Powder Metallurgy and Metal Ceramics. Vol. 35. Nos.

3-4, 1996

HEAT CAPACITY AND ENTHALPY OF A COPPER-PHOSPHORUS SOLDER

A. I. Kriklya, A. S. Bolgar, UDC 546.56' 18+536.63'722

A. V. Blinder, and V. B. Chernogorenko

In the soldering of products made of copper and its alloys, silver solders can be replaced by solders based on alloys
of the system C u - P [1, 2]. It has been established [3] that this system contains the following phases: a solid solution of
phosphorus in copper; the phosphide Cu3P, which melts congruently at 1295 K; the diphosphide CuP 2, which melts at 1164
K. The C u - C u 3 P system has a diagram of the eutectic type on the copper side, the eutectic point corresponding to a
phosphorus content of 8.4% (mass) and a temperature of 987 K. At the eutectic temperature, 1.7% (mass) phosphorus
dissolves in copper. An alloy with a phosphorus content close to the eutectic concentration (7-8% (mass)) is used as solder.
In order to perform the various calculations associated with soldering and unsoldering and determining the service
properties of the resulting joint, it is necessary to have information on the thermophysical and thermodynamic characteristics
of the alloy. These characteristics must be obtained by direct experimentation. The literature contains information [4] on the
vaporization of phosphides of copper and their thermodynamic characteristics, but there is no data on the heat capacity or
enthalpy of copper-phosphorus solders. Thus, our goal here is to study the thermodynamic properties of a copper-phosph-
orus solder (7.9% (mass) P) within a broad range of temperatures.
As the solder, we used castings of a copper-phosphorus alloy (7.9% (mass) P) obtained from commercial-grade
copper phosphide and degassed with additions of carbon trichloride. The heat capacity of the solder was determined within
the temperature range 150-650 K with the use of an IT-s-400 meter.
Experimental values of the heat capacity of a copper-phosphorus solder
(7.9% (mass) P), J . g - l - K - I
T, K. . . . . . . . . . . . . . . . . . . . . 148 173 198 223 248 273 298
~.,(/3 . . . . . . . . . . . . . . . . . . . 0,3270 0,3470 0,3651 0,3829 0,3930 0,4080 0,4161
T, ~ . . . . . . . . . . . . . . . . . . . . 323 348 373 398 ,123 448 473
C*,(~ . . . . . . . . . . . . . . . . . . . . 0,4190 0,4259 0,4290 0,4320 0,4349 0,4440 0,4449
7;, K. . . . . . . . . . . . . . . . . . . . . 498 523 548 573 598 623 648
~,,,(7) . . . . . . . . . . . . . . . . . . . . 0,4471 0,4500 0,4430 0,4459 0,4481 0,4500 0,4510

The operation of the meter is based on the use of the comparison method, involving a dynamic C-calorimeter with a
heat-meter and an adiabatic casing. The specimen is placed in the metal ampoule and heated monotonically with it by a flow
of heat supplied continuously to the ampoule through the heat-meter. The meter was calibrated and certified using pure
copper [5]. The total error of heat capacity within the indicated temperature range was about 5 %. The measurement results
were then smoothed. The standard deviation of the experimental values of heat capacity from the smoothed values was
0.15%. By using the method in [6] to extrapolate the smoothed values of heat capacity to zero temperature with the assump-
tion of the absence of any kind of transformation below 150 K (no such transformation has been observed in pure copper),
we obtained standard values of the main thermodynamic functions of the solder: Cp (298.15 K), SO (298.15 K), ¢I,° (298.15
K), respectively equal to 0.415, 0.533, 0.259 J . g - l . K - l ; H° (298.15 K) -- H 0 (0 K) = 81.4 j . g - I We should point out
that the values obtained here are close to the corresponding parameters of pure copper.
The enthalpy of the copper-phosphorus solder was studied by the mixing method within the temperature interval
400-1300 K. The study was conducted on a high-temperature differential calorimeter made by the "Setaram" company. The
features of experiments of this type were described in [7]. We made alternate use of test and standard (copper) specimens in
order to calibrate the unit in a furnace at each test temperature. The measurement error was + 1.5%,

Institute of Problems of Materials Science, National Academy of Sciences of the Ukraine, Kiev. Translated from
Poroshkovaya Metallurgiya, Nos. 3/4(384), pp. 103-106, March-April, 1996. Original article submitted January 26, 1995.

1068-1302/96/3534-0205515.00 ©1996 Plenum Publishing Corporation 205

 Cp °, J/(g'K) 8
Cp 0" J/(g-K)
0,5-- 3

o.s- °/,S.~/~

0,4

I I I
O,4! I~/~~~1
o 6 12 p, %
300 600 900 1200 r, K Cu Cu a P

Fig. 1 Fig. 2

Fig. 1. Temperature dependence of the heat capacity of a copper-phospho-

rus solder (1), copper (2), and the eutectic mixture Cu + Cu3P (3).
Fig. 2. Isotherms of the heat capacity of the eutectic mixture Cu + Cu3P.

Experimental values of the enthalpy ( j . g - l ) of a copper-phosphorus solder

T, K ................ 400 498 574 652 724 793 859 922
/'~(T}--- I~(298,15 K) .... 44,12 87,94 123,6 159,6 192,9 225,6 257,6 287,7
T, K . . . . . . . . . . . . . . . . . 976 996* 1024" 1081 lit4 1179 1240 1298
Hu(7) --- ~ (298,15 K).. . 313,8 335,0 439,6 582,0 602,7 609,2 628,3 647,1

Mixture of solid and liquid phases

The sudden change in enthalpy seen above 976 K was due to melting of the solder. The melting point, refined by
differential-thermal analysis, was determined to be 988 K. This value nearly coincides with the value indicated in the
literature [3]. Values of the enthalpy of the copper-phosphorus solder in the solid state were analyzed by the least-squares
method with the use of the Meyer--Kelly equation. As the boundary conditions, we used the standard value of heat capacity
and the triviality of H°(T) - H°(298.15 K) at 298.15 K. The resulting equation has the form:

//°(7")--/-/°(298,15 K)= 5,8419.10--~7¢+ 4,739.10-~T~_

(i)
+5538 T-"--160,4, yg-l.

On the average, the heat capacity of the solder up to the melting point was 8% higher than that of pure copper. This differ-
ence is too small to create significant internal stresses at the boundary between the copper (or its alloys) and the cop-
per-phosphorus solder. Thus, it is not an obstacle to heat transfer, as has been shown in practice.
The temperature dependence of the enthalpy of the solder in the liquid state can be ~escri~d by the equation
HU('/'}- /'/°(298,15 K)=4,081.I0 --~ T+ 133,1, J-g-l. (2)
We can use Eqs. (I) and (2) to determine the heat of fusion of the solder. It was found to be equal to 216.5 j . g - I (the value
for pure copper is 205.4 j . g - l ) .
With allowance for Eqs. (I) and (2), we tabulated values of enthalpy, heat capacity, entropy, and corrected Gibbs
energy for the copper-phosphorus solder (Table i). Although the heat of fusion of pure copper and the solder are close, the
heat capacity of the solder in the liquid phase is 20% lower. This might be related to the formation of associates in the melt.
We should also point out that there is an inflection on the heat capacity curve of copper in the pre-fusion region. This
inflection is usually associated with the formation of thermal vacancies and anharmonic vibration of the atoms of the crystal-
line lattice. No nonlinear increase in the heat capacity of the solder was seen in the pre-fusion region.
Since the solder is a eutectic mixture based on copper and its phosphide Cu3P, we calculated its heat capacity (curve
3 in Fig. i) using the additivity rule. The data on the heat capacity of Cu3P and copper was taken from [4, 5]. The solubility
of phosphorus in pure copper was not considered. We obtained satisfy agreement (within 3%) between the theoretical and
experimental values of heat capacity (Fig. 1) in the high-temperature region (600-984 K).

206
 TABLE 1. Thermodynamic Functions of a Copper-Phosphorus Solder (7.9%
(mass) P) in the Range 298.15-1300 K

F,K ] Ho(~H~¢298'
q~l(T)'J'g-I'K-IJ.g-I
ISK)'I...Cp0(T)'
.. J'g-I IS°(T)"Jg'-IK' -I
298,15
300
0
0,77
0,415
0,416
0,533
0,535
0,533
0,533
400 43,95 0,444 0,659 0,549
500 89,10 0,458 0,760 0,582
600 135,3 0,466 0,844 0,619
700 182,1 0,471 0,916 0,656
800 229,4 0,475 0,979 0,693
900 277,0 0,478 1,035 0,728
987 318,7 0,480 1,070 0,757
987 535,9 0,408 1,300 0,757
1000 541,2 0,408 1,305 0,764
1100 582,0 0,408 1,344 0,815
1200 622,8 0,408 1,380 0,860
1300 663,6 0,408 1,412 0,902

Thus, at high temperatures (up to the melting point), the heat capacity and other characteristics of cop-
per-phosphorus solders with different contents of phosphorus can be calculated by using the additivity rule
Cp=xCp(Cu) + (l--x) Cp(Cu3P), (3)

where x is the mass fraction of copper in the specific solder; Cp(Cu) and CpCu3P are the specific heats corresponding to each
temperature. The heat capacity isotherms shown in Fig. 2 for the eutectic mixture Cu + Cu3P make it possible to determine
the heat capacity of copper-phosphorus solders with different phosphorus contents at different temperatures.

REFERENCES

, I. E. Petrushina, Concise Handbook for Solderers [in Russian], Mashinostroenie, Moscow (1991).
2 S. V. Loshko and N. F. Loshko, Soldering of Metals [in Russian], MashinostroenJe, Moscow (1988).
3. Ya. A. Ugai, V. R. Pshestanchik, O. N. Gukov, and V. Z. Anokhin, "Phase diagram of the C u - P system," Izv.
Akad. Nauk SSSR N~eorg. Mater., 8, No. 6, 1015-1018 (1972).
4. S. P. Gordienko and G. Sh. Viksman, "High-temperature behavior and thermodynamic properties of the compounds
Cu3P and CUP2," Poroshkovaya Metallurgiya, No. 7, 82-85 (1985).
5. R. Hultgren, P. Desai, D. Hawkins, et al., Selected Values of the Thermodynamic Properties of the Elements,
Amer. Soc. Met., Ohio (1973).
6. A. S. Bolgar, A. V. Blinder, L. M. Novoseletskaya, et al., "Low-temperature heat capacity of borides of molybde-
num," Zh. Fiz. Khim., 62, No. 4, 909-913 (1988).
7. A. I. Kriklya, Thermodynamic Properties of Sulfides of Rare-Earth Metals of the Cerium Subgroup and Gadolinium.
Author's Abstract of Chemical Sciences Candidate Dissertation (1986).

207