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Interaction between Ti or Cr containing copper alloys and porous graphite

substrate

Conference Paper · January 1998

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Natalia Sobczak Jerzy J. Sobczak

Instytut Mechaniki Precyzyjnej; Foundry Research Institute in Cracow AGH University of Science and Technology in Kraków
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Foundry Research Institute in Cracow Polish Academy of Sciences
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 INTERACTION BETWEEN Ti OR Cr CONTAINING COPPER
1
ALLOYS AND POROUS GRAPHITE SUBSTRATE

N. SOBCZAK, J. SOBCZAK, P. ROHATGI*, M. KSIAZEK,

W. RADZIWILL, J. MORGIEL**
Foundry Research Institute, 73 Zakopianska St., 30-418 Cracow, POLAND
*
University of Wisconsin-Milwaukee, Milwaukee, P.O. Box 784, WI 53201, USA
**
Polish Academy of Sciences, 25 Reymonta St., 30-059 Cracow, POLAND

ABSTRACT
The effect of Cr and Ti additions to copper on wetting and infiltration of porous graphite have
been investigated using the sessile drop method. TEM, EDS, EMPA analyses and optical
microscopy were used to characterize the structure and chemistry of interfaces. The data have
been analyzed in terms of effective impregnation of porous carbon assemblies by liquid copper
alloys. Wetting behavior was noted to be similar to that observed on compact carbon materials. Ti
and Cr, as active alloying elements to copper, promote the reactive wetting of a graphite due to
formation of carbides (TiC or Cr3C2 and C7C3, respectively). Compared to Ti, Cr has a greater
effect on improvement of wettability, however it forms a thick and compact reaction product layer
that blocks the penetration of the alloy into the open porosity of graphite. In contrast, the TiC layer
is characterized by nonuniform structure and discontinuities resulting in significant in situ reactive
infiltration with Cu-Ti alloys.

INTRODUCTION
The study of wettability in Cu/C system is of great interest in terms of practical
applications, like brazing graphite or diamond using copper alloy brazes [1,2],
production of copper matrix composites reinforced with graphite fibers, demanding high
thermal conductivity, stiffness and strength but low thermal expansion and density [3-5],
production of copper alloys containing graphite particles [6], as potential material for
replacement of the lead containing copper alloys, which are widely used in plumbing
and bearing applications for their high machinability.
The Cu/C system is a typical nonreactive system, characterized by lack of mutual
solubility as well as formation of stable carbides. It explains that carbon in either
elemental or graphite state is nonwettable by liquid pure copper and most of industrial
copper alloys [1]. Studies of [1, 7-9] on wettability and reactivity between copper melts
and different compact carbon materials (vitreous carbon, diamond, single graphite
crystals, special types of graphite characterized by low porosity) have shown that the
periodic table 3-d alloying elements promote reactive wetting due to formation of their
carbides. In present work, the investigation of interaction between porous graphite
material and binary copper alloys containing Ti and Cr has been done and analyzed in
terms of their effectiveness on wetting as well as on infiltration phenomena that are
important for elaboration of the real technological processes.

Proc. Int. Conf. HIGH TEMPERATURE CAPILLARITY

29 June – 2 July 1997, Cracow, Poland
Edited by N. Eustathopoulos and N. Sobczak
146 N. SOBCZAK, J. SOBCZAK, P. ROHATGI et al.

EXPERIMENTAL PROCEDURE
The sessile drop method was adopted for study of wetting behavior and reactivity in
the chosen systems. The wettability experiments were carried out under dynamic
vacuum of 1 mPa on the equipment described in [10]. The graphite substrate discs of
18x5mm size were made from electrode graphite (type K, Polgraph SA – Poland)
characterized by 18 vol.% of average total porosity, 8 vol % of open porosity and 3.6
µm of average pore radius. The histogram of pore size distribution is shown in Fig. 1.
Before experiments, the graphite substrates were polished, cleaned in acetone and
annealed in vacuum at 950°C.

Fig. 1. Histogram of pore size distribution Fig. 2. Wettability of porous graphite by pure
in graphite. copper and its Cu-Ti and Cu-Cr alloys.

The metal samples were pure copper and its binary alloys with Cr (0.88, 1.0, 10
wt.%) and Ti (10, 17.4, 28 wt.%). Estimated chemical composition of the alloys were
obtained by in situ technique [7], directly during wettability experiments by joint
melting of pure metal specimens (Cu 99.98 %, and Ti or Cr with less than 0.1 wt.%
impurities) fresh cleaned mechanically on all their faces immediately before experi-
ments. After the wettability experiments, the specimens were mounted, sectioned,
polished and examined by means of optical microscopy, TEM, EDS and SADP
analyses.

RESULTS AND DISCUSSION

The wetting behavior of pure copper or Cu-Ti and Cu-Cr alloys on chosen graphite
(Fig. 2) is similar to that found on compact carbon materials in [1,7-9 ] Ti as well as Cr
reduces the contact angle and the wetting of graphite appears at 1100°C with CuTi17.4
and CuCr0.88 alloys after approx. 1 and 5 minutes, or at 1200°C with CuCr10 and
CuCr1.0 alloys after 1 and 3 minutes, respectively. The Cu-Ti drops decrease their
volume due to in situ reactive infiltration of the alloy into the open porosity of the
substrate. High titanium content alloy CuTi28 intensively wets and completely spreads
on a graphite immediately after its melting that together with fast infiltration results in
disappearance of a drop from the graphite substrate. Samples obtained with all three Cu-
Ti alloys (Fig. 3a, b) are characterized by the presence of the alloy impregnated graphite
region formed under the drop, dispite the lack of wettability by CuTi10 alloy due to the
drop oxidation (Fig. 3a). The volume of this region increases with time and titanium
 INTERACTION BETWEEN Ti OR Cr CONTAINING COPPER ALLOYS... 147

content. In spite of a good wetting the depth of infiltration with Cu-Cr alloys for the
same infiltration time of 30 minutes is negligible (note higher magnification of Fig. 3c
compared to Fig. 3 a, b). This difference is apparently due to the difference in the nature
of the reaction products noted at the drop/substrate interfaces.

Fig. 3. Microstructure of Cu alloy/graphite cross sections:

a) CuTi10.8 alloy, x50; b) CuTi17.4 alloy, x50; c) CuCr1 alloy, x500.

Using TEM and EDS (Fig. 4) analyses it was identified that Cr forms a reaction
product layer whose thickness decreases from the center (5 µm) to the the periphery (0.1
µm) of the drop and consists of two types of carbides: Cr3C2 (major) and Cr7C3 (minor,
noted mainly at the drop-side interface). At about 3/4 of the lenght of the drop/substrate
148 N. SOBCZAK, J. SOBCZAK, P. ROHATGI et al.

boundary the reaction product layer of 0.5-5 µm thickness is continuous while

outside
 INTERACTION BETWEEN Ti OR Cr CONTAINING COPPER ALLOYS... 149

Fig. 4. TEM bright field image of reaction product layer at the CuCr1/graphite interface and
corresponding EDS and SADP patterns for: a) Cr3C2 noted inside the layer; b) Cr7C3 noted near
the contact with CuCr1 drop.
150 N. SOBCZAK, J. SOBCZAK, P. ROHATGI et al.

Fig. 5. TEM bright field image of reaction product layer at the CuTi17.4/graphite interface and
corresponding EDS and SADP patterns for TiC precipitates of different sizes:
a) 1-2 µm, b) 0.5 µm, c) 0.1 µm.
 INTERACTION BETWEEN Ti OR Cr CONTAINING COPPER ALLOYS... 151

this region the layer of approx. 0.1 µm thickness appears island-like, but in both cases
the layer is coherent-bonded to the substrate. These results are in agreement with
thermodynamical calculations [9] suggesting that Cr3C2 is the most stable phase in the
Cu-Cr/graphite system and data [11] confirming the formation of Cr7C3 along with
Cr3C2. According to [7], liquid copper as well Cu-Cr alloys wet freshly formed Cr3C2
phase (contact angle is 50° and 26°, respectively), however very compact reaction
product layer at the drop/substrate boundary appears to close the open pore channels
and, after their initial penetration, to block further infiltration of the Cu-Cr alloys. In a
contrast, Ti forms a reaction product layer characterized by nonuniform structure and
discontinuities (Fig. 5). It consists of separate precipitates whose size and morphology
depend on their location, but a number of EDS and SADP patterns taken from different
precipitates has shown the same chemical composition and structure indicating the TiC
carbide. The typical EDS and SADP patterns are presented in Figure 5. In the reaction
product layer, corresponding with the central part of the drop, the precipitates have a
size of approx.1-2 µm and a block morphology. In the drop direction, they decrease in
size up to 0.5 µm and become spherical. In the substrate-side region the precipitates are
very fine (0.15 µm) and also spherical.
Taking into account that contrary to chromium, Ti additions have a positive effect
on decreasing of the melting temperature of copper, the results of microstructural
examinations suggest that for the synthesis of Cu/C composite materials based on
infiltration phenomena (powder metallurgy, pressureless infiltration process), titanium
looks to be a better agent to improve compatibility between copper matrix and carbon
materials. In spite of a greater effect of chromium on decreasing of the contact angle
values, the strong interaction of Cu-Cr alloys with carbon materials leads to the
formation a thick reaction product layer which makes any deeper penetration of the
alloy into open porosity impossible.

CONCLUSIONS
Wetting behavior of Cu-Cr or Cu-Ti alloys in contact with porous graphite substrate
is similar to that observed on compact carbon materials, i.e. Ti and Cr as active alloying
elements to copper promote reactive wetting of porous graphite due to the formation of
their carbides at interfaces. The phenomenon of in situ reactive infiltration of the alloy
into porous graphite is significant with Cu-Ti alloys and negligible with Cu-Cr alloys
due to difference in the nature of the formed carbides. Contrary to Ti, chromium forms
dense and continuous reaction product layer which appears to block the penetration of
the alloy into a graphite porosity. The results of this study suggest that for liquid state
processing synthesis of composite materials based on Cu/C system, titanium is a better
wetting agent.

ACKNOWLEDGMENTS
This publication is based on the work sponsored by the Polish-American Maria
Sklodowska-Curie Joint Fund II in cooperation with the Ministry of Industry and Trade
 152 N. SOBCZAK, J. SOBCZAK, P. ROHATGI et al.

(Poland) and the National Institute of Standards and Technology (USA) under the
Project No MP/NIST-92-90.

REFERENCES
1. Yu. Naidich and G. A. Kolesnichenko Reactions of Metallic Melts with Diamond
and Graphite Surfaces, Naukova Dumka, Kiev, 1967.
2. T. Takamori, M. Akanuma - Ceram. Bull., 48, 734 (1969).
3. J. O. Diaz, D. L. McDanels in Transactions of the 6th Symposium on Space Nuclear
Power Systems, University of New Mexico, Albuquerque, NM, 1989, pp. 199-204.
4. D. A. Hutto, J. K. Lucas, W. C. Stephens in Proc. of the 31’st International SAMPE
Symposium and Exhibition, SAMPE, 1986, pp. 1145-1153.
5. S.M. De Vincent, G. M. Michal - J. Mat. Eng. and Perf., vol. 2, 3, 323 (1993).
6. P.K. Rohatgi, K. Kim, A. Saigal, J. Sobczak, N. Sobczak, D. Nath in Processing,
Properties, and Applications of Cast Metal Matrix Composites, edited by P. K.
Rohatgi, TMS, 1996, pp. 271-288.
7. D. Mortimer, M. Nicholas - J. Mater. Sci., 8, 640 (1973).
8. K. Nogi, Y. Osugi, K. Ogino - ISIJ, vol. 30, 1, 64 (1990).
9. S. M. De Vincent, G. M. Michal - Met.Trans, 24A, 53 (1993).
10. N. Sobczak, M. Ksiazek, W. Radziwill, J. Morgiel, L. Stobierski in Proc. Second Int.
Conf. „High Temperature Capillarity-97”.
11. A. Gard, S.M. Vincent, D.L. Ellis in Proc. ICEM-13, 17-22 July, 1994, Paris,
France, pp. 285-286.

Corresponding author: N. Sobczak, fax: 48-12-2665478; E-mail: natalie@iod.krakow.pl

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