor of 10 to 100 lower than in the case of SIMS. The spe-
cific sensitivity depends on the actual element, sputter rate, counting time per ele-
ment etc.
An advantage of the e-beam and laser-SNMS compared to plasma-SNMS is, that
a lateral resolution can be obtained which is similar to that of SIMS. The lateral reso-
lution in the case of plasma SNMS is equal to the analysis area, i.e. a few mm2.Plasma-
SNMS has also no possibility for eliminating crater sidewall effects, although this
seems not to be a great problem due to the large crater size. Above that, with e-beam
and laser-SNMS,no problems with the relatively high level of residual gases (O,C,N)
in plasma SNMS, occur.
An advantage of the plasma mode is the high current density at low bombard-
ment energy which implies high sputter rates (typically 0.5 nm s-l) combined with
high depth resolution. It should however be mentioned that as with SIMS, the depth
resolution is mostly limited by the roughness of the corroded sample and the bot-
tom of the sputtered crater. The problems which might occur due to uneven sputter-
ing of various scale parts due to the low sputtering energy in plasma SNMS, can be
avoided by using the HF-mode.
Argon is a very suitable primary ion in SNMS-analysisbecause during sputtering
with Ar ions the vast majority of the sputtered particles are neutrals and only very
few ions are formed. This fact, which is disadvantageous in SIMS analysis, is benefi-
cial for SNMS because there the neutrals are used for analysis of the specimen.
The main advantage of SNMS compared to SIMS is its far better quantification.
Due to the decoupling of sputtering and ionisation, the relative ion yield is largely
independent from the sputtered matrix and therefore the 'matrix effect' is strongly
reduced although it still exists.
The relative sensitivity factors determined in SNMS analysis of completely differ-
ent materials sometimes differ, however the variation is generally within f 50%,
whereas in SIMS they can vary by several orders of magnitude. Because of this slight
variation of the sensitivity factors, also SNMS should be used with some caution if it
is to be applied for routine quantification of unknown materials. In depth profiling
it should be taken into account, that for the case of a sample which is laterally het-
erogeneous, differential sputtering can introduce an apparent matrix effect.
Figure 4 shows a typical example of a simple quantification procedure for depth
profiles of a multi-layered corrosion scale on the intermetallic Ti-48A1-5Nb (in at.%)
determined with plasma SNMS. The measured intensities (Fig. 4(a))were corrected
for isotope abundance and multiplied with sensitivity factors determined from a
standard steel sample. These corrected intensities were added (Fig. 4(b)) and then
normalised with respect to the sum of all corrected intensities (Fig. 4(c)). In this way
quantified depth profiles are obtained which describe the actual concentrations in
the corrosion layer as well as in the alloy with reasonable accuracy. The scale con-
sists of four separate layers: two Ti0,-rich layers (one in the outer, one in the inner
part of the scale) which are separated by an alumina based scale; a nitride-rich layer
is formed at the scale/metal interface.An important result is, that, contrary to SIMS,
nitrogen can readily be detected if present in sufficiently high concentrations.
It is interesting to note, that in the measured, non-quantified intensities (Fig.4(a)),
e.g. the A1 profile shows a relative maximum near the scale/metal interface. This is
also the case in the corrected total intensity (Fig.4(b), sputter time around 1600 s).In
the corrected/normalised profiles, however, the relative maximum near the inter-
face is evened out by the quantification method (Fig. 4(c)). This is caused by the fact
that the RSFs are largely matrix independent in this case. Therefore the sum of the
corrected intensities is approximately proportional to the sputter rate. Figure 4(b)
shows that the sputter rates are very high in the alloy (sputter time > 1800 s) and
especially at the oxide/metal interface (1800 s).They are extremely low in the inter-
mediate alumina-rich layer (- 200-500 s). As the corrected intensities of the meas-
ured elements are normalised in respect to the total intensity, which reflects the sputter
rate, differences in sputter rate in the various phases are evened out by the normali-
sation.
I -i'-
0 1000 2000 .1 Do
a> Sputter time /s
/--
---.-F-
v)
n I-toto1
0
(corrected with sensitivity factors)
\1ES
\ 1 Et05-
x a-
.-v,
-1J
C
a)
-C
v
0 lo00 2000 3000

b) Sputter time / s
0 1000 2000 )O
c> Sputter time /s
Fig. 4 Plasma-SNMS analysis, direct bombardment mode, primary energy of Ar+800 V , of
corrosion scale on Ti-48Al-5Nb, composition in at.%, after ZOO h oxidation at 800°C in air,
scale thickness around 2 pm; (a) measured, non-corrected intensities; (b) sum of intensities,
corrected with sensitivity factors, AI = 0.35, Ti = 0.65, Nb = 0.7,O = 7.0, N = 2.0; (c) profiles
quantified by isotope correction of measured intensities, multiplication by sensitivity factors and
normalisation in respect to sum of corrected intensities.
If the sum of the corrected intensities can be assumed to be proportional to the
sputter rate, the total corrected intensity might be used for depth calibration of the
time axis. If the crater depth is measured at the end of the analysis by an absolute
method, e.g. using a standard depth profiling equipment (pertometer), multiplica-
tion of the time axis with the sum of the corrected intensities (Fig. 4(b)) and subse-
quent normalisation to the measured crater depth yields in most cases a good ap-
proximation of the concentration depth profile as a function of distance from the
gas/oxide interface [21].
Plasma SNMS has some disadvantages compared to SIMS or e-beam/laser SNMS.
Especially in the analysis of elements like C and Si a redeposition from the plasma
can occur which makes the analysis of small concentrations of these elements unre-
liable. The deposition on the wall of the reaction chamber may lead to a 'memory
effect' which can, however, be evened out by heating the equipment by burning the
plasma for several hours. The fact that the analysis chamber is made from steel,
means that a contamination of the plasma, e.g. by Fe or Cr can occur, which makes
very low concentrations of these elements in the specimen difficult to analyse. Fig-
ure 5 shows an example of the analysis of Cr-impurity in an alumina scale formed
on an FeCrAl-ODS-alloy. It is obvious, that the very low Cr concentrations (around
0.2%) in the alumina near the scale/alloy interface are not properly detected with
plasma SNMS. This contamination of the plasma by the reaction wall material can
be reduced by covering the walls of the analysis chamber, e.g. with tantalum.
3.3. Tracer Methods

Both SIMS and SNMS do not detect pure elements but the various isotopes of the
elements. Therefore both methods are potentially suitable for studying diffusion
processes in oxide scales using oxygen and/or metal tracers. A frequently applied
method is the two-stage oxidation technique, in which the specimen is first oxi-
dised in l6Oand subsequently in I S 0 . On changing the gas from l6Oto l8O,the speci-
men should not be cooled because this can lead to cracking of the oxide due to ther-
mally induced stresses. Analysis of the oxygen isotopes in the oxide scale formed
during the two-stage oxidation using SIMS or SNMS theoretically allows the deter-
mination of the oxide growth processes [21].
For determining the growth process, most researchers analyse the distribution of
the single atomic species I6Oand ISO.Sometimes problems in SIMS analysis might
occur due to the presence of water vapour, e.g. absorbed in cracks and or pores
formed after specimen cooling, due to mass interference of l8Oand H,160.The over-
lapping of these species can be avoided by using high mass resolution or by simulta-
neously detecting hydroxide ions (masses 17 and 19) [22].Some authors claim, that
the most unequivocal information concerning the growth processes in the scale can
be obtained by measuring cluster ions (MI60+,lSOl60,etc.) rather than the single
atomic species [14,17].Other researchers however state, that the use of these cluster
ions can lead to erroneous conclusions.
The matrix-effect, which has been discussed in Section 3.1. (p.192) concerning
SIMS, can also lead to problems in the correct interpretation of the oxygen isotope
<-----Alumina scale-----> <---.-----Alloy
2 -.-. ___... .
/--,
/
;'---=---e-
I
Fig. 5 CY-and Fe-distribution in an alumina scale on an Fe-13Cr-3Al ODS alloy, composition

in wt%, after 3 h oxidation at 11OOOC, scale thickness around 1 pm, measured by Plasma-SNMS,
e-beam SNMS and MCst-SIMS /181. SIMS, Cs+, 5.5 K e y impact angle 76 ",charge compensa-
tion by electronfiooding, optical gating, e-beam SNMS, 10 K e y Ar+, no charge compensation,
electronic gating, plasma SNMS, direct bombardment mode, 0.8 KeV AT+,no gating.
distribution after two-stage oxidation. Assuming that the matrix effect will be the
same for both oxygen isotopes, the 1s0/160-ratiois often used to get information
Concerningthe relative distributionof the isotopes. However, especially in cases where
an l80enriched gas rather than pure I s 0 is being used in the second oxidation stage,
this relative l80distribution does not always give correct results. Probably the use of
fully quantified depth profiles, including all major and minor elements present in
oxide and/or alloy, is the best method for obtaining reliable results concerning the
correct isotope distribution. A fully quantified profile is important because knowl-
edge of the time dependence of the distribution of other alloy constituents in the
scale is sometimes helpful in deriving the correct growth process in cases where the
oxygen isotope distributions do not allow unequivocal determination of the trans-
port phenomena [23].This last mentioned case frequently occurs because the natu-
rally grown oxide scales do not possess ideally flat interfaces. Therefore in practice it
is difficult to determine from the tracer distribution whether the scale is growing by
cation diffusion (leading to a stepwise lSOprofile in the outer part of the scale) or by
oxygen lattice diffusion (leading to a high lSOconcentration at the outer scale sur-
face which gradually decreases towards the scale/metal interface) [21].The unequivo-
cal determination of the growth phenomena is especially difficult if parallel diffu-
sion processes prevail. In such cases modelling of the diffusion phenomena, Le. com-
parison of measured with calculated profiles can be helpful to derive scale growth
phenomena [21].Also SIMS imaging [24], i.e. the mapping of lSOand l60in various
areas of the scale or on tapered cross sections, can contribute to the understanding of
the scale growth process. Imaging is especially useful, and perhaps even required, if
the growth processes in the scale locally differ due to rapid transport paths like grain
boundaries or cracks (Fig. 6). However, it should be mentioned, that the correct in-
terpretation of the SIMS images can also in this case be hampered by the matrix
effect, especially if the scale is not single-phase. Imaging by a quantifiable technique
such as MCs+-SIMSor e-beam/laser SNMS seems most suitable. In that case a quan-
tification procedure as described in Sections 3.1. and 3.2. should be applied to every
analysed point.
3.4. Rutherford Backscattering Analysis (RBS)

In Rutherford backscattering analysis (RBS) the specimen to be analysed is bom-
barded by a beam of a-particles with energy of approximately 0.9-3 MeV. The en-
ergy of the backscattered particles depends on the atomic number of the atom at
which the particle is scattered and the distance of this atom from the specimen sur-
face. Therefore RBS is a non-destructive depth profiling method which is element
and depth sensitive. Although a standard is needed to calibrate the experimental
set-up, RBS can more or less be considered as a non-destructive, absolute method
The quantitative depth-information requires an iterative fitting procedure. In most

labs the programme RUMP is being used [26].The information depth is ca. 0.5-2 ym
depending on the primary energy. The depth resolution is typically 10-30 nm, and
will therefore in most cases be determined by the irregularities of the oxide scale. A
major requirement for the successful application of RBS is that the surfaces of the
specimens have to be flat. An important limitation in using RBS is the overlapping
of signals [27]. Figure 7 shows RBS spectra of an alumina scale on an yttria-contain-
ing FeCrAl alloy. The measured intensity at the high energy edge of Fe unequivo-
cally reveals the presence of a low concentration of this element at the alumina sur-
face. The yield at slightly lower energies however, might be caused by the presence
of Fe in greater depth or/and by Cr and/or Ti at the surface. Therefore, reliable in-
202 High Temperatiire Corrosion Research and Testing
Fig.6 SIMS imagingof l8Odistribution in taper section of an alumina scale formedduring two-
stage oxidation, 160/180, of an FeCrAl ODs alloy at 1100°C. The analysis was made near the
interface of the oxideformed in the first and that formed in the second oxidation stage. Distribu-
tion of l8O in old scale indicates oxygen transport along grain boundaries 1251.
depth information on the elements Fe, Cr, Ti cannot be derived. The situation is
different if a high-Z-element like Y is incorporated in the scale. Only then, quantita-
tive in-depth concentration of this element, in this case up to around 0.3 pm, can be
obtained. Because of the mentioned significant limitations, RBS cannot be consid-
ered as a suitable technique for standard depth profiling of corrosion scales. The
method can sometimes be advantageous if heavy elements are to be analysed in a
light matrix. For analysis of light elements in a heavy matrix, nuclear reaction analy-
sis (NRA) can in some cases be suitable.
3.5. The Electron Spectroscopic Methods: Auger Electron Spectroscopy (AES)

X-ray Photo electron Spectroscopy (XPS))
Auger electrons are secondary electrons which are emitted after excitation of a solid
by a sufficiently energetic primary electron beam. Auger electrons possess a specific
energy as long as they are not scattered within the sample. As those scattering proc-
esses already occur in very thin layers, Auger electrons can only escape from a very
thin surface layer. By an energy analyser Auger electrons are detected with respect
to their energy. In combination with an ion sputtering device AES is used to record
depth profiles.
For XPS analysis the sample is irradiated by X-rays of a fixed wave length. Elec-
trons are removed from electron-core levels within the sample by the X-ray photons.
The removed photoelectrons have element specific energies if they leave the solid
400 500 600 700 800

Channel
Fig. 7RBS-Spectra, aparticles, 2 MeV showing Y, Fe(Cr, Ti), impurity in the outer part of an
alumina scale on an FeCrAI-ODS alloy after various oxidation times at 1100°C 1271.
from a very thin surface layer. By performing an energy analysis emission of the
different photoelectrons can be recorded. The electronic core levels of the atoms within
a sample may be slightly different in energy for different chemical surroundings of
the emitting atom. If those energy differences (shifts) are detected, they give infor-
mation on the bonding state of the atom.
The vacuum conditions for applying both methods should be at least mbar in
order to avoid contamination (mainly by carbon) during analysis and to be able to
use the advantage of high surface sensitivity of the two methods.
The energy of the primary electrons to be applied for Auger analysis depends on
one hand on the kind of instrument to be used but on the other hand on the kind of
information to be derived from the AES measurements. Most of the older analog
AES systems were designed for primary energies up to about 5 keV at maximum
and the lateral resolution to be realised for AES studies was rather limited. In mod-
ern instruments primary energies up to 30 keV may be used which allow a much
better resolution. The signal intensity will be reduced for higher primary energies (>
5 keV), because of a decrease in ionisation probability, but the background intensity
will increase and will thus result in a change of the signal/background ratio with
primary energy. Compromise values of 5-15 keV are recommended for the primary
electrons to be used for AES studies.
A change in electron beam current density only produces a change in the signal
to noise ratio and hence in the precision of the AES analysis. Values to be used again
depend on the type of Auger system, transmission of the analyser, spatial resolution
to be required and on the sensitivity of the specimen with respect to degradation by
the primary electron beam. Considering the different types of instruments, the fol-
lowing classification according to beam diameter, beam current and beam current
density may be given:
Type of Spot size Beam Beam current

AES system beam diameter current density
(PA) (mA cm-?
Analog -
large 100 -5 -0.5
systems small -3 -0.05 -6-10
Auger large -10 -0.05 -0.5

microprobes small -0.05 -0.001 -500
I I
The advantage of the possible high lateral resolution of modern Auger microprobes
has the disadvantage of fairly high beam current densities as a consequence. This
may be a problem because of sample degradation due to reduction for oxides like
SiO, which is very sensitive to reduction under the influence of the primary electron
beam. Quite often it is possible to recognise oxide reduction by observing the low
energy features in the Auger spectrum. Most of the oxide forming elements of im-
portance for high temperature corrosion studies exhibit separated Auger features in
the low energy range which are characteristic of the metallic and the oxide state of
the element.
The influence of the energy resolution of the analyser on AES measurements
especially on quantitative data is often strongly underestimated. It is assumed and
quite often also published in handbooks on AES, that Auger signals always have a
natural line width of several eV. But this is not true. For example, the KLL Auger
signals of several elements like Al, Mg, Si which are of importance for high tempera-
ture corrosion studies, have a natural line width of only about 1eV or even less. To
perform a reliable Auger analysis on those metals, the energy resolution AE during
analysis should be better than 1eV. The KLL Auger signal of A1 for example, has an
energy of about 1400 eV and to realise AE = 1 eV the energy resolution has to be
0.07%. Fortunately, the energy width of the KLL Auger signals for the oxides of Al,
Si, Mg are much broader as may be recognised from the data in Fig. 8 comparing the
Mg(met) signal with that of Mg(oxide). Therefore, the problem of the influence of
energy resolution on AES peak height measurements is drastically reduced in this
case. But it should always be kept in mind that this might become a problem as soon
as the quantification of AES results for metallic atoms has to be considered. On the
other hand, high energy resolution for AES measurements may be useful to distin-
guish different oxides by energy shifts for the oxygen KLL Auger signal, as demon-
strated by Fig. 9 for A1,0, and Cr,O,. As long as no Auger signals of rather low line
width have to be expected, the following values for the energy resolution setting of
the analyser are recommended:
AE/E = 0.5% for survey scans

AEIE = 0.2to 0.3% for narrow scans.
For X-ray irradiation normally A1-K, or Mg-K, sources are used. The Mg-source
gives a slightly better energy resolution because of the smaller natural line width for
the Mg-K,-radiation. If photo electron peaks overlap with Auger peaks a change of
the X-ray anode can help to separate the peaks. The X-ray conditions are not very
critical except for degradable samples, e.g. unstable oxides. In those cases, lower
energies and low current densities should be used in order to prevent changes in
these surfaces. Standard running conditions for the X-ray sources are 15 keV for the
accelerating voltage of the electrons and 20 mA emission current.
The conditions for recording spectra are:
Spectrum Pass energy Step width Time per step

Survey 50 eV 0.5 eV 20-50 ms
Narrow scan 20 eV 0.1 eV 50-200 ms
For element analysis using AES or XPS peak overlapping may occur within the
recorded spectra, e.g. if the following elements have to be detected simultaneously:
Fe/Mn, Cr/O, Cl/Mo, Cl/B, Ti/N etc. Similar quite numerous problems exist for
............ ...... - .... - -. - __.. __ .. -. ._. .. ...... -_ ... . __ __ . . . . . . . ,- .
i MPI OUSSELDORF
M G....O 1 O i . O A T ~ii!tjioii i / i
Auger
Lcvei
- Spectrum
1 / i
V.G.Scientific
Ikirli. 1 /
........... --
1
- ..... -. . . . .
...
MPI DUSSELOORF
NICR1004,DAT T l i ? g I ~ r1~ / 1
Auger
......\ l i V..< --' I
- Spectrum
1 / 1 ...
..... .-
V.G.Scientific
I'llll\t
. / .. 1-. .
1 -.-
Radiation
.
.......
I
I
A1203 HOK Count R n t s
1500
C s t a o S12.
500 I ) . !I11 I!V
Ousll Time
U ,...,/--
I
No o f Channmls
-500
t NO o f Scans
S Time f o r flogion
srr
-1500
-
Cr LMM and 0 - KLL
7 7 0
hc qu i r 0 d
UL) :id 1 , ' $ - < ' I114
Platted
,
-2500 --
450 460 470 430 500 510 520
490 530 540 550
Kinetic Energy / eV
N120Cr ltll)
Fig. 9 Oxygen-KLL signalfor Cr,O, and Al,O,, 10 keV primary energy.
XI'S. For XI'S the separation of overlapping XPS-and Auger peaks by changing the
anode type was already mentioned. For all other cases it is recommended to look in
the recorded spectra for element specific peaks which are not the main peaks for this
element. For instance, for the system Cr/O it is useful to characterise Cr by AES
using the Cr LVV at about 570 eV energy instead of using the main Cr LMV signal at
539 eV energy.
The ability to distinguish different chemical binding states of an element by XPS
studies is well known, but the power of AES to characterise binding states is often
strongly underestimated because of the limited energy resolution of the CMA ana-
lyser which are most frequently used for AES studies.
The capabilities of AES to characterise different chemical states will be demon-
strated by two examples. The first example is an AES study on a zinc plated steel
sample having a thin zinc oxide layer on the surface. Zinc is characterised using AES
for the oxide state by a main peak which is shifted by about 2 eV to lower energies.
The energy resolution AE necessary to resolve those two peaks has to be better than
2 eV, which means better than 0.2%. Figure 10 illustrates that the separation is possi-
ble for 0.1% energy resolution using a HSA (hemispherical sector analyser) equipped
system. The second example shows results of an Auger analysis of small carbide
inclusions within the metal matrix of the intermetallic FeA1. This example shows the
excellent energy resolution of an HSA equipped AES system. As may be derived
from an inspection of Fig. 10 the energy separation between AIFeAland Alex, is quite
large and may be detected even for rather poor energy resolutions of the AES sys-
tem. To separate the A1 signal of AIFeAl and the A&, carbide a much better energy
resolution of about 0.05% is necessary. The separated signals of the A1-KLL signal
for the different binding states may be used to record individual Auger maps as
reproduced in Fig. ll(b).
r i
320 I-----' A 1
c - - 1
^li v\A
-
0
u 54
n res. 0.1%
50 "\
S
- - -
46 i-
975 980 985 99(1 995 1000 1005 1010 1015 1020 102
Kinetic Energy / eV
Fig. 10 Zn-LMM Auger signal recorded for 0.5and 0.1 % energy resolution at 10 keV primary
energy.
1300 1302 i3ui 1306 1 3 ~1300 ~ ixu 1 3 ~ 1 13911 1400

K l n u t k Eiier'gy / ttV
Fig. 22 (a) High energy resolution AE spectra of the Al-KLL signal for AI,O,, FeAI, AI and
Al,C,, resolution 0.02%, 10 keV primary energy.
In the case of oxides, numerous examples exist in the literature demonstrating
how different oxidation states of one element or the oxide and metallic state of an
element may be distinguished by XPS measurements. A well-known, problematic,
example is the XPS characterisation of iron in the ionisation of FeO, Fe2+and Fe3+.
Extensive experience of the investigator, a careful use of special fitting routines for
Me recording spectra and the use of well-defined standards is necessary to identify
the different oxidation states of iron. In some cases, where the energy shift caused by
the change in the chemical state is too small (Cuo/Cul+)it is recommended that
quantitative evaluation by X-ray induced Auger peaks is used to obtain a more com-
plete picture of the chemical state of the element.
For the characterisation of high temperature corrosion layers it is important to
obtain in-depth information. Depth profiles of the sample composition when using
surface analytical methods can be obtained by successive removal of surface layers
by sputtering with Ar ions of sufficient energy (1-5 keV) and then analysing during
sputtering the momentary 'free' surface by a surface analytical method like AES or
XPS. Further general methods to get information on the depth distribution of ele-
ments within layers is to cut carefully the layer on the sample at quite small angles
with respect to the surface to get an enlarged cross section of the layer and to analyse
this cross section after sputter cleaning within the surface analytical system by AES.
(For XPS studies of those systems normally the lateral resolution is too bad). Cutting
of the sample may be performed in different ways.
The surface layers to be analysed by depth profiling using AES or XPS may be
divided into different groups according to their thickness:
(a) Very thin layers of 1-5 nm thickness may be analysed by angle resolved AES
or XPS measurements.
(b) Ar ion sputtering may be used for layer thicknesses of 3-100 run.
Fig. 11 (b) Al-Mappingfor FeAl and Al,C, and SEM.

(c) For 100-2000 nm thick layers depth profiling, lapping or ball cratering may
be applied.
(d) For thicknesses > 2 mm of the layer lapping or ball cratering is recommended.
The different methods will be discussed briefly with respect to their application
to high temperature corrosion samples.
In general, it is sufficient to use Ar ions as the gas source. The ion beam energy
most commonly used is 3 keV, but lower energies may be applied if the samples are
easily degradable or if a particularly good depth resolution is required. Preferably
the beam should be rastered across the sample surface to obtain a flat sputter crater
bottom and a good depth resolution. However, in studying HT-corrosion scales the
depth resolution is mostly determined by the roughness of the specimen.Addition-
ally, the depth resolution during depth profiling may be increased by inhomogeneous
sputtering caused by crystallinity effects. This is illustrated in Fig. 12, comparing Ar
ion sputter depth profiles of a 100 nm thick Ta20, layer on a Ta substrate, grown by
electrochemical methods, and an iron oxide layer of similar thickness grown on a Si
wafer at high temperature under a well defined oxidising atmosphere [28]. In gen-
eral, for XPS studies the analysed areas are quite large (severalmm2)and most of the
ion guns produce insufficient current densities-if the ion beam is rastered over such
areas-to be able to record depth profiles. Typical angles of incidence for the ion beam
during sputtering are in the range of 0-60" with respect to the surface normal. De-
pending on the thickness of the layer to be removed by ion sputtering, ion current
densities should be in the range of 1 to ca. 50 pA cm-2.
The crater edge resulting from ion beam sputtering on the etched sample surface
exposes the layer cross-section in a similar manner to that produced by angle lap-
ping of the layered sample. One large difference in using the crater edge is in the
resulting angles between the surface and the crater edge walls. In the case of angle
lapping the angle is usually in the order of 2 21" or greater. For the crater edge pro-
filing method this angle may be orders of magnitude less [29].
Mechanical lapping through the selvedged layer at some angle to the original
surface is an approach, which is especially useful for deeper interfaces. Analysis is
achieved by scanning the electron beam across the lapped face either mechanically
by moving the sample manipulator or by beam raster. The depth resolution is con-
trolled by the angle of the lap and the lateral resolution of the probe.
A variation of straight lapping is ball cratering [30] in which a shallow spherical
pit is ground into the surface and the spatially resolved probe is moved across the
crater and thus to greater depths. Craters are more rapidly produced than an angle
lap, but both methods have a drawback in that the surfaces still have to be ion etched
prior to analysis due to contamination from the mechanical grinding and the atmos-
phere. During ball cratering also phase constituents may be smeared out if too high
loads are applied during grinding.
For very thin oxide layers an alternative approach simply relies upon altering the
surface sensitivity by rotating the specimen such that the analyser receives electrons
from increasing angles 8 off normal. For these experiments a very clean sample is
needed. A problem which has become increasingly apparent is the determination of
sputter time, min
Fig. 12 Comparison o f A E S sputter profilesfor a Ta,O, layer on Tu substrate and an iron oxide
layer on a Si wafer. Oxide thickness in both cases about ZOO nm and nearly identical sputter
conditions.
the correct depth profile from the set of angle resolved measurements. There is no
unique solution from the data set and it is possible to obtain an incorrect interpreta-
tion of the results. The possible error may be reduced by increasing the number of
angles at which the results are taken.
By far the most problematic point to be considered with respect to the application
of electron spectroscopic methods, is the quantification of measured data. The best
way to perform quantification is to use in-house elemental sensitivity factors (being
characteristic for each instrument) and to use peak areas for the quantification. To
improve the accuracy of the results for those specimens, the elemental sensitivity
factors should be corrected by matrix factors [31] taking into account the differing
backscattering coefficients and electron inelastic mean free path lengths. The use of
in-house sensitivity factors on the other hand makes comparisons between different
investigations quite difficult, as no general control about the quality of those sensi-
tivity factors exists. This control could be established by well prepared round robins
on well defined reference samples. The experimental data on those samples should
be quantified by using the in-house sensitivity factors as well as handbook sensitiv-
ity factors. Because this has not been so far realised, it may be better to continue
using handbook sensitivity data for the quantification of AES and XPS data for pub-
lished results.
In order to find a compromise for all different types of AES instruments which
exist in practice, an energy resolution of 0.5% of the analyser and primary energies
of 3,5 or 10 keV should be chosen because handbook sensitivity data exist for these
experimental parameters [32].
Sample charging during analysis by electron spectroscopic methods is of impor-
tance for the application of those methods on high temperature corrosion layers. For
thin films a conduction path for electrons through the film into the conduction
substrate may be produced by increasing the excitation voltage to 10 or 20 keV. On
the other hand, higher energies of the incoming electrons may more easily lead to
the degradation of sensitive samples. Therefore, a compromise has to be made for
samples which tend to degrade under the electron primary beam. For samples ex-
posing flat surfaces a change in the angle of incidence of the electron beam with
respect to the sample surface may be successful. For analysis of small areas, charg-
ing can be reduced by placing a conducting surface (metal strip, deposited Au or
Ag) near the region to be analysed. For thick layers or bulk non-conducting samples,
it may be helpful to reduce the incident beam voltage and/or the beam current den-
sity for the primary electrons. A further method to be applied, especially successful
for XPS measurements, is the use of broad beam, low energy electron guns (so-called
’flood guns’).
The oxide scale adhesion strongly depends on the chemical and structural com-
position of the oxide/metal interface. An easy method to enable a surface analytical
examination of their interface is to remove the oxide layer within the preparation
chamber of the surface analytical system or directly within the chamber for analysis
and to analyse the ‘spalled’ surface. Removing the oxide layer by ion sputtering up
to the oxide/metal interface will not be successful for analysing the interface com-
position because of a loss in depth resolution when the interface is reached. The
depth resolution decreases with increasing depth into the removed layer. Removal
of the oxide layer leaving the oxide/metal interface as a 'free surface' may be achieved
by different methods, e.g. fracturing or bending of thin samples or by metal (Ni for
example) plating, resulting in stresses within the oxide layer and leading to spalling
of the oxide. The most simple method to induce oxide spalling however, is the bend-
ing method. Thin foils of the oxidised material are fixed on one end on a sample
holder. The free end of the foil is bent within the vacuum system by using a wobble
stick or a sample transfer fork. This method was applied to study the interface
oxide/metal of several FeCrAl alloys undoped and doped with Ti, Ce and Y [33].An
example is given in Fig. 13. The oxide scale was partly removed by bending the
sample within the AES system. The first three figures show SEM images of an oxide
free part of the sample (some oxide parts are left). The surface exhibits a rather high
surface roughness and additionally voids are detected. Within some voids precipi-
tates (carbides, nitrides or sulphides) are visible. Sulphur imaging (Fig. 13(d))clearly
demonstrates strong enrichment within the larger voids and at somewhat lower level
also within the micro voids in the rest of the surface.
3.6. Glow Discharge Optical Emission Spectroscopy (GDOES)

For GDOES a glow discharge is maintained between the sample (cathode) and an
electrode with an area of several mm2. The sample is sputtered by ions within the
glow discharge whereas ions and neutrals emitted from the sample are excited by
collisions with Argon ions or electrons thereby emitting element specific light. The
element specific wave length of the light is analysed by an optical spectrometer.
The GDOES method is mainly applied to depth profiling of thicker surface layers
(0.5-200 pm) of coatings on steels, like Zn coated, galvanised, phosphated and Ni
plated steels or near resistant hard coatings on steels. But also application of GDOES
on oxide layers is also increasing [34-391. GDOES applications of depth profiles on
thin oxide layers (< 0.05 pm) and their comparison with AES depth profiles was
demonstrated [40].
The layers to be analysed should be flat, conducting, well adherent to the substrate
and vacuum resistant (non-porous, without cracks). Which discharge mode (U=
const., i = const., P = const.) should be chosen for depth profiling of oxide/corrosion
scales seems difficult to answer. Whereas some investigators prefer the i = const.
mode, since it provides a positive ignition behaviour of the discharge, other opera-
tors use the U = const. mode because of a more reliable quantification of the depth
profiles. The choice of the optimal discharge parameter settings for a good depth
resolution in combination with satisfying detection limits is somewhat problematic
as depth resolution and detection sensitivity are opposite effects. Optimal discharge
conditions for a 8 mm GD-lamp at the U = const. mode and a discharge voltage
setting of 600-700 V If possible, both modes should be applied for the analysis to
have a comparison for the analysis results.
The suitability of the commercially implemented quantification procedures of the
different equipment strongly depends on the quality of the alloy layers which are
used as calibration samples. The intensity scaling for the light elements, like 0, N
Fig. 13 SEM- and AES-images of the interface oxidelmetal after removal of the oxide layer
within the A E S system (see text); (a-c) SEM images; ( d ) sulphur image corresponding to the
SEM image in Fig. 13(c).
and C should be performed with reference samples with a similar concentration of
the light elements within the discharge plasma as the sample system to be analysed.
A general recommendation for reference materials with respect to GDOES in-depth
profiles of oxide scales cannot be given. Pressed powder mixtures of oxides and
conducting materials like Cu or oxide coatings (sputtered layers) are being tried as
reference materials [41].
A problem for analysing porous corrosion scales by GDOES can arise by air leak-
age of the Grimm-type glow discharge tube at the cathode plate O-ring. If still leak-
age is observed for porous samples, leaks may be sealed by back coating of the sam-
ple with a dense metal layer or by using an evacuated capsule to cover the sample
back.
The standard experimental parameter set which should be registered for each
GDOES analysis independent of the actual sample is: voltage, current, pressure, totaI
light and the emission lines Ar I, Ar 11,O I, 0 11, N I, N 11, C I and C 11.
4. Acknowledgement
We would like to thank the following colleagues for their valuable contributions: J.
Angeli, H. Bishop, U. Breuer, A. Elschner, W. Fischer, H. Gnaser, M. Graham, H.
Hantsche, V. Hoffmann, H. Holzbrecher, A. Huntz, R. Hussey, Y.Ikeda, J. Jedlinski,
A. John, M. Kopnarski, R. Muller, H. Oechsner, S. Oswald, U. Rothaar, K. Schmidt, I?
Schaaf, H. Strehblow, M. Stroosnijder, S. Suzuki, M. Uhrmacher and K. Wittmaak.
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20. K. Koch, D. Sommer and D. Grunenberg, Mikrochim. Acta, 1990,11,101.
21. W. J. Quadakkers, A. Elschner, W. Speier and H. Nickel, Appl. Surf. Sci., 1991, 52,271.
22. A. Gil, J. Jedlinski, J. Slowik, G. Borchardt and S. Mrowec, Microscopy of Oxidation -2 (Eds
S. Newcomb and M. Bennett), The Institute of Materials, London, 1993, p.214.
23. S. Basu and J. Halloran, Oxid. Met., 1987,27,143.
24. H. Bishop, Microscopy ofoxidation - 2 (Eds S. Newcomb and M. Bennett), The Institute of
Materials, London, 1993, p. 14.
25. D. Clemens, K Bongartz, W. Speier, R. Hussey and W. J. Quadakkers, Fresenius J. Anal.
Chem., 1993,346,318.
26. Nucl. Inst. Method., 1992, B66, 1.
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28. H. Viefhaus, K. Hennesen, M. Lucas, E. M. Muller-Lorenz and HJ. Grabke, Surf. Interf.
Anal., 1994,21,665.
29. N. J. Taylor, J. S. Johannessen and W. E. Spicer, Appl. Phys. Lett., 1976,29(8),115.
30. V. Thompson, H. E. Hintermann and L. Chollet, Surf. Technol., 1979, 8,42.
31. P. M. Hall and J. M. Morabito, Surf. Sci., 1979,83,391.
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41. J. Angeli, Voest-Alpine Stahl, Linz, Austria; private communication.
List of Abbreviations
AE Acoustic Emission
AEM Analytical Transmission Electron Microscopy
AES Auger Electron Spectroscopy
ASTM American Society for Testing and Materials
CEN Comite Europeen Normalisation
CFR Contaminant Flux Rate
COST Cooperation Europeenne dans la Domaine de la Recherche

Scientifique et Technique
CTEM Conventional Transmission Electron Microscopy
EDM Electro Discharge Machining
EDS Energy Dispersive X-ray Spectroscopy
EELS Electron Energy Loss Spectroscopy
ELNES Energy Loss Near Edge Structure
EPMA Electron Probe Microanalysis
ECN Electrochemical Current Noise
EPN Electrochemical Potential Noise
ESEM Environmental Scanning Electron Microscope
FBC Fluidised Bed Combustor
GDOES Glow Discharge Optical Emission Spectroscopy
HREM High Resolution Electron Microscopy
HSAC Hemispherical Sector Analyser

xii List of Abbreviations
HVEM High Voltage Electron Microscopy
MOR Modulus of Rupture
NIST National Institute of Standards and Technology
PACVD Plasma Assisted Chemical Vapour Deposition
RBS Rutherford Back Scattering
RHED Reflection High Energy Electron Diffraction
SAM Scanning Auger Microscopy
SIMS Secondary Ion Mass Spectroscopy
SNMS Secondary Neutral Mass Spectroscopy
TEM Transmission Electron Microscopy
TLA Thin Layer Activation
VAMAS Versailles Agreement on Materials And Standards
XPS X-ray Photoelectron Spectroscopy
XRD X-Ray Diffraction

INDEX
Index Terms Links
A
Accelerated testing
objections to 79
Acoustic emission
in cyclic oxidation testing 107
as in situ technique 44
Adhesion
at Al2O3/NiAl interface 181
at IN939/TiON interface 166
at TiN/SiO2 interface 166
of scales
factors affecting 177 212
improved by Y and Zr 182
Alkali metal salts
in hot salt corrosion 86
Alumina
tubes, in furnaces 55
ASTM
committee C28 on ceramics 138
‘round robin’ on hot salt corrosion testing 86
Analytical transmission electron microscopy (AEM) 177
Auger electron spectroscopy (AES)
to characterise different chemical states 207
description of 203
for identification of corrosion products 28 39
quantification of measured data 212
sputter profiles 210
This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links
B
Back scattered electron image
in SEM 149
Balances
automatic, recording 53
Bending beam
in measuring scale stresses 46
Block on ring system
for wear studies 123
Bright field imaging
in CTEM 177 181
Buoyancy effects
in gas flow 60
for thermally induced stresses 106
C
Carburisation
gas atmospheres for 72
CEN
TC 184 on ceramics 139
Ceramics, advanced
advantages of 136
guidelines for test method for 143
oxidation/corrosion of 136
Japanese oxidation standard on 141
standards, activities in 137
standards, list of 138 140
Characterisation
of high temperature scales 158
surface analytical techniques for, summarised 159
Chromia scales
on Cr studied by surface microscopy 165

Index Terms Links
Ciné photography
in recording topographical changes 43
Coal gasifiers
COST 501 programme 71
Component inserts see Probes
Compositional studies
in situ 42
Constant load creep tests 117
Contact resistance
measurement in sliding wear tests 131
Contaminant flux rate
in gas turbines 87
Continuous measurements see also
Thermogravimetry
in oxidation studies 52
Conventional transmission electron
microscopy (CTEM) 177
Coordinate machines
to map profiles of probes 7
Corrosion see also Oxidation, Scales
rate, measurement of 23
with mechanical or thermal stresses see
Chapter 7 – see also Stresses
COST 50 87
COST 501 71
Cracking
of scales, studied in situ 44
Creep
curves
in constant load conditions 117
in constant strain conditions 118
in mechanical stress/corrosion tests 117
tests
in recommendations for testing 105

Index Terms Links
Creep (Cont.):
types of 113
Cyclic oxidation see also Stresses
in furnace tests 12
Cyclic thermogravimetry
D
Dark field imaging
in CTEM 177
Dean test
for hot salt corrosion 86
Depletion of scale forming elements
in corrosion rate evaluation 24
in guidelines for discontinuous measurements 34
Deposit induced corrosion see also Melts, Solids
in ethylene crackers 99
in evaporators 96
in fluidised bed combustors (FBC) 98
in superheaters 95
guidelines for testing 101
origin of 85
purpose of testing 99
Deposition rates
importance of, in hot salt testing 94
Depth sensing submicron indentation techniques
for mechanical properties of oxide scales 47
Discontinuous gravimetry 52
see also Chapter 3
Discontinuous measurements
definition of 12 29
furnace exposure procedures 12
in high temperature corrosion see Chapter 2
participants in round robin test on 35
questionnaire on 13

Index Terms Links
Discontinuous measurements (Cont.):

recommended guidelines for 29
test procedures in 13
testing methods for 12
Drying agents
vapour pressures over 82
E
Electrical resistance probes
in situ techniques 40
use of, as test methods 9
Electrochemical techniques
in situ techniques, using 40
as test methods 9
Electron energy loss spectroscopy (EELS)
in AEM 177
Electron probe microanalysis (EPMA)
guidelines for (discussed) 152
for identification of corrosion products 28 146 151
of TiN-SiO2 interface 166
Electrostatic fields
avoidance of, in furnace tubes 55
Ellipsometry
Energy and wavelength dispersive element
analysis in post-exposure analysis 8
Energy dispersive X-ray spectroscopy (EDS)
in AEM 178
Energy-loss-near-edge-structure(ELNES)
of EELS spectra 178
Environments in high temperature corrosion
characterisation of 3
gas analysis of 3
particulate flows in 3

Index Terms Links
Environments in high temperature corrosion (Cont.):

reference elements and compounds
for 3
surface deposits in 3
Environmental scanning electron microscope (ESEM)
use up to 1000°C 43
Erosion corrosion see also Wear
centrifugal acceleration rig for 126
in fluidised hed conditions 127
jet impingement rig 127
methods for accelerated particle flow in 126
nature of 125
nozzle ejector for 126
pipework loop for 126
presentation of data from tests on 132
rotor arm for 126
tests 126
whirling arm rig for 127
Ethylene crackers
corrosion in 99
European oxidation standard for ceramics see also CEN
development of 143
work towards 143
Evaporator corrosion in power station boilers 96
F
Fatigue tests
in high temperature mechanical tests 105 114
Finish
importance of material – in tests 6
Fluidised bed combustors (FBC)
corrosion in 98
erosion–corrosion test rig 129
Fractography
in surface microsurgery 160

Index Terms Links
Friction, coefficient of
measurement in sliding wear tests 131
Furnace exposure tests 12
evaluation of specimens from 22
furnace design for 17
for oxidation of ceramics 141
procedures in 13 14
specimen geometry and preparation for 20
specimen support hardware in 19
start up procedures in 15
for hot salt corrosion 86
thermogravimetry in 13
G
Gas analysis
in corrosion measurements 39
Gas atmospheres
for carburisation 72
for chloridation 75
definition and preparation of see Chapter 5
preparation of 80
reference 78
for sulphidation 70
thermodynamic and kinetic considerations 64
Gas chromatography see gas analysis
Gas consumption
measurement of, in in situ techniques 39
Gas turbine engines
COST 50 programmes on 87
hot salt corrosion in 86
Glow discharge optical emission spectroscopy (GDOES)
description of 213
Guidelines (for discontinuous measurements
of high temperature corrosion)
for assessment of corrosion damage 32

Index Terms Links
Guidelines (for discontinuous measurements

of high temperature corrosion) (Cont.):
definition of 29
for test apparatus 30
for test piece geometry 31
for test procedures 31
scope of 29
H
Heat transfer
importance of, in use of probes 4
High resolution electron microscopy (HREM) 177
interpretation of 179
High sensitivity measurements
on very oxidation resistant materials 58
High voltage electron microscopy (HVEM)
in study of topographical changes 43
Hot corrosion test methods
in furnace exposure procedures 12
Hot salt corrosion
definition 86
testing 86
round robin tests in 86
Hot stage environmental cells
in in situ measurements 41
I
In situ measurement techniques see Chapter 3
methods
definition of 37
difficulties with 37
future requirements 47
Inert gas atmospheres
in thermodynamic studies 58

Index Terms Links
Internal attack
of 20Cr/25Ni/Nb 171
Internal penetration
International Energy Agency
work on ceramics 139
Interference layer metallography
vs back scattered electron images 149
Ion milling
in TEM sample preparation 179
Isothermal oxidation
in furnace exposure test procedures 12
stress free testing 104
Isotopic labelling
as adjunct to SIMS 40
J
Japan Fine Ceramics Association 137
Japanese oxidation standard 141
K
Kinetics of high temperature corrosion
introduction to 62
in oxidation 64
L
Lapping
precision, for surface microsurgery 164
Laser Raman spectroscopy
in identification of corrosion products 28
in measuring scale stresses 46
in monitoring scale formation 39
Linear voltage differential transducer
for remote monitoring in thermogravimetry 52

Index Terms Links
M
Magnetic fields
avoidance of, in furnace tubes 55
Manometric methods see Gas Consumption
Mass change see also Thermogravimetry
Matrix effect
in SIMS depth profile measurements 193
Measurements
in plant 2
Mechanical properties see also Creep, Fatigue
evaluation of, in discontinuous testing 29
techniques for measurement of scale 44 47
tests
data to be measured 111
experimental procedures in 116
specimens for 116
types of 112
Melts
corrosion in presence of see Chapter 6
Mensuration see also Post-exposure metrology
limitations of 9
of specimens (probes) 6
Metallography
advantages of 147
coating preparation for 147
cross-section, preparation for 147
in high temperature studies 147
Microbalance see also Thermogravimetry, in situ techniques
replacement for spring balances 39
use of 39

Index Terms Links
Microstructural changes
techniques for following 43
Microsurgery procedures
for high temperature corrosion characterisation 158
principles in 159
Monitors
definition of 2
N
National Institute of Standards and Technology (NIST)
data base for ceramic properties 138
NiAl
oxidation of 182
Nomarski technique see Phase contrast
O
Optical methods
as in situ techniques 40 43
in microsurgery metallography 160
Oxide thickness
P
Phase contrast techniques
in microsurgery metallography 160
Pin-on-disc system for wear studies 123
Pin-on-flat system for wear studies 123
Plant measurements, guidelines for
see Chapter 1; see also Mensuration, probes
Plasma assisted chemical vapour deposition (PACVD)
in preparing TiN-SiO2 coating 166
Post-corrosion studies
vs in situ studies 38

Index Terms Links
Power station boilers

evaporator corrosion 96
superheater corrosion 95
Probes
air cooled, example of 5
criteria for use of 2
definition of 2
design of, cooled 4
uncooled 4
mensuration of 6
tube insert, with variable wall
thickness 6
Q
Questionnaire on in situ methods
results from 38
R
Reaction chambers (tubes)
in furnaces 55
Real time experimentation see in situ studies
Reference atmospheres for corrosion testing 78
Reflection high energy electron diffraction (RHED)
in monitoring scale development 39
Resonant frequency
Round robin tests
comparison of ASTM/VAMAS results 91
in hot salt corrosion testing
by ASTM 86
by VAMAS 87
results from 88
Rutherford back scattering (RBS)
for non-destructive depth profiling 201

Index Terms Links
S
Scale
adhesion see Adhesion
characteristics
by discontinuous measurements 27
by in situ methods 38
thickness from contact resistance 131
stresses measurement of 46
Scanning Auger microscopy (SAM)
use of back scattered electrons in 149
in monitoring topographical changes 43
for scale characterisation 27
Scanning tunnelling microscopy
in future high resolution microscopy 44
Scratch techniques
used in situ 41
Sea water
artificial, used in hot salt testing 87
Secondary ion mass spectroscopy (SIMS)
for identification of corrosion product 28 39
review of method 192
in surface microsurgery of chromia scale 168
Secondary neutral mass spectroscopy (SNMS) 196
compatibility with SIMS 197
laser- 196
plasma- 196
compared with laser SNMS and SIMS 199
review of techniques 196
Section loss
Selected area electron diffraction in CTEM 177
Silica tubes
in furnaces 55

Index Terms Links
Sliding wear
corrosion 132
tests at high temperatures 123
Solids
corrosion in presence of see Chapter 6
Spall collecting 107
Spallation
avoidance of, in cross-section preparation 148
in corrosion rate evaluation 25 44
induced by bending 213
Specimens, test see also Probes
in cyclic testing 110
geometry and surface preparation of 20 54
shape of 54
support hardware for 19
suspension 54 107
Spring balances
Strain rate
in mechanical testing, importance of 117
Stress free isothermal testing 104
Stresses see also Mechanical properties
and crack growth 105
and creep 105
and data to be measured 111
and fatigue 105
and interaction with corrosion 105
and thermal cycling (cyclic testing) 106
mechanical and thermal, origins of 104
types of tests with thermally induced- 106
Sulphates
alkali metal-, in hot salt corrosion 86
Sulphidation 70

Index Terms Links
Surface analysis techniques see also AEM,

AES, EPMA, EDS, EELS, ELNES,
ESEM,HREM, HVEM, RBS, SAM,
SIMS, SNMS, TEM, XPS
comparison of techniques in 190
in high temperature corrosion research 189
sample preparation for 190
T
Taper section
preparation for metallography 148
precision-, preparation for surface microsurgery 163
Temperature
achievement of range of, with tube insert 6
importance of, in testing 3
Test methods see also monitoring, probes
electrical resistance probes in 9
electrochemical techniques in 9
experimental design in 8
Thermal stresses with mechanical stresses
and corrosion see Chapter 7
Thermogravimetry see Chapter 4
see also Cyclic thermogravimetry
in furnace exposure test procedures 13
method of starting experiments in 56
Thermodynamics of gas mixtures 64
Thermoelements (thermocouples)
care with use of, calibration 55 111
Thin layer activation to monitor spallation 45 110
TiN-SiO2 coating
adhesion of 166
Topographical changes see Microstructural changes

Index Terms Links
Tracer methods
in surface analysis techniques 199
Transmission electron microscopy (TEM)
in analysis of high temperature corrosion 177
application of, in oxidation studies 180
in monitoring microstructural changes 43
sample preparation for 179
techniques in 177
U
Ultrasonic measurements
for probe thickness 7
V
VAMAS
ceramics work in 138
classification system in 138
hot salt corrosion testing in 87 139
Vibration technique
in measurement of scale mechanical
properties 47
Video recording
of topographical changes 43
W
Wear see also Erosion corrosion
corrosion and see Chapter 8
damage, measurement of
in erosion corrosion 131
in sliding wear corrosion 131
data, presentation of 132
definition of 121
erosive 121
specimen types for 123
synergistic effects of, with corrosion 121

Index Terms Links
Wear see also Erosion corrosion (Cont.):

test methods for 122
Weldments
importance of oxidation behaviour of 55
Whirling arm in erosion corrosion test 127
X
X-ray diffraction (XRD)
in determining scale stresses 46
in post exposure analysis 8
X-ray photo electron spectroscopy (XPS)
description of 203
quantification of measured data from 212
X-ray structure analysis
information on standards for 155
Z
Zirconia electrolyte
for maintaining and measuring pO2 39

Guidelines For Methods of Testing and Research in High Temperature Corrosion (1995)

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Guidelines For Methods of Testing and Research in High Temperature Corrosion (1995)

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European Federation of Corrosion

A Working Party Report on

Guidelines for Methods of

Published for the European Federation of Corrosion

THE INSTITUTE OF MATERIALS

01995 The Institute of Materials

All rights reserved

British Libray Cataloguing in Publication Data

Neither the EFC nor The Institute of Materials

Design and production by

Made and printed in Great Britain

Series Introduction ........................................................................................................... vii

List of Abbreviations ......................................................................................................... xi

1 Guidelines for Plant Measurements of High Temperature .............................. 1

2 Discontinuous Measurements of High Temperature Corrosion...................11

3 In Situ Measurement Techniques ....................................................................... 37

5 Definition and Preparation of Gas Atmospheres ............................................ 62

6 Corrosion in the Presence of Melts and Solids ................................................. 85

7 Simultaneous Corrosion and Mechanical or Thermal Stresses ...................104

8 Corrosion and Wear or Erosion ....................................................................... 121

9 Oxidation/Corrosion of Advanced Ceramics: A Review of the .................136

10 Metallography, Electron Microprobe and X-Ray Structure ......................... 147

12 The Application of Transmission Electron Microscopy in the .................... 177

13 The Application of Surface Analysis Techniques in High ........................... 189

lndex ................................................................................................................................. 218

D. B. MEADOWCROFT and J. E. OAKEY*

2. Selection of Exposure Conditions

2.2. Characterisationof the Environment

(b) Determination of particulate flows, compositions and size ranges, in order to

(c) Analysis of surface deposits after removal of the specimens. It is necessary

(d) Exposure of reference elements and compounds in order to determine the

3. Design of Probes and Component Inserts

3.2. Cooled Corrosion Specimens

Material finish is important in all corrosion experiments and is considered in many

(c) The use of co-ordinate machines to accurately map profiles of a specimen

(i) Vernier callipers or micrometers can be used to give an indication of wastage

6. Other Post-Exposure Analyses

It is essential that consideration is given to the design of the overall programme to

8. Other Methods of Predicting Metal Loss

8.1. Electrochemical Techniques

8.2. Electrical Resistance Probes

3. Atmosphere characterisation is very important in enabling sensible lifetime pre-

Discontinuous Measurements of High

High temperature oxidation/corrosion has been an important technological subject

2. Testing Methods for the Discontinuous Measurement of Oxidation

2.1. Scope of this Study

3. Furnace Exposure Test Procedures

Usage Proportion Temp. Range of Preferred Preferred

(A) Isothermal 34 400-1500 100-50 000 650-1000 2000,5000

(B)Cyclic Oxidation 10 250-1500 100-50 000 900-1150 2000,5000

( C ) GasPhase 32 250-1500 100-10,000 650-900 1000,5000

(D) Hot Salt Corrosion 24 500-1100 100-2000 600, 650, 500+

removal time adopted by the laboratories returning questionnaires, together with

Specimen Removed at Number of Citations Preferred Removal Times

Furnace Exposure Test Environment

(A) Isothermal Oxidation (i) Air

(C) Gas Phase Corrosion Oxidising/high PO, Reducing/low PO,

(i) O,+SO, (xi) H, t H,S

(D)Hot Corrosion (i) Na2S04

*Sodium vanadyl vanadate (Na.V.V.)

3.1. Furnace Design

Table 4. Test apparatus -furnace design"