U.S. patent number 3,840,367 [Application Number 05/226,013] was granted by the patent office on 1974-10-08 for tool alloy compositions and methods of fabrication.
Invention is credited to Erwin Rudy.
United States Patent |
3,840,367 |
Rudy |
October 8, 1974 |
TOOL ALLOY COMPOSITIONS AND METHODS OF FABRICATION
Abstract
A composition of material comprising a titanium molybdenum
carbide and an iron group metal binder is disclosed which is
particularly useful as a metal cutting tool. The carbide phase of
the composition is substantially richer in carbon than the prior
art. For any given metal exchange ration, the carbide phase
contains more carbon than the composition line TiC-Mo.sub.2 C for
the same ratio. Also, the carbide phase can contain higher amounts
of molybdenum than was used in the prior art.
Inventors: |
Rudy; Erwin (Beaverton,
OR) |
Family
ID: |
22847201 |
Appl.
No.: |
05/226,013 |
Filed: |
February 14, 1972 |
Current U.S.
Class: |
51/293; 419/15;
75/240; 428/932 |
Current CPC
Class: |
C22C
29/06 (20130101); Y10S 428/932 (20130101) |
Current International
Class: |
C22C
29/06 (20060101); C22c 029/00 () |
Field of
Search: |
;29/182.7,182.8
;75/202,203,204 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Suzuki, H. et al., Chem Abs., No. 114998 Vol. 74, 1971, Q01 A51.
.
Fukatsu, T. et al., Chem Abs., No. 3965c Vol. 63, 1965, Qd1A51.
.
Schwarzkopf P. et al., Cemented Carbides, Macmillan, New York,
1960, p. 91, TP 770 53..
|
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Schafer; R. E.
Attorney, Agent or Firm: Reagin; Ronald W.
Claims
What is claimed is:
1. A composition of material comprising sintered carbide-binder
metal in which said carbide has titanium and molybdenum as its base
metal and has a gross composition falling within the area EFGH of
FIG. 1, and in which said binder is selected from the iron group
metals and comprises between 5 and 25 weight percent of the
composition.
2. A composition of material according to claim 1 in which said
carbide has a gross composition falling within the area E'F'G'H' of
FIG. 1.
3. A composition of material according to claim 2 in which said
binder is selected from the group consisting of nickel and cobalt
and comprises between 8 and 12 weight percent of the
composition.
4. A composition of material according to claim 1 in which up to 30
mole percent of the total amount of titanium in the composition is
replaced by a material chosen from the group consisting of hafnium,
niobium and tantalum.
5. A composition of material according to claim 1 in which up to 50
mole percent of the total amount of molybdenum in the composition
is replaced by tungsten.
6. A composition of material according to claim 5 in which up to 10
mole percent of the combined amounts of molybdenum and tungsten in
the composition is replaced by chromium.
7. A composition of material according to claim 1 in which up to 25
mole percent of the total amount of carbon in the composition is
replaced by nitrogen.
8. A composition of material according to claim 1 in which up to 20
mole percent of the total amount of titanium in the composition is
replaced by vanadium.
9. The method of forming a composition of material comprising a
sintered carbide-binder metal in which said carbide has titanium
and molybdenum as its base metal and has a predetermined gross
composition falling with the area EFGH of FIG. 1, comprising the
steps of:
forming a homogeneous solid solution powder alloy of (Ti,Mo)C which
contains a higher mole percent molybdenum than said predetermined
gross composition,
adding a sufficient amount of titanium monocarbide to said
homogeneous solid solution powder alloy so that said powder alloy
and said titanium monocarbide together have said predetermined
gross composition,
adding binder material to said mixture,
mechanically blending said mixture until it has a uniform
consistency,
compacting said mixture into a desired shape, and
sintering the composites so formed at an elevated temperature.
10. The method of claim 9 which further comprises the step of
grinding the sintered composite into predetermined shape to form a
metal cutting tool.
Description
The present invention relates to improved cemented carbide alloys
and more particularly to improved monocarbide alloys of titanium
and molybdenum which are substantially richer in carbon than the
prior art alloys of those metals and which, with a proper binder
from the iron metal group, exhibits superior wear resistant
characteristics.
Early efforts to improve the wear-resistance of sintered cemented
carbides, such as WC-Co, and WC-TiC-TaC-Co, for steel cutting
resulted in tool materials based on the system TiC-Mo.sub.2 C-Ni.
Such a system was proposed as early as 1931 in Austrian Patent No.
160,172. More recent developments of such systems are reported by
R. Kieffer and F. Benesovsky in Hartmetalle (Vienna, Springer,
1965). Certain improvements of the tool materials based on
TiC-Mo.sub.2 C-Ni through addition of molybdenum to the nickel
binder to enhance wettability of the titanium carbide and thus
increase strength of the sintered carbide is disclosed in U.S. Pat.
No. 2,967,349. This finding of improved performance of the carbide
alloys at carbon concentrations less than corresponding to the
composition line TiC-Mo.sub.2 C was essentially subsstantiated by
mechanical property and hardness measurements in a study by R.
Kieffer and D. Fister reported at Plansee berichte fur
Pulvermetallurgie, Bd. 18 (1970), pp 246-253.
Wear resistance of these improved tools, which can be termed
TiC-Mo.sub.2 C-Mo-Ni tools, in cutting soft and medium hard steels
is generally much higher than the tungsten carbide-based sintered
carbides, but tool reliability is usually low because of their
brittleness and their tendency to notch at the scale line. As a
result, the full potential of their inherent high wear and
cratering resistance is rarely realized in practice. An additional
shortcoming of the tool materials is their inability to machine
hard steels, such as steels having a Rockwell hardness (R.sub.c) of
50 or higher, at competitive metal removal rates. Current usage is
thus limited to machining of soft to medium hard low alloy steels
under light cutting conditions, and machining of cast irons and
steels.
Efforts to adapt the TiC-Mo.sub.2 C-Mo-Ni tool materials for
roughing steels by decreasing their brittleness through higher
binder contents met only with limited success. When this is done,
their wear resistance appears substantially impaired and the high
binder tools show a marked tendency to plastically deform at
increased thermal loads.
It is accordingly an object of the present invention to provide an
improved composition of material which exhibits improved wear
resistant characteristics.
It is another object of the present invention to provide an
improved monocarbide alloy of titanium and molybdenum which is
substantially richer in carbon than such prior art alloys and
which, generally, also contains more molybdenum than is proposed by
the prior art.
It is another object of this invention to provide such alloys which
are stable in the presence of iron group metal binder alloys, in
particular nickel, and which afford cemented carbide tool materials
superior in their overall characteristics to the TiC-Mo.sub.2
C-Mo-Ni tool alloys.
It is a further object of this invention to provide such alloys
which can be cemented using cobalt and iron, without causing
embrittlement of the alloys by formation of brittle intermetallic
phases of or of .eta.-carbides, such as observed in carbon alloys
with compositions falling in the area bounded by TiC-Mo.sub.2 C-Mo
and TiC-Mo.sub.2 C-Mo-Ti.
Briefly stated, in accordance with the present invention, cemented
carbide alloys are provided which are based on the monocarbide
solid solution (Ti, Mo)C and which have carbon contents higher than
the composition line TiC-Mo.sub.2 C. This monocarbide solid
solution is cemented with an iron group metal binder which forms
between 5 and 25 percent by weight of the total composition. The
carbon content higher than the composition line TiC-Mo.sub.2 C is
greater for higher exchange ratios of molybdenum for titanium. For
example, it has been discovered in the present invention that from
6 to 60 percent of the titanium in the monocarbide can be exchanged
for molybdenum. For the composition (Ti.sub..94 Mo.sub..06) C.sub.z
the value of z can range from 0.972 to 0.985. This is contrasted
with a value of z of 0.969 on the composition line TiC-Mo.sub.2 C
for this metal exchange ratio. For the composition (Ti.sub..40
Mo.sub..60) C.sub.z, in which 60 percent of the titanium has been
exchanged for molybdenum, the value of z can range from 0.71 to
0.90. This is contrasted with a value of z of 0.70 on the
composition line TiC-Mo.sub.2 C for this metal exchange ratio.
In the preferred range of the present invention, from 12 to 50
percent of the titanium in the monocarbide has been exchanged for
molybdenum. For the composition (Ti.sub..88 Mo.sub..12) C.sub.z,
the value of z can range from 0.95 to 0.97. For the composition
(Ti.sub..50 Mo.sub..50) C.sub.z, the value of z can range from 0.78
to 0.88. In the preferred range of the invention, the monocarbide
solid solution within the ranges just described is cemented with
between 8 and 12 percent by weight of an iron group metal binder,
preferably nickel or cobalt or a combination of these metals.
For a complete understanding of the present invention, together
with an appreciation of its other objects and advantages, please
see the following detailed description of the invention and the
attached drawings, in which:
FIG. 1 is a graphical representation of the monocarbide solid
solution phase of the present invention and also shows the
composition of the carbide alloys of the prior art tool
developments in this area which were discussed above;
FIGS. 2 and 3 wear curves comparing the wear of tools according to
the present invention and according to the prior art when subjected
to identical test conditions; and
FIGS. 4 through 6 show the wear rate of tools in accordance with
the present invention as a function of the exchange ratio of
molybdenum for titanium (or the mole percent of molybdenum in the
total metal content) for different test conditions.
The compositions of the carbide component used in the fabrication
of the carbide-binder metal composites of the invention can be
expressed either in atomic percent of the constituent elements, for
example as Ti.sub.u Mo.sub.v C.sub.w (u + v + w = 100), where u, v,
and w are, respectively, the atomic percent of titanium, molybdenum
and carbon present in the alloy; or as relative mole fractions of
metal and interstitial elements in the form (Ti.sub.x
Mo.sub.y)C.sub.z, (x + y = 1), whereby x and y are, respectively,
the relative mole fractions (metal exchange) of titanium and
molybdenum, and z measures the number of gramatoms carbon per
gramatom metal.
It is noted that 100.sup.. y defines mole percent molybdenum
exchange in (Ti.sub.x Mo.sub.y)C.sub.z, and 100.sup.. x defines
mole percent titanium exchange. The two sets of composition
variables are readily interconverted by the relations
u = 100.sup.. x/1+z v = 100.sup.. y/1+z w = 100.sup.. z/1+z x =
u/u+v y = v/u+v z = w/u+v
The latter method of defining the overall composition of the
carbide component, the designation (Ti.sub.x Mo.sub.y)C.sub.z, is
particularly useful in describing the concentration spaces of
interstitial alloys and is used throughout the remainder of this
specification.
FIG. 1 is a graphical representation of the gross composition of
the monocarbide solid solution (Ti.sub.x Mo.sub.y)C.sub.z and
illustrates this phase of the composition of the present invention
as well as the composition of the carbide alloys of the prior art
tool developments in this area. The format of FIG. 1 was selected
to show these compositions rather than the conventional triangular
graph for showing ternary systems because in such a graph the
ranges discussed below would be poorly shown due to excess
compressions.
The ordinate in FIG. 1 is the subscript z in the composition
(Ti.sub.x Mo.sub.y)C.sub.z, while the abscissa is the subscript y.
Of course, the abscissa also defines x, since x + y = 1. The
ordinate is also shown as atomic percent carbon of the gross
composition, with this atomic percent being equal to z/1 + z. The
ordinate is linear for z, and is thus somewhat non-linear for
atomic percent carbon. The abscissa is also shown as the percent
exchange ratio of molybdenum for titanium, or the mole percent of
molybdenum in the total metal content. This mole percent is equal
to 100.sup.. y.
The line 10 in FIG. 1 represents the composition line Ti-C-Mo.sub.2
C, or the composition in the chosen notation of a mixture of TiC
and Mo.sub.2 C for varying ratios of the two compounds. The area
bounded by ABCD represents the composition range investigated by R.
Kieffer and D. Fister in the above referenced report. The area
bounded by AB'C'D' represents the gross composition of most current
commercial tools in this area. The composition at the point D',
(Ti.sub..87 Mo.sub..13)C.sub..936 approximately corresponds to the
prior art comparison tool TiC-Mo.sub.2 C-Ni discussed below, and
the point midway between B' and C', or (Ti.sub..09
Mo.sub..91)C.sub..91, when combined with a binder of 10 percent
nickel, represents the optimum composition for the tools described
in the above mentioned U.S. Pat. No. 2,967,349. This is the
approximate composition of the prior art comparison tool
TiC-Mo.sub.2 C-Mo-Ni discussed below.
The gross carbide composition of the tool alloys in accordance with
the present invention generally fall within the composition area
bounded by EFGH, but preferably within the more confined area
E'F'G'H'. Carbide alloys located outside the area E'F'G'H', but
inside the area EFGH, provide alloys of lesser quality when
employed as cutting tools, but have other useful applications. In
the chosen notation, the composition point, E' corresponds to
(Ti.sub..87 Mo.sub..13)C.sub..97, point F' to (Ti.sub..87
Mo.sub..13)C.sub..95, point G' to (Ti.sub..50 Mo.sub..50)C.sub..78,
and point H' to (Ti.sub..50 Mo.sub..50)C.sub..88. Point E
corresponds to (Ti.sub..94 Mo.sub..06)C.sub..985, point F to
(Ti.sub..94 Mo.sub..06)C.sub..972, point G to (Ti.sub..40
Mo.sub..60)C.sub..71, and point H to (Ti.sub..40
Mo.sub..60)C.sub..90.
It is seen from FIG. 1 that the carbide phase of the composition of
the present invention is characterized by being substantially
richer in carbon than the prior art composition. For any given
metal exchange ratio, the composition contains more carbon than the
composition line TiC-Mo.sub.2 C for the same ratio. The prior art
had assumed that this composition line represented the maximum
possible carbon content for any given exchange ratio. Also, in
accordance with the present invention, higher amounts of molybdenum
can be used than was possible with the prior art compositions. As
is discussed in more detail below, this enables tools to cut under
severe machining conditions as well as the light machining
conditions to which the prior art TiC-Mo.sub.2 C-Mo-Ni tools were
limited.
The carbide-metal composites of the invention may be fabricated by
several different powder metallurgy techniques. A typical
fabrication procedure is as follows: A mixture of carbide and
binder alloy in the desired proportions are ball-milled in
stainless steel jars for 3 to 4 days, using tungsten carbide-cobalt
alloy balls and naphta or benzene as milling fluid. Depending on
the power density, 3 to 5 weight percent pressing lubricant,
usually paraffine, is added in solution with a suitable solvent
such as benzene. The solvent for the paraffine is then evaporated,
and the dry powder mixture compacted into the desired shapes at
pressures ranging between 6 and 10 tons per square inch. The
pressing lubricant is then removed by heating at temperatures
between 200.degree. and 700.degree.C under vacuum and the compacts,
stacked on suitable support materials such as graphite, are
sintered for 1 to 11/2 hrs. at temperatures between 1350.degree.
and 1450.degree.C under vacuum. For the evaluation of the alloys of
the invention are machine tools, the sintered parts are ground on
diamond wheels to the desired tool geometry.
A typical fabrication procedure for an alloy containing titanium
and molybdenum in the molar ratios 6:4 and having a carbon content
of 47.9 atomic percent, is described below. The composition of this
alloy in the previously described notation is (Ti.sub..60
Mo.sub..40) C.sub..87.
A carefully blended powder mixture consisting of 46 weight percent
TiC, 52.17 weight percent Mo.sub.2 C and 1.83 weight percent carbon
was hot pressed in graphite dies at approximately 2000.degree.C to
a density corresponding to about 75 percent of the theoretical. The
compacts were then placed in a graphite container, homogenized for
3 hours at 2000.degree.C under a vacuum of 3 .times. 10.sup.-.sup.5
torr. and then crushed and ball milled to yield a grain size of
less than 47 micrometers. The master alloy powder was then analyzed
and homogeneity was ascertained by X-ray diffraction.
Compositions formed in the manner just described can be termed
prehomogenized solid solutions. Another method for making the
compositions of the present invention is to first form such a
prehomogenized solid solution which is a molybdenum rich
monocarbide solid solution, such as (Ti.sub..30
Mo.sub..70)C.sub..85 and then reactively sintering it with suitable
quantities of titanium monocarbide and binder material to bring the
gross composition of the material to the desired levels.
Aside from the routine fabrication variables, choice of composition
of the carbide ingredient for a given gross composition of the
composite strongly influences microstructure and phase distribution
and, as a result, the properties of the sintered compacts. Thus,
for example, very fine-grained composites are obtained by the
reactive sintering method just discussed. The fine-grained
structures in such composites are attributable to dissolution of
the carbide components in the binder at sintering temperatures and
reprecipitation of the more stable, equilibrium carbide solid
solution from the liquid binder alloys. Concurrent with these
dissolution/precipitation reactions are reactions involving a
preferential transport of molybdenum-rich monocarbide solid
solution to the titanium carbide grains to form an alloyed surface
layer which, owing to its higher molybdenum content, is better
wetted by the binder alloy and thus affords a stronger bond than is
possible between TiC and binder metal alone. In general, the bulk
of the carbide grains in such composites, if properly fabricated,
will have a grain size equal or less than that in the as-milled
condition. Wear-resistance, but especially top catering resistance,
in machine-tool applications appears markedly improved by the
presence of unreacted TiC in the core of a fraction of the carbide
grains. Tendency towards plastic deformation under high cutting
loads is somewhat higher than in composites prepared from preformed
solid solutions and binder alloy with the same gross composition.
Consequently, a lower binder content is used in reactively sintered
composites for machine tool applications.
In general, studies of the performance of the alloys of this
invention as machine tools revealed that fabrication of the
composites by reactive sintering is advantageous for alloys in
which the gross metal exchange in the carbide is less than 40 mole
percent molybdenum. Performance of reactively sintered composites
with more than 40 mole percent molybdenum in exchange in cutting
soft to medium hard steels (R.sub.c -45) is slightly better than of
tools prepared from prehomogenized solid solutions, while the
performance is about equal in cutting hard steels.
Those skilled in the art can devise other methods of making the
compositions of the invention. For example, carbide deficient gross
compositions could be formed, mixed with binder and sintered in a
carburizing atmosphere.
The following tables and graphs show the performance of a large
number of tools having different composotions within the range of
the invention and also give comparison data for a number of prior
art tools which were subjected to the same test conditions. Four
different test conditions were used. These are designated Test
Condition A, Test Condition B, Test Condition C and Test Condition
D. The test bars consisted of 4340 steel in four different hardness
ranges, R.sub.c 22 to 29, R.sub.c 33 to 38, R.sub.c 46 to 50, and
R.sub.c 50 to 55. Unless otherwise noted, test conditions referred
to in the tables were:
TEST CONDITION A (wear test)
4340 steel, R.sub.c 22 to 29; cutting speed, 500 surface feet per
minute; feed rate, 0.0151 inch per revolution; depth of cut, 0.060
inch; no coolant. SNG 433 inserts.
TEST CONDITION B (roughing test)
4340 steel, R.sub.c 22 to 29; cutting speed, 500 surface feet per
minute; feed rate, 0.0203 inch per revolution; depth of cut, 0.125
inch; no coolant. SNG 433 inserts.
TEST CONDITION C
4340 steel, R.sub.c 33 to 38; cutting speed, 500 surface feet per
minute; feed rate, 0.0102 inch per revolution; depth of cut; 0.060
inch; no coolant. SNG 433 inserts.
TEST CONDITION D (finishing hardened steel)
4340 steel, R.sub.c 46 to 55; cutting speed, 250 surface feet per
minute; feed rate, 0.0051 inch per revolution; depth of cut, 0.050
inch; no coolant. SNG 432 inserts.
The wearland was measured at suitable time intervals with the aid
of a tool microscope. Plastic deformation of the cutting edge and
crater depth were measured on a metallograph. The flank data
presented in the graphs and tables refer to the uniform wear zone
of the tools.
To obtain a comparative performance evaluation of the composites of
the invention, a cross section of representative tools from
different manufacturers were also tested under identical conditions
and the best performing tools selected as comparison standards.
Tools from the C-5 and C-6 class carbides manufactured by different
companies proved fairly equivalent and are thus not specifically
identified in the tables. Large differences in the cutting
performance of the C-7 and C-8 class of carbides were noted,
however, in machining fully hardened 4340 steel. The grade K7H
manufactured by the Kennametal Company, 1000 Lloyd Avenue, Latrobe,
Pennsylvania was selected as the main comparison tool for this
particular application because this is a tool which is widely used
commercially for this type of machining.
The following four examples, which are representative of the
compositions of the present invention, describe in detail four
specific compositions and the manner in which they were fabricated.
FIGS. 2 and 3 and the following Tables 1 through 4 show the
performance of these four examples and of the leading prior art
tools when subjected to the above described test conditions.
EXAMPLE 1
A powder blend consisting of 91.50 weight percent of an alloy
(Ti.sub..60 Mo.sub..40)C.sub..87 and 8.50 weight percent nickel was
prepared as a prehomogenized solid solution in the manner described
above and the compacts sintered for 1 hour and 10 minutes at
1385.degree.C under vacuum. Average linear shrinkage during
sintering was 16.4 percent. Average grain size of the carbide phase
was approximately 4 micrometers and the hardness was 93.0 on the
Rockwell A scale.
EXAMPLE 2
A powder blend consisting of 48.4 weight percent of a
prehomogenized solid solution having the composition (Ti.sub..30
Mo.sub..70)C.sub..80, 42.1 weight percent TiC [resulting in a gross
carbide composition of (Ti.sub..70 Mo.sub..30)C.sub..914 ], and
9.50 weight percent nickel were reactively sintered in the manner
described before and sintered for 1 hour and 30 minutes at
1380.degree.C under vacuum. Linear shrinkage during sintering was
16.1 percent and the grain size of the carbide phase approximately
4 micrometers. The microstructure of the carbide grains consisted
of a core of unconverted titanium carbide surrounded by an outer
shell of compositionally graded titanium-molybdenum monocarbide
solid solutions, with the outermost layer approximately
corresponding to a carbide containing approximately (Ti.sub..45
Mo.sub..55)C.sub.z. A hardness of 92.9 on the Rockwell A scale was
measured for the sintered composite.
EXAMPLE 3
A powder blend consisting of 33.6 weight percent of a
prehomogenized solid solution having the composition (Ti.sub..30
Mo.sub..70)C.sub..80, 55.1 weight percent TiC [resulting in a gross
carbide composition of (Ti.sub..80 Mo.sub..20)C.sub..944 ], 5.65
percent nickel and 5.65 percent cobalt, was reactively sintered in
the manner described before the compacts sintered for 1 hour and 30
minutes at 1395.degree.C under vacuum. The carbide phase in the
sintered compact had an average grain size of 3 micrometers and the
measured hardness of the composite RA = 93.1.
EXAMPLE 4
A powder blend of 56.7 weight percent (Ti.sub..85
Mo.sub..15)C.sub..951, 31.3 weight percent (Ti.sub..70
Mo.sub..30)C.sub..91 [resulting in a gross carbide composition of
(Ti.sub..80 Mo.sub..20)C.sub..94 ], and 12 percent cobalt was
processed in the manner described before and resulting compacts
sintered for 1 hour and 15 minutes at 1395.degree.C under vacuum.
Average carbide grain size in the sintered part was approximately 3
microns and the hardness R.sub.A = 92.8.
Table 1
__________________________________________________________________________
Wear Pattern of the Tools Described in Examples 1 through 4 in
Comparison to Commercial Sintered Carbides. Test Condition A Total
Cutting Time WEAR PATTERN* Crater Tool Minutes A B C D Depth
Remarks
__________________________________________________________________________
Example 1 40.00 <.001" .006" .010" .005" .0031" -- Example 2
60.20 <.001" .005" .007" .003" .003" -- Example 3 31.79
<.001" .007" .006" .002" .002" -- Example 4 79.05 <.001"
.008" .012" .002" .0034" -- K7H 49.89 .002" .010" .021" .006"
.0085" -- TiC-Mo.sub.2 C-Mo-Ni 46.03 <.001" .007" .012" .038"
.0023" Failed .times..020" by chipping at scale line
__________________________________________________________________________
(*) Wear Pattern Nomenclature: A....Notch due to crater breakout
B....Corner wear C....Flank wear D....Notch at scale line
Table 2
__________________________________________________________________________
Wear Pattern of the Tools Described in Examples 1 through 4 in
Comparison to Commercial Sintered Carbides. Test Condition B Total
Cutting Time Wear Pattern* Crater Edge Re- Tool Minutes A B C D
Depth Deform marks
__________________________________________________________________________
Example 1 8.18 <.001" .004" .004" .006" .0015" <.0005" not
failed Example 2 10.05 <.001 .006+" .005" .004" .0015" <.0005
not failed Example 3 5.06 <.001" .007" .006" .003" .001" .002"
-- K7H 9.82 .020" .008" .006" .014" .0052" <.0005" chipped at
scale line TiC-Mo.sub.2 C-Mo-Ni 4.68 <.001" .010+" .008" .022"
.0017" .0028" chipped at scale line C-5 1.70 .006" .020" .016"
<.002" .0067" .0045" --
__________________________________________________________________________
(*) Wear pattern nomenclature same as Table 1.
Table 3
__________________________________________________________________________
Wear Pattern of the Tools Described in Examples 1 and 2 in
Comparison to Commercial Sintered Carbides Test Condition C Total
Cutting Time Wear Pattern* Crater Tool Minutes A B C D Depth
Remarks
__________________________________________________________________________
Example 1 45.58 <.001" .006" .008" .002" .002" -- Example 2
60.66 <.001" .005" .006" <.002" .0021" -- K7H 34.87 .001"
.009" .012" .004" .005" -- TiC-Mo.sub.2 C-Mo-Ni 53.24 .004" .005"
.007" .007" .0015" --
__________________________________________________________________________
(*) Wear Pattern Nomenclature same as Table 1.
Table 4
__________________________________________________________________________
Wear Pattern of the Tools Described in Examples 1 and 2 in
Comparison to Commercial Sintered Carbides - Test Condition D Total
Hardness Cutting Time Wear Pattern* Crater Re- Tool of Steel
Minutes A B C D Depth marks
__________________________________________________________________________
Exam- R.sub.c 51 to 54 107.42 <.001" .006-" .008" <.001"
.00075" not ple 1 failed Exam- R.sub.c 55 to 57 9.82 <.001"
.004-" .004" <.001" -- not ple 1 failed Exam- R.sub.c 47 to 49
157.77 <.001" .005" .006" <.001" .0007" not ple 2 failed K7H
R.sub.c 49 to 52 88.47 .021" .007" .010+" .001" -- chipped at (A)
K7H R.sub.c 55 to 57 9.96 <.001" .005+" .024" .001" -- edge
break- down
__________________________________________________________________________
(*) Wear Pattern Nomenclature same as Table 1
FIGS. 2 and 3 are graphical representations of some of the tests
which provided the data for Tables 1 and 4 respectively. FIG. 2
shows the averaged corner and flank wear as a function of cutting
time for tools formed from the above Examples 1 and 2 and the prior
art tools TiC-Mo.sub.2 C-Mo-Ni and K7H when subjected to the Test
Condition A. Curve 12 shows the wear of the K7H tool, curve 14 the
wear of the TiC-Mo.sub.2 C-Mo-Ni tool, curve 16 the wear of the
Example 1 tool and curve 18 the wear of the Example 2 tool.
FIG. 3 shows the averaged corner and flank wear as a function of
cutting time for tools formed from the above Examples 1 and 2 and
the prior art tool K7H when subjected to the Test Condition D. No
curve for the prior art tool TiC-Mo.sub.2 C-Mo-Ni is shown since
this tool failed almost instantly when subjected to this test
condition. Curve 20 shows the wear of the K7H tool when machining
steel having a hardness of R.sub.c = 49 to 52. Curve 22 shows the
wear of the Example 1 tool when machining steel having a hardness
of R.sub.c = 51 to 54. Curve 24 shows the wear of the Example 2
tool when machining steel having a hardness of R.sub.c = 47 to
49.
It is seen from the curves of FIGS. 2 and 3 that the same
compositions according to the present invention have superior wear
characteristics over both the best prior art tool for the moderate
Test Condition A, the tool TiC-Mo.sub.2 C-Mo-Ni, and the best prior
art tool for the more severe Test Condition D on hardened steel,
the tool K7H.
The following Table 5 shows the wear rate of a large number of
tools formed from specific compositions in accordance with the
present invention and also of several prior art tools when
subjected to the Test Condition A.
Table 5
__________________________________________________________________________
Gross Observed Wear Rates Composition of Mils per Minute Carbide
Phase Binder Flank Crater Remarks
__________________________________________________________________________
(Ti.sub..5 Mo.sub..5)C.sub..85 12% Co .21 .13 (Ti.sub..6
Mo.sub..4)C.sub..82 3.6%Ni,7%Co .40 .09 Brittle (Ti.sub..7
Mo.sub..3)C.sub..90 6%Fe,6%Ni .09 .07 Slight plastic deform.
(Ti.sub..65 Mo.sub..35)C.sub..82 9% Co -- -- Brittle (Ti.sub..60
Mo.sub..40)C.sub..84 9% Ni -- .10 -- (Ti.sub..60
Mo.sub..40)C.sub..82 9.5%Ni .17 .075 -- (Ti.sub..50
Mo.sub..50)C.sub..85 8.8%Co .125 .071 -- (Ti.sub..80
Mo.sub..20)C.sub..93 12% Co .068 .04 -- (Ti.sub..80
Mo.sub..20)C.sub..92 5.65%Ni,5.65%Co .085 .063 Slight edge deform.
(Ti.sub..70 Mo.sub..30)C.sub..90 5%Ni, 5%Co .10 .089 -- (Ti.sub..86
Mo.sub..14)C.sub..94 11%Ni .066 .04 -- (Ti.sub..87
Mo.sub..13)C.sub..94 12.5%Ni .11 .067 -- (Ti.sub..80
Mo.sub..20)C.sub..92 11%Ni .063 .04 -- (Ti.sub..75
Mo.sub..25)C.sub..89 12%Ni .08 .067 Slight edge deform. (Ti.sub..75
Mo.sub..25)C.sub..92 10.5%Ni .065 .05 -- (Ti.sub..70
Mo.sub..30)C.sub..90 11.5%Ni .08 .063 Slight edge deform
(Ti.sub..70 Mo.sub..30)C.sub..90 9.8%Ni .065 .05 -- (Ti.sub..68
Mo.sub..32)C.sub..89 10.5%Ni .06 .053 -- (Ti.sub..60
Mo.sub..40)C.sub..87 10.3%Ni .12 .10 Slight edge deform (Ti.sub..60
Mo.sub..40)C.sub..84 10.5%Ni .16 .08 Slight Edge deform (Ti.sub..60
Mo.sub..40)C.sub..87 8.5%Ni .08 .073 -- (Ti.sub..54
Mo.sub..46)C.sub..84 8.5%Ni .12 .09 -- (Ti.sub..40
Mo.sub..60)C.sub..81 8%Ni .25 .27 -- (Ti.sub..50
Mo.sub..50)C.sub..81 7%Ni .128 .084 -- (Ti.sub..50
Mo.sub..50)C.sub..82 12%Ni .16 .097 -- (Ti.sub..54
Mo.sub..46)C.sub..894 8.5%Ni .123 .085 trace excess carbon. Prior
Art Tools
__________________________________________________________________________
C-5, C-5A 1.3-1.7 .40-.80 typical tool life 7 to 10 minutes C-6,
C-7 .28-.40 .12-.18 -- TiC-Mo.sub.2 C-Ni .15-.25 .03-.06 Notching
at scale line TiC-Mo.sub.2 C-Mo-Ni .09-.21 .05 Severe notching at
scale line. Cast Carbide (Ti-W-C base) .30-.35 .09 -- TiN coated
C-5 (for life of coating) .12-.18 .03-.10 Typical tool life 35
minutes TiC coated C-6 (for life of coating) .14-.16 .08-.12 --
__________________________________________________________________________
The following Table 6 shows the wear rate of representative prior
art commercial carbide tools when subjected to the Test Condition
B:
Table 6
__________________________________________________________________________
Carbide Range of Observed Wear Rates Class Mils per Minute Flank
Crater REMARKS
__________________________________________________________________________
C-5, C-5A 9. to 12 4 to 5 3 to 5 mils thermal deformation at 1.5
minutes C-6, C-7 .55 to .85 .5 to .7 1 to 3 mils thermal
deformation after 5 to 10 minutes. TiC-Mo.sub.2 C-Mo-Ni .7 to .9
.35 to .45 Frequent tool break- age, 2 to 3 mils thermal
deformation after 4 to 6 minutes
__________________________________________________________________________
The corresponding wear rates for tools formed from compositions
according to the present invention are shown in FIG. 5, described
below.
The following Table 7 shows the wear rates of representative prior
art commercial carbide tools when subjected to Test Condition
D:
Table 7
__________________________________________________________________________
Carbide Hardness of Range of Observed Class Test Steel Flank Wear
Rates, Mils per Minute Remarks
__________________________________________________________________________
C-2 R.sub.c 51 to 55 Rapid Failure Poor finish C-5 R.sub.c 51 to 55
Rapid Failure Poor finish C-6,C-7 R.sub.c 52 to 55 1.5 to 3.0
Frequent fail- ure by corner delamination on steels with R.sub.c
>54 C-6,C-7 R.sub.c 46 to 48 .08 to .15 -- K7H R.sub.c 49 to 52
.08 Good finish TiC-Mo.sub.2 C-Ni R.sub.c 51 to 54 -- Failure on
contact TiC-Mo-Ni R.sub.c 49 to 52 -- Failure by corner delamin-
ation after .1 to 5 minutes TiC-Mo-Ni R.sub.c 46 to 49 -- Failure
by corner delamin- ation usually at start of second pass
__________________________________________________________________________
The corresponding wear rates for tools formed from compositions
according to the present invention are shown in FIG. 6, described
below.
FIGS. 4, 5 and 6 show the wear rate of tools formed from
compositions in accordance with the present invention as a function
of the exchange ratio of molybdenum for titanium, or the mole per
cent molybdenum in the total metal content of the carbide phase,
for different test conditions. In FIG. 4 the curve 26 shows the
averaged corner and flank wear rates and the curve 28 shows the top
cratering rate for Test Condition A. In FIG. 5 the curve 30 shows
the averaged corner and flank wear rates and the curve 32 shows the
top cratering rate for Test Condition B. FIG. 6 shows averaged
corner and flank wear rates for Test Condition D. The curve 34
shows these rates for machining hardened steel having an R.sub.c =
46 to 49. The curve 36 shows these rates for machining hardened
steel having an R.sub.c = 50 to 55. These curves, when viewed
together, show that, within the composition range of the present
invention, for progressively more severe machining test, it is
desirable to have higher exchange ratios of molybdenum for
titanium.
It is noted that the curves of FIGS. 4 through 6 are shown
independent of the carbon content, or the subscript z in (Ti.sub.x
Mo.sub.y)C.sub.z. This is because it has been found that, within
the range of the present invention as shown in FIG. 1, the
performance of a tool is a function of the metal exchange ratio,
but for a given metal exchange ratio varies very little with
changes in carbon. This is contrasted with the prior art
compositions in which the carbon content was critical, and in which
slight changes in the carbon content could change a satisfactory
material into a very brittle material. Thus, it is much easier to
formulate the compositions of the present invention.
The composition of the present invention is formed from the above
described carbides bonded with a binder from the iron metal group,
such as nickel, cobalt and iron. The binder can form from 5 to 25
percent by weight of the composition. If too little binder is used,
the composition will be too brittle. If too much binder is used,
the composition will be too soft and will deform. Preferably, the
binder forms from 8 to 12 percent by weight of the composition.
The selection of the proper binder is somewhat dependent upon the
mole per cent molybdenum in the carbide phase of the composition.
For compositions in which the carbide phase contains less than 40
mole per cent molybdenum, cutting performance of cobalt or nickel
bonded tools is considered equivalent. Carbides with more than 55
mole per cent molybdenum show embrittlement when using a cobalt
binder. Iron binders are useful only for carbides containing less
than 35 mole per cent molybdenum. Carbides with more than 60 mole
percent molybdenum are unstable in the presence of cobalt and iron
and decompose under formation of titanium-richer monocarbide
solutions, .eta.-carbides, and free carbon. .eta.-carbide formation
is especially pronounced in substantially carbon-deficient carbide
solutions.
The properties of the carbide-metal composites can be extensively
modified by alloying. The following summary of the effects of the
principal alloying ingredients are based on performance studies of
the composites as tool materials in turning 4340 steel. However,
low level alloying with other elements may also be accomplished
without departing from the spirit of the invention.
1. Substituting vanadium for up to 20 percent of the amount of
titanium present proves essentially inert with respect to cutting
performance. Carbide grain growth during sintering, however,
appears enhanced, necessitating lower sintering temperatures and
more careful temperature control in the fabrication of
vanadium-alloyed composites.
2. Niobium, tantalum, and hafnium added in exchange for up to 30
mole per cent of the titanium in molybdenum-rich alloys, or alloys
containing more than 40 mole per cent molybdenum, decrease tool
deformability and thus permits the use of higher binder contents
than is possible with the unalloyed composite. Alloying of high
titanium alloys with these elements does not result in beneficial
effects.
3. Addition of zirconium in exchange for titanium causes a marked
decrease in the performance of the composites as machine tools.
4. Tungsten can be alloyed in substantial quantities (up to 50 mole
per cent) in exchange for molybdenum in the composites of the
invention without impairment of performance. Small additions of
tungsten (less than 5 mole per cent in exchange for molybdenum) are
beneficial in retarding grain growth during sintering. Titanium
carbide-rich alloys containing more than 70 mole per cent TiC are
especially insensitive towards higher concentrations of tungsten,
while molybdenum-rich alloys tend to reject free graphite from the
solid solution if the tungsten exchange for molybdenum exceeds 20
mole per cent. Formation of free graphite can be avoided by
lowering the carbon content of the alloys between 0.5 and 1.5
atomic per cent. The use of cobalt and iron-base binders is not
recommended for substantially carbon-deficient, tungsten-containing
carbides, as they invariably cause embrittlement of the composite
by .eta.-carbide formation.
5. Low level (less than 10 mole percent) additions of chromium in
exchange for molybdenum (or for molybdenum and tungsten if tungsten
is also used) appeared to be inert, while larger additions resulted
in a pronounced decrease in the performance of the composites as
machine tools.
6. Addition of nitrogen in partial replacement (up to 25 mole
percent) for carbon slightly improves wear-resistance of the
composites under light cutting conditions.
Alloying with other transition metal carbides was accomplished by
using preformed solid solutions of these carbides with TiC, such as
(T,W)C.sub. z and (Ti,Hf)C, or with MoC.sub.z, such as, for
example, (Ta,Mo)C.sub.z and (V,Mo)C.sub.z. Preparation of these
carbide solid solutions was analogous to the procedures described
for the titanium-molybdenum carbide alloy.
The following Table 8 shows the wear rates for a number of tools
formed from compositions incorporating some of the alloy
substitutions just discussed when these tools were subjected to
Test Condition A:
Table 8
__________________________________________________________________________
Gross Observed Wear Rates Composition of Mils per Minute Carbide
Phase Binder Flank crater Remarks
__________________________________________________________________________
(Ti.sub..4 Ta.sub..1 Mo.sub..5)C.sub..85 11%Ni .28 .19 Brittle
(Ti.sub..4 Ta.sub..1 Mo.sub..5)C.sub..85 13%Ni .19 .16 --
(Ti.sub..4 V.sub..1 Mo.sub..5)C.sub..84 12%Ni .18 .13 --
(Ti.sub..72 Nb.sub..08 Mo.sub..20)C.sub..94 13%Ni .12 .07 --
(Ti.sub..72 V.sub..08 Mo.sub..20)C.sub..93 13%Ni .12 .07 --
(Ti.sub..6 Mo.sub..3 W.sub..1)C.sub..93 9%Ni -- -- Excess carbon
(Ti.sub..6 Mo.sub..36 W.sub..04)C.sub..87 9%Ni .08 .07 --
(Ti.sub..8 Mo.sub..15 W.sub..05)C.sub..94 11.3%Ni .06 .04 --
(Ti.sub..5 Mo.sub..3 W.sub..1)C.sub..82 9.3%Co -- -- Brittle
(Ti.sub..5 Hf.sub..1 Mo.sub..4)C.sub..86 9%Ni .09 .08 -- (Ti.sub..4
Zr.sub..1 Mo.sub..5)C.sub..86 11%Ni .60 -- Edge chipping (Ti.sub..7
Mo.sub..3)(C.sub..76 N.sub..14) 10%Ni .06 .04 --
__________________________________________________________________________
The composites of the invention also may be modified and adapted
for special applications by surface coatings of wear-resistant
alloys based on carbides and nitrides of the refractory transition
metals.
The data shown in the above discussed tables and graphs is
representative of many other alloys within the range of the
invention which were prepared and tested. It becomes evident from a
comparison of the performance data that the carbide-metal
composites of this invention afford a substantial improvement of
the existing carbides in terms of tool reliability, wear
performance, and versatility of application. It is noted from the
results presented that the molybdenum-richer compositions are
particularly suited for rough cutting soft and medium hard steels
and for machining hardened steels, while the titanium-richer
composition (greater than 70 mole percent titanium) are better
suited for light cutting and finishing of soft and medium hard
steels. The wear data also indicate that no performance advantage
in cutting steels is being gained by increasing the titanium
exchange in the composites of the invention substantially above 80
mole percent (approximately 69 weight percent TiC): tool
reliability decreases rapidly, especially in somewhat heavier cuts,
and the failure mechanisms become similar to those of the prior art
TiC-Mo.sub.2 C-Mo-Ni tool materials.
While the principal application of the new composite materials of
the invention is envisioned to be in the area of machine tools,
their high wear-resistance will make them also suitable for
applications where currently tungsten carbide-based cemented are
used, such as wear-resistant linings, gage-blocks, bearings, etc.,
and for milling and drilling in the mining industry.
While the invention is thus disclosed and many specific embodiments
described in detail, it is not intended that the invention be
limited to those shown embodiments. Instead, many modifications
will occur to those skilled in the art which fall within the spirit
and scope of the invention. It is intended that the invention be
limited only by the appended claims.
* * * * *