Oxides and Hydroxides

of Aluminum
Alcoa Technical Paper No. 19, Revised

Karl Wefers
Chanakya Misra

Alcoa Laboratories
1987

Copytight” Aluminum Company of America

., _
 Preface

One hundred years after the invention of the Bayer Process for the production of aluminum oxide,
new uses are still being found for this material. in advanced ceramics, separations and catalysts,
the manufacture of integrated circuits as well as in composite systems.

This revised edition of Alcoa Laboratories Technical Pa~r No. 19 includes discussions of how our
understanding of the stmcture and properties of aluminum oxides has progressed since the original
was published in 1972. The first Technical Paper on this subject was published in 1953 by
Dr. Allen S. Russell.

1 believe it is entirely appropriate for this revision to be published in the year in which both Alcoa
and the Bayer Process conclude their first century.

Dr. Peter R. Bridenbaugh

Acknowledgments

The authors wish to thank their colleagues of Alcoa Laboratories who contributed to this monograph
1 by supplying data, photomicrographs, and many helpful suggestions: A. Pearson, J, J. Ptasienski,
D. R. Micholas, W. T. Evans, G. A. Nitowski, L. F. Wiesennan, C. Bates, and D. Tzeng. Special
/ thanks go to D. E. Thomas and his associates for their excellent work in reproduction and printing
~ and Mrs. M. Weber for her diligent and patient typing of the many revisions of the manuscript.

Tbe encouragement and support by the directors of Alcoa Laboratories is great fully acknowledged; so
is the critical review of the manuscript by Mr. W. B. Frank of Alcoa, Dr. A. S. Russell (Alcoa, ret. )
I and Dr. J. Dillard of Virginia Tech. Mr. R. S. Zhu and Dr. R. L. Snyder of Alfred University
supplied the computer-generated stmcture models. We thank them, and we are indebted to the many
colleagues in industry and academia who responded so well to the first edition of TP 19 and
encouraged us to undertake this revision.
Karl Josef Bayer introduced his elegant process for the industrial production of afuminum oxide 100 years ago, in 1887. Since
then, the basic concept of the process - hydrothermal digest of bauxite, crystallization of aluminum trihydroxide from a
supersaturated sodium aluminate solution, thermal conversion of the trihydroxide to anhydrous aluminum oxide has remained
unchanged.

More than 30 million tons of aluminum oxide we produced each yew, most of it being used for the smcltin8 of aluminum. Tbe
remaining part of the annual production finds application in areas which utilize the high melting point, excellent mechanical
strength, electrical resistivity, or chemical inertness of aluminum oxide. Refractory, we= resistant ceramic parts, equipment for
chemical processing, and high voltage insulators are the classical products. Newer applications include substrates for integrated
circuits and reinforcing fibers for pot ymer and metal-based composites.

Surface oxides on aluminum and its alloys play an important role in corrosion and protection from corrosion, in adhesive bonding,
coating, and laminating of metal. They are also applied in the manufacture of capacitors and electronic devices such as MOM
(Metal Oxide Metal) transistors.

The unique surface properties of the stmcturally and stoichiometrically disordered transition aluminas are utilized in catalysis and
separation technology.

Many of these applications were driven by an increasing scientific understanding of the chemical, structural, and surface
properties of aluminum hydroxides and oxides. The foundations for this fascinating field of science and engineering were laid by a
generation of researchers, many of whom were these authors’ teachers, mentors, or older colleagues. F. C. Fr~, H. Ginsberg,
A. S. Russell, J. Newsome, H. Stumpf are some of the names that come to mind.

The authors were introduced to the field of alumina science at a time when refined techniques of stmctural, thermal, and electron
microscopic analysis had made it possible to correlate chemical and physical properties with CIYSM structure and
micromorphology at a level of a few nanometers. Recent advances in theoretical solid state chemistry and, in the past decade, the
emergence of surface probes ~rmitting the study of monolayer or small clusters of atoms, further increased our understanding of
the effect of non-ideal stmcture and composition on functional properties of aluminas.

Because of the authors’ personal
viewpoint. An attempt has ken
which oxides and hydroxides of
aluminas, tbe authors have used
of inorganic chemistry.
experience and interest, the following monograph is somewhat biased towards a stmctural
made to demonstrate the structural and chemical principles that xe common to the many forms in
aluminum occur. Rather than trying to give an exhaustive review of the vast literature on
the concept of stmcture-pro~rty relationships to deal with an extensive and still very active wea
 Oxides and Hydroxides of Aluminum

TABLE OF CONTENTS

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
Introduction .... ....... ......... .... ........ .... ...... .................................... .......... ii

1. Wlstory and Nomenclature .... .... ............ ...... ......................................... ..... 1

2. Properties of Aluminum Hydroxides and Oxides ....... ... .............................. ............. 2

2.1 Alumina Gels and Gelatinous Aluminas ............... ... . . . . . .. . . . .... . ... ... .............. 3’
2.11 Gelatinous Aluminas Formed by Acid-Base Reactions ... ... . . . . . .. . . . .... . ... ... .............. 2
2.12 Gelatinous Aluminas Prepared by Otber Chemical Routes .. . . . . . .. . . . .... . .. . ... ............ .. 4
2.13 The Structural Evolution of Gelatinous Alumina . . . . . . . . ... . . . . . .. . . . ... . ... ... . ..... .. ...... 5
2.14 Gelatinous Boehmite or Pseudoboehmite .............. ... . . . . . .. . . . .... . ... ... .............. 8

2.2 Aluminum Tribydroxides .... . . . . . . . . . . . . . . . ... ......... . . . . ............ ... . . .. . . . . . . . . . . . 10

2.21 Gibbsite ............ .. ..... . . . . . . . . . . . . . . . ... ......... . . . . ............ ... . . .. . . . . . . . . . . . 10
2.22 Bayerite .... ........ .. .. ... . . . . . . . . . . . . . . . ... ......... . . . . ............ ... . . .. . . . . . . . . . . . 11
2.23 Nordstrandite ....... .. .. ... . . . . . . . . . . . . . . . ... ......... . . . . ............ ... . . .. . . . . . . . . . . . 12
2.24 Doyleite . . . . . . . . . . . . . .. .. ... . . . . . . . . . . . . . . . ... .. ....... . . . . .... ........ . .. . . .. . . . . . . . . . . . 13
2.25 Interrelationships .... .. ..... . . . . . . . . . . . . . . . ... ......... . . . . .... ........ ... . . .. . . . . . . . . . . . 14

2.3 Aluminum Oxide Hydroxides . . .... . . .. . ... . . . . . . . . . . . . .... . .. . . . . .... . . . . . .. . .. . . . . . . . . . . . 15

2.31 Boehmite .................. . .. .. . . .. . ... . . . . . . . . . . . . ... . . .. . . . . .... . . . . . .. . .. . . . . . . . . . . . 15
2.32 Diaspora . . . . . . . . . . . . . . . . . . . . .... . . .. . ... . . . . . . . . . . . . ... . . .. . . . . .... . . . . . .. . .. . . . . . . . . . . . 17
2.33 K1-Alz030r Tobdite . . . . . . . . . . .... . . .. . ... . . . . . . . . . . . . .... . .. . . . . ... . . . . . . . . . . . . . . . . . . . 17

2.4 Aluminum Oxide . . . ......... . . . ... . ... . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 18
2.41 Corundum, a-Alz03 ......... . . . ... . ... . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 18
2.411 Crystal Structure .. ......... . . . ... . .. . . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... .. ..... .. 18
2.412 Preparation ....... ......... . . . ... . .. . . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 20
2.413 Thermal Properties . ......... . . . ... . .. . . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ...... . .. 20
2.414 Diffusion and Related Properties . ... . .. . . ... . . . . . . .. .. . . . . . . . .... ....... . . .. . . . ... ....... .. 23
2.415 Electrical Properties ......... . . . ... . ... . ... . . . . . . .. .. . . . . . . . ... ........ . . .. . . . ... ....... .. 24
2.416 Dielectric Properties ......... . . . ... . ... . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 25
2.417 Optical Properties .. ......... . . . ... . ... . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 26
2.418 Magnetic Properties ......... . . . ... . ... . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 2s
2.419 Mechanical Properties ....... . . . ... . ... . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 28
2.4110 Surface Properties . ......... . . . ... . ... . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 29
2.42 Aluminum Suboxides ........ . . . ... . ... . ... . . . . . . .. .. . . . . . . . ........... . . .. . . . ... ....... .. 35

2.5 Appendix to Section 2- IR Spectra and X-Ray Data

3. Binary and Ternary Alumina Systems ................ ... ........... ................... ............. 36

3.1 The A1203-H20 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

3.11 Phase Relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.12 Volubility of A1203 in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

3.2 The Na20-A1203 System . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . ... .... . . . . . . . . . . . . . . . . . . . . . .. 39

3.21 Phases Occurring in the System . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . ... .... . . . . . . . . . . . . . . . . . . . . . .. 39
3.22 Sodium Aluminate NaAIOz . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . .. . .... . . . . . . . . . . . . . . . . . . . . . .. 39
3.23 Sodium Beta Aluminas . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . ... .... . . . . . . . . . . . . . . . . . . . . . .. 40
3.24 Beta Aluminas as Solid Electrolytes. . . .. . . . . . . . . . . . . . . . . . . . . . . ... .... . . . . . . . . . . . . . . . . . . . . . .. 42

3.3 The Na20-A1203-H20 System ....... ........ ........................................ ..... .. 43

.. .
111
Alcoa Laboratories

TABLE OF CONTENTS (continued)

-

4. Phase Relations of Aluminum Hydroxides and Oxides Under

Nonequilibrium Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

4.1 Properties and Applications of Calcined Hydroxides . ... . ..... .... ......... ....... ............ 46 (

4.2 Thermal Decompositions of Aluminum Trihydroxides ... . ..... .... ......... ....... ............ 46
4.21 Gibhsite .......... .... .... .. ... ....... ......... ... . ..... .... ......... ................... 46
4.22 Bayerite and Nordstrandite .. ...... ...... ......... ... . ..... .... ......... ................... 48

4.3 Decomposition of Aluminum Oxide Hydroxides ..... . .. . . . . . . .. . . . . . . . . . .. . . .. . . . . . . . . . ... . . . 48

4.31 Boehmite ... ....... ............. ............... . .. . . . . . . .. . . . . . . . . . .. . . .. . . . . . . . . . ... . . . 48
4.32 Diaspore . . . . ................... ............. ... . .. . . . . . . .. . . . . . . . . . .. . . .. . . . . . . . . . ... . . . 50
4.33 Other Methods for Preparing Transition Aluminas . . . .. . . . . . . .. . . . . . . . . . .. . . .. . . . . . . . . . ... . . . 51

4.4 Structures of Transition Aluminas. .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .. . . . . . . . ... .. . . . . 51

4.41 Chi and Kappa Alumina . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .. . . . . . . . ... .. . . . . 52
4.42 Etaand Theta Alumina . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .. . . . . . . . ... .. . . . . 52
4.43 Gamma and Delta Alumina ..... . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .. . . . . . . . ... .. . . . . 53

4.5 Texture and Surface Properties of Transition Aluminas . . . . . .. . . .. . . . .. ... . . .. . . . . . . .. . . . . . . .. 54

4.51 Development of Porosity . . . . . . . . . . . . . . . . . ........... . . . . .. . . .. . . . .. ... . . .. . . . . . . .. . . . . . . .. 54
4.52 Relationships Between Texture and Structure .......... . . . . .. . . .. . . . .. ... . . .. . . . . . . .. . . . . . . .. 60
4.53 Properties of Active Alumina Surfaces . . . . . ........... . . . . .. . . .. . . . .. ... . . .. . . . . . . .. . . . . . . .. 60

5. Surface Oxides on Aluminum Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

5.1 Oxides Formed by Solid-Gas Reactions ............. ... ... .. .... ......... ................... 64

5.2 Tbe Reaction of Aluminum Surfaces with Water . .... ... ..... .... ......... ................... 66

5.3 Oxides Formed by Anodic Polarization of Aluminum . .. . ... . . ... . . .. . . . . . . . . . .. .. .. . . . . . . .... 68

5.31 Non-Porous Oxide Films . .. . . . . . . . . . . .. .. ....... . .. .. . ... . . ... . . .. . . . . . . . . . .. .. .. . . . . . . .... 68
5.32 Porous Anodic Oxides . . . . . . . . . . . . . . .. .. ....... . .. .. . ... . . ... . . .. . . . . . . . . . .. .. .. . . . . . . .... 69
5.321 Properties . . . . . . . . . . . . . . . . . . . . . . . . . .. .. ....... . .. .. . ... . . ... . . .. . . . . . . . . . .. .. .. . . . . . . .... 69
5.322 Applications of Porous Anodic Films . . .. .. ....... . .. .. . ... . . ... . . .. . . . . . . . . . .. .. .. . . . . . . .... 73

6. Bibliography ........ .. .... .... .... ...... ...... .......... ... ..... .... .... ..... . .................. 75

No. -— Title

2.1 2.1 Volubility of AI(OH)3 as Function of pH . . . . . . . . . . . . . . ... . . . . . .... .. . . .. 3

2.2 2.11 Aging of Aluminum Hydroxide Gel, X-Ray Pattern . . . . ... . . . . . .... .. . . .. 3
2.3 2.12 Fibrillar Gelatinous Aluminum Hydroxide ........... . ... . . . . . .... .. . . .. 4
2.4 2.13 Formation of Polynuclear Rings by Condensation ..... . ... . . . . . .... .. . . .. 6
2.5 2.13 DeprotonationlCondensationReactionsLeadingtoChains .. . . . . . .... .. . . .. 7
2.6 2.13 Tabular Gibbsite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . .... .. . . .. 7
2.7 2.13 Bayerite Somatoid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . .... .. . . .. 8
2.8 2.21 Aggregates of Technical Gibbsite . ..... .... .... ..... . ... . . . . . .... .. . . .. 10
2.9 2.21 Structure of Gibbsite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . .... .. . . .. 11
2.10 2.25 Layer. Stacking in Al(OH)3 . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . .... .. . . ..

iv
 Oxides and Hydroxides of Aluminum

FIGURES (continued)

No. Title 1Page No.

=
2.11 2.31 Boehmite Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 15
2.12 2.31 Structures of Boehmite and Diaspore . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 16
2.13 2.32 Diaspore Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 17
2.14 2.411 Corundum Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 18
i 2.15 2.411 Structure of Corundum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 19
2.16 2.413 Cell Parameters of &-A1203 as a Function of Temperature ... .. .. . . . . . . . . . 19
2.17 2.413 Specific Heat of a-A1203 as a Function of Temperature . . . ... .. .. . . . . . . . . . 22
2.18 2.413 Thermal Expansion of a-A1203 as a Function of Temperature .. .. . . . . . . . . . 24
I 2.19 2.413 Thermal Conductivity of a-A1203 as a Function of Temperature .. . . . . . . . . . 24
2.20 2.414 Self Diffusion of Al and O in A1Z03 . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 24
2.21 2.415 Electrical Conductivity of a-A1203 as a Function of Temperature . . . . . . . . . . 26
2.22 2.5 X-Ray Diagrams of Aluminum Oxide and Hydroxides ....... .. .. . . . . . . . . . 34
2.23 2.5 Infrared Spectra of Aluminum Hydroxides . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 35

3.1 3.11 Phase Diagram A1203-Hz0 . . . . . . . . . . . . . . . . . . . . . . . ........ ..... ....... . 36

3.2 3.12 Soluhility of Gibbsite in Water . . . . . . . . . . . . . . . . . . . ........ ..... ....... . 38
3.3 3.13 Stability Ranges of Aluminum Hydroxy Complexes in Water . . . . . . ....... . 39
3.4 3.21 Na20-A1203 Pbase Diagram . . . . . . . . . . . . . . . . . . . . . . ........ ..... ....... . 40
3.5 3.23 Structures of ~ and ~ Aluminas ................. ........ ... .. ....... . 41
3.6 3.3 Phase Diagram Na20-A1203-H20 ................ . ........ ... .. ....... . 44
3.7 3.3 Volubility of A1203 as a Function of Temperature and Concentration of Na20 45
3.8 3.3 Solution Isotherms in the System Na20-A1203-H20 .. ........ ... .. ....... . 45

4.1 4.1 Transformation Sequence AI(OH)3 + AliOj . . . . . . . . . . . . . ... ....... . ... . . 47

4.2 4.21 Acicular Gibbsite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... ... .... . ... . . 48
4.3 4.21 Acicular Corundum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... ... .... . ... . . 48
4.4 4.21 Surface Area vs. Temperature of Calcined Gibbsite . . . . . . ... ... .... . ... . . 49
4.5 4.21 DTA - Curves of Heated Hydroxides ............. .... . . ... ... .... . ... . . 49
4.6 4.21 Tabular Alumina from Gibbsite Calcined with Fluoride . . . ... ... .... . ... . . 50
I 4.7 4.33/4.4 X-Ray Diffraction Patterns of Transition Aluminas . . . . . . . ... ... .... . ... . . 52
4.8 4.51 Chi Alumina lo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... ... .... . ... . . 56
4.9 4.51 Chi Alumina llc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... ... .... . ... . . 56
4.10 4.51 Eti Alumina llc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... ... .... . ... . . 57
4.11 4.51 Kappa Alumina from AcicuIar Gibbsite . . . . . . . . . . . . . . . . . ... ... .... . ... . . 58
4.12 4.51 Kappa Alumina llcof Gibbsite, Reordering . . . . . . . . . . . . . . ... ... .... . ... . . 58
4.13 4.51 Alpha Alumina from Acicular Glbbsite . . . . . . . . . . . . . . . . . ... ... .... . ... . . 59
4.14 4.51 Alpha Alumina, Primary Crystals and Pores . . . . . . . . . . . . ... ....... . ... . . 59
4.15 4.51 Gamma Alumina from Boebmite . . . . . . . . . . . . . . . . . . . . . . . ... ....... . ... . . 60
4.16 4.53 Configurations of Surface Hydroxyl Groups . . . . . . . . . . . . . ... ....... . ... . . 61
4.17 4.53 Five Coordination of Surface Hydroxyl Groups . . . . . . . . . ... ....... . ... . . 62
4.18 4.53 Adsorption of First and Second Layer of Water on A1203 . ... ....... . ... . . 62

5.1 5.1 Growth and Transport Mechanisms of Thermal Oxides, Schematic . . . . ..... 65
5.2 5.1 Progressive Recrystallization of Amorphous Surface Oxide on Aluminum ... 66
,,
5.3 5.2 Multilayered Hydroxide Film on Aluminum . . . . . . . . . . . . . . . . . . . . . . . . ... .. 67
I 5.4 5.2 Duplex Film on Al Formed in Boiling Water . . . . . . . . . . . . . . . . . . . . . . . ... .. 68
5.5 5.31 Voltage-Current Relationships in Anodizing Al . . . . . . . . . . . . . . . . . . . . . . ... .. 68
5.6 5.31 “Tunnel’’E tchedAlw ithBarrierOxide ................... ........ ... .. 69
5.7 5.321 Initial Cell Development ................................. ........ ... .. 70
5.8 5.321 Texture of Porous Anodtc Oxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... .. 71
5.9A-C 5.321 Cross Section, Surface and Fragments of Porous Anodic Oxide . . . . . . . ... .. 72, 73
5.10 5.321 Cells of Anodic Oxide Advancing into Metal . . . . . . . . . . . . . . . . . . . . . . . . ..... 73
5.11 5.322 Cross Section of Sealed Anodic Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 74

v
Alcoa Laboratories (

INDEX OF TABLES

Table No. = Title

— -

1.1 1 Comparison of Nomenclature 2

2.1 2.21 Mineralogical Properties of Oxides and Hydroxides 12

2.2 2.21 Structural Properties 13

2.3 2.21 Thermodynamic Properties 21

2.4 2.21 Values of Coefficients for Specific Heat Equations 22

2.5 2.413 Selected Values of Thermal Properties of A1203 23

2.6 2.414 Possible Disorder Mechanisms in AlzOA 25

2.7 2.416 Dielectric Properties of Corundum 27

2.8 2.418 Magnetic Properties 28

2.9 2.419 Mechanical Properties of Corundum 29, 30

2.10 2.5 Infrared Absorption Frequencies 32

2.11 2.5 X-ray Diffraction Data 35

3.1 3.12 Ion Activity Products 38

3.2 3.24 Structural Properties of ~-Aluminas 42

4.1 4.4 X-ray Diffraction Data for Transition Aluminas 54

4.2 4.4 Structural Properties of Transition Aluminas 55

4.3 4.53 IR Frequencies of Surface Hydroxyl Groups 63

vi

1. History and Nomenclature
Materials with a styptic or astringent pro~rty were called
“alumen” by tbe Remans. These may have included impure
forms botb of afuminum sulfate and alum, which occur
naturally in volcanic areas, Al”men seems to be the source of
tbe word alumina (Bec@ann, 1846).
The recognition of alumina evolved gradually as the
composition of afum became ktter understocmi. Hoffman in
1722 held that the base of alum was a distinct “earth,” and Pott
(1754) called the base “thonichte erde” or “terre argilleuse”
(clay earth). Marggraf in 1754 showed that the earth of alum
was a distinct substance, that existed in natural clays, and that
it could k extracted by sulfuric acid. His memoirs gave rise to
the term “argil pur” as the name of the earthy base of alum. De
Morveau in 1786 argued that since alum was designated “se]
alumineux ,“ the pro~r name for the base should be “alumine.”
This latter term has been Anglicized to alumina. In 1821,
Berthier described a sediment rich in alumina which he found
in the vicinity of Les Baux, a small town near Aries in the
Provence district of France, This sediment, named bauxite, was
considered an aluminum mineral of the composition
A1203 2H20, with some iron. Not before the end of the
nineteeth century was bauxite recognized as a sedimentq rock
containing aluminum hydroxide and oxide hydroxide, as well
as various amounts of iron minerals, aluminum silicates, and
titanium dioxide.
A mineral from India, having the composition A1203, was
described in 1798 by Greville under the name corundum. The
mineral dlaspore was described by Hauy in 1801; it was
analyzed by Vauquelin in 1802 and shown to be A1203 H20.
Hauy (1801) named it diaspore from the Greek for “scatter,”
because it flew apart when heated. In 1805, Davy analyzed a
mineral and named it hydrargillite after the Greek words hyder
and arg ylles for water and clay. Later, however, other workers
showed this mineral to be aluminum phosphate. Dewey in 1820
found a mineral he called gibbsite in honor of G. Gibbs, an
American mineralogist. Analyses by Torrey in 1822
corresponded with the formula Al(OH)j or A1203 3H20. The
name hydrargillite was applied later to a similar mineral found
in the Urals; both names are still employed, but gibbsite is
prefemed in the USA.
Bohm and Niclassen (1924) identified another aluminum
mineral by X-rays, Bobm (1925) found it to k an isomer of
diaspore and showed a purified bauxite from Les Baux to
consist predominantly of this phase, De Lapparent (1927)
suggested that the mineral k called Whmit. B6hm ( 1925) also
discovered an alufinum compound isomeric with gibbsite.
Fricke (1928) suggested the name bayerite for this material
kcause he thought it was the product of the Bayer process. In
tbe next year, Fricke (1929) recognized his error, but the name
has been continued. Gibbsite is produced in the Bayer process.
Oxides and Hydroxides of Aluminum
Rankin and Merwin in 1916 assigned the prefix beta to a
high-temprature alumina that, according to later experience
(Ridgway et al. 1936), contains alkali or alkaline earth atoms.
Corundum was differentiated as alpha alumina. As several
forms of “beta alumina” have ken distinguished, tbe foreign
cation was made part of the name, i.e., sodium kta alumina.
Barlett (1932) assigned the name zeta to the phase formed with
lithium.
Haber in 1925 divided the aluminum and ferric hydroxides into
two series, alpha and gamma. The apparent failure of this
system to differentiate the aluminum trihydroxides prompted a
renaming of individual phases (Edwards et al. 1930). The
symbol alpha was applied to the form more abundant in nature.
In this nomenclature, bayerite was beta trihydrate, and the
phases gibbsite, Mhmit (spelled “boehmite” in the United
States), and diaspore were designated alpha trihydrate, alpha
monoh ydrate, and beta monoh ydrate, respective y. Weiser and
Milligan (1934) and Weiser (1935) later adopted the Haber
series and classified bayerite as alpha uihydroxide.
The designation gamma was given originally by Ulrich (1925)
to an undescribed alumina. This term has been used in many
cases for all the alumina transition forms encountered in the
Iow-temprature calcination of aluminum compounds and in the
oxidation of aluminum. Stumpf et al. (1950) restricted the
name gamma to the product obtained in the dehydration
sequence of boehmite at >800K.
As new forms have been identified, they have been assigned
Greek letters. Tbe uniqueness of many of these has been
disproved.
Table 1 shows the nomenclature systems for those aluminas
most frequently confused in tbe literature. Obviously, a
universal standard nomenclature is highly desirable, An attempt
in this direction was made in 1957 when, in West Germany, a
symposium on “alumina” nomenclature was held. The results
of this meeting were reported by Ginsberg et al, (1957). The
following nomenclature, was suggested
a. Use of the chemically correct term “hydroxide” instead of
“hydrate,” namely: aluminum trihydroxide, instead of
alumina trihydrate; aluminum oxide hydroxide, instead of
alumina monohydrate.
b, Use of the nomenclature of Alcoa for the transition
aluminas, but avoiding the term “phase”, use “form”
instead, e.g., “chi form”, “kappa form,” “gamma form”.
c. In honor of Van Nordstrand, use the name nordstrandite for
the trihydroxide discovered by him.
In the internationally accepted crystallographic nomenclature
the prefix a is generally applied to hexagonal close packed and
1
Alcoa Laboratories

Table 1.1 (aero-gel). Depnding onthemethod ofpreparation, the solid

Comparison of Nomenclatures may & present as discrete particles ranging in size from a few ,<
nanometers to micrometers, or it can form three-dimensional,
Accepted ~lymeric networks in which domains of solid are linked to (
Mineral Chemical Crystallographic others via chemical bonds. Structural order ranges from X-ray (
Name Composition Designation Alcoa (1930) indifferent (amorphous*) to crystalline. Composition (i. e., the
oxide-to-water ratio and amount of impurities) varies with the
Gibbsite Aluminum y-Al(OH)3 Alpha alumina conditions of preparation, as does thes~cific surface area.
Hydrargillite trihydroxide trihydrate
The following chapters will emphasize the stmcture and
composition of the solid phase, the gelatinous aluminas.
Bayerite Aluminum a-Al(OH)3 Beta alumina However, their proprfies canonly be fully understood in the
trihydroxide trihydrate context of the chemistw and texture of the two-phase systems,
the gels.

Nordstrandite Aluminum AI(OH)3 Gelatinous aluminas have ken studied for a number of
trihydroxide reasons. Colloidal aluminum hydroxides play an important role
in the chemistry of soils. Certain alumina gels strongly adsorb
acids. Because aluminas are not toxic to humans, they ag
Aluminum Y-AIOOH Alpha alumina widely used as antacids. Also, since particle size, surface area,
oxide monohydrate and water content of gels can be varied over a wide range, they
hydroxide we useful precursors for the manufacture of aluminas for
catalysis md adsorption.
Dlaspore Aluminum a-AIOOH Beta alumina
oxide monohydrate Polymeric network and particulate gels can be prepared by
hydroxide controlled hydrolysis of aluminum alkoxides dissolved in
organic solvents. These gels are used for the preparation of
Aluminum CK-A1203 Alpha alumina porous ceramic hodles, thin coatings, and granulm alumina of
oxide high purity.

Inorganic chemists andcolloid andsoilscicntists have

investigated the precipitation and aging khaviorof gelatinous
related stmctures, They-phases have cubic close packed aluminas for more fban40 years. G. C. Bye, R. Fricke,
lattices or structural elements of this symmetry. This system of H. Ginsberg, P. H. Hsu, D. Pa@e, K. S. W. Sing,
classification is used in the USA for iron and manganese S. Teichner, K. Torkar, H. B. Weiser, and their collaborators
compounds isostructural with the aluminum oxides and represent the most prominent working groups. Ceramists and
hydroxides. Itisalso applied tothecubic V,and the hexagonal pharmaceutical chemists have entered this tield more recently.
(bigonal) a-alumina. E. Matijevi6 andhls coworkers extensively studied the
preparation of monodisprsed, colloidal aluminum hydroxides
Toeliminatk fhe existing inconsistencies we will use the by controlled precipitation and aging of alumina gels.
mineral names and the crystallographic nomenclature S. L. Hem, J. C. White, andcollaborator sinvestigatedfhe
fhroughouttbis monograph. composition and stmcture of gels and their effect on acid
adsorption, neutralization, and ion exchange. B. Yoldas was
2. Properties of Aluminum Hydroxides and Oxides one of the early workers in the rapidly expanding field of
controlled hydrolysis of aluminum organic compounds for the
The chapters of this section are arranged according to the preparation of ceramic alumina bodies and thin films.
sequence of phases occurring in the alumina-water system with
increasing temperature or crystalline order. 2.11 Gelatinous Aluminss Formsdby Acid-Bsse Reactions

2.1 Alumina Gels and Gelatinous Aiuminss Aluminum hydroxides xe amphoteric. They are soluble in
strong acids and strong bases. In aqueous solutions of
The term alumina gel covers a wide variety of two-phase
systems in which colloidal aluminum hydroxide or oxide
●These terms i.dicatc lack of sufficientlong-rangeorder to prcduce a
hydroxide isthepredominant solid phase. The second phase diffraction pattern with X-ray$in tbe O,l-O.2nm wavelengthrange. Few solids
can be water, a mixture of water and an organic solvent, or air xc ~ly amo~ho.s i.e., witiout any shon-rmgesncmral .rderat all.

2
 Oxides and Hydroxides of Aluminum

intermediate pH their volubility is very low (see Chapter 3. 12) GA 202,6.2

Figure 1 schematically shows the volubility of A1(OH)3 as a

Oh
function of pH. Because of the steep slope of tbe volubility
curve, a small change in pH can cause considerable
4h (Gelatinous Boehmite)
superraturatlon and, consequently, rapid precipitation. As a
result, the first precipitate is generally of colloidal size and of
low crystalline order. Colloidal aluminum hydroxide is
8h
hydrophilic and easily coagulates to gels.

Several factors determine the degree of crystalline order,

particle size, and chemical composition of gelatinous aluminas 12h
temperature, rate of precipitation, final pH, ionic composition,
concentration of starting solutions and time of aging
(Figure 2.2).

Rapid neutralization of aluminum salt solutions with bases 16h

leads to gels rich in water which contain variable amounts of
residual acid anions, The water content may be as high as I
5 moles per mole of A1203.

A first attempt to classify the solid phases in gels precipitated

from aluminum salt solutions was made by WiOstitter et al.
(1925). Three ty~s were distinguished: Ca, CB, and Cy.

7 I I I I I I

‘“u
6

Aging of Aluminum Hydroxide Gel,

pH 9, 300K, X-Ray Patterns
.E 5
= Figure 2.2
~

=E4 According to these authors and later investigators Kraut et al.

= (1942), Fricke and Schmti (1948), Souza Santos et al. (1953),
E and Watson et al. (1955, 1957) Ca is X-ray indifferent, It
l.i transforms in a few hours to C13 which consists of fibrils. The
53 diffraction pattern of CD shows broad lines of boehmite, while
~ loss on ignition indicates 2.2 moles H20 per mole A1203. C13 is
x
g slowly converted to CT, a mixture of gibbsite and bayerite.
2
z The sequence, X-ray indifferent poorly crystallized boehmite
crystalline trihydroxide also occurs in the precipitates formed
1 by rapid neutralization of alkaline aluminate solutions.

Gelatinous aluminas prepmed by neutralization of concentrated

I I I I I I aluminum salt solutions at temperature below 29OK have low
.0
Crystalline order and very small particle size. The rate of aging
0123456789 101112
(i.e., transformation of the solid phase to ordered aluminum
i) hydroxide) is also very slow under these temperature and pH
Volubility of AI (OH)3 as a Function of pH conditions. Anions adsorbed on the solid retard the aging
(schematic) process. Sema, White, and Hem (1977) repofled the results of
Figure 2.1 an investigation of tbe interaction between anions and

3
Alcoa Laboratories
aluminum hydroxide gels and discussed previous work by Hsu
and Bates (1964), Hem et al. (1970), Matijevit and Stryker
(1966), and others. They infemed from infrared analysis that
gels precipitated in the presence of nitrate, sulfate, and
carbonate ions behave “as a positively charged polymeric
materi al.” While the interaction of nitrate appeared to be
predominantly electrostatic, sulfate and carbonate were found to
coordinate with aluminum ions. The carbonate ion has the
strongest retarding effect on aging of alumina gels.
Gels in which the initial molar ratio of carbonate to aluminum
is as high as 1.2 can be prepared by reacting sodium carbonate
solution with aluminum nitrate. Repeated washing with neutral
water lowers this ratio to a constant value of 0.45, while
sodium can be practically eliminated from the gel by this
treatment according to Sema, White, and Hem (1977).
The easy removal of sodium indicates that such gels do not
contain dawsonite (NaAl (OH)2C03), hut an X-ray indifferent
aluminum hydroxy carbonate. Dawsonite gels are precipitated
via different routes (e. g., reaction of carbon dioxide with
sodium aluminate solutions).
Other than carbonate, acid anions such as chloride or nitrate
can be removed from aluminum hydroxide gels by washing
with a large excess of water or by dialysis. Green and Hem
(1974) reported that the concentration of chloride in a gel
which has been prepared by neutralization of an aluminum
chloride solution decreased in proportion to the volume of wash
water used. As the chloride content decreased, viscosity of the
gel increased, while negative electrophoretic mobility
diminished at the same rate.
Removal of acid anions accelerates aging (i.e., consolidation
and crystallization of the solid). At temperatures below about
350K, the end product is gibbsite if the pH of the solution is
lower than 5.8 and higher than about 9. Bayerite forms in the
pH range of 5.8 to 9. Nordstrandite may occur as a transition
from bayerite to gibbsite under some conditions (see
Chapter 2.25).
2.12 Gelatinous Aluminas Prepared hy Other Chemical
Routes
The strong interaction of freshly precipitated alumina gels with
ions from the precursor solutions makes it very difficult to
prepare them in pure form. To avoid this complication, two
alternate synthesis routes are available: the reaction of
depassivated aluminum metal with water, and hydrolysis of
aluminum alkyls or alkoxides.
As early as 1908, H. W1slicenus observed that a slightly
amalgamated aluminum surface exposed to moist air reacts
rapidly to form bundles of fibrous material. According to
Watson et al. (1957), these fibers contain approximately
4
(
4 moles HZO per mole of Al*O,. They are composed of parallel
arrays of fibrils which we 7-8 nm in diameter and several
micrometers long (Figure 2.3).
If depassivated aluminum is immersed in liquid water, an X-ray
indifferent reaction product of very small (<1 Wm) particle size
is formed. It converts to well crystallized bayerite, a-Al (OH)3,
within hours as first reported by Schmih (1946).
Thin films of gelatinous aluminum hydroxide grow on pas3ive
(oxidized) aluminum metal that is exposed to water at
temperatures below about 375K (see Chapter 5.2)
Aluminum alkyl compounds of the general composition A1(R)3
react with water to form aluminum hydroxide and the
respective alkane, e. g., AI(CH3)3 + 3H20 +
Al(OH)J + 3CH4.
In 1946, H. Schmih described the preparation by hydrolysis of
triethyl aluminum of very pure, X-ray indifferent aluminum
hydroxide gel for chromatographic applications. This reaction is
highly exothennic. Aluminum alkyl compounds are unstable in
the presence of oxygen, water vapor, or other oxidants and
may ignite spontaneously.
Aluminum alkoxides, AI(OR)3, (aluminum alcoholates) are less
reactive and their hydrolysis is easier to control. An early
report of the preparation of alumina gels from aluminum
alcoholates was given by Adklns (1922). Harris and Sing
(1958) and Torkm and Eggh~ (1961) are among the workers
who later investigated the physical and chemical properties of
gels prepared by this method.
i
.- ,>,
: .,
., .
.,2
K. Wefers M,ootfx
Fibrillar Gelatinous Aluminum Hydroxide
Figure 2.3
I

When a solution of aluminum alkoxide in alcohol, benzene, or
other organic solvent is mixed with water, the overall reaction
can be described by two equations:
1. AI(OR)3 + 3H20 e Al(OH)J + 3ROH
2. Al(OR), + 2H20 - Al OOH + 3ROH
In both cases the initial reaction products are X-ray indifferent.
Poorly crystallized boehmite ~pse”doboebmite”) develops after
) a few hours of aging the precipitate. If an excess of more than
20 times the stoichiometric amount of water is used, bayerite is
the final crystalline phase that forms at temperatures below
350K. At a molar ratio of H20 to A1203 ktween 5 and 6,
aluminum oxide hydroxide is the end product. Boehmite or the
less ordered “pseudoboehmite” is the only phase ~cun-ing if
the temperature exceeds 350K during the hydrolysis reaction or
)
during aging of an initially amorphous precipitate, A
“pseudoboehmite” having particle sizes of 10-50 nm is
produced commercially as a by-product of the manufacture of
linear alcohols from long-chain aluminum alkoxides.
Several other variables, besides temperature and molar
ratio of water, determine the pro~rties of gels prepared from
aluminum alkoxides. The composition of the alkoxide, the ty~
t of solvent and its miscibility with water, presence of
electrolytes, and tbe pH of the solution arc factors which
influence tbe final product. Since S. Teicbner and coworkers
(1969, 1970) reported the prepmation of alumina aerogels, and
I B. Yoldas (1975) showed that transparent ceramic bodies can
be obtained by pyrolyzing suitable alumina gels, interest in this
subject has increased substantially, particularly among
ceramists.
Ingebrethsen and Matijevit (1984) reported hydrolysis by moist
air of aerosols of aluminum secondary butoxide to be a
convenient method for producing particles of gelatinous
aluminum hydroxide which have a very uniform size of about
100 nm. Crystallite 10-100 nm in size are obtained if
hydrolysis in the liquid phase of an aluminum alkoxide is
followed by ~ptization of tbe freshly formed gel and a
hydrothermal treatment.
In the procedure described first by Yoldas ( 1975), the sol
obtained after acid peptization of the hydrolysis product is
gelled by removing part of the liquid phase, or by adding a
suitable electrolyte which neutralizes tbe positive sutiace charge
of the colloidal particles, After gelling has occurred, further
removal of liquid decreases the volume of the gel by one-third
to two-thirds. The resulting transparent, ~rous body can be
fired to about 800K without undergoing major additiond
shrinkage,
Oxides and Hydroxides of Aluminum
Teicbner et al. (1970) pinted out that the internal porosity of
alumina gels partially collapses if a liquid-vapor interface
develops inside the pores during evaporation. The system will
decrease the resulting capilkuy pressure by coalescing small
pres; i.e., increasing the average pore size. These workers
produced aerogels having s~cific sutiace areas of over
500 m2/g by extracting the liquid phase under su~rcrhical
conditions to avoid the formation of an interface.
A serious obstacle for the manufacture of lager, monolithic
ceramic bodies has been the unsolved problem of controlling
shrinkage and cracking. These occur in the drying step and
when the gel is fued to the temperatures necessary for the
formation of stable aluminum oxide. Major industrial use of
sol-gel technology, therefore, has been limited to thin films,
dip coats, fibers, and alumina ptiicles such as abrasives.
Much of the know-how deve[opd during the past decade in the
field of sol-gel technology bas been reflected in the patent
literature. A review of tbe state of the art was given by
Z.elinski and Uhlmann in 1984.
2.13 The Structural Evolution of Gelatinous Aluminas
In the preceding chapters, it was shown that gelatinous
aluminas can be produced by a numkr of different chemical
processes. However, in all cases the initial precipitate lacks
sufficient long-range crystalline order to give an X-ray
diffraction pattern. In an attempt to detenninc the short-range
order in the “amorphous” solid, Ceiling and Clocker (1943),
Bale and Schmidt (1959), and Petz (1968) ~rformed
small-angle X-ray scattering experiments. Results indicate that
the aluminum ions in these early precipitates are octahedrally
cwrdinated as they are in crystalline aluminum hydroxides. No
distinction can be made by X-ray techniques between O, OH,
and H20. Pmicle sizes are on the order of 2.5 nm, while
aggregates may measure several tens of nanometers, Neutron
scattering analysis by Christensen et al. (1982) gave essentially
the same results; high resolution electron microscopy confirms
these findings.
If the “amorphous” solid remains in contact with the liquid, it
will transfom into one of tbe ordered hydroxides or oxide
hydroxides. The rate and path of this transformation are
complex functions of the chemistry of precipitation and tbe
environment prevailing during aging,
Much understanding of these processes was provided by soil
and water chemists who investigated the hydrolysis reactions in
dilute solutions of aluminum sails. Major contributions were
made by Marbe and Bentur (1961), Hsu and Bates (1964),
Hem and Robemon (1967), Schoen and Robemon (1970), and
Smith and Hem (1972).
5
Alcoa Laboratories

GA ~24, ,
The predominate ionic s~cies in dilute, acidic solutions of
aluminum salts is

0
●
6[Al(H20):+] - 12H + - 12H20
[AI(H20),]3+ +Ale(OH):j.12H20

Hem and Roberson (l.c. ) assume that deprotonation can occur

due to the strong polarization of the water molecules by the Al
ion. As a result, a divalently charged complex forms
AI,0(OH):;.16H20
Al(H20)~+ = Al(OH)(H20)~+ + H+

which will dimerize by condensation

2Al(OH)(H20)~+ - A12(OH)2(H20)~+ + 2H20

The stmcture of the dlmer is a double-octahedron which is

connected via common hydroxyls. A132(oH)~y.28H20

De~nding on the chemical environment and the temperature,

the condensationlply merization (polycondensation) reaction
can proceed in one of two ways:

1. Forming chains by litilng octahedra through common

edges. (
2. Forming hexagonal rings which further coalesce to l~ge
polynucleas complexes.

In both the chain and the palynuclear ring configuration, the

positive charges and number of water molecules per aluminum Al=(OH);~.36H20
ion decrease as the polycondensation progresses. me
pro~rtion of hydroxyl ions increase to an upper limit of 2
OH: 1 Al for the chain polymer and approaches 3 in the @
hexagonal arrangement. Figure 2,4 schematically represents the Refi Hsu and Bates 1964
coalescence of rings, as suggested by Hsu and Bates (1964) Hem and Roberson 1967
and Hsu ( 1977). Figure 2.5 shows the transition from a linear Nail, White and Hem 1976
aquo-hydroxopolymer to a fully dehydrated AIOOH-chain,
together with the antiparallel double chain which constitutes the ‘Each external apex rapreaants an Al(H20)& complex
structural element of crystalline AIOOH (see Figure 2,12 in
Chapter 2.32).
Formation of Polynuclear Rings by Condensation
The positive charge carried by the solute precursors and by the Figure 2.4
larger, solid plynuclear complexes explains the strong bonding
of anions to the gel and the formation of hydroxy salts at
higher anion concentrations; e.g., aluminum hydroxy chlorides. crystals (Figure 2.6), Somatoids* of bayerite (Figure 2.7) form
Anion complexes on the surface of the solid must k by the stacking of AI(OH)3 platelets perpendicular to their basal
hydrolyzed kfore further growth can occur via shared hydroxyl planes,
ions; hence, the observed retarding effect of anions on the
crystallization of gels (Nail, White, and S, L. Hem, 1976). If Under the conditions which favor the proposed
edge hydroxyls of the polynuclear complexes me capped by polycondensation mechanism that results in chain-like polymers
hydrogen bnding of polybydroxy compounds such as sorbhol, (OH/Al s 2), fibrillar and sheet-like morphologies of the
further Pcdycondensation also is inhibited (Nail et al., 1. c.), gelatinous material develop, These conditions are high salt
concentration, i.e., low water activity (Hsu, 1967), low
Coalescence of hexagonal ring complexes eventually leads to
nucleation and growth of tabular, pseudohexago”al gibbsite ‘See Chapter 2.22.

6
 Oxides and Hydroxides of Aluminum

hydroxyl concentration or temperatures above about 350K.

Bugosh (U.S. Patent, 1959) described the preparation of
tibrillar, gelatinous khmite from acidic solutions. Llppens
(1961) reported a sheet-like morphology of gels (“wrinkled
tissue papr”). ~is gelatinous material contains porly
crystallized khmite. It can be peptized by diliute mineral
acids. Plefre and Uhlmann (1986) prepared an X-ray indifferent
(“su~r-amorphous”) gel they believe to be composed of
swollen and folded sheets of boehmite, The swelling is ascribed
to intercalation of water within the double layers of wtahedra
which me the stmcturaf elements of boehmite. This gel has
been produced by hydrolyzing aluminum butoxide. The
precipitate was ~ptized with 0,28 N HN03 before gelling and
drying.

Gelatinous hydroxides prepared by hydrolysis of alkoxides

(Chapter 2. 12) develop via reaction paths analogous to those

.. >“,,,

J. J. Ptasienskl 75,000X

2[Al(H20)~+
+

– H+-AI(H20)50H2+]
W8
– 2H20 -A12(OH)2(H20):+
+
Tabular Gibbsite

which govern the precipitation

Figure 2,6

and aging of hydroxides formed

from aluminum salt solutions.
Y-—–—––?
Gelatinous boebmite forms in the same environments that lead
to chain polymers from aluminum salt precursors, namely, low
water-to-afuminum ratios, low pH, or tem~ratures above
350K. It is conceivable that cross-linklng or end-to-end
connection of chains via residual alkoxide groups aids the
Y-–—–—–ii development of larger particles or of domains in a continuous,
–H20
Al(OH)n(H20):+ —- AlO OH ~lymeric network gel:

~o o! \/\/
o 00
\/\/
0

–4H20- Al Al Al
/A’\ / \ /\/\
-* g8; OH OR . . RO OH

x
However, Lippens’ (1961) model of the bonding of [AIOOH]2
Al(OH)n(H20):+ – (OH + OH- H20 + O) - H20-IA1202(OH)21. double chains in pseudoboehmite would account for the same
effect:
above ~lane ● Al
OH-

o 0--
below o OH OH
@
H20 I I
Al-O . HOH . O-Al
in plane
@ ; J, J, ~
!
Deprotonatio”/Condensation Reactions Leading to Chains I 1-
Figure2.5 OH OH

7
I
Alcoa Laboratories
J. J. Ptasienskl 40,000X
Bayerite Somatoid
Figure2.7
This bonding mechmism may also operate between colloidal
p~icles in particulate gels, in addition to, or replacing, van
der W~al’s forces.
The literature, so far, has not been ve~ explicit shout the bond
chemistry of the so-called p] ymeric net work gels produced by
controlled hydrolysis of aluminum afkoxides. Schlenker (1956,
1958) discussed the suucture of “Alukones,” which are
hydrocarbon compounds such as Iong-chain fatty acids
cross-linked via aluminoxane bonds. These bonds were
introduced by reacting aluminum afkoxides with suitable
functional groups. Evidence has not yet been presented for an
analo80us cross linking of the inorganic polymer [A1ooH]. by
hydrocarbon groups. The question remains whether
“inte~netrating network gels of chemically linked
hydrocarbon and alumina polymers can k produced, or if such
gels constitute a mixture of organic and inorganic colloids.
When aluminum alkoxides are hydrolyzed with a Iwge excess
of water, the rapidly precipitated, amorphous solid pafiially
converts to pseudoboehmite before stable, crystalline aluminum
trihydroxide forms. Gelatinous products precipitated from
alkaline aluminate solutions or from acidic salt solutions, but
aged at high pH, undergo the same sequence of structural
stages. The appexance of gelatinous boehmite as a - generally
very short lived . intermediate stage eve” at low temperatures
aPPe~s tO contradict the assumption that low pH or low
activity of water ue preconditions for the chain polymerization,
However, this contradiction can be resolved when we consider
8
the steep S1OFS of the volubility curve of aluminum hydroxide
that is shown in figure 2.1. As mentioned above, precipitation
can occur very rapidly upon a slight change in PH. Whether
acidic salt solutions are neutralized by alkali or aluminate
solutions are treated with C02 or mineral acids, the initial I
precipitate will include anions due to its positive surface
charge. Topochemical reaction (polycondensation) inside the
solid satisfies the second condition, i.e., low activity of water.
Gelatinous khmite can therefore form, but will be converted
to Al(OH)J by a solution reaction of the solid with the mother I
liquor
AIOOH + H20 + OH-+ Al(OH); ~ Al(OH)T + OH”
and
AI(OH)3 + AI(OH)I e 2A1(OH)3 + OH-
The latter reaction prevails in the spontaneous precipitation of
aluminum trihydroxide from supersaturated aluminate solutions
or when crystallization is induced by seeding. Gelatinous
intermediates do not occur under both conditions.
2.14 Gelatinous Boehmite or Pseudoboehmite
In the preceding chapters we referred to the product occurdng
as an intermediate stage in the aging sequence of aluminum
hydroxide gel as pseudoboemite, gelatinous boehmite or poorly
crystallized boehmite. All these terms have ken used
interchangeably in the literature. They describe a solid, the I
X-ray diffraction pattern of which shows broad lines that
coincide with the major reflections of well crystallized
Y-AIOOH. Depending on the method of preparation of the
material, the diffraction lines are shifted to varying degrees
toward higher d-values; the largest increase in the lattice
constant is measured in the direction of the b-axis (OkO).
Pseudoboebmite generally contains more water than the 15% by
weight corresponding to the composition A1203 H20. Up to
30% has been reported.
When aged under aqueous solutions at temperatures lower than
350K, pseudoboehmite converts to crystalline AI(OH)3, the
phase thermodynamically stable in this temperature range (see
phase diagram, Figure 3. I ) This observation has supported the
view that “pseudoboemite” is a transitional stage in the aging
of aluminum hydroxide gels rather than Y-AIOOH of a particle
size small enough to cause X-ray line broadening. Calvet et al.
introduced the term pseudoboemite in 1953. Pa@e et al. (1958)
assumed that intedayer water caused the difference between
“mineral” boehmite and the gelatinous material. Lippens (1961)
concluded that in “gelatinous” boehmite tbe (AIOOH)l chains
of the boehmite structure are linked via double hydrogen
bridges provided by water molecules (see Chapter 2. 13). He I

showed an increase of the ““it ~eII dime”sio”s i“ the
b-direction proportional to the amount of water exceeding
I H20 per A1203. Bye a“d Robinson (1974) believed that the
major portion of the excess water is present as a SUfiaCe
monolayer on the generally small (<20 nm) crystallite; only a
minor amount being responsible for lattice strain. Baker and
Pearson (1974) rejected Pa@e’s and Lippen’s intercalation
model, ascribing all excess water to HZO coordinated to Al on
crystal surfaces.
Tettenhorst and Hoffmann (1980), having investigated 32
boehmite samples prepared under varying conditions, concluded
that “pseudoboehmite consists of similar octahedral layers but
lacks the three-dimensional order of boehmite because of a
restricted number of unit cells along (b). ” “It contains more
water which is commordy intercalated ktween octahedral
layers.” Hsu ( 1967) considered psuedoboehmite to be an
incompletely dehydrated boehmite, while Pierre and Uhlmann
( 1986) assume a random intercalation of water.
This incomplete review of pertinent literature would indicate a
significant divergence of interpretation if one assumed the
subject to be a stoichiometrically, stmcturally, and
thennodynamirally defined phase. It was shown in preceding
chapters that gelatinous boehmite can be formed in a variety of
chemical environments, but always represents an intermediate
stage in the polycondensation of less ordered aluminum
aquo-hydroxo complexes.
The aging via polycondensation of a gelatinous precipitate is
predominantly a topochemicai process; i.e., it takes place either
in the solid phase or by solid/solute interactions over very short
transport distances due to the microporous texture of the gel.
Unlike the precipitation of a crystalline compound, such as a
simple ionic salt from a homogeneous solution, the
topchemical transformation of the shon-range ordered (X-ray
indifferent) aquo-hydroxo complex to the long-range ordered
AIOOH is a progressive process. As a result, the gels in
general are structurally and compositionally inhomogenous;
longer-range ordered areas may & embedded in an
“amorphous” matrix.
Because of this inhomogeneity, there obviously is no
meaningful correlation between the stmctural properties of the
“X-ray active,” ordered material and the stoichiometry; i.e., the
A1203:H20 ratio, of the entire solid. Difficulties arise not only
from the unknown proportion of hydrates to oxide-hydroxide,
but also kcause of the different forms in which water can k
present.
If one excludes “mobile” water in meso and macro pores,
molecula H20 can be associated with the gelatinous solid in
several ways. AS a result of incomplete polycondensation, H20
can occupy oxygen or hydroxyl positions in the stmct”re of
longer-range ordered chains. This induces lattice strain because
Oxides and Hydroxides of Aluminum
of the distortion of the AI(0,0H)6 coordination polyhedr%
there is also an increase of the cell dimensions in addition to a
positive charge, resulting from the replacement of a negative
ion by the changeless water molecule.
Water adsorbed on the surface of a particle is bonded by
hydrogen or dipole bonds, the ty~ and strength of the bond
being determined by the stmctural configuration of the
adsorbing site, as shown schematically below:
H H O-Al-OH H
HOA14 / \o/ \o/
\/\ /\
H H O-Al-OH H
The contribution of the first layer, chemisorkd water, to the
structure and composition of the longer-range ordered solid is
significant, due to the small particle size of the gelatinous
oxide hydroxide. Assuming an approximate density of 3 g/cm3
for gelatinous A1OOH, ideal cubic panicles of 10 nm (100~)
edge length would have a specific surface area of 200 m2/g, or
24,000 m2/mole of A1203 H20. At a surface coverage of 10
H20 molecules per nm2 (10 ~2 per molecule), a monolayer
represents approximate y 0.35 mole of H20 per mole of
A1203 H20, Considering the larger surface area of
nonisometric particles and the actual ranges of particle sizes
and surface areas reported in the literature, values of 0,5 mole
and greater are realistic,
Another consequence of the small particle size (which can be
equivalent to only a few (AIOOH) layers in the short directions
of acictdar crystallite) and the concomitant large
surface-to-mass ratio is the likelihmd that panicle surfaces may
be linked by hydrogen bonding of chemisorbed water,
.[HO -Al - O]H -0- HIO - Al - OH]n
as discussed in the preceding chapter. Whether this linkage
represents structural intercalation of water, or agglomeration of
particles, depends on one’s point of view, This type of bonding
of water cmxists with the other forms of association throughout
the gel, The temperature and chemistry of synthesis and the
degree of aging determine which form of water association
dominates. DTA and infrared analyses by various workers
(e.g., Tettenhorst and Ho ffmann, l.c.; Hem et al., l.c.) clearly
show a broad range of bond energies for H20 and OH, the
proportion of H20 increasing with lower precipitation
temperatures and shoner times of aging of the gelatinous
material.
This discussion shows that each of the models proposed i“ the
literature applies to cenain aspects of the stmcture and
composition of the gelatinous material. Most authors agree that
the oxide-hydroxide double chain is the basic structural
9
Alcoa Laboratories

element, the same configuration that makes up the lattice of

Y-AIOOH, boehmite. In the authors’ opinion it is irrelevant that
gelatinous hohmite transfoms to .AI(OH)3 when aged at
temperature below 350-370K. The formation of the [AIO, OH,
H20] chain plymer is a kinetically controlled process.
Whether this material transforms to crystalline A1OOH or
AI(OH)3 de~nds ultimately on the temperature and pressure
conditions, i.e., the phase field in the A1203-H20 system, and
not on composition or degree of crystalline order. In view of its
predominant stmctural features, the authors prefer the term
“gelatinous kehmite” for this material.

2.2 Aluminum Trihydroxides

2.21 Gibbsite
J. J. Ptaslenski mx
Al(OH)j, gibbsite, is the principal constituent of bauxites of the
tropic region. ~is mineral also occurs in North American and
European deposits. Gibbsite bauxites ae mostly, although not Aggregate of Technical Gibbsite
exclusively, of tertiary or younger age. Figure 2.8

The crystal habit of natural gibbsite is usually pseudohexagonal

tabular, while that of synthetic gibbsite is determined by the
conditions of cvstallization.
Grains of gibbsite precipitated in the Bayer process are
aggregates of tabular and prismatic crystals (Fig. 2.8). Gibbsite
usually contains a few hundredths to several tenths of a percent
of alkali metal ions. The highest alkali concentrations xe found
in technical trihydroxide produced in the Bayer process.
Ginsberg and Koster (1952) and Wefers ( 1965) showed that
sodium is atomically dispersed in the c~stal lattice of gibbsite.
Wefers (1962) also repofied on the effect of sodium and
ptassium ions on the morphology of gibbsite. Crystals grown
from sodium aluminate solution had a tabular habit.
Pseudohexagonal, elongated prisms prevailed when gibbsite
was precipitated from ~tassium aluminate solutions. (See also
Misra and White, 1971).
Elongated prisms will also form if gibbsite is grown from
sodium aluminate solutions under conditions of low
super-saturation and high temperature (>330 K), The reasons
for the preferential growth of the prism faces or the basal
planes are not well understood.
Ginsberg et al. (1962), Torkar et al, ( 1960), Wefers (1962,
1967), and Saalfeld et al, (1968) believe that alkali ions are
necessary to stabilize the gibbsite structure. Barnhisel and Rich
(1965), however, stated that gibbsite forms from gels if the pH
is less thm 5.8; Schoen and Roberson (1970) confirmed this
obsewation. The relationships between the structure of
aluminum trihydroxides and the conditions of preparation will
be discussed in Chapter 2.25,
Pauling ( 1930) first proposed the concept of the gibbsite
structure which was subsequently confirmed by Megaw (1934).
Double layers of OH ions, with Al ions occupying two-thirds
of the octahedral interstices within the layers, form the basic
structural element. The hydroxyls of adjacent layers are situated
directly oppsite each other, i.e., in a cubic packing. Thus, the
sequence of OH ions in the direction perpendicular to the
planes is AB-BA-AB-BA (Fig. 2.9).
This su~rposition of layers and the hexagonal arrangement of
Al ions lead to channels through the lattice parallel to the
c-axis. The hydroxyl ions in the gibbsite stmcture are
considerably deformed. Hydrogen bridges originating from the
dipoles operate between OH groups of adjacent double layers.
From proton magnetic resonance measurements Kroon and v.d.
Stol~ (1959) deduced a model of the spatial distribution of
these H-bonds.
The monoclinic symme~ of the gibbsite lattice, i.e., its
deviation from a hexagonal close packing of the hydroxyl ions,
can he described as a displacement of the double layers relative
to each other in the direction of the a-axis. An additional
displacement in the same plane, but in the direction of the
b-axis, was determined by Saalfeld (19@). He analyzed the
stmcture of single crystals of gibbsite from the Ural mountains.
Several crystals showed the additional displacement of the
double layers which reduced their symmetry to triclinic. The
indices of refraction were identical for monoclinic and triclinic
gibbsite. The angle of the optical axes, 2V, was found to be O

10
Alcoa Laboratories

Table 2.1
I
Mineralogical Properties of Oxides and Hydroxides

I
Index of Refraction nD
Mobs
Phase a P Average :Ieavage Brittleness iardness Luster Reference

Gibbsite 1.566 1.566 1.587 ... . (001) Tough 2-1 /2 to Pearly Dana
Perfect 3-1/2 Vitreous

Bayerite 1.563 . . ... ,., ,, Montoro

Boehmite 1.649 1.6596 1.665 . . (010) 3-112 to :rvin and Osborn

4 Bonshtedt-
Kupletskaya

Oiaspore 1.702 1.722 1.750 (010)0 Brittle 6-1 /2 to Brilliant Dana

Perfect 7 Pearly

l-- T
I o I Average

Corunduma
1760m I 1
None@ Tough wher
compact
9@ Pearly
Adamantine
Dana

achromatic dispersion e, – c,= o~ – WC= 0.011 (Castor).

NO along optic exis = 1.74453 + ~
@Knoop hardness 1525-2000 (Castor 1
@Fracture uneven to conchoidal; parting (0001).
@Value in Ewin and Osborn is misprint.

by crystal faces. These sha~s, reflecting the interplay of
crystallization forces with the environment, resemble hour
glasses, cones, or spindles (Fig. 2.7).
the name bayerite II, since structure and growth features were
{
closely related to those of bayerite. In honor of the author, this
,
trihydroxide was later called nordstrandite.

Bayerite is produced commercially—principally for the Pap&e et al. ( 1958) confirmed the existence of the new form of
manufacture of catalysts or other applications which require an Al(OH)J and published a more complete X-ray diagram. /
aluminum hydroxide of high purity. Physical properties of Shimizu, Mi yashige and Funaki (1958) reproduced Pa@e’s
bayerite are listed in Table 2.1. results.

2.23 Nordstrandite
Van Nordstrand, Hettinger and Keith ( 1956) publisbed the
X-ray diagram of an aluminum tribydroxide which differed
from the diffraction patterns of gibbsite and bayerite. They
obtained this trihydroxide by precipating a gel from aluminum
chloride or nitrate solutions with ammonium hydroxide.
Upon aging under the mother liquor at a pH of 7.5 to 9 the gel
converted to tbe crystalline phase. Van Nordstrand proposed
Hauschild ( 1963) showed that very pure nordstrandite can be
prepared by reacting aluminum, aluminum hydroxide gel or
hydrolyzable aluminum compounds with aqueous solutions of
alkylenedlamines, especially ethylene diamine.
After Van Nordstrand’s and Pa@e’s X-ray diffraction diagrams
had been published, nordstrandite was identified as a
component of tropical red soils (terra rossa) in West Sarawak
(Wall et al., 1962) and on the island of Guam (Hathaway and
Schlanger, 1962).

12
 Oxides and Hydroxides of Aluminum

I
I
Van Nordstrand and co-workers (1956) ~onsjdered nordsv~dite
a screw dislocation polymorph of the gibbsite lattice. Llppens
(1961) proposed a structure i“ which two double layers with
gibbsite sequence and two double layers with bayerite sequence
6re 6Jtematel y stacked,
I Saalfeld and Mehrotra ( 1966) analyzed single c~stals from
S6rawak. They found a triclinic unit cell containing 8AI(OH)3.
Sadfeld and Jarchow (1968) refined the stmcture, ~inting out
that the sequence of layers is AB-AB as in bayerite; on tbe
other hand, OH ions of adjacent double layers ze located
OPPsite each other. This places the lattice of “ordstrandite
between those of bayerite and gibbsite. Bosmans (1970)
c~lculated a structural model based on the Oiclinic space group
PI.
From infrared spectra, Hauschild (1963) concluded that the
layers in the nordstrandite stmcture are linked by hydrogen
bonds.
SOuctural data of nordstrandite are listed in Table 2.2.
Although the technical production of nordstrandite is covered
by patents (Hauschild, 1964), the material has not been used
commercially to date.
2.24 Doyleite
In 1985, Chao et al, reponed the structure determination of an
AI(OH)3 form which they named doyleite. This mineral is
found at Mont St. Hilaire and on Montre6J Islmd, both in
Que&c. At the former site, it crystallizes in tbe tabular habit
tyPical fOr gibbsite; at the latter it fores irregular prismatic a“d
tabular c~stals clustered in aggregates.
Triclinic symmetry was determined, space group PI or Pi. The
infrared spectim resembles that of nordstrandite. Suuctural
data indicate that in this form of A1(OH)3, the stacking
sequence of the hydroxyl double layers can be considered an
intermediate between that of triclinic gibbsite and nordstrandlte,
Chemical analysis shows Si02, FeO, Na20, md CaO to be
major contaminants. Whether or not this material can k

Table 2.2.
Structural P20perti~
}

1,
Molecules
Cystal Space Per Unit Unit MS Length, nm Densily
Phase Formula System — Group Cell a bc Angle _g/cm3 Referene

Gibbsite AI(OH)3 C;h 4 0.8664 0.5078 0.9136 2.421 Saalfeld and Wedde

Gibbsite AI(OH)3 Trictinic 16 1.733 1.006 0.973 94” 10! Saalfeld (1960)
92. 08;
9o” 0<
Bayerite Al(OH)a Monoclinic 2 0.5062 0,6671 0.4713 90” 27’ 2.531 Rothbauer

Nordstrandite AI(OH)3 Trictinic 2 0.5114 0.5082 0.5127 70~ 16 ❑osmans

74° 0,
56” 28,

Boehmite AIOOH Orthohombic 2 0.2866 0.1223 0.3692 3.012 Corbato et al,

Diaspore AIOOH OrihorhomMc 2 0.4396 0.9426 0.2644 3.443 Swanson and Fuyat

Tohdite 5A1203H20 Hexagonal 1 0.5576 - 0.8766 3.724 Yamaguchi

A1203 Hexagonal 2 0.4759 - 1.2992 3.985 Phillips et al.

(Rhomkhedral)

1- Roth
2- Fricke and Severin
3- Dana
4- Alma Lab.
5- Toropv

13
Alcoa Laboratories

GA202464 a and the b axes. The reasons for these energetically less
favorable managements of the layers are not well understood.

Schoen and Roberson (1970) assume a different degree of

Bayerite
Layer Stacking in AI(OH)3
Figure 2.10
considered a fourth modification
open to further debate.
B polarization of the hydroxyl ions to & responsible for
variations betw=n tbe layers of gibbsite, bayerhe, and
nordstrandite. In all three forms, the individual layers are,
A
-- however, chemically and structurally identical, all main
vafencies of the A12(OH)6 “molecule” being satisfied within a
A
layer. The symmetry of the hydrogen bonds between the
sheets, therefore, is more likely the result rather than the cause
B of the arrangement of layers relative to each other.
--
1
A Stronger evidence points to impurities as a factor determining
c
the stacking sequence of the hydroxyl in double layers.
B Synthesis of Al(OH), from very pure aluminum and water, or
--
via hydroxylation of pure, active alumina, always leads to
B
bayerite. Gels prepared by hydrolysis of aluminum butoxide
recrystallize to bayerhe after prolonged aging under very pure,
A neutral water (Bye and Robinson, 19M).
--
[ B
G~ns&rg et d. (1961, 1962) have ~inted out that in the
A reaction sequence
--
aluminumsalt solution+ gelatinoushydroxide - .Vstalline trihydr.xide
Nordatrandite
bayerite occurs as the initial crystalline phase. Aging under
concentrated ammonium hydroxide solutions (125 and 250 g
NH3 per liter) leads to nordstrandite as a final product. If the
mother liquor contains NaOH or KOH, bayerite is converted to
gibbsite. Nordstrandite will also transform to gibbsite in sodium
or potassium hydroxide solutions, according to these authors.
Hauschild (1963) claimed that nordstrandite is not converted to
of Al(OH)J should be left gibbsite by aging under 0.01 normal NaOH or 2 ~rcent KOH
solutions.

2.25 Interrelationships Wefers (1967), investigating the system Na20-A1203-H20,

The stability relationships of the aluminum trihydroxides have
been the subject of much debate, Natural abundance of gibbsite
has often been used as an argument to support the assumption
that this form of AI(OH)3 is the thermodynamically most
stable. Experimental data (Wefers, 1967), however, indicate
that bayerite is more stable than gibbsite. This should be
expected as the bmcite-type bayerite structure has the highest
symmetry of all structural variants of Al(OH)q, and also is the
densest (see Table 2.2).
As demonstrated in Figure 2.10 the structures of gibbsite,
bayerite, and nordstrandite differ only in the stacking order of a
common stmctural element, (he [A12(OH)6]n double layer. In
the structure of monoclinic gibbsite, these layers are displaced
in one directon (a-axis) relative to the stacking sequence in
bayerite. In triclinic gibbsite, nordstrandite and doyleite, the
strata are shifted to varying degrees in botb the dbection of the
found the transformation bayerite * gibbsite to be
irreversible. Gibbsite was formed by a solution-redeposition
process, growing epitaxially on bayerite somatoids. Epitaxial
growth on the nealy isostructural bayerite reduces the energy
of nucleation considerably, mtilng the solution reaction the
rate determining step in the process of transformation. This
may explain the discrepancy between the results of Ginsberg et
al. and Hauschild. Wefers concluded that gibbsite does not
have a field of stability in the binary system A1203-H20, as all
samples produced under various conditions contained sodium.
The concentration of Na could be related to temperature and
supersaturation.
Hauschild (1964) prepared gibbsite essential y free of alkali by
hydrolyzing triethyl aluminum in an aqueous solution of
ethanolamine. The precipitate showed broadened X-ray
diffraction lines of gibbsite. It contained less than 10 ppm
Na20, but 0.2 prcent N and small amounts of organic

14
I Oxides and Hydroxides of Aluminum
I

t
material. Hauschild assumed that ethanolamine occupied anion
vacancies in the gibbsite lattice,
According to Bamhisel and Rich (1965), Hem and Roberson
(1967), and other authors, acid conditions favor the
precipitation of gibbsite from dilute solutions. This process
involves, as shown in Chapter 2.13, the polymerization via a
deprotonation and condensation reaction of a positively
charged, aluminum-aquo complex,
Hydronium ions could conceivably be incorporated in the
structure in the same way as are alkali ions in gibbsite
precipitated from alkali aluminate solutions, Excess positive
chages may also be provided through a substitution of Al]+ by
Si4+, a possibilityy to be considered in the case of the naturally
occurring doyleite and triclinic gibbsite.
I
lead to the formation of the aluminum oxide hydroxide (see
Chapter 4.2 1). AI(OH)3 heated above 375K under water or
dilute alkaline solutions is quantitatively converted to boehmitc.
An electron micrograph of hydrothermally grown boehmite is
shown in Figure 2.11.
The stmcture of boehmite (Ftgure 2. 12) consists of double
layers in which the oxygen ions xe in cubic packing. These
layers are composed of chains formed by double molecules of
AIOOH which extend in the direction of the a-axis (Ewing,
1935; Reichert and Yost, 1946; Milligan and McAtee, 1956).
Hydroxyl ions of one double layer we located over the
depression between OH ions in the adjacent layers. The double
layers ze linked by hydrogen bonds between hydroxyl ions in
neighboring planes. Average O-O distance of the hydrogen
bridges is 0.27 nm.

Determiwdtion of the position and structural significance of

impurities in Al(OH)l plymorphs remains a challenging _.. ..__
problem which appears solvable by today’s powerful techniques
of structure analysis.

If foreign ions should, indeed, be the cause of the stmctural

vatiet y of Al(OH), forms, the question of their relative
thermodynamic stability would k irrelevant.

2.3 Aluminum Oxide Hydroxides

2.31 Boehmite

This modification of AIOOH is a major constituent in many

bauxites of the Meditcmanean ty~. The mineral ~curs
together with gibbsite in deposits of Tertiary and UpFr
Cretaceus age. In many bauxites of older Mesozoic strata,
boehmite is the only aluminum hydroxide. It forms the fine
crystalline matrix of these aluminum ores, usually mixed with
highly dispersed iron oxide and hydroxide.

Bmhmite can be precipitated by neutralizing aluminum salts or

aluminate solutions at temperatures near and above the boiling
point of water. Treating amalgamated (activated) aluminum
with boiling water is another method of preparation. Aluminum
covered with an oxide film reacts very slowly under these
conditions. The reaction product formed on the sutiace consists
of X-ray indifferent material and gelatin~us boehmite; i.e., the
poorly crystallized, hydrated form described in Chapter 2.1. In
the autoclave, crystalline boehmite grows at a measurable rate
above 375K. Increase in pH reduces the minimum temperature
necess~ for the conversion of bulk aluminum to AIOOH.
Formation of behmite by a solid state reaction is observed W,mxlx
J. J. Ptasienski
when gibbsite is heated in air to temperatures between =380
and 575K. Conversion of the trihydroxide to measurable
amounts of AIOOH requires rapid heating and coarse particles.
[t is, therefore, assumed that locally high water vapor pressures Boehmite Crystals
generated within Imge gibbsite grains during rapid dehydration Figure 2.11

15
,,
L
Oxides and Hydroxides of Aluminum

ere has been considerable discussion regarding the exact These chains xe, however, arranged in a nearly hexagonal
position of hydrogen in tbe boehmite structure. If an close packing; whereas, the arrangement in b~hmite is cubic
orthorhombic uni~ cell is assumed to include two layers of A schematic representation of the stacking of the (2A 100H).
t 4AIOOH and to &long to the space group Cmcm (D];), chains was given by Llp~ns (1961); it is shown in
hydrogen bonds should be symmetric. Recent refinements of Figure 2.12.
the stmcture (Hill, 1981, and Corbat6 et al., 1985) place
hydro8en asymmetrically between bonded pairs of oxygen ions. Refinements of the diaspore structure were published by Ewing
Corbato et al. concuded ibat hydrogens are located in two (1935) and Hopp (1940). Busing and Levy (1958) established
positions, king closer to one oxygen than to the comsponding more precise hydrogen positions by neutron diffraction. There
one in the next layer, Thus, the structure is kst described in is agreement among investigators that the A106 coordination
space group Cmcm, Russell et d, (1978) found evidence, by octahedra are distorted, resulting in two Al-O hnd Iengtbs of
infrared spectroscopy, for Cmc (C~~) rather than Cmcm (Dj~) 0.185 and 0.198 nm, respectively. While Busing and Levy’s
symmetry. results indicate the presence of hydrox yl ions, stmcturc
calculations by Giese et al. (1971) favor a more ionic proton.
Boehmite in bauxites is an important raw material for the
production of aluminum oxide. Fine crystalline, synthetic No conunerciaJ use or large-scale synthesis of diaspore has
tihmite is produced as a precursor for activated (transition) been reponed so far. Use of diaspore bauxites as a raw material
aluminas used in tbe manufacture of catalysts and absorbents. for alumina production via the Bayer or tbe sinter process goes
back almost one hundred years, but has been abandoned in
2.32 Diaspore many countries in favor of gibbsitic bauxites which require
considerable y lower processing temperatures. Acicular crystals
Dlaspore occurs in the high al”mi”a clays of east central typical fOr diaspre are shown in Figure 2,13.
Missouri and central Pennsylvania. This mineral is also a major
constituent of bauxites in Greece, Romania, and Europan 2.33 KI-A1203 or Tohdite
Russia, Metamorphic rocks, such as the alumina-rich shales of
China, often contain considerable quantities of this aluminum In 1951, Houben reported to have found an alumina form of
oxide hydroxide. the composition 5A1203.H20. Torkar and Krischner (1960)
synthesized a similm compound by hydrothermal treatment of
Because diaspore is usually associated with older bauxites and aluminum or gelatinous alumina in the temperature range of
metamorphic rinks, high pressure and elevated temperature
were believed necessary for the formation of this mineral. The
hydrothermal synthesis of diaspore at temperatures above ~°C
reported by Laubengayer and Weiss (1943), seemed to confirm
this theory, Occasionally, however, diaspore grows epitaxially
on natural corundum c~stals, obvious] y formed by weathering
of tbe aluminum oxide. Koster (1955) identified diaspore in
laterite deposits in Indiq i.e., as a product of soil formation.
This indicates that diaspore can form at ambient temperatures
and pressures. Wefers (1967) synthesized diaspore
hydrothermally below 370K, using coprecipitated iron and
aluminum hydroxide gels as a starting material. Goethite,
a-FeOOH, which crystallizes spontaneously below 370K at
ambient pressure, provided the substrate for epitactic growth of
the isostmctural aluminum oxide hydroxide, thus reducing the
nucleation energy for diaspore,

The structure of diaspore (Figure 2. 12) was first investigated by

Deflandre (1932) and Takane (1933). As in the lattice of
boehmite, the basic elements are chains of double molecules.

Ho o
\ / \A,
Al
\/\ Diaspore Crystals
o OH Figure 2.13

17
 {i.
4
Alcoa Laboratories

650 to 8013K at pressures between - 10il to 3W bar. X-ray
diffraction data, but no structural information, were given of
this reaction product which these workers called KI.
Yamaguchi et al. ( 1964) determined the structure of a new
mineral named tohdite which they found to be identical with
Torkar’s KI with regard to composition and the temperature
pressure conditions of formation. The same authors later
described in detail various methcds of synthesis (1966) and a
refinement of the structure (1969) of this alumina. Although
named a “hydrate” by Yamaguchi et al., infrared analysis
showing an OH-stretch frequency of 3240 cm–l and the
dehydration tem~rature ktween 1100 and 1200K (Yamaguchi
et al., 1964) indicate an oxide hydroxide. The OH-stretch
adso~tion band lies between two strong bands of Y-A1OOH,
boehmite.
The stmcture of tohdite-KI is closely related to those of kappa
and beta alumina (see Chapters 4.41 and 3.2). Yamaguchi et
al. (1964, 1969) calculated a hexagonal unit cell with the
lattice parameters
a. = 0.5576 nm, co = 0.8768 nm
space group P6Cmc. The unit cell contains one formula unit;
i.e., 10 Al, 160, 2 H. About one-fifth of the aluminum ions
we in tetrtiedral coordination, tbe other ones are surrounded
by six oxygen. Yamaguchi et al. did not determine hydrogen
positions. In view of the similarity of the tohdite lattice with
the structure of kappa alumina, and considering the high
tem~rature of dehydration, a rather “metallic” hydrogen ion
can be assumed. One may, therefore, conclude that the layer
structure contains spinel* blinks in which charge balance for
tetrahedral sites occupied by the trivalent aluminum is provided
by protons:
Data on stmcture and physical properties of tohdhe-KI we
included in Tables 2.1 and 2.2.
2.4 Aluminum Oxide
2.41 Corundum, a-A1203
Corundum, a-Al*03, is the only thermodynamically stable
oxide of aluminum. Occurrence of corundum is commonly
associated with igneous and metamorphic rocks. It is the chief
component of the abrasive mineral emery. Red and blue gem
quality corundum crystals are known as ruby and sapphire,
respectively. The red color of mby is derived from the presence
of chromium and that of blue sapphire is related to the presence
of iron and titanium.
2.411 Crystal Structure
Corundum crystallize> in the hexagonal-rhombohedral system,
space group D~d or R3C. This stmcture type is often referred to
as “corundum structure” in crystallography. Hexagonal tabular
and prismatic crystal habits are most common (Figure 2. 14).
The c~stal structure of corundum was fully investigated by
Pauling and Hendricks (1925) following emlier work by Bragg
and Bragg (19 16). Refinements have been published later by
Newnham and DeHaan (1962) and Cox et al. ( 1979).

(A13+H+O:-)lV 2 (Al;+O~-)vl

As this composition is very close to the reported formula

5A1203H20, tohdile may be an ordered hydrogen spinel.
DeBoer and Houben (1952) suggested gamma alumina to he
hydrogen spinel. Later work showed that this transition alumina
has a defect spinel stmcture with high degree of disorder and a
random distribution of hydroxy l-ions (see Chapters 4.43 and
4.53),

Further work is needed to ascemain the exact positions of

hydrogen in the structure of tohdite. The thermodynamic
stability in the A1203-H20 system and the relationship to other
alumina phases must also b established. A comparison with
the H20-beta alumina synthesized by Saalfeld et al. (1968) by J. J. Ptaslenski 800X
exchanging sodium ions with water molecules (Chapter 3.2)
would also yield valuable information.
Corundum Crystals
‘nomal spinel: (MeO)lv(M.203)V1,exampleMgA1204 Figure 2.14

18
Alcoa Laboratories
this reason the actual Al-O-Al hnd angles in corundum show
considerable departure from ideal vafues for regular wtahedra.
Because of their identical structures, solid solutions of A1203
with Cr20g md Fe203 are possible over a wide range of
concentrations. The A1203-C1203 series of mixed crystals
prepared by reaction ~tween the oxides at 15W-16CH3K have
ken investigated by Thilo et al. (1955) who have reported cell
parameters for 22 different compositions. Similar studies for
A1203-Fe203 solid solution have been published by Mum and
Gee (1955). Corundum can lake up approximately 20% Fe203
in solid solution at 1700K.
2.412 Preparation
Corundum can be synthesized by thermal and bydrothemal
metbcds, Aluminum oxide is formed by tberrnal dehydration of
aluminum hydroxides. The extent of conversion to the
comndum structure de~nds on the temperature and time of
thermal treatment. Total conversion occurs on heating abve
15WK for more than one hour, Technical grades of “calcined”
aluminas, used for aluminum smelting, ceramics, abrasives
etc., represent materials with different degrees of conversion to
a-A1203, varying from 5 to 100%, The tem~rature and rate of
conversion is affected by impurities and “mineralizers. ” The
size of corundum crystals formed is a complex function of
precumor hydroxide, temperature, time and calcination
environment. The presence of fluoride ions is known to
facilitate the growth of a-A1203 crystals at lower tem~ratures.
Fused corundum is produced by melting calcined alumina in an
electric arc furnace. “Tabular alumina” is composed of large,
well developed, tablet-like a-A1203 crystals. It is produced by
heating aluminum oxide made by dehydration of gibbsite to a
temperature close to the fusion temperature.
The Vcmeuil method has been used for the preparation of large
single crystals of comndum includlng jewel quality sapphire
and ruby crystafs. In this process, an oxygen-hydrogen flame is
used to fuse tine A1203 pwder. The molten oxide solidifies on
a seed c~stal, The cimling rate is carefully controlled to
produce single cwstals measuring several centimeters in size.
Single crystals of appreciable size can also be grown from
melts containing lead fluoride or cryolite as ineri flux
(Timofejeva and Woskanjan, 1963; Klekr and Fehli”g, 1965).
Chemical vapor deposition of a-A1203 has ken studied
extensively. This process may involve pyrolytic decomposition
of aluminum alkoxides (Aboaf, 1967) high temperature
(> 15WK) hydrolysis of aluminum chloride (Wong and
Robinson, 1970) and of aluminum ff”oride (LOcsei, 1962).
Comndum is also formed by direct oxidation of aluminum
metal with oxygen at high temperatures. The reaction is highly
exothennic; fused corundum is produced if a sufficiently high
tem~ramre is maintained (Griffiths, 1981).
20
The hydrothemd formation of ct-A1203 is discussed in
Chapter 3.1. Laudise and Ballman (1958) have descrikd the
hydrothetmd synthesis of large crystals of sapphire, High
growth rates were obtained by the use of Na2C03 solution as a
solvent at temperatures above 670K and pressures in excess of
20W bars. Doping with chromium, realized by the addition of
sodium dicbromate to the solvent, resulted in the formation of
synthetic mby.
Alumina ceramics made by the sintering of poly-crystalline
a-alumina we of considerable technical and commercial
importance. The properties of the find product are controlled
by the different steps of the fabrication process, Dense, sintered
articles of afumina are prepared by forming tine a-Alz03
powder to the required shape (either by d~ compaction or by
slip casting) and subsequently fting to bigb temperatures
(18@-21MK) to produce sintering and eliminate porosity. The
fact that A1203 can be sintered to theoretical density was first
demonswated by Cabmn and Christensen in 1956 and
subsequently by Coble (1959). These and others have shown
the imptiance of suppressing grain growth for pore elimination
and the role of smafl additions of MgO in achieving this.
Techniques for preparation, and properties of fibrous alumina
crystals, so-caf led “Whiskers,” have ~n studied intensively in
recent years. The tensile strength of single crystal whiskers can
be several orders of magnitude higher than that of the
plycrystalline bulk material. Values of 5,500 MPa
(8 X 105 lbs/in2) have ken measured for corundum whiskers
(Levitt, 1966). The product is currently of considerable interest
for the fabrication of fiber reinforced polymer, metal and
ceramic composite materials.
Several metbcds of growing alumina whiskers, generally from
the gas phase, have been described. Campbell ( 1963) reacted
AlC13 with C02 in the presence of H2 at 1500K, Grimshaw, et
al (1975), have described a process in which gaseous AIC13 is
passed over a mixture of alumina and carbon at 1700-2100K to
form aluminum monochloride and CO. This stream is then
passed over a zone of lower temperature, 1300- 1500K where
tbe reaction is reversed producing A1203 whiskers.
Decomposition of “spun” fibers made from aluminum
compounds and organic binders has ken used to produce
polycrystalline alumina fibers and filaments. Gitzen (1970) has
reviewed methods of preparation and properties of alumina
whiskers and fibers.
Alumina is an important high temperature ceramic material and
its properties have been explored thoroughly.
2.413 Thermal Properties
Data and reviews of thermal pro~rties of alumina have ken
previously compiled by Gitzen (1970), Dorre and Htibner
 Oxides and Hydroxides of Aluminum

(1984), JANAF (197S), NBS (19S2), U.S. Geol. Survey
(1979), Thermophysi.al Institute (1977), CRC Handbook of
Material Science (1975) and many other publications, A
summary of important and recent results is discussed in the
following.
Melting Point
Literature values range from 2310 to 2329K (2037” to 2056°C).
Tbe value of 23273 6K (2054 * &C) was recommended by
Schneider (1970) from tbe results of cm~rative measurements

Table 2.3.
Thermodynamic Data

298,15K (25°C) and 0.1 MPa (1 bar)

Molar AH; AG; s“ Cp

—
vol.
Substance MW State cm3/mol kJ/mol Jlmol K

AI(OH)3 78.004 Cryst. 31.956 –1293.2 –11 55.0 68.44 91.7

gibbsite

AI(OH)3 78.004 Cryst. –1288.2 –11 53.0

bayerite

AIOOH Cryst. 19.55 –990,4 –915.9 46.43 65.6

boehmite

AIOOH 59,989 Cryst. 17.76 –999.8 –921 .0 35.33 53.3

diaspore

a-A1203 101.981 Cryst. 25.575 –1675.3 –1562.3 50.92 79.0

P-A1203 – 1657

y-A120~ – 1657

K-A1203 – 1662

8-A1203 – 1666.5

AIO 42.981 Gas 67 41 218.4 30.9

A120 89.982 Gas –145 –173 252 52.0

A1202 85.962 Gas –395 –400 281 67.2

Sources: (1) NBS Tables of Chemical Thermodynamic Properties Vol. 11, 1982,
Muddlement No. 2.
(2) JANAF Thermochemical Tables, 1976 Supplement, and Third Edition, 1965
(3) Geological Survey Bulletin 1452, Reprinted with Corrections,
1979.
(4) Kuyunko et al. (1983)

21
Alcoa Laboratories

Table 2.4 to the C-axis and of a polyc~stalline material in the

Equation for Cp temperature range of 100- 1100K. The anisotropy of the
CP(TK) J/mol.K = a + bT – CT-2 hexagonal comndum stmcture causes the expansion coefficient
parallel to the C-axis to be higher than that perpendiculu to it
Temperature
Range, K b c
by about 10%. Klein (1958) showed a nearly constant ratio of
a
the expansion coefficients in the two directions between
Gibbsita 240-500 50.46 179.49 x 10-3 10.96 x 105 300-2000K. The values for pcdycrystalline alumina are
intermediate ktween those for the two single crystal
Boehmite 240-600 56.23 82,93 13,60
orientations. Expansion coefficient data up to 2 100K we
240-600 46.94 64.16 11.30
reprted by Nielsen and Leipld (1963) for polycrystal line
Diaspore
alumina. Yates etal. ( 1972) reported results between 373 to
Corundum 296-1500 114.77 12.80 35.44 I073K for single crystal and calculated the mean GrOneisen
parameter as a function of temperature. The Thennophysical
Sollrce: Kuyunko et al. (1963) Research Institute has publisbed a graphical presentation of
published data including a recommended curve for m-A1203
single crystals.

by nine groups in seven countries. Reported values for entbalpy As shown in Figure 2.18, the thermal expansion cm fticient for
change on melting 6re in tbe range of 107.5 ? 5.4 to alumina approaches a constant value at high temperatures
118.4 t 2.5 kJ/mol. similar to heat capacity behavior. This is in accordance with
theoretical predictions and was verified by Hoch and
Boiling Point Vemardakis for Q-A1203 ( 1975),

Brewer and Semcy (1951) reported the boiling point of
a- A1203 to be 3803K (3530”C). Yudin and K6rklit (1966)
re~rt a value of 3990K (37 17°C) for the boiling point and the
heat of vaporization to be 1976.1 k.flmol. We consider these
data to have little practical meaning as aluminum oxide
decomposes to suboxides (Chapter 2.42) at this temperature,
Thermal Conductivity
Data on thermal conductivity of alumina ue well documented
and generally consistent, Charvat and Klngery (1957) published
values for both single crystals and plycrystalline sintered
materials. In sintered alumina the thermal conductivity must k

Thermodynamic Data

Recent values for heats of formation, Gibbs free energy and GA 20

entropy at 298. 16K are given in Table 2,3, I I I I I I I I

A large number of heat capacity (Cp) determinations over a

wide temperature range have been published, A survey of
literature by Dhmars and Douglas (1971) includes some twenty
previous studies. Correlations have hen published by Robie et
al. (1978) and Kuyunko et al. (1983) in the form:

Cp=a+bT–+
T

Values of the coefficients we given in Table 2.4. As shown in

figure 2.17, the specifc heat at constant volume, Cv,
approaches the tberrnodynamic value of 3R (=24.94
J/g atom K) at high temperature, a-A1203 has been used as a
calorimetric standad.
VI I I I I I I I
0 200 400 600 800 10001200140016001800
Thermal Expansion Temperature K

Thermal expansion of U-A1203 bas ken studied by Wachtman I

et al. (1962) who determined the relative linear thermal Heat Capacity of a-A120J as a Function of Temperature

I
expansion of single crystal a-A1203 parallel and perpendicular Figure 2.17

22
 Oxides and Hydroxides of Aluminum

1,
Table 2.5
Selected Thermal Properties of a-A1203 at Various Temperatures

Linear
Tharmal
Expansion
Thermal
Temperature Heat Capacity Thermal Conductivity _
K “c * ~ cal/cm. s.°C J/cm.s.K lPK~l O”s

100 –173 0.03 0.126 1.075 4.5 0.6

200 –73 0.12 0.502 0.196 0.82 3.3

\
298 25 0.18 0.753 0.110 0.46 5,5 0.075
I
\ 400 127 0.22 0.0773 0.324 7.1 0.058
0.920

\ 500 227 0.25 1.046 0.0579 0.242 7.5 0.039

600 327 0.26 1,088 0.0451 0.189 7.9 0.030

800 527 0.28 1.172 0.0310 0.130 8.5 0.022

~
1000 727 0.29 1,216 0.0251 0.105 9.1 0.017

1200 927 0.296 1.238 9.6 0.013

1400 1127 0.298 1.247 10.1 0.012

1600 1327 0.30 1.255 10.5 0.011

corrected for porosity. The relation K = Kp/( 1-p), where Kp is
the experimental thermal conductivity and p the prosity, has
been generally used. Representative thermal conductivity data
of several investigators are presented in Figure 2.19. The
variation of thermal conductivity with temperature shows a
minimum. This arises from the mechanisms of heat transport.
At low temperatures, the rate of heat transport is related to the
mean free path of phonons between two collisions which varies
with Iff K. At higher temperatures, electromagnetic radiation
becomes the dominating mechanism (K & T3). Data of Charvat
and Kingery show that the minimum for single crystal alumina
occurs at 11OL-i 200K compared to about 1500K for the
polycrystalline material; the difference has been explained on
the basis of greater transparency of the single crystal. Nishijima
et al. ( 1965) fitted the equation: k = A/(B + T) + CT3 to their
experimental data. Results of Fltzer and Weisenburger (1974)
are in good agreement with those of Charvat and Kingery. The
significant effect of small amounts of impurities on thermal
conductivity arises out of the loss of regularity of the ionic
arrangement of the crystal lattice.
2.414 Diffusion and Related Properties
Diffusion, pmiculady at high temperatures, is the principal
mechanism underlying several properties of alumina including
electrical conductivity, sintering, grain and crack growth at
elevated temperatures, and creep. There is a considerable
volume of experimental observations in the published literature
describing these phenomena in A1203, However, because of
their strong dependence on preparation methods, impurity
content and environmental factors, data and their interpretation
lack consistency and are often confusing,
The nonstoichiometry of well-crystallized comndum is very
small, so is the defect concentration. Mohapatra and Kroger
( 1978) proposed that Schottky disorder is the main atomic
disorder mechanism in alumina. However, many experimental
results of diffusion controlled phenomena can be and have been
interpreted in terms of Frenkel disorders. Thus, the question of
which disorder mechanism determines the bhavior of pure and
doped A1203 remains ambiguous.

23
Alcoa Laboratories

I I I I I I I I Self diffusion of aluminum and oxygen in alumina at high

12 Polycrystalline temperatures has been studied by direct measurements using
IIc - axis tracers (Oishi and Kingery, 19@, Paladlno and Kingeg, 1962)
and from plastic deformation investigations (Cannon et al.,
1980). Data from recent publications are presented in
Figure 2.20.

2.415 Electrical Conductivity

An important diffusion related property of alumina is electrical

conduction. Alumina is a ve~ good electrical insulatoq it
i retains high electrical resistivity to very high temperatures. The
VI 1 I I I I I I I accurate measurement of true electrical conductivity of a vev
o
o 200 400 600 60010001200140016001800 high resistance material at high temperatures is very dlfticult as
Temperature, K it is of the same order of magnitude as that for surface and gas
conduction. There is strong evidence that data published before
Thermal Expansion ofa-A1203as a Function
of Temperature
figure 2.18 GA2024610

2300 2000 1700 1500

The concentration of Schottky defects in pure a-A1203 new the
melting pint has ken estimated to k of the order of 10– 12. I I I
This concentration is orders of magnitude smaller than that
caused by even very small amounts of impurities. Evidently,
obsewed diffusion related phenomena are linked primarily to –lo
Aluminum ion in
defects caused by the presence of impurities rather than
polycrystslline A1203
intrinsic defects in pure A1103. Dome and Hiibner ( 1984) have
tabulated (reproduced in Table 12.6) energies for the formation
of various defects in alumina. –11

\
~
\
“g –12
Oxygen ion in
GA a,i, , o polycrystalline A1203
I I I I I I I
1.2 ; –13
A
1.0

0.8 –14

0.6
\ Polycrystalline Oxygen ion
\ 0.4 –15
crystal A1203
0.2
___ _ I I I I I I
I I I 1 0
0 200 400 600 6001000120014001600 laOO 0.46 0.50 0.54 0.68 0.62 0.66
Temperature, K
103~(K)

Thermal Conductivity of a-A1203 as a Function

of Temperature Self Diffusion of Al and O in AIz03
Figure 2.19 Figure2.20

24
 Oxides and Hydroxides of Aluminum

Table 2.6
Possible Disorder Mecbani9ms in A1203

r
Type of disorder Equation of formation and Formation energy Preexponential
equilibrium constant Hi/n, in eV term, exp(S~nk)

Frenkel disorder Al~l – All+V~L 10.0 ~,o-4

of Al
[Vfi] = [Ali]=K~fi) 8.3

4.45

KFl{~l)=l .32 1018 exp (–4.45/kT) cm-3

Frenkel disorder o~ e o~+v~ 7.0

of o
[vO]=[O(] = K$(~} 7.1

Schoftky disorder null * 2vfi + 3V0 5.7 ~,o-4

I
5.2

4.1
‘~=:’vol=(:)
‘5K5”5 3.83

K~/5 = 1,3tj 10I9 exp (–3.83/kT) cm-3

Intrinsic electronic null~e’ + h’ 5.18 150

disorder
[h’] = [e’]= Kj’2

KJJ2 = 3,14. 101g ~ exp (–5.18/kT) cm-3

Source: Dorre and HUbner

i’
,) 1971 are not reliable. Figure 2,2 I shows results from literature
published during 1960-1973.
The electrical conductivity is a function of temperature, oxygen
partial pressure (po2), impurity (or dopant) content and grain
size (for polycrystalline alumina). Behavior with respect to p02
shows a minimum in the range of 10–6 and 10-4 bar. This has
ken interpreted in terms of contributions by different
conducting species, Two types of hhavior have been obsewed.
In one, found in alumina containing “acceptor” type dopants
such as Mg, Fe, Co or V, conductivity is mainly ionic at low
and electronic at high oxygen partial pressures, The reverse is
found when “donor” dopants, TI, Y, H, Si are present. Thus
the electrical behavior of A1203 is primarily dependent on the
tY~ and amOunt of doping and the interaction of the dopa”t
with oxygen.
In polycrystalline alumina, the grain boundaries have been
identified as zones of increased conductivity -- resulting in
much higher overall conductivities than those of single crystals.
Conductivity increases with decreasing grain size (Bozkan and
Moulson, 1971),
2.416 Dielectric properties
The low dielectric loss and high permittivity of alumina have
led to wide applications in electronic ceramics, and
consequent] y, its dielectric properties have been thoroughly
investigated and documented.
Dielectric properties (dielectric constant, dielectric loss tangent)
of corundum were extensively investigated and publisbed by

25
Alcoa Laboratories

K polarization) in pure and doped corundum is low. This was

borne out by the fact that the dielectric loss in these samples
2000 1000 750 500
even at 102 Hz and 373K is very low (tan 8< 0.0005). The
I I I I similar ionic radii of Al (0.057 rim), Cr (0,064 rim), and V
(0.065 nm) suggest that Cr and V enter the A1203 lattice
without much distortion of the lattice. The frequency-dependent
increase in the dielectric constant (K) at temperatures above
473K, the large dielectric loss at the higher temperatures and
the larger changes in K and tan 8 (with temperature) in the Cr
and V doped crystals are attributed to space charge polarization
and the contribuiton made by the dopants to defect
concentration. The frequency-dependent increase in dielectric
constant with temperature is apparently due to increase in ionic
polarization at higher temperatures.

The dielectric breakdown of alumina has been shown to be

caused by two mechanisms: intzinsic (electronic or avalanche)
and thermal. The former is impoflant in the case of thin tilms
of amorphous aluminas and is generally used to describe.low
temperature phenomena. The thermal breakdown mechanism is
more complex and depends, in addition to intrinsic
characteristics, on such factors as geometry and frequent y and
wavefom of applied electric voltage.

Miyazawa and Okada (1951) reported that the electrical

L I I I
strength of a 70 pm thick layer of alumina (exact structure not
specified) was constant at 2 X I@ V/cm from room
5 10 15 20 25 temperature to 1073K and then decreased to 6 x 103 V/cm at
104/T(K) 1600K. Brht and Davis (1971) studied plycrystalline a-A120S
“Lucalox” samples from rwm temperature to 1373K concluded
that an avalanche bre~down recurred at <725K, where a
Electrical Conductivity of a-A1203 as a Function maximum strength of 3.3 X 105 V/cm was observed. The
of Temperature strength decreased at higher temperatures. This was attributed
Figure 2.21 to a thermal breakdown mechanism.

Yoshimura and Bowen (1981) studied the dc electrical strength

Von H]ppel (1953, 1954, 1959) up to the temperature of
I073K (Table 2.7) Data for highter frequencies (1010 Hz) and
temperatures (23WK) have been re~rted by Lhovchenko et al
(1983). Hill (1974) d,scussed experimental techniques for the
precise determination of the dielectric propefiies of
polycrystzlline alumina ceramics ad gave data for microwave
frequencies of 1010 Hz.
Dielectric propeflies of single crystals of a-A1203 and of
a-A1203 doped with chromium and vanadium were studied by
Govinda and Rao (1975). The results were interpreted in terms
of the polarization mechanisms operating at vtious frequencies
and temperatures. These authors found that among the four
polarizations (electronic, ionic, dipolar, and space charge)
contributing to the dielectric constant of A1203 only electronic
md ionic polarization are present at a temperature of 300K.
The concentration of defects (contributing to. space charge
of sapphire and pcdycrystalline alumina up to the temperature
of i673K. The electrical strength was essentially the same for
both the materials. The rmm temperature value of >106 V/cm
for a 100 pm thick sample decreased gradually with
temperature to 2.6 X 105 V/cm at 1173K, then dropped rapidly
to 2 X 104 V/cm at 1673K. The electrical strength decreased
with the saznple thickness; it was inversely proportional to the
thickness for samples thicker than 600 pm at 1473K. The
breakdown behavior above 1173K was described by a thermal
breakdown model.
2.417 Optical Properties
I
a-A1203 (corundum, sapphire) is usually uniaxial negative,
though twinning could give rise to anomalous biaxial character.
Colors found in corundum crystals are related to the amount of
other ions replacing aluminum: ruby has 2 to 3% Cr203 while
sapphire contains Fe3+ and TI, yellow comndum may have NI

26
 Oxides and Hydroxides of Aluminum

Table 2.7
Dielmtric Properties of Corundum

Dielectric
LOSS
Temperature Frequency Uelectric Dielectric LOSSTangent
I Constant (Dissipation Factor)

\
Sapphire@ Sapphirea
Sntered Aluminaa
“C/K Cycle51s0c L OptiC tiS II optic hs L Optic tis II Optic Axis (99.9%A120.)

25/298 1O“ 8.34 11.55 0.000012 10.5 0.00066

10“ 9.34 11.55 10.5 0.00031
10“ 9.34 11.55 10.5 0.00011
10. 9.34 11.55 10.5
6.5 X 10” 9.34 11.55 0.00003 o.oom86 9.6 0.00049
(0.00026)@
50/323 10- 9.36 11.58 0.00001 0.000016 10.6 0.0015
I 10. 9.36 11.56 10.6 0.00056
10. 9.36 11.56 10.6 0.00019
10. 9.36 11.58 10.6 0,0001
8.5 X 10° 9.36 11.5a 0.000032 0.00009 9.7

100/373 10- 9.41 11.ea 0.0002 0.000038 10.7

1O* 9.41 11,66 0,00001 10.7
10. 9.41 11.66 10.7
10“ 9.41 11.8J3 10.7
6.5 X 10” 9.41 11.ea 0.000036 0.000086 9.7

200/473 10- 9.53 11.87 0.00012 0,00017 12.0 ‘0.20

10. 9.53 11.67 0.000036 0.000024 10.6 0.033
10. 9.53 11.87 0.000012 0.00001 10.6 0.0067
10. 9.53 11.87 10.8 0.0016
1, 8.5 X IO. 9.53 11.87 0,00011 9.6 0.00062
) (;:003)
300/573 10. 9.65 12.09 0.00062 0,00066 21.6
1O“ 9,65 12,09 0.00023 0.00015 12.6 0.33
10s 9.65 12.09 0.000078 0.00005 11,2 0.06
10s 9.65 12,09 0.000037 11.1 0.012
8,5 X 10° 9.65 12.09 0,000062 0.00013 9.9 0.00076
! (0.00034)
400/673 10“ 9.82 12.35 0.0033 0.003 100 1.03
10“ 9.78 12.3 0.001 0.0009 21.5 1.17
10. 9.76 12.3 0.00036 0.0003 13.1 0.30
10. 9.76 12.3 0.00016 11.5 0.062
i 8.5 X IOC 9.76 12.3 0.00008 0,00014 10.0 0.001
(;0.)
‘? 500/773 10- 10.02 12,7 0.026 0.015 257
10. 9.95 12.55 0.005 0.0035 69 1.10
10° 9,92 12.55 0.0012 0.0017 19.0 0.80
10- 9.92 12.55 0.00056 0.0011 13 0.24

I 600/873
8,5 X 10m

10“
9.92

10.55
12,55

13.15
0.000093

0,21
0.00015

0.16
10.1 0,0016
(0,00048)

10“ 10.17 12.63 0.032 0,021

10“ 10.07 12.63 0.0054 0,0036
10“ 10.07 12.W 0.0011 0.0017
8.5 X 10° 10,07 12.63 0.00013 0.00017 10.2 0,003
(0.00062)
700/973 10° 13.15
10“ 10.26 13.15
10“ 10,26 13.15
8.5 X 10° 10.26 13,15 0.00021 0,00019 10.3 0.0059
(0.00093)
8OOI1O73 8.5 X 10- 10.40 13,50 0.00043 0.00021

@ Oata from MIT Technical Report 126: von Hippel (1953, 1959)
w values In parenthesis were obtained from a difterent sample of sintered alumina
@ All measurements of sintered alumina at 6.5 x 10” were made with electric field perpendicular to the direction of processing. At other
frequencies the field was parallel.
Alcoa Laboratories

or Fe3+; brown varieties have Fe3+ and Mn and green cO1Orhas 2.418 Magnetic Prowrties
been attributed to V, Mo, Ni and Fez+.
Magnetic susceptibility of aluminum oxides and hydroxides was
measured by Selwood (1950) and m given in Table 2.8.
The refractive indices are fairly constant and the commonly
Additional data for a-A1203 were re~rted by Rao and Leela
accepted values are El .760 and 61,768. Measurements of E
(1953).
and m for synthetic sapphire were reported by Jeppesen (1958)
for various wavelengths from 690.7 to 253.6 nm. leppesen also
2.419 Mechanical Properties
determined the temperature cm fficients for refractive indices
and bircfringence. me refractive index of sapphire has also
Due to its wide use as a structural ceramic material, the
been reported by Malitson et al. (1958). Other reports of data
mechanical pro~rties of aluminum oxide have been extensively
on optical constants of sapphire have been published by:
studied and documented. These studies have covered both
single crystals of a-A1203 (Imge crystals of sapphire have been
Lowenstein (1961) -270 to 1000 #m
generally used) and polycrystalline sintered products. The
Russell and Bell (1967) -50 to 400 #m
mechanical khavior of the latter is, as would k expected,
Lang and Wolfe (1983) -0.3 to 25 Wm
strongly influenced by the micros~cture. A thorough
discussion of the subject is given in the monograph of Dorre
The temperature dependence of the far-infrared ordin~-ray and Hiibner (1984).
optical constants of sapphire was determined by Cook and
Perkowitz (1985) for frequencies ktween 30 and 230 cm-1. The elastic khavior of the hexagonal comndum crystal is
Optical constants of a-A1203 at 27W-30WK have been described by six elastic constants of the general 6 X 6 elasticity
reported by Klabukov et al. (1983). matrix. These constants and values for the compliance have
been experimentally determined by Wachtman et al. (1960)
Bhagavantam and Venkatarayedu (1939) predicted eighteen who have also reviewed previous reports. Strong anisotropic
frequencies for a-A1203 of which two symmetric and five bebavior was expected and observed. The variation of elastic
doubly degenerate ones should be Raman active. Krishnan constants in the temperature raoge of 77-850K was determined
(1947) found the Raman frequencies and their relative by Wachtman et al. (1961) and by Tefft (1966).
intensities to be 375 (8), 417 (10), 432 (4), 450 (2), 578 (3)
@2 (6), and 751 (7) cm-l. The Raman spsctrum of a-A120q In plycrystalline alumina, which can k considered isotropic
was confirmed by Rarnm in 1951. on a macroscopic scale, the Young’s modulus and the shear
modulus can k estimated from the orientation de~ndent
Pure a-A1203 is neither phosphorescent nor fluorescent
although 0.000 I % of chromic oxide produced a distinct
fluorescence (Kroger, 1948). Experimentally, ruby has been
found to exhibit fluorescence in the famous RI and R2 regions
at 694.27 and 692.85 nm as a resonance process (MendenhaO Table 2.8
and Wood, 1914; Wieder, 1959) and when pumpsd with Magnetic Susceptibility
electric fields, in the absorption bands at 250, 400, and 560 nm Unib of 106; Data of Selwnod
(Maiman, 1960). Ruby has been used as a laser material. Its
Form Susceptibility
behavior as a macroscopic fluorescing and laser material was
discussed by Mahan et al. (1969). The Faraday effect in ruby
and corundum was investigated by Boiko and Soika (1984) G!bbsite –0.43
who showed that the angle of rotation for the plane of high
–0.46
polarization at 632.8 nm is a linear function of magnetic field
strength.
Boehmite –0.37

The emissivity of alumina decreases from 0.98 at room –0.34

Gamma Alumina
temperature to 0.9 at 373K, 0.8 at 673K, 0.5 at I023K, 0.3 at
1273K, 0.18 at 1873K, and 0.12 at 3073K (Heilman, 1936; Corundum –0.23
Michaud, 1949; Kilham, 1949; Taylor and Edwards, 1939;
Leedy, 1954). The monochromatic emissivity at 655 nm is
0.15 in the temperature range of 1273- 1873K (Michaud, 1949). See also Rao and Leela for more values on corundum.
Pascal found partially dehydrated gibbsite nearly
Infrarsd spctra data are given in Table 2.11, identical with corundum.

Za
 Oxides and Hydroxides of Aluminum

Table 2.9
Mechanical Properties of Corundum

25° C Unless Otherwis Noted

Property Condtions Values, psi Alumina Reference

Plastic Constants 72.0.10 Corundum Wachtman et al (1960)

23.7.10 Corundum Wachtman et al (1960)
16.1.10 Corundum Wachtman et al (1960)
–3.4.10W Corundum Wachtman et al (1960)
72.2.1 W Corundum Wachtman et al (1960)
21,4.10. Corundum Wachtman et al (1960)

Plastic Compliance Sll 2.35.10cm2. dynl Tetft

S12 -0.72 .10cm2. dyn> Corundum TeHt
S1? –0.37.10”cm2. dynl Corundum Tefft
Sll 0.49.1 Ocmz. dynl Corundum Tefft
s?, 2.17.1 Ocm2. dynl Corundum Tefft
S11 6.94.10”cm2. dynl Corundum Tetft

Mtiulus of Elasticity Z&c 52.6.10” Sapphire Wachtman and Lam

500”C 48.1.10 Sapphhe Wachtman and Lam
1ooo~c 43.5.10 Sapphire Wachtman and Lam
1zoo-c 41.9. IW Sapphire Wachtman and Lam

25-C 59,3.10 POlycWstalfine Crandall et al

500”C 57.3,10 POlycVstalline Crandall et al
1Oovc 54.9.10 Polycrystalline Crandall et al
1zoo-c 53.6,10 Crandall et al

Bending Strength Plates 44,300-1 15,600(2) Corundum Klassen-Noklyudova

24,000-36,000 RAE S!”tered171 Roberfa and Wan
1ooo~c 16,000.22,000 Sapphire Roberta and Wan
25°C 37,000(1)26,000(21 Sapptire Roberta and Watt
1ooo~c 43,000(1)32,000(2) Sapphire Roberla and Watt

43,000-131,000 SaDDhire Wachtman and Maxwell (1954)

94,000 -t55,000 Sapphire Wachtman and Maxwell (1954)
17,000-50,000(540~c) Sapphire Wachtma” and Maxwell (1954)

Modulus of F6gidity 25°C 23.3( Reuss).24.l(Voigt) Sapptire Wachtman et al (1960)

25-C 23.3 hot pressed
zero porosity Lang
25-C 23.9 cold pressed
zero porosity Lang

Poisson’s Ratio 25°C 0.257@ cold pressed

zero porosity Spriggs and Brissette
25.1 OOOQC 0,32@ Sintered Ryshkewilch (1942)
1400”C o.45@ Sntered Ryshkewitch (1942)

I Volume Changea o.oo355@ Sapphire Bridgma”

Impact Strength 43,000 Sntered Moore
Strength 800”C 27,000 Sintered StavrolaNs and Norton
1ooo~c 24,000 Sintered Stavrolatis and Notion
115rc 16,000 sintered Stavrolaks and Noflo”
1300”C 11,000 Sintered Stavrolalds and Notion
1500”C 3,400 Sintered Stavrolakis and Notion

29
Alcoa Laboratories

Table 2.9
Mechanical Properties of Corundum

25° C Unless Otherwis Noted

Properly Condtions Values, psi Alumina Reference

Tension, luration,
Temp. psi hr

T
Strain 1300°C Observable 3ntered Stuvrolukim and Norton
1Ooo”c 7,200 402 10 10-2% 7AE Roberts and Watts
sintered @
1Ooo”c 20,000 769 1 10-2% ?AE Roberts and Watts
sintered @
1Ooo”c 15,100 77 0.49% ;apphre Wachtman and Maxwell (1954)

1Ooo”c 12,000 431 1.52% ;apphre Wachlman and Maxwell (1954)

llOO°C 17,100 95 ,08% ;apphite Wachtman and Maxwell (1954)

IIOO”C 13,100 431 2.06% Sapphire Wachtman and Maxwell (1954)

1200”C 12,100 53 0.7% 3appMre Wachtman and Maxwell (1954)

1300”C 7,250 3 2.34% 3apphhe Wachlman and Mwell (1954)

13oo”c 8,620 44 32% Sapphire Wachtman and Maxwell (1954)

Compressive Strength 25°C 443,000 to 495,000 Sapphire Pavlushkin

25°C 50,(XX) Polycrystalline Ryshkewitch (1941)
4oo~c 213,000 POlycrystalline Ryshkewitch (1941)
1Ooo”c 128,000 POlycrystalline Ryshkewitch (1941)
16oo~c 7,100 Polycrystalhne Ryshkewitch (1941)

Tensile Strength 21,000 Polycrystalline Schwarlz

20”C 37,400 Polycrystalline Ryshkewitch (1941)
800”C 19,500 Polycwstalfine Schwartz
80°C 33,900 POlycVstal line Ryshkewitch (1941)
1300”C 11,600 POlyc~stalhne Schwartz
1300”C 6,400 Polycfystalline Ryshkewitch (1941)
14oo~c 7,300 Polycvstalline Schwartz
1400”C 4,200 Polycrystal fine Ryshkewitch (1941)
1460”C 1,500 Polycwstaline Ryshkewitch (1941)
15oo~c 0 Polycrystaline Ryshkewitch (1941)

45” to c-axis

30”C 71,000 Sapphire Wachtman and Mawell (1954)

300”C 52,5600 Sapphire Wachtman and Maxwell (1954)
800”C 52,500 Sapphire Wachtman and M~well (1954)
11Oo”c 88,000 SappNre Wachtman and Maxwell (1954)
30° to c.mis 100,000 SappMre Castor
45” to c-ais 78,000 Sapphire Castor
60mto c-axis 65,000 Sapphire Cstor
75- to c-axis 94,000 Sapphire castor

@ Optic misl length oftestpiece. Benlinplane ofoptic aXis I

~ Optic misl length oftestpiece. Benl Ltoplane ofoptic aXis
@ Four point loading. Angle between rodaxis and slip
@ 10,000 kg/cm2(142,200 psi)
@ Heating 1500to1900"C followed byslowcoofing increased strength
@ No.nits
~ ipecifiigravity 3.48-3.62
0 Specific gravity 3.61
0 Specific gravity 3.76
@ Crushing

30

values of the respective single-crystal mcduli. These values are
given in Table 2.9,
Conrad (1965) reviewed the mechanical behavior of sapphire
with respect to plastic flow involving slip, twinning, creep, and
fracture. Sapphire deforms plastically above about 100K; the
stress for yielding and the amount of strain before fracture are
strongly dependent on tbe strain rate. This yield bebavior at
elevated temperatures is characterized by tbe presence of up~r
and lower yield points whose values depend on the temperature
and the strain rate.
[n the aluminum oxide crystal, sliD can occur in the three
different systems; i e., ba~al, prismatic, and pyramidal. The
most_common mode of deformation is basal slip in the
<1 I 20> direction; the prismatic and pyramidal slip systems
are activated at high temperatures of > 1900K. Kronberg (1957)
applied dislocation concepts to determine the significance of
crystallographic orientation on slip behavior.
Twinning has been observed frequently in single-crystal and
polycrystalline alumina and is considered to be an important
plastic deformation mechanism (Kronberg, 1957). On
examination of sapphire specimens tested in compression,
Stofel and Conrad ( 1~63) found two distinct types of twins,
one puallel to the (O11 I ) plane and the other parallel to the
basal plane. It was established that twinning occurred only at
lower temperatures and high strain rates.
Creep is an important deformation process for aluminum oxide
at high temperatures. The mechanisms involved include
diffusional creep at small and intermediate stresses (Cannon
and Coble, 1975) and non-viscous Nabarro climb type creep at
high stresses (Weetiman, 1968). The effects of temperatures
and stress on the creep rate of sapphire was studied by Rogers
et al. (1961) in the range of 1250- 150i)K and by Cbang (1960)
at 1750 -2200K.
The modulus of rupture of both sapphire and polyctystalline
alumina as a function of temperature was reprtcd by Jackson
and Roberts (1955). For single crystals, the modulus of rupture
passed through a minimum at 873K and returned to its room
temperature value at 1273K. The same behavior was observed
by Wachtman and Maxwell (1959).
According to Conrad ( 1965), the fracture of 60” oriented
sapphire rods in tension, bending, and compression generally
occurs on a plane approximately normal to the tensile stress
and the fracture surface is conchoidal. The fracture stress
decreases with increase in previous plastic strain, independent
of temperature and strain rate. The mechanism of failure seems
to be the interaction of edge dislocations with pre-existing
surface cracks. When twinning occurs, the fracture surface
tends to follow the twin interface suggesting that this is weaker
Oxides and Hydroxides of Aluminum
than the untwinned crystal. _~e O“ oriented crystals, stressed in
bending, fractured along {O111} planes. This observation
suggests cleavage fracture. Detailed discussions of mechanical
proprties of Polycrystalline aluminum oxide ceramics including
strength-grain size relationships, fracture strength, thermal and
mechanical shock proprties, fatigue, hardness, etc., can be
found in books by Gitzen (1970) and by Dome and Hiibner
( 1984).
2.4110 Surface Properties
Surface related properties of aluminum oxide such as
adsorption, catalytic activity, wetting, sintering khavior are the
results of the atomic and electronic arrangement of the surface
which differs from that of the bulk crystal. A recent review by
Henrich ( 1985) Wints to the lack of investigations of the
surface pro~rties of a-A1203 in spite of the technical and
commercial importance of this material. One practical reason
is, since A1203 is an excellent insulator (optical band gap
9.5 eV), the electron spectroscopic techniques, applied
successfully to metal and semiconductor surfaces, are difficult
to apply.
The LEED (Low Energy Electron Diffraction) technique bas
been mostly used to study the surface of A1203. Notable arc tbe
works of Charig (1967), Chang (1968), French and Somorj ai
( 1970), and Wei and Smith (1972). Most of the measurements
were made on the (Oi)Ol) basal plane of a-A1203 crystals.
At moderate temperatures, the (WO 1) face of U-A1203 exhibits
the two-dimensional hexagonal 1 X 1 lattice of aluminum atoms
expected from the bulk crystal stmcture. French and Somorjai
showed that the ( 1 x 1) bulk-like structure remains up to about
1250K under vacuum. On further increase of temperature a
new ordered surface structure designated at (~ x W)
(rotated 30”) appears. Subsequent beating to even higher
temperatures (- 1700K) produces the ordered (fix ~)
(rotated 9“) surface structure, This surface was shown to be
oxygen deficient with composition corresponding to A120 (or
A1O).
Two other crystal faces, (101 2) and ( 11~3), have been studied
(Cbang, 1969). They have (2 X 1) and (4 X 5) surface
structures, respectively, at high temperatures (> 1~K).
In reality, an atomically flat surface is unlikely and surface
steps and vacancies have considerable influence on surface
behavior. The only information that is available on defects on
AllO, surfaces come from Auger spectroscopy work by Olivier
and Poirier ( 198 I).
Other investigations using UPS (ultraviolet photoelectron
spectroscopy) (Bianconi et al., 1979), electron energy loss
(Olivier and Poirier, 198 1), and surface pho”on loss
Alcoa Laboratories

spectroscopes (Liehr et al., 1984) have not shown any unusual Mass spectrometric studies of vapor over alumina at high
electronic structure of the surface. temperatures ( 1900-26WK) have been used to identify and
determine thermodynamic parameters of the different species
Experimental investigations of specific surface energy of A1203 (Far&r et al., 1972; Ho and Bums, 1980). Both groups of
have used two techniques - liquid metal contact angle and the workers claim the formation of the species A102 and A1202 in
~ndant-drop method. Values range from 1.0 J/mz at 1273K to addition to AIO and A120 and have reponed partial pressures .
0.65 a! the melting temperature (Norton et al., 1953; for the various s~cies. !
Rasmussen and Nelson, 197 1). (
Literature data on thermodynamic pro~rties of the different
2.42 Aluminum Suboxides suboxides of aluminum we given in Table 2.3.
/
The only confirmed suboxides of aluminum are A120 and AIO, 2.5 IR-Spectra and X-ray Data
though spectroscopic identification of other species such as
A1202, A102 has been repofied at high temperatures.
Table 2.10
Infrared Spectra of Oxides and Hydroxides
Brewer and Searcy (1951) concluded from vapor pressure
studies that the two suboxides of aluminum A120 and AIO (Wave Number vs. Intensity)
must exist in the gas phase. Hoch and Johnston ( 1954) studied Ph.% OH Stretch OH ESnd unassigned AI-O Stretch fleference~
the reactions: (I) 4AI( 1) + A1203(s) - 3A120(s) and (2)
Al(I) + A1203(s) ~ 3AIO(S) between 1300K and 23WK by ~btite 3616.6 (M) 1015,2 (VS) 909.1 (W) 741.8 (S) Fredrick,o”
means of a high temperature X-ray technique. Tbe study Hannah
indicated the formation of solid A120 and AIO above certain
temperatures. At 13WK no reaction occurred. Between 1373K 3518.6 (S) W.3 (M) 626.4 (M~

and 1773K A120(s) is formed according to ~uation ( I). 3428.2 (VS) 794.9 (s)
Between 1773K and 1873K bth reactions (1) and (2) occur 2376,4 (M)
simultaneous] y; whereas, above 1873K only reaction (2) 2361,3 (S)
occurs. On cooling or rapid quenching both compounds
dispropofiionate into Al and A1203. X-ray diffraction patterns Bayerite 3533.6 (M) 1016.2 (s) 662,1 (M) 776.4 (S) Fredrickson ‘.
showed that both the compounds are cubic, the lattice constants Hannah
being 0.498 nm for A120 at 1373K and 0.567 nm for AIO at
3518.6 (M) 975.6 (S) 613.0 (M).
1973K.
24w,2 (M) 719.4 (MP (

The literature until 1967 was extensively reviewed by NO1 ,3 (M)

Mackenzie ( 1968) who also summarized the properties of AIO

and A120. Giltesen et al. ( 1968) and Yanagida and Kroger 1142,6 (M) 740.7 (S) Fredrickson
~hJ),22~6(s)
( 1968) reinvestigated the system Al-AlzOj and critically Hannah

discussed the results of previous investigations. Both groups 3079.8 (s) 1069,5 (S)
A
agreed that no suboxides of alumium exist in the solid state.
Daswre 2924.0 (VS) 1069,5 (S) 720,0 (VS) Cabannes-
Yamaguchi ( 1974) concluded from electron diffraction studies cm c
that solid A120 and AIO are formed at the bound~ between
the Y-A1203 and the Al metal surface in the oxide layer on
2341,9 (M) 959.7 (s)
aluminum. The lattice constant of the cubic suboxide was
reported to vary bstween 0,406 and 0,430 nm, The 2114.2 (M)

aluminum-rich layer may be due to the incorporation of oxygen 1984.1 (M)

Corundum 614,6 (M) 759,9 (Vs) Ha...
into the metal lattice (Eberhardt and Kunz, 1978), or the
reduction of excess A13+ ions in the interface region (Wefers 802,0 (s) K.les.va

and Wallace, 1976). 559,0 (M]

490,0 (W)
Ivanov et al. (1973) made an electron diffraction study of the
450,2 (S)
aluminum suboxide A120 molecules formed by heating
AIIOJ-Al mixtures at 23~K to 2400K. They showed that the
A120 molecule has C2V symmetry; the Al-O distance is 0.173 M= Mediumlntensi~ S = Slrong VS = Vefy Str.ng W = Weak

tO. Wl nm and the AI-O-AI bond angle is 141 ~ 5 degrees, .= Shoulder

a See also Adler (1950)

32
 Oxides and Hydroxides of Aluminum

Table 2.11
X-Ray Diffraction Data of Aluminum Hydroxid~ and Oxide
B, ,. d,t a!. ,1 , Cu
t a.A 113 Al, 3 ,1(C 3 i . <20 .
— —
dA dA ul hkl .iA VIj hkl dA hkl d.4 1 dA hti dh hkl
s — — — — —
4.71 w? 4.e486 m m 4.79 w 010 71 Om 11 c m Iw 3.479 012
,m

I
4.% 1IO,om 4.371, 7[ 110 4.32 25 ml 59 ,10 : m2 2.s2 Iw
4.14
3,B
011
,m
4,3,87 x m 4.21 ,8 101 2!4 ,m E * 140,03? 23
25
10,
102
2,379
2.185
,40
M
3.35W 1> m2 4,16 12 lW 5= 9m 131
3.20 11,,02, + 3.3122 x 112 3,89 12 110 4W L? m ; 051 7Ea 110 2.W5 113

2.659 121 3.1829 2! 112 3.61 8 11, 396 101 8W m 5c0 103 1,% 202
2.53, m 3.1OW 1: 3.43 6 011 3% 04a 770 6 m 416 m , .74a 024
2,510 2.46* 2! ;: 3.03 4 011 317 ,11 E62 4 151 352 112 1.ml 116
2.W k? 2.45= x 02< 2.W 4 111 131 ,2, 527 6 w 3= ml 1.W 211
2.W 210 2.4224 1: 9W 2.71[ 2 110 077 140 453 6 231 192 m 4.5!4 122

2,356 CQ2 2.W1 55 311 2,%1 2?1 9)4 131 4X 0 W2 115 mz 1,510 018
2.274 012 2.W71 4 121 2,4M 1; 120,402 815 C41 412 2 ,80 WI 203 1.4M 124
2.222 201,131+ 2.28= lE 312 2.45! 101 7W 396 2 022 605 122 1.374 Om
2.IM Zza 2,24Ed 2C o= 2.3% 2: 020,201 712 ;? w 6 171 M 105 1.=, 125
2.16n M 2.1924 l= 2.= 6 121 678 141 369 2 2W 623 w 1,276 m

2.1E4 211 2.1647 27 312 2,271 w 112 m 221 312 8 25, w la $.m3 ,.0.1!
2.1% 211 2.~5 114 2,217 4 240,021 m 240 m 4 511 X2 1.* 119
2.075 ,, 2,022+ 2.W9 : 313 ZIG 4 112 570 w 224 2 H al m 1.1898 220
1.B3 140 2.0234 222 2.11: 2 242,m2 522 231 m 2 3m 4,9 ms I,lm 306
1.%3 221 1,m 28 023 2.074 4 2W,221 680 lm,15f 178 4 2W 394 220 1.1470 223
— — — . —
1.969 Ml 1.9637 e 123,222 2.01i 25 121 431 Zm 1711 2 C62 328 222,131 I.lmz 314
1.9%7 1.U2 322 i .991 021 4= w 1- 4 274 281 132 1.1255 312
1.W E 1.75%7 : 024 ,.97$ 111 w m 137 6 m2 265 125 1.1246 ?28
, .m 141 1.7W 4 124 1.M: m 376 WI !152 222 251 m 1.W 1.2.1,
, ,8% a32 ,.6974 4 124 1.m2 211 w I*2 ~17 : .U1 217 1~,107. 1.W1 ).0.1:

4.765 231 1.M5 30 314 1,877 012 3m m C459 2 w 197 al 1,0781

1.723 ~2,132+ 4.6576 9 224,130 1,821 120 m ml 0284 351 led 1.M26 ;:
1,695 212 4.5926 7 414 1.W4 222 289 37,,170 9W3 ; 262 114 m:i7 1.0175 02
1.W 212 ?,%65 7 315 120,212 279 251 9818 2 096 al ,W8 0.5978 1,2,1!
T.6% 310 1.5739 8 m,mo 022 256 321 9%6 2 371 0.9857 1,1.1:

1.W Z& t .%25 3 m 13L,21O 243 W,132 9310 2 w 0.9819 404

1.&l l= 1.W 216,=+ 211,311. 218 C42 9247 2 W,3Z Owl 31
?,=8 051 I .45n ; ~,324 112,312 m WI 9105 2 282 0.%13 ,2.1
1.m 222,W2+ 1.W5 18 415 lC.3 1783 w 9023 2 ,33 0,9%5 318
1.572 m,003 1.4115 19 =2 731,102, I739 142 B937 2 %2 0,9?78 2=

,.554 311,241+ 1.mzl 13 316 !408 Ml BSQ7 2 053 o.su7e 326

1,5a 142 1.W 6 332 !C03 m B~ 2 lW 0.5Q52 ),1.1
, .Sm 442 , .m !0 0% N23 410 W7 2 al 0.8591 410
1.492 321 1,-11 7 Wle 2 m 0,- m
1.W m 1.3247 4 E ue6 4 .5,
— — —
1.478 232,023+ 1.=99 3 416
1.457 330 1.2316 3 6=
,W
1.45 Om i .2267
1.al 2W I,zl Ea 240,425
1.4m 123 1.2116 142

1,416 1.1791 118

t 1.397 ;: 1.14Q 624
1.392 ml,lm+ 1.m M
1.%7 061,03 I .mze 632
1.370 251

1.= 251
1.m 312
1.W 312,242+
I , .3?3 18,,m+
1,3m 213

1.311 322
1.305 322
1.277 344,223+
1.265 4C!
1.2W
a

33
Alcoa Laboratories

GA 202’

I I I 1 I I I I I I I

100
};

80
Bayerite Boehmite
a - AI(OH)3 y - AIOOH
60

40 i I

20

0
I A> dA 1 h LIA
I I I I I I I I I I I I I I
100

80 Nordstrandite fNaapore
Al(OH), a - AIOOH

60

L
40

20

I JIL, I
0
I I I I I I 1 I I I I I I
100
Gibbsite Corundum
y - AI(OH)3 a - A1203
80

60 1

40

20

0 — I L
20.00 30.00 40.00 50.00 60.00 70.00 80.00 20.00 30.0040.00 60.00 60.00 70.00 60.00
2“ THETA, CU Km

X-Ray Diagrams of Aluminum Oxide and Hydroxides

Figure 2.22

34
 Oxides and Hydroxides of Aluminum

0.2,246 t3
I I I I I 1 I I

t,

I I I I I I I I I I I I I I I I I I I I I I I I I 1.

I I I I I I I I I I I I I I I I I I I

Bayerite - a-Al(OH)S

I I I I I I I I I I I I I I I I I I I I I I I I I I

I I I I I I I I I I I I I I I I I I I

Boehmite - y -AIOOH

1 I I I I I I I I I I I I I I I I I I I I I I I I I

I I I 1 I I I I I I I I I I I I I I I I I I I 1 I

I 1 I 1 I I I I I I I I I I I I I I I I I I
4000 3000 2000 1000 400
cm-l

Infrared Spectra of Aluminum Hydroxides

Figure2.23
Alcoa Laboratories

3. Binary md Ternary Alumina Systems transformation temperatures by decreasing the activity of water
I
as shown by Wefers (1967) for the system Na20-A1203-H20.
3.1 The A1203-H20 System Phase transformations proceed via an intermediate solute phase
(Kennedy, 1959; Neuhaus and Heide, 1965; Wefers (1967)
Tbermcdynarnics and phase relations of the A1203-H20 system
have received considerable attention in the technical literature. As the sum of tbe molar volumes of A1OOH + H20 is greater
Results of numerous studies have found application in such than the moku volume of Al(OH)j, the conversion temperature
diverse areas as geochemistry, soil chemistry, alumina increases with higher pressure. For the same reason the
extraction from bauxite, ceramics, corrosion of aluminum, and transition temperature boehmite/diaspre is lowered by
for the experimental verification of therm~ynamic concepts increasing pressure, because tbe moku volume dlmisbes from
and relations. 19.87 to 17.44 cm3 in the phase reaction. The density of
diaspore (3.44 g/cm3) is higher than that of boehmite (3.ol
3.11 Phase Relations g/cm3).

Phase relations in the A1203-H20 system have been
experimentally studied by Laubengayer and Weiss (1943),
Ervin and Osbom (1951), Kennedy (1959), Neuhaus and Heide
(1965), Fyfe and Godwin (1962), Fyfe and Hollander (19@),
Haas and Holdaway (1970), Matsushita et al. (1967), and
Haas (1972). Some of these authors have compared
experimental observations with thermodynamic calculations and
discussed discrepancies, Studies were carried out under
bydrothennal conditions with mixtures of water and aluminum
hydroxide in closed bombs. Kennedy ( 1.c. ) also used a
piston-anvil apparatus for experiments at pressures higher than
2 kbar. Torkar and Krischner (1960) studied formation of solid
phases in the reaction of aluminum metal with water at
temperatures between 600 and 8WK and water vapor (steam)
pressures up to 300 bar.
Below 575K the spontaneously crystallizing oxide-hydroxide
phase is always boehmite. Spontaneous growth of dlaspre has
been observed only above 575K and 2Ctilbar pressure.
However, in experiments using diaspre seed crystals, growth
of diaspore occurs at temperatures as low as 450K at the
expense of boehmite. The reverse reaction has not been
observed. Wefers (1967) bas reported epitactic growth of
dlaspore on isomorphous goetbite (a FeOOH) at temperatures
klow 373K.
~ese observations have led to the conclusion that boebmitc is
metastable in the A1203-H20 system. However, bmhmite
formation is kinetically favored at low temperatures and
pressures due to its lower density; afso bcause common

The stability relationships of the three trihydroxides, bayerite,

gibbsite, and nordstrandite were discussed in Chapter 2.25. It
was concluded that bayerite is the stable phase in pure water at
373 473 573 673
298K. This conclusion is further supported by the higher
density of 2,53 g/cm3 for bayerite compared to 2,42 g/cm3 for
gibbsite; dehydration of boehmite to bayerite at very high
pressures (Dachselt and Pitz, 1957), and on extreme grinding
(Gout et al., 1983), and the formation of bayerite during
‘“””m :
dehydration of rapidly dehydrated gibbsite (Section 4.2 I). ,,

!’OO[’”
““!$n
Bayerite is also the only ~hydmx~de which can be synthesized $
by reaction of aluminum and water.

Figure 3,1 is a representation of phase relations in the

A1203-H20 system developed from the data of Kennedy (l.c.) ~

,Ou
and Neuhaus and Heide (l.c.),

AI(OH)3 transforms hydrothermally to AIOOH at around 373K.

No significant differences in the temperature of conversion
have so far been reported for tbe three trihydroxides. As the
rate of conversion is very slow near the equilibrium
temperature of around 373K, the exact temperature cannot be o 100” 20W 300” 400” So””c
accurately determined from direct experiments but only by
extrapolation and thermodynamic calculations, The rate is
increased significantly under higher pH (alkaline) conditions Phase Diagram A1203-H20
(Gins&rg and Koster, 1952), Dissolved salts lower the F,gure 3.1

36

structural elements in the crystal lattices of AI(OH)3 and
i boehmite allow epitactic growth of boehmite on the
trihydroxide. Both factors lower the nucleation energy. A tme
phase boundary does not exist between diaspore and hoehmite
in the A1203-H20 phase diagram. The coexistence of boehmite
and diaspore in many clays and bauxites may be explained by
the extremely low volubility of boehmite in the pH range of
natural waters, Though this is the generally accepted view, free
energy calculations published by Gout and Dandurand (1983)
indicated that boehmite may have a stability field in the
system.
Fyfe and Hollander (1964) determined the equilibrium
temperature for conversion of oxide-hydroxide to oxide
a-AIOOH = CK-A1203+ H20 (liquid)
to be 640 & 7K under pressure corresponding to the water
vapor pressure (=200 bar), This agrees with data of Kennedy,
Neubaus and Heide, and Haas. Haas determined the
diaspore-comndum equilibrium by observing expituy of
diaspore on corundum above 660K and 1.5 kbar pressure.
Ex~rimental equilibrium points were used to derive
thermodynamic data which allowed calculation of the
equilibrium curve below 660K. The curve passes through 170
bar at 64(3K. The equilibrium curve in P-T coordinates has a
~sitive slope which means that the transformation tem~rature
increases with pressure. Thenntiynamic considerations suggest
that reduction of water activity shifts the diaspore-comndum
equilibrium towards lower temperatures. This was verified
ex~rimentally in the Na20-A1203-H20 system (Wefers, 1967).
The transformation of boehmite to comndum occurs at
somewhat higher temperatures of around 675K at <200 bar
pressure. Since behmite has no stability field in the
t) A1203-H20 system, a boehmite-comndum equilibrium line has
no significance. Itis likely that this converion occurs via
diaspore as an intermediate phase, but no direct ex~rimental
evidence is available. The rate of transformation of both
boehmite and diaspore to comndum increases when the
volubility is raised by increasing the pH of the solution.
Thenntiynamic data for compounds in the A1203-H20 system
have been analyzed for consistency by many reviewers
(Kuyunko et al., 1983). Values given in Table 2.3 are
compiled from recent publications.
Several forms of aluminum oxides (KI, a*, and autocalve-y),
reprted by Torkar and Krischner (1960) in low pressure (<300
bar) hydrothermal ex~riments at 600-800K may k considered
metastable. Of these, only the KI form (also known as Tohdlte,
Chapter 2.23) has a well defined X-ray diffraction pattern.
Tohdite converts to a-A1203 at 675K and 2W bar pressure.
Oxides and Hydroxides of Aluminum
3.12 Volubility of A1203 in Water
The volubility of the compounds in the A1203-H20 system is
another area of interest. Volubility is primarily a function of
temperature and PH. which determine the nature of the ionic
species in solution. Volubility is very small in the pH range of
4.5-8.5. In the A1203-H20 system, the stable solid phases in
equilibrium with the solution are:
<375K - trihydroxide (gibbsite**or bayerite) Al(OH)J
375-640K - oxide hydroxide (diaspore) a-AIOOH
>640K oxide (comndum) a-A1203
Volubility data for the hydroxides have been reported by many
workers, particular] y at high pH values which relate to tbe
Bayer process for alumina extraction from bauxite. Volubility
data also have been used to develop and refine thermodynamic
properties, and for comparison with calorimetric
determinations. Discrepancies have ken frequently encountered
and attempts made to reconcile them (Parks, 1972; May et al.,
1979).
Though there is much discussion on the nature of the ionic
s~cies in solution, no clear picture has yet emerged. There is
general agreement that at room temperature tbe mononuclear
A13+ ion exists in acidic solutions &low pH 4. As the pH is
increased, a seties of bydroxy -aluminum complexes is formed,
There is much controversy as to which complexes are stable.
Some authors find that their volubility data are adequately
represented by mononuclear complexes of the type A1(OH) ~-”
with n in the range of O = n <4, i.e., A13+ to Al(OH)~, Some
find it necess~ to assume the existence of plymeric
complexes. The mtiel propsed by Hem and Roberson (1967)
may & considered a gd example of the latter. They pro~sed
that at pH values two or more units blow tbe pint of
minimum aluminum volubility (about pH 6), the aluminum ion
is cwrdinated by six water molecules. The strong positive
charge of the Al 3+ ion polarizes each water molecule and, as
pH increases, eventually drives off a proton forming the
monomeric complex ion Al(OH)(OH2)~ + At abut pH 5 this
complex ion and tbe hydrated A13+ ion are equal in abundance;
more hydrated A13+ ions exist at lower pH and more of the
complex ions at higher pH values. Two of these complex ions
may join by losing two water molecules to form a dimec
[A11(OH)2(OH,),~’
*-1” Icmary systems
37
Alcoa Laboratories

Further deprotonation, dehydration, and polymerization of Table 3.1

monomem and dimem yields a ring structure of six octabedrally Ion Activity Product3
coordinated aluminum ions with the formula
Al(OH)a + 3H+ % A13+ + H20 “Kw= 1.29 X 106
[A16(OH),2(OH),2]6+
AI(OH)3 + 2H+ s AIOH2+ + 2H20 ‘K~l = 1.33 X 103
Coalescence of rings into layers by further growth and stacking
of layers results in the formation of crystalline aluminum AI(OH)3 + H+ s AI(OH)J + H20 ‘K~2 = 9.49 X 10-3
bihydroxide (see Chapter 2. 13).
AI(OH)3 + H20 s AI(OH)I + H+ ‘K% =8.94 X 10-i5
More recently, May et d. (1979) determined volubility curves
at 298K for synthetic and natural gibbsite from pH 4 to 9. The AI(OH)3 s Al(OH)~
solubilit y curve obtained for synthetic gibbsite is shown in
Figure 3.2. The slight inflection at pH 6.7 was indicative of the
possibility that a solid phase less soluble than gibbsite controls
the solution composition above pH 6.7. However, this phase
could not be identified.
Ionic equilibria in the temperature range of 370-570K,
Ion activity products re~fied by May et al. (l.c.) for various corresponding to equilibrium solid phases of diasporelboehmite, (
solute species are listed in Table 3.1. also have kn studied experimentally by several investigators.
Data of previous work for boehmite have ken reviewed and
The calculated concentrations of the individual mononuclear Al additional results reported by Kuyunko et al. (1983). Diaspore
ion species in equilibrium with gibhsite are also shown as solubllity was investigated by Wefem (1967), Dmzbinina
functions of pH in Figure 3,2. (1955), and Bemshteyn et al, (1965). The high temperature
equilibrium at pH above 7 has been shown (Kuyunko et al., I
At pH abve 8.5 the volubility of aluminum increases very 1983) to involve the possible presence of the species Al(OH)~
sharply with the formation of Al(OH)i– ions. This part of the in the aqueous phase.
volubility curve has been extensively studied kcause of its
imponance to the industrial Bayer process for alumina Several workers have determined the volubility of corundum in
extraction from bauxite (Chapter 3.3). water at high temperatures, Becker et al, (1983), Ragnwsdottir
and Walther (1985) have reviewed earlier work and provided
additional data. Morey (1957) reported corundum solubilities at
775K and 1,04 kbar, Anderson and Bumham (1967) and
Bmnham et al. (1973) undertook experiments at 775-975K and
0.2024614
–3 6 kbar. Ganeyev and Rumy3ntsev (1974) reported experimental
\
I I I I I
results from 640-780K at 0.2 to 2 kbm and the most recent
\ - — Natural gibbaite
work of Ragnarsdottir and Walther (1985) gives data ktween
–4 \ — Synthetic gibbsite 675-975K and I-3 kbar. All these studies show wide variations
\
in the volubility results in the range of 1-4 ppm Al with no
\
/ app~ent effect of temperature and pressure. The sol”bility
\ / results have ken interpreted on the assumption of the
\ /
/ formation of Al(OH)~ as the dominant solute species.
\ 0
\ /
\ / Using the equilibrium constants for the aqueous phase
\ /@, / reactions, Kbodakovskii et al. ( 1980) have calculated the
–7 -.
. prevalence of the different hydroxo-aluminum species at
L/’ vtious pH and temperature conditions. As can be seen in
–8 Figure 3.3, the stability ranges of the cationic form of

4 5 6 7 8 9 10
aluminum decreases sharply with increasing temperature. The
activity of the dissolved neutral hydroxo complex Al(OH)~
!
PH increases correspondingly. As a result, the volubility of
aluminum hydroxide and comndum in acidic solutions
decreases with increasing temperature. The ratio of Al(OH)~ to
Volubility of Gibbsite in Wster Al(OH)~ solute species is practically independent of
Figure 3.2 temperature.

38
 Oxides and Hydroxides of Aluminum

- 12) in the temperature range 1075 to 1325K. The structure of

this phase is very similar to that of mullite and is likely to k
600 the same as that observed by Pemotta and Young (1974).
Barker et al. (1984) identified three sodium rich aluminates,
Na7A1308, Na,7A15016, and Na5A104, in a study of reactions of
sodium oxide with a-A1203. These compounds are isostructural
with corresponding sodium rich compounds in the iron and
gallium systems.

The high temperature (> 1000K) region of the Na*O-A120~

system has been studied by several investigators. The hterature
up to 1967 was critically examined and reviewed by DeVries
and Roth (1969). These authors also proposed two versions of
a phase diagram of the Na20-A1203 system based on available
data. Subsequent investigations by Llebertz (1971) and hCars
et al. (1972) were aimed at resolving uncenainties in the
previous reprts. The remaining uncertainties have been
discussed more recently by Stevens and Binner (1984), who
questioned the existence of several phases.

The alumina-rich, high temperature area of the phase diagram

that was proposed by LeCars et al. in 1972 is shown in
300
Figure 3.4. Four solid phases occur in this region: NaA102,
I I I I p-alumina, fl-alumina, and u A1203. The system has a eutectic
1 3 5 7 ktween 8 NaA102 and p-alumina at 1855K (not shown in the
figure) and a perhectic between p-alumina and a-A1203 at
PH approximate y 2275K.

Stabifity Ranges of Aluminum Hydroxy

Complexes in Water
Figure 3.3
3.2 The Na20-A1203 System
3.21 Phases Occurring in the System
Sodium oxide forms a numkr of compunds with aluminum
oxide. The molar ratio of Na20 to AlzOJ of phases repofied in
the literature ranges from 1 to 12. Compounds having molar
ratios of 1:5 and higher age generally formed at temperatures
ahve 1300K. The composition of structurally defined phases
can vary, some of the many forms descrikd in the literature
may be compositional variations of a structure type.
Well established phases are, besides Na20 and A120J, the 1:1
sodium aluminate NaAIOz and the so-called beta afuminas. The
latter phases range in composition from Na20 5A1203 to
-Na20 9A1203. A molu ratio of Na20 to A1203 of 1:11 was
assumed by some authors (see klow).
Several other compounds in the Na20 system have been
reported in the literature. Elliott and Huggins (1975) found a
phase designated at A-Na20 XA1203 (with x varying from 3 to
3.22 Sodium Aluminate NaA102
The 1:1 sodium aluminate NaA102 can & prepared by heating
mixtures of aluminum oxide, hydroxides, or salts with sodium
hydroxide or carbonate to about 12COK. Decom~sition of
dawsonite (A1203 Na20 2C02 2H20) yields sodium
aluminate at temperatures of 901.-1 ~K.
Stiium aluminate (1:1) has ken found to exist in three
allotropic forms (Thery, Briancon, and Collogues, 1961). The
p-NaA102 modification is stable to 743K; above this
tem~rature it transforms to the y-form. The p-form is
ortborbomblc; its unit cell contains four molecules of NaA102.
The structure is similw to that of ~-NaFe02, with which it
forms a series of solid solutions. The transformation to
Y-NA1O* at 743K is reversible. The bigher temperature
‘y-modification is tetragonal. A third modification, ij.NaA102,
has ken shown to occur akve 1683K (Tbery, Lejus,
Briancon, and Collogues, 1961).
In the presence of moisture, NaA102 rapidly hydrolyzes to
aluminum trih ydroxide at room temperature. The melting point
of NaA102 has been reported to be 1923K. However, when
heated in air, it loses sodium oxide above 1273K and
decomposes to aluminates richer in A1203, the so-called beta
aluminas.

39
Alcoa Laboratories

GA 2“,4
During preparation of ~-alumina, the metastable form
~-alumina is often encountered. Beta” is considered a
2300 Liquid nonstoichiometic form with sodium oxide contents between
“q= Na20 5A1203 and Na20 8.5 A1203. There has been some
disagreement on the stabOity region of this form in the
/’ Na20-A1203 phase diagram. CoOongues, Thery, and Boilot
(1978) suggest that ~-alumina is metastable in the pure
Na20-A1203 binary system.

Beta” always occum together with 13, regardless of the method

13+A1203 of preparation. According to LeCars (1972), 13° is imeversibly
transformed to 13at 1823K. The region of coexistence of the
two phases is shown in Figure 3.4. However, it has ken found
that in the presence of additions such as MgO and U20, the ~
phase can be stabilized even at temperatures as high as 2~K
(Imai and Harata, 1972). Also, the replacement of A13+ by
Ga3+ shifts the existence range and stability of the phases
1300 (Boilot, Tbery, and Collogues, 1973). The ~ phase kcomes
more stable; pure ~-gallate can be obtained without the
presence of the ~-form for a small composition range.

Bragg et af. (1931) and Beevers and Ross (1937) determined

80 90 100
the main structural features of p-alumina which they assumed
Mole “IoA1203 to have a composition of Na10 .11 A1203, They found
hexagonal symme~, space group D~h-P63/MMC. Lattice
Na20-A1203 Phase Diagram constants are ~ = 0.558 nm, co = 2.245 nrn, The unit cell is
Figure 3.4 composed of two spinel-like blocks separated at a mirror plane
by a loosely packed layer of oxygen and sodium ions, This
layer is linked to the blinks by bridging oxygen ions
(Figure 3.5a). Vacant sites in these planes give rise to mobility
of the sodium ions resulting in high values for two-dimensional
3.23 Sodium Beta Aluminas ionic conduction (u E 10-20 cm– 1 at room temperature).

Sodium beta alumina was first reported by Rankin and Merwin Beta’’-glumina has rhombohedral symmetry, the space group is
(1916) who considered il to be a new modification of A1203, D3d-R3m;
Later investigations by Stillwell ( 1926), Bragg et al. (1931),
Beevers and Brobult (1936), Beevers and Ross (1937), and
~= bO=0.56nm, CO=3.3 nm
Adelskold (1938) showed that sodium oxide is necessary for
the formation of beta alumina, The unfortunate designation has
been continued in the literature nevertheless. The unit cell contains three spine] blocks of the same ty~ as
those in ~-alumina (Figure 3 ,5b). The ideal composition of
Beta-alumina is prepared by vtious methcds. Rankin and Na20 .5.33 AlzOq is obtained by the presence of two sodium
Merwin (1916) observed small hexagonal platelets of ~-alumina ions in an interlayer which is not a mirror plane.
on cwling of molten aluminum oxide, Sodium ~-alumina
crystallizes from melts containing aluminum oxide and sodium Both ~ and ~ are nonstoicbiometric. According to Collogues
oxide or other sodium compounds such as sodium fluoride, et al. (1984), electric charge in nonstoichiometric
compensation
sodium hexafluoroaluminate (cryolite), or sodium nitrate. ~-alumina is obtained by an excess of oxygen ions in
Foster (1964) determined the phase field of p-alumina in the interstitial positions; in ~ excess positive charges are balanced
Nti-Na3AlF6-A1203 system, Saalfeld (1956) grew p-alumina through replacement of Al 3+ by ,Ower.vale”t cation. Besides
epitactically on corundum crystals which he had exposed to Collogues et al, (l.c.), Fanington and Briant (1979), Roth et
cryolite vapr or fused cryolite at 13WK. The literature al. (1976) and Stevens and Binner (1984) also reviewed the
describes a number of other reactions ktween aluminum oxide structure, composition, and conductive properties of
and hydroxides and alkali metal compounds that lead to the ~-aluminas.
formation of ~-alumina,

40
Alcoa Laboratories

Two-dimensional disorder of the sodium ions located in the
intedayers between spinel blocks allows high mobility of these
ions. The result is not only high ionic conductance, but also
significant ion exchange properties. Monovalent ions such an
Lit, K+, Rb+, Ag+, Cu+, H30+, NH4+ can be completely
exchanged. Only partial exchange is possible with divalent ions
such at Mg2+, Ca2+, or S?+ (Kummer, 1972).
3.24 Beta Aluminas as Sofid Electrolytes
Since the discovery of the fast ionic conductivity of sodium
beta alumina (Weber and Kummcr, 1967), research into the
propefiies of this material has grown rapidly, particularly work
in connection with the development of the sodium-sulfur
battery. This battery uses as an anode molten sodium which is
separated from the molten sodium polysul fide cathode by a
solid electrolyte, p-alumina. During operation, sodium ions
migrate through the p-alumina, producing sodium polysulfides
at the cathode. Electrons flowing in tbe external circuit
generate an open circuit voltage of 2.08 V.
Tubes made of polycrystalline p-alumina are generally used in
these batteries. Both sintering and fusion processes are
employed in the fabrication of these tubes. A crystal growth
technique called “edge defined film fed growth” (EFG) has
been developed to produce large single crystals having a
constant cross section (Cocks and Stormont, 1974). According
to the methods of synthesis described in the literature, the ~“
phase is the predominant component of the solid electrolytes
(Collogues et al., 1978).
requirements critical to commercial development of the
sodium-sulfur battery.
The formation of an MgO I IA1203 magnesium aluminate
which has ~-alumina strocture was reported by Bragg et al.
(193 I). Kordes (1935) synthesized the Li20 5A1203 lithium
aluminate and showed that this compound crystallizes in the
spine! (more correctly, inverse spinel) structure. The lithium
ions occupy octahedral and tetrahedral sites in the cubic,
close-packed oxygen lattice; no lithium-oxygen layers are
present between spinel blocks. This compound has been named
“lithium zeta.” Lejus and CoOongues (1961) and kjus (1964)
showed a variability of zeta-alumina composition between
Li20 5A1203 and L120 8A1203.
Scholder and Mansmann (1963) showed that ~-alumina type
structures are also formed with K20, Rb20, and CS20. They,
however, concluded that botb these and sodium ~-alumina are
I:6 compounds of the general type A20 6M203. This
assumption is not acceptable in view of the variability of
composition of ~-alumina discussed earlier.
Hexa aluminates of alkaline earth oxides, AEO 6A1203
(AE = Ca, Sr, Ba), are also reported in tbe literature
(Adelskold, 1938; Ligerquist, 1937). The structures of these
compounds are of the magnetoplumbite type of the
conesponding femite system. This type is very similar to the
p-alumina structure.

Production techniques are constantly being improved to meet Structural data on p-alumina and related compounds are
mechanical, themal, corrosion, conductivity, and other summarized in Table 3.2.

Table 3.2
Strucural Properties of Beta Aluminas
Motecules Unit MS Length, nm
Crystal Space per Density
Phase Formula System Group Unit Cell a b c g/cm3 Reference

Beta Sodium NaA102 Orthorhombic c% 4 5376 5216 .7075 2.693 Th6ry and
Aluminate Briancon
Gamma Sodium N*102 Tetragonal 5325 .7056 Th6ry and
Aluminate Btiancon
Sodium Beta Na20 11 A1203 Hexagonal D;h 1 ,558 2.245 3.24 Beevers and
Brohult
Sodium Beta Na20 5AIz03 Hexagonal ,561 3.395 Th6ry and
Briancon
Potassium K20 11A1203 Hexagonal i ,556 2.267 3.30 Beevers and
Beta Brohult
Magnesium MgO 11A1203 Hexagonal 1 .556 2.255 Bragg et al.
Beta
Calcium Beta Cao 6A1202 Hexagonal 2 .554 2.1B3 Lagerquist
et al

Strontium SrO 6A1203 Hexagonal 2 .556 2.195 L~gerquist

Beta et al
Barium Beta BaO 6A1203 Hexagonal 2 ,558 2,267 3.6$ Adelsk61d

Lithium Zeta Li20 5A1203 cubic 2 .790 3,61 Kordes; Braun

~ToroPov; Toropov al Galakhov

42
I

3.3 The Na20.A1103-H20 System
This system is the basis of the hydrothermal Bayer process
which is the most widely used process for producing aluminum
oxide from bauxite, Worldwide, the annual production exceeds
30 million tons.
In the Bayer process, bauxite is treated at temperatures between
415 and 560K with caustic solutions containing 140 to 350 g
Na20 per liter. Temperatures and sodium oxide concentrations
are selected according to the aluminum hydroxide mineral
prevailing in tbe bauxite and the type of pressure vessels
f Glastonbury ( 1969) in a review on the nature of sodium
(autoclaves) available.
I The digest reactions are
Al(OH)t + NaOH % Na+ + A1(OH)I
AIOOH + H20 + NaOH s Na+ + Al(OH)~
In the first step of the process sodium aluminate solutions are
obtained having a molar ratio Na20:A1203 between 1.5 and
1.7. To recover the dissolved aluminum hydroxide tbe liquor is
diluted, if necessary, to 130 to 150 g Na20 per liter and cooled
to 315-335K. Large quantities of recirculated seed gibbsite (up
to 400’?6 of the amount dissolved) are added and the suspension
is stirred. Gibbsite crystallizes out until a molar ratio of about 4
is reached. Above 375K, boehmite is the crystallization
product,
Tbe khavior of aluminate solutions is remarkable in two ways:
For one, they must be diluted for the precipitation of hydroxide
to be initiated. Moreover, gibbsite crystallizes only after
intensive seeding, even though tbe solutions are highly
supersaturated at 3 15-335K.
At low concentrations (less than 1 molar) the monomeric
hydroxy-aluminate prevails. This was found by Jabr and
Pemoll ( 1965) who applied EMF and diffusion measurements
to study the ionic stmcture of tbe solute species, Moolenaa et
al. ( 1970) confirmed this result. These workers investigated
sodium aluminate solutions using infrared and Raman
spectroscopy as well as Nuclear Magnetic Resonance, Their
data were consistent with the existence of the tetrahedral
Al(OH)~ ion. At concentrations above 1.5 molar, condensation
of tbe tetrahydroxy. aluminate occurs, leading to the species
[(OH), A1O Al(OH),]’-. According to Moolenaar, tbe
monomeric and the dimeric ions cxxist in solutions of
concentrations up to 6 moku.
Oxides and Hydroxides of Aluminum
Concentrated sodium aluminate solutions me extremely viscous.
Wefers (1967) suggested that, besides polymerization of tbe
Al(OH)~ ion, association of the hydrated complexes through
hydrogen bonds can be tbe cause of the high viscosity, Thus,
several factors may account for the unusual crystallization
behavior of aluminate solutions. The high viscosity reduces the
rate of diffusion. Furthermore, tbe transition solute - solid
requires activation energies for the following steps: breaking of
the hydrogen fwnds; breaking up of tbe dimeric (or higher
polymeric) complexes that do not tit into the AI(OH)3 lattice;
finally, change of the A1-cwrdination number from 4 to 6.
aluminate solutions concluded that considerable hydrogen
bonding ktween aluminate ions xcurs at moderate
concentrations. Dehydration of AI(OH); to AIO~ takes place
when the concentration exceeds 25% Na20. The solid-liquid
equilibria in the ternary system indicate that this dehydration is
not merely a function of concentration, but also depends
strongly on the temperature, Solution isotherms for 303 and
333K have been given by Fricke and Jucaitis (1930). Sprauer
and Pierce (1940) have examined the solution equilibria at
298K, Cistjakova (1964) at 293K, Solution ~lythenns, based
on their own work and literature data, were compiled by Volf
and Kuznetsov (195 I ) and Russell, Mwards, and Taylor
(1955). Berecz and Szita (1970) determined solubilities in tbe
system AI(OH)3 - NaOH-H20 by an electrochemical method.
Isothermal sections of the phase diagram Na20-A1203-H20 at
333, 368, 423, and 623K, published by Wefers in 1967, are
shown in Figure 3,6. Pol ytherms replotted from We fers’ data
are represented in Figures 3.7 and 3.8,
Several solid phases are in equilibrium with the solution. At tbe
lowest temperature, 333K, AI(OH)3, NaOH H20, and a
sodium aluminum bydroxo hydrate, -2 NaA101 2.5H20,
cmxist with the liquid phase. The point of maximal volubility;
i.e., the nonvariant point at which trihydroxide and aluminate
we in equilibrium with the solution, lies near the concentration
21 wt. % Na20 and 20 wt. % A1203. Between 343 and 348K, at
22% Na20 and 237. A1203, AIOOH forms as a fourth solid
phase in equilibrium with the liquid. This may indicate the
occurrence of a dehydrated aluminate ion, AIO~, in tbe
solution.
Assuming that gibbsite and diaspore are the thermodynamically
stable phases in the ternary system, Wefers (1967) determined
solution polythems using equal amounts of y-Al(OH)3 and
a-AIOOH as solids. The inflections in the polythenns shown in
Figure 3.7 coincide with an increase of a-AIOOH at higher,
and a growing proprtion of y-Al(OH)3 at lower temperatures.
The inflections can & extra~lated to 373K at 070 Na20, and
to 348K at 22% Na20, 23% A1203, The temperature of the
43
 ..-. . .
Alcoa LaDoratorles

transition AI(OH)3 + AIOOH + H20 is obviously
the activity of water.
At 368K the solution field has widened, NaOH has replaced
NaOH H20; and Al(OH)J, AIOOH and 2NaA102 5H20 are
coexisting solid phases. The hydroxo aluminate hydrate
decompses to ~-NaA102 above 41 OK; AIOOH is the only
solid phase in the A1203-H20 boundary system.
a function of With increasing temperature, the solution field widens and the
nonvariant pint moves toward tbe Na20-A1203 axis. The
solubllity curve straightens out, approaching a constant molar
ratio Na20:A120q. Slightly above 595K (the melting point of
NaOH in the Na20-H20 bundary system) AIOOH becomes
unstable at the point of maximum volubility. a-A1203 forms,
widening its phase field with increasing temperature
(Figure 3.6D). At 633K, diaspre is replaced by corundum at
O% Na20.

GA 20246 .,8

H20 H20

t.laOH
I(OH)3
70 70

N OH
2 Na A102-2.5 H20
90 90

4
Na20~A12Q3 ..2Q ~A,203

H,O H,O

Phase Diagram Na20-A1203-H20

Figure 3.6

44

—
 Oxides and Hydroxides of Aluminum

I I I system, causing a concomitant decrease of the transformation

temperatures.

Wt. “h NasO From systematic seeding experiments with gibbsite and

m - AIOOH bayerite, Wefers ( 1967) concluded that bayerite dms not have a
17.5
stability field in the system Na20-A1203-HI0. Gibbsite
y - AI(OH)3 15 precipitated from sodium aluminate solutions contains small
amounts of Na20. The sodium concentration is lowest when
12.5 gibbsite crystallizes at low supersaturation; i.e., under
16 near-equilibrium conditions.
7.5
5 The solution-p~cipitation cycle of the Bayer process,
\
& particularly the fact that solutions must be diluted to induce
crystallization, is explained by the diagram in Figure 3.8: A
323 373 423
solution having the concentration and molar ratio represented
Temperature, K by Point A in the plot is used to dissolve aluminum hydroxide
at temperature B, until saturation is reached. Datution to
concentration C and cooling to temperature D supersaturates the
Volubility of A1203 as a Function of Temperature and
solution by the amount C-D. Crystallization accelerated by
Concentration of Na20
seeding brings the alumina concentration to point D. By
Figure3,7 vacuum evaporation, the spent solution is brought back to the
initial concentration A. Formation of gibbsite particles involves
nucleation, growth, and agglomeration mechanisms (Misra and
White, 197 1), Rates of crystal growth are very slow only a
a-AiOOH as solids. The inflections in the polytbenns shown i“ few micrometers PI hour. For this reason, the large quantities
Figure 3.7 coincide with an increase of a-AIOOH at higher, of gibbsite “seed” crystals are needed to obtain an economically
and a growing proportion of Y-AI(OH)3 at lower tem~ratures. acceptable yield of gibbsite in a reasonable time period.
The inflections can be extrapolated to 373K at O% Na20, and
to 348K at 22% Na20, 23% A1203, The temperature of the
transition Al(OH)q ~ AIOOH + H20 is obviously a function of
the activity of water. G. m246.20

I I I
1.0 1
At 368K the solution field has widened, NaOH has replaced
NaOH HZO; and Al(OH)~, A1OOH and 2NaA102 5H20 are
cmxisting solid phases. The hydroxo aluminate hydrate
decomposes to 13-NaA102 above 41 OK; AIOOH is the only
solid phase in the A1203-H20 boundary system.

With increasing temperature, the solution field widens and the

nonvariant point moves toward the Na20-A1203 axis. The
volubility curve straightens out, approaching a constant molx
ratio Na20A1203. Slightly above 595K (the melting pint of
NaOH in the Na20-H20 boundary system) AIOOH &comes
unstable at the point of maximum volubility. a-A1203 forms,
widening its phase field with increasing temperature
(Figure 3.6D). At 633K, diaspore is replaced by corundum at
O% Na20.
0 10 20 30 40
Wt. “k Na20
The transition temperatures Al(OH)j ~ AIOOH - A1203
determined in the ternary system at 0% Na20 agree with those
published for the AIZ03-H20 boundary system (Chapter 3.2), Solution Isotherms h the System Na20-A1203-H20
Higher Na20 conce”tratio” lowers the activity of water in the Figure3.8

45
 Alcoa Laboratories
4. Phase Relations of Aluminum Hydroxides and Oxides
Under Nonequilibrium Conditions
4.1 Properties and Applications of Calcined Hydroxides
Large quantities of metallurgical alumina (30 X 106 t each year)
are produced by thermal decomposition of technical gibbsite at
ambient pressure. In the early years of the now century old
Bayer and Hall-Heroult processes, it was recognized that
calci nation temperatures of 1400- 1500K were needed to obtain
an anhydrous A1203. This is a more than 800K higher
temperature than that required for the conversion of hydroxide
to corundum under the equilibrium pressure of water in the
system A1203-H20 (Figure 3. I ).
While the fully calcined oxide was found to be identicd with
the mineral corundum, it was discovered that heating afuminum
hydroxide to temperatures lower than that required for complete
dehydration, produced a material with unique pro~rties. Cross
reprted as early as 1879 that gibbsite dehydrated at
tem~ratures klow 1lWK is a desiccant. Johnson (1912)
determined the adso~tion limit for water to be 18% by weight.
Later investigations revealed that partially dehydrated aluminum
hydroxides not only reversibly adsorb water, but also anions,
hydrated cations, and a num~r of organic compounds. High
specific surface area and prosity, thermal stability and
chemical purity, as well as easy agglomeration and shaping,
made such aluminas attractive materials for chemical
processing.
Partially and fully calcined aluminas are employed as supports
for metal catalysts (Oberlander, 1984). In a number of catalyst
systems the alumina support is not inert, but contributes to the
reaction. By itself, “active” alumina is an effective catalyst for
isomerization, dehydration, and dehydrogenation reactions. The
commercially most significant application is the catalytic
removal of hydrogen sulfide from gas streams, according to the
Claus reaction:
2H2S + S02 -i 2H20 + 3S
The preparation of aluminas for catalytic processes and for
separation technology has been described in countless patents
and publications since the 1940s. It was soon recognized that
specific properties such as surface area, pre size distribution,
or catalytic activity could be controlled by varying heating rate,
calcination temperature and furnace atmosphere. Tbe strong
influence of composition and structure of tbe starting material
on final properties also became apparent,
Scientific understanding of the relationships ktween structural
transformations that occur in tbe course of thermal treatments
of hydroxides and the chemical and physical properties of the
products developed concurrently with an increasing commercial
46
—
application. With the emergence of improved tecbniq”es for
chemical and physical characterization of solids and reactions
in heterogeneous systems, progressive y dee~r insight was
gained into the kinetics of dehydration, micro-morphology,
c~stal stmcture of calcination products, the development of
surface area and porosity, and lately, the configuration and
reactions of surface sites at tbe atomic level. Besides many
individual investigators, institutes and research groups directed
by the following scientists have made valuable contributions to
this field of physical chemistry: J. H. DeBoeq R. Fticke;
H. Ginsberg; G. F. Hiittig; J. W. Newsome; A. S. Russell;
R. Tertian and D. Pap&e; and K. Torkw.
Stumpf et al. in 1950 published the results of extensive X-ray
diffraction studies showing that, in the course of thermal
transformation of aluminum hydroxides, a series of stmctural
forms develops the properties of which are determined by the
stmcture of the starting material and the temperature of
calcination. Later investigations by numerous workers
confined the principal features of the structures determined by
Stumpf as well as the reaction paths.
A general scheme of the decomposition sequence is illustrated
in Figure 4.1.
4.2 Thermal Decomposition of Aluminum Trihydroxides
4.21 Gibbsite
Achenbach (1931) and Damerell et al. (1932) reported that
gibbsite crystals after complete conversion to comndum retain
their original habits. A comparison of the scanning electron
micrograpbs in Figure 4.2 and Figure 4.3 demonstrates this
pseudomorpbic transformation. A large internal porosity
develops in the process of conversion, as the density increases
from 2.42 to 3.98 g/cm3, Loss of water, development of
porosity and internal surface area, and change of density with
increasing temperature are presented graphically in Figure 4.4.
More than 20% of the mass is lost in the temperature range
between 450K and 650K; another 10-1270 within tbe following
2CX3K.The remaining bydroxyl ions are driven off
progressively; anhydrous a-A1203 is obtained at a calcination
temperature of 1375- 1450K.
The reaction path and kinetics of tbe dehyroxylation process are
influenced by pmicle size of tbe gibbsite, rate of heating, and
the water vapor pressure in the atmosphere surrounding tbe
hydroxide, This is illustrated by the DTA curves in Figure 4.5.
A coarse, technical gibbsite undergoes a sharp endothermic
reaction above 450K, which is followed by an exotberntic
enthalpy change around 5WK and a second strong endotbertnic
maximum near 625K, A weaker endothermic effect occurs at
800-825K, and an exotherrnic peak at approximately 1450K.
The sample having a particle size smaller than one micron only
 .- -- . .
oxides and Hydroxides Ot-Aluminum

“c
100 200 300 400 500 600 700 800 900 1000 1100 1200
I I I I I I I I [ I I I

CHI 9 Kappa I Alpha

=~

*“ Gamma I Delta 1 Theta I Alpha

Diaspore — Alpha

I I I I I I 1 I I I I I
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
K

Transformation Sequence A1(OH)3 + A1203

Figure 4.1

shows one strong endothermic reaction between 475K
620K.
DeBoer et al. (1954) recognized that the exothennic reaction
near 500K is caused by the formation of boehmite, Y-A1OOH
as a result of hydrothermal conditions occurring inside coarse
gibbsite particles from which water cannot rapidly evaporate.
Boehmite forms concurrently with chi-alumina, a disordered,
nonstoichiometric oxide containing several percent residual
hydroxide (Glemser and Rieck, 1956).
The Y-AIOOH does not develop in particles of gibbsite small
enough to let water escape without significant increase in
pressure.
The chl-form is replaced by kappa-alumina above IOCOK. The
temperature range in which this transition alumina occurs
depends on the thermal and chemical history of a particular
sample; particular y the content of alkali metal ions affects
transformation (Ginsberg et al,, 1957). Kappa alumina has a
loss on ignition of 1-2%. Only after prolonged heating above
1400K is this value diminished to 0.1 -0.2%, as complete
conversion to corundum is obtained.
and An X-ray indifferent (“amorphous”) transition form,
... ...—..-
rho-alumina. is obtained bv “flash calcination. ” i.e.. heati”~
the hydroxide for a few seconds in a fluidized bed employing
gas temperatures higher than 1100K, Rho-alumina is also
formed as a result of rapid heating of gibbsite to 575-700K in
high vacuum. Upon heating in air at higher temperatures, rho
transforms to eu-alumina, above 11WK to theta which
converts to alpha-aluminum oxide at 1400K.
Rho alundna is very reactive because of its high free energy
resulting from lattice disorder and kuge surface area. In contact
with water, rho afumina reacts to form crystalline a-Al(OH)3 or
Y-A1OOH, depending On temperature and PH20 (Tertian and
Pap6e, 1958). This reaction proceeds at a significant rate even
at temperatures below 373K; itis utilized commercially for
agglomerating ~d shaping flash calcined alumina through
interlocking bayerite crystals grown on the surfaces of ptiicles.
The partially hydroxylated agglomerates retain their shapes
after a subsequent dehydroxylation treatment (“re-activation”) at
750-SOOK (Osmont and Emerson, 1965).
Smafl amounts of fluoride in the furnace atmosphere drastically
change the sequence of dehydrox ylation. Ch]-alumina dircctl y

47
Alcoa Laboratories

transition form, theti-alumina, occurs above 1070-1120K. This

alumina is converted to corundum above 140iIK in air.
Calcination under high vacuum leads to X-ray indifferent
rho-alumina, which subsequently transforms to eta, theta, md
alpha. Among others, Tertian and Pa@e (1958), Torkar,
Egghart et d. (1961), Sato (1962), and Torkar and Bertsch
(1961 ) investigated the sequence of dehydroxylation of
bayerite. The latter workers reported that bayerite containing
alkali metal oxides decomposes at lower temperatures, sodium
oxide having the greatest effect. Russell and Cochran (1950)
measured the surface area of calcined bayerite. They found a
slightly greater specific surface area at optimum calcination
temperature than for gibbsite.

According to Hauschild (1963) the dehyroxylation sequence of

nordstrandite is identical with that of bayerite.

D. R. Micholas 4,0mx 4.3 Decomposition of Aluminum Oxide Hydroxides

Acicular Gibbsite
4.31 Boehmite
Figure4.2

Goton (1955) re~tid heating of well crystallized boehmite at

converts to corundum near 1200K; the tsansfonnation is
indicated by a sharp exothennic effect (we Figure 4.5) which
occurs as the surface area decreases by a factor of akut lCO
from >30 m2/g, and the loss on ignition falls below 0.2%
(Wefers, 1964). Tabular crystals of corundum are formed
(Figure 4.6).
a rate of 4. 5“ pr minute to produce a strong endothermic effect
at 780K. The total heat required for debydroxylation was 145
k.f/mole. Debydmxylation to a residual 0.1 mole of HIO ~r
mole of A1203 could & achieved also by prolonged heating at
725K. The specific surface aea increases to <100 m2/g, and a
transition alumina, gamma (Ubich, 1925) forms.
I

Berates, chlorides and fluoroborates also have been used as

“mineralizers,” i ,e., agents which affect transformation
temperature, rate of transformation and size and habit of the
crystalline product. A number of procedures were described in
the patent literature and in technical publications (e. g.,
Gopienko et al., 1970; Cherdron et d., 1981; Kruse and
Hausner, 1979), The chemical reactions involved in the
mineralization process, however, have not been citified so far.

4.22 Bayerite and Nordstrandite

The crysti lattices of bayerite, nordstrandite, and gibbsite m

made up of identical stmctural elements that are stacked in a
slightly different pattern, as was shown in Chapters 2.22-2.23.
It is, therefore, not surprising that tbe debydroxylation
sequences of the three trihydroxides we very similar.

The DTA and TGA curves of coarse or tine grained bayerite D. R. Mlchdas 4,MDX
and gibbsite me nearly identical. Some boehmite forms due to
intergranular hydrothermal conditions in lmge particles of
bayerite. Finely divided material transfoms between 500K and Acicular Corundum
620K to the highly disordered eta-alumina. A. ktter ordered Fignm 4.3

4s
 200

/ 400

I
000

I
~c
800

I
?Ow

I
1200

/
/“
k
., !0246

,
,,

3.9
Oxides and Hydroxides of Aluminum

200 400 600 800 100012001400

GA 20246.24

LI
‘\ /.- ~ ien.ily
~~~~~~~~Gibbsite + 0.1 wt.”A AIF3
/
/ +

i
sP. s.fiace .,.,

\ L.JSSon ignition

I I I I I I I I
30
\ 400 600 80010001200140016001800
~-
K (C. Bates)
35
0 500 700 9W 1100 ~300 15~
K

-c “c
200 WO 600 800 1000 1200 200 400 600 800 1000 1200 1400
0, m,,. 2,
I I I I I I I I I I I I I 1 I
— Boehmite
----- Gelatinous Boehmite
sPec. .. fiac. are. . . . . . . . . ... Diaspore

‘r 400
i I
600
I
600
I I
1000 120014001600
K
I I I
1800
(C. Bates )
I
t
I I I I I

Surface Area vs. Temperature of Calcined Gibbsite DTA - Curves of Heated Hydroxides
F,gure 4.4 Figure4.5

49
Alcoa Laboratories

(1959). Torkar and Mostad (1962) disputed this claim. They

attributed the black color to carhn originating from the
reduction of COZ adsorbd by the gel.

I
Saalfeld (19@) found the sequence gamma-theta-alpha alumina
when heating oriented aggregates of boehmite formed by
hydrothermal treatment of large gibbsite crystals. According to
Tertian and Pa@e (1958), L1ppens (1961), and Sato (1962),
delta-alumina occurs as an intermediate between gamma and
theta.

Lippens and DeBoer (19@), Saalfeld and Mehrotra (1965), and

Wilson (1979) showed by electron diffraction that the
transformation from boehmite to theta-alumina proceeds
topotactically. * Although differing in details, the workers
agreed on tbe close relationship between the stmcture of
ttoehmite and those of the transition forms, As a result of a
J. J. Ptaslenskt 2,fmox
kinetic study of the transformation of well crystallized

Tabular Alumina from Gibbsite Calcined with Fluoride

Figure 4.6
boehmite, Wilson and McConnell (1980) concluded that the
sequence gamma-delta-theta is kinetically favored because of
the structural similarities among the three forms. They did,
I
bowevcr, point out that the reaction sequence and kinetics
depend on the propetiies of tbe original boehmite. This does 1
not only apply to extremes such as gelatinous and well
crystallized boehmite, but also to highly crystalline y-AIOOH

Goton’s data agree well with the tindings of Lippens (1961)

prcpaed hydrothermally at various temperatures ranging from
420K to 570K, as shown by Tsuchida et al. (1980). According
to these workers, the activation energy for the
I
who investigated the dehydroxylation of well c~stallized and Y-AIOOH-?-AII03 transition can range from 220 to 325
of gelatinous kehmite. The latter material develops surface KJlmole depending on the tem~rature of preparation of the
area and transition aluminas similar to those forming in the boehmite sample and the water vapor pressure prevailing during
decomposition sequence of bayerite. This was confirmed by debydrox ylation. Wilson and McConnell (1.c. ) reponed values
Abrams and bw (1969). These workers investigated the of 185-205 KJ/mole. These examples demonstrate the difficulty
thermal decom~sition of the fibrous hoehmite described by of assigning definite pro~rties to the metastable phase;
Bugosh (1959). They found the fibrous AIOOH to consist of Y-AIOOH, and the transition forms.
well crystallized and gelatinous boehmite. The well crystallized
part decom~sed to gamma, then formed theti-alumina which 4.32 Dla.spttre
was followed by alpha, The gelatinous form converted to eta,
then via theta to alpha. (See also Clark and Lanutti, 1983). The DTA cume of diaspore is similw to that of boehmite; an
endothermic peak lies between 770K and 820K. Prolonged
X-ray indifferent (“amorphous”) gelatinous hydroxide beating leads to dehydroxylation at lower temperatures. Tbe
undergoes a succession of transition forms similar to that of equilibrium temperature for the transformation
gelatinous boehmite. Up to about 900K, the product of a-AIOOH s a-A1203 was calculated to be 630K by Fyfe and
dehydroxylation remains X-ray indifferent, Above this Hollander ( 19@). These workers determined tbe free energy of
temperature a poorly ordered, spinel-type transition alumina formation of a-A1203 at 298K as 1835 kJ/mole.
develops, which transforms to theta near 1300K and to a-A1203
above 1450K (Sate, 1972). The spinel-t ype transition alumina X-ray diffraction patterns of decomposed diaspore show
has ken referred to as eta, gamma, or “gamma prime.” This comndum as the only crystalline reaction product. Because of
inconsistency reflects the difficulty of differentiating these tbe stmctural similtit y ktween close-packed
the hexagonal
poorly crystallized forms solely on the basis of a few, broad lattices of diaspore and comndum, the phase transformation
diffraction peaks. requires relatively small rearrangements of the oxygen and the
aluminum psitions. From single-ctystal diffraction patterns
Teichner’s group claimed that an oxygen-deficient, black,
n-type semiconducting transition alumina can be obtained by
heating gelatinous hydroxide to 770K at a pressure of 10-6 bar (“shofl-mge, in-situ smcture rewgeme.t)

50

De flandre ( 1932) concluded that the conversion of diaspore to
corundum takes place in situ (topotactic), the a~ b, c axes of
the oxide hydroxide becoming the c, a, and [ 1I .0] directions of
a-A1203. Schwiersch (1933) confirmed Deflandre’s observation
by an optical study of the orientation of newly formed
corundum with respect to the decompscd diaspore crystal.
Ervin (1952) reported identical results.
Upon complete dehydroxylation diaspore loses approximately
1590 of its original weight. Contraction of the remaining solid
causes a system of regularly spaced cracks to develop. These
are oriented parallel to (001), and ~rpendiculm to (O10), tbe
main plane of cleavage of diaspore, At calcination temperatures
~low about 107OK, corundum nucleates within the lath-shaped
segments of the former diaspore in the form of crystallite of a
few tens nm diameter, Electron diffraction patterns of the
nonrecrystallized material surrounding the comndum particles
indicate a linear texture. The refractive index of the partially
convefied oxide, n~ = 1.60, is considerably lower than that of
diaspore or comndum (We fers, 1962).
Lima-de-Faria ( 1963) found satellite reflections in single c~stal
X-ray patterns of partially converted diaspore. This worker
concluded that an intermediate state of structure occurs during
transformation, caused by an alternating sequence of areas with
ordered and disordered cation distribution. Lima-de-Faria also
described a pore system which developed during calcination.
He determined the activation energy for tbe dehydroxylation to
be -100 kJ/mole.
The transition aluminas cannot be considered tme polymorphs
of A1203. The low temperature forms in particulw contain
hydroxyl ion. Moreover, the sequence of transformation is not
reversible; i.e., neither a- A1203 nor any of the high
temperature forms can k converted to one of the transition
aluminas that occur at lower temperatures. They may,
therefore, be classified as thermodynamically unstable,
although reasonably reproducible, states of structural
reordering. This point of view is supported by the fact that the
stmcture of the stwing material determines the type and
sequence of transition forms in the course of thermal
decomposition.
The schematic diagram of Figure 4. I only indicates general
ranges in which the transition forms occur, but should not be
considered a “phase diagram. ” More than one form may be
present simultaneously within a particle of decomposed
hydroxide; the low temperature transition aluminas initially
develop as domains in an X-ray indifferent matrix.
4.33 Other Methods for Preparing Transition Aluminas
Some of tbe transition aluminas can be prepared by methods
other than thermal decomposition of hydroxides, Stumpf and
Russell (unpublished) identified transition aluminas on heating
-.. -- ..- . . .
Oxides and Hydroxides 01”Aluminum
ammonium alum. Rooksby (1950) noted kappa-alumina in tbe
thermal decomposition of hydrated aluminum chloride. Fricke
and Jockers (1950) found gamma type alumina upon heating
AIC13 6H20. Caglioti and D’Agostino (1936) produced a
transition alumina by blowing a stream of air rapidly through
molten aluminum.
Eta-alumina is formed from tbe oxidation of aluminum at
temperatures near its melting pint (Hunter and Fowle, 1956)
as well as in anodic oxidation of aluminum under certain
conditions.
A fused alumina-aluminum nitride mixture, containing 0.347.
N, yielded a pattern similm to that of delta (brig and Foster,
1961 ). Delta-alumina has also been obtained by combustion of
aluminum in air or oxygen, and of aluminum carbide in oxygen
(Foster et al., 1956; Wmenberg, 1952; Schneider and Gattow,
1954).
Rooksby and Rmymans (1961) prepared delta-alumina by
igniting ammonium alum impregnated with ammonium
molybdate, by quenching molten alumina, by rapid
condensation after passing an oxygen-hydrogen flame through
vapor from an aluminum chloride bath.
Plummer (1958) found that gamma- or alpha-alumina passed
through an oxygen-hydrogen flae formed well-develo~d
crystals of delta- and theta-alumina, provided the final ptiicles
were spheres of less than 15 microns diameter. Larger pmicles
were alpha-alumina, Thus, extremely rapid solidification of
molten alumina, and ~ssibly contamination by nitrogen or
carbon, stabilize delta-alumina.
Foster (1959) reported a new alumina having an X-ray pattern
simiku to that of the aluminum silicate, mullite, This material
was designated iota-alumina, itformed during rapid quenching
of c~olite-alumina melts. Slow cooling gave comndum as the
only equilibrium phase. This mullite-like form was metastable
and transformed through eta-alumina to alpha-alumina on
heating above 1400K. Saalfeld (1962) described a similar form
having slightly smaller lattice constants. He called it a
modification of A1203 with sillimanite structure, It is doubtful
whether this material is a transition alumina, or rather a
compound in tbe system NaF-A1203.
4.4 Structures of Transition Aluminm
A comparison of tbe X-ray diffraction patterns of the transition
aluminas is given in Figure 4.7; Table 4.1 lists the most recent
d-values published for these forms, structure data are compiled
in Table 4.2.
To emphasize tbe relationships between tbe structures of the
precursors a“d the transition aluminas, in the following sections
these forms will be grouped according to the debydroxylation
sequences discussed above.
51
Alcoa Laboratories

4.41 Chi and Kappa Alumina

Stumpf et al. indexed X-ray diffraction patterns of chi alumina

assuming a cub]c (not spinel-type) unit cell having a lattice
constant of 0.795 nm. Saalfeld (1960) examined aggregates of
chi formed in heated single crystals of gibbsite. He calculated a
hexagonal cell with the parameters.

+ = 0,556 nm co= 1.344 nm

space group P61m or P631mcm

Certain stictural elements of the pseudohexagonal gihbsite

lattice remain, es~cially the arrangement of anions in the
direction of the a-axis. Chi-alumina has a layer structure, the
aluminum ions occupying octahedral sites within the hexagonal
oxygen layers. The stacking sequence of the layers is strongly
disordered, perpendiculw to the c-mis.
I
Brindley and Chm (1961) also determined a hexagonal
structure with

~ = 0.557 nm, co= 0.864 nm

Thew workers pointed out that the structure of chi-alumina a:

contains appreciable amounts of hydroxyl iuns.
eta

SaaJfeld calculated a hexagonal layer structure for kappa

chi
alumina. The kuge cell contains 28 A1203. Lattice constants are P

G = 0.971 nm, co= 1.786 nm.

80° 60” 40” 20”

A layer sequence ABAC-CABA. with aluminum in bth
octabedrd and tetrahedral sites show some similarity with the 20 CUK,,
structure of ~-aluminas. According 10 Brindley (1961), two
types of hexagonal kappa exist, one with N = 0.970 nm, the X-RaY Oiflraction Patterns of Transition Aluminas
other with % = 1.678 nm. Figure4.7

With the loss of almost all OH ions, the anion lattice of kappa
is htter ordered than that of the low temperature chi-form. In
addition, a reordering of cations takes place in the transition chi
+ kappa,

Space groups have not been reported for the two kappa forms,
While in the normal Me3+Me2+ spine] 32 oxygen ions and 24
kcause of the unceflainties of interpreting powder diffraction
metal ions make up the unit cell, only 21 1/3 A13+ are
data of marginally crystallized specimens (see Figure 4.7),
available for the cation psitions in eta as well as in the
isostructural gamma alumina, Lippens (1961) assumed eta to be
4.42 Eta and Theta Alumina
tetragonally deformed. According to Yamaguchi and Yanagida
(1964) the degree of tetragonal deformation is a function of the
Eta alumina has a spinel structure, Stumpf et al. (1950) residual OH.content, The cub]c close-packed stacking of
detemined the cubic lattice constant to be oxygen ions in the stmcture of eta is one-dimensionally
disordered in the direction perpendiculm to the c-axis of the
do = 0.79 nm precursor bayerite (Lippens and OeBoer, 1964). John, Alma,

52

and Hays (1983) used solid-state nuclear magnetic resonance
(NMR) to determine the coordination of Al in transition
aluminas. They found 35 * 4% of the AI ions in eta”on
tetrahedral sites. Cation vacancies, therefore, appea to be
equally distributed over tetrahedral and octahedral psitions.
The same workers showed that in theta alumina prepared from
boehmite, the aluminum ions were almost exclusively in
octahedral coordination. This is in contrast to Sadfeld’s (1960)
stmcture analysis who assumed Al ions to preferentially occupy
tetrahedral sites. Theta alumina is isostructural with ~-Ga203,
which can be grown in large single crystals (Roy, Hill, and
Osbom, 1953; Kohn, Katz, and Brcder, 1957). Geller (1960)
and Saalfeld (1c.) used single crystals to determine the
structure of @-Ga203. Saalfeld inte~reted powder data of theta
alumina on the basis of the ~-Ga203 structure. He calculated a
monoclinic cell, C~h C2/m having the constants:
a. = 1,124 “m, b. = 0,572 nm, co = 1.174 nm, P = 103”20’
The stmcture is a deformed spinel lattice and may be
considered an intermediate between the cubic packing of the
low-temperature transition aluminas and the hexagonally close
packed comndum.
4.43 Gamma and Delta Alumina
The stmcture ofgamma alumina is also of thespinel type, but
it is significantly more tetragonally deformed than the eta
lattice.
Saalfeld and Mehrotra (1965) determined the lattice constants
to be:
G = 0.562 nm, co= 0.780 nm
W1lsOn (I 979) gave:
aO=0.796nm, CO=0.781 nm
These authors, as well as Llppens and DeBoer (1964),
investigated the structure of 8amma by selected area electron
diffraction. Allthree groups conclude tbattbe oxygen sublattice
of gamma alumina is fairly well ordered, much more so than
that of eta alumina. Tbe reason forthc difference in order of
the two spinel-type stmctures lies in the stmcturesof the
precursors: the bayerite lattice ismade up of single layers of
Al(OH)6mtahedra, and two water molecules me lost during
dehydroxylation. Intbeboehmite structure, theoctabedra form
cubic packed double layers; only one H20 is driven off in the
thermal transformation.
As is the case with the eta structure, tbe AIIvAIVI* spinel
lattice ofgamma contains cation vacancies. Saalfeld and
*IV.V1 = Cmrdinati.n .umkm
Oxides and Hydroxides of Aluminum
2 Mehrotra (1965) assumed all octahedral sites to be occupied,
the cation vacancies being confined to the tetrahedral
interstices. This was confirmed by John, Alma, and Hays
(1983) who found, by NMR, only 25 t 4% of the tetrahedral
~sitions wcupied, rather than the one-third (8 of 24) available
in the spinel stmcture.
Because gamma alumina contains several Wrcent hydroxyl
ions, DeBoer and Houben (1952) klieved it to k a hydrogen
spinel, analogous to the lithium spinel described by Kordes
(1935). Soled (1983) postulated tha the hydroxyl ions are a
necessary component of the defect structure of gamma (and
eta), their number tilng equal to the number of cation
vacancies. The composition of this transition form,. therefore,
can be expressed ax
A12D0,402.8(0H)0.4**
The structure of delta alumina is related to that of gammw the
long-range order having increased so that the unit cell can &
described as a triple block of spinels (Lippens, 1961; Saalfeld
and Mehrotra, l.c.). Tertian and Pa@e (1958) gave lattice
parameters for a tetragonal structure as
~ = 0.797 nm, co= 2.347 nm
According to Lippens (1961) the dimensions ue
a. = 0.794 nm, co = 2.350 nm
Wilson (1979) reprted
an = 0.796 nm, co = 2.342 nm
While Rmksby and Rmymans (1961) calculated
~ = 0.796 nm, CO= 1.170 nm
i.e., a tetragonal cell half the size of that described by the other
workers. Their material, however, had been prepared by
different routes (see Section 4.4). This was also pointed out hy
Lippens and Steggerda (1.c. ) These authors discussed the reason
why delta alumina does not appew as a transition in the
decomposition sequence of bayerite or gelatinous boehmite.
They conclude that the formation of the triple spinel block
requires a shucturd rearrangement in a direction that crosses
the major pore system in dehydrated bayerhe, and is
~rpendlcul= to tbe shofi dimension of gelatinous boehmite
particles. Reorderin8,
**❑ represent vacancy
53
Alcoa Laboratories

Table 4.1

rT
X-Ray Diffraction Data of Transition Alumin8s

r
Cti Eta G mma KaI 3 c 3

—
dA Ill, hkl dA hkl dA 1/11 hkl dA F
— dA 1111 hkl dA <
— hkl
~
2,40 40 311 4.6 40 111 4.56 40 111 6.2 30 5.70 2 200 7.6 4 101
2,27 20 222 2.6 20 220 2.80 20 220 4.5 20 5.45 10 001 6.4 4 102, 004
2.11 30 321 2,40 60 311 2.39 60 311 4.2 10 4.54 16 201 5,53 4 ill
1.98 20 400 2,27 30 222 2.28 50 222 3.04 40 2.837 80 400,401 5.10 e 112
1.53 10 311, 333 1,97 60 400 1.977 100 400 2,79 60 2,730 65 202,002 4,57 12 113
1.39 100 440 1.52 20 333 1.520 30 511 2.7o 20 2.566 14 111 4.07 12 114, 105
1.40 100 440 1.395 100 440 2.57 60 2.444 60 111 3.61 4 115
1.21 10 533 1.140 20 444 2.41 30 2.315 45 401,310 3.23 4 116

L1.14
1.03
20
10
444
563
1.027
0.989
.884
10
10
10
731
800
840
2.32
2.26
2.16
40
10
10
2.257
2.019
1.9544
35
45
8
402,202
311,112
601
3.05
2.861
2,728
4
8
30
107, 214
117
222
.806 20 844 2.11 60 1,9094 30 600,312 2,601 25 302, 116
2.06 30 1.7998 14 510 2,460 60 312
I 1
1.99 40 1.7765 6 602,402 2.402 16 313
1.95 20 1.7376 4 403 2.315 8 314, 305
1.87 60 1.6607 2 601 2.279 40 226. ,
1.82 30 1.6216 6 203,511 2.160 4 1.1.10
1.74 20 1.5715 2 113 1,986 75 400
1.64 60 1.5426 25 313 1,953 40 1.0.12
1,54 10 1,5120 6 603 1.914 12 318
1.49 30 1.~63 25 113,801 1.827 4 319, 2,2.1
1.45 30 1.4526 25 020 1.810 8 $26, 3.1.1
1.4 80 1.4264 10 600,710 1.628 8 !,1.14
1.39 I00 1.3883 I 00 712,512 i .604 4 513
1.34 30 1.538 8 1.1.15
1.12 10 1,517 16 523, 516
1,06 10 1.456 8 440

1
1.04 5 1.407 50 4.0,12
1.02 5 1.396 100
1.01 40
).994 20

therefore, requires such a high activation enerEv that it cannot DeBoer, R. Fricke, B, Imelik, A. S. Russell, K. S. W, Sing,
proceed at a sufficient rate ii the temperature ~~gion in which S. Teichner and B. Tertian are among the resewchers most
delta alumina occurs. At higher temperatures the fomation of prominent in this field. A summa3y of the literature up to 1970
the better ordered theta alumina is favored. was given by Lippens md Steggerda (1970).

It was shown in Chapter 4.21 that a large sufiace area develops

4.5 Texture and Surface Properties of Transition as a result of the pseudomo~hic transformation of gibbsite
Aluminas (Figure 4.4). The dehydroxylation of bayerhe, nordstrandite or
gelatinous hydroxide follows the same general pattern,
4.51 Development of Porosity indicating that the common chemistry of the hydroxides
determines the reaction sequence, rather than the small
The evolution of specific surface area and i“temal porosity in souctural differences.
the course of the thermal decomposition of aluminum
hydroxides has received as much attention as have the Feitknechtet al. (1961 )considered diffusion ofprotons to be
structural changes described in the preceedi”g sections, J. H. theinitial step inthe dehydration reaction. Freund (1967)

54
 Oxides and Hydroxides of Aluminum

Table 4.2
Strucural Properties of Trasition Aluminas

Molecules Unit IS Leng! m

Space per Density
Form Cwstal System Group Unit Cell a b c Angle a cm

Gamma Tetragonal .562 ,780 3.2a Saalfeld and

Mehrotra

Delta Orthorhomtic 12 .425 1,275 1.021 3.2~ Stumpf et al

Tetragonal .790 2.34 Rooymans

Eta Cubic (Spinel) 0; 10 .790 2.5– Stumpf et al

3.6m
Theta Monoclinic C;h 4 1.124 .572 1.174 103~20< 3.56@ Saalfeld (1960)

Cti cubic 10 .795 3.o@ Stumpl et al

Hexagonal .556 1.344 Saalfeld (1960)
Hexagonal .557 8.64 Brindley and Choe

Kappa Hexagonal 28 9.71 ,1786 ... ,.. 3.1.3.3@ Saalfeld (1960)

Hexagonal 9.70 .1766 Brindley and Choe
Hexagonal ., ...,.. 1.678 .1786 Brindley and Choe

Iota Orthorhomtic 4 .773 .778 .292 3.71 ~ Stumpt et al

Otihorhomhc D~h or 3 .759 .767 .287 3.0 Saalfeld (1960)
CL

a ~~~ ~~,e~

pointed OU1 that thermal dissociation of the hydroxyl most
likely is not the source of protons for the reaction:
O--- H+ OH* O+HOH
The OH-stretch vibration occurs neu 370Q cm-1; the thermal
equivalent of which is an excitation temperature of -55WK for
this vibrational state. This is about an order of magnitude
higher than the temperature of the dehydration maximum for
AI(OH)3. Freund assumes that in the temperature range in
which dehydroxylation occurs, the energy levels of single and
double protonated states of the OH ion are broad enough, and
overlap sufficiently, to permit proton exchange between
adjacent OH ions via an inelastic tunneling process. H20
molecules formed through this mechanism diffuse out of the
Iatticc via anion vacancies (Frettnd, 1965). Assuming random
remo~al of hydroxyls, Freund argues that complete
dehydroxylation of aluminum hydroxide is not possible at low
and moderate temperatures, ad that the rate of decomposition
should slow down after about two-thirds of the OH-ions have
been removed (equivalent to a 10% loss on ignition for
trihydroxides). The reason in both cases is the spatial
separation of hydroxyls, i.e., remaining OH-ions have no
hydroxyls for nearest neighbors. Freund’s arguments are
supported by the experimental evidence.
Rocquerol et al. ( 1975, 1978) also imply diffusion of water via
a “step process,” i.e., vacancy hopping. They consider the
“structural channels” in the gibbsite lattice, which originate
from superposition of the “empty” hydroxyl octahedra in the
direction of the c-axis (see Figure 2.9), to be favored diffusion
paths. At high decomposition rates the (CKII) planes between
two layers of mtahedra are also prefemed sites for the removal
of water.

55
Alcoa Laboratories
The porosity and concomitant large specific surface area of
transition aluminas are the result of the rapid loss of mass that
is not accompanied by a decrease of the external dimensions of
hydroxide particles. Much work has been done to relate
s~cific surface area, size and shape of pres, as well as pore
volume to tbe properties of the starting material and the
conditions of the dehydration process. In earlier investigations,
gas adsorption and resorption techniques, and mercury
porosimetry were applied to gain insight into the texNre of
porous transition afuminas. High-resolution electron microscopy
has been used since the 1960’s to directly observe and measure
morphological features inferred from the earlier, indirect
experimental approaches.
J. J. Ptaslenskl 2S0,000X
Chi Alumina lC
Figure 4.8
56
The large surface area developing in the initial, rapid stage of
dehydration of trihydroxides (figure 4.4) is attributed to a
system of slit-shaped pores which are less than 2 nm wide.
This pore system was earlier descrikd as consisting of <I nm
wide, rod-shaped pores oriented perpendicular to the basal
plane of the trihydroxides, and slit-shaped, 2-3 nm pores
parallel to these planes. “Ink bottle” sbaps were deduced from
BET adsorptiotidesorption isotbenns, obviously based on a
combination of the two morphological features (de Boer et al,
1954, 1956). Lippens (1961), Wefers (1964) and others showed
by transmission electron microscopy that a sponge-like texture
develops within a coherent solid. Paraflel pores located in the
cleavage plane (001 ) separate the solid into Iamellae that are on
K. Welem 220,41xlx
Chi Alumina Ilc
Figure 4.9
—

the order of 2-3 nm thick, about twice the average pore width.
A network of imegukuly shaped slits, about 1 MI wide,
extends Perpendic”laly to, and is connected with, the pores
parallel to (001). Figures 4,8, 4.9, and 4.10 show these pre
systems in particles of chi and eta alumina, The intersecting
pore systems divide tbe Iamellae into interconnected, irregularly
shaped domains of solid. These measure on the average less
than 10 nm in their longest dimension, equivalent to the length
of about 10-15 A 106 octahedra. It is obvious from the electron
micrographs that the surfaces of the solid domains are “rough
on an atomic scale and do not represent refined crystal faces.
Tbe longer-range periodicity necessary for the generation of an
X-ray diffraction pattern is provided by an approximately
parallel alignment of the irregukir domains in the layers of the
Al(OH)3-precursor.
J. J. Ptasienski 400,000X
Eta Alumina Ilc
Rg”re 4.10
Oxides and Hydroxides of Aluminum
Surface areas resulting from this porosity can exceed 400 m2/g.
Lippens (1961), Lippens and Steggerda (1970) and Wilson and
Stacey (1981) pointed out that the surface areas measured by
gas adsorption methods, particularly when nitrogen is used,
generally are lower than those calculated from microscopically
measured values for pore size and spacing. The obvious reason
is the limited access to, or incomplete tilling with gas
molecules of pores smaller than about 1 nm. Limitations of the
microscopic methcd lie in the dlfticulty of precisely
determining and measuring outlines and dimensions of highly
imegulm Pres, and differentiating micropores from clusters of
vacancies. The dimensions of both these morphological features
overlap; the definition, therefore, is arbitr~.
Total pore volume of transition aluminas having maximal
specific surface areas is in the range of 0.2 cm3/g A1203. If the
calcination temperature is raised above 650-700K, the surface
area diminishes (Figure 4.4), but the pore volume increases
slightly. As shown in Figure 4.4, tbe adsorption of water at
high PH20 reaches its maximum nez the first inflection of the
down slope of the surface area-versus-temperature curve,
staying nearly constant up to about 980K (Wefers 1964).
These data indicate that the smallest pores contribute the major
part of the kirge specific sutiaces areas formed below 650K,
but are not all accessible to water. Bridging of nmow (1-2 nm)
pre openings as a result of dipole interaction of water is the
most probable cause. Whh increasing temperature, the small
domains of solid coalesce into lager, more stable weas of
oxide. As a result, the spacing between solid domains
increases; so does the volume accessible to water molecules for
surface adsorption and capilkuy condensation.
At temperatures exceeding approximately 10WK, reordering is
no longer confined to short-range consolidation witbin the layer
skeleton of the decomposed trihydroxide, Activation energies
ae sufficient for three-dimensional sintering to take place, thus
removing the steric hindrance for the formation of long-range
ordered, crystalline oxide. Figures 4.11 and 4.12 show aciculas
gibbsite crystals heated to 1100K. Although tbe.layer texture of
the precursor is still obvious, Imellae have fomed that are
20-40 nm thick, about 10 times the thickness of the layers in
the particles of chi and eta shown in Figures 4,9 and 4,10, The
lamellae occur simultaneously with the formation of kappa
alumina. They aIe embedded in a network consisting of
interconnected crystallite and pres, each on the order of
10-30 nm in size, equivalent to a surface area of approximately
30-50 m2/g. This estimate is in good agreement with BET
surface areas determined for this transition alumina,
The orientation and morphology of the crystallite seen in the
high magnification microgmph of Rgure 4.12 suggest that the
transformation ch] + kappa is a reconstructive and not a
topotactic process.
 I
Alcoa Laboratories }

The dehydration of well-crystallized hoehmite causes a system

of Iarnellar pores to develop (Figure 4, 15) which are oriented
parallel to the (100) direction of the boehmite crystal. Wilson
(1979) and Wilson and Stacy (198 1) measured average pore
widths of 0.8-1 nm; the spacing between the pores was
determined to be between 3.5 and 4 nm.
(

Surface areas obtained by dehydmxylation of boehmite we on

the order of less than 100 m2/g, pore volumes generally <0.08
cm3/g. The smaller values, compared to those measured with
;? decomposed trihydroxides, reflect the loss of only 10-12% of
mass during the initial phase of dehydrox ylation. Wilson,

K. Wefers 80.000X

Kappa Alumina from Acicular Gibbsite

Figure 4.11

The morphological pattern established in the temperature range

from 1000 to 1100K persists beyond the formation of a-A1203
at temperatures above 1450K. Lamellae continue to increase in
thickness by fusion, as demonstrated in Figure 4.13. The gaps
between Iamellae also grow with increasing densification,
because the hahit and parallel texture of the original gibbsite
crystal are retained (Figure 4.3). In fragments of oxide having
network texture, a comsening of crystallite and pores is
aPP~nt, aS shOwn in Figure 4.14. These morphological
changes shift the average pore size into the range of
100-200 nm. While the surface area diminishes to 1-3 m2/g, tbe
~re volume remains near 0.1 cm3/g A1203. K. Wefers 250,WOX

Complete recrystallization which obliterates tbe habit of the Kappa Alumina Ilc of Gibbsite
precursor and the porosity, occurs at calcination temperatures Reordering by Bridging Lamellae
exceeding 1800K. Fi8ure4.12

58
 Oxides and Hydroxides of Aluminum

-1
I
I

,)

.. ‘~

K. Wefem 20,MXIX K. Wefers 2m,ooox

Alpha Alumina from Acicular Gihhsite Alpha Alumina, Primary Crystals and Pores
Figure4.13 Figure4.14

>

McConnell and Stacy (1980) found that surface area, pore
volume and spacing of the lamellw pores are controlled by the
water vapor pressure prevailing during dehydration at
temperatures below 700K. Llppens and Steggerda (l.c. ) showed
that the microporosity of dehydrated boehmite decreased
sharply above 850K, leaving a surface area of less than
I 20 mzlg, but not affecting the lamellw shape of the pores.
The dehydroxylation of gelatinous boehmite follows a different
pattern. High surface areas exceeding 600 m2/g can by
obtained, as discussed in Chapter 2.12, by extracting the liquid
phase from gels. The surface area of the resulting,
open-network aerogels is the surface of the c~stallites forming
tbe network, and thus a function of the crystallite size, which
may be as small as 2-3 nm. Dehydroxylation at temperatures
between 450 and 750K does not lead to significant additional
porosity, due to the small size of the solid particles, as Llppens
and Steggerda (1.c.) pointed out. Loss of water causes the
crystallite to shrink and the network to progressively collapse,
leaving surface areas comparable to those obtained by
decomposition of crystalline trihydroxides.

59
—

Alcoa Laboratories

domains separated by gaps (pores) that are as wide as 5 to 20

oxygen ion diameters,

For these reasons, structural consolidation is confined to

short-range reordering witbin the domains. A spinel. type
arrangement is energetically y favored as it can incorporate
octabedrdly and lower - tetrahedrally coordinated aluminum.
Hydrogen ions may k retained in areas of cation deficit to
bafance excess negative charges.

Significant sintering and three-dimensional fusion of layers

occurs above 1lWK, as was demonstrated in the preceding
section. brig-range reordering, thus, kcomes possible, The
resulting delta, kappa, and theta forms represent, to varying
degrees, structure transitions from the spinel-type to the
hexagonally close-packed corundum lattice.

Reordering of the oxygen sublattice precedes that of the cation

sublattice of the high temperature transition forms. Hydrogen
ions are retained in these structures until the conversion to
comndum is completed (see L,O. I. values in Figure 4.4A). Tbe
cause/effect relationship is not clem are protons retained
because of locaf charge imbalance due to the cation disorder, or
does the presence of protons in A13+ “positions” lower the
driving force for the diffusion of A13+ ions into tbe respective
interstitial sites? The observed rapid crystallization of corundum
at temperatures around 11OOK in furnace atmospheres
containing fluoride ions appears to suppofl tbe latter
J. J. Ptasienski 300,DOOX explanation: fluorine is likely to react with protons to form HF,
a stable gaseous species in this temperature range, Removal of
protons creates negatively charged sites which accelerate the
Gamma Alumina from Boehmite diffusion of cations. As this process takes place in the earlier
Figure4.15 stages of the Iamellar texture, distinctly tabular corundum
crystals should be ex~cted. These have been observed
(Wefers, 19@),

The interde~ndence of micro-morphology and stmcture

4.52 Relationships Bet ween Texture and Structure
Crystal structure and texture of the transition aluminas are
closely related. Although the stmctures of individual transition
forms differ in some details, they can & grouped into low and
high temperature types that are characterized by common
stmctural and micro-mo~hological features.
The eta, chi, and gamma forms occur in a temperature region
(<1 lWK) in which diffusion rates are low, and in which
progressive loss of mass in form of hydroxyl and hydrogen ions
leads to lower cmrdination numbers for a sig”ifica”t fraction of
the aluminum ions, and the breaking “p of the solid into small
explains the strong effect of the precursor on the path of
reordering of tic thermally decomposed hydroxides and
oxide-hydroxides. In the writers’ opinion, tbe structural details
and distinctions of the individual forms have been somewhat
over-emphasized in the literature, leaving the impression that
they are thermodynamically defined polymorpbs of A1203,
rather than transitional stages in a continous solid-state
reordering process,
4.53 Properties of Active Alumina Surfaces
The term “active” or “activated aluminas describes transition
forms which have the capability of catalyzing certain chemical
reactions and chemisorbing a variety of molecula and ionic
species. This reactivity develops concurrently with tbe changes
in stoichiometry, texture, and structure that occur in the prmess
of deh ydrox ylation.

60
 Oxides and Hydroxides of Aluminum

Fully dehydroxylated, crystalline a-A1203 is not active, neither

are the well-ordered trihydroxides and oxide hydroxides of
aluminum. Activity is directly related to the defect stmcture of
the transition forms. ~Is relationship has been the subject of
numerous investigations.

Tamele (1950) ascribed the obsewed hwis acidity (electron

acceptor) to exposed, coordinatively unsaturated (CUS)
aluminum ions. Brbnsted-acid (proton donor) properties of
afumina surfaces were discussed by Trambouie and Pernn
(1953) and Mapes and E1schens (1954), Cornelius et al. (1955)
assumed “strained” oxygen bridges, resulting from the
condensation of two adjacent hydrox yl ions, to be the
catalytically active centers. Flockbari et al. (1966, 1969)
pointed out that active alumina surfaces exhibit both electron
acceptor and electron donor properties, and can catalyze
oxidation as well as reduction reactions.

Peri in 1965 developed a model for the progressive

dehydroxylation of a cubic (100) surface plane. He used a
statistical treatment (Monte Carlo) of m assumed, random
interaction of hydroxyl ions in a surface monolayer, Tbe
computer model demonstrated that an ordered, planar (Peri, 1965)
oxygetihydroxyl lattice is maintained until two-thirds of the
hydroxyl ions have been removed. Further condensation of Configurations of Surface Hydroxyl Groups
adjacent OH-ions creates local dlsordeL at 90.4% removal of Figure4.16
bydroxyl ions, no pair of neighboring OH-ions is left.

Surface migration of protons or hydroxyl ions is required for

any additional dehydration (see also Freund’s arguments,
referenced in Chapter 4.51).

The sutiace states resulting from the removal of all OH-pairs

are shown in Figure 4.16. According to Peri’s model, five
combinations exist of bydroxyl ions with oxygen and CUS
aluminum ions (the latter located in the next lower layer). Five
OH-stretch vibrations are registered in the infrared spectrum of
the transition aluminas chi, eta, and gamma. Peri tentatively
related the frequencies of these OH-stretch vibrations to tbe
number of oxygen ions adjacent to the respective hydroxyls.
Knozinger and Ratnasamy (1978) refined Peri’s mcdel,
extending it to include (111) and (110) planes. These authors
calculated net chages for the five types of surface hydroxyls,
taking into account that aluminum ions to which they ue linked
can be either tetrahedral y mtahedrall y coordinated. A graphic
representation of the five hydroxyl configurations is given in
Figure 4.17. In the top row the most basic hydroxyls xe
shown. These c6ny a net chmge of –0.5 and are coordinated
to one Alrv or Alvl ion, respectively. The OH-group linked to
three octahedrally coordinated aluminum ions (bottom) has the
most acidic character.
The geometric models developed by Peri and Knozinger and
Ratnasamy are somewhat idealized. Es~cially the assignment
of particular configurations to defined c~stal planes appears
questionable in light of the microscopic evidence which
indicates that tbe internal surfaces of transition aluminas are
“rough” on the scale of the size of Al-O coordination polyhedra
(see Figures 4.10 and 4. 11). The concept, nevenheless, is in
good agreement with experimental observations.
Considerable research effort has been directed at understanding
the contribution of specific sites to adsorption and catalytic
surface reactions. Rosynek and Hightower (1972) classified
sites according to their specific reactivity; i, e,, isomerization of
butene, chemiso~tion of butene, hydrolysis of ketones and
nitrites, and D ~ H exchange, respectively. However, even an
apparently simple reaction such as the adsorption of C02 IIIaY
involve more than one site. Parkyns (1969) and Monema et al.
(1977) showed that, depending on the degree of
dehydroxylation of the alumina surface and the C02-pressure,

61
Alcoa Laboratories

GA 202,628 More than one site also is involved in the cbemisorption of

water. As shown schematically y in Figure 4.18, a Lewis acid
site is hydroxylated and an adjacent Br6nsted base (0-)
H H protonated in the fust-layer reaction. Tbe second layer is
o adsorbed via dipole bonds with surface hydrox yls. While this

I
Al
\i’/ second layer, as well as liquid water tilling pores as a result of
capill~ condensation, can be desorbed at temperatures lower

/l\ /;\ than 400K, removal of the fust layer requires “reactivation” at
higher temperatures.

\l/
Al
0\
Al
/l\ /l\ OH OH “ 2024’2’

—O—Al—O—Al—O —
/l\ /l\
I
– HOH

\l/
H

0 \l/ I o–

/y\ A, /y\
—O— AI+ —O— AI— O —
/l\ /l\ , /l\
+ HOH
Five Coordination of Surface Hydroxyl Groups
Figure 4.17 OH \ OH

—O—AI—O—AI—O —

/l\ /\\
+ 2HOH
H H H H
four configurations of the adsorbed species occur, including a \o/ \/
bicarbonate group formed via transfer of a hydroxyl ion: o

o H

Al—O—C
/
Al
/O\ C=o H
\ /

\ \/ i’ ?
o 0 —o—Al—o—Al—o —
/l\ /l\
Al—O o
\ /
C=o Al—O—C
/ \ Adsorption of First and Second Layer of Water on A1203
Al—O OH Figure 4.1!3

62
 Oxides and Hydroxides of Aluminum

Table 4.3 base). On alumina prepared at 775K and above, the

IR Frequencies of Surface Hydroxyl Groups combination of an electron-donor oxygen (f.ewis base) with a
CUS Al ion is believed to catalyze this reaction. Ghorbel et al.
Wave No. No. of Adjacent Net Charge (1973, 1974) pointed out that electron acceptor and electron
~m-l
Oxygens on OH “Peri-Type” donor sites are involved in tbe catalytic isomerization of
I-butene, and that these sites can ~ deactivated by selective
? 3700-3710 0 +0.5 c poisoning with bases such as ammonia and acids such as acetic
acid, respectively. Knozinger (1976) gave a comprehensive
3730-3735 1 +0,25 E review of !he literature concerning selective poisoning of active
, sites to probe their catalytic reactivity.
3740-3745 2 0 B
Basic and acidic propemies of alumina surfaces have been
3760-3780 3 –0.25 D enhanced by treatment with alkali (Scokart et al., 1981) or
halogen ions (Peri, 1966, 1968).
3785-3800 4 –0.5 A
1 Much work remains to be done before a comprehensive
understanding of tbe relationships between composition,
electronic properties, geometric configuration, and chemical
reactivity of the shon-range ordered surfaces of transition
Flockhart et al. (1965) found that the catalytic reduction of alumina can be developed. The advent of surface analytical
tetracyanmthylene on active alumina formed at temperatures tools capable of probing structures and interactions at the
[’ below 625K is associated with a surface hydroxyl (Br6nsted atomic level has greatly accelerated progress towards this goal.

63
Alcoa Laboratories

5. Surface Oxides on Aluminum Metal also related to the use of aluminum and aluminum oxide in
microelectronic devices.
5.1 Oxides Formed by Sofid-Gas Reactions
There appears to be general agreement that oxygen adsorbs
Aluminum owes its usefulness as a commercial metal to the dissociatively on aluminum. Batra and Klein man ( 1984), in a
properties of the surface films which it forms in contact with review of the literature on oxygen interactions with aluminum
the atmosphere. In an ambient environment, elemental surfaces, pointed out that the breaking of the O-O bond in 02
aluminum is thermodynamically unstable with respect to its to form two Al-O bonds results in an energy gain of about
oxides and hydroxides. The reaction 5 eV or 482 k.flmole. Simultaneous occupation of surface and
subsurface sites by oxygen was shown to be the first step of the
2AI + 1.502- A1203 – 1675,7 K] interaction of 01 with Al( I I I ) planes (Flodstrom et al. 1978;
Erskine and Strong, 1982; Crowell, Chen, and Yates, 1986).
is highly exothemic. Aluminum also readily reduces water, as According to the latter authors, A1203 begins to form when a
the standard potential of the electrode reaction critical number of oxygen atoms cluster together after
prolonged exposure to 01 or when temperature is increased.

~ A13+ + e- ~~ Al”, EO = 1.706 V

Similw mechanisms have hen reported for Al( 100) and
AI(1 10) crystal faces (Batra and Kleinman, l.c., Cocke,
is considerably negative, Johnson and Merrill, 1984),

Surface films on aluminum can form by one or more of the After a continuous layer of A1203 has been established, further
following reactions: growth follows exponential rate laws. According to the theory
of Cabrera and Mott (1948/49), thin films grow at low
(1) 2 AI+ 1.502 -A1203 temperature predominantly by cation migration, therefore,
inverse logarithmic rate laws are observed. Electron transport
(2) 2 Al + 3 H20 + AI,03 + 3 Hj takes place by tunneling; this limits the film thickness to less
than 5 nm in the temperature range in which thenno-ionic
(3) Al + 2 H20~ AIOOH + 1,5 H2 emission of electrons dms not contribute significantly to charge
transport. Kirk and Hu&r (1968) reported that film grow[h and
(4) Al + 3 H20- AI(OH), + 1.5 Hz change of work function are pressure dependent and follow a
logarithmic rate law. Fehln and Mott ( 197 I) modified the
Secondary reactions of the surface film with water are original Cabrera-Mott theory by assuming cation and anion
controlled by pH20 and temperature: migration, the driving force being a space charge resulting from
a cation excess and anion deficit near the metalloxide boundary
(4) A1203 + H20 ~ 2 AIOOH and the reverse nem the oxidelair interface, This growth
mechanism is consistent with a logarithmic time function. A
(5) AlzO, + 3 H20 -2 Al(OH)j defect stmcture near the metalloxide interface consisting of
excess metal combined with oxygen vacancies which trap two
(6) AIOOH + 2 H20 ~ Al(OH)J electrons each was propsed by Greenberg and Wright i“ 1955.
Heine and Sperry ( 1965) found a metal-rich region extending
Oxide layers developing near room temperature in oxygen or more than IO- 15 nm into the oxide (see also Pryor, 1971 ).
dry air reach a limiting thickness of 2-4 nm after several hours,
They are generally considered to be non-crystalline, but Lawless in 1974 critical] y reviewed much of the work on thin
shon-range, cubic ordered stmcture has ken observed by Pryor oxide films. He pointed out that discrepancies regarding results
( 1971). At an estimated density of -3 g/cm3 of the short-range and interpretation of mechanisms are mainly attributable to the
ordered oxide, the molar volume increases by a factor of -1,7 experimental difficulties of precisely determining mass and
in reaction ( I). Because of this strongly positive volume thickness changes of very thin oxide layers.
change, the surface films are continuous even at oxide
thicknesses only 2.3 “m, thus Iimiti”g mass transfer to With increasing temperature up to about 650K the amorphous
solid-state (lattice) diffusion, The initial stages of oxidation nature of the A1203 films remains unchanged. Rate laws were
have received considerable attention in recent years; in part due reported to be paralinear; i.e., changing to linear after an initial
to the availability of ultra-high vacuum instrumentation parabolic function at temperatures exceeding 700K, as shown
providing tbe means for creating tmly clean aluminum sutiaces schematically in Figure 5.1. The rate of mass gain changes
and precise dosing of gases, Much of tbe renewed interest is back to an exponential function after several hours at these

64

—

650- 700K
i
Growth and Transport Mechanisms of Thermal
Fignre S.1
temperatures (Cochran and Sleppy, 1961; Gulbransen and
Wysong, 1947).
The transition from a parabolic (logarithmic?) to a linear time
function coincides with the occurrence of crystalline transition
alumina of the gamma or eta form. This was first observed by
deBrouck&re (1945). Doherty and Davis (1963) showed that
cVstaIline transition alumina nucleates at the metalloxide
interface. Nucleation is very likely epitactic, as the difference
between the lattice parameters of Al (2 x 0,404
nm = 0.808 nm) and spinel-type transition forms (~ of
eta = 0.79 nm) is VeIY small, Recent high-resolution electron
microscopy bas confirmed such oriented growth (Ackland et
al., 1986).
Dignam et al., ( 1966) assumed that the crystalline alumina
grows laterally and vertically by continuous oxidation of metal,
and not by recrystallization of tbe amo~hous film. Oxygen,
therefore, must be supplied from the atmosphere. Considering
the slow rate of lattice diffusion in a refractoy oxide such as
A1203 at temperatures below 900K, the linear growth rate is
consistent with a phase boundary (zero-order) reaction between
oxygen and metal. This reaction mechanism requires open
Oxides and Hydroxides of Aluminum
.“ w
Non - linear (expon.)
Al metal
D
~ ~::~ho.a
~, - A1203
Oxides, Schematic
pathways ktween atmosphere and metal. Flaws in the
amorphous layer, wbicb occur simultaneously with the
crystallization of transition alumina, most likely provide such
channels. Whether these flaws ind~cate a partial
recrystallization and formation of interfaces within tbe
amorphous oxide (Wefers, 1981), or whether they are caused
by a different mechanism, is still being debated, Observations
by Bianconi et al. ( 1979) support tbe recrystallization
mechanism, This is also clemly seen in tbe micrographs of
Figure 5.2 A and B.
Continued lateral growth of transition alumina crystallite
eventually results in a continuous layer of thick crystalline
oxide which limits oxygen transport to grain boundary diffusion
or lattice diffusion. Both processes follow no”.linear rate laws.
me interface ktween the afumi””m a“d the crystalline as WeII
as the amorphous oxide layers is sharp. Tlmsit et al. ( 1985)
showed that Al( 111 ) and (1 10) oriented i“tefiace~ bet~ee”
metal and non-crystalline oxide are “rough” on an atomic scale
only, with step heights not exceeding two interplan~ spacings.
Neither Timsit et al. (l.c.) nor Ackland et al. (I,c. ) found
evidence of a transition zone of cubic suboxide
65
Alcoa Laboratories

(a. = 0.406 – 0.430 nm) which has bee. reported hy

Yamaguchi in 1975.

The effect of water vapor on the oxidation of pure aluminum

has not been clearly established. At temperature exceeding
650K, rates and mechanisms ap~ar to he very simila for dry
and “moist” (PH2 <100 mbar) atmospheres, as shown by
Cocbran and Sleppy (l.c.), Smeltzer (1956), Blackbum and
Gulbransen (1960), and Breaks~are (1970), ‘l’be reaction
products w AI*03 and H2, according to reaction (2). Evidence
for the formation of hydroxides has not been reported.

Little information is available regarding tbe composition and

growth rates of surface films forming in moist atmospheres at
temperatures below 450”K. One may speculate that the
injection of (OH)– into the near-surface region of negative
space charge requires a lower activation energy than the
transfer of the 02- ion. Reduction of H+ may drive the
cathmiic reactioq i.e., the extraction of electrons at grain
boundaries or defect sites. In careful studies of the composition
of air-formed films (<10 nm thick), Miller (1986) found a ratio
of oxygen to alutinum of 1.5 near the metalloxide interface,
but a 2 to 1 ratio near the oxide/air bound~, suggesting a
composition approaching A1OOH in this region. Much more
Nucleation of Gamma Transforming Amorphous Oxide work is needed to close the gap kt ween studies of first-layer
interactions of clem Al surfaces under ultra-high vacuum
condhions, and the reasonably well known properties of thick
films grown at high temperatures.

5.2 The Reaction of Aluminum Surfaces with Water

The reaction with water of aluminum and its alloys has been of
concern to corrosion chemists almost since the beginning of
commercial use of the metal. It was shown in Chapter 2.12 that
aluminum which has ken depassivated by slight amalgamation ,f
of its surface vigorously reacts with cold water or moist air
until all metal is consumed. Passive aluminum; i.e., metal
protected by a continuous oxide film, is on the other band
practically stable even in boiling water. Reaction with water or
steam at temperatures below 400K under certain conditions
reinforces the protective properties of the surface oxide. This
phenomenon has been known and commercially utilized for
decades. The literature on this subject was summarized by
Altenpohl in 1962. ,

A number of researchers have studied growth mechanisms md

properties of hydroxide films formed by reaction of aluminum
surfaces with water. An extensive review of the
aluminum-water system was published by Alwitt in 1976.

J.J. Ptaslenskl/K. Wefem 1Oojmx

Several workers, Hart (1957), Bernard and Randall (1961 ), and
Progressive R&rystalliz.ation of Amorphous Surface Oxide Vedder and Verrnilyea (1969) observed that, in the temperature
on Afuminum range between 293K and 373K, increase in mass of the surface
Fiwre 5.2 films follows exponential time laws after an induction period,

66
 Oxides and Hydroxides of Aluminum

the duration of which is inversely proportional to temperature.

While Vedder and Vermilyea proposed a pwabolic rate,
indicating a diffusion controlled reaction, Alwitt (l. c.) pointed
out that the exponent of the rate equation varies with
tem~rature.

Mass change data are not unambiguous indicators of growth

rates, because neither composition nor mo~hology of sutiace
films on aluminum ~e uniform. Hart (1957) was one of the
first researchers to find that the films formed between 293K
and 353K are layered an amorphous layer near the metal
intetiace is followed by a zone consisting of gelatinous
boehmite; bayerhe or well crystallized boehmite grow on the
outer surface (Figure 5.3). The ratio of the three strata changes
with temperature, pH, and time of exposure. when formed at
room temperature, films may be made up of only two optically
distinguishable layers, both of them consisting of X-ray
indifferent f’amorphous”) material (We fers, 1961),
D. R. Mlcholas Io,ooox A
Bayerite occurs during exposures of up to 350-360K at ambient
pressure. Well crystallized boehmite develops in the outer
region of the films at higher temperatures. Dachille et al.
( 1971) showed that bayerite may persist up to 425K if the
Cryst. AIOOH
pressure is raised above 675 bars. Although A1OOH is the
I AI (OH,,\ , Al (OH); SOI.
? stable phase under these temperaturelpressure conditions (see
figure 3. I), the phase reaction

Al(OH)g - AIOOH + H20

which results in an increase in moleculz volume, may be

kinetically hindered at higher pressures, especially if nuclei of
Y-AIOOH are not present. At temperatures exceeding
425-450K, the surface hydroxides recrystallize and form a
discontinuous layer of individual boehmite crystals which no A Al Immersed in Watar, 1 day st 335K
E Film Texture, Schematic
longer protects the metal (Altenpohl, 1962; Wefers, 1961).
Diaspore, a-AIOOH, corundum a-A120q, or transition aluminas
are tbe reaction products at higher temperatures and pressures
(Alwitt, 1976). Multilayered Hydroxide Film on Aluminum
Figure 5.3
It is obvious from these observations that the interaction of
aluminum surfaces with water produces the same phases and
follows reaction paths similar to those observed with
hydroxides precipitated from homogeneous solution.

According to the phase diagram A1203-H20 (Figure 3.1), the

thin, air-formed surface oxide on aluminum is unstable at
temperatures lower than 635K in the presence of water. Below
-360K, a porous layer of gelatinous hydroxide is fomed by
the reaction of tbe oxide according to Quation 4 in
Chapter 5.1. The concomitant thinning of the continuous oxide
barrier initiates diffusion of aluminum ions which become
hydrated as they enter the porous gel.
deprotonationlcondensatoin process depicted in Figure 2.5, thus
increasing the thickness of the gelatinous layer, At the
gel/liquid interface, crystalline hydroxide is precipitated by a
solutionlredeposition reaction. Temperature and pressure
determine which phase is formed. Crystals of boehmite are
shown in Figure 5.4 which represents aluminum treated in
boiling water for 8 hours.

Due to the ve~ low volubility of aluminum in pure water, the The layered texture of the surface films reflects the
solvated Al-ions precipitate, most likely via the predominant transport mechanisms and relative activities of

67
Alcoa Laboratories

practice of commercial “anodizing” has been summarized in a

number of biwks; e.g., Wemick and Pinner (1972), Henley
(1982).

Countless andlzing systems and procedures; i.e., combinations

of electrolyte chemistry, temperature, voltage, and current,
have kn descrikd during more than 90 years of research and
development in this field. The oxide films produced,
nevertheless, can & grou~d - with some simplification - into
only two types: non-porous “barrier” oxides and porous anodlc
films. Barrier oxides form in electrolytes in which aluminum
oxide is not significantly soluble, while prous coatings
develop in electrolytes which dissolve A1203. This
differentiation, again, is somewhat simplistic but will be
helpful in the context of this short summary of the complex
subject.
J. J. Ptssiensld 8,000X

Figure 5.5A shows the voltage/cument relation of a cell in

Duplex Film on Al Formed in Boiling Water which an aluminum electrcde is anodically polarized; e.g., in a
F,g”re 5.4 neutral solution of scdium borate and boric acid. After the
voltage has been applied, the current surges briefly before
decaying exponentially to a ve~ low value. This process
repeats itself each time the voltage is raised to a higher level.
A current-limiting passivation layer is formed, the thickness of
which is a linear function of the anodic electrode potential. In
aluminum and water both the oxide adjacent to the metal and the absence of chemical dissolution of the oxide, the film
the topochemically formed gelatinous hydroxide develop as a thickness corresponds to 1.4 nm ~r volt of anodic potential, or
result of the diffusion of aluminum ions into and through a a minimum field strength of 7.1 X 106 V/cm.
continuous barrier. The development of the outer, crystalline
layer is a function of volubility; i.e., pH and temperature. The
ratio of aluminum to oxygen changes accordingly: it is tbe
highest, 0.66, in the A1203 region near the metal surface;
decreasing to around 0.5 in gelatinous hoehmite
(AIOOH + aq, ) and 0,33 in AI(OH)3, bayerite. GA 202,632
I I I I
To obtain an optimally protective coating, it is obviously
advantageous to promote the growth of tbe two inner, diffusion
controlled barriers and to suppress the recrystallization reaction
which transforms tbe continuous, gelatinous hydroxide,
Treatment of aluminum surfaces for shon times (<1 h) with
unsaturated steam at 380-400K meets these requirements.

5.3 Oxidss Formed by Anodic Polarization of Aluminum

I
5.31 Non-Porous Oxide Films

A widely used method of forming surface oxides on aluminum ——

is the ancdic polarization of tbe metal in liquid, aqueous and
Time 101 1 Oz 103 104 see
non-aqueous electrolytes, or in plasma environments containing
oxygen-beting sWcies. Surface films of varying thickness,
composition, and texture can k produced by selecting A: highly, E moderately, C: non-solvent electrolyte
appropriate electrical and chemical conditions. Detailed reviews
of tbe electrochemistry of anodic oxidation as well as of the
stmcture and composition of anodic films were given by Voltage-Current Relationships in Anodizing Al
Tajima (1970) and Diggle, Downie, a“d Gouldi”g (1969). The Fiwre S.5

6s
1’
Oxides and Hydroxides of Aluminum
;

‘, Current efficiency is close to 10Q% of the theoretical Fxaday

equivalent under these conditions. Ultimate thickness of the
1, barrier oxides is limited by their dielectric strength. Breakdown
by sparking occurs at cell potentials above 600.7W V,
corresponding to a film thickness of -0,85-1 pm.

The current flowing across the harrier is ionic at tield strengths

higher than the minimum value. Below this limit, tbe small,
residual current is electronic and probably related to local
impurities. Both aluminum and oxygen ions are mobile under
tbe influence of tbe high field, contributing equally to film
growth at the metalloxide and the metallelectrolyte interface.
This was found by Davies et al, (1965) and Xu et al. ( 1985)
who used radioactive (Xe12s) marker techniques to study tbe
relative movement of cations and anions during film formation.
A transport numkr of -0,5 for A13+ was detemined in both
investigations.

Major contributions to the understanding of profxrties and W. T. EvanS 3,000X

growth mechanisms of anodic oxides were made by
A. Giintberscbultze, D, A, Vermilyea, M, J, Dignam, W. J. “Tunnel” Etched Al with Barrier Oxide
Bernard, N. F. Mott, G. C. Wocd, and their work groups. Figure 5.6

me barrier films consist of almost pure A1203; they contain

generally less than 1% electrolyte anion and water. Oxides
formed at less than 2Ctl-3W V are X-ray indifferent; eta and
gamma transition aluminas have been found in film,.. .p,uduced
at higher potentials, Being optically featureless even at
dimensions of a few nanometers, barrier films can be used to
replicate aluminum surfaces for transmission electron
microscopic examination.
The main application for barrier oxides is in electrolytic
capacitors. Although the dielectric constant of the oxide films
is only moderate (K = 8- 10), high capacitance Fr unit area is
obtained by etching the aluminum substrate before anodic
oxidation. A special electrolytic etching procedure leaves deep,
crystallographically oriented “tunnels” which are tilled with the
anodic oxide, as shown in Figure 5.6.
which oxide is formed and dissolved are equal, Such
conditions, under which the anodic current efficiency is zero,
Xe employed in “electropolishing”, a form of controlled
electrolytic etching of aluminum and its alloys. Numerous
combinations of electrolyte chemistry, cument, voltage, and
temperature have been reprted in the literature which produce
andlc films having properties that place them between the
non-porous barrier layer and the thin (<5 nm) oxide remaining
after electropolishing.

Plasma anodization of aluminum is employed in the
manufacture of microelectronic devices to form insulating films
in-situ. tittle is known about growth mechanisms and
structures of these films. A review of this technique was given
by Hyde and Yep in 1976.
5.32 Porous Anodic Oxide Coatings
Oxide films having a very distinctive texture develop in
electrolytes containing sulfuric, oxalic, and phosphoric acid,
Two examples of the anodic polarization behavior of aluminum
in these electrolytes are given in Figure 5.5: curve B shows the
current vs. time transient of an aluminum anode polarized at
constant potential in 370 oxalic acid, a moderately solvent
electrolyte. Curve C represents the current vs. time relation
observed when 1590 sulfuric acid, a strong solvent, it used,

5.321 Properties Both curves digress from the exponential decay of current
which occurs after the formation of a continuous barrier layer
When aluminum is anodically ~l&zed in electrolytes which of 1,4 rim/V (curve A). Having passed through a minimum,
dissolve aluminum oxide, the current-limiting barrier thickness current recovers to a constant level (C) or again slowly declines
of 1.4 nmlV generally cannot be obtained. Ionic current, with time (B). (If the anodlc current is held constant, voltage
therefore, continues to flow. In the extreme case, the rates at rises in case B).

69
Alcoa Laboratories

In the first few seconds of anodic polarization, a barrier layer

grows as it does in a non-solvent electrolyte (A). Recovery of
ionic current is the result of a stmctural and morphological
change of the initial btier. bcalized reaction sites develop in
which a thinner (<1.4 rim/V) oxide advances into the metal
substrate (Figure 5.7). First shaped almost hemispherically, the
penetrating oxide “cells” elongate into hollow cylinders closed
by a rounded bottom, Being thinner and, therefore, absorbing
fewer electrons, the cell bottoms appear light in the electron
micrograph. The annular cell walls, which are oriented parallel
to the electron beam, appe~ dark due to the longer path length
and higher absorption of the electrons. Ap~aring first in areas
of higher free energy such as subgrain boundaries, the cells
rapidly cover the electrode surface, attaining a polygonal,
ideally hexagonal, cross section as they fill the available space.

Once the cell pattern has ken established, it remains

unchanged while the oxide continues to grow (at constant
electrcde ptential). The length of the cells; i.e., total film
thickness, may reach more than 100 pm. Their diameter is a
function of voltage and electrolyte composition. It ranges from
2.6 to 3.0 nmlV. Pores formed in moderately solvent
electrolytes measure less than one-third of the cell diameteq
larger pores of more than 1 rim/V develop in aggressive
solutions.

The mo~hology of a thick, cellular oxide film is schematically

represented in Figure 5.8. Setoh and Miyata (193 I ) and
Rummel (1936) fust recognized the porous nature of thick
anodic oxides. These workers ~stulated a duplex structure of
anodic coatings on the basis of measured electrical proprties: a
high-im~dance layer of less than 100 nm thickness adjacent to
the metal surface, covered by a second layer the (low) G. A. Nitowskl 25.000X
impedance of which is nearly independent of thickness. Direct
evidence of the porous texture was provided by electron
microscopic investigations of Fischer and Kurz in 1942. Keller, Initial Cell Development
Hunter, and Robinson published the now classical Alcoa model Figure 5.7
in 1953. Although they microscopically analyzed mostly
replicas of the metalloxide and oxidclair interfaces, and very
thin oxide films sepaated from the metal (as did Fischer and
Kurz), their concept agrees in its essential features with the
model of Figure 5.8, Electron micrographs of cross sections electrochemicafly active “barrier” while anodic oxidation is
later published by Booker, Wood, and Walsh (1955), Akahori proceeding. Aluminum and anions are transported through this
(1961), and Ginskrg and Wefers (1962, 1963) contimed and barrier along the lines of force of a cone-shaped field. As the
added minor details to the Alcoa model (Figure 5.9). cell advances into the substrate by oxidizing metal, the apex of
the field also moves downward and the upper portions of the
The concept of the duplex structure only describes the electrical cell bttom become cell wall. Consequently, each cell is an
pro~rties of the celhdar oxides. There is no structural or individual entity which grows independently of others.
compositional separation between the barrier and the porous Advancing single cells and their circula cross sections are
pan of the cellular oxides. Any distinction is a functional one. shown in Figure 5.10. The non-uniform progression of cells
The rounded bottom of the cells constitutes the had been induced by a sudden increase in current.

Pore
Cell wall
\
Barrier layer
(cell bottom)
i
rexture of Porous AndIc
Figure 5.8
Whereas the diameter of the cells is a function of the anodic
voltage, both pore volume and chemical composition of the
anodic films are determined by tbe electrolyte. As early as
1899, Norden reported that anodic films formed on aluminum
in dilute sulfuric acid contained 13% S03 and almost 15%
H20. Infrued analysis indicates sulfate ion to be the
predominant species. The concentration varies; it is determined
by current density, concentration, and temperature of the
electrolyte. Anodic coatings produced in oxalic acid contain
between two and five percent oxalate iow similar amounts of
phosphate are found if phosphoric acid is used as the
electrolyte. (Films formed in chromic acid have a poorly
developed cell texture; they are repotied to be practically free
of chromate ion; Tajima, 1970. )
Oxid’es and Hydroxides of Aluminum
Sealed cells
t
Ofide
The Pre volume of anodic films is controlled by the solvent
pwer of the electrolyte. Values near 209. were measured with
coatings produced in 15% H2S04 at 300K (Mason, 1957).
Porosity may be as low as 5% in films formed in dilute (<2%)
sulfuric acid at 280K. Specific surface area is a function of the
~rosity. For an ideal oxide of 10 pm thickness, having cell
diameter of 30 nm and a ~re diameter of 10 nm, a surface
area of abut 45 m2 per mz of geometric surface (1 mz X 10
pm = 1 cm3) can be calculated. At a density of nearly 3 glcm],
this value comespnds to approximately 15 m2/g.
Porosity is an indirect measure of the current efficiency of the
anodic process. The larger the pre size at a given cell
diameter, the lower the current efficiency. It is obvious from
Alcoa Laboratories

F. A. Mozelewsld 4,000 x

Surface of Anodic Oxide

Figure5.9B

10,000
Cross Section and Surface
of Porous Anodlc Oxide
Rpre 5.9A
the mcdel of Figure 5.8 that porosity or current efficiency can
be expressed as cell wall thickness in nanometers pr volt (at
the bottom of the cell; in the upper portions, chemical attack
during immersion in the electrolyte causes some additional
thinning). Values ranging from 0,85 to to 1.25 rim/V have ken
reported (Diggle et al., 1969; Tajima, 1970). As 1.4 rim/V
corresponds to a current efficiency of 100Yo, only -6090 of the
aluminum ions contribute to film formation at 0.85 nmlV.
x
formed oxide is not likely to be the cause of the uniform
~rosity and the defined, voltage-dependent barrier layer
thickness.
Both anions and cations are moved into and across the ceil
bottom (banier) by the electrical field. The chemical
composition of the electrolyte, current density, and tem~rature
are the factors which determine the fraction of aluminum ions
moving into the electrolyte without forming oxide (“field
assisted dissolution”) and the amount of acid anion incorporated
into the film, It remains an own question if there is a causal
relationship ktween the loss of aluminum ions and the
incorporation of multivalent cations such as sulfur, phosphoms,
or carhn.

A comprehensive understanding is still lacking of the
electrochemical and chemical reactions involved in the
fomation of porous anodic oxides, especially the development
of the unique regular, cell texture, There appears to be general
agreement that a purely chemical dissolution of anodically
In the cell wall, the concentration of electrolyte anions is
highest near the pore and decreases towards the periphery
(Ginsberg and Wefers, 1963; Thompson et al., 198 I ). It has
ken suggested that a thin (<50-60 nm) “shell” of aluminum
oxide is formed by a solid-state reaction at the metal interface,
 Oxides and Hydroxides of Aluminum

5.322 Application of Porous Anodic Films

Porous coatings are widely used to enhance the appearance and

improve the corrosion resistance of fabricated alumium parts.
Building, automotive, and aircraft industries provide the largest
markets. Coatings can be colored by several methods. One is
the impregnation of the pores with dyes such as azo dyes or
anthraqu inone derivatives (Tajima, 1970). Precipitation of
inorganic pigments in the ~res; e.g., iron hydroxides, is
another commercial process. Widely used for the coloration of
architectural panels is electrolytic deposition of metal. By
cathodic polarization of freshly anodized aluminum workplaces
in appropriate plating baths, Pres are partially filled with

. .

1
W.T. Evans lul,ooox

Fragments of Anodic Oxide

Figure 5.9C

and that aluminum ions moving across this layer precipitate

anion-rich, microcrystalline cell wall material by reaction with
the electrolyte (Thompson et al., 1978). Electron micrographs
of cells produced at high voltage show, indeed, a distinctly
different morphology of the outer “shell” and the inner pore
wall material-(Figu~e 5 .9C, from Wefers and Wallace, i97@
see also Thompson et al., 1978). This interesting concept
would give the term “duplex film” a new definition. The .
similarity to the dual-layer texture of hydrothermally formed
surface films may k more than coincidental. These, too,
consist of a zone of pure oxide produced by a solid-state
reaction and an outer layer resulting from a solution-deposition
process, as was shown in Chapter 5.2.
K. Wefers 15,000X
Many questions remain unanswered. These authors consider the
relationship &tween the electrolyte composition and the
unique, regular cell texture the most impoflant puzzle to be Cells of Anodic Oxide Advancing into Metal
solved. Figure 5.10

73
Alcoa Laboratories

bismuth, copper, nickel, and other metafs. So-called integral

color prmesses use specific electrolytes and voltagelcument
control to produce color centers (Frenkel-type defects) in the
anodic oxide (Tajima, 1970; Wefers and Wallace, 1976).
Pigmentation of the anodic films can be achieved by the use of
afloys containing constituents which do not oxidize in the
coatings process.

The protection given to the metal by thick porous oxides is

greatly improved hy a hydrothermal treatment of the coatings in
boiling water or steam. In the “sealing” process, the pore wall
material reacts with water to form gelatinous boehmite and
amorphous oxide hydroxide:

Alx(anion)Y + H20 ~ AIOOH + acid

A1203 + H20 ~ 2 AIOOH

The reaction proceeds Wrpendiculm to the pre walls,

eventually tilling the pore with aluminum oxide hydroxide
(Hoar and Wood, 1962; Wefers, 1973). The morphology of
sealed oxides is shown schematically y in Figure 5.8 and in the
electron micrographs of Figure 5.1 I.

Interesting applications for anodic oxides were proposed by

Grubitsch et al. (1961), Honicke ( 1983), and Rai and
Ruckenstein (1975). Gmbitsch et al. suggested the use of
porous oxides as microporous filters for the separation of
isotopes, vims, or proteins. Honicke, and Rai and Ruckenstein
used anodic oxides as catalysts and as substrates for
catalytically active metals. Dehydration of alcohols and
~,- ‘ -= -’-- -“””- J isomerization of alkenes are examples of reactions which xe
catalyzed byanodic oxides (see also Cockeet al. 1984).
F. A. Mozelewskl 15,000X

There are many more commercial applications for prous

Cross Section of Sealed Anodic Oxide anodic coatings. Their discussion would exceed the scope of
Figure 5,11 this monograph.

74

—
 Oxides and Hydroxides of Aluminum

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