Table Of ContentMICROSCOPY
OF OXIDATION
ORGANISING COMMITIEE
G. J. Tatlock (Chairman, University of Liverpool).
M. J. Bennett (AEA Industrial Technology, Harwell,
Co-editor, Conference Proceedings).
H. E. Evans (Nuclear Electric, Berkeley Nuclear Laboratories,
Berkeley).
H. M. Flower (Imperial College).
P. J. Goodhew (University of Liverpool).
1.A. Little (University of Cambridge).
G.W. Lorimer (Manchester Materials Science Centre,
Co-editor, Conference Proceedings).
S. B. Newcomb (University of Cambridge).
1.Upton (Conference Department, The Institute
of Metals).
MICROSCOPY
OF OXIDATION
Proceedings of the First International Conference
held at the University of Cambridge, 26-28 March, 1990
M J BENNETT AND G W LORIMER
EDITORS:
Sponsored and organised by the Materials Science Division
of The Institute of Metals with the co-sponsorship of
The Institute of Physics and The Royal Microscopical Society
THE INSTITUTE OF METALS
1991
Book Number 500
Published in 1991 by The Institute ofMetals
1Carlton House Terrace, London SW 1Y5DB
and
The Institute ofMetals
North American Publications Center
Old Post Road, Brookfield VT05036
USA
©1991 The Institute of Metals.
Allrights reserved.
British Library Cataloguing in Publication Data
Microscopy of oxidation.
1.Oxidation
I.Bennett. M. 1.(Michael John) 1933- II. Lorimer. G.W.
ITI.Institute ofMetals 1985-
541.393
ISBN 0-901462-90-X
American Library ofCongress Cataloging in Publication Data
Applied for
Compiled by Pic A Publishing Services from original typescripts
and illustrations supplied by the authors
Cover design: Jenni Liddle
Printed and bound in Great Britain
CONTENTS
PREFACE ix
SECTION ONE: Introduction 1
(1)Hightemperaturecorrosionofmetals 2
P Kolstad (UniversityofOslo,Norway)
(2)ThestudyofoxidescalesusingSIMS 10
M J Graham (NationalResearchCouncilofCanada,Ottawa,Canada)
(3)ApplicationsofLEEDandaugerelectronmicroscopyinthestudyofhightemperature 19
corrosionmechanisms
HJ Grabke and H Vie.fhaus (Max-PlanckInstitutfurEisenforschung,Dusseldorf,FRG)
SECTION TWO: Growthandfailureof ironoxidescales 35
(4) ASIMSinvestigationoftheoxidationofironinoxygen 36
M Montgomery, D GLees (UniversityofManchester/UMIST,UK)and PL Harrison (NationalPower,
Leatherhead,UK)
(5) Coatingsforrusty steel:useofanalyticaltechniquestoelucidatecorrosionbehaviour 42
NL Thomas (leI Chemicals &Polymers,Runcom,UK)
(6) Observationsonsilicatesinscaleonalow-alloysteel 49
JSmuts and HJDe Klerk (IscorLtd,Pretoria,RSA)
(7) Effectofmicrostructureonthehightemperatureoxidationbehaviouroflowalloyferriticsteel 58
R K Singh Raman, A SKhanna and JB Gnanamoorthy (IndiraGandhiCentreforAtomicResearch,
Kalpakkam,India)
(8) BoroninhibitedsteamoxidationofFe-CralloysstudiedusingEELS 64
PN Rowley and JA Little (UniversityofCambridge,UK),RBrydson (ImperialCollege,London,UK)
and SR JSaunders (NationalPhysicalLaboratory,Teddington,UK)
(9) Analyticalelectronmicroscopyof9wt%Cr- 1wt%Mosteels 70
I M Reaney (UniversityofEssex,UK)and GWLorimer (UniversityofManchester/UMIST,UK)
(10) Carburisation-oxidation interactionsinbreakawayscaling 77
SB Newcomb and WM Stobbs (UniversityofCambridge,UK)
(11) Healing layerformationinFe-Cr-Sialloys 84
SB Newcomb and WM Stobbs (UniversityofCambridge,UK)
vi CONTENTS
SECTION THREE:Growth and failure of chromia scales 91
(12) A TEM study of the oxide scale formed on chromium metal during high temperature oxidation 92
P Fox, D GLees and G WLorimer (University of Manchester/UMIST, UK)
(13) The oxidation of chromium 98
H M Flower and P Gould (Imperial College, London, UK) D P Moon and ATTuson
(UKAEA, Harwell, UK)
(14) Effects of water vapour on oxide growth on 304 stainless steel at 900°C 113
A SKhanna (IGCAR, Kalpakkam, India) and PKolstad (University of Oslo, Norway)
(15) The role of silicon in maintaining protective oxidation in 20%Cr austenitic stainless steel to 119
high temperatures
R CLqbb and HE Evans (National Power, Berkeley, UK)
(16) The oxidation behaviour of high-Cr cast irons in achloride-containing iron ore sintering environment 125
HJDe Klerk and] Smuts (Iscor Ltd, Pretoria, RSA)
(17) Changes in the sub-scale microstructure of arhenium-containing 'Y!'Ya'lloy as a function of its oxidation 135
and creep
SB Newcomb and WM Stobbs (University of Cambridge, UK)
SECTION FOUR:Growth and failure of alumina scales 143
(18) The nucleation sites of 'Y-AI203in thermal oxide films on aluminium 144
K Shimizu, A Gotoh and K Kobayashi (Keio University, Riyoshi, Japan), GE Thompson and G C lVood
(Corrosion and Protection Centre, UMIST, Manchester, UK)
(19) SIMS investigations of the transport phenomena in chromia and alumina scales on ODS alloys 149
WJ Quadakkers, WSpeier, II Holzbrecher and If Nickell (Kernforschungsanlage Julich, Julien, FRG)
(20) Alumina scale growth at zirconia/MCrAIY interface: A microstructural study 161
L Lelait, SA Alperine and RMevrel (ONERA, Chatillon, France)
(21) Morphology of oxide scales on Ni3Alexposed to high temperature air 169
JHDeVan (Oak Ridge National Laboratory, TX, USA),] A Desport and H EBishop (Harwell Laboratory,
Didcot, UK)
(22) Structural studies of internal oxides in nickel aluminium alloys 176
GJ Tatlock, R WDevenish (University of Liverpool, UK) and] SPunni (UKAEA, Dounreay, UK)
(23) Metallographic characterization of the transition from internal to external oxidation of Nb-Ti-AI alloys 183
R A Perkins (Lockheed Missiles & Space Co., Palo Alto, CA, USA) and GII Meier
(University ofPittsburgh, PA, USA)
(24) In situ TEM investigation of the oxidation of titanium alumide alloys 193
G Welsch (Case Western Reserve University, Cleveland, OR, USA), SLFriedman (Cornell University,
New York, NY, USA)and AIKahveci (Alcoa Research Center, PA, llSA)
(25) Protective Al203 scale formation on NbAl3 -base alloys 206
JDoychak and M GHebsur (NASA Lewis Research Center Group, Brookpark, OR, USA)
(26) Microscopy of the corrosion of high-temperature coatings 225
GH Meier and F SPettit (University of Pittsburgh, PA, USA)
vii
CONTENl'S
(27) Astudyof theeffectofmagnesiumadditionsontheoxidegrowthmorphologiesonliquid 238
aluminiumalloys
SA /mpey, D 1 Stephenson and 1RNicholls (CranfieldInstituteofTechnology,Bedford,UK)
(28) Theeffect ofSiCparticlesontheoxidationbehaviourofcompositeswithAI,AI-Mg 245
andAl-Limatrices
P Prangnell, SBNewcomb and WM Stobbs (UniversityofCambridge,UK)
(29) TheuseofimagingSIMSinastudyof anoxidizedCoNiCrAIYcoating 252
D GLees and D Johnson (UniversityofManchester/UMIST,UK)
SECTION FIVE: Reactiveelementeffects 257
(30) TheeffectofsulfurcontentonA~03 scaleadhesion 258
1L Smialek (NASALewisResearchCenter,Cleveland,OH,USA)
(31) Effects ofreactive elementsonoxidescaledeformationandcrackingbasedon 271
submicronindentation testing
P F Tortorelli, 1R Keiser and W COliver (OakRidgeNationalLaboratory,OakRidge,TN,USA)
and KR Willson (GenevaCollege,BeaverFalls,PA,USA)
(32) Theeffect ofreactive elementsontheoxidationbehaviourofFe-Cr-AIalloys 278
1Jedlinski and GBorchardt (TechnischeUniversitutClausthal,ClausthalZellerfeld, FRG)
and SMrowec (InstituteofMaterialsScience,Krakow,Poland)
SECTION SIX: GrowthandfractureofscalesonTi,Zr,Si,NiandC-basedmaterials 285
(33) Hotsaltstresscorrosioncrackingintitaniumalloys 286
K Seebaruth, SB Newcomb and WM Stobbs (UniversityofCambridge,UK)
(34) Themicrostructuralandcompositional analysisofoxidesonZr-2.5wt%Nbinrelationtotheirrole 292
aspermeation barriers todeuterium uptakeinreactorapplications
B D Warr, EM Rasile, A M Brennenstuhl and MB Elmoselhi(Ontario HydroResearchDivision,Toronto,
Ontario,Canada)N SMcIntyre (UniversityofWesternOntario,London,Ontario,Canada)and SB Newcomb
and WM Stobbs (University ofCambridge,UK)
(35) Defectsandinterfacial structureinGe/Si layers 299
D Fathy and M Sayah (ABOI,Tehran,Iran)
(36) Oxidationandliquid-aluminiumdegradationofengineeringceramics 305
M WJohnston and JA Little (UniversityofCambridge,UK)
(37) SIMSstudiesofthetransportofoxygentraceringrowingnickeloxidescalesformedat600-900°C 311
A WHarris,A Atkinson, D P Moon and SMountfort (MaterialsDevelopmentDivision,
HarwellLaboratory,UK)
(38) Effectofdispersedoxides uponoxidationofnickel 318
N Zhang, R1Bishop and R E Smallman (UniversityofBirmingham,UK)
(39) Competitive interfacereactionsintheoxidationofNi-Cralloys 329
SB Newcomb (UniversityofCambridge,UK)and L WHobbs (MassachusettsInstituteofTechnology,
Cambridge,MA,USA)
(40) Oxidationinatemperaturegradient 336
SMalik and A VChadwick (UniversityofKent,Canterbury,UK)
viii
CONTENTS
(41) Oxidation behaviour and protection of carbon-carbon composites 342
FJBuchanan and JA Little (University of Cambridge, UK)
(42) Isochronal oxidation experiments on boride and carbide powders 347
M Stewart (National Physical Laboratory, Teddington, UK)
SECTION SEVEN: Newer techniques 355
(43) The internal attack of 20%CrI25%Ni/Nb stainless steel, revealed by selective etching 356
JA Desport and M JBennett (Materials Division Development, Didcot, UK)
(44) Observation of oxide/metal interface using scanner Auger microscopy with an in situ scratch technique 362
P YHou (Lawrence Berkeley Laboratory, Berkeley, CA, USA) and J Stringer (Electric Power Research
Institute, Palo Alto, CA, USA
(45) Acomparison of in situ and ex situ oxidation processes for ZnTe and CdTe surfaces as studied by 369
high-resolution electron microscopy
PLu and D J Smith (Arizona State University, Tempe, AZ, USA)
(46) The use of microlithographic markers in electron microscopy of high-temperature oxidation processes 374
CKKim. S-K Fan and L WHobbs (Massachusetts Institute of Technology, Cambridge, MA, USA)
(47) Sequential scanning electron microscopy study of oxide scale failure and regrowth 381
A TTuson and MJBennett (Materials Development Division, Harwell, UK)
(48) Nucleation and growth of surface oxides and sulphides formed on Fe-Cr-Ni alloys during exposure to 387
H2-CO-~O-~S atmospheres
J F Norton, SCanetoli and K Schuster (CEC Institute of Advanced Materials, Petten, The Netherlands)
(49) The uses of the Fresnel method in the study of oxidation 395
SB Newcomb. F MRoss. D Ozkaya and WM Stobbs (University of Cambridge, UK)
(50) Oxidation of a ferritic stainless steel containing 17%Cr studied by Raman laser spectroscopy 402
and nuclear reaction analysis
H Chaudanson, FArmanet, GBeranger, J Godelewski (CNRS-Universite de Technologie de Compicgne,
Compiegne, France), A Hugot-Legoff, SJoiret andM Lambertin (CNRS-Universite P et M Curie,
Paris, France)
(51) Real time studies of uranium dioxide oxidation 411
JB Price, MJ Bennett and FL Cullen (Materials Development Division, Harwell Laboratory, UK),
J FNorton and SR Canetoli (JRC Petten Establishment, Petten, The Netherlands)
SECTION EIGHT: The future 419
(52) The future of the microscopy of oxidation 420
J E Castle (University of Surrey, Guildford, UK)
Index 426
PREFACE
The First International Conference on the Microscopy of Oxidation was held at Selwyn College, Cambridge, from the
26-28 March, 1990. The conference was sponsored andorganised by theMaterials Science Division ofThe Institute of
Metals with the co-sponsorship ofThe Institute ofPhysics and The Royal Microscopical Society.
The direct observation and analysis of oxides, together with the identification of factors which influence oxidation
reactions, are essential steps towards afundamental understanding of the oxidation of alloys under service conditions.
Afully quantitative description oftheprocesses involved isstill some way off, but major improvements in microscopy
and analytical techniques have brought thisgoal one stage nearer. Hence itappeared timely tohold aninternational con-
ference with the central theme of theapplication of microscopy inoxidation studies. The excellent response totheCall
for Papers, the high quality of thepapers and posters presented and thelively discussions which followed both theOral
and Poster sessions ensured that the meeting was asuccess.
It ishoped to hold the Second International Conference on theMicroscopy of Oxidation in the Spring of 1993.
G.W.Lorimer
MJ.Bennett
