Alloys and Compounds of d-Elements with Main Group Elements. Part 2

447 Pages·2001·9.2 MB·English

by  T. OHOYAMA (auth.)

Ref. p. 59] 1.5.4 3d elements and C, Si, Ge, Sn or Pb 1
1 Magnetic properties of 3d, 4d, and 5d elements,
alloys and compounds
1.1 - 1.4 See Subvolume III/32A
1.5 Alloys and compounds of 3d elements with main group elements
1.5.1 - 1.5.3 See Subvolume III/32B
1.5.4 3d elements and C, Si, Ge, Sn or Pb
1.5.4.1 Introduction
Phase diagram and crystal structure
Phase diagrams of the binary systems have been revised in various aspects in the last decade [90m].
Solubility limits for 3d-elements and the intermediate phases are listed in Table 1.
In the Tables 2 – 11, the values of the lattice parameters given are those at room temperature
unless otherwise mentioned. The Pearson symbol [91v] and/or the space group are reported for those
structures to which no "Strukturbericht" symbols have been given.
Magnetic properties
Magnetic properties of alloys and compounds between 3d elements and 4B-group elements are being
investigated continuously. Only the alloys and compounds for which new data are available have
been listed in the Tables 2 – 11.
Arrangement of materials
The arrangement of the compounds and alloys is the same as in the former edition.
In the D0 (Fe Al) and L2 (Heusler alloy) types of crystal structure, the occupation of atomic
3 3 1
sites by atoms can be described in terms of four interpenetrating fcc sublattices with origins at
(0 0 0), (1/4 1/4 1/4), (1/2 1/2 1/2) and (3/4 3/4 3/4), which are designated in the current convention
as A, B, C, and D sublattices, respectively, though not completely unified. In the following this
designation is adopted. As for the D0 structure, the sublattices D, B and A + C consist of 4a, 4b and
3
8c sites, respectively, of the space group Fm3- O5. In the former edition LB III/19C (the figure on
h
p.1 and the following), these A, B, C and D sublattices were designated as B, C, D and A,
respectively.
Landolt-Börnstein
New Series III/32C
2 1.5.4 3d elements and C, Si, Ge, Sn or Pb [Ref. p. 59
Table 1. Solubility limits and intermediate phases in the binary systems of 3d elements with C, Si,
Ge, Sn or Pb. See [90m] unless otherwise stated. The phase diagrams are also represented in [92b].
The crystallographic data are compiled in [91v]. Neither metastable nor impurity-stabilized phases
are listed here except for the case of cementite, Fe C. If only phase names are listed, the composition
3
ranges are shown in atomic percentages of the respective 4B group elements. The terminal phases at
the 4B element side are not shown, sincee the 3d elements are almost insoluble. Crystal structures are
given in parentheses by the "Strukturbericht" type symbol [58p, 90m, 91v, 92b]. If these are missing,
the crystal system is indicated according to the following abbreviations. mono: monoclinic, ortho:
orthorhombic, rhomb: rhombohedral, hex: hexagonal, tetr: tetragonal, cub: cubic. See also [90E1] for
Co-Si and Co-Ge systems.
C Ti V Cr Mn
(b Ti) 0-0.6% (A2) HT (V) 0-4.3% (A2) (Cr) 0-0.3% (A2) (d Mn) 0-0.1% (A2) HT
(a Ti) 0-1.6% (A3) a V2C (ortho) Cr23C6 (D84) (g Mn) 0-13% (A1) HT
Ti2C (cub) b V2C (L'3) Cr7C3 (D101) (b Mn) 0-0.5% (A13) HT
TiC (B1) b 'V2C (hex) HT Cr3C2 (D510) (a Mn) 0-6.5% (A12)
V4C3–x (rhomb) e 13.5-24.5% (?) HT
VC (B1) Mn C (D8 )
23 6 4
V6C5 (mono) g) Mn3C (D011) HT
V8C7 (cub) Mn5C2 (mono) HT
Mn C (D10 )
7 3 1
Fe Co Ni
(d Fe) 0-0.4% (A2) HT (a Co) 0-4.2% (A1) HT (Ni) 0-2.7% (A1)
(g Fe) 0-9.06% (A1) HT (e Co) 0% (A3)
(a Fe) 0-0.096% (A2)
Fe C (D0 ) metastable
3 11
Si Ti V Cr Mn
(b Ti) 0-3.5% (A2) HT (V) 0-7% (A2) (Cr) 0-9.5% (A2) (d Mn) 0-2% (A2) HT
(a Ti) 0-0.5% (A3) V3Si (A15) Cr3Si (A15) (g Mn) 0-2.8% (A1) HT
Ti3Si (tetr) V5Si3 (D8m) b Cr5Si3 (?) HT (b Mn) 0-16.7% (A13) HT
Ti5Si3 (D88) V6Si5 (ortho) HT a Cr5Si3 (D8m) (a Mn) 0-6% (A12)
Ti5Si4 (tetr) VSi2 (C40) CrSi (B20) R 12-15.75% (rhomb)
TiSi (B27) CrSi2 (C40) n 16.2-18.75 (ortho)
TiSi2 (C54) b Mn3Si (D03) HT
a Mn Si (?)
3
Mn Si (tetr)
5 2
Mn Si (D8 )
5 3 8
MnSi (B20)
MnSi (tetr) b)
1.75–x
Landolt-Börnstein
New Series III/32C
Ref. p. 59] 1.5.4 3d elements and C, Si, Ge, Sn or Pb 3
Si Fe Co Ni
(g Fe) 0-3.2 (A1) HT (a Co) 0-16.4% (A1) HT (Ni) 0-15.8% (A1)
(a Fe) 0-19.5% (A2) (e Co) 0-18.4% (A3) b Ni Si (L1 )
1 4 2
a 10-22% (B2) Co Si (tetr) HT b Ni Si (mono) HT
2 3 2 3
a 10-30% (D0 ) b Co Si (?) HT b Ni Si (mono) HT
1 3 2 3 3
b Fe Si (hex) HT a Co Si (C23) g Ni Si (hex)
2 2 31 12
h Fe Si (D8 ) HT CoSi (B20) d Ni Si (ortho)
5 3 8 2
e FeSi (B20) CoSi2 (C1) q Ni2Si (hex) HT g)
z a FeSi2 (tetr) HT f) e 'Ni3Si2 (?) HT
z b FeSi2 (ortho) f) e Ni3Si2 (ortho)
NiSi (B31)
b NiSi (?) HT
2
a NiSi (C1)
2
Ge Ti V Cr Mn
(b Ti) 0-? (A2) HT (V) 0-4.5% (A2) (Cr) 0-11% (A2) (d Mn) 0-3.3% (A2) HT
(a Ti) 0-? (A3) V3Ge (A15) Cr3Ge (A15) (g Mn) 0-13% (A1) HT
Ti5Ge3 (D88) V5Ge3 (D8m) b Cr5Ge3 (D8m) HT (b Mn) 0-9% (A13) HT
Ti6Ge5 (ortho) V11Ge8 (ortho) a Cr5Ge3 (hex?) (a Mn) 0-1.5% (A12)
TiGe2 (C54) V17Ge31 (tetr) Cr11Ge8 (ortho) e Mn3Ge (D019) HT c)
CrGe (B20) e -Mn Ge (D0 ) c)
1 3 22
Cr11Ge19 (tetr) z Mn Ge with sub-phases
2.6
z and z (hex) HT [87K2]
1 2
k Mn Ge (ortho) [84O1]
5 2
c Mn Ge (B8 ) HT
2 2
h Mn Ge (D8 )
5 3 8
q Mn Ge (ortho) [84O2]
11 8
Fe Co Ni
(g Fe) 0-3.4% (A1) HT (a Co) 0-17.5% (A1) HT (Ni) 0-12% (A1)
(a Fe) 0-17.5% (A2) (e Co) 0-18% (A3) b Ni Ge (L1 )
3 2
a 10-22% (B2) Co Ge (A15?) HT g Ni Ge (?) HT
2 3 3
a 1 15.2-22% (D03) Co5Ge2 (hex) HT d Ni5Ge2 (hex) HT
e Fe3Ge (D019) HT a Co5Ge3 (ortho) Ni2Ge (C23)
e 'Fe3Ge (L12) HT b Co5Ge3 (B82) e Ni5Ge3 (B81) HT
b 33.5-41% (B81) CoGe (mono) e 'Ni5Ge3 (mono)
h 40.8-43.5% (B82) HT Co5Ge7 (tetr) Ni19Ge12 (mono) HT
Fe6Ge5 (mono) CoGe2 (ortho) g) Ni3Ge2 (B81) HT
FeGe (mono) HT NiGe (B31)
(B35) HT
(B20)
FeGe (C16)
2
Landolt-Börnstein
New Series III/32C
4 1.5.4 3d elements and C, Si, Ge, Sn or Pb [Ref. p. 59
Sn Ti V Cr Mn
(b Ti) 0-17.5% (A2) HT (V) 0-16% (A2) (Cr) 0-2% (A2) (d Mn) 0-10% (A2) HT
(a Ti) 0-12.5% (A3) "V3Sn" 20-21% (A15) (g Mn) 0-7% (A1) HT
Ti3Sn (D019) V2Sn3 (Cb=Mg2Cu) a) (b Mn) 0-11% (A13) HT
Ti2Sn (B82) (a Mn) 0-1% (A12)
Ti5Sn3 (D88) Mn3Sn (D019) d)
b Ti Sn (hex) HT Mn Sn (B8 ) e)
6 5 2 2
a Ti Sn (ortho) MnSn (C16)
6 5 2
Fe Co Ni
(g Fe) 0-0.8% (A1) HT (a Co) 0-2% (A1) HT (Ni) 0-10.6% (A1)
(a Fe) 0-9.2% (A2) (e Co) 0-0.2% (A3) Ni3Sn (hex) HT
Fe5Sn3 (B82) HT b Co3Sn2 (B81) HT Ni3Sn (D019)
Fe3Sn2 (rhomb) HT a Co3Sn2 (ortho) Ni3Sn2 (hex) HT
FeSn (B35) CoSn (B35) Ni3Sn2 (B81)
FeSn2 (C16) CoSn2 (C16) Ni3Sn4 (mono)
Pb Ti V Cr Mn
(b Ti) 0-16% (A2) HT insoluble insoluble insoluble
(a Ti) 0-4.2% (A3) Ti Pb
4
(D0 )
19
Ti Pb (?)
2
Fe Co Ni
insoluble insoluble insoluble
a) See also [94W2] for the composition.
b) Also designated as MnSi2–x or MnSi» 1.7.
c) See [88Y2] for the transition temperature.
d) Composition range is more Mn-rich than Mn Sn.
3
e) Also designated as Mn Sn .
7 4
f) Sometimes designated as a or b FeSi2, instead of z a or z b FeSi2.
g) See also [91C1] for space groups.
1.5.4.2 Ti and V alloys and compounds
Though progress is seen in thermal, structural, or electrical investigation and in high-pressure
synthesis of new compounds, rather few relevant magnetic data are available. The former includes
the identification of the symmetry of an ordered structure in a cubic, B1 (NaCl) type compound
TiC with carbon vacancy to be of the space group R3m [92T1], as well as new data on the lattice
0.59
constants of TiSn , which are referred to in a work on resistivity measurements and listed in Table 2.
2
Landolt-Börnstein
New Series III/32C
4 1.5.4 3d elements and C, Si, Ge, Sn or Pb [Ref. p. 59
Sn Ti V Cr Mn
(b Ti) 0-17.5% (A2) HT (V) 0-16% (A2) (Cr) 0-2% (A2) (d Mn) 0-10% (A2) HT
(a Ti) 0-12.5% (A3) "V3Sn" 20-21% (A15) (g Mn) 0-7% (A1) HT
Ti3Sn (D019) V2Sn3 (Cb=Mg2Cu) a) (b Mn) 0-11% (A13) HT
Ti2Sn (B82) (a Mn) 0-1% (A12)
Ti5Sn3 (D88) Mn3Sn (D019) d)
b Ti Sn (hex) HT Mn Sn (B8 ) e)
6 5 2 2
a Ti Sn (ortho) MnSn (C16)
6 5 2
Fe Co Ni
(g Fe) 0-0.8% (A1) HT (a Co) 0-2% (A1) HT (Ni) 0-10.6% (A1)
(a Fe) 0-9.2% (A2) (e Co) 0-0.2% (A3) Ni3Sn (hex) HT
Fe5Sn3 (B82) HT b Co3Sn2 (B81) HT Ni3Sn (D019)
Fe3Sn2 (rhomb) HT a Co3Sn2 (ortho) Ni3Sn2 (hex) HT
FeSn (B35) CoSn (B35) Ni3Sn2 (B81)
FeSn2 (C16) CoSn2 (C16) Ni3Sn4 (mono)
Pb Ti V Cr Mn
(b Ti) 0-16% (A2) HT insoluble insoluble insoluble
(a Ti) 0-4.2% (A3) Ti Pb
4
(D0 )
19
Ti Pb (?)
2
Fe Co Ni
insoluble insoluble insoluble
a) See also [94W2] for the composition.
b) Also designated as MnSi2–x or MnSi» 1.7.
c) See [88Y2] for the transition temperature.
d) Composition range is more Mn-rich than Mn Sn.
3
e) Also designated as Mn Sn .
7 4
f) Sometimes designated as a or b FeSi2, instead of z a or z b FeSi2.
g) See also [91C1] for space groups.
1.5.4.2 Ti and V alloys and compounds
Though progress is seen in thermal, structural, or electrical investigation and in high-pressure
synthesis of new compounds, rather few relevant magnetic data are available. The former includes
the identification of the symmetry of an ordered structure in a cubic, B1 (NaCl) type compound
TiC with carbon vacancy to be of the space group R3m [92T1], as well as new data on the lattice
0.59
constants of TiSn , which are referred to in a work on resistivity measurements and listed in Table 2.
2
Landolt-Börnstein
New Series III/32C
Ref. p. 59] 1.5.4 3d elements and C, Si, Ge, Sn or Pb 5
Survey
Properties Figure Table
TiSi a, b, c 2
2
V Si (T T)–1 (T), K(T), K(c ) 1, 2
3 1 g
VSi s (H), c (T) 3, 4
2 m m
Table 2. Supplement to Table 2 in LB III/19C,
subsect. 1.5.4.2. Lattice constants of TiSi [87T1].
2
TiSi
2
Crystal structure orthorhombic, C54
a [Å] 8.270
b [Å] 4.800
c [Å] 8.552
0.12 – 0.03 0
V Si 29Si inV Si
3 3
0.10 – 0.07
– 0.05
–1]
K
–1–1ation rate ([sTT)1000...000468 ––– 000...111951Knight shift[%]K Knight shift[%]K –– 00..1150
x
a
el
R – 0.20
0.02 – 0.23
0 – 0.27 – 0.25
0 50 100 150 200 250 300 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
TemperatureT [K] Susceptibility c [10–6cm3g–1]
g
Fig. 1. V Si. Temperature dependence of the spin-
3 Fig. 2. V Si. Knight shift K of 29Si vs. magnetic mass
lattice relaxation rate (T T)–1 and Knight shift K of 3
1 susceptibility c plot [86S3].
29Si [86S3]. g
Landolt-Börnstein
New Series III/32C
6 1.5.4 3d elements and C, Si, Ge, Sn or Pb [Ref. p. 59
10 160
VSi HIIc VSi
2 2
150
–1] 8 –1ol] 140 HIIc
ol m
3G cmm 6 –630cm 130
[sm [1cm
Magnetization 24 Susceptibility 111200 H c
100 T
90
0 10 20 30 40 50 60 0 40 80 120 160 200 240 280
Magnetic fieldH[kOe] TemperatureT [K]
Fig. 3. VSi2. Dependence of magnetization s m on an Fig. 4. VSi2. Temperature dependence of the molar
applied magnetic field H parallel to the c axis at 4 K magnetic susceptibility c m in a magnetic field parallel
[93G2]. or perpendicular to the c axis [93G2].
1.5.4.3 Cr alloys and compounds
Most of the work in the last decade is related to the spin-density-wave antiferromagnetism of Cr.
Dilute alloys of Cr have been investigated extensively, as reviewed by [94F1]. See also subsect.
1.1.1.3 in LB III/19A.
Survey
Composition x Properties Figure Table
Cr Si 0.0142...0.00343 thermal expansion D l/l(T) 5
1–x x
0.005 c (T) 6
ij
0.0185 r (T;p) 7
0.0085 Q(T) 8
0...0.0046 x-T magnetic phase diagram 9
CrSi c (T–1) 10 3
2 m
CrGe Si 0...0.15 c (T) 11
1–x x g
Cr Ge 0...0.0105 x-T magnetic phase diagram 12
1–x x
0.0051...0.0089 p-T magnetic phase diagram 13
Cr Sn 0.0007...0.0118 Mössbauer spectra 14
1–x x
0...0.030 x-T magnetic phase diagram 15
(Cr Si ) V 0...0.0031 thermal expansion D l/l(T) 16
0.987 0.013 1–x x
(Cr Si ) Mn 0.0017…0.0232 thermal expansion D l/l(T) 17
0.987 0.013 1–x x
Landolt-Börnstein
New Series III/32C
6 1.5.4 3d elements and C, Si, Ge, Sn or Pb [Ref. p. 59
10 160
VSi HIIc VSi
2 2
150
–1] 8 –1ol] 140 HIIc
ol m
3G cmm 6 –630cm 130
[sm [1cm
Magnetization 24 Susceptibility 111200 H c
100 T
90
0 10 20 30 40 50 60 0 40 80 120 160 200 240 280
Magnetic fieldH[kOe] TemperatureT [K]
Fig. 3. VSi2. Dependence of magnetization s m on an Fig. 4. VSi2. Temperature dependence of the molar
applied magnetic field H parallel to the c axis at 4 K magnetic susceptibility c m in a magnetic field parallel
[93G2]. or perpendicular to the c axis [93G2].
1.5.4.3 Cr alloys and compounds
Most of the work in the last decade is related to the spin-density-wave antiferromagnetism of Cr.
Dilute alloys of Cr have been investigated extensively, as reviewed by [94F1]. See also subsect.
1.1.1.3 in LB III/19A.
Survey
Composition x Properties Figure Table
Cr Si 0.0142...0.00343 thermal expansion D l/l(T) 5
1–x x
0.005 c (T) 6
ij
0.0185 r (T;p) 7
0.0085 Q(T) 8
0...0.0046 x-T magnetic phase diagram 9
CrSi c (T–1) 10 3
2 m
CrGe Si 0...0.15 c (T) 11
1–x x g
Cr Ge 0...0.0105 x-T magnetic phase diagram 12
1–x x
0.0051...0.0089 p-T magnetic phase diagram 13
Cr Sn 0.0007...0.0118 Mössbauer spectra 14
1–x x
0...0.030 x-T magnetic phase diagram 15
(Cr Si ) V 0...0.0031 thermal expansion D l/l(T) 16
0.987 0.013 1–x x
(Cr Si ) Mn 0.0017…0.0232 thermal expansion D l/l(T) 17
0.987 0.013 1–x x
Landolt-Börnstein
New Series III/32C
Ref. p. 59] 1.5.4 3d elements and C, Si, Ge, Sn or Pb 7
Composition x Properties Figure Table
(Cr Si ) (V,Mn) 0...0.006 (V), x-T magnetic phase diagram 18
0.987 0.013 1–x x
0...0.0073 (Mn)
Cr Mn Ge s (T) 19
0.79 0.21
Cr Mn Ge 0.1...0.6 x-T magnetic phase diagram 20
1–x x
Table 3. Supplement to Table 4 in LB III/19C,
subsect. 1.5.4.3. Magnetic and related properties
of CrSi [90O1].
2
CrSi
2
Crystal structure hexagonal, C40
a [Å] 4.242
c [Å] 6.342
Magnetism dia
15.0
Cr Si Cr Si
1-x x 0.984 0.016
12.5
10.0
T
–40] x=0.0142 2(cid:215)10–4 N
[1 7.5
/Dll /Dll
n n
ansio 5.0 0.0179 ansio
p p
Ex 2.5 Ex
0
0.0343
– 2.5
50 100 150 200 250 300 350 400 50 100 150 200 250 300 350 400
a TemperatureT [K] b TemperatureT [K]
Fig. 5. Cr Si . Temperature dependence of thermal [110] direction of a single crystal with x = 0.016
1–x x
expansion D l/l (a) polycrystals [88A1], (b) along the [93L1].
Landolt-Börnstein
New Series III/32C
8 1.5.4 3d elements and C, Si, Ge, Sn or Pb [Ref. p. 59
4.0 1.05
Cr Si
0.995 0.005
3.8 1.04
T
–2m] sf T –2m] T TN
N 3.6 N N 1.03 sf
110 110
1 1
[ [
c11 c44
3.4 1.02
L T P L T P
3.2 1.01
50 150 250 350 450 50 100 150 200 250 300 350 400
a TemperatureT [K] b TemperatureT [K]
3.6 1.50
1.48
–2] 3.4
11)/2[10N m 3.2 Tsf T –211[10N m] 11..4464 Tsf T
+ 2c44 N )/2c12 N
+(cc1112 3.0 –(c11 1.42
1.40
L T P L T P
2.8 1.38
50 150 250 350 450 50 100 150 200 250 300 350
c TemperatureT [K] d TemperatureT [K]
Fig. 6. Cr Si . Temperature dependence of the wave states, respectively. The broken curves show the
0.995 0.005
elastic constants. (a) c , (b) c , (c) (c +c +2c )/2, estimated non-magnetic behaviour based on the curve
11 44 11 12 44
(d) (c –c )/2. P: paramagnetic state; T and L: for Cr–5 at% V [93A2].
11 12
transverse and longitudinal incommensurate spin
Landolt-Börnstein
New Series III/32C