Ca-Cd – Co-Zr

668 Pages·1993·24.154 MB·English

by  B. Predel (auth.), O. Madelung (eds.)

Ca-Cd 1
Ca-Cd (Calcium-Cadmium)
Phase diagram
The first (cid:150) more preliminary (cid:150) investigations (thermal analysis) have been performed by Donski [08Don1]
(see Hansen et al. [58Han1]). These results could be corrected to some extent by Nowotny [46Now1] (but see
also Iandelli [49Ian1]). At last Bruzzone has determined the whole phase diagram very carefully using
thermal, metallographic and X-ray methods [72Bru1].
The results obtained were redrawn by Moffatt [78Mof1] and also were taken as a basis for Fig. 1. It
should be mentioned that the existence of the intermediate phase Ca Cd could be confirmed by Merlo
3 2
[76Mer1].
Fig. 1. Ca-Cd. Phase diagram.
Crystal structure
Crystallographic data for intermediate phases are listed in Table 1 (see also Villars et al. [85Vil1]).
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Ca-Cd 2
Table 1. Ca-Cd. Crystal structure and lattice parameters of intermediate phases.
Phase Structure Type a [nm] b [nm] c [nm] Ref.
Ca Cd tetr Gd Al 0.8864 0.8020 72Bru1, 78Mof1
3 2 3 2
CaCd fcc CsCl 0.3839 49Ian1, 72Bru1
α-CaCd hex MgZn 0.5993 0.9654 46Now1, 72Bru1
2 2
β-CaCd orth CeCu 0.4924 0.7548 0.8450 72Bru1
2 2
Ca Cd hex Ag Gd 1.3465 0.9787 72Bru1
14 51 51 14
CaCd cub Cd Y 1.5680 72Bru1
6 6
References
08Don1 Donski, L.: Z. Anorg. Chem. 57 (1908) 193.
46Now1 Nowotny, H.: Z. Metallkde. 37 (1946) 31.
49Ian1 Iandelli, A.: Rend. Seminar. Fac. Sci. Univ. Cagliari 19 (1949) 133.
58Han1 Hansen, M., Anderko, K.: "Constitution of Binary Alloys", New York: McGraw-Hill Book
Comp., 1958.
72Bru1 Bruzzone, G.: Gazz. Chim. Ital. 102 (1972) 234.
76Mer1 Merlo, F.: J. Less-Common. Met. 50 (1976) 275.
78Mof1 Moffatt, W.G.: "Binary Phase Diagrams Handbook", Schenectady, N.Y.: General Electric
Comp. 1978.
85Vil1 Villars, P., Calvert, L.D.: "Pearson’s Handbook of Crystallographic Data for Intermetallic
Phases", Metals Park, Ohio: Am. Soc. Metals, Vol. 2, 1985.
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Ca-Ce 1
Ca-Ce (Calcium-Cerium)
Phase diagram
Using metallographic methods Zverev has found that in the Ca-Ce system a miscibility gap is existing in
the liquid state [55Zve1]. After some adjustments, Gschneidner jr., Gschneidner jr. et al. and Gschneidner et
al. [61Gsc1, 74Gsc1, 87Gsc1] have published a phase diagram, which is taken to draw Fig. 1.
Fig. 1. Ca-Ce. Phase diagram.
References
55Zve1 Zverev, G.L.: Dokl. Akad. Nauk SSSR 104 (1955) 242.
61Gsc1 Gschneidner jr., K.A.: "Rare Earth Alloys", Princetown, N.Y.: D. Van Norstrand Co. Inc.
1961, p. 133.
74Gsc1 Gschneidner jr., K.A., Verkade, M.E.: "Cerium-Calcium" in: Selected Cerium Phase
Diagrams, IS-RIC-7, Rare Earth Information Center, Iowa State Univ., Ames, IA, 1974.
87Gsc1 Gschneidner jr., K.A., Calderwood, F.W.: Bull. Alloy Phase Diagrams 8 (1987) 511.
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Ca-Cl 1
Ca-Cl (Calcium-Chlorine)
Phase diagram
Staffanson has applied solubility measurements and differential thermal analysis to determine the phase
equilibria in the subsystem Ca-CaCl [59Sta1]. The results were taken to draw Fig. 1. For earlier work see
2
Eastman et al. [50Eas1] and Cubicciotti et al. [49Cub1].
Fig. 1. Ca-Cl. Phase diagram of the CaCl -Ca subsystem.
2
References
49Cub1 Cubicciotti, D., Thurmond, C.D.: J. Am. Chem. Soc. 71 (1949) 2149.
50Eas1 Eastman, E.D., Cubicciotti, D.D., Thurmond, C.D.: "Temperature-Composition Diagrams
of Metal-Metal Halide Systems", in: "The Chemistry and Metallurgy of Miscellaneous
Materials: Thermodynamics", L.L. Quill (ed.), Natl. Nucl. Energ. Ser. IV-19B, New York:
McGraw-Hill Book Comp., 1950.
59Sta1 Steffansson, L.-I.: "The Physical Chemistry of Metals in their Molten Halides", Thesis,
Univ. of London, 1959.
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Ca-Co 1
Ca-Co (Calcium-Cobalt)
Phase diagram
Hashimoto et al. have investigated by dilatometric and magnetic measurements Co-rich Ca-Co-alloys in
respect to the (α-Co)(cid:150)(ε-Co) phase transformation [37Has1]. The results, reviewed by Hansen et al.
[58Han1], are given in Fig. 1. Obviously there are no intermediate phases in this system as Rolland et al.
have found from melting experiments [80Rol1].
Fig. 1. Ca-Co. Partial phase diagram.
References
37Has1 Hashimoto, U.: Nippon Kinzoku Gakkaishi 1 (1937) 177.
58Han1 Hansen, M., Anderko, K.: "Constitution of Binary Alloys", New York: McGraw-Hill Book
Comp., 1958.
80Rol1 Rolland, G., Saindrenan, G., Milor, J.N., Bezin, S.: J. Less-Common Met. 72 (1980) 23.
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Ca-Cr 1
Ca-Cr (Calcium-Chromium)
Phase equilibria or intermetallic phases are not known in this system (Venkatraman et al. [85Ven1]).
References
85Ven1 Venkatraman, M., Neumann, J.P.: Bull. Alloy Phase Diagrams 6 (1985) 335.
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Ca-Cs 1
Ca-Cs (Calcium-Caesium)
Phase diagram
Klemm et al. have found that there is a broad miscibility gap in the liquid state in the Ca-Cs system [67Kle1].
Moffatt has redrawn the phase diagram, which is taken as a basis for Fig. 1 [87Mof1]. Pelton has reviewed
this system [85Pel1].
Fig. 1. Ca-Cs. Phase diagram.
References
67Kle1 Klemm, W., Kunze, D.: Proc. Intern. Symp. on Alkali Metals, London, Chem. Soc. Spec.
Publ. No. 22, 1967, 3.
85Pel1 Pelton, A.D.: Bull. Alloy Phase Diagrams 6 (1985) 168.
87Mof1 Moffatt, W.G.: "Binary Phase Diagrams Handbook", Schenectady, N.Y.: General Electric
Comp. 1987.
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Ca-Cu 1
Ca-Cu (Calcium-Copper)
Phase diagram
Since 1906, the phase equilibria of the Ca-Cu system have been investigated several times: Stockem
[06Sto1], Donski [08Don1], Baar [11Baa1] (thermal and metallographic analysis), Haucke [40Hau1] and
Nowotny [42Now1] (X-ray diffraction experiments), Schumacher et al. [30Sch1] (microscopic
observations, electrical resistivity measurements), and Ssyromjatnikov [31Ssy1].
A reliable revision of the phase equilibria has been performed by Bruzzone [71Bru1] (differential thermal
analysis as well as X-ray diffraction experiments). The results of this latter work have been taken by
Chakrabarti et al. [84Cha1] to develop an assessed phase diagram, which was taken as a basis for Fig. 1. Phase
equilibria determined by Kuznetsov et al. [80Kuz1] (differential thermal analysis, metallographic and X-ray
diffraction investigations) at the Cu-rich side of the system are similar to those given in Fig. 1 on page 6.
Fig. 1. Ca-Cu. Phase diagram.
Crystal structure
Crystallographic data for intermediate phases are listed in Table 1.
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Ca-Cu 2
Table 1. Ca-Cu. Crystal structure and lattice parameters of intermediate phases.
Phase Structure Type a [nm] b [nm] c [nm] Ref.
Ca Cu orth Ca Cu 0.6126 0.4161 1.453 82For1
2 2
α-CaCu orth α-CaCu 3.880 0.4271 0.5894 81Mer1
β-CaCu mon β-CaCu 1.947 0.4271 0.5880 81Mer1
α = 94.3°
CaCu hex CaCu 0.5074 0.4074 71Bru1
5 5
Thermodynamics
By direct mixing calorimetry Sommer et al. have determined the enthalpy of mixing for liquid Ca-Cu
alloys at 1120 K and 1225 K [83Som1]. The results are plotted in Fig. 2. There is no remarkable
temperature dependence of ∆HL. For concentrations >77 at% Cu, ∆HL values have been calculated using
an association model.
To determine thermodynamic activities for liquid alloys vapor pressure measurements have been
performed by Bogoslovsky et al. [69Bog1] and Bykov et al. [83Byk1]. The results presented by the latter
authors seem to be the more reliable ones and have been taken to draw Fig. 3.
The Gibbs free energy of formation for CaCu has been determined by Chiotti [64Chi1] (measure-
5
ments of hydrogen pressure in equilibrium) and Notin et al. [79Not1] (EMF measurements). From the
temperature dependence of the resulting values the enthalpy of formation can be calculated. Djamshidi et
al. measured calorimetrically the enthalpy of formation for CaCu [80Dja1]. The most reliable value
5
seems to be that found by Djamshidi et al. (solution calorimetry) [80Dja1]:
∆HS =−7.8(13)J mol-1.
CaCu5
This value agrees relatively well with the results from Chiotti et al. [64Chi1], whereas the value obtained
by Notin et al. [79Not1] is much more exothermic (−10.5 J mol−1).
From measurements performed by Chiotti et al. [64Chi1] there results a value for the entropy of
formation amounting to
∆SS =−0.6(10)J mol-1K-1
CaCu5
(see Chakrabarti et al. [84Cha1]).
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Ca-Cu 3
Fig. 2. Ca-Cu. Enthalpy of mixing of liquid alloys at 1125 and 1225 K. Solid line: experimental, broken line:
calculated.
Fig. 3. Ca-Cu. Thermodynamic activities for liquid alloys at 1273 K.
References
06Sto1 Stockem, L.: Metallurgie 3 (1906) 148.
08Don1 Donski, L.: Z. Anorg. Chem. 57 (1908) 193.
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