7255152

TOL- 51902
PHASE DIAGRAMS OF THE ELEMENTS
David A. Young
&
September 11, 1975
aiS
1
Prepared for U.S. Energy Research & Development

Administration under contract No. W-7405-Eng-48
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UCRL-51902

David A. Young
MS. date:
September 11, 1975
OlSTRIBUTt0 npTu,5
revivor
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-

Abstract
for each diagram.
A summary of the pressure-
The crystal
temperatur phase diagrams of the
structure of each solid phase is
elements is presented, with graphs
identified and discussed.
of the experimentally determined
is aimed at encouraging further
This work
solid-solid phase boundaries and
experimental and theorerirl research
melting curves.
on phase transitions in the
Comments, including
theoretical discussion, are provided
elements.
Introduction
Phase diagrams are useful as
compact summaries of large amounts of
experimental data.
As such thay
they may be quite common at ultrahigh

pressures where the atomic s h e l l
structure exhibits stepwise break
provide an important challenge for

theory, since accurate computation of
phase transitions typically requires
down.
Another aspect of phase diagrams
that has attracted much attention i s
a very high degree of accuracy in
the recurrence of patterns in the
s o l i d - and l i q u i d - s t a t e theoretical
diagrams of closely related elements.
models.
To date there have been very
few f i r s t - p r i n c i p l e s calculations of
This has been used successfully in

predicting the structure*? and proper
one-component pressure-temperature
t i e s of high pressure phases.
phase diagrams.
certain phase transitions observed at
The experimental study of phase

boundaries has led Co the discovery
Thus,
relatively low pressure provide

important clues about the behavior of
of such unexpected phenomena as
materials at much higher pressure.
isostructural phase transitions and
Deeper theoretical understanding of
melting curve extreraa.
observed phase behavior w i l l thereby
A qualitative
theoretical understanding of these
allow quantitative prediction of
phenomena has been achieved, and work
properties of materials at much higher
1B continuing in this area.
pressures where experiments are d i f f i
The s i g
nificance of these phenomena if
that
cult to perform.
It may also be
hoped chat an adequate theory of
and one or more paragraphs of com
phase diagrams for elements w i l l pro
ments are provided.
mote the more complex task of describ
the comment? Include information on
When appropriate,
ing phase behavior in compounds and
the l a t e s t theoretical understanding
multi~component systems.
of Che phase diagram.
This report i s aimed at encour
structures found among the elements
aging theoretical and experimental

research on phase t r a n s i t i o n s .
Cursory
descriptions of complex crystal
It i s
are included i n the comments.
For
d e t a i l s of structures, however, che
a summary of the experimental data

obtained to date on the phase diagrams
reader should consult Donohue's The
of the elements.
Structures of the Elements.
Only s o l i d and
The bibliography i s not
liquid phases are shown; the l i q u i d vapor boundary i s not considered
exhaustive, since only the most
here.
recent papers are c i t e d .
The temperature abscissa i s
However, the
always referred :o zero Kelvin in
reader can e a s i l y work back froo the
order to illustrate, the true s i z e s of
reference? in the recent papers to
the various f i e l d s of phase s t a b i l i t y .
the e a r l i e r ones.
Commonly occurring s o l i d phases are
the work cited here was done since
The gveat bulk of
labelled with abbreviations: bcc
1960.
body-centered cubic (two atoms per

unit c e l l ) , fee face-centered
phase diagrams for the elements

2 3
e x i s t , ' but they are already
cubic, hep - hexagonal close packed,
beginning to be dated by continuing
and dhep - double hexagonal.
research.
Other
solid phases are identified according
Very recently, J. F.
Cannon has published a c r i t i c a l
to the 14 l a t t i c e types l i s t e d in
Appendix A.
Two other useful surveys of
review of the behavior cf the

4
Dashed l i n e s in the
elements at high pressures.
figures indicate extrapolations or
Cannon's review and the present one
poorly determined phase boundaries.
cover much the same ground, and i t i s

hoped that these surveys w i l l f i l l the
For each element where data are
gap l e f t by ten years of active
available, a phase diagram i s 3hoi.n
research.
-2-
Phase Ditgrams
HYDROGEN
ni\
I
The phase diagram o f hydrogen
i s shown in Fig. I.
Solid and liquid
1
I
hydrogen are composed of diatomic

molecules interacting according to
HYDROGEN
L^fCubic)
van der Waals and electric-quadrupole

forces.
Solid hydrogen and deuterium
in thermodynamic equilibrium ( i . e . . ,
para-H, and ortho-D,) c r y s t a l l i z e
Hexogono!
with the molecules centered on hep

lattice sites.
The molecules are
e s s e n t i a l l y freely rotating.
For
ortho-rich H. or pars-rich D. the

stable s t a t e at zero Kelvin i s cubic,
with the molecules centered on an

fee l a t t i c e and presumably ordered,
Fig. 1.
20
40
Temperature - K
60
The phase diagram of hydrogen.
with axes pointing along body

diagonals.
As the cubic l a t t i c e is warmed
kbar.
Theoretical calculations
to about 2 K, a first-order transition
suggest that pure o-D and P~H_ should
(probably marfcensitic,
have transitions to rotationally
involving the
motion of planes of molecules) to the

hexagonal phase occurs*
Further
warming then apparently leads to an

order-disorder t r a n s i t i o n .
This
occurs as the librating molecules

begin to rotate freely.
The temper
ordered cubic l a t t i c e s at zero Kelvin

and compressions corresponding to
pressures of a few tens of kilobars. S
Recently there has been great interest
in theoretical arid experimental
investigations of the i n s u l a t o r - t o -
ature of the crystallographic
metal phase transition in hydrogen,
transition i s a function of pressure
which is exepcted to occur in the

9
megabar range.
The three molecular
and concentration of spin s t a t e s .

The phase boundary indicated by
solid isotopes melt in a regular
the das.i.d l i n e in Fig. 1 i s for 70%
sequence, and the melting curves
o-H-, which has been measured to 5.3
have been determined to 3.5 kbar. 10
HELIUM
The phase diagram of helium is
shown in Figs. 2-6.
The cohesive
energy of solid and liquid helium is

entirely due to very
forces.
weak van der Waals
Because of the strong
quantum effects observed in the solid

and liquid phases, the phase diagram
of helium has been extensively
studied and worked out in detail."*11,12
Both isotopes 3 and 4 are liquid at
T " 0 and p = 0 as the result of aero
point motion.
10
Under pressure, both
liquids solidify.
pressures above 0.1 kbar, both solids
Fig. 2.
are hep and show a transition to fee

around 15 K and above 1 kbar. (Figs.
2 and 5)
20
Temperature ~ K
At zero Kelvin and
The phase diagram ot

helium - 3 .
0.25
In Tie, a bec phase appears
below 0,1 kbar and the melting pres

sure has minimum at 0.32 K (Fig. 3 ) .
In
0.20
He, the bec field is very small,
and is replaced by hep at the lowest

temperatures (Fig. 6 ) . The melting
curve of
-S 0.15 -
He has a very flat minimum
at 0.78 K.
This curve has been
extended to 14 kbar, at which pres

sure the melting temperature is 7? K.
0.10=
3
In
He the normal Fermi liquid
persists down to a temperature of
0.05 -
1 mK, where a transition to recently

discovered superfluid phases occurs
13
(Fig. 4 ) .
The boundary separating
2
4
Temperature - K
the normal Fermi liquid from the A

and B su?erfluid phases represents a
second-orn>;c phase transition, like
Fig. 3.
The phase diagram of

helium - 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

helium - 3 .
i
3

helium - 4 .
Fig. 6.
t h a t in
i
,
i\ .
1
2
Temperature - K
He.
The A-B phase boundary
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
are thought t o be superfluids t h a t

r e s u l t from weak coupling of fermions
s i m i l a r t o t h a t found in supercon
ductors.
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

helium - 4.
shown in Fig. 7.
-5-
Upon cooling to
80
'
1
LITHIUM
60
'
which suggests t h a t a melting point

maximum w i l l occur a t a somewhat
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
The bcc phase i s about
P% more dense, giving r i s e t o t h e

negative slope of the phase boundary.
The hep-bec phase boundary has been
/,
600
Temperature - K
Fig. 7.
Beryllium has a
t r a n s i t i o n from hep t o bcc j u s t
determined to 60 kbar.
The same
study yielded two other r e s i s t a n c e

anomalies belcw 1000 K t h a t appear to
The phase diagram of lithium.
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
about 80 K, l i t h i u m changes from bcc
than to genuine phase t r a n s i t i o n s .
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
sharp drop i n r e s i s t a n c e at 70 kbar

and 296 K, which i s shown by the
c i r c l e in Fig. 7.
The s t r u c t u r e of
500
the high pressure phase i s not
1000
1500
Temperofure - K
known. The melting curve of l i t h i u m

has been determined to 60 kbar.
Fig. 8.
The melting temperature becomes

n e a r l y constant a t t h i s p r e s s u r e ,
-6-

beryllium.
2000
at pressures above 100 kbar and tem
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 e r a t u r e s near 2000 K, but the
d i s c o n t i n u i t y at 93 kbar and 293 K,

but other i n v e s t i g a t o r s have been
19
unable t o repeat t h i s r e s u l t .
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
The melting curve has been determined

to 60 kbar.
Solid boron i s covalently bonded.
CARBON
The phase diagram i s e s s e n t i a l l y

unknown.
Many different
crystal
The phase diagram of carbon is
s t r u c t u r e s of boron have been

described in the l i t e r a t u r e *
shown in Fig. 9.
but
This phase diagram
has been the subject of much experi
t h e i r r e l a t i o n s h i p to one another i s
mental work owing to the problem of
unclear.
producing artificial diamonds.
Furthermore, contamination
of boron with metals and the formation

of boron-rich borides has a strong
effect on the c r y s t a l s t r u c t u r e .
It
i s suspected t h a t many of the s t r u c

tures reported for pure boron a r e i n
fact those c- b o r i d e s .
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
complex s t r u c t u r e can be resolved i n t o

groups of linked lcosahedra of boron
atoms.
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.
The phase diagram of carbon.
Shock wave experiments
However, the very high temperatures

and pressures involved have made the
up to a
fdw hundred kbar c l e a r l y show the
measurement of the phase boundaries
graphite-diamond t r a n s i t i o n , but t h i s
extremely d i f f i c u l t , and the phase
i s dominated by nonequilibrium e f f e c t s
diagram cannot be s a i d t o be firmly
and the i n i t i a l s t a t e of the g r a p h i t e .

26
The s i g n i f i c a n c e of shock data
established.
Graphite, the s t a b l e phase at
i n d i c a t i n g a new phase at yet higher
low p r e s s u r e s , has hexagonal l a t t i c e
p r e s s u r e i s s t i l l uncertain.
symmetry.
r e c e n t l y , Vereshchagin's group has
Graphite c o n s i s t s of plane
s h e e t s of covalently bonded atoms.

The sheets are bonded to each o t h e r
by weaker van der Waals forces.
The
high pressure diamond phase i s cubic,

with e i g h t atoms per unit c e l l .
Each
atom i s covalently bonded to four
Very
observed a t r a n s i t i o n from the diamond

to a m e t a l l i c phase at pressures of
27
They a l s o
approximately 1 Mbar.
observed t h a t the t r a n s i t i o n pressure

drops with increasing temperature,
which i s s i m i l a r t o the behavior of
neighbors located at the corners of
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.
Because diamond i s metastable at

room temperature and p r e s s u r e , the
free energy difference between graphite
and diamond can be computed from
The melting temperature of

graphite shows a maximum near 5000 K
and 50 kbar according to recent
28
Uncertainties in the tempera
work.
measured thermodynamic d a t a , and the
t u r e measurements are l a r g e .
graphite-diamond phase boundary can

24
be e s t a b l i s h e d .
This has been done
of diamond has not been reported, but
Melting
the melt ng curve i s assumed to have
with reasonable accuracy up t o 1200 K.
a negative slope by analogy with
and 40 kbar.
silicon.
Beyond t h i s , the a c t u a l
transformation of graphite to diamond

in t r a n s i t i o n - m e t a l matrices has been
24
c a r r i e d out.
These measurements
extend the phase boundary t o 80 kbar.
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
in the s o l i d and l i q u i d phases i s
results.
Together with the melting
Nitrogen
composed of diatomic molecules
curve, t h i s y i e l d s a g r a p h i t e -
weakly bonded to each o t h e r by van der
diamond-liquid t r i p l e point near 100
Waals and electrlc-quadrupole forces.

29
Three s o l i d phases are known.
In
kbar and 3500 K.
'
'
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 cubic a phase, the molecules are

centered on an fee lattice with the
molecular axe* pointing along body
diagonals.
This ordering is pre
sumably stabilized by quadrupolar

forces.
At 36 K, the cubic phase
transforms to a hexagonal phase in

which the molecules are centered on
an hep lattice and are thought to be
rotatlonally disorderad.
The Y phaae
is a tetragonal structure with two

molecules par unit call. The molecules
are packed In shsats with the mole

nitrogen.
cular axes all aligned and lying In
-9-
the plane of the s h e e t .
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
of the molecular axis s h i f t s by 90
ordering of the spins in the t r i p l e t
from one sheet to the next.
ground s t a t e .
The
A t r a n s i t i o n to the
s o l i d - s o l i d phase boundaries have
rhomb oh e d r a l 0 phase, which i s para
been determined t o about 10 kbar

(Fig. 10) 30 The melting curve has
magnetic, takes place a t 24 K.
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
t r a n s i t i o n to the cubic Y phase, a l s o

paramagnetic, takes place with l a r g e
This phast.
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
close packed with d i s t o r t i o n s i n t r o
s o l i d and l i q u i d phases i s composed
duced by the non-spherical molecules.
of diatomic molecules weakly bonded

by van der Waals and e l e c t r i c quadrupole forces.
are known.
10
All
of these phases may be regarded as
Three s o l i d phasa
The s o l i d - s o l i d phase boundaries have

32
been determined to a few kbar
The
melting curve has a l s o been determined
33
to 3.5 kbar.
The monoclinic a phase
FLUORINE
i'i'i'r
OXYGEN
The phase diagram of fluorine

is shown in Fig. 13.
Fluorine in Che
solid and liquid is composed of

diatomic molecules weakly bonded by
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
Fig. 12. The phnsa diagram of oxygen.

-10-
Fig. 13. The phase diagram of fluorine.
van der Waals and electric-qttadrupole

forces.
At low temperatures fluorine
i s tnonoclinic with a s t r u c t u r e very

s i m i l a r to a - 0 2
At 46 K a t r a n s i t i o n
with a large volume change takes

place t o cubic g-luorine.
This
phase i s i s o s t r u c t u r a l with Y-0-,

and the l a t t i c e i s r o t a t i o n a l l y d i s
ordered.
The s i m i l a r i t y between
B-F and y-Oo i s seen in the close

2
agreement in the t r a n s i t i o n temperatures

and the melt temperatures i n the two
elements.
The a-$ phase boundary in
Fig. 13 a s determined from the AH

and AV of t r a n s i t i o n 5,34 The melt
W
50
ing curve has been determined to

only a few b a r s .
100
Temperature - K
Fig. 14. The phase diagram of neon.
NEON
The phase diagram of neon is

shown in Fig. 14.
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.
Solid neon i s fee.
The
malting curve has been determined to

10 k b a r .
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
change leads to a bec structure which

persists up to melt.
400
Temperature - K
The phase
Fig. 15. The phase diagram of sodium.
boundary separating the two phases
-11-
i | i i I i | i i i i | i i
MAGNESIUM
has not been reported, but the densi

t i e s are so nearly equal
40
that the
i n i t i a l value of dl/dp should be close

to zero, as indicated in Fig. IS.
Static high pressure measurements in
the solid up to 600 kbar reveal no

phase changes.
30
The melting curve
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
ments on magnesium under s t a t i c h i g h
Fig. 16. The phase diagram of

magnesium.
pressure show indications of a slug

gish phase transition near 100 kbar. 37
The structure of the high pressure
phase i s undetermined.
The melting
curve has been determined to 40 kbar'38
80
i i i | i i i i | i i i i
and the results have been corrected
ALUMINUM
to the atmospheric-pressure melting
60
point In Fig. 16.
S 40h
n
ALUMINUM
fee
f Liquid
20The phase diagram o f aluminum i s

shown I n F i g , 1 7 .
fee.
S o l i d aluminum i s
S t a t i c high preaaure measure
0UJ
ments tentatively indicate a p a r t i a l

39
transformation to hep at 205 kbar.
The melting curve haa been determined
40
to 60 kbar.
-12-
*!
500
1000
Temperature - K

aluminum.
1500
250
SILICON
i i i i | i i i i | i i I i | i i
SILICON
The phase diagram of s i l i c o n i s

shown in Fig. 18.
200-
Normal s o l i d s i l i c o n
Tetragonal
(white tin)
i s covalently bonded semiconductor

with the cubic diamond s t r u c t u r e .
.3150
S t a t i c high pressure measurements

show a sharp drop in r e s i s t i v i t y near
41
200 kbar.
Subsequent x-ray work
100
showed t h i s phase to have the t e t r a 42

gonal white t i n s t r u c t u r e .
Here
each atom has four nearest neighbors
50
and two next nearest neighbors lying

s l i g h t l y f a r t h e r away.
The accurate
determination of the phase boundary
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
of s i l i c o n compressed above 100 kbar

has yielded a complex cubic form with
43
16 atoms per unit c e l l .
This
Fig. 18. The phase diagram of silicon.
uncertainty in the phase diagram i s

indicated by a dashed l i n e i n Fig. 18.
At low p r e s s u r e s , s o l i d s i l i c o n melts
to a more-dense m e t a l l i c l i q u i d .
30
The melting curve Has been measured

to 200 kbar, and a c l e a r - c u t t r i p l e
44
point occurs at ISO kbar.
Shock
wave experiments a l s o show phase
t r a n s i t i o n s i n the 100-200 kbar
45
region,
but t h e i r p r e c i s e nature
' I ' ' '

PHOSPHORUS
20-
Jiof-
Ortho rhombic
Liquid
i s unknown.
PHOSPHORUS
500
1000
Temperature - K
The phase diagram of phoaphorua

I s shown i n Fig. 19.
Of Che various
1500
FiE. 19. The phaae diagram of

phosphorus.
a l l o t r o p i c form of phosphorus that

-13-
have been prepared, black phosphorus
molecules) per unit cell in a very
appears to be the most stable phase
complex arrangement.
at atmospheric pressure.
the solid is monoclinic, with 48
Black phos
Above 360 K,
phorus has an orthorhombic structure
atoms (6 molecules) per unit cell.
consisting of puckered layers of
The orientations of two of the six
covalently bonded atoms.
molecules in each unit cell are dis

ordered.
At room temperature and about

50 kbar, black phosphorus undergoes
There is much disagreement about
a phase change to a rhombohedral
the structures of the high pressure
lattice, isostructural with arsenic.46
phases and the phase boundaries
A further transition near 110 kbar
separating them.
to a simple cubic structure was also

46
observed.
The rhombohedral lattice
shown in Fig. 20 is due to Vezzoli,
is a simple distortion of the simple
the solid were detected by means of
cubic, and thus the phase transition
volumetric, optical, and electrical-
is easily reversible.
resistance techniques.
Conductivity
studies indicate that the cubic phase

47
is metallic.
Solid-solid phase
et al.
The phase diagram
The phase boundaries in
The phase transitions are often

difficult to detect, as indicated by
boundaries have not been determined.
the dashed boundaries in Fig. 19.
The melting curve of othorhombic
The large number of phases can be
black phosphorus has been determined

48,49
to about 20 kbar
conformational changes in the S
understood as a series of stepwise

g
rings
with changes in temperature and

pressure.
The structures of the
SULFUR
phases other than the well-known I
and 11 have not been worked out,
The phase diagram of sulfur is

shown in Fig. 20.
although there is evidence that phase
The literature on
the allotropy of sulfur presents the
XII is monociinic, with closely
most complex and confused situation
packed helical chains of atoms
of all the elements.
under room conditions is composed of
similar to the selenium and tellurium

53
rfructures.
Resistance measurements
covalently bonded S rings that inter
on sulfur compressed to 400 kbar
act with each other through van der
showed no transition to a metallic

.. 54
scate.
Waals forces.
Solid sulfur
Below 360 K at atmos
pheric pressure sulfur has an ortho-
The melting curve shows a number
rhombic lattice with 128 atoms (16
of definite cusps attributed to the

-14-
SULFUR
40 -
Monocltnic
II
Fig. 20. The phase diagram of eulfur.

-15-
intersection of solid-solid phase
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 .
"phases" (indicated by letters) in
t u r e , composed of
Solid
c h l o r i n e has an orthorhombic
struc
approximately
the liquid using DTA techniques.
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 .
These regions in the liquid appear to
m e l t i n p curve has been determined
be different polymeric states result
7 kbar.
The
to
ing from the breakup of the Sg rings.

The nature of the transitions joining
ARGON
the liquid phases is not clearly

understood.
The lower portion of the
The phase diagram of argon is
melting curve given by Vezzoli t_ al.
shown in Fig. 22.
has been independently confirmed.
and liquid is composed of atoms weakly
Argon in the solid
bonded by van der Waals forces.
Solid
argon is fee.
The melting curve has

31
been determined to 26 kbar.
CHLORINE
The phase diagram of chlorine is
shown in Fig. 21.
Chrlorine in the
POTASSIUM
solid and liquid states exists as

The phase diagram of potassium is
iir-
shown in Fig. 23.
CHLORINE
bcc.
.s
30
4 -
Solid potassium is
No martensitic transition of the
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

chlorine.
Fig. 22.
-16-
The phase diagram of argon.
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
potassium.
kind occurlng i n Li and Na i s
1000
1500
Temperature Fig. 24. The phase diagram of calcium.
found
in potassium upon cooling t o 5 K.

However, S t a g e r and Drickamer
found
measurements at 77 K showed a sharp
two r e s i s t a n c e anomalies a t 280 kbar
rise in resistance near 140 kbar and
and 360 kbar a t 77 K.
t i o n s were not observed at 296 K.
a subsequent sharp drop near 400

58
kbar.
These data were ascribed to
The authors suggest t h a t the more
two rather sluggish phase transitions,
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
first cu . semimetallic, then to a
gous t o the low temperature t r a n s i t i o n
metallic phase.
in Li and Na.
rough accord with later Soviet

59
work.
The melting curve of calcium
The melting curve of
potassium has been determined t o

80 k b a r .
1 6
These data are in
SCANDIUM
CALCIUM
Scandium is hep at atmospheric
The phase diagram of calcium is

shown in Fig. 24. Under room condi
pressure.
tions calcium i* fee.
sistance measurements at room temper
Near 700 K at
one atmosphere it undergoes a transi

tion to a bcc structure.
Static high pressure re
ature showed no evidence of a phase

change to 140 kbar.
The phase
Shock wave
boundary has been measured to 30
measurements by Carter, e_t_ al_. showed
kbar.
a kink in the u -u curve at

s p
High pressure resistance

-17-
approximately 350 kbar.
This was
Shock wave experiments show a
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.
strong break in the u -u curve for

s p
No kink
titanium, indicating a phase change
was found i n the shock v?ave work of

Gust and Royce.
1812 K.
occurring at 175 kbar.
Scandium melts a t
The nature
of this phase transition has not been
The melting curve has not
determined.
been r e p o r t e d .
1941 K.
Titanium melts at
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
phase transitions have been reported.
transformation to a bec phase occurs
Vanadium melts at 2178 K.
near 1150 K. The phase boundary has
melting curve has not been reported.
The
been determined to about 110 kbar,

where a triple point occurs.
CHROMIUM
The low temperature, high pressure ui

The phase diagram of chromium i
phase may be regarded as a distorted
shown in Fig. 26. Pure chromium is
bec lattice with hexagonal symmetry.
antiferromagnetic below 311 K and
This structure has three atoms per
paramagnetic above this temperature.
unit cell and two distinct types of
Although there has been some contro
atomic positions.
versy about various allotropes of
T T
7"l""l""-
mp
hep
bcc
1000
^-'Tetragonal
J
J
I2
U-iquid;:
*. i i i 1 i ' 1111 11 1 11i
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

titanium.

chromium.
-18-
50
chromium, it Is probable that the

paramagnetic phase is simple bcc up
to the melting point.
I I I I I I 1 I I I I l I I I I
MANGANESE
Below 311 K,
the paramagnetic phase transforms to
40
an antiferromagnetic phase by a firstorder phase transition.
This phase
_8 30
is in a spin-density wave state In
Liquid
which the polarization is perpendicular

to the wave vector.
This magnetic
8 20
state is inconsistent with the reten

Cubic
tion of full cubic symmetry, and the
lattice instead takes on a very slight
(a)
10
orthorhombic distortion of the bcc

lattice.
At 123 K, another first-order
tr
|_iiiiL_
0
500
sition occurs to a new antiferro
which the polarization and wave vectors

are parallel.
1000
1500
Temperature - K
magnetic spin-density wave state in
This phase has a small
Fig.
27.

manganese.
tetragonal distortion of the bcc

lattice.
The lattice distortions in
the magnetic phase are too small to be

detected with present x-ray techniques.
The phase boundaries have been deter
mined to 8 kbar.
'
Static pressure
measurements at room temperature to

55 kbar show no other phase changes.
Chromium melts at 2148 K.
centered cubic l a t t i c e with 58 atoms

p e r u n i t c e l l and 4 d i f f e r e n t
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
occurs t o t h e fi form, thought t o have
20 atoms p e r u n i t c e l l and 2 types of

atomic p o s i t i o n s .
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
The phase diagram of manganese

i s shown i n F i g . 27.
t o the bcc 6 phase o c c u r s .
There a r e four
a l l o t r o p e s , a l l of cubic symmetry.
transition
The 'phase
boundaries and the melting curve have

71
been determined t o 40 kbar.
The a form has a complex body

-19-
IRON
ct-y, ct-e, and y~e phase boundaries

72
have been determined to 200 kbar.

The phase diagram of iron is
shown in Fig. 28.
The y-& transition and the melting
The phase diagram
curve have been determined to 52
and especially the melting curve of
kbar, where they meet in a triple

73
point.
The melting curve of the
iron is of great interest because of

the problem of the state of the
Y phase has been extended about 5

earth's core and the origin of the
geomagnetic field.
73
kbar beyond the t r i p l e p o i n t .
Under room condi
tions iron is ferromagnetic and has

a bcc structure.
COBALT
At 1044 K it passes
through the Curie point and near 1200
The phase diagram of cobalt is
K it transforms to the fee phase.
shown in Fig. 29.
The bcc phase once again becomes
ture cobalt is hep.
stable before melting.
depending on the sample grain size, a
Above 100
At room tempera
At a temperature
kbar, the bcc phase transforms to a
sluggish phase change to fee occurs.
nonferromagnetic hep phase.
For large crystal grains the trans
The
formation temperature is 661 K.
The
phase boundary has been measured to

50 kbar.
Cobalt melts at 1765 K.
The melting curve has not been

reported.
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.
The phase diagram of i r o n .
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
The phase diagram of cobalt.
80
I1I I 1
COPPER
The phase diagram of nickel i s

shown in Fig. 30.
fee.
Solid n i c k e l i s
60
The melting curve has been
'
40
80
" " I "
" I " ' I

NICKEL
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
The phase diagram of n i c k e l .
Fig. 31.
The phase diagram of copper.
COPPER
The phase diagram of copper is
shown in Fig. 31.
Solid coppfer is
fee.

75
7 ' 1 ' 1 '

ZINC
80
ZINC
J 60 -
The phase diagram of zinc i s

shown i n Fig. 32.
Solid zinc has a
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
d i s t o r t e d hep l a t t i c e , with the c / a
~
:
f Liquid
20
, 1 . *
. 1 . 1 /
2C10 400 600 8(10 1000 12C
Temperature - K
s o l i d - s o l i d phase changes are found

up t o 200 kbar.
The melting curve
Fig. 32.
-21-
The phase diagram of zinc.
80 L
GALLIUM
' ! '
Solid gallium at
'
TZ\
60
atmospheric pressure has an ortiiorhombic structure with eight atoms

per unit cell.
Orthorhombic
(III)
The phase diagram of gallium is

shown in Fig. 33.
GALLIUM
Each atom in this
I 40
structure has one nearest neighbor

and six other near neighbors somewhat
farther away.
At atmospheric pressure
gallium melts just above room temper
20-
ature, and the melting temperature
Orthorhcmbic
initially decreases with increasing

pressure.
(M
Gallium II is probably
body centered tetragonal.
I
I I
100
200
300
Temperature - K
The high-
temperature gallium-III phase is a

complex orthorhombic lattice with
40 atoms per unit cell.
Fig. 33.
The phase
400
The phase diagram of gallium.
boundaries, including the melting
250
| I I i | I i I
curve, have been determined to

,. ,.
78,79
75 kbar.
GERMANIUM
200
GERMANIUM
*
.
The phase diagram of germanium

Tetragonal
(white tin)
- 150
Solid germanium
under room conditions is a semicon
ductor with the cubic diamond struc60

ture. Above 100 kbar shock wave
and electrical resistance measure41
indicate the appearance of a
ments
new phase.
_
1
-
Cubic
(diamond)
This phase is metallic,
with the tetragonal white tin struc

ture.
Liquid
100
i l i t i i i . X i . i l
500
There remains some uncertainty
1000
1500
Temperature - K
concerning new phases obtained from

81
quenching experiments.
The cubictetragonal phase boundary and the
Fig. 34.
-22-

germanium.
netting curve have been determined up

44
to 200 kbat.
' ' I ' ' '
ARSENIC
60
ARSKNIC
The phase diagram of arsenic la
40
shown in Fig. 35. Ac atmospheric
pressure arsenic crystallizes in Che

prtnltlvc rhoabohedral laccice
characteristic of the group VB

elements-
Rhombohedral
Liquid
20
High pressure resistance
measurements shoved no anomaly up Co

82
200 kbar.
However, arsenic that
0
had been compressed to ISO kbar

showed a tetragonal structure, which
-iJ_
500
1000
1500
Temperature - K
may represent a high pressure phase.S3

Fig. 35.
The phase diagram of arsenic.
up to 60 kbar.
SELENIUM
I ' I ' I ' !

SELENIUM
The phase diagram of selenium is
60
shown in Fig. 36. Solid selenium at

lou pressure has a hexagonal crystal
structure composed of covalently
bonded helical chains of atoms. In
40
this state selenium is a semicon
Hexagonal
ductor. Near 130 kbar, a resistance

discontinuity is observed, and selenium
20 -
becomes a metallic conductor. *

An attempt to determine the structure
of this high pressure form was
87
unsuccessful.
The melting curve
has been determined Co 60 kbar.
I I I/I
200 400 600 800 1000 1200
Temperature - K
It shows a clear maximum in tempera

ture.
Fig. 36. The phase diagram of selenium.

-23-
BROMINE
140 kbar rather than 200 k b a r .
59
The lower transition is Indicated in

The phase diagram of bromine Is
Fig. 39 by a dashed line.
shown In Fig. 37.
These
Solid bromine Is
transitions are thought to correspond
composed of diatonic molecules held

to those observed in cesium at low
together by weak van der Haals
pressure.
forces.
The upper transition Is
The solid has an orthorhombic

likely to be due to a shift In the
structure, analogous to chlorine.

electronic configuration of the
Indirect evidence for a phase transi
rubidium atoms.
tion in solid bromine at 35 kbar has
91
been reported,
but no details of
the phase boundary or the structure
of the new phase are available.
The melting curve

The melting temperature appears to be
approaching a maximum near 80 kbar.
The
melting curve has been determined to

,
56,89
10 kbar.
STRONTIUM
KRYPTON
The phase diagram of strontium

Under room
conditions strontium is metallic with

The phase diagram of krypton is
an fee structure.
shown In Fig. 38.
pressure at room temperature or
krypton consist of atoms bonded by

weak van der Waals forces.
Is fee.
With increasing
Solid and liquid
The solid

36 92
'
below, strontium becomes semi94

metallic.
Hear 35 kbar, a phase
transition to the metallic bcc struc
ture occurs.
The unusual change
from a more efficient to a less effi

RUBIDIUM
cient packing with increasing pres
The phase diagram of rubidium Is
shown in Fig. 39.
electronic transitions mentioned.
At low pressures
solid rubidium is bcc.
sure appears to be due largely to the
Beyond the 3S kbar transition,
Bundy and
strontium shows metallic conductivity
Strong found a sharp resistance jump

93
near 75 kbar and room temperature.
with no indication of further trans
Stager and Drickamer found a sharp
itions up to 500 kbar.
rise In resistance near 200 kbar at
phase boundary intersects the p = 0
two temperatures.
Soviet work con
axis at 830 K.
The fcc-bcc
This boundary and the
firmed the 75 kbar transition, but
meltiig curve have been determined
found the next transition near 135-
to 40 kbar.
-24-
80
"HP
BROMINE
' ~T
RUBIDIUM
10
60
ji
2
_
OrthorhombTc
40
3
i
20
O0j - Fig. 37.
I
. I
100
200
300
Temperature - K
200
400
F i
The phase diagram of bromine.
'
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
The phase diagram of krypton.

-25-
I J U
500
1000
1500
Temperature - K
strontium.
hep phase transforms to bcc.
YTTRIUM
The
t r i p l e point joining the three phases

Solid yttrium at low pressure is
hep.
Above 110 kbar, yttriur.

95
becomes a superconductor,
A itudy
occurs near 60 kbar and 1000 K.
The
phase bounds.-ies have been uorked out

to 70 kbar.
of the pressure dependence of the
Vereshchagln observed
a sharp change of slope i n the
transition temperature indicates the
resist
ance as a function of pressure near
presence of several superconducting

96
However, these
100 kbar, but what t h i s means i s

97
A shock-wave study of
modifications.
unclear.
modifications are not thought to have

different crystal structures, but
zirconium showed a sharp break in the
rather arise from slight changes in
u -u curve at 260 kbar, which preP

66
band structure.
sumably indicates a phase change.
Zirconium melts at 2123 K .
Static resistance measurements
6 3
The
to 250 kbar shew no phase transition

97
anomalies.
Shock-wave experiments
by Gust and Royce showed a kink in Che
the u -u curve at 280 kbar.
s p
The
authors suggested that the kink
i i i i | i i i > | i i i i | i rn | n i _
ZIRCONIUM
80
indicated the stiffening of the solid

as inner electron cores overlapped.
Carter, e_t _ai. saw a kink
" Hexagonal !
in tk&
an explanation.
Yttrium melts at
63
1775 K.
been reported.
:y
60
u -u curve at 370 kbar and suggested

s p
a sluggish low pressure transition as
40
3
*?
ZIRCONIUM
hep
20
bcc
Liquid
The phase diagram of zirconium

mp\
Zirconium under
room conditions I s hep.
under com
pression i t transforms to the hexagonal

w phase i s o s t r u c t u r a l with u-titanium.
This i s a d i s t o r t e d bec phase.
Near
n
"0
500
1ill I 1 1 1 ulMI i L I 1000 1500 2000

Temperature - K

zirconium.
1140 K at atmospheric pressure the

-26-
RUTHENIUM
KI0BIW1
Solid ruthenium in hep.
Solid niobium is bcc. No
2741 K.
Com
pression to 400 kbar at room tespera99

tur* showed no change of phase.
resistance anomalies have been found

97
below 250 kber.
Niobium melts at
Ruthsnium melts at 2SS3 K .
6 3
The
been reported.
MOLYBDENUM
RHODIUM
The phase diagram of rhodium i s
The phase diagram of molybdenum

is shown in Fig, 42.
Solid molybdenum
is bcc.
An approximate melting curve

98
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
Solid palladium i s f e e .
um melts a t 1825 K.
Palladi
The m e l t i n g
curve has not been r e p o r t e d .

100
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.

molybdenum.
Fig.
-27-
43.
The phase diagram of rhodium.
to 250 kbar showed no strong

97
38
SILVER
anomalies.
The phase diagram of silver Is

shown In Fig. 44.
fee.
Solid silver Is
Compression to 300 kbar at room
INDIUM
temperature shows no evidence of a

phase change.
The phase diagram of indium i s
The melting curve
shown In F i g . 46.
Solid indium i s
body centered t e t r a g o n a l .
Compression
at room temperature t o 300 k ar shows
CADMIUM
no i n d i c a t i o n of any phase changes.

The phase diagram of cadmium Is
The melting curve has been d e t e r
shown In Fig. 45. Solid cadmium Is

hep.
mined t o 80 k b a r .
7 8
Compression In the 100-200 kbar
range shows small anomalies In the

resistance and hexagonal c/a ratio,
The phase diagram of t i n
and a sluggish phase transition has

37
been suggested as an explanation.
shown in F i g . 47.
is
Below 290 K at
Independent resistance measurements
Fig.
44.
200
400
600
800
Temperature - K
Temperature - K
The phase diagram of s i l v e r .
-26-
Fig. 45.
The phase diagram of cadmium.
1 1 1 1
iNDIUM
atmospheric pressure, tin i s cubic
80
:
|
diamond l i k e s i l i c o n and germanium.

Above this temperature tin has the
tetragonal white t i n structure with
60-
i "o
Tetragonal
/
/
four atoms per unit c e l l .
In this
structure each tin atom has four
Liquid
nearest neighbors at the vertices of

a flattened tetrahedron.
Two more
neighbors l i e s l i g h t l y farther 3way.
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
temperatute near 90 kbar, the white

tin transforms to a body-centered
Fig. 46.
The phase diagram of indium.
tetragonal structure with two atoms

per unit c e l l .
The boundary joining
the two phases has been approximately

determined to 95 k b a r .
'
1 0 4
Tht
melting curve has also been determined

. , , ,.
103,104
to 75 kbar.
*
100
1 0 3
ANTIMONY
80
The phase diagram of antimony is
60
40 -
shown in Fig. 48.
Tetragonal
(white tin)
Solid antimony
under room conditions is rhombohedral,

isostructural with arsenic.
At room
temperature, antimony has two phisa
20-
transitions, one near 70 kbar and one
Cubic
^(diamond)
near 85 kbar ( c i r c l e s ) .
105
The 70-
kbar transition is sluggish and appar
200
400
600
Temperature - K
800
ently has a very small volume change.

The phase II structure is simple
cubic, which corresponds to the
Fig. 47.
The phase diagram of t i n .
elimination of the low pressure
-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>
ductor, with a hexagonal structure
- \sn
composed of covalently bonded helices

packed together.
Liquid
This structure can
be regarded as a distortion of the

simple cubic lattice.
20
Solid tellurium
under room conditions is a semicon
Rh'ombohedral \
Near 40 kbar
at room temperature (circle), a

transition to a metallic phase occurs.
I I I
0
500
'
'
1000
'
'
'
The structure of this phase has not

108
yet been determined.
Near 70 koar
1500
Temperature - K
at room temperature (circle), a
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

antimony.
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
tion, at 85 khar i s wore strongly

marked, with n o t i c e a b l e volume and
r e s i s t a n c e changes.
The s t r u c t u r e
80
of phase I I I i s u n c e r t a i n , but recent

worfe suggests a t e t r a g o n a l s t r u c t u r e
analogous t o t h a t found i n a r s e n i c at
high p r e s s u r e s .
Phase I I I shows
82
good m e t a l l i c c o n d u c t i v i t y .
The
melcing curve has been determined to
70 kbar.
'
Two cusps, i n d i c a t i n g
"^
Rhombohedral (III)
60
ll
; 40
Hexagonal
20
t r i p l e p o i n t s , have been found, one

at 3.9 kbar, and the other at 57 kbar.
Stishov and Hkhomlrova
-i
"0
assumed
J i g . 49.
t i o n s , as indicated in Fig. 48.

-30-
L
200
J_
400
J
L
600
800
Temperature - K
that the two t r i p l e p o i n t s corresponded

t o the two room temperature t r a n s i
TELLURIUM

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
the diatomic moleculea within the
The s o l i d - s o l i d phase boundaries and
orthorhombic unit cell.
the melting curve have been d e t e r

mined t o about 70 k b a r .
At higher pressures, above 100
A definite
maximum i n the melting temperature
kbar, the resistance of iodine drops

113
rapidly to a metallic value.
Here
i s found near 10 kbar.
It is thought that the I molecules
IODINE
structure.
dissociate into an atomic metallic

It is not clear whether
this is a continuous or an abrupt

The phase diagram of iodine is
shown in Fig. 50.
transition.
Solid iodine at
low pressures is composed of diatomic
plot of u
molecules in an orthorhombic lattice,
at approximately
Given a transition to
the metallic phase at a much lower
No clearly defined phase
pressure, this break is likely to
transition has been found at moder

ate pressures,
vs u
700 kbar.H4
isostructural with solid bromine and

chlorine.
Shock wave experiments
on iodine show a strong break in the
represent a phase transition from
but an x-ray study
one metallic phase of iodine to
of the solid to 60 kbar showed a con
another.
tinuous shifting of x-ray

112
reflections.
This was interpreted
as a shifting of the orientations of
XENON
50 -
' i r
'
The phase diagram of xenon is
IODINE
shown in Fig. 51. Solid and liquid

xenon are composed of atoms bonded
u
o
M
40by weak van der Waals forces.
g 30-
Solid
xenon is fee.

92
Orrhorhombic
i 20CESIUM
10-
The phase diagram of cesium is

0L0
200
400
600
800 1000
shown in Fig. 52. Cesium has been

intensively studied because of its
Temperature - K
unusual properties.
Fig. 50.
The phase diagram of iodine.
Solid cesium at
atmospheric pressure is bcc. At
-31-
room temperature the bcc phase t r a n s

forms t o fee at 23 kbar.
Further
compression y i e l d s two more phase

t r a n s i t i o n s only about 1 kbar apart
near 42 kbar.
The f i r s t new phase
i s also f e e , but the s t r u c t u r e of the

second (IV) has not yet been d e t e r
mined.
The s o l i d - s o l i d phase
boundaries have been determined,
'
and they show very weak temperature

depenlence, except that t h e upper
200
400
fee phase apparently disappears a t
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 phase diagram of xenon.
and has e x c i t e d much c u r i o s i t y .
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
to 5d character of the conduction

120
Although details of this
CESIUM
band.
IV
theory have been criticized, it is
>.. 4 0
fcc^
fee
widely agreed to be qualitatively
~"
correct.
.a:
r
30
K
10
s o l i d cesium occurs near 125 kbar,

accompanied by a large increase in
5
resistance.
This phase (V) e x h i b i t s
bcc
superconductivity and i t has been

suggested t h a t the phase i s
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
The melting curve of cesium has

been worked out to 55 k b a r .
1 1 7 , 1 1 8
Two melting temperature maxima occur
Fig. 52.
The phase diagram of cesium.
near the bcc-fcc transition.
-32-
The
decreasing melting temperature of
i i i i I i r i i I 11 i i i
BARIUM
the close-packed fee phase i s due to
the density of the l i q u i d increasing

beyond t h a t of the s o l i d .
This phe
nomenon has been ascribed t o the

smearing out i n the l i q u i d of the
sharp e l e c t r o n i c t r a n s i t i o n observed
in the s o l i d .
Liquid
Thus the volume con
t r a c t i o n in the l i q u i d can be thought

of as a smoothly varying change in.
r e l a t i v e concentration of two
electronic species,
whereas i n
the s o l i d t h i s change t a k e s place a l l

at once.
'
'
500
The melting curve of
'
'
'
'
'
1000
'
1500
Temperature - K
phase IV once again takes on a normal

appearance.
Fig. 53.
The phase diagram of barium.
BARIUM
The phase diagram of barium is
shown in Fig. 53.
Solid barium at
atmospheric pressure is bcc.
At room
Drickamer
found a further transi
temperature, a well-marked phase

122
transition occurs at 55 kbar.
tion at 144 kbar and room tempera
The high pressure phase has been

123
determined to be hep.
There is
study that this was a melting transi
ture, and inferred from a detailed
tion.
Later work indicated a solid129
disagreement over the trajectory of

solid transition instead.
the bec-hep phase boundary, since

further transition at 240 kbar was
DTA measurements
show dp/dT > 0

125
found at 77K, presumably to yet
while resistance measurements

show dp/dT < 0.
evidence
another solid phase.
Additional
supports the first possi
bility, which is shown in Fig. 53.
The melting
curve has been determined to about
nn it.
124,125,128
, .
90 k b a r ,
*
*
and three
A second phase transition to a phase
melting-curve maxima appear.
(III) of unknown structure has also
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
while t h e second a s c r i b e s i t to the
LANTHANUM
i n t e r s e c t i o n of the Hugoniot and the

The p h a s e d i a g r a m o f
i s shown i n F i g . 5 4 .
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.
The fcc-bcc boundary
and the melting curve have been

determined to n e a r l y 40 kbar.
From 0 t o 580 K,
the s t a b l e phase i s dhcp.
At 580 K,
CERIOM
a pftase t r a n s i t i o n to an fee phase

occurs with a decrease i n volume.
The phase diagram of cerium is
The dhep-fee phase boundary has been

131
worked out to 24 kbar.
At 1130 K,
shown in Fig. 55.
a t r a n s i t i o n t o a bec phase occurs,
At zero Kelvin and atmospheric
and melting occurs near 1200 K.
pressure, cerium is fee.
E l e c t r i c a l r e s i s t a n c e measurements
approximately 100 K and 45'J K, a
made to 250 kbar sfiow a smalt r e s i s t
dkep phase is stable.
ance anomaly near 100 kbar, which
and 1000 K, the fee phase is again
This unusual
diagram has been intensively studied.
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 .
stable, with the difference that the
Ttyo s e t s of shock wave .xperiments show kinks i n t h e u s-u_,p curve
Y phase is ferromagnetic while the

a phase is paramagnetic.
A bec phase
for lanthanum a t 250 kbar*2 ^ a

61
225 kbar
The dhcp phase disappears at low
the fcinfc t o xenon core r e p u l s i o n s , 62
pressures.
then intervenes just before melting.
The first report ascribes
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.

lanthanum.
Fig. 55.
-34-
Liquid
7) L '
_|
facc
1_L ' ' " I I

500
1000
1500
Temperature - K
The phase diagram of cetium.
The unique feature of the cerium
rx-y phase boundary and ct-a* phase
diagram is the isostructural a -* y
boundary leads to points very near
phase transition, which ends in a
one another on the melting curve.
critical point estimated from

134
resistance measurements
to lie at
Stager and Drickamer reported a
17.5 kbar and 550 K.
A considerable
theoretical effort has been made to

explain the a * y phase transition
further possible phase change near

138
160 kbar a t room temperature.
Two
s e t s of shock wave data give d i s c o r 61,62 _
dant r e s u l t s .
In one c a s e , a
1fc
represented a promotion of the
kink in the u -u curve was found at

s p
61
480 kbar and ascribed to melting.
In the o t h e r case, no kink was
localized 4f electron to the delocal-
*
found.
and critical point.
The earliest
theories assumed that the transition
i2ed 5d band.
135
6 2
The melting curve of cerium has

134
The
Later theories
modified this by assuming only a

135
partial 4f derealization .
Such
models imply a definite increase in
the melting temperature around 33
the number of conduction elections as
kbar.
the pressure is Increased.
in terms of isotherms s i m i l a r i n
But
remarkable feature i s a minimum In

Jayaraman explains the minimum
this is contradicted by positron-
shape to the s u p e r c r i t i c a l isotherms
annihilation experiments that
observed in the v i c i n i t y of the

134
liquid-vapor c r i t i c a l p o i n t .
indicate no change in the number of

135
conduction electrons.
In general
it could be said that the y -* a

transition results from the Inter
These isotherms r e f l e c t the rapid

decrease in the s i z e of the cerium
atoms in the s o l i d phase as the
pressure i s increased.
action of the 4f and conduction

electrons, but the precise model of
this interaction is disputed.
Further compression of cerium
leads to another phase transition in
the 50-60 kbar range.
The new
PRASEODYMIUM
The phase diagram of praseodymium
Normal s o l i d
phase (a ) has been determined to be

orthorhoiribic, isostructural with
137
a-uranium.
The phase boundary has
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
been determined over a r e l a t i v e l y
The t r a j e c t o r y of the dhep-fee phase
short temperature range, but i t i s
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
boundary and the melting curve have

131
1 -
60
40
|"i i
PRASEODYMIUM
80
The phase diagram of neodymium
i s shown i n Fig. 57.

\
20
fee
NEODYEtCH
dhcp\
\
_L
500
Liquid "
y
V . I #.
1000
Under room
conditions neodymium i s dhep.
High
pressure tf-ray s t u d i e s at room

temperature show a t r a n s i t i o n to the
139
fee phase near 50 kbar ( c i r c l e ) ,
This t r a n s i t i o n i s very d i f f i c u l t t o
. . 1 , .
1500
Temperature - K
d e t e c t , and the i n t e r s e c t i o n of the

phase boundary with the p 0 a j d s ,

praseodymium.
although suspected, could not be

140
directly measured.
Instead, a
because i t i s extremely sluggish and
temperature of 960 K is inferred from
apparently q u i t e s e n s i t i v e to
a generalized
1UX rare earth phase
diagram,
Impurities.
An approximate value for
the zero-pressure t r a n s i t i o n
temperature i s 833 K. **
Resistance
80 -
measurements t o 500 kbar show
"
-\ 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-
pressure phases of unknown s t r u c t u r e

138
above Che fee phase.
Two s e t s of shock-wave experiments
show kinks i n the u - u
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.
A bec phase appears
60 --
dh
-36-
=p
"
/
/
Lc
'
Liquid
20
_L, 1 1 . 1 1 1 1 \ l
0
0
Fig. 57.
The bcc-fcc phase
/
/
500
J 1 I !..!__)
1000
1500
Temperature - K
neodyroium.
on neodymium up to 600 kbar showed
1 1 1 1 | 1 I 1 1 | 1 1I I | I l
80
SAMARIUM
anomalies in the 100-200 kbar region

at d i f f e r e n t temperatures, which
1 60
could correspond t o another h i g h 138

pressure phase t r a n s i t i o n .
1
V
Two s e t s of shock-wave experiments
and 250 kbar.
The f i r s t report ascribes the kink t o

62
xenon-core r e p u l s i o n s ,
while the
second i d e n t i f i e s i t with melting. 61
A bcc phase appears before melt.
I bee
40
20 _
Rhombohedral
(Siti)
!
n
0
500
Fig. 58.
curve have been determined t o 60

kbar.
xl
1
"
/Liquid"
i 1 1 ill A 1 l_
1000
1500
Temperature - K
The
bcc-fcc phase boundary and the melting
5
c
show kinks in the u -u curve for

s p
neodymium at 280 kbar
dhcp

samarium.
henceforth c a l l e d "Sm-type." R e s i s t
ance measurements to 600 kbar at
PROMETHIUM
room temperature show anomalies near

50 kbar and 160 kbar t h a t might cor
respond t o phase t r a n s i t i o n s 138 The
Promethium I s dhcp at room

temperature and p r e s s u r e . 142
Prom
ethium has not been extensively worked

with because the element i s unstab7i,
and the most-easily a v a i l a b l e isotcpe
has a h a l f - l i f e of 2.6 y e a r s .
40 kbar and 623 K ( c i r c l e ) .

Two s e t s of shock wave e x p e r i
ments show kinks in the u -Up curve
s
The
melting temperature i s 1315 K.
dhcp phase appears in samarium near
for samarium a t 310 kbar*>2 and 270
No
kbar.
The f i r s t report a s c r i b e s
the kink to xenon-core repulsions 62
high-pressure work has been reported.
while the second i d e n t i f i e s i t with

melting.
SAMARIUM
The phase diagram of samarium i s
shown in Fig. 58.
A phase assumed to be
bcc appears before melt-
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
Under room condi
tions samarium has a close-packed
boundary i s assumed to represent the

131
Sra-type-dhcp-bcc t r i p l e p o i n t .
s t r u c t u r e of rhombohedral symmetry.
The b c c - s o l i d phase boundary and the
The arrangement of close-packed
melting curve have been determined to

131
60 kbar.
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
atmospheric pressure i s bcc.
phase transformation. Bakanova

146
et a l .
found a kink i n the u -u
s p
curve at 386 kbar and ascribed t h i s
t o an e l e c t r o n i c rearrangement.
Below
It Is possible that the anomalies
88.6 K, europium i s antiferromagnetic,
in the shock data correspond with the

138
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.
The t r a n s i t i o n has been

144
determined t o be f i r s t o r d e r ,
ascribed t o a d i v a l e n t - t r i v a l e n t
which means t h a t the bcc l a t t i c e i s
According t o t h i s theory, the
which has been
e l e c t r o n i c phase t r a n s i t i o n .
very s l i g h t l y d i s t o r t e d in the mag
anomalously d i v a l e n t europium becomes
n e t i c phase, as in the case of
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.
The pressure dependence of
the t r a n s i t i o n has been determined t o

145
90 kbar.
I t has been suggested
that as the l a t t i c e becomes l e s s com
The europium melting
curve has been detei-mined to 70
.,
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 ,
appears near 30 kbar.
the f i r s t - o r d e r t r a n s i t i o n simply
analogy between the behavior of

europium and barium has been pointed
out.
stops at about 20 kbar and gives way

to a pure second-order transition.
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
u -u curve at 106 kbar, and sugs p

gested t h a t t h i s corresponds to t h e
i n t e r s e c t i o n of Hugoniot and melting

curve.
Gust and Royce
500
1000
1500
Temperature - K
found
anomalous behavior in the 180-360
Fig. 59.
kbar range and suggested a sluggish

-38-

europium.
e l e c t r o n i c t r a n s i t i o n in the
GADOLINIUM
solid.
A bcc phase appears before melt,

The p h a s e d i a g r a m of
i s shown i n F i g . 6 0 .
gadolinium
Under room
conditions gadolinium i s hep.
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 .
The phase diagram of terbium is

shown in Fig. 61.
been reported at 27 kbar (circle),
and the high pressure phase has been

determined to be the Sm-type.
repulsions,
while the second i d e n t i f i e s
A resistant
anomaly indicating a transition has
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
Under room condi
tions terbium is hep.
Two s e t s o f s h o c k wave e x p e r i
s
and
a kink i n t h e bec-hep phase boundary
Resistance measurements to 500 kbar
i t w i t h an
show smooth behavior and no clear
1 -
GADOLINIUM
40
1
. Rhombohedral
(Sm-type)
1
1000
2000

gadolinium.
^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
The phase diagram of terbium.
Two s e t s of shock-wave e x p e r i
ments show kinks in the u -u curve
s p
evidence of further phase t r a n s i 138

tions.
The approximate hcp-Smtype boundary i s based on a g e n e r a l
ly 1
for dysprosium at 480 k b a r
ized r a r e - e a r t h phase diagram.
6 2
and 305
The f i r s t report a s c r i b e s
the kink to xenon-core r e p u l s i o n s , 62
Shock-wave experiments show a

kink in the u -u curve at 400
61
61
kbar.
This i s ascribed t o melting.
s
61
kbar
while the second I d e n t i f i e s i t with
melting.
The bcc-hcp boundary and
the melting curve have been d e t e r
The bcc-hcp phase boundary and the
mined to 25 and 8 kbar,
melting curve have been determined

131
t o about 25 kbar.
respectively.
DYSPROSIUM
HOLMIUM
The phase diagram of holmium i s
The phase diagram of dysprosium

shown i n Fig. 63.
Under room
conditions dysprosium is hep.
Under room condi
t i o n s holmium i s hep.
A transition
t o the Sm-type phase occurs a t 65

149
kbar
and room temperature.
Resistance measurements on holmium t o
transition to the Sm-type phase occurs

at 45-50 kbar and room tempera-
60,149
. ^
ture.
on dysprosium show anomalies near
D
600 kbar show no c l e a r evidence of
200 k b a r , which may i n d i c a t e a phase
any f u r t h e r phase changes.
transition.
15
2 10 -
1000
2000
3000
Temperature - K
Fig. 62.

dysprosium.
Fig. 63.
-40-
'
(L-bcc
_i_i_Li
1
HOLMIUM
hep
Liquid _
I
1000
2000
Temperature - K
3000
The phase diagram of holmium.

kink in the u -u curve of holtnium
s p
at 440 kbar, which i s ascribed to
melting 61 The hcp-bcc phase
THULIUM
The phase diagram of thulium i s
shown i n Fig. 65.
boundary and the melting curve have

131
been determined t o 10 kbar.
A transition
to the Sm-type phase occurs a t room

149
temperature near 110 kbar.
Resistance measurements t o 500 kbar
show no clear evidence of any further
138
phase changes.
The phase diagram of erbium i s

shown in Fig. 64.
Under room condi
tions thulium I s hep.
Under room condi
kink in the u - u curve, which i s

A t r a n s i t i o n to
61
No bec phase
149 ascribed t o melting.
131
has been detected before melt.
the Sm-type phase occurs at 90 kbar.
Resistance measurements made to 600
131
kbar show no i n d i c a t i o n of a phase
t o 10 kbar.
transition.
1
tions erbium i s hep.
15
Shock wave experiments show a
kink in the u -u
curve at 440 kbar,

61
which i s ascribed t o melting.
No
131 The melting curve has been
bec phase has been detected before
131
melt
ERBIUM
Kw
1
0
I
0
1
1000
.
2000
,
3000
3000
Temperature - K
Fig, 64.
,
1
1000
2000
Temperature - K
Fig. 65. The phase diagram of thulium.
| I I I i |
Liquid
"'"" -
'
hep
hep
5 -
1 5
'
_g 10 -
determined to 10 kbar
""
! THULIUM 1
1 1 1 1 11
.,
The phase diagram of ytterbium
The phase diagram of erbium.

-41-
is shown in Fig. 66. Eelow 300 K
metallic phase.
153
These changes
3
have been explained in term? of the

opening and closing of band gaps with
154
Increasing pressure.
The fcc-bcc
147
phase boundary has been determined,
and it intersects the p 0 axis above
1000 K.
Stephens
reports that a new
hep phase appears between the fee and

bcc phases below 15 kbar, but this may
be the result of impurities.
pressure-independent resistance
anomaly variously observed at 743
K
1 4 7
and 898 K ,
1 5 5
has been ascribed
to another phase transition.

0
500
1000
1500
Static
compression of ytterbium at room
Temperature - K
temperature to 280 kbar shows no fur

ytterbium.
ther resistance anomalies above 40

153
kbar
Three s e t s of shock-wave e x p e r i
and 2 kbar, ytterbium exists in a

151
diamagnetic hep phase.
A
ments show kinks i n the u - u curve

ft?
s P
a t 130 k b a r ,
160 k b a r ,
and 490
146
kbar.
The kinks a r e a s c r i b e d t o
6 1
martensitic phase transformation at

300 K and atmospheric pressure pro
xenon-core r e p u l s i o n , m e l t i n g , and
duces a paramagnetic fee phase. The
electronic phase transitions,
hep-fee phase boundary has been
respectively.
determined, and it is clear that the

152
hep phase disappears above 2 kbar.
Rosengren consider the 130 kbar
At room temperature, increasing
anomaly to indicate an electronic

phase transition Involving a shift
p r e s s u r e causes a serieB of changes

in r e s i s t i v i t y .
Johansson and
from the divalent to the trivalent

141
The
ionic state in the solid
Below 20 kbar
between 20 and 40 kbar it behaves like
melting curve has been determined to

147
35 kbar.
The ytterbium phase
a semiconductor, and at 40 kbar a
diagram closely resembles that of
phase change takes place to a bcc
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
low pressures i s hep.
Compression t o
230 bbar at room temperature causes a

t r a n s i t i o n to the Sin-type l a t t i c e .
J 10
Pressure -
Solid l u t e t i u m at
1 1 1
The phase diagram of lutetium i s

shown in Fig. 67.
1 -;
hep
1 Liquid ..
The hcp-Sm-type phase boundary has

not been determined.
The melting
0
curve has been determined t o 10

kbar 131
i
1000
ll
2000
"
3000
Temperature - K
Fig.
HAFNIUM
Under roost conditions

hep.
hafnium
is
67.
The phase diagram of l u t e t i u m .
TAHTALUM
At atmospheric pressure a
The phase diagram of tantalum
t r a n s i t i o n occurs near 2270 K t o a

bcc phase.
The bcc phase i s s l i g h t l y
Solid tantalum
is bcc.
more dense than the hep, implying a

negative value of dp/dT for the phase
boundary.

158
T
A static-high-pressure
search for the hexagonal ID phase

found in titanium and zirconium
failed t o show any change of phase.
Three s e t s of shock-wave e x p e r i
ments showed anomalies in the u -u
curve.
6 2
'
6 6
'
1 4 6
Gust and R o y c e "
ascribed a kink at 600 kbar t o xenoncore r e p u l s i o n .
McQueen, t al -
ascribed a d i s c o n t i n u i t y a t 400 kbar

to a s o l i d - s o l i d phase t r a n s i t i o n .
146
Bakanova, e_t a l .
ascribed a kink
at 450 kbar to an e l e c t r o n i c t r a n s i
tion.
Hafnium melts at 2495 K .
5 3
1000

reported.
Fig. 68.
-43-
2000
3000 ' 4000
Temperature - K
The phase diagram of tantalum.
TUNGSTEN
IRIDIUM
The phase diagram of tungsten is

shown in Fig. 69.
bcc.
Solid tungsten is
Solid iridium is fee.
Room
temperature compression to 175 kbar

159
showed no phase transition.

Iridium
63
The melting curve
melts at 2716 K.
has not been reported.
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.
The phase diagram of tungsten.
Solid rhenium is hep.
Static
compression of rhenium at room temper

ature to 350 kbar showed no phase
transitions.
3433 K.
1000
2000
Temperature - K.
Rhenium melts at
been reported.
Fig. 70.
3000
The phase diagram of platinum.
OSMIUM
Solid osmium is hep.
melts at 3300 K.
Osmium
The melting curve
has not been determined.
The phase diagram of gold is

shown in Fig. 71.
-44-
Solid gold is
'
80 -
Pressure -
J 60 -
'
'
MERCURY
Rhombohedral v
(a)
Tetragonal
"
20
/ LiquidM~
' ^/\A .
200
400
600
Temperature - K
Fig. 72.
The phase diagram of mercury.
Temperature - K
Fig. 71-
The phase diagram of gold.

A third phase, named y, has
fee.

75
been found at very low temperatures

by straining the solid.
Its struc
ture and equilibrium phase boundaries

MERCURY
have not yet been determined
164
The
melting curve of mercury has been

The phase diagram of mercury is
shown in Fig. 72.
Solid mercury at
low temperatures has a body centered

THALLIUM
tetragonal structure.
each rlom
In this phase
has two nearest neighbors
The phase diagram of thallium is
and eight second nearest neighbors.
shown in Fig. 73.
With increasing temperature, a
atmospheric pressure, thallium is hep.
transformation to a rhombohedral
Above 500 K, it is bcc.
structure occurs.
pressure fee phase occurs above 35
This structure may
Below 500 K at
A high
be regarded as a distorted fee
kbar and 388 K.
lattice.
phase boundaries have been determined
The tetragonal-rhombohedral
The solid-solid
phase boundary has been determined
to 60 kbar.
to 65 kbar.

-45-

78
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
The phase diagram of thallium.

Fig. 74.
The phase diagram of lead.
LEAD
phases.
The phase diagram of lead i s
shown i n Fig. 74.
pressure i s fee.
The low pressure s o l i d phase
i s rhombohedral, i s o s t r u c t u r a l with
Solid lead at low
arsenic and antimony.
At 137 kbar and
Conflicting
claims have been made for the s t r u c
room temperature a t r a n s i t i o n t o a
165,166 _.
.
The phase
boundary has not been determined.
ture of phase I I , with no c l e a r

1
83
agreement.
Duggin
suggests that
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
hep phase occurs.
to 60 k b a r .
the high pressure phase of a r s e n i c .
7 7
A study of phase VI at 90 kbar at

room temperature has shown i t to be
BISMUTH
bcc.
shown i n Fig. 75.
This diagram i s of
s p e c i a l importance t o high pressure
V I I I , and VI meet i n a t r i p l e point
physics because i t s many phase t r a n s i

t i o n s have been used as c a l i b r a t i o n
standards.
The phase boundaries shown
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,
The phase diagram of bismuth i s
at 135 k b a r ,
1 6 9
and the VI-IX phase
boundary then proceeds t o higher
There i s s t i l l controversy
over the e x i s t e n c e of some t r a n s i t i o n s ,
p r e s s u r e s . This boundary was p r e

170
temperature
and 300
sumably
detected
in akbar
study at The
room
and r a t h e r l i t t l e x-ray s t r u c t u r e work
melting curve has been determined t o
has been done on the high p r e s s u r e
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.
The phase diagram of bismuth.

-47-
i
800
POLONIUM
RADIUM
At atmospheric pressure and below

room temperature, polonium has a
Solid radium is bcc at room
rimple cubic structure, the only
temperature. Radium melts at 973

63
K.
Wo high pressure work has been
known example of this structure in
reported.
the elements at zero pressure.
sluggish phase transition occurs
ACTINIUM
somewhere near room temperature (291327 K)
Solid actinium is fee at room
to a simple rhombohedral
temperature. Actinium melts at 1323

63
K.
No high pressure work has been
reported.
form which is a slight distortion of

the simple cubic.
The rhombohedral
form is slightly more dense,

leading to a negative dp/dT. The
THORIUM
phase boiuidary has not been deter

mined.
Polonium melts at 519 K.

Solid thorium under room c o n d i
tions i s fee.
reported.
Superconductivity
measurements t o 160 fcbar show an

anomaly t h a t could be due t o a phase
173
At atmos
ASTATINE
change near 70 kbar.
p h e r i c p r e s s u r e near 1670 K, thoritim
Astatine is a very unstable
transforms t o a bcc p h a s e .
element and its physical properties
The
volume change of the t r a n s i t i o n
have not been determined.
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.
The crystal structure of solid
Thorium melts
The m e l t i n g curve has
not been determined.
radon has not been reported. Radon

172
melts at 202 K. ' The melting curve
has not been determined.
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 .
Francium is a very unstable

element and its physical properties
Metal s o l i d i f i e d from the melt i s
have not been determined.
s u g g e s t i n g t h a t t h i s i s the high
48.
fee,
temperature form of the solid.
URANIUM
No
direct measurements of phase transi

The phase diagram of uranium is
tions have heen made, however.
shown in Fig. 76.
Protactinium melts at about 1810

174
K.
structure with four atoms per unit
reported.
60
Under room condi
tions solid uranium has an orthorhombic
- 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.
All but one of the seven known s o l i d
At 940 K and atmospheric
pressure, a transition to a complex
phases e x i s t at atmospheric p r e s s u r e .
tetragonal form with 30 atoms per
The low pressure portion of the
unit cell occurs.
The precise space
group remains to be determined.
phase diagram and i t s high p r e s s u r e

continuation are shown in s e p a r a t e
At
1050 K another phase transition leads
figures.
to a bcc phase.
i s monoclinic, with 16 atoms per unit
The solid-solid
The low temperature a phase
phase boundaries have been deter
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
mined, and indicate a triple point for
t i n c t types of atomic p o s i t i o n s .
the three phases near 30 kbar.
3 phase i s also monoclinic, with 34
atoms per unit c e l l and 7 types of
to 40 k b a r .
positions.
1 7 6
The
Both of these s t r u c t u r e s
are q u i t e i r r e g u l a r and are d i f f i c u l t

t o c o r r e l a t e with close-packed forms.
NEPTUNIUM
At high pressure only a and $

The phase diagram of neptunium
e x i s t , and the a-0 phase boundary
Under room
shows a temperature maximum.
The $
conditions neptunium i s orthorhombic,
phase transforms t o orthorhombic
with eight atoms per unit c e l l and
*Y below 3.5 kbar and to 5, with
two d i s t i n c t types of atomic p o s i
undetermined s t r u c t u r e , above t h i s
tions.
pressure.
At 550 K and atmospheric
pressure a phase t r a n s i t i o n to a
There i s a |S--liquId
t r i p l e point near 27 kbar.
t e t r a g o n a l phase with four atoms

per unit c e l l and two types of atomic
p o s i t i o n s occurs.
appears above 840 K.
The next two phases are fee (<5)

and body centered t e t r a g o n a l ( 6 ' )
A bcc phase
The s o l i d - s o l i d
which e x i s t only a t low p r e s s u r e s .
phase boundaries and the melting
The 6 ' phase i s followed by bcc ( e ) ,
curve have been determined t o 35

,,
177
kbar.
which melts to a more dense l i q u i d .

The t e t r a g o n a l 6 ' phase i s intermedi
a t e i n s t r u c t u r e between fee and b c c .
The E phase disappears at a t r i p l e
PLUTONIUM
point below 20 kbar.

i s shown i n Figs. 76 and 79.
The s o l i d - s o l i d
phase boundaries and the melting
The phase diagram of plutonium
curve have been determined to 140
The
kbar.
plutonium diagram I s very complex.
-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
The phaBe diagram of neptunium.
-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.
The phase diagram of plutonium.
dashed line in Fig. 80.
AMERICIuM
Static com
pression of americium at room tempera

ture shows a resistance change at 90
kbar, which may represent a continua
The phase diagram of americium

Americium under
room conditions is dhcp.
1 8 1
1300 K leads to a new phase, which
but with very
little change in volume.
182
Keating at atmospheric pressure above
There is
evidence for a transition to an fee

phase at 920 50 K ,
tion of the dhep-fee phase boundary
Stephens < al. suggest is bcc.

The fcc-bcc phase boundary and melting
The dhep-
fec phase boundary is therefore
curves have been determined to 35

182
approximately represented by a vertical ,.
kbar.
-52'
1501
-i
1
1
r
PLUTONIUM
-|
(-
Liquid
_L
200
400
600
Temperature - K
800
Fig. 79. The phase diagram of plutonium.
-53-
1000
1200
CURIUM
i i i i | I I i I | i i I I |
AMERICIUM
40
Depending on the method of

preparation, curium metal is found to
3 0
have either an fee or a dhcp struc
ture under room conditions.

bcCs
2 20
The estimated melting point is 1620

174
K.
dhcp
I
' ' '
F c C
No
phase boundary has been reported.
. Liquid \ l I
10 L_
The fee
phase has the higher density.
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.

americium.
Here the dhcp phase is the more

dense.
The estimated melting point
i s 1260 K.174 No high pressure work

has been reported.
-54-
References
1.
J. Donohue, The Structures of the Elements (Wiley, New York, 1974).
2.
W. Klement, Jr., and A. Jayaraman, Progr. Solid State Chem. 3. 289 (1966).
3.
V. V. Evdokimova, Soviet Phys. Psp. English Transl. 9. 54 (1966) [Dsp.

Fiz. Nauk 8, 93 (1966)].
4.
J. F. Cannon, J. Phys. Chem. Ref. Data 3, 781 (1974).
5.
L. Meyer, Adv. Chem. Phvs. 16, 343 (1969).
6.
R. J. Lee and J. C. Raich, Phvs. Rev. BS. 1591 (1972).
7.
S. A. Dickson and H. Meyer, Phys. Rev. 138, A 1293 (1965).
8.
J. Felsteiner and Z. Friedman, Phys. Rev. B8, 3996 (1973).
9.
G. A. Neece, F. J. Rogers, and W. G. Hoover, J. Comp. Phvs. 7. 621 (1971).
10.
R. L. Mills and E. R. Grilly, Phvs. Rev. 101, 1246 (1956).
11.
J. Wilka, Liquid and Solid Helium (Clarendon Press, Oxford, 1967).
12.
W. E. Keller, Helium - 3 and Helium - 4 (Plenum Press, New York, 1969).
13.
0. V. Lounasmaa, Contemp. Phys. 15, 353 (1974).
14.
D. Gugan, Can. J. Phys. 41. 1381 (1963).
15.
R. Stager and H. G. Drickamer, Phys. Rev. 132, 124 (1963).
16.
H. D. Luedemann and G. C. Kennedy, J. Geophys. Res. 73. 2795 (1968).
17.
M. Francois and M. Contre, Conference International sur la Metallurgie

du Beryllium (Grenoble, 1965) p. 201.
18.
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RBC/gw
-63-
Appendix A: The Space Lattices

Lattice
Axes
Angles
primitive (simple) cubic

body-centered cubic
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-

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TOL- 51902

PHASE DIAGRAMS OF THE ELEMENTS

Prepared for U.S. Energy Research & Development

"ttSTRlBUTtOM OF THIS DOCUMENT IS UNUML?:"

Printed in the United States of America

LAM/HENCE UVERMOFE LABORATORY

PHASE DIAGRAMS OF THE ELEMENTS

September 11, 1975

PHASE DIAGRAMS OF THE ELEMENTS

A summary of the pressure-

temperatur phase diagrams of the

structure of each solid phase is

elements is presented, with graphs

identified and discussed.

of the experimentally determined

is aimed at encouraging further

solid-solid phase boundaries and

experimental and theorerirl research

on phase transitions in the

theoretical discussion, are provided

they may be quite common at ultrahigh

provide an important challenge for

a very high degree of accuracy in

the recurrence of patterns in the

diagrams of closely related elements.

To date there have been very

This has been used successfully in

t i e s of high pressure phases.

certain phase transitions observed at

The experimental study of phase

relatively low pressure provide

of such unexpected phenomena as

materials at much higher pressure.

isostructural phase transitions and

Deeper theoretical understanding of

melting curve extreraa.

observed phase behavior w i l l thereby

theoretical understanding of these

allow quantitative prediction of

phenomena has been achieved, and work

properties of materials at much higher

1B continuing in this area.

pressures where experiments are d i f f i

nificance of these phenomena if

hoped chat an adequate theory of

and one or more paragraphs of com

phase diagrams for elements w i l l pro

ments are provided.

mote the more complex task of describ

the comment? Include information on

ing phase behavior in compounds and

the l a t e s t theoretical understanding

of Che phase diagram.

This report i s aimed at encour

structures found among the elements

aging theoretical and experimental

descriptions of complex crystal

are included i n the comments.

d e t a i l s of structures, however, che

a summary of the experimental data

reader should consult Donohue's The

Structures of the Elements.

The bibliography i s not

liquid phases are shown; the l i q u i d vapor boundary i s not considered