REINFORCEMENT OF NICKEL WITH CARBIDE-COATED CARBON FIBERS

V. E. Ovcharenko, O. A. Kashin,
E. F. Dudarev, I. A. Lapsker,
and L. A. Turovets
UDC 621.762
For the manufacture of the majority of constructions operating at high temperatures
materials of high specific strength are required. This requirement tan be fulfilled by
using heat-resistant nickel alloys reinforced with high-strength carbon fibers. A major
obstacle hindering production of such composite materials is nickel-activated graphitization
of carbon fibers at temperatures above 800~ as a result of which the strength of the fibers
and hence of the composite as a whole sharply falls.
Various protective (carbide, nitride, and carbonitride) coatings have been employed
with the aim of suppressing the physicochemical reaction of carbon fibers with their nickel
matrix [1-8]. In the work described below carbon fibers were coated with titanium carbide.
This was performed by immersing the fibers in a carbide-forming copper--titanium (Cu + 25
wt.% Th) melt. The copper in this melt acted as a carbide-forming-element carrier
which was chemically inactive with respect to carbon. The presence of the above-mentioned
quantity of titanium resulted in the carbide-forming alloy having the lowest possible melting
point [9] and at the same time ensured good wetting of the carbon fibers by the melt [I0].
Carbide-coated carbon fibers were obtained by immersing for a short time (30 sec) bundles
consisting of 300 VMN-4 fibers in the carbide-forming melt at I150~ in a vacuum corresponding
to i0 -~ mm Hg. X-ray structural studies and electron probe microanalyses demonstrated that :
the carbide coatings on the carbon fibers were of composition TiC and thickness ~ 0.8 um. They
were continuous and evenly thick, and their shape accurately reproduced the configuration of
the fiber cross section (Fig. i). At the points of close packing of the fibers in a bundle
the carbide coatings of adjacent fibers sometimes joined together.
As a result of the coating of the carbon fiber bundles in the carbide-forming melt
200-~m-diameter filaments were obtained consisting of carbide-coated carbon fibers and a
copper--titanium matrix (Fig. 2). The fibers occupied ~ 50% of the volume of these filaments.
The strength of the filaments, which was preserved up to a temperature of IO00~ attained
40 kgf/mm 2 (see below).
Effect of Temperature on Strength of Bundles of Carbon Fibers
Coated in Cu--33 at.% Ti Melt
Te s t Temp. , ~ 20 400 800 900 1000
Te ns i l e s t r e ngt h a t , 39 4! 41 ~ 39
k g f / = a
In this connection, it was considered of interest to explore the possibility of employ-
ing bundles of carbon fibers coated in a carbide-forming melt for reinforcing nickel matrices.
Bundles of coated fibers were electroplated with nickel and annealed for various periods of
time at 800, 900, and II00~ in a vacuum corresponding to i0 -~ mm Hg. Tensile tests revealed
that even shortannealing at any of the temperatures investigated had markedly decreased the
strength of filament specimens (Fig. 3). However, the strength of individual fibers separated
out of the filaments by pickling had remained unchanged. Metallographlc examinations of micro-
graphs of cross sections of nickel-plated bundles composed of carbon fibers coated in a Cu-Ti
melt established the following. The heat treatment of such a specimen leads to the formation,
at the interface between the bundle and nickel coating, of micropores, whose amount and size
grow with increasing annealing time. Ultimately, the nickel coating almost completely detaches
itself from the bundle. The rate of the exfoliatlon process increases with rise in annealing
temperature.
Siberian Physicotechnical Institute. Translated from Poroshkovaya Metallurgiya, No.
10(202), pp. 43-46, October, 1979. Original article submitted December 20, 1978.
0038-5735/79/1810-0713507.50 9 1980 Plenum Publishing Corporation 713
Fig. 1 Fig. 2
Fig. i. Micrograph of cross sections of carbon fibers coated
in carbide-forming copper--titanium melt (secondary electrons),
x 1500.
Fig. 2. Micrograph of bundle of carbon fibers coated in carbide-
forming copper--titanium melt, 150.
ot, kgf/ mm 2
g ~ ~ g ~h
Fig. 3. Variation of tensile strength
of nickel-plated carbon fibers coated
by immersion in carbide-forming melt with
time of annealing at various temperatures:
i) 800; 2) 900; 3) Ii00; 4) 900C after
preannealing, removal of old nickel coating,
and deposition of new.
The formation of pores at the interface in a carbide-coated bundle plated with nickel
alters the character of fracture of a specimen of the composite (Fig. 4). The fracture of
the composite as a whole (Fig. 4a) gradually changes into a series of fractures, first of
the nickel shell and then of the fibers, with some of the latter being pulled out of the
matrix. Of course, the strength of such specimens decreases, tending to some value determined
by the strength of the bundle of carbide,coated carbon fibers. Thus, the adverse effect of
heat treatment at 800-II00C on the strength of nickel-plated bundles of carbon fibers coated
by immersion in a carbide-forming copper-titanium melt is a result of the formation of dif-
fusional porosity at their interfaces. The formation and growth of the porosity is clearly
due to the diffusional mobility of copper in nickel being greater than that of nickel in
copper [9].
Electron probe microanalyses of the distribution of copper and titanium on cross sections
of bundles of carbon fibers coated by immersion in a copper-titanium melt revealed that their
surface layers consisted of pure copper. The high volume concentration of carbon fibers in
such a Bundle hinders the migration of copper from the central part of a specimen toward the
nickel deposit interface, thereby assisting the localization of the diffusional porosity at
this interface. It is reasonable to assume that removal of the surface layer from a bundle
would decrease the intensity of interdiffusion at its interface.
Dissolution of the matrix of a bundle of coated carbon fibers in an acid may damage
the carbide coatings on the fibers. Because of this, in our work the surface copper layer
was removed by stripping of the copper-impregnated nickel coating (after 5-h annealing at
900@C). This was followed by the application of another nickel coating. The resultant
specimens were annealed for various periods of time at 900=C and then subjected to tensile
tests (Fig. 3, curve 4). It was found that the removal of copper from the surface of a
714
Fig. 4. Fractograms of nickel-plated bundles of carbon fibers
coated by immersion in copper--titanium melt, x 150: a) before
annealing; b) after annealing at 800~ i0 h; c) the same, 25 h;
d) at IIO0~ 1 h; e) the same, 3 h.
bundle of carbon fibers coated by immersion in a carbide-forming melt, involving heat treat-
ment together with its nickel coating, substantially increases the strength of the composite
material.
Thus, the feasibility has been established in principle of increasing the specific heat
resistance of nickel by reinforcing it with bundles of carbon fibers coated by immersion in a
carbide-forming melt. In such a case, however, it is necessary to prevent the elements of
the carbide-forming alloy from dissolving preferentially in the nickel matrix. This can be
achieved, e.g., by additionally alloying the carbide-forming alloy or by alloying the nickel
matrix.
LITERATURE CITED
I. L. Aggour, E. Fitzer, and W. Weisukiler, "Microprobing and x-ray diffraction analysis
of titanium carbide, titanium nitride, and titanium carbonitride deposited at tempera-
tures of Ii00 and 1500~ '' High Temp.--High Pressures, 6, 73-84 (1974).
2. Brit. Pat. No. 1331728, Dec. 22, 1971.
3. French Pat. No. 2121277, Aug. 18, 1972.
4. Brit. Pat. No. 1325291, Aug. I, 1973.
5. Brit. Pat. Appl. No. B221/00/c23B5/045/50, Oct. 30, 1974.
6. U.S. Pat. No. 3823029, July 9, 1974.
7. U.S. Pat. No. 3953647, Apr. 27, 1976.
8. French Pat. No. 2192067, Feb. 8, 1974.
9. M. Hansen and K. P. Anderko, Constitution of Binary Alloys, McGraw-Hill, New York (1957).
i0. Yu. V. Naidich, Contact Phenomena in Metallic Melts [in Russian], Naukova Dumka, Kiev
(1972).
ii. D.M. McKee and V. I. Mimeault, "Surface properties of carbon fibres," Chem. Phys.
Carbon, ~, No. 8, 151-245 (1973).
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