CA1078225A - Metallurgical composition embodying hard metal carbides, and method of making - Google Patents
Metallurgical composition embodying hard metal carbides, and method of makingInfo
- Publication number
- CA1078225A CA1078225A CA323,323A CA323323A CA1078225A CA 1078225 A CA1078225 A CA 1078225A CA 323323 A CA323323 A CA 323323A CA 1078225 A CA1078225 A CA 1078225A
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- titanium
- nickel
- composition
- tungsten
- carbon
- Prior art date
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Abstract
ABSTRACT OF THE DISCLOSURE
A hard wear resistant metallurgical composition which in general is a combination of tungsten, titanium, nickel and carbon and may include other elements such as chromium. In preparing the composition, tungsten carbide is admixed by milling with nickel and titanium and subsequently sintered.
The titanium may react with carbon from the tungsten carbide and the released tungsten may alloy with nickel to form a tough binder. The characteristics of the end product may be tailored by controlling the proportions of the various components of the composition including adjustment of the amount of titanium added to the mixture. By this control, the end product may be made magnetic or non-magnetic without losing desirable characteristics of strength, hardness and wear resistance.
A hard wear resistant metallurgical composition which in general is a combination of tungsten, titanium, nickel and carbon and may include other elements such as chromium. In preparing the composition, tungsten carbide is admixed by milling with nickel and titanium and subsequently sintered.
The titanium may react with carbon from the tungsten carbide and the released tungsten may alloy with nickel to form a tough binder. The characteristics of the end product may be tailored by controlling the proportions of the various components of the composition including adjustment of the amount of titanium added to the mixture. By this control, the end product may be made magnetic or non-magnetic without losing desirable characteristics of strength, hardness and wear resistance.
Description
` 1078225 .: .
The present invention relates to metallurgical compositions embodying metal carbi`des, in particular, hard metal carbide6, and is especially concerned with a composition that can ~e tailored as to characteristics including that of being nonmagnetic or magnetic while remaining hard and wear resistant.
Many hard wear resistant metallurgical compositions embodying hard metal carbides are known, and most thereof are quite satisfactory for the intended use. An application for hard wear resistant carbide materials in connection with which there has not, heretofore, been satisfactory materials are those uses in which the hard wear resistant material must be nonmagnetic.
For example, machines in which magnetic tapes are employed often require wear resistant guides and the like for supporting and guiding the tapes. Still other cases will suggest themselves in which a hard wear resistant, or structurally strong, member is required where magnetic interactions are undesirable and in these cases, also non-magnetic carbide materials would be highly useful.
While the metallurgical composition according to the present invention can, as will be shown, be made nonmagnetic, magnetic variations of the composition have also been found highly useful in places where the composition must be hard and wear resistant and/or noncorrosi~e and/or noncontaminating or where the material must be extremely hard as in connection with a tool composition.
With the foregoing in mind, a primary objective of the present invention is the provision of a metallurgical composition embodying hard metal carbides which has the possibility of being formulated so as to be nonmagnetic but which will retain the desirable attributes of hard carbide metallurgical ~078ZZS
compositions.
Another ohject is the provision of a metallurgicalcomposition of the nature referred to which can ~e so compounded prior to the formation thereof as to be either nonmagnetic or magnetic when completed.
A still further object is the provision of a metallurgical composition embodying hard metal carbides which is satisfactory for use as a tool and which can be compounded to vary in magnetic properties at room temperature to the state of being nonmagnetic.
BRIEF SUMMARY OF THE INVENTION:
The metallurgical composition according to the present invention is concerned primarily-with tungsten, titanium, nickel, carbon compositions and to which may be added a certain amount of chromium and other carbides. The composition of the present invention can be compounded in such a manner as to be either nonmagnetic or magnetic while s~ill having the desirable characteristics of hard wear resistant cemented carbides.
Thus, in accordance with the present teachings, there is provided a sintered cemented carbide product the compositions of which comprises tungsten carbide, titanium carbide and a binder alloy comprising tungsten-nickel in which the ratio of the tungsten in the binder alloy to the binder is from 2 to 28 per cent by weight. By one aspect the above product is non-ferromagnetic and has a ratio of tungsten in the binder alloy to the binder alloy of 15 to 28 per cent by weight. By another aspect the above product has ferromagnetic properties and has a ratio of tungsten in the binder alloy to the binder alloy of less than 14 per cent by weight.
The hard metal carbides, including tungsten carbide and titanium carbide, are nonmagnetic so that a metallurgical composition embodying hard metal carbides can be made provided a suitable metal binder sy-stem is employed which is also nonmagnetic.
A binder metal for a cemented carbide composition should be tough and should also wet the carbide. A nickel binder system is, thus, a preferred binder because nickel wets the carbide compounds and is tough. Nickel, furthermore, although being itself ferromagnetic, can be alloyed with tungsten, which is also nonmagnetic, without undergoing a phase change upon heating or upon cooling from the liquid phase over a relatively broad alloying range and an alloy of this material can be selected which is nonmagnetic. By nonmagnetic, a material is referred to which has magnetic permeability near unity and which is lacking in the ability to become magnetized or to exhibit induced magnetism, namely, a material with 0 Oersted coexcive force.
When the more common binder metal, cobalt, is employed as a binder, and the composition is adjusted to be, or to approach being, nonmagnetic, the binder phase of the composition becomes extremely br;ttle due to the formation of Co3W3C and the composition is, thus, defective for many uses. The present invention overcomes this objection by including titanium in the composition and employing nickel or nickel and chromium as the basic binder metal.
When titanium, tungsten carbide and nickel, with or without some chromium, are admixed in powder form, compacted and heated so that a liquid phase is formed containing W, C
and some or all of the titanium in solution, then the carbon can associate itself with the titanium to form titanium carbide or a solid solution of TiC with WC, or both, because the free energy of formation for forming TiC is more favorable then for forming WC, Thus, tungsten is freed during sintering ~0~782Z5 to alloy with a binder metal or metals.
The mass balance is calculated so the stoichiometric excess W during sintering can alloy with the nickel and result in a magnetic or nonmagnetic binder alloy. The carbon balance with respect to the titanium must take into account the non-stoichiometric nature of TiC as less than one carbon atom per titanium atom is sufficient to form titanium carbide.
Thus, by including titanium in the mixture, carbon is removed from the melt because of the affinity of titanium for the carbon, and an alloy of nickel and tungsten and/or titanium is formed during sintering. It has been found that a fairly wide range of composïtions according to the present invention will result in the production of a nonmagnetic alloy having the same crystal structure as pure nickel, namely, face centered cubic.
While carbon deficient tungsten carbide can be employed with a nickel binder to yield a nickel-tungsten alloy binder after sintering, extremely- close control of the respective levels of nickel and carbon are required and an impractical control situation arises.
It has been found that small, less than 0.5 weight per cent, titanium metal additions as described herein very effectively inhibit grain growth during sintering and result in a fine grained structure and consequently improved strength.
A particular advantage of the present invention is to be found in the fact that, once the analysis of the WC
component is ascertained to reveal the amount of carbon in the WC component, the amount of Ti to add to the composition can readily be calculated. Formu~ation and control are thus greatly simplified.
The exact nature of the present invention will become more apparent upon reference to the following specificatïon ~0782Z5 giving specific examples and to the accompanying drawings in which:
Figure 1 is a graph giving weigfit per cent titanium to charge.
Figure 2 is a part of the nickel-tungsten phase diagram showing, in particular, the magnetic transformation character-istics of nickel-tungsten alloys.
DETAILED DESCRIPTION OF THE INVENTION:
The compositions according to the present invention can be compounded by closely analyzing each constituent for the carbon, oxygen, nitrogen and metallic impurities. The amount of Ti required to release the quantity of tungsten from the tungsten carbide to produce the nickel-tungsten alloy composition can then be calculated or determined experimentally.
In making the calculations, the tungsten level desired in the binder and the nickel content are established and the equations giving the desired amount of titanium, or tungsten, are solved.
In preparing the compositions, the powders charged in the mixture before sintering have about the following percentages by weight:
Nickel - 3.0 - 25.0 Titanium - .05 - 2.0 Tungsten Carbide- Balan~e In addition chromium may also be included in the range of 0.0 to 2.0 per cent by weight.
Figure 1 shows how much titanium to charge with tungsten carbide having the indicated total carbon content and negligible oxygen, nitrogen and metallic impurities. In the graph, the weight % of Ni in the composition is always 10.
The other 90% of the composition is made up of WC and Ti.
~078Z25 Thus, for example, at 1 wt~ ~ Ti, there will be 89 wt~ %
WC. Each line of the graph shows the amount of Ti to be supplied to obtain the indicated weight % of W in the b;nder.
TABLE I
Weight % Titanium to charge to a 10 Wt. % Nickel balance tungsten carbide composition (the WC having 6.10 Wt. % carbon content and negligible impuritiesl to obtain the calculated 10, 2a, or 25 Wt. ~ W/(W + ~î~ in the binder alloy as a function of carburization of the tïtanium addition.
Est.
Calculated Wt. % Atom Wt. ~ Wt. % Ti to Ratio Nickel W/(W + Ni~ Char~e C/Ti 0.283 0.6 la 10 0.240 0.7 0.208 0.8 0.187 0.9 0.879 0.6 2a 0.748 0.7 la 20 0.654 0.8 0.585 0.9 1.242 0.6 1.077 0.7 la 25 0.940 0.8 0.831 0.9 Chrom;um metal additions may be made to the composition, as will be explained more fully hereinafter, and help to further inhibit grain growth and also to stabilize the non-magnetic properties when the composition is to be nonmagnetic.
Chromium has produced good results and for a 10 weight %
nickel composition, a 1 weight % chromium level produced satisfactory results.
The chromium metal addition is not essential to achieve nonmagnetic properties. It can react with and take up some of the carbon by forming carbides of chromium, and it can also alloy with the nickel.
Titanium can be supplied in the form of powders of titanium metal, any alloy of titanium with nickel, not , 10~8ZZS
necessarily TiNi eutetic composition or as a hydride of titanium~ The last ment;oned form is preferred because it is less reactive then the pure metal and can be milled readily.
Also, it is less expensive than an alloy of titanium with nickel while, furthermore, the hydrogen that is evolved from titanium hydride during the early stages of sintering can be beneficial because it can be effective for reducing surface oxides, particularly those which form on nickel.
The nonmagnetic capability of the type of composition disclosed herein is important but there are other applications for the composition wherein chemical inertness and strength and wear resistance are the principal characteristics desired.
Nonmagnetic grades of the composition, as mentioned, are particularly useful for magnetic tape guides and the like.
Both magnetic and nonmagnetic grades of the composition are useful as cutting tools and the like and also as tools for use in glass making and the like where cobalt contamination is detrimental.
The following chart gives a num~er of examples of compositions, the first five thereof being nonmagnetic grades and the last two being magnetic grades:
~078Z25 ~a~
tn ~1 a~ o ~ ~ ~r o ~ n ~ ~ ~ I~ ~D
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al ~ H
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O o O O O ~ o o ~,1 U
o ~ ooo o o o æ O a~ O cn ~, O O s~ o z ,~ ~1 ~ ~ ~1~ I I
~-æ ~
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u~
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S~ O In ~1 ~1 ~ ~ O ~1 ~ z _~ O O O O O O ~ ~ ra x a) E~
~1 q ~ ~ ~ ~ ~ ~D 1~ ___.
x ~ ~ ~
* * *
1C~78Z25 The last two columns of the chart~ the first of which gives transverse rupture strength, and the otHer of which giYeS
hardness on the Rockwell "A" scale, have two values for each composition. The reason for this is that the upper number of each pair is the value obtained when the composition is compacted and vacuum sintered and the second value is for a vacuum sintered speciment subjected to reheating in the presence of a high pressure inert gas.
In making any of the compositions referred to above, conventional m;lling procedures may be followed. A tungsten carbide lined mill with tungsten carbide milling media therein is preferably employed to avoid contamination. This mixture is milled for about 4 to 15 days and then processed in a conventional manner to arrive at a sintered end product.
Sintering may be accomplished at from about 1350 to about 1550 degrees Centigrade for a period of about 0.25 to
The present invention relates to metallurgical compositions embodying metal carbi`des, in particular, hard metal carbide6, and is especially concerned with a composition that can ~e tailored as to characteristics including that of being nonmagnetic or magnetic while remaining hard and wear resistant.
Many hard wear resistant metallurgical compositions embodying hard metal carbides are known, and most thereof are quite satisfactory for the intended use. An application for hard wear resistant carbide materials in connection with which there has not, heretofore, been satisfactory materials are those uses in which the hard wear resistant material must be nonmagnetic.
For example, machines in which magnetic tapes are employed often require wear resistant guides and the like for supporting and guiding the tapes. Still other cases will suggest themselves in which a hard wear resistant, or structurally strong, member is required where magnetic interactions are undesirable and in these cases, also non-magnetic carbide materials would be highly useful.
While the metallurgical composition according to the present invention can, as will be shown, be made nonmagnetic, magnetic variations of the composition have also been found highly useful in places where the composition must be hard and wear resistant and/or noncorrosi~e and/or noncontaminating or where the material must be extremely hard as in connection with a tool composition.
With the foregoing in mind, a primary objective of the present invention is the provision of a metallurgical composition embodying hard metal carbides which has the possibility of being formulated so as to be nonmagnetic but which will retain the desirable attributes of hard carbide metallurgical ~078ZZS
compositions.
Another ohject is the provision of a metallurgicalcomposition of the nature referred to which can ~e so compounded prior to the formation thereof as to be either nonmagnetic or magnetic when completed.
A still further object is the provision of a metallurgical composition embodying hard metal carbides which is satisfactory for use as a tool and which can be compounded to vary in magnetic properties at room temperature to the state of being nonmagnetic.
BRIEF SUMMARY OF THE INVENTION:
The metallurgical composition according to the present invention is concerned primarily-with tungsten, titanium, nickel, carbon compositions and to which may be added a certain amount of chromium and other carbides. The composition of the present invention can be compounded in such a manner as to be either nonmagnetic or magnetic while s~ill having the desirable characteristics of hard wear resistant cemented carbides.
Thus, in accordance with the present teachings, there is provided a sintered cemented carbide product the compositions of which comprises tungsten carbide, titanium carbide and a binder alloy comprising tungsten-nickel in which the ratio of the tungsten in the binder alloy to the binder is from 2 to 28 per cent by weight. By one aspect the above product is non-ferromagnetic and has a ratio of tungsten in the binder alloy to the binder alloy of 15 to 28 per cent by weight. By another aspect the above product has ferromagnetic properties and has a ratio of tungsten in the binder alloy to the binder alloy of less than 14 per cent by weight.
The hard metal carbides, including tungsten carbide and titanium carbide, are nonmagnetic so that a metallurgical composition embodying hard metal carbides can be made provided a suitable metal binder sy-stem is employed which is also nonmagnetic.
A binder metal for a cemented carbide composition should be tough and should also wet the carbide. A nickel binder system is, thus, a preferred binder because nickel wets the carbide compounds and is tough. Nickel, furthermore, although being itself ferromagnetic, can be alloyed with tungsten, which is also nonmagnetic, without undergoing a phase change upon heating or upon cooling from the liquid phase over a relatively broad alloying range and an alloy of this material can be selected which is nonmagnetic. By nonmagnetic, a material is referred to which has magnetic permeability near unity and which is lacking in the ability to become magnetized or to exhibit induced magnetism, namely, a material with 0 Oersted coexcive force.
When the more common binder metal, cobalt, is employed as a binder, and the composition is adjusted to be, or to approach being, nonmagnetic, the binder phase of the composition becomes extremely br;ttle due to the formation of Co3W3C and the composition is, thus, defective for many uses. The present invention overcomes this objection by including titanium in the composition and employing nickel or nickel and chromium as the basic binder metal.
When titanium, tungsten carbide and nickel, with or without some chromium, are admixed in powder form, compacted and heated so that a liquid phase is formed containing W, C
and some or all of the titanium in solution, then the carbon can associate itself with the titanium to form titanium carbide or a solid solution of TiC with WC, or both, because the free energy of formation for forming TiC is more favorable then for forming WC, Thus, tungsten is freed during sintering ~0~782Z5 to alloy with a binder metal or metals.
The mass balance is calculated so the stoichiometric excess W during sintering can alloy with the nickel and result in a magnetic or nonmagnetic binder alloy. The carbon balance with respect to the titanium must take into account the non-stoichiometric nature of TiC as less than one carbon atom per titanium atom is sufficient to form titanium carbide.
Thus, by including titanium in the mixture, carbon is removed from the melt because of the affinity of titanium for the carbon, and an alloy of nickel and tungsten and/or titanium is formed during sintering. It has been found that a fairly wide range of composïtions according to the present invention will result in the production of a nonmagnetic alloy having the same crystal structure as pure nickel, namely, face centered cubic.
While carbon deficient tungsten carbide can be employed with a nickel binder to yield a nickel-tungsten alloy binder after sintering, extremely- close control of the respective levels of nickel and carbon are required and an impractical control situation arises.
It has been found that small, less than 0.5 weight per cent, titanium metal additions as described herein very effectively inhibit grain growth during sintering and result in a fine grained structure and consequently improved strength.
A particular advantage of the present invention is to be found in the fact that, once the analysis of the WC
component is ascertained to reveal the amount of carbon in the WC component, the amount of Ti to add to the composition can readily be calculated. Formu~ation and control are thus greatly simplified.
The exact nature of the present invention will become more apparent upon reference to the following specificatïon ~0782Z5 giving specific examples and to the accompanying drawings in which:
Figure 1 is a graph giving weigfit per cent titanium to charge.
Figure 2 is a part of the nickel-tungsten phase diagram showing, in particular, the magnetic transformation character-istics of nickel-tungsten alloys.
DETAILED DESCRIPTION OF THE INVENTION:
The compositions according to the present invention can be compounded by closely analyzing each constituent for the carbon, oxygen, nitrogen and metallic impurities. The amount of Ti required to release the quantity of tungsten from the tungsten carbide to produce the nickel-tungsten alloy composition can then be calculated or determined experimentally.
In making the calculations, the tungsten level desired in the binder and the nickel content are established and the equations giving the desired amount of titanium, or tungsten, are solved.
In preparing the compositions, the powders charged in the mixture before sintering have about the following percentages by weight:
Nickel - 3.0 - 25.0 Titanium - .05 - 2.0 Tungsten Carbide- Balan~e In addition chromium may also be included in the range of 0.0 to 2.0 per cent by weight.
Figure 1 shows how much titanium to charge with tungsten carbide having the indicated total carbon content and negligible oxygen, nitrogen and metallic impurities. In the graph, the weight % of Ni in the composition is always 10.
The other 90% of the composition is made up of WC and Ti.
~078Z25 Thus, for example, at 1 wt~ ~ Ti, there will be 89 wt~ %
WC. Each line of the graph shows the amount of Ti to be supplied to obtain the indicated weight % of W in the b;nder.
TABLE I
Weight % Titanium to charge to a 10 Wt. % Nickel balance tungsten carbide composition (the WC having 6.10 Wt. % carbon content and negligible impuritiesl to obtain the calculated 10, 2a, or 25 Wt. ~ W/(W + ~î~ in the binder alloy as a function of carburization of the tïtanium addition.
Est.
Calculated Wt. % Atom Wt. ~ Wt. % Ti to Ratio Nickel W/(W + Ni~ Char~e C/Ti 0.283 0.6 la 10 0.240 0.7 0.208 0.8 0.187 0.9 0.879 0.6 2a 0.748 0.7 la 20 0.654 0.8 0.585 0.9 1.242 0.6 1.077 0.7 la 25 0.940 0.8 0.831 0.9 Chrom;um metal additions may be made to the composition, as will be explained more fully hereinafter, and help to further inhibit grain growth and also to stabilize the non-magnetic properties when the composition is to be nonmagnetic.
Chromium has produced good results and for a 10 weight %
nickel composition, a 1 weight % chromium level produced satisfactory results.
The chromium metal addition is not essential to achieve nonmagnetic properties. It can react with and take up some of the carbon by forming carbides of chromium, and it can also alloy with the nickel.
Titanium can be supplied in the form of powders of titanium metal, any alloy of titanium with nickel, not , 10~8ZZS
necessarily TiNi eutetic composition or as a hydride of titanium~ The last ment;oned form is preferred because it is less reactive then the pure metal and can be milled readily.
Also, it is less expensive than an alloy of titanium with nickel while, furthermore, the hydrogen that is evolved from titanium hydride during the early stages of sintering can be beneficial because it can be effective for reducing surface oxides, particularly those which form on nickel.
The nonmagnetic capability of the type of composition disclosed herein is important but there are other applications for the composition wherein chemical inertness and strength and wear resistance are the principal characteristics desired.
Nonmagnetic grades of the composition, as mentioned, are particularly useful for magnetic tape guides and the like.
Both magnetic and nonmagnetic grades of the composition are useful as cutting tools and the like and also as tools for use in glass making and the like where cobalt contamination is detrimental.
The following chart gives a num~er of examples of compositions, the first five thereof being nonmagnetic grades and the last two being magnetic grades:
~078Z25 ~a~
tn ~1 a~ o ~ ~ ~r o ~ n ~ ~ ~ I~ ~D
_ O ~iN ~i ~i~i (~ 0O OO o h C~ ~ ~ c~ ~ a~ a~ ~ c~ C~ 00 $ 1~
~J~
U~ ~
al ~ H
~ u~ oo u~ ~ ~ ~ ~ CO _I ~ er O In S~ ~J) O ~ ~ ~ ~ ~ N ~1 ~t ~r ~ ~ ~ ~
~ ' ~;
a) u~
O ~ U ~
h ~ n o o O o O
O O ~ ~ a~
o 1~ a~
O
~ ,: ' U~ S~ ~
E~
~ ~ a~
~ 3~ z u~ ~ o H u~ ~ + ~ ~ ~ ~ ~ ,1 ,~
H ~ ~i h U~ ' ~lo P~
E~ ~ ~ :
~ ~ ,i ,i _i ,i ~ ,i _i ' ' B ~ ~
u~ m m m m m m m h O
h ~ O o~
~ O~ a~ o .,1 ~ h J~ o o o ~ ~ o o O
~,1 _ w O E~~1In Q. O I` U) ~In ou~
. . . O ~
O o O O O ~ o o ~,1 U
o ~ ooo o o o æ O a~ O cn ~, O O s~ o z ,~ ~1 ~ ~ ~1~ I I
~-æ ~
E~
u~
u ~
S~ O In ~1 ~1 ~ ~ O ~1 ~ z _~ O O O O O O ~ ~ ra x a) E~
~1 q ~ ~ ~ ~ ~ ~D 1~ ___.
x ~ ~ ~
* * *
1C~78Z25 The last two columns of the chart~ the first of which gives transverse rupture strength, and the otHer of which giYeS
hardness on the Rockwell "A" scale, have two values for each composition. The reason for this is that the upper number of each pair is the value obtained when the composition is compacted and vacuum sintered and the second value is for a vacuum sintered speciment subjected to reheating in the presence of a high pressure inert gas.
In making any of the compositions referred to above, conventional m;lling procedures may be followed. A tungsten carbide lined mill with tungsten carbide milling media therein is preferably employed to avoid contamination. This mixture is milled for about 4 to 15 days and then processed in a conventional manner to arrive at a sintered end product.
Sintering may be accomplished at from about 1350 to about 1550 degrees Centigrade for a period of about 0.25 to
2.0 hours at 0.02 to 0.75 Torr.
It will be understood that during sintering tungsten released from tungsten carbide ~y the capturing of the carbon by titanium, can form what is referred to as Eta phase in combination with nickel and carbon, or if the composition contains chromium, with chromium and carbon.
Such a phase might be represented as Ni3W3C. This material will not, if present in small amounts, detract from the physical or magnetic properties of the material and serves as a part of the binder of the sintered composition.
Modifications may be made within the scope of the appended claims.
.. . . . . . . . .
:' ' , .:; :.
It will be understood that during sintering tungsten released from tungsten carbide ~y the capturing of the carbon by titanium, can form what is referred to as Eta phase in combination with nickel and carbon, or if the composition contains chromium, with chromium and carbon.
Such a phase might be represented as Ni3W3C. This material will not, if present in small amounts, detract from the physical or magnetic properties of the material and serves as a part of the binder of the sintered composition.
Modifications may be made within the scope of the appended claims.
.. . . . . . . . .
:' ' , .:; :.
Claims
1. The method of inhibiting grain growth during sintering in a powder metal compact which is formed from hard metal carbides and nickel which comprises adding about 0.05 to about 2.0 weight per cent Ti to the mixture from which the compact is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA323,323A CA1078225A (en) | 1975-07-25 | 1979-03-13 | Metallurgical composition embodying hard metal carbides, and method of making |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA232252A CA1054401A (en) | 1975-07-25 | 1975-07-25 | Metallurgical composition embodying hard metal carbides, and method of making |
| CA323,323A CA1078225A (en) | 1975-07-25 | 1979-03-13 | Metallurgical composition embodying hard metal carbides, and method of making |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078225A true CA1078225A (en) | 1980-05-27 |
Family
ID=25668036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA323,323A Expired CA1078225A (en) | 1975-07-25 | 1979-03-13 | Metallurgical composition embodying hard metal carbides, and method of making |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1078225A (en) |
-
1979
- 1979-03-13 CA CA323,323A patent/CA1078225A/en not_active Expired
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