HIGH

TEMPERATURE OF CERAMICS

CORROSION

J.R. Blachere F.S. Pettit

Department of Materials Science and Engineering University of Pittsburgh Pittsburgh. Pennsylvania

NOYES DATA CORPORATION Park Ridge, New Jersey,U.S.A.

Copyright @ 1989 by Noyes Data Corporation Library of Congress Catalog Card Number: 88-38242 ISBN: O-8155-1188-4 Printed in the United States Published in the United States of America Noyes Data Corporation Mill Road, Park Ridge, New Jersey 07656 10987654321 by

Library

of Congress Cataloging-in-Publication

Data

Blachere, J.R. High temperature corrosion of ceramics / by J.R. Blachere and F.S. Pettit. cm. P. Bibliography: p. Includes index. ISBN O-8155-1188-4 : 1. Ceramic materials--Corrosion. I. Pettit, F.S. (Frederick S.), 1930. II. Title. TA455C43B57 1989 620.1404217--dc19 88-38242 CIP

Other No yes Publications

CERAMIC

RAW MATERIALS
Edited by D.J. De Renzo

The broad-based ceramics Industry encompasses all types of glass; refractones; abrasives; whitewares. such as porcelain and pottery, structural clay materials; etc. Increasing use of advanced ceramic materials in the automotive and aerospace Industries, as well as in such diverse areas as electronics and medical devices, IS expected to push the demand for raw materials far beyond that associated with the traditional ceramics industry. Prepared directly from manufacturers data sheets and tables at no cost to, nor influence from, the contributing companies, this book Parr I Alumina Alumina Chrome Alumina Zirconia Aluminum Nitride Aluminum Titanate Andalusite Antimony Compounds Ball Clays Barium Compounds Bauxite Beryllium Oxide Bismuth Compounds Bone Ash Borates Borax Boric Acid Boron Boron Carbide Boron Nitride Calcium Compounds Carbon Celestite Chlorite Mineral Chrome Ore Chromium Oxide Clays (Miscellaneous) Cobalt Compounds -. . Cofemamte Copper 8 Copper Oxide Cordierite Corundum Diatomaceous Earlh Dolomite Feldspar Ferrites Fireclay Flint Clay Fluorspar Fluxes Frits Garnet Graphite Iron Oxide Kaolin Kyanite Lanthanide Compounds Lead Compounds Lime Limestone Lithium Compounds Magnesia Magnesite Manganese Compounds Mica Mullite Nepheline Syenite Nickel Compounds Ochre Periclase Petalite Phosphates

provides chemical and physlcal property data for more than 1000 products supplied by 181 ceramic raw material suppliers in the U.S. and Canada. Part I is an alphabetical listing of 99 raw material categories. Raw material suppliers are then included alphabetically under each category, along with their product information. The categories in Part II include additives; semiprocessed materials, some of which are available as unfinished shapes or substrates; and materials intended for specific end uses. Raw materials categories are: Potassium Compounds Pyrophyllite Duartz Rutile Sand Silica Silicon Silicon Carbide Silicon Nitride Sillimanite Slags Soapstone Soda Ash Sodium Silicate Sodium Sulfate Spars Spine1 Spodumene Stannates Stannic Oxide Strontium Carbonate Talc Titanates Titanium Boride Titanium Carbide Titanium Dioxide Titanium Nitride Ulexite Vermiculite Whiting Wollastonite Yttrium Oxide Zinc Oxide Zircon Zirconates Zirconia Zirconium Boride Zirconium Nitride

Part II Binders Ceramic Additives Ceramic Adhesives, Potting Materials, and Putty Ceramic Coatings Ceramic Colors Ceramic Fibers and Whiskers Ceramic Materials Ceramic Precursors Dielectric Compositions Dispersing Agents Electronic Ceramics Reagents Glazes Glaze Stains Pie20 Compositions Refractory Materials Sealing and Solder Glasses

ISBN O-8155-1143-4

(1987)

8% x 11

900

pages

Foreword

This

book

describes in this In addition

high to

temperature study pure were single

corrosion silica, crystals

of ceramics. silicon or CVD

The nitride

materials typical The

inengiby also

vestigated carbide. neering conditions Na2S04 performed. tures, changes major electron silicon

particular the of hot Some hot various

alumina,

and silicon corrosion were

materials,

materials were deposits. The

purities

were

included gaseous

in the study. corrosion and

corrosion gaseous corrosion of pure of A the

in which corrosion was oxygen surfaces and the of for studied

was enhanced at lower

and oxidation at IOOOC observed x-ray of

experiments

temperaelectron were nitride the and in the

in the presence in morphology This of tools

and oxygen were related the

containing

SO2 and SOs. The

in the scanning microanalysis oxide on silicon thickness

microscope.

instrument

research.

method

measurement

microprobe carbide.

was developed

experiments

In the use of materials parent and this that, in most While then, resistance. study,

at elevated instances, may can

temperatures corrosion certain investigate

in harsh resistant

environments, to provide than The metallic

it is apcorrosion alloys of and purpose

ceramics be more with react

are the best choice environments.

ceramics ceramics

polymers,

was to systematically generally applicable materials to

the corrosion

of ceramics

to develop

a theory

to all ceramics. for use in a variety a variety of corrosive of cercerIn to

A great number environments. amics amic order materials to used in general,

of ceramic In order exposed number study in this

are available a theory investigate of different

to develop to

applicable

to the corrosion of representative

it was necessary

a number of experiments were

corrosive

environments. resistance environment to

keep the

at a reasonable by being the likelihood immune of their

number, to the used being

the ceramic

materials corrosion or by corrosion practice

selected

on the basis by which environments

was developed, developing were and their passivity. selected severity.

in particular, Furthermore, upon the based

produce in

encountered

vi

Foreword

The

information by J.R.

in the book Blachere of Energy,

is from December

High 1987.

Temperature

Corrosion

of Ceramics, for the

prepared

and F.S. Pettit

of the University

of Pittsburgh

U.S. Department The table

of contents

is organized

in such a way

as to serve as a subject in the book.

index

and provides easy access to the information

contained

Advanced composition and production methods developed by Noyes Data Corporation are employed to bring this durably bound book to you in a minimum of time. Special techniques are used to close the gap between manuscript and completed book. In order to keep the price of the book to a reasonable level, it has been partially reproduced by photo-offset directly from the original report and the cost saving passed on to the reader. Due to this method of publishing, certain portions of the book may be less legible than desired.

NOTICE
The materials the in this book United States were prepared Government as an account of Energy. nor any of employees, or imfor nor the Depart-

of work Neither ment their plied, the mation, rights. Final tion

sponsored

by the U.S. Department

of Energy, contractors,

nor any of their employees, sub-contractors, makes or their any warranty, or usefulness not infringe

nor the Publisher, accuracy,

express

or assumes any legal liability completeness, product its use would apparatus,

or responsibility

of any inforor rep-

or process disclosed

resents that

privately-owned

determination or procedure reader when

of the for

suitability

of any

informauser, of

use contemplated that caution

by any

and the manner the user. The be exercised atures, before

of that

use, is the sole responsibility with ceramics should

is warned advice

must always

dealing

at high temper-

and expert

be sought at all times

implementation.

Contents and Subject Index

INTRODUCTION.........................................l EXPERIMENTAL

. . . . . . . . .. . . . . Special Techniques . .. . .. . . . . . . . Measurement of Oxide Thickness . Measurement of Contact Angles. . . . .

PROCEDURES. Experimental Conditions Cross Sections and Related Techniques

. . . .

. . . . .

. . . . .

. . . .

. . . . .

.......... .......... .......... .......... .......... .......... ...... ...... ...... ...... ...... ......

.6 .6 .7 .7 .9 .9

GASEOUS

CORROSION

Introduction. Silica.

....................... .............................
of Silica and Alumina.

. . . . 11
. . . . 11 ... 11 . . . 11

Gaseous Corrosion

..........

................................ .............................. Alumina

Gaseous Corrosion HOT HOT HOT CORROSION CORROSION CORROSION of Silicon OF SILICA. OF ALUMINA. OF SILICON Nitride and Silicon Carbide

. . 13

. . . . 14 . .16 .21

. . . . . .

. . . . . .. . . . . . . . . . .
AND

. .. . . . . .

. . . .

. . . . .. . . . . . . .
NITRIDE.

CARBIDE

SILICON

. . .26

REFERENCES..........................................30 APPENDIX IN SULFUR A-GASEOUS OXIDE CORROSION F.S. Pettit OF SILICA AND ALUMINA

ENVIRONMENTS

. . . . . . . . . . . . . . . . . . . . . . . . 31

H. R. Kim, J. R. Blachere, Introduction.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Gaseous Corrosion of Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . 33

vii

viii

Contents

and Subject

Index

Experimental Materials

Procedure. .............. ....................... Experiments. .................... Results and Discussion ................ Silica. ......................... Alumina ....................... General Results. ................ Thermodynamics Single Crystal Polycrystalline of Sulfate Formation

..................
Aluminas.

..........

.................. Conclusions ....................... References ........................

General Discussion. APPENDIX B-HOT CORROSION OF SILICA.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. .35

. . . . . .

. .35 . .35
.37

. .37
. .39 . .39 . .41

. .43 . .43 : :53 52 . .55

. .5B

.................

M. G. Lawson, Introduction.

H. R. Kim,

F.S. Pettit,

J. R. Blachere

.................................... ................................... Experimental Procedure ............................. Materials ..................................... Gaseous Corrosion. .............................. ................................. Hot Corrosion. Results and Discussion .............................. Gaseous Corrosion. .............................. Wetting by Sulfates .............................. ................................. Hot Corrosion. ......................... Kinetics of Crystallization. General Discussion. .............................. .................. Discussion of Crystallization Kinetics ..................... Hot Corrosion of Silica Formers. Conclusions ..................................... ..................................... References.
Hot Corrosion. APPENDIX M.G. C-HOT CORROSION OF ALUMINA .

. 58 : :60 59 : :60 60 . .60

63

. . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.63 .64 .66 176 72 .82 .85 .86 .87

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.89 .89 .95 .95 .97 .97 .97

102 107 107 109 112 113 115

Lawson,

F.S. Pettit, Procedure

J.R. Blachere

Introduction.

. . . .. . . . . . Materials . . . . . . . . . . . . . . Hot Corrosion Experiments. . Results and Discussion . . . . . . . Wetting . . . . . . .. . . . Hot Corrosion of Al*Os .. . . Results, Acidic Conditions . . .
Experimental Single High Low Results, Medium Crystal Purity Purity Purity Alumina. Polycrystalline Polycrystalline Polycrystalline

. . . . . . . .

. . . . . . .

. . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alumina.

Alumina. Alumina

. . . . . . . .

. . . . . .

. . . .

. . . . . . . . . . .

. .

Basic Conditions

. . . . . . .

. . . . ..

Contents

and Subject

Index

ix

. .. . . . . Medium Purity Polycrystalline Alumina. . Low Purity Polycrystalline Alumina .. . . Discussion of Results . . . . . . . . . . . . . . . . References. . . . . . . .. . . .. . . . . . . .. .
Single Crystal High Purity Polycrystalline Alumina APPENDIX SILICON D-HOT CARBIDE CORROSION OF SILICON NITRIDE AND

. . . . . . . . .. . . . .

. . . . . . . .

116 116 118 119 122 136

...............................
F.S. Pettit

. . . . . . .

. . . 137 . . . . 137 . . 137 . . 138 . . 152 . 157 . . . . 161

J. R. Blachere, D. F. Klimovich,
Introduction. Experimental Acidic Acidic Procedure

................................ ......................... Results and Discussion ..........................

Hot Corrosion Hot Corrosion of Silicon of Silicon Nitride. of Silicon Carbide

............
Nitride.

Discussion Model

of the Hot Corrosion for the Oxidation Under Acidic Model

.....

............
of Silicon

and Hot Corrosion Conditions

Carbide Proposed Defect Oxidation

..............
of Silica

..........................
and Stoichiometry Carbide

Structure

.......

.................. Acidic Hot Corrosion. ...................... References. .................................

of Silicon APPENDIX E-PUBLICATIONS

. . . 168 . . . . . 169 . . . . 170 . . . . 172 . . . 178 . . . . 182

184 185

References.

............................. .......................................

Introduction
In the use of materials is apparent corrosion metallic at elevated temperatures in harsh environments, to provide than it

that in most instances resistance.

ceramics

are the best choice

While ceramics ceramics

may be more corrosion can react with certain investigate

resistant

alloys and polymers, of this program

environments. the corrosion of

The purpose ceramics

was to systematically generally materials

and to develop

a theory

applicable

to all ceramics. for use in a variety of

A great number of ceramic corrosive of ceramics ceramic environments. in general,

are available

In order to develop it is necessary to a number

a theory applicable a variety corrosive

to the corrosion of representative environments. the ceramic to or In

to investigate of different

materials

exposed

order to keep the number of experiments materials corrosion used in this study were selected was developed, passivity. in particular, Furthermore,

at a reasonable

number,

on the basis by which resistance

by being immune to the environment the environments used to produce

by developing were selected

corrosion

based upon the likelihood

of their being encountered

in practice

and their severity. A material is in equilibrium practice achieved material elevated is considered to be immune to a particular Total or complete required environment immunity when it

with that environment.

is rare in to be

but in some cases the amount of reaction is very small, and consequently are very small. temperatures, For example,

for equilibrium

the changes

in the properties

of the

when Al303 is heated

in oxygen at

the oxygen activity

in the Al.303 may not be the same as into or removed from the Al303 Upon obtaining long

that in the gas, and oxygen will be incorporated depending equilibrium upon the oxygen activities between

in the Al303 and in the gas.

the Al303 and the gas, which may require

extremely

High Temperature

Corrosion

of Ceramics

times depending upon the temperature, the Al303 does not exhibit any significant changes in mechanical properties. The concentrations of point defects in the

Al303 however will change and there could be significant changes in properties such as electrical and ionic conductivities. Nevertheless, in terms of a corrosion

reaction the Al303 may be considered to be immune to this gaseous environment. Alumina and silica are two ceramic materials which can be considered to be immune to many environments which are extremely corrosive to metallic systems, and therefore these two materials were studied in the present investigation. The

purity and structure of these ceramics can also affect their behavior in different corrosive environments and therefore these two parameters were also examined in the present investigation. Four types of crystalline Al303 were studied of

varying purity as defined in Table I. Only one type of silica was studied. As described in Table I it was of relatively high purity and was vitreous. Passivity to corrosive environments is achieved by the formation of a reaction product barrier through which the reactants involved in the corrosion process must diffuse. The development of passivity is the principal means by

which metallic alloys achieve resistance to corrosive environments, but passivity is also an important mechanism in certain ceramic materials, depending upon the ceramic and upon the environment causing corrosion. For example, Si3N4 and

Sic react with most environments encountered at elevated temperatures and resistance to corrosion is achieved via the formation of a passive reaction product barrier. Furthermore, Al303 can react with gaseous environments containing sufficient SO3 to form sulfates and again the properties of the sulfate reaction product play a significant role in the corrosion properties.
Si3N4

In the present studies

and SIC specimens with purities as defined in Table I were therefore used.

TABLE I - MATERIALS UNDER STUDY

Designation S.C. 998 995

Material Sapphire
poly

Purity (Wt%) -99.99 99.8(0.1MgO, O.llSiO2)

Supplier Saphikon Lucalox (G.E.) AlSi Mag 772 (3M) or ADS 995 (Coors) S-697 (Saxonburg) Corning Deposits Al, 02) Airesearch W.J. Choyke W. J. Choyke 7940 & Composites

A120; (a)

poly A1203 (a)

99.6 - 99.5(0.17 M@ 0.17 Si02) 97.4 (0.75 MgO, 1.6SiO2 0.1 Na20) 99.99 99.99 93(6Y203Fe, 99.99
99.98

975 Silica SIN CVD SiN H.P. Sic SC. Sic CVD Sic H.P.

poly A1203 (a) fused silica CVD*Si3N4 H.P.** Si 3N4 s.c.*** (a6H S.C.)

CVE (Sic) H.P. (aSiC)

94(3Al203,

2.5W, Fe, 02)

Norton

NC-203

*
**

Chemical

Vapor Deposition

*** +

Single Crystal Polycrystalline Alumina

Hot Pressed

High Temperature

Corrosion

of Ceramics

When ceramic materials are used in practical applications, a variety of corrosive environments can be encountered. Most of these environments will

contain oxygen but other reactants such as sulfur, nitrogen, carbon and chlorine can also be present. Moreover, deposits such as metallic sulfates, carbonates or

chlorides may also accumulate upon exposed surfaces and substantially affect the corrosion processes. In the case of studies concerned with the corrosion of

metallic alloys it has been useful to examine corrosion reactions in environments of increasing severity extending from gaseous environments containing oxygen, to mixed gases containing one or more reactants in addition to oxygen, and finally considering the effects of deposits such as Na3S04, Na3C03 or NaCl. The environments used in the present studied are identified in Table II. These environments consisted of gases containing oxygen, and other reactants such as sulfur, carbon and hydrogen at temperatures of 700, 1000 and 14OOOC. The effects of deposits were studies by using Na3S04 deposits in O3-SO3-SO3 gas mixtures at temperatures of 700 and 1000C. These conditions were selected because they are frequently present in many environments encountered in practice. Furthermore, as established from studies using metallic alloys, the

principles established from studies using these selections should be generally applicable to other corrosive systems. In the following sections of this report the experimental procedures will be described and then a summary of the results will be presented and discussed. Some of these results have been presented in previous reports for this program.(l) Other results are included in student theses and are also presented Consequently, some of

in drafts of papers about to be submitted for publication.

the results will not be repeated in this report but will be referred to by references or by draft papers included in appendices in the present report.

introduction

Results obtained from studies using gaseous environments will be discussed first and then results obtained from studies using deposits on silica, alumina, Sic and Si3N4 will be presented in sequence.

Experimental
Experimental Conditions

Procedures

The materials that were studied in this program and the environments that were used to produce gaseous corrosion and hot corrosion attack have been briefly discussed previously in this report (Tables I and II). The ceramics that were studied (Table I) consisted of Al3O3, SiO3, Sic and Si3N4. A range of purities were examined in the case of Al3O3, Sic and Si3N4. Single crystals of SIC and Al303 were also studied and compared to polycrystalline specimens. The gas compositions that were used are presented in Table II. Gas mixtures consisting of O3-SO3-SO3 were used in both gaseous corrosion studies and the hot corrosion studies. Hot corrosion experiments were also performed in pure oxygen. The gaseous corrosion studies were performed at temperatures of 700, 1000 and 1400C whereas the hot corrosion investigations used temperatures of 700 and 1000C. When O3-SO3-SO3 mixtures were used at 700C, this mixture

was passed over a platinum catalyst to ensure that equilibrium was achieved. The catalyst was not required to achieve equilibrium at 1OOOOC.The flow of the gas was 1 cm3/s. The experimental procedures have been discussed in detail in previous reports and are also discussed in Appendices A, 0, C and D. The procedure usually consisted of exposing specimens in a horizontal tube furnace at a fixed temperature to a flowing gas stream of fixed composition. In the case of the hot

corrosion studies the specimens were coated with deposits of Na3S04 for

Experimental Procedures

investigations at 1000C, or a NaSS04-CoSO4 equimolar solution for studies performed at 700C. These deposits were applied on specimens by spraying warm specimens with an aqueous solution saturated with NaSS04 or the sulfate mixture. Most specimens were diamond polished and they were ail cleaned before the experiments. The characterization techniques consisted of morphological studies in the

light microscope and particularly the Scanning Electron Microscope (SEM) with microanalysis of salient features by EDS (Energy Dispersive X-ray Spectroscopy) and WDS (Wavelength Dispersive X-ray Spectroscopy used particularly for light elements). These techniques were supplemented by X-ray diffraction, weight

change measurements and in some cases surface analysis techniques (ESCA). A large number of other techniques were used in special cases they are SIMS, ISS, FTIR, Laser beam ellipsometry. Furthermore, since after the corrosion tests some deposited salt often remained on the sample, the Nag.504 was washed off to reveal the sample surface. The samples were characterized before and after this washing.

Experience has shown that the examination of the sample before washing is extremely fruitful, and the observed morphologies have taken many forms. The washwater was analyzed as described in a previous report (l); this analysis is now a routine semi-quantitative method which allows the identification of the

elements dissolved in the salt and the stoichiometry of the salt.

Special techniques Measurement of oxide thickness A method using WDS measurements in the electron microprobe (EPMA) was adapted from that described by Yakovitz and Newbury to estimate the The

thickness of coatings from the intensities of emitted characteristic X-rays.

High Temperature

Corrosion

of Ceramics

intensity of the oxygen Ka line is used in the present research to measure the thickness of oxide layers generated on non-oxide materials. This intensity is measured under constant conditions (say 1OkVaccelerating voltage and 2 x lo8 A beam current) for a scale and a bulk standard of pure fused SiO2. Both samples are coated with 200A of carbon. The ratio k of their intensities corrected for background is correlated to the thickness of the oxide layer. The calibration curve for the relationship between the k ratio and the oxide thickness was calculated with a computer program written for this research following the semiempirical approach of Yakovitz and Newbury(2) to generate the Q (pz) curve which is the intensity of X-ray generated at a weighted PZ depth into the sample. This calculation includes many corrections and correlations used to predict the characteristic X-ray intensity. It must be understood that the data available for these corrections (such as absorption) for light elements is relatively poor and that this calibration can only be approximate. based on light element are usually not used quantitatively. Measurements

However the method

developed in this research gives good reproducibility ? 2% for thickness measurements on silica layers up to about 0.8pm - lum. It was published recently(3) and more details will be found in Appendix E which contains a copy of the article on this measurement. It must be emphasized that since the characteristic X-ray intensity for oxygen is used to calculate the oxide This

thickness, a stoichiometric silica (SiO2) was assumed in the calculations.

may lead to significant error if the composition of the scale deviates markedly from that assumed in the calculations. However the method is quite

reproducible and has a high spatial resolution. The direct measurement of scale thicknesses on cross sections in the SEM is probably not better than + 10% in accuracy considering magnification

Experimental Procedures

calibration and other sources of error under the best conditions.

It is good down

to about lum and depends greatly on the thickness of the layer (constancy and magnitude). In some cases the scales are difficult to separate from the substrates in cross sections in the SEM.

Measurement of contact angles The contact angles of the deposits have been measured in the SEM at room temperature using a method previously described by Murr(4). The wetting angle is particularly important since deposits often break into droplets decreasing the area of interaction between the sample and the melt. After coating with carbon (about ZOOA)the samples are placed in a tilted position in the SEM which allows the location of the drop under the electron beam and then they are tilted further to a vertical position to record the profile of the drop. The edges of the drops are enlarged for the measurement. A number of drops are measured under those conditions on the same sample. Experience with the measurements show that their reproducibility is about f: 2O. Since this reproducibility is very good, it has been possible to establish when two wetting behaviors occurred simultaneously on the same sample.

Cross sections and related techniques The study of cross sections is necessary for a number of measurements. However the samples are often damaged (silica and silica formers) during exposures and processing. Also, cross sections are often desired with salt on the sample, so

that sawing or polishing in wet media has been avoided to preserve the soluble sodium compounds. or fractured. Most cross sections were either dry-cut with a diamond saw

Fractured specimens show structural features well as has been

10

High Temperature

Corrosion

of Ceramics

established

in many studies of the microstructure of ceramics.

The multilayer

nature of the scale and sometimes its apparent layered growth is shown clearly in cross sections. The cross sections can also be used directly for the measurement

of oxide layer thickness (~l~rn). In some cases salt drops have been crossed by the fracture giving valuable information. However the lack of flat cross sections

has limited the use of the crystal spectrometers of the electron microprobe. In many cases the deposit drops do not adhere welt to the sample surface after cooling so that the underside of the drops and the area of the sample which was under the drops can be examined and analyzed at least qualitatively. Mechanical bursting of bubbles in surface layers and removal of drops are also used to study the underlying microstructure prior to washing of the specimens.

Gaseous
Introduction

Corrosion

The results from the gaseous corrosion studies will be discussed by considering first the studies of silica and alumina, and then the studies performed using Sic and Si3N4.

Gaseous Corrosion of Silica and Alumina The gaseous corrosion of silica and alumina were performed at temperatures of 700, 1000 and 14000C in a number of different gas environments which included oxygen, 02-H20-H2, 02-CO2-CO and O2-SO2-SO3 gas mixtures (Table II). The

results obtained from these studies are discussed in detail in Reference 1 and Appendix A. The specific conclusions developed from these studies are as follows: Silica (1) Devitrification of silica glass to cristobalite took place rapidly under all atmospheres studied at 14OOOC. The rate of crystallization increases with increasing temperature and time. (2) The devitrified layer undergoes a displacive transformation with a large volume change on cooling which causes cracking. Such a transformation in crystalline SiO2 is important with regards to the use of crystalline SiO2 scales on Sic, Si3N4 and metallic alloys as protective barriers for high temperature applications. (3) The silica is significantly affected when exposed to low oxygen pressure at 1400C. Silica weight losses occurred after exposure to either wet hydrogen or a CO-CO2 gas mixture and are related to the decomposition of silica in the low oxygen pressure and the reaction of either hydrogen or CO with silica to form SiO vapor and either H20 or CO2 gas. Weight losses increase with increasing temperature and decreasing oxygen pressure.

11

12

High Temperature

Corrosion

of Ceramics

Gaseous Corrosion

13

(4) No significant reaction of silica in CO2 or 02 was observed at all temperatures except for devitrification at 14OOOC.

(5) Silica is very resistant to attack by SO2-SO3-02 gas mixture under the test conditions.

Alumina (1) Alumina is resistant to attack by H2-H20-02 gas mixture but impurities The

in the alumina materials such as SiO2 and Na20 can result in volatilization. volatilzation is favored by low oxygen pressures and high temperatures. (2) Alumina is very resistant to attack by CO2 gas.

(3) Alumina is resistant to corrosion by SO2-SO3-02 gas mixtures. Some reactions occurred especially at high SO3 pressures (e.g. 7~10~~ atm. SO3) and low temperature (7OOOC). (4) Corrosion of alumina in SO3 containing gas can occur even on the highest purity alumina where reaction products with activities less than unity are formed. It may be due to the formation of a solid solution of Al2(SO4)3 with Al203 or a nonstoichiometric sulfate. The observed sulfur was identified as a ~+6 (as in sulfate) by ESCA. (5) Degradation of alumina in SO3 containing gas becomes more severe when Mg or Ca containing impurities are present, and it increases as impurity content increases. The formation of products occurs preferentailly along the grain boundaries (i.e., on the impurity second phases at the grain boundaries). (6) Corrosion of alumina in SO3 containing gas becomes more favorable at higher SO3 pressures and lower temperature (e.g. at 7000 than 1000C), since a lower SO3 pressure is necessary to form sulfate at 700C than at 1000C. severity of corrosion increases with time. The

14

High Temperature

Corrosion

of Ceramics

Gaseous Corrosion

of Silicon Nitride

and Silicon Carbide only at 1400C in

The gas induced corrosion

of Si3N4 and SIC was studied

oxygen and at 1OOOoC in an 02 - SO2 - SO3 gas mixture pressure of 0.01 atm. These limited studies

with an initial SO2 to determine occurred if

were performed on these materials

devitrification and to provide 1ooooc.

of the silica scales formed baseline data for comparison

at 1400C, at

with the hot corrosion

studies

The studies

in oxygen at 1400C showed varying results material.

depending Sic

upon the

form of the substrate crystallization

In the case of the single crystal was observed. and cracked These scales

of the silica scales

which were about

1 urn thick after patterns original

12 hours of oxidation to radiate

upon cooling to form star centers indicating the

that were believed

from nucleation of the amorphous

nuclei of the crystallization

layer into cristobalite. samples were thicker in

The silica scales which formed most cases than those formed after surface 12 hours of oxidation. and contained

on the polycrystalline on the single crystals

of Sic being about 10 urn exhibited a glazed The lack of the by

The hot pressed

silicon carbide

bubbles resulting

from CO and CO2 evolution. particularly

crystallization glass structure.

was attributed

to impurities,

Al2O3, stabilizing however

Some cristobalite

was identified

in these scales

XRD along with a large glass peak.

The hot pressed of cristobalite

silicon nitride and enstatite

also formed (MgSiO3). nitrides There was compared 12 hours to

a 10 urn thick scale which was composed The CVD silicon nitride, developed virtually specimens of oxidation an extremely no change

which was much purer than the other silicon thin silica scale after morphology 12 hours of oxidation. specimens

in surface

of the oxidized

prior to oxidation

and the weight change of specimens limits of the techniques

after

was below the detection

used in this program

Gaseous Corrosion

15

to measure weight change. No impurities were detected in these silica scales on CVD silicon nitride which XRD analyses showed to be a mixture of cristobalite and glass. The sintered silicon nitride developed a scale composed of glass containing some cristobalite. Yttrium silicate crystals were observed to protrude

out above the surface of the silica scale. Impurities influenced the oxidation of this material substantially. The results obtained from the studies performed at 1400C show that the oxidation of SIC and SiSN4 is dependent upon the structure and composition of the silica scales that are formed upon these materials. Glassy silica provides a more protective reaction product barrier than crystalline silica, however, the incorporation of impurities into the glassy silica can cause the protectiveness of the glass structure to be decreased very substantially by promoting devitrification. At 1000C the pressure of SO2 and SO3 in the gas mixture along with oxygen did not significantly affect the oxidation of pure silicon nitride or pure silicon carbide compared to oxidation in pure oxygen. The major effect of SO2 and SOS occurred when the specimens contained impurities. While the effects of impurities were significant but not documented extensively, these effects were not as substantial as those observed at 1400C, since the impurities cannot concentrate in the oxide scale at 1000C and thereby affect the protective properties of the glassy silica scales.

Hot Corrosion of Silica

The results obtained from the studies on the hot corrosion of silica are presented and discussed in more detail in Appendix B of this report. In the following the important results from these studies are briefly summarized. Specimens of fused silica (Corning 7940) about 1 cm x 1 cm square and 1 mm thick were exposed to a variety of conditions known to cause the hot corrosion of metallic alloys. The experimental procedures have been described in the experimental section of this report. Results from four different sets of experimental conditions will be discussed in this summary. These experiments were performed at 700 and 1000C. The deposits of Na3S04 which were applied to the specimens surfaces were liquid at 1OOOoC. At this temperature two different gas compositions were used. One consisted of an SO3-03 gas mixture and the other was pure oxygen. The SO3 pressure in the gas mixture was 1.5 x 10e3 atm. When Na3S04 is exposed to gases containing SO3 the activity of Na90 in the sulfate is inversely proportional to the SO3 pressure. If the activity of Na30 in the sulfate is taken as a measure of the basicity of the Na3S04, higher SO3 pressures established less basic, or more acidic melts, whereas the gas containing only oxygen causes the more basic liquid sulfate to develop. Similar sets of experiments were performed at 700C however at this temperature the SO3 pressures in the gas mixtures was 7 x 10m3atm. Furthermore the deposit applied to the specimen surfaces was Na3S04 - 50 mole percent CoSO4 since pure Na$304 is liquid at 700C. melts at about 883OC and the sulfate mixture

16

Hot Corrosion

of Silica

17

The liquid sulfate deposits wetted the silica specimens in varying amounts depending upon the experimental conditions. Time at temperature and the

thickness of the deposit also affected wetting. Generally the liquid deposits wetted the silica more completely under basic conditions. At 1000C under

basic conditions the salt wetted most of the coupon after 1 hour with a wetting angle of 20. After 24 hours the wetting was continous. At this temperature and under acidic conditions droplets of liquid were formed with wetting angles Of 24O, and 130 on large droplets ( 0.2 mm dia), after 24 hours. Wetting was not as complete at 7OOoC. In the case of basic conditions droplets with wetting angles between 13 -240C were observed after 24 hours, whereas under acidic conditions the angles ranged between 36 - 49O. At 7000C under acidic conditions some limited localized attack of the silica was observed under of the salt droplets. No evidence of devitrification of

the silica was observed. After water washing to remove the salt, small weight losses (0.1 - 1 mg/cm2) were detected and small voids were evident in the silica where salt droplets had been present prior to water washing. The voids were more concentrated near the perimeter of the droplets. Analysis of these results has been complicated by the decomposition of the CoSO4 in the liquid via the reaction, coso4 * coo + so3

since the SC3 pressure in the gas was lower than the equilibrium pressure required to maintain the initial liquid deposit. The principal deposit reaction of the

with the silica should involve the Na20 component of liquid since conditions

sulfates and sulfides of silicon are not stable under the experimental that were employed. Hence,

a reaction of the following type seema plausible, + ~~03

XSiO2 + YNa2S04 = YNaZO-XSi02

18

High Temperature

Corrosion

of Ceramics

Inspection becomes

of this reaction shows that the formation less favorable as the SO3 pressure

of sodium silicate It is believed

phases that the

is increased.

SOS pressure permit silicate sulfate

in the melt over most of the specimen formation. However, some dissolution

surfaces

is too high to in the -fused

of silica occurred

at localized

regions under the drops, in particular

along the sulfate This

silica interface localized affect

which caused voids to be evident upon water washing. is believed to result from impurities

dissolution

in the silica which

its stability. Under basic conditions at 700C the complication from decomposition of

the CoSO4 component the gas phase.

of the liquid was more severe since there was no SOS in spherulites were observed beneath the salt drops. because

Cristobalite

Weight change measurements some cobalt oxide resulting specimen surfaces.

after water washing were not meaningful from decomposition of CoSO4 remained

upon the under the

Since dissolution and this process

of the fused silica was observed

acidic conditions,

is believed to involve NaSO, such a reaction The important result obtained at

would also be expected

in the more basic melt.

7000 under basic conditions was observed beneath

however is that crystallization Since crystallization

of the fused silica was not observed must

the salt droplets.

at 700C under acidic conditions, be established at some specific

the activity

of NaSO in the liquid deposit to proceed.

level in order for crystallization cristobalite was observed

At 1OOOoCunder acid conditions all of the droplets, from the droplets. but no devitrification

to form beneath away at

of the fused silica was evident under acidic conditions

The weight losses of specimens

1000C were less than at 700C. silicate

This can be accounted

for by less sodium

being formed at the higher temperature.

Hot Corrosion

of Silica

19

The most extensive conditions surface interface exposures: thickness isothermal

degradation

of the vitreous product

silica occurred

under basic

at 1OOOoC. A layered reaction

was formed over the total from the salt-specimen after very long fused silica. rate law under proceeded products The The

of the fused silica specimens. the following sequence sodium silicate, of the crystallized conditions.

Proceeding

of phases was observed cristobalite,

tridymite,

unaffected

silica conformed

to a parabolic

Under cyclic conditions

this crystallization

more rapidly and conformed spa&d observed from the specimen parabolic

to a linear rate law since the crystalline aa a result of thermally induced stresses.

rate has been accounted

for by assuming the crystallization There is no

of the fused silica is caused by sodium from the liquid deposit. question however, that some sodium silicate was formed.

Analyses of wash water, products are formed early in phases is

shows that more water soluble corrosion process than after long reaction

the corrosion

times when the crystalline to form silicates

have been formed. dependent

Such results suggest that the reaction of the liquid deposit

upon the composition

and the structure

of silica.

Also as the silicate As discussed significantly corrosion significant

becomes richer in silica it is less soluble in water. previously in the section on gaseous corrosion, silica was not No

affected

by any of the gas environments was detected

used in these studies.

nor devitrification degradation

at 700 or 1OOOOC. On the other hand in SOS-02 gas mixtures, This degradation and

of fused silica was observed deposits processes were present.

in oxygen, when liquid sulfate by two different, activity but related,

occurred upon the

both of which were dependent

of NaSO in the deposit. was devitrification.

The process which caused the most severe This process increased as the Na70 activity It requires in a

degradation

the liquid was increased

and it occurred

at both 700 and 1000C.

20

High Temperature

Corrosion

of Ceramics

threshold thermally thermally silicate latter

Nag0 activity.

It was especially

severe

when the specimens

were of

cycled since the crystallized induced stresses. as a reaction

products

spalled under the influence involved the formation

The other process

of sodium that this silica of by

product on the surfaces

of fused silica.

It appears

process

is less prevalent silica, nevertheless

when the liquid is reacting this reaction This reaction

with crystalline as the activity

than vitreous

also increases

Nag0 in the liquid is increased. impurities

also appears to be affected

in the fused silica when its driving force is low.

Hot Corrosion of Alumina

The results obtained presented and discussed from the studies on the hot corrosion of alumina are important

in detail in Appendix C. In the following

results are summarized. The weight changes measured small but not negligible. after hot corrosion of the aluminas reactions were

They were due to offsetting

such as the precipitation

solution of Al203 into the sulfate

melt, the silica and silicate

mostly due to impurity phases and the precipitation oxygen. corrosion.

of Co0 at 7OOoC in pure than for gaseous

In general the weight changes appear greater

The sulfate tended to wet the aluminas partially conditions a function (~20~ after 24 hours). of time apparently The wetting

at 7OOoC under acidic as

of the purer aluminas decreased into the sulfate At higher a little. and

as some alumina dissolved

reduced the affinity temperature The wetting conditions

of the sulfate

for the alumina substrates. the wetting

(lOOOC) under similar conditions was better

improved

at 1000C under basic conditions tended to increase tendency the wetting

than under acidic tendency. The wetting Good which

as the impurities

is an indication wetting

of the reaction

of the sulfate

with the substrate. and the substrate

results in more contact the corrosion.

area between

the sulfate

also promotes

The single crystal

alumina tended to react very little results more reaction

with the Na2S04 and under acidic

in line with the gaseous corrosion conditions

occurred

than under basic conditions. of the polycrystalline of orientation,

The single crystal

has basal orientation. of the

The corrosion

aluminas indicated with greater attack

that the corrosion

grains is a function

of planes away from the

21

22

High Temperature

Corrosion

of Ceramics

basal orientation. melt.

This result is expected

for solution of a single crystal

in a

Under acidic conditions,

at 7OOoC sulfates

of aluminum

and magnesium on all the

were formed and after long exposures polycrystailine silicate silica. materials.

globular silica was observed

This shows that under the most acidic conditions by the melt generating gradient sulfates

impurities The required

are attacked solubility

and precipitating of alumina

is set for continued The precipitation

dissolution

by acid fluxing and precipitation probably cristobalite, the substrate corrosion

of silica.

of silica globules, with The

occurs in the sulfate

melt away from the interface of the substrate.

and is not related

to the microstructure

is concentrated

near the grain boundaries

at 700C and occurs on a the regions under the sulfate at the grain boundaries. and alumina is At

wider scale at 1OOOoC. At the higher temperature melt are smooth with no marked preferential 1000C magnesium incorporated sulfate attack

and calcium sulfate

are formed

in sodium aluminum silicates. significant corrosion occurred at 700 and 1000C. aluminum The overall

Under basic conditions At 1000C sodium magnesium silicates attack were formed.

aluminum silicates

and sodium calcium

The salt on cooling contained was limited

Mg, Al and some Ca.

of the alumina grains

under the more basic conditions corrosion was evident in the

at 1000C and significant micrographs. The impurities polycrystalline

intergranular

played a major role on the corrosion particularly at high temperature

behavior

of the

aluminas,

(lOOOC), in pure of basic fluxing of the with the silicates Sodium

oxygen (basic conditions). single crystal, present

While there was little evidence promote reaction

the high Nag0 activities

at the grain boundaries

of the polycrystalline

materials.

aluminum silicates

grew from the melt with transport

of silica and other oxides

Hot Corrosion

of Alumina

23

along the grain boundaries. grain boundaries silicate silicates

This is illustrated

by the perfect

decoration

of the

of high purity polycrystalline

alumina with crystals

of this in the

after long term cyclic exposures. formed near triple points.

Some magnesium

was present

With the more impure aluminas various alkaline

more silicate and

was formed and the crystals potassium which were present crystals

contained

earth elements

as impurities

in the materials.

While this fluxed grains is It is

growth of silicate interesting,

feeding from grain boundaries role in the corrosion

and impurity of the alumina.

it plays a fundamental

proposed that the impurity reactions activity

which form sodium silicates

lower the Na30

and raise the SO3 locally in the melt.

This more acidic Na3S04 then can in the melt by acidic fluxing. will

dissolve the alumina grains by formation The two reactions, proceed the grain reaction

of sulfate

and the grain boundary reaction

cooperatively,

as the ion needed for one is produced mechanism is proposed

by the other. of

Therefore polycrystalline

a fundamental

for the hot corrosion As shown

alumina in which the impurities

play a major role.

above they have a major influence most technical coatings ceramics.

even on 99.8% purity alumina,

which means on

This may apply also to alumina scales grown on but in a general manner since they do not contain mechanism applies. the alumina even at silica-

on superalloys

based impurities

for which the following the sulfate

Under acidic conditions, though conditions unit activity.

tends to dissolve

are not favorable

for the formation by acid fluxing.

of aluminum sulfate The formation of

The alumina is dissolved in the field of stability experiments.

aluminum sulfate gaseous corrosion be established

of alumina was already observed melt a wide range of activities little or no attack

in the can

In a sulfate

locally.

Under basic conditions

of single crystal particularly in at

alumina was observed high temperature

although basic fluxing should be possible,

(more basic conditions).

However this is not promoted

24

High Temperature

Corrosion

of Ceramics

presence

of silica-based

impurities

which are present aluminas. favoring

at the grain boundaries

and

as second phases in the polycrystalline conditions so that intermediate

The impurities the attack

modify the local and

activities

of the silicates

the dissolution basic conditions environment, activity silicates

of the alumina in the sulfate of this study.

prevail under the acidic and the set by the gaseous

Under acidic initial conditions,

the sulfate

tends to dissolve alumina and as this is done the is increased. This promotes thus decreasing the attack of the

of Nag0 in the sulfate which are dissolved

in the sulfate cooperatively.

the Nag0 activity. of Na70 At and

The two reactions

can proceed

At 700C the activity and SiO7 is precipitated. by the same mechanism

was always too low to form sodium silicates 1000C, higher Nag0 activities sodium aluminosilicates melt tends to attack of neighboring as discussed are generated

are formed.

Under basic initial conditions, phases, thus promoting The two reactions

the sulfate

the acidic impurity

the dissolution cooperatively

alumina by acid fluxing. earlier. just presented

proceed

The mechanisms were attacked

explain that the polycrystalline

aluminas

under both acidic and basic conditions are extremely attack

of the experiments,

however the processes evidence of catastrophic

slow and there was no experimental Under the would lead to slow acidic conditions by

even after 400 hours exposure. mechanisms

circumstances continuous

one may ask if any of the proposed without replenishment

attack

of the salt although

provide some of the requirements. sodium sulfate factor it appears

However in view of the rate of attack processes

that in many industrial before

in which it could be a saturated or

the sulfate

will be replenished

it might become

depleted. conditions

Higher temperatures

might increase

the rate of corrosion

and basic

might become predominant

under usual (percent

or less) sulfur

Hot Corrosion

of Alumina

25

concentrations

in the atmosphere, since sulfate

however deposits

the sulfate

vapor pressure

then will

limit the corrosion temperatures.

are no longer formed

at higher

Hot Corrosion of Silicon Carbide and Silicon Nitride

The results of recent Appendix D. Important The hot corrosion presence experiments are presented below. has been studied and basic, in and discussed in detail in

results

are summarized

of silicon nitride

and silicon carbide

of Na9SO4, under acidic,

1% SO9-balance

oxygen initially

pure oxygen, conditions corrosion

in the temperature

range 900-1000C.

During basic hot it

the salt wets completely

the samples while during acidic corrosion increases the rate of oxidation

breaks up in droplets. thickness between oxidation.

The hot corrosion

and the

of the oxide layers formed increases the drops) to basic hot corrosion

markedly from acidic (measured than for dry rapidly and

and both are greater

The oxide layers formed tend to be vitreous For the purer materials the sulfate droplets

and devitrify

under the liquid sulfate. very limited in between

devitrification

was sparse

under acidic conditions.

In general,

clearly different conditions.

behaviors

are observed

for the pure materials

under the two

They are controlled

by the activity

of sodium oxide in the sulfate oxidize and

melt near the interface the oxide dissolved

with the substrate.

In all cases the materials the sulfate

into the sulfate. activity

For acidic conditions,

does not

wet the oxide, and a surface atmosphere the vitreous

of sodium oxide in equilibrium droplets.

with the into

is set up in between silica and modifies

the sulfate it.

The sodium diffuses

26

Hot Corrosion

of Silicon Carbide

and Silicon

Nitride

27

Under basic conditions, was consumed

a thick product layer was formed The ceramics melt.

and the NagSO4 and

slowly in the reaction. into the sulfate

oxidize at their surfaces builds up at the in silica, the silicate

the oxide dissolves interface cristobalite

The Nag0 activity As the silicate

and a silicate is nucleated

layer is formed. at the interface.

enriches

After long exposures,

phase remains

on top of the silica and the sulfate The melt contains

left is in small isolated

drops

on top of the silicate. as indicated otherst5).

a high concentration

of silica initially by

by the wash water analysis and it has also been well documented The observations are consistent that the reaction with the mechanism proposed by than

Mayer and Riley(S) except

is much slower with Nags04 is offered

for NagCOS which they studied. product layer since greater samples. Under acidic conditions reactivity

Some protection

by this complex of the

degradation

was observed

after preoxidation

(1.5~10-~ atm SOS), poor wetting However the oxidation

and little was enhanced

with the salt were observed. the sulfate drops.

even between in detail.

This oxide growth between

the drops was studied

The oxide formed was mostly vitreous.

In these regions a very thin into the silica rapidly

layer rich in sodium is detected formed.

(~10 A thick) and sodium diffuses droplets

The silica layers formed under the sulfate by spherulitic crystallization

devitrified

into cristobalite They were thicker

or random globular formation. outside the drops except were similar. to be similar The for

than the vitreous

layer formed

the C-side silicon carbide thicknesses surfaces

for which these thicknesses

of oxide formed under the drops tended C-side silicon carbide

for all three

(CVD silicon nitride,

and Si-side silicon carbide) layers formed under basic

studied but they were still smaller than the product

28

High Temperature

Corrosion

of Ceramics

conditions.

This is generally

consistent

with a mechanism

determined

by the surface. there

liquid phase and therefore

independent

of the nature of the substrate

Indeed for the basic conditions was no more differentiation A model was proposed correlates

and under the droplets

for acidic conditions

in the behavior of C-side and Si-side silicon carbide. of random cristobalite globules which Selective the

for the formation obtained

with the results

for the hot corrosion

of bulk silica.

attack of the substrate spherulite fibrils.

occurs by transport

through the liquid phase between

The acidic hot corrosion essentially enhanced oxidation.

which occurs between The kinetics

the sulfate

droplets

is

of this hot corrosion of oxynitride.

of silicon Some evidence how this The

nitride are complicated of this formation

apparently

by the formation

was obtained

in this research.

It is not clear presently

thin layer formed during the oxidation silicon carbide has different

slows down the oxidation

so strongly.

behavior for the carbon-side they oxidize parabolically energies

and for the silicon-side. at different rates.

During the acidic hot corrosion Kinetic data and apparent of each side.

activation

were obtained

for the hot corrosion

In order to interpret of silicon carbide.

these results, However,

it was logical to modify a model a satisfactory explanation of the

for the oxidation oxidation

of silicon carbide had not been proposed. results of others, oxidation a model was developed by diffusion vitreous on the

Based on the oxidation premise that the parabolic

is controlled

of oxygen through silica is formed with different of silicon, silicon in

the oxide layers to the substrate all cases, the different oxygen deficient

interface.

Although

rates of oxygen transport structures produced

are associated

vitreous

in the oxidation

carbide C-side and silicon carbide Si-side. for the oxidation

Tentative

mechanisms

were proposed

of the two sides of silicon carbide

in which the oxides are formed

Hot Corrosion

of Silicon

Carbide

and Silicon

Nitride

29

under different defect structures.

oxygen pressures The observed

and therefore

are expected

to have different constants and

trends in the variation compared

of the parabolic

for the acidic hot corrosion that of silicon are predicted activation consistent energies

of these materials qualitatively

to their oxidation High apparent are generally

by these

models.

such as those measured

for hot corrosion

with the models although that for the silicon-side

of silicon carbide

could not be estimated. The behavior impurities of engineering materials is strongly influenced by the

they contain.

MgO and Y3O3 tend to segregate

toward the surface under

during oxidation acidic conditions as the conditions atmosphere. these materials between

and hot corrosion. so that wetting

They lower the acidity of the sulfate is improved and thicker

oxide layers are formed with the for

are more basic than promoted the wetting

by equilibrium

Conversely,

is not as good under basic corrosion The impurities set conditions

as for the purer ones.

intermediate for the

those promoted

by the equilibria experiments.

with the atmospheres Alumina impurities

selected

basic and acidic corrosion do not segregate alumina entering

in the silicon carbide or hot corrosion. The

to the product

layer formed on oxidation

the oxide layer appears to stabilize

it against devitrification. of the hot corrosion of

Great progress

has been made in the understanding The corrosion

silicon nitride and silicon carbide. conditions

varies with environmental of sodium. The of silica.

and it was shown to be controlled correlates

by the activity

behavior observed In particular devitrification preferential corrosion

well with the results on the hot corrosion

the major role played in the degradation is emphasized attack occurred by these results.

of the scales by their

It was shown also that Overall the hot The atomic and

locally under acidic corrosion. is well understood qualitatively.

of these materials proposed

mechanisms

for the oxidation

and hot corrosion studies.

of silicon nitride

silicon carbide suggest directions

for further

1.

J.R. Blachere and P.S. Pettit High Temperature DOE Report ER45117-2, March 1988 a) DOE Report ER45117-1, June 1985 b) DOE Report ER10915-4, June 1984 C) a) b)

Corrosion

of Ceramics

2.

H. Yakovitz and D.E. Newbury, SEM/1976/1, IIT Research Institute, Chicago, IP, p. 151. References J.I. Goldstein et al., Scanning Electron Microscopy and X-ray Microanalysis, Plenum, No. 4, 1981, p. 354. and D.F. Klimovich, J. Am. Ceram. Sot., 70 [ll] C324-C326 in Metals and Alloys, Addison-Wesley,

3. 4. 5. 6.

J.R. Blachere (1987).

L.E. Murr, Interfacial Phenomena Reading, Mass., 1976, p. 67. N.S. Jacobson,

J. Am. Ceram. Sot., 69 [l] 74-82 (1986).

M.I. Mayer and F.L. Riley, J. Mat. Sci., l3, (1978) 1319-1328.

30

Appendix A-Gaseous Corrosion of Silica and Alumina in Sulfur Oxide Environments

H.R. Kim, J.R. Blachere and F.S. Pettit

Abstract: A fused crystalline SOjsilica of high purity and alumina impurity The silica levels in single crystal and polyto mixtures resistant the silica. SO3 of

forms with

different

xiere exposed

SO2~02 at

700C and 1000C. environments.

and alumina

are very with

to corrosion Sulfates pressures. intensity

in these

No reaction at

was observed

formed

on the aluminas occurred

particularly under less

low temperature conditions

and high and with

The reaction with increasing

severe

greater

impurity

content,

particularly

Ca and Mg.

Supported

by the

U.S.

Department

of

Energy

under

Agreement

Number

DE-ACOZ-8 lER109 15-A000

Presented Society

in

part

to

the

1982 Fall

meetings

of

American

Ceramic

in Cambridge,

Mass.

31

32

High Temperature

Corrosion

of Ceramics

I. Ceramics are considered

INTRODUCTION actively for is components because of they advanced have high power systems

operating
ness

at high

temperatures.

(1) This

refractorithrcugh

chemical

stability over

and mechanical the past twenty

properties years. (*)

much improved been

extensive successful the needed present peratures coatings

research in recent

They have and it

partially that the tem-

demonstration in reliability

projects of

may be anticipated result from

improvements

components

will

emphasis

on ceramic parts

processing. rePlacing

Ceramics superalloys, alloys

may be used as from

at high barrier

as monolithic or as coatings corrosion not

thermal

protecting problems.

metallic

environments

which

cause

them severe

One should
Corrosion to the the of steel

assume

however by oxide

that melts

ceramics such

are

totally

corrosion are

resistant. costly on

refractories and glass of these energy deposits the Si3N4

as slags research but little

and glasses has been is

industries. in deep in

As a result melts, (3)

performed the

corrosion df

ceramics materials systems of

known about

corrosion in advanced In addition, tend such of in the

gaseous

atmospheres. corrosive

The environments of the combustion.

encountered

may contain salts such

products

as NaZSO4 mpy form on It has been

components that molten

and ceramics

to enhance as AlZO3,

gaseous

corrosion.

shown recently with

and yttria-stabilized The gaseous not only

ZrO2 can react corrosion the of ceramics

deposits studied to in of is

Na2S04 in this

SO3 gas.(b) (5,6)

has been of

research

to establish

susceptibility of those

ceramics

corrosion systems

by gaseous but also

atmospheres as of the baseline salt

representative for research

encountered hot silica they nitride corrosion

energy crramics( discussed

on the of since

1 C i n presence here. These scales

deposits). are of great

The corrosion importance

and alumina perform and silicon

materials

as protective carbide

on superalloys environments.

and SiOZ forms

on silicon

in oxidizing

Appendix

A-Gaseous

Corrosion

33

II.

GASEOUS CORROSION OF CERAVICS

Gaseous just the that metals metallic in the as in corrosion are

corrosion the case process of

of the are

ceramics gaseous ultimately of with

can occur corrosion controlled

by a variety of metals by the the

of

mechanisms Moreover, the products In by species and the

and alloys. nature of

formed

as a result reaction being

reaction the via gas

between is almost of

gas and the

ceramic.

and alloys elements gas.

always electron

characterized to reducible states the

oxidized of the

transfer are

The cations possible

ceramics

already

in oxidized First, oxygen

following

corrosion to higher

processes states which

can be proposed. in the into case the of

cations

may be oxidized would could of the result result phase

as an oxidant Such a process of stoichrometry of chrome-

in oxygen in the

being

incorporated of This new phases plays

ceramic.

formation oxidized. with

or merely role

changing with

being

a major

degradation

based Second, the form

refractories the atoms of the

temperature of for

and particularly the gas

atmosphere

cyclings. compounds with depend but with to

or molecules ceramic,

may form more stable silicon type of nitride reaction of the reacts will

cations silicon

example This

oxygen on the effects

dioxide of the

and nitrogen. formed displaced the or

properties produced h third duction reactions could ation in the

products

upon the by the

surface oxygen of

ceramic be very

by the elements possibility of SiOz (s)

can also

important. as the reSuch and form-

involves to SiO (g) would

formation the

volatile of

species (s)

such to CrOj

oxidation

CrpOj gaseous

(g). layers the

probably

involve

diffusion to

through those of of the

boundary involving Finally, affinity such

proceed of

at rates

fast

compared on the

processes ceramics.

condensed such

phases

surface

molecules for the

gas

as SOj. or its

CO2 or Hz0 may possess oxide and react to

a significant form compounds

cationic carbonates

component

as sulfates

or hydrates.

34

High Temperature

Corrosion

of Ceramics

The rates corrosion

of

such

processes and rather corrosion

will

be dependent

upon transport

through

products

complicated ceramics ceramics is usually of is

mechanisms expected which

may prevail. to be similar has been in studied some extensively

The gaseous respects in the to the

of of It

corrosion (gv 3l the rate relative density porosity

in melts modelled reactants

literature involve the overall on the the the

as a dissolution and products

process. which often reaction the viscosity

The kinetics determine rate of in by

transport of the

corrosion rate in solid, at the are the

process. of the

The corrosion various the phases,

depends the the the liquid, liquid, liquid, size

corrosion gradient of the

liquid,

concentration of the solid

gradient phases the the system. rate

the wettability interface major and the factors faster in than resulting of of

the boundary and the Fine pore

layer

geometry controlling coarse

of

The grain of

structure materials

dissolution.

grain

dissolve grain

grain

materials. of the

The liquid solid grains

may penetrate by the liquid

into

the

boundaries influence

in engulfment

(9,101 the

.The

the microstructure corrosion geometries studies grain

on the so that

corrosion for

complicates studies This the role is

greatly Simple valid

interpretation with gaseous pore simple

experiments

fundamental

systems for the

and microstructures since except for should

must be used. wetting play effect,

also size,

corrosion

grain

structure

and the

boundaries

a similar There is

as in liquid literature only

corrosion. on the oxidation of silicon of nitride simple for and oxides

significant (*l! the

silicon appears Silica of For

carbide

literature

on gaseous

corrosion particulary volatilizes with in wet

to be on their at high

reduction under

and volatilization low oxygen and/or losses pressures by reaction observed

silica.

temperature

forming or CO (12*13! at

SiO (g) instance,

by thermal significant

decomposition weight

hydrogen hydrogen

were

(51

Appendix

A-Gaseous

Corrosion

35

1400oc. to lose

Alumina impurities are low only

is

much more such

resistant at high high

to conditions temperatures.

of

this

tvpe

and tends losses of of

as sodium at very can (15)

Significant of the order

alumina Steam at of of

observed

temperatures,
with are this silica

19OOOC. (14)

temperatures refractories.

form hydrates However, there

resulting on the

in degradation Influence

silicate sulfur

no reports is discussed

oxide

gases

on alumina III.

and silica;

below.

EXPERINENTAL PROCEDURE

(1)

Materials They include four aluminas relatively given and a fused high I. silica which and flat were were obtained from

commercial A brief the is in

suppliers

in
is

densities

configurations. selected to investigate crystal

description of

in Table

The aluminas on the

influence a transparent the form of

microstructure substrate with

and impurities (0001)

corrosion. The (L)

The single material is

orientation. (S) and

almost (S)

transparent alumina

washers;

(M) are gross

white effects size

substrates. of impurities. than (L)

The more The (S) alumina (2)

impure

was included a much finer will

to show the average

and (MI aluminas (19Urn). Their

have

grain

L-kin I 1

microstructure

be discussed

later

as needed.

Experiments Flat specimens as received, cleaned ( z l~l.cm) polished were or exposed to sulfur oxide
eases at ml and lno~~c

in either they were

relief

polished and alcohol

conditions. and then

Prior heated

to exposure in were flowing passed contact turbine the

thoroughly at

in acetone

oxyeen over with

atmosphere a platinized the samples.

IOOOoC for at the

one hour.

The ~02 and 02 mixtures of the experiments relevance instances performed were s~ally

catalyst

temperature were selected enough

before to gas

The conditions

to have in most

operations. decomposition environments.

The SO3 pressures of Na2Sfl4

were

high

to prevent in the same

in hot

corrosion of

exueriments the gases

The initial

SO2 contents

1%. 0.1%

and

TABLE Designation Silica 8.C. L M S Materials fused silica sapphire a-A1203* u-A1203* a-A1203*

I. MATERIALS

UNDER STUDY % Purity (Imp) Suppliers Corning 7940(l)

3 2.20 3.97 3.97 3.89 3.74

99.89 99.99 99.79 99.6 97.4

(0.1 H20)

Saphikon(2) (0.1 MSO. 0.11 Lucalox (3)

SiO2) (0.17 t&O, AlStiS 772 (4) 0.17 SiO2) (0.75 ugo, +l.6SiO2, O.lNa20 S-697 (5)

* Polycrystalline

(1) (2)

Corning

Glass

Tyco Laboratories Electric, Lamp Div. Prod. Div.

(3) General

(4) 3M, Technical (5) Saxonburg

Ceramic

Ceramics.

Inc.

Appendix

A-Gaseous

Corrosion

37

0.01% of II.

with

the balance

02 for

a total

pressure equilibrium

of

one

atmosphere

and a flow are shown in day

race

about

lcm3/sec.

The corresponding times were were usually

SO3 pressures ware varied exposures examined the the

Table

The exposure

one week but in of

from one to also

to one the exposure. with

month. product Since about (SEM). of the

Some experiments development the materials o 200A of This carbon

performed

sequential sample,

follow before

on the are

same area

the

electrically

non-conductive in

samples

were Electron

coated

prior

to any observation at 700C

Scanning

Microscope exposure of procedure

carbon in

was oxidized sequential exposed with the

in 02 before It the

any additional by comparison time that this

samples

experiments. only once for of

was checked same total

duplicate did not

samples interfere

results tools

the

sequential SMs

experiments. equipped analysis. formed with Energy diffraction quantities. Analysis

The major dispersive X-ray

investigative Spectrometers to identify were also

were for

the

(EDS)

elemental when they

X-ray

(XRD) was used Some specimens (ESCA) after balance before

the

products

in sufficient for Chemical

analyzed The weight

by Electron of the

Soectroscopy

exposure. and after

specimen

was checked

on an analytical

the experiments. IV. Results and Discussion in any of that the experiments. change of It D.Img/ of can

No significant be shown, cm2 of product with considering

weight the

change size of

was measured the to samples, the

a weight of

exposed about

surface lum thick.

corresponds

formation were

a continuous discrete using layer

layer

The corrosion the surface, they are

products they could

usually

and often SEM the

little

coverage

of

be detected to a continuous

the of

EDS order

and ESCA, but I urn thickness. (1) Silica Silica No visible is

in no case These

were

equivalent described in

products

the

following.

very

resistant formed

to attack

by SD2-

SO3 atmospheres by EDS or

at

700 or

1DDOC. exposure

product

and no sulfur

was detected

ESCA after

38

High Temperature

Corrosion

of Ceramics

Tr\BLEII:

Environmental Conditions A1203 and Silica

in Experiments

on

Gas

Initial Pressure (Atm)

Pressure 7oooc

(Atm) at 1ooooc

02 SO2 SO3 02 SO2 SO3 02 SO2 SO3

Sl. 10-2

Ll . 2.9 7.2 x 10-3 x 10-3

-1. 8.7 1.3 %I. x 10-4 x 1O-4 8.7 1.3 %I. x 10-5 x 10-5 8.7 x 10-5 x 10-4 x 10-4 x 1O-3 x 10-3

%I. 10-3

Sl. 2.9 7.2

-1. 10-4

Sl. 2.9 7.2

1.3 x 10-5

Appendix

A-Gaseous

Corrosion

39

up to one month. dynamic high for data the for

where silicon

is

no evidence sulfate.

of

sulfate

formation of

and there the

is

*o

thermotoo

The oxygen sulfide.

pressure

experiments

was

formation were

of

silicon above

No experiments Sulfate

in C3-SO3-So3
is less favorable

atmospheres
as

performed

1OOOoC since

formation of the silica

the

temperature the exposures at

increases. 700 or

.No devitrificatioa 1OOOoC.

glass

was observed

after (2) (a)

Alumina General

Results samples were exposed to all including are the three atmospheres at 700cC to observe III. in This the

The alumina and the cable 1000C evolution is based

in extensive of the

experiments products. types sulfur

sequential summarized observation

exposures in Table of of formed detection, was indicated of

The results of results:

on three of

products sulfates

SEM. the

detection only

by EDS and the amounts close the to table of

identification were of

by ESCA. Since the of analytical products (P)

very

small were in

products limit

in many cases the formation

and

techniques is If the reported only

their only

when it

by at products,

least Su

two techniques. was placed It of sulfur in

one

technique

suRRested

the presence

table. that the products were sulfates by the of purer the combined valency observations of the replicas this

was established in the products

by EDS and the

identification on the

sulfur 1 elements

as S-6

as in in

sulfates the

by ESCA. Moreover, were the was only

aluminas

de:ec:cd (L) that were

products also

aluminum and sulfur. thus

Extraction leading to the

on exposed conclusion sulfates

samples

showed sulfate

same combination, on the purer

aluminum

formed manner is with

aluminas,

Mg and Ca samples. to form and are

identified clearly decreasing

in a similar shows that there

on the more impure tendency impurity general

Table111 sulfates with with

an increasing increasing These

temperature, in the

contents trends

increasinR

SO3 pressure

atmosphere.

TABLE Results of Alumina Corrosion Experiment

III in SO3 Gas at 700 add 1000C for One Week

Tempe'rature (OC) 700

SO3 pressure (atm.) in approx. 1 atm 02 7.2 x 10-3 7.2 x IF4 7.2 x IO-' 1.3 x 10-3 1.3 x 10-4 1.3 x 10-5

Single Crystal Alumina P P N N N N

Polycrystalline (L)99.8% M)99.5% P P P P SU N P P P P SU

Aluminas S)97.4%"

P 1' P P P SU

P: N: su: *

Sulfur containing products present No sulfur containing products Presence of sulfur suggested but not confirmed Purity

Appendix

A-Gaseous

Corrosion

41

consistent (b)

with

thermodynamic analysis. formation

Thermodynamics of sulfate Considering the reaction:

Al*03+ 3SO3(g)= Al*(S04)3 at equilibrium one has: g_ a Al2 W4)3 a Al203 and the SO3 pressure The stability generated unit for the equilibrium Figure
(pso3j3

between hl2(SO4) 3 can be calculated. were

diagrams of

1 for A1303 in SO3-SO3 atmospheres equilibrium conditions reactions

bv considering for for

the appropriate phases.

assuming

activity

the solid

The test

and the relevant are shown on the

boundaries diagrams.

the HgO- Mg SO4 and CaO- CaSO4 equilibria

The oxide-sulfate
lower temperatures.

equilibrium Furthermore, increases tendency

boundaries

shift

to lower SO3 pressures mixture temperature. of 02- SO3 the Therefore,

ac

for a given initial with decreasing to form at lov experimentally: for sulfate

eqdlibfiumSO3 sulfates

pressure

have a greater

temperatures It is also

as shown by comparison obvious from Figure 1

of Figures that

la and 16 and observed required

the SO3 pressures

formations

increase activity this

from CaSO4 conditions the increase

CO ?IgSO4 and finally CaSC4 and YgSO4 will in product formation

co A12(SO4; 3 so thar under similar form more readily with increasing than contents Al?(SO4)3

explains

of CaO and YgO.

*Preliminary sulfates

results formed

obtained

by Raman spectroscopy (16)

also

indicated

that

on S alumina

42

High Temperature

Corrosion

of Ceramics

cao C&m*
4-

WN Me

log

POY
-lo -

Al203

A12(so4

-1a

-10 4

A12S3
-1(1 0 I

log

Psoa

Ow
4-

log

Por
-10 *

log
Figure 1.

PSOl

Stability diagrams for A1203 in SO@03 atmospheres at: (a) 700C (b) 1OOOoC. The experimental conditions (+) and the boundaries for CaO and MgO are also shown.

Appendix

A-Gaseous

Corrosion

43

Cc)

Single
Very

Crystal

little

reaction the

of

the

single at

crystal 700C and

alumina IOCWC.

was observed A few thin one week exposure but to to

during tetragons the highest the was was the material most inter-

exposure about

to any of

gas mixtures were detected III).

no

0.5 pa

on a side of

after

an exposure the same time could

of of

SO3 pressures mediate detected found gas

7000C (Table of SC3 at

For

pressure

70CC were lower

products indicated

be found

sulfur

by EDS and sulfates after

by ESCA analysis. at 700C the nor

NO sulfur for any of crystal were

exposure
at the

to

the

SD3 pressure results

compositions by for not be

IOOOoC. These environment

show that experimental of

single

was affected favorable should

when the

conditions

reaction. formed

The stability in any of

diagrams

Figure These

1 show that Al2(SC4)3 diagrams have been (e.g.

the experiments. of the

constructed Al2(SO4)3 considered (d) at

however less these

for

unit

activity activity may be

phases. in

Solid Al2O3)

solutions or other

than unit diagrams Aluminas aids the

dissolved formed.

phases not

in

Polycrystalline The sintering

added

to the its

(L)

material

degrade limits

its

purity

but

it

is

anticipated No magnesium The role of to of

that

MgO isilithin was found less clear

solubility

in A120,. or the electron microprobe.

spine1 Sin2 If its is

by optical and it is this

metallography may have enhanced would

solubility

in presence to segregate does not

MgD.(L6) the grain

solubility but

exceeded, has not but (17)

it
been

be expected

boundaries, at grain is

observed. even

MgO apparently though its average

segregate ion in this

greatly lnrterial

boundaries srr.alL.

Ca does

concentrat_

very

44

High Temperature

Corrosion

of Ceramics

More products crystal the three material.

were

evident were 7OOC.

on the evident

(L)

alumina

compared of

to

the

single to all of

Products at

after

exposures Figure

one week amount of were also

gas mixtures with increasing

As shown in

2 the

products observed than produce at any

increased at the

SO3 pressure. at

Corrosion III),

products but at

higher

SO3 pressure to the but formed

1OOOnC (Table

in less

quantity not

7oonc. observable

Exposure

intermediate sulfates on the were (L)

SO3 pressure identified did

1OOWC did

products

on specimens vary for were

by EDS and ESCA. the which cuboids. such of the as laths are

The products same exposure shown in Figure

alumina of

apparently, detected small

conditions.

Two types

morphologies (L) altiina.

2 and 3 for

as received but also

One is are grain

The other and films. grain strong due while

contains

many cuboids were of

other

shapes

evident faces

The prodlicts other faces of

concentrated grains

on certain exhibited

same a

these

no products of but the grain.

indicating This could the

influence to such

crystallographic segregation of

orientation impurities on these

nay be any products.

in part

surface

in no case or in

impurities

as Ca or Mg be detected ?iore corrosion

surfaces formed are all

products materials crystal. at the

on the

aluminas and of on all the

L.

M, S than on the impurity

single

crystal. than the all

These single

polycrystalline were at formed least more

greater

content materials at

Products 700C and

polycrystalline higher (Table impurity tha the

under 1000%.

conditions

under readily

SO3 pressure III) and were

In general.

products

formed

larger

and in greater in Figure

quantity relief for

(Figure

4) with

increasing in that

content.

The samples

4 were 700C

polished

and exposed

same axpari-nt products

(7 x 10-3atm.S03at at grain

one week).

It

shows

also

form preferentially

boundaries.

Appendix

A-Gaseous Corrosion

45

Figure

2.

(L) alumina surfaces (A) as received, B,C,D, exposed for one week at 700oC to 7 x 10-4 atm. 503 and 7 x 10-3 atm. 503 respectively. More products form at higher P503 (5EM)

46

High Temperature

Corrosion of Ceramics

Figure

3.

L alumina surfaces exposed to 7 x 10-3 atm. SQJ at 700oC for one week. A shows various morphologies of reaction products and 8 only a few discrete ones. (SEM).

Appendix

A-Gaseous Corrosion

47

Figure

4.

Relief polished polycrystalline A1203 surfaces exposed to 7 x 10-3 atm. 803 at 700oC for one week (a) L , (b) M, (c) another M-type (d) 8 aluminas. Products increase in size and quantity with decreasing A1203 purity. They form preferentially along grain boundaries. (8EM).

48

High Temperature

Corrosion

of Ceramics

Two types
atm SO3 for with or

of

products

were found
one other
was

on the
larger

(M) alumina,

exposed

to

7 ~10~~

one week at in it

700c.

and was a magnesium in size

sulfate little

no ca1ci.m

and the

smaller

was a CaSOh with

no magnesium. The lowest purfty (S) alumina had of the mosf product in both number Si, and Mg,

size Ca. solid

after

exposure.

EDS analysis

the

products

Indicated calcium MgSDq

S, Al,

They appear solutions. silicate in (S)

to be mainly The larger grains occur

magnesium products

sulfate, mostly

sulfate which

and their formed on impurity

were

magnesium phase( s) and along be on grains the of

identified grains

by EDS before of the size

exposure. of the

The impurity alumina CaSO4, grains appeared of the to large

as large

grain grain

boundaries. boundaries. and of included

Some smaller (Fi_eure products in the 51.

products, As indicated

mostly

by analysis techniques. that silicate (S) phases

products are

extracted products. of It

by replica is believed the

silicon silicon

and aluminum is present Al is is

the

as silica probably expected

formed dissolved

by reaction in the

SO3 with

impurities this
talc and clay

while

sulfates. the

In the impurity

alumina, Since

aluminum
are

to come mostly aids. of the corrosion of

from

used

as sintering

The evolution in of Figure exposures which 6, for from are

products

as a function sample

of (S)

time after

is

shown a sequence impurity number and the arrow

the

same area days to

a relief-polished The products micrograph

three darker relief

30 days. initial

nucleate

on the

phases contrast

on the polishing.

due to a weak acomic grow wirh coalescence marked by

and the

The products latter of stages.

coarsening is

occurring

ddring sulfate

the

The product content.

a calcium-magnesium

unknown aluminum

Appendix

A-Gaseous Corrosion

49

Figure

5.

Relief-polished 5 alumina exposed to 7 x 10-3 atm. 503 700oC for one week. EDS spectra (1) whole micrograph, areas indicated by numbers. (5EM).

at 2,3,4

50

High Temperature

Corrosion of Ceramics

Figure

6(a).

Same area of relief-polished (S) alumina exposed to 7 x 10-3 atm. SQ3 at 700oC. (A) before exposure, (6) for 3 days, (C) for 10 days, (D) for 30 days. (SEM).

Appendix
51

A-Gaseous Corrosion

~ tD... QJ CJ ..:3 ~'C .- 0. 00 .c QJ VI 0... ~ ~ /;;,~ 0 ~ CJ ~

E
'C:3 0 QJ '6' ~ ~ 0. QJ..~ ..~QJ ~ E ..r/)0. ~0.U QJ~r5 ..~ ~.,;< o.~.. ~:3 UVl ~o~ l1Jo.o

. VI ~QJ

<~~.. QJ

.. 'C0.~ ~... QJ ~U~ ~ ~bD

E ~C::

r/) <.0...0 ~~/;;, :3 ~ II .. ~ ~

52

High Temperature

Corrosion

of Ceramics

V. GENERAL DISCUSSION Ihe results silica than the the with occur and alumina metallic alloys. that are have been obtained in the present studies show that gas mixture when studies

considerably Nevertheless.

more resistant reaction are that of of

to sulfur-oxygen such materials

do occur present

thermodynamic experimental silica were

and kinetic conditions possible. reactions

conditions were In the such case

appropriate. of

In the the

no reactions alumina, affected

gas mixtures did of the

however, by the

reactions purity

and these

were

significantly

specimens. On the on the reactions with the than at this aluminas building possible in the it appears perhaps by solid case of the that to a layer of sulfate is than first absorbed The

sample are

thicknesses of crystal

giester the sulfate

a monolayer.

solutions single

probably the impurities form at lower to in PSO3 form out at

alumina other

and with sulfate

materials. sulfate

Calcium so that

sulfate their of

and magnesium solid solutions

aluminum PSO3.

maybe anticipated cannot be ruled

lower

The formation no such the is

intermediate are K20.3

compounds

point

although occur in

sulfates of

known with

Ca and Mg. Intermediate above 300% a mixed phases

compounds sulfdte and the role part the

sulfation formed.

A1203 in which were produced

K~u(Su4)3 grain of the

(lg).Sulfates for by the

on the aluminas;

impurity

boundaries the sulfate

as documented formation

the more impurities

impure

however, a major in

control in all the

appears explains

to play at least The formation is that

polycrystalline role only for of the

aluminas grain the of

studied. in force

This this for

prominent may not nuclei

boundaries driving sulfates. are alumina

corrosion. sulfate point due to

impurities also provide

increase the

but

growth the

A major formed, itself

when greater

reaction

products

involving

impurities of the

their

thermodyhamic

stability,

reaction

becomes

possible.

Appendix

A-Gaseous

Corrosion

53

The observation content with in is consistent where

that with

corrosion data in

of the

alumina literature

is

dependent reaction

upon of

impurity Sic and Si3N4

(19) for

oxygen

impurities products

such

as Mg and Ca have significantly on such

been modify

found the

to accumulate protective

the oxidation of the of

and thereby that are

properties

scales results

formed

materials. with the alumina the samples, of

In view deposits alumina of (hot

the

that

have been

obtained

Na7S04

can be expected because will is liquid. of

to significantly products should

influence have

corrosion

corrosion) This effect

these

significant

solubilities are formed

in NazS.04. such below solution emphasis that

be especially Moreover,

pronounced liquids the This

when temperatures to be involving with

the

Na7304

can be expected of is phases continuing

the melting of

ooint

Na7SOh due to phases. of ceramics.

formation research

Na7S04 and impurity corrosion

major

on the hot

IV CONCLUSIONS

(1) (2) (3)

(4)

Silica

and alumina was of

are

very

resistant

to

corrosion

by SO3 gases.

No interaction Small amounts

found

between were

SO3 and fused formed on the

silica. aluminas. under the more favorable quantities

products

The products conditions and at lower

identified on the high

as sulfates purity

formed

only

sapphire.

They

formed

in greater materials.

PSC3 on the more impure trends of from the sulfate

polycrystalline are are

(5)

The general with in

formation which at higher the

in qualitative that the corrosion

agreement of alumina

predictions SO3 gases

thermodynamics favorable that

becomesmore It is of of is

SO3 pressures sulfate with the time. dominated

and lower formed on the

temperatures. Single (6) (7) (8) crystal

suggested

aluminum solution with with

stabilized corrosion corrosion

by solid increases increases the

alumina. content.

The severity The severity In the

the the

impurity

polycrystalline

aluminas

impurities

the

corrosion

54

High Temperature

Corrosion

of Ceramics

by formation
The corrosion

of various products

solid-solutions

of

CaSO;- MgS04 on impurity

and

Alp

(So,)-,

formed preferentially

phases and at grain

boundaries.

Acknowledgements: The authors materials, preparation thank the 3M and Saxonburg M. Zedar Ceramics for Companies contributions for donating to the

B. Draskovich, of

and L. Fisher

the manuscript.

Appendix

A-Gaseous

Corrosion

55

References: 1. Anon., " Reliability of Ceramics for Heat Engine Applications". National Materials Advisory Board, Commission in Sociotechnical Systems NMAB-357. 2. A.F McLean, "Ceramic Technology for Automotive Turbines"
~~11. AIII.

&ram.

Sot. 61 (8) 861-71 (1982) 3. A.R. Cooper, "Kinetics of Refractory Corrosion" Ceram. Eng. Sci. Proc. 2. 1963-89 (1981) 4. R.H. Barkalow and F.S. Pettit, "Mechanisms of Hot Corrosion Attack of Ceramic Coating Materials" Conf. on Advanced Materials for Alternate Fuel Capable Directly Fired Heat Engines, Castine. Maine, Aug. 1979. 5. H.R. Kim u Gaseous Corrosion of Oxide Ceramics" M.S. Thesis University of Pittsburgh, 1983. 6. H.R. Kim, J.R. Blachire and F.S. Pettit "Gaseous Corrosion of Ceramics", paper 11411.164th Meeting Electrochemical Society, Washington, D.C. Oct. 1983.
7.

B. Draskovich, J.R. Blachere and F.S. Pettit, "Hot Corrosion of Silicon Nitride and Silicon Carbide", Basic Sci. Div. Fall Neeting sot., Columbus, Ohio, 1983 Am. Gram.

8.a W.D. Kingery, H.K. Bowen and D.R. Uhlmann, "Introduction to Ceramics", 2nd edition, Wiley, 1976. b. A.R. Cooper, Jr and W.D. Kingery, "Dissolution in Ceramic Systems: I Molecular diffusion. Natural Convection and Forced Convection Studies of Sapphire Dissolution in Calcium Aluminum Silicate", J. Am. Ceram. Sot. 41 (1) 37-43 (1964)

56

High Temperature

Corrosion

of Ceramics

c.

L. Reed and L.R. Barrett, "The Slagging

of Refractories CSUII. SOC. 63 ~~h

II lhe Kinetics of Corrosion", Trans. Brit. 534 (1964) 9.

M. Millard. H. Wuttig and H.U. Anderson, "Influence of Grain Boundaries on Liquid Corrosion of Al203 and N&l" sot. May 1982 paper No. 76-SII-82, An. Gram.

10. K.K. Kappmeier, ItThe Importance of Microstructural Considerations in the Performance of Steel Plant Refractories" in Ceramic Microstructures, R.M. Fulrath and J.A. Pask eds. Wiley, 1968, p.22 lla..D. Cubicciotti and K.H. Lau "Kinetics of Oxidation of Hot-Pressed Silicon Nitride Containing Magnesia", J. Am. Gram. 512-17 (1978) b. S.C. Singhal "Oxidation Kinetics of Hot Pressed SIC". J. Mat. Sci l_l, 1246-53 (1976) 12. R.A. Gardner, "The Kinetics of Silica Reduction in Hydrogen" J. Solid State Cliem9 336-44 (1974) 13. M.S. Crowley, "Hydrogen-Silica Reactions in Refractories" Bull. 14. Am. Ceram. Sot. 46 (7) 679-82 (1967) Sot. 61 (11-12)

L.J. Trostel, Jr, "Stability of Alumina and girconia in Hydrogen", Am. Ceram. Sot. Bull 46 (12) 950-52 (1965).

15.

D.E. Day and F.S. Gac. "Stability of Refractory Castables in SteamN2 and Steam-CO Atmospheres at 199OC, "Bull Amer. Ceram. Sot. 5f! (7 1 644-48 (1977)

16. 17.

A. Negelberg, private communication. I.K. Lloyd and H.K. Bowen "Iron Tracer Diffusion in Aluminum Oxide" J. Amer. Ceram. Sot. 64 (12) 744-47 (1981)

Appendix

A-Gaseous

Corrosion

57

18s. W.C. Johnson "Magnesium Distributions at Grain Boundaries in Sintered A1203 Containing Mg A1204 Precipitates," J. Am. Gram. 234-237 (1978). b. P.E.C. Franken and A.P. Cehring 'Grain Boundaries Analysis of ?!gO-Doped A1203", J. Sot. 61 (5-6)

Nat. Sci., l6, 384-88 (1981)

19. N.G. Krlshnan and R.W. Bartlett "Kinetics of Sulfation of Reduced Alunite" Environ. Sci. Tech, ,1,923-929 (1973)

Appendix
M.G. Lawson,

B- Hot Corrosion of Silica

H.R. Kim, F.S. Pettit and J.R. Blachere

INTRODUCTION There is a great emphasis which is dependent science parts, on advanced on higher working temperatures materials. As progress for heat engines

has been made in the reliability of ceramic

and technology they are beginning stress

of ceramics

leading to greater

to be incorporated device&).

in car engines

and other high serious resistance While in under

temperature-high candidates

Since ceramics understanding

are becoming

for these applications, conditions related

their corrosion

environmental ceramic

to these uses becomes oxides are quite stable

important.

compounds,

in particular

at high temperatures

air, the stability encountered, material e.g.

of ceramics

under various conditions must be established.

which might be At high temperatures metals in oxygen, a and

in a heat engine,

may not be stable of a material systems,

in presence

of some gases, i.e.

the degradation In combustion generated compounds complex

by reaction

with gases is called gaseous corrosion. such as NagC03, Nags04 may be these in a

various compounds to combustion

in addition condense

gases t2). Below some temperatures enhance

in the engine and often

the gaseous corrosion

process

named hot corrosion.

This type of degradation in ceramics.

is well known in

superalloys

but has not been studied

in detail

Silica forms as a protective atmospheres superalloys. on silicon carbide

scale at high temperatures and silicon nitride

in oxidizing on because However Although

and on some coatings environments

Vitreous silica is protective

in clean oxidizing

it is continuous

with some ability to self heal at higher temperatures. it is less protective in properties as it begins to crystallize@). from the same materials Ceramic Society

above llllO-12000C growing scales To be submitted

may differ

in bulk, it was

to the Journal of the American

58

Appendix

B-Hot

Corrosion

of Silica

59

believed corrosion ceramics

that valuable

information

could be obtained

from a study of hot of the hot corrosion relevant of to

of silica as a part of a systematic

investigation

(4). This paper covers the study performed with deposits of sodium sulfates.

under conditions

gas turbines,

HOT CORROSION Hot corrosion they affect materials. applies: is dependent upon temperature and the gas atmosphere since

the stability If the deposit

of the deposit

and its reactivity

with high temperature equation (1)

is in equilibrium

with the atmosphere,

Na2S04 (1) = SO3 (g) + Na20 (1) Kl = PSO3. a(Na20)

(1)

The activity temperature activity viceversa. equilibrium

of Na20 and the pressure

of SO3 in the melt are fixed by the by Kl. For pure Na2S04, and (1) for the for its

and PSO3 in the atmosphere

as defined

can be taken as unity, and as a(Na20) increases, An Na20 activity between of 2~1O-l~ was calculated

PSO3 decreases from equation

the melt and the S03-containing

atmosphere

selected

the hot corrosion lower. In presence

experiments

at 1OOOoC. The corresponding

activity

at 7OOoC is

of pure oxygen, the activity (l), it is expected to increase

of Na20 in the melt is not to values of the order of 10-6

defined by reaction

to 10s4 since SO3 and SO2 are evolved from the Na2S04 to the gas. These values are high and such Na2S04 melts are considered equilibrium of the deposit with the atmosphere basic. However only at the

may be established

beginning of the hot corrosion specific reactions

process and acid or basic behavior depends on the the sulfate and the ceramics.

that occur between

60

High Temperature

Corrosion

of Ceramics

EXPERIMENTAL

PROCEDURE

Materials The experiments reported here were all performed on a high purity fused

silica (Corning 7940). The major impurities ppm of chlorine. samples All other impurities

are 1OOOppmof water and lo-100 The

were in the ppm or subppm range.

were cut to about 1x1 cm in area and polished prior to exposure.

Gaseous Corrosion The samples mixtures were exposed in tube furnaces catalyst at 700 and 1000C. SO3-03 gas

flowed through a platinized The initial SO3 contents

in the furnace

before passing over

the samples.

of the gas were usually 1, 0.1 or O.Ol%, The corresponding equilibrium The exposure Weight changes

balance oxygen at a total pressure

of 1 atmosphere.

PS03 and PSO3 are given in table I. The gas flow rate was 1 cm3/s. time was usually one week but varied from one day to one month. were checked on an analytical balance.

The major tool was an SEM equipped EDS and crystal spectrometers by

with X-ray spectrometers WDS) for elemental

(Energy Dispersive,

microanalysis.

These experiments

were supplemented

ESCA. (X-ray photoelectron

spectroscopy).

Hot Corrosion The polished specimens aqueous solution were placed on a hot plate and sprayed layer of sulfate with an

of Na3S04 to form a continuous The samples

usually with a foil

loading of 5mg/cm2.

were placed in a boat lined with platinum Flow conditions conditions

and exposed in tube furnaces catalysts were as described

for times of 1 to 495 hours. for gaseous corrosion.

and of

The extreme

Appendix

B-Hot

Corrosion

of Silica

61

Table I SO3 Pressures Temp. (OC) 700

for Corrosion

Experiments S03(atm.) 7x10-3 (2) 7x10-4 7x10-5 1.5x10-3 (2) 1.5x10-4 1.5x10-5 (1)

Initial (SO2) (1) 1 0.1 0.01 1 0.1 0.01

1000

(1) (2)

96 S02-Balance Environments

02 - total pressure for Hot corrosion

1 atm.

experiments.

62

High Temperature

Corrosion

of Ceramics

table

I were selected

since they correspond

to relatively

acidic and basic oxygen (acidic) and

conditions.

They are the initial mixture of 1% S02-balance Since Nags04

pure oxygen (basic) at 700 and 1000C. equimolar experiments mixture

is not molten at 700C, an Cycling

of CoSO4 and Na2SO4 was used at that temperature. with or without

were also performed

water washing and reapplying

the salt usually on a 45 hours cycle. The weight of the coupons was checked sensitivity of 0.1 mg before salt application on an analytical and after balance with a

exposure once the salt was The washing

washed off in 10 cm3 of high purity water per cm2 of exposed area. lasted 20 minutes samples in an ultra sonic cleaner. The washwater

of some of the adapted previously coupon and was obtained

was analyzed

by EDS in the SEM using a procedure was deposited

(5~6). A single drop of the washwater dried. The deposit

on a beryllium and the spectrum

left on the coupon was analyzed after subtraction

processed

semi-quantitatively*

of a water spectrum

under the same conditions were examined

and scaled to the same background.

The specimens of

in the light microscope

and the SEM before and after removal for microanalysis crystalline products

the salt, however

the SEM with its X-ray spectrometers When possible,

were were

the major tools of this investigation. identified by X-ray diffraction

with a diffractometer. on photographs Contact

The wetting of the droplet

angle of the profiles taken

salt on the substrates

was measured

in the SEM at room temperature. by this method(7). micrographs The crystallized

angles have been measured were measured

previously

thicknesses

on SEM

of cross sections

of the coupons.

* SSQ software

by Tracer-Northern

Appendix

B-Hot

Corrosion

of Silica

63

RESULTS AND DISCUSSION Gaseous corrosion The gaseous corrosion(*) corrosion(g). was studied for comparison were detected, with the hot were visible in the of the specimens

No weight changes

no products

SEM and no sulfur was detected

by EDS or ESCA on the surface

after exposures smallest

up to one month under the conditions

given in table I. While the would require examination a

weight change that could be measured

(0.1mg/cm2)

uniform deposit

of the order of 1 urn, the SEM with careful An estimate

and

ESCA are much more sensitive. products in the SEM is

of the detection

limits of discrete

10m7 to lo-* g/cm2. SEM could be detected microanalysis 10mg g/cm2. No evidence

Under these assumptions*

sulfur in the products technique, not a

seen in the

by EDS. ESCA is a surface and its detection

technique,

limits were of the order of lo-* to

of degradation

or formation

of solid products

containing

sulfur

was found in these experiments. no reports expected of the existence

This might have been expected

since there are

of a silicon sulfate,

and no silicon sulfide was since the oxygen pressure of silicon sulfide has been above 1000C because No at 700 and

to form under the experimental

conditions

was always around one atmosphere. discussed sulfate recently(lOl.

The formation

No experiments less favorable

were performed

deposition

becomes

at higher temperatures.

devitrification

of the silica was observed

after any of these exposures

1OOOoCin many experiments reported

for times as long as 720 hours.

Others have

that SO2 has a fluxing action on fused silica.

* A 1% coverage with islands 20nm thick containing 20% sulfur was assumed for the calculation of the limits of detection using SEM and EDS. In ESCA, 0.1% of a sampling depth of 5nm was assumed.

64

High Temperature

Corrosion

of Ceramics

Wetting by sulfates The wetting angles of the salts used in the hot corrosion They are given in table II. The general experiments wetting varied morphology

with the environments. developed occured

in a few minutes at the temperature with time with the wetting wetted the silica better small droplets increasing

of the experiments.

Some evolution In general

from 1 hour to 24 hours.

the sulfate

under basic conditions were formed.

than acidic conditions

under which discrete conditions

After 24 hours under acidic and 13O on an at 1000C

at 1OOOoCthe wetting

angle was 24O on the droplets

exceptionally the salt wetted measured;

large drop about 0.02cm across. most of the coupon after 24 hours the wetting

Under basic conditions

1 hour, and a wetting

angle of 2O was

after

was continuous. wetting

In some cases, the salt formed drops of several sizes and different angles were observed measurements for different size-range (table II). The wetting

angle

were very reproducible

for given size range.

The angles reported terminology wetting are

are called wetting

angles and not contact was reached. of atmosphere

angles since the latter

may imply that equilibrium with time and the influence occuring between the sulfate

It is clear from the increased on the wetting that reactions

and the silica surface, with the affinity wetting

even under acidic conditions. the liquid and the

The wetting substrate conditions

tends to increase

between

surface reflects

and the greater the higher affinity by careful

of the silica by the salt under basic

of the basic salt for the acidic silica. of the same areas of samples between sites. cycles, This

It was established which were cycled, that the droplets suggested

microscopy

with washing off the salt and reapplication preferentially local attack

did not reform

on previous droplet

that no preferential

would occur under acidic conditions. reported below.

This conclusion

was substantiated

by a long term experiment

Appendix

B-Hot

Corrosion

of Silica

65

Table II Wetting Angles of Na2 SO4 on Silica (O)

lhr. Acidic 52

7oooc (1) 24hr. 36-49 t3)

lhr.

1ooooc (2) 24hr. 13-24 t3) 0

Basic

26 t4)

(1) (2) (3) (4)

(Nag Co) SO4 Na2 SO4 Range of angles with drop sizes - smaller angles for larger drops. Salt phase separated.

66

High Temperature

Corrosion

of Ceramics

Hot Corrosion Under acidic conditions, droplets. the deposit mg/cm2 localized suggested in water. losses. At 700C the weight by washing there 24 hours. the salt did not wet well the silica and it formed changes were small, for example, after after removing

were losses of 0.1 mg/cmz of devitrification

1 hour and 1.1 Some

after

No evidence

was apparent.

corrosion

occurred

under the droplets, formed

as shown in figure 1. It is by dissolution of sodium silicate

that this wormy void texture This corrosion The attack was very limited preferentially

as indicated

by the small weight of the after

occurred an interaction

under the salt at the perimeter No spalling occurred was washed and salt had a strong texture This attack observation

drops suggesting

with the atmosphere. of the silica. cycles. The sample

495 hours of cyclic exposure reapplied exposure surface droplets (5 mg/cm2) between

The substrate sodium.

after

and a region 33 urn thick contained of the coupons is consistent did not reform

over the whole that the of the salt. and the silica

with the separate after

at the same locations

reapplication had improved

Under acidic conditions, was devitrifying characteristic Devitrification was detected than at 700C. compared silicate probably established spherulate

at 1000C the wetting After

under the drops. patterns occurred outside intermediate

24 hours the cristobalite spherulitic

formed

between

and globular (figure 2). of attack

also under very small drops and no evidence The weight loss of 0.3 mg/cm2, by the greater stability

the drops.

was smaller

This can be explained

of the cristobalite of less sodium

to the vitreous to dissolve offered

silica which will result in the formation The cristobalite protection occured

in the salt. some general

layer which did not spall silica but it was not between the

to the vitreous

if preferential

attack

at the boundaries

fibrils as reported

for silicon carbide

under similar conditions(l2).

Appendix

B-Hot

Corrosion of Silica

67

Figure I.

Hot corrosion of fused silica under acidic conditions, 24 hoursat 700oC. SEM of sulfate drop area after washing off sulfate showing wormy voids formed preferentially at edge of drop.

68

High Temperature

Corrosion of Ceramics

Figure

2.

Fused silica exposed for 24 hours under acidic conditions showing coarsened spherulites under sulfate drops (after washing).

Appendix

B-Hot

Corrosion

of Silica

69

Under basic conditions at 7OOoCthe salt tended to decompose with extensive formation of cobalt oxide which complicated

the interpretation

of the

data, particularly weight change. Under the salt drops there was limited formation of cristobalite spherulites mixed with some random globules after 24 hour exposure and some localized cracking (figure 3) but there was no evidence of spalling or extensive attack of the substrate. The most extensive degradation of vitreous silica occurred under basic conditions at 1OOOoC. After 1 hour the salt wetted the coupon almost completely and a layer of cristobalite spherulites had formed under the salt. As shown in figure 4, the fibrils of the spherulites had already broken down significantly into arrays of globules. The spherulites had grown to impingement with radii of the order of 30 pm, underlining the high velocity of the surface crystallization. After 24 hours nothing was left of the spherulitic surface Cristobalite

morphology as tridymite had formed at the silica-salt interface. separates the tridymite from the vitreous silica.

After 212 hours the tridymite

near the surface had coarsened into laths about 15 pm wide and over 60 pm long. The crystalline layer spalled extensively. The washwater analysis indicated that significant silicon was water soluble with the sulfate after 1 hour, however this was no longer found after 10 or 100 hours. The sulfur was never depleted as the Na/S ratios in the water remained of the order of 2 (t 0.4). This suggests that less reaction occurred after a continuous crystalline layer was formed and that at the longer times sodium silicates with low solubility in the sulfate at 1OOOoC formed between the crystalline silica and the sulfate. It became clear, as the previous results were obtained, that the major mode of degradation of vitreous silica under hot corrosion conditions was due to the crystallization and associated spailing. Qualitatively the extent of the degradation at constant time increased in the order:

70

High

Temperature

Corrosion

of Ceramics

Figure 3.

Fused silica exposed under basic conditions at 700oC for 24 hours. Limited nucleation occured in small portions of drop areas.

Appendix

S-Hot

Corrosion of Silica

71

Figure

4.

Fused silica exposed to basic conditions at lOOOoC for 1 hour. The fibrils of the spherulites have broken up into globular arrays.

72

High Temperature

Corrosion

of Ceramics

Acidic 7000 < Basic 700 < Acidic 1000 < Basic 1000C The degradation equilibrium emphasized increases with increasing Nag0 activity in the salt and decreasing results quantitative

PSO3 under these conditions. the degradation associated

Since the hot corrosion with the devitrification,

data was obtained

on the crystallization.

Kinetics

of Crystallization of crystallized conditions silica was measured on fused silica under The The of the

The thickness basic hot corrosion measurements isothermal

at 1000C for times up to 300 hours. region of fractured

were made on the unspalled

specimens.

kinetics

are shown in figure 5. They are for the propagation interface. The plot is parabolic and the incubation with exposure

cristobalite-glass under an hour. 46 hours. as described

time is cycles of

A long term experiment cycles,

was performed

In between previously. cycled.

the salt was washed off and new salt was reapplied the samples and had

Since this was done at room temperature, Extensive spalling of the crystalline

were thermally the thickness propagated

layer occured

of the remaining at the interface.

silica glass was measured The plot of the thickness

where the fracture crystallized

for 6 cycles

is given in figure 6. The plot is linear instead crystallized experiment

of parabolic

and the total thickness In a separate reapplication It

(about 1000 urn) is over twice that without of 100 hours total duration,

cycling.

a sample was cycled without after

of salt by cooling to room temperature had the same layered cycled or uncycled, tridymite structure

1 hour and 10 hours of exposure. after the long exposures, layer, a layer

as the other samples

(figure 7). One can identify

a thin sodium silicate The crystallized

layer and a cristobalite

layer over the glass.

had a thickness

of the order of 400 urn which is also about twice the thickness

Appendix

B-Hot

Corrosion

of Silica

73

I/2 TIME (Hours)

l/2

Figure

5.

Kinetics corrosion

of cr,stallization of silica at lODOW in Oxygen.

glau

during

basic

hot

74

High Temperature

Corrosion

of Ceramics

900
800

600

500 400

300 200

IOC

CYCLES (48 Hour, Resa It)

Figure 6.

Kinetics of crystallization of silica glass exposed to basic hot corrosion at 1OOOoC in Oxygen, with 45 hours cycles and reapplication of sulfate. Note linear kinetics.

Appendix

B-Hot

Corrosion of Silica

75

+"..'0 01 ~ C

1n~0I C tI ~
.-~ +" '0>.>. Col'O .0tI In 01 ... tI .-~ In~~oIC+"ba .a .-~ .. -tI C tI .-.c .->.+" '0 tI .;n .c ~In 0 01 e +" .-

0 .-In -

M-ln

0.

~ .-

tI .-.c -+"w

><..'0... ..~ 0 -.Clnol 0I...~+"

~

tI
C 0

tI 1n~>.C ~ .'0 ~~.Cln In ~ E-o .~O .c IntI OO~:c CO-~ ba O

c ...
..+" 0 ....

4i...0InUO~ 1n0 eO Inoln... E o ~ .~

U .C..

tI

~
GI .. ~ ~

76

High Temperature

Corrosion

of Ceramics

crystallized

for the same time under isothermal and the change

conditions.

The larger rates

of

crystallization strong influence

in the type of kinetics

under cycling show the damage under and

of the salt on the crystallization is due to the stresses of the salt.

but the increased generated

the cycling

experiments

during the cycling

not to the replenishing

General

Discussion was greater under basic than under acidic conditions. The

The wetting wetting

angle decreased

in the sequence:

Acidic 700 > Basic 700 > Acidic 1000 > Basic 1000C The increased wetting at higher temperature (lOOOC) under acidic conditions as predicted a substrate from and a is

due to a decreased equation

acidity

of the salt at higher temperature free energy of a reaction energy balance between

(1). The negative

liquid enters the wetting behavior indicate

in the interfacial tendency

of a sessile drop so as to increase Therefore the wetting on it

of the solid by the liquid(ll). the influence

of the salt and in particular a tendency towards

of the atmosphere to a reaction

basic fluxing according

of the form: (2)

xSi02 + yNa20 = yNa2OxSiO2

I(2 = a&/

(aSiO2)x. (aNa2O)y activity asil=l, y=l and x=2, the equilibrium 11. Therefore reaction 2 should proceed conditions

Assuming constant

that the silicate

at 1000C gives aNa20=9.2xlOis greater

to the right when aNa for equilibrium should therefore performed

than this value.

The experimental

with 1.5x lo-5 atm So2 which correspond not be .sufficient to form the silicate.

to aNa20=2xlO-15 A similar analysis was

by Jacobson

et. al for the corrosion

of silicon carbide(13).

However

Appendix

B-Hot

Corrosion

of Silica

77

the wetting

behavior,

the crystallization

and the reaction

of the sulfate

with the so

silica indicate

that the equilibrium

is shifted

to much lower values of aNa

that at least locally all conditions basic to permit least partially for reaction

for this work might have been sufficiently to the right. This can be explained phase and the phase was observed to form under at

2 to proceed

by aSiO2 > 1 since the glass is not an equilibrium decrease its stability. at 1000C. A discrete silicate

OH and Cl impurities

under long term basic exposures strongly basic conditions

It is only expected activity

where the silicate

might get close to 1. In the the silicate formed is

less basic experiments dissolved in the sulfate

and early in the basic experiments and has activities

much less than 1. the fused silica and the sodium sulfate,

Some limited

reaction

occurs between

even under the less basic conditions these conditions, accumulated hot corrosion

at 700C (acidic 700C in table I.) Under of the salt, significant The quantitative (2) was limited effect hot corrosion of the of cobalt under all in

with cyclic replenishing

over long term exposures. on the basis of reaction

interpretation

by the presence

the melt at 700C and the overwhelming conditions except

of the crystallization

the less basic (acidic 7OOOC). Neglecting between

these complications,

the major interactions They are the dissolution salt and diffusion basic conditions, exposure

the salt and the silica occur at their interface. formed via reaction (2) in the

in the salt of the silicate

of sodium into the vitreous the Si content

silica.

Accordingly,

under the more

of the washwater

increases

early during the crystallizes; after a

but decreases

later as the silica at the interface

long time a silicate washing). observed clusters

layer is detected

on top of the crystallized this reaction

silica (after leading to the

Under the less basic condition, wormy texture. in the fused silica. It is proposed

is localized

that the reaction

begins at impurity only to one

The OH and Cl impurities

are connected

78

High Temperature

Corrosion

of Ceramics

silicon and they may generate susceptible to attack

microregions

with more open structures

more (acidic

under reaction

(2). Since for the less basic condition is small, the influence

7OOoC), the driving force for the reaction is emphasized products and it will be suppressed As a result

of these defects of the gaseous

by increases

in concentration

in the salt.

it occurs

more readily is released

near the edge of the salt

drops (figure

1) where the SO3 produced these defects observed after

more easily to the atmosphere.

Under more basic conditions in the surface interaction morphology

may play a role, but it is not as obvious corrosion. Others have reported no

of Na2SOq with fused silica under acidic conditions(14). experiments which included

This was not

the case in any of the present Some of that difference impurities expected expected discussed to contain

lower temperatures. of the environment here are are

in behavior

may be due to the influence in combustion studied

above.

Silica scales formed

OH impurities,

so that the samples of industrial

to be more representative rapidly

applications. diffusion In type III silica

Sodium diffuses coefficients

into fused silica with reported

(DNa) of the order of 10s6 cm2/s at 1000C(15). experiments, it was pointed

glass such as used in the present sodium. In a recent discussion

the OHs may slow down the out that impurity and structure

seem to affect modifier(17)

DNa( 13). Sodium can be incorporated the reaction: Na20 + Si-0-Si

in the glass as a network

through

= 2Si-O- + 2Na+

(3)

(CSiO)2. (CNa)2 g3 =_________________ Cst. aNa in which an oxygen bridge (Si-0-Si) oxygens to incorporate network modifiers, has been broken into two single bonded The sodium ions, as near the single bonded

the oxygen into the network. in holes of the structure

are located

Appendix

B-Hot

Corrosion

of Silica

79

oxygens.

The oxygen bridges

most likely to be broken are the more strained is Cst. Although

in

the structure(l6), associated

and their concentration

the sodium ions are These

with single bonded oxygens are important

they are mobile in the structure. of silica formers

considerations concepts oxidation

in the oxidation

and similar of water on the to increase

have been used by Schaeffer of silicon(lg). The penetration of Nat0

to discuss the influence of sodium is expected

rapidly with the activity and probably the mobility

in the melt as it increases

the driving force of Na+. Diffusion diffusion(20). of

of Na+ for the low concentrations in terms by reaction

sodium in silicate Initially

glass has been discussed

of a vacancy

it must enter the glass structure If this reaction present

3 which could be rate between protons the

controlling.

is slow it is likely that ion exchange

of the hydroxyls situation

in the glass and sodium might play a role. of the silica glass.

However, of

is modified

by the crystallization is very difficult

Diffusion the

sodium through channels

cristobalite

since it does not contain is probably easier

of vitreous

silica or quartz.

Diffusion

along the grain

boundaries. Since it breaks up the network, crystallization member rings. reaction 3 is expected to promote the to 6-

of silica and the required In this research, (acidic,

rearrangement

of the network

the silica did not crystallize

under the lower under the more increased with (3). to

Na30 activity basic condition.

700C) but it did at the same temperature the extent of the crystallization discussion

Qualitatively, as expected

the Nag0 activity From reaction (aNaaO)*.

from the previous

and reaction

3, the concentration

of single bonded oxygens of sodium on the crystallization

is proportional

The strong influence

of silica is well

know in ceramics(21), conditions

here it has been shown that under basic hot corrosion proceeds at a rate of the same order as in oxygen or an enhancement

at 1OOOoC the crystallization

that observed

above 1400C on the same materials

80

High Temperature

Corrosion

of Ceramics

of many orders of magnitude results on the crystallization

due to the sodium. of sodium silicate

This is in line with previous glasses(21). Much greater rates

of crystallization, soda silica glasses

of the order of 0.1 mm/min. with Na20 contents

have been observed

at 1000C in

of the order of 1%. This shows that only to obtain the

very low concentrations crystallization

of sodium, in the ppm range are necessary observed

rates of the order of 0.01 -0.1 um/min.

here. Na20 activities silica,

Under the more basic conditions, lead to dissolution however

at 1000C, the greater

in the salt as well as sodium penetration

in the vitreous The

this is short lived because of the onset of devitrification. and the resulting spalling as the specimens inversions

devitrification a-g cristobalite contraction degradation under cycling penetration degradation

are cooled through

the

and the a-B-y tridymite

as well as the differential for most of the degradation scale and little

of the crystalline

phases on cooling are responsible The increased

of fused silica under basic conditions. is due to the cracking

and spalling of the crystalline

of the salt through the cracks. was observed with no significant

In line with this conclusion, increase

under cycling for the less

basic condition

at 7OOoC (acidic 7OOoC) for which the silica did not crystallize. for most of the observed conditions degradation the crystallization

Since it was responsible

of silica under hot corrosion The crystalline instead similarity cristobalite conditions spherulitic nucleate of tridymite between

will be discussed

extensively. which forms of the greater silica(221. The

phase formed initially

was always cristobalite because

since a lower energy path is available the structures of high cristobalite (figure 2-4).

and vitreous

was globular cristobalite formation.

in morphology

Under the more basic to their

globules were aligned in radial arrays related Under less basic conditions the spherulites

did not by the drops

under all the salt drops or over the whole areas covered

Appendix B-Hot

Corrosion of Silica

81

and for less basic conditions even after globules between different reacts nearly 500 hours. randomly

yet (acidic 700C) no crystallization Under the intermediate conditions,

was observed cristobalite formed or in by two

formed

under the drops where no spherulites that the crystallization

spherulites. mechanisms

This suggests depending

was initiated

on the Na20 activity.

In both cases the sulfate and shown in reaction reactions (1) and

with the silica by basic fluxing as discussed with SO3 pressure Na20 activities spherulites, is obtained

earlier

2. The relationship

by combining nucleated

(2). Under the greater glass interface their fibrils,

the cristobalite

at the sulfateof

and formed however

with the well-known suggest

radial morphology concentration These

the previous

results

that a threshold

must be reached fibrils coarsen arrangements

for the nucleation

of the spherulites

at the interface.

and break down due to interfacial of globules. The spherulites

instability

giving the radial layer in which down the

grow in a thin surface

high Na20 activities network, (reaction

promote

the crystallization

of silica by breaking

3) and silica is transported

rapidly through the liquid phase. basic conditions, the surface ions dissolved

On the other hand under intermediate reaction of the sulfate diffuse

with the silica is less extensive, into the sulfate

the silicate

in the sulfate crystallization silicon, decreased reaction

away from the interface

on which no of

is initiated. as silicate,

At the same time it is likely that the solubility in the sulfate decreases as the activity

probably

of Na20 is Thus as the

as reported proceeds

by Kim(22) in the same range of activities. gradients of Na20 activity

at the interface,

and SO3 pressure as it diffuses

are set up across the salt. away from the interface precipitation cristobalite

The solubility

of the silicate

decreases

leading to supersaturation

and homogeneous the random globules of

of silica in the salt which generates (figure 3).

82

High Temperature

Corrosion

of Ceramics

Discussion of Crystallization Kinetics The crystallization of silica which has rapid parabolic kinetics under the more basic isothermal conditions is not controlled by the transport of reactants or products through the crystalline layer, since the crystal has the same composition as the glass. As already discussed qualitatively, the very large rates of crystallization are associated with high Na30 activities. The sodium breaks

oxygen bridges according to reaction (3). It is proposed that the crystallization begins when a threshold Na30 activity is present at the silica glass-sulfate interface generating sufficient concentrations of oxygen bridges to allow the local rearrangement of the network to the crystalline form. This could occur by a mechanism similar to that proposed by Fratello et. a&18) for the high pressure transformation of fused silica to quartz. The sodium in Si-0-Na groups would play a role similar to that of hydrogen in SiOH bonds, although the ONa bonds are more ionic than the OH bonds and as a result they were considered ionized in reaction (3). Since it is less tightly bound to the oxygen and because of size considerations, the Na+ is more mobile than the protons(24). The active defects sre still the non-bridging oxygens which are very mobile in combination with either thermally created single bonded oxygens, SiOH or other SiO- Na+ groups. The single bonded oxygens can attack oxygen bridges by simultaneous bond formation and breaking, and reshape the network into six member rings. After nucleation the crystallization front propagates at rates many orders of magnitude greater than in the pure system. From the present results this is due to the sodium which catalyses the crystallization. It has to be present at the

cristobalite-glass interface, although it could not be detected with the electron microprobe, except in special cases. Only very small quantities of sodium are required for the previous mechanism which can rapidly propagate a crystal ledge into the glass.

Appendix

B-Hot

Corrosion

of Silica

83

In such an interfacial the controlling kinetic

reaction

a sodium can rapidly rearrange Si-0 bond(l@.

many bonds and Adapting this of the of have a

step is the break up of a strained of the interface

model the rate of advance

(u) should be a function to the concentration The hydroxyls

stoichiometry

of the silica and directly

proportional

sodium which take the place of the hydroxyls mobility previously sessile(z51. 3 to 4 orders of magnitude that most hydroxyls smaller

in the model.

than Nalz41. It has been suggested silicas are strongly bound and nearly

in synthetic

The sodiums are highly mobile although

in small concentrations. in the moving interface. Soon this cristobalite

The concentration During the induction diffusion is essentially

of sodium ions is not constant period some sodium diffuses stopped by the formation

into the glass. of a continuous

layer, as discussed cristobalite-glass and essentially Neglecting cristobalite, interface

earlier. interface

In the proposed

model, the sodium at the through the glass

is supplied by this original diffusion crystalline

trapped

once a significant

layer has formed. in the

any diffusion

through the crystalline

layer and the solubility

one can approximate with the cristobalite initially

the concentration

of Na in the glass at the area, representing as a function the

as a spike of constant

sodium injected

into the glass, which spreads

of time

(figure 8). This spread which is due to the sodium diffusion slowed by the rejection

into the glass is front. Based to

of the sodium ahead of the crystallization of sodium CNa at the interface decrease

on this model, the concentration decrease

is expected

with time in line with the observed Quantitatively the constant

of the rate of

crystallization. as:

sodium in the spike can be written

cNa.(Dt)+ = s

84

High Temperature

Corrosion

of Ceramics

idym.

%I,0

Figure 8.

Proposed mechanism of crystallization of silica during basic hot corrosion. (1) Diffusion of Na into glass, nucleation of cristobalite; (2) A continuous layer of cristobalite forms rejecting Na; (3) with cristobalite growth the Na concentration at the cristobalite-glass interface decreases by diffusion into the glass.

Appendix

B-Hot

Corrosion

of Silica

85

in which D is the diffusion

coefficient u is

of Na+ into the glass and t is the time.

And the rate of crystallization

u = dx/ dt = A CNa+ = A S / (Dt)*

which integrates independent x=kt*

to x = B tt / Dt and if D is

of time, x takes the form:

which predicts the thickness constant

the observed

parabolic

behavior.

In the previous

discussion, at

x is

of the crystallized

layer while S, A, B, and k are constants

temperature. is supplied mostly

One could still assume that the sodium at the interface be diffusion through the crystalline changes

layer by grain boundary diffusion

however

the cristobalite to tridymite parabolic

grain size by over an order of magnitude side without significant

and it transforms from the reaction,

at the salt interface Furthermore

departures

behavior.

Na is not consumed

in the crystallization interface and since it

it is rejected catalyzes

into the glass at the cristobalite-glass one cannot expect behavior.

the crystallization parabolic

a falling rate of crystallization it is concluded that the

such as the observed mechanism proposed

Therefore

above provides

a better

explanation.

Hot Corrosion

of Silica Pormers results are in general agreement with the protective properties on

The present

of silica scales on ceramics superalloys.

(silicon carbide

and silicon nitride)

and coatings

The silica was not affected

by the SO3-SO3 containing

environments conditions.

of this study, however

sodium plays a dramatic

role under hot corrosion

86

High Temperature

Corrosion

of Ceramics

The vitreous particularly crystallization

silica has a tendency

to react

with Na2S04 by basic fluxing, it is very sensitive cycling. to Under not will

at low PSO3, but more importantly which promotes

spalling through temperature affected

these conditions

silica scales should be strongly to silica formers.

and fundamentally of these conclusions

afford good protection

The validity the nature

depend on the purity of the silica formed, with the sealest sensitive

of the impurities

associated are more

and the rate of growth of the scale since thick scales It is likely that OH impurities Although only indirect promote

to spalling.

the hot corrosion here, it is

and crystallization. expected

indications

are presented

from the role of OH in glasses( 18p2@. This is important structural applications since water is a major product

for high of

temperature combustion.

The results than vitreous devitrification.

suggest

also that some silicate

scales

might be more desirable without

silica if they could be used at high temperatures

CONCLUSIONS - No evidence of gaseous corrosion was obtained in atmospheres containing initially up to 1% SO2 and balance oxygen at 700 and 1000C for times up to 720 hours. - No devitrification was observed experiments in pure oxygen. under these conditions and similar

- The wetting of the silica by the sulfate varied significantly with the PSO3 and the Nap0 activity. It increased with aNa20. It was greater under basic than under acidic conditions at both temperatures. Under basic conditions at 1000C the wetting was complete. - In all cases there was a tendency with the activity of Na20. towards basic fluxing which increased

- Some limited corrosion was observed under acidic conditions at 7000C. At 1000C under the same conditions, the silica devitrified and little reaction was observed between the salt and the silica.

Appendix

B-Hot

Corrosion

of Silica

87

- The most extensive degradation of vitreous silica occurs by crystallization and the associated spalling during temperature cycling. In general it increased with the activity of Na20 and was very severe under basic conditions (pure oxygen atmosphere) at 1000C. - The sodium accelerates (catalyzes) dramatically the devitrification of silica and the rate of crystallization at 1000C under basic conditions is of the same order as that observed by others at 1400C in air (without sodium). - The kinetics of crystallization at 1OOOoC under basic conditions were parabolic with a short incubation time. Cycling increased the damage and changed the kinetics to linear. The extra damage was associated with the strains due to cycling not with additional salt applications. - The parabolic behavior observed under isothermal conditions can be explained with a model in which the crystallization is controlled by the sodium at the crystal-glass interface which diffuses into the glass prior to crystallization. - The need for the development of vitreous ceramics and metallic alloys is stressed. coatings for the protection of

Acknowledgements The authors gratefully of the Department acknowledge the support of Basic Energy Science Division

of Energy for their financial

support.

REFERENCES M. Taguchi, Adv. Ceram. Heat Engine Ceramics, Mat. 2 [4] 754-762 (1987). Bull. Am. Ceram. Sec. 64 [Z] 268-294 (1985). Oxidation of

1.

a. b.

2.

N. Birks and G.H. Meier, Introduction Metals, Arnold 1984, Chap. 8. P.J. Jorgensen et. al, J. Am. Ceram.

to High Temperature

3. 4. 5. 6. 7. 8.

Sot. 42 (12) 613-616 (1959). of Ceramics, M.S.

J.R. Blachere and F.S. Pettit, High Temperature Corrosion DOE Basic Energy Sciences DEFG OZ-84-ER45117. B. Draskovich, Hot Corrosion of Silicon Mitride Thesis, University of Pittsburgh (1984). J.I. Goldstein et. al, Scanning Electron Plenum, (1981), p. 378. L.E. Murr, Interfacial (1975), p. 69. Phenomena

and Silicon Carbide,

Microscopy

and X-ray Microanalysis,

in Metals and Alloys, Addison-Wesley, M.S. Thesis, University of

H.R. Kim, Gaseous Corrosion Pittsburgh (1983).

of Oxide Ceramics

88

High Temperature

Corrosion

of Ceramics

9.

M.G. Lawson, Hot Corrosion of Pittsburgh (1987). 0.0.

of Silica and Alumina,

M.S. Thesis,

University

10. 11. 12. 13. 14. 15. 16. 17. 16. 19 20. 21. 22. 23. 24. 25. 26.

Vander Biest et. al, J. Am. Ceram.

Sot. 70 [7] 456-59 (1987).

I.A. Aksay et. ai, J. Phys. Chem. 78 [12] 1178-1183 (1978). J.R. Blachere et. al, Paper #77-BEG-86P, Sot., New Orleans (1986). N.S. Jacobson, N.S. Jacobson 1987. G.H. Prischat, G.H. Prischat Workshop on Corrosion Basic Science Div. Am. Ceram. Nov. 1987. Nov.

in Ceramics,

Pennstate,

et. al, Workshop on Corrosion J. Am. Ceram.

in Ceramics,

Pennstate,

Sot 5_1[9] 528-530 (1968). Solids 7l, 77-85 (1985). Wiley (1976) p. 103.

and W. Beier, J. of Non-CrystaLline to Ceramics,

W.D. Kingery et. al, introduction V.J. FrateIlo

et. al, J. Appl. Phys. 51 [12] 6160-64 (1980). J. of Non-Crystalline Solids, 38 and 39 (1980), 545-550.

H.A. Schaeffer,

Z. Boksay: Mass Transport in Non-Crystalline Solids, in The Physics of Non-Crystalline Solids, G.H. Frischat, Ed. Trans. Tech., (1977) p. 428. H. Rawson, Inorganic Reference 17, p. 314. University of Pittsburgh, (198-). Glass-Forming Systems, Academic Press (1967), p. 53.

G.M. Kim, M.S. Thesis, R.H. Doremus,

Glass Science,

p. 168. 3 19 (1966).

R.W. Lee and D.L. Fry, Phys. Chem. Glasses, Reference 24, p. 229.

Appendix
M.G.

C-Hot
Lawson,

Corrosion of Alumina
F.S. Pettit, and J.R. Blachere

INTRODUCTION Failures due to corrosion limit the selection of materials in countless operations. The corrosion of ceramic materials is a significant factor limiting the design of new systems for coal gasification, coal liquification, energy conversion, thermal storage, and the battery storage of power. (l) Advances in the science and technology of processing, fabricating, and testing of brittle materials have resulted in ceramic parts with mechanical properties acceptable in a broad range of energy related applications. Severe material degradation is common in environments where the combustion of fuel occurs. As superalloys and complex cooling systems have been developed the operating temperatures of turbine engines has been raised to increase their efficiency. Many of the raw materials used in superalloys are expensive and can Low heat rejection diesel

be obtained from a limited number of foreign sources.

and gas turbine engines are in development which allow a substantial decrease in the size of power source, primarily due to the elimination of bulky cooling systems.(2T3) The continuing development of more efficient and compact engines as well as the reduction of cost and dependence on strategic materials is dependent on advances in materials technology. In addition to being inherently refractory

and resistant to corrosion, most ceramic materials are available from domestic sources and are much less expensive than the elements used in superalloys. Although ceramics tend to be refractory, the corrosion of ceramics occurs at an appreciable rate in many systems. This is reflected in cost of refractoris used by the steel and glass industries. The research resulting from the

89

90

High Temperature

Corrosion

of Ceramics

widespread

use of ceramics

as vessels

to hold and direct of the corrosion

the flow of molten

metal

and glass has led to an understanding of a melt. Alumina pure forms. superalloys. of deposits corrosion is an excellent It is also generated Its corrosion

of ceramics

in the presence

bulk refractory

which is used in impure and fairly of coatings on

as a scale which is protective

resistance

to gases at high temperatures, was studied

in presence Gaseous

which may enhance

the corrosion in appendix

in this research.

of alumina was discussed relevant to turbine

A. The conditions

of this study

are particularly by SO2-02

applications

since the gases were generated

mixtures

and the deposits

were Na2 S04. of 0.2 atm or from the

In a turbine greater

engine at 1000C, gases have oxygen pressures of about 10e4 to lo- 5. f4) Deposits

and SO3 pressures

results

condensation

of gases produced sodium.

when burning fuels with sodium and sulfur impurities of condensed Na2S04 at equilibrium reaction: (11

in air-containing with gas mixtures

The composition

will be governed

by the decomposition

Na2S04 = Na20 + SO3 K1 = [aNa or so42assuming = 02- + so3 [PSO3]

(21 The Na20 and SO3 dissolved in the

that the salt is at unit activity.

melt are the basic and acidic species, During hot corrosion deposit deposit substrate determine the activity

respectively. of Na20 and pressure of reaction. of SO3 in the of the of the

the type and extent

The composition

in an engine can be determined material with components

by the gas phase or by the reaction in the salt. If the activity

of Na20 is high the

and the pressure

of SO3 is low or nil, solid oxides exhibit

a basic solubilityin

melt as in the reaction:

Appendix

C-Hot

Corrosion

of Alumina

91

MO + 02- = M022If the activity

of Na20

(3) of SO3 is high, solid oxides exhibit

is low and the pressure

an acidic solubility

in the melt as in the reaction: MO = M2+ + 02(4) of SO3 in the deposit solubility are within an is observed. with a

If the activity intermediate

of Na20 (i.e. 02-) and pressure range then the oxide is stable the degradation

and negligible

More specifically,

of an Al203 substrate

by reaction

molten Na2S04 film may proceed

by acidic or basic fluxing reactions: (3) (6) mechanism are

3 Na2SO4(1) + Al203 = Al2(SO4)3 + Na20 Na2S04(1) + Al203 = s NaA102 + SO3(g) of Al203 occurs by either

The regions where the hot corrosion shown on the stability The solubilities have been measured Figure 2.(7-g) diagrams

in Figure l.@y6) of Na2S04

of many oxides over a range of compositions experimentally. Results

for Al203 and SiO2 are shown in oxides are displaced acidity or basicity to the of those

Plots of the solubilities

of different

left and right of each other depending oxides. Alloys resistant by the formation transport to degradation

on the relative

at elevated

temperatures

are characterized

of continuous or oxidant

compact species.

solid oxide scales with a low rate of In addition, The extent the volatilization of degradation rate of by hot

of metallic

the oxides in the scale must be negligible. corrosion is partially determined

by the solubility

of the oxide scale in the

molten salt. Where the solubility a function of the acidity of the oxide in the molten salt deposit or basicity of the melt, corrosion is low or is not at a

may proceed

rapid rate until the liquid is saturated. corrosion rate decreases.

When the solution reaction

stops the

92

High Temperature

Corrosion

of Ceramics

LOG

P
O2 -10

BASIC FLUXING

AIO;

-20 LOG

-10 &03

Figure

l(a).

:Stability diagram showing phases of alumina that can be stable in Na2SO4 at 700C, and defining regions where acidic or basic fluxing are possible. Dashed lines are SO4 isobars (atm).

Appendix

C-Hot

Corrosion

of Alumina

93

BASIC LOG P
02

FLUXING

AIO;
-a

1 -8

I / / / / / /

-16 IO / /

-10.6, IO / / 1 /

t 1
ACIDIC
FLUXING

-s IO / / t / I

A13+

A203

AG3
0
Y

-Y

LOG

Ps,

Figure l(b).

Stability diagram showing phases of alumina that can be stable in NaZSO4 at 1000C, and defining regions where acidic or basic fluxing are possible. Dashed lines are sulfur isobars. Very high SO3 pressures are required for acidic fluxing. Refractory metal oxides are believed to make acidic fluxing favorable at lower SO3 pressures as indicated by the displaced boundary (arrows).(ll)

94

High Temperature

Corrosion

of Ceramics

Figure

2.

Solubilities

of alumina

in fused Na2S04

at 927OC.

Appendix

C-Hot

Corrosion

of Alumina

95

In acidic or basic conditions and precipitation a negative gradient activity gradient

sustained

attack

results

if solution

of oxide is by The in the

of the oxide in the salt away from the oxide-salt of the solubility

interface

of the oxide across the salt film.(lO-lll by the local variation solution and

in the solubility of Nat0

of the oxide is established

(i.e. 09-) across the film.

The resultant

precipitation passivating rates.

of the oxide produces oxide scale on a metallic

a porous scale.

The growth of a nonresults in high corrosion

engine component

In acidic conditions is derived

sustained

attack

may arise when the acidic component when an in

from the gas phase.(5p12*131

Als o, acid fluxing can result

acidic component the deposit. fluxing results in Na$304. molybdates manner, promote

comes from the solid phase and reduces more acidic.

the Na90 activity Alloy induced acid

This causes the melt to become from the solution of refractory the formation

metal components of tungstates,

of superalloys and

More specifically, reduces

vanadates,

the oxide ion concentration of the vanadium

in the melt.(121

In a similar

the oxidation acidic fluxing.

which is contained

in many fuels can

EXPERIMENTAL

PROCEDURE

Materials The materials aluminas containing chosen are single crystal different alumina and three poiycrystalline They have

levels of impurity Their sources

and microstructures.

been discussed

in previous

reports.

were given in Table I of the The chemical

first part of this report. analysis

The single crystal aluminas

is 99.99% pure.

of the polycrystalline

is given in Table I.

96

High Temperature

Corrosion

of Ceramics

TABLE I Chemical Analysis of Polycrystalline (units: wt%) Low PP 0.02 0.07 0.75 0.02 1.65 O.OOl^ 0.09 Alumina Alumina

Aluminas* High PP**

Fe203 CaO

Med PP O.Ol^ 0.02 0.17 O.Ol^ 0,17 0.0010.02

O.Ol^ 0.01,. 0.10 O.Ol^ 0.11 O.OOl^ O.OOl^

MgO
Ti02 SiO2 K20 Na20 ** High PP = Med PP Low PP = =

High Purity Polycrystalline Medium Purity Polycrystalline Low Purity Polycrystalline

Alumina

Undetected,

Limits of detection

Appendix

C-Hot

Corrosion

of Alumina

97

Hot Corrosion

Experiments had areas about 1 x 1 cm which were polished they were usually coated with 5 mg/cm2 Some samples for cycle, down to 1 urn of Na2S04 were also

All specimen diamond. After

cleaning,

and exposed subjected

for various times from 1 to 100 hours. exposures with 45 hours exposure cycles.

to cyclic

and washing and

reapplication

of Na2SO4 between

Two temperatures 1% SO2-balance

700C and 1000C oxygen at a total to give

and two atmospheres, pressure

pure 02 and initially

of 1 atm, were used in the experiments. and the SC2 containing

The pure 02 tended

basic conditions

atmospheres

set up acidic environments passage of

with pSO3 = 1.5 x 10e3 atm at 1000C and pSO3 = 7 x 10N3 atm after the initial mixture over a platinized catalyst at 700C. Since Na2S04

melts at

883OC, the sulfate

used at 700C was an equimolar

mixture

of Na2S04 and CoSO4

which was molten at that temperature. The changes characterized in morphology and products focused on the samples were (EDS

mostly with the SEM, and its X-ray spectroscopy After exposures and observations

attachment

and WDS) for microanalysis.

of the samples,

they were washed and the weight changes water was analysed When sufficient These procedures as required

were measured

to iO.l mg. The wash microprobe method.

using a semiquantitative

products

were formed,

they were identified in previous reports.

by X-ray diffraction.

were described

in detail

RESULTS AND DISCUSSION

Wetting The wetting measured angles for the 1 hour and 24 hours isothermal exposures were

and are given in Tables II, and III. In most cases the wetting

morphology

98

High Temperature

Corrosion

of Ceramics

TABLE II WETTING DATA Al203 1 & 24 Hour Isothermal 1 HR Low PP MS04 BM(S) LD18O SD 40 MS04 300 7oooc ACIDIC 24 HR MS04 140 RP=50 MS04 220 RP=48O MS04 200 MS04 220 KEY: MS04 Exposures 1000/24

Na2S04 190

Med PP

Na2S04 130 RP 2O NC Na2SO4 120 Na2S04

High PP sxtaI

MS04 8O MS0 140

180

(Na2,CO)S04 CWContinuous Wetting NCNearly Continuous Wetting PSPhase Separated Drop Wetting Angle (Cobalt Oxide+SaIt) BMBimodal (Two Wetting Angles) BM(S)Angles f(Drop Size) LDLarger Drop Wetting Angle SDSmaller Drop Wetting Angle BM(H)Angles = f(Drop Habit) RFReaction Product Angle

Appendix

C-Hot

Corrosion

of Alumina

99

TABLE III WETTING DATA Al203 1 & 24 Hour Isothermal 1 HR Low PP 1ooooc
Exposures

BASIC 24 HR

700/24 MS04 PS =16O MS04 PS =14o MS04 PS =14o MS04 PS 200

Na2SO4 30 NC Na2SO4 cw

Na2SO4 BM(H1 40/21 Na2S04 cw

Med PP

High PP

;$2s04

Na2S04 40 Na2S04 E KEY: MS04 cw NC PS

sxtsl

~o~so4

WwWSO4

Continuous Wetting Nearly Continuous Wetting Phase Separated Drop Wetting Angle (Cobalt Oxide+Salt) BM Bimodal (Two Wetting Angles) BM(S1 Angles - f(Drop Size) LD Larger Drop Wetting Angle Smaller Drop Wetting Angle SD BM(H1 Angles = f(Drop Habit) Reaction Product Angle RP

100

High Temperature

Corrosion

of Ceramics

which distinguished was nearly developed except

each set of exposure minutes after

conditions,

atmosphere,

and temperature, temperatures

the coupon reached

the furnace

in a few eases. The phase separation of the (Na2,Co)SO4 deposit used in the 700C exposures by thermodynamics. After cobalt

only occurred exposure

in the oxygen atmosphere

were composed

as predicted

the deposits

of Na2S04 and masses of equiaxed a discontinuous wetted

oxide crystals. surface.

The cobalt oxide formed

layer on the substrate

The cobalt oxide was preferentially from wetting

by the molten salt which

was prevented

the alumina substrate. wetting angles were measured resulted product on some of the of

In some cases two distinct coupons. Bimodal wetting

morphologies a reaction

from the phase separation in the deposit.

the salt or from the formation the difference II and III. The wetting In acidic conditions in contact

In other cases in Tables

angle was a function

of drop size as reported

of all the aluminas the wetting

exposed

in acidic conditions

was limited.

angle observed between

on the two higher purity aluminas 1 and 24 hours of exposure at

(High PP and single crystal) 700C. The wetting

increased

angle observed between

on the two lower purity aluminas at 700C.

(LowPP No trend in

and MedPP) decreased the wetting

1 and 24 hours of exposure is apparent. In general,

with composition

the wetting

angle of the The

salt on the aluminas reaction

in acidic conditions

is lower at 1OOOoC than at 700C. with the molten salt results of the droplets.

of the more impure aluminas reaction products

in the formation There is less as the

of multiple reaction

and the spreading

on the two higher purity substrates approaches the equilibrium

and the wetting wetting angle.

decreases

angle of contact

Appendix

C-Hot

Corrosion

of Alumina

101

In basic conditions 1000C than at 700C. salt at 700C affected

the wetting However, the results.

angle of the salt on the alumina

is lower at

the crystallization

of cobalt oxide from the the wetting of the

At both temperatures, in basic conditions angle occured

alumina by the salt is more extensive In generai, a slight decrease

than acidic conditions. between the wetting 1 hour and 24 generally

in the contact

hours in basic conditions increases

at 1000C. content

In basic conditions of the substrate.

with the impurity

The lower purity aluminas

were wetted

much more extensively This is attributed of impurity

by the molten salt than were the higher to the fact that the wetting behavior is

purity aluminas. affected

by the reaction

phases with the basic component by an increase in temperature. where partial

of the

melt, sodium oxide, which is promoted Photographs coupons occurred specific important

taken during long term exposures did not provide substantial evidence

wetting

of the of

of the repeated each cycle.

wetting This is

areas of a coupon when salt was reapplied since localized attack

before

could be very damaging. was poor and the resultant When the deposit of the salt, especially contact is in

In those experiments angle was high, relatively thick the effect the vicinity

where the wetting thick droplets

were observed.

of the atmosphere

on the composition

of the substrate,

may be significantly layer.

less than when the salt wet the angle is observed, is increased

coupon in a thin continuous the area for reaction and the distance salt-gas interface

On coupons where a low wetting and salt-gas interfaces

at both the oxide-salt

over which the oxidant is decreased. angle is low. in corrosion

must be transported

inward from the

Hence, the corrosion John observed

rate may be enhanced in salt film thickness

when the contact results

that an increase

in a decrease

rate, for exposures

of alloys with significant

solubility

in the molten salt.(141

102

High Temperature

Corrosion

of Ceramics

Hot Corrosion

of Al203 long term exposure with thermal measured cycling and the reapplication

Even after

of the salt the total weight changes even after

were very small, less than 1 mg/cm2, recorded for 1, 24,

500 hours of cyclic exposure.

The weight changes

405, and 495 hour experiments A globular silica reaction coupons from the exposures crystalline silicate reaction

are listed in Tables IV,V, and VI. product was observed atmosphere on the washed polycrystalline at 700C. Well defined

made in either products

were observed

on the washed polycrystalline After exposure, the silica

coupons from expures or silicate concentrated reaction

in either

atmosphere

at 1000C.

products

were etched acid.

from some of the coupons using are listed in Table VII. that these reaction in significant content

hydrofluoric

The weight decreases

The weight losses due to the etching products quantities were present

of the coupons indicate substrates

on the washed polycrystalline

which were not unreasonably

large compared

to the impurity

of the samples. The weight changes the coupon surface at both temperatures oxide on the surfaces must be affected completely by the smaller by the melt. area of reaction when

was not wetted

In acidic conditions of cobalt increased

all the materials

lost weight.

The formation

of the coupons exposed

at 700C in basic conditions recorded

the weight of the samples. particularly

The weight changes materials, sign.

for any of the exposures,

of the polycrystalline

are probably the result of two or Also, a combination of both gaseous during exposure. in the same

more contributions, and hot corrosion

possibly of opposite occurred over fractions

of the coupon surfaces to gaseous corrosion

Coupons of the same materials atmospheres

were exposed

for 168 hours (appendix of 0.1 mg.

A) and no weight changes

were detected

with a sensitivity

Appendix

C-Hot

Corrosion

of Alumina

103

TABLE

IV

WT CHANGE ALUMINA [mg/cm2] 1 & 24 Hour Isothermal Exposures

BASIC 1OoOoC LOWPP MedPP HighPP sxtal BASIC 7OOoC LOWPP MedPP HighPP sxtal ACIDIC LOWPP MedPP HighPP sxtal ACIDIC LOWPP MedPP HighPP sxtel 1OOOoC 7OOoC

1 HR 0 0 - 0.5 - 0.1

24 HR + 0.2 0.1 1.1 0.4

+ 0.4 + 0.1 0 + 0.1 1HR 0.1 0.8 0.5 0.1 24 HR - 0.2 - 0.4 - 0.2 0 24HR - 0.3 -0.3 - 1.1 - 0.3 LowPP MedPP HighPP sxtal = = = =

Saxonsburg 3M Lucallox Single crystal

104

High Temperature

Corrosion

of Ceramics

TABLE V WT CHANGE 495 HR Cyclic ALUMINA [mg/cm2] + ResaIt)

Exposure (45 HR Cycles ACIDIC 700C

Material Cycle LOWPP -0.2 2 3 4 5 6 7 a 9 10 11 -0.1 0 0 0 -0.1 0 0 -0.1 -0.1 0 MedPP -0.3 -0.1 0 0 -0.1 -0.1 0 +0.1 -0.1 0 0 -0.1 0 0 0 0 0 0 HighPP -0.3 -0.1 0 0 SXtal 0 0 0 0 0 -0.1 0 0 0 -0.1 0

-0.6

-0.6

-0.5

-0.2

Appendix

C-Hot

Corrosion

of Alumina

105

TABLEVI WTCHANGE ALUMINA[mg/cm2]

405 HR Cyclic Exposure(45 Cycles ResaIt) HR + BASIC 1000C

Material
Cycle 1 2

LOWPP -0.2 +0.3 0 0 0 0 0 0 0

MedPP 0 -0.1 +0.1 -0.1 0 0 0 0 0

HighPP 0 0 0 0 0 0 0 0 0

SXtal 0 0 0 0 0 0 -0.1 0 0

3 4 5 6 7 8 9

+0.1

-0.1

-0.1

106

High Temperature

Corrosion

of Ceramics

TABLE VII
RESULTS HP ETCH WT CHANGE ALUMINA [mg/cm2] Exposed Samples Etched in HP BASIC 1000C LOWPP MedPP HighPP ACIDIC 700C 24 HR 0 - 0.7 405 HR - 0.6 - 0.3 0 495 HR - 0.3 - 0.1 - 0.1 24 HR 0 - 1.0

LOWPP MedPP HighPP ACIDIC 1000C

LOWPP MedPP

Appendix

C-Hot

Corrosion

of Alumina

107

The data given in Table VIII were obtained processing performed of the EDS spectra

from the semiquantitative This analysis at 700C. was

taken from the wash water.

on 1, 10, and 100 hour exposures

in acidic conditions

Results,

Acidic

Conditions in acidic conditions were emphasized because sulfate

The 700C exposures formation is favored

at the low temperature

for a given SO2 pressure.

Single Crystal

Alumina reaction was detected after 1 hour of exposure. After 24 hours

At 700C limited The wetting of exposure 100 microns Negligible exposure. 100 hours.

was spotty and a wetting the wetting in diameter reaction Aluminum A limited

angle of 14O was measured.

angle was 22 o. The EDS spectra indicated that limited solution

of many drops below of Al had occurred. after 100 hours of

was detected

on the washed substrate present after

ions were consistently

in the wash water at 1, 10, 10 and 100 hours of exposure. it is assumed that

amount of Si was detected

Since negliglble limited

silicon was present of the samples

in the single crystal, occurred

contamination

and that the levels of Si detected The alumina furnace tube in

for the single crystal which the samples cyclic exposure, the coupon.

alumina are not significant.

were heated networks

may have been a source of Si. After 495 hours of were observed over portions of

of shallow depressions

The coupon exposed perimeters EDS spectra to several of drop areas.

at 1000C for 24 hours exhibited A significant

a faint etching

at the

amount of Al was present The substrate angle of 180.

in some of the by drops up

of the salt at the drop edges. millimeters across with a wetting

was wetted

108

High Temperature

Corrosion

of Ceramics

TABLE VIII Wash Water Analysis, Al203 Exposures 700C Acidic Conditions

Material LOWPP

Element

1 Hour

10 Hour

100 Hour

Na S Si Al Mg Ca co 0** MedPP Na S Si
Al

17.0 14.0 0.99 2.0 2.4 0.00 4.1 60.0

18.0 14.0 0.96 1.2 1.3 0.00 4.2 60.0

16.0 14.0 1.4 2.2 1.3 0.00 3.5 61.0

18.0 13.0 0.94

2.2

19.0 11.0 1.5 ::: 0.00 3.9 58.0

Ci 0 HighPP

Mb?

co

1.8 0.00 4.2 59.0

16.0 13.0 3.6 1.5 I?00 3.3 61.0

Na S Si Al ME Ca co 0

17.0 15.0 0.46 1.0 1.4 0.00 3.0 62.0

19.0 15.0 0.00 0.52 1.0 0.00 3.9 61.0

17.0 16.0 0.40 0.66 0.43 0.00 3.9 62.0

sxtal
Na S Si Al I% Ca co 0 19.0 15.0 0.00 0.60 0.81 0.00 3.9 61.0 18.0 15.0 0.46 1.3 1.6 0.00 3.7 61.0 16.0 16.0 0.56 0.16 0.00 0.00 4.4 63.0

**

by stoichiometry

Appendix

C-Hot

Corrosion

of Alumina

109

High Purity Polycrystalline At 700C limited substrate area. was wetted

Alumina was detected covering after 1 hour exposure. The

reaction

by two large patches

about half of the coupon

A wetting After

angle of 8Owas measured. the wetting angle was approximately 20. The

24 hours of exposure and typically

drops were patchy was indicated spectra substrate

under 1000 microns across.

The solution

of Al These

by some of the EDS spectra the presence the preferential silicate

of salt at the edges of drops.

also indicate revealed

of significant solution

amounts of Si. Washing the

of alumina grains and the presence A few Na and

of a fine poorly defined isolated significant patches

along the edges of the drop areas. 10 to 20 microns across, containing

of cobalt sulfate

amount of Si were observed. of alumina grains throughout A thin discontinuous the drop areas was evident after

The etching

100 hours of exposure.

layer of silica on the edges of grains Aluminum ions were consistently

in a drop area is shown in Figure 3 (top). present in the wash water after After portions

1, 10, and 100 hour exposures. small thin patches of individual solution of silica covered In

495 hours of cyclic exposure and fractions and preferential

of the substrate

grains (Figure 3, bottom).

these areas the etching

of grains was apparent. by several discrete

The coupon exposed drops about 2 millimeters were detected revealed

at 1000C for 24 hours was wetted across with a 12O wetting angle.

Traces of Al and Si

in EDS spectra

of salt at the drop edges.

Washing the substrate layer with traces layer covers a large

the presence

of a thin poorly defined in some spectra.

silica-containing

of Na and Mg detected fraction

This discontinuous

of the grains in the drop areas (Figure 4, top).

110

High Temperature

Corrosion

of Ceramics

Figure 3.

High purity polycrstalline alumina exposed in acidic conditions at 700oC or 100 hours {top) and 495 hours {bottom). Etched grains in drop areas and thin patches of silica are shown on washed substrates.

Appendix

C-Hot

Corrosion of Alumina

111

Figure 4.

High, medium, and low purity polycrystalline aluminas (top, middle, and bottom, respectively) exposed in acidic conditions at lOOOoCfor 24 hours. Silicate reaction products on washed substrates are shown.

112

High Temperature

Corrosion

of Ceramics

Medium Purity Polycrystalline Alumina At 700C after 1 hour of exposure a significant amount of Al and a limited amount of Si were indicated by the EDS spectra of drops. Wetting was spotty except for a single large patch of salt covering about a fifth of the coupon area. The droplets were typically 10 to 200 microns across. A wetting angle of 30 was measured. A few isolated patches of cobalt sulfate 10 to 20 microns across and containing Na and a significant amount of Si were observed. After 24 hours exposure the wetting was spotty with some small patches. Substantial solution of Al was indicated by the EDS spectra of salt in drops with a measured wetting angle of 22O, and in droplets containing larger well defined crystals richer in Al with a wetting angle of about 48O. Washing the substrate revealed that fine poorly defined bands a few microns wide, containing Co, Si, and traces of Mg and Ca, skirted large fractions of the perimeters of the large drop areas. In the drop areas, some of the grain boundaries had been etched. The etching of grains throughout the drop areas is evident after 100 hours of exposure. Small globules rich in Si scattered on raised blocky areas 20 to 30 microns across were observed. Aluminum and Mg ions were consistenly present

in the wash water at 1, 10, and 100 hours in much greater concentrations than for the single crystal or the high purity polycrystalline material. The concentration of Mg detected after 10 hours of exposure was relatively large. The concentration of Si ions in the wash water was also much greater, and increased drastically between 10 and 100 hours. After 495 hours of cyclic exposure patches of a continuous layer of well defined globular silica covered portions of the substrate. The etching of grains was apparent.

Appendix

C-Hot

Corrosion

of Alumina

113

The coupon exposed at 1000C for 24 hours was wetted nearly continuously over some portions of the surface and by discrete droplets with a 13O wetting angle in other areas. In both areas, substantial amounts of Ca, Mg, Si, Al, a limited amount of Ba, and traces of K were present in EDS spectra of the salt. Washing the substrate revealed the presence of numerous well defined sodium aluminum silicate and sodium magnesium aluminum silicate crystals scattered across the substrate (Figure 4, middle). Also, smaller sodium magnesium aluminum silicate crystals had formed as platelets aligned in parcels on the substrate. Some crystals were present in groups but in most cases they protruded from grain boundaries where discontinuous etching had occurred.

Low Purity Polycrystalline Alumina At 700C after 1 hour of exposure the wetting was spotty with some larger patches of salt over 500 microns across. Wetting angles of la0 for the larger drops and 40 for the droplets were measured. A significant amount of Al and a limited amount of Si were indicated by the EDS spectra of drops. Blocky crystals about 20 microns across were visible below the salt in several droplets. After 24 hours of exposure patches of salt nearly as large as 2000 microns across wetted the substrate. Substantial solution of Al was indicated by the EDS spectra of salt in drops with a measured wetting angle of 14O. Sulfate drops with a wetting angle of about 500 contained well defined sulfate crystals rich in Al. Some of the crystals contained Al and Mg as well as Si (Figure 5). Washing the substrate revealed that a thin poorly defined layer as large as 100 microns wide containing Co, Si, a significant amount of Mg, and traces of Ca skirted the perimeters of the larger drop areas. In the drop areas a relatively even etching between the grains had occurred. A few isolated patches of cobalt sulfate 10 to

30 microns across and containing Na and a significant amount of Si were observed.

114

High Temperature

Corrosion of Ceramics

Figure 5.

Low purity polycrystalline alumina exposed in acidic conditions at 700oC for 24 hours. Salt crystals containing Al and Mg are shown (top and bottom).

Appendix

C-Hot

Corrosion

of Alumina

115

The etching isothermal have formed the globules

of grains throughout Distributions

the drop areas is evident

after

10 hours of

exposure.

of silica globules about 1 or 2 microns across After 100 hours of exposure present many of in the

on fractions coalesced.

of the drop areas. Aluminum

and Mg ions were consistently concentrations

wash water at 1, 10, and 100 hours in much greater single crystal or high purity polycrystalline materials.

than for the of Si

The concentration observed

ions in the wash waters between

was also much greater,

but the increase

10 and 100 hours was not as great as that observed material. exposure a thin discontinuous

for the medium

purity polycrystalline After covered

495 hours of cyclic of the substrate.

layer of silica

portions

The etching

of grains was apparent. by drops up to 3000 was also In

The coupon exposed

at 1000C for 24 hours was wetted wetting

microns across with a measured observed, particularly

angle of 19O. Spotty wetting

in the areas outside the perimeters amounts

of the larger drops. of Ba and K were the selective containing

both areas, substantial present solution in EDS spectra

of Ca, Mg, Si, Al, and traces Washing the substrate Well defined

of the salt.

revealed

of grains in the drop areas. in limited

aluminum silicate

Na and Ca formed were present Results,

quantities

(Figure 4, bottom).

Minor amounts

of Mg

along with the Ca in a few of the crystals.

Basic Conditions in basic conditions were emphasized because more short

The 1OOOoC exposures extensive reaction occurred

at the higher temperature

when preliminary

term exposures

were made in oxygen. in contact

At 700C a large fraction throughout

of the molten due to

salt did not remain the formation

with the substrate

the exposure

of cobalt oxide.

116

High Temperature

Corrosion

of Ceramics

Single Crystal At 700C phase separation of the salt occurred within 24 hours of exposure. The wetting was patchy and irregular. A wetting angle of about 20 was measured. The concentration of Al ions was limited to the EDS spectra of a few small drops, where the molten salt had remained in contact with the substrate. Cobalt oxide separated the sulfate from the substrate over most of the area of the larger drops. No reaction was detected after 1 hour of exposure at 1000C. A wetting angle of loo was measured and broad patchy wetting covered large areas of the coupon. After 24 hours of exposure an So wetting angle was measured. Some sodium aluminum silicate was observed after 405 hours of cyclic testing at 1000C. Negligible quantities of Si are present in the as-received

substrate material. The alumina furnace tube is a likely source of the Si.

High Purity Polycrystalline Alumina At 700C phase separation of the salt occurred within 24 hours of exposure. The wetting was patchy and irregular. A wetting angle of about 14O was measured. Traces of Si and limited concentrations of Al ions were indicated by the EDS spectra of small drops where the molten salt had remained in contact with the substrate. A network of globular silica associated with Co formed on the substrate in the perimeter of the larger drop areas. From the morphology of the washed substrate it appeared that preferential solution of grains and growth of Si rich needles had occurred in the drop areas. The growth direction of the needles was constant across the surface of each grain (Figure 6, top). A few larger needles were observed at or near the triple points between grains and contained significant amounts of Ca.

Appendix

C-Hot

Corrosion of Alumina

117

Figure 6.

High purity polycrystalline alumina exposed in basic conditions at 700oC for 24 hours (top) and 1000oC for 405 houl'S (bottom). Oriented silica rich needles (top) and silicate reaction products at grain boundaries (bottom) are shown on washed substrates.

118

High Temperature

Corrosion

of Ceramics

After hemispherical Crystals

1 hour of exposure silicates formed

at 1000C a distribution across the substrate silicate between

of well defined in the drop areas.

surface

of sodium aluminum

5 and 10 microns across protruded A wetting angle of

from beneath

the salt near the centers

of some of the drop. a 4O wetting

So was measured. A distribution anomalously formation magnesium

After 24 hours of exposure had formed

angle was measured. Some pattern of

of globular silicate

in the drop areas.

large globules contained of sodium aluminum aluminum silicate after silicate

Ca and Mg. A consistent along grain boundaries

and sodium on

at the triple points between

grains was apparent (Figure 6, bottom).

the washed substrate preferential solution

405 hours of cyclic exposure of certain

The

of the surfaces

grains is apparent.

Medium Purity Polycrystalline At 700C, phase separation exposure. The wetting was patchy

Alumina of the salt occurred A wetting within 24 hours of angle of about 14O

and irregular.

was measured. remained

The EDS spectra

of small drops where the molten salt had indicated that significant amounts revealed of Ca,

in contact

with the substrate in the salt.

Si, Al, and Mg were present pronounced etching

Washing the substrate

the of silica

of the grains in drop areas accompanied layer of silica.

by the deposition of globular

a poorly defined associated After

discontinuous

A sparse network in the perimeter

with Co formed

on the substrate

of the drop areas. a continuous film

1 hour of exposure

at 1OOOoCthe salt had formed amounts

over most of the coupon. in EDS spectra numerous of the salt.

Substantial

of Ca, Mg, Si, and Al were present revealed crystals the presence scattered of across where

Washing the substrate

well defined

magnesium

aluminum silicate

the substrate

and a random distribution

of vugs up to 20 microns across

Appendix

C-Hot

Corrosion

of Alumina

119

preferential continuous partially

solution wetting

of the substrate

occurred.

After 24 hours of exposure surface which was

the

of the coupon resulted with poorly defined

in a substrate

covered

crystals. amounts

Some of the crystals,

particularly of

the one near vugs, contained

substantial

of Si and Mg. Small patches On the unwashed in the

a thin layer of silica were also observed

on the substrate.

sample large peaks for Ca, Ba, Mg, Al, Si and traces EDS spectra of the salt. Rosettes

of K were present

about 10 to 15 microns across were present of Be were present after in the salt (Figure 405 hours of cyclic 7,

in

some areas where substantial top). The pronounced Numerous etching

amounts

of grains was apparent

exposure.

bunches of poorly defined surface.

sodium aluminum silicate

crystals

were scattered

over the substrate

Low Purity Polycrystalline

Alumina of the salt occurred A wetting within 24 hours of angle of about 16O

At 700C phase separation exposure. The wetting

was patchy and irregular.

was measured. remained

The EDS spectra

of small drops where the molten salt had indicated that significant amounts of Ca, revealed over in many of

in contact

with the substrate

Al, Mg and Si were present a dense network portions

in the salt (Figure 8). Washing the substrate with Co on the substrate

of globular silica associated A significant

of the drop areas.

amount of Mg was present silicate.

the globules suggesting After

that they were a magnesium

1 hour of exposure

at 1OOOoC the salt had formed A wetting

a nearly continuous

film on over half of the coupon surface. Substantial amounts

angle of 3O was measured. in EDS spectra salt crystals of

of Ca, Ba, Mg, Si, Al, and K were present

the salt, both in the salt film and in small groups of well defined rich in impurity ions. Washing the substrate revealed

a fine globular silicate

120

High Temperature

Corrosion of Ceramics

Figure

7.

Medium purity polycrystalline alumina exposed in basic conditions at lOOOoCfor 24 hours. A multi-phase deposit with rosettes containing Ca, Ba, Al, Si, Mg, and K (top) and a typical multi-phase deposit containing Ca, Al, Si, Mg and K (bottom) are shown.

Appendix

C-Hot

Corrosion of Alumina

121

Figure 8.

Low purity polycrystalline alumina exposed in basic conditions at 700oC for 24 hours. Salt crystals containing Ca, Mg, Al, and Si are shown (top and bottom).

122

High Temperature

Corrosion

of Ceramics

containing

a significant

amount of Mg. An intermittent

distribution

of larger

globules up to over 2 microns across contained Ca. A random distribution of vugs typically had

below 10 microns across where preferential occurred was also observed.

solution of the substrate

After 24 hours of exposure A wetting

a bimodal wetting

morphology

had developed. across. A

angle of 4O was measured

on drops as large as 4000 microns of holes and branches A 21 wetting

thin discontinuous

film of salt with a network of the molten salt. On the unwashed

was left

behind by the dewetting on the edges of the film. Al ions and traces salt.

angle was measured concentration of the of

sample a substantial

of Ca, Si, and Mg were indicated tabular

by the EDS spectra

On the washed sample well defined

crystals

of sodium magnesium crystals containing Ca

aluminum silicate were observed

and blocky sodium aluminum silicate

(Figure 9, top). of poorly defined grains was apparent silicate after 405 hours of cyclic free

The etching exposure.

Blocky crystals

of sodium magnesium

were predominantly

of Ca and had become exposure

less well defined

than after

24 hours of isothermal on some sites on

(Figure 9, bottom). probably

A phase rich in Al and Mg formed aluminate spineL

the substrate, Discussion

magnesium

of Results increase the attack

of the polycrystalline

Impurities molten sulfate. grain boundaries phases.

aluminas

by the at the

This effect

is enhanced

by their pronounced

segregation, second

and at the triple points between of exposure was dominated

grains in impurity

In each condition materials

the hot corrosion by the reactions

of the lower purity of the impurity silicate

polycrystalline

phases with the melt.

Appendix

C-Hot

Corrosion of Alumina

123

Figure 9.

Low purity polycrystalline alumina exposed in basic conditions at 1000oC for 24 hours (top) and 405 hours (bottom). Aluminum silicate crystals containing Ca left and Na right (top) and Mg and Na (bottom) are shown on washed substrates.

124

High Temperature

Corrosion

of Ceramics

The data available the composition Si are present stability

on the solubility

of alumina in Na2SO.t as a function applicable when significant amounts

of of

of the salt is not directly in the melt. occurred The formation

of phases not predicted

by thermodynamic work on

diagrams

at less than unity activity

as in the previous

gaseous corrosion Activities between However,

(Appendix A). of Na20 in the salt as great as 10-6 to 10e4 at temperatures have been reported. during the exposures is not known. Impurities of of a for the and In

7OOoC and 1000C in an oxygen atmosphere the actual activity of Na20 in the deposits

the profile of the activity the exposures

across the thickness

of the deposits

of alumina the salt tended wetting

to form discrete of the substrate

droplets. increase

which result in more extensive degradation thinner by increasing

the extent

the area of attack

and promoting

the formation This is observed

molten salt film as discussed aluminas, particularly

in the introduction.

polycrystalline

under basic conditions. all the coupons exposed were covered by

At 400C in acidic conditions discrete indicates droplets of salt.

The data obtained

from the analysis of the wash water below 2.0 for Since no

that the atomic sodium to sulfur ratios were significantly (Table VIII). This is true for all four aluminas.

all times of exposure insoluble products atmosphere

rich in Na were detected, the deposit

it is likely that SO3 from the of the melt shifted formed toward in solution

enriched

as the composition

being less acidic because in the melt. The presence all exposures

aluminum sulfate

and other sulfates

of Al in the wash waters are

and the weight losses recorded with the

fOrtTIatiOn of

for

in these conditions

COnSiStent

A12(S0.+)3.

The wash water indicates the salt, probably

that Mg was present

as a soluble reaction

product

in

MgSO4, since it is stable at lower pressures

of SO3 than

Appendix

C-Hot

Corrosion

of Alumina

125

Al3(SO4)3.

The well defined

sulfate

crystals

in Figure 5, contain

substantial

amounts of Al and significant was observed

amounts of Mg. An abundance

of these crystals

on the two least pure aluminas. silica was present on portions of all of the

After 495 hour cyclic exposures substrates but the single crystal

(Figure 10, top). The solution

of Si rich impurity materials 10 (bottom).

phases at the grain boundaries resulted

of the two lower purity polycrystalline of surface grains as in Figure

in a marked lack of connectivity

At 700C in acidic conditions of alumina is the formation (Appendix A). A mechanism term exposures is proposed substrate-salt negative

the principal

reaction

during the hot corrosion for gaseous corrosion

of Al3(SO4)3, as was observed for the reactions

which occurred

during the long It

of the less pure polycrystalline

aluminas has been developed.

that the acidic solution of alumina lowers the pressure interface below that at the salt-gas interface,

of SO3 at the in a

resulting

solubility

gradient

for silica across the molten salt layer and satisfying silicates are dissolved from the toward

the Rapp-Gotto

criteria

for fluxing. (11) Impurity

grain boundary areas on the substrate. the salt-gas precipitation interface they advance

As the silicate into a negative

ions are transported gradient

solubility

and the

of nearly pure SiO3 results.

The coalesence,

growth,

and coarsening of

of the SiO3 which is precipitating globular silica patches precipitation salt interface on fractions

from the melt results of the substrate

in the formation Because the

surface.

of SiO3 in the melt occurs some distance the size and shape of the patches of the substrate. of the reaction of silicates products present

away from the substrate-

of globular silica were not dictated

by the microstructure The morphology Figure 11. The solution

are shown in the schematic

in

at the grain boundaries

and as impurity to the

grains lowers the local Na30 activity

of the melt in a manner analogous

126

High Temperature

Corrosion

of Ceramics

Figure 10.

Medium purity polycrystalline alumina exposed in acidic conditions at 700C for 495 hours. Globular silica (top) and etched grains (bottom) are shown on washed substrates.

Appendix

C-Hot

Corrosion

of Alumina

127

S/G

Distance

O/S

= Oxide-salt Interface = Salt-gas Interface

S/G

Q = Impurity Silicate Phases R = Globular Silica Reaction Product S = Sulfate Deposit Containing (Al, Mg, Si) A = Alumina Grains at Substrate Surface Solution Reaction at A: 3NagSO4 + Al303 = Al3(SO4)3 + 3Na30 B = Intergranular Attack Solution Reaction at B: Silicate + Nag0 = Na3O*xSiOg (in sulfate) C = Away from Oxide-Salt Interface where Melt is More Acidic Precipitation Reaction at C: Na3O.xSiOg (in sulfate) = xSiO3 + Nag0 (in sulfate) (Between grains and impurity phases at substrate surface Reaction A + Reaction B: 3NagSOq + Al303 + xSilicate = Al3(SO4)3 + 3NagO-xSi0g) Figure 11.

Schematic diagram of the morphology of reaction products on polycrystalline aluminas exposed in acidic conditions at 7OOoC.

128

High Temperature

Corrosion

of Ceramics

way in which the solution sodium certain oxide concentration superalloys.(11~131

of refractory

oxides in molten

Na3S04 lowers the

of salt deposits The formation

during the alloy induced fluxing of of Al3(SO4)3 and MgSO4 occurs solution of silicates, impurities raising in the

concomitant

to and in the vicinity and increasing surface.

of the localized the solubility Intergranular

the Nag0 activity vicinity decrease

of the silicate corrosion

of the substrate

results

in a substantial

in the connectivity

of the grains of the substrate. is controlled interface products of of the by

For the proposed the inward transport across the thickness

model it is likely that the rate of reaction of reactive species (i.e. SO3) from the salt-gas

of the film or by the transport interface. proceeds silicates

of soluble reaction that the transport

away from the substrate-salt reactant and product species

This assumes

more slowly than the dissolution at the substrate however, surface. there

alumina grains or of impurity could not be measured that it is correct. detected exposed effect

The kinetics is some evidence of Al were of the samples has greater for

to check this statement,

As mentioned

above, higher concentrations

in the drop edges than in the bulk of the salt on several in low temperature on the chemistry acidic conditions. The SO3 atmosphere

of the salt at the drop edges because or Na30 to surface is minimized.

the distance

transport

of SO3 to interface

At 1OOOoC in acidic conditions discrete droplets of salt, except material

all of the coupons exposed

were wetted

by

for the exposure

of the medium purity wetting was observed. After Weight

polycrystalline

where nearly continuous

losses were recorded well defined crystals

for all the exposures

in these conditions. of silicates

exposure, on

with the form and chemistry substrates.

were observed

the washed polycrystalline

Appendix

C-Hot

Corrosion

of Alumina

129

The silicates

on the washed substrates

of the polycrystalline

materials silicate

after 24 hours of exposure

were shown in Figure 4. A fine poorly defined of the drop areas on the high impurity crystals containing substantial

covers grains over large portions substrate.

Sodium aluminum silicate

amounts silicate

of

Mg cover portions crystals substrate. present containing

of the medium purity substrates. substantial amounts

Sodium aluminum

of Ca cover portions

of the low purity are

In the drop areas on the washed substrates in substantial quantities, the substrates

where the crystals

are etched

more deeply than on drop areas the exposed at

similar exposed at 700C in acidic conditions. intergranular corrosion which had been observed

Within the etched on the samples

700C was absent (Figure 12). The salt deposits on the two least pure materials exposure. contained significant of most of the in

amounts of Al, Si, Mg, and Ca after smaller salt droplets the salt as sulfates atmosphere do not contain (Figure 13, top).

The EDS spectra

Al or Si, so the Ca and Mg are in solution Since the partial pressure of SO3 in the

at 1000C was less than at 7OOoC, the formation by thermodynamics, but was observed the formation

of Al2(SO4)3 would for gaseous of the CaS04

not have been predicted corrosion occurred (Appendix

A). Under acidic conditions

at 1000C but not at 700C although

it is stable at both temperatures. of impurity silicate by the of the

This is believed

to be the result of more severe degradation The uniform etching

phases at the higher temperature. formation

of the substrate, in the basicity crystal

of Al2(SO4)3, could result from local decreases interface in areas of copious silicate on the unwashed

melt at the oxide-salt The multi-phase

growth.

salt deposit

medium purity substrate

shown in Figure 13 (bottom) The lighter

is characteristic

of the two least pure materials. of the

blocky phase contains

Ca, Si, Al, and Mg, and the remainder

130

High Temperature Corrosion of Ceramics

Figure 12.

Medium purity polycrystalline alumina exposed in acidic conditions at 1OOOoC for 24 hours. Sodium aluminum silicate reaction products and etching of drop area are shown on washed substrates.

Appendix C-Hot

Corrosion of Alumina

131

Figure

13.

Low and medium purity polycrystalline aluminas (top and bottom, respectively) exposed in acidic conditions at 1000C for 24 hours. Sulfate crystals containing Ca, Si, Al, and Mg (bottom) are shown.

132

High Temperature

Corrosion

of Ceramics

salt contains Al.

The two phase salt droplet silicates

reaction

product

morphology

must in the

be linked to the growth of aluminum substrate. As a result concomitantly of the substrate

at surface

heterogenieties

microstructure

unique reactions and produced

occurred local variations

over different

areas of the substrate The formation preferentially The results

in the composition aluminum silicate

of the melt. crystals

of a network

of well defined and

occurred

at the grain boundaries and the morphology of the

triple points of the microstructure. products as follows. pressure grains. described earlier

and shown schematically

in Figure 14 can be explained the local SO3 near the alumina

As the alumina grains are dissolved and the Nag0 activity Nap0 activity

by the sulfate, accordingly

decreases

increases

The increased

promotes

the transport

of Nag0 in the melt

to the grain boundaries where it reacts silicates

and grains of silicate forming

phases in the low purity aluminas, sodium silicates sulfates. and alumina the acidity As the and a

with these silicates,

as well as calcium

and magnesium

This maintains

of the sulfate transport deeper similar reactions

melt thus promoting

the dissolution

of the alumina grains.

is rapid at 1000C, the corrosion

under the sulfate

is quite uniform

than at iOOC. At lower temperatures, mechanism cooperate attack operates but the transport

700C under acidic conditions, is slower and the acid and basic leading to strong

mostly near the grain boundaries (Figure 11). in basic conditions formation

inter-granular

The results to interpret substrate

of the exposures

at 700C are more difficult on the

due to the extensive surface.

of cobalt oxide crystals for the exposures. of alumina

Weight gains were recorded indicate that significant

Photomicrographs the substrates.

amounts

were etched did not

from

The formation

of nearly pure silica on the substrate

occur nearly as extensively

as at 700C in acidic conditions.

Appendix

C-Hot

Corrosion

of Alumina

133

r I0
I I

_ _----

,s 00 i

I I

L-_-_-_-I

+ -+

Transport Na20

of

Transport

so;

of

Q = Silicate Reaction Products 0 = Original Substrate Surface Multi-phase Deposit R = Bulk of Deposit Sulfate Containing (Al, Mg, Ca, Si) S = Other Phases Complex Reaction Products Containing

Silica

A = Alumina Grains at Substrate Surface Solution Reaction at A: 3Na3SO4 + Al303 = Al3(SO4)3 + 3Na30 B = Intergranular Areas at Substrate Surface Reaction at B: Na3SO4 + Mg-, Ca-, Al- silicate = NaSO*silicate + MgSO4 + CaSO4 + Al3604)3

Figure 14.

Schematic diagram of the morphology of reaction products on polycrystalline aluminas exposed in acidic conditions at 1000C.

134

High Temperature

Corrosion

of Ceramics

The presence was not detected temperature silicate

of CaS04 in the salt on the two lower purity aiuminas, on samples exposed in acidic conditions attack at the same of the impurity

which

(700C),

may be due to a more severe The conditions

in the oxygen atmosphere.

in the oxygen atmosphere

are

not conducive conditions.

to the type of sustained Significant amounts

fluxing which occurred

at 700C in acidic in the salt.

of both Si and Al were dissolved

Because of the depletion formation generated sulfate. In basic conditions aluminas occurred. emphasizing

of the basic component

of the melt due to the products

of cobalt oxide, it is likely that the initial dissolution at the aluminum oxide-salt interface

were silica and aluminum

at 1000C the most extensive

wetting

of all four of the

The lower purity materials of the impurities.

were wetted Vugs developed

more extensively at some of the

the influence

triple points between Even after the single crystal polycrystalline boundaries

grains on the surfaces

of the two least pure substrates. negligible formed reaction was detected on

405 hours of cyclic exposure substrate. Aluminum

silicates

on the substrates silicates at grain

of the

materials.

They were sodium aluminum aluminum aluminum silicates silicates

and sodium magnesium Sodium calcium formed

at triple points on the high and sodium magnesium A variety of multiafter of sulfate

purity substrate. aluminum silicate phase deposit exposure

on the lower purity substrate. formed

morphologies

on the two least pure materials consisted of mixtures

at IOOOoC in oxygen. silicates

These deposits

with various aluminum elements contained

of sodium, potassium in the substrates.

and the rare earth

as impurities

Appendix

C-Hot

Corrosion

of Alumina

135

The formation would be predicted

of NaA102 as the primary on the basis of solubility

reaction

product

in the deposits

data published material,

by Rapp (Figure 2). the degradation of the and in the of the

While this may be the case for the single crystal polycrystalline formation materials cannot silicates be analyzed

without

consideration

of aluminum

which occurred

on the substrates the multiple

molten salt. of the deposits

This is obvious when one considers on the two least pure materials.

phase morphology

Relatively

small weight gains and losses were recorded Intergranular corrosion resulted

for the exposures in a decrease The

at

1000C in basic conditions. connectivity of the surface

in the

grains of the two lower purity substrates. indicate that the formation

weight changes silicates occurred silicate between

and photomicrographs

of alumina

and the solution of alumina were not as extensive in acidic conditions impurities at the same temperature. in the melt towards promoted

as that which that the

It is proposed

shift the activities

values intermediate thus similar. increases the

the acidic and basic conditions behaviors acidicity

by the atmosphere,

making the corrosion However, dissolution the greater of alumina.

at 1000C under both atmospheres of the melt under acidic conditions the cooperative

Under basic conditions impurities

reactions forming

initiate various

with the attack

of the silicates

by the basic sulfate

sodium alumina silicates of the melt providing formation is limited

including those of the rare earths.

This raises the pSO2 This sulfate than under

for acidic solution and the silicate

of the alumina grains. is more extensive corrosion.

formation

acidic conditions,

leading

mostly to intergranular

136

High Temperature

Corrosion

of Ceramics

REFERENCES 1. Wachtman, John B., et. al., An Evaluation of Needs and Opportunities for Fruitful Fundamental Research in Ceramics, Ceramic Bulletin, Vol. 57, No. 1 (1978), pp. 19-24. Johnson, Project, D.R., et.al., Ceramic Technology for Advanced Heat Engines Ceramic Bulletin, Vol. 64, No. 2 (1985), pp. 276-280. Cummins Engine Company, Private Communication.

2. 3. 4.

T. Yonushonis,

Goebel, J.A. and F.S. Pettit, Na2SO4 - Induced Accelerated Oxidation (Hot Corrosion) of Nickel, Metallurgical Transactions, Vol. 1 (1970), pp. 1943-1954. Giggins, C.S. and F.S. Pettit, Hot Corrosion Degradation of Metals and Alloys - A Unified Theory, Pratt and Whitney Aircraft, Report No. FR11545 (1979). Goebel, J.A., P.S. Pettit and G.W. Goward, Mechanisms for the Hot Corrosion of Nickel-Base Alloys, Metallurgical Transactions, Vol. 4 (1973), pp. 261-278. Jose, P.D., D.K. Gupta and R.A. Rapp, Solubility of Alpha - Al203 in Fused Na2S04 at lOOoK, J. Electrochem. Sot., Vol. 132, No. 3 (1985), pp. 735-737. Shi, D.Z. and R.A. Rapp, The Solubility of SiO2 in Fused Na2S04 at 900C, J. Electrochem Sot., Vol. 133, No. 4 (1986), pp. 849-850. Kim, G.M., The Effect of Contaminants and Solubilities of SiO2 In Fused at 1200K, Masters Thesis, University of Pittsburgh, 1982.

5.

6.

7.

8. 9.

Na2S04

10.

Rapp, R.A. and K.S. Goto, The Hot Corrosion of Metals by Molten Salts, Symposium Fused Salts, Electrochemical Society Meeting (Pittsburgh, 1979). Rapp, R.A. and K.S. Goto, Fused Salts, (J. Braunstein eds.), Electrochemical Society, 1978. and J.R. Selman,

11.

12.

Birks, N. and G.H. Meier, Introduction to High Temperature Metals (London: Edward Arnold, 1983), pp. 146-158.

Oxidation

of

13.

Shores, D.A., New Perspectives on Hot Corrosion Mechanisms, H&$ Temperature Rapp, R.A. (ed.), (Houston: National Association of Corrosion Eng., 1983), pp. 493-501. John, R.C., Corrosion of Metals by Liquid Na2C03, State University, 1979. Doctoral Thesis, Ohio

14.

Appendix

D-Hot
J.R. Blachere,

Corrosion of Silicon Nitride

D.F. Klimovich and F.S. Pettit

and Silicon Carbide

INTRODUCTION Silicon nitride and silicon carbide are two ceramics materials considered seriously for structural applications at high temperatures. They form a protective In

silica scale in oxidizing atmosphere which is quite stable thermodynamically. highly corrosive environments such as those prevailing in incinerators or gas turbines burning low grade fuels, SiOz may be attacked due to the pressure of SOS, CO2 as well as oxides of metallic impurities (e.g. NagO, Na$O& It has

been shown in this program that Nap0 is the corrosive agent in the hot corrosion of silica in contact with NagSO4 deposits (Appendix B). In particular the sodium oxide promote devitrification and the crystalline layer formed tends to spa11 under temperature cycling. Using the results for silica as foundation, the

mechanisms and the extent of the hot corrosion of silicon nitride and silicon carbide must be established.

EXPERIMENTAL PROCEDURE The general procedures have been discussed in previous report&) and in

previous parts of this report. The materials are shown in Table I of the main report. High purity materials (single crystal silicon carbide and CVD silicon nitride) were studied in detail. Morphological studies of the corrosion were performed on these materials and representative engineering materials usually characterized by a significant level of impurities added during processing particularly as sintering aids. The two atmospheres used throughout the experiments were SOg-02 mixtures with a total pressure of 1 atmosphere. One contained 1% SO2 initially, which generated a pressure of 1.5 x 1W3 atm of SO3 at 1000C. The other was pure oxygen. The gases flowed at the rate of 1 cm5/s.
137

Usually the sodium

138

High Temperature

Corrosion

of Ceramics

sulfate

was applied with a surface

loading of 5 mg/cmz

on polished

substrates. on the

The surface

loading as well as the temperature The times of exposure

were varied

in the studies

purer materials. standard techniques scanning

varied from 1 hour to 168 hours, with The usual characterization strongly on the features by

times of 24 and 168 hours for all materials. were used as described electron microscope earlier.

They depended

(SEM) with microanalysis measurements

of salient

EDS and WDS. The thickness developed

based on X-ray spectroscopy, where used for scale of thicknesses on cross sections in the SEM. in

for this part of the research(2),

under 1 pm. Above 1 urn they were measured These experiments particular surface were supplemented

with a number of other techniques, measurements,

X-ray diffraction,

weight change

and many types of as needed exposure of the in

analysis (ESCA, SIMS, ISS). The methods The morphology

will be discussed after

the text of this appendix. before and after

was characterized in water.

washing off the soluble materials as described earlier.

Analysis

wash water was performed

RESULTS AND DISCUSSION The results morphologies, carbides(1~3~4). conditions of 24 and 168 hours exposures, earlier after in particular the product and silicon

were described Scale thickness

for the various silicon nitrides 168 hours under gaseous,

acidic and basic (CVD and

are compared

in Fig. 1 and table I. For the purer materials of oxide formed oxidation, increased

single crystal) corrosion,

the thickness

in order from gaseous This

which was essentially

acidic and then basic corrosion. whose behavior is

trend is no longer clear for the more impure specimens dominated the sulfate by the impurities. was not depleted Under basic conditions on any samples

it must be emphasized

that

which were not preoxidized

before

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

139

168 hour:

sic-c

Sic-Si

Si3

IV,

Figure

1.

Thickness of layers formed for the oxidation, corrosion of C-side and S-side single crystal CVD silicon nitride after 168 hours at 1000C sulfate drops for acidic corrosion). Note that increase as OxA&.

acidic and basic hot silicon carbide and (measured between oxide thicknesses

140

High Temperature

Corrosion

of Ceramics

Table I Thickness
Gaseous SC SC -

of oxide scales after Acidic 0.6

168 hours exposures Basic

(urn)

si
c

0.11

12-25
SC SC -

0.5 _0.78 0.07** 0.9 2.5

1.1 1.2 (1.8)* 0.61 0.3 (1.41) 4.3 - 7.1 1.3 (2.1) 7.7 -- 1.4 (24 hrs) -6 1.5 - 2.1 2.4 - 3.2

CVD SC HP SC CVD SN HPSN Sin SN

Values in parenthesis are for spherulites under sulfate drops. For acidic corrosion the values not parethesis were measured between the droplets. 0.045 by WDS, 0.06 by ellipsometry, 0.09 SEM

**

SC SC -Si

= = = = = = =

single crystal single crystal

Sic, silicon side Sic, carbon side

SC SC-C CVD SC HP SC CVD SN HP SN Sin SN

CVD silicon carbide Hot pressed silicon carbide

CVD silicon nitride Hot pressed Sintered silicon nitride

silicon nitride

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

141

exposure

to the corrosion.

Experiments

on preoxidized

specimens

with thick complete

scales (>lO um)(3) and on bulk fused silica(s) consumption before of the sulfate on these materials

lead to the essentially as indicated

by EDS of the surface (table II). This

washing and by the semiquantitative tendency

wash water analysis

shows the fundamental

for the reaction + SO3 (1) and the silicate indicative with Impurities on of a

Nags04 In many cases, no sulfate

+ SiOq = Na silicate

could be detected

in the washwater This is probably

overall stoichiometry gradient crystalline in the silicate silicas

was about NagSiO3. composition

as the silicates

in equilibrium composition.

are richer

in silica than this average as surface silicates)(1p3).

in large amounts preoxidation

slowed this reaction yttrium

phases were formed

(Mg silicates,

For the purer materials while reaction which controls silicate Therefore samples oxidized materials

not preoxidized

it is clear from these results

that

(1) occurs under basic hot corrosion, the amount of silicate layers decreases formed

it is the rate of oxidation through the

and the transport

and sulfate

the rate of oxidation This is indicated

as the scale thickens.

the scale is protective. not only formed more as indicated not preoxidized.

since the preoxidized

more silicates by greater

which was water soluble but they weight gains (after scales washing) than the same were formed at 14OOoC,

Since the preoxidation extensively

they had crystallized

and cracked

during cooling before

application

of the salt and were not protective Under basic conditions reacts

during the hot corosion. wets completely the sample surface and

the sulfate

with the scale as it forms leading to very thick silicate (table I). This has been documented acceleration of oxidation

layers even on the

purer silicon nitride who reported

by Mayer and Riley(G) of NagCOS.

a transient

with injection

142

High Temperature

Corrosion

of Ceramics

Table II Wash Water Analysis From Basic Hot Corrosion Material Si02 At% (PO)(l) 25 52 22 50 0 53 -_ (PO) 59 SO3 At% 33 0 27 2 62 12 -_ 13 (168 Hours, 1000C) Na20 At% 42 47

SC SC

SC SC

CVD SC CVD SC (PO) CVD SN CVD SN (PO) SN SN SN SN

48

52

38 35 -27

SC SC

= Silicon Carbide

single crystal

CVD SC CVD SN Sin SN (1) PO

= CVD silicon carbide = CVD silicon nitride = Sintered silicon nitride in 02 for 10 hours at 1400C

= Preoxidized

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

143

With Na2S04 the reaction hours. Also the extent formed thicker

is milder(3~4~71 as all sulfate is affected possibly

was not consumed

in 168

of the reaction scales except

by impurities

and the purer silicon

materials carbide

for the hot pressed aid.

which contained for segregation present

alumina as a sintering in the scale either

The alumina showed no or hot corrosion. phase. The As

preference aluminum discussed

on oxidation

in the scale tended report,

to stabilize

the glassy silicate

in a previous

magnesium

and yttrium

tend to segregate conditions.

into the MgC in on

scale on oxidation. particular the surface corrosion

They complicate silicates

also the hot corrosion and tends to promote conditions. continuous

forms magnesium

basic conditions the acidic these

under acidic environmental on the impure samples formed

In general silicate

layers,

layers and

were quite thick for hot pressed were similar in morphology Early in the research under acidic conditions conditions. understand and establish crystal

silicon nitride

and sintered

silicon nitride

to those observed it became apparent

under basic conditions. that some hot corrosion corrosion under basic in order to occured

in addition

to the expected for shorter

Data on pure materials the fundamental

times

were needed

mechanisms

of hot corrosion degradation.

under acidic conditions Therefore the single for 1 to 24 hours the

if it could lead to significant

silicon carbide

and the CVD silicon nitride

were exposed

under standard temperature

acidic conditions

at 1OOOoC. In other experiments

and Na2S04 loading were varied as necessary. the sodium sulfate The wetting does not wet the siliconnitride

Under acidic conditions and silicon carbide both materials. variation completely.

angle was of the order of 40 for was bimodal (fig. 2). There was a but it was not consistent However the values

The drop size distribution

in the values of the wetting time or nature

angles measured of the sample.

with drop size, exposure

144

High Temperature

Corrosion

of Ceramics

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

145

observed

were greater

than measured

on fused silica under similar conditions. of time is shown in figure 2 for single as a layer around 120C to those in fig. 2 were As shown in the figure the as a result of a coarsening and they are usually (fig. 2). and CVD

The evolution crystal

of the deposit

as a function

silicon carbide.

The deposit

which was sprayed similar

breaks up as the sulfate observed smaller process. surrounded after droplets

melts and morphologies

a few minutes of exposure tend to disappear

at 1000C.

with time, probably

The large drops do not move on the surface after

10 to 24 hours by bands free of small droplets of acidic corrosion for single crystal

The kinetics silicon nitride

silicon carbide

are shown in figures

3-5 for times from 1 to 24 hours at 1000C. of vitreous droplets. oxide measured in in The

The plots of figures between,

3 and 4 were for thicknesses away from the sulfate

and generally

All the thicknesses

these two figures order to minimize

were obtained the influence

by the same method (X-ray spectroscopy(2)) of systematic errors in the interpretation.

data for silicon carbide of time suggesting show clearly function

plots as good straight behavior.

lines as function

of the square root do not

a parabolic

The kinetics as a function

for silicon nitride

this trend and are plotted

of time in figure 3a and as a data

of the square root of time in figure 3b. The lines for oxidation workers and interpolated from previous experiments

from previous research

in this enhances even

indicate

that the hot corrosion,

even under acidic conditions

the formation between

of the oxide layers in all cases for the purer materials

the salt droplets. applied per unit area of surface surface loading. was varied

The amount of sodium sulfate from 0, 0.1 and 5 mg/cm2, for oxidation, independent

the standard

While higher than that the sulfate droplets is

the growth of the vitreous of the surface

scale between

loading as shown in fig. 4. The data for different

146

High Temperature

Corrosion

of Ceramics

1000-

CVDSN /

/ /

-0

2 J;
v)

5 i

/ /
/

Hot

Corrosion

500.
/

/ / /

---Q

Oxidation

168 TIME(HR)

Figure 3.

Thickness of scale formed in the acidic hot corrosion silicon nitride at 1000C (5mg/cm2 of NaZSOq). (a) linear plot

of CVD

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon Carbide

147

/ / / / / //

/O
01
I--_-_-l

d
I
I

I.0

5.0
VT

9.0
(h OUTS ) L

13.0

Fimre

3.

(b) parabolic Figure 3(a).

plot measured between

the drops of

148

High Temperature

Corrosion

of Ceramics

C-side

1.0

5.0

7rme

12 (/+%)

Figure

4.

(a) Thickness of scale formed at 1OOOoC in the Acidic hot

corrosion of single crystal silicon carbide. Three different loadings of NaZSO4 on the surface 5mg/cm2 (A), less than 0.1mg/cm2 () and 0.0mg/cm2 (0) fell on the same parabolic plot. The data for silicon and carbon side fall on two separate lines. (parabolic)

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

149

H(t) -0

---

--

--

--

A--I

5.0 TIME *H *I

Figure

4.

(b)

Parabolic plots comparing of the data of figure 4(a) for single crystal silicon carbide (solid lines) with the oxidation of silicon (D + G )8 and single crystal silicon carbide (for carbon side () and silicon side (A) (Harris) 22 at IOOOoC.

150

High Temperature

Corrosion

of Ceramics

SPHERULITES UNDER DROPS 22

O-SC(C) ASC(Si) /

____I_
0

O-CVDSN

0 0
A i-.---. I3

l:o

l/2 I/2

510

TIME

(HR

Figwe

5.

Thickness of spherulites (oxides) formed under the sulfate droplets for the C-side and Si-side of single crystal silicon carbide and CVD silicon nitride (Acidic hot corrosion at 1000C). The solid line corresponds to the data of figure 4 for the acidic hot corrosion of C-side silicon carbide.

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

151

surface samples

loadings

fall on the same lines.

No salt was applied initially

on the

with 0 mg/cm2 loading but they were exposed with the other samples, through vapor transport. The independence salt activity a of

and they picked salt apparently the data on the surface maintained constant through aNa

loading is consistent

with a constant

the vapor phase and a fixed pSOS (1.5 x 10e3 atm) setting at 1000C according to the reaction

for the experiments

Na2S04 = Na20 + SO3 Kg = aNa20.pS03/aNa$304 No sulfate could be detected on the vitreous scale by SIMS and ISS, but sodium the formation This conclusion in detail of a and

was found by ISS in the surface silicate

layers of the scale suggesting of the scale.

layer about 10 A thick at the surface

the role of sodium in the acidic hot corrosion but it underlines in basic corrosion.

will be discussed

below, from that

that the role of sodium is different

in acidic corrosion

The rate of oxide build up under the sulfate corrosion on the purer silicon nitride except

droplets

formed

during acidic than

and silicon carbides

is much greater

that outside the droplets crystallizes

for C-side SIC as shown in fig. 5. The silica cristobalite material spherulites. at the center parabolic The evolution of the behavior which

rapidly under the salt forming thickness of this spherulitic

of the average droplets,

measured

after washing,

follows approximate

is close to that calculated at that temperature. fine crystalline

from Deal and Grove%(*) data for oxidation

of silicon

However this is fortuitous

since this part of the scale is

material

which grows from the melt.

152

High Temperature

Corrosion

of Ceramics

Acidic Hot Corrosion

of Silicon Nitride with the vertical

The data of figure 3a, is fairly linear with an intercept axis at about 80 A. This suggests with the present corrosion although electronic experiments.

an initial oxide layer which is not consistent were cleaned in HF prior to the hot

The samples

experiments

so that an oxide layer close to 100 A is not expected as established in the like the

some oxygen and water are always readsorbed, industry. The silicon carbide samples y-intercept

which were pretreated

silicon nitride data extrapolate measurements

do not have a significant essentially

(fig. 4). The silicon carbide The method of thickness

through the origin.

by X-ray spectroscopy

is also pushed to its limit with the very error in the measurements explanation does not is

thin oxide layers formed, appear responsible formed on oxidation

but a systematic

for this intercept. as discussed

Another

is that oxynitride

below. on the product layers formed on the

Laser ellipsometry samples

measurements

of table III were consistent given in the table. silica.

with an index of refraction

of 1.75 and the

thicknesses

This index of refraction thickness

is much higher than 1.46, are larger than those of were not

the one for vitreous figure 3 measured conclusive oxynitride.

The corresponding

by X-ray spectrometry

(Oku). IR measurements

since the spectrometer The method in general

could not reach the major peak for the silicon did not appear sensitive Tressler reflection to the presence of

silicon oxynitride

and was not pursued further. after extensive specular

et al. recently

reached

the same conclusion

FTIR spectroscopy@). layers formed

ESCA data is still expected. on CVD silicon nitride spectrometry crystal

The thickness

of the glassy product

were generally

lower when measured

by X-ray

than measured

on cross sections

in the SEM. For the Sic single in the

the thicknesses

measured

by X-ray were larger than measured

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon Carbide

153

Table III Scale Thickness of Selected Samples (A)

X-ray (4) A CVD SN (1) CVD SN (2) CVD SN (3) 450 120 130

Ellip (5) A 605 356 326

(1)
(21

CVD silicon nitride exposed to gaseous corrosion balance 02 for 168 hours at 1000C. CVD silicon nitride at 91OOC. CVD silicon nitride at 955OC. X-ray spectrometry exposed exposed [2] courtesy Terry OKeefe to acidic hot corrosion to acidic hot corrosion

1% SO2-SO3 for 24 hours for 24 hours

(3) (4) (51

Laser beam ellipsometry R & D.

Westinghouse

154

High Temperature

Corrosion

of Ceramics

SEM(2). The of thicknesses on the silicon nitride thickness measurements

in the SEM on very thin layers such as those formed and subject to errors but the trend in the layer formed on the by

are difficult

is consistent

with an oxynitride agreement

silicon nitride. ellipsometry. consistent

This is in qualitative Further

with the results data indicated

obtained

analysis of the ellipsometry

that it was of silica

with a graded film of oxynitride

with possibly an overlayer

50-100 A thick ( in contact graded layers of oxynitride The present results

with the atomsphere). apparently

Raider et al.(lO) reported of silica. of silica which

without overlayer

are in line with an initial formation by the surface reaction:

would be rapid and controlled

Si3N4 + 3 02 = 3 Si02 + 2 N2 giving very steep linear kinetics reaction 3, the pressure favoring

(3)

for short times in figure 3. As a result of rises and the oxygen potential of oxynitride decreases the at

of nitrogen the formation

the interface silicon nitride

which grows between

and the vitreous oxynitride

silica as proposed previously(ll). is expected bound. to be more difficult

Diffusion than through the

through the vitreous

silica(12) since it is more tightly layered scale becomes

The transport at steady state mechanisms

of oxygen through this giving parabolic of the in

rate controlling of the three

kinetics(l3). thickness

The sequence

and the distortion

data due to the formation calculation

of oxynitride

instead

of the silica assumed for the linear 24 hours.

the thickness

from X-ray spectrometry

are responsible

shape of the plot of figure 3a. The scale grows more slowly after thickness after 168 hours was measured

The

as 1 pm by X-ray spectroscopy

and 1.2

urn by imaging of cross section would be required became parabolic to establish after

in the SEM. However data for longer times yet if the growth had reached steady state and at lower

one week exposure.

Some data was obtained

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

155

temperatures

and shorter times in an attempt

to determinethe because

activation

energy of the

of the linear process early kinetics. The formation has been proposed

but this was not justified

of the complexity

of silicon oxynitride by previous

during the oxidation

of silicon nitride convincingly

workers but often not demonstrated which could not be interpreted (141, others

since they usually used one technique unambiguously.

Hench used IR spectroscopy and concluded

a combination

of ESCA

and depth profiling oxidation

that an oxynitride

was formed

during the of this readily and

of silicon nitride.

Others report

only silica as the product is prepared

oxidation(l@.

In the electronic layer.

industry silicon oxynitride Comparison

and used as passivating material indicated formed

of the vapor deposited deposits

oxynitride on silicon oxidation(lO).

by thermal

oxidation

of silicon nitride

that graded oxynitride

layers were formed measurements

by thermal

ESCA and index of refraction conclusions. formed Tressler

were used to reach these extensive characterization of scales methods

et a1.(gy13) performed

on oxidation

of silicon and silicon nitride SIMS, FTIR, ellipsometry under the silica. for a layered

using many different and concluded

such as etch back rates, of silicon oxynitride

that a thin layer

formed

The steady state the layers are controlled treated

kinetics

scale growing by transport through the scale.

through This was two case in

by the mobility of a specie

in detail by Yurek et al.( 17) for the diffusion

of metal ions through In the present

layers of oxide scale to oxidize at the gas-scale oxygen must diffuse through two layers,

interface.

the silica and then the oxynitride occurs at the nitride

order to oxidize the silicon nitride. oxynitride-silica is assumed interface

Part of the oxidation

and the other at the silica-silicon is controlling(g~l*)

interface. for

It

that oxygen transport

as generally

accepted

156

High Temperature

Corrosion

of Ceramics

dry oxidation difficult

of silicont lg).

Since diffusion

through

the oxynitride state

is more conditions that the

than through silica, the oxynitride than the oxide layer.

layer under steady

should be thinner thickness

Based on(17), it is expected controlled steady state

of the layers under diffusion y/x = Kpoxy/ Kpsil

will be given by (4)

in which y, x, Kpoxy, Kpsil are the thicknesses formation respectively. on silicon nitride of individual

and the rate constants and silica,

for the

layers of oxynitride y+x can be written

Kp* for the total thickness Kp* = (1 + Y/x)~ Kpsil

(5) kinetics would be similar to those

and if y is small Kp* = Kpsil. Then the overall of a silica layer forming distinct oxide layers. oxynitride directly

on silicon nitride.

This discussion

assumes layer

To a first approximation

the formation except

of a graded

of vitreous

would not change this conclusion distance than a layer of specific

that this layer This is

will spread over greater expected

composition.

from the previous

kinetic arguments to increase distribution

since the mobility as the nitrogen

of oxygen decreases.

through the oxynitride The detailed concentration conclusion

is expected

content

shape of the nitrogen dependence is consistent

would depend on the specific through the layer. The

of the diffusion

coefficient

with the graded layer found by ellipsometry of the scale found by X-rays.

and the of

large oxygen content

The index of refraction of the scale,

the scale appears high for the proposed

graded structure

this may

be due to the fact that steady state was not achieved samples. The conclusions

yet in the ellipsometry with the extensive except that they conditions. constants of

of this analysis are in agreement of silicon nitride

work of Tressler

et al.cg) on the oxidation

found a lower index of refraction They find high actication energies

to films grown under different

for both the linear and parabolic

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

157

a Deal and Grove analysis(*)

for the oxidation

of CVD silicon nitride and

between

1100 and 13OOOC. They conclude highactivation energies compared

that the low rate of oxidation

to silicon must be due to transport

of oxygen

through the silicon oxynitride kcal/mole between for the parabolic oxygen molecular

and it must be rate-controlling. activation

The 110-120

energy seem to rule out the rate control through vitreous silica. While to

or ionic diffision molecular,

oxygen transport,

particularly

through the oxynitride

is expected

be slower and with a higher activation analysis based on the formation controlling.

energy than for fused silica the previous scale suggests that it cannot be rate

of layered

Discussion

of the Hot Corrosion

of Silicon Nitride is very slow. The larger oxidation added for sintering rates(20) as shown and

The oxidation observed in previous

of silicon nitride studies

were due to impurities

in this research

in the gaseous corrosion

(and hot corrosion)

of CVD, sintered on the

hot pressed silicon nitride

as shown in table I. The oxide layers formed than observed

high purity silicon nitride (CVD) were thinner single crystal conditions. or CVD silicon carbide This may not establish in this respect

on the high purity or hot corrosion superior in older to

under the same oxidation that silicon nitride

is intrinsically as stated

silicon carbide literature.

but it is certainly

not inferior

The oxidation

of silicon nitride

is much slower than that of silicon although and it appears oxygen range but for silicon are similar

at 1000C in both cases a vitreous transport through the scale controls

oxide scale is formed

in both cases in that temperature different and not established already discussed

the detailed nitride.

mechanisms

are apparently

The general

features

of acidic corrosion

158

High Temperature

Corrosion

of Ceramics

for silicon nitride

was

and silicon carbide

and in particular The presence

the growth of the scale of Na20 on the surface of The

increased

under acidic corrosion.

the sample, behavior

supplied as Na2S04 (or Na2C03 etc...)

modifies

this oxidation.

of the Na20 depends on its activity 2. From the equilibrium by the SO3 pressure constant

in the sulfate

melt as determined of sodium oxide is reports. Under the by

by reaction

Kp, the activity in previous

then determined acidic conditions aNa

as described

(here at 1000C, a pSO3 of 1.5~10~~ atm was selected) reacts little with the silica formed

is small and the sodium sulfate of the silicon nitride

oxidation

or silicon carbide

as indicated formed

by the high values on the purer

of the wetting specimens expected,

angles on bulk silica(5) and on the scales above. Some penetration by the reaction = 2 -Si-O- + 2 Naf aNa20.Csiosi

as reported loosening

of Na20 into the silica scale is

the network

Na20 + -Si-O-Si-

(6)

Kg = [Csio12.[CNa+12/ * [Csio14/aNa20 This reaction should be applicable

also to the oxygen bridges of the oxynitride. molecular scales, diffusion of oxygen and a higher rate of interface

As a result of this opening of the network nitrogen oxidation. is increased through the vitreous

thus generating to the reaction

It is likely that the sodium ion diffuses as proposed for silicon, transition

where it is reduced

it was proposed

also that it would The sodium experiments and ISS, but

help in the silicon-oxide may affect

structural

at the interface(21). phase. In the present microprobe

also the stability

of the oxynitride

sodium has been suggested the evidence dissolved diffusion

in the scale with the electron Only very small amounts to reaction

is not conclusive.

of sodium need to be interstitial the

in the network according in silica glass as discussed

6 in order to increase

later for SIC. Under acidic conditions

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

159

rate of oxidation

of CVD silicon nitride discussed

is increased

between

the droplets

probably by the mechanism

above.

A very thin (slOA) layer rich in the droplets, by surface it did not contain diffusion or vapor any

sodium was found by ISS on the scale between sulfur. transport This adsorbed layer fed by the droplets

would supply the sodium into the glass. under the sulfate starts droplets oxidizes more rapidly After than

The silicon nitride outside and crystallization exposure out(l). droplets. the surface

early (in the first hour).

24 hours of stood

and washing off the salt the region which were under the droplets The corresponding The crystal-glass of the sample. thicknesses interfaces in Table I were measured provide high diffusivity outside the

paths normal to regions

Some liquid is present concentrated

in the intercrystalline

in which sodium and other impurities Thus the crystallization thicker provides

during the crystallization. paths for oxygen leading penetration to

fast transport drops and greater

scale under the sulfate

of the scale under

the intercrystalline spherulites

regions such as the interfilamentary

regions of the

shown in figure 6. for pure materials, vitreous scales are formed occurs

Under acidic conditions which crystallize in between

very slowly outside the droplets.

Some crystallization is extremely

the droplets

but it is sparse and the growth disperse

slow as 168 hours

judged by a few very small spherulites exposure. nucleation The difference started

in the glass even after

in growth rates

is illustrated drop.

in figure 6 where The growth away from the in detail in appendix (or

under the edge of a sulfate

drops appear slower yet than in this example. A, the crystallization aNa20) in the structure, oxide reaction of vitreous silica depends

As discussed

on the Oxygen ion activity in the network. those defects

and the presence (reaction

of defects 6) provides

The sodium and tends to

with the network

160

High Temperature

Corrosion of Ceramics

~6.

Acidic hot corrosion of CVD silicon nitride at lOOOoC. Under the sulfate drops (washed off in micrographs) the oxide crystallizes as spherulites. After 24 hours the spherulites coarsen to globular arrays.

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

161

occur preferentially at the interface between the salt and the sulfate where aNa is highest. Under acidic conditions, in close proximity to the atmosphere

(outside the sulfate droplets) the gaseous potentials remain close to pSO3~1.5 x 1V3 atm and ~02~1 atm and the aNa is low. Under the sulfate droplets, the

oxygen and SO3 are more difficult to replenish as they are depleted by the oxidation reaction at the silicon nitride-oxide or sulfate interfaces. equation (2) and so3 = so2 + l/202 K7 = (p02)li2 .pSO2/pSO3 (7) Based on

The activity of Na20 is raised under the sulfate droplets (it is higher than outside) and the crystallization is promoted under the droplets.

Acidic Hot Corrosion Of Silicon Carbide The morphologies of the samples of single crystal silicon carbide after exposures were described previously (lp3) and for short times are generally similar to those described above for the silicon nitrides (see fig. 2). They are characterized by the formation of sulfate droplets separated by smooth vitreous regions. The spherulitic growth of cristobalite occurs rapidly under the drops and it is generally similar to the behavior observed on the silicon nitride (fig.6). Preferential attack occurs also under regions between the cristobalite crystals as shown in Figure 7 in which the silicon oxide has been etched away. The kinetics of acidic hot corrosion for single crystal silicon carbide at 1OOOoC are plotted as a function of the square root of time in figure 4 and they fall on two distinct lines both higher than the oxidation data of Harris(22) sketched on the figure. The two lines have been associated with the carbon side and the silicon side of the single crystal. In agreement with the oxidation results

162

High Temperature

Corrosion

of Ceramics

of Harris and Tressler et al.(g) the carbon-side is the fast or thick side and the silicon-side is the thin or slow side. Hot corrosion data was obtained also at 955OC and 910 oC. The data at 910C are plotted in figures 8 and 9 and both sides still show parabolic behavior at that temperature. Activation energies for

the growth of oxide scale in the temperature range 910-1000C were determined from the parabolic constants B* calculated from x2 = Bt in which x is the scale thickness at time t. The thickness measurements were all performed by one method (X-ray spectroscopy) in order to minimize the influence of systematic errors. The plots of figures 10 and 11 give activation energies of 34 and 118 kcai/mole for the carbon-side and the silicon-side, respectively. Silicon carbide is a polar crystal and has different basal surfaces (0001) and (0001)(23) which can be differentiated by a number of methods based on different surface morphologies after high temperature wet oxidation or attack by fused salts(24). The present hot corrosion experiments resulted in milder attack but it was clear after extensive experience that slight differences in morphologies existed between the two surfaces which allowed their identification. Namely

after hot corrosion for long times, the silicon side between the droplets appeared as-polished except for some interference colors on the thicker scales and the carbon-side was rougher, duller in texture. Different oxidation behaviors have

been reported(g*22) for the two sides. This difference in behavior was no longer apparent at high temperatures (1400-15OOoC). Similar basic hot corrosion behaviors were found for the two sides in this research at 10000C(1~3~4(. Under acidic hot corrosion, the vitreous scale between the droplets grows faster on the

*B was determined also by the Deal Grove formulation but it gave the same results since the data plotted as functions of t1/2 falls on good straight lines extrapolating through the origin (fig. 3,7,8).

Appendix

D-Hot

Corrosion of Silicon Nitride and Silicon Carbide

163

~7.

Acidic Hot CorroSion 0( silicon carbide single crystal (lOOOOC). The substrate was attacked under the spherulites as shown after disSOlution 0( oxide in HF.

164

High Temperature

Corrosion

of Ceramics

31OC KINfllCS

5000

4000

3000 3 x I? 5 0 5

2000

000

0 0.00
2.00 4.00 6.00 a.00

SQRT(TIME(HR))

Figure 8.

Kinetics of acidic hot corrosion of C-side single crystal carbide at 910C (parabolic plot). Note reproducibility

silicon of data.

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

I65

91OC KINETICS
600

SI

500

4oc

z x Y $ I! F

300

200

100

0
0 2.00 4.00 SQRT(TIME(HR)) 6.00 8.00

Figure 9.

Kinetics of acidic hot corrosion of Si-side single crystal carbide at 91OoC (parabolic plot).

silicon

166

High Temperature

Corrosion

of Ceramics

ACTIVATION ENERGY 1400

i 3.80

13.60

13.40 G 5 1320

13.00

i 2.80

12.60 0. 78 0.80 1000/T

0.82

0.84

Figure 10.

Arrhenius plot for the acidic hot corrosion silicon carbide.

of C-side

single crystal

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

167

ACTIVATION 13.0

ENERGY

St

12.0

1 1 .O

10.0

8.0

3.78

0.80 1000/-T

0.82

0.84

Figure

1.

Arrhenius plot for the acidic hot corrosion silicon carbide.

Si-side single crystal

168

High Temperature

Corrosion

of Ceramics

carbon side than on the silicon side as reported on figure 4 both sides show well defined results the carbon-side was parabolic

by Harris for oxidation. behaviors

However

parabolic

while in Harris over

and the silicon side had linear kinetics For the hot corrosion the apparent

the broad time scale of the experiments. activation carbon-side. energy

of the slow side (Si) is much larger than that of the fast

Model for the Oxidation Conditions

and Hot Corrosion

of Silicon Carbide

under Acidic

In order to discuss the hot corrosion conditions oxidation. dependent in between the sulfate

of silicon carbide

under acidic its is to occur. as

drops, it is important

to understand

The formation on the transport diffusion

of silica scales

on silicon and on silica formers for the oxidation

of oxygen to the substrate

The molecular established temperature diffusion.

of oxygen through

the scale might be rate controlling that as the oxygen

for silicon dry oxidation. is increased Others contributions

It has been proposed(g)

are made by the network of CO produced

have argued that the diffusion is rate controlling

in the oxidation is

of silicon carbide

and since the size of the two molecules Considering recent the

about the same it is difficult experiments(g) oxidation it is concluded

to distinguish(z5). that transport

of oxygen is controlling

of silicon carbide

at low temperatures

(below c 14OOoC). In earlier was controlling of C-side at higher silicon at low

work it was concluded temperatures(l*).

that the diffusion

of C-products

They found two regimes

in the oxidation

carbide from 1200-1500C, temperatures (216kUmole) silicon carbide

one with low activation

energy (123kJ/mole)

and the other with high activation at 1 atm pressure of oxygen.

energy at high temperatures the oxidation of silicon-side energy

However

had only one regime

associated

with a high activation

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

169

(240kJ/mole controlled several

in 1 atm of oxygen). by oxygen transport contribute

The kinetics

of the carbon-side satisfactorily vacancy

oxidation that

were modelled to this transport;

assuming

processes

diffusion

in the network in the 1200-1350C In the

and molecular analysis(g).

interstitial The molecular diffusion

diffusion diffusion

were considered dominates

specifically

at low temperatures

while the vacancy temperature similar

dominates

at high temperatures the oxidation

1350-1500C.

range of the present except

experiments slower

of the carbon side is energy diffusion and of

to that of silicon,

with the same activation

linear dependence

of B on the oxygen pressure (gl. The molecular the kinetics. At low oxygen pressure through the scale. for the complete

oxygen is dominating appears to control

a vacancy

mechanism

the oxygen transport energy

The silicon side is temperature range of These

slower and has a high activation 1200-1500C(gl. results Harris reported

linear behavior of the defect

at low temperatures. structure

must be considered reactions,

in terms

of the silica scale for the oxidation

and the surface

then mechanisms

will be proposed

and then for the hot corrosion.

Proposed

Model model is concerned with the lower temperature range

The following around 1000C. il ii) iii) iv)

It addresses: the different rates of oxidation and C-side silicon carbide the enhancement role of Na20) the activation of oxidation energies and hot corrosion for Si-side (the

under acidic hot corrosion

for hot corrosion constant, relative to that

the magnitude of B, the parabolic for silicon oxidation

170

High Temperature

Corrosion

of Ceramics

It is based on:

the variation in stoichiometry of vitreous silica with its formation under different ~02 at the reaction interfaces. This variation in stoichiometry and the associated defect structure modify the transport of oxygen through the scale the oxidation results of others summarized above the oxygen transport model of Tressler and Speartg) applied to lower temperatures the surface analysis results of Muehloff et a1.(26) our acidic hot corrosion results.

ii) iii) iv) v)

Defect Structure and Stoichiometry of Silica Vitreous silica is not often considered non-stoichiometric in the glass

literature although glassy structures which are great solvents allow greater variation in composition than the corresponding crystals. It is known that the

silica formed under oxygen deficient environments crystallizes more slowly than similar silica formed under more oxidizing conditions(27). Silicon rich silica has

been prepared in the electronic industry. Fratello et a1.(28) discussed the influence of OH impurities on the crystallization of silica on the basis of the defects and stoichiometry of vitreous silica. While the defect structure of

vitreous materials is relatively controversial for strpctural defects and mass transport, the electronic defects have been studied in great detai1(2gy30). In general it is accepted that the SiOg glass structure is built with SiO4 tetrahedra connected through oxygen bridges to form a continuous random network. Thus structural defects may extend to any kind of orderin$31). The major defects in

silica have been reviewed by Motttao); they are dangling bonds in particular the well known single bonded oxygen, but also 3 bonded silicon. They include also oxygen vacancies in oxygen bridges as well as Si-Si bonds. The single bonded

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

171

oxygens tend to form in silicate associated expect with network

glasses

to accommodate

extra oxygens It is reasonable to

modifying

ions in the structure.

that oxygen vacancies It is anticipated Reaction

and Si-Si bonds are favored also that compensating defects

under oxygen deficient can be generated and an oxygen vacancy

conditions. thermally.

8 generates

2 single bonded oxygens

2 Si-0-Si = Si- -Si + ZSi-0 nil = Vo + 2SiO K8 = [Vo] [SiO12 = Cv [SiO12 in which [V,] = C, is the concentration network. equation Under low oxygen pressure so familiar for crystalline of oxygen vacancies oxygen vacancies oxides

(8)

Si- -Si in the

could form by the

00 = Vo + I/2 02 + 2e K = [e12 [Vo] [~02]~/~ = 4Cv3 [~02]l/~ where the vacancies supplied directly assumed are formed at the oxide-gas interface and the oxygen is [e] is

by the atmosphere

and the electron

concentration

to be supplied

only by the reaction that the oxygen

so that [e] = 2 Cv. It is more molecules are dissolved of dissolved Reaction into the oxygen 9 occurs oxygen

appropriate

here to consider

glass at the scale-gas proportional

interface

with the concentration through

to the oxygen pressure

Henrys law.

inside the scale under pO2 lower than at the interface is that dissolved in that environment Si-0-Si (concentration

and the molecular Cm) so that (9)

= Vo + l/2 02 dis + 2 Si-

Kg = 4Cv3 Cm112 in which the electronic includes the dissolution equation charges are associated with silicon dangling The formation bonds and Kg in

of 02 gas into the glass. unrealistic

of electrons

9 may have appeared in vitreous

since silica is an insulator. form such as dangling

However, bonds on

they exist commonly

silica in trapped

172

High Temperature

Corrosion

of Ceramics

silicon shown in equation contains conduction positive

9. It has been shown that thermally charge centers.

grown silica electronic

and negative

Silica films support

during anodization(32). structure is built up on 5 and 6 member These rings provide network-modifying over 3A(33). rings which are tortuous paths for the than the of a

The vitreous randomly diffusion distributed

on 3 dimensions. and impurity

of gas molecules

ions smaller In the growth by the

size of the windows in the structure, scale the growth formation flux may introduce channel

a little

anisotropy

to this structure

of more aligned

in the flux direction(34). in order to explain

Larger channels silicon oxidation

less

than 50A in diameter and reported

have been postulated

from observations

in the TEM(35).

Oxidation

of Silicon Carbide of silicon carbide at the reaction interface except generates in presence of this

The oxidation very low oxygen pressures of free carbon, calculation considered carbon. interface defects:

which cannot

be calculated Sic-SiO2-C.

exactly

for the ternary

equilibrium

The results

which gives pO2 of the order of 10m30 atm at 1000C can be a lower bound for the oxidation of materials not containing excess

If active

oxidation

does not occur the silica formed

at the reaction of corresponding equilibrium

is expected vacancies,

to be oxygen deficient 3-bonded silicons

with the formation

and possibly Si pairs. the concentration

Thermal

of the type of equation oxygens

8 will suppress

of single bonded

CJoxid = mNB/2x in which CJoxid is the sum of the oxidant oxidation and N, B, x are the number fluxes which contribute

(10) to the in 1 cm3

of oxygen molecules

incorporated

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

173

of scale, constant

the parabolic m is determined

constant

and the scale thickness, between

respectively. oxidants

The

by the mass balance

and products(g). molecular in

Two types of contribution which molecules silica and network defects. mechanism Assuming equation of oxygens

are made to the transport are transported through

of oxygen, channels,

in the vitreous

contribution

which can occur through

the various network is by a vacancy

that the major mode of network 10 becomes DvCv + DmCm = mNb/2

transport

(11) the vacancy Therefore and molecular the kinetics contribution of of the two

in which Dv, Dm, Cv and Cm are respectively diffusivities oxidation transport and concentrations, of silica formers respectively.

may depend on the relative

paths which are determined Different stoichiometries of dissolved

by the stoichiometry on formation

of the scale at a of the scale will

given temperature. result in different

oxygen pressures through

equations

8 and 9. Under low oxygen and on the basis

pressure

the quantity

oxygen (Cm) will be depressed of oxygen vacancies mechanism of a gradual

of equation tending diffusion.

9 the concentration

(Cv) will be increased over transport change by molecular

to favor transport

by a vacancy

This in line with the proposal at high pressures of silicon(g).

from molecular for the

mass transport thermal

to ionic mass transport Based on equations of silicon carbide

at low pressures

oxidation

8,9 and 11 one can explain in the low temperature range in

the oxidation

and hot corrosion

which oxygen transport

is assumed

to be rate controlling. of silicon in 1 atm of dry oxygen, and equation 11 becomes to pO2 and it has for the

First let us consider molecular diffusion

the oxidation

is dominating

the transport@) constant

simply DmCm = NB/2. an activation energy

The parabolic

B is proportional

Q = 28 kcal/mole

which is similar

to that measured

174

High Temperature

Corrosion

of Ceramics

permeability

of molecular

oxygen through bulk vitreous

silica(331.

As discussed is

later, slightly

if one assumes

that the silica scale formed because it was formed Although than DvCv.

on C-side silicon carbide

oxygen deficient

under a low pO2 (Cm decreased), than for the oxidation transport of oxygen

then by equation of silicon, dominates by Tressler

9, Cv increased.

it is smaller Molecular

DmCm is still greater but from equation

11, B is smaller

than for silicon.

This was observed and an On

et al.tgl, this oxidation dependence similar

has activation

energy (27kcaVmole)

oxygen pressure

to that measured

for silicon oxidation. was formed

the other hand if the scale on the silicon-side under very low oxygen pressure, and Cv increased network diffusion activation

of silicon carbide

by the same reasoning

Cm is greatly

depressed and the

since Cv * Kg/(Cm) li6. controls the oxidation

So that now DvCv>>DmCm resulting

in a much lower B, a higher Therefore for the It postulates of

energy (55-60 kcal/mole) model it is possible obtained by others

and a low pO2 dependence(gl. to derive a consistent picture

with the proposed oxidation different results

for silicon and silicon carbide. on silicon-side

conditions

of formation

of the scales below.

and carbon-side

silicon carbide

which are discussed earlier

As discussed at different This indicates character rates

the two sides of single crystal

silicon carbide

oxidize

for long periods of time at lower temperature the two sides maintain their separate

below 1300 C. their specific identity ion et after

that under those conditions

as they oxidize.

The two sides maintain

grinding and polishing bombardment

as shown in the present to mix the surface. had different

experiments

and after

(sputtering)

It was shown also by Muehloff under low pressure

a1.(261 that the two surfaces oxidation.

stabilities

Under ultra high vacuum the carbon side was observed to graphitize

to cover with until 13000K. At

carbon above 900 K while the Si-side did not start

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

175

that temperature

the graphitization maintained

of the carbon-side qualitatively

was extensive.

The two

sides of silicon carbide

their relative

rates of oxidation surface

during the early oxidation mixing due to sputtering. explained the evolution

for thicknesses

of silica up to 20A, even after

This carbonization

of the of the carbon side was at the site

of silicon under the very low oxygen pressure

of the reaction Sic + l/2 02 = CO + Si Under 1 atm of oxygen, sides is maintained however it is assumed that this difference (12) in stability of the two

and that silicon still tends to volatilize in the reaction

from the C-side,

both carbon and oxygen are oxidized SIC + 02 = SiO + CO

(13) at the reacting interface SiO is

In the pO2 range (s~O-~O atm) which is expected the prominant possible vapor specie in the Si-0 system(36).

As shown in figure

12, it is

by this reaction

to always maintain

the order of the Si and carbon atoms of the The SiO is but not at

at the interface silicon carbide oxidized

so that on the C-side as it oxidizes

carbon is always at the surface the C-side behavior.

thus maintaining

as it meets with higher oxygen pressure

near the interface

the interface results oxidizes

and the silica forms as a rough porous scale and a rough interface oxidation reaction. As the oxidation is filled. proceeds the SiO

from the active

in the pores so that the scale porosity

The scale is formed

under higher pO2 than is found at the interface stoichiometric. On the Si-side, oxygen is adsorbed penetration between the silicons

and it will be more

are at the surface

and it is proposed

that by

first on the silicon (figure 13) and the carbon is oxidized this oxide layer always maintaining silicon

of oxygen through

the oxide and the SIC in line with the Si character

of that side.

This in

176

High Temperature

Corrosion

of Ceramics

1)

SiC

Figure 12.

Model for oxidation of C-side silicon carbide. A rough interface is formed and the C-side is maintained at the interface during oxidation. The SO2 is formed away from the interface.

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

177

Sic

Sic

3)

Atmosphere

I02

01 Sib

sic

Figure 13.

Model for oxidation of Si-side silicon carbide. nature of the interface is maintained.

The silicon side

178

High Temperature

Corrosion of Ceramics

line with the results of Harris (linear kinetics of oxidation) as the CO would form under the silica layer and desorption of CO from that position could control the oxidation. At higher temperatures or in presence of sodium this desorption is no and parabolic kinetics are observed. The scale is formed as

longer rate controlling

under very low oxygen pressure and it is expected to be very oxygen deficient discussed earlier. oxygen deficient The scale formed under these conditions would be more than that formed on the C-side. In the oxidation of SiC the

network transport and the molecular transport add to supply the oxygen. This interplay between the two types of transport processes is underlined as the temperature of oxidation is increased and their relative contributions change for

the C-side and the Si-side. As the temperature

is increased, transport by the energies increases

vacancy and other network mechanisms with high activation rapidly and becomes a major contributor

to the oxidation of the carbon side. The

oxidation of the silicon-side has been increasing also since it was dominated by the network transport processes. As the temperature is increased the mobility increases also in the SiC interfaces and they can no longer be differentiated the mechanisms of fig. 12 and 13 and around 1350oC the two sides oxidize at about the same rate with the same activation Therefore the proposed model is qualitatively energy as reported by Tressler(9). consistent with the data on the by

oxidation of silicon and silicon carbide, now we shall apply it to our acidic hot corrosion results.

Acidic Hot Corrosion As discussed earlier acidic hot corrosion is oxidation enhanced by the presence Na2Q at a low activity. Na2Q enters into the silica structure by

reaction 6 and generates single bonded oxygens thus modifying the defect

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

179

concentrations

in the vitreous

silica.

Single bonded oxygens are oxygen excess of oxygen deficient defects through

defects reactions

which lower the concentration of the type

2 Si-0-Si = Si- -Si + 2 Si-OK14 = [Vo] [Si-O12 = Cv [Si-012 Therefore as Na20 is introduced into the scale,

(14) it tends to increase the vacancy the single

bonded oxygen concentration (eq. 14) which inturn increases

(eq. 6), this decreases the molecular

concentration in the glass sum of

oxygen concentration which is the algebraic

(eq. S).This can be written equations 6, 14 and 9.

as a single equation

Na20 = 2 Na+ + l/2 02 gas + 2eKl6 = [Na+][02]1/2 showing the Cm is proportional such as those formed transport and increase [e12/aNa20 Therefore

(15)

to aNa20*.

in oxygen deficient network

scales

on silicon carbide molecular

the sodium will decrease

transport

as it drives the scales towards

more

stoichiometric

compositions. oxidation model will now be applied According to the previous to the discussion,

This result and the previous acidic corrosion the oxidation controlled paragraph, molecular corrosion

of C-side silicon carbide.

under 1 atmosphere diffusion

dry oxygen at low temperatures as DmCm >> DvCv. Na20 increases giving greater compared

(1OOOoC) is

by molecular

As shown in the previous Cv, therefore for the acidic under

in the hot corrosion transport is enhanced

Cm and decreases parabolic constant

of C-side silicon carbide

to that for oxidation

*Equation 15 may be considered as the dissolution of sodium oxide in the glass in an interstitial position (network modifier). Interpretation beyond the relationship between aNa and [02dis] could be misleading since defects in the glass structure are required to accommodate the Na+ ions and the electrons. Therefore equations 6, 9 and 14 appear more representative of the reactions occuring in the glass.

180

High Temperature

Corrosion

of Ceramics

corresponding increased is similar silicon(*).

conditions.

In our experiments

the parabolic

constant

B was cm2js which of

by a factor

of about 4 at 1000C.

It was about 3x lo-l4

to B=3.2xlO-I4 This result

cm2js of Deal and Grove for the oxidation of silicon carbide

is in line with the scales

being more

stoichiometric

under acidic corrosion

than those formed

in dry oxygen oxidation of scales by oxidation analysis the

and with lower oxygen pressures of silicon carbidethan activation permation oxidation energy

expected

in the formation

in the oxidation

of silicon.

From the previous

for acidic hot corrosion

is expected

to be that of the

of molecular

oxygen through vitreous and silicon. Therefore

silica, the same as for the it should be 26-28 kcal/mole. higher because plotted in figures of the 11 and 12

of silicon carbide measured

The 34 kcal/mole

is close but significantly The parabolic constants

nature of the experiment. were determined Na20 activity. total pressure catalyst at constant The initial

sulfur content mixture

in the atmosphere

and not constant

of 1% S02-balance

oxygen at one atmosphere over the (equation 7). pSO3 an

was used at all three temperatures. decreasing pSO3 for increasing

After passage temperatures

it generated

From equilibrium and therefore apparent diffusion

relation

2 the activity temperature.

of Na20 increases

with decreasing with aNa20, for molecular

with increasing

Since B increases

activation

energy greater

than the 26-28 kcal/mole

of oxygen and the oxidation of 02 molecules

of silicon and C-side SIC will be measured. by reaction 15 will be dominating the to

When the generation activation energy

for diffusion

will be increased

since B will be proportional

DmCm and both terms 15 that Cm o (K aNa20P temperature dependences

will depend on temperature. in which both K and aNa and n is a fractional considered

It can be seen from reaction have exponential such as 2/9 obtained the enthalpy of

exponent

from the defect reaction

equations

in this report. defect

However

15 and in general

the operating

equations

are not known so that

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

181

it is doubtful

that an exact temperature

dependence

can be derived.

It is clear higher than activation may not be

that the activation that for oxidation. energy (34 kcal/mole) representative dominate

energy for hot corrosion The difference between

should be significantly the measured diffusion apparent

and that for molecular the activity

(27 kcal/mole)

because

of sodium may be too low to completely suggest that the two mechanisms

the transport.

Simple considerations oxygen molecules

of generation magnitude

of the diffusing

were of the same order of Experiments with higher

in the present produced

experimental

conditions.

Na30 activities

by initial gas mixtures

such as 0.1% SOZ-balance

oxygen would answer this question. For the acidic hot corrosion reasoning dominated constant decreases contribution reactions equation in defect transport temperature as observed B extrapolated activation activity is applicable, by network however transport of Si-side silicon carbide, the parabolic (vacancy oxidation the same general to be

was expected

mechanism)

with a low parabolic by the hot corrosion the molecular

B. As for the C-side, the network

the Na30 introduced

contribution

(lowers Cv) and increases to equations

(raises Cm) according considered Cm increases

6, 9, and 14 or 15. In the since Cm = k/Cv6 in Therefore contributions if and at what dramatically to the change to the

rapidly as Cv decreases

9 and Dm >> Dv by about 4 orders of magnitude. concentration affect dramatically the relative to state

of oxygen although the molecular experimentally.

it is not possible flux became

dominant.

B is increased

It is increased

by a factor

of about 16 compared

from the oxidation

data of Tressler

et al.tgl.

The large apparent the Na30

energy increases between

is due to the same effect with temperature the results

as for the carbon-side, above.

as discussed

A quantitative is

correlation

for C-side and Si-side acidic hot corrosion

being considered.

182

High Temperature

Corrosion

of Ceramics

REFERENCES 1. J.R. Blachere and P.S. Pettit High Temperature (a) DOE Report ER45117-2, March 1986 (b) DOE Report ER45117-1, June 1985 (c) DOE Report ER10915-4, June 1984 J.R. Blachere and D.F. Klimovich, *J. Am. Ceram. (1987) paper appended in Appendix E. B.S. Draskovich, D.F. Klimovich, MA thesis, University University Corrosion of Ceramics

2. 3. 4, 5. 6. 7.

Sot. 70 [ll] C324-C326 1985. in preparation. 1987, (Appendix B).

of Pittsburgh, of Pittsburgh,

M.S. thesis,

M.G. Lawson, M.S. thesis,

University

of Pittsburgh,

M.I. Mayer and F.L. Riley, J. Mat. Sci., 13, (1978) p. 1319-1328. (a) (b) N.S. Jacobson, J. Am. Ceram. Sot., e, [l] 74-82 (1986). N.S. Jacobson and J.L. Smailek, J. Am. Ceram. Sot., a [8] (1985), p_ 432-39.

8. 9. 10. 11. 12. 13. 14. 16. 17. 18. 19. 20.
91

B.E. Deal and A.S. Grove, J. Appl. Phys., 36 (1965), p. 3770. R.E. Tressler and K.E. Spear, GRI Report GRI-87-0088, 1987.

S.I. Raider et. al., J. Electrochem. S.C. Singhal, Ceramurgia R.H. Doremus, R.E. Tressler

Sot., 123 [4] (1976), p. 560. 2 [3] 123-130 (1976).

International,

Glass Science,

Wiley 1973, p. 121. GRI-86/0066, 1985.

and K.E. Spear, GRI Report,

L.L. Hench et. al., Ceram. I. Franz and W. Laugheinrich

Eng. and Sci. Proc., 3 [9] (1982), p. 587-595.

G.J. Yurek et. al, Oxid. Metals, 4 265 (1974). J.A. Costello F.P. Fehlner, and R.E. Tressler, Low Temperature J. Am. Ceram. Oxidation, Sot., 64, (1981) p. 327-331 .

Wiley 1986, p. 211. Heat Engines, Noyes

D.C. Larsen et. al, Ceramic 1985, p. 234. Reference 19

Materials

for Advanced

-*.

Appendix

D-Hot

Corrosion

of Silicon

Nitride

and Silicon

Carbide

183

22.

(a) (b)

R.C.A. Harris and R.L. Call, in Silicon Carbide 1973, R.C. Marshall et. al., eds., University of South Carolina Press, 1974, p. 329. R.C.A. Harris, J. Amer. Ceram. Sot., 68, 1975, p. 7-9. Semiconductor,

23. 24. 25. 26. 27. 26.. 29. 30. 31. 32. 33. 34. 35. 36.

J.W. Faust Jr., in Silicon Carbide, A High Temperature J.R. OConnor and J. Smiltens, (Pergamon, 1960). Ibid, pv 403. D.M. Mieskowski (a) (b) et. al., J. Am. Ceram.

sot., 67, (1984), C17-Cl8

L. Muehloff et.al., J. Appl. Phys., fl [7] (1986), p. 2558-2563. Ibid, fl [8] (1986), p. 2842-2853. Glass Forming Systems, Academic Press (1967), p. 53.

H. Rawson, Inorganic V.J. Fratello D.L. Griscom,

et. al., J. Appl. Phys., 51 [12] (1980), p. 6160-6164. MRS Bulletin, June 16/ August 15, 1987.

N.F. Mott, Adv. Phys., 3, Reference Reference Reference 19 p. 67 19 p. 233 12 p. 133

1977, p. 363.

A.G. Revesz and H.A. Schaeffer, Reference 19 p. 230

J. Electrochem.

Sot., 129, 1982, p0 357.

U.S. Department of Energy, Thermochemical Stability Diagrams for Condensed Phases and Volatility Diagrams - DOE/FE/13547-01, May 1980.

Appendix

E-Publications

Many presentations are:

have been made on this research.

The most recent

ones

- Hot Corrosion

of Non Oxide Ceramics Corrosion

[l] and Silicon Carbide [2]

- High Temperature

of Silicon Nitride

The research

is being written

up for publication.

These publications

are: [3]

- Oxide Thickness * Hot Corrosion

- Hot Corrosion

Measurements

in the Electron B) [4] C) [5]

Probe Microanalyzer

of Silica (Appendix

of Alumina (Appendix of Silicon Nitride

- Hot Corrosion - Hot Corrosion - Corrosion

and Silicon Carbide

[6] [7]

of High Purity Silicon Carbide [8]

and Silicon Nitride

of Ceramics

The first paper is appended. need further work. The material

Appendix in Appendix available.

B is ready for submission. C will be submitted next.

The others Reprints will

be supplied as soon as they become

Appendix

E-Publications

185

REFERENCES

1.

J.R. Blachere, D.F. Klimovich and F.S. Pettit, Hot Corrosion of Non Oxide Ceramics, paper # , Fail meeting, Basic Science Div. Am. Ceram. Sot., Nov. 5, 1966. J.R. Blachere, D.F. Klimovich and F.S. Pettit, High Temperature Corrosion of Silicon Nitride and Silicon Carbide, Invited paper, Workshop on Corrosion of Ceramics, Penn State, Nov. 12-13, 1967. J.R. Blachere and D.F. Klimovich, Oxide Thickness Measurement in the J. Am. Ceram., 70 [ll], C324-C326 (1967). Electron Probe Microanalyzer, M.G. Lawson et al., Hot Corrosion Am. Ceram. Sot. M.G. Lawson et al., Hot Corrosion Ceram Sot. B.S. Draskovich in preparation. of Silica, ready for submission to J.

2.

3.

4.

5.

of Alumina,

in preparation

for J. Am.

6.

et al., Hot Corrosion

of Silicon Nitride

and Silicon Carbide, and

7.

D.F. Klimovich et al., Hot Corrosion Silicon Carbide, in preparation. F.S. Pettit and J.R. Blachere,

of High Purity of Silicpn Nitride of Ceramics, in preparation.

a.

Corrosion

186

High Temperature

Corrosion

of Ceramics

, wh,ch the/(X) reel,, for dx X-ray,

funcoons prwdc rbaorpo along [he prthr

the cor1 ,hc cocffip IS the

of Ihe chrraccsc + I

Oxide Thickness Measurement in the Electron Probe Microanalyzer

J. K. BLACHERE*

,cr,s,,c delccwr.

,, 15 dcfmcd

ar I,,/,,)

wh,ch s/p

I, the mar, abwrpr, f the tilm. and $

event for the hnc measured I; the titm. is the denrny

AND D. E KL~MOV~CH*
f P,,,,burgh. P,,t,burph.

cepamle~ f Mawnrtr Sacncr and E.ng,nrennp. Vlw,#ty Pcnniytunlr ,526, An X-ray Thr

method/or

rhe meosuremenfs for silica

of the thickness
tilms on silicon

of wpporred
nrrride

rhmjilms

in

Ihe micromobr

is modified

and silicon

carbide.

L3keff angle. The ex~en~~vc. but slmplc. ealcuta,mns are dr,cr,bcd ,n dclrd ,n Ref, ? and 3. They rcpon ~4 rcwl,, tar ,mgteelemcnl tilmr For muloclemcnl lilms. It 15 powble I obtam buth Ihc tilm rhrcknos nod Ihe cmpo,mon by mcrrur,ng r( ~1,s for all co,noonems of Ihe film. In txxh CBYI, all Acrclclclrl effccr, (atomic number. rbrorpo. nnd lluoreicencct arc a\rumrd nept~glblc il, mlfhr be cxpccwd I a first ~ppruxmu,~ fur lhm f,lm,

inctvhrrirs o/rhe o.&rn Ka linrbre measured on bulk SIO- und on rhe/i/m. The derivation of the colibrarion curve giving the rhicknru of the film from rhe rario of rhesr inrensiries is ourlined. The method has been used /or srl~ca Jilnts rhwwr rhrr~~ I um wirh a lawral resolurion of a few micromrrurs.
X,DE 0. nctded thxkness for mnny Ihe rczareh mcasuremen,s arc The m~enuty-thickness rclaoonsh~p is nor

applications such as on rhc oxidation and hot corro-

SL of uhcon node and sdxon carbblde. Many methods hzve been used LOassess the evluon of Ihe oxidaoon process; bowever. they arc often mdlrect or desuuctive. Fur ~rtimcc. wghc changes arc the nc, rewll of simuluncous rcacu~ whxh g,ve lfvxing comnbuuona. More dwcct mcahrrmcnts arc oficn dependent on etchmg or frxurc of the specimens Other methud> dppbcrble to rhm films ax very dceur.w bu! do nor have spatial re)oIulion. The ctecrron prtw microanalyzer IEPMA) otfcrr a nundcslruct~vc means of mcaurimg ttlc Thickness of suppancd films wnh a high lalcral resoluuon which we have uxd for rihca films a silicon nilnde and silicon carb,dc.

slmplc smcc the Xaya generdlcd are a function of depth I the sample. and they are abrorbed rccordmg Lo the prrh of their cx~l from rhc samolc The mrcroan~lyrir of dun tilmr has bee revxwcd by Guldslem. In order 1 calculate rhe inw&ry of the X-rays genernled in [hc aample. Yakowtz and Newbury rooaed a emomeal aooruach bdscd on ii&g Ihe X-raydepfh ~roducrion ewe +(pzt to rhe combmmoo of a parabola and an ripmrnt,~l. The mdss rhicknrss p: IS ,hc prduct f ,he d,,ww from Ihc rurfacc

oi

The menrny of characteristz X-rays, yeneraed by a ctec~ron barn for an element conlrmcd m a thin titm and not in the
bubruale. 15 related 1 the thickness of the thm film and cmpw~n of the sample.

: by the drnrlry p f Ihc sample m Ihrt lhlchne,,. Cornoared t Ihnr for a bulk a!&ard of Ihe co&wlion of Ihe tilm. the @(pi) ~rvc for the lhm tilm IS tnmcrred at [he mas, tblckncs, pz, of dw lilm and it mctudo P mo,hf~ed b;rckscattering y!eld of the cIcc~rs wh,ch accoum, fur the sub,,ra,c cnlr~bu!wn The mwn~~ty of the charnclerwc X-rays emmcd frum the film II compared to thrl en,,rled by a bulk ,tand.ud of Ihe film ma!eriA The in!may r.11, I, of these I~ncr. which can be mr~wed. IS prpon~onrt 1 tbr rat of Ihc mlcn&llcs 1 the lilm l/L) standard /,: of lhc X-raya gencrafrd 1 [hat generated I a bulk

The prcw, method was adrpled Lo meas~remcnta of the ,hxknos of s,hca films on sd,cn carb,de md s,hc mmde wng lhc oxygen Ko hnc t,, appllulu LO light elcmcms tatamlc oumbcr Z< req&cd scvcr.d mod,f,caun, ,,ncc the low-energy X-ray, p&wed ,,re wungly absortxd and Ihe ab,rprw crrec,,n 13 w_mlarge I use Ihe approruna~c/(~) rales. The mwn,mc,,~ crlsut,md for Eq d,ffercm trum Ihe mc.,rured m,c,meS 1. becau,e of ~brvp,, .lhe X-rry, SC grncrad A! var,, dcplh, I ,hr san~ptc and I calcul~!c I,. lhe,r m,cn,,,y must be mtcgraad over dw depth of prwtucuon:

tI)

xe

C I)

For

un4

ahsorou

[he ~lal

mtcn,W

Appendix

E-Publications

187

November\

#(PZ)

00

r
1987 h,k Parabolic h

IO

loo
Thickness

1000
,nm,

IXOO

kh

and 0.1425

were calcul.Acd

rer~ctwely

for

bulk SIO,. S,,N,. md SIC The>e value) were blamed for a pnmrry clec~ron barn ener~v elem;;l,al Therefore, in which simdar fic,en,. of IO keV bv m~erwlrtwn elcmcmal of the of drta of He;r,ch;nd rddmon cclf~c,en,~. .~e so cc&

mars-weighted

the fdm and Ihe wb\,rrtcs brckscartermp ua,

and iir IS calculr,sd from mca,ured ,,cn,,,,eh as

the prcdlcled

dxa, .I ca,a,

Iha, of the ondc.

urcd for dll

film thxknesse$ rouhmg I an enor es,,mr,ed I br <I% of ,bc film dnckne\ses for xhca X[-@z-t&f glass on s,bcon nitride ,ubw.oes

(p:-h++

j]

in which If 15 Ihe X-WV m,es,,v measured from Ihe f~irn md /Z ;s rhu lot& mcawed fur the bulk aodard. The mwgration for /: ,s over ,hr mas lh,ckness of [he film and Ihrl for Ihe bulk mtenwy is over Ihe uhole depth of X-ray producd p:, g,ven by Ihe X-ray praluc!, range of Hemnch. Equroon (4) ha, ken wed rucce,rfully by KelM,. Ttw mwosmc, of Eq (4) were integrated I clozd form u~,e Ihe arabolic-exThe arrumrd 4(p:c) cwve 1s sketched I Fig. I. For [he prrabohc ,eg,on

The inlegrrl for Ihe parabolic and exponenoal r.eg,on 8 a lhxkness p ,uch as

and slightly over 1% for sd~con crrbrde wbsorlo. For other subsmale-tilm comb,a,,,. when ,h,r a,aump,, 1s no, \rhd. a film b;rcksca,tenp cwflicwn, wt be calculawd as a funcoon 1 p:, d.,. I. aod h are different for lilm .md wb,trr,e. Cabbra curve, of 1, II film ihlckncss were calculr~ed u,,h a compu,er u,mg Eq. (4) and Ihe mclhod oullmcd above. S,l,ca glr,s u!,h .I den,,,y of 2 2 g/cm was ured for the lilm I ,dI ma rage. ma,, Ih,ckne,,. and ab,rp,,on COICUIIu,. The cahbrat, cunc 1, ,houn m Fig. 2 for sdx carbldc md ,dxo mmde ,ubwa,es.

pi,>p:>l.Sh

1s

x
wnh

-(pz,?+K(p-_.-I

IShI 5hl

(8)

ponenwd expresrm- &p;) for

Q=exP[P&&-X

j] 1.Shx

lip.-J=h~(~:-h)(a-k)+k
and for the rrponenwl rrg,o

(5) I;=I,
(for pi = I.Sh)

were

The inteosmes of Ihe x)pc measured 1 a ,ca,~

Ku line
elcc~

The panme,er,

C&B and h are a funck.

exp(w

(6)

don of [he backscattering clewon yield. Using values for the bulk matenal, the Ite,,,y for lhr bulk standard I, crlculaed: ,.=I, ifor pr=pz,)

m,croscope* fmcd wlh IWO ud\slmglh disperwe spec,rmctcn equ~ptwd for hgh, eleme, .mrly~r. All wmple, uere coaled w,lb &a~, 20 m of carbon. Duphcnle mmsurcment~ were made ,,muluncously wth ,hr IWO spec,rme,ers ill a .,ccelcrdlion voltage of IO kV and a beam curre, of 20 rA. The ra,as kr tie calculaled from Ihe measured intms,l~es corrected for background. The oxide Ihicknes,es CA be read from Fig. 2: ntedd. a am~ple m,erp&on program and E.q. (4) were used LOgel them more exacdy. The meawremelS are very reproducible. and a standard error of 1% or less IP c;rlcula!ed for Le values corre,pondme 10 th,cknesxs >IW nm for a se, 01 lob-s co,m,~ on pea, md background. for film and srandsrd. I, i, ~mprowd by lhr comblnarlon of several of these measuremen,,. They were uwlly repcrIed at ,hr ,ame we and it, sevrral Icat~ons of

in which Ihe parameters 6, k. and h are cab culzued followmg Keuwr and Goldstem. The mlegral for Ihe parabolic reg,. for a dwknes, ,x<l 5h. IP

However, for thm films Ihe elrcrron backxa,,er yield mcludes a conrnbution from the subwale. Approx~ma,~na of Ihe da, of Cusslet were u,rd prev~ou,ly wed m lh,s case Some var,~,,s dnd on Ihe

(7)

electron ,rrnrm,ra~n cwffiwn, of the ,ubauele were also med. The aweme vales of Ihe backsca,ter cwfticlen, of the film ,huld be thrl of the ,ub,rrate for a film mfmwly lhm md lbsl 01 Ihe bulk film mr,er,;ll for a IhIck film. I tb,, case. bilckscaltrr cocffic~ent?, of 0.1316. 0 I37 I,

188

High Temperature

Corrosion

of Ceramics

Communicdonr
Table I. Oxide Thickness Comparison* Ilwkncncu (PI, SImplc

of rhe American

Ceramic

Societv better

November

1987

SUN+ Oxan Eq (I) for tits La\k. As

2. httle addmonal the sofr X-ray, lhrckness produced

shown in Rg. SEM energy beau% a, xygro

can bc measured w,th dur higher electron deep in tbe sample by hght elements such are almost completely absorbed ,lopc of the of Tb,s rc~ults m Ihe shallow rhe two curves for low film

I
: 4 2

SIC. SC
SIC. SIC, SC Sic. SC SI,N, SI,N.. CVD

Typr

WDS 0.32 0.20 0.31 0.17 0.10 0.05

0.21 0.13 0.30 0.11 0.09 0.12 lr-

curve for duckcr tilms and Ihe prormuty ducknose,. signlftcanl Imermedmte as 20 kV

electron beam energies such not provide

.sc=nng!x clyrul. WDS..X.R) yzuuu.

mlcmuulvrir. ud sEM=lnugw

did

impmvemcn~~

similar

momholoev

a Ihe

surface

Of the

by as much as 30 to 50%. repmducibday of the X-ray

However.

tbe

The X-ray melhod ,u,r dexnbed has bee used consi~~rntly I our rebesrch for the measoremeot of StOl films wrh thicknesses from producibdtry SEM. IO m I 1.0 pm with a reThicker of a few percent.

sample. It I; esu&red

that tix rcprcduc~-

method 1s ex-

bdtty of Ihe thicknesses measured by this procedure was of Ihe order of II. REIWLTS AND Discuss& The Ihicknenes of glassy regions of xzde layers formed by oxidation and hot corrouon on GIlcon carbide and silicon nitnde al IooOC were measured bv lhls in mothal and by unagrng of cross sec& tbe SEM. The mraruremen~s by SEM Imaging

cellent. and Ihe meahurements are srraightforward. Reuter clawned an accuracy of

+10%

for the thicknesses of lhin films of N,. and Au on various substrates Application method I hgh! elements Ismce Ihe physical

films were imaged m cros) secuon m the a procedure whtch is earbe, and more The X-ray method I, nonand ha a lswal rraoluuon oi a II ;IllWS a correlauon of rorasureznen~ with surface fca;malyaccurare than dzscussed earher for the thanncr films. do,,uc,,ve tb~kneas

Al. Cu.

measured by a slmdill. method of the X-ray quanuties, creases the uncenrmry

such as roass absorpoon coeffiAlso. X-ray absorplnn wavemra-

few mrcrolnel~r,;

cientb. used in Ihe caIcuIa11ons are not as well estabhshed. play, a mqor ,eng,hs. role for Lhe longer wnh Ihe SEM

The rcsulls are gwe I Table 1.

[ores such a, spheruhlrs or glassy regtom. Other techniques such as chemical sir. opr~cal mwferometry. ad elhp5m-

proved difficult for films under I gm duck. The magnX~ar~n was cahbraled wilh staodud latex spheres. The samples were fractured and brhdv elched I HBF. to reveal the oxide idye;. They had been carbon coated pnor 1 fracrure to observe tie morphology of the wface. and I, was found that dos coating helped mantain Ihe surIace edge of the oxide lilm during etching. The samples were recoated to avold chargmg I Ihe electron beam and the coating dwkea,es were large compared lo some of the ride layers of Table 1. Under tbr cd#ins of Ihe measurements. il is expxred lhar Ihe resolution of the SEM did not reach 10 em. The experimenrai difficulties in the SEM imagmg of these thin Inyen resulled in large experimenlal scaLLer and poor accuracy. II is estimated that the uncexiaintv of tbe thicknesses measured dlrecrly I Ihe SEM could be as high as 40 to 50% for the dunner oxide films. As shown I Table I, rhe LW methods gwc tie same order of magmwde but their results differ

Con~parison

sure,,,en,s ruaeerts that the accuracy ,sbe,rer dun 30-g. The shape of the callbrat, curve of F,g. 2 sgge,t, Ihat thick-

euy. whrle roorc accur.~~c. do no! offer lhls lateral re,o1u~~ whtch 1s highly dewable in roatmal5 sc~cnce.

nessts inIhc rang~l0nmlo0.8 I pm to

can

be measured: these values correspond ap roxlmatelv to the linear part of tbe curve. lower se1 by counring statisLies. For the thicker lilms, the sens~liwly decreass as the curve of Fig. 2 levels off. It was clamxd lhrl the ongmal method \yas reasonably accumte up 1 306 of dx bulk inter~cf~on volume, correspondmg in this car to <0.5 ,.un. However. the more extensive absorprion correction performed

ihe

iimir is

dir

here should allow

the range of the lea-

surements to be extended Increasing the pnmuy electron energy should also increase Ihe film thicknesses which can be measured by generaling Xrays deeper in! the sample. This WPI shown for metal films with Eq. (I). A calibruion cuwe for 30.kV prunary elecmoos was generated wrh Eq. (4). which 16