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TOL- 51902

PHASE DIAGRAMS OF THE ELEMENTS

David A. Young

&
September 11, 1975

aiS
1

Prepared for U.S. Energy Research & Development


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

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UCRL-51902

PHASE DIAGRAMS OF THE ELEMENTS


David A. Young

MS. date:

September 11, 1975

OlSTRIBUTt0 npTu,5

revivor

IStWUMtTED

Contents
Abstract

Introduction

Phase Dlagraas

Hydrogen

Helium

Lithium

Berylliua

Boron

Carbon

Nitrogen

Oxygen

10

Fluorine

10

Neon

11

SodiuD

11

Magnesium

12

Aluminum

12

Silicon

13

Phosphorus

13

Sulfur

14

Chlorine

16

Argon

16

Potassium

16

Calcium

17

Scandium

17

Titanium

la

Vanadium

IS

Ch.'omium

. . . . <

IB

Manganese

19

Iron

20

Cobalt

20

Nickel

21

Copper

'.

21

Zinc

21

Glllu

21!
-ill-

Germanium

22

Arsenic

23

Selenium

23

Bromine

24

Krypton

24

Rubidium

24

Strontium

24

Yttrium

26

Zirconium

26

Niobium

27

Molybdenum

27

Technetium

27

Ruthenium

27

Rhodium

27

Palladium

27

Silver

28

Cadmium

28

Indium

28

Tin

28

Antimony

29

Tellurium

30

Iodine

31

Xenon

31

Cesium

31

Barium

33

Lanthanum

34

Cerium

24

Praseodymium

35

Neodymium .

36

Promethium

37

Samarium

37

Europium

.-

38

Gadolinium

39

Terbium

39

Dysprosium

40

Holmlum

40
-iv-

Erbium

41

Thulium

41

Ytterbium

41

Lutetlum

43

Hafnium

43

Tantalum

43

Tungsten

44

Rhenium

44

Osmium

44

Iridium

44

Platinum

44

Gold

44

Mortury

45

Thallium

45

Lead

46

Bismuth

46

Polonium

48

Astatine
Radon

48
~

Francium

48
48

Radium

48

Actinium

48

Thorium

48

Protactinium

48

Uranium

49

Neptunium

50

Plutonium

50

Aroericium

52

Curium

54

Berkellura

54

References
Append!* A:

55
The Space Lattices

64

-v-

PHASE DIAGRAMS OF THE ELEMENTS


Abstract
for each diagram.

A summary of the pressure-

The crystal

temperatur phase diagrams of the

structure of each solid phase is

elements is presented, with graphs

identified and discussed.

of the experimentally determined

is aimed at encouraging further

This work

solid-solid phase boundaries and

experimental and theorerirl research

melting curves.

on phase transitions in the

Comments, including

theoretical discussion, are provided

elements.

Introduction
Phase diagrams are useful as
compact summaries of large amounts of
experimental data.

As such thay

they may be quite common at ultrahigh


pressures where the atomic s h e l l
structure exhibits stepwise break

provide an important challenge for


theory, since accurate computation of
phase transitions typically requires

down.
Another aspect of phase diagrams
that has attracted much attention i s

a very high degree of accuracy in

the recurrence of patterns in the

s o l i d - and l i q u i d - s t a t e theoretical

diagrams of closely related elements.

models.

To date there have been very

few f i r s t - p r i n c i p l e s calculations of

This has been used successfully in


predicting the structure*? and proper

one-component pressure-temperature

t i e s of high pressure phases.

phase diagrams.

certain phase transitions observed at

The experimental study of phase


boundaries has led Co the discovery

Thus,

relatively low pressure provide


important clues about the behavior of

of such unexpected phenomena as

materials at much higher pressure.

isostructural phase transitions and

Deeper theoretical understanding of

melting curve extreraa.

observed phase behavior w i l l thereby

A qualitative

theoretical understanding of these

allow quantitative prediction of

phenomena has been achieved, and work

properties of materials at much higher

1B continuing in this area.

pressures where experiments are d i f f i

The s i g

nificance of these phenomena if

that

cult to perform.

It may also be

hoped chat an adequate theory of

and one or more paragraphs of com

phase diagrams for elements w i l l pro

ments are provided.

mote the more complex task of describ

the comment? Include information on

When appropriate,

ing phase behavior in compounds and

the l a t e s t theoretical understanding

multi~component systems.

of Che phase diagram.

This report i s aimed at encour

structures found among the elements

aging theoretical and experimental


research on phase t r a n s i t i o n s .

Cursory

descriptions of complex crystal

It i s

are included i n the comments.

For

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

a summary of the experimental data


obtained to date on the phase diagrams

reader should consult Donohue's The

of the elements.

Structures of the Elements.

Only s o l i d and

The bibliography i s not

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

exhaustive, since only the most

here.

recent papers are c i t e d .

The temperature abscissa i s

However, the

always referred :o zero Kelvin in

reader can e a s i l y work back froo the

order to illustrate, the true s i z e s of

reference? in the recent papers to

the various f i e l d s of phase s t a b i l i t y .

the e a r l i e r ones.

Commonly occurring s o l i d phases are

the work cited here was done since

The gveat bulk of

labelled with abbreviations: bcc

1960.

body-centered cubic (two atoms per


unit c e l l ) , fee face-centered

phase diagrams for the elements


2 3
e x i s t , ' but they are already

cubic, hep - hexagonal close packed,

beginning to be dated by continuing

and dhep - double hexagonal.

research.

Other

solid phases are identified according

Very recently, J. F.

Cannon has published a c r i t i c a l

to the 14 l a t t i c e types l i s t e d in
Appendix A.

Two other useful surveys of

review of the behavior cf the


4

Dashed l i n e s in the

elements at high pressures.

figures indicate extrapolations or

Cannon's review and the present one

poorly determined phase boundaries.

cover much the same ground, and i t i s


hoped that these surveys w i l l f i l l the

For each element where data are

gap l e f t by ten years of active

available, a phase diagram i s 3hoi.n

research.

-2-

Phase Ditgrams
HYDROGEN

ni\
I

The phase diagram o f hydrogen

i s shown in Fig. I.

Solid and liquid

1
I

hydrogen are composed of diatomic


molecules interacting according to

HYDROGEN

L^fCubic)

van der Waals and electric-quadrupole


forces.

Solid hydrogen and deuterium

in thermodynamic equilibrium ( i . e . . ,
para-H, and ortho-D,) c r y s t a l l i z e

Hexogono!

with the molecules centered on hep


lattice sites.

The molecules are

e s s e n t i a l l y freely rotating.

For

ortho-rich H. or pars-rich D. the


stable s t a t e at zero Kelvin i s cubic,

with the molecules centered on an


fee l a t t i c e and presumably ordered,

Fig. 1.

20
40
Temperature - K

60

The phase diagram of hydrogen.

with axes pointing along body


diagonals.
As the cubic l a t t i c e is warmed

kbar.

Theoretical calculations

to about 2 K, a first-order transition

suggest that pure o-D and P~H_ should

(probably marfcensitic,

have transitions to rotationally

involving the

motion of planes of molecules) to the


hexagonal phase occurs*

Further

warming then apparently leads to an


order-disorder t r a n s i t i o n .

This

occurs as the librating molecules


begin to rotate freely.

The temper

ordered cubic l a t t i c e s at zero Kelvin


and compressions corresponding to
pressures of a few tens of kilobars. S
Recently there has been great interest
in theoretical arid experimental
investigations of the i n s u l a t o r - t o -

ature of the crystallographic

metal phase transition in hydrogen,

transition i s a function of pressure

which is exepcted to occur in the


9
megabar range.
The three molecular

and concentration of spin s t a t e s .


The phase boundary indicated by

solid isotopes melt in a regular

the das.i.d l i n e in Fig. 1 i s for 70%

sequence, and the melting curves

o-H-, which has been measured to 5.3

have been determined to 3.5 kbar. 10

HELIUM
The phase diagram of helium is
shown in Figs. 2-6.

The cohesive

energy of solid and liquid helium is


entirely due to very
forces.

weak van der Waals

Because of the strong

quantum effects observed in the solid


and liquid phases, the phase diagram
of helium has been extensively
studied and worked out in detail."*11,12
Both isotopes 3 and 4 are liquid at
T " 0 and p = 0 as the result of aero
point motion.

10

Under pressure, both

liquids solidify.

pressures above 0.1 kbar, both solids

Fig. 2.

are hep and show a transition to fee


around 15 K and above 1 kbar. (Figs.
2 and 5)

20

Temperature ~ K

At zero Kelvin and

The phase diagram ot


helium - 3 .

0.25

In Tie, a bec phase appears

below 0,1 kbar and the melting pres


sure has minimum at 0.32 K (Fig. 3 ) .
In

0.20

He, the bec field is very small,

and is replaced by hep at the lowest


temperatures (Fig. 6 ) . The melting
curve of

-S 0.15 -

He has a very flat minimum

at 0.78 K.

This curve has been

extended to 14 kbar, at which pres


sure the melting temperature is 7? K.

0.10=

3
In

He the normal Fermi liquid

persists down to a temperature of

0.05 -

1 mK, where a transition to recently


discovered superfluid phases occurs
13
(Fig. 4 ) .
The boundary separating

2
4
Temperature - K

the normal Fermi liquid from the A


and B su?erfluid phases represents a
second-orn>;c phase transition, like

Fig. 3.

The phase diagram of


helium - 3 .

30

0.05

HELIUM-3

0.04 --

bcc (Solid)

0.05

.
A liquid

i | n rr

HELIUM-4 1
hep
1

0.04 _-

.
0.03 --

bcc

-3 0.03

Y"/

8 0.02
B liquid

0.02

'

Liquid 11

/Fermi liquid

0.01 _-

0.01 -

j / ,
1 , 1 ,
0.001
0.002
0.003
Temperature - K

The phase diagram of


helium - 3 .

i
3

The phase diagram of


helium - 4 .

Fig. 6.

t h a t in

i
,
i\ .
1
2
Temperature - K

He.

The A-B phase boundary

i s a f i r s t - o r d e r phase t r a n s i t i o n , and
i t j o i n s the Fermi l i q u i d at a t r i critical point.

The A and B f l u i d s

are thought t o be superfluids t h a t


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

In

He the normal f l u i d ( I )

undergoes a second-order t r a n s i t i o n
(A-transition) to a s u p e r f l u i d phase
( I I ) , which a r i s e s from the BoseEinstein condensation as i t i s modi
fied by the He-He p a i r i n t e r a c t i o n s
(Fig. 6 ) .

0
Fig. 5.

10
20
Temperature - K

30

LITHIUM
The phase diagram of lithium is

The phase diagram of


helium - 4.

shown in Fig. 7.

-5-

Upon cooling to

80

'
1
LITHIUM

60

'

which suggests t h a t a melting point


maximum w i l l occur a t a somewhat

greater pressure.

BERYLLIUM
The phase diagram of beryllium

40

i s shown in Fig. 8.
Liquid

20

jf

bcc
ep :
1
n ._u_
0
200

before melt.
V-

1
400

The bcc phase i s about

P% more dense, giving r i s e t o t h e


negative slope of the phase boundary.

The hep-bec phase boundary has been

/,
600

Temperature - K
Fig. 7.

Beryllium has a

t r a n s i t i o n from hep t o bcc j u s t

determined to 60 kbar.

The same

study yielded two other r e s i s t a n c e


anomalies belcw 1000 K t h a t appear to

The phase diagram of lithium.

correspond to f l u c t u a t i o n s in the
hexagonal c/a l a t t i c e r a t i o , r a t h e r

about 80 K, l i t h i u m changes from bcc

than to genuine phase t r a n s i t i o n s .

to a close-packed (cp) s t r u c t u r e .
The i d e n t i t y of t h i s s t r u c t u r e (or
s t r u c t u r e s ) i s not yet agreed upon.
This i s a m a r t e n s i t i c t r a n s i t i o n with
a considerable temperature h y s t e r e s i s .
The change i n t r a n s i t i o n temperature
with pressure i s very s m a l l , as
14
me'isurements to 3 kbar have shown.
Stager and Drickamer

have found a

sharp drop i n r e s i s t a n c e at 70 kbar


and 296 K, which i s shown by the
c i r c l e in Fig. 7.

The s t r u c t u r e of
500

the high pressure phase i s not

1000

1500

Temperofure - K

known. The melting curve of l i t h i u m


has been determined to 60 kbar.
Fig. 8.

The melting temperature becomes


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

The phase diagram of


beryllium.

2000

at pressures above 100 kbar and tem

S t a t i c high pressure r e s i s t a n c e
18
showed a

measurements by Marder

p e r a t u r e s near 2000 K, but the

d i s c o n t i n u i t y at 93 kbar and 293 K,


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

p r o b a b i l i t y of sample contamination
in t h i s work was l a r g e . Boron
22
very s l i g h t l y upon melting
23
near 2350 K,
which implies a melt
ing curve with p o s i t i v e slope. The
melting curve has not been d i r e c t l y
measured.
expands

The melting curve has been determined


to 60 kbar.

Solid boron i s covalently bonded.

CARBON

The phase diagram i s e s s e n t i a l l y


unknown.

Many different

crystal

The phase diagram of carbon is

s t r u c t u r e s of boron have been


described in the l i t e r a t u r e *

shown in Fig. 9.

but

This phase diagram

has been the subject of much experi

t h e i r r e l a t i o n s h i p to one another i s

mental work owing to the problem of

unclear.

producing artificial diamonds.

Furthermore, contamination

of boron with metals and the formation


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

It

i s suspected t h a t many of the s t r u c


tures reported for pure boron a r e i n
fact those c- b o r i d e s .

Liquid

S o l i d i f i c a t i o n of l i q u i d boron
y i e l d s the "S-rhombohedral" s t r u c t u r e
with 105 atoms per unit c e l l and 16
d i s t i n c t atomic p o s i t i o n s .

This very

complex s t r u c t u r e can be resolved i n t o


groups of linked lcosahedra of boron
atoms.

I t i s l i k e l y to be the s t a b l e

phase at low p r e s s u r e s .
S t a t i c high pressure r e s i s t a n c e
measurements up t o 250 kbar show no
20
evidence of phase t r a n s i t i o n s .

2000

4000

6000

Temperature - K

21
Wentorf
reported a new boron
polymorph of unknown structure obtained
-7-

Fig. 9.

The phase diagram of carbon.

Shock wave experiments

However, the very high temperatures


and pressures involved have made the

up to a

fdw hundred kbar c l e a r l y show the

measurement of the phase boundaries

graphite-diamond t r a n s i t i o n , but t h i s

extremely d i f f i c u l t , and the phase

i s dominated by nonequilibrium e f f e c t s

diagram cannot be s a i d t o be firmly

and the i n i t i a l s t a t e of the g r a p h i t e .


26
The s i g n i f i c a n c e of shock data

established.
Graphite, the s t a b l e phase at

i n d i c a t i n g a new phase at yet higher

low p r e s s u r e s , has hexagonal l a t t i c e

p r e s s u r e i s s t i l l uncertain.

symmetry.

r e c e n t l y , Vereshchagin's group has

Graphite c o n s i s t s of plane

s h e e t s of covalently bonded atoms.


The sheets are bonded to each o t h e r
by weaker van der Waals forces.

The

high pressure diamond phase i s cubic,


with e i g h t atoms per unit c e l l .

Each

atom i s covalently bonded to four

Very

observed a t r a n s i t i o n from the diamond


to a m e t a l l i c phase at pressures of
27
They a l s o

approximately 1 Mbar.

observed t h a t the t r a n s i t i o n pressure


drops with increasing temperature,
which i s s i m i l a r t o the behavior of

neighbors located at the corners of

the semiconductor-to-metal t r a n s i t i o n s

a tetrahedron.

i n s i l i c o n and germanium.

Because diamond i s metastable at


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

The melting temperature of


graphite shows a maximum near 5000 K
and 50 kbar according to recent
28
Uncertainties in the tempera

work.

measured thermodynamic d a t a , and the

t u r e measurements are l a r g e .

graphite-diamond phase boundary can


24
be e s t a b l i s h e d .
This has been done

of diamond has not been reported, but

Melting

the melt ng curve i s assumed to have

with reasonable accuracy up t o 1200 K.

a negative slope by analogy with

and 40 kbar.

silicon.

Beyond t h i s , the a c t u a l

transformation of graphite to diamond


in t r a n s i t i o n - m e t a l matrices has been
24
c a r r i e d out.
These measurements
extend the phase boundary t o 80 kbar.

NITROGEN
The phase diagram of nitrogen i s

The dashed l i n e i s a l i n e a r e x t r a p

shown in F i g s . 10 and 1 1 .

o l a t i o n of the lower-temperature

in the s o l i d and l i q u i d phases i s

results.

Together with the melting

Nitrogen

composed of diatomic molecules

curve, t h i s y i e l d s a g r a p h i t e -

weakly bonded to each o t h e r by van der

diamond-liquid t r i p l e point near 100

Waals and electrlc-quadrupole forces.


29
Three s o l i d phases are known.
In

kbar and 3500 K.

'

'

8 --

'-

NITROGEN

1
Tetragonal

^ S

4 -

Hexagonal

(0)
2 --

Cubic
(a)

/
/

Liquid

i
20

i
40

1 ^T
60

80

100

120

Temperature - K
Fig. 10. The phase diagram of nitrogen.

the cubic a phase, the molecules are


centered on an fee lattice with the
molecular axe* pointing along body
diagonals.

This ordering is pre

sumably stabilized by quadrupolar


forces.

At 36 K, the cubic phase

transforms to a hexagonal phase in


which the molecules are centered on
an hep lattice and are thought to be
rotatlonally disorderad.

The Y phaae

is a tetragonal structure with two


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

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.

ground s t a t e .

The

A t r a n s i t i o n to the

s o l i d - s o l i d phase boundaries have

rhomb oh e d r a l 0 phase, which i s para

been determined t o about 10 kbar


(Fig. 10) 30 The melting curve has

magnetic, takes place a t 24 K.

t o about 25 kbar
been determined
dete
2i
(Fig. 11)

although m a r t e n s i t l c .

OXYGEN

volume change at 44 K.

This

t r a n s i t i o n i s d e f i n i t e l y f i r s t order,
Another

t r a n s i t i o n to the cubic Y phase, a l s o


paramagnetic, takes place with l a r g e
This phast.

shows some r o t a t i o n a l d i s o r d e r .
The phast diagram of oxygen i s
shown in Fig. 12.

Oxygen in the

close packed with d i s t o r t i o n s i n t r o

s o l i d and l i q u i d phases i s composed

duced by the non-spherical molecules.

of diatomic molecules weakly bonded


by van der Waals and e l e c t r i c quadrupole forces.
are known.

10

All

of these phases may be regarded as

Three s o l i d phasa

The s o l i d - s o l i d phase boundaries have


32
been determined to a few kbar
The
melting curve has a l s o been determined
33
to 3.5 kbar.

The monoclinic a phase

FLUORINE

i'i'i'r
OXYGEN

The phase diagram of fluorine


is shown in Fig. 13.

Fluorine in Che

solid and liquid is composed of


diatomic molecules weakly bonded by

1.5

- ' 1

S;
Pressure -

J 1.0

Temnertiture - K

Cubic
/ / /

0.5
- Monoclinic(a)
0

60

'

L
40

111 1

J-Z-J
20

1 '

1 1 IT|

Monoclinic/ Rhombohedral
(a)
/ (,

FLUORINE

1
20

1
40

1,1

60

80

Temperature - K

Fig. 12. The phnsa diagram of oxygen.


-10-

Fig. 13. The phase diagram of fluorine.

van der Waals and electric-qttadrupole


forces.

At low temperatures fluorine

i s tnonoclinic with a s t r u c t u r e very


s i m i l a r to a - 0 2

At 46 K a t r a n s i t i o n

with a large volume change takes


place t o cubic g-luorine.

This

phase i s i s o s t r u c t u r a l with Y-0-,


and the l a t t i c e i s r o t a t i o n a l l y d i s
ordered.

The s i m i l a r i t y between

B-F and y-Oo i s seen in the close


2

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


and the melt temperatures i n the two
elements.

The a-$ phase boundary in

Fig. 13 a s determined from the AH


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

50

ing curve has been determined to


only a few b a r s .

100

Temperature - K
Fig. 14. The phase diagram of neon.

NEON

The phase diagram of neon is


shown in Fig. 14.

Neon in the s o l i d

and l i q u i d s t a t e s i s composed of
atoms weakly bound by van der Waals
forces.

Solid neon i s fee.

The

malting curve has been determined to


10 k b a r .

3 6

SODIUM
The phase diagram "f sodium is
shown in Fig. 15.
is hep.

Below 36 K, sodium

At 36 K a martensitic phase

200

change leads to a bec structure which


persists up to melt.

400

Temperature - K

The phase
Fig. 15. The phase diagram of sodium.

boundary separating the two phases

-11-

i | i i I i | i i i i | i i

MAGNESIUM

has not been reported, but the densi


t i e s are so nearly equal

40

that the

i n i t i a l value of dl/dp should be close


to zero, as indicated in Fig. IS.
Static high pressure measurements in

the solid up to 600 kbar reveal no


phase changes.

30

The melting curve

I-

has been determined to 80 kbar.

Liquid

hep

10
MAGNESIUM
The p h a s e diagram o f magnesium i s
shown i n F i g . 1 6 .
hep.

Ql I I I

S o l i d magnesium i s

[I I i I I I I
500
1000
1500
Temperature - K

R e s i s t i v i t y and x - r a y m e a s u r e

ments on magnesium under s t a t i c h i g h

Fig. 16. The phase diagram of


magnesium.

pressure show indications of a slug


gish phase transition near 100 kbar. 37
The structure of the high pressure
phase i s undetermined.

The melting
curve has been determined to 40 kbar'38

80

i i i | i i i i | i i i i

and the results have been corrected

ALUMINUM

to the atmospheric-pressure melting

60

point In Fig. 16.

S 40h
n

ALUMINUM

fee

f Liquid

20The phase diagram o f aluminum i s


shown I n F i g , 1 7 .
fee.

S o l i d aluminum i s

S t a t i c high preaaure measure

0UJ

ments tentatively indicate a p a r t i a l


39
transformation to hep at 205 kbar.
The melting curve haa been determined
40
to 60 kbar.
-12-

*!

500
1000
Temperature - K

Fig. 17. The phase diagram of


aluminum.

1500

250

SILICON

i i i i | i i i i | i i I i | i i

SILICON

The phase diagram of s i l i c o n i s


shown in Fig. 18.

200-

Normal s o l i d s i l i c o n

Tetragonal
(white tin)

i s covalently bonded semiconductor


with the cubic diamond s t r u c t u r e .
.3150

S t a t i c high pressure measurements


show a sharp drop in r e s i s t i v i t y near
41
200 kbar.
Subsequent x-ray work

100

showed t h i s phase to have the t e t r a 42


gonal white t i n s t r u c t u r e .
Here
each atom has four nearest neighbors

50

and two next nearest neighbors lying


s l i g h t l y f a r t h e r away.

The accurate

determination of the phase boundary

shear s t r e s s e s .

'

500
1000
Temperature

i s complicated by i t s s e n s i t i v i t y to
In a d d i t i o n , recovery

1500

of s i l i c o n compressed above 100 kbar


has yielded a complex cubic form with
43
16 atoms per unit c e l l .
This

Fig. 18. The phase diagram of silicon.

uncertainty in the phase diagram i s


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

30

The melting curve Has been measured


to 200 kbar, and a c l e a r - c u t t r i p l e
44
point occurs at ISO kbar.
Shock
wave experiments a l s o show phase
t r a n s i t i o n s i n the 100-200 kbar
45
region,
but t h e i r p r e c i s e nature

' I ' ' '


PHOSPHORUS

20-

Jiof-

Ortho rhombic

Liquid

i s unknown.
PHOSPHORUS

500
1000
Temperature - K

The phase diagram of phoaphorua


I s shown i n Fig. 19.

Of Che various

1500

FiE. 19. The phaae diagram of


phosphorus.

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


-13-

have been prepared, black phosphorus

molecules) per unit cell in a very

appears to be the most stable phase

complex arrangement.

at atmospheric pressure.

the solid is monoclinic, with 48

Black phos

Above 360 K,

phorus has an orthorhombic structure

atoms (6 molecules) per unit cell.

consisting of puckered layers of

The orientations of two of the six

covalently bonded atoms.

molecules in each unit cell are dis


ordered.

At room temperature and about


50 kbar, black phosphorus undergoes

There is much disagreement about

a phase change to a rhombohedral

the structures of the high pressure

lattice, isostructural with arsenic.46

phases and the phase boundaries

A further transition near 110 kbar

separating them.

to a simple cubic structure was also


46
observed.
The rhombohedral lattice

shown in Fig. 20 is due to Vezzoli,

is a simple distortion of the simple

the solid were detected by means of

cubic, and thus the phase transition

volumetric, optical, and electrical-

is easily reversible.

resistance techniques.

Conductivity

studies indicate that the cubic phase


47
is metallic.
Solid-solid phase

et al.

The phase diagram

The phase boundaries in

The phase transitions are often


difficult to detect, as indicated by

boundaries have not been determined.

the dashed boundaries in Fig. 19.

The melting curve of othorhombic

The large number of phases can be

black phosphorus has been determined


48,49
to about 20 kbar

conformational changes in the S

understood as a series of stepwise


g

rings

with changes in temperature and


pressure.

The structures of the

SULFUR
phases other than the well-known I
and 11 have not been worked out,

The phase diagram of sulfur is


shown in Fig. 20.

although there is evidence that phase

The literature on

the allotropy of sulfur presents the

XII is monociinic, with closely

most complex and confused situation

packed helical chains of atoms

of all the elements.

under room conditions is composed of

similar to the selenium and tellurium


53
rfructures.
Resistance measurements

covalently bonded S rings that inter

on sulfur compressed to 400 kbar

act with each other through van der

showed no transition to a metallic


.. 54
scate.

Waals forces.

Solid sulfur

Below 360 K at atmos

pheric pressure sulfur has an ortho-

The melting curve shows a number

rhombic lattice with 128 atoms (16

of definite cusps attributed to the


-14-

SULFUR

40 -

Monocltnic

II

Fig. 20. The phase diagram of eulfur.


-15-

intersection of solid-solid phase

d i a t o m i c m o l e c u l e s bonded t o n e i g h b o r s

boundaries. In addition,
Vezzoli
52
et al.
have discovered a number of

b y van d e r Waals f o r c e s .

"phases" (indicated by letters) in

t u r e , composed of

Solid

c h l o r i n e has an orthorhombic

struc

approximately

the liquid using DTA techniques.

c l o s e - p a c k e d l a y e r s of m o l e c u l e s .

These regions in the liquid appear to

m e l t i n p curve has been determined

be different polymeric states result

7 kbar.

The
to

ing from the breakup of the Sg rings.


The nature of the transitions joining

ARGON

the liquid phases is not clearly


understood.

The lower portion of the

The phase diagram of argon is

melting curve given by Vezzoli t_ al.

shown in Fig. 22.

has been independently confirmed.

and liquid is composed of atoms weakly

Argon in the solid

bonded by van der Waals forces.

Solid

argon is fee.

The melting curve has


31
been determined to 26 kbar.

CHLORINE
The phase diagram of chlorine is
shown in Fig. 21.

Chrlorine in the

POTASSIUM

solid and liquid states exists as


The phase diagram of potassium is

iir-

shown in Fig. 23.

CHLORINE

bcc.

.s

30

4 -

Solid potassium is

No martensitic transition of the

i
''i
ARGON

/-

-20Orthorhombic

Liquid

10

fee
f

Liquid

"
100
200
Temperature - K
Fig. 21.

300

1 , 1 . 1
100
200
300
400
Temperature - K

The phase diagram of


chlorine.

Fig. 22.
-16-

The phase diagram of argon.

80

1
'
1 - I'"
POTASSIUM

40

30

j:

o 20

1 60
1 40

tfc

bcc

20

, ,y

200

10
,

400

600

Temperature - K
500
Fig. 23. The phase diagram of
potassium.
kind occurlng i n Li and Na i s

1000

1500

Temperature Fig. 24. The phase diagram of calcium.

found

in potassium upon cooling t o 5 K.


However, S t a g e r and Drickamer

found

measurements at 77 K showed a sharp

two r e s i s t a n c e anomalies a t 280 kbar

rise in resistance near 140 kbar and

and 360 kbar a t 77 K.

t i o n s were not observed at 296 K.

a subsequent sharp drop near 400


58
kbar.
These data were ascribed to

The authors suggest t h a t the more

two rather sluggish phase transitions,

These t r a n s i

dramatic second t r a n s i t i o n i s a n a l o

first cu . semimetallic, then to a

gous t o the low temperature t r a n s i t i o n

metallic phase.

in Li and Na.

rough accord with later Soviet


59
work.
The melting curve of calcium
has been determined to 40 kbar.

The melting curve of

potassium has been determined t o


80 k b a r .

1 6

These data are in

SCANDIUM

CALCIUM

Scandium is hep at atmospheric

The phase diagram of calcium is


shown in Fig. 24. Under room condi

pressure.

tions calcium i* fee.

sistance measurements at room temper

Near 700 K at

one atmosphere it undergoes a transi


tion to a bcc structure.

Static high pressure re

ature showed no evidence of a phase


change to 140 kbar.

The phase

Shock wave

boundary has been measured to 30

measurements by Carter, e_t_ al_. showed

kbar.

a kink in the u -u curve at


s p

High pressure resistance


-17-

approximately 350 kbar.

This was

Shock wave experiments show a

a s c r i b e d to a sluggish low p r e s s u r e
s o l i d - s o l i d phase change.

strong break in the u -u curve for


s p

No kink

titanium, indicating a phase change

was found i n the shock v?ave work of


Gust and Royce.
1812 K.

occurring at 175 kbar.

Scandium melts a t

The nature

of this phase transition has not been

The melting curve has not

determined.

been r e p o r t e d .

1941 K.

Titanium melts at
The melting curve has not

been reported.

TITANIUM

VANADIUM
The phase diagram of titanium is
shown in Fig. 25. At room temperature
and pressure titanium

is

hep.

Vanadium is bcc.

No solid-solid

phase transitions have been reported.

transformation to a bec phase occurs

Vanadium melts at 2178 K.

near 1150 K. The phase boundary has

melting curve has not been reported.

The

been determined to about 110 kbar,


where a triple point occurs.

CHROMIUM

The low temperature, high pressure ui


The phase diagram of chromium i

phase may be regarded as a distorted

shown in Fig. 26. Pure chromium is

bec lattice with hexagonal symmetry.

antiferromagnetic below 311 K and

This structure has three atoms per

paramagnetic above this temperature.

unit cell and two distinct types of

Although there has been some contro

atomic positions.

versy about various allotropes of

T T

7"l""l""-

mp

hep

bcc
1000

^-'Tetragonal

J
J

I2

U-iquid;:

*. i i i 1 i ' 1111 11 1 11i

500

CHROMIUM

o
3 6
/ TITANIUM

1111II11 1 1 I I 11111 | I I I 1

- Hexagonal
: (w)
i

sure - kbar

J 111111111

V i i i i*
1500 2000 2500

Temperature - K

Liquid -

Orrhoihombic
bcc

mp

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

Fig. 25. The phase diagram of


titanium.

Fig. 26. The phase diagram of


chromium.
-18-

50

chromium, it Is probable that the


paramagnetic phase is simple bcc up
to the melting point.

I I I I I I 1 I I I I l I I I I
MANGANESE

Below 311 K,

the paramagnetic phase transforms to

40

an antiferromagnetic phase by a firstorder phase transition.

This phase
_8 30

is in a spin-density wave state In

Liquid

which the polarization is perpendicular


to the wave vector.

This magnetic
8 20

state is inconsistent with the reten


Cubic
tion of full cubic symmetry, and the
lattice instead takes on a very slight

(a)
10

orthorhombic distortion of the bcc


lattice.
At 123 K, another first-order
tr

|_iiiiL_
0
500

sition occurs to a new antiferro

which the polarization and wave vectors


are parallel.

1000

1500

Temperature - K

magnetic spin-density wave state in

This phase has a small

Fig.

27.

The phase diagram of


manganese.

tetragonal distortion of the bcc


lattice.

The lattice distortions in

the magnetic phase are too small to be


detected with present x-ray techniques.
The phase boundaries have been deter
mined to 8 kbar.

'

Static pressure

measurements at room temperature to


55 kbar show no other phase changes.
Chromium melts at 2148 K.

centered cubic l a t t i c e with 58 atoms


p e r u n i t c e l l and 4 d i f f e r e n t

70

of atomic p o s i t i o n s .

types

At atmospheric

p r e s s u r e n e a r 1000 K, a t r a n s i t i o n

The

occurs t o t h e fi form, thought t o have

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 .

MANGANESE

Near 1370 K a

t r a n s i t i o n t o t h e fee Y phase o c c u r s ,
and near 1520 K a f u r t h e r

The phase diagram of manganese


i s shown i n F i g . 27.

t o the bcc 6 phase o c c u r s .

There a r e four

a l l o t r o p e s , a l l of cubic symmetry.

transition
The 'phase

boundaries and the melting curve have


71
been determined t o 40 kbar.

The a form has a complex body


-19-

IRON

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


72

have been determined to 200 kbar.


The phase diagram of iron is
shown in Fig. 28.

The y-& transition and the melting

The phase diagram

curve have been determined to 52

and especially the melting curve of

kbar, where they meet in a triple


73
point.
The melting curve of the

iron is of great interest because of


the problem of the state of the

Y phase has been extended about 5


earth's core and the origin of the
geomagnetic field.

73
kbar beyond the t r i p l e p o i n t .

Under room condi

tions iron is ferromagnetic and has


a bcc structure.

COBALT

At 1044 K it passes

through the Curie point and near 1200

The phase diagram of cobalt is

K it transforms to the fee phase.

shown in Fig. 29.

The bcc phase once again becomes

ture cobalt is hep.

stable before melting.

depending on the sample grain size, a

Above 100

At room tempera
At a temperature

kbar, the bcc phase transforms to a

sluggish phase change to fee occurs.

nonferromagnetic hep phase.

For large crystal grains the trans

The

formation temperature is 661 K.

The

phase boundary has been measured to


50 kbar.

Cobalt melts at 1765 K.

The melting curve has not been


reported.

60

111 I I I 111 ] 11 1 I 11 I I I ( I 11 I

COBALT

_ 50

I 40
30

1 20
*
500

1000

1500

2000

Temperature - K

Fig. 28.

The phase diagram of i r o n .

fee

'q

u i d

"

mp

100 11 i i I i I I i 11 i i) Ii i t i I i i i i
0
500 1000 1500 2000 2500
Temperature - K

Fig. 29.
-20-

hep

The phase diagram of cobalt.

80

I1I I 1

COPPER

The phase diagram of nickel i s


shown in Fig. 30.
fee.

Solid n i c k e l i s

60

The melting curve has been

determined to 80 kbar.

'
40

80

" " I "

" I " ' I


NICKEL

fee

0 60
-Q

20
4 0

fee

| Liquid

/Liquid

1 20

at

0.

i I . . . . I i i , I i ill i I . , , ,
500 1000 1500 2000 2500

"0

500

Temperature - K

Temperature - K

Fig. 30.

I / I !
1000
1500

The phase diagram of n i c k e l .

Fig. 31.

The phase diagram of copper.

COPPER
The phase diagram of copper is
shown in Fig. 31.

Solid coppfer is

fee.

The melting curve has been


75
determined to 65 kbar.

7 ' 1 ' 1 '


ZINC

80

ZINC

J 60 -

The phase diagram of zinc i s


shown i n Fig. 32.

Solid zinc has a

r a t i o considerably g r e a t e r than i d e a l .
Under p r e s s u r e , t h i s ratio shows
unusual f l u c t u a t i o n s , but no c l e a r - c u t

| 40

hep

d i s t o r t e d hep l a t t i c e , with the c / a

~
:

f Liquid

20

, 1 . *
. 1 . 1 /
2C10 400 600 8(10 1000 12C
Temperature - K

s o l i d - s o l i d phase changes are found


up t o 200 kbar.

The melting curve

has been determined to 60 kbar.

Fig. 32.
-21-

The phase diagram of zinc.

80 L

GALLIUM

' ! '

Solid gallium at

'

TZ\

60

atmospheric pressure has an ortiiorhombic structure with eight atoms


per unit cell.

Orthorhombic
(III)

The phase diagram of gallium is


shown in Fig. 33.

GALLIUM

Each atom in this

I 40

structure has one nearest neighbor


and six other near neighbors somewhat
farther away.

At atmospheric pressure

gallium melts just above room temper

20-

ature, and the melting temperature

Orthorhcmbic

initially decreases with increasing


pressure.

(M

Gallium II is probably

body centered tetragonal.

I
I I
100
200
300
Temperature - K

The high-

temperature gallium-III phase is a


complex orthorhombic lattice with
40 atoms per unit cell.

Fig. 33.

The phase

400

The phase diagram of gallium.

boundaries, including the melting

250

| I I i | I i I

curve, have been determined to


,. ,.
78,79
75 kbar.

GERMANIUM
200

GERMANIUM

*
.

The phase diagram of germanium


is shown in Fig. 34.

Tetragonal
(white tin)

- 150

Solid germanium

under room conditions is a semicon

ductor with the cubic diamond struc60


ture. Above 100 kbar shock wave
and electrical resistance measure41
indicate the appearance of a

ments

new phase.

_
1
-

Cubic
(diamond)

This phase is metallic,

with the tetragonal white tin struc


ture.

Liquid

100

i l i t i i i . X i . i l

500

There remains some uncertainty

1000

1500

Temperature - K

concerning new phases obtained from


81
quenching experiments.
The cubictetragonal phase boundary and the

Fig. 34.

-22-

The phase diagram of


germanium.

netting curve have been determined up


44
to 200 kbat.

' ' I ' ' '

ARSENIC
60

ARSKNIC
The phase diagram of arsenic la

40

shown in Fig. 35. Ac atmospheric

pressure arsenic crystallizes in Che


prtnltlvc rhoabohedral laccice

characteristic of the group VB


elements-

Rhombohedral

Liquid

20

High pressure resistance

measurements shoved no anomaly up Co


82
200 kbar.
However, arsenic that
0

had been compressed to ISO kbar


showed a tetragonal structure, which

-iJ_

500
1000
1500
Temperature - K

may represent a high pressure phase.S3


The melting curve has been determined

Fig. 35.

The phase diagram of arsenic.

up to 60 kbar.
SELENIUM

I ' I ' I ' !


SELENIUM

The phase diagram of selenium is

60

shown in Fig. 36. Solid selenium at


lou pressure has a hexagonal crystal
structure composed of covalently
bonded helical chains of atoms. In

40

this state selenium is a semicon

Hexagonal

ductor. Near 130 kbar, a resistance


discontinuity is observed, and selenium

20 -

becomes a metallic conductor. *


An attempt to determine the structure
of this high pressure form was
87
unsuccessful.
The melting curve

has been determined Co 60 kbar.

I I I/I
200 400 600 800 1000 1200
Temperature - K

It shows a clear maximum in tempera


ture.

Fig. 36. The phase diagram of selenium.


-23-

BROMINE

140 kbar rather than 200 k b a r .

59

The lower transition is Indicated in


The phase diagram of bromine Is
Fig. 39 by a dashed line.
shown In Fig. 37.

These

Solid bromine Is
transitions are thought to correspond

composed of diatonic molecules held


to those observed in cesium at low
together by weak van der Haals
pressure.
forces.

The upper transition Is

The solid has an orthorhombic


likely to be due to a shift In the

structure, analogous to chlorine.


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

The melting curve

has been determined to 80 kbar.


The melting temperature appears to be
approaching a maximum near 80 kbar.

The

melting curve has been determined to


,
56,89
10 kbar.

STRONTIUM

KRYPTON

is shown in Fig. 40.

The phase diagram of strontium


Under room

conditions strontium is metallic with


The phase diagram of krypton is
an fee structure.
shown In Fig. 38.

pressure at room temperature or

krypton consist of atoms bonded by


weak van der Waals forces.
Is fee.

With increasing

Solid and liquid

The solid

The melting curve has been


36 92
'

below, strontium becomes semi94


metallic.
Hear 35 kbar, a phase
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
shown in Fig. 39.

electronic transitions mentioned.

At low pressures

solid rubidium is bcc.

sure appears to be due largely to the

Beyond the 3S kbar transition,

Bundy and

strontium shows metallic conductivity

Strong found a sharp resistance jump


93
near 75 kbar and room temperature.

with no indication of further trans

Stager and Drickamer found a sharp

itions up to 500 kbar.

rise In resistance near 200 kbar at

phase boundary intersects the p = 0

two temperatures.

Soviet work con

axis at 830 K.

The fcc-bcc

This boundary and the

firmed the 75 kbar transition, but

meltiig curve have been determined

found the next transition near 135-

to 40 kbar.

-24-

80

"HP

BROMINE

' ~T
RUBIDIUM

10
60

ji

2
_

OrthorhombTc

40
3

i
20

O0j - Fig. 37.

I
. I
100
200
300
Temperature - K

200

400

F i

The phase diagram of bromine.

'
1
KRYPTON

'

tfia

600

Temperature - K
8-

50

12
10

3 9

h a s e

*> P
diagram of
rubidium.

1 i i | i i I i | i i i i | I

1 -r

STRONTIUM

40

30

I
|

fee

Liquid

bec

20-

,.
0

l / ,

100
200
Temperature - K

10

300

Fig. 40.
Fig. 38.

/ Liquid

The phase diagram of krypton.


-25-

I J U
500
1000
1500
Temperature - K
The phase diagram of
strontium.

hep phase transforms to bcc.

YTTRIUM

The

t r i p l e point joining the three phases


Solid yttrium at low pressure is
hep.

Above 110 kbar, yttriur.


95
becomes a superconductor,
A itudy

occurs near 60 kbar and 1000 K.

The

phase bounds.-ies have been uorked out


to 70 kbar.

of the pressure dependence of the

Vereshchagln observed

a sharp change of slope i n the

transition temperature indicates the

resist

ance as a function of pressure near

presence of several superconducting


96
However, these

100 kbar, but what t h i s means i s


97
A shock-wave study of

modifications.

unclear.

modifications are not thought to have


different crystal structures, but

zirconium showed a sharp break in the

rather arise from slight changes in

u -u curve at 260 kbar, which preP


66

band structure.

sumably indicates a phase change.

Zirconium melts at 2123 K .

Static resistance measurements

6 3

The

melting curve has not been reported.

to 250 kbar shew no phase transition


97
anomalies.
Shock-wave experiments
by Gust and Royce showed a kink in Che
the u -u curve at 280 kbar.
s p

The

authors suggested that the kink

i i i i | i i i > | i i i i | i rn | n i _
ZIRCONIUM

80

indicated the stiffening of the solid


as inner electron cores overlapped.
Carter, e_t _ai. saw a kink

" Hexagonal !

in tk&

an explanation.
Yttrium melts at
63
1775 K.
The melting curve has not
been reported.

:y

60

u -u curve at 370 kbar and suggested


s p
a sluggish low pressure transition as

40
3
*?

ZIRCONIUM

hep
20

bcc

Liquid

The phase diagram of zirconium


i s shown in Fig. 41.

mp\

Zirconium under

room conditions I s hep.

under com

pression i t transforms to the hexagonal


w phase i s o s t r u c t u r a l with u-titanium.
This i s a d i s t o r t e d bec phase.

Near

n
"0

500

1ill I 1 1 1 ulMI i L I 1000 1500 2000


Temperature - K

Fig. 41. The phase diagram of


zirconium.

1140 K at atmospheric pressure the


-26-

RUTHENIUM

KI0BIW1

Solid ruthenium in hep.

Solid niobium is bcc. No

2741 K.

Com

pression to 400 kbar at room tespera99


tur* showed no change of phase.

resistance anomalies have been found


97
below 250 kber.
Niobium melts at
The melting curve has not

Ruthsnium melts at 2SS3 K .

6 3

The

been reported.

melting curve has not been reported.

MOLYBDENUM

RHODIUM
The phase diagram of rhodium i s

The phase diagram of molybdenum


is shown in Fig, 42.

Solid molybdenum

is bcc.

An approximate melting curve


98
has been determined to 90 kbar.

shown i n F i g . 4 3 .
fee.

Solid rhodium i s

The melting curve has been

approximately determined t o 80
kbar.

3 8

'

7 4

TECHNETIUM
Solid technetium is hep.
63
Technetium melts at 2443 K.
The
melting curve has not been reported.

Solid palladium i s f e e .
um melts a t 1825 K.

Palladi

The m e l t i n g

curve has not been r e p o r t e d .


100

ii'r

100

MOLYBDENUM
80 -

I 60tbcc
40

20

0.

1000

2000

Liquid

J
3000

i
1000

Temperature - K

2000

3000

Temperature - K
Fig.

42.

The phase diagram of


molybdenum.

Fig.
-27-

43.

The phase diagram of rhodium.

to 250 kbar showed no strong


97
The melting curve has
38
been determined to 50 kbar.

SILVER

anomalies.

The phase diagram of silver Is


shown In Fig. 44.
fee.

Solid silver Is

Compression to 300 kbar at room

INDIUM

temperature shows no evidence of a


phase change.

The phase diagram of indium i s

The melting curve

shown In F i g . 46.

has been determined to 65 kbar.

Solid indium i s

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

Compression

at room temperature t o 300 k ar shows

CADMIUM

no i n d i c a t i o n of any phase changes.


The phase diagram of cadmium Is

The melting curve has been d e t e r

shown In Fig. 45. Solid cadmium Is


hep.

mined t o 80 k b a r .

7 8

Compression In the 100-200 kbar

range shows small anomalies In the


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

and a sluggish phase transition has


37
been suggested as an explanation.

shown in F i g . 47.

is

Below 290 K at

Independent resistance measurements

Fig.

44.

200

400

600

800

Temperature - K

Temperature - K
The phase diagram of s i l v e r .
-26-

Fig. 45.

The phase diagram of cadmium.

1 1 1 1
iNDIUM

atmospheric pressure, tin i s cubic

80

:
|

diamond l i k e s i l i c o n and germanium.


Above this temperature tin has the

tetragonal white t i n structure with

60-

i "o

Tetragonal

/
/

four atoms per unit c e l l .

In this

structure each tin atom has four

Liquid

nearest neighbors at the vertices of


a flattened tetrahedron.

Two more

neighbors l i e s l i g h t l y farther 3way.

20

1 J l/i
200
400

1 I
600

The diamond-to-white-tin
boundary has been determined to about
102
50 K and 10 kbar.
At room

800

Temperature - K

temperatute near 90 kbar, the white


tin transforms to a body-centered

Fig. 46.

The phase diagram of indium.

tetragonal structure with two atoms


per unit c e l l .

The boundary joining

the two phases has been approximately


determined to 95 k b a r .

'

1 0 4

Tht

melting curve has also been determined


. , , ,.
103,104
to 75 kbar.
*

100

1 0 3

ANTIMONY

80

The phase diagram of antimony is

60

40 -

shown in Fig. 48.

Tetragonal
(white tin)

Solid antimony

under room conditions is rhombohedral,


isostructural with arsenic.

At room

temperature, antimony has two phisa

20-

transitions, one near 70 kbar and one

Cubic
^(diamond)

near 85 kbar ( c i r c l e s ) .

105

The 70-

kbar transition is sluggish and appar

200
400
600
Temperature - K

800

ently has a very small volume change.


The phase II structure is simple
cubic, which corresponds to the

Fig. 47.

The phase diagram of t i n .

elimination of the low pressure

-29-

I i | I i I i | i i i i | I

100
80

TELLURIUM

ANTIMONY
The phase diagram of tellurium

\ Tetragonal

is shown in Fig. 49.

- \(o

60

a>

ductor, with a hexagonal structure

- \sn

composed of covalently bonded helices


packed together.

Liquid

This structure can

be regarded as a distortion of the


simple cubic lattice.

20

Solid tellurium

under room conditions is a semicon

Rh'ombohedral \

Near 40 kbar

at room temperature (circle), a


transition to a metallic phase occurs.

I I I

0
500

'

'

1000

'

'

'

The structure of this phase has not


108
yet been determined.
Near 70 koar

1500

Temperature - K

at room temperature (circle), a

Fig. 48.

f u r t h e r t r a n s i t i o n to a rhombohedral
108
This phase i s

The phase diagram of


antimony.

l a t t i c e occurs.

i s o s t r u c t u r a l with 3-polonium.
Studies of superconductivity at high
rhombohedral d i s t o r t i o n .

Hie t r a n s i

pressures i n d i c a t e p o s s i b l e new

tion, at 85 khar i s wore strongly


marked, with n o t i c e a b l e volume and
r e s i s t a n c e changes.

The s t r u c t u r e

80

of phase I I I i s u n c e r t a i n , but recent


worfe suggests a t e t r a g o n a l s t r u c t u r e
analogous t o t h a t found i n a r s e n i c at
high p r e s s u r e s .
Phase I I I shows
82
good m e t a l l i c c o n d u c t i v i t y .
The
melcing curve has been determined to
70 kbar.

'

Two cusps, i n d i c a t i n g

"^

Rhombohedral (III)

60

ll

; 40

Hexagonal

20

t r i p l e p o i n t s , have been found, one


at 3.9 kbar, and the other at 57 kbar.
Stishov and Hkhomlrova

-i
"0

assumed

J i g . 49.

t i o n s , as indicated in Fig. 48.


-30-

L
200

J_

400

J
L
600
800

Temperature - K

that the two t r i p l e p o i n t s corresponded


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

TELLURIUM

The phase diagram of


tellurium.

phases a t s t i l l h i g h e r p r e s s u r e s .

109

the diatomic moleculea within the

The s o l i d - s o l i d phase boundaries and

orthorhombic unit cell.

the melting curve have been d e t e r


mined t o about 70 k b a r .

At higher pressures, above 100

A definite

maximum i n the melting temperature

kbar, the resistance of iodine drops


113
rapidly to a metallic value.
Here

i s found near 10 kbar.

It is thought that the I molecules

IODINE

structure.

dissociate into an atomic metallic


It is not clear whether

this is a continuous or an abrupt


The phase diagram of iodine is
shown in Fig. 50.

transition.

Solid iodine at

low pressures is composed of diatomic

plot of u

molecules in an orthorhombic lattice,

at approximately

Given a transition to

the metallic phase at a much lower

No clearly defined phase

pressure, this break is likely to

transition has been found at moder


ate pressures,

vs u

700 kbar.H4

isostructural with solid bromine and


chlorine.

Shock wave experiments

on iodine show a strong break in the

represent a phase transition from

but an x-ray study

one metallic phase of iodine to

of the solid to 60 kbar showed a con

another.

The melting curve has been

tinuous shifting of x-ray


112
reflections.
This was interpreted

determined to 50 kbar.

as a shifting of the orientations of

XENON

50 -

' i r

'

The phase diagram of xenon is

IODINE

shown in Fig. 51. Solid and liquid


xenon are composed of atoms bonded

u
o
M

40by weak van der Waals forces.

g 30-

Solid

xenon is fee.

The melting curve has


92
been determined to 7 kbar.

Orrhorhombic

i 20CESIUM

10-

The phase diagram of cesium is


0L0

200

400

600

800 1000

shown in Fig. 52. Cesium has been


intensively studied because of its

Temperature - K

unusual properties.
Fig. 50.

The phase diagram of iodine.

Solid cesium at

atmospheric pressure is bcc. At

-31-

room temperature the bcc phase t r a n s


forms t o fee at 23 kbar.

Further

compression y i e l d s two more phase


t r a n s i t i o n s only about 1 kbar apart
near 42 kbar.

The f i r s t new phase

i s also f e e , but the s t r u c t u r e of the


second (IV) has not yet been d e t e r
mined.

The s o l i d - s o l i d phase

boundaries have been determined,

'

and they show very weak temperature


depenlence, except that t h e upper
200

400

fee phase apparently disappears a t

600

low temperatures.

Temperature - K
Fig. 51.

The i s o s t r u c t u r a l fcc-fcc t r a n s i
tion occurs with a 9% volume change,

The phase diagram of xenon.

and has e x c i t e d much c u r i o s i t y .

The

f i r s t t h e o r e t i c a l attempt a t an
explanation proposed t h a t the t r a n s
60

50

.
-

formation r e p r e s e n t s a s h i f t from 6s

'' ' 1

"T

to 5d character of the conduction


120
Although details of this

CESIUM

band.

IV

theory have been criticized, it is

>.. 4 0

fcc^

fee

widely agreed to be qualitatively

~"

correct.

.a:

r
30

K
10

s o l i d cesium occurs near 125 kbar,


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

bcc

superconductivity and i t has been


suggested t h a t the phase i s

t r a n s i t i o n - m e t a l - l i k e , with increased
95

Liquid -

1
0

A further sluggish t r a n s i t i o n i n

d-electron character,

l/l

200
400
Temperature - K

600

The melting curve of cesium has


been worked out to 55 k b a r .

1 1 7 , 1 1 8

Two melting temperature maxima occur

Fig. 52.

The phase diagram of cesium.

near the bcc-fcc transition.

-32-

The

decreasing melting temperature of

i i i i I i r i i I 11 i i i
BARIUM

the close-packed fee phase i s due to

the density of the l i q u i d increasing


beyond t h a t of the s o l i d .

This phe

nomenon has been ascribed t o the


smearing out i n the l i q u i d of the
sharp e l e c t r o n i c t r a n s i t i o n observed
in the s o l i d .

Liquid

Thus the volume con

t r a c t i o n in the l i q u i d can be thought


of as a smoothly varying change in.
r e l a t i v e concentration of two
electronic species,

whereas i n

the s o l i d t h i s change t a k e s place a l l


at once.

'

'

500

The melting curve of

'

'

'

'

'

1000

'

1500

Temperature - K

phase IV once again takes on a normal


appearance.

Fig. 53.

The phase diagram of barium.

BARIUM
The phase diagram of barium is
shown in Fig. 53.

Solid barium at

atmospheric pressure is bcc.

At room

Drickamer

found a further transi

temperature, a well-marked phase


122
transition occurs at 55 kbar.

tion at 144 kbar and room tempera

The high pressure phase has been


123
determined to be hep.
There is

study that this was a melting transi

ture, and inferred from a detailed

tion.

Later work indicated a solid129

disagreement over the trajectory of


solid transition instead.

the bec-hep phase boundary, since


further transition at 240 kbar was
DTA measurements

show dp/dT > 0


125

found at 77K, presumably to yet

while resistance measurements


show dp/dT < 0.
evidence

another solid phase.

Additional

supports the first possi

bility, which is shown in Fig. 53.

The melting

curve has been determined to about

nn it.
124,125,128
, .
90 k b a r ,
*
*
and three

A second phase transition to a phase

melting-curve maxima appear.

(III) of unknown structure has also

seems l i k e l y t h a t e l e c t r o n i c phase
changes s i m i l a r t o those observed in
130
cesium are occurring i n barium.

been reported.

Stager and

-33-

It

while t h e second a s c r i b e s i t to the

LANTHANUM

i n t e r s e c t i o n of the Hugoniot and the


The p h a s e d i a g r a m o f
i s shown i n F i g . 5 4 .

lanthanum

melting curve.

Lanthanum

e x h i b i t s t h r e e s o l i d phases at atmos
pheric pressure.

The fcc-bcc boundary

and the melting curve have been


determined to n e a r l y 40 kbar.

From 0 t o 580 K,

the s t a b l e phase i s dhcp.

At 580 K,

CERIOM

a pftase t r a n s i t i o n to an fee phase


occurs with a decrease i n volume.

The phase diagram of cerium is

The dhep-fee phase boundary has been


131
worked out to 24 kbar.
At 1130 K,

shown in Fig. 55.

a t r a n s i t i o n t o a bec phase occurs,

At zero Kelvin and atmospheric

and melting occurs near 1200 K.

pressure, cerium is fee.

E l e c t r i c a l r e s i s t a n c e measurements

approximately 100 K and 45'J K, a

made to 250 kbar sfiow a smalt r e s i s t

dkep phase is stable.

ance anomaly near 100 kbar, which

and 1000 K, the fee phase is again

This unusual

diagram has been intensively studied.

Between

Between 450 (c

may i n d i c a t e a phase t r a n s i t i o n .

stable, with the difference that the

Ttyo s e t s of shock wave .xperiments show kinks i n t h e u s-u_,p curve

Y phase is ferromagnetic while the


a phase is paramagnetic.

A bec phase

for lanthanum a t 250 kbar*2 ^ a


61
225 kbar

The dhcp phase disappears at low

the fcinfc t o xenon core r e p u l s i o n s , 62

pressures.

then intervenes just before melting.

The first report ascribes

40

I I | I I I I | I I

r-|-r-r

133
I | I I I I | I I I I| T

80

LANTHANUM I

CERIUM
Orthorhombic 1

1 60

40,

Ll'qui'd'

20U (a)
dhcp
I I I I,

500

1000

1500
0

Temperchjre - K
Fig. 54.

The phase diagram of


lanthanum.

Fig. 55.

-34-

Liquid

7) L '

_|

facc

1_L ' ' " I I


500
1000
1500
Temperature - K

The phase diagram of cetium.

The unique feature of the cerium

rx-y phase boundary and ct-a* phase

diagram is the isostructural a -* y

boundary leads to points very near

phase transition, which ends in a

one another on the melting curve.

critical point estimated from


134
resistance measurements
to lie at

Stager and Drickamer reported a

17.5 kbar and 550 K.

A considerable

theoretical effort has been made to


explain the a * y phase transition

further possible phase change near


138
160 kbar a t room temperature.
Two
s e t s of shock wave data give d i s c o r 61,62 _
dant r e s u l t s .
In one c a s e , a
1fc

represented a promotion of the

kink in the u -u curve was found at


s p
61
480 kbar and ascribed to melting.
In the o t h e r case, no kink was

localized 4f electron to the delocal-

*
found.

and critical point.

The earliest

theories assumed that the transition

i2ed 5d band.

135

6 2

The melting curve of cerium has


134
The

Later theories

modified this by assuming only a


135
partial 4f derealization .
Such

been determined to 70 kbar.

models imply a definite increase in

the melting temperature around 33

the number of conduction elections as

kbar.

the pressure is Increased.

in terms of isotherms s i m i l a r i n

But

remarkable feature i s a minimum In


Jayaraman explains the minimum

this is contradicted by positron-

shape to the s u p e r c r i t i c a l isotherms

annihilation experiments that

observed in the v i c i n i t y of the


134
liquid-vapor c r i t i c a l p o i n t .

indicate no change in the number of


135
conduction electrons.

In general

it could be said that the y -* a


transition results from the Inter

These isotherms r e f l e c t the rapid


decrease in the s i z e of the cerium
atoms in the s o l i d phase as the
pressure i s increased.

action of the 4f and conduction


electrons, but the precise model of
this interaction is disputed.
Further compression of cerium
leads to another phase transition in
the 50-60 kbar range.

The new

PRASEODYMIUM
The phase diagram of praseodymium
i s shown in Fig. 56.

Normal s o l i d

phase (a ) has been determined to be


orthorhoiribic, isostructural with

137
a-uranium.

The phase boundary has

praseodymium I s dhep.

A room-

temperature t r a n s i t i o n to an fee
phase occurs a t 40 kbar ( c i r c l e ) . 139

been determined over a r e l a t i v e l y

The t r a j e c t o r y of the dhep-fee phase

short temperature range, but i t i s

boundary i s d i f f i c u l t to follow

i n t e r e s t i n g t h a t extrapolation of the-35-

~r i i i | i i i i | m i

boundary and the melting curve have


131
been determined to 70 kbar.

1 -

60

40

|"i i

PRASEODYMIUM

80

The phase diagram of neodymium

i s shown i n Fig. 57.


\

20

fee

NEODYEtCH

dhcp\
\
_L

500

Liquid "

y
V . I #.
1000

Under room

conditions neodymium i s dhep.

High

pressure tf-ray s t u d i e s at room


temperature show a t r a n s i t i o n to the
139
fee phase near 50 kbar ( c i r c l e ) ,
This t r a n s i t i o n i s very d i f f i c u l t t o

. . 1 , .
1500

Temperature - K

d e t e c t , and the i n t e r s e c t i o n of the


phase boundary with the p 0 a j d s ,

Fig. 56. The phase diagram of


praseodymium.

although suspected, could not be


140
directly measured.

Instead, a

because i t i s extremely sluggish and

temperature of 960 K is inferred from

apparently q u i t e s e n s i t i v e to

a generalized
1UX rare earth phase
diagram,
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

80 -

measurements t o 500 kbar show

"

-\ I T ] T T T T ' | 1 \ l-JTTTNEODYMIUM

s e v e r a l anomalies above t h a t a t 40
kbar, and suggest two more high-

pressure phases of unknown s t r u c t u r e


138
above Che fee phase.
Two s e t s of shock-wave experiments
show kinks i n the u - u

curve for
P 62
praseodymium at 300 kbar
and 270
kbar.
The f i r s t report ascribes
62
the kink t o xenon-core r e p u l s i o n s ,
while the second t e n t a t i v e l y a s c r i b e s
8

i t to an e l e c t r o n i c rearrangement In
the l i q u i d .
before melt.

A bec phase appears

60 --

dh

-36-

=p

"

/
/
Lc

'
Liquid

20
_L, 1 1 . 1 1 1 1 \ l

0
0
Fig. 57.

The bcc-fcc phase

/
/

500

J 1 I !..!__)

1000

1500

Temperature - K
The phase diagram of
neodyroium.

on neodymium up to 600 kbar showed

1 1 1 1 | 1 I 1 1 | 1 1I I | I l

80

SAMARIUM

anomalies in the 100-200 kbar region


at d i f f e r e n t temperatures, which

1 60

could correspond t o another h i g h 138


pressure phase t r a n s i t i o n .

1
V

Two s e t s of shock-wave experiments

and 250 kbar.

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


62
xenon-core r e p u l s i o n s ,
while the
second i d e n t i f i e s i t with melting. 61
A bcc phase appears before melt.

I bee

40

20 _

Rhombohedral
(Siti)

!
n
0
500

Fig. 58.

curve have been determined t o 60


kbar.

xl
1

"

/Liquid"
i 1 1 ill A 1 l_
1000
1500

Temperature - K

The

bcc-fcc phase boundary and the melting

5
c

show kinks in the u -u curve for


s p

neodymium at 280 kbar

dhcp

The phase diagram of


samarium.

henceforth c a l l e d "Sm-type." R e s i s t
ance measurements to 600 kbar at

PROMETHIUM

room temperature show anomalies near


50 kbar and 160 kbar t h a t might cor
respond t o phase t r a n s i t i o n s 138 The

Promethium I s dhcp at room


temperature and p r e s s u r e . 142

Prom

ethium has not been extensively worked


with because the element i s unstab7i,
and the most-easily a v a i l a b l e isotcpe
has a h a l f - l i f e of 2.6 y e a r s .

40 kbar and 623 K ( c i r c l e ) .


Two s e t s of shock wave e x p e r i
ments show kinks in the u -Up curve
s

The

melting temperature i s 1315 K.

dhcp phase appears in samarium near

for samarium a t 310 kbar*>2 and 270

No

kbar.

The f i r s t report a s c r i b e s
the kink to xenon-core repulsions 62

high-pressure work has been reported.

while the second i d e n t i f i e s i t with


melting.

SAMARIUM
The phase diagram of samarium i s
shown in Fig. 58.

A phase assumed to be

bcc appears before melt-

An i n f l e c t i o n

i n the b c c - t o - c l o s e - p a c k e d - s o l i d phase

Under room condi

tions samarium has a close-packed

boundary i s assumed to represent the


131
Sra-type-dhcp-bcc t r i p l e p o i n t .

s t r u c t u r e of rhombohedral symmetry.

The b c c - s o l i d phase boundary and the

The arrangement of close-packed

melting curve have been determined to


131
60 kbar.

layers in t h i s s t r u c t u r e i s ababcbcac,
37-

EUROPIUM
The phase diagram of europium i s
shown in Fig. 59,

Solid europium at

atmospheric pressure i s bcc.

phase transformation. Bakanova


146
et a l .
found a kink i n the u -u
s p
curve at 386 kbar and ascribed t h i s
t o an e l e c t r o n i c rearrangement.

Below

It Is possible that the anomalies

88.6 K, europium i s antiferromagnetic,

in the shock data correspond with the


138

with a h e l i c a l arrangement of s p i n s ,
and i t becomes paramagnetic above t h i s

resistance anomaly

temperature.

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


144
determined t o be f i r s t o r d e r ,

ascribed t o a d i v a l e n t - t r i v a l e n t

which means t h a t the bcc l a t t i c e i s

According t o t h i s theory, the

which has been

e l e c t r o n i c phase t r a n s i t i o n .

very s l i g h t l y d i s t o r t e d in the mag

anomalously d i v a l e n t europium becomes

n e t i c phase, as in the case of

more r a r e - e a r t h - l i k e aa the p r e s s u r e

chromium.

increases.

The pressure dependence of

the t r a n s i t i o n has been determined t o


145
90 kbar.
I t has been suggested
that as the l a t t i c e becomes l e s s com

The europium melting

curve has been detei-mined to 70

.,
147,148
kbar.

.
A temperature maximum
fc

p r e s s i b l e with increasing p r e s s u r e ,

appears near 30 kbar.

the f i r s t - o r d e r t r a n s i t i o n simply

analogy between the behavior of


europium and barium has been pointed
out.

stops at about 20 kbar and gives way


to a pure second-order transition.

144

The close

S t a t i c high-pressure r e s i s t a n c e
measurements show a sharp change near
150 kbar and room temperature, which
probably corresponds to an e l e c t r o n i c
phase t r a n s i t i o n 138 The t r a n s i t i o n
pressure appears to decrease with
138
temperature.
Three s e t s of shock
wave experiments show anomalies in
61,62,146
the u - u , curve.
Carter
ej; jal.6 1 * found a d i s c o n t i n u i t y i n the
s

u -u curve at 106 kbar, and sugs p


gested t h a t t h i s corresponds to t h e

i n t e r s e c t i o n of Hugoniot and melting


curve.

Gust and Royce

500

1000

1500

Temperature - K

found

anomalous behavior in the 180-360

Fig. 59.

kbar range and suggested a sluggish


-38-

The phase diagram of


europium.

e l e c t r o n i c t r a n s i t i o n in the

GADOLINIUM

solid.

A bcc phase appears before melt,


The p h a s e d i a g r a m of
i s shown i n F i g . 6 0 .

gadolinium

Under room

conditions gadolinium i s hep.

was t a k e n t o b e h c p - S m - t y p e - b c c t r i p l e
131
point.
The m e l t i n g c u r v e h a s b e e n

~_4
/ n ,kLb a r . 1 3 1 , 1 4 8
d e t e r m i n e d^ t. o 40

t r a n s i t i o n t o the samarium-type

phase

o c c u r s a t a b o u t 25 k b a r ( c i r c l e ) a t
149
room t e m p e r a t u r e .
The h c p - S m - t y p e
phase boundary has not been
determined.

Resistance

TERBIUM

directly

measurements
60 138

t o 500 k b a r show n o a n o m a l i e s .

The phase diagram of terbium is


shown in Fig. 61.

been reported at 27 kbar (circle),

and the high pressure phase has been


determined to be the Sm-type.

repulsions,

while the second i d e n t i f i e s

A resistant

anomaly indicating a transition has

m e n t s show k i n k s i n t h e u - u
curve
62
f o r g a d o l i n i u m a t 260 k b a r
and
345 k b a r .
The f i r s t r e p o r t a s c r i b e s
the kink to xenon-core

Under room condi

tions terbium is hep.

Two s e t s o f s h o c k wave e x p e r i
s

and

a kink i n t h e bec-hep phase boundary

Resistance measurements to 500 kbar

i t w i t h an

show smooth behavior and no clear

1 -

GADOLINIUM
40

1
. Rhombohedral
(Sm-type)

1
1000

2000

The phase diagram of


gadolinium.

^x

1
1
1
TERBIUM

20-

'
0

Fig. 6 1 .
-39-

^-bec

Liquid

hep

3000

1
X

10 -

Temperature - K
Fig. 60.

Rhombohedral
(Sm-type)

30-

hep

L^bcc

40

Pressure
to

f 30

_
-

1, -

1000
2000
Temperature - K

3000

The phase diagram of terbium.

Two s e t s of shock-wave e x p e r i
ments show kinks in the u -u curve
s p

evidence of further phase t r a n s i 138


tions.
The approximate hcp-Smtype boundary i s based on a g e n e r a l
ly 1

for dysprosium at 480 k b a r

ized r a r e - e a r t h phase diagram.

6 2

and 305

The f i r s t report a s c r i b e s

the kink to xenon-core r e p u l s i o n s , 62

Shock-wave experiments show a


kink in the u -u curve at 400
61
61
kbar.
This i s ascribed t o melting.
s

61

kbar

while the second I d e n t i f i e s i t with

melting.

The bcc-hcp boundary and

the melting curve have been d e t e r

The bcc-hcp phase boundary and the

mined to 25 and 8 kbar,

melting curve have been determined


131
t o about 25 kbar.

respectively.

DYSPROSIUM

HOLMIUM

The phase diagram of holmium i s

The phase diagram of dysprosium


is shown in Fig. 62.

shown i n Fig. 63.

Under room

conditions dysprosium is hep.

Under room condi

t i o n s holmium i s hep.

A transition

t o the Sm-type phase occurs a t 65


149
kbar
and room temperature.
Resistance measurements on holmium t o

transition to the Sm-type phase occurs


at 45-50 kbar and room tempera-

60,149
. ^
ture.
Resistance measurements
on dysprosium show anomalies near
D

600 kbar show no c l e a r evidence of

200 k b a r , which may i n d i c a t e a phase

any f u r t h e r phase changes.

transition.
15

2 10 -

1000

2000

3000

Temperature - K
Fig. 62.

The phase diagram of


dysprosium.

Fig. 63.
-40-

'

(L-bcc

_i_i_Li

1
HOLMIUM

hep

Liquid _

I
1000
2000
Temperature - K

3000

The phase diagram of holmium.

Shock-wave experiments show a


kink in the u -u curve of holtnium
s p
at 440 kbar, which i s ascribed to
melting 61 The hcp-bcc phase

THULIUM
The phase diagram of thulium i s
shown i n Fig. 65.

boundary and the melting curve have


131
been determined t o 10 kbar.

A transition

to the Sm-type phase occurs a t room


149
temperature near 110 kbar.
Resistance measurements t o 500 kbar
show no clear evidence of any further
138
phase changes.
Shock-wave experiments show a

The phase diagram of erbium i s


shown in Fig. 64.

Under room condi

tions thulium I s hep.

Under room condi

kink in the u - u curve, which i s


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

15

Shock wave experiments show a

kink in the u -u

curve at 440 kbar,


61
which i s ascribed t o melting.
No
131 The melting curve has been
bec phase has been detected before
131
melt

ERBIUM

Kw

1
0

I
0

1
1000

.
2000

,
3000

3000

Temperature - K
Fig, 64.

,
1
1000
2000
Temperature - K

Fig. 65. The phase diagram of thulium.

| I I I i |

Liquid

"'"" -

'
hep

hep

5 -

1 5

'

_g 10 -

determined to 10 kbar

""

! THULIUM 1

1 1 1 1 11

.,

The phase diagram of ytterbium

The phase diagram of erbium.


-41-

is shown in Fig. 66. Eelow 300 K

metallic phase.

153

These changes
3

have been explained in term? of the


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

reports that a new

hep phase appears between the fee and


bcc phases below 15 kbar, but this may
be the result of impurities.

pressure-independent resistance
anomaly variously observed at 743
K

1 4 7

and 898 K ,

1 5 5

has been ascribed

to another phase transition.


0

500

1000

1500

Static

compression of ytterbium at room

Temperature - K

temperature to 280 kbar shows no fur

Fig. 66. The phase diagram of


ytterbium.

ther resistance anomalies above 40


153
kbar
Three s e t s of shock-wave e x p e r i

and 2 kbar, ytterbium exists in a


151
diamagnetic hep phase.
A

ments show kinks i n the u - u curve


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

martensitic phase transformation at


300 K and atmospheric pressure pro

xenon-core r e p u l s i o n , m e l t i n g , and

duces a paramagnetic fee phase. The

electronic phase transitions,

hep-fee phase boundary has been

respectively.

determined, and it is clear that the


152
hep phase disappears above 2 kbar.

Rosengren consider the 130 kbar

At room temperature, increasing

anomaly to indicate an electronic


phase transition Involving a shift

p r e s s u r e causes a serieB of changes


in r e s i s t i v i t y .

Johansson and

from the divalent to the trivalent


141
The

ionic state in the solid

Below 20 kbar

between 20 and 40 kbar it behaves like

melting curve has been determined to


147
35 kbar.
The ytterbium phase

a semiconductor, and at 40 kbar a

diagram closely resembles that of

phase change takes place to a bcc

strontium.

y t t e r b i u m behaves l i k e a m e t a l ,

-42-

33

LUTETIUM

LUTETIUM

low pressures i s hep.

Compression t o

230 bbar at room temperature causes a


t r a n s i t i o n to the Sin-type l a t t i c e .

J 10
Pressure -

Solid l u t e t i u m at

1 1 1

The phase diagram of lutetium i s


shown in Fig. 67.

1 -;
hep

1 Liquid ..

The hcp-Sm-type phase boundary has


not been determined.

The melting
0

curve has been determined t o 10


kbar 131

i
1000

ll
2000

"
3000

Temperature - K
Fig.

HAFNIUM

Under roost conditions


hep.

hafnium

is

67.

The phase diagram of l u t e t i u m .

TAHTALUM

At atmospheric pressure a
The phase diagram of tantalum

t r a n s i t i o n occurs near 2270 K t o a


bcc phase.

The bcc phase i s s l i g h t l y

Solid tantalum

is bcc.

more dense than the hep, implying a


negative value of dp/dT for the phase
boundary.

is shown in Fig. 68.

An approximate melting curve


158
has been determined to 60 kbar.
T

A static-high-pressure

search for the hexagonal ID phase


found in titanium and zirconium
failed t o show any change of phase.
Three s e t s of shock-wave e x p e r i
ments showed anomalies in the u -u
curve.

6 2

'

6 6

'

1 4 6

Gust and R o y c e "

ascribed a kink at 600 kbar t o xenoncore r e p u l s i o n .

McQueen, t al -

ascribed a d i s c o n t i n u i t y a t 400 kbar


to a s o l i d - s o l i d phase t r a n s i t i o n .
146
Bakanova, e_t a l .
ascribed a kink
at 450 kbar to an e l e c t r o n i c t r a n s i
tion.

Hafnium melts at 2495 K .

5 3

1000

The melting curve has not been


reported.

Fig. 68.
-43-

2000
3000 ' 4000
Temperature - K
The phase diagram of tantalum.

TUNGSTEN

IRIDIUM

The phase diagram of tungsten is


shown in Fig. 69.
bcc.

Solid tungsten is

Solid iridium is fee.

Room

temperature compression to 175 kbar

An approximate melting curve


159

showed no phase transition.


Iridium
63
The melting curve

melts at 2716 K.

has been determined to 50 kbar.

has not been reported.

PLATINUM
The phase diagram of platinum is
shown in Fig. 70.
fee.

Solid platinum is

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
transitions.
3433 K.

1000
2000
Temperature - K.

Rhenium melts at

The melting curve has not

been reported.

Fig. 70.

3000

The phase diagram of platinum.

OSMIUM
Solid osmium is hep.
melts at 3300 K.

Osmium

The melting curve

has not been determined.

The phase diagram of gold is


shown in Fig. 71.

-44-

Solid gold is

'

80 -

Pressure -

J 60 -

'

'

MERCURY
Rhombohedral v

(a)

Tetragonal

"

20

/ LiquidM~

' ^/\A .

200

400

600

Temperature - K

Fig. 72.

The phase diagram of mercury.

Temperature - K
Fig. 71-

The phase diagram of gold.


A third phase, named y, has

fee.

The melting curve has been


75
determined to 65 kbar.

been found at very low temperatures


by straining the solid.

Its struc

ture and equilibrium phase boundaries


MERCURY

have not yet been determined

164

The

melting curve of mercury has been


The phase diagram of mercury is
shown in Fig. 72.

determined to 65 kbar.

Solid mercury at

low temperatures has a body centered


THALLIUM
tetragonal structure.
each rlom

In this phase

has two nearest neighbors

The phase diagram of thallium is

and eight second nearest neighbors.

shown in Fig. 73.

With increasing temperature, a

atmospheric pressure, thallium is hep.

transformation to a rhombohedral

Above 500 K, it is bcc.

structure occurs.

pressure fee phase occurs above 35

This structure may

Below 500 K at

A high

be regarded as a distorted fee

kbar and 388 K.

lattice.

phase boundaries have been determined

The tetragonal-rhombohedral

The solid-solid

phase boundary has been determined

to 60 kbar.

to 65 kbar.

been determined to 50 kbar.


-45-

The melting curve has


78

6 0

40

20

_-

Fig. 73.

1 1 1 l~ '
THALLIUM

fee

/
_ /

80

~\

/
40
fee

hep

60
-

/ _

bcc

- n -i i | i i i i | i i i i | i i
LEAD

Liquid

80 --

20
'Liquid

1 \

200

400
600
Temperature - K

,,,/

800

500

1000

1500

Temperature - K

The phase diagram of thallium.


Fig. 74.

The phase diagram of lead.

LEAD

phases.
The phase diagram of lead i s
shown i n Fig. 74.
pressure i s fee.

The low pressure s o l i d phase

i s rhombohedral, i s o s t r u c t u r a l with

Solid lead at low

arsenic and antimony.

At 137 kbar and

Conflicting

claims have been made for the s t r u c

room temperature a t r a n s i t i o n t o a
165,166 _.
.
The phase

boundary has not been determined.

ture of phase I I , with no c l e a r


1
83
agreement.
Duggin
suggests that

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

hep phase occurs.

to 60 k b a r .

the high pressure phase of a r s e n i c .

7 7

A study of phase VI at 90 kbar at


room temperature has shown i t to be
BISMUTH

bcc.

shown i n Fig. 75.

This diagram i s of

s p e c i a l importance t o high pressure

V I I I , and VI meet i n a t r i p l e point

physics because i t s many phase t r a n s i


t i o n s have been used as c a l i b r a t i o n
standards.

The phase boundaries shown

are a s y n t h e s i s of s e v e r a l
,.
84,168,169 '
.
studies.
The phases XX,

The phase diagram of bismuth i s

at 135 k b a r ,

1 6 9

and the VI-IX phase

boundary then proceeds t o higher

There i s s t i l l controversy

over the e x i s t e n c e of some t r a n s i t i o n s ,

p r e s s u r e s . This boundary was p r e


170
temperature
and 300
sumably
detected
in akbar
study at The
room

and r a t h e r l i t t l e x-ray s t r u c t u r e work

melting curve has been determined t o

has been done on the high p r e s s u r e

55 k b a r .
-46-

8 4

' r

140 -

'

BISMUTH

IX

->

120 -

100 -

bcc
VIII

80 -

(VI)

\\

60

\
\

/'\

K. s
m

IV

40 -

Tetragonal

(III)

/
Liquid

2 0 -Rhombohedral

to

'
1

i
200

\
i ., .

i
400

600

Temperature - K
Fig. 75.

The phase diagram of bismuth.


-47-

i
800

POLONIUM

RADIUM

At atmospheric pressure and below


room temperature, polonium has a

Solid radium is bcc at room

rimple cubic structure, the only

temperature. Radium melts at 973


63
K.
Wo high pressure work has been

known example of this structure in

reported.

the elements at zero pressure.

sluggish phase transition occurs

ACTINIUM

somewhere near room temperature (291327 K)

Solid actinium is fee at room

to a simple rhombohedral

temperature. Actinium melts at 1323


63
K.
No high pressure work has been
reported.

form which is a slight distortion of


the simple cubic.

The rhombohedral

form is slightly more dense,


leading to a negative dp/dT. The

THORIUM

phase boiuidary has not been deter


mined.

Polonium melts at 519 K.


Solid thorium under room c o n d i

The melting curve has not been

tions i s fee.

reported.

Superconductivity

measurements t o 160 fcbar show an


anomaly t h a t could be due t o a phase
173
At atmos

ASTATINE

change near 70 kbar.

p h e r i c p r e s s u r e near 1670 K, thoritim

Astatine is a very unstable

transforms t o a bcc p h a s e .

element and its physical properties

The

volume change of the t r a n s i t i o n

have not been determined.

is

zero t o w i t h i n experimental e r r o r .
The t r a j e c t o r y of th^ phase boundary

RADON

has n o t been r e p o r t e d .
at 2024 K.

The crystal structure of solid

Thorium melts

The m e l t i n g curve has

not been determined.

radon has not been reported. Radon


172
melts at 202 K. ' The melting curve
has not been determined.

PROTACTINIUM
FRANCIDM
Solid p r o t a c t i n i u m under room
c o n d i t i o n s i s body centered t e t r a g o n a l .

Francium is a very unstable


element and its physical properties

Metal s o l i d i f i e d from the melt i s

have not been determined.

s u g g e s t i n g t h a t t h i s i s the high
48.

fee,

temperature form of the solid.

URANIUM

No

direct measurements of phase transi


The phase diagram of uranium is

tions have heen made, however.

shown in Fig. 76.

Protactinium melts at about 1810


174
K.
No high pressure work has been

structure with four atoms per unit

reported.

60

Under room condi

tions solid uranium has an orthorhombic

- i i i i

URANIUM

40

20 -

Orthorhombic
(a)

bcc
<T>
Liquid
Tetragonal

500
Fig. 76.

1000
Temperature - K
The phase diagram of uranium.
-49-

1500

cell.

All but one of the seven known s o l i d

At 940 K and atmospheric

pressure, a transition to a complex

phases e x i s t at atmospheric p r e s s u r e .

tetragonal form with 30 atoms per

The low pressure portion of the

unit cell occurs.

The precise space

group remains to be determined.

phase diagram and i t s high p r e s s u r e


continuation are shown in s e p a r a t e

At

1050 K another phase transition leads

figures.

to a bcc phase.

i s monoclinic, with 16 atoms per unit

The solid-solid

The low temperature a phase

phase boundaries have been deter

c e l l and S c r y s t a l l o g r a p h i c a l l y d i s

mined, and indicate a triple point for

t i n c t types of atomic p o s i t i o n s .

the three phases near 30 kbar.

3 phase i s also monoclinic, with 34

The melting curve has been determined

atoms per unit c e l l and 7 types of

to 40 k b a r .

positions.

1 7 6

The

Both of these s t r u c t u r e s

are q u i t e i r r e g u l a r and are d i f f i c u l t


t o c o r r e l a t e with close-packed forms.
NEPTUNIUM

At high pressure only a and $


The phase diagram of neptunium
i s shown in Fig. 77.

e x i s t , and the a-0 phase boundary

Under room

shows a temperature maximum.

The $

conditions neptunium i s orthorhombic,

phase transforms t o orthorhombic

with eight atoms per unit c e l l and

*Y below 3.5 kbar and to 5, with

two d i s t i n c t types of atomic p o s i

undetermined s t r u c t u r e , above t h i s

tions.

pressure.

At 550 K and atmospheric

pressure a phase t r a n s i t i o n to a

There i s a |S--liquId

t r i p l e point near 27 kbar.

t e t r a g o n a l phase with four atoms


per unit c e l l and two types of atomic
p o s i t i o n s occurs.

appears above 840 K.

The next two phases are fee (<5)


and body centered t e t r a g o n a l ( 6 ' )

A bcc phase
The s o l i d - s o l i d

which e x i s t only a t low p r e s s u r e s .

phase boundaries and the melting

The 6 ' phase i s followed by bcc ( e ) ,

curve have been determined t o 35


,,
177
kbar.

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


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

PLUTONIUM

point below 20 kbar.


i s shown i n Figs. 76 and 79.

The s o l i d - s o l i d

phase boundaries and the melting

The phase diagram of plutonium

curve have been determined to 140

The

kbar.

plutonium diagram I s very complex.

-50-

1 7 4

'

1 7 8

'

1 8 0

<

r-

NEPTUNIUM

40-

30

20Or'horhombic

I Tetragonal

Liquid'
10-

01

L.

500

Fig. 77.

'

1000
Temperature - K

The phaBe diagram of neptunium.

-51-

L l

1500

PLUTONIUM

'/

1 '

8 Monoclinic. 1

6 --

^ k /

(0)

Monoclinic
(a)

1
|
f

/
[

""ec
(e)

1
1

Liquid

1
1

2 Orrhorhombi<v

'

Tetragona
'(5')

rfcc\

200

400

\
600

1
800

1000

"

1200

Temperature - K

Fig. 78.

The phase diagram of plutonium.

dashed line in Fig. 80.

AMERICIuM

Static com

pression of americium at room tempera


ture shows a resistance change at 90
kbar, which may represent a continua

The phase diagram of americium


is shown in Fig. 80.

Americium under

room conditions is dhcp.

1 8 1

1300 K leads to a new phase, which

but with very

little change in volume.

182

Keating at atmospheric pressure above

There is

evidence for a transition to an fee


phase at 920 50 K ,

tion of the dhep-fee phase boundary

Stephens < al. suggest is bcc.


The fcc-bcc phase boundary and melting

The dhep-

fec phase boundary is therefore

curves have been determined to 35


182
approximately represented by a vertical ,.
kbar.
-52'

1501

-i

1
1
r
PLUTONIUM

-|

(-

Liquid

_L
200

400

600
Temperature - K

800

Fig. 79. The phase diagram of plutonium.

-53-

1000

1200

CURIUM

i i i i | I I i I | i i I I |

AMERICIUM

40

Depending on the method of


preparation, curium metal is found to

3 0

have either an fee or a dhcp struc

ture under room conditions.


bcCs

2 20

The estimated melting point is 1620


174
K.
No high pressure work has been

dhcp
I
' ' '

F c C

No

phase boundary has been reported.

. Liquid \ l I
10 L_

The fee

phase has the higher density.

II

reported.

I I I ! l/i/l I

S00
1000
1500
Temperature - K

BERKELIUM
Berkelium metal prepared by high
temperature reduction contains a
mixture of dhcp and fee structures.

Fig. 80.

The phase diagram of


americium.

Here the dhcp phase is the more


dense.

The estimated melting point

i s 1260 K.174 No high pressure work


has been reported.

-54-

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RBC/gw
-63-

Appendix A: The Space Lattices


Lattice

Axes

Angles

primitive (simple) cubic


body-centered cubic

a - b - c

o - 3 " Y " 90

a b ji c

aB-Y-90

a^b^c

a B = Y = 90

a^bjc

o - Y 90" ^

face-centered cubic
primitive tetragonal
body-centered tetragonal
primitive orthorhombic
base-centered orthorhombic
body-centered orthorhombic
face-centered orthorhombic
primitive monoclinic

base-centered monoclinic
triclinic

a # b # c

o ^ M l

rhombohedral

a b - c

a 0 =Y

hexagonal

a - b ]< c

ot = g - 90, Y = 12

-64-