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Publication numberUS3916497 A
Publication typeGrant
Publication dateNov 4, 1975
Filing dateFeb 11, 1974
Priority dateFeb 16, 1973
Also published asDE2407410A1, DE2407410B2
Publication numberUS 3916497 A, US 3916497A, US-A-3916497, US3916497 A, US3916497A
InventorsDoi Hidekazu, Nishigaki Kenichi
Original AssigneeMitsubishi Metal Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Heat resistant and wear resistant alloy
US 3916497 A
Abstract
A heat resistant and wear resistant alloy of the carbide-dispersion and precipitation-hardening type, to be used for cutting tools, etc., has a basic composition consisting, in weight percent based on the total weight of said alloy, of from 10 to 90% dispersed particles composed of one or more kinds of carbides or composite carbides of transition metals from Groups 4a, 5a and 6a and the balance being from 50 to 70% Ni, from 2 to 10% Ti, from 0.5 to 10% Al, and one or more kinds of alloy elements selected from the group consisting of from 1 to 10% Fe, from 1 to 20% Co, and from 1 to 20% Cr, said alloy further containing one or more kinds of alloy elements selected from the group consisting, in weight percent based on the weight of a Ni-base matrix, of no more than 5% Nb, no more than 10% Ta, no more than 20% Mo, no more than 20% W and no more than 5% V.
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United States Patent 1 1 et a1.

[75] Inventors: Hidekazu Doi; Kenichi Nishigaki,

both of Omiya, Japan [73] Assignee: Mitsubishi Metal Corporation,

Tokyo, Japan [22] Filed: Feb. 11, 1974 [21] Appl. No.: 441,125

[30] Foreign Application Priority Data Feb. 16, 1973 Japan 48-18329 [52] U.S. Cl. 29/1823; 29/1827; 75/.5 BC; 75/122; 75/171; 148/325 [51] Int. 1C1. C22C 29/00 [58] Field of Search 75/.5 BC, 203, 204, 122, 75/171; 29/1827, 182.8, 171; 148/32, 32.5

[56] References Cited UNITED STATES PATENTS 3,502,463 3/1970 Holtz, Jr. 75/.5 BC X 3,502,464 3/1970 Holtz, Jr. 75/171 3,576,681 4/1971 Barker et a1... 75/171 X 3,615,376 10/1971 Ross 75/171 3,655,458 4/1972 Reichman 75/203 X Prill et a1. 75/203 X Dalal et a1. 75/171 Primary Examiner-L. Dewayne Rutledge Assistant Examiner-Arthur J. Steiner Attorney, Agent, or FirmF1ynn & Frishauf [57] ABSTRACT A heat resistant and wear resistant alloy of the carbide-dispersion and precipitation-hardening type, to be used for cutting tools, etc., has a basic composition consisting, in weight percent based on the total weight of said alloy, of from 10 to 90% dispersed particles composed of one or more kinds of carbides or composite carbides of transition metals from Groups 4a, 5a and 6a and the balance being from 50 to 70% Ni, from 2 to 10% Ti, from 0.5 to 10% Al, and one or more kinds of alloy elements selected from the group consisting of from 1 to 10% Fe, from 1 to 20% C0, and from 1 to 20% Cr, said alloy further containing one or more kinds of alloy elements selected from the group consisting, in weight percent based on the weight of a Ni-base matrix, of no more than 5% Nb, no more than 10% Ta, no more than 20% Mo, no more than 20% W and no more than 5% V.

8 Claims, 1 Drawing Figure US. Patent Nov. 4, 1975 IOOO- SOO- Q \L PRESENT \QIVENTION /SKH4 260 460 BOO 8C0 IOIOO TEMPERATURE (C) NOTEI COMPOSITION OF ALLOY OF THE PRESENT lNVENTION 20%Ti0- 20% vvc35/o Ni3/Ji (COMPOSITION \N EXAMPLE 4) HEAT RESISTANT AND WEAR RESISTANT ALLOY RELATED APPLICATION This application is related to application Ser. No. 441,106, filed Feb. 11, 1974.

The present invention relates to heat-resistant and wear-resistant alloys prepared by utilizing in combination the principles of dispersion strengthening due to the dispersion of carbide particles and of precipitation hardening through the formation of y'-phase [Ni- Al(Ti)] in a Ni-base matrix.

Alloys according to the present invention find their use as materials for cutting tools, wear-resisting tools for hot or cold working, etc. Accordingly, the alloys must have high strength and toughness at room temperature as well as at elevated temperatures, in addition to excellent anti-welding properties.

Hitherto, the materials used for cutting tools have been carbon tool steel, high speed steel, WC base-hard alloy, TiC base cermet, etc. Carbon tool steel and high speed steel are tough but the toughness tends to'decrease sharply at temperature over about 600C, so the tools made of such materials are used only in a low cutting range within which less heat is generated.

At increased cutting speeds, the WC base-hard alloys are best, although they suffer from such as being somewhat lower in anti-welding properties and in wearresistance. Furthermore, the use of a tool made of such materials in the high speed cutting range gives rise to a demand for greater resistance to oxidation, because the cutting edge of a tool is subjected to a higher temperature than the rest of the tool. Therefore, within the high speed cutting range TiC base cermet, which has excellent oxidationresistance, finds a wide range of uses.

An alloy according to the present invention is provided as a sintered tool material, which contains one or more kinds of carbides of transition metals selected from the Groups 4a, 5a and 6a in the form of dispersion phase, and the balance of a composition of a Ni-base superalloy and is characterized in that the total amount of carbides or composite carbides is in the range from 10 to 90%, based on the total weight of said alloy and the balance thereof is a composition of Ni-base super alloy, in which is precipitated a 'y'-phase [Ni Al(Ti)].

The features of the alloy according to the present invention are that they retain the high strength and toughness obtained by containing in the Ni-base matrix high melting point metals, such as Ta, Nb, W, Mo, V, etc. and at the same time do not decrease in strength at a temperature up to 700C to 800C, due to the excellent heatresistance of the matrix and the high strength of the precipitated 'y-phase at an elevated temperature. In addition, alloys of the present invention provide, in combination, excellent high resistance to wear and oxidation as a result of the carbide phases dispersed in the alloys.

As is clear from the foregoing, the alloys according to the present invention are superior in the properties required for tool materials and can be provided over a wide range of cutting modes, from light to heavy, load by controlling the carbide phase and the amount and nature of binder phase in addition they are superior in properties required for tool materials for cold or hot working tools.

Alloys according to the present invention provide excellent cutting characteristics, particularly in the low cutting speed range, in which high speed steel finds its principal application. High speed steel, in general, contains MC, M C and M C type carbides dispersed therein. The hardness of M C and M C type carbides does not go as high as 1800 to 2100 in terms of Vickers hardness. ln contrast thereto, the hardness of the principal carbides of the present invention, such as for in- 10 stance, TiC, goes as high as 3000 3200 (Vickers hardness). Also, they have good wettability to the matrix of Ni base super alloys as well as high oxidation resistance. The result is that the excellent properties of TiC are well reflected in the cutting performance of tools which contain it.

When the alloys of the present invention are used for cutting tools to be used in a low speed cutting range, the total amount of one or more kinds of carbides or composite carbides contained in the alloy should preferably be in the range of from 20 to On the other hand, the Ni-base super alloy matrix functioning as a binding phase in the present invention has a basic composition consisting, in weight percent, of from 50 to 70% Ni, from 2 to 10% Ti and from 0.5 to 10% Al, said alloy further containing one or more kinds of alloy elements selected from the group consisting of from 1 to 10% Fe, from 1 to 20% Co, from 1 to 20% Cr, one or more kinds of alloy elements selected from the group consisting, in weight percent based on the Ni-matrix, of no more than 5% Nb, no more than 5% V, no more than 10% Ta, no more than 20% Mo and no more than 20% W.

In this respect, Ti and A] are essential as constituents for forming a y'phase [Ni Al(Ti)] which plays a major role in precipitation-hardening. If the amounts of Ti and A1 are insufficient, less amount of the -y-phase will be precipitated and the resulting alloy will have lowered heatresistance. For this reason, a Ti'content of at least 2% and an Al content of at least 0.5% are neces sary. However, if the content of Ti and A] respectively exceed 10%, an undesirable brittle n-phase (Ni Ti) or NiAl phase will be formed. Fe and Co dissolve either in a Ni-matrix or in 'y-phase as solid solution, thereby raising the recrystallization temperature. If the Fe or Co content is less than 1%, their effects will be decreased, while the. Fe content is more than 10% and the Co content is more than 20%, then the excellent heat resistance of the Ni base matrix will be lowered. Cr dissolves in a Ni-matrix and y'-phase as solid solution, thus improving oxidation-resistance significantly. A Cr content of less than 1% decreases the effect of Cr, while a Cr content of more than 20% causes brittleness of the alloy.

W, Mo, Ta, Nb and V each partially dissolve in a Nimatrix, while partially forming carbides. These elements dissolved in a Ni-matrix effectively improve strength of an alloy at elevated temperatures. However, in case the amount of such elements is excessive, the toughness of the alloy will be decreased. Of these elements, M0 is best to improve the strength of boundaries of carbide particles and a binding phase, because the Mo added forms Mo-rich composite carbides surrounding the surface of a starting carbide, which exhibit good affinity to the Ni-base binding phase.

The alloy of the present invention may further con tain one or more kinds of alloy elements selected from the group consisting, in weight percent based on the Nimatrix, of no more than 0.1% B, from 0.01 to 2.0% Zr,

no more than 1% Hf, no more than 0.5% Mg, no more than 1%, in total, of rare earth elements, (such as La, Y, Ce, etc.), no more than 0.5% P, no more than 3% Si and no more than 5% Mn.

A small amount of B, Zr, Mg, Hf, P and rare earth elements, if added, gives advantages such as improved deoxidation and desulfurization of the Ni-matrix, strengthening of grain boundaries and refining of crystal grains. However, if the amount of such elements added is excessive, the result is increased brittleness, because of the formation of compounds. Si and Mn give effects the same as those of B, Zr, Mg, etc. and dissolve in a Ni-matrix, thereby strengthening grain boundaries and improving the effects of heat treatment. An Si content of over 3% and a Mn content of over 5% forms compounds, leading to increased brittleness.

Other than the elements above described, the addition, on the basis of the total weight of Ni-base matrix, of no more than 1% C, no more than 0.1% N, no more than 0.5% Cu, no more than 0.5% Re, no more than 0.5% Ba, no more than 0.5% Rh, or no more than 0.5% Be is effective. These elements may be added in place of the aforesaid small amount of elements or in combination therewith. I

When the amount of C,N, Be, Re, Cu, Rh, etc. added is very small, they dissolve in a Ni-matrix as solid solution, improving the strength of the matrix. However, if too much of such elements is added, brittleness of the alloy increases.

When carbide dispersion, precipitation hardening type alloys of the present invention are used in a high speed cutting range, higher wear resistance and oxidation resistance are required, as compared with low speed cutting. To obtain these properties, a considerable amount of one or more kinds of carbides or composite carbides of transition metal from Groups 4, 5a and 6a should be contained in the alloy. More specifically, the total weight of carbides or composite carbides contained in'the alloy should be from 60 to 90% and dispersed in a binding phase of the alloy. In this respect, since y-phase is precipitated in the binding phase, the strength of the alloy at elevated temperatures will be much improved, as compared with the case where precipitated particles are not contained in the binding phase. More particularly, when comparing the conventional alloy with those of the present invention in terms of the use of the same amount of binder phase, those according to the present invention are much harder at an elevated temperature, so that wear resistance during continuous cutting is improved. Suppose that the wear resistance ofa level the same as that of the conventional alloy is desired; then the amount of binder phase may be increased, thereby providing more improved intermittent cutting capability.

Tools which are employed as hot compression dies, hot extrusion punches, hot drawing dies, hot working rolls, hot forging dies, etc. for hot working are subjected to a high temperature for a relatively long period of time. Therefore, in addition to the usual resistance against wear and impact, and creep-resisting and antiwelding properties, they must be hard enough to resist softening and deformation at the elevated temperature due to the temperature rise during service. For such applications, there are among the alloys according to the present invention sintered tool materials of Ni-base super alloys containing from 10 to 60% by weight of one or more kinds of carbides or composite carbides of transition metals from Groups 4a, 5a, and 6a, in the form ofa dispersion phase and the balance of a composition of a Ni-base super alloy. The prior art carbon tool steel and high speed steel which have been widely used tend to soften at a temperature of above 600C and thus are not usable, and in addition such tools present insufficient anti-welding properties.

According to alloys of the present invention, the temperature at which softening starts may be increased to 800C, because the strength of the binding phase at an elevated temperature is improved due to the precipitation of a 'y'-phase. Furthermore, alloys according to the present invention provide the characteristics required in too] materials for hot working, due to the excellent wear resistance and anti-welding properties provided by the carbide particles.

The accompanying graph shows hardness at elevated temperatures of an alloy of the present invention in comparison with high speed steel (JlS-SKH 4).

The following examples are illustrative of several aspects of the present invention. Unless otherwise indicated, the percentage given for alloying elements is weight percent based on total weight of alloy.

EXAMPLE 1 10% WC of a size of 1 was added to 20% TiC powder of 3p. in size which had been obtained by crushing commercially available TiC of minus mesh in a wet type ball mill. Then the following were added to this TiC-WC mixture: 35% Ni, 10% Co, 5% Fe, 10% NiAl (Ni Al 7 3), 2% Ti, 5% Mo and 3% Cr. These added powdery elements form a binding phase for the carbide particles. The powder mixture thus prepared was wet-mixed, compacted, sintered under vacuum of 10 mm Hg at 1350C for 1.0 hour. The sintered product was subjected to solution treatment at 1 C for 4 hours and thereafter to aging treatment at 750C for 4 hours.

The hardness of the alloy thus obtained was 63 RC (Rockwell C scale).

EXAMPLE 2 The following were added to TiC powder of 3p. in size; 5% Co, 40% Ni, 7.9% NiAl (Ni Al 7:3), 2% Ti, 5% Fe, 5% Cr, 5.09% Mo and 0.01% B. These powdery elements form a binding phase for the carbide particles. The powder mixture thus prepared was wetmixed, compacted, sintered under vacuum at 1350C for 1.0 hour, subjected to solution treatment under vacuum at 1 150C for 4 hours, then oil-quenched and tempered at 760C for 3 hours. The hardness of the thus obtained alloy after measurement was on the Rockwell hardness C scale, 57 after sintering, 55 after quenching, and 62 after tempering, respectively. The transverse rupture strength was 180 kglmm The cutting test results of such tool alloys are shown in Table 1 which shows the superiority of the alloys of the present invention in wear resistance and smoothness of finished surface.

Table 1 Cutting conditions Work Material AlSl 4340 Feed 01 mm/rev. Depth of Cut 1.0 mm Cutting time 2.0 minutes 0.08 good finished Table l-continued Cutting conditions The following were added to 40% WC powder of 3p. in size and (WTi)C of 3p. in size; 5.09% Co, 30% Ni, 5% NiAl (Ni Al 7:3), 3% Cr, 2% Fe, 2.9% Ti, 1% Ta, 001% B and 1% Mn. The powder mixture thus prepared was mixed, compacted, sintered under vacuum of 10' mmHg at 1400C for 1 hour, subjected to solution treatment under vacuum at 1 120C for 4 hours, then oil-quenched, and finally tempered at 800C for 4 hours. The hardness of the alloy was as high as 74 on the Rockwell C scale, and the transverse rupture strength was 220 kg/mm EXAMPLE 4 The following were added to powder of 20%, by weight, based on the total weight of the resulting powder mixture, of TiC of 1 in size and 20% WC of 1 in size; 35% Ni, 3% Ti, 6% NiAl (Ni Al =7 3), 10% Co, 5% M0, 0.5% Si and 0.5% Mn. The powder mixture thus prepared was mixed, compacted, sintered under vacuum at 1350C for 1.0 hour, subjected to solution treatment at 1150C for 4 hours, then oil-quenched and finally tempered at 800C for 2 hours. The hardness of the alloy thus obtained was 64 on the Rockwell C scale, and the transverse rupture strength thereof was 210 kg/mm. The hardness of the alloy thus obtained in comparison with a high speed steel (JlS, SKH 4) is shown in FIG. 1. The chemical composition of JIS SKI-1 4 is C 0.7 0.85, Si 0.40, Mn 0.40, P 0.03, S 0.03, Cr 3.804.5, W 17- 19, V 1 1.5 and C09- 11. It was found that the conventional high speed steel softened at about 600C, whereas the softening point of the alloy of the present invention was about 800C.

EXAMPLE 5 The following were added to 60% TiC of 3p. in size, 10% NbC of 3p. in size and 5% WC of 1p, in size; 4% Co, 12% Ni, 3.09% NiAl (Ni A1 7 3), 2% Ti, 1% Fe, 1% Cr, 0.01% B, 1.5% Mo, and 0.4% Ta. The powder mixture thus prepared was wet-mixed, compacted under a pressure of 1 t/cm, sintered under vacuum of 10 mmHg at 1400C for 1.0 hour, subjected to solution treatment at 1120C for 4 hours, then oilquenched and finally tempered at 800C for 2 hours. The hardness of the alloy thus obtained was 91.5 on the Rockwell A scale, and the transverse rupture strength thereof was 140 kg/mm".

EXAMPLE 6 The following were added to 15% (TiTa)C, 10% WC and 9% Cr C each being of In in size; 40% Ni, 1.8% Ti, 5% NiAl (Ni A1= 7:3), 3.5% Fe, 5% Co, 5% Cr, 5% M0, 0.4% C, 0.5% Mn, and 0.3% Cu. The powder thus prepared was wet-mixed, dried, compacted, sintered under vacuum of 10 mmHg at 1350C for 1 hour and cooled in the furnace. The hardness of the alloy thus obtained was 60 on the Rockwell C scale, and the transverse rupture strength thereof was 170 6 kg/mm The cutting test reveals that alloys of the invention are superior to SKH 4.'

EXAMPLE 7 The following were added to 20% (TiZr)C, 5% WC and 5% Mo c each being of 1p. in size: a Ni-base super alloy powder consisting of50% Ni, 4% Ti, 5% Al, 5% Fe, 10% Co, 10% Cr, 0.3% Be, 7% Mo, 2% Ta and 6.7% W. The powder thus prepared was mechanically mixed, then dried, compacted, sintered under vacuum of 10- mmHg at 1320C for 1 hour, subjected to solution treatment under vacuum at 1120C for 4 hours and, lastly, tempered. The hardness of the alloy thus obtained was about 66 on the Rockwell C scale, and the transverse rupture strength thereof was 240 kg/mm EXAMPLE 8 The following were added to 30% WC and 10% TaC each being of 1p. in size: 5% C0, 30% Ni, 10% NiAl (Ni :A] 7 :3), 3% Ti, 10% M0, 0.5% C, 1% Si, and 0.5% Mn. The powder thus prepared was mixed, compacted, sintered under vacuum of 10* mmHg at 1380C for 1.0 hour, subjected to solution treatment under vacuum at 1120C for 4 hours, oil-quenched and finally tempered at 800C for 4 hours. The hardness of the alloy thus obtained was about 69 R and the transverse rupture strength thereof was 250 kg/mm EXAMPLE 9 The following were added to 20% (TiZr)C and 10% Mo C each being of 1;; in size: the Ni-base super alloy powder consisting of 50% Ni, 10.08% Cr, 10% Co, 0.3% C, 3% Ti, 5.3% A1, 8% Mo, 13% W, 0.01% B, 0.01% Ce and 0.3% Si. The powder thus prepared was wet-mixed, compacted under a pressure of 1 t/cm, sintered under vacuum of 10 mmHg at 1320C for 1.0 hour, oil-quenched, tempered at 800C for 2 hours. The hardness of the alloy thus obtained was 64 R and the transverse rupture strength thereof was 170 kg/mm.

EXAMPLE 10 The following were added to 50% (TiMo)C, 20% WC and 5% TaC each being of 1p. in size: 2% Ti, 1.89% Co,15% Ni, 2% Cr, 3% MM (Ni A1 7 3), 1% M0, 0.1% C and 0.01% B. The powder thus prepared was wet-mixed, compacted, sintered under vacuum at 1370C for 1 hour, subjected to solution treatment at 1200C for 4 hours, oil-quenched, tempered at 800C for 2 hours. The hardness of the alloy thus obtained was 91 R and the transverse rupture strength thereof was kg/mm.

EXAMPLE 1 1 The following were added to 15% TiC and 5% TaC each being of 1p. in size: 45% Ni, 5% Cr, 8% Co, 1.95% Si, 0.05% Cu, 10% MA] (Ni 2 A1 7 3), 2% Ti, and 8% Mo, which elements were used to form the binding phase of the present invention. The powder thus prepared was wet-mixed, sintered under vacuum of 10' mmHg at 1320C for 1 hour, subjected to solution treatment at 1080C for 4 hours, oil-quenched, and finally tempered at 720C for 5 hours. The hardness of the alloy thus obtained was 51 R and the transverse rupture strength there' o f was 250 kg/mm.

What we claim is:

A 1. A powder metallurgy sintcred alloy having a basic composition consisting essentially of, in weight percent based on the total weight of said alloy, from 10 to 90% of substantially uniformly dispersed preformed particles composed of at least one carbide or composite carbide of transition metals of Groups 4a, 5a and 6a and the balance a nickel base matrix consisting essentially of from 50 to 70% Ni, from 2 to 10% Ti, from 0.5 to 10% Al, at least one alloy element selected from the group consisting of from 1 to 10% Fe, from 1 to 20% Co, and from l. to 20% Cr, and at least one alloy element (B), in an amount sufficient to impart high temperature strength, selected from the group consisting, in weight percent based on said Ni-base matrix, of-up to 5% Nb, up to 10% Ta, up to 20% Mo, up to 20% W and up to 5% V, and said alloy element (A) dissolving in said Ni-base matrix in the form of a solid solution.

2. An alloy as defined in claim 1, wherein said alloy further contains at least one alloy, element selected from the group consisting, in weight percent based on the Ni-base matrix, of up to 1.0% C, up to 0.1% N, up to 0.5% Cu, up to 0.5% Re, up to 0.5% Ba, up to 0.5% Rh and up to 0.5% Be.

. 3. An alloy as defined in claim 5, wherein said alloy further contains at least one alloy element selected from the group consisting, in weight percent based on the Ni-base matrix, of up to 0.1% B, from 0.01 to 2.0% Zr, up to 1.0% Hf, up to 0.5% Mg, up to 1.0%, in total, of rare earth elements, up to 0.5% P, up to 3.0% Si, and up to 5% Mn.

4. An alloy as defined in claim 3, wherein said alloy further contains at least one alloy element selected from the group consisting, in weight percent based on Ni-base matrix, of up to 1.0% C, up to 1.0% N, up'to 0.5% Cu, up to 0.5% Re, up to 0.5% Ba, up to 0.5% Rh, and up to 0.5% Be.

5. A powder metallurgy sinteredalloy havinga basic composition consisting essentially of, in weight percent based on the total weight of said alloy, from 10 to 90% of substantially uniformly dispersed preformed particles composed of at least one carbide or composite carbide of transition metals of Groups 4a, 5a and 6a and the balance a nickel base matrix consisting essentially of from to 70% Ni, from 2 to 10% Ti, from 0.5 to 10% Al, at least one alloy element (A) selected from the group consisting of from 1 to 10% Fe, from 1 to 20% Co, and from 1 to 5% Cr, and at least one alloy element (B), in an amount sufficient to impart high temperature strength, selected from the group consisting, in weight percent based on said Ni-base matrix, of up to 5% Nb, up to 10% Ta, up to 20% Mo, up to 20% W and up to 5% V, andsaid alloy element (A) dissolving in said Ni-base matrix in the form of a solid solution.

6. An alloy as defined in claim 5, wherein said alloy further contains at least one alloy element selected from the group consisting, in weight percent based on the Ni-base matrix, of up to 1.0% C, up to 0.1% N, up to 0.5% Cu, up to 0.5% Re, up to 0.5% Ba, up to 0.5% Rh and up to 0.5% Be.

7. An alloy as defined in claim 5, wherein said alloy further contains at least one alloy element selected from the group consisting, in weight percent based on the Ni-base matrix, of up to 0.1% B, from 0.1 to 2.0% Zr, up to 1.0% Hf, up to 0.5% Mg, up to 1.0%, in total, of rare earth elements, up to 0.5% P, up to 3.0% Si, and upto5%Mn. I

8. An alloy as defined in claim 7, wherein said alloy further contains at least one element selected from the group consisting, in weight percentbased on the Nibase matrix, of up to '1 .0% C, up to 1.0% N, up to 0.5% Cu, up to 0.5% Re, up to 0.5% Ba, up to 0.5% Rh, and up to 0.5% Be.

UNITED STATES PATENT OFFICE @TFCATE F EQTTUN PATENT NO. 3,916,497 DATED November 4, 1975 INVENTOR(S) HIDEKAZU DOI et al It is certified that error appears in the ab0veidentified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 38: replace "oxidationresistance" with oxidation-resistance Column 1, line 56: replace Y with Y' Column 1, after line 38: insert the following as a new paragraph:

-- The accompanying figure shows the influence of alloy composition and temperature on the hardness of the alloy.

Column 7, line 9: replace "element selected" with element (A) selected Column 7, line 25, Claim 3: replace "5" with l Eigned and Sealed this [SEAL] fourth Day Of May 1976 Arrest:

RUTH C. MASON Arresting Officer UNITED STATES PATENT OFFICE fiERHMQATE EQHGN PATENT NO 3,916,497

DATED 1 November 4, 1975 INVENTOR(S) HIDEKAZU DOI et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 38: replace "oxidationresistance" with oxidation-resistance Column 1., line 56: replace Y with Y' Column 1, after line 38: insert the following as a new paragraph:

----- The accompanying figure shows the influence of alloy composition and temperature on the hardness of the alloy.

Column 7, line 9: replace "element selected" with element (A) selected Column 7, line 25, Claim 3: replace "5" with l and gril this fourth Day Of May 1976 [SEAL] Attesi:

RUTH C. MASON Allvsting Officer

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Classifications
U.S. Classification75/236, 420/457, 72/467, 75/246, 420/448
International ClassificationC22C29/10, C22C29/06, C22C19/05, C22C1/05, C22C32/00, C22C29/08
Cooperative ClassificationC22C32/0052, C22C29/067
European ClassificationC22C29/06M, C22C32/00D2