Beruflich Dokumente
Kultur Dokumente
David A. Young
&
September 11, 1975
aiS
1
i\\m LAWRENCE
K a i LABORATORY
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OlSTRIBUTt0 npTu,5
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IStWUMtTED
Contents
Abstract
Introduction
Phase Dlagraas
Hydrogen
Helium
Lithium
Berylliua
Boron
Carbon
Nitrogen
Oxygen
10
Fluorine
10
Neon
11
SodiuD
11
Magnesium
12
Aluminum
12
Silicon
13
Phosphorus
13
Sulfur
14
Chlorine
16
Argon
16
Potassium
16
Calcium
17
Scandium
17
Titanium
la
Vanadium
IS
Ch.'omium
. . . . <
IB
Manganese
19
Iron
20
Cobalt
20
Nickel
21
Copper
'.
21
Zinc
21
Glllu
21!
-ill-
Germanium
22
Arsenic
23
Selenium
23
Bromine
24
Krypton
24
Rubidium
24
Strontium
24
Yttrium
26
Zirconium
26
Niobium
27
Molybdenum
27
Technetium
27
Ruthenium
27
Rhodium
27
Palladium
27
Silver
28
Cadmium
28
Indium
28
Tin
28
Antimony
29
Tellurium
30
Iodine
31
Xenon
31
Cesium
31
Barium
33
Lanthanum
34
Cerium
24
Praseodymium
35
Neodymium .
36
Promethium
37
Samarium
37
Europium
.-
38
Gadolinium
39
Terbium
39
Dysprosium
40
Holmlum
40
-iv-
Erbium
41
Thulium
41
Ytterbium
41
Lutetlum
43
Hafnium
43
Tantalum
43
Tungsten
44
Rhenium
44
Osmium
44
Iridium
44
Platinum
44
Gold
44
Mortury
45
Thallium
45
Lead
46
Bismuth
46
Polonium
48
Astatine
Radon
48
~
Francium
48
48
Radium
48
Actinium
48
Thorium
48
Protactinium
48
Uranium
49
Neptunium
50
Plutonium
50
Aroericium
52
Curium
54
Berkellura
54
References
Append!* A:
55
The Space Lattices
64
-v-
The crystal
This work
melting curves.
Comments, including
elements.
Introduction
Phase diagrams are useful as
compact summaries of large amounts of
experimental data.
As such thay
down.
Another aspect of phase diagrams
that has attracted much attention i s
s o l i d - and l i q u i d - s t a t e theoretical
models.
few f i r s t - p r i n c i p l e s calculations of
one-component pressure-temperature
phase diagrams.
Thus,
A qualitative
The s i g
that
cult to perform.
It may also be
When appropriate,
multi~component systems.
Cursory
It i s
For
of the elements.
Only s o l i d and
here.
However, the
the e a r l i e r ones.
1960.
research.
Other
Very recently, J. F.
to the 14 l a t t i c e types l i s t e d in
Appendix A.
Dashed l i n e s in the
research.
-2-
Phase Ditgrams
HYDROGEN
ni\
I
i s shown in Fig. I.
1
I
HYDROGEN
L^fCubic)
in thermodynamic equilibrium ( i . e . . ,
para-H, and ortho-D,) c r y s t a l l i z e
Hexogono!
e s s e n t i a l l y freely rotating.
For
Fig. 1.
20
40
Temperature - K
60
kbar.
Theoretical calculations
(probably marfcensitic,
involving the
Further
This
The temper
HELIUM
The phase diagram of helium is
shown in Figs. 2-6.
The cohesive
10
liquids solidify.
Fig. 2.
20
Temperature ~ K
0.25
0.20
-S 0.15 -
at 0.78 K.
0.10=
3
In
0.05 -
2
4
Temperature - K
Fig. 3.
30
0.05
HELIUM-3
0.04 --
bcc (Solid)
0.05
.
A liquid
i | n rr
HELIUM-4 1
hep
1
0.04 _-
.
0.03 --
bcc
-3 0.03
Y"/
8 0.02
B liquid
0.02
'
Liquid 11
/Fermi liquid
0.01 _-
0.01 -
j / ,
1 , 1 ,
0.001
0.002
0.003
Temperature - K
i
3
Fig. 6.
t h a t in
i
,
i\ .
1
2
Temperature - K
He.
i s a f i r s t - o r d e r phase t r a n s i t i o n , and
i t j o i n s the Fermi l i q u i d at a t r i critical point.
The A and B f l u i d s
In
He the normal f l u i d ( I )
undergoes a second-order t r a n s i t i o n
(A-transition) to a s u p e r f l u i d phase
( I I ) , which a r i s e s from the BoseEinstein condensation as i t i s modi
fied by the He-He p a i r i n t e r a c t i o n s
(Fig. 6 ) .
0
Fig. 5.
10
20
Temperature - K
30
LITHIUM
The phase diagram of lithium is
shown in Fig. 7.
-5-
Upon cooling to
80
'
1
LITHIUM
60
'
greater pressure.
BERYLLIUM
The phase diagram of beryllium
40
i s shown in Fig. 8.
Liquid
20
jf
bcc
ep :
1
n ._u_
0
200
before melt.
V-
1
400
/,
600
Temperature - K
Fig. 7.
Beryllium has a
determined to 60 kbar.
The same
correspond to f l u c t u a t i o n s in the
hexagonal c/a l a t t i c e r a t i o , r a t h e r
to a close-packed (cp) s t r u c t u r e .
The i d e n t i t y of t h i s s t r u c t u r e (or
s t r u c t u r e s ) i s not yet agreed upon.
This i s a m a r t e n s i t i c t r a n s i t i o n with
a considerable temperature h y s t e r e s i s .
The change i n t r a n s i t i o n temperature
with pressure i s very s m a l l , as
14
me'isurements to 3 kbar have shown.
Stager and Drickamer
have found a
The s t r u c t u r e of
500
1000
1500
Temperofure - K
2000
S t a t i c high pressure r e s i s t a n c e
18
showed a
measurements by Marder
p r o b a b i l i t y of sample contamination
in t h i s work was l a r g e . Boron
22
very s l i g h t l y upon melting
23
near 2350 K,
which implies a melt
ing curve with p o s i t i v e slope. The
melting curve has not been d i r e c t l y
measured.
expands
CARBON
Many different
crystal
shown in Fig. 9.
but
t h e i r r e l a t i o n s h i p to one another i s
unclear.
Furthermore, contamination
It
Liquid
S o l i d i f i c a t i o n of l i q u i d boron
y i e l d s the "S-rhombohedral" s t r u c t u r e
with 105 atoms per unit c e l l and 16
d i s t i n c t atomic p o s i t i o n s .
This very
I t i s l i k e l y to be the s t a b l e
phase at low p r e s s u r e s .
S t a t i c high pressure r e s i s t a n c e
measurements up t o 250 kbar show no
20
evidence of phase t r a n s i t i o n s .
2000
4000
6000
Temperature - K
21
Wentorf
reported a new boron
polymorph of unknown structure obtained
-7-
Fig. 9.
up to a
graphite-diamond t r a n s i t i o n , but t h i s
i s dominated by nonequilibrium e f f e c t s
established.
Graphite, the s t a b l e phase at
p r e s s u r e i s s t i l l uncertain.
symmetry.
Graphite c o n s i s t s of plane
The
Each
Very
approximately 1 Mbar.
the semiconductor-to-metal t r a n s i t i o n s
a tetrahedron.
i n s i l i c o n and germanium.
work.
t u r e measurements are l a r g e .
Melting
and 40 kbar.
silicon.
Beyond t h i s , the a c t u a l
NITROGEN
The phase diagram of nitrogen i s
The dashed l i n e i s a l i n e a r e x t r a p
shown in F i g s . 10 and 1 1 .
o l a t i o n of the lower-temperature
results.
Nitrogen
curve, t h i s y i e l d s a g r a p h i t e -
'
'
8 --
'-
NITROGEN
1
Tetragonal
^ S
4 -
Hexagonal
(0)
2 --
Cubic
(a)
/
/
Liquid
i
20
i
40
1 ^T
60
80
100
120
Temperature - K
Fig. 10. The phase diagram of nitrogen.
The Y phaae
-9-
The d i r e c t i o n
i s a n t i f e r r o i r a g n e t i c , due to the
ground s t a t e .
The
A t r a n s i t i o n to the
t o about 25 kbar
been determined
dete
2i
(Fig. 11)
although m a r t e n s i t l c .
OXYGEN
volume change at 44 K.
This
t r a n s i t i o n i s d e f i n i t e l y f i r s t order,
Another
shows some r o t a t i o n a l d i s o r d e r .
The phast diagram of oxygen i s
shown in Fig. 12.
Oxygen in the
10
All
Three s o l i d phasa
FLUORINE
i'i'i'r
OXYGEN
Fluorine in Che
1.5
- ' 1
S;
Pressure -
J 1.0
Temnertiture - K
Cubic
/ / /
0.5
- Monoclinic(a)
0
60
'
L
40
111 1
J-Z-J
20
1 '
1 1 IT|
Monoclinic/ Rhombohedral
(a)
/ (,
FLUORINE
1
20
1
40
1,1
60
80
Temperature - K
At 46 K a t r a n s i t i o n
This
The s i m i l a r i t y between
50
100
Temperature - K
Fig. 14. The phase diagram of neon.
NEON
Neon in the s o l i d
and l i q u i d s t a t e s i s composed of
atoms weakly bound by van der Waals
forces.
The
3 6
SODIUM
The phase diagram "f sodium is
shown in Fig. 15.
is hep.
Below 36 K, sodium
At 36 K a martensitic phase
200
400
Temperature - K
The phase
Fig. 15. The phase diagram of sodium.
-11-
i | i i I i | i i i i | i i
MAGNESIUM
40
that the
30
I-
Liquid
hep
10
MAGNESIUM
The p h a s e diagram o f magnesium i s
shown i n F i g . 1 6 .
hep.
Ql I I I
S o l i d magnesium i s
[I I i I I I I
500
1000
1500
Temperature - K
R e s i s t i v i t y and x - r a y m e a s u r e
The melting
curve has been determined to 40 kbar'38
80
i i i | i i i i | i i i i
ALUMINUM
60
S 40h
n
ALUMINUM
fee
f Liquid
S o l i d aluminum i s
0UJ
*!
500
1000
Temperature - K
1500
250
SILICON
i i i i | i i i i | i i I i | i i
SILICON
200-
Normal s o l i d s i l i c o n
Tetragonal
(white tin)
100
50
The accurate
shear s t r e s s e s .
'
500
1000
Temperature
i s complicated by i t s s e n s i t i v i t y to
In a d d i t i o n , recovery
1500
30
20-
Jiof-
Ortho rhombic
Liquid
i s unknown.
PHOSPHORUS
500
1000
Temperature - K
Of Che various
1500
complex arrangement.
at atmospheric pressure.
Black phos
Above 360 K,
separating them.
is easily reversible.
resistance techniques.
Conductivity
et al.
rings
SULFUR
phases other than the well-known I
and 11 have not been worked out,
The literature on
Waals forces.
Solid sulfur
SULFUR
40 -
Monocltnic
II
d i a t o m i c m o l e c u l e s bonded t o n e i g h b o r s
boundaries. In addition,
Vezzoli
52
et al.
have discovered a number of
b y van d e r Waals f o r c e s .
t u r e , composed of
Solid
c h l o r i n e has an orthorhombic
struc
approximately
c l o s e - p a c k e d l a y e r s of m o l e c u l e s .
7 kbar.
The
to
ARGON
Solid
argon is fee.
CHLORINE
The phase diagram of chlorine is
shown in Fig. 21.
Chrlorine in the
POTASSIUM
iir-
CHLORINE
bcc.
.s
30
4 -
Solid potassium is
i
''i
ARGON
/-
-20Orthorhombic
Liquid
10
fee
f
Liquid
"
100
200
Temperature - K
Fig. 21.
300
1 , 1 . 1
100
200
300
400
Temperature - K
Fig. 22.
-16-
80
1
'
1 - I'"
POTASSIUM
40
30
j:
o 20
1 60
1 40
tfc
bcc
20
, ,y
200
10
,
400
600
Temperature - K
500
Fig. 23. The phase diagram of
potassium.
kind occurlng i n Li and Na i s
1000
1500
found
found
These t r a n s i
dramatic second t r a n s i t i o n i s a n a l o
metallic phase.
in Li and Na.
1 6
SCANDIUM
CALCIUM
pressure.
Near 700 K at
The phase
Shock wave
kbar.
This was
a s c r i b e d to a sluggish low p r e s s u r e
s o l i d - s o l i d phase change.
No kink
Scandium melts a t
The nature
determined.
been r e p o r t e d .
1941 K.
Titanium melts at
The melting curve has not
been reported.
TITANIUM
VANADIUM
The phase diagram of titanium is
shown in Fig. 25. At room temperature
and pressure titanium
is
hep.
Vanadium is bcc.
No solid-solid
The
CHROMIUM
atomic positions.
T T
7"l""l""-
mp
hep
bcc
1000
^-'Tetragonal
J
J
I2
U-iquid;:
500
CHROMIUM
o
3 6
/ TITANIUM
1111II11 1 1 I I 11111 | I I I 1
- Hexagonal
: (w)
i
sure - kbar
J 111111111
V i i i i*
1500 2000 2500
Temperature - K
Liquid -
Orrhoihombic
bcc
mp
1 \, , ,'
0 . J_ 11 1 i i i 1 i i i 1 i i
500 1000 1500 2000 2500
Temperature - K
50
I I I I I I 1 I I I I l I I I I
MANGANESE
Below 311 K,
40
This phase
_8 30
Liquid
This magnetic
8 20
(a)
10
|_iiiiL_
0
500
1000
1500
Temperature - K
Fig.
27.
'
Static pressure
70
of atomic p o s i t i o n s .
types
At atmospheric
p r e s s u r e n e a r 1000 K, a t r a n s i t i o n
The
MANGANESE
Near 1370 K a
t r a n s i t i o n t o t h e fee Y phase o c c u r s ,
and near 1520 K a f u r t h e r
There a r e four
a l l o t r o p e s , a l l of cubic symmetry.
transition
The 'phase
IRON
73
kbar beyond the t r i p l e p o i n t .
COBALT
At 1044 K it passes
Above 100
At room tempera
At a temperature
The
The
60
111 I I I 111 ] 11 1 I 11 I I I ( I 11 I
COBALT
_ 50
I 40
30
1 20
*
500
1000
1500
2000
Temperature - K
Fig. 28.
fee
'q
u i d
"
mp
100 11 i i I i I I i 11 i i) Ii i t i I i i i i
0
500 1000 1500 2000 2500
Temperature - K
Fig. 29.
-20-
hep
80
I1I I 1
COPPER
Solid n i c k e l i s
60
determined to 80 kbar.
'
40
80
fee
0 60
-Q
20
4 0
fee
| Liquid
/Liquid
1 20
at
0.
i I . . . . I i i , I i ill i I . , , ,
500 1000 1500 2000 2500
"0
500
Temperature - K
Temperature - K
Fig. 30.
I / I !
1000
1500
Fig. 31.
COPPER
The phase diagram of copper is
shown in Fig. 31.
Solid coppfer is
fee.
80
ZINC
J 60 -
r a t i o considerably g r e a t e r than i d e a l .
Under p r e s s u r e , t h i s ratio shows
unusual f l u c t u a t i o n s , but no c l e a r - c u t
| 40
hep
~
:
f Liquid
20
, 1 . *
. 1 . 1 /
2C10 400 600 8(10 1000 12C
Temperature - K
Fig. 32.
-21-
80 L
GALLIUM
' ! '
Solid gallium at
'
TZ\
60
Orthorhombic
(III)
GALLIUM
I 40
At atmospheric pressure
20-
Orthorhcmbic
(M
Gallium II is probably
I
I I
100
200
300
Temperature - K
The high-
Fig. 33.
The phase
400
250
| I I i | I i I
GERMANIUM
200
GERMANIUM
*
.
Tetragonal
(white tin)
- 150
Solid germanium
ments
new phase.
_
1
-
Cubic
(diamond)
Liquid
100
i l i t i i i . X i . i l
500
1000
1500
Temperature - K
Fig. 34.
-22-
ARSENIC
60
ARSKNIC
The phase diagram of arsenic la
40
Rhombohedral
Liquid
20
-iJ_
500
1000
1500
Temperature - K
Fig. 35.
up to 60 kbar.
SELENIUM
60
40
Hexagonal
20 -
I I I/I
200 400 600 800 1000 1200
Temperature - K
BROMINE
59
These
Solid bromine Is
transitions are thought to correspond
The
STRONTIUM
KRYPTON
With increasing
The solid
determined to 12 kbar.
ture occurs.
At low pressures
Bundy and
two temperatures.
axis at 830 K.
The fcc-bcc
to 40 kbar.
-24-
80
"HP
BROMINE
' ~T
RUBIDIUM
10
60
ji
2
_
OrthorhombTc
40
3
i
20
I
. I
100
200
300
Temperature - K
200
400
F i
'
1
KRYPTON
'
tfia
600
Temperature - K
8-
50
12
10
3 9
h a s e
*> P
diagram of
rubidium.
1 i i | i i I i | i i i i | I
1 -r
STRONTIUM
40
30
I
|
fee
Liquid
bec
20-
,.
0
l / ,
100
200
Temperature - K
10
300
Fig. 40.
Fig. 38.
/ Liquid
I J U
500
1000
1500
Temperature - K
The phase diagram of
strontium.
YTTRIUM
The
The
Vereshchagln observed
resist
modifications.
unclear.
band structure.
6 3
The
The
i i i i | i i i > | i i i i | i rn | n i _
ZIRCONIUM
80
" Hexagonal !
in tk&
an explanation.
Yttrium melts at
63
1775 K.
The melting curve has not
been reported.
:y
60
40
3
*?
ZIRCONIUM
hep
20
bcc
Liquid
mp\
Zirconium under
under com
Near
n
"0
500
RUTHENIUM
KI0BIW1
2741 K.
Com
6 3
The
been reported.
MOLYBDENUM
RHODIUM
The phase diagram of rhodium i s
Solid molybdenum
is bcc.
shown i n F i g . 4 3 .
fee.
Solid rhodium i s
approximately determined t o 80
kbar.
3 8
'
7 4
TECHNETIUM
Solid technetium is hep.
63
Technetium melts at 2443 K.
The
melting curve has not been reported.
Solid palladium i s f e e .
um melts a t 1825 K.
Palladi
The m e l t i n g
ii'r
100
MOLYBDENUM
80 -
I 60tbcc
40
20
0.
1000
2000
Liquid
J
3000
i
1000
Temperature - K
2000
3000
Temperature - K
Fig.
42.
Fig.
-27-
43.
SILVER
anomalies.
Solid silver Is
INDIUM
shown In F i g . 46.
Solid indium i s
body centered t e t r a g o n a l .
Compression
CADMIUM
mined t o 80 k b a r .
7 8
shown in F i g . 47.
is
Below 290 K at
Fig.
44.
200
400
600
800
Temperature - K
Temperature - K
The phase diagram of s i l v e r .
-26-
Fig. 45.
1 1 1 1
iNDIUM
80
:
|
60-
i "o
Tetragonal
/
/
In this
Liquid
Two more
20
1 J l/i
200
400
1 I
600
The diamond-to-white-tin
boundary has been determined to about
102
50 K and 10 kbar.
At room
800
Temperature - K
Fig. 46.
'
1 0 4
Tht
100
1 0 3
ANTIMONY
80
60
40 -
Tetragonal
(white tin)
Solid antimony
At room
20-
Cubic
^(diamond)
near 85 kbar ( c i r c l e s ) .
105
The 70-
200
400
600
Temperature - K
800
Fig. 47.
-29-
I i | I i I i | i i i i | I
100
80
TELLURIUM
ANTIMONY
The phase diagram of tellurium
\ Tetragonal
- \(o
60
a>
- \sn
Liquid
20
Solid tellurium
Rh'ombohedral \
Near 40 kbar
I I I
0
500
'
'
1000
'
'
'
1500
Temperature - K
Fig. 48.
f u r t h e r t r a n s i t i o n to a rhombohedral
108
This phase i s
l a t t i c e occurs.
i s o s t r u c t u r a l with 3-polonium.
Studies of superconductivity at high
rhombohedral d i s t o r t i o n .
Hie t r a n s i
pressures i n d i c a t e p o s s i b l e new
The s t r u c t u r e
80
'
Two cusps, i n d i c a t i n g
"^
Rhombohedral (III)
60
ll
; 40
Hexagonal
20
-i
"0
assumed
J i g . 49.
L
200
J_
400
J
L
600
800
Temperature - K
TELLURIUM
phases a t s t i l l h i g h e r p r e s s u r e s .
109
A definite
IODINE
structure.
transition.
Solid iodine at
plot of u
at approximately
Given a transition to
vs u
700 kbar.H4
another.
determined to 50 kbar.
XENON
50 -
' i r
'
IODINE
u
o
M
g 30-
Solid
xenon is fee.
Orrhorhombic
i 20CESIUM
10-
200
400
600
800 1000
Temperature - K
unusual properties.
Fig. 50.
Solid cesium at
-31-
Further
The s o l i d - s o l i d phase
'
400
600
low temperatures.
Temperature - K
Fig. 51.
The i s o s t r u c t u r a l fcc-fcc t r a n s i
tion occurs with a 9% volume change,
The
f i r s t t h e o r e t i c a l attempt a t an
explanation proposed t h a t the t r a n s
60
50
.
-
formation r e p r e s e n t s a s h i f t from 6s
'' ' 1
"T
CESIUM
band.
IV
>.. 4 0
fcc^
fee
~"
correct.
.a:
r
30
K
10
bcc
t r a n s i t i o n - m e t a l - l i k e , with increased
95
Liquid -
1
0
A further sluggish t r a n s i t i o n i n
d-electron character,
l/l
200
400
Temperature - K
600
1 1 7 , 1 1 8
Fig. 52.
-32-
The
i i i i I i r i i I 11 i i i
BARIUM
This phe
Liquid
whereas i n
'
'
500
'
'
'
'
'
1000
'
1500
Temperature - K
Fig. 53.
BARIUM
The phase diagram of barium is
shown in Fig. 53.
Solid barium at
At room
Drickamer
tion.
Additional
The melting
nn it.
124,125,128
, .
90 k b a r ,
*
*
and three
seems l i k e l y t h a t e l e c t r o n i c phase
changes s i m i l a r t o those observed in
130
cesium are occurring i n barium.
been reported.
Stager and
-33-
It
LANTHANUM
lanthanum
melting curve.
Lanthanum
e x h i b i t s t h r e e s o l i d phases at atmos
pheric pressure.
From 0 t o 580 K,
At 580 K,
CERIOM
E l e c t r i c a l r e s i s t a n c e measurements
This unusual
Between
Between 450 (c
may i n d i c a t e a phase t r a n s i t i o n .
A bec phase
pressures.
40
I I | I I I I | I I
r-|-r-r
133
I | I I I I | I I I I| T
80
LANTHANUM I
CERIUM
Orthorhombic 1
1 60
40,
Ll'qui'd'
20U (a)
dhcp
I I I I,
500
1000
1500
0
Temperchjre - K
Fig. 54.
Fig. 55.
-34-
Liquid
7) L '
_|
facc
A considerable
*
found.
The earliest
i2ed 5d band.
135
6 2
Later theories
kbar.
in terms of isotherms s i m i l a r i n
But
In general
The new
PRASEODYMIUM
The phase diagram of praseodymium
i s shown in Fig. 56.
Normal s o l i d
137
a-uranium.
praseodymium I s dhep.
A room-
temperature t r a n s i t i o n to an fee
phase occurs a t 40 kbar ( c i r c l e ) . 139
boundary i s d i f f i c u l t to follow
i n t e r e s t i n g t h a t extrapolation of the-35-
~r i i i | i i i i | m i
1 -
60
40
|"i i
PRASEODYMIUM
80
20
fee
NEODYEtCH
dhcp\
\
_L
500
Liquid "
y
V . I #.
1000
Under room
High
. . 1 , .
1500
Temperature - K
Instead, a
apparently q u i t e s e n s i t i v e to
a generalized
1UX rare earth phase
diagram,
Resistance measurements
Impurities.
the zero-pressure t r a n s i t i o n
temperature i s 833 K. **
Resistance
80 -
"
-\ I T ] T T T T ' | 1 \ l-JTTTNEODYMIUM
s e v e r a l anomalies above t h a t a t 40
kbar, and suggest two more high-
curve for
P 62
praseodymium at 300 kbar
and 270
kbar.
The f i r s t report ascribes
62
the kink t o xenon-core r e p u l s i o n s ,
while the second t e n t a t i v e l y a s c r i b e s
8
i t to an e l e c t r o n i c rearrangement In
the l i q u i d .
before melt.
60 --
dh
-36-
=p
"
/
/
Lc
'
Liquid
20
_L, 1 1 . 1 1 1 1 \ l
0
0
Fig. 57.
/
/
500
J 1 I !..!__)
1000
1500
Temperature - K
The phase diagram of
neodyroium.
1 1 1 1 | 1 I 1 1 | 1 1I I | I l
80
SAMARIUM
1 60
1
V
I bee
40
20 _
Rhombohedral
(Siti)
!
n
0
500
Fig. 58.
xl
1
"
/Liquid"
i 1 1 ill A 1 l_
1000
1500
Temperature - K
The
5
c
dhcp
henceforth c a l l e d "Sm-type." R e s i s t
ance measurements to 600 kbar at
PROMETHIUM
Prom
The
No
kbar.
The f i r s t report a s c r i b e s
the kink to xenon-core repulsions 62
SAMARIUM
The phase diagram of samarium i s
shown in Fig. 58.
A phase assumed to be
An i n f l e c t i o n
i n the b c c - t o - c l o s e - p a c k e d - s o l i d phase
s t r u c t u r e of rhombohedral symmetry.
layers in t h i s s t r u c t u r e i s ababcbcac,
37-
EUROPIUM
The phase diagram of europium i s
shown in Fig. 59,
Solid europium at
Below
with a h e l i c a l arrangement of s p i n s ,
and i t becomes paramagnetic above t h i s
resistance anomaly
temperature.
ascribed t o a d i v a l e n t - t r i v a l e n t
e l e c t r o n i c phase t r a n s i t i o n .
more r a r e - e a r t h - l i k e aa the p r e s s u r e
chromium.
increases.
.,
147,148
kbar.
.
A temperature maximum
fc
p r e s s i b l e with increasing p r e s s u r e ,
the f i r s t - o r d e r t r a n s i t i o n simply
144
The close
S t a t i c high-pressure r e s i s t a n c e
measurements show a sharp change near
150 kbar and room temperature, which
probably corresponds to an e l e c t r o n i c
phase t r a n s i t i o n 138 The t r a n s i t i o n
pressure appears to decrease with
138
temperature.
Three s e t s of shock
wave experiments show anomalies in
61,62,146
the u - u , curve.
Carter
ej; jal.6 1 * found a d i s c o n t i n u i t y i n the
s
500
1000
1500
Temperature - K
found
Fig. 59.
e l e c t r o n i c t r a n s i t i o n in the
GADOLINIUM
solid.
gadolinium
Under room
was t a k e n t o b e h c p - S m - t y p e - b c c t r i p l e
131
point.
The m e l t i n g c u r v e h a s b e e n
~_4
/ n ,kLb a r . 1 3 1 , 1 4 8
d e t e r m i n e d^ t. o 40
t r a n s i t i o n t o the samarium-type
phase
o c c u r s a t a b o u t 25 k b a r ( c i r c l e ) a t
149
room t e m p e r a t u r e .
The h c p - S m - t y p e
phase boundary has not been
determined.
Resistance
TERBIUM
directly
measurements
60 138
t o 500 k b a r show n o a n o m a l i e s .
repulsions,
A resistant
m e n t s show k i n k s i n t h e u - u
curve
62
f o r g a d o l i n i u m a t 260 k b a r
and
345 k b a r .
The f i r s t r e p o r t a s c r i b e s
the kink to xenon-core
Two s e t s o f s h o c k wave e x p e r i
s
and
i t w i t h an
1 -
GADOLINIUM
40
1
. Rhombohedral
(Sm-type)
1
1000
2000
^x
1
1
1
TERBIUM
20-
'
0
Fig. 6 1 .
-39-
^-bec
Liquid
hep
3000
1
X
10 -
Temperature - K
Fig. 60.
Rhombohedral
(Sm-type)
30-
hep
L^bcc
40
Pressure
to
f 30
_
-
1, -
1000
2000
Temperature - K
3000
Two s e t s of shock-wave e x p e r i
ments show kinks in the u -u curve
s p
6 2
and 305
The f i r s t report a s c r i b e s
61
kbar
melting.
respectively.
DYSPROSIUM
HOLMIUM
Under room
t i o n s holmium i s hep.
A transition
60,149
. ^
ture.
Resistance measurements
on dysprosium show anomalies near
D
transition.
15
2 10 -
1000
2000
3000
Temperature - K
Fig. 62.
Fig. 63.
-40-
'
(L-bcc
_i_i_Li
1
HOLMIUM
hep
Liquid _
I
1000
2000
Temperature - K
3000
THULIUM
The phase diagram of thulium i s
shown i n Fig. 65.
A transition
15
kink in the u -u
ERBIUM
Kw
1
0
I
0
1
1000
.
2000
,
3000
3000
Temperature - K
Fig, 64.
,
1
1000
2000
Temperature - K
| I I I i |
Liquid
"'"" -
'
hep
hep
5 -
1 5
'
_g 10 -
determined to 10 kbar
""
! THULIUM 1
1 1 1 1 11
.,
metallic phase.
153
These changes
3
pressure-independent resistance
anomaly variously observed at 743
K
1 4 7
and 898 K ,
1 5 5
500
1000
1500
Static
Temperature - K
xenon-core r e p u l s i o n , m e l t i n g , and
respectively.
Johansson and
Below 20 kbar
strontium.
y t t e r b i u m behaves l i k e a m e t a l ,
-42-
33
LUTETIUM
LUTETIUM
Compression t o
J 10
Pressure -
Solid l u t e t i u m at
1 1 1
1 -;
hep
1 Liquid ..
The melting
0
i
1000
ll
2000
"
3000
Temperature - K
Fig.
HAFNIUM
hafnium
is
67.
TAHTALUM
At atmospheric pressure a
The phase diagram of tantalum
Solid tantalum
is bcc.
A static-high-pressure
6 2
'
6 6
'
1 4 6
McQueen, t al -
5 3
1000
Fig. 68.
-43-
2000
3000 ' 4000
Temperature - K
The phase diagram of tantalum.
TUNGSTEN
IRIDIUM
Solid tungsten is
Room
melts at 2716 K.
PLATINUM
The phase diagram of platinum is
shown in Fig. 70.
fee.
Solid platinum is
approximately determined to 50
159,162
*
kbar.
1000
2000
3000
4000
Temperature - K
Fig. 69.
Static
1000
2000
Temperature - K.
Rhenium melts at
been reported.
Fig. 70.
3000
OSMIUM
Solid osmium is hep.
melts at 3300 K.
Osmium
-44-
Solid gold is
'
80 -
Pressure -
J 60 -
'
'
MERCURY
Rhombohedral v
(a)
Tetragonal
"
20
/ LiquidM~
' ^/\A .
200
400
600
Temperature - K
Fig. 72.
Temperature - K
Fig. 71-
fee.
Its struc
164
The
determined to 65 kbar.
Solid mercury at
In this phase
transformation to a rhombohedral
structure occurs.
Below 500 K at
A high
lattice.
The tetragonal-rhombohedral
The solid-solid
to 60 kbar.
to 65 kbar.
6 0
40
20
_-
Fig. 73.
1 1 1 l~ '
THALLIUM
fee
/
_ /
80
~\
/
40
fee
hep
60
-
/ _
bcc
- n -i i | i i i i | i i i i | i i
LEAD
Liquid
80 --
20
'Liquid
1 \
200
400
600
Temperature - K
,,,/
800
500
1000
1500
Temperature - K
LEAD
phases.
The phase diagram of lead i s
shown i n Fig. 74.
pressure i s fee.
i s rhombohedral, i s o s t r u c t u r a l with
Conflicting
room temperature a t r a n s i t i o n t o a
165,166 _.
.
The phase
phase I I I i s t e t r a g o n a l , s i m i l a r t o
to 60 k b a r .
7 7
bcc.
This diagram i s of
are a s y n t h e s i s of s e v e r a l
,.
84,168,169 '
.
studies.
The phases XX,
at 135 k b a r ,
1 6 9
There i s s t i l l controversy
55 k b a r .
-46-
8 4
' r
140 -
'
BISMUTH
IX
->
120 -
100 -
bcc
VIII
80 -
(VI)
\\
60
\
\
/'\
K. s
m
IV
40 -
Tetragonal
(III)
/
Liquid
2 0 -Rhombohedral
to
'
1
i
200
\
i ., .
i
400
600
Temperature - K
Fig. 75.
i
800
POLONIUM
RADIUM
reported.
ACTINIUM
to a simple rhombohedral
The rhombohedral
THORIUM
tions i s fee.
reported.
Superconductivity
ASTATINE
transforms t o a bcc p h a s e .
The
is
zero t o w i t h i n experimental e r r o r .
The t r a j e c t o r y of th^ phase boundary
RADON
has n o t been r e p o r t e d .
at 2024 K.
Thorium melts
PROTACTINIUM
FRANCIDM
Solid p r o t a c t i n i u m under room
c o n d i t i o n s i s body centered t e t r a g o n a l .
s u g g e s t i n g t h a t t h i s i s the high
48.
fee,
URANIUM
No
reported.
60
- i i i i
URANIUM
40
20 -
Orthorhombic
(a)
bcc
<T>
Liquid
Tetragonal
500
Fig. 76.
1000
Temperature - K
The phase diagram of uranium.
-49-
1500
cell.
phases e x i s t at atmospheric p r e s s u r e .
At
figures.
to a bcc phase.
The solid-solid
c e l l and S c r y s t a l l o g r a p h i c a l l y d i s
t i n c t types of atomic p o s i t i o n s .
to 40 k b a r .
positions.
1 7 6
The
Both of these s t r u c t u r e s
Under room
The $
undetermined s t r u c t u r e , above t h i s
tions.
pressure.
pressure a phase t r a n s i t i o n to a
There i s a |S--liquId
A bcc phase
The s o l i d - s o l i d
PLUTONIUM
The s o l i d - s o l i d
The
kbar.
-50-
1 7 4
'
1 7 8
'
1 8 0
<
r-
NEPTUNIUM
40-
30
20Or'horhombic
I Tetragonal
Liquid'
10-
01
L.
500
Fig. 77.
'
1000
Temperature - K
-51-
L l
1500
PLUTONIUM
'/
1 '
8 Monoclinic. 1
6 --
^ k /
(0)
Monoclinic
(a)
1
|
f
/
[
""ec
(e)
1
1
Liquid
1
1
2 Orrhorhombi<v
'
Tetragona
'(5')
rfcc\
200
400
\
600
1
800
1000
"
1200
Temperature - K
Fig. 78.
AMERICIuM
Static com
Americium under
1 8 1
182
There is
The dhep-
1501
-i
1
1
r
PLUTONIUM
-|
(-
Liquid
_L
200
400
600
Temperature - K
800
-53-
1000
1200
CURIUM
i i i i | I I i I | i i I I |
AMERICIUM
40
3 0
2 20
dhcp
I
' ' '
F c C
No
. Liquid \ l I
10 L_
The fee
II
reported.
I I I ! l/i/l I
S00
1000
1500
Temperature - K
BERKELIUM
Berkelium metal prepared by high
temperature reduction contains a
mixture of dhcp and fee structures.
Fig. 80.
-54-
References
1.
2.
W. Klement, Jr., and A. Jayaraman, Progr. Solid State Chem. 3. 289 (1966).
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
-55-
23.
24.
25.
26.
27.
28.
29.
30.
31.
J. iJ. Grace and G. C. Kennedy, J. Phvs. Chem. Solids 28. 977 (1967).
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
-56-
47.
48.
49.
50.
51.
52.
53.
54.
R. E. Harris and G. Jura in Elemental Sulfur. B. Meyer, Ed. (Interscience, New York, 1965) p. 179.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65. A. Jayaraman, W. Klement, Jr., and G. C. Kennedy, Phys. Rev. 131. 644
(1963).
66.
67.
68.
9.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
(1965).
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
121.
122-,
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
237 (1970).
134.
135.
136.
137.
138.
139.
140.
141.
142.
143.
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
-61.
618 (1963).
158.
159.
160.
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
172.
173.
174.
175.
176.
177.
178.
-62-
179.
180.
181.
182.
RBC/gw
-63-
Axes
Angles
a - b - c
o - 3 " Y " 90
a b ji c
aB-Y-90
a^b^c
a B = Y = 90
a^bjc
o - Y 90" ^
face-centered cubic
primitive tetragonal
body-centered tetragonal
primitive orthorhombic
base-centered orthorhombic
body-centered orthorhombic
face-centered orthorhombic
primitive monoclinic
base-centered monoclinic
triclinic
a # b # c
o ^ M l
rhombohedral
a b - c
a 0 =Y
hexagonal
a - b ]< c
ot = g - 90, Y = 12
-64-