TOL- 51902

PHASE DIAGRAMS OF THE ELEMENTS

David A. Young

&
September 11, 1975

aiS
Prepared for U.S. Energy Research & Development
1
Administration under contract No. W-7405-Eng-48

i\\m LAWRENCE
K a i LABORATORY

"ttSTRlBUTtOM OF THIS DOCUMENT IS UNUML?:"

 NOTICE
"Th raport prtfwtd M n MCOWI O( work
-
OOMOM*fcyliw UHHM g l i m Corawit. NcftlMr
Ikt lUHtd SttUs Mr MM UMMM StaM EMTCT
KtMweh * DmJoMWrt Adaiatamttect aor My
of t M r t * H * y c * \ M t My ol H * cmitncWn,
strifcoAtncton, ---- *---

MCflM Of My tofDHMUM,
Mwalw, pnimtt r prwiM JbctatH. or
rtpr that kt Mt M M not tafflaM
prWHtty-owMd rfchU."

Printed in the United States of America

Available from
National Technical Information Service
U. S. Department of Commerce
5285 Port Royal Road
Springfield, Virginia 22151
Price: Printed Copy $ *; Microfiche $2.25

NT iS
*Pagea Selling Price
1-50 $4.00
51-150 $5.45
151-325 $7.60
326-500 310.60
501-1000 $13.50
 DUtrlbudon Category
VC'i

m
LAM/HENCE UVERMOFE LABORATORY
Ufcift<rfCallbmM^imio*C*ftrt/5SO

UCRL-51902

PHASE DIAGRAMS OF THE ELEMENTS

David A. Young

MS. date: September 11, 1975

M
OlSTRIBUTt0 npTu,5 revivor IStWUMtTED
 Contents

Abstract 1
Introduction 1
Phase Dlagraas 3
Hydrogen 3
Helium 4
Lithium 5
Berylliua - 6
Boron , 7
Carbon 7
Nitrogen 8
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 48
Radon ~ 48
Francium 48
Radium 48
Actinium 48
Thorium 48
Protactinium 48
Uranium 49
Neptunium 50
Plutonium 50
Aroericium 52
Curium 54
Berkellura 54
References 55
Append!* A: The Space Lattices 64

-v-
 PHASE DIAGRAMS OF THE ELEMENTS
Abstract
A summary of the pressure-
temperatur phase diagrams of the
elements is presented, with graphs
of the experimentally determined
solid-solid phase boundaries and
melting curves. Comments, including
theoretical discussion, are provided
Introduction
Phase diagrams are useful as
compact summaries of large amounts of
experimental data. As such thay
provide an important challenge for
theory, since accurate computation of
phase transitions typically requires
a very high degree of accuracy in
s o l i d - and l i q u i d - s t a t e theoretical
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
one-component pressure-temperature
phase diagrams.
The experimental study of phase
boundaries has led Co the discovery
of such unexpected phenomena as
isostructural phase transitions and
melting curve extreraa. A qualitative
theoretical understanding of these
phenomena has been achieved, and work
1B continuing in this area. The s i g
nificance of these phenomena if that
for each diagram. The crystal
structure of each solid phase is
identified and discussed. This work
is aimed at encouraging further
experimental and theorerirl research
on phase transitions in the
elements.
they may be quite common at ultrahigh
pressures where the atomic s h e l l
structure exhibits stepwise break
down.
Another aspect of phase diagrams
that has attracted much attention i s
the recurrence of patterns in the
diagrams of closely related elements.
This has been used successfully in
predicting the structure*? and proper
t i e s of high pressure phases. Thus,
certain phase transitions observed at
relatively low pressure provide
important clues about the behavior of
materials at much higher pressure.
Deeper theoretical understanding of
observed phase behavior w i l l thereby
allow quantitative prediction of
properties of materials at much higher
pressures where experiments are d i f f i
cult to perform. It may also be
hoped chat an adequate theory of
phase diagrams for elements w i l l pro
mote the more complex task of describ
ing phase behavior in compounds and
multi~component systems.
This report i s aimed at encour
aging theoretical and experimental
research on phase t r a n s i t i o n s .
a summary of the experimental data
obtained to date on the phase diagrams
of the elements. Only s o l i d and
liquid phases are shown; the l i q u i d -
vapor boundary i s not considered
here. The temperature abscissa i s
always referred :o zero Kelvin in
order to illustrate, the true s i z e s of
the various f i e l d s of phase s t a b i l i t y .
Commonly occurring s o l i d phases are
labelled with abbreviations: bcc
body-centered cubic (two atoms per
unit c e l l ) , fee face-centered
cubic, hep - hexagonal close packed,
and dhep - double hexagonal.
solid phases are identified according
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
figures indicate extrapolations or
poorly determined phase boundaries.
For each element where data are
available, a phase diagram i s 3hoi.n
and one or more paragraphs of com
ments are provided. When appropriate,
the comment? Include information on
the l a t e s t theoretical understanding
of Che phase diagram. Cursory
descriptions of complex crystal
structures found among the elements
are included i n the comments. For
It i s
d e t a i l s of structures, however, che
reader should consult Donohue's The
Structures of the Elements.
The bibliography i s not
exhaustive, since only the most
recent papers are c i t e d . However, the
reader can e a s i l y work back froo the
reference? in the recent papers to
the e a r l i e r ones. The gveat bulk of
the work cited here was done since
1960. Two other useful surveys of
phase diagrams for the elements
2 3
e x i s t , ' but they are already
beginning to be dated by continuing
Other research. Very recently, J. F.
Cannon has published a c r i t i c a l
review of the behavior cf the
4
elements at high pressures.
Cannon's review and the present one
cover much the same ground, and i t i s
hoped that these surveys w i l l f i l l the
gap l e f t by ten years of active
research.
-2-
 Phase Ditgrams

HYDROGEN
ni\
I HYDROGEN
The phase diagram o f hydrogen
L^fCubic)
i s shown in Fig. I. Solid and liquid
hydrogen are composed of diatomic 1
I
molecules interacting according to 2
van der Waals and electric-quadrupole
forces. Solid hydrogen and deuterium
Hexogono!
in thermodynamic equilibrium ( i . e . . ,
para-H, and ortho-D,) c r y s t a l l i z e
J
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
0 20 40 60
stable s t a t e at zero Kelvin i s cubic,
Temperature - K
with the molecules centered on an
fee l a t t i c e and presumably ordered, Fig. 1. 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
(probably marfcensitic, 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
ature of the crystallographic
transition i s a function of pressure
and concentration of spin s t a t e s .
The phase boundary indicated by
the das.i.d l i n e in Fig. 1 i s for 70%
o-H-, which has been measured to 5.3
suggest that pure o-D and P~H_ should
have transitions to rotationally
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 -
metal phase transition in hydrogen,
which is exepcted to occur in the
9
megabar range. The three molecular
solid isotopes melt in a regular
sequence, and the melting curves
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 weak van der Waals
forces. 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. Under pressure, both 10 20 30
liquids solidify. At zero Kelvin and Temperature ~ K

pressures above 0.1 kbar, both solids Fig. 2. The phase diagram ot
helium - 3 .
are hep and show a transition to fee
around 15 K and above 1 kbar. (Figs. 0.25
2 and 5) In Tie, a bec phase appears
below 0,1 kbar and the melting pres
sure has minimum at 0.32 K (Fig. 3 ) . 0.20
In He, the bec field is very small,
and is replaced by hep at the lowest
temperatures (Fig. 6 ) . The melting
-S 0.15 -
curve of 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
the normal Fermi liquid from the A
Temperature - K
and B su?erfluid phases represents a
Fig. 3. The phase diagram of
second-orn>;c phase transition, like helium - 3 .
 0.05 i | i | i | r 0.05
- HELIUM-3 .
1
i i | n rr
HELIUM-4 1
0.04 -- bcc (Solid) 0.04 _- hep 1

bcc /
. . - -
0.03 -- -3 0.03
A liquid Y"/

1
^ 0.02 - 8 0.02

1
B liquid /
Liquid 11 1

'
/Fermi liquid
0.01 _- 0.01 -

1
i
- -
, j / , 1 , 1 , . i , i\ . i 1

0.001 0.002 0.003 1 2 3

Temperature - K Temperature - K
The phase diagram of Fig. 6. The phase diagram of
helium - 3 . helium - 4 .

t h a t in 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 Bose-
Einstein 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 10 20 30 LITHIUM
Temperature - K
The phase diagram of lithium is
Fig. 5. The phase diagram of
helium - 4. shown in Fig. 7. Upon cooling to

-5-
 - 1 ' 1 ' -
80 LITHIUM which suggests t h a t a melting point
maximum w i l l occur a t a somewhat
- O -
greater pressure.
60 -
BERYLLIUM

The phase diagram of beryllium

40
i s shown in Fig. 8. Beryllium has a
Liquid 1
- t r a n s i t i o n from hep t o bcc j u s t
before melt. The bcc phase i s about
-
20
bcc jf
/
V-

-
P% more dense, giving r i s e t o t h e
negative slope of the phase boundary.
ep : The hep-bec phase boundary has been
n ._u_ 1 . 1 /, determined to 60 kbar. The same
0 200 400 600
study yielded two other r e s i s t a n c e
Temperature - K
anomalies belcw 1000 K t h a t appear to
Fig. 7. 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
the high pressure phase i s not 500 1000 1500 2000
known. The melting curve of l i t h i u m Temperofure - K
has been determined to 60 kbar.
Fig. 8. The phase diagram of
The melting temperature becomes beryllium.
n e a r l y constant a t t h i s p r e s s u r e ,
-6-
 S t a t i c high pressure r e s i s t a n c e at pressures above 100 kbar and tem
18
measurements by Marder showed a 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, p r o b a b i l i t y of sample contamination
but other i n v e s t i g a t o r s have been in t h i s work was l a r g e . Boron
19 22
unable t o repeat t h i s r e s u l t . expands very s l i g h t l y upon melting
23
The melting curve has been determined
near 2350 K, which implies a melt
to 60 kbar. 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.

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 shown in Fig. 9. This phase diagram
described in the l i t e r a t u r e * but 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. Furthermore, contamination producing artificial diamonds.
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 .

S o l i d i f i c a t i o n of l i q u i d boron Liquid
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 2000 4000 6000
evidence of phase t r a n s i t i o n s .
21 Temperature - K
Wentorf reported a new boron
polymorph of unknown structure obtained Fig. 9. The phase diagram of carbon.

-7-
However, the very high temperatures
and pressures involved have made the
measurement of the phase boundaries
extremely d i f f i c u l t , and the phase
diagram cannot be s a i d t o be firmly
established.
Graphite, the s t a b l e phase at
low p r e s s u r e s , has hexagonal l a t t i c e
symmetry. 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
neighbors located at the corners of
a tetrahedron.
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
measured thermodynamic d a t a , and the
graphite-diamond phase boundary can
24
be e s t a b l i s h e d . This has been done
with reasonable accuracy up t o 1200 K.
and 40 kbar. 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.
The dashed l i n e i s a l i n e a r e x t r a p
o l a t i o n of the lower-temperature
results. Together with the melting
curve, t h i s y i e l d s a g r a p h i t e -
diamond-liquid t r i p l e point near 100
kbar and 3500 K.
Shock wave experiments up to a
fdw hundred kbar c l e a r l y show the
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
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
i n d i c a t i n g a new phase at yet higher
p r e s s u r e i s s t i l l uncertain. Very
r e c e n t l y , Vereshchagin's group has
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
approximately 1 Mbar. They a l s o
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
the semiconductor-to-metal t r a n s i t i o n s
i n s i l i c o n and germanium.
The melting temperature of
graphite shows a maximum near 5000 K
and 50 kbar according to recent
28
work. Uncertainties in the tempera
t u r e measurements are l a r g e . Melting
of diamond has not been reported, but
the melt ng curve i s assumed to have
a negative slope by analogy with
silicon.
NITROGEN
The phase diagram of nitrogen i s
shown in F i g s . 10 and 1 1 . Nitrogen
in the s o l i d and l i q u i d phases i s
composed of diatomic molecules
weakly bonded to each o t h e r by van der
Waals and electrlc-quadrupole forces.
29
Three s o l i d phases are known. In
 ' 1 ' 1 1 '-
/ NITROGEN
8 -- -
1

Tetragonal

-
1

4 - ^ S \ -
1

Hexagonal
(0)

2 -- Cubic / -
(a) /

- Liquid -
i . / i 1 ^T 1 1 i
20 40 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
The phase diagram of
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. The ground s t a t e . 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 magnetic, takes place a t 24 K. This
(Fig. 10) 30 The melting curve has 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,
been determined
dete t o about 25 kbar although m a r t e n s i t l c . Another
2i
(Fig. 11) 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
OXYGEN volume change at 44 K. This phast.
shows some r o t a t i o n a l d i s o r d e r . All
The phast diagram of oxygen i s of these phases may be regarded as
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
The s o l i d - s o l i d phase boundaries have
by van der Waals and e l e c t r i c - 32
been determined to a few kbar The
quadrupole forces. Three s o l i d phasa
melting curve has a l s o been determined
are known. The monoclinic a phase 33
to 3.5 kbar.

n FLUORINE
10 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
1
1 ' 1 ' -
S; FLUORINE
Monoclinic/ Rhombohedral
(a) / (, J 1.0 J
Pressure -

1 1 IT|

Cubic
0.5
111 1

- Monoclinic(a) / / /
i *
J-Z-J L 0
1
, 1 , 1 1,1
20 40 60 20 40 60 80
Temnertiture - K Temperature - K

Fig. 12. The phnsa diagram of oxygen. Fig. 13. The phase diagram of fluorine.

-10-
 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
W

and AV of t r a n s i t i o n 5,34 The melt 50 100

ing curve has been determined to Temperature - K
only a few b a r s .
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
3 6
10 k b a r .

SODIUM

The phase diagram "f sodium is

shown in Fig. 15. Below 36 K, sodium
is hep. At 36 K a martensitic phase
200 400
change leads to a bec structure which
Temperature - K
persists up to melt. The phase
boundary separating the two phases Fig. 15. The phase diagram of sodium.

-11-
 i | i i I i | i i i i | i i
has not been reported, but the densi MAGNESIUM
t i e s are so nearly equal that the 40
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 30
2
the solid up to 600 kbar reveal no
phase changes. The melting curve
has been determined to 80 kbar.
I- hep Liquid

10

MAGNESIUM

Ql I I I [I I i I I I I
The p h a s e diagram o f magnesium i s
500 1000 1500
shown i n F i g . 1 6 . S o l i d magnesium i s Temperature - K
hep. 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
pressure show indications of a slug magnesium.
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
point In Fig. 16. 60

S 40h
ALUMINUM
n fee f Liquid
20-
The 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
ments tentatively indicate a p a r t i a l
L
0UJ 500
i
1000
*!
1500
39 Temperature - K
transformation to hep at 205 kbar.
The melting curve haa been determined Fig. 17. The phase diagram of
40 aluminum.
to 60 kbar.
-12-
 250 i i i i | i i i i | i i I i | i i
SILICON
SILICON
The phase diagram of s i l i c o n i s
200- Tetragonal
shown in Fig. 18. Normal s o l i d s i l i c o n (white tin)
i s covalently bonded semiconductor
with the cubic diamond s t r u c t u r e .
S t a t i c high pressure measurements .3150

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 '

i s complicated by i t s s e n s i t i v i t y to 500 1000 1500

shear s t r e s s e s . In a d d i t i o n , recovery Temperature
of s i l i c o n compressed above 100 kbar
has yielded a complex cubic form with Fig. 18. The phase diagram of silicon.
43
16 atoms per unit c e l l . This
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 T ' I ' ' '
The melting curve Has been measured PHOSPHORUS
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
20-
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 Ortho rhombic Liquid
region,
45
but t h e i r p r e c i s e nature Jiof-
i s unknown.

PHOSPHORUS
500 1000 1500
Temperature - K
The phase diagram of phoaphorua
I s shown i n Fig. 19. Of Che various FiE. 19. The phaae diagram of
a l l o t r o p i c form of phosphorus that phosphorus.

-13-
have been prepared, black phosphorus
appears to be the most stable phase
at atmospheric pressure. Black phos
phorus has an orthorhombic structure
consisting of puckered layers of
covalently bonded atoms.
At room temperature and about
50 kbar, black phosphorus undergoes
a phase change to a rhombohedral
lattice, isostructural with arsenic.46
A further transition near 110 kbar
to a simple cubic structure was also
46
observed. The rhombohedral lattice
is a simple distortion of the simple
cubic, and thus the phase transition
is easily reversible. Conductivity
studies indicate that the cubic phase
47
is metallic. Solid-solid phase
boundaries have not been determined.
The melting curve of othorhombic
black phosphorus has been determined
48,49
to about 20 kbar
SULFUR
The phase diagram of sulfur is
shown in Fig. 20. The literature on
the allotropy of sulfur presents the
most complex and confused situation
of all the elements. Solid sulfur
under room conditions is composed of
covalently bonded S rings that inter
act with each other through van der
Waals forces. Below 360 K at atmos
pheric pressure sulfur has an ortho-
rhombic lattice with 128 atoms (16
-14-
molecules) per unit cell in a very
complex arrangement. Above 360 K,
the solid is monoclinic, with 48
atoms (6 molecules) per unit cell.
The orientations of two of the six
molecules in each unit cell are dis
ordered.
There is much disagreement about
the structures of the high pressure
phases and the phase boundaries
separating them. The phase diagram
shown in Fig. 20 is due to Vezzoli,
et al. ~ The phase boundaries in
the solid were detected by means of
volumetric, optical, and electrical-
resistance techniques.
The phase transitions are often
difficult to detect, as indicated by
the dashed boundaries in Fig. 19.
The large number of phases can be
understood as a series of stepwise
conformational changes in the S rings
g
with changes in temperature and
pressure. The structures of the
phases other than the well-known I
and 11 have not been worked out,
although there is evidence that phase
XII is monociinic, with closely
packed helical chains of atoms
similar to the selenium and tellurium
53
rfructures. Resistance measurements
on sulfur compressed to 400 kbar
showed no transition to a metallic
.. 54
scate.
The melting curve shows a number
of definite cusps attributed to the
 T
SULFUR

40 -

I 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 b y van d e r Waals f o r c e s . Solid
52 c h l o r i n e has an orthorhombic struc
et al. have discovered a number of
"phases" (indicated by letters) in t u r e , composed of 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 . The
These regions in the liquid appear to m e l t i n p curve has been determined to
be different polymeric states result 7 kbar.
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. Argon in the solid
has been independently confirmed. and liquid is composed of atoms weakly
bonded by van der Waals forces. Solid
CHLORINE argon is fee. The melting curve has
31
been determined to 26 kbar.
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- T shown in Fig. 23. Solid potassium is
CHLORINE bcc. No martensitic transition of the

.s 30 | ! i ''i
ARGON

- /-
4 - -20-

Orthorhombic Liquid
-

fee
10-
f Liquid

"
100 200 300 1 , 1 . 1
Temperature - K 100 200 300 400
Temperature - K
Fig. 21. The phase diagram of
chlorine. Fig. 22. The phase diagram of argon.

-16-
 1 ' 1 - I'" 40
80 - POTASSIUM -
i

1 60 _ 30
1

1 40
tfc

20
bcc
j:
1 o 20

n
0
i , ,y
200 400
,

600
10

Temperature - K
500 1000 1500
Fig. 23. The phase diagram of
potassium. Temperature -

Fig. 24. The phase diagram of calcium.

kind occurlng i n Li and Na i s 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. These t r a n s i a subsequent sharp drop near 400
58
t i o n s were not observed at 296 K. kbar. These data were ascribed to
The authors suggest t h a t the more two rather sluggish phase transitions,
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. These data are in
in Li and Na. The melting curve of rough accord with later Soviet
potassium has been determined t o 59
work. The melting curve of calcium
1 6
80 k b a r . has been determined to 40 kbar.

CALCIUM SCANDIUM

The phase diagram of calcium is Scandium is hep at atmospheric

shown in Fig. 24. Under room condi pressure. Static high pressure re
tions calcium i* fee. Near 700 K at sistance measurements at room temper
one atmosphere it undergoes a transi ature showed no evidence of a phase
tion to a bcc structure. The phase change to 140 kbar. Shock wave
boundary has been measured to 30 measurements by Carter, e_t_ al_. showed
kbar. High pressure resistance a kink in the u -u curve at
s p
-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 strong break in the u -u curve for
s p
s o l i d - s o l i d phase change. No kink
titanium, indicating a phase change
was found i n the shock v?ave work of
occurring at 175 kbar. The nature
Gust and Royce. Scandium melts a t
of this phase transition has not been
1812 K. The melting curve has not
determined. Titanium melts at
been r e p o r t e d .
1941 K. The melting curve has not
been reported.
TITANIUM
VANADIUM
The phase diagram of titanium is
shown in Fig. 25. At room temperature Vanadium is bcc. No solid-solid
and pressure titanium is hep. A phase transitions have been reported.
transformation to a bec phase occurs Vanadium melts at 2178 K. The
near 1150 K. The phase boundary has melting curve has not been reported.
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 1111II11 1 1 I I 11111 | I I I 1
J 111111111
7"l""l""- 8
CHROMIUM

sure - kbar

- Hexagonal o
: (w) i 3 6
^-'Tetragonal
Liquid -
s

/ TITANIUM J V
^ Orrhoihombic

mp J mp
~ hep
bcc U-iquid;:
I2 bcc

1 \, , ,'
*. i i i 1 i ' 1111 11 1 11i
V i i i i* 0 . J_ 11 1 i i i 1 i i i 1 i i
500 1000 1500 2000 2500 500 1000 1500 2000 2500
Temperature - K Temperature - K

Fig. 25. The phase diagram of Fig. 26. The phase diagram of
titanium. chromium.

-18-
 chromium, it Is probable that the 50 I I I I I I 1 I I I I l I I I I

paramagnetic phase is simple bcc up MANGANESE

to the melting point. Below 311 K,

the paramagnetic phase transforms to 40

an antiferromagnetic phase by a first-

order phase transition. This phase
_8 30
is in a spin-density wave state In
which the polarization is perpendicular Liquid
to the wave vector. This magnetic
8 20
state is inconsistent with the reten
Cubic
tion of full cubic symmetry, and the
(a)
lattice instead takes on a very slight
10
orthorhombic distortion of the bcc
lattice.
At 123 K, another first-order 0|_iiiiL_
tr sition occurs to a new antiferro 0 500 1000 1500
Temperature - K
magnetic spin-density wave state in
which the polarization and wave vectors Fig. 27. The phase diagram of
manganese.
are parallel. This phase has a small
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
centered cubic l a t t i c e with 58 atoms
mined to 8 kbar. ' Static pressure
p e r u n i t c e l l and 4 d i f f e r e n t types
measurements at room temperature to
70 of atomic p o s i t i o n s . At atmospheric
55 kbar show no other phase changes.
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
Chromium melts at 2148 K. The
occurs t o t h e fi form, thought t o have
melting curve has not been reported.
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 . Near 1370 K a
MANGANESE
t r a n s i t i o n t o t h e fee Y phase o c c u r s ,
The phase diagram of manganese and near 1520 K a f u r t h e r transition
i s shown i n F i g . 27. There a r e four t o the bcc 6 phase o c c u r s . The 'phase
a l l o t r o p e s , a l l of cubic symmetry. boundaries and the melting curve have
The a form has a complex body 71
been determined t o 40 kbar.

-19-
IRON
The phase diagram of iron is
shown in Fig. 28. The phase diagram
and especially the melting curve of
iron is of great interest because of
the problem of the state of the
earth's core and the origin of the
geomagnetic field. Under room condi
tions iron is ferromagnetic and has
a bcc structure. At 1044 K it passes
through the Curie point and near 1200
K it transforms to the fee phase.
The bcc phase once again becomes
stable before melting. Above 100
kbar, the bcc phase transforms to a
nonferromagnetic hep phase. The
ct-y, ct-e, and y~e phase boundaries
72
have been determined to 200 kbar.
The y-& transition and the melting
curve have been determined to 52
kbar, where they meet in a triple
73
point. The melting curve of the
Y phase has been extended about 5
73
kbar beyond the t r i p l e p o i n t .
COBALT
The phase diagram of cobalt is
shown in Fig. 29. At room tempera
ture cobalt is hep. At a temperature
depending on the sample grain size, a
sluggish phase change to fee occurs.
For large crystal grains the trans
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 hep J fee L
'q u i d
"
1 20 mp
* 10-
0 11 i i I i I I i 11 i i) Ii i t i I i i i i
500 1000 1500 2000 0 500 1000 1500 2000 2500
Temperature - K Temperature - K

Fig. 28. The phase diagram of i r o n . Fig. 29. The phase diagram of cobalt.

-20-
 80 I1I I 1
COPPER
The phase diagram of nickel i s
shown in Fig. 30. Solid n i c k e l i s
fee. The melting curve has been
60
determined to 80 kbar. '

40
1 1
" " I " " I " ' I
80 NICKEL fee

0 60
-Q 20
4 0 fee
i
1 20
/Liquid | Liquid

at
i I . . . . I i i , I i ill i I . , , , I / I !
0. "0 500 1000 1500
500 1000 1500 2000 2500
Temperature - K
Temperature - K

Fig. 30. 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. The melting curve has been
75
determined to 65 kbar.

7 ' 1 ' 1 ' | i | i

ZINC 80 ZINC

The phase diagram of zinc i s J 60 - / ~

shown i n Fig. 32. Solid zinc has a | 40 / :
hep f Liquid
d i s t o r t e d hep l a t t i c e , with the c / a
r a t i o considerably g r e a t e r than i d e a l . 20
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 ( I . 1 . 1 / , 1 . *
2C10 400 600 8(10 1000 12C
s o l i d - s o l i d phase changes are found Temperature - K
up t o 200 kbar. The melting curve
has been determined to 60 kbar. Fig. 32. The phase diagram of zinc.

-21-
 80 L ' ! ' I I ' TZ\
GALLIUM GALLIUM

The phase diagram of gallium is Orthorhombic

(III)
shown in Fig. 33. Solid gallium at
60
atmospheric pressure has an ortiio-
rhombic structure with eight atoms
2
per unit cell. Each atom in this
structure has one nearest neighbor I 40
and six other near neighbors somewhat
farther away. At atmospheric pressure
gallium melts just above room temper
ature, and the melting temperature
20-
initially decreases with increasing Orthorhcmbic
pressure. Gallium II is probably
(M
body centered tetragonal. The high- I I I
temperature gallium-III phase is a 0 100 200 300 400
complex orthorhombic lattice with Temperature - K
40 atoms per unit cell. The phase Fig. 33. The phase diagram of gallium.
boundaries, including the melting
250 | I I i | I i I
curve, have been determined to GERMANIUM
,. ,. 78,79
75 kbar.
200
GERMANIUM
* Tetragonal
. (white tin)
The phase diagram of germanium - 150
is shown in Fig. 34. Solid germanium
under room conditions is a semicon
Liquid
ductor with the cubic diamond struc- | 100
60
ture. Above 100 kbar shock wave
and electrical resistance measure- _ Cubic
41 5 0
1-
(diamond)
ments indicate the appearance of a
new phase. This phase is metallic,
with the tetragonal white tin struc i l i t i i i . X i . i l
ture. There remains some uncertainty 500 1000 1500
concerning new phases obtained from Temperature - K
81
quenching experiments. The cubic- Fig. 34. The phase diagram of
tetragonal phase boundary and the germanium.

-22-
netting curve have been determined up 1
' ' I ' ' '
44 ARSENIC
to 200 kbat.
60

ARSKNIC

The phase diagram of arsenic la

40
shown in Fig. 35. Ac atmospheric

pressure arsenic crystallizes in Che 3
prtnltlvc rhoabohedral laccice
characteristic of the group VB i 20
Rhombohedral Liquid

elements- High pressure resistance

measurements shoved no anomaly up Co
82
200 kbar. However, arsenic that -iJ_
had been compressed to ISO kbar 0 500 1000 1500
showed a tetragonal structure, which Temperature - K
may represent a high pressure phase.S3
The melting curve has been determined Fig. 35. The phase diagram of arsenic.
up to 60 kbar.

SELENIUM

The phase diagram of selenium is

I ' I ' I ' !
SELENIUM
shown in Fig. 36. Solid selenium at 60
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 I I I/I
unsuccessful. The melting curve 0 200 400 600 800 1000 1200
has been determined Co 60 kbar. 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. These
shown In Fig. 37. 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. The upper transition Is
forces. 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. The melting curve
tion in solid bromine at 35 kbar has
has been determined to 80 kbar.
91
been reported, but no details of
The melting temperature appears to be
the phase boundary or the structure
approaching a maximum near 80 kbar.
of the new phase are available. The
melting curve has been determined to
, 56,89 STRONTIUM
10 kbar.

The phase diagram of strontium

KRYPTON is shown in Fig. 40. Under room
conditions strontium is metallic with
The phase diagram of krypton is
an fee structure. With increasing
shown In Fig. 38. Solid and liquid
pressure at room temperature or
krypton consist of atoms bonded by
below, strontium becomes semi-
weak van der Waals forces. The solid 94
metallic. Hear 35 kbar, a phase
Is fee. The melting curve has been
36 92 transition to the metallic bcc struc
determined to 12 kbar. '
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 sure appears to be due largely to the

shown in Fig. 39. At low pressures electronic transitions mentioned.

solid rubidium is bcc. Bundy and Beyond the 3S kbar transition,

Strong found a sharp resistance jump strontium shows metallic conductivity

93 with no indication of further trans
near 75 kbar and room temperature.
Stager and Drickamer found a sharp itions up to 500 kbar. The fcc-bcc

rise In resistance near 200 kbar at phase boundary intersects the p = 0

two temperatures. Soviet work con axis at 830 K. 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
BROMINE "HP ' ~T
RUBIDIUM
10

60

2 ji
_ OrthorhombTc I
40
3

i
20
2

1 I . I
O0j - - 100 200 300 400 200 tfia 600
Temperature - K Temperature - K
F i 3 9 h a s e
Fig. 37. The phase diagram of bromine. 8- - *> P diagram of
rubidium.

50 1
1 i i | i i I i | i i i i | I
12 1 ' 1 ' 1 -r STRONTIUM
KRYPTON

10 - 40

2 30
I

r
|

20-
r

-
|

fee / Liquid bec / Liquid

i

4 10

2
,. l / , 1 . 1 1
I J U
0 100 200 300 0 500 1000 1500
Temperature - K Temperature - K

Fig. 40. The phase diagram of

Fig. 38. The phase diagram of krypton. strontium.
-25-
 YTTRIUM hep phase transforms to bcc. The
t r i p l e point joining the three phases
Solid yttrium at low pressure is
occurs near 60 kbar and 1000 K. The
hep. Above 110 kbar, yttriur.
phase bounds.-ies have been uorked out
95
becomes a superconductor, A itudy
to 70 kbar. Vereshchagln observed
of the pressure dependence of the
a sharp change of slope i n the resist
transition temperature indicates the
ance as a function of pressure near
presence of several superconducting
96 100 kbar, but what t h i s means i s
modifications. However, these 97
unclear. A shock-wave study of
modifications are not thought to have
zirconium showed a sharp break in the
different crystal structures, but
u -u curve at 260 kbar, which pre-
s
rather arise from slight changes in P 66
band structure. sumably indicates a phase change.
6 3

Static resistance measurements Zirconium melts at 2123 K . The

to 250 kbar shew no phase transition melting curve has not been reported.
97
anomalies. Shock-wave experiments
by Gust and Royce showed a kink in Che
the u -u curve at 280 kbar. The
s p
authors suggested that the kink i i i i | i i i > | i i i i | i rn | n i _
80
ZIRCONIUM
indicated the stiffening of the solid
as inner electron cores overlapped. " Hexagonal ! -
Carter, e_t _ai. saw a kink in tk&

:y
u -u curve at 370 kbar and suggested 60
s p
a sluggish low pressure transition as
-
an explanation. Yttrium melts at
63
1775 K. The melting curve has not
40
- -
been reported. 3
*?

ZIRCONIUM
1 hep bcc

20 - Liquid
The phase diagram of zirconium
mp\
i s shown in Fig. 41. Zirconium under
room conditions I s hep. under com
n 1ill I 1 1 1 ulMI i L I -
pression i t transforms to the hexagonal "0 500 1000 1500 2000
w phase i s o s t r u c t u r a l with u-titanium. Temperature - K
This i s a d i s t o r t e d bec phase. Near
Fig. 41. The phase diagram of
1140 K at atmospheric pressure the zirconium.

-26-
KI0BIW1 RUTHENIUM

Solid niobium is bcc. No Solid ruthenium in hep. Com

resistance anomalies have been found pression to 400 kbar at room tespera-
97 99
below 250 kber. Niobium melts at tur* showed no change of phase.
6 3
2741 K. The melting curve has not Ruthsnium melts at 2SS3 K . The
been reported. melting curve has not been reported.

MOLYBDENUM RHODIUM

The phase diagram of molybdenum The phase diagram of rhodium i s

is shown in Fig, 42. Solid molybdenum shown i n F i g . 4 3 . Solid rhodium i s
is bcc. An approximate melting curve fee. The melting curve has been
98
has been determined to 90 kbar. approximately determined t o 80
3 8 7 4
kbar. '
TECHNETIUM

Solid technetium is hep.

63
Solid palladium i s f e e . Palladi
Technetium melts at 2443 K. The
melting curve has not been reported. um melts a t 1825 K. 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 60t-
bcc

40

20
Liquid

0.
1000 2000
J J
3000
i
1000 2000 3000
Temperature - K
Temperature - K
Fig. 42. The phase diagram of
molybdenum. Fig. 43. The phase diagram of rhodium.

-27-
SILVER to 250 kbar showed no strong
97
anomalies. The melting curve has
The phase diagram of silver Is 38
been determined to 50 kbar.
shown In Fig. 44. Solid silver Is
fee. Compression to 300 kbar at room INDIUM
temperature shows no evidence of a
phase change. The melting curve The phase diagram of indium i s

has been determined to 65 kbar. shown In F i g . 46. Solid indium i s

body centered t e t r a g o n a l . Compression

CADMIUM at room temperature t o 300 k ar shows

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 mined t o 80 k b a r . 7 8

hep. Compression In the 100-200 kbar

range shows small anomalies In the
resistance and hexagonal c/a ratio,
and a sluggish phase transition has The phase diagram of t i n is
37 shown in F i g . 47. Below 290 K at
been suggested as an explanation.
Independent resistance measurements

0 200 400 600 800

Temperature - K Temperature - K

Fig. 44. The phase diagram of s i l v e r . Fig. 45. The phase diagram of cadmium.

-26-
 1 1 1 1 1 1 1 atmospheric pressure, tin i s cubic
iNDIUM diamond l i k e s i l i c o n and germanium.
80 - Above this temperature tin has the
: / tetragonal white t i n structure with
| 60- - four atoms per unit c e l l . In this
: / structure each tin atom has four
i "o Tetragonal / - nearest neighbors at the vertices of
/ Liquid -
i a flattened tetrahedron. Two more
neighbors l i e s l i g h t l y farther 3way.
20
- The diamond-to-white-tin
I 1 J l/i 1 I 1 boundary has been determined to about
200 400 600 800 102
50 K and 10 kbar. At room
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
1 0 3 1 0 4
determined to 95 k b a r . ' Tht
melting curve has also been determined
. , , ,. 103,104
100 to 75 kbar. *

ANTIMONY
80
I The phase diagram of antimony is
i 60 shown in Fig. 48. Solid antimony
Tetragonal under room conditions is rhombohedral,
(white tin)
40 - isostructural with arsenic. At room
temperature, antimony has two phisa

Cubic transitions, one near 70 kbar and one

20-
^(diamond) near 85 kbar ( c i r c l e s ) . 105
The 70-
kbar transition is sluggish and appar
0 200 400 600 800 ently has a very small volume change.
Temperature - K 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 TELLURIUM
100 ANTIMONY
The phase diagram of tellurium
\ Tetragonal
80 is shown in Fig. 49. Solid tellurium
- \(ov under room conditions is a semicon
ductor, with a hexagonal structure

a>
60

- \sn composed of covalently bonded helices

packed together. This structure can
Liquid be regarded as a distortion of the
simple cubic lattice. Near 40 kbar
20
Rh'ombohedral \ at room temperature (circle), a
transition to a metallic phase occurs.
0 I I I 1
' ' ' ' '
The structure of this phase has not
500 1000 1500
108
yet been determined. Near 70 koar
Temperature - K
at room temperature (circle), a

Fig. 48. The phase diagram of f u r t h e r t r a n s i t i o n to a rhombohedral

108
antimony. l a t t i c e occurs. This phase i s
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 T
TELLURIUM
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 "^ Rhombohedral (III)
worfe suggests a t e t r a g o n a l s t r u c t u r e S
60 S
analogous t o t h a t found i n a r s e n i c at s
high p r e s s u r e s . Phase I I I shows ll V
82 ; 40
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

E
70 kbar. ' Two cusps, i n d i c a t i n g 20 Hexagonal
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. -i L J_ J L
Stishov and Hkhomlrova assumed "0 200 400 600 800
that the two t r i p l e p o i n t s corresponded Temperature - K
t o the two room temperature t r a n s i
J i g . 49. The phase diagram of
t i o n s , as indicated in Fig. 48. tellurium.
-30-
 109
phases a t s t i l l h i g h e r p r e s s u r e s . 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 At higher pressures, above 100
mined t o about 70 k b a r . A definite kbar, the resistance of iodine drops
113
maximum i n the melting temperature rapidly to a metallic value. Here
i s found near 10 kbar. It is thought that the I molecules
dissociate into an atomic metallic
IODINE structure. It is not clear whether
this is a continuous or an abrupt
The phase diagram of iodine is transition. Shock wave experiments
shown in Fig. 50. Solid iodine at on iodine show a strong break in the
low pressures is composed of diatomic
plot of u vs u D at approximately
molecules in an orthorhombic lattice,
700 kbar.H4 Given a transition to
isostructural with solid bromine and
the metallic phase at a much lower
chlorine. No clearly defined phase
pressure, this break is likely to
transition has been found at moder
represent a phase transition from
ate pressures, but an x-ray study
one metallic phase of iodine to
of the solid to 60 kbar showed a con
another. The melting curve has been
tinuous shifting of x-ray
determined to 50 kbar. '
112
reflections. This was interpreted
as a shifting of the orientations of XENON

n ' i r The phase diagram of xenon is

50 - IODINE shown in Fig. 51. Solid and liquid
xenon are composed of atoms bonded
u 40-
o by weak van der Waals forces. Solid
M
xenon is fee. The melting curve has
g 30- Orrhorhombic 92
been determined to 7 kbar.
a
i 20-
CESIUM
10-
The phase diagram of cesium is
0L-
0 200 400 600 800 1000 shown in Fig. 52. Cesium has been

Temperature - K intensively studied because of its

unusual properties. Solid cesium at

Fig. 50. The phase diagram of iodine. 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
fee phase apparently disappears a t
200 400 600
low temperatures.
Temperature - K
The i s o s t r u c t u r a l fcc-fcc t r a n s i
Fig. 51. The phase diagram of xenon. tion occurs with a 9% volume change,
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 formation r e p r e s e n t s a s h i f t from 6s
"T '' ' 1
. CESIUM to 5d character of the conduction
120
band. Although details of this
50 - IV /
theory have been criticized, it is

- widely agreed to be qualitatively
>.. 4 0 fcc^
L ~"
1 correct.
.a: A further sluggish t r a n s i t i o n i n
r - fee \
30 s o l i d cesium occurs near 125 kbar,
accompanied by a large increase in

K -
bcc
J
resistance.
5
This phase (V) e x h i b i t s
superconductivity and i t has been
suggested t h a t the phase i s
10 t r a n s i t i o n - m e t a l - l i k e , with increased
Liquid -
95
1 l/l d-electron character,
0 200 400 600 The melting curve of cesium has
Temperature - K 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. The

-32-
decreasing melting temperature of i i i i I i r i i I 11 i i i n
the close-packed fee phase i s due to BARIUM
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 Liquid
in the s o l i d . 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 1
' ' ' * ' ' ' ' * '

the s o l i d t h i s change t a k e s place a l l 0 500 1000 1500

at once. The melting curve of 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 tion at 144 kbar and room tempera
122
transition occurs at 55 kbar. ture, and inferred from a detailed
The high pressure phase has been study that this was a melting transi
123 tion. Later work indicated a solid-
determined to be hep. There is
129
disagreement over the trajectory of
solid transition instead. A
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
another solid phase. The melting
show dp/dT < 0. Additional
curve has been determined to about
evidence supports the first possi
nn it. 124,125,128 , .
bility, which is shown in Fig. 53.
90 k b a r , * * and three
A second phase transition to a phase
melting-curve maxima appear. It
(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
been reported. * Stager and changes s i m i l a r t o those observed in
130
cesium are occurring i n barium.
-33-
 LANTHANUM while t h e second a s c r i b e s i t to the
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 lanthanum
melting curve. The fcc-bcc boundary
i s shown i n F i g . 5 4 . Lanthanum
and the melting curve have been
e x h i b i t s t h r e e s o l i d phases at atmos
determined to n e a r l y 40 kbar.
pheric pressure. 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 shown in Fig. 55. This unusual
131
worked out to 24 kbar. At 1130 K, diagram has been intensively studied.
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. Between
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. Between 450 (c
ance anomaly near 100 kbar, which and 1000 K, the fee phase is again
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 .xperi- Y phase is ferromagnetic while the
ments show kinks i n t h e u s-u_,p curve
e
a phase is paramagnetic. A bec phase
for lanthanum a t 250 kbar*2 ^ a then intervenes just before melting.

225 kbar
61 The dhcp phase disappears at low
The first report ascribes
the fcinfc t o xenon core r e p u l s i o n s , 62 133
pressures.

40 I I | I I I I | I I r-|-r-r I | I I I I | I I I I| T
LANTHANUM I 80 CERIUM

Orthorhombic 1
1 60

Ll'qui'd' 40,

20U (a) Liquid _|

dhcp facc

500 1000
I I I I,
1500
7) L '
1_L ' ' " I I I
Temperchjre - K 0 500 1000 1500
Temperature - K
Fig. 54. The phase diagram of
lanthanum. Fig. 55. The phase diagram of cetium.

-34-
 The unique feature of the cerium
diagram is the isostructural a -* y
phase transition, which ends in a
critical point estimated from
134
resistance measurements to lie at
17.5 kbar and 550 K. A considerable
theoretical effort has been made to
explain the a * y phase transition
and critical point. The earliest
theories assumed that the transition
represented a promotion of the
localized 4f electron to the delocal-
135
i2ed 5d band. Later theories
modified this by assuming only a
135
partial 4f derealization . Such
models imply a definite increase in
the number of conduction elections as
the pressure is Increased. But
this is contradicted by positron-
annihilation experiments that
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
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
1
phase (a ) has been determined to be
orthorhoiribic, isostructural with
137
a-uranium. The phase boundary has
been determined over a r e l a t i v e l y
short temperature range, but i t i s
i n t e r e s t i n g t h a t extrapolation of the-35-
rx-y phase boundary and ct-a* phase
boundary leads to points very near
one another on the melting curve.
Stager and Drickamer reported a
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 .
1fc
In one c a s e , a
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
6 2
*
found.
The melting curve of cerium has
134
been determined to 70 kbar. The
remarkable feature i s a minimum In
the melting temperature around 33
kbar. Jayaraman explains the minimum
in terms of isotherms s i m i l a r i n
shape to the s u p e r c r i t i c a l isotherms
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 .
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.
PRASEODYMIUM
The phase diagram of praseodymium
i s shown in Fig. 56. Normal s o l i d
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
The t r a j e c t o r y of the dhep-fee phase
boundary i s d i f f i c u l t to follow
 ~r i i i | i i i i | m i |"i i boundary and the melting curve have
131
80 PRASEODYMIUM been determined to 70 kbar.

60 1 - NEODYEtCH

40 - \ fee
1
1 _ The phase diagram of neodymium
i s shown i n Fig. 57. Under room
\ 1 Liquid " conditions neodymium i s dhep. High
20 dhcp\ 1 ~ pressure tf-ray s t u d i e s at room
\ y b c e
temperature show a t r a n s i t i o n to the
_L
139
V . I #. . . 1 , . fee phase near 50 kbar ( c i r c l e ) ,
500 1000 1500
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
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 ,
Fig. 56. The phase diagram of although suspected, could not be
praseodymium. 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 1UX rare earth phase
a generalized
diagram, Resistance measurements
Impurities. An approximate value for
the zero-pressure t r a n s i t i o n
temperature i s 833 K. ** Resistance 1
-\ I T ] T T T T ' | 1 \ l-JTTT-
measurements t o 500 kbar show 80 - " NEODYMIUM
s e v e r a l anomalies above t h a t a t 40
kbar, and suggest two more high-
60 -- -
pressure phases of unknown s t r u c t u r e
/

r
138 ~ '
above Che fee phase. f
\ " /
Two s e t s of shock-wave experiments /
show kinks i n the u - u curve for Liquid
8
/
P 62 ~ dh

praseodymium at 300 kbar and 270 =p \ Lc

kbar. The f i r s t report ascribes 20
62
the kink t o xenon-core r e p u l s i o n s , _L, 1 1 . 1 1 1 1 \ l J 1 I !..!__)
0 500 1000 1500
while the second t e n t a t i v e l y a s c r i b e s
0 Temperature - K
i t to an e l e c t r o n i c rearrangement In
the l i q u i d . A bec phase appears Fig. 57. The phase diagram of
before melt. The bcc-fcc phase neodyroium.

-36-
 on neodymium up to 600 kbar showed 1 1 1 1 | 1 I 1 1 | 1 1I I | I l
80
anomalies in the 100-200 kbar region SAMARIUM
at d i f f e r e n t temperatures, which
could correspond t o another h i g h - 1 60 -
dhcp
138
pressure phase t r a n s i t i o n . 1
V
Two s e t s of shock-wave experiments 40 I bee -
show kinks in the u -u curve for
s p
15
c
X
X
X s
, .
neodymium at 280 kbar and 250 kbar. 20 _ Rhombohedral xl

The f i r s t report ascribes the kink t o

(Siti) 1 / "
/Liquid"
62
xenon-core r e p u l s i o n s , while the n ! i 1 1 ill A 1 l_
second i d e n t i f i e s i t with melting. 61 0 500 1000 1500
A bcc phase appears before melt. The Temperature - K

bcc-fcc phase boundary and the melting Fig. 58. The phase diagram of
curve have been determined t o 60 samarium.

kbar. henceforth c a l l e d "Sm-type." R e s i s t

PROMETHIUM
Promethium I s dhcp at room
temperature and p r e s s u r e . 142
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 .
melting temperature i s 1315 K.
high-pressure work has been reported.
SAMARIUM
The phase diagram of samarium i s
shown in Fig. 58. Under room condi
tions samarium has a close-packed
s t r u c t u r e of rhombohedral symmetry.
The arrangement of close-packed
layers in t h i s s t r u c t u r e i s ababcbcac,
ance measurements to 600 kbar at
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
Prom
dhcp phase appears in samarium near
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
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
while the second i d e n t i f i e s i t with
melting. 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
boundary i s assumed to represent the
131
Sra-type-dhcp-bcc t r i p l e p o i n t .
The b c c - s o l i d phase boundary and the
melting curve have been determined to
131
60 kbar.

37-
 EUROPIUM phase transformation. Bakanova
146
et a l . found a kink i n the u -u
The phase diagram of europium i s s p
curve at 386 kbar and ascribed t h i s
shown in Fig. 59, Solid europium at
t o an e l e c t r o n i c rearrangement.
atmospheric pressure i s bcc. Below
It Is possible that the anomalies
88.6 K, europium i s antiferromagnetic,
in the shock data correspond with the
with a h e l i c a l arrangement of s p i n s , 138
and i t becomes paramagnetic above t h i s resistance anomaly which has been
temperature. The t r a n s i t i o n has been ascribed t o a d i v a l e n t - t r i v a l e n t
144
determined t o be f i r s t o r d e r , e l e c t r o n i c phase t r a n s i t i o n .
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
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. The pressure dependence of increases. The europium melting
the t r a n s i t i o n has been determined t o curve has been detei-mined to 70
145
90 kbar. I t has been suggested ., 147,148 . fc

that as the l a t t i c e becomes l e s s com kbar. A temperature maximum

p r e s s i b l e with increasing p r e s s u r e , appears near 30 kbar. The close
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
stops at about 20 kbar and gives way europium and barium has been pointed
144 out.
to a pure second-order transition.
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
s

ej; jal.6 1 * found a d i s c o n t i n u i t y i n the

u -u curve at 106 kbar, and sug-
s p
gested t h a t t h i s corresponds to t h e 0 500 1000 1500
i n t e r s e c t i o n of Hugoniot and melting Temperature - K
curve. Gust and Royce found
anomalous behavior in the 180-360 Fig. 59. The phase diagram of
kbar range and suggested a sluggish europium.

-38-
GADOLINIUM e l e c t r o n i c t r a n s i t i o n in the solid.
A bcc phase appears before melt, and
The p h a s e d i a g r a m of gadolinium
a kink i n t h e bec-hep phase boundary
i s shown i n F i g . 6 0 . 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
conditions gadolinium i s hep. A 131
point. The m e l t i n g c u r v e h a s b e e n
t r a n s i t i o n t o the samarium-type phase
d e t e r m i n e d^ t. o 40
~_4 / n ,kLb a r . 1 3 1 , 1 4 8
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
TERBIUM
phase boundary has not been directly
determined. Resistance measurements The phase diagram of terbium is
60 138
shown in Fig. 61. Under room condi
t o 500 k b a r show n o a n o m a l i e s . *
tions terbium is hep. A resistant
Two s e t s o f s h o c k wave e x p e r i
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 s p
been reported at 27 kbar (circle),
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 and the high pressure phase has been

the kink to xenon-core repulsions, determined to be the Sm-type.

while the second i d e n t i f i e s i t w i t h an Resistance measurements to 500 kbar

show smooth behavior and no clear

| i | 1 -

GADOLINIUM _ 40 1 1 1 1 1
TERBIUM
40 1 -
. Rhombohedral L^bcc Rhombohedral
30-
1 (Sm-type) (Sm-type) ~
f 30
] :
2 ^x

r
X
Pressure

X 1
X
1

X
20- X ^-bec
o
to

X
i

X
% Liquid
_

hep
hep \

o

10 -
i

n 1 1
1000
Temperature - K
2000 3000
-

0
' .
1000
,
2000
Temperature - K
.
1, - 3000

Fig. 60. The phase diagram of

gadolinium. Fig. 6 1 . The phase diagram of terbium.

-39-
evidence of further phase t r a n s i - Two s e t s of shock-wave e x p e r i
138 ments show kinks in the u -u curve
tions. The approximate hcp-Sm-
s p
type boundary i s based on a g e n e r a l for dysprosium at 480 k b a r 6 2
and 305
ly 1 61
ized r a r e - e a r t h phase diagram. kbar The f i r s t report a s c r i b e s
Shock-wave experiments show a the kink to xenon-core r e p u l s i o n s , 62
kink in the u -u curve at 400 while the second I d e n t i f i e s i t with
s p
61 61
melting. The bcc-hcp boundary and
kbar. This i s ascribed t o melting.
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 x
respectively.
t o about 25 kbar.

DYSPROSIUM HOLMIUM

The phase diagram of dysprosium The phase diagram of holmium i s

is shown in Fig. 62. Under room shown i n Fig. 63. Under room condi
conditions dysprosium is hep. A t i o n s holmium i s hep. A transition
transition to the Sm-type phase occurs t o the Sm-type phase occurs a t 65
149
at 45-50 kbar and room tempera- kbar and room temperature.
60,149 . ^
ture. Resistance measurements
D
Resistance measurements on holmium t o
on dysprosium show anomalies near 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 1
1
1
1 '
- HOLMIUM ;

2 10 - (L-bcc .
_i_i_Li

hep 1 Liquid _
* 5

-
0 1000 2000 3000 1 I
0 1000 2000 3000
Temperature - K
Temperature - K
Fig. 62. The phase diagram of
dysprosium. Fig. 63. The phase diagram of holmium.

-40-
 Shock-wave experiments show a THULIUM
kink in the u -u curve of holtnium
s p The phase diagram of thulium i s
at 440 kbar, which i s ascribed to
shown i n Fig. 65. Under room condi
melting 61 The hcp-bcc phase
tions thulium I s hep. A transition
boundary and the melting curve have
131 to the Sm-type phase occurs a t room
been determined t o 10 kbar. 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
Shock-wave experiments show a
shown in Fig. 64. Under room condi
kink in the u - u curve, which i s
tions erbium i s hep. A t r a n s i t i o n to 61 s p

149 ascribed t o melting. No bec phase

131
the Sm-type phase occurs at 90 kbar. has been detected before melt.
Resistance measurements made to 600 The melting curve has been determined
131
kbar show no i n d i c a t i o n of a phase x
t o 10 kbar.
transition.
15 1

Shock wave experiments show a ., ! THULIUM 1 '

kink in the u -u curve at 440 kbar, -
s p
61
1 1 1 1 11

which i s ascribed t o melting. No _g 10 -

131 The melting curve has been
bec phase has been detected before
131
melt hep
determined to 10 kbar 5 - 1

"" 1 1
i "'"" -
ERBIUM

- - 1 1 , ,
Kw 0 1000 2000 3000
3

Temperature - K
'
hep Liquid Fig. 65. The phase diagram of thulium.
1 5
| I I I i |

n I 1 .
0 1000 2000 3000
Temperature - K The phase diagram of ytterbium
Fig, 64. The phase diagram of erbium. is shown in Fig. 66. Eelow 300 K

-41-
 153
metallic phase. 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. A
pressure-independent resistance
anomaly variously observed at 743
1 4 7 1 5 5
K and 898 K , has been ascribed
to another phase transition. Static
0 500 1000 1500
compression of ytterbium at room
Temperature - K
temperature to 280 kbar shows no fur
Fig. 66. The phase diagram of ther resistance anomalies above 40
ytterbium. 153
kbar
Three s e t s of shock-wave e x p e r i
and 2 kbar, ytterbium exists in a ments show kinks i n the u - u curve
151 ft? s P
diamagnetic hep phase. A
6 1
a t 130 k b a r , 160 k b a r , and 490
martensitic phase transformation at 146
kbar. The kinks a r e a s c r i b e d t o
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. Johansson and
determined, and it is clear that the Rosengren consider the 130 kbar
152
hep phase disappears above 2 kbar. anomaly to indicate an electronic
At room temperature, increasing phase transition Involving a shift
p r e s s u r e causes a serieB of changes from the divalent to the trivalent
141
in r e s i s t i v i t y . Below 20 kbar ionic state in the solid The
y t t e r b i u m behaves l i k e a m e t a l , melting curve has been determined to
147
between 20 and 40 kbar it behaves like 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.

-42-
 33 1 , 1 , .
LUTETIUM LUTETIUM -

The phase diagram of lutetium i s ~

1 1 1
J 10
shown in Fig. 67. Solid l u t e t i u m at
1 -;

Pressure -
low pressures i s hep. Compression t o
230 bbar at room temperature causes a hep 1 Liquid ..
t r a n s i t i o n to the Sin-type l a t t i c e . _
The hcp-Sm-type phase boundary has
not been determined. The melting J
curve has been determined t o 10 0 1 i , ll , "
1000 2000 3000
kbar 131
Temperature - K
Fig. 67. The phase diagram of l u t e t i u m .
HAFNIUM

Under roost conditions hafnium is TAHTALUM

hep. 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
is shown in Fig. 68. Solid tantalum
bcc phase. The bcc phase i s s l i g h t l y
more dense than the hep, implying a is bcc. An approximate melting curve
158
negative value of dp/dT for the phase has been determined to 60 kbar.

boundary. A static-high-pressure T

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
6 2 6 6 1 4 6 P
curve. ' ' Gust and R o y c e "
ascribed a kink at 600 kbar t o xenon-
core 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
5 3
tion. Hafnium melts at 2495 K .
1000 2000 3000 ' 4000
The melting curve has not been
Temperature - K
reported.
Fig. 68. The phase diagram of tantalum.

-43-
TUNGSTEN IRIDIUM

The phase diagram of tungsten is Solid iridium is fee. Room

shown in Fig. 69. Solid tungsten is temperature compression to 175 kbar
bcc. An approximate melting curve showed no phase transition. Iridium
159 63
melts at 2716 K. The melting curve
has been determined to 50 kbar.
has not been reported.

PLATINUM

The phase diagram of platinum is

shown in Fig. 70. Solid platinum is
fee. The melting curve has been
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
1000 2000 3000
transitions. Rhenium melts at
Temperature - K.
3433 K. The melting curve has not
been reported. Fig. 70. The phase diagram of platinum.

OSMIUM

Solid osmium is hep. Osmium

melts at 3300 K. The melting curve The phase diagram of gold is
has not been determined. shown in Fig. 71. Solid gold is

-44-
 1
' 1 ' 1 '
80 - MERCURY

Rhombohedral v j I
J 60 - (a) X / -

Pressure -
Tetragonal / /
( ( J )
" / / LiquidM~

20
/ /
' ^/\A .
0 200 400 600
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. The melting curve has been been found at very low temperatures
75
determined to 65 kbar. by straining the solid. Its struc
ture and equilibrium phase boundaries
MERCURY 164
have not yet been determined The
melting curve of mercury has been
The phase diagram of mercury is
determined to 65 kbar.
shown in Fig. 72. Solid mercury at
low temperatures has a body centered
THALLIUM
tetragonal structure. In this phase
each rlom has two nearest neighbors The phase diagram of thallium is
and eight second nearest neighbors. shown in Fig. 73. Below 500 K at
With increasing temperature, a atmospheric pressure, thallium is hep.
transformation to a rhombohedral Above 500 K, it is bcc. A high
structure occurs. This structure may pressure fee phase occurs above 35
be regarded as a distorted fee kbar and 388 K. The solid-solid
lattice. The tetragonal-rhombohedral phase boundaries have been determined
phase boundary has been determined to 60 kbar. The melting curve has
to 65 kbar. 78
been determined to 50 kbar.

-45-
 1 1 1 1 1 l~ ' 1 - n -i i | i i i i | i i i i | i i
80 -- THALLIUM
80
LEAD

6 0 - fee j - 60 -
i /
- / 1 -

40 _- _ / / _ 40

i
~\ bcc fee / Liquid

20 - hep \ 20
'Liquid
-
1 1 \ / 1 ,,,/
0 200 400 600 800 0 500 1000 1500
Temperature - K Temperature - K
Fig. 73. The phase diagram of thallium.
Fig. 74. The phase diagram of lead.

LEAD
phases. The low pressure s o l i d phase
The phase diagram of lead i s i s rhombohedral, i s o s t r u c t u r a l with
shown i n Fig. 74. Solid lead at low arsenic and antimony. Conflicting
pressure i s fee. At 137 kbar and 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 ture of phase I I , with no c l e a r
165,166 _. . 1 83
hep phase occurs. The phase
boundary has not been determined. agreement. Duggin suggests that
The melting curve has been determined 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
7 7 the high pressure phase of a r s e n i c .
to 60 k b a r .
A study of phase VI at 90 kbar at
room temperature has shown i t to be
BISMUTH bcc. The phase boundaries shown
The phase diagram of bismuth i s are a s y n t h e s i s of s e v e r a l
,. 84,168,169 ' .
shown i n Fig. 75. This diagram i s of
studies. The phases XX,
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 1 6 9
at 135 k b a r , and the VI-IX phase
t i o n s have been used as c a l i b r a t i o n
boundary then proceeds t o higher
standards. There i s s t i l l controversy
p r e s s u r e s . This boundary was p r e
over the e x i s t e n c e of some t r a n s i t i o n s , temperature and 300 170
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 . 8 4

-46-
 ' r i 1
i ' 1 1
140 -- , BISMUTH -

- IX -

120 -- -

->

100 -- -

bcc
VIII
80 - - (VI) ~

- \\ -
\
V \
60
1 /'\
K. s m \
IV [ \
40 - Tetragonal 1 /
(III) /

Liquid

2 0 -- -

Rhombohedral \
to \
'
1 i i ., . i i \ i i i
200 400 600 800
Temperature - K
Fig. 75. The phase diagram of bismuth.
-47-
POLONIUM
At atmospheric pressure and below
room temperature, polonium has a
rimple cubic structure, the only
known example of this structure in
the elements at zero pressure.
sluggish phase transition occurs
somewhere near room temperature (291-
327 K) to a simple rhombohedral
form which is a slight distortion of
the simple cubic. The rhombohedral
form is slightly more dense,
leading to a negative dp/dT. The
phase boiuidary has not been deter
mined. Polonium melts at 519 K.
The melting curve has not been
reported.
ASTATINE
Astatine is a very unstable
element and its physical properties
have not been determined.
RADON
The crystal structure of solid
radon has not been reported. Radon
172
melts at 202 K. ' The melting curve
has not been determined.
FRANCIDM
Francium is a very unstable
element and its physical properties
have not been determined.
RADIUM
Solid radium is bcc at room
temperature. Radium melts at 973
63
K. Wo high pressure work has been
reported.
A
ACTINIUM
Solid actinium is fee at room
temperature. Actinium melts at 1323
63
K. No high pressure work has been
reported.
THORIUM
Solid thorium under room c o n d i
tions i s fee. Superconductivity
measurements t o 160 fcbar show an
anomaly t h a t could be due t o a phase
173
change near 70 kbar. At atmos
p h e r i c p r e s s u r e near 1670 K, thoritim
transforms t o a bcc p h a s e . The
volume change of the t r a n s i t i o n 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
has n o t been r e p o r t e d . Thorium melts
at 2024 K. The m e l t i n g curve has
not been determined.
PROTACTINIUM
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 .
Metal s o l i d i f i e d from the melt i s fee,
s u g g e s t i n g t h a t t h i s i s the high
48.
temperature form of the solid. No URANIUM
direct measurements of phase transi
The phase diagram of uranium is
tions have heen made, however.
shown in Fig. 76. Under room condi
Protactinium melts at about 1810
174 tions solid uranium has an orthorhombic
K. No high pressure work has been
structure with four atoms per unit
reported.

60 - i i i i r T 1 1 r

URANIUM

40

20 - Orthorhombic bcc
(a) <T>

Liquid
Tetragonal

1 1 , 1

500 1000 1500

Temperature - K

Fig. 76. The phase diagram of uranium.

-49-
cell. At 940 K and atmospheric
pressure, a transition to a complex
tetragonal form with 30 atoms per
unit cell occurs. The precise space
group remains to be determined.
1050 K another phase transition leads
to a bcc phase. The solid-solid
phase boundaries have been deter
mined, and indicate a triple point for
the three phases near 30 kbar.
The melting curve has been determined
to 40 k b a r . 1 7 6
NEPTUNIUM
The phase diagram of neptunium
i s shown in Fig. 77. Under room
conditions neptunium i s orthorhombic,
with eight atoms per unit c e l l and
two d i s t i n c t types of atomic p o s i
tions. At 550 K and atmospheric
pressure a phase t r a n s i t i o n to a
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. A bcc phase
appears above 840 K. The s o l i d - s o l i d
phase boundaries and the melting
curve have been determined t o 35
,, 177
kbar.
PLUTONIUM
The phase diagram of plutonium
i s shown i n Figs. 76 and 79.
plutonium diagram I s very complex.
All but one of the seven known s o l i d
phases e x i s t at atmospheric p r e s s u r e .
The low pressure portion of the
phase diagram and i t s high p r e s s u r e
At continuation are shown in s e p a r a t e
figures. The low temperature a phase
i s monoclinic, with 16 atoms per unit
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 . The
3 phase i s also monoclinic, with 34
atoms per unit c e l l and 7 types of
positions. 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.
At high pressure only a and $
e x i s t , and the a-0 phase boundary
shows a temperature maximum. The $
phase transforms t o orthorhombic
*Y below 3.5 kbar and to 5, with
undetermined s t r u c t u r e , above t h i s
pressure. There i s a |S--liquId
t r i p l e point near 27 kbar.
The next two phases are fee (<5)
and body centered t e t r a g o n a l ( 6 ' )
which e x i s t only a t low p r e s s u r e s .
The 6 ' phase i s followed by bcc ( e ) ,
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
point below 20 kbar. The s o l i d - s o l i d
phase boundaries and the melting
The curve have been determined to 140
1 7 4 1 7 8 1 8 0
kbar. ' '
-50-
 -
< 1 1 1 r- I 1 1 1 1 1 1 f

NEPTUNIUM

40-

30

20-
Or'horhombic I Tetragonal

Liquid'

10-

01 i J L. ' i I L l I I
500 1000 1500
Temperature - K

Fig. 77. The phaBe diagram of neptunium.

-51-
 1 , 1 ,
'/
8 -

-
PLUTONIUM

Monoclinic. 1
(0)
I

^ k /
1 ' -
6 -- Monoclinic 1 -
(a) |

/ ""ec 1
f
/ [ (e) 1 Liquid
- -
1

2 -

1
1

Orrhorhombi<v / J Tetragona
'(5')
1

'
rfcc\

"
, , , / \ 1 1 .
200 400 600 800 1000 1200
Temperature - K

Fig. 78. The phase diagram of plutonium.

AMERICIuM dashed line in Fig. 80. Static com

pression of americium at room tempera
ture shows a resistance change at 90

The phase diagram of americium kbar, which may represent a continua

tion of the dhep-fee phase boundary
182
is shown in Fig. 80. Americium under
room conditions is dhcp. There is Keating at atmospheric pressure above
evidence for a transition to an fee 1300 K leads to a new phase, which

phase at 920 50 K , 1 8 1
but with very Stephens < al. suggest is bcc.

little change in volume. The dhep- The fcc-bcc phase boundary and melting

fec phase boundary is therefore curves have been determined to 35

approximately represented by a vertical ,.
kbar.
182

-52'
1501 r -i 1 1 1 r -| . (-
PLUTONIUM

Liquid

_L
200 400 600 800 1000 1200
Temperature - K

Fig. 79. The phase diagram of plutonium.

-53-
 CURIUM
i i i i | I I i I | i i I I |
40 AMERICIUM
Depending on the method of
preparation, curium metal is found to
3 0 have either an fee or a dhcp struc
i i
ture under room conditions. The fee
bcCs phase has the higher density. No
2 20
phase boundary has been reported.
. Liquid \ l I
The estimated melting point is 1620
10 L_ dhcp K.
174
No high pressure work has been
F c C
I II reported.
' ' ' I I I ! l/i/l I
S00 1000 1500
BERKELIUM
Temperature - K
Berkelium metal prepared by high
temperature reduction contains a
mixture of dhcp and fee structures.
Fig. 80. The phase diagram of Here the dhcp phase is the more
americium.
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. A. R. Marder, Science 142. 664 (1963).

19. H. D. Stromberg and D. R. Stephens, An Automatic Calibration System for

Measuring Electrical Resistance at High Pressures. ASME, Rept. 64 -
WA/PI - 13 (1965).

20. L. F. Vereshchagin, A. A. Semerchan, S. V. Fopova, and N. N. Kuzln,

Soviet Phvs. Dokladv English Transl. 7. 692 (1963) [Dokl. Akad. Nauk
SSSR145., 757 (1962)].

21. R. H. Wentorf, Science 147. 49 (1965).

22. N. D. Stout, Lawrence Livermore Laboratory personal communication

(July, 1975).

-55-
23. N. D. Stout, R. W. Mar, and W. 0. J. Boo, High Temp. Sci. 5. 241 (1973).

24. F. P. Bundy, H. P. Bovenkerfc, H. M. Strong, and R. H. Wentorf, Jr.,

J. Chem. Phys. 35, 383 (1961).

25. P.. G. McQueen and S. P. Marsh, LASL Pept. GMX - 6 - 607 (unpublished, no
date) p. 41.

26. B. J. Alder and R. H. Christian, Phys. Rev. Lett. 7, 367 (1961).

27. L. F. Vereshchagln, E. N. Yakovlev, B. V. Vinogradov, V. P. Sakun, and

G. N. Stepanov, High Temp. - High Press. 6_, 505 (1974) .

28. N. S. Fateeva and L. F. Vereshchagin, JETP Lett. English Transl. 13, 110
(1971) [EhETF Pis. Red. 13, 157 (1971)].

29. A. F. Schuch and R. L. Mills, J. Chem. Phys. 52, 6000 (1970).

30. C. A. Swenson, J. Chem. Phys. 23. 1963 (1955).

31. J. iJ. Grace and G. C. Kennedy, J. Phvs. Chem. Solids 28. 977 (1967).

32. R. Stevenson, J. Chem. Phvs. 27, 673 (1957).

33. R. L. m i l s and E. R. Grilly, Phvs. Rev. 99, 480 (1955).

34. J. A. Jahnke, J. Chem. Phvs. 4, 336 (1967).

35. G. C. Straty and R. Prydz, Phys. Lett. 31A, 301 (1970).

36. R. K. Crawford and W. B. Daniels, J. Chem. Phys. 5_5, 5651 (1971).

37. H. G. Drickaraer, R. H. Lynch, R. L. Clendenen, and E. A. Perez-Albuerne,

Solid State Phvs. 19., 135 (1966).

38. G. C. Kennedy and R. C. Newton, in Solids Under Pressure. W. Paul and

D. W. Warschauer, Eds. (McGraw-Hill Book Co, New York, 1963) Ch. 7.

39. N. N. Roy and E. G. Steward, Nature 224. 905 (1969).

40. J. Lees and B. H. J. Williamson, Nature 208. 278 (1965).

41. S. Minomura and H. G. Drickamer, J. Phvs. Chem. Solids 23. 451 (1962).

42. J. C. Jamieson, Science 139, 762 (1963).

43. R. H. Wentorf, Jr., and J. S. Kasper, Science 139, 338 (1963).

44. F. P. Bundy, J. Chem. Phys. 41, 3809 (1964).

45. W. H. Gust and E. B. Royce, J. Appl. Phys. 42, 1897 (1971).

46. J. C. Jamieson, Science 139, 1291 (1963).

-56-
47. R. E. Harris, R. J. Vaisnys, H. Stromberg, and G. Jura, in Progress in
Very High Pressure Research. F. P. Bundy, W. R. Hubbard, Jr., and H. H.
Strong, Fds. (Wiley, New York, 1961) p. 165.

48. L. J. Long, G. B. Guarlse, and A. Marani, Corsi Semin. Chim. 5_, 97 (1967;.

49. A. Marani, G. B. Guarise, Chim. Ind. (Milan) 50, 663 (1968).

50. G. C. Vezzoli, F. Dachille, and R. Roy, Science 168. 218 (1969).

51. G. C. Vezzoli, F. Dachille, and R. Roy, Inorg. Chem. 8, 2658 (1969).

52. G. C. Vezzali, F. Dachille, and R. Roy, J. Polymer Sci., Part A-l. 2.

1557 (1969).

53. G. C. Vezzoli and R. J. Zeto, Inorg. Chem. , 2478 (1970).

54. R. E. Harris and G. Jura in Elemental Sulfur. B. Meyer, Ed. (Inter-

science, New York, 1965) p. 179.

55. S. Block and G. J. Piermavini, High Tegp.-High Press. 5_, 567 (1973).

56. S. E. Babb, Jr., J. Chen. Phys. 50, 5271 (1969).

57. A. Jayaraman, W. Klement, Jr., and G. C. Kennedy, Phys. Rev. 132, 1620
(1963).

58. R. A. Stager and H. G. Drickamer, Phvs. Rev. 131. 2524 (1963).

59. L. F. Vereshchagin, A. A. Seroerchan, N. N. Kuzin, and Yu. A. Sadkov,

Soviet Phvs. Doklady English Transl. 14, 557 (1969) [Dokl. Akad. Nauk
SSSR 186, 1045 (1969)].

60. H. D. Stromberg and D. R. Stephens, J. Phys. Chem. Solids 25, 1015 (1964).

61. W. J. Carter, J, N. Fritz, S. P. Marsh, and R. G. McQueen, J. Phvs. Chem.

Solids 36. 741 (1975).

62. W. H. Gust and E. B. Royce, Phys. Key. B8, 3595 (1973).

63. K. A. Gschneidner, Jr., Solid State Phvs 16. 275 (1964).

64. F. P. Bundy, Phase Diagram of Titanium. General Electric, Rept. 63-RL-3481C

(1963).
65. A. Jayaraman, W. Klement, Jr., and G. C. Kennedy, Phys. Rev. 131. 644
(1963).
66. R. G. McQueen, S. P. Marsh, J. W. Taylor, J. N. Fritz, and W. J. Carter,
in High-Velocity Impact Phenomena. R. Kinslow, Ed. (Academic Press, New
York, 1970) Ch. 7.

67. M. 0. Steinitz, L. H. Schwartz, J. A. Marcus, E. Fawcett, and W. A. Reed,

Phys Rev. Lett. .23, 979 (1969).

-57-
68. H. Umebayashi, G. Shirane, B. C. Frazer, and W. B. Daniels, J. Phys. Soc.
Japan 24, 368 (1968).

u 9. T. Mitsui and C. T. Tomizuka, Phys. Rev. 137, A 564 (1965).

70. W. E. Evenson and H. T. Hall, Science 150, 1164 (1965).

71. E. Rapoport and G. C. Kennedy, J. Phys. Chem. Solids. 27, 93 (1966).

72. F. P. Bundy, J. Appl. Phys. 36_, 616 (1965).

73. H. M. Strong, R. E. Tuft, and R. E. Hanneman, Metall. Trans. 4_, 2657

(1973).

74. H. M. Strong and F. P. Bundy, Phys. Rev. 115, 278 (1959).

75. J. Akella and G. C. Kennedy, J. Geophvs. Res. 2i. 4969 (1971).

76. R. H. Lynch and H. G. Drickamer, J. Phys. Chem. Solids 26, 63 (1965).

77. J. Akella, J. Ganguly, R. Grover, and G. Kennedy, J. Phys. Chem. Solids

34., 631 (1973).

78. A. Jayaraman, W. Klement, Jr., R. C. Newton, and G. C. Kennedy, J. Phvs.

Chem. Solids 24, 7 (1963).
J
79. W. Buckel and W. Gey, Z. Phys k 176, 336 (1963).

80. W. H. Gust and E. B. Royce, -,. Appl. Phys. 43., 4437 (1972).

81. C. H. Bates, F. Dachille, and R. Roy, Science 147, 860 (1965).

82. L. F. Vereshchagin, A. A. Semerchan, N. N. Kuzin, and S. V. Popova, Soviet

Phys. Doklady English Transl. 6_, 41 (1961) [Dokl. Akad. Nauk SSSR 136,
320 (1961)].

83. M. J. Duggin, J. Phys. Chem. Solids 33. 1267 (1972).

84. W. Klement, Jr., A. Jayaraman, and G. C. Kennedy, Phvs. Rev. 131, 632
(1963).

85. A, S. Balchan and H. G. Drickamer, J. Chem. Phys. 37, 1948 (1961).

86. B. M. Riggleman and H. G. Drickamer, J. Chem. Phys. 37. 446 (1962).

87. D. R. McCann and L. Cartz, J. Chem. Phvs. 56., 2552 (1972).

88. W. Klement, Jr., L. H. Cohen, and G. C. Kennedy, J. Phvs. Chem. Solids 27,
171 (1966).

89. I. E. Paukov, E. Yu. Tonkov, and D. S. Mirinskii, Russ. J. Phys. Chem.

English Transl. 41, 995 (1967) [Zh. Fiz. Khim. 41, 1857 (1967).

90. C. SuBse, R. Epain, and B. Vodar, Compt. Rend. 258, 4513 (1964).

-58-
 91. C. E. Weir, G. J. Piermarini, and S. Block, J. Chem. Phvs. 50, 2089 (1969).

92. P. H. Lahr and W. G. Eversole, J. Chem. Eng. Data 7. 42 (1962).

93. F. P. Bundy and H. M. Strong, Solid State Phys. 13, 81 (1962).

94. D. B. McWhan, T. M. Elce, and P. H. Schmidt, Phys. Rev. 177, 1063 (1969).

95. J. Wlttlg, Phvs. Rev. Lett. 24_, 812 (1970).

96. N. B. Brandt, I. V. Berman, and Yu. P. Kurkin, JEIP Lett. English Transl.
20, 8 (1974) [Zh ETF Pis. Red. 20, 20 (1974)].

97. L. F. Vereshchagin, A. A. Semerchan, H. N. Kuzln, and S. V. Popova,

Soviet Phvs. Doklady English Transl. 6_, 391 (1961) [Dokl. Akad. Nauk
SSSR138, 84 (1951)].

98. N. S. Fateeva and L. F. Vereshchagin, JETP Lett. English Transl. 14, 153
(1974) [ZhETF Pis. Red. 14, 233 (1971)].

99. R. L. Clendenen and H. G. Drickamer, J. Phvs. Chem. Solids 25. 865 (1964).

100. L. Liu and W. A. Bassett, J. Appl. Phvs. 44, 1475 (1973).

101. R. W. Vaughan and H. G. Drlckamer, J. Phvs. Chem. Solids 26. 1549 (1965).

102. 1. N. Nikolaev, N. P. Mar'ln, V. N. Panyushkln, and L. S. Pavlykov,

Soviet Phvs. Solid State English Transl. 14, 2022 (1973).[Fiz. Tverd.
fela 14, 2337 (1972)].

103. A. Jayaraman, W. Kleoent, Jr., and G. C. Kennedy, Phys. Rev. 130, 540
(1963).
8 7 5
104. T. D. Barnett, V. E. Bean, and H. T. Hall, J. Appl. Phys. .37.. (1965).

105. T. N. Kolobvanina, S. E. Kabalkina, L. F. Vereshchagin, and L. V. Fedina,

Soviet Phvs. JETP English Transl. 2 8 , 88 (1969) [Zh. Eksp. Teor. Fiz. 55,
164 (1968)].

106. S. S. Kabalkina, T. N. Kolobyanina, and L. F. Vereshchagin, Soviet Phvs.

JETP English Transl. 31, 259 (1970) [Zh. Eksp. Teor. Fiz. 58, 486
(1970)].

107. S. M. Stishov and N. A. Tikhoiuirova, Soviet Phva. JETP English Transl. 21,
810 (1965) [Zh. Eksp. Teor. Fiz. .48, 1215 (1965)].

108. J. C. JamleBon and D. B. McWhan, J. Chem. Phvs. 43, 1149 (1965).

109. I. V. Bennan, Zh. I. Bynzarov, and Yu. P. Kurkin, Soviet Phvs. Solid
State English Tranal. 14, 2192 (1973) [Eiz. Tverd. Tela 14, 2527 (1972)].

110. F. A. Blum, Jr., and B. C. Deaton, Phvs. Rev. 137. A 1410 (1965).

111. R. Grover, A. S. Kusubov, and H. D. Stromberg, J. Chem. Phys. 47, 4398

(1967) *

-59-
112. S. S. Kabalklna, T. N. Kolobyanina, and I.. F. Vereshchagin, Soviet Phys.
Doklady English Transl. U_, 50 (1967) [Dokl. Akad. Nauk SSSR 172. 313
(1967)].

113. B. M. Riggleman and H. G. Drickamer, J. Chem. Phys. 3_8, 2721 (1963).

114. B. J. Alder and R. H. Christian, Phys. Rev. Lett. .4, 450 (1960).

115. W. Klement, Jr., L. H. Cohen, and G. C. Kennedy, J. Chem. Phvs. 44,

3697 (1966).

116. H. I. Hall, L. Merrill, and J. D. Barnett, Science 146, 1297 (1964).

117. G. C. Kennedy, A, Jayaraman, and R. C. Newton, Phvs. Rev. 126. 1363

(1962).

118. A. Jayaraman, R. C. Newton and J. M. McDonough, Phys. Rev. 159, 527

(1967).

119. D. B. McWhan and A. L. Stevens, Solid State Commun. 7_, 301 (1969).

120. R. Sternheimer, rhys. Rev. 2 8 , 235 (1950).

121. E. Rapoport, Phys. Rev. Lett. 2p_, 345 (1967).

122-, J. C. Haygarth, I. C. Getting, and G. C. Kennedy, J. Appl. Phvs. 38,

4557 (1967).

123. J. D. Barnett, R. B. Bennion, and H. T. Hall, Science 141, 534 (1963).

124. A. Jayaranan, W. Klement, Jr., and G. C. Kennedy, Phvs. Rev. Lett. 10,
387 (1963).

125. 3. C. Beaton and D. E. Bowen, Appl. Phys. Lett. jt_, 97 (1964).

126. C. Susse and R. Epain, J. Chim. Phys. 63, 1580 (1966).

127. J. P. Bastide, C. Susse, and R. Epain, Compt. Rend. Ser. C 267, 857
(1968).

128. J. P. Bastide and C. Susse, High Temp.-High Press. 2, 237 (1970).

129. H. G. Drickamer, Solid State Phys. 17, 1 (1965).

130. J. Wittig and B. Matthias, Phys. Rev. Lett. 22_, 634 (1969).

131. A. Jayaraman, Phys. Rev. A 139, 690 (1965).

132. L. F. Vereshchagin, A. A. Semerchan, and S. V. Popova, Soviet Phvs.

Dokladv English Transl. 6_, 488 (1961) [Dokl. Akad. Nauk SSSR 138, 1059
(1961)].

133. K. A. Gschneidner, Jr., R. 0. Elliot, and R. R. MacDonald, J. Phys.

Chem. Solids 23, 555 (1962).

-60-
134. A. Jayaraman, Phys. Rev. 137, A 179 (1965).

135. R. F. Gempel, D. P.. Gustafson, and J. D. Wlllenberg, Phvs. Rev. B5,

2082 (1972).

136. E. King, J. A. Lee, I. R. Harris, and T. F. Smith, Phys. Rev. Bl,

1380 (1970).

137. F. H. Ellinger and W. H. Zacharisen, Phvs. Rev. Lett. 32, 773 (1974).

138. R. A. Stager and H. G. Drickamer, Phvs. Rev. 133, A 830 (1964).

139. G. J. Piermarini and C. E. Weir, Science 144, 69 (1964).

140. E. Bucher, C. W. Chu, J. P. Malta, K. Andres, A. S. Cooper, E. Buehler,

and K. Nassau, Phys. Rev. Lett. 2, 1260 (1969).

141. B. Johansson and A. Rosengren, Phvs. Rev. Bll, 2836 (1975).

142. P. G. Pallmer and T. D. Chikalla, J. Less-Common Metals 24. 233 (1971).

143. A. Jayaraman and R. C. Sherwood, Phys. Rev. 134, A 691 (1964).

144. R. L. Cohen, S. Hufner, and K. W. West, Phvs. Rev. 184. 263 (1969).

145. D. B. McWhan, P. C. Souers, and G. Jura, Phvs. Rev. 143, 385 (1966).

146. A. A. Bakanova, I. P. Dudoladov, and Yu. N. Sutulov, Soviet Phys. Solid

State English Iransl. 11, 1515 (1970) [Fiz. Tverd. Tela 11, 1881
(1969)].

147. A. Jayaraman, Phvs. Rev. 135, A 1056 (1964).

148. D. R. Stephens, J. Phvs. Chem. Solids 26. 943 (1965).

149. D. B. McWhan and A. L. Stevens, Phvs. Rev. 154, 438 (1967).

150. D. R. Stephens and Q. Johnson, J. Less-Common Metals 17, 243 (1969).

151. E. Bucher, P. H. Schmidt, A. Jayaraman, K. Andres, J. P. Malta, K. Nassau,

and P. D. Dernier, Phys. Rev. B 2 , 3911 (1970).

152. M. Rleux and D. Jerome, Solid State Comm. 9_, 1179 (1971).

153. R. A. Stager and H. G. Drickamer, Science 139. 1284 (1963).

154. P. C. Souers and G. Jura, Science 140, 481 (1963).

155. H. T. Hall and L. Merrill, Inorg. Chem. 2, 618 (1963).

156. L. Liu, J. Phys. Chem. Solids 36. 31 (1975).

157. J. C. Jamieson, Science 140, 72 (1963).

-61.
158. N. S. Fateeva and L. F. Vereshchagin, Soviet Phys. Dokladv English Transl.
16, 322 (1970) [Dokl. Akad. Nauk SSSR 197, 1060 (1971)].

159. L. F. Vereshchagin and N. S. Fateeva, Soviet Phys. JETP English Transl.

2JS, 597 (1969) [Zh. Eksp. Teor. Fiz. 55, 1145 (1968)].

160. L. Liu, T. Takahashi, and W. A. Bassett, J. Phys. Chem. Solids 31. 1345
(1970).

161. R. M. Schock and Q. Johnson, Phvs. Met. Metallog. English Transl. 31,
No. 5, 213 (1971) [Fiz. Metal. Metalloved 31, 1101 (1971)].

162. N. R. Mltra, D. L. Decker, and H. B. Vanfleet, Phvs. Rev. 161, 613

(1967).

163. W. Klement, Jr., A. Jayaraman, and G. C. Kennedy, Phys. Rev. 131, 1

(1963).

164. J. S. Abell, A. G. Crocker, and H. W. King, Phil. Mag. 2JL, 207 (1970).

165. T. Takahasi, H. K. Mao, and W. A. Bassett, Science 165, 1352 (1969).

166. H. Mil, I. Fujishlro, M. Senoo, and K. Ogawa, High Temp.-High Press. 5_,
155 (1973).

167. P. Schaufelherger, H. Merx, and M. Contre, High Temp .-High Press. 5_,
221 (1973).

168. N. A. Tikhomirova, E. Yu. Tonkov, and S. M. Stishov, JETP Lett. English

Transl. 3, 60 (1966) [ZhFET Pis. Red. 3_, 96 (1966)].

169. C. G. Homan, J. Phvs. Chem. Solids (to be published).

170. C. G. Homan, T. E. Davidson, and D. P. Kendall, Appl. Phys. Lett. 26,

615 (1975).

171. J. M. Goode, J. Chero. Phys. 26, 1269 (1957).

172. G. L. Pollock, Rev. Mod. Phvs. 36,, 748 (1964).

173. W. A. Fertig, A. R. Moodenbaugh, and M. B. Maple, Phys. Lett. 38A,

517 (1972).

174. J. A. Lee and M. B. Waldron, Contcmp. Phys. 13, 113 (1972).

175. W. Klement, Jr., A. Jayaraman, and G. C. Kennedy, Phys. Rev. 129, 1971
(1973).

176. J. Ganguly and G. C. Kennedy, J. Phys. Chem. Solids 34. 2272 (1973).

177. D. R. Stephens, J. Phys. Chem. Solids 27. 1201 (1966).

178. D. R. Stephens, J. Phys. Chem. Solids 24. 1197 (1963).

-62-
179. R. G. Liptai and R. J. Frlddle, \ Leas-Common Metals 10, 29? (1966).

180. C. Roux, P. le Roux, and M. Rapln, J. Nucl. Mater. 0, 305 (1971).

181. D. B. McWhan, B. B. Cunningham, and J. C. Wallman, J. Inorg. Nucl.
Chen. 24, 1025 (1962).

182. D. R. Stephens, H. D. Stromberg, and E. M. Lllley, J. Phys. Chem.

Solids 29. 815 (1968).

RBC/gw

-63-
 Appendix A: The Space Lattices

Lattice Axes Angles

primitive (simple) cubic

body-centered cubic a - b - c o - 3 " Y " 90
face-centered cubic

primitive tetragonal
a b ji c aB-Y-90
body-centered tetragonal

primitive orthorhombic
base-centered orthorhombic a^b^c a B = Y = 90
body-centered orthorhombic
face-centered orthorhombic i

primitive monoclinic
a^bjc o - Y 90" ^
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-