U.S. patent number 3,816,081 [Application Number 05/327,071] was granted by the patent office on 1974-06-11 for abrasion resistant cemented tungsten carbide bonded with fe-c-ni-co.
This patent grant is currently assigned to General Electric Company. Invention is credited to Thomas Eugene Hale.
United States Patent |
3,816,081 |
Hale |
June 11, 1974 |
ABRASION RESISTANT CEMENTED TUNGSTEN CARBIDE BONDED WITH
Fe-C-Ni-Co
Abstract
The use of between 3 percent and 9 percent by weight of an alloy
of iron, nickel and cobalt as the bonding agent for fine-particle
(1 micron or less) tungsten carbide compact provides a material
having enhanced abrasion resistance without incurring significant
changes in transverse rupture strength.
Inventors: |
Hale; Thomas Eugene (Warren,
MI) |
Assignee: |
General Electric Company
(Detroit, MI)
|
Family
ID: |
23275017 |
Appl.
No.: |
05/327,071 |
Filed: |
January 26, 1973 |
Current U.S.
Class: |
75/237; 75/240;
75/242; 419/15; 419/17 |
Current CPC
Class: |
C22C
29/067 (20130101) |
Current International
Class: |
C22C
29/06 (20060101); C22c 001/05 (); C22c
029/00 () |
Field of
Search: |
;29/182.7,182.8
;75/203,204 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Schafer; R. E.
Claims
What I claim as new and desire to secure by letters patent in the
United States is:
1. A hard, sintered compact consisting of 91 to 97 percent by
weight of tungsten carbide base particles bonded by an alloy
consisting of 8 to 20 percent by weight of nickel, 5 percent to 15
percent by weight of cobalt, 0.8 to 1.4 percent by weight of
carbon, and the balance iron.
2. A hard, sintered compact as claimed in claim 1 wherein the
carbide contains between 0.5 and 1.0 percent by weight of tantalum
carbide.
3. A hard, sintered compact as claimed in claim 1 wherein the
bonding alloy consists of about 15 percent by weight of nickel,
about 10 percent by weight of cobalt, and about 0.8 percent by
weight of carbon.
Description
BACKGROUND OF THE INVENTION
Cemented carbides are well known for their unique combination of
hardness, strength and abrasion resistance and are, accordingly,
extensively used for such industrial applications as cutting tools,
drawing dies, wear parts, and other applications requiring these
properties. They are produced by powder metallurgy techniques
involving the liquid phase sintering of one or more refractory
carbides of Groups IV, V and VI of the Periodic Table with one or
more of the iron group metals. The iron group metal exists as a
matrix or binder in the sintered alloy and acts to bond or cement
the refractory carbide particles together.
For ferrous alloy metal-cutting applications either mixed carbides
of WC-TiC-TaC(NbC) or pure TiC are used since the presence of TiC
and TaC enhance wear and deformation resistance for this type of
application. For most other applications either pure tungsten
carbide or tungsten carbide with minor additions of TaC, NbC, or Cr
is used since tungsten carbide imparts superior abrasion resistance
and strength to cemented carbides.
When the carbide is based upon pure WC, with or without minor
additions of TaC, NbC, or Cr, the matrix or binder metal is almost
exclusively cobalt since the use of cobalt results in lower
porosity and superior strength and hardness compared with results
obtained when nickel or iron is used, especially when the matrix
metal content is relatively low, such as 10 volume percent or less.
One notable exception is the use of an iron-nickel-carbon alloy as
disclosed in Humenik et al., U.S. Pat. No. 3,384,465. When properly
composed and treated in accordance with Humenik et al., an
iron-nickel-carbon alloy can produce a WC based cemented carbide
with enhanced strength and toughness.
In applications where maximum abrasion resistance is desired and
imposed stresses are low to medium, such as grit blast nozzles or
wear protection plates, WC-Co compositions having 5 to 10 percent
matrix content and a fine carbide grain size are used. Usually a
small amount (0.1 to 1.0 wt. percent) of one of several additions
known to minimize grain growth during sintering (TaC, NbC, or Cr)
is added. While it is known that an even finer WC grain structure
would produce higher abrasion resistance, this is very difficult to
achieve in practice since grain growth does occur and the rate of
grain growth during sintering is higher for finer starting grain
sizes.
It is a principal object of this invention to provide cemented
carbide compositions having unusually high abrasion resistance. It
is an additional object of this invention to provide cemented
carbide compositions having unusual resistance to grain growth
during sintering. It is an additional object of this invention to
provide a process for producing such compositions.
SUMMARY OF THE INVENTION
This invention is based upon the unexpected finding that grain
growth of the WC phase during sintering is substantially less when
the matrix phase is an iron-based alloy present in low
concentration. In accordance with the invention a cemented carbide
alloy composed of tungsten carbide with a minor addition (0.5-1.0
percent) of tantalum carbide and a matrix consisting of 3 to 9
percent by weight of the total of an alloy of 8 to 20 percent
nickel, 5 to 15 percent cobalt, 0.8 to 1.4 percent carbon and the
balance iron is prepared. The starting tungsten carbide powder
should be very fine, with an average particle size of no more than
one micron and preferably in the 0.5 to 0.8 micron range. The other
ingredient powders shoud also be fairly fine, preferably in the 1
to 5 micron average particle size range. It is necessary to add
carbon in an amount in sufficient excess of the desired final
amount to allow for carbon losses sustained through subsequent
processing, especially the sintering step. The finally desired
carbon content can be best characterized as that amount which is
just large enough to prevent formation of the eta phase, a compound
of nominal composition W.sub.3 Fe.sub.3 C. Larger amounts of carbon
are undesirable since this causes some grain growth to occur. The
proper final carbon content for the preferred compositions of this
invention lies in the range of 0.8 to 1.4 percent of the matrix
portion of the total composition. The amount of excess carbon
necessary to obtain the desired final amount depends upon the
particular processing techniques employed.
DESCRIPTION OF PREFERRED EMBODIMENTS
Useful articles within the scope of this invention can be made
without the addition of nickel and cobalt. However, these alloying
elements are preferred because they provide enhanced abrasion
resistance and strength over and above that obtained through the
use of a straight iron-carbon matrix. To be useful, the nickel
content should be sufficient to allow the matrix phase to partially
or fully transform from its high temperature austenitic form to its
low temperature martensitic form at moderately fast cooling rates
(comparable to air cooling) rather than allowing the formation of
Fe.sub.3 C to occur, since the formation of Fe.sub.3 C causes some
reduction in strength. The useful range of nickel content is from
about 8 to about 20 percent by weight of the matrix portion and the
preferred range is from 10 to 14 percent of the matrix phase
portion.
The presence of cobalt is important for its ability to aid the
sintering of the cemented carbide alloy to a low porosity state
with resulting beneficial effects upon abrasion resistance and
strength. For this purpose, cobalt additions of 5 to 15 wt. percent
of the matrix portion are effective.
The properly composed starting powders are wet ball milled using a
WC-Co lined mill and WC-Co balls and a fluid such as acetone for a
period sufficient to grind the powder to a very fine size and
produce an intimate mixture of the constituent powders. For these
purposes a milling period of 2 to 4 days is necessary for the
starting ingredients and milling conditions employed. The milled
slurry is then dried in a hydrogen atmosphere oven and a pressing
lubricant such as paraffin wax is added in an amount of about 1.5
percent of the weight of the powder. The powder is then pressed in
molds to the desired shape using a pressure of about 30,000 psi and
the paraffin is removed by firing the parts in a dry hydrogen or
vacuum atmosphere at a temperature of 500.degree. to
600.degree.C.
The pressed and dewaxed parts are then sintered in a hydrogen or,
preferably, a vacuum furnace to a temperature of 1,350.degree. to
1,450.degree.C and held at that temperature for 15 to 30
minutes.
In the as-sintered state, the matrix phase usually contains large
amounts of Fe.sub.3 C and, sometimes, graphite flakes. This is due
to the slow cooling rate from sintering which occurs when large
production scale furnaces are used, especially when the parts are
vacuum sintered. To transform the matrix phase into the more
desirable austenite or austenite plus martensite form, it is
necessary to reheat the parts briefly to a temperature sufficiently
high (1,200.degree.-1,300.degree.C) to dissolve the Fe.sub.3 C and
graphite and then cool at a fairly fast rate (1 to 5 minutes from
1,000.degree. to about 200.degree.C). In this solution-treated
condition, nearly maximum abrasion resistance and strength are
obtained, as will be illustrated in one of the following examples.
Slight additional gains can be obtained by low-temperature treating
followed by a tempering treatment. The low-temperature treatment
causes the formation of additional amounts of martensite and the
tempering treatment provides some stress relief of the highly
strained martensite phase.
The superior hardness and abrasion resistance that can be obtained
through the use of iron-based alloy-bonded tungsten carbide will be
demonstrated in the following examples:
EXAMPLE 1
A composition was prepared consisting of 4,000 grams total of a
powder mixture containing 94% WC of about 1.0 micron average
particle size, 1% TaC and 5 percent of a matrix portion composed of
75 percent carbonyl iron containing 0.8 percent carbon, 15 percent
nickel and 10 percent cobalt. Nine grams of carbon were added to
this mixture to establish the desired final carbon content. The
powder mixture was then ball-milled 3 days in a 7-inch diameter
mill lined with WC-Co and containing 12 kg. of 1/4-inch diameter
WC-Co balls and 2,000 cc. of acetone. The ball-mill charge was then
dried, paraffinized, pressed into compacts, preheated at
500.degree.C in H.sub.2 to remove the paraffin and sintered 30
minutes at 1,400.degree.C in vacuum.
Subsequent to sintering, some of the parts were then
solution-treated 5 minutes at 1,300.degree.C followed by fast
cooling, then cooled to liquid nitrogen temperature, and then
tempered by heating one hour at 300.degree.F in air. Tests of
hardness, abrasion resistance, and transverse rupture strength were
made at each stage of processing after sintering to determine the
effect of the thermal treatments. The abrasion test apparatus
consisted of a rotating 61/2 inch diameter, 1/2-inch wide steel
disk which contained on its periphery particles of aluminum oxide
grit obtained by having the lower portion of the disk submerged in
a slurry of the grit and water. The periphery of the rotating disk
was forced against a flat pad of the cemented carbide to be tested
using a force of 40 pounds. The test duration consisted of 1,500
revolutions of the disk at a speed of 100 rpm. Fresh slurry was
used for each test. The volume of material abraded away was then
determined by measuring the weight loss of the pad. The results
obtained are shown in Table I. The abrasion test results are
reported as the reciprocal of the volume loss since the number so
obtained is of convenient size and is directly proportional to the
abrasion resistance of the material being tested. Included in Table
I are test results for a 93.5% WC--0.5% TaC--6% Co cemented carbide
composed of the same starting particle sizes used for the
iron-based matrix composition and subjected to comparable
processing conditions.
TABLE I
__________________________________________________________________________
Trans- Abrasion verse Processing Hardness Resistance Rupture
Composition Stage R.sub.A l/vol loss (cc) Strength
__________________________________________________________________________
94% wC-1% TaC-5% (74% Fe-15% Ni-10% Co-1C%) As sintered 93.5 92
257,000 do. Above + solution treated 93.5 111 187,000 do. Above +
liq. N2 treated 93.7 100 190,000 do. Above + 300.degree.F tempered
93.7 113 204,000 93.5% WC-0.5% TaC-6% Co As sintered 92.9 55
260,000
__________________________________________________________________________
It can be observed that at any stage of processing the WC-iron
alloy composition has higher hardness and abrasion resistance than
does the comparable WC-Co material. It is also evident that a
significant increase in abrasion resistance is obtained by
solution-treating the WC-iron alloy material, although this is
accompanied by a strength reduction. The additional thermal
treatments provide slight additional benefit in the form of
optimizing the combination of strength and abrasion resistance.
When the microstructures of the two compositions were viewed at
1,500 power it was observed that the WC-iron alloy material had a
noticeably finer WC grain structure, apparently caused by the
superior ability of the iron alloy to inhibit wC grain growth
during sintering.
EXAMPLE 2
A composition consisting of 94% WC--1% TaC--5% (74% Fe--15% Ni--10%
Co--1C) was prepared as in Example 1 above with the exception that
the starting WC powder particle size was somewhat finer, averaging
about 0.85 microns. Abrasion test pads and transverse rupture
strength test bars were prepared and processed through the full
thermal treatment sequence shown in Example 1 above. For comparison
purposes a composition consisting of 93 % WC--1% TaC--6% Co was
prepared using the same WC powder. It should be noted that the
matrix phase contents of these two compositions are equal on a
volume basis. They differ on a weight basis because of their
differing densities. The resulting properties are shown in Table
II.
TABLE II
__________________________________________________________________________
Abrasion Transverse Hardness Resistance Rupture Composition R.sub.A
l/vol. loss (cc) Strength
__________________________________________________________________________
94% WC-1% TaC-5% (74% Fe-15% Ni-10% Co-1C%) 94.1 191 185,000 93%
WC-1% TaC-6% Co 93.4 70 192,000
__________________________________________________________________________
In this case the abrasion resistance of both compositions is higher
than their counterparts in Table I, apparently due to the use of
finer WC powder. The iron-alloy matrix composition, however, made
much more effective use of the finer starting WC powder than did
the cobalt matrix composition, resulting in a nearly doubled
abrasion resistance compared with about a 30 percent increase for
the cobalt-matrix composition. This even more clearly demonstrates
the superior ability of the iron-alloy matrix to inhibit grain
growth during sintering.
EXAMPLE 3
A 4,000-gram batch of a composition consisting of 94% WC of about
0.85 micron average particle size and 5 percent iron containing 1
percent carbon was prepared and processed as in Example 1 above.
The resulting hardness and abrasion resistance were 93.3 and 118,
respectively, and the transverse rupture strength was 160,000 psi.
While not as good as the comparable composition containing nickel
and cobalt in the matrix phase, the straight iron-carbon matrix
alloy composition has utility since its abrasion resistance is
significantly higher than can be easily obtained using a cobalt
matrix.
EXAMPLE 4
For 4,000-gram batches of compositions consisting of WC of about
0.85 micron average particle size and varying amounts of matrix
powders to compose a matrix composition 15% Ni--10% Co--1% C and
the balance Fe ranging in matrix content from 3 to 9 weight percent
were prepared and processed as in Example 1 above. The resulting
hardness, strength and abrasion resistance were then determined for
each composition in order to establish the useful range of matrix
content. The results are shown in Table III along with results
obtained for a comparably prepared composition consisting of 93%
WC--1% TaC--6% Co.
TABLE III
__________________________________________________________________________
Abrasion Transverse Hardness Resistance Rupture Composition R.sub.A
l/vol. loss Strength
__________________________________________________________________________
96% WC-1% TaC-3% (74% Fe-15% Ni-10% Co-1C%) 94.0 135 175,000 94%
WC-1% TaC-5% (74% Fe-15% Ni-10% Co-1C%) 94.0 175 180,000 92% WC-1%
TaC-7% (74% Fe-15% Ni-10% Co-1C%) 93.2 95 190,000 90% WC-1% TaC-9%
(74% Fe-15% Ni-10% Co-1C%) 93.0 60 240,000 93% WC-1% Tac-6% Co 93.4
70 190,000
__________________________________________________________________________
It can be seen that as a function of the amount of matrix phase
present, the abrasion resistance is optimized at about the 5 weight
percent level and that there is no advantage in increasing the
matrix content to above 9 percent since the abrasion resistance
drops to a level below that which can be obtained using a
conventional cobalt matrix.
* * * * *