Provisional Ho-Y

Ho-Y (continued)
Cu-Ti
phase in this system is from 8.5 to 100 at.% Y. The esti-
mate of the termination of the bcc phase at 8.5 at.% Y is Fig. 2 Ho-Y Lattice Spacings
subject to rather wide error (i.e., the termination point 0.366 , , , , 0.576
could lie anywhere in the range 1 to 30 at.% Y) and should o, [] [70Mar] o
be determined experimentally.
0.364 0 ~ . 0.574

Lattice Spacings
.,~ 0.362 o [] - 0.572
Markova et al. [70Marl determined the ternary Dy-Ho-Y
phase diagram using distilled metals of 99.5 to 99.7
(wt.?)% purity, but containing O, Ca, Cu, Fe, and Ta as
impurities. They reported lattice spacings for the system
.~,~0.360~ / -0.570~
by means of triangular diagrams showing lines of equal
value for the a and c axes. Lattice spacings for the Ho-Y 0.358 0.568 "~
system were obtained by scaling one side of their ternary
diagram. The lattice spacings for Ho and Y listed by
Markova et al. have small deviations from the accepted 0.356 0.566'
values for the pure metals as listed in [78Bea], so adjust-
ments have been made to the lattice spacings of their
alloys. The adjusted data are shown in Fig. 2. A positive 0.564
deviation from Vegard's law behavior is seen for the a
lattice parameter at all alloy compositions. The adjusted c t [] 0.562
spacing data show scatter about the Vegard's law line with
0.56178
no general trend.
t t ~ t 0.560
Thermodynamic Properties 0 20 40 60 80 100
Ho Yttrium, at.%
Nelson and Legvold [61Nel] calculated entropy changes
involved in the demagnetization of Y-0.6 at.% Ho and Straight lines representing Vegard's law behavior are based on
Y-1.0 at.% Ho single crystals. These changes were found the accepted values for the pure metals as given in [78Bea].
to be about 15% of that expected if the alloy behaved as an K.A. Gschneidner, Jr. and F.W. Calderwood, 1982.
ideal paramagnetic substance. They observed a large con-
tribution to the heat capacity in the range 0.7 to 1.2 K, 70Mar" Markova, I. A., Terekhova, V. F., and Savitskii, E. M., Izv.
which they attributed to magnetic spins. Akad. Nauk SSSR, Metal., (6), 170 (1970); TR: Russ. Metall.,
(6), 106 (1970).
73Spe: Spedding, F. H., Sandeen, B., and Beaudry, B.J., J. Less-
Cited References Common Met., 31, 1 (1973).
6lNel: Nelson, D.T. and Legvold, S., Phys. Rev., 123, 80 (1961). 78Bea: Beaudry, B.J. and Gschneidner, K.A., Jr., in Handbook
67Mar: Markova, I. A., Terekhova, V. F., and Savitskii, E. M., Izv. on the Physics and Chemistry of Rare Earths, Vol. 1 --Metals,
Akad. Nauk SSSR, Neorg. Mater., 3, 392 (1967); TR: Inorg. Gschneidner, K. A., Jr. and Eyring, L., Ed., North-Holland Pub-
Mater., 3, 343 (1967). lishing Co., Amsterdam, 215 (1978).
Ho-Y evaluation contributed by K.A. Gschneidner, Jr., Director, and F.W. Calderwood, Rare-earth Information Center, Ames Laboratory, Iowa State
University, Ames, Iowa 50011. This work was supported by the Department of Energy through the Joint Program on Critical Compilation of Physical and
Chemical Data coordinated through the Office of Standard Reference Data, National Bureau of Standards. Additional support was contributed by: Th.
Goldschmidt AG, Essen, West Germany; Molycorp, Inc., Union Oil Co. of California, Los Angeles, CA; Reactive Metals & Alloys Corp., West Pittsburg, PA;
Ronson Metals Corp., Newark, NJ; and Santoku Metal Industry Co. Ltd., Kobe, Japan. Literature searched through 1981. Professor Gschneidner is the
ASM/NBS Data Program Category Editor for binary rare-earth alloys.

The Cu-Ti (Copper-Titanium) System

63.546 47.88

By J. L. Murray
National Bureau of Standards

Equilibrium Diagram appear. Ti-rich and Cu-rich compounds (Ti2Cu and TiCu4)
also are present. Experimental phase diagram data are
The Ti-Cu phase diagram (Fig. 1) shows a depression of the uneven in accuracy, in the sense that the structures and
melting points of both components, so that the overall compositions of the compounds were carefully determined
shape of the liquidus has a minimum near the center of the and verified, but m a n y of the boundaries involving liquid
diagram, In the composition range 50 to 67 at.% Cu, a and solid solution phases were examined in only one study
series of closely spaced, structurally related compounds [52Jou]. Metastable phase equilibria have been studied

Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983 81

Cu-Ti Provisional

Fig. 1 Assessed Ti-Cu Phase Diagram

Weight Percent Copper

0 10 20 30 40 50 ,~ 70 80 90 100
1 7 0 0 | ....... I,,, ..... ~,,,i,,,,I ..... ,,,I ...... ,,,I ...... , ..... , ......... , .... J .... , ...... ~"r .........

0 =- 6 3 H a h
~ A --- 6 2 Z w i
1500 \ ", + ~ 66Ere
I ~ ", x -= 7 9 V i g

(.9 1300 ~
, ,,
, ,, L

1100 '\ ",,

~ ~ I005~ ~,

71111-

500 ......... , ......... r ......... J........ t ....... t . . . . . . . . . r ........ [ . . . . . .

10 2:0 30 40 50 60 70 80 '''~ '' 100
Ti Atomic Percent Copper Cu

Including selected experimental data. J. L. Murray, 1983.

intensely. This includes the decomposition of supersatu- First we discuss the reported evidence for the existence
rated cph and fcc solid solutions and the formation of of Ti3Cu: [51Kar] found a compound in nearly pure form
noncrystalline alloys in the composition range 35 to at 25 and 27.5 at.% Cu, but found that the alloys were
74 at.% Cu. severely contaminated. The stoichiometry Ti3Cu also was
assumed by [70Lue, 52Rau], though without any direct
The equilibrium solid phases of the Ti-Cu system are the
evidence. [67Gar] claimed to have established the exis-
following:
tence of both Ti3Cu and Ti2Cu by means of X-ray dif-
9 The solid solutions based on the pure components: fraction and optical microscopy, but they did not give
cph (aTi), the stable form of Ti below 882 ~ bcc (flTi), enough details of the experiments to assess the accuracy
the stable form of Ti between 882 ~ and the melt; of their work.
and fcc (Cu). The m a x i m u m solubilities of Cu in (aTi)
Evidence for the existence of Ti2Cu comes from [52Jou],
and (/3Ti) are 1.6 and 13.5 at.% at 790 and 1005 ~ re-
[61Enc], [62Mue], [63Mue], [70Ble], and [71Wil]. [52Jou],
spectively. The maximum Ti solubility in (Cu) is 8 at.%
[61Enc], [62Mue], and [63Mue] were able to prepare essen-
at 885 ~
tially single-phase Ti2Cu alloys. [61Enc, 62Mue, 63Mue]
9 The stoichiometric compound Ti2Cu with the MoSi2
related the structure of Ti2Cu to that proposed by [51Kar]
structure.
for the hypothetical Ti3Cu phase, which strongly suggests
9 The equiatomic compound TiCu with the B 11 structure.
that the same phase was observed by them and by [51Kar].
TiCu has a composition range of 48 to 52 at.% Cu and
We consider that the work of [61Enc, 62Mue, 63Mue] es-
melts congruently at 985 ~
tablished the existence of Ti2Cu.
9 The stoichiometric compounds Ti3Cu4, Ti2Cu3, and
Ti2Cu with related tetragonal crystal structures. The work of [71Wil, 70Ble] on age-hardening in super-
9 The compound TiCu4 with composition range 78 to saturated (aTi) has shown that Ti2Cu is in equilibrium
80.9 at.% Cu. Several metastable ordered structures with (aTi) below the eutectoid at 790 ~ [71Wil] used
can form in this composition range before the appear- selected area electron diffraction to identify the structure
ance of equilibrium TiCu4. of the precipitates from supersaturated (a Ti); [70Ble] used
X-ray microprobe analysis to identify the composition of
Information on the three-phase equilibria and congruent the precipitates. We consider that the identification of
and pure metal transformations are summarized in Table 1. Ti2Cu by [70Ble, 71 Wil] as the phase in equilibrium with
(aTi) established that there is no additional equilibrium
Ti2Cu and (flTi)/L Boundaries. There has been some dis- phase of intermediate composition.
agreement about whether the Ti-rich compound has the
stoichiometry Ti3Cu or Ti2Cu. The existence of Ti2Cu with The composition range of existence of Ti2Cu was examined
the bct MoSi2 structure and the absence of Ti3Cu are by [63Mue, 66Ere]; [66Ere] placed the composition range
now established. as 30 to 33 at.% Cu at 800 ~ based on the microstructural

82 Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983

 Provisional Cu-Ti

Table 1 Three-Phase Equilibria, and Congruent and Pure Metal Transformations

Compositions, Temperature,
Phases J at.% Cu ~ ~ Type
(/3Ti) + L ~ Ti2Cu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13.5 36.5 -+ 1.5 33.3 1005 Pelitectic
(/~i) ~ (aTi) t Ti2Cu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4 1.6 33.3 790 • 5 Eutectoid
L ~ Ti2Cu + TiCu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 33.3 48 960 • 5 Eutectic
TiCu + L ~ Ti3Cu4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 62.5 57.1 925 • 10 Peritectic
Ti3Cu4 + L ~ TiCu2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57.1 71 66.7 890 -+ 10 Peritectic
Ti3Cu4 + TiCuz ~ TizCu3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57.1 66.7 60 875 • 10 Peritectoid
L ~ TiCu2 + TiCu4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73 66.7 ~78 875 • 10 Eutectic
TiCu2 ~- Ti2Cu3 + TiCu4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66.7 60 ~78 870 -+ 10 Eutectoid
L + (Cu) ~ TiCu4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 92 80.9 885 • 10 Peritectic
L ~- TiCu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 985 • 10 Congruent
Pure component transformations
(flTi) ~ (~Ti) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0 882
L ~ (~l~i) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0 1670
L ~- (Cu) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 1083 o o .

C a l c u l a t e d (Fig. 1)
(/3Ti) + L ~ Ti2Cu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12.7 37.2 33.3 994 Peritectic
(./3Ti) ~ (c~Ti) + Ti2Cu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4 1.5 33.3 790 Eutectoid
L ~- Ti2Cu * TiCu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 33.3 50 97t Eutectic
TiCu + L ~ Ti3Cu~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 61.6 57.1 927 Peritectic
L + (Cu) ~ TiCu, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76.5 93.2 80 885 Peritectic
L ~ TiCu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 980 Congruent

Table 2 Experimental Data on Reactions Involving Ti2Cu

Temperature, Composition, Reaction
Reference *C at,% Cu type Reaction
[52Jou] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . Peritectic (/.r + L ~, Ti~Cu
990 43 Eutectic L ~ Ti2Cu + TiCu
[66Ere] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 960 43 Eutectic L ~ (/3Ti) + Ti~Cu
1003 31 Eutectic L --~ Ti2Cu + TiCu
1015 33.3 Congruent L --* Ti~Cu
[82Shu] .............................. ... >30 Peritectic (flTi) + L --, Ti2Cu
. . . . 43 Eutectic L--, Ti~Cu + TiCu
[53Trz] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 960 43 Eutectic L --* (/3Ti) + Ti2Cu
1009 -31 Eutectic L --, Ti2Cu + TiCu
1015 33.3 Congruent L --* Ti2Cu

work. On the other hand, [63Mue] used closely spaced The (flTi) liquidus has n e v e r been d e t e r m i n e d and few
alloys for X - r a y s t r u c t u r e d e t e r m i n a t i o n a n d found a d a t a [52Jou] a r e a v a i l a b l e on t h e (flTi) solidus, as shown
33.3 at.% Cu alloy to be most n e a r l y single-phase, with by the d a s h e d lines in Fig. 1. Based on solidus and (flTi)/
g r e a t e r a m o u n t s of second phase in 32.8 and 33.8 at.% ((/3Ti) + Ti2Cu) d a t a from [52Jou], t h e m a x i m u m solubil-
Cu alloys. In the p r e s e n t evaluation, the X-ray d a t a are ity of Cu in (flTi) is 13.5 +- 1.5 at.% Cu. The composition of
preferred and the compound has been shown as stoichio- the liquid a t the peritectic is a p p r o x i m a t e l y 35.5 § 2 at.%
metric in Fig. 1. Cu. T h e r m o d y n a m i c c a l c u l a t i o n s w e r e used in the p r e s e n t
a s s e s s m e n t to predict t h e (flTi) l i q u i d u s and solidus, a n d
Ti2Cu is formed by the peritectic reaction (~Ti) + L--~ the r e s u l t s of the c a l c u l a t i o n s were used to plot t h e s e
Ti2Cu a t 1005 -+ 5 ~ [82Shu]. There a r e discrepancies in b o u n d a r i e s in Fig. 1. The f l / ( ~ + Ti2Cu) b o u n d a r y also is
the l i t e r a t u r e concerning the type of this reaction. [66Ere] d r a w n from a t h e r m o d y n a m i c c a l c u l a t i o n and is consistent
and [53Trz] claimed t h a t the eutectic r e a c t i o n L ---,/3 + with the m e t a l l o g r a p h i c d a t a of [52Jou].
Ti2Cu occurs at 1003 ~ and t h a t TizCu m e l t s c o n g r u e n t l y
a t ]015 ~C (see Table 2). [52Jou] observed a p e r i t e c t i c (~TJ)/(flTO Boundaries. T h e e u t e c t o i d r e a c t i o n (~Ti)--~
decomposition of Ti2Cu. [Shunk~ p r e f e r r e d t h e r e s u l t s (aTi) + Ti2Cu occurs a t 790 • 5 ~ t h e compositions of
of [52Jou] to those of [53Trz] because t h e i r s a m p l e s had (aTi) and (flTi) a t 790 ~ a r e 1.6 • 0.1 a n d 5.4 +- 0.3 at.%
been arc-melted r a t h e r t h a n melted in refractory crucibles, Cu, respectively. E x p e r i m e n t a l d a t a a r e given in Table 3
which cause contamination. However, [66Ere] also used
and plotted in Fig. 1.
arc-melted alloys of a p p a r e n t l y good purity, and t h e y show
a eutectic as-cast m i c r o s t r u c t u r e at 31 at.% Cu. In order [51Mcq] and [52Jou] d i s a g r e e d by a p p r o x i m a t e l y 10 ~ in
to resolve this discrepancy, [82Shu] e x a m i n e d a n as-cast the f l / ( a + fl) b o u n d a r y a t fixed composition, with the
microstructure in a 30 at.% Cu alloy, which h a d been pre- hydrogen p r e s s u r e d a t a of [51Mcq] h a v i n g the lower tem-
pared with p a r t i c u l a r care to m a i n t a i n p u r i t y of t h e alloy. peratures. The t h e r m o e l e c t r i c p o w e r d a t a of [79Vig] a r e
The microstructure supports the peritectic reaction; there- in b e t t e r accord with [52Jou] t h a n w i t h [51Mcq]. This dis-
fore, the peritectic reaction has been t e n t a t i v e l y accepted. crepancy b e t w e e n the h y d r o g e n p r e s s u r e d a t a and classi-
F u r t h e r work on the Ti-rich liquidus is needed. cal m e t a l l o g r a p h i c d e t e r m i n a t i o n s h a s been reported in

Bulletin of Alloy P h a s e D i a g r a m s Vol. 4 No. 1 1983 83

Cu-Ti Provisional

Table 3 (aTi)/(flTi) Boundaries

(aTi) fll(a + ~)
composition, composition,
Reference at.% Cu at.% Cu Temperature, ~ Method
[51Mcq] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . "'" 0.5 867 Hydrogen pressure
9-- 1.0 855
9.. 2.0 840
9-" 3.5 817
9.. 5.0 795
. . . . . . 776(a)
0.5 "" 830
1.0 "" 790
[79Vig] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9.. 1.8 860 -+ 10 Thermoelectric power
-1.4 "" 780 -+ 5
1.29 "" 775
1.12 "" 765
0.78 "" 735
0.47 "" 690
0.17 "" 600
0.11 "" 550
0.05 "" 500
0.03 "" 475
[63Luz]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.4 -+ 0.1 9.. 550 Metallography, hardness,
0.45 -+ 0.1 9.. 700 electrical resistivity
[62Bor] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.8-1.1 9.. 400-750 Metallography
[52Jou] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4 5.4 798(a) Metallography,
4.4 818 thermal analysis
2.0 850
[70Ble] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 795 -+ 3(a) Lattice parameters
[66Ere] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 800(a) Thermal analysis
[71Will, 71Wi12]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -1.4 9.. 798(a) TEM
(a) Eutectoid temperature.

all Ti systems for which such data exist; therefore, the data Table 4 Experimental Data on the TiCu Liquidus
of [52Jou, 79Vig] are preferred. Composition, Temperature,
The b o u n d a r i e s of the (aTi) region are based on data from Reference at.~ Cu ~ Method
[79Vig, 70Ble, 52Jou, 71Wil]. The metallographic data [52Jou] . . . . . . . . . . . 50 972(a) Thermal analysis
of [62Bor, 63Luz] do not disagree significantly, but are (heating, cooling)
less precise t h a n the lattice p a r a m e t e r and thermoelectric [66Ere] . . . . . . . . . . . 48 982 Thermal analysis
power data. The most restricted solubilities of Cu in (aTi) 50 984(a)
[79Vig] have been chosen also because of the possibility of 53 971 (Except for congruent
58 936 melt, data were
not observing small precipitates u s i n g optical microscopy.
59 930 read from the
Measured eutectoid t e m p e r a t u r e s v a r y between 776 to published graph,
780 ~ [51Mcq, 79Vig] a n d 798 to 800 ~ [52Jou, 66Ere, -+5 ~
t h e r m a l analysis]. [70Ble] reported lattice p a r a m e t e r s [53Trz] . . . . . . . . . . . 50 982(a) Thermal analysis
[52Rau] . . . . . . . . . . 51 -905 Thermal analysis
of e q u i l i b r i u m (aTi) as a function of temperature: the
(cooling)
m i n i m u m i n the lattice p a r a m e t e r (which should be at
the eutectoid t e m p e r a t u r e ) a n d the r e l a t i o n between lat- (a) Congruentmelt.
tice p a r a m e t e r s above a n d below the eutectoid tempera-
ture provide additional indirect i n f o r m a t i o n on the (aTi)
boundaries. I n this evaluation, the eutectoid t e m p e r a t u r e at compositions c o n t a i n i n g excess Ti, and the tetragonal
of 7 9 0 - 5 ~ was chosen to b r i n g about the best com- CuAuI structure compositions c o n t a i n i n g excess Cu. The
promise a m o n g various data. The m a x i m u m solubility of existence of two compounds was not verified by subse-
Cu in (aTi) is t a k e n as 1.6 at.% a n d the a / ( a + fl) and q u e n t investigations [65Sch, 66Ere]; therefore, a single
ot/(a + Ti2Cu) curves intersect at 790 ~ compound has been shown i n Fig. 1. If TiCu had two
The present t h e r m o d y n a m i c calculations reproduce the allotropes, a diffusionless t r a n s f o r m a t i o n probably would
(aTi)/(flTi) b o u n d a r i e s well w i t h i n the estimated error, occur at some composition a n d should be r e v e a l e d in
and calculated tie lines were used to draw the boundaries the microstructure of a near-equiatomic alloy; this, how-
in Fig. 1. The a/(Ti2Cu + a) b o u n d a r y was d r a w n directly ever, has not been observed. It is possible t h a t the second
t h r o u g h the d a t a of [79Vig]; a l t h o u g h t h e r m o d y n a m i c compound observed by [51Karl was Ti3Cu4.
calculations qualitatively reproduce this boundary, TiCu undergoes c o n g r u e n t m e l t i n g at 985 -+ 10 ~ [52Jou,
the e x p e r i m e n t a l data are more precise t h a n the c u r r e n t 66Ere, 53Trz] (Table 4). These data are all c o n s i s t e n t
calculations. w i t h i n the estimated error.
E q u i a t o m i c TiCu. [51Kar, 52Rau] found two compounds The width of the single-phase TiCu field was e x a m i n e d by
n e a r the equiatomic composition: a t e t r a g o n a l B 11 phase [51Kar, 66Ere]. On the Ti-rich side, the two reports are

84 B u l l e t i n of Alloy Phase D i a g r a m s Vol. 4 No. 1 1983

 Provisional Cu-Ti

consistent: 48 at.% [66Ere], 47 at.% [51Karl. On the [53Trz] and [66Ere] agreed that a solid state transforma-
Cu-rich side, the data of [51Karl must be discarded be- tion occurs about 20 ~ below the eutectic, and that another
cause reaction with the crucible caused contamination. transformation occurs in the solid state at about the same
Therefore, data of [66Ere] have been used, and the maxi- temperature as the eutectic and between about 60 and
mum width of TiCu has been set to 48 to 52 at.% Cu. 67 at.% Cu. Finally, [65Sch] found that, at 850 ~ TiCu4 is
in equilibrium with Ti2Cu3.
Composition Range 55 to 75 at.% Cu. Between the con- Given the reaction types and compositions, and the com-
gruent melting point of TiCu and the eutectic reaction positions of the intermetallic compounds, one can now
at 73 at.% Cu, there occurs a cascade of peritectic reac- show that the phase diagram must have the topology given
tions involving the compounds Ti3Cu4, Ti2Cu3, TiCu2, and
by [65Sch, 66Ere]. Other constructions, such as that of
TiCu4. These peritectic reactions and additional solid [53Trz], require the omission of a compound. For the reac-
state reactions obscure the existence of several inter- tion temperatures, the data of [53Trz] are consistently
metallic compounds and make interpretation of micro-
higher than those of [66Ere]. Preliminary DSC results of
structures difficult.
[82Shu] favor the higher reaction temperatures. Errors of
-+10 ~ are attached to the temperatures given in Table 1,
[65Sch] and [66Ere] made consistent structural identifica-
but the differences between temperatures of the various
tions of the phases Ti3Cu4, Ti2Cu3, and TiCu2. In addition,
reactions are better known.
the phase initially identified as TiCu3 was shown to exist
over a range of compositions near TiCu4 [79Eco, 63Pie,
66Ere]. [62Zwi] postulated a congruently melting com- TiCu4. The stoichiometry TiCu3 was first attributed to the
pound Ti3Cu7 based on optical observations of melting phase here designated TiCu4 [39Lav, 51Kar, 52Jou, 53Trz].
points and metallographic data. This compound has [51Karl attributed to this phase ordered and disordered
forms, and a composition range of 75 to 79 at.% Cu. Later
not been subsequently verified, and reactions involving
X-ray work clearly showed that the alloys at 75 at.% Cu
Ti3Cu7 have not been included in Table 5.
contained two phases, Ti2Cu3 and TiCu4 [68Van, 69Sin].
[66Ere] reported the composition range of TiCu4 as 78
By means of etching studies and microprobe analysis of
to 80 at.% Cu. [66Van] and [62Zwi] measured the com-
as-cast samples, [63Pie] identified the compositions of the
liquid in the series of three-phase equilibria. Peritectic position of TiCu4 in equilibrium with Ti2Cu3 as 78.9
reactions occurred at 62.5, 71, and 77 at.% Cu, and a and 77.8 at.% Cu, respectively. [79Eco] determined the
composition of TiCu4 in equilibrium with (Cu) as 80.9 at.%
eutectic reaction occurred at 73 at.% Cu. Between 62.5
Cu. The composition range, therefore, is taken as 78 to
and 73 at.% Cu, therefore, two compounds form from the
80.9 at.% Cu.
melt. TiCu4 was shown as melting congruently by [58Vig,
53Trz]; however, the microprobe and metallographic work [66Zwi] found that contamination by oxygen tends to
of [52Jou, 66Ere, 63Pie] showing TiCu4 as forming by a stabilize TiCu4 at compositions that are enriched in Ti.
peritectic reaction are preferred. Because the alloys used by [51Karl suffered significant

Table 5 Reaction Temperatures Between 60 and 76 at.% Cu

Temperature, Composition,
Reaction Reference ~ ~pe at.% Cu(a)
TiCu + L ~ Ti3Cu4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [66Ere] 918 Peritectic 62.5 -+ 0.5
[52Jou] 916 Peritectic
[53Trz] 935 Peritectic
Ti3Cu4 + L ~ TiCu~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [66Ere] 878 Peritectic 71 -+ 1
[52Jou] -880 Undetermined
[53Trz] 892 Peritectic
[66Zwi] 895 Eutectic
L ~ TiCu2 + TiCu4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [66Ere] -860 Eutectic 73 -+ 1
[52Jou] -873 Eutectic
[53Trz] 880 Eutectic
[66Zwi] 898 Eutectic
[52Rau] 875 Eutectic
Ti3Cu4 + TiCu2 ~ Ti2Cu3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [66Ere] 865 Peritectoid ...
[53Trz] 885 Peritectoid
[52Jou] -875 (b)
[65Sch] >870 Peritectoid
TiCu2 ~ TiCu4 + Ti2Cu3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [66Ere] 850 Eutectoid ...
[53Trz] 872 Eutectoid
[66Zwi] 865 Eutectoid
[65Sch] >860 -+ 10 Eutectoid
[69Sin] >850 Eutectoid
L + (Cu) ~ TiCu4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [66Ere] 870 Peritectic 77 -+ 1
[66Zwi] -925 Peritectic
[53Trz] 895 Eutectic
[52Jou] 885 Peritectic
[52Rau] 890 Peritectic
[58Vig] 870 Eutectic
(a) From [63Pie]. (b) Uninterpreted thermal arrests.

Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983 85

Cu-Ti Provisional

Table 6 Experimental Data on the (Cu) Liquidus and Solidus

Liquidus Solidus
Temperature, Composition, Temperature, Composition,
Reference ~ at.% Cu ~ at.% Cu Method
[66Ere] . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1037 95.6 953 94.9 Thermal analysis
1019 89.4
958 83.9
939 83
909 79.7
886 75.9
877 73.6
870(a) ""
[52Rau] . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060 96.7 900 95.7 (95.1) Liquidus by thermal analysis
1040 91.2 925 (95.8)
1022 90.7 950 96.6
1016 87 1000 (97.9) Solidus by X-ray
1012 85.5 1050 (>98.8) (metallography)
960 83.1
1006 80.2
890(a) ""
[53Trz] . . . . . . . . . . . . . . . . . . . . . . . . . . . . 930 80 . . . . . . Thermal analysis
1016 90.1
1050 94.2
895(a) "'
[52Jou] . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1000 81.2 . . . . . . Thermal analysis
950 75
885(a) ""
[59Saa]. . . . . . . . . . . . . . . . . . . . . . . . . . . . 967 92.5 . . . . . . Metallography, error
970 93.9 estimated as -+15 ~
987 95
992 96.1
1012 97.8
>900(a) ""
[66Zwi]. . . . . . . . . . . . . . . . . . . . . . . . . . . . -925(a) 75 . . . . . . X-ray, metallography
[58Vig]. . . . . . . . . . . . . . . . . . . . . . . . . . . . 870(a) . . . . . . . . .
[31Kro] . . . . . . . . . . . . . . . . . . . . . . . . . . . 9. . . . . 900(a) 95 Thermal analysis
[32Hen] . . . . . . . . . . . . . . . . . . . . . . . . . . . 878(a) . . . . . . . . . . . .
(a) Peritectic temperature.

reaction with silica tubes, this may explain the discrep- treated at 900 ~ solidus and solvus data of [59Saa] sug-
ancy of their data. [79Eco] did not verify an order/disorder gest that the maximum solubility is unrealistically large:
transition, but found that variation in the degree of order approximately 11 to 15 at.% Ti. It may be that the alloys
occurs depending on the method of preparation. of [59Saa] were contaminated with oxygen, in light of the
work of [66Zwi], which showed an increase in the Ti solu-
(Cu) Liquidus, Solidus, and Solvus. The assessed liquidus bility in (Cu) with oxygen content.
and solidus curves are approximately straight lines be-
tween the melting point of Cu and the end compositions of The maximum solubility of Ti in (Cu) is 8 -+ 1 at.%, and
the peritectic reaction at 890 -+ 10 ~ 77 and 92 at.% Cu. the solubility decreases to less than 0.1 at.% at 400 ~
Pure Cu melts at 1084.84 ~ [81BAP]. Thermal analysis Data on the (Cu) solvus are given by [59Saa, 63Hah,
data on the (Cu) liquidus were given by [52Rau, 53Trz, 62Zwi, 52Rau, 53Trz, 60Kal, 58Vig] (Table 7). At tempera-
52Jou, 66Ere] (Table 6). In the range 0 to 19 at.% Ti, the tures below 600 ~ lower solubilities [62Zwi, 63Hah] are
data of [52Jou, 53Trz, 66Ere] define a smooth curve, with preferred. The solvus, Fig. 1, is the result of the present
an uncertainty of -- 15 ~ The data of [52Rau] lie above thermodynamic calculations in which the Gibbs energy
this curve, but are not qualitatively inconsistent with it. of TiCu4 was optimized with respect to the solvus data of
Beyond 19 at.% Ti, liquidus data of [52Jou, 52Rau, 31Kro] [62Zwi, 63Hah].
lie about 70 ~ above the data of [66Ere, 53Trz]. These
anomalously high melting points would require the peri-
tectic reaction at 77 at.% Cu to occur above 950 ~ contrary Metastable Phases
to all observations; therefore, they have been rejected. Cu-rich alloys have long been known to age-harden [31Kro,
The composition of the liquid at the peritectic temperature 31Sch, 59Saa]. Following [75Lau], the accepted descrip-
is based on the metallographic and microprobe examina- tion of the kinetics of decomposition of the supersaturated
tion of as-cast alloys by [63Pie]. [63Pie] determined the (Cu) solid solution is: a solid solution containing more than
composition at which the primary phase changes from about 4 at.% Ti begins to undergo spinodal decomposition
(Cu) to TiCu4. Solidus data were reported by [59Saa, into Ti-enriched and -depleted disordered phases during
66Ere, 52Rau] and show significant discrepancies. In quenching [73Cor, 75Lau]. In the early stages of aging,
particular, the data of [59Saa] imply that the solidus has sidebands (or satellite reflections) in electron or X-ray dif-
an inflection, for which no physical or thermodynamic fraction data indicate the presence of a periodic lattice
explanation can be given. Except for a single alloy heat strain due to oriented, coherent particles; i.e., composition

86 Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983

 Provisional Cu-Ti

waves in the (100) direction [59Man, 62Heu, 66Sat, 81Ciz, [59Man, 72Mic, 73Cor, 74Lau1]. Ti-rich clusters are also
76Dat]. After a critical composition of the Ti-rich clusters observed in alloys c o n t a i n i n g less t h a n 4 at.% Ti, b u t
is reached, ordering begins. [75Lau] t e n t a t i v e l y ascribed ordering does not occur in t h e e a r l y stages of decompo-
the L l o structure to an e a r l y t r a n s i t o r y precipitate; a D l o sition. [59Doi] studied t h e effect of aging t r e a t m e n t on
s t r u c t u r e forms as a p e r s i s t e n t m e t a s t a b l e c o m p o u n d microstructure; [72Mic, 73Cor] c o r r e l a t e d m i c r o s t r u c t u r e
[71Hak, 73Kni, 7 4 L a u l , 74Lau2, 75Lau]. The m e t a s t a b l e and m e c h a n i c a l properties.
ordered precipitates a r e coherent w i t h the fcc m a t r i x and
form i n s i t u from t h e d i s o r d e r e d p r e c i p i t a t e . F i n a l l y , E x p e r i m e n t a l d a t a on t h e coherent solvus a n d spinodal
i n c o h e r e n t TiCu4 is f o r m e d as t h e e q u i l i b r i u m p h a s e a r e s u m m a r i z e d in Table 8 a n d plotted in Fig. 2. Concern-
ing t h e coherent solvus, which is t h e (Cu)/((Cu) + D l a )
Table 7 Experimental Data on the (Cu) Solvus boundary, no discrepancy h a s been reported w i t h the w o r k
of [71Hak, 7 4 L a u l , 75Lau]. C o n c e r n i n g t h e s p i n o d a l ,
Temperature, Composition, however, t h e r e are discrepancies.
Reference ~ at.% Ti Method
[59Saa] . . . . . . . 675-700 2.2 Metallography [ 7 5 L a u ] p l a c e d t h e s p i n o d a l a b o u t 35 ~ b e l o w t h e
750-775 3.9 c o h e r e n t solvus. [75Lau] b r a c k e t e d t h e s p i n o d a l t e m -
805-830 5.0 p e r a t u r e by c o m p a r i n g m i c r o s t r u c t u r e s of alloys aged a t
825-850 6.1 a t e m p e r a t u r e t h a t was reached by up-quenching from
850-875 7.5 room t e m p e r a t u r e to m i c r o s t r u c t u r e s of alloys aged a t
[53Trz] . . . . . . . 300 1.4 Lattice parameters the s a m e t e m p e r a t u r e , b u t a p p r o a c h e d from a previous
6OO 2.5
870 6_5 aging t e m p e r a t u r e above t h e c o h e r e n t solvus. [75Lau]
[60Kal] . . . . . . . 800 5_6 Metallography used the coarseness of the m o d u l a t e d microstructure a s
75O 4_2 an indication of w h e t h e r t h e alloy passed t h r o u g h t h e
6OO 1.3 spinodal before the final quench. [74Dut, 75Vail, on t h e
5OO -0.4 other hand, used only a g i n g t r e a t m e n t s at single t e m p e r a -
[52Rau] ... 400 0.5 X-ray (values in tures. [74Dut, 77Dut, 78Dut] d i s t i n g u i s h e d b e t w e e n a
5OO 0.8 parentheses), plate-like vs a m o d u l a t e d m i c r o s t r u c t u r e to roughly esti-
6OO 1.6 (1.2) microscopy m a t e the spinodal curve. [75Vai] considered the absence of
7OO 2.3 (2.5) p r e c i p i t a t e - f r e e zones n e a r g r a i n b o u n d a r i e s a t e s t of
8OO 3.9 (3.9)
85O 5.1 (4.8) w h e t h e r spinodal decomposition h a d occurred. The work of
[63Hah] . . . . 700 1.7 Electrical resistivity [75Lau] is preferred as a b e t t e r m e a s u r e of w h e t h e r a n
6OO 1.0 alloy h a s passed t h r o u g h t h e spinodal. [73Tsul, 73Tsu2]
50O 0.5 placed t h e spinodal a t considerably lower t e m p e r a t u r e s
4OO O.35 t h a n [75Lau] by m e a n s of s m a l l - a n g l e X-ray scattering.
[62Zwi] . . . . . . 895 7.2 Electrical conduc- The discrepancy between [73Tsul, 73Tsu2] and [75Lau]
85O 5.9 tivity, m a y be caused e i t h e r by double B r a g g s c a t t e r i n g or by a
7OO 2.0 metallography failure of t h e l i n e a r spinodal t h e o r y for the e x p e r i m e n t
50O 0.4 done by [73Tsul, 73Tsu2].
[58Vig] . . . . . . 300 1.5 Hardness, electrical
40O 1.6 resistivity Ti-Rich A l l o y s . Ti-rich (flTi) t r a n s f o r m s m a r t e n s i t i c a l l y to
5OO 20
6OO 2.5 the cph s t r u c t u r e d u r i n g quenching. The addition of Cu to
7OO 3.3 (flTi) does not cause the bcc s t r u c t u r e to be r e t a i n e d after
8OO 56 quenching a t any composition [73Zan, 7 0 W i l l , 70Wil2].
85O 7.9 This f e a t u r e is u n u s u a l in alloys of Ti w i t h / 3 - s t a b i l i z i n g
87O 9.6 elements; it occurs because of diffusional decomposition
9OO 6.7 processes t h a t are r a p i d in bcc (/3Ti). The m a r t e n s i t e h a s
95O 4.5 a massive m i c r o s t r u c t u r e for compositions between 0 a n d
[51Kar] . . . . . . ... 6.5 Maximum solu- 3.8 at.% Cu, and an a c i c u l a r morphology at g r e a t e r Cu
bility, lattice
parameters content [ 7 0 W i l l , 70Wil2]. [60Sat] m e a s u r e d the M~ ( s t a r t
t e m p e r a t u r e s ) of the m a r t e n s i t i c /3---)a t r a n s f o r m a t i o n :

Table 8 Coherent Solvus and Spinodal (Cu-Rich Alloys)

Coherent solvus Spinodal
Composition, Temperature, Composition, Temperature,
Reference at.% Ti vC at.% Ti ~ Method
[74Lau, 75Lau] ............................ 1.3 510 3.9 -710 Reversion (TEM)
2.0 640 . . . . . .
4.0 735 . . . . . .
6.7 790 . . . . . .
[75Vai] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2 720 . . . . . . TEM
[76Nis] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9. . . . . 4.2 >500 --.
[76Dat] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9. . . . . 5.2 400-500 --.
[73Tsu, 73Tsu2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9. . . . . 5.2 350
[74Dut, 77Dut] . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9. . . . . 2.0 -300 TEM
3.0 -450
4.0 -575
5.0 -630

Bulletin of Alloy P h a s e D i a g r a m s Vol. 4 No. 1 1983 87

Cu-Ti Provisional

Fig. 2 Metastable Phase Equilibria in Cu-Rich Alloys

Weight Percent Copper

lO 20 3o 4o ~o 6o To so 9o loo
,:.~:.b,(., ..... I..,,....I ..... ~..,I ...... ,,,I ...... ,,.J ...... ,.,.I ..... , .... J .... , ...... J.,, . . . . . .
ltY/U u
"-. SUPERSATURATED(Cu)
"9 El = 7 5 L a u : C o h e r e n t solvus
~-~ o =- 7 5 L a u : S p i n o d a l
151111 9~ a =- 74Dut: Spinodal
"4. AMORPHOUSALLOYS
"" + ~ 81Sak: Crystallization temp.
9, x ~ 82Woy: Crystalhzat]on temp.
It ",

0 ,, ".. L
1100 ~ I083~
9 1{]05 C 9
(flTi) /2-...............F - ' ~ ' ~ ~

[.-,
70o r II FI
500

o 1o zo 3o 4o ~o 8o To 8o 9o lOO
Ti Atomic Percent Copper Cu
Solid lines are equilibrium boundaries; dashed line is the metastable, coherent solvus ((Cu)/(Cu) + D1.) boundary; dotted line is the spinodal.
Data points are the crystallization temperature of the glass. J.L. Murray, 1983,

(3.6 at.% Cu, 700 ~ (5.6 at.% Cu, 600 ~ (7.4 at.% Cu, Table 9 Crystallization Temperatures
500 ~ (9.0 at.% Cu, 400 ~ of Amorphous Alloys
Age-hardening occurs in supersaturated (aTi) produced Crystallization
either by quenching from the single-phase (aTi) region or Composition, temperature,
by the martensitic transformation. Precipitation of Ti2Cu Reference at.% Cu ~
takes place by two processes: (a) heterogeneous nuclea- [81Sak) . . . . . . . . . . . . . . . . . . . 31 357
tion and growth of Ti2Cu at dislocations, and (b) uniform 35 366
nucleation of thin plates or discs of a coherent Cu-rich 39 384
i n t e r m e d i a t e precipitate [71Wil]. The fully coherent 43 407
precipitate has the cph structure. The first precipitates 50 407
58 428
appear as thin discs 3 to 4 nm in their maximum dimen- 66 424
sion. As the particles grow without thickening, coherency 70 419
is partially lost, first on the edge of the disc, then on the 72 404
fiat faces. At this stage, the precipitate can be identified 75 354
as Ti2Cu by selected area diffraction. The ordering reac- [82Woy] . . . . . . . . . . . . . . . . . . . 35 380
tion occurs in situ rather than by redissolution of the 43 395
intermediate phase [71Wil, 70Lue]. 50 430
60 420
Additional work on microstructures and mechanical prop- 66.7 360
erties as a function of tempering, aging, or cooling rate was [79Sak] . . . . . . . . . . . . . . . . . . . 66.7 403(a)
done by [55Hol, 73Zan, 76Zan]. [80Pel] compared the de- (a) Glasstransition temperature.
composition kinetics of s u p e r s a t u r a t e d cph solutions
formed by quenching from the (aTi) region to those of
martensitically transformed fl by means of thermoelectric technique [81Sak, 82Woy]. Crystallization temperatures
power and TEM measurements. are listed in Table 9. The local structure of the glass was
studied primarily by neutron diffraction and also by X-ray
Rapid Solidification. [68Ray] reported the formation of a diffraction and EXAF techniques [79Sak, 80Rao, 80Sak,
noncrystalline phase in splat-quenched alloys in the com- 81Sak, 81Fuk]. An unusual "pre-peak" in the structure
position range 65 to 70 at.% Cu. [73Po]] also showed that factor was observed by all investigators and attributed to
by splat quenching, glassy alloy films could be prepared in chemical short-range order. [81Sak] also observed similar,
the composition ranges 36 to 44 and 59 to 67 at.% Cu. It but less intense, ordering in the liquid phase. On the basis
was later observed that glasses could be formed over the of correlation distances, [80Rao] compared the short-range
range 30 to 75 at.% Cu using the chill-block melt-spinning ordered structure to that of TiCu2.

88 Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983

 Provisional Cu-Ti

Metastable crystalline phases were also observed in rap- structure. The body-centered and face-centered tetragonal
idly solidified alloys. [71Gie] found a metastable phase, cell parameters are related as:
TiCu3(m), which is distinct from the equilibrium com-
pounds. The solid solubility of Ti in (Cu) can be extended Cbct = 3Cfet
to 20.2 at.% Ti, according to [73Pol], or to 17 -+ 2 at.% Ti, a~r = 2 a~t
according to [71Gie]. [75Pol] found that the bcc solid solu-
tion is the first crystalline phase to form upon heating TiCu. [51Kar] found two phases of near-equiatomic com-
amorphous alloys (after 10 min at 300 ~ position: the Ti-rich structure was B 11, and the Cu-rich
structure was CuAuI. The Llo structure has not been
Crystal Structures and Lattice Parameters verified by any subsequent investigation; the B 11 struc-
ture has been generally accepted as the equilibrium
The crystal structures of the equilibrium and meta- structure [66Ere].
stable phases are summarized in Table 10; more detailed
structural information and lattice parameters for the com-
Ti3Cu4, Ti2Cu3, and TiCu2. The structures of Ti3Cu4 and
pounds are given separately in Tables 11 and 12, re-
Ti2Cu3 have been fully determined. A disagreement be-
spectively. The crystal structures fall into the following
tween [65Sch] and [66Ere] on Ti2Cu3 stemmed partly from
classes: the orthorhombic structures TiCu2 and TiCu4, ap-
a misinterpretation of the abbreviated description of
proximating twelve-fold coordination, and the tetragonal
the structure given by [64Sch, 65Sch]. [65Sch] detected
structures Ti2Cu, TiCu, Ti3Cu4, and Ti2Cu3, approximat-
diffraction lines that would not be allowed if the struc-
ing eight-fold coordination.
ture chosen by [66Ere] were correct: Therefore, we have
Ti2Cu. Three problems that originally confused the identi- chosen the structure reported by [65Sch]. [65Sch, 66Ere,
fication of the structure of Ti2Cu were: (a) identifications 68Pfe] all attributed to Ti2Cu the tetragonal Au2V struc-
of the stoichiometry as Ti3Cu rather than Ti2Cu [52Jou, ture; no complete determination of atom positions has
67Gan], (b) the appearance of a ternary oxide phase, and yet been made.
(c) the difficulty of recognizing the equilibrium structure
using X-ray diffraction. [39Lav] found a phase, Ti2Cu, TiCu4 and TiCu3(m). [51Kar] thought that the equilibrium
with the ordered fcc Fe3W3C structure. [51Kar] found a compound richest in Cu had the stoichiometry TiCu3 and
face-centered tetragonal phase in the binary alloy, and the composition range 75 to 79 at.% Cu. [71Gie] discovered
Fe3W3C structure only as the ternary phase Ti3Cu30, with that a metastable phase TiCu3(m) formed during rapid
a large solubility of Ti in it. [52Ros], however, concluded solidification. The symmetry is the same as that found
that the Fe3W3C structure belongs to a true binary phase. by [51Kar], but the s t r u c t u r e has been s e p a r a t e l y
[61Enc, 70Lue] verified the face-centered tetragonal struc- tabulated, because the unit cell found by [71Gie] differs
ture; the X-ray data of [52Jou] are consistent with the significantly in shape from the [51Kar] cell.
same fct lattice [61Enc]. [62Mue, 63Mue] discovered addi- The structure determinations of TiCu4 by [68Pfe, 69Sin]
tional low-angle forward reflecting lines in the X-ray are given in Tables 10 and 11. The unit cell upon which
diffraction pattern that could not be attributed to the fct the structure is indexed differs from the one that was origi-
structure. Because the X-ray scattering amplitudes of Ti nally proposed by [51Kar], and that is still often used to
and Cu are not too far apart, the structure of Ti2Cu is describe the lattice [72Mic, 76Vai, 77Dut]. The unit cells
difficult to determine unambiguously using X-ray diffrac- are related by:
tion; neutron scattering was used to unambiguously iden-
tify the structure as MoSi2. [71Wil] verified the MoSi2 C[51Kar] ---~ 0.4C[68Pfe]

Table 10 Ti-Cu Crystal Structure Data

Stability Pearson Strukturbericht
Phase range, at.% Cu symbol designation Space group Prototype Type Source
Equilibrium phases
(aTi) . . . . . . . . . . . . . . . . . . . . . . 0-1.6 hP2 A3 D~hP63/mmc Mg Hexagonal -..
(/3Ti) . . . . . . . . . . . . . . . . . . . . . . 0-13.5 c/2 A2 09hIm3m W Cubic ...
(Cu). . . . . . . . . . . . . . . . . . . . . . . 100-92 cF4 A1 05hFm3m Cu Cubic ...
Ti2Cu . . . . . . . . . . . . . . . . . . . . . 33.3 tI6 Cllb D~hI4/mmrn MoSi2 Tetragonal [63Mue]
TiCu . . . . . . . . . . . . . . . . . . . . . . 48-52 tP4 B 11 D74hP4/nmm TCuTi Tetragonal ...
Ti3Cu4 . . . . . . . . . . . . . . . . . . . . 57.1 t/14 ... D~TI4/mmm Ti3Cu4 Tetragonat [65Sch]
Ti2Cu3 . . . . . . . . . . . . . . . . . . . . 60 tP 10 ... DThP4/nmm Ti2Cu3 Tetragonal [65Sch]
TiCu2 . . . . . . . . . . . . . . . . . . . . . 66.7 oC 12 ... 14A m m 2
C2v Au2V Orthorhombic [65Sch]
TiCu4 . . . . . . . . . . . . . . . . . . . . . 78-80.9 mP20 ... D~2Pnma Au4Zr Monoclinic [68Pfe]
Metastable phases
/3' . . . . . . . . . . . . . . . . . . . . . . . . ... t/10 D la C54h14/m MoNi4 Tetragonal [75Lau]
TiCu3 . . . . . . . . . . . . . . . . . . . . . .-- oP8 DOa D~2Pmnm flCu3Ti Orthorhombic [71Gie]
/3" 9. . . . . . . . . . . . . . . . . . . . . . . "" tP2 Llo D~hP 4 / m m m AuCuI Tetragonal [75Lau]
Other structure identifications not accepted in this evaluation
Ti2Cu3 . . . . . . . . . . . . . . . . . . . . ... tIlO ... D~14/mmm -.. Tetragonal [66Ere]
TiCu3(/3) . . . . . . . . . . . . . . . . . . ... oC4 ... C~Cmc21 /3'Cu3Ti Orthorhombic [51Kar]
/3'TiCu3 . . . . . . . . . . . . . . . . . . . ... oP8 ... D~,Pmmn /3Cu3Ti Orthorhombic [51Kar]
TiCu . . . . . . . . . . . . . . . . . . . . . . ... tP2 Llo D~hP4/mmm AuCuI Tetragonal [51Kar]

Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983 89

 Cu-Ti Provisional

Table 11 Detailed Structures of Compounds

Phase A t o m positions Coordinates Parameter Reference
Ti3Cu4 . . . . . -. . . . . . . . . . . . . . . . . . . . . . . . . . 2 Ti (a) (0 0 0) [65Sch, 66Ere]
4 Ti (e) (0 0 z) (0 0 -z) 0.295
4 Cu (e) (0 0 z) (0 0 -z) 0.135
4 Cu (e) (0 0 z) (0 0 -z) 0.430
Ti2Cu3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Ti (c) (0.25 0.25 z) (0.75 0.75 -z) 0.145 [65Sch]
(0.25 0.25 z) (0.75 0.75 -z) 0.565
6 Cu (c) (0.25 0.25 z) (0.75 0.75 -z) 0.955
(0.25 0.25 z) (0.75 0.75 -z) 0.755
(0.25 0.25 z) (0.75 0.75 -z) 0.335
TiCu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Cu (e) (0 0.5 z) (0.5 0 -z) 0.1 [51Kar, 66Ere]
2 Ti (e) (0 0.5 z) (0.5 0 -z) 0.65
Ti2Cu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Cu (a) (0 0 0) (0.5 0.5 0.5)
4 Ti (e) (0 0 z) (0.5 0.5 0.5 + z) 0.339 [62Mue, 63Mue]
(0 0 -z) (0.5 0.5 0.5 - z)
TiCu3(m) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Ti (a) -+(0.25,0.5 + z, 0.25) 0.19 -+ 0.02 [71Gie]
2 Cu (b) -+(0.75,0.5 - z, 0.25)
4 Cu (f) -+(x,z, 0.25), -+(x + 0.5, -z,0.25) x - 0

Table 12 Lattice Parameters of Compounds Table 13 Lattice Parameters of (Cu)

Lattice p a r a m e t e r s , n m Lattice
Phase Reference a b c Composition, parameter,
Reference at.~ Ti a
Ti2Cu . . . . . . [66Ere] 0.2943 ... 1.0784
[53Trz] . . . . . . . . . . . . . . . . . . . . . . . . . 0.48 0.3616
[62Mue] 0.2944 ." 1.0786
1.0 0.3617
[70Ble] 0.295 ... 1.078
3.15 0.3625
[61Enc] 0.2944(a) ... 1.083
4.0 0.3627
[63Mue] 0.29438 "" 1.07861
5.78 0.3640
-+0.00000 ... -+0.00001
0.3107 ... 0.5919 [51Kar] . . . . . . . . . . . . . . . . . . . . . . . . 0 0.3609
TiCu . . . . . . [66Ere]
5.0 0.3616
[51Kar] 0.3108 ... 0.5887
6.5 0.3620
Ti3Cu4 .... [66Ere] 0.3126 -.- 1.9964
[70Kru] . . . . . . . . . . . . . . . . . . . . . . . . 0 0.36150
[65Sch] 0.312 -.. 1.994
1.19 0.36179
Ti2Cu3 . . . . [65Sch] 0.313 ... 1.395
2.46 0.36255
[66Ere] 0.3140 ... 1.3962
3.51 0.36306
[68Pfe] 0.3137 ... 1.4024
4.65 0.36352
TiCu2 . . . . . [65Sch] 0.438 0.797 0.449
6.25 0.36389
[66Ere] 0.4363 0.7997 0.4478
7.77 0.36421
[68Pfe] 0.437 0.795 0.448
0.4522 0.4344 1.2897 [62Heu] . . . . . . . . . . . . . . . . . . . . . . . . 4.3 0.3636
TiCu4 . . . . . [66Ere]
4.5 0.3634
[79Eco] 0.453o~1 0.4342+~ 1.293o~3
5.0 0.3633
[66Van] 0.4531 0.4343 1.2929
0.4503 0.4313 1.2860 [52Rau] . . . . . . . . . . . . . . . . . . . . . . . . 0.97 0.36158
[51Kar](b)
1.35 0.36160
[62Heu](b) 0.450 0.436 1.28
2.05 0.36163
[69Sin] 0.4526 0.4345 1.2924
0.4530 0.4342 1.2930 2.85 0.36169
[68Pfe]
3.25 0.36171
[76Vail(b) 0.4503 0.4313 1.2860
[60Nes] . . . . . . . . . . . . . . . . . . . . . . . . 5.9 0.3620
TiCu3(m)... [71Gie] 0.5450 0.4426 0.4307
[56Sim] . . . . . . . . . . . . . . . . . . . . . . . . 0.6 0.3618
TiCu4(m)... [74Lau2] 0.584 ... 0.362
0.9 0.3620
(a) Converted from fct to bct cell. (b) Converted from [51Karl cell. 2.5 0.3624
3.8 0.3629
4.0 0.3630
U s i n g s e v e r a l e l e c t r o n m i c r o s c o p y t e c h n i q u e s , [79Eco] 5.1 0.3635
v e r i f i e d t h a t t h e s t r u c t u r e s h o u l d be i n d e x e d on t h e l a r g e r [73Poll . . . . . . . . . . . . . . . . . . . . . . . . . 20.2 3.703
u n i t cell. M o d i f i c a t i o n s to t h e p o s i t i o n s of a t o m s w i t h i n t h e
u n i t cell, p r o b a b l y a c l u s t e r i n g of Ti a t o m s w i t h i n t h e cell,
a r e r e q u i r e d in o r d e r to fully e x p l a i n t h e [79Eco] T E M Lattice parameters of t h e (Cu) solid s o l u t i o n a r e g i v e n in
d a t a . [80Eco] g a v e a d d i t i o n a l i n f o r m a t i o n on i n t r i n s i c Table 13. L a t t i c e p a r a m e t e r s m e a s u r e m e n t s for (aTi) w e r e
d i s o r d e r a n d c o m p l e x f a u l t s w i t h i n t h e TiCu4 s t r u c t u r e , m a d e by [70Ble] as a f u n c t i o n of s o l u t i o n t e m p e r a t u r e
v e r i f y i n g t h e o r i g i n a l o b s e r v a t i o n by [ 5 1 K a r l of d i f f e r e n t r a t h e r t h a n composition; (flTi) l a t t i c e p a r a m e t e r s h a v e
d e g r e e s of o r d e r d e p e n d i n g on t h e h e a t t r e a t m e n t . n o t b e e n m e a s u r e d b e c a u s e (flTi) c a n n o t be r e t a i n e d
m e t a s t a b l y to r o o m t e m p e r a t u r e .
T i C u 4 ( m ) . [73Kni] a t t r i b u t e d a n L12 s t r u c t u r e to t h e i n t e r -
mediate ordered precipitate from the supersaturated
(Cu) solution. [ 7 1 H a k , 7 4 L a u 2 , 7 5 L a u ] d e m o n s t r a t e d t h a t Thermodynamics
t h e correct s t r u c t u r e is D I , , a n d t h a t t h e o b s e r v a t i o n s of
[73Kni] also a r e c o n s i s t e n t w i t h t h i s s t r u c t u r e . [60Nes, E x p e r i m e n t a l t h e r m o d y n a m i c d a t a a r e s u m m a r i z e d in
6 2 H e u ] r e p o r t e d a n fct i n t e r m e d i a t e p h a s e w i t h q u i t e dif- Table 14. T h e d a t a f r o m [ H u l t g r e n ] on t h e bcc p h a s e a r e
ferent lattice parameters. based on o n l y two T i - r i c h compositions, a n d t h e experi-

90 B u l l e t i n of A l l o y P h a s e D i a g r a m s Vol. 4 No. 1 1983

 Provisional Cu-Ti

Table 14 Experimental Thermodynamic Data on Integral Excess Quantities

Value, Temperature, Composition
Reference Function J/mol K r a n g e , at.% Cu Method
[Hultgren] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . gL(a) -270 -+ 1000 1800 7-14 Mass spectrometry
g, trri,(a) 7 050 -+ 1000 1473 7-14
[82Kle] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . HL(mix) - 2 950 1373 30 Calorimetry
-3150 35
~3 370 39.2
- 3 490 44.8
- 3 740 50.2
- 4 210 50
- 3 810 50
- 3 720 54.8
- 4 030 60.0
- 3 420 64.7
-3170 69.2
- 2 560 74.8
- 2 020 80.4
-930 90.6
-533 94.6
-298 96.7
- 102 98.9
[80Gac] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . g~cu,(a) -245 000 1140 98 Solid cell emf
(a) gi = G~s/x(1 - x).

Table 15 Heats of Formation, J/mol, [79Ari] m e a s u r e d the p r e s s u r e of h y d r o g e n in e q u i l i b r i u m

J/mol 9 K, at 773 K with Ti-Cu compounds and t h e i r h y d r i d e s to d e t e r m i n e
activities in t h e hydrogen-free alloys. S t a n d a r d e n t h a l p i e s
S t a n d a r d free and entropies of TiCu4, TiCu, and Ti2Cu were reported.
e n e r g y of Free e n e r g y
Phase Reference formation (L as R e f e r e n c e )
Zero e n t r o p y of f o r m a t i o n was r e p o r t e d for TiCu4 a n d
TiCu. In Table 14, the o r i g i n a l s t a n d a r d Gibbs energies
TiCu4 . . . . . . [79Ari] -22600 -+ 900 -19080 + 10.13 T of formation a r e t r a n s f o r m e d to t h e corresponding com-
[78Kau] -18945 + 10.88 T pound Gibbs energies referenced to t h e liquid state a n d
[This work] -23428 + 14.13 T
TiCu . . . . . . . [79Ari] -18800 § 300 -26219 + 10.88 T compared to the compound Gibbs e n e r g i e s calculated from
[78Kau] -24456 + 10.88 T the phase d i a g r a m .
[This work] -20368 + 7.30 T
Ti2Cu . . . . . . [79Ari] -26300 +- 200 -26841 + 11.30 T
[78Kau] -23 131 + 10.09 T Thermodynamic Calculations
[This work] - 2 4 702 + 11.39 T Previous t h e r m o d y n a m i c calculations of the Ti-Cu system
were done by [70Kau, 78Kau]. [70Kau] used t h e r e g u l a r
s o l u t i o n a p p r o x i m a t i o n for a l l t h e s o l u t i o n p h a s e s ;
m e n t a l u n c e r t a i n t y is c o m p a r a b l e to the m e a s u r e d quan- [78Kau] used additional a s y m m e t r y t e r m s in t h e inter-
tities themselves. action Gibbs energies. We h a v e done f u r t h e r calculations
in order to compare Gibbs e n e r g y functions w i t h the most
[81Yok] and {82Kle] m a d e calorimetric i n v e s t i g a t i o n s of
recent t h e r m o d y n a m i c d a t a a n d the p r e s e n t a s s e s s m e n t
the e n t h a l p y of m i x i n g of liquid alloys at 1373 K in the
of the d i a g r a m , and to predict the (flTi) liquidus, which
composition r a n g e 30 to 100 at.% Cu. The two studies
has not been e x p e r i m e n t a l l y d e t e r m i n e d . As a f u r t h e r ap-
differ in two respects:
plication of t h e r m o d y n a m i c calculations, Gibbs e n e r g y
9 E n t h a l p i e s of m i x i n g of the Ag-Cu system were used for functions provide the s t a r t i n g point for modeling of t h e
calibrations by [81Yok]; [82Kle] r e m e a s u r e d t h e Ag-Cu m e t a s t a b l e phase equilibria. F o r t h e o r e t i c a l work on t h e
system and corrected t h e Ti-Cu results of [81Yok]. formation of a m o r p h o u s alloys, t h e r m o d y n a m i c calcula-
9 After recalculation of the h e a t s m e a s u r e d by [81Yok], tions provide e x t r a p o l a t i o n s of To curves to low t e m p e r a -
t h e r e were s t i l l u n e x p l a i n e d d i s c r e p a n c i e s b e t w e e n tures and a n a s s e s s m e n t of t h e probable v a l i d i t y of t h e
[81Yok] a n d [82Kle] a t compositions a w a y from 50 extrapolations.
at.% Cu. The Gibbs energies of the solution phases are r e p r e s e n t e d
In Table 15 we give the r e s u l t s of the l a t e r s t u d y only.* as:
[80Gac] e s t i m a t e d t h e excess Gibbs e n e r g y of (Cu) a t G i = F~i(1 - x ) + F ciu x + R T ( x In x + (1 - x) ln(1 - x))
98 at.% Cu, 1140 K, u s i n g the solid cell e m f method. The +x(1-x)[B i+ C i(1- 2x) + D i ( 6 x 2 - 6 x - 1)]
formation of oxides m a d e t h e GxS(Cu) value v e r y uncer-
tain: comparison of the m e a s u r e d Gxs(Cu) with t h a t of the where i d e s i g n a t e s the phase; x, the a t o m fraction of Cu; F~,
liquid and the phase d i a g r a m indicate t h a t this v a l u e the lattice s t a b i l i t y p a r a m e t e r s of the pure metals; and B ~,
is too low. C ~ and D i, t h e i n t e r a c t i o n p a r a m e t e r s .
We have given p a r t i c u l a r a t t e n t i o n to t h e t h e r m o d y n a m i c s
*Note in press: Additional emf and calorimetric work on liquid alloys have of the liquid. Two compound p h a s e s (Ti2Cu3, TiCu2) were
recently been reported by 182Soml. not modeled because t h e r e is n e i t h e r a n y t h e r m o d y n a m i c

Bulletin of Alloy P h a s e D i a g r a m s Vol. 4 No. 1 1983 91

Cu-Ti Provisional

Table 16 Thermodynamic Models It is most convenient to consider two composition ranges

of the Solution Phases for the liquid Gibbs energy, 0 to 50 and 50 to 100 at.%,
because all Gibbs energies fitted to the data (whatever the
Lattice stabilities of the pure components, J/mol, J / m o l 9 K model) reach a maximum of approximately - 4 0 5 0 J/mol
FL(Ti) = 0 between 50 and 55 at.% and two polynomials can be
Fbcc(Ti) = -16234 + 8.368 T matched at.this composition.
Fr = -20585 + 12.134 T
Ffor = -17238 + 12.134 T
FL(CU) : 0 The Range 75 to 100 at.% Cu. The data (2a-2b) were used
Fbr162 = -9498 + 8.786 T to examine the following questions: Is the Gibbs energy
Fcph(Cu) = - 12 426 + 10.878 T determined from the enthalpy of mixing consistent with
Ffoo(Cu) = -13054 + 9.623 T the phase diagram? In particular, is an excess entropy
Solution phases, J/mol term required? The fcc phase was modeled as a regular
solution, with an interaction parameter determined by the
Phase Parameter [This work] [78Kau] solidus curve. The resulting liquidus curve is consistent
Cu-rich L. . . . . . . . . . . . . . . BL - 12 000 - 14 644 with the peritectic reaction. Next, the Gibbs energy of
CL 3 539 --2 929 TiCu4 is determined by the solvus data. If the enthalpy and
DL 8 278 0 entropy of formation of TiCu4 differ significantly from
Ti-rich L . . . . . . . . . . . . . . . BL -- 16 009 -- 14 644 those determined experimentally, then excess entropies
CL 566 --2 929 must play a significant role in the fcc phase, and possibly
(flTi) . . . . . . . . . . . . . . . . . . . B~c 4 300 5 858
(aTi) . . . . . . . . . . . . . . . . . . . Bcph 16 500 18 410 in the liquid phase as well. When the solvus data were
(Cu). . . . . . . . . . . . . . . . . . . . afcr 4 600 4 602 matched by optimizing the Gibbs energy of TiCu4, good
agreement was obtained with both the heat of formation of
TiCu4 and the solvus. This suggests that excess entropies
data nor sufficient phase diagram data to determine both are not necessary to model the solution phases in the range
enthalpies and entropies. The other compound phases, 75 to 100 at.% Cu.
Ti2Cu, TiCu, Ti3Cu4, and TiCu4, are modeled as stoichio-
metric compounds. The results of the present calculations
for the solution phases are summarized in Table 16. Calcu- The Range 0 to 35 at.% Cu. In this composition range, we
lated compound Gibbs energies are given in Table 15. have neither thermochemical data nor liquidus data in-
volving the bcc phase. Therefore, we will not be able to
First, the liquid was examined solely on the basis of draw detailed quantitative conclusions about the Gibbs
thermodynamic data. Then, several possible representa- energies. First, we ask whether the liquid Gibbs energy
tions of the liquid Gibbs energy were compared with the determined by thermochemical data is consistent with the
critical phase diagram data. The following experimental phase diagram at high temperature by fitting a regular
data are critical for the determination of the Gibbs energy solution bcc interaction parameter to the data (3a). The
functions of the solution phases: result is that this liquid Gibbs energy is not consistent
(1) The enthalpy of mixing of the liquid [82Kle] with the phase diagram and leads to a wide two-phase
(2a) The compositions of liquid and (Cu) at the peritectic (fl + L) region, which is incompatible with the eutectic
reaction L + (Cu) --> TiCu4 at 1158 K (77 -+ 1 and reaction (4b). We, therefore, tried a subregular solution
92 + 0.5 at.% Cu, respectively) model for the Ti-rich liquid, and it significantly improved
(2b) The (Cu) solvus the agreement between the calculated and assessed phase
(3a) The compositions of liquid and (flTi) at the peritectic diagrams.
reaction L + (flTi) --, Ti2Cu at 1278 K (13.5 - 1.5 The regular solution parameter of the cph phase was de-
and 36.5 -+ 2.5 at.% Cu, respectively) termined using data (3b), and the Gibbs energy of Ti2Cu
(3b) The compositions of (aTi) and (flTi) at the eutectoid was then calculated from the three-phase equilibria (3a,
reaction (flTi) --* Ti2Cu + (aTi) at 1063 K (1.5 -+ 0.1 3b). The width of the two-phase (cph + bcc) region pro-
and 5.4 -+- 0.1 at.% Cu, respectively) vides an additional test of the consistency of the bcc Gibbs
(4a) The congruent melting point of TiCu, at 1258 K energy. The heat of formation of Ti2Cu agrees well with
(4b) The eutectic composition, 43 at.% Cu, at 1233 K the [79Ari] data; this again suggests that excess entropies
(4c) The peritectic composition, 62.5 at.% Cu, at 1198 K are not necessary to reproduce the critical features of the
phase diagram. The shape of the (aTi) solvus was approxi-
Liquid Phase Thermodynamics (0 to 100 at.%) mately matched by the calculation.
A subregular solution (two-parameter) model can fit the
enthalpy data in the range 40 to 70 at.% Cu, but not at The Range 35 to 75 at.% Cu. Finally, the equilibria in-
Cu-rich concentrations; a three-term expansion succeeds volving TiCu must be examined (data 4a-4c). These three
in reproducing the enthalpy of mixing data of [82Kle]. points on the TiCu liquidus were used to determine the
Depending on the weight assigned to the data points for Gibbs energy of TiCu. The liquidus curve and TiCu Gibbs
Ti-rich alloys, the Gibbs energy obtained from optimiza- energy are both in satisfactory agreement with experi-
tions varied at Ti-rich compositions, though all the optimi- mental data, and this completes the calculation of
zation fitted the Cu-rich data within the errors. This is an the diagram.
artifact of fitting to polynomial expansions, because data
were available only for Cu contents greater than 30 at.%, In summary, the Gibbs energies given in Table 16 repre-
and the optimized Gibbs energy function is unreliable, sent our present best estimates based on both available
therefore, in the Ti-rich region. Thus, phase diagram data thermodynamic and phase diagram data. The phase dia-
are also essential for determining the Gibbs energy of the gram calculated from these Gibbs energies is shown in
liquid at Ti-rich compositions. Fig. 3.

92 Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983

Provisional Cu-Ti

Fig. 3 Calculated Ti-Cu Phase Diagram

Weight Percent Copper

10 20 30 40 50 60 70 80
1700 ....... ] ..... t ........ I ......... I ......... I ......... I .......... I........... ~. "J,,i .........
rpH-sl:mm~)

151111 84

0 ~+,

~ ,
~ 1100- 1083~

"-. ~ ~ "~

500! , ......... ,,,, , ......... , ......... r ......... , ......... i ........ , ......... i ......... , ......... , ......... i
o 1o ~o 3o 40 ~o 6o 70 8o go zoo
Ti Atomic Percent Copper Cu
Note the absence of two equilibrium phases, TiCu2 and Ti2Cu3. Dashed lines are the calculated To curves of the fcc and bcc solid solu-
tions. J.L. Murray, 1983.

Metastable Equilibria and cph and fcc Solid phase diagram data. Moreover, we have no experimental
Solutions information on excess entropy contributions that would
allow us to make a temperature extrapolation with more
The decomposition of the supersaturated cph and fcc solid certainty. Finally, the Gibbs energies of the solid phases
solutions into two disordered phases before the precipi- are also extrapolated far beyond the composition ranges
tation of the metastable or equilibrium compound phases over which they have been determined. Therefore, the To
strongly suggests that both of these solid solution phases curves are subject to improvement, when appropriate ex-
exhibit metastable miscibility gaps. In particular, evi- perimental data become available: for example, emf data
dence has been found for spinodal decomposition of the fcc on the liquid and solid phases, and bcc liquidus data.
solid solution, indicating that an alloy of about 5 at.% Ti
is within the metastable spinodal even at about 973 K. Cited References
Based on our present u n d e r s t a n d i n g of the thermo-
dynamics of this system, it appears improbable that the 31Kro: W. Von Kroll, "Tempered Titanium-Copper Alloys",
Z. Metallkd., 23, 33-39 (1931) in German. (Equi Diagram;
spinodal decomposition is the effect of large positive excess Experimental)
Gibbs energies such as those that give rise to approxi- 31Sch: E.E. Schumacher and W.C. Ellis, "Age Hardening of
mately symmetrical equilibrium miscibility gaps in, for Copper-Titanium Alloys", Metal and Alloys, 2, 111 (1931).
example, Ag-Cu, Cd-Zn, or Al-Zn. Rather, the spinodal (Meta Phases; Experimental)
decomposition appears to be the result of subtle variations 32Hen: F.R. Hensel and E.I. Larsen, "Age Hardening Copper-
of the curvature of the Gibbs energy as a function of com- Titanium Alloys", Trans. AIME, 99, 55-64 (1932). (Equi
position, and the contribution of short-range ordering may Diagram)
have to be included in a thermodynamic analysis that 39Lav: F. Laves and H.J. Wallbaum, "On the Crystal Chemistry
accounts for the spinodal decomposition. of Titanium Alloys", Naturwissenschaften, 27, 674-675 (1939)
in German. (Crys Structure; Experimental)
To Curves 51Kar: N. Karlsson, "An X-Ray Study of the Phases in the
Copper-Titanium System", J. Inst. Met., 79, 391-405 (1951).
To curves, the locus of points where the Gibbs energies of (Crys Structure; Experimental)
two phases are equal, are of interest for guiding interpre- 51Mcq: A. D. McQuillan, "The Application of Hydrogen Equilib-
tations of the results of rapid solidification experiments, rium-Pressure Measurements to the Investigation of Titanium
because when the temperature is depressed below To, it Alloy Systems", J. Inst. Met., 79, 73-88 (1951). (Equi Diagram;
becomes thermodynamically favorable for a metastable Experimental)
*52Jou: A. Joukainen, N.J. Grant, and C.F. Floe, "Titanium-
liquid to crystallize without compositional segregation. Copper Binary Phase Diagram", Trans. AIME, 194, 766-770
In Fig. 3, we show calculated To curves of the fcc and bcc (1952). (Equi Diagram; Experimental)
phases. The Gibbs energies of all three phases (liquid, bcc, 52Rau: E. Raub, P. Walter, and M. Engel, "Alloys of Titanium
and fcc) are extrapolated beyond the temperature range in with Copper, Silver and Gold", Z. MetaUkd., 43, 112-118 (1952)
which they can be tested against either thermochemical or in German. (Equi Diagram; Experimental)

Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983 93

Cu-Ti Provisional

52Ros: W. Rostoker, "Observations of the Occurrence of Ti2X 197-198 (1965) in German. (Equi Diagram; Experimental)
Phases", Trans. AIME, 194, 209-210 (1952). (Equi Diagram; *66Ere: V. N. Eremenko, Y.I. Buyanov, and S. B. Prima, "Phase
Experimental) Diagram of the System Titanium-Copper", Porosh. Met., Akad.
*53Trz: W. Trzebiatowski, J. Berak, and T. Romotowski, "The Nauk Ukr. SSR, 6(6), 77-87 (1966) in Russian; TR: Sov. Powder
Copper-Titanium System", Roczniki Chemii, 27, 426-437 (1953) Met., (6), 494-502 (1966). (Equi Diagram; Experimental)
in Polish. (Equi Diagram; Experimental) 66Sat: K Sato, "Direct Observations on Precipitation in Copper-
55Ho1: P.C. Holden, A.A. Watts, H.R. Ogden, and R.I. Titanium Alloys", Trans. Jpn. Inst. Met., 7, 267-272 (1966).
Jaffee, "Heat Treatment and Mechanical Properties of Ti-Cu (Meta Phases; Experimental)
Alloys", Trans. AIME, 203, 117-125 (1955). (Meta Phases; 66Van: J.H.N. Van Vucht, "Influence of Radius Ratio on the
Experimental) Structure of Intermetallic Compounds of the ABa Type",
56Sire: W. Simon, "Dissertation Work", Berg Akad. Clausthal J. Less-Common Met., 11, 308-322 (1966). (Crys Structure;
(1956) in German. (Lattice Parameters; Experimental) Experimental)
58Vig: V. N. Vigdorovitch, A. N. Krestovnikov, and M V. Malitsev, 66Zwi: U. Zwicker, E. Kalsch, T. Nishimura, D. Ott, and H.
"Phase Diagram of the Copper-Titanium System", Izv. Akad. Seilstorfer, "Effect of Impurities on the Phase Equilibria of Cu-
Nauk SSR Otcl. Tech. Nauk, (2), 145-148 (1958) in Russian. rich Copper-Titanium Alloys", Metall., 20 (12), 1252-1255 (1966)
(Equi Diagram; Experimental) in German. (Equi Diagram; Experimental)
59Doi: T. Doi, "On the Structure Changes Produced by Aging 67Gar: Yu.V. Gardina, L.T. Gordeeva, L.G. Timonina, and
of Cu-Ti Alloy", Acta Met., 7, 291-292 (1959). (Meta Phases; N.R. Zifferman, "Metallic Compounds in the Ti-Cu System",
Experimental) MetaUoved. Term. Obrab. Metall., (2), 10-11 (1967); TR:
59Man: J. Manenc, "Existence of Precipitation Stages in the Met. Sci. Heat Treat., (2), 85-86 (1967). (Equi Diagram;
Age-Hardening of Cu-Based Ti Alloys", Acta Met., 7, 807-808 Experimental)
(1959) in French. (Meta Phases; Experimental) 67Sai: K. Saito, K. Iida, and R. Watanabe, "The Ageing Behaviour
59Saa: M.J. Saarivirta and H. S. Cannon, "Copper-Titanium Al- of Cu-4 wt.% Ti Alloy", Trans. Nat. Res. Inst. Met., 9(5), 21-27
loys Have High Strength", Metal Progress, 72 (2), 81-84 (1959). (1967). (Meta Phases; Experimental)
(Equi Diagram; Experimental) 68Pfe: H.U. Pfeifer, S. Bhan, and K. Schubert, "On the Struc-
60Kal: K. R Kalinin and M. Z. Spiridonova, "Investigation of the tures of Ti-Ni-Cu and Quasi-Homologous Alloys", J. Less-
Properties of Copper-Titanium Alloys", Tr. Gos. Nauchn-Issled. Common Met., 14, 291-302 (1968) in German. (Crys Structure;
Proektn. Inst. Obrab. Isvetn. Met., 18, 46-57 (1960) in Russian. Experimental)
(Equi Diagram; Experimental) 68Ray: R. Ray, B.C. Geissen, and N.& Grant, "New Non-
60Nes: E.G. Nesterenko and K.V. Chuistov, "Structural Trans- Crystalline Phases in Splat-Cooled Transition Metal Alloys",
formations in the Aging of Copper-Titanium Alloy", Fiz. Met. Scripts Met., 2, 357-359 (1968). (Meta Phases; Experimental)
Metalloved., 9(3), 415-421 (1960) in Russian; TR: Phys. Met. 69Sin: A. K. Sinha, "Close-Packed Ordered AB3 Structures in Bi-
MetaIiogr., 9(3), 81-86 (1960). (Meta Phases; Experimental) nary Transition Metal Alloys", Trans. AIME, 245, 237-240
60Sat: T Sato, S. Hukai, and Y.C. Huang, "The Ms Points of (1969). (Crys Structure; Experimental)
Binary Titanium Alloys", J. Aust. Inst. Met., 5(2), 149-153 70Ble: P.A. Blenkinsop and R.E. Goosey, "A Study of the Age
(1960). (Meta Phases; Experimental) Hardening Reaction in Titanium-2~z Copper", Sci. Technol.
61Enc: E. Ence and H. Margolin, "A Study of the Ti-Cu-Zr System Appl. Titanium, Proc. Intl. Conf., R.I. Jaffee and ME. Promisel,
and the Structure of Ti2Cu", Trans. AIME, 221,320-322 (1961). Ed., 783-793 (1970). (Equi Diagram; Experimental)
(Crys Structure; Experimental) 70Kau: L. Kaufman and H. Bernstein, Computer Calculation of
62Bor: N. G. Boriskina and K. P. Myasnikova, "Solubility of Iron, Phase Diagrams, Academic Press (1970). (Thermo; Theory)
Manganese and Copper in a-Titanium", Titan. Ego Splavy, 70Kru: W. E. Krull and R.W. Newman, '~The Lattice Parameter
Akad. Nauk SSR Inst. Met., 7, 61-67 (1962) in Russian. (Equi of the a Copper-Titanium Solid Solution", J. Appl. Cryst., 3,
Diagram; Experimental) 519-521 (1970). (Lattice Parameter; Experimental)
*62Heu: U. Heubner and G. Wasserman, "Investigation of Pre- 70Lue: G. Luetjering and S. Weissmann, "Mechanical Properties
cipitation and Tempering Behavior of Supersaturated Cu-Ti and Structure of Age-Hardened Ti-Cu Alloys", Met. Trans., 1,
Solid Solutions", Z. Metallkd., 53, 153-154 (1962) in German. 1641-1649 (1970). (Equi Diagram; Experimental)
(Meta Phases; Experimental) 7OWill: J. C. Williams, D.H. Polonis, and R. Taggart, "An Elec-
62Mue: M.H. Mueller, M.V. Nevitt, and H.W. Knott, "A Study tron Microscopy Study of Phase Transformations in Titanium-
of the Ti-Cu-Zr S y s t e m and the S t r u c t u r e of Ti2Cu", Copper Alloys", Sci. Technol. Appl. Titanium, Proc. Intl. Conf.,
Trans. A1ME, 224, 611-612 (1962). (Crys S t r u c t u r e ; R.I. Jaffee and N.E. Promisel, Ed., 733-743 (1970). (Meta
Experimental) Phases; Experimental)
*62Zwi: U. Zwicker, "Tempering and Mechanical Properties of 70Wil2: J.C. Williams, R. Taggart, and D. H. Polonis, "The Mor-
Copper-Titanium Alloys", Z. Metallkd., 53, 709-714 (1962) in phology and Substructure of Ti-Cu Martensite", Met Trans.,
German. (Equi Diagram; Experimental) 1, 2265-2270 (1970). (Meta Phases; Experimental)
63Luz: I.P. Luzhikov, V.M. Novikova, and A.P. Mareev, 71Gie: B.C. Giessen and D. Szymanski, "A Meta Phase
"Solubility of el-Stabilizers in a-Titanium", Metalloved~ Term. TiCua(m)", J. Appl. Cryst., 4, 257-259 (1971). (Meta Phases)
Obrab. Metalloo., (2), 13-16 (I963) in Russian; TR: Met. Sci. 71Hak: T. Hakkarainen, Thesis, Helsinki Univ. of Technology
Heat Treat., (2), 78-81 (1963). (Equi Diagram; Experimental) (197t). (Meta Phases; Experimental)
~ H a h : H.D. Hahlbohm, "Electrical, Magnetic and Galvano- 71Wil: J. C. Williams, R. Taggart, and D. H. Polonis, "An Electron
Magnetic Measurements of Copper-Titanium and Gold- Microscopy Study of Modes of lntermetallic Precipitation in
Titanium", Z. MetaUkd., 5, 515-518 (1963) in German. (Equi Ti-Cu Alloys", Met. Trans., 2, 1139-1148 (1971). (Meta Phases;
Diagram; Experimental) Experimental)
63Mue: M. H. Mueller and H.W. Knott, "The Crystal Structures 72Mie: H.T. Michels, I.B. Cadoff, and E. Levine, "Precipitation-
of TizCu, Ti2Ni, Ti4Ni20, and Ti4Cu20", Trans. AIME, 227, Hardening in Cu-3.6 Wt. Pet. Ti', Met. Trans., 3, 667-674
674-678 (1963). (Crys Structure; Experimental) (1972). (Meta Phases; Experimental)
*63Pie: P. Pietrokowsky and J.R. Maticich, "The Use of the 73Cor: J.A. Cornie, A. Datta, and W.A. Sofia, "An Electron
Electron-Microprobe Analyzer in the Study of Binary Metal Microscopy Study of Precipitation in Cu-Ti Sideband Alloys",
Alloy Systems", X-Ray Optics and X-Ray Microanalysis, 3rd Met. Trans., 4, 727-733 (1973). (Meta Phases; Experimental)
Intl. Symp., 591-602, (1963). (Equi Diagram; Experimental) 73Kni: R. Knights and R Wilkes, "The Precipitation of Titanium
648eh: K. Schubert, H.G. Meissner, and W. Rossteutscher, in Copper and Copper-Nickel Base Alloys", Acta Met., 21,
"Structure Data on Metallic Phases (11)", Naturwissenschaften, 1503-1514 (1973). (Meta Phases; Experimental)
51,, 507 (1964) in German. (Crys Structure; Experimental) 73Po1: A.F. Polesya and L .S. Slipchenko, "Formation of Amor-
*65Seh: K. Schubert, "On the Constitution of the Titanium- phous Phases and Meta Solid Solutions in Binary Ti and Zr
Copper and Titanium-Silver Systems", Z. Metallkd., 56(3), Alloys with Fe, Ni and Cu", Akad. Nauk SSSR Metally, (6),

94 B u l l e t i n of Alloy P h a s e D i a g r a m s Vo[. 4 No. 1 1983

Provisional Cu-Ti

173-178 (1973); TR: Russ. Met., (6), 103-107 (1973). (Meta fl-Phase in Dilute Copper-Titanium Alloys", Phys. Stat. Sol. (a),
Phases; Experimental) 52, 201-210 (1979). (Crys Structure; Experimental)
73Tsu1: T. Tsujimoto, K. Saito, and K. Hashimoto, "X-Ray Small- 798ak: M. Sakata, N. Cowlam, and H.A. Davies, "Neutron Dif-
Angle Scattering Study on the Early Stages of the Decom- fraction Measurement of the Structure Factor of a CuTi Metal-
position in a Cu-4 wt% Ti Alloy", J. Jpn. Inst. Met., 37(1), 67-72 lic Glass", J. Phys. F.: Metal Phys., 9(12), L235-L240 (1979).
(1973) in Japanese. (Meta Phases; Experimental) (Meta Phases; Experimental)
73Tsu2: T. Tsujimoto, K. Hashimoto, and K. Saito, "X-Ray Small- *79Vig: G. Vigier, J. M. Pelletier, and J. Merlin, "Determination
Angle Scattering Study on the Later Stages of the Decom- of Copper Solubility in Titanium and Study of Ti-Cu Solid Solu-
position in a Cu-4 wt% Ti Alloy", J. Jpn. Inst. Metal., 37(1), tion Stability by Thermoelectric Power Measurements",
61-67 (1973) in Japanese. (Meta Phases; Experimental) J. Less-Common Met., 64, 175-183 (1979). (Equi Diagram;
73Zan: A. Zangvil, S. Yamamoto, and Y. Murakami, "Electron Experimental)
Microscopic Determination of Orientation Relationship and 80Eco: R. C. Ecob, J.V. Bee, and B. Ralph, "Some Ordering Phe-
Habit Plane for Ti-Cu Martensite", Met. Trans., 4, 467-475 nomena in the/3 Cu4Ti Phase", J. Micro., 119, Pt. 1, 153-161
(1973). (Meta Phases; Experimental) (1980). (Crys Structure; Experimental)
74Dut: J. Dutkiewicz, "The Influence of Temperature on the Age- 80Gac: J.C. Gachon, J.P. Hilger, M. Notin, and J. Hertz, "En-
ing of Copper-Titanium Alloys", Bull. Acad. Polon. Sci., 22(4), thalpies and Free Enthalpies of Formation for Dilute Binary
323-328 (1974). (Meta Phases; Experimental) Solid Solutions Cu-M (M in the First Long Period)", J. Less-
74Laul: D.E. Laughlin and J.W. Cahn, "Ordering in Copper- Common Met., 72, 167-192 (1980). (Thermo; Experimental)
Titanium Alloys", Met. Trans., 5, 972-974 (1974). (Meta Phases; 80Rao: D. Raoux, J.F. Sadoc, P. Lagarde, A. Sadoc, and A.
Experimental) Fontaine, "Local Structure in a Cu2Ti Amorphous Alloy by
74Lau2: D. E. Laughlin and J. W. Cahn, "The Crystal Structure of EXAFS and X-Ray Scattering", J. Phys. Colloq. C8, 41(8),
the Metastable Precipitate in Copper-Based Copper-Titanium C-207-C-210 (1980). (Meta Phases)
Alloys", Scripta Met., 8, 75-78 (1974). (Crys Structure; 80Sak: M. Sakata, N. Cowlam, and H. A. Davies, "Measurements
Experimental) of Compositional Order in Binary Metallic Glasses", J.
75Lau: D. E. Laughlin and J. W. Cahn, "Spinodal Decomposition Phys. Colloq. C8, 41(8), C-190-C-193 (1980). (Meta Phases;
in Age Hardening Copper-Titanium Alloys", Acta Met., 23, Experimental)
329-339 (1975). (Meta Phases; Experimental) 80Peh J.M. Pelletier, G. Vigier, R. Borrelly, and J. Merlin,
75Po1: A. F. Polesya and L. S. Slipchenko, "Metastable Phase with "Isothermal Decomposition of Solid Solutions in a Ti-2.5 wt Cu
bcc Lattice in the Copper-Titanium System", Izv. Vyssh. Alloy", Titanium '80, Sci. and Techn., Proc. 4th Intl. Conf. on
Uchebn. Zaved. Tsvetn. Metall., (6), 144-147 (1975) in Russian. Titanium, H. Kimura and O. Izumi, Ed., 1408-1417 (1980).
(Meta Phases; Experimental) (Meta Phases; Experimental)
75Vai: T.K. Vaidyanathan and K. Mukherjee, "Continuous 81BAP: "Melting Points of the Elements", Bull. Alloy Phase
Precipitation in Cu-Rich Cu-Ti Binary and Cu-Ti-A1 Ternary Diagrams, 2(1), 145-146 (1981).
Alloys," J. Mat. Sci., 10, 1697-1710 (1975). (Meta Phases, (Cu); 81Ciz: P. Cizinsky and J. Pesicka, "The Spinodal Decomposition
Experimental) of Cu-Ti Alloys", Czech J. Phys. B, 31, 752-755 (1981). (Meta
76Dat: A. Datta and W.A. Sofia, "The Structure and Properties of Phases; Experimental)
Age Hardened Cu-Ti Alloys", Acta Met., 24, 987-1001 (1976). 81Fuk: T. Fukunaga, K. Kai, N. Masaaki, N. Watanabe, and K.
(Meta Phases; Experimental) Suzuki, "High Resolution Short-Range Structure of Ni-Ti and
76Vai: T.K. Vaidyanathan and K. Mukherjee, "Precipitation Cu-Ti Alloy Glasses by Pulsed Neutron Total Scattering", Proc.
in Cu-Ti and Cu-Ti-Alloys, Discontinuous and Localized 4th Int. Conf. on Rapidly Quenched Metals (Sendai), 347-350
Precipitation", Mat. Sci. Eng., 24, 143-152 (1976). (Meta Phases; (1981). (Meta Phases; Experimental)
Experimental) 81Sak: M. Sakata, N. Cowlam, and H.A. Davies, "Chemical
76Zan: A. Zangvil, S. Yamamoto, and Y. Murakami, "Morphology Short-Range Order in Liquid and Amorphous Cu66Ti34Alloys",
and Substructure of Ti-Cu Martensite and Its Aged Marten- J. Phys. F.: Metal Phys., 11, L157-L162 (1981). (Meta Phases;
site", Trans. Jpn. Inst. Met., 17, 575-581 (1976). (Meta Phases; Experimental)
Experimental) 81Yok: H. Yokokawa and O. J. Kleppa, "Thermochemistry of Liq-
77Dut: J. Dutkiewicz, "Mechanism of Spinodal Decomposi- uid Alloys of Transition Metals. I I . - (Copper and Titanium) at
tion. Discontinuous Precipitation and Ordering in Aged Alloys 1372 K", J. Chem. Thermodyn., 13(8), 703-715 (1981). (Thermo;
with F.C.C. Lattice", Sci. Bull. Stan. Stas. Univ. Min. and Experimental)
Met., No. 675, Bull. 80, 56-99 (1977) in Polish. (Meta Phases; 82Kle: O.J. Kleppa and S. Watanabe, "Thermochemistry of
Experimental) Alloys of Transition Metals: Part III. Copper-Silver, -Titanium,
78Dut: J. Dutkiewicz, "Spinodal Decomposition, Ordering, and -Zirconium, and -Hafnium at 1373 K', Met. Trans., 13B,
Discontinuous Precipitation in Deformed and Aged Copper- 391-401 (1982). (Thermo; Experimental)
Titanium Alloys", Metals Technol., 5(10), 333-340 (1978). (Meta 82Shu: R. Shull, A. McAlister, and J. Murray, (1982) to be pub-
Phases; Experimental) lished. (Equi Diagram; Experimental)
78Kau: L. Kaufman, "Coupled Phase Diagrams and Thermo- 828om: F. Sommer, K.-H. Klappert, I. Arpshofen, and B. Predel,
chemical Data for Transition Metal Binary Systems-III", "Thermodynamic Investigation of Liquid Copper-Titanium
Calphad, 2(5), 117-146 (1978). (Thermo; Experimental) Alloys", Z. Metallkd., 73, 581-584 (1982). (Thermo)
*79Ari: M. Arita, R. Kinaka, and M. Someno, "Application of the 82Woy: C. Woychik and T. B. Massalski, private communication
Metal-Hydrogen Equilibration for Determining Thermo- (1982). (Meta Phases; Experimental)
dynamic Properties in the Ti-Cu System", Met. Trans., IOA,
529-534 (1979). (Thermodynamics; Experimental)
79Eco: R. C. Ecob, J.V. Bee, and B. Ralph, "The Structure of the *Indicates key paper.

Ti-Cuevaluation contributedby Joanne L. Murray, Center for Materials Research, National Bureau of Standards. Thermodynamiccalculationshave been
made using computer programs generouslymade available by E.-Th. Henig and H.L. Lukas, of the Max-PlanckInstitute, Stuttgart, Federal Republicof
Germany.This work wasjointly fundedby the Officeof Naval Research and the NationalBureau of Standardsthrough the MetallurgyDivisionand the Office
of Standard Reference Data. Literature searched through 1981. Dr. Murray is the ASM/NBS Data Program Category Editor for binary titanium alloys.

Bulletin of Alloy Phase D i a g r a m s Vol. 4 No. 1 1983 95