52 J.G. SERENI
z.O
&
E 2
E 20
T(K)
8 12
I I i i i i |
/o'
'Jm : CMdT oO
o,, °
~I o C)
m oOO
,- oo
Celo3 T ; ° /
~o ~ i ' Ce A[ 2
0 2 4
T(K)
10
Fig. 30. Internal magnetic energy of CeI% and CeA12 as obtained from specific heat (C) ) and neutron scattering ( • and • ), after Peyard (1980).
LOW-TEMPERATURE BEHAVIOUR OF CERIUM COMPOUNDS 53 distribution. In this case, it was found that Ce has to change its valence to fit into the actual AV/V value (Sereni 1982b).
The most significant conclusions that we extract from our systematic study are:
(i) C e - C e compression, D < 2r(Ce3+), does not necessarily induce valence in- stability. Cubic local symmetry with a high coordination n u m b e r is required for a strong f electron hybridization. Specific heat results show, from the large 7LT and 7m- values and the entropy deficit, that the f conduction band hybridization is important anyway.
(ii) The ferromagnetic behaviour of Ce is related to its local symmetry (it only occurs in noncubic systems) and with the C e - C e spacing (there is a reduced range for D between a b o u t 4.1 A and 3.65 A).
(iii) The cubic c o m p o u n d s where Ce has a quartet as C F ground state, undergo quadrupolar transitions at or about TN.
(iv) The characteristic temperature Tm of the nonmagnetically ordered c o m p o u n d s has two different ranges of values: T m < 10 K (HF) and T m > 100 K (IV).
(v) Specific heat measurements show that spin fluctuations are present in IV compounds with large 7 values ( >/50 mJ K - 2/Ce atom) and small volume contrac- tions (AV/V <<, 1.5%).
As we have stated, the a m o u n t of experimental data on Ce compounds had already reached the "critical mass" to allow us, at present, to correlate some apparently independent systems. However, as the experimental information grows, the need for a more thorough condensation of the information becomes apparent. In that sense we see that the literature is richer in theoretical reviews (see, e.g., Newns and Read 1987, Fulde 1988, Schlottmann 1989) than in experimental ones. It is therefore necessary to have more experimental reviews concerning, e.g., the magnetic and transport proper- ties, in order to increase the applications of the theoretical models to real systems.
Acknowledgements
The author is indebted to Drs J.P. K a p p l e r and G.L. Nieva, who have been closely involved with m a n y experimental aspects of these studies. He gratefully acknowledges Ms N. Badino for reading this review, Ms R. Cohen and A. Cohen for typing the manuscript, and Ms M. Rangone for drawing the illustrations.
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Handbook on the Physics and Chemistry of Rare Earths, Vol. 15 edited by K.A. Gschneidner, Jr. and L. Eyring
© Elsevier Science Publishers B.V., 1991
Chapter 99
R A R E E A R T H C A R B I D E S
GIN-YA ADACHI, NOBUHITO IMANAKA and ZHANG FUZHONG Department of Applied Chemistry, Osaka University, Suita, Osaka 565, Japan
Contents
1. Introduction 62
2. Binary rare-earth-carbon phase diagram 63
2.1. Two prototypes of binary rare-earth-carbon phase diagrams 63
2.2. General characteristics of phase diagrams of the light-lanthanide~zarbon systems 67 2.3. General characteristics of phase diagrams of the heavy-lanthanide~carbon systems 69 2.4. Phase relationship and formation of carbides in the En C and Yb-C systems 73
2.5. Formation of the scandium carbides 76
2.6. Summary of the formation of the binary rare earth carbides 77
3. Crystal structures of the binary rare earth carbides 85
3.1. Crystal structure of the RC 2 compounds 85
3.2. Crystal structure of the R2C 3 compounds 87
3.3. Crystal structure of the R15C~9 compounds 91
3.4. Crystal structures of the R3C and R2C compounds 93
3.5. Structure of the first-stage intercalation compounds EuC 6 and YbC 6 96
3.6. Structure of the Sc4C 3 compound 96
3,7. Summary of the crystal structure of the binary rare earth carbides 97 4. Pseudobinary system: mixed rare earth carbides and solid solutions of the rare earth carbides
and the actinide carbides 99
4.1. Mixed rare earth dicarbides (R 1_~R;)C2 with different structures 99
4.2. Mixed rare earth carbide (R 1 _~Rx)15C19 102
4.3. Solid solutions of the rare earth carbides and the uranium carbides 102
4.4. Solid solutions (Ca, Y)C z and (Th, Y)zC 3 105
5. Thermodynamic properties of binary rare earth carbides 105
5.1. Thermodynamic stability of gaseous rare earth carbides 105
5.2. Thermodynamic properties of the solid state rare earth carbides 113
6. Ternary rare-earth-X-carbon phase diagrams and ternary carbides 115
6.1. Phase diagrams and formation of ternary carbides in R B-C systems 115
6.2. The R-(A1, Ga, In, TI) C systems 126
6.3. The R-(Si, Ge, Sn, Pb)-C systems 127
6.4. The rare-earth-(iron, cobalt, nickel)-carbon systems 131
6.5. Ternary rare-earth-metal-platinum-group-metal carbon systems 148
6.6. Ternary R - M n (Tc and Re) carbides 150
6.7. The rare-earth-metal-(chromium, molybdenum, tungsten) carbon
systems 152
7. Carbides of rare-earth-metal (oxygen, nitrogen, hydrogen, halogens) 153
7.1. Rare earth oxycarbides 153
61