The Constitution Diagram TantaIum-Iridium

William H. Ferguson, Jr., Bill C. Giessen, a n d Nicholas J. Grant

Ta-lr alloys have been examined over the com- purity, supplied by the Bishop Co., Malvern, Pa.
plete range of compositions using metallographic Both powders were -200 mesh. Table I lists the
and X-ray techniques. The terminal solid-solubility analyses a s given by the suppliers.
limits, solidus temperatures, and intermediate A standard procedure was employed in making the
phases were determined. There are four inter- alloy buttons, which was described in detail in Refs.
mediate phases: o, tetragonal, analogous to a (Fe- 5 and 6, and which included repeated arc-melting of
C r ) ; 0 , . orthorhombic; az,tetragonal; and a TaZr,, powder compacts and determination of the composi-
cubic, AuCu, s t w c t u r e . Of these, o and a, melt tion by the weight-balance method. This is especially
peritecticaLly, a , decomposes peritectoidally , and justifiable due to the similar vapor pressures of
a TaIrs has a congruent meltingpoint. Three peri- tantalum and iridium. In the critical parts of the dia-
tectic and one eutectic reactions occur. gram, a spacing of 1/2 at. pct was used, based on
premelted master alloy material. The observed
structures and X-ray spectra were consistent with
the composition sequence of the alloys. Table II lists
THE Ta-Ir phase diagram has not been treated in the final alloy atomic percentages with the calculated
the literature. Intermetallic phases and terminal percent e r r o r of composition. Cross sections repre-
solid solubilities have been described and esti- sentative in grain size and composition were selected
mated.'-4 The previous findings have been confirmed for the study, a s described in Ref. 5. Based on prior
in this work. A complete diagram with additional experience, no contamination from the tungsten elec-
phases and solidus curves is presented. trode was considered.
Temperature measurements were obtained using a
EXPERIMENTAL METHODS Leeds and Northrup optical pyrometer and have been
described extensively in Refs. 5 and 6.
Starting materials were tantalum powder of 99.8 All heat treatments were made in the high-vacuum
pct purity, supplied by the National Research Corp., tantalum tube furnace mentioned in Ref. 5.
Cambridge, Mass., and iridium powder of 99.9 pct Samples annealed in tantalum containers cooled
Table I. Analyses of Metals Used from 1800" to 1 0 0 0 " ~in 5 sec; those annealed in
Element Ta, P P ~ 11, ppm
ceramic crucibles cooled over the same range in 15
to 30 sec. The thermal treatments a r e listed in
- Table 111.
-
- All specimens were homogenized at 1735C for 24
- hr. Tantalum-rich compositions were treated in tan-
50
- talum buckets. Iridium-rich compositions were an-
- nealed in tantalum buckets below the eutectic tem-
30 perature of 1950C; up to 2200C, tungsten-lined tan-
-
3 talum baskets were used; and above 2200C thoria
3 crucibles were used. It was found that refractory
-
- oxides (in early stages of the investigation alumina
- crucibles were used up to 1800C and thoria cru-
- cibles were used to 2 4 0 0 " ~ )give off minute amounts
10
- of oxygen and thereby influence the microstructure
1 considerably, o r react directly with the alloys.
-
50 Table \I.Compositions of Ta-lr Alloys, in Atomic Percent Ir
1
major
200
-

W I L L I A M H. F E R G U S O N , JR., Junior Member AIME,

formerly Research Assistant, Department of Metallurgy, Massa-
chusetts Institute o f Technology, Combridge, Mass., i s now
Coptoin, United States Army, 5 5 t h Transportation Battalion
Aircraft Maintenance. BILL C. GIESSEN, Junior Member
AIME, and N I C H O L A S J . G R A N T , Member A I M E a r e DSR
Research Staff Member and Professor o f Metallurgy, respec-
tively, Massachusetts lnstitute o f Technology.
Manuscript submitted December 28, 1962. IMD

TRANSACTIONS O F
THE METALLURGICAL SOCIETY O F AIME VOLUME 227, DECEMBER 1963-1401
 Table Ill. Schedule of Heat-Treatments for Ta-lr Table IV. Lattice Parameters of Intermediate Phases and a Ir

1525OC 2 days Phase and At. Pct 0 '

1630' C 3 days Structure Ir Lattice Parameters, A Accuracy
1785OC 1 day
1940c 1 day
2045OC 16 hr
2250C 2 hr a 20.0 9.968 5.197 t0.004
235OoC 1 / 2 hr tetragonal 25.0 9.928 5.159
30.0 9.888 5.121
All solidus points were measured using the techni-
que described by ~ a ~ ~ e rutilizing~ o r ta tantalum
~ al b, Co ao3bo c,
orthorhombic 57.0 2.830 4.803 13.661 t0.002 + 0.006
black body to which the specimen was fastened with
thoria o r zirconia insulation. Solidus points were ob- aa a. c0 c/a a,, c,
tetragonal 59.0 3.988 3.859 0.967 t 0.002
tained by heating steps of approximately 2 0 " ~ .Since
the pyrometer calibration was made in the s a m e way, a-Talr, 70 3.907
cubic 75 3.886
no significant e r r o r s were introduced other than
those due to failure to recognize incipient melting. a-Ir 90 3.857
cubic 100 3.839 t 0.002
Metallographic examination was utilized a s a confir-
mation of the accuracy of the observations.
The liquidus temperatures of the o phase in the
range from 17 to 44 at. pct I r were obtained by the and
use of an X-ray method described in detail in Ref. 8.
For metallographic observation, specimens were
etched with a 50 pct HF acid solution for composi- was found by observing the disappearance of primary
tions containing l e s s than 25 at. pct I r , and electroly- cores in as-cast alloys o r extrapolating t o zero. The
tically in concentrated HC1 for compositions of 25 at. phase boundaries were determined microscopically
pct I r and greater. The HF etch stains a tantalum and were checked for the a -iridium solid solution by
brown, but does not attack o. The electrolytic etch the lattice-parameter method. Metallographic ex-
differentiates the remaining phases by selective at- amination is believed to be accurate to i 1 at. pct for
tack, staining, and grain-boundary attack. boundaries drawn as solid lines, which i s also held
X-ray analysis was used to resolve the o, a , , a,, to be true for the extrapolation below 1 5 0 0 " ~due to
and a - T a I r s structures and to determine lattice their slight slopes.
parameters. Powder specimens were prepared by
grinding and stress-relieving at the original anneal- RESULTS
ing temperature. The patterns were taken employing The phase diagram is presented in Fig. 1. It i s
a 114.6-mm camera and CrKa o r CuKa radiation. marked by the occurrence of the following four inter-
Powder patterns were made of all compositions mediate phases:
above 12 pct Ir, with the exception of the 53.9 pct
sample, which required the machining of a fine-rod o = (tetragonal, analogous to o, Fe-Cr): be-
specimen. For the high tantalum compositions which tween 11.4 at. pct I r at 2475C and 41.0
did not contain significant amounts of brittle mate- at. pct I r at 1950C;
rial, flat platelets were hammered out and annealed. a , = (orthorhombic): between 50.4 at. pct
The patterns then were taken on an XRD-5 diffracto- I r at 1950C and about 61 at. pct I r at
meter with CuK, radiation. The limits of e r r o r a r e 2120C;
given together with typical results in Table IV. a, = (tetragonal): between 58 and 59 at. pct
The temperatures of all nonvariant reactions in- I r at 1800C.
volving liquid were found by solidus measurements a TaIrs = (cubic, AuCUS structure): between 66.5
from microscopically homogeneous specimens. The at. pct I r at 2120C and 76.5 at. pct I r
temperature of the peritectoid reaction at 2380C.
The lattice parameters of these phases and their
dependence on the concentration a r e given in Table
was found by X-ray and microscopic observation of
w.
a Tantalum has a maximum solid solubility of 7.2
specimens quenched from above o r below the reac-
at. pct I r at 2475C.
tion temperature. The concentration of the solid
o forms peritectically at 2475C:
phases involved was obtained by extrapolating the
phase boundaries to the temperatures of the eutectic
o r peritectic reactions. The composition of the liquid
and forms a eutectic with a, at 1950C:
in

a, forms by a peritectic reaction at approximately

was found from as-cast specimens; the liquid in 2120" C:
TRANSACTIONS O F
1402-VOLUME 227, DECEMBER 1963 THE METALLURGICAL SOCIETY OF AlME
 WEIGHT PER CENT IRIDIUM
27000 10 20 30 40 50 60 70 80 90

I\ "\ ' I i j I '

I I

Fig. l - T h e Ta-Ir constitution d ~ a g r a m .

Legend: 0 one phase; two phase;
A melting not observed; A melting ob-
served; by X-ray analysis; X liq-
uidus measured, Ref. 8.

10 20 30 40 50 60 70 80 90 100
ATOMIC PER CENT IRIDIUM

Fig. 2-8.0 at. pct I r , 24 h r , 1735"C, and 2 h r , 225OoC, Fig. 4-49.2 at. pct I r , 24 hr, 1735"C, and 13 h r , 1915C.
etchant I, X200. ff ~ a ( g r a y )+ a (white). Reduced approxi- etchant 11, X200. o (dark) + a, (white). Reduced approxi-
mately 17 pct f o r reproduction. mately 17 pct f o r reproduction.

Fig. 3-39.5 at. pct I r , 24 h r , 1735"C, then used for a melt- Fig. 5-58.5 at. pet I r , 24 h r , 1735"C, and 13 h r , 1855C.
ing-point determination a t 2045C. etchant 11, X500. etchant 11, X500. a TaIrS c o r e s (rounded, gray), surrounded
a (gray) + a, (white). Reduced approximately 17 pct for by ff2 (white, twinned) in matrix of a, (gray). Reduced ap-
reproduction. proximately 17 pct f o r reproduction.

TRANSACTIONS OF
THE METALLURGICAL SOCIETY OF AlME VOLUME 227, DECEMBER 1963-1403
Fig. 6-64.0 at. pct I r , 24 hr, 1735"C, and 72 hr, 163O0C, Fig. 8-79.0 at. pct Ir, 24 hr, 1735"C, and 16 hr, 2045"C,
etchant 11, X500. ff TaIr3 (light-gray dendrites, note preci- etchant 11, X500. Dendrites of a TaIr, (gray) + precipitate
pitation of ff2 on seams) + a 2 (white, lightly twinned). Re- of a TaIr3 (gray) in a Ir (light). Reduced approximately 15
duced approximately 17 pct for reproduction. pct for reproduction.

Fig. 7-64.0 at. pct Ir, 24 hr, 1735"C, and 14 hr, 2095"C,
thoria crucible, etchant II, X500. Single-phase tetragonally Fig. 9-85.5 at. pct Ir, 24 hr, 1735"C, and 16 hr, 2045"C,
distorted ff TaIr3 (nonequilibrium). Reduced approximately etchant II, X500. ff TaIrS (dark) + ff I r (light). Reduced ap-
17 pct for reproduction. proximately 15 pct for reproduction.

13 h r ) i l l u s t r a t e s the determination of the @,-stability

range. This alloy was annealed below the peritectoid
a, f o r m s by a peritectoid reaction a t 1860C: t e m p e r a t u r e of 1860C; c o r e s of a TaIrs (rounded,
gray) r e a c t with a , ( g r a y matrix) forming walls of
a, (light-colored). L a r g e twins can b e noticed in the
Finally, a peritectic e x i s t s a t about 2380C: a, phase. The s a m e alloy annealed a t 1 9 8 5 " ~ f o r 16
h r shows no a, and i s almost one phase a,. Fig. 6
(64.0 at. pct I r , 1735"C, 24 h r , and 1630C, 72 hr) is
a, Iridium has a solid solubility for tantalum of about taken f r o m the 0 2 + 0 T a I r j field: dendrites of
16 at. pct a t 2380C. a TaIr3 (gray) lie in a m a t r i x of a, (white twinned).
The phase diagram i s illustrated by the following T h e r e is incipient precipitation of a, f r o m the tan-
microsections. Fig. 2 (8.0 at. pct I r , 1 7 3 5 " ~ 24, hr, talum-rich outer zones of the cored a TaIr3. Fig. 7
and 2250c, 2 hr) shows brown a-tantalum solid shows the s a m e alloy after annealing for 14 h r a t
solution with s o m e white o phase. Fig. 3 (39.5 at. pct 2095C in a thoria crucible before quenching. The
I r , 1735"C, 24 hr, and 2045C) is p a r t of a. melting- s t r u c t u r e is one phase; s t r o n g twinning has o c c u r r e d
point determination, showing p r i m a r y unmelted o and the powder pattern i s now one phase, tetragonal.
phase, with resolidified eutectic o and f f , . Fig. 4 This s t r u c t u r e is not regarded a s in equilibrium, a s
(49.2 at. pct I r , 1735"C, 24 h r , and 1915"C, 13 h r ) will b e discussed l a t e r .
shows d a r k o and white a,. This picture i s included The s t r u c t u r e of a 79 at. pct I r alloy (1735"C, 24
to document the absence of a high-temperature phase h r , and 16 h r a t 2045"C), given in Fig. 8, shows the
in this range analogous to a 3( ~ a - ~ h ) . gray p r i m a r y dendrites of a TaIr3 and the white
Fig. 5 (58.5 at. pct I r , 1735"C, 24 h r , and 1855"C, m a t r i x of ff iridium with a somewhat coarsened g r a y
TRANSACTIONS O F
1404-VOLUME 227, DECEMBER 1963 THE METALLURGICAL SOCIETY OF AlME
precipitate of a TaIrs. The a-iridium solid solution Table V. X-ray Diffraction Pattern of a, (Ta-lr)
appears to be one phase under X1000, the precipitate
becoming visible only after annealing, e.g., at 1525C 57 At. Pct 11, CrK, Radiation
for 2 days. A view of the orientation of the precipi-
tate, which i s presumably along the cube edges of the
a iridium matrix, i s provided by Fig. 9 of an 85.5 at. sin% Intensity
pct I r alloy (1735"C, 24 hr, and 16 h r at 2 0 4 5 " ~ ) .The
(h k 1) obs calc est calc*
identical orientation of matrix and a -iridium preci-
pitate i s also borne out by X-ray powder patterns of
coarse-grained material showing identical location
of the a-iridium and a TaIrs spots (differing only in
the d value).
The interpretation of the X-ray results was facili-
tated by comparison with known patterns. o could be
clearly identified. The superlattice lines of a TaIrs
could not be obtained due to the almost identical
scattering factors of tantalum and iridium, but its
existence is proved firstly by the occurrence of a
separate fcc lattice around 75 at. pct Ir, secondly by
the analogy to TaRh3 where ordering is o b ~ e r v e d , ~
and lastly by previous result^."^'^
The observed sin% values of a, a r e compared with
the calculated values in Table V. The a l structure,
which was identified in the system Ta-Rh, and which
i s marked by some ductility, has been discussed in
the paper on the Ta-Rh ~ y s t e m The . ~ observed inten-
sities a r e very close to those observed and calculated
for a I( Ta-Rh), which a r e therefore included into
Table V. However, by analyzing eight reflections as
*
described i n Ref. 5 a value of ye = 0.04 0.01 was
*
found, as compared with ye = 0.05 0.01 for a1 'Calculated for a , (Ta-Rh), R e f . 5.
( ~ a - R h ) .This determines the crystal structure of
al: space group ~ 2 5 1 , - Pmcm; atomic positions: lower limit. However, the formation of large grains
makes it likely that little supercooling occurs.
tantalum: 4 (i) with yi = 0.32; zi x - 0.083; b ) The formation of a,. Based on micrographs
2 (e) with ye 0.04; like Fig. 7, it was initially assumed that there was a
continuous transition from a TaIr3 to at high tem-
iridium: 4 (j) with yj x 0.82; zj = -0.083;
peratures. Later, avoiding ceramic crucibles alto-
2 (f) with yf % 0.54. gether, it became evident that this i s not the case
f i e a, powder pattern was inde3ed on the basis of a for pure alloys and that between 1860" and 2120C
fct cell (ao = 3.9881, co = 3.859A, c/a = 0.967 with 4 a TaIrs i s in equilibrium with a , ; this limits the
atoms per cell). Although it i s possible that the unit existence of the stable a , phase to lower tempera-
cell i s of the AuCu type (2 Ta in 000; 1/2 1/2 0; 2 Ir tures. It i s not known whether this stability is in
in 1/2 0 1/2; 0 1/2 1/2) with the excess iridium part due to small amounts of impurities o r annealing
atoms randomly occupying the 1/2 1/2 0 positions, stresses. A tetragonal phase with 0.967 < c/a < 0.978
no analysis of the atomic distribution in the off- occurs between 60 and 66.5 at. pct I r between about
stoichiometric phase could be carried out due to the 2050" and 2120C. It is found mostly in two-phase
similarity of the scattering factors mentioned above. structures with either a1 o r a TaIrs, usually s t a r t s
Only the fundamental lines of the fct structure at the surface of the specimen, and i s metallographi-
were observed. Therefore, a more complex struc- cally marked by strong twinning. Since often there
ture with a larger unit cell cannot be ruled out. is a gradual transition to untwinned a T a r , and the
amount of transformed material depends on concen-
DISCUSSION tration, time, temperature, and crucible, it is as-
sumed that interstitial impurities increase the solu-
Among the main characteristics of the phase dia- bility of tantalum in a T a r s under formation of a
gram the following merit some dfscussion: tetragonally distorted AuCus lattice.
a) The determination of the o-phase liquidus line. It is not clear whether the twin markings docu-
The liquidus points a r e derived, s e e Ref. 8, under the mented in Fig. 7 a r e due to s t r e s s e s accompanying
assumption that no supercooling of the melt takes the formation of the tetragonal structure o r whether
place in the arc-furnace. If this i s not the case, the they a r e traces of ordering taking place through a
calculated temperatures will be too low; the liquidus twinlike shear process. A striated microstructure
line presented here i s therefore to be regarded a s a due to s t r e s s e s is presented in Fig. 6(d) of Ref. 9 for
TRANSACTIONS O F
THE METALLURGICAL S O C l E P l O F AlME VOLUME 227, DECEMBER 1963-1405
the Co-Pt system; for a further discussion of the 15 and 25 at. pct I r at 1200C, compared to about 17
microstructural changes associated with the forma- to 34 at. pct I r in this investigation. The difference
tion of an ordered tetragonal lattice, s e e Ref. 10. may be explained by the different heat treatments
c) The melting points in the iridium-rich region of used (72 4r
at 1525"C, a s compared to 72 h r at
the diagram. Although the melting point of iridium is 1200C)., 'Extrapolating from the heating schedule
assumed to be 2454"c,11 it was found to be 2357" * used, it would seem to be necessary to anneal for 10
25C under the conditions described. In another to 20 days a t 1200C to reach equilibrium. For a
study, l3apperportl2 found 2378C for the same i r i - composition of 25 at. pgt I r lattice parameters of
dium metal. These low values a r e probably due to a a0 = 9.938~4,co = 5.172A (no limit of e r r o r given) a r e
reaction of the iridium with the thoria chips at this presentgd, a s compared with a0 = 9.928L4, co = 5.159L4
temperature. Since in iridium-rich specimens an- (*0.004A) found by the authors.
nealed above 2250C (at lower temperatures tungsten napt ton^ lists both a (melting peritectically) and
crucibles can be used without contamination) some TaIr3, which i s confirmed here.
oxide formation on grain boundaries i s found, the r e -
sults above 2250C, including the postulated peritec- ACKNOWLEDGMENTS
tic reaction, a r e tentative and drawn in broken lines. The authors wish to acknowledge with thanks the
d ) The precipitation of ff TaIr3 in ff Ir. No indica-
assistance of Misses Hanna Ibach and Ursula Stark
tion for an appreciable d o p e of the a - I r solvus line
in the experimental work, a s well a s the informative
with rising temperatures could be found below and cooperative discussions and assistance from
2200C; X-ray lattice-parameter measurements (up staff members at Nuclear Metals, Inc., Westinghouse
to 1650" C) and metallographic observations agree. Electric Co., and Massachusetts Institute of Tech-
On the other hand, the composition of the liquid phase
nology. Financial support was provided by Wright
in the reaction cu TaIr3 + L = a I r i s found to be ap- Air Development Division, U. S. Air Force, AF
proximately 84.5 at. pct I r by metallography. It is
33(616)-6023.
possible that the slope of the solvus line changes
markedly at higher temperatures o r that the quench- REFERENCES
ing rate was not sufficient to suppress precipitation.
The formation of oversaturated a -1r solid solution on 'A. E. Dwight and P. A. Beck: Trans. Met. S o c . AIME, 1959, vol.
solidification through failure of (Y TaIr3 to nucleate 215, p. 976.
'M. Nevitt and J . Downey: 1. Metals, 1957, vol. 9, p. 1072.
also has to be considered. The precipitation struc-
'A. G. Knapton: J . Less-Common Metals, 1960, vol. 2, p. 113.
ture was at first interpreted a s a eutectic between 'C. W. Haworth: I. L e s s - C o m m o n Metals, 1960, vol. 2, p. 125.
(Y TaIr3 and (Y Ir, but, since as-cast alloys do not 'B. C. Giessen, H. Ibach, and N. J . Grant: The Constitution Diagram
show any such structure under XlOOO and the growth Tantalum-Rhodium, accepted for publication, Trans. Met. S o c . .41hfE,
of the a -TaIr3 particles i s typical for a precipita- 6B. C. Giessen, R. Nordheim, and N. J . Grant: T r a n s . Met. Soc. AIME,
tion process, this explanation was adopted. 1961, vol. 221, p. 1009.
'Wight Air Development Division, USAF, Technical Report 60-132,
Further studies of the diagram should clarify the
p. 16.
existence of the tetragonal phase associated with 'B. C. Giessen and N. J . Grant: An X-ray Method to Determine the
twinning between 60 and 65 at. pct I r at 2100C, Liquidus in High Temperature Binary P h a s e Diagrams, Trans. diet. S o c .
should establish the a -1r solvus line above 2200c, AIME, 1963, vol. 227, p. 535.
and should include a heat treatment below 1500C. 'J. B . Newkirk, R. Smoluchowski, A. H. Geisler, and D. L . Martin:
Finally, previous findings in the literature a r e dis- AIME Trans., 1950, vol. 188, p. 1249.
cussed. Dwight agd ~ e c k list
' the ordered structure lo]. S. Bowles and A. S. Malin: J. Australian Inst. Metals, 1960,
vol. 5, p. 131.
TaIr3 (ao = 3.889A). This a. value agrees well with "M. Hansen: C o n s t i t u t i o n o f Binary A l l o y s , McGraw-Hill Book Co.,
that given in Table IV (a0 = 3.886 i 0.002&. N. Y . , 1958.
Nevitt and Downey2 have found a to exist between "E. J. Rapperport: ASD Technical Report, 60-132, part 11, p. 27.

TRANSACTIONS O F
1406-VOLUME 227, DECEMBER 1963 THE METALLURGICAL SOCIETY O F AIME