U.S. patent number 3,668,748 [Application Number 04/857,376] was granted by the patent office on 1972-06-13 for process for producing whisker-reinforced metal matrix composites by liquid-phase consolidation.
This patent grant is currently assigned to American Standard Inc.. Invention is credited to Amarnath P. Divecha, Henry Hahn, Robert A. Hermann, Paul J. Lare, Fred Ordway, Jr., Orville B. Van Blaricon.
United States Patent |
3,668,748 |
Divecha , et al. |
June 13, 1972 |
PROCESS FOR PRODUCING WHISKER-REINFORCED METAL MATRIX COMPOSITES BY
LIQUID-PHASE CONSOLIDATION
Abstract
A fiber-reinforced metal composite of desired shape is produced
by consolidating a mixture of the metal matrix and the fibers under
pressure with the mixture maintained at a temperature in which the
matrix system is partly in the liquid phase and partly in the solid
phase, utilizing a liquid-phase extrusion die cavity of
predetermined volume. With approximately one quarter of the matrix
system in the liquid phase, and containing up to approximately 50
percent by volume of oriented fibers or whiskers, the material of
the composite billet is extruded into the die cavity in order to
consolidate the composite billet to the volume of the die cavity,
in which the desired shape is to be formed. Heating is discontinued
when the cavity is filled completely by the semi-molten metal fiber
composite.
Inventors: |
Divecha; Amarnath P. (Falls
Church, VA), Lare; Paul J. (Bowie, MD), Ordway, Jr.;
Fred (Bethesda, MD), Hermann; Robert A. (Rockville,
MD), Van Blaricon; Orville B. (Alexandria, VA), Hahn;
Henry (Fairfax, VA) |
Assignee: |
American Standard Inc. (Falls
Church, VA)
|
Family
ID: |
25325855 |
Appl.
No.: |
04/857,376 |
Filed: |
September 12, 1969 |
Current U.S.
Class: |
29/419.1;
29/527.5; 164/97; 164/319; 419/47; 29/DIG.47; 164/76.1; 164/120;
419/10; 419/24; 419/48 |
Current CPC
Class: |
B21C
29/00 (20130101); B21C 23/01 (20130101); C22C
47/08 (20130101); Y10T 29/49801 (20150115); B22F
2998/00 (20130101); Y10T 29/49988 (20150115); B22F
2998/00 (20130101); Y10S 29/047 (20130101); C22C
47/04 (20130101) |
Current International
Class: |
C22C
47/08 (20060101); B21C 29/00 (20060101); B21C
23/01 (20060101); C22C 47/00 (20060101); B23p
017/00 (); B22f 003/24 () |
Field of
Search: |
;29/419R,419G,420,527.5,527.7,DIG.47 ;164/120,319,76,321 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Campbell; John F.
Assistant Examiner: Reiley, III; Donald C.
Claims
We claim:
1. A process for producing a fiber-reinforced composite having
oriented fibers by means of a single hot forming operation, said
process comprising placing a billet of a matrix of metal and fibers
adjacent a liquid-phase extrusion die cavity in a position
intermediate said die cavity and a plunger, solely induction
heating said billet and die cavity to a temperature only
sufficiently in excess of the solidus temperature of said matrix to
achieve melting of about 20-25 percent of the metal of said matrix,
the volume of material in said billet being only slightly in excess
of the internal volume of said die cavity, moving said plunger in a
direction and for a predetermined distance selected to extrude
material of said billet into said die cavity with only slight
overage of matrix material such that shear flow of the matrix
material occurs and the fibers become oriented along the direction
of shear, and immediately thereafter terminating induction heating
of said billet and die cavity.
2. The process according to claim 1, wherein said billet contains
up to 50 percent by volume of ceramic fibers.
3. The process according to claim 2, wherein said fibers are
substantially commonly oriented in said semi-molten billet.
4. The process of producing a fiber-reinforced metal composite
having oriented fibers by means of a single hot forming operation,
said process including heating a fiber-alloy billet composed of up
to 50 percent of fibers in a metal alloy powder to a temperature
sufficient to convert not more than 50 percent of the alloy to the
liquid phase but less than the melting point of said fibers, while
the billet is positioned adjacent to a liquid-phase extrusion die
cavity of volume substantially equal to the volume of said billet,
and applying pressure to the semi-molten billet thus produced to
extrude said billet substantially entirely into said cavity such
that shear flow of the matrix material occurs and the fibers become
oriented along the direction of shear, and thereafter terminating
heating of the billet in said cavity.
5. The process according to claim 4 wherein said metal matrix is up
to 25 percent liquid in said semi-molten state of said billet.
6. The process according to claim 5 wherein said matrix is
aluminum-2.5 percent silicon alloy.
7. The process according to claim 6 wherein said fibers are silicon
carbide.
8. The process according to claim 1 wherein said fibers are
composed of a material selected from the group consisting of
silicon carbide and alpha alumina.
9. The process according to claim 3 wherein said fibers possess a
coating of magnetic material and are oriented in a magnetic field
during formation of said billet.
10. The combination according to claim 1, wherein after solidifying
of said billet and die cavity following terminating of said
heating, removing fiber-reinforced composite from said cavity.
Description
BACKGROUND OF THE INVENTION
The present invention relates generally to the reinforcement of
metal matrixes with high-strength ceramic fibers (whiskers), coated
with suitable metals, or uncoated, and more particularly to
apparatus and processes for incorporation of the fibers in a matrix
using a method of consolidation and extrusion inherently producing
a preferred fiber orientation. The term fiber includes but is not
limited to SiC, B, Al.sub.2 O.sub.3.
In the application of Divecha et al., Ser. No. 626,190, filed Mar.
27, 1967, entitled "Preparation of Fiber-Reinforced Metal
Composites by Compaction in the Liquid-Phase," of common assignee
herewith, now U.S. Pat. No. 3,441,392, issued Apr. 29, 1969,
several prior art methods of producing fiber-reinforced composites
are discussed, and it is observed that one of the principal
problems encountered in obtaining fiber-reinforced metal composites
has been the lack of suitable processes capable of producing
specimens in sizes sufficiently large for practical use and for
meaningful evaluation of working characteristics.
One basic requirement in the production of the successfully
reinforced composite is the capability of the composite to transfer
load from one whisker or fiber to another. Another requirement is
that there be a strong bond at the whisker-matrix interface.
Wetting of the fibers by the matrix is also essential, and it has
been found, for example that pure molten nickel bonds to alumina
fibers under prolonged contact of about 30 minutes or more, and
that addition of slight amounts of chromium (approximately 1
percent) also enhances wetting of the fibers.
In typical prior art processes the fibers undergo random
orientation during formation of the composite, and consequently the
compacted and extruded material is of lower strength than could be
achieved by selective orientation of the fibers. Moreover,
considerable fiber fracture occurs during the consolidation
process. In the process disclosed in the aforementioned Divecha et
al patent, compaction is performed at temperatures at which the
metal matrix is maintained in its semi-molten region. More
specifically, the matrix material is mixed in powder form with the
coated or uncoated fibers, the latter in loose separated form, and
the resulting mixture placed in the die of a conventional
hot-pressing apparatus where it is heated to a temperature slightly
below the solidus of the system. At that point, a predetermined
constant pressure is applied to the metal matrix-fiber system and
the temperature of the composite is then raised until the state of
the system experiences a cross-over into the semi-molten region of
the matrix. Pressure is maintained until desired compaction is
achieved, the matrix completely encapsulating the fibers after
which the composite is cooled and removed and hot rolled to produce
a preferred fiber orientation. Prior to the hot rolling operation,
the process produces dense bodies consisting of randomly oriented
whiskers in the metal matrix. In order to retain liquid metal
within the die cavity while the composite is under pressure at
consolidation temperatures, extremely close tolerances are
maintained between the solid punch and die cavity of the press
mechanism.
While the process as disclosed in detail in the aforementioned
Divecha et al. patent is highly advantageous over processes
disclosed in the art prior thereto, it is not without its
limitations. In particular, while the composites produced are
substantially larger than those produced by earlier-employed
techniques, they are nevertheless still of relatively small size,
necessarily limited by existing mechanical apparatus. For example,
such structural shapes as rods, I-beams, tubing, and channels are
not readily fabricated by this process because of the usual size
requirements of those articles. In addition, a hot rolling step is
ultimately necessary to ensure whisker orientation in the preferred
direction. The process is best employed to produce solid
cylindrical shapes as an initial product prior to further machining
or other processing. Other shapes may be produced, but are less
desirable economically because of the special die designs involved,
as well as material costs and availability.
In the co-pending application of Lare et al., Ser. No. 799,329,
filed Feb. 14, 1969 now abandoned, entitled "Process for
Consolidation and Extrusion of Fiber-Reinforced Composites," and
commonly assigned with respect to this application, there is
disclosed a process for producing fiber-reinforced composites in a
single continuous operation in which extrusion of the composite
into the desired shape immediately follows consolidation of the
fiber-matrix system into the reinforced composite, without the
requirement of transfer of the composite to another press. In that
invention the press includes a die cavity having one or more
orifices, each of which is normally closed by a seal of sufficient
rigidity to withstand consolidation pressure exerted on the
fiber-matrix system, but which seal is itself adapted to undergo
extrusion to permit the immediately priorthereto consolidated body
to be extruded via the respective die orifice (also termed the
extrusion port). After the "green" i.e., unconsolidated
fiber/powder mixture is placed into the die, the entire assembly is
heated slowly from room temperature to a temperature slightly above
the solidus temperature of the mixture, that is, to a temperature
at which the matrix is in the liquid phase or in a semi-molten
state. During this period, the system is maintained under
relatively low pressure in the range from approximately 2,000 to
approximately 5,000 pounds per square inch (psi), in a manner
similar to that disclosed in the aforementioned Divecha et al
patent, until the desired consolidation is achieved. However, in
accordance with the Lare et al. invention, upon conclusion of the
consolidation cycle the temperature is reduced to a value between
the solidus and matrix melting point (a state which may be
characterized as a "mushy" phase), and the pressure on the
consolidated system or composite is increased to a value sufficient
to rupture the seal and to extrude the composite via the extrusion
port. This range of temperature values, at which pressure in excess
of the consolidation pressure is applied to the composite for
extrusion thereof, is critical.
In particular, in the latter invention extrusion is performed at a
temperature at which the shear strength and tensile strength of a
matrix are sufficiently low to permit ready flow of the matrix
material, such that the fibers are merely carried with the matrix
in the direction of matrix deformation. While the precise
temperature is dependent upon the character and concentration of
fibers or whiskers, it resides in a relatively narrow range quite
close to the melting point of the matrix.
It has been found that this temperature range near the melting
point of the matrix produces some surface tearing of the composite,
and additionally that fiber fracture occurs in significant
proportions.
It is a principal object of the present invention to provide a
process for producing fiber-reinforced metal matrix composites
which overcomes one or more of the disadvantages of the prior art
processes.
SUMMARY OF THE INVENTION
Briefly, according to the present invention, a process for
producing fiber-reinforced metal matrix composites is performed by
consolidation entirely in the semi-molten putty-like state. In
brief, a composite billet is prepared which incorporates the
desired fibers, such as alumina and/or silicon carbide, in a metal
matrix, the billet containing up to about 20 percent by volume of
oriented whiskers (fibers). The whisker orientation may be
controlled by a magnetic orientation system in which the fibers
themselves follow the magnetic lines of force, provided they have
been coated with magnetizable metal. The entire assembly is heated
to approximately 585.degree. C, in the case of a matrix alloy
composed of 2.5 percent silicon and the balance aluminum, this
temperature being above the solidus temperature to maintain from
about 20 to about 25 percent of the metal matrix in the liquid
phase. At this point, pressure is applied to the billet for
compaction thereof into a closed die cavity, the billet volume
being slightly in excess of that formed by the cavity. A ram
associated with the press in which the billet is contained is
forced against the billet to produce a pressure of from 2,000 to
5,000 psi thereon in order to produce flow of the putty-like
material. The ram travel is accurately monitored, and the heating
is ceased when the billet has been entirely transferred to the
cavity. The extent of travel of the ram is predetermined to insure
that the cavity is entirely filled by the semi-molten metal
composite. Since the volume of the composite is substantially
identically equal to the volume of the closed die cavity, complete
densification is achieved.
By use of the process of the present invention many complex shapes,
such as nuts, bolts, engine blocks, turbine blades, and so forth,
may be formed with reliable composite strength as a consequence of
the high aspect ratio and controlled orientation of the fibers and
the complete compaction of the final composite member. Only the
closed die configuration need be altered according to shape of the
composite to be formed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified schematic diagram of a press employing a
closed die cavity for preparation of a rod shaped composite;
and
FIG. 2 is a schematic diagram of a press, similar to that shown in
FIG. 1, except that the closed die cavity of this embodiment is
used for preparation of a tubular or cup-shaped composite.
DESCRIPTION OF THE PREFERRED PROCESS
Suitable fibers (whiskers) for use in reinforcing the metal matrix
include alpha alumina (sapphire) and silicon carbide, Carbon, Boron
or the like of fiber diameters ranging upwardly to approximately 30
microns and of lengths up to about one-half inch. The fibers may be
either coated with suitable metal or uncoated, or both. An example
of a suitable coated fiber is sapphire which has been plated with a
thin coating of nickel. Such fibers are available from several
sources, one of which is General Technologies Corporation, of
Reston, Virginia.
In preparation of each fiber-reinforced metal composite by
compaction or consolidation in the liquid phase of the matrix, the
use of an alloy as the matrix is preferred over the use of a pure
metal, since liquid phase hot pressing requires a system having a
distinct two-phase region (i.e., liquid plus solid). Either mixture
or prealloyed powders of the matrix components may be utilized, but
the prealloyed powder has the advantage of a known melting point,
whereas the melting point of the mixture must usually be
ascertained by experimentation. Moreover with the prealloyed powder
there is less probability of producing a non-homogenous structure
as a result of the formation of an undesirable intermetallic phase
during heating and compaction.
Some of the many suitable mixed and prealloyed powders for
preparation of the fiber-reinforced composite include prealloyed
atomized powder composed of 10.2 percent by weight of silicon, 0.03
percent magnesium, 0.67 percent iron, and the balance aluminum, of
sufficient fineness to pass a standard No. 325 screen, Al-2.5 Si
minus 400 mesh prealloyed atomized powder; Al-Cu minus 325 mesh
prealloyed atomized powder composed of 4.5 Cu, balance Al; 7075 Al
minus 325 mesh prealloyed atomized powder composed of 0.3 Si, 0.6
Fe, 2.1 Cu, 0.2 Mn, 2.2 Mg, 0.2 Cr, 0.10 Ni, 4.7 Zn, balance Al,
all of the foregoing powders available from Reynolds Aluminum
Company, Richmond, Virginia; Nichrome, 80 Ni-20Cr minus 325 mesh
prealloyed atomized powder; Nickel -- 2 percent by weight silicon
mixed powders; 99.7 percent pure nickel powder, 4-7 microns,
prepared by carbonyl process, available from International Nickel
Company, of Reston, Virginia; 98 percent pure silicon powder, minus
325 mesh, available from Consolidated Astronautics, New York; and
nickel minus 325 mesh prealloyed atomized powder, composed of 1 Si,
1 Mn, balance Ni, available from Hoeganaes Sponge Iron Company of
New Jersey.
The following is an example of a process according to the
invention, in which an extremely dense silicon carbide
fiber-reinforced aluminum-silicon composite is prepared in a
desired shape.
After the silicon carbide fibers have been dispersed or separated
in known manner, as by agitation is isopropanol, a prealloyed
atomized powder or mixed powder, composed of 2.5 weight percent
silicon and the balance aluminum, passing a standard No. 400
screen, is added to the resulting slurry in an amount to produce a
metal matrix containing up to 50 percent by volume of silicon
carbide fibers. In this specific example the volumetric percentage
of SiC fibers is 15 percent. Preferably the fibers have diameters
in the range from one to three microns and lengths up to about
one-half inch. The constituents of the fiber-metal mixture are
thoroughly mixed by stirring or agitation for a period of several
minutes, during which the mixture may be filtered by aspiration
through filter paper.
In order to achieve superior distribution of the composite fibers
and to provide higher strength of the ultimate composite material,
particularly at the higher fiber concentrations (up to about 40
percent by volume), it is advantageous to use an oriented-fiber
matrix mixture. This may be achieved by depositing a thin film of
magnetic material such as nickel on the fibers, by an appropriate
method such as thermal decomposition of a volatile compound such as
nickel carbonyl, Ni(CO).sub.4. The metallized whiskers are then
dispersed with the matrix powder to produce a slurry in isopropanol
as described earlier. By filtration of the slurry through filter
paper in a magnetic field the metallized fibers are deposited on
the paper in parallel alignment.
Thereafter, the mixture is dried for compaction or consolidation in
a press, such as the hot pressing apparatus shown in FIGS. 1 and 2.
The matrix-fiber mixture (billet) 10 is placed adjacent to a die
cavity 12 which is closed by a blocking plate aligned with the
orifices of the cavity, the latter forming the shape of the final
extruded composite. The press is heated by induction coils 17, the
low melting alloy of aluminum -- 2.5 percent silicon of the present
example being processed using a tool steel die 18, although a
graphite die suitable for higher melting alloys may be employed, if
desired. It is desirable, in any event, to employ a plunger or ram
20 and block 22 of graphite to prevent seizing, despite the use of
low melting alloys. For a tool steel die, the walls of the die
cavity may be coated with suitable lubricant such as molybdenum
disulfide to permit rapid ejection and complete extrusion of the
composite following consolidation.
The die may be encompassed by a graphite layer 23, and encased in a
fused silica tube 25 as is typical of conventional hydraulic hot
pressing apparatus. Induction heating coil 17 is wound about the
silica tube 25, and a temperature sensing element such as
thermocouple 28 may extend into a recess 29 within graphite layer
23 to allow monitoring of the temperature of the press at a point
in close proximity to the fiber-matrix mixture.
After insertion of the fiber-alloy mixture 10 into the die cavity,
the die is heated by the induction unit to approximately
585.degree. C which is above the solidus temperature of the
mixture, thereby melting about 20 to about 25 percent of the metal
in the case of the aluminum--2.5 percent silicon alloy. When the
matrix is heated to a temperature in excess of the solidus
temperature, pressure of 2,000 psi to 5,000 psi is applied by the
ram to force the billet 10 into the closed die cavity 12. The
billet volume is slightly in excess of that of the cavity. The
movement or travel of the hydraulic ram 20 is monitored. When a
predetermined position is reached, at which the cavity is entirely
filled by the semi-molten metal composite, the heating is
discontinued. It should be noted that the billet will not flow
under ordinary conditions because the low percentage of liquid
matrix and the presence of the fibers therein result in a
putty-like consistency.
Only the shape of the die cavity need be changed to conform to the
desired shape of the extruded composite. Movement of the punch or
ram serves to form the billet into the shape of the die cavity. The
composite billet excess is minimal or negligible because the
material is almost entirely forced into the container cavity during
entry of the ram therein. The effect is formation of the desired
shape under total compressive or triaxial force to achieve
substantially complete densification, and a porosity much lower
than has heretofore been achieved. In addition, there is virtually
no waste of composite material under compaction, because it is
assured in advance that the billet is of sufficient volume
(substantially equal to the volume of the cavity) to be
consolidated entirely within the die cavity.
The die assemblies shown in FIGS. 1 and 2 are substantially
identical except for the shape of the die (and hence, of the die
cavity). In FIG. 1, die 18 is provided with an elongated axial hole
constituting the cavity 12, to permit formation of rod-shaped
composites. In FIG. 2, die 18, in conjunction with graphite
container 23, forms a tubular cavity 12 to permit formation of
cup-shaped composites.
It is to be emphasized that according to the present invention a
fiber-reinforced metal composite is consolidated by the monitored
movement of a punch or ram of a press to force the semi-molten
putty-like composite billet entirely into a closed die cavity of
desired shape. Since the volume of the billet is substantially
equal to or slightly in excess of the volume of the cavity, it is
assured that essentially the entire billet is transferred to the
cavity, and consolidation under total compressive or triaxial
forces assures that nearly complete densification is achieved
(i.e., voids are virtually absent from the consolidated
composite).
A desirable fiber orientation exists in the resulting consolidated
composite by virtue of the flow taking place during the process,
which tends to align the fibers along the direction of shear. Thus
a comparatively complex shape may be readily obtained with
reinforcing fibers oriented differently at different points, the
various orientations being such as to provide optimum strength of
the piece at each point.
* * * * *