Gases and Carbon in Metals

73 Pages·1984·17.696 MB·English

by  E. Fromm, W. Hehn, H. Jehn, G. Horz

FACHINFORMATIONSZENTRUM ENERGIE · PHYSIK · MATHEMATIK GMBH KARLSRUHE
Physik Oaten
Physics Data
Gases and Carbon in Metals
(Thermodynamics, Kinetics, and Properties)
Pt. XXI: Group I B Metals (1)
Copper (Cu)
E. Fromm, W. Hehn, H. Jehn, G. Horz
Max-Planck-lnstitut tor Metallforschung, lnstitut tur
Werkstoffwissenschaften, Stuttgart, Germany
1984 Nr. 5-21 ISSN 0344-8401
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PREFACE
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The Editors
CONTENTS
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Introduction 2
~
Copper-Hydrogen . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . • • 5
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Copper-Deuterium 10
Copper-Tritium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Copper-Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
. . . .. . . . . . . . . . . . . . . . . ' . . . . . . . . . . . . . . . . . .
Copper-Oxygen 11
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Copper Alloys-Hydrogen 21
Copper Alloys-Deuterium 23
Copper Alloys-Carbon 24
Copper Alloys-Oxygen 25
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Literature 33
INTRODUCTION
General '
This issue is part of a series of data on "Gases and Carbon in Metals" which supplements the data compilation in
the book "Gase und Kohlenstoff in Metallen" (Gases and Carbon in Metals), edited by E. Fromm and E. Geb
hardt, Springer-Verlag, Berlin 1976. The present survey includes results from papers published after the copy
deadline and recommends critically selected data. Furthermore it comprises a bibliography of relevant litera
ture.
Each part of this series refers to metals belonging to one or severals groups of the periodic table of elements
and compiles data and references on the interaction of the metals with hydrogen, carbon, nitrogen, and oxygen.
System of Presentation
The sequence of the metals treated within one issue is the same as in the corresponding groups of the periodic
table. For each element the information is given in two parts. In a first section data are listed and in a second sec
tion the relevant literature is compiled. For each element, firstly data on binary systems are presented, starting
with hydrogen and followed by carbon, nitrogen, oxygen, and rare gases. Within· one metal-metalloid system
the data are listed under topics such as solubility, solubility limit, dissociation pressure of compounds, vapour
pressure of volatile oxii::les, thermodynamic data, diffusion, transport parameters (effective valence, heat of
transport), permeation of gases through metals, gas absorption and gas desorption kinetics, compound forma
tion kinetics, precipitation kinetics, and property changes. The definition of some topics referring to equilibria in
metal-gas systems is given in Table I.
Following the data on binary systems, the data ofternary systems are presented, beginning with systems which
contain one metal and two gases or one gas and carbon and continuing with systems with two metals and one
gas or carbon. Within a ternary 'System the topics are arranged in the same way as in binary systems.
The literature at the end of the data sheets for a given metal and its alloys includes not only the bibliography of
papers containing quantitative results listed in the data sheets but also further selected papers that give either
qualitative information on gases or carbon in metals or additional data that do not fit the relatively narrow scope
of the present series. The content of each paper referred to is characterized by the full title, the chemical sym
bols of the systems treated and additional keywords (see Table II).
Form of Presentation
The data are presented in the form of tables giving the quantitative formulae and the range of validity by listing
limiting values of parameters such as temperature, pressure, and concentration. If in addition to the data in the
book "Gases and Carbon in Metals" one or more new sets of values or relations are available, the relation
recommended by the present authors is indicated by an asterisk. This relation is either the critically selected
value from the mentioned book or one of the new formulae or an average from critically selected data. The for
mulae, which are presented in the simplest form, are taken directly from the literature, are calculated from rela
tions given in the papers concerned, or are evaluated from experimental results and further informations. They
refer to the reaction equations preceding the formulae. The thermodynamic data are always based on 1 g
atom H, C, N, or 0 or 1/2 mol H2, N2, or 02.
- 2 -
In the case of data on constitution and thermochemistry an attempt has been made to recommend a com
plete set of mutually consistent equations. From this point of view for well investigated systems the revision of
the whole set of data. established in the book "Gases and Carbon in Metals". due to minor deviations of a single
new value is only the justified. if the new set of data is able to describe the thermodynamics of the whole system
more reliably.
Units, Keywords, and Citation
The units used in this series are. in contrast to the units used in the book "Gases and Carbon in Metals", taken
from the SI-system. Table Ill gives symbols and units for some quantities that are frequently used.
Log xis written for log oX; the solid, liquid, or gaseous state of metals or compounds is indicated by (s). (I). or (g).
1
e. g. Al(s) solid aluminium; H(in Al(s)) denotes hydrogen dissolved in solid aluminium.
The topics in the data sheets are normally given in full Ieng ht, whereas in the literature section the keywords are
abbreviated. The meaning of the keywords used is given in Table II.
A reference number after the data indicates that the formula or values are taken directly from the paper cited.
after being converted into SI-units. If one or more reference numbers are set into brackets. the data are eva
luated on the basis of results or curves published in the corresponding papers. The publications cited have an
additional number. the documentaUon number (Doc. No.), under which the papers or their abstracts are filed in
the documentation on gases and carbon in metals at the Max-Planck-lnstitut tor Metallforschung, lnstitut tor
Werkstoffwissenschaften, Stuttgart (West Germany).
Table I
TOPIC DEFINITION
c. o.
solubility concentration of H, N. or rare gases in solid or liquid metals or alloys
in equilibrium with gaseous H2, N2, 02, rare gases. or gas mixtures such as
H20/H2• NH3/Hi. CH4/H2• This concentration depends on gas pressure and
temperature (p-T-c equilibria). The equation for the solution reaction of hydrogen
in solid metals, e. g., is 112 H2 - H(in Me(s)).
solubility limit maximum concentration of H. C. N, or 0 in solid or liquid metals or alloys in
(terminal solubility) equilibrium with a solid or liquid second phase (13 phase); it depends only on
+
temperature. The equation of this reaction is. e. g., MeH(s) - H(in Me(s)) Me(s).
dissociation pressure pressure of dissociation or decomposition of a solid or liquid compound Cl3 phase);
it depends on temperature. In the present data sheets this pressure corresponds
to the gas partial pressure of the three phase equilibrium a solution + 13 + gas
+
phase. The equation of this reaction is, e. g., MeH(s) = Me(s) 1/2H2.
+ +
plateau pressure gas partial pressure of the three phase equilibrium phase I phase II gas.
+
where phases I and II may be solid or liquid, e. g. o-Me(s) 13-Me(s).
+ +
Me(s) Me(I). or Me(I) MeH(I).
- 3 -
Table II
KEYWORDS TOPICS
canst constitution, phase diagrams of binary and ternary systems
phases and compounds
sol solubility of gases in metals in equilibrium with the gas phase (p-T-c)
solubility limit
th. dyn thermodynamic data of solution, compound formation, etc.
diff diffusion, thermo-and electrotransport
permeation
kin kinetics of gas absorption or desorption
compound formation kinetics
ppt precipitation processes in supersaturated solutions
prop(m) mechanical properties (hardness, yield strength, yield stress, tensile strength,
uniform elongation, reduction in area, elongation at fracture, ductile-brittle
transition temperature, etc.)
prop(p) physical properties (electrical resistivity, critical temperature of superconductivity,
magnetic susceptibility, lattice parameter, density, viscosity, internal friction, etc.)
Table Ill Symbols and Units used
QUANTITY SYMBOL UNITS USED
Temperature T K
Pressure p Pa (1 Pa - 1 N · m2 - 0.0075 torr)
Mole fraction x
Gibbs standard reaction energy J · mor1 (1J · mor1 .... 0.239 cal · mor1)
Standard reaction enth~lpy J · mor1
Standard reaction entropy J · K-1 · mor1
(reference state for gases:
p = 1.01325 x 105 Pa= 1 atm;
for dissolved atoms:
x = 1 (ideal dilute solution))
Gas constant R 8.314 J · K1 • mor1
Diffusion coefficient D
Permeability p molecules · m·1 · s·1 • Pa·'h
Reaction rate v
- 4 -
Cu- COPPER
Cu-H Copper-Hydrogen
-
system Topic Formula Ref.
-
cu-H solubility H in Cu(s)
*
log x = 1/2 log PH - 4. 77 - 2426/T (B, 9, 10,
8 2
5 197)
(770 - 1356 K, Pff < 1x10 Pa)
2
log XH = 1/2 log I1f - 4.94 - 2179/T (10)
2
5
(770 - 1356 K, % < 1x10 Pa)
2
log x = 1/2 log PH - 4.64 - 2868/T (9)
H 2 5
(867 - 1300 K, Pg < 1 x 10 Pa)
2
log XH = 1/2 log PH2 - 4. 21 - 2004/T 197
5
(1007 - 1343 K, PH < 1x10 Pa)
2
H in Cu ( 1)
* log x = 1/2 log PH - 4. 35 - 2250/T (B, 10)
8 2
(1356 - 1823 K)
log XB = 1/2 log PH2 - 4.25 - 2393/T (6)
5
(1284 - 1923 K, Pa < lx10 Pa)
2
log x = 1/2 log PH - 4.36 - 2250/T 8
8 2
(1356 - 1598 K)
- 5 -
Data
System Topic Formula Ret.
Cu-H solubility H in Cu(l)
log XH = 1/2 log PH2 - 4.31 - 2280/T 7
5
(1373 - 1573 K, PH < 1 x 10 Pa)
2
= (10)
log x 1/2 log p - 4.37 - 2200/T
82
H 5
(1379 - 1820 K, PH < 1x10 Pa)
2
=
Cu-H thermodyn. 1/2 H H(in Cu(s))
2
data
* t:iGo = 46440 + 43.40 T (B,9,10,
197)
(770 - 1356 K)
t:iGo = 41720 + 46.65 T 10
(770 - 1356 K)
6Go = 54900 + 40. 90 T (9)
(867 - 1300 K)
!:iGo = 38370 + 32. 71 T 197
(1007 - 1343 K)
1/2 H2 = H(in Cu(l))
* 6Go = 43070 + 35.36 T (B, 10)
(1356 - 1823 K)
6Go = 45810 +33.40 T ( 6)
(1284 - 1923 K)
- 6 -