US3733667A - Para-magnetic hard alloys - Google Patents

Para-magnetic hard alloys Download PDF

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US3733667A
US3733667A US00179496A US3733667DA US3733667A US 3733667 A US3733667 A US 3733667A US 00179496 A US00179496 A US 00179496A US 3733667D A US3733667D A US 3733667DA US 3733667 A US3733667 A US 3733667A
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carbide
percent
para
weight
nickel
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H Myashita
T Nishimura
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TOMONO S JA
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H Myashita
T Nishimura
Tomono S
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder

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  • ABSTRACT PARA-MAGNETIC HARD ALLOYS The present invention relates to para-magnetic hard alloys having a high toughness suitable for manufacture of dies, heat resistant material and structural members, especially clocks or watches in the field for which nonmagnetism is required.
  • Hard alloys are generally prepared by the sintering process of carbide of metals included in IV, V and VI Groups in the periodic table, especially tungsten carbide with an iron group metal as a binder, generally cobalt, and they are used in a wide variety of applications such as cutting tools, dies or heat resisting materials. All of the iron group metals, i.e. iron, cobalt and nickel, used as a binder metal, however, are ferro-magnetic elements, and therefore, the hard alloys prepared with these binder metals are ferro-magnetic ones.
  • a para-magnetic tungsten-carbidenickel alloy may be prepared by limiting the carbon content of the tungsten carbide to 5.95 percent by weight on the basis of tungsten carbide, but a decrease of the carbon content deteriorates the toughness of the alloy due to the generation of a double carbide.
  • nickel and molybdenum are used as a binder composition for a carbide composition primarily consisting of tungsten carbide, and a part of said nickel is replaced by an eutectic Ni-P composition, or a part of said tungsten carbide particles are previously coated with the Ni-P composition by the electroless plating.
  • the resulting mixture is then sintered.
  • the molybdenum is dissolved in the nickel, rendering the metallic binder phase para-magnetic, thus obtaining a novel hard alloy of a high toughness with a carbon content without generating free carbon or a double carbide.
  • the present invention is based on the abovementioned founding.
  • the para-magnetic hard alloys of the present invention may be produced by the sintering process of mixed particles consisting of 70-99 percent by weight of a carbide composition primarily comprising tungsten carbide with or without one or more members selected from a group consisting of tantalum carbide, titanium carbide, niobium carbide, vanadium carbide, chromium carbide, zirconium carbide and hafnium carbide and l-30 percent by weight of the binder composition comprising 2-30 percent by weight of a Ni-P composition containing 8-l4 percent by weight of phosphorus, -50 percent by weight of molybdenum and nickel constituting the remainder.
  • the mixed particles may contain the carbide particles previously coated with the Ni-P composition by the electroless plating.
  • the reason for restricting the content of the carbide composition to 70-99 percent by weight is based on the fact that lesser content than 70 percent by weight substantially decreases the hardness of the produce and larger content than 99 percent by weight deteriorates the toughness to an impractical extent.
  • the other carbides such as tantalum carbide, titanium carbide, niobium carbide, vanadium carbide, chromium carbide, zirconium carbide or hafnium carbide may be added as a simple substance as the conven tional manner, or may be added after the production of a double carbide with the tungsten carbide. When two or more kinds of different carbides are to be added, they may be in a form of a solid solution carbide.
  • Nickel is used as the binder metal for the reasons that it produces an alloy having the substantial same physical properties as that of a cobalt bonded alloy or cemented carbide, and that the Curie point of nickel is the lowest out of the iron group metals.
  • molybdenum is converted into a carbide form during the sintering process, but it may be used for the reason that when dissolved in nickel in an amount more than 9 percent by weight, molybdenum imparts a para-magnetism at the room temperature.
  • the reason for restricting the added amount of molybdenum in the binder composition to 15-50 percent by weight is based on the facts that with the amount less than l5 percent by weight, the molybdenum content in the binder phase decreases less than 9 percent by weight producing the ferro-magnetism, and with the content over 50 percent by weight, the hardness of an alloy deteriorates substantially.
  • novel paramagnetic WC base hard alloys having a hightoughness by the addition of the binder comprising nickel, molybdenum and the eutectic Ni-P composition.
  • EXAMPLE 1 Particle mixture comprising 81 percent by weight of tungsten carbide having a grain size of 1.4 microns, 1 percent of which being coated with NiP powders con taining 10 percent by weight of phosphorus by the electroless plating, 7 percent by weight of molybdenum having a grain size of 1.2 microns and 12 percent by weight of nickel having a grain size of L3 microns is thoroughly mixed in a solvent of acetone with a ball mill for 72 hours. After the mixing, the mixture is pressmolded and vacuum sintered for 1 hour at the temperature of l,300 C under the similar steps for the convert tional hard alloys to produce a para-magnetic hard alloy in accordance with the present invention.
  • the resulting alloy exhibits the para-magnetism, in other words the magnetic saturation is zero.
  • the Curie point exhibiting the term-magnetism are obtained at 127 K (146 C) as shown in the accompanying graph of reciprocal susceptibility v. absolute temperature.
  • the product shows the hardness of HRA 906 and the transverse rupture strength of 150. Kg/sq.
  • EXAMPLE 2 An alloy prepared in the same vacuum sintering process as in Example 1 from a particle mixture comprising 73 percent by weight of tungsten carbide having a grain size of 1.5 microns, 15 percent by weight of nickel having a grain size of 1.3 microns, 10 percent by weight of molybdenum having a grain size of 1.2 microns and 2 percent by weight of Ni-P composition containing 1 1 percent by weight of phosphorus shows the para-magnetism at the room temperature, a hardness of HRA 88.6 and a transverse rupture strength of 168 Kg/sq. mm.
  • Para-magnetic WC base hard alloy prepared bv the sintering process from a particle mixture comprising l-3O percent of a nickel base binder composition conbide. zirconium carbide and hafnium carbide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

Para-magnetic WC base hard alloys comprising a carbide composition primarily consisting of tungsten carbide and a binder consisting of nickel and molybdenum wherein a part of said nickel is replaced by an eutectic Ni-P composition.

Description

EJIIEIM SIaies Patent [191 Miyashita et a1. May 22, 1973 [5 1 PARA-MAGNETIC HARD ALLOYS References Cit d [76] Inventors: Hirotoahi Miyashita, 4724 Ozasa UNITED STATES PATENTS Danchl; Tomio Nishimura, 225 Gaza Notame; Sumiharu Tom, 2,711,009 6/1955 Redmond et a1. ..75 203 802 0m Shimay FOREIGN PATENTS OR APPLICATIONS kuoka, Japan 217,445 10/1957 Australia ..75/203 [22] Flledz Sept. 10, 1971 211 App]. No: 179 496 Primary Examiner-Benjamin R. Padgett Assistant Examiner-B. Hunt Att0rneyLinton & Linton {52] [1.8. CI. ..29/182.7, 29/182.8, 75/203,
[57] ABSTRACT PARA-MAGNETIC HARD ALLOYS The present invention relates to para-magnetic hard alloys having a high toughness suitable for manufacture of dies, heat resistant material and structural members, especially clocks or watches in the field for which nonmagnetism is required.
Hard alloys are generally prepared by the sintering process of carbide of metals included in IV, V and VI Groups in the periodic table, especially tungsten carbide with an iron group metal as a binder, generally cobalt, and they are used in a wide variety of applications such as cutting tools, dies or heat resisting materials. All of the iron group metals, i.e. iron, cobalt and nickel, used as a binder metal, however, are ferro-magnetic elements, and therefore, the hard alloys prepared with these binder metals are ferro-magnetic ones.
It is known that a para-magnetic tungsten-carbidenickel alloy may be prepared by limiting the carbon content of the tungsten carbide to 5.95 percent by weight on the basis of tungsten carbide, but a decrease of the carbon content deteriorates the toughness of the alloy due to the generation of a double carbide.
We improved the above-mentioned difficulty by an invention wherein nickel and molybdenum are used as a binder composition for a carbide composition primarily consisting of tungsten carbide, and a part of said nickel is replaced by an eutectic Ni-P composition, or a part of said tungsten carbide particles are previously coated with the Ni-P composition by the electroless plating. The resulting mixture is then sintered. We found that during said sintering process the molybdenum is dissolved in the nickel, rendering the metallic binder phase para-magnetic, thus obtaining a novel hard alloy of a high toughness with a carbon content without generating free carbon or a double carbide.
The present invention is based on the abovementioned founding.
The para-magnetic hard alloys of the present invention may be produced by the sintering process of mixed particles consisting of 70-99 percent by weight of a carbide composition primarily comprising tungsten carbide with or without one or more members selected from a group consisting of tantalum carbide, titanium carbide, niobium carbide, vanadium carbide, chromium carbide, zirconium carbide and hafnium carbide and l-30 percent by weight of the binder composition comprising 2-30 percent by weight of a Ni-P composition containing 8-l4 percent by weight of phosphorus, -50 percent by weight of molybdenum and nickel constituting the remainder. Alternatively, the mixed particles may contain the carbide particles previously coated with the Ni-P composition by the electroless plating.
The reason for restricting the content of the carbide composition to 70-99 percent by weight is based on the fact that lesser content than 70 percent by weight substantially decreases the hardness of the produce and larger content than 99 percent by weight deteriorates the toughness to an impractical extent.
The other carbides such as tantalum carbide, titanium carbide, niobium carbide, vanadium carbide, chromium carbide, zirconium carbide or hafnium carbide may be added as a simple substance as the conven tional manner, or may be added after the production of a double carbide with the tungsten carbide. When two or more kinds of different carbides are to be added, they may be in a form of a solid solution carbide.
Nickel is used as the binder metal for the reasons that it produces an alloy having the substantial same physical properties as that of a cobalt bonded alloy or cemented carbide, and that the Curie point of nickel is the lowest out of the iron group metals.
A part of the molybdenum is converted into a carbide form during the sintering process, but it may be used for the reason that when dissolved in nickel in an amount more than 9 percent by weight, molybdenum imparts a para-magnetism at the room temperature.
The reason for restricting the added amount of molybdenum in the binder composition to 15-50 percent by weight is based on the facts that with the amount less than l5 percent by weight, the molybdenum content in the binder phase decreases less than 9 percent by weight producing the ferro-magnetism, and with the content over 50 percent by weight, the hardness of an alloy deteriorates substantially.
Further, the reason for the step in which a part of nickel particles is replaced by the eutectic Ni-P composition containing 8-14 percent by weight of nickel, and then the total nickel is added to control the carbide formation of molybdenum by reducing the eutectic temperature of the sintered product and to render the binder composition para-magnetic by increasing the molybdenum content in the binder phase. Also, when a part of the carbide particles previously coated with the Ni-P composition containing 8-14 percent by weight of nickel by the electroless plating is used, the carbide formation of molybdenum is further prevented to improve the effect to increase the molybdenum content in the binder phase.
As mentioned above, it is possible to prepare novel paramagnetic WC base hard alloys having a hightoughness by the addition of the binder comprising nickel, molybdenum and the eutectic Ni-P composition.
The present invention will be further described by way of the following Examples.
EXAMPLE 1 Particle mixture comprising 81 percent by weight of tungsten carbide having a grain size of 1.4 microns, 1 percent of which being coated with NiP powders con taining 10 percent by weight of phosphorus by the electroless plating, 7 percent by weight of molybdenum having a grain size of 1.2 microns and 12 percent by weight of nickel having a grain size of L3 microns is thoroughly mixed in a solvent of acetone with a ball mill for 72 hours. After the mixing, the mixture is pressmolded and vacuum sintered for 1 hour at the temperature of l,300 C under the similar steps for the convert tional hard alloys to produce a para-magnetic hard alloy in accordance with the present invention.
The resulting alloy exhibits the para-magnetism, in other words the magnetic saturation is zero.
The Curie point exhibiting the term-magnetism are obtained at 127 K (146 C) as shown in the accompanying graph of reciprocal susceptibility v. absolute temperature. The product shows the hardness of HRA 906 and the transverse rupture strength of 150. Kg/sq.
EXAMPLE 2 An alloy prepared in the same vacuum sintering process as in Example 1 from a particle mixture comprising 73 percent by weight of tungsten carbide having a grain size of 1.5 microns, 15 percent by weight of nickel having a grain size of 1.3 microns, 10 percent by weight of molybdenum having a grain size of 1.2 microns and 2 percent by weight of Ni-P composition containing 1 1 percent by weight of phosphorus shows the para-magnetism at the room temperature, a hardness of HRA 88.6 and a transverse rupture strength of 168 Kg/sq. mm.
We claim:
1. Para-magnetic WC base hard alloy prepared bv the sintering process from a particle mixture comprising l-3O percent of a nickel base binder composition conbide. zirconium carbide and hafnium carbide.
1L 2 x x t

Claims (1)

  1. 2. A para-magnetic WC base hard alloy as claimed in claim 1 including at least one member selected from a group consisting of tantalum carbide, titanium carbide, niobium carbide, vanadium carbide, chromium carbide, zirconium carbide and hafnium carbide.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4280841A (en) * 1977-09-27 1981-07-28 Nippon Tungsten Co., Ltd. Method for manufacturing a mechanical seal ring
US20140093419A1 (en) * 2012-10-02 2014-04-03 Hon Hai Precision Industry Co., Ltd. Mold made of nickel-phosphorus alloy
US20180052211A1 (en) * 2014-02-24 2018-02-22 Northrop Grumman Systems Corporation Customized magnetic susceptibility materials

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711009A (en) * 1952-10-08 1955-06-21 Kennametal Inc Corrosion resistant sintered stock containing mixed carbides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711009A (en) * 1952-10-08 1955-06-21 Kennametal Inc Corrosion resistant sintered stock containing mixed carbides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4280841A (en) * 1977-09-27 1981-07-28 Nippon Tungsten Co., Ltd. Method for manufacturing a mechanical seal ring
US20140093419A1 (en) * 2012-10-02 2014-04-03 Hon Hai Precision Industry Co., Ltd. Mold made of nickel-phosphorus alloy
US20180052211A1 (en) * 2014-02-24 2018-02-22 Northrop Grumman Systems Corporation Customized magnetic susceptibility materials
US10451690B2 (en) * 2014-02-24 2019-10-22 Northrop Grumman Systems Corporation Customized magnetic susceptibility materials

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