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Book Review Volume 3 A Electronic and Magnetic Properties of Metals and Ceramics (Part I). Edited by K. H. J. Buschow

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reducing the scope of use of the book. An emphasis could
have been placed on the limitations which are not so much
a lack of will or skill to tit data, but of suitable instrumentation. time, or amenable reacting systems. Obtaining data of
sufficient quality to justify pursuit of calculation of the pressure and temperature derivatives of A V * and A H * respectively is seldom possible. Again, although this would have
broadened the purpose of the book, it would have benefited
from the inclusion of a section devoted to interpretation of
derived parameters, and explaining how this contributes to
understanding the chemical processes being studied. However, all the treatments experimentalists require are collected
together here in one convenient source with each method
easily accessible and referenced. This alone merits a place for
this book in chemistry libraries and in the personal collections of thermodynamicists and kineticists.
Colin D.Hubbard
Department of Chemistry
University of New Hampshire
Durham, N H (USA)
Materials’ Science and Technology. A Comprehensive Treatment. Series editors: R. W Cahn, P. Huusen, and E. J.
Kuinzer. VCH Verlagsgesellschaft, Weinheim/VCH Publishers. New York.
Volume 3 A: Electronic and Magnetic Properties of Metals
and Ceramics (Part[). Edited by K. H. J. Buschow, 1991.
XIV. 641 pp.. hardcover D M 430.00.--ISBN 3-527268 16-2/0-89573-691-8
Volume 4: Electronic Structure and Properties of Semiconductors. Edited by W. Sciztoter, 1991. XVI, 603 pp., hardcover DM 430.00. - ISBN 3-527-2681 7-0/0-89573-692-6
Volume 7: Constitution and Properties of Steels. Edited by
F: B . Pickering, 1992. XVI, 824pp., hardcover
DM 430.00. --ISBN 3-527-26820-010-89573-695-0
Volume 15: Processing of Metals and Alloys. Edited by R. W
Cuim, 1991. XIV, 628 pp., hardcover D M 430.00.--ISBN
The new IS-volume series “Materials Science and Technology” covers the properties. manufacture, and processing
of materials, and their specific areas of use. It brings together
the know-how of chemists, physicists, and engineers, and
shows how fundamental research and applications-orientated research can be made to interact most effectively and
The first volume to appear, in 1991, was Volume 5, “Phase
Transformations in Materials”, and has already been reviewed in the context of the series as a whole (Angew. Ciiem.
1992, 104, 245; Atipw.. Clzem. Int. Ed. Engf. 1991,30, 1521).
U p to now Volumes 2A, 3 A, 4. 5A. 7,9,14, and 15 have been
published, and four of these (3 A, 4. 7, 15) are reviewed here.
During the planning of Volume 3 (“Electronic and Magnetic Properties of Metals and Ceramics”) it already became
clear that it would hardly be possible to treat all the necessary aspects and phenomena of this subject in a single volume, and it was decided to have two volumes. The second of
these (Vol. 3 B) has not yet appeared, but the chapter titles
have already been given as: “Magnetic Properties of Spinel
Ferrite”; “Electronic Properties of Liquid, Amorphous, and
Quasicrystalline Alloys”; “Invar Alloys” ; “Magnetic
Recording Materials”; “Hydrogen in Pure Metals and Solid
Solutions”; “Ternary Hydrides” ; “Soft Magnetic Metallic
Materials” ; “Permanent Magnet Materials”; ”Magnetostrictive Materials”.
The first chapter of Volume 3 A deals with the calculation
of electronic structures. The ability to perform such calculations for the highly complex systems of interest to materials
science has come with the availability of very fast computers.
Chapter 2 is concerned with the magnetooptical properties
of metals, alloys, and compounds. After an introduction to
the fundamentals (theory and measurement techniques),
some special materials are described and their properties
discussed (alloys and compounds of 3 d metals. materials
based on lanthanoids and actinoids, and mixed 3d-4f and
3d-5f compounds). Chapter 3 is devoted to electron transport properties of “normal” metals, including the behavior
of electrons in magnetic fields, electrical resistivity, the Hall
effect. thermoelectric power, etc. Chapter 4 covers superconductivity, with discussions of the Bardeen-Cooper~4chrieffer (BCS) and Ginzburg-Landau (GL) theories; the oxide
high-temperature superconductors are also described, of
course. In Chapter 5 the focus of interest turns to the magnetic properties of metallic systems, then Chapter 6 deals
with ultrathin films and superlattices (epitaxy). The book
concludes with Chapter 7 on Fermi surfaces in strongly coupled electronic systems. This, like Chapter I , treats the topic
in a fundamental way, and includes instructive comparisons
of experimental results with band structure calculations.
Volume 4 (“Electronic Structure and Properties of Semiconductors”) presents the basic concepts of modern semiconductor physics. starting from the fundamentals of ideal
semiconductors and continuing through the physics of defects and heterostructures (artificial semiconductors) to
amorphous semiconducting systems. Chapter 1 (“Band Theory Applied to Semiconductors”) and Chapter 2 (“Optical
Properties and Charge Transport”) are of an introductory
nature. They cover the basic theory needed to understand the
formation of energy bands in solids with three-dimensional
structures and structures of lower dimensionality and in
amorphous materials, the investigation of band structures by
measuring intrinsic optical properties. charge transport, and
nonlinear optics. Chapter 3 deals with the simplest types of
point defects, the intrinsic defects that occur in crystal structures where some atoms have changed their positions or are
missing altogether; essentially one is concerned here with
vacancies, interstitial sites, and sites at which anions or
cations have been changed (“antisites”). As examples of different types the chapter discusses silicon (an elemental semiconductor), ZnSe (a 11-VI semiconductor), and GaAs (a
111-V semiconductor). In Chapter 4 (“Deep Centers in Semiconductors”) the discussion moves on from intrinsic defects
to doped materials (e.g.. with nitrogen and transition metals
as dopants in silicon or compound semiconductors, chalcogens in silicon, and DX centers--in which D represents a
donor and X an unknown effect--in the mixed crystal system A1,Ga -,As). Silicon and gallium arsenide are nowadays the most important semiconducting materials used in
the manufacture of electronic and optoelectronic components, and Chapter 5 (“Equilibria, Nonequilibria, Diffusion,
and Precipitation”) is concerned particularly with these materials and the behavior of their point defects (whether intrinsic or produced by doping). Moving on from point defects, Chapters 6 (“Disiocations”) and 7 (“Grain Boundaries
in Semiconductors”) deal with these more extended types of
defects and their effects on the physical properties of semiconductor materials, from both the phenomenological and
theoretical standpoints. Newer manufacturing techniques,
including the now highly developed methods of epitaxial
growth, make it possible to produce artificial materials and
components with special properties that depend on the presence and concentration of interhces. Chapter 8 gives the
reader an insight into basic concepts whereby one can describe the structural characteristics of such interfaces and
understand how they confer special electronic properties on
these materials. The tendency towards increasing miniaturization has also resulted in a move from two-dimensional to
one-dimensional systems. Lithographically produced heterostructures such as those of the system GaAs-Al,Ga, -.As
are suitable for studying the quantum Hall effect in a quasione-dimensional electron gas, as described in Chapter 9
(“The Hall Effect in Quantum Wires”).
For nearly twenty years now there has also been much
interest in the possibilities of using amorphous silicon (e.g.,
for photovoltaic devices). However. the pure phase contains
such a high concentration of defects that it is unsuitable for
electronic components. It was accidentally found during the
manufacture of amorphous silicon from silane that the concentration of defects could be considerably reduced by introducing hydrogen to saturate the proportion of free silicon
valences that are present, and this proved to be the breakthrough needed. The interesting material thus obtained is
described in Chapter 10 (“Material Properties of Hydrogenated Amorphous Silicon”). Lastly Chapter 11 contains
an up-to-date review of the doping of silicon with 3 d elements (see also Ch. 5). The unusual and interesting physical
properties that this gives are. however. accompanied by
some disadvantages. Aspects of the behavior of 3 d elements
in the host structure that are discussed here are solubility,
diffusion, electronic structure (at high temperatures), and
separating out by nucleation.
Silicon is undoubtedly one of the most important materials in the present “silicon age”. A metallic material that still
continues to be of great importance to human activities and
is produced in vast quantities worldwide is the system that
we loosely call “steel”, and this is the subject of Volume 7
(“Constitution and Properties of Steels”).
The world production of steel in 1989 was 783 million
tonnes. The plentiful natural occurrence and availability of
iron ores is enough in itself to guarantee this class of materials a long-term future, let alone the unique properties that
make steel suitable for such a wide variety of uses. The subject of metallography covers many aspects: chemical constitution, phases, alloys, equilibria and nonequilibria between
phases, structure and microstructure, precipitation processes, and many more. Chapter 1 (“Microstructure and Transformations in Steel”) introduces the basic tools for understanding the subject: phase diagrams for the iron-carbon
system, microstructures such as cementite, ferrite. pearlite,
martensite, and bainite, precipitation reactions in ferrite and
austenite, etc. Chapter 2 (“Structure-Property Relationships in Steels”) is concerned mainly with microstructures
(dimensions of the matrix-grain structure, crystallographic
texture, and grain size distribution). This provides the essential key to understanding and controlling the mechanical
properties. Chapter 3 (”Steelmaking and Non-Metallic Inclusions”) describes steel production, then Chapter 4 (“Processing- conventional Heat Treatments”) deals with the
heat treatment stages (annealing, normalizing, quenching,
tempering. case-hardening) that are used to control the microstructure and phase composition. Thermomechanical
processing, which is the subject of Chapter 5, also has an
important role in determining the microstructure and phase
composition of steels, and the same applies to cold-working
and work-hardening, as described in Chapter 6. The factors
influencing the malleability of steels and methods for controlling it are discussed in Chapter 7. The following chapters
are devoted to steels with special properties and uses. as
follows. Chapter 8: high strength low-alloyed steels (build-
ing and construction steels with small amounts of vanadium,
niobium, or titanium); Chapter 9: steels with medium to
high carbon contents ( 2 0.30 wt.% C), used for railway
tracks, for example; Chapter 10: heat-treated forging steels
(0.45 wt.%C. 1.5 wt.% Mn); Chapter 1 I : creep-resistant
steels for applications at high pressures and temperatures;
Chapter 12: stainless steels containing I 1 wt.% or more of
chromium; Chapter 13: tool steels with especially high
strength and hardness; Chapter 14: high temperature resistant “superalloys” with iron, nickel, or cobalt as the main
constituent; Chapter 15: cast iron. i.e. iron-based alloys containing C. Si. Mn. s, and P as the main alloying elements,
with Al, Bi, and Sb as minor additives, and further additives
to influence the matrix structure (Mo, Cu, Ni, Sn) and/or the
graphite morphology (Mg, Ce. Ti). To complete and round
off Volume 7, Chapter 16 deals with the welding of steel and
Chapter 17 with surface treatments.
Volume 15. the last of the four reviewed here. is entitled
”Processing of Metals and Alloys”. Practical aspects are
closely linked to results from basic research, but the main
emphasis throughout is on applications. The first task facing
the editor of this volume, R. W. Cahn, was to decide which
topics to include and which to leave out, since this was to be
a concise treatment. Among the aspects excluded was mechanical shaping; Cahn explains this in the preface as follows: “I took the view that these topics have become part of
the province of mechanical engineering. of continuum mechanics in particular (just as extractive metallurgy is virtually
part of chemical engineering today)”. In Chapter 1 (“Solidification Processing”) the various types of structures that can
result from solidification (dendritic. cellular, planar, single
phase or multiphase, etc). are described and are discussed in
the context of particular process conditions. Important variables influencing the outcome include the solidification rate
and the heat flow. Chapter 2 is devoted exclusively to rapid
solidification processes. Methods range from those based on
spraying and on falling droplets to atomization and the
quenching of molten films. Chapter 3 is concerned with the
surface treatment of metals and alloys using laser beams, e.g.
from a C 0 2 laser. Chapter 4 deals with powder metallurgy
(the production. characterization, granulation, and sintering
of powders, and molding at high temperatures). Chapter 5
describes how high energy ball-milling can be used not only
for uniform mixing but also to produce special alloys not
obtainable in any other way. For example, oxide particles
can be finely dispersed in metallic systems to give oxide dispersion strengthened (ODS) alloys. This method can be used
to significantly increase the mechanical strength of an alloy
matrix, as the mobility of dislocations is thereby reduced.
Chapter 6 is concerned with ion implantation and mixtures
produced using ion beams. The particular interest of this
method is that it can be used to form metastable alloys not
obtainable i n other ways, new compositions and structures,
and (not least) new intermediate phases. From Chapter 7
(“The Epitaxy of Metals”) and Chapter 8 (“Metallic Multilayers”) it becomes evident that the uses of epitaxy and multilayer methods are by no means confined to the semiconductors field, but also extend to metals and alloys. Chapter 9
deals with recrystallization and recovery (the ”healing” of
defects), and Chapter 10 with the measurement and control
of texture. Other aspects that arise here are the growth and
migration of grain boundaries, nucleation, deep drawing and
molding, and ferromagnetic anisotropy. The last three chapters of Volume 15 are concerned with special processes and
materials. Chapter 11 (“Electrodeposition of Metals and Alloys”) describes new developments in the surface treatment
of metallic materials (coating, etc.). Chapter 12 (“Solidifica-
tion Processing under Microgravity”) examines the topical
question of whether the modification of solidification processes under weight loss conditions (microgravity) can be
usefully applied to make new materials or to optimize properties. Chapter 13 (“Cluster Assembly of Nanophase Materials”) describes the preparation, characterization, and properties of materials in which a very high proportion of the
atoms are in “grain boundary” type situations (i.e. with “ordered” regions and “grain” dimensions of less than 100 nm).
Despite the fact that the “Materials Science and Technology” series involves over 200 authors from all parts of the
world (about 50 in these four volumes alone), the editors
have succeeded well in guiding their contributions so as to
present a unified overall picture. This in itself is an achievement that should not be underestimated. Moreover, the
quality of the contributions is very high, and represents the
current state of the art in every case.
It was certainly a good decision on the part of VCH to
publish this series. The time was ripe for it; to quote the
preface: “This bold new field (Materials Science and Technology) is now in need of an all-inclusive reference source-one that meets the demands of theorists and practitioners
from every area of materials research, in research institutes
and universities as well as in industrial research and development”.
I t is this reviewer’s conviction that materials science and
fundamental research are not opposites but form a unified
whole. It is not sufficiently recognized that the problems
and questions of basic research are very close to those of
materials science, as this series impressively demonstrates.
The volumes published so far deserve to reach a wide readership. and one can confidently predict that this assessment
will also hold for the series as a whole.
Riidiger Kniep
der Technischeri Hochschule Darmstadt (FRG)
Kinetics and Mechanism of Reactions of Transition Metal
Complexes. 2nd Edition. By R. G. Wilkins. VCH Verlagsgesellschaft, Weinheim/VCH Publishers, New York, 1991.
XV, 465 pp., hardcover D M 148.00.--ISBN
3-52728253-X/1-56081-125-0; Softcover D M 68.00.--ISBN
3-527-28389-711-56081 -1 98-6.
The author has thoroughly revised and updated the first
edition of this book published in 1974, thereby maintaining
its position as one of the classic textbooks dealing with the
reaction mechanisms of transition metal complexes. Noticeable changes from the first edition mainly involve recent
developments in this area, such as the application of photochemical, NMR, and high pressure techniques to elucidate
the intimate details of reaction mechanisms. In addition,
more information on biological aspects of coordination
chemistry (bioinorganic kinetics) is given and a few examples
from organometallic chemistry are included. With this book
the author has fulfilled a serious need for a textbook dealing
with inorganic reaction mechanisms that is suitable for students up to graduate level.
The approach used in the revised edition is similar to that
of the first edition. The first three chapters are devoted to the
acquisition of experimental data in order to determine the
empirical rate law, and the formulation of theoretical mechanisms that are in agreement with the experimental findings.
In these chapters many chemical examples are used to illustrate the meaning of the formal mathematics. The following
four chapters present a systematic treatment of the mechanisms of substitution, oxidation-reduction and isomerization reactions, as well as the reactivity of coordinated ligands
in transition metal complexes. The last chapter includes a
systematic summary of the mechanistic features of complexes of different transition elements. Each chapter contains a
detailed list of references (between 96 and 370) and selected
bibliography (between 2 and 18), and a set of stimulating and
illustrative problems (between 10 and 34). Hints to solutions
of these problems are given in a separate chapter.
This is the first mechanistic textbook in which the application of pressure as a kinetic parameter in the study of transition metal complexes is described at an appropriate level.
Significantly, the author states on page 65 that “the rate law
gives the composition of the activated complex (transition
state)-nothing more nor less--but yields no clue about how
it is assembled”. He emphasizes on page 110 that “a careful
compilation of as many kinetic parameters as possible can
lead to overwhelming support for a mechanism”; thus all
activation parameters (AH’, AS’, and A V ” ) should be considered. This general philosophy will find strong support
from students and researchers in this area.
Highlights of the textbook include an attractive balance
between theoretical aspects and real chemical systems, a
compact but complete treatment of ligand substitution processes, and a well presented chapter on oxidation-reduction
reactions. The numerous references to biochemically-related
systems will attract the attention not only of inorganic
chemists, but also of biochemists interested in the role of
transition metal complexes in biological systems. The book
really has something for everyone, and should be well accepted by students.
To summarize, the publication of this textbook has fulfilled the longstanding need for such an updated book in the
general area of inorganic reaction mechanisms. The experience of the author in research and teaching on the kinetics
and mechanisms of reactions of transition metal complexes
has resulted in a well-balanced and well presented textbook.
The presentation is of a high technical quality, and the text
is easy to follow. The price of the paperback copy is very
reasonable and should fit the average student budget. It is
highly recommended to students and researchers in this field.
Ralph Wilkins will receive a sincere appreciation from many
inorganic kineticists for providing this thoroughly revised
Rudi win Eldili
Institut fur Anorgankche Chemie
der Universitat Witten/Herdecke (FRG)
A Wandering Natural Products Chemist. (Series: Profiles,
Pathways, and Dreams.) By I(.Nukanishi. American Chemical Society, Washington, D.C.. 1991. XXIII, 230 pp.,
hardcover $24.95. --ISBN 0-8412-1775-0
Seventy Years in Organic Chemistry. (Series: Profiles. Pathways, and Dreams.) By 7: Nozoe. American Chemical Society, Washington, D.C., 1991. XIX, 267 pp., hardcover
$24.95. --ISBN 0-841 2-1 769-6
With the appearance of the autobiographies of Nakanishi
and Nozoe the series “Profiles, Pathways, and Dreams” is
now half completed. Looking at the half-time score in this
22-volume series, the verdict so far is that the excellent first
impression has not diminished in any respect. Gradually the
pieces of this mosaic are beginning to fit together to form a
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