Table Of ContentIRON-
Binary Phase Diagrams
Ortrud Kubaschewski
Binary Phase Diagrams
With a Preface by
Oswald Kubaschewski
With 103 Figures and 3 Tables
1982
Springer-Verlag Berlin Heidelberg GmbH
Dr. rer.-nat. Ortrud Kubaschewski-von Goldbeck
Lehrstuhl fUr Metallurgie der Kernbrennstoffe
und Theoretische Hlittenkunde
RWTH Aachen
Kopernikusstrasse 16
D - 5100 Aachen
Federal Republic of Germany
ISBN 978-3-662-08026-9 ISBN 978-3-662-08024-5 (eBook)
DOI 10.1007/978-3-662-08024-5
Library of Congress Cataloging in Publication Data
Kubaschewski, Ortrud, 1922-. Iron - binary phase diagrams.
Bibliography: p. 1. Iron. 2. Binary systems
(Metallurgy). 3. Phase diagrams. 1. Title.
TN693.17K84 1982 669'.961 82-10263
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Preface
At the official dinner of a· meeting in May 1939, I was seated next to
Max Hansen. When I congratulated him on the well deserved success of
his "Aufbau der Zweistoff-Legierungen", he smiled: "yes, it was a struggle
with the hydra, and so it has taken me seven years", meaning that whenever
he had thought to have finished the phase diagram of a particular system,
new evidence would turn up like the new heads of the Greek monster.
There is no need to point out the importance of assessed phase diagrams
to metallurgists or even anyone concerned with the technology and applica
tion of metals and alloys. The information contained therein is fundamental
to considerations concerning the chemical, physical and mechanical properties
of alloys. Hansen's German monograph was followed by a revised English
edition in 1958 with K. Anderko and the supplements by R.P. Elliott (1965) and
F.A. Shunk (1969). All those who have made use of these volumes will admit
that much diligent labour has gone into this work, necessary to cope with the
ever increasing number of publications and the consequent improvements.
In view of the large amount of experimental evidence it has become
advisable to subdivide the subject matter and to deal with the binary phase
diagrams of individual metals in turn. Mrs Kubaschewski had already elaborated
the phase diagrams of a number of metals of interest to reactor technology
for the International Atomic Energy Agency and then turned her attention
to iron. I have been in the position to bear witness to the painstaking work
that she has put into the construction of such diagrams shown on the fol
lowing pages. A vast amount of experimental, often conflicting, evidence
had to be sifted. Thoughts had to be exerted on the position and the limits
of nearly every phase, the thermodynamic conditions being always ob
served. And all this is presented in an improved form on so-called 'raster
paper'. The phase boundaries are based mainly on the results of con
ventional experimental methods, but there are certain boundaries which
are better ascertained by thermochemical calculation. The author has taken
this into account.
It may well be asked whether in these days of thermochemical calcula
tions of phase diagrams (e.g. CALPHAD), one might not store the relevant
heat and entropy values of each phase on a computer and let this do the
working out. This is certainly true for the evaluation of ternary and higher
phase diagrams. However, the binary systems should be treated separately,
namely in the way chosen here. In the earlier days when we developed
the thermochemical method for describing equilibrium diagrams (in which,
incidtmtally, Miss von Goldbeck was also involved), William Hume-Rothery
would protest by saying: "you may be able to correct certain phase
boundaries by calculation but you cannot predict the existence of inter
metallic phases". This is correct, at least at the present state of knowledge
concerning the causes of chemical stability of phases. One may add that
thermochemical calculations cannot be based on the results of calorimetric
and Gibbs energy measurements alone, in particular when the diagrams
are more complicated. So I used to reply to Hum-Rothery that the real
value of the thermochemical method lay in the possibility of extrapolating
v
Preface from the binary into the multicomponent ranges, whereas in the binaries
it is merely used for adjustments. The problem of predicting phases that
do not appear in the binary border systems becomes less and less prominent
the greater the number of component elements there are per system. The
reason for this is the increasing influence of the entropy of mixing which
favours the stability of the disordered solutions and thus depresses (T!1S
term!) the appearance of any ordered phase to lower, in practice less
important, temperatures.
I usually distinguish between 'phase diagrams' and 'equilibrium diagrams',
the former being derived wholly from conventional measurements, the
latter from thermochemical calculations. One may safely say that the present
series of binaries approaches the status of equilibrium diagrams. Hence,
I submit that the author has coped with the hydra and expect that many
of these diagrams will remain valid in detail for quite a number of years
to come.
Aachen, May 1982 Oswald Kubaschewski
Acknowledgements
The author is most grateful to Prof. Dr. O. Knacke who offered her the
hospitality of his laboratory and his assistance in many ways, to Prof.
Dr. Drs. h.c. O. Kubaschewski for continued interest, advice and, in particular,
for meticulously checking the English, to Dipl. Ing. R. Steffen for critically
reading the manuscript, to Mrs. G. Stusser and Mrs. E. Klein who made such
an excellent job in drawing the raster diagrams and to the Commission of
the European Communities, Division Steel, without whose financial assistance
this work could not have been accomplished.
Ortrud Kubaschewski
VI
Contents
Notation IX
Introduction . 1
Fe-Ag Iron-Silver. 3
Fe-Li (Na, K) Iron-Alkaline Metals 4
Fe-AI Iron-Aluminium. · (Figs. 1-3) 5
Fe-Am Iron-Americium . 10
Fe-As Iron-Arsenic · (Fig. 4) . 10
Fe-Au Iron-Gold · (Fig. 5). 13
Fe-B Iron-Boron · (Fig. 6) . 15
Fe-Ba Iron-Barium 18
Fe-Be Iron-Beryllium · (Figs. 7, 8) 18
Fe-Bi Iron-Bismuth. 22
Fe-C Iron-Carbon · (Figs. 9-12) 23
Fe-Ca Iron-Calcium . 26
Fe-Cd Iron-Cadmium 26
Fe-Co Iron-Cobalt · (Figs. 13, 14). 27
Fe-Cr Iron-Chromium · (Figs. 15, 16). 31
Fe-Cu Iron-Copper · (Figs. 17-20) 35
Fe-Eu Iron-Europium 38
Fe-Ga Iron-Gallium . · (Figs. 21-24) 38
Fe-Ge Iron-Germanium · (Fig. 25) 43
Fe-H Iron-Hydrogen · (Figs. 26, 27) . 46
Fe-D Iron-Deuterium · (Fig. 28) 48
Fe-T Iron-Tritium · (Fig. 28) 49
Fe-Hf Iron-Hafnium. · (Fig. 29) 50
Fe-Hg Iron-Mercury. · (Fig. 30) 52
Fe-In Iron-Indium · (Fig. 31) 53
Fe-Ir Iron-Iridium · (Fig. 32) 55
Fe-La Iron-Lanthanum. · (Fig. 33) 57
Fe-Mg Iron-Magnesium . · (Fig. 34) 59
Fe-Mn Iron-Manganese . · (Fig. 35) 61
Fe-Mo Iron-Molybdenum · (Figs. 36-38) 64
Fe-N Iron-Nitrogen. · (Figs. 39, 40) . 67
Fe-Nb Iron-Niobium. · (Fig.41) 70
Fe-Ni Iron-Nickel · (Figs. 42-44) 73
Fe-O Iron-Oxygen . · (Fig.45) 79
Fe-Os Iron-Osmium . · (Figs. 46, 47) . 82
Fe-P Iron-Phosphorus. · (Figs. 48, 49) . 84
Fe-Pb Iron-Lead. · (Figs. 50, 51) . 87
Fe-Pd Iron-Palladium · (Fig. 52) 88
Fe-Pt Iron-Platinum. · (Fig. 53) 91
VII
Contents Fe-Pu Iron-Plutonium · (Figs. 54, 55) . 94
Fe-R Iron-Rare Earth Metals (Figs. 56-68) 96
Fe-Ce Iron-Cerium · (Figs. 56, 57) . 97
Fe-Pr Iron-Praseodymium. (Fig. 58) 100
Fe-Nd Iron-Neodymium · (Fig. 59) 101
Fe-Pm Iron-Promethium · (Fig. 60) 103
Fe-Sm Iron-Samarium · (Fig. 61) 104
Fe-Gd Iron-Gadolinium . · (Fig. 62) 106
Fe-Tb Iron-Terbium . · (Fig. 63) 108
Fe-Dy Iron-Dysprosium. · (Fig. 64) 110
Fe-Ho Iron-Holmium · (Fig. 65) 111
Fe-Er Iron-Erbium · (Fig. 66) 113
Fe-Tm Iron-Thulium. · (Fig.67) 114
Fe-Lu Iron-Lutetium. · (Fig. 68) 116
Fe-Re Iron-Rhenium · (Fig. 69) 118
Fe-Rh Iron-Rhodium · (Fig. 70) 120
Fe-Ru Iron-Ruthenium . · (Fig. 71) 123
Fe-S Iron-Sulphur . · (Figs. 72, 73) . 125
Fe-Sb Iron-Antimony · (Figs. 74, 75) . 128
Fe-Sc Iron-Scandium · (Fig. 76) 131
Fe-Se Iron-Selenium · (Fig. 77) 133
Fe-Si Iron-Silicon · (Figs. 78, 79). 136
Fe-Sn Iron-Tin · (Figs. 80, 81) . 139
Fe-Sr Iron-Strontium 142
Fe-Ta Iron-Tantalum · (Figs. 82, 83) . 143
Fe-Tc Iron-Technetium. · (Figs. 84, 85) . 146
Fe-Te Iron-Tellurium · (Fig. 86) 148
Fe-Th Iron-Thorium . · (Fig. 87) 150
Fe-Ti Iron-Titanium . · (Figs. 88-90) 152
Fe-TI Iron-Thallium. 156
Fe-U Iron-Uranium. · (Figs. 91, 92) . 157
Fe-V Iron-Vanadium · (Figs. 93-95) 160
Fe-W Iron-Tungsten · (Figs. 96, 97) . 164
Fe-Y Iron-Yttrium . · (Fig.98) 168
Fe-Yb Iron-Ytterbium · (Fig.99) 170
Fe-Zn Iron-Zinc · (Figs. 100, 101) . 172
Fe-Zr Iron-Zirconium · (Figs. 102, 103) . 175
Appendix Table 1. Physico-chemical properties of the elements 179
Table 2. Structural types of elements and compounds 183
Table 3. Numerical differences between the Internatio-
nal Practical Temperature Scale of 1968 and
that of 1948 185
VIII
Notation
For the convenience of the reader, the following drawing indicates the
various lines that are being used for the description of the phase boundaries
in the diagrams of this monograph:
assessed
uncertain
secondary reaction
- . - . - . - magnetic transformation
°C i.e. gap between horizontal and vertical line
indicates: (solid) solubility unknown
a (metal) pertaining to pure metal
a-metal pertaining to solution in metal
IX
Introduction
This monograph is concerned with the binary equilibrium diagrams of iron
with all the elements of the Periodic Chart except the halogens. Innumer
able publications concerning these diagrams are available, and here is an
attempt to correlate and assess the literature data. The monograph may be
to some extent incomplete, but it is hoped to be a help to all who have to
deal with the metallurgy of iron and steel and even metallurgists in general.
The procedure of compilation has been as follows. The starting point
has naturally been the classic work of Hansen [A] with its successors
published by Elliott [B] and Shunk [C]. The thermochemical tables of
Hultgren et al. [D] have also frequently been consulted. From there on
(say, 1967) the literature has been searched and recorded well into 1981.
A series of reviews edited by Ageev, 1968 to 1977 [E], !;las been a great
help, in particular with regard to those Russian publications on which to
lay hands had been difficult. Since the number of pUblications concern
ing the binary phase diagrams of iron is astronomic, a strict selection of
references had to be made so as not to overload the text. Earlier publica
tions (if not quoted) may be traced via the compilations just mentioned.
Some of the recent publications may have been overlooked but others, if
they are just repetitive, have been disregarded deliberately.
The melting point of iron accepted here is 1,536°C, and the transforma
tion temperatures are 911 °C and 1,392 °C, and these temperatures apply
to all the phase diagrams to follow, original results being consequently
adjusted where necessary. The ferromagnetic transformation has its maxi
mum at 767-771 °C although the corresponding heat capacity versus tem
perature hump is spread over a much wider range. These temperatures as
well as those for the other elements (see Table 1, Appendix) are based
on the International Practical Temperature Scale 1968, revised 1975 and
denoted IPTS-68. Secondary reference points have been assessed and listed
by Crovini et al. [F]. Other melting and transformation points are from
Hultgren's compilation [D] (updated to IPTS-68, where necessary) and from
more recent re-determinations quoted in the original literature. Unfortunate
ly, many investigators do not state the temperature scale they have used.
Table 1 (Appendix), in addition to the transition temperatures, also lists
the relative atomic mass, crystal structure and density of the elements.
The arrangement of the systems is the alphabetical order in terms of
chemical symbols of the component elements except for the alkali metals
(appearing under 'Alk') and the rare earth metals (Fe-R), and here Eu and
Yb are exceptions in that they are listed in the normal alphabetical sequence.
The Fe-R systems are discussed in the following sequence: Ce, Pr, Nd,
Pm, Sm, Od, Tb, Dy, Ho, Er, Tm, Lu (see 'Contents').
It should be noted that the pertinent references are listed immediately
at the end of the text for every system.
Care has been taken to mention in the texts the modes of alloy prep
aration and the purity of the component metals as quoted by the in
vestigators. Unless stated otherwise, % always indicate weight percent.
-SI units are used where applicable.
1
Introduction Compared with the earlier compilations, the following advances are
claimed. Phase boundaries could be pursued to lower temperatures thanks
to improved experimental methods and longer times of annealing. Partly,
new data for the magnetic properties are included in the text and in the
diagrams. The emphasis is still on results obtained by conventional methods.
However, results of thermochemical calculations are taken into consider
ation. (For a discussion of the thermochemical approach, see for instance
[G].) This is particularly useful, no, indispensable when it comes to the extra
polation of solid solubilities to lower temperatures or to the assessment
of solidus curves which are prone to slow equilibration (e.g. Cr-Fe).
It is generally more difficult to assess accurately the temperature and
composition of solid-solid transformations because the differences in Gibbs
energy, representing 'driving force', may be very small and the rates of
equilibration consequently very slow. This is particularly true when a com
pound exhibits two or three modifications of the Laves structures. These
are so similar in co-ordination that little energy is needed for the re-arrange
ment of the atoms. (See also [H].)
Only stable phases are included in the diagrams-with a few exceptions
(e.g. Fe-C, Fe-N). Martensitic transformations, metallic glasses and the
so-called phases are not included but are occasionally mentioned in the
(U
text. In future works of this nature, it may be desirable to say more about
metastable phases. However, since their number is infinite, it is difficult
to see where to draw the line.
Concerning the notation of phases, the one accepted by the majority
of authors is also used here, but it should be borne in mind that it is some
times controversial. Agreement will eventually be reached by general con
sent but is not a matter for the present compiler. Greek letters are used
to denote solid solutions. Intermetallic phases are designated by Greek letters
or stoichiometric compositions or both.
Since the present author has been asked to continue this work by up
dating the binary phase diagrams of iron whenever desirable, she would
be grateful for any reprints of new investigations pertaining to the subject
matter of this monograph.
The following references pertain to the above but will also appear in
the following texts with their Latin capitals.
References
A Hansen, M.; Anderko, K.: Constitution of Binary Alloys. New York: McGraw
Hill 1958
B Elliott, R.P.: Constitution of Binary Alloys, First Supplement New York:
McGraw-Hill 1965
C Shunk, F.A.: Constitution of Binary Alloys, Second Supplement New York:
McGraw-Hill 1969
D Hultgren, R.; Orr, R.L.; Anderson, P.D.; Kelley, K.K.: Selected Values of
Thermodynamic Properties of Metals and Alloys. New York: Wiley 1963 and
Supplements
E Ageev, N.V. (Ed.): Phase Diagrams of Metallic Systems 1968-1977, Acad. Sci.
USSR, Moscow 1979
F Crovini, L.; Bedford, R.E.; Moser, A.: Extended List of Secondary Reference
Points. Metrologia 13 (1977) 197
G Kubaschewski, 0.; Barin, I.: Phase Equilibria in Condensed Systems. Pure
Appl. Chern. 38 (1974) 469
H Elliott, R.P.: Trans. ASM 53 (1960) 321
2
