ELECTROCRYSTALLIZATION

Fundamentals of Nucleation
And Growth
ELECTROCRYSTALLIZATION
Fundamentals of Nucleation
And Growth

by

Alexander Milchev
Institute of Physical Chemistry
Bulgarian Academy of Sciences
Sofia, Bulgaria

KLUWER ACADEMIC PUBLISHERS

NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW
eBook ISBN: 0-306-47552-9
Print ISBN: 1-4020-7090-X

©2002 Kluwer Academic Publishers

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For my family,
for my mother and my sister
and for my teacher Academician R.Kaischew
Contents

Preface ix

1. THERMODYNAMICS OF ELECTROCHEMICAL
NUCLEATION 1

1.1 General concepts 1

1.2 Nucleation work 11
1.3 Theory of mean sepration works 46
1.4 Atomistic considerations 68

2. KINETICS OF ELECTROCHEMICAL NUCLEATION 83

2.1 General formulation 83

2.2 Classical theory of stationary nucleation 89
2.3 Atomistic theory of stationary nucleation 106
2.4 Non-stationary nucleation 128

3. STOCHASTIC APPROACH TO NUCLEATION 165

3.1 Temporal distribution of clusters 165

3.2 Spatial distribution of clusters 177

4. ELECTROCHEMICAL CRYSTAL GROWTH 189

4.1 Growth of an individual crystal face 189

4.2 Growth of a hemispherical liquid drop 203
viii

5. MASS ELECTROCRYSTALLIZATION 219

5.1 General concepts 219

5.2 Progressive and instantaneous nucleation without overlap 220
5.3 Progressive and instantaneous nucleation with overlap 228

Author Index 255

Subject Index 263

Preface

“Electrocrystallization is a particular case of a first order phase

transition” and “Electrocrystallization is a particular case of
electrochemical kinetics” are two statements that I have heard and read many
times. I do not like them for a simple reason: it is annoying to see that the
subject to which you have devoted more than 30 years of your life may be
considered as a “particular case”. Therefore, I decided to write this book in
which Electrocrystallization is the main subject.
To become competent in the field of Electrocrystallization one should
possess knowledge of Electrochemistry, Nucleation and Crystal Growth,
which means knowledge of Physical Chemistry, Physics and Mathematics.
That is certainly difficult and in most cases those who study
Electrocrystallization are either more electrochemists, or more physical
chemists, or more physicists, very often depending on whom has been their
teacher. Of course, there are scientists who consider themselves equally
good in all those fields. Very frequently they are, unfortunately, equally bad.
The difference is essential but strange enough, it is sometimes not easy to
realize the truth immediately.
Being a pupil of the Bulgarian Crystal Growth School I feel myself closer
to Nucleation and Crystal Growth than to Electrochemistry and this has left
an imprint on my book. For instance, I did not always follow the
Electrochemical Convention. Just a simple example: the cathodic current and
the cathodic overpotential are defined as positive quantities. I do apologize
to my readers for that but frankly speaking my sense of guilt is not too strong
because many others do that also.
It was not my aim to include in this book everything that may concern the
electrochemical phase formation. Instead, I tried to write a comprehensible
introduction to the fundamentals of the initial stages of
x

Electrocrystallization, which are dominated by nucleation and growth of the

first clusters of the new phase. For the sake of simplicity, I have considered
the electrochemical formation and growth of single component, solid and
liquid phases. The electrochemical deposition of alloys, the formation of gas
bubbles, the growth of compact galvanic coatings, as well as metal
electrodissolution are subjects beyond the scope of this book. To put it
briefly, the book does not contain all that one should know of
Electrocrystallization to ensure a good success in this extremely interesting
field. However, I would like to believe that it does contain a lot of what one
could not be without.
I tried to offer a readable exposition of the topic, in simple terms,
providing a detailed theoretical description of the phenomena involved. In
some cases I have described also the most relevant aspects of the
experimental studies of electrochemical nucleation and growth, including
some important methods for acquiring and analyzing experimental results. I
think that the book is suitable not only for specialists in
Electrocrystallization but also for graduate and PhD students, as well as for
scientists from diverse but related fields like pure and applied
electrochemistry, electrocatalysis, corrosion, electrochemical adsorption,
materials science etc. Those who are interested in further reading could find
additional information on general Nucleation and Crystal Growth and on
Electrocrystallization in many excellent books and review articles. The
Reference List attached to this Preface contains only a small part of what is
worth reading.
It should be mentioned here that I have endeavored to cite everybody who
has made significant contributions to the field of Electrocrystallization.
However, I feel sure that many excellent papers have been missed and I
apologize to those colleagues who will not find their names in my
References. It is a matter of lacking information and/or poor memory, not of
bad intention. I should add that I always tried to cite the authors’ original
publications, even when they have been published a long time ago. I realize
that it would be more convenient for the reader to find the information
needed in some recent review of another author, in which those publications
have been mentioned and even discussed. This is, however, my way to pay
tribute to our predecessors.
Initially, I thought that it would not be difficult to describe the
fundamentals of Electrocrystallization and that I would be able to write the
book among other things. However, it turned out that “What is important
and what to miss?”, “What to say in details and what just to mention?” are
not at all easy questions to answer. Gradually, the book occupied all my time
including the weekends and even my summer vacation and this aroused the
merited rebuke of my family: my 9 years old son, my 19 years old daughter
 xi

and my dear wife. However, they succeeded to stand by me and I thank them
cordially for that. At this place somebody may say: “Yes, but he did the job
and he did it by the time fixed!” Not at all! I missed all deadlines.
Fortunately, the Publishers did not press me and I thank them very much for
their understanding.
I should say that I learned a good lesson from all this. On another
occasion I will first write the book and then fix a deadline, not vice versa as I
did this time. Well, I have one excuse for being late. This book had to be
written in a co-authorship with my colleague Prof. Benjamin Scharifker from
the University “Simon Bolivar”, Caracas, Venezuela. Due to unpredictable
circumstances, however, Ben was able to participate in the preparation of the
first 30 pages only and I had to do the rest alone. I thank him for his
gratuitous help.
There are many other people to whom I should express my sincere
gratitude and not because they helped me directly in the writing of this book
but because of the fruitful scientific contacts that we have had during my
work in the field of Electrocrystallization. For understandable reasons I
cannot mention the names of all of them. However, I should not miss my
younger co-workers Dr. E.Michailova, Dr. V.Tsakova and Miss I.
Lesigiarska; my colleagues Prof. S.Stoyanov, Prof. I.Markov, Prof.
D.Kaschchiev, Prof. D.Stoychev, Prof. I.Krastev, Prof. Chr.Nanev, Prof.
M.Paunov and Prof. I.Gutzov from the Institute of Physical Chemistry of the
Bulgarian Academy of Sciences (IPC, BAS); my colleagues Prof.
V.Bostanov, Prof. G.Staikov, Prof A.Popov and Prof. T.Vitanov from the
Central Laboratory of Electrochemical Power Sources, (CLEPS, BAS); Dr.
T.Chierchie (University of Bahia Blanca, Argentina), Prof. M.Sluyters-
Rehbach and Prof. J.H.Sluyters (University of Utrecht, The Netherlands);
Prof. Cl.Buess-Herman (Free University of Brussels, Belgium), Prof.
L.Heerman (Catholic University of Leuven, Belgium), Prof. G.Kokkinidis
and Prof. A.Papoutsis (University of Thessaloniki, Greece), Prof. K.Juettner
(University of Karlsruhe, Germany) and Prof. A.Danilov (Institute of
Physical Chemistry, Russian Academy of Sciences).
I owe a debt of gratitude to my elder colleagues from whom I learned a
lot: Prof. E.Budevski (CLEPS, BAS), Prof. Sir G.Hills (University of
Southampton, UK), Prof. R.Lacmann (University of Braunschweig,
Germany), Prof. W.J.Lorenz (University of Karlsruhe, Germany), the late
Prof. J.Malinowski (CLAPHOP, BAS) and the late Prof. S.Toschev (IPC,
BAS).
My most sincere gratitude is due to my teacher Academician R.Kaischew,
the founder (together with the late Prof. I.Stranski) of the Bulgarian School
of Crystal Growth. Without these two outstanding scientists this School
would not exist.
xii

Finally, I should not forget to thank also the Alexander von Humboldt
Foundation, Germany for the generous equipment support offered to my
research group. Some experimental results obtained with this equipment are
included in this book.
Last not least I thank my co-worker Mrs. L.Dragomirova for her precise
technical assistance during the preparation of this book.

Alexander Milchev

27 February 2002
Sofia

REFERENCES

(The asterisks mark the books and reviews in which Electrocrystallization is not or is only
partly concerned.)

1.* J.W.Gibbs, Collected Works, New Haven, 1928, Vol. 1.

2.* M. Volmer, Kinetik der Phasenbildung, Teodor Steinkopf Verlag, Leipzig,
Dresden, 1939.
3.* W.K. Burton, N.Cabrera and F.C.Frank, Phil.Trans.Roy.Soc., A243( 1951)299.
4.* Ja.I.Frenkel, Kinetic Theory of Liquids, Dover, New York, 1955.
5.* K.J.Vetter, Elektrochemische Kinetik, Springer-Verlag, 1961.
6. M.Fleischmann and H.R.Thirsk, in Advances in Electrochemistry and
Electrochemical Engineering, Ed. P.Delahay and C.Tobias, Interscience,
New York, 1962.
7.* J.P.Hirth and G.M.Pound, Condensation and Evaporation, Pergamon, Oxford,
1963.
8. J.O’M.Bockris and G.A.Razumney, Fundamental Asdpects of
Electrocrystallization, Plenum Press, New York, 1967
9.* A.C.Zettlemoyer (Editor), Nucleation, Dekker, New York, 1969.
10.* H.R.Thirsk and J.A.Harrison, A Giude to the Study of Electrode Kinetics,
Academic Press, London, 1972
11.* S. Toschev, in Crystal Growth: An Introduction, Ed. P. Hartmann, North-Holland
Publ. Co, 1973, p.1.
12.* B.B.Damaskin and O.A.Petrii, Elektrochimicheskaya Kinetika, Visshaya Shkola,
Moskow, 1975 (in Russian).
13. A.N.Baraboshkin, Electrocrystallization of Metals from Molten Salts (in Russian),
Moskow, Nauka, 1976.
 xiii

14.* A.C.Zettlemoyer (Editor), Nucleation Phenomena, Adv.Colloid.Interface Sci.,

Vol.7, 1977.
15.* S.Stoyanov, in Current Topics in Material Sciences, Ed. E.Kaldis, North - Holland
Publ. Co, Vol. 3, 1978.
16.* A.C.Zettlemoyer (Editor), Second Special Issue on Nucleation Phenomena,
Adv.Colloid. Interface Sci., Vol.10, 1979
17.* R.Kern, G.Le Lay and J.J.Metois, in Current Topics in Material Sciences, Ed. E.
Kaldis, North - Holland Publ. Co, 1979, Vol. 3, p.131.
18.* R. Kaischew, Selected Works, Bulg. Acad. Sci., 1980 (in Bulgarian).
19.* S.Stoyanov and D.Kashchiev, in Current Topics in Material Sciences, Ed.
E.Kaldis, North - Holland Publ. Co, 1981, Vol. 7, p.69.
20. E.Budevski, in Comprehensive Treatise of Electrochemistry, Vol.7, B.E. Conway,
J.O'M. Bockris, S.U.M. Khan, R.E.White (Eds.), Plenum Press, NY, 1983, 399.
21.* A.A. Chernov, Modern Crystallography, Vol.3, Springer, Berlin, 1984.
22. A.I.Danilov and Yu.M.Polukarov, Uspekhi.Khimii, 56(1987)1082.
23. B.R.Scharifker, in Electrochemistry in Transition from the 21th to the Century,
O.J.Murphy, S.Srinivasan and B.Conway (Eds.), Plenum Press, New York, 1992.
24.* I.Markov, Crystal Growth for Beginners, World Scientific, Singapore, 1995.
25.* I.Gutzow and J.Schmelzer, The Vitreous State, Springer, Berlin, 1995.
26. E.Budevski, G.Staikov and W.J.Lorenz, Electrochemical Phase Formation - An
Introduction to the Initial Stages of Metal Deposition, VCH, Weinheim, 1996.
27. Ju.D.Gamburg, Electrochemical Crystallization of Metals and Alloys, Janus-K,
Moskow, 1997
28. G.Staikov, W.J.Lorenz and E.Budevski, in Imaging of Surfaces and Interfaces
(Frontiers of Electrochemistry, Vol.5), 1999.
29.* D.Kashchiev, Nucleation: Basic Theory with Applications, Butterworth
Heinemann, Oxford, 2000.
30.* B.Mutaftschiev, The Atomistic Nature ofCrystal Growth, Springer, Berlin, 2001.