Nothing Special   »   [go: up one dir, main page]

US20100166595A1 - Phosphor-bronze alloy as raw materials for semi solid metal casting - Google Patents

Phosphor-bronze alloy as raw materials for semi solid metal casting Download PDF

Info

Publication number
US20100166595A1
US20100166595A1 US12/278,921 US27892107A US2010166595A1 US 20100166595 A1 US20100166595 A1 US 20100166595A1 US 27892107 A US27892107 A US 27892107A US 2010166595 A1 US2010166595 A1 US 2010166595A1
Authority
US
United States
Prior art keywords
phosphor
mass
semi
bronze alloy
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/278,921
Inventor
Keiichiro Oishi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Shindoh Co Ltd
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Shindoh Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Shindoh Co Ltd filed Critical Mitsubishi Shindoh Co Ltd
Assigned to MITSUBISHI MATERIALS CORPORATION, MITSUBISHI SHINDOH CO., LTD. reassignment MITSUBISHI MATERIALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OISHI, KEIICHIRO
Publication of US20100166595A1 publication Critical patent/US20100166595A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/007—Semi-solid pressure die casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/025—Casting heavy metals with high melting point, i.e. 1000 - 1600 degrees C, e.g. Co 1490 degrees C, Ni 1450 degrees C, Mn 1240 degrees C, Cu 1083 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent

Definitions

  • the present invention relates to a phosphor-bronze alloy as raw materials for Semi Solid Metal casting that can be used to produce a phosphor-bronze alloy cast having fine grains by Semi Solid Metal casting (semi-solid alloy casting) without agitating a molten metal.
  • a Cu—Sn copper alloy containing copper and tin as major components and a minute amount of P is known as a phosphor-bronze alloy.
  • a forging phosphor-bronze alloy having a component composition containing Sn of 3.5 to 9.0 mass %, phosphor of 0.03 to 0.35 mass %, and a balance of Cu and inevitable impurities and a casting phosphor-bronze alloy having a component composition containing Sn of 9.0 to 15.0 mass %, phosphor of 0.05 to 0.5 mass %, and a balance of Cu and inevitable impurities are defined in the JIS standard.
  • Patent Document 1 Japanese Unexamined Patent Publication No. H6-234049
  • An object of the invention is to provide a phosphor-bronze alloy as raw materials for Semi Solid Metal casting that can produce a phosphor-bronze alloy cast having fine grains by Semi Solid Metal casting without using a member for agitating the molten metal.
  • a semi-solid phosphor-bronze alloy obtained by using a phosphor-bronze alloy which was obtained by adding Zr of 0.0005 to 0.04 mass % to a phosphor-bronze alloy containing Sn of 4 to 15 mass % and P of 0.01 to 0.25 mass %, as a raw alloy, completely melting the phosphor-bronze alloy into a liquid phase, and cooling the molten phosphor-bronze alloy, and a semi-solid phosphor-bronze alloy obtained by re-melting the ingot are both excellent in flowability.
  • (B) A semi-solid phosphor-bronze alloy obtained by using a phosphor-bronze alloy, which was obtained by adding Zn of 0.1 to 7.5 mass % to the phosphor-bronze alloy according to (A) containing Zr of 0.0005 to 0.04 mass % and P of 0.01 to 0.25 mass % as a raw alloy, completely melting the phosphor-bronze alloy into a liquid phase, and cooling the molten phosphor-bronze alloy, and a semi-solid phosphor-bronze alloy obtained by re-melting the ingot are both excellent in flowability.
  • the invention provides the following based on the above-mentioned study result:
  • a phosphor-bronze alloy as raw materials for Semi Solid Metal casting having a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass % and a balance of Cu and inevitable impurities.
  • a phosphor-bronze alloy as raw materials for Semi Solid Metal casting having a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, Zn of 0.1 to 7.5 mass %, and a balance of Cu and inevitable impurities.
  • the component composition of the phosphor-bronze as raw materials for Semi Solid Metal casting according to (1) or (2) may have a component composition further containing one or more kinds of Pb of 0.01 to 4.5 mass %, Bi of 0.01 to 3.0 mass %, Se of 0.03 to 1.0 mass %, and Te of 0.01 to 1.0 mass %.
  • the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention is melted to produce a semi-solid phosphor-bronze alloy in a solid-liquid mixture slurry and the semi-solid phosphor-bronze alloy is cast using a conventional method, a fine and granular ⁇ primary phase is generated or an ⁇ solid phase coexists in the liquid phase of the semi-solid phosphor-bronze alloy. Accordingly, even when an agitating apparatus is not used, it is possible to cast the semi-solid phosphor-bronze alloy without damaging the flowability of the semi-solid phosphor-bronze alloy. In addition, it is an advantage that the crystal grains of the phosphor-bronze alloy cast obtained by casting the semi-solid phosphor-bronze alloy are further reduced in size, thereby further enhancing the mechanical strength.
  • a phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention has a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, and a balance of Cu and inevitable impurities.
  • the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention may have a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, Zn of 0.1 to 7.5 mass % and a balance of Cu and inevitable impurities.
  • the component composition of the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention may contain Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, Zn of 0.1 to 7.5 mass %, and a balance of Cu and inevitable impurities.
  • An ingot of the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention, the component composition of which is adjusted, is produced and stored in advance, a semi-solid phosphor-bronze alloy is produced by re-melting a necessary amount of the ingot of the phosphor-bronze alloy as raw materials, and a semi-solid phosphor-bronze alloy cast having fine grains can be manufactured by casting the semi-solid phosphor-bronze alloy.
  • Sn has a function of improving the flowability of the molten alloy by means of addition to Cu, improving the corrosion resistance of the cast, and improving the mechanical strength and the wear resistance.
  • the content is less than 4 mass %, it is not preferable because the mechanical strength is small and the flowability of the molten alloy is reduced.
  • the content is greater than 15 mass %, it is not preferable because the casting property is deteriorated and the resultant cast is hard and brittle, thus reducing the mechanical strength. Accordingly, the content of Sn contained in the phosphor-bronze alloy for Semi Solid Metal casting according to the invention is defined in the range of 4 mass % to 15 mass %.
  • Zr has a function of promoting the generation of fine and granular ⁇ primary crystals in a semi-solid state, improving the flowability of the semi-solid phosphor-bronze alloy, and reducing the size of the crystal grains of the phosphor-bronze alloy cast,
  • the content thereof is less than 0.0005 mass %, it is not preferable because the reduction in size of the crystal grains is not sufficient.
  • the content is greater than 0.04 mass %, it is not preferable because the crystal grains of the cast increase in size.
  • the content of Zr contained in the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention is defined in the range of 0.0005 mass % to 0.04 mass %.
  • P has a function of promoting the generation of fine granular ⁇ primary crystals in a semi-solid state, improving the flowability of the semi-solid phosphor-bronze alloy, and reducing the size of the crystal grains of the phosphor-bronze alloy cast.
  • the content thereof is less than 0.01 mass %, it is not preferable because the reduction in size of the crystal grains is not sufficient.
  • the content is greater than 0.25 mass %, it is not preferable because intermetallic compounds with a low melting point are generated, making it brittle. Accordingly, the content of P contained in the phosphor-bronze alloy for Semi Solid Metal casting according to the invention is defined in the range of 0.01 mass % to 0.25 mass %.
  • Zn has a function of further improving the flowability of the semi-solid phosphor-bronze alloy, lowering the melting point, and enhancing the corrosion resistance and is thus added as needed.
  • the content thereof is less than 0.1 mass %, it is not preferable because the desired effect is not obtained.
  • the content thereof is greater than 7.5 mass %, it is not preferable because the flowability of the resultant cast is deteriorated. Accordingly, the content of Zn contained in the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention is defined in the range of 0.1 mass % to 7.5 mass %.
  • the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention may further contain one or more kinds of Pb, Bi, Se, and Te and the like as needed.
  • Pb be in the range of 0.01 mass % to 4.5 mass %
  • the content of Bi be in the range of 0.01 mass % to 3.0 mass %
  • the content of Se be in the range of 0.03 mass % to 1.0 mass %
  • the content of Te be in the range of 0.01 mass % to 1.0 mass %.
  • the phosphor-bronze alloy as raw materials for Semi Solid Metal casting has the above-mentioned component composition
  • the phosphor-bronze alloy as raw materials for Semi Solid Metal casting is melted to produce a semi-solid phosphor-bronze alloy in a solid-liquid mixture slurry and the semi-solid phosphor-bronze alloy is cast using a conventional method, a fine and granular ⁇ primary phase is generated or an ⁇ solid phase coexists in the liquid phase of the semi-solid phosphor-bronze alloy. Accordingly, even when an agitating apparatus is not used, it is possible to cast the semi-solid phosphor-bronze alloy without damaging the flowability of the semi-solid phosphor-bronze alloy. In addition, it is an advantage that the crystal grains of the phosphor-bronze alloy cast obtained by casting the semi-solid phosphor-bronze alloy are further reduced in size, thereby further enhancing the mechanical strength.
  • ingots of phosphor-bronze alloys as raw materials for Semi Solid Metal casting (hereinafter, referred to as phosphor-bronze alloys as raw materials according to examples of the invention) according to Examples 1 to 75 of the invention and phosphor-bronze alloys as raw materials for Semi Solid Metal casting (hereinafter, referred to as phosphor-bronze alloys as raw materials according to comparative examples) according to Comparative Examples 1 to 6, which have the component compositions shown in Tables 1 to 6, were produced.
  • the average grain sizes of the ⁇ solid phase were measured by etching the cutting surfaces of the quenched samples with nitric acid and then observing the cutting surfaces with an optical microscope.
  • the semi-solid phosphor-bronze alloys produced from the phosphor-bronze alloys as raw materials according to Examples 1 to 75 of the present invention were better in flowability than the semi-solid phosphor-bronze alloys produced from the phosphor-bronze alloys as raw materials according to Conventional Examples 1 and 2 and that the fine and granular ⁇ solid phase was generated in the liquid phase of the semi-solid phosphor-bronze alloys obtained by melting the phosphor-bronze alloys as raw materials according to Examples 1 to 75 of the present invention, thereby obtaining a cast having fine grains even when the semi-solid phosphor-bronze alloy is cast without agitation.
  • the phosphor-bronze alloys as raw materials according to Comparative Examples 1 to 6 containing Sn, Zr, and P that depart from the conditions of the invention are not preferable since dendrite is generated, the reduction in size of the crystal grains is insufficient in the semi-solid state thereof, or the alloys are brittle.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Continuous Casting (AREA)

Abstract

A phosphor-bronze alloy as raw materials for Semi Solid Metal casting has a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, and a balance of Cu and inevitable impurities, further containing Zn of 0.1 to 7.5 mass % as needed, and further containing one or more kinds of Pb of 0.01 to 4.5 mass %, Bi of 0.01 to 3.0 mass %, Se of 0.03 to 1.0 mass %, and Te of 0.01 to 1.0 mass % as needed.

Description

    TECHNICAL FIELD
  • The present invention relates to a phosphor-bronze alloy as raw materials for Semi Solid Metal casting that can be used to produce a phosphor-bronze alloy cast having fine grains by Semi Solid Metal casting (semi-solid alloy casting) without agitating a molten metal.
  • Priority is claimed on Japanese Patent Application No. 2006-035003, filed Feb. 13, 2006, the content of which is incorporated herein by reference.
    • BACKGROUND ART
  • A Cu—Sn copper alloy containing copper and tin as major components and a minute amount of P is known as a phosphor-bronze alloy. A forging phosphor-bronze alloy having a component composition containing Sn of 3.5 to 9.0 mass %, phosphor of 0.03 to 0.35 mass %, and a balance of Cu and inevitable impurities and a casting phosphor-bronze alloy having a component composition containing Sn of 9.0 to 15.0 mass %, phosphor of 0.05 to 0.5 mass %, and a balance of Cu and inevitable impurities are defined in the JIS standard.
  • When the phosphor-bronze alloys are melted and cast by the use of known methods, dendritic α primary crystals are crystallized in the molten phosphor-bronze alloys and thus the flowability of the molten alloy is poor, thereby deteriorating the casting property at a low temperature. In order to solve this problem, when a slurry-phase semi-solid phosphor-bronze alloy is produced by strongly agitating the molten phosphor-bronze alloy in a temperature range between the liquidus temperature and the solidus temperature and the semi-solid phosphor-bronze alloy is cast, dendrite generated in the solid-liquid mixture slurry is segmentalized by the agitation and the α primary crystal solid in the solid-liquid mixture slurry is formed in a sphere, thereby maintaining the flowability at a high solid phase ratio. Accordingly, a method of casting a phosphor-bronze alloy cast having a structure including fine grains and granular crystals has been suggested, which is termed a Semi Solid Metal casting method (see Patent Document 1).
  • [Patent Document 1] Japanese Unexamined Patent Publication No. H6-234049
    • DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
  • However, in executing the Semi Solid Metal casting method in which the molten metal is agitated, since it is necessary to perform the agitation under the control of a molten metal temperature, an apparatus needs to be increased in size. Accordingly, superfluous gas may be introduced into the molten metal under some conditions. The molten metal temperature needs to be lowered in consideration of wear damage. However, the generation of the dendrite structure cannot be completely suppressed even when the known phosphor-bronze alloy is agitated in a semi-solid state. Accordingly, the flowability of the molten metal is markedly deteriorated, thereby finally causing casting failure.
  • The invention is contrived in view of the above-mentioned problems. An object of the invention is to provide a phosphor-bronze alloy as raw materials for Semi Solid Metal casting that can produce a phosphor-bronze alloy cast having fine grains by Semi Solid Metal casting without using a member for agitating the molten metal.
    • Means for Solving the Problems
  • Therefore, the inventors studied in order to enhance the flowability of the semi-solid phosphor-bronze alloy without using an agitating member for segmentalizing and granulating dendrite in a liquid phase and to produce a phosphor-bronze alloy cast having fine grains without casting failure even when the semi-solid phosphor-bronze alloy is cast at a low temperature. As a result, the following observations (A) to (D) were found,
  • (A) A semi-solid phosphor-bronze alloy obtained by using a phosphor-bronze alloy, which was obtained by adding Zr of 0.0005 to 0.04 mass % to a phosphor-bronze alloy containing Sn of 4 to 15 mass % and P of 0.01 to 0.25 mass %, as a raw alloy, completely melting the phosphor-bronze alloy into a liquid phase, and cooling the molten phosphor-bronze alloy, and a semi-solid phosphor-bronze alloy obtained by re-melting the ingot are both excellent in flowability. Accordingly, it was found that it is possible to produce a phosphor-bronze alloy cast having fine grains by casting the semi-solid phosphor-bronze alloy and that it is not necessary to perform an agitation process in a semi-solid alloy, unlike in the case of known examples.
  • (B) A semi-solid phosphor-bronze alloy obtained by using a phosphor-bronze alloy, which was obtained by adding Zn of 0.1 to 7.5 mass % to the phosphor-bronze alloy according to (A) containing Zr of 0.0005 to 0.04 mass % and P of 0.01 to 0.25 mass % as a raw alloy, completely melting the phosphor-bronze alloy into a liquid phase, and cooling the molten phosphor-bronze alloy, and a semi-solid phosphor-bronze alloy obtained by re-melting the ingot are both excellent in flowability. Accordingly, it was found that it is possible to produce a phosphor-bronze alloy cast having fine grains by casting the semi-solid phosphor-bronze alloy and that it is not necessary to perform an agitation process in a semi-solid alloy unlike in the case of known examples.
  • (C) It was found that a phosphor-bronze alloy having a component composition further containing one or more kinds of Pb of 0.01 to 4.5 mass %, Bi of 0.01 to 3.0 mass %, Se of 0.03 to 1.0 mass %, and Te of 0.01 to 1.0 mass % in addition to the phosphor-bronze alloy according to (A) or (B) exhibits the same advantages.
  • (D) It was found that the reason for the excellent flowability in the semi-solid alloy state of the phosphor-bronze alloy according to (A), (B), or (C) is that fine and granular α primary crystals are crystallized instead of dendrite in the course of cooling and solidifying the phosphor-bronze alloy according to (A), (B), or (C) after completely melting the phosphor-bronze alloy into a liquid phase and that fine and granular α primary crystals coexist in the liquid phase of the semi-solid phosphor-bronze alloy obtained by re-melting the phosphor-bronze alloy according to (A), (B), or (C).
  • The invention provides the following based on the above-mentioned study result:
  • (1) A phosphor-bronze alloy as raw materials for Semi Solid Metal casting, having a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass % and a balance of Cu and inevitable impurities.
  • (2) A phosphor-bronze alloy as raw materials for Semi Solid Metal casting, having a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, Zn of 0.1 to 7.5 mass %, and a balance of Cu and inevitable impurities.
  • (3) The component composition of the phosphor-bronze as raw materials for Semi Solid Metal casting according to (1) or (2) may have a component composition further containing one or more kinds of Pb of 0.01 to 4.5 mass %, Bi of 0.01 to 3.0 mass %, Se of 0.03 to 1.0 mass %, and Te of 0.01 to 1.0 mass %.
    • Advantages of the Invention
  • When the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention is melted to produce a semi-solid phosphor-bronze alloy in a solid-liquid mixture slurry and the semi-solid phosphor-bronze alloy is cast using a conventional method, a fine and granular α primary phase is generated or an α solid phase coexists in the liquid phase of the semi-solid phosphor-bronze alloy. Accordingly, even when an agitating apparatus is not used, it is possible to cast the semi-solid phosphor-bronze alloy without damaging the flowability of the semi-solid phosphor-bronze alloy. In addition, it is an advantage that the crystal grains of the phosphor-bronze alloy cast obtained by casting the semi-solid phosphor-bronze alloy are further reduced in size, thereby further enhancing the mechanical strength.
    • BEST MODE FOR CARRYING OUT THE INVENTION
  • Hereinafter, the invention will be described in detail.
  • A phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention has a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, and a balance of Cu and inevitable impurities.
  • The phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention may have a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, Zn of 0.1 to 7.5 mass % and a balance of Cu and inevitable impurities.
  • The component composition of the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention may contain Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, Zn of 0.1 to 7.5 mass %, and a balance of Cu and inevitable impurities.
  • An ingot of the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention, the component composition of which is adjusted, is produced and stored in advance, a semi-solid phosphor-bronze alloy is produced by re-melting a necessary amount of the ingot of the phosphor-bronze alloy as raw materials, and a semi-solid phosphor-bronze alloy cast having fine grains can be manufactured by casting the semi-solid phosphor-bronze alloy.
  • The reasons for defining the component composition of the raw materials phosphor-bronze alloy for Semi Solid Metal casting according to the invention as described above will be described.
  • Sn:
  • Sn has a function of improving the flowability of the molten alloy by means of addition to Cu, improving the corrosion resistance of the cast, and improving the mechanical strength and the wear resistance. When the content is less than 4 mass %, it is not preferable because the mechanical strength is small and the flowability of the molten alloy is reduced. On the other hand, when the content is greater than 15 mass %, it is not preferable because the casting property is deteriorated and the resultant cast is hard and brittle, thus reducing the mechanical strength. Accordingly, the content of Sn contained in the phosphor-bronze alloy for Semi Solid Metal casting according to the invention is defined in the range of 4 mass % to 15 mass %.
  • Zr:
  • With its coexistence with P, Zr has a function of promoting the generation of fine and granular α primary crystals in a semi-solid state, improving the flowability of the semi-solid phosphor-bronze alloy, and reducing the size of the crystal grains of the phosphor-bronze alloy cast, When the content thereof is less than 0.0005 mass %, it is not preferable because the reduction in size of the crystal grains is not sufficient. On the other hand, when the content is greater than 0.04 mass %, it is not preferable because the crystal grains of the cast increase in size. Accordingly, the content of Zr contained in the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention is defined in the range of 0.0005 mass % to 0.04 mass %.
  • P:
  • With the coexistence of Zr, P has a function of promoting the generation of fine granular α primary crystals in a semi-solid state, improving the flowability of the semi-solid phosphor-bronze alloy, and reducing the size of the crystal grains of the phosphor-bronze alloy cast. When the content thereof is less than 0.01 mass %, it is not preferable because the reduction in size of the crystal grains is not sufficient. On the other hand, when the content is greater than 0.25 mass %, it is not preferable because intermetallic compounds with a low melting point are generated, making it brittle. Accordingly, the content of P contained in the phosphor-bronze alloy for Semi Solid Metal casting according to the invention is defined in the range of 0.01 mass % to 0.25 mass %. Zn:
  • Zn has a function of further improving the flowability of the semi-solid phosphor-bronze alloy, lowering the melting point, and enhancing the corrosion resistance and is thus added as needed. When the content thereof is less than 0.1 mass %, it is not preferable because the desired effect is not obtained. On the other hand, when the content thereof is greater than 7.5 mass %, it is not preferable because the flowability of the resultant cast is deteriorated. Accordingly, the content of Zn contained in the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention is defined in the range of 0.1 mass % to 7.5 mass %.
  • Other components:
  • The phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention may further contain one or more kinds of Pb, Bi, Se, and Te and the like as needed. When the components are contained in the phosphor-bronze alloy, it is preferable that the content of Pb be in the range of 0.01 mass % to 4.5 mass %, the content of Bi be in the range of 0.01 mass % to 3.0 mass %, the content of Se be in the range of 0.03 mass % to 1.0 mass %, and the content of Te be in the range of 0.01 mass % to 1.0 mass %.
  • By making the phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to the invention have the above-mentioned component composition, when the phosphor-bronze alloy as raw materials for Semi Solid Metal casting is melted to produce a semi-solid phosphor-bronze alloy in a solid-liquid mixture slurry and the semi-solid phosphor-bronze alloy is cast using a conventional method, a fine and granular α primary phase is generated or an α solid phase coexists in the liquid phase of the semi-solid phosphor-bronze alloy. Accordingly, even when an agitating apparatus is not used, it is possible to cast the semi-solid phosphor-bronze alloy without damaging the flowability of the semi-solid phosphor-bronze alloy. In addition, it is an advantage that the crystal grains of the phosphor-bronze alloy cast obtained by casting the semi-solid phosphor-bronze alloy are further reduced in size, thereby further enhancing the mechanical strength.
    • EMBODIMENTS Embodiment 1
  • By preparing conventional cathode copper as a raw material, feeding the cathode copper into an electrical furnace, melting the cathode copper in an atmosphere of Ar gas, adding Sn and P thereto when the temperature of the molten copper is 1200° C., adding Zn, Pb, Bi, Se, Te, and the like thereto as needed, and finally adding Zr thereto, a molten phosphor-bronze alloy was produced. By casting the molten phosphor-bronze alloy, ingots of phosphor-bronze alloys as raw materials for Semi Solid Metal casting (hereinafter, referred to as phosphor-bronze alloys as raw materials according to examples of the invention) according to Examples 1 to 75 of the invention and phosphor-bronze alloys as raw materials for Semi Solid Metal casting (hereinafter, referred to as phosphor-bronze alloys as raw materials according to comparative examples) according to Comparative Examples 1 to 6, which have the component compositions shown in Tables 1 to 6, were produced.
  • By melting a phosphor-bronze alloy containing Sn of 9 mass %, P of 0.35 mass % and a balance of Cu and inevitable impurities and being available on the market and a phosphor-bronze alloy containing Sn of 6 mass %, P of 0.1 mass % and a balance of Cu and inevitable impurities and being available on the market in an atmosphere of Ar gas, molten phosphor-bronze alloys of a temperature of 1200° C. were produced. By casting the molten phosphor-bronze alloy, ingots of phosphor-bronze alloys as raw materials for Semi Solid Metal casting (hereinafter, referred to as phosphor-bronze alloys as raw materials according to Conventional Examples) according to Conventional Examples 1 and 2 having the component composition shown in Table 6 were produced.
  • By cutting out parts of the ingots of the phosphor-bronze alloys as raw materials according to Examples 1 to 75 of the present invention, the phosphor-bronze alloys as raw materials according to Comparative Examples 1 to 6, and the phosphor-bronze alloys as raw materials according to Conventional Examples 1 and 2 and heating the cut-out ingots at a predetermined temperature between the solidus temperature and the liquidus temperature to re-melt the ingots, semi-solid phosphor-bronze alloys were produced. Quenched samples were produced by rapidly quenching the semi-solid phosphor-bronze alloys. By observing the structures of the quenched samples with an optical microscope, the shapes of the α solid phase coexisting with the liquid phase in the semi-solid phosphor-bronze alloys were estimated and the average grain sizes thereof were measured. The results are shown in Tables 1 to 6.
  • The average grain sizes of the α solid phase were measured by etching the cutting surfaces of the quenched samples with nitric acid and then observing the cutting surfaces with an optical microscope.
  • TABLE 1
    α solid phase in
    Phosphor- quenched sample
    bronze as raw Component composition (mass %) Average grain
    materials Sn Zr P Zn Pb Bi Se Te Cu shape size (μm)
    The 1 6 0.031 0.08 — — — — — balance granular 100
    Present 2 4 0.018 0.01 — — — — — balance granular 200
    Invention 3 7 0.015 0.07 — — — — — balance granular 50
    4 8 0.0094 0.05 — — — — — balance granular 40
    5 9 0.0060 0.09 — — — — — balance granular 30
    6 10 0.0015 0.11 — — — — — balance granular 40
    7 11 0.0008 0.16 — — — — — balance granular 70
    8 12 0.028 0.13 — — — — — balance granular 50
    9 13 0.039 0.19 — — — — — balance granular 120
    10 14 0.003 0.21 — — — — — balance granular 30
    11 15 0.0005 0.25 — — — — — balance granular 120
    12 5 0.0008 0.11 7.5 — — — — balance granular 80
    13 7 0.0015 0.16 5   — — — — balance granular 50
    14 9 0.0060 0.13 2.5 — — — — balance granular 30
    15 11 0.0094 0.19 0.3 — — — — balance granular 25
  • TABLE 2
    α solid phase in
    Phosphor- quenched sample
    bronze as raw Component composition (mass %) Average grain
    materials Sn Zr P Zn Pb Bi Se Te Cu shape size (μm)
    The 16 9 0.0008 0.08 — 4.3 — — — balance granular 80
    Present 17 8 0.0015 0.01 — 3.5 — — — balance granular 200
    Invention 18 10 0.0060 0.07 — 2.3 — — — balance granular 25
    19 11 0.0094 0.05 — 1.1 — — — balance granular 25
    20 4 0.015 0.09 — 0.5 — — — balance granular 100
    21 7 0.018 0.11 — 0.1 0.72 — — balance granular 45
    22 13 0.031 0.16 — 0.02 0.03 0.03 — balance granular 50
    23 6 0.028 0.13 — — 2.43 — — balance granular 50
    24 7 0.039 0.19 — — 2.35 — — balance granular 100
    25 9 0.003 0.21 — — 1.23 — — balance granular 60
    26 12 0.0005 0.25 — — 0.66 — — balance granular 150
    27 14 0.0003 0.11 — — 0.05 — — balance granular 100
    28 8 0.0015 0.16 — — 0.01 0.05 — balance granular 90
    29 10 0.0060 0.13 — — 0.02 0.06 0.01 balance granular 25
    30 13 0.0094 0.19 — 0.01 — 0.03 0.01 balance granular 50
  • TABLE 3
    α solid phase in
    Phosphor- quenched sample
    bronze as raw Component composition (mass %) Average grain
    materials Sn Zr P Zn Pb Bi Se Te Cu shape size (μm)
    The 31 5 0.0008 0.08 — — — 0.11 — balance granular 120
    Present 32 8 0.0015 0.01 — 0.1  — 0.06 — balance granular 200
    Invention 33 10 0.0060 0.07 — — — 0.21 — balance granular 30
    34 11 0.0094 0.05 — — 0.3  0.45 — balance granular 25
    35 15 0.015 0.09 — — — 0.15 — balance granular 30
    36 7 0.018 0.11 — — — 0.7  — balance granular 45
    37 4 0.031 0.16 — — — 1.0  — balance granular 120
    38 6 0.028 0.13 — 0.01 0.01 0.03 0.01 balance granular 50
    39 7 0.039 0.19 — — 0.01 — 0.11 balance granular 100
    40 9 0.003 0.21 — 0.01 — — 0.05 balance granular 60
    41 12 0.0005 0.25 — — — 0.03 0.08 balance granular 150
    42 14 0.0008 0.11 — — — — 0.15 balance granular 100
    43 8 0.0015 0.16 — — — — 1.0 balance granular 90
    44 10 0.0060 0.13 — — — — 0.7 balance granular 25
    45 13 0.0094 0.19 — — — — 0.23 balance granular 50
  • TABLE 4
    α solid phase in
    Phosphor- quenched sample
    bronze as raw Component composition (mass %) Average grain
    materials Sn Zr P Zn Pb Bi Se Te Cu shape size (μm)
    The 46 5 0.0008 0.08 0.5 4.33 — — — balance granular 100
    Present 47 8 0.0015 0.01 2 3.35 — — — balance granular 150
    Invention 48 10 0.0060 0.07 4 2.23 — — — balance granular 30
    49 11 0.0094 0.05 6 1.11 0.01 — — balance granular 25
    50 15 0.015 0.09 0.1 0.5  — 0.03 — balance granular 50
    51 7 0.018 0.11 1 0.11 — — 0.01 balance granular 50
    52 13 0.031 0.16 4 0.05 — — — balance granular 90
    53 6 0.028 0.13 7 — 2.43 — — balance granular 30
    54 7 0.039 0.19 2 — 1.85 — — balance granular 120
    55 9 0.003 0.21 0.3 — 1.23 — — balance granular 60
    56 12 0.0005 0.25 4 — 0.66 0.03 — balance granular 150
    57 14 0.0008 0.11 5 — 0.35 — 0.01 balance granular 100
    58 8 0.0015 0.16 1 — 0.06 — — balance granular 70
    59 10 0.0060 0.13 3 — 0.05 — — balance granular 30
    60 13 0.0094 0.19 2 — — 0.03 0.01 balance granular 60
  • TABLE 5
    α solid phase in
    Phosphor- quenched sample
    bronze as raw Component composition (mass %) Average grain
    materials Sn Zr P Zn Pb Bi Se Te Cu shape size (μm)
    The 61 5 0.0008 0.08 2 — — 0.11 — balance granular 90
    Present 62 8 0.0015 0.01 0.3 0.09 0.05 0.06 — balance granular 200
    Invention 63 10 0.0060 0.07 4 — — 0.21 — balance granular 30
    64 11 0.0094 0.05 7 — — 0.15 — balance granular 60
    65 15 0.015 0.09 0.2 — — 0.95 — balance granular 45
    66 7 0.018 0.11 3 — — 0.35 — balance granular 50
    67 13 0.031 0.16 2 — — 0.35 — balance granular 100
    68 6 0.028 0.13 0.5 0.05 0.05 0.03 0.01 balance granular 60
    69 7 0.039 0.19 2 — — — 0.11 balance granular 120
    70 9 0.003 0.21 3 0.01 — 0.03 0.05 balance granular 60
    71 12 0.0005 0.25 4 — 0.01 0.05 0.01 balance granular 150
    72 14 0.0008 0.11 0.5 — — — 0.15 balance granular 120
    73 8 0.0015 0.16 6 — — — 0.45 balance granular 80
    74 10 0.0060 0.13 3 — — — 0.95 balance granular 30
    75 13 0.0094 0.19 1 — — — 0.23 balance granular 50
  • TABLE 6
    α solid phase in
    Phosphor- quenched sample
    bronze as raw Component composition (mass %) Average grain
    materials Sn Zr P Zn Pb Bi Se Te Cu shape size (μm)
    Comparative 1  3* 0.006 0.07 — — — — — balance granular 400
    Example 2 16* 0.006 0.07 — — — — — balance dendrite-phase —
    3 8 0.0003* 0.07 — — — — — balance dendrite-phase —
    4 6 0.042* 0.03 — — — — — balance granular 400
    5 10  0.015 0.008* — — — — — balance dendrite-phase —
    6 9 0.005 0.26* — — — — — balance dendrite-phase —
    Conventional 1 9 — 0.35 — — — — — balance dendrite-phase —
    2 6 — 0.10 — — — — — balance dendrite-phase —
    Mark * represents a value departing from the conditions of the present invention.
  • It is estimated from the results shown in Tables 1 to 6 that the fine and granular α solid phase coexists with the liquid phase in the semi-solid state of the phosphor-bronze alloys as raw materials according to Examples 1 to 75 of the present invention, since the α solid phase of all the quenched samples was finely granular. On the other hand, it is estimated that dendrite was generated in the semi-solid state of the phosphor-bronze alloys as raw materials according to Conventional Examples 1 and 2, since the α solid phase of the quenched samples of the phosphor-bronze alloys as raw materials according to Conventional Examples 1 and 2 was in a dendrite phase.
  • Accordingly, it can be seen that the semi-solid phosphor-bronze alloys produced from the phosphor-bronze alloys as raw materials according to Examples 1 to 75 of the present invention were better in flowability than the semi-solid phosphor-bronze alloys produced from the phosphor-bronze alloys as raw materials according to Conventional Examples 1 and 2 and that the fine and granular α solid phase was generated in the liquid phase of the semi-solid phosphor-bronze alloys obtained by melting the phosphor-bronze alloys as raw materials according to Examples 1 to 75 of the present invention, thereby obtaining a cast having fine grains even when the semi-solid phosphor-bronze alloy is cast without agitation. It can also be seen that the phosphor-bronze alloys as raw materials according to Comparative Examples 1 to 6 containing Sn, Zr, and P that depart from the conditions of the invention (the range of component composition of the invention) are not preferable since dendrite is generated, the reduction in size of the crystal grains is insufficient in the semi-solid state thereof, or the alloys are brittle.
    • Embodiment 2
  • By cutting out parts of the ingots of the phosphor-bronze alloys as raw materials according to Examples 1 to 75 of the present invention, produced in Embodiment 1, the phosphor-bronze alloys as raw materials according to Comparative Examples 1 to 6, and the phosphor-bronze alloys as raw materials according to Conventional Examples 1 and 2 and completely melting the cut-out ingots, molten phosphor-bronze alloys in a liquid phase were produced. Semi-solid phosphor-bronze alloys maintained at a predetermined temperature between the solidus temperature and the liquidus temperature were produced by cooling the molten phosphor-bronze alloy thereafter. Quenched samples were produced by rapidly quenching the semi-solid phosphor-bronze alloys. By observing the structures of the quenched samples with an optical microscope, the shapes of the α solid crystals generated in semi-solid phosphor-bronze alloys were estimated and the average grain sizes thereof were measured. The results were the same as Embodiment 1.
    • INDUSTRIAL APPLICABILITY
  • When a phosphor-bronze alloy as raw materials of the present invention for Semi Solid Metal casting is melted to produce a semi-solid phosphor-bronze alloy in a solid-liquid mixture slurry and the semi-solid phosphor-bronze alloy is cast using a conventional method, a fine and granular α primary phase is generated or an α solid phase coexists in the liquid phase of the semi-solid phosphor-bronze alloy. Accordingly, even when an agitating apparatus is not used, it is possible to cast the semi-solid phosphor-bronze alloy without damaging the flowability of the semi-solid phosphor-bronze alloy. In addition, it is an advantage that the crystal grains of the phosphor-bronze alloy cast obtained by Semi Solid Metal casting phosphor-bronze alloy are further reduced in size, thereby further enhancing the mechanical strength. Accordingly, the invention is industrially very useful.

Claims (4)

1. A phosphor-bronze alloy as raw materials for Semi Solid Metal casting having a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, and a balance of Cu and inevitable impurities.
2. A phosphor-bronze alloy as raw materials for Semi Solid Metal casting, having a component composition containing Sn of 4 to 15 mass %, Zr of 0.0005 to 0.04 mass %, P of 0.01 to 0.25 mass %, Zn of 0.1 to 7.5 mass %, and a balance of Cu and inevitable impurities.
3. The phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to claim 1, wherein the component composition further contains one or more kinds of Pb of 0.01 to 4.5 mass %, Bi of 0.01 to 3.0 mass %, Se of 0.03 to 1.0 mass %, and Te of 0.01 to 1.0 mass %.
4. The phosphor-bronze alloy as raw materials for Semi Solid Metal casting according to claim 2, wherein the component composition further contains one or more kinds of Pb of 0.01 to 4.5 mass %, Bi of 0.01 to 3.0 mass %, Se of 0.03 to 1.0 mass %, and Te of 0.01 to 1.0 mass %.
US12/278,921 2006-02-13 2007-02-09 Phosphor-bronze alloy as raw materials for semi solid metal casting Abandoned US20100166595A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2006-035003 2006-02-13
JP2006035003A JP2007211324A (en) 2006-02-13 2006-02-13 Raw material phosphor bronze alloy for casting half-melted alloy
PCT/JP2007/052403 WO2007094265A1 (en) 2006-02-13 2007-02-09 Raw material phosphor bronze alloy for casting of semi-molten alloy

Publications (1)

Publication Number Publication Date
US20100166595A1 true US20100166595A1 (en) 2010-07-01

Family

ID=38371451

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/278,921 Abandoned US20100166595A1 (en) 2006-02-13 2007-02-09 Phosphor-bronze alloy as raw materials for semi solid metal casting

Country Status (4)

Country Link
US (1) US20100166595A1 (en)
JP (1) JP2007211324A (en)
CN (1) CN101384386A (en)
WO (1) WO2007094265A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100946936B1 (en) * 2009-12-01 2010-03-09 조주현 Cu-p-se brazing alloy
JP5590328B2 (en) * 2011-01-14 2014-09-17 三菱マテリアル株式会社 Phosphorus-containing copper anode for electrolytic copper plating and electrolytic copper plating method using the same
CN103740971B (en) * 2013-11-29 2016-01-06 余姚市宏骏铜业有限公司 A kind of bronze bearing
JP5928624B1 (en) * 2015-03-04 2016-06-01 株式会社 大阪合金工業所 Bronze alloy for musical instrument and percussion instrument using the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927467A (en) * 1987-02-10 1990-05-22 Mitsubishi Denki Kabushiki Kaisha Method for producing thin plate of phosphor bronze
US5853505A (en) * 1997-04-18 1998-12-29 Olin Corporation Iron modified tin brass
US6132528A (en) * 1997-04-18 2000-10-17 Olin Corporation Iron modified tin brass
US6136103A (en) * 1997-12-19 2000-10-24 Wieland-Werke Ag Copper-tin-titanium alloy
US6346215B1 (en) * 1997-12-19 2002-02-12 Wieland-Werke Ag Copper-tin alloys and uses thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5789449A (en) * 1980-11-21 1982-06-03 Sumitomo Electric Ind Ltd Method of manufacture of copper alloy for conducting electricity
JPH07113143B2 (en) * 1987-03-20 1995-12-06 三菱電機株式会社 Method for producing high strength copper alloy
JPH06172896A (en) * 1992-12-04 1994-06-21 Nikko Kinzoku Kk High-strength and high-conductivity copper alloy
JP3303878B2 (en) * 1996-09-09 2002-07-22 東陶機器株式会社 Method and equipment for producing brass
JP4043342B2 (en) * 2002-10-25 2008-02-06 株式会社神戸製鋼所 Phosphor bronze
DK1777305T3 (en) * 2004-08-10 2011-01-03 Mitsubishi Shindo Kk Copper base alloy casting with refined crystal grains
KR101050638B1 (en) * 2005-09-30 2011-07-19 미쓰비시 신도 가부시키가이샤 Molten solidified material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927467A (en) * 1987-02-10 1990-05-22 Mitsubishi Denki Kabushiki Kaisha Method for producing thin plate of phosphor bronze
US5853505A (en) * 1997-04-18 1998-12-29 Olin Corporation Iron modified tin brass
US6132528A (en) * 1997-04-18 2000-10-17 Olin Corporation Iron modified tin brass
US6136103A (en) * 1997-12-19 2000-10-24 Wieland-Werke Ag Copper-tin-titanium alloy
US6346215B1 (en) * 1997-12-19 2002-02-12 Wieland-Werke Ag Copper-tin alloys and uses thereof

Also Published As

Publication number Publication date
CN101384386A (en) 2009-03-11
WO2007094265A1 (en) 2007-08-23
JP2007211324A (en) 2007-08-23

Similar Documents

Publication Publication Date Title
US20090294087A1 (en) Brass alloy as raw materials for semi solid metal casting
JP5879244B2 (en) Aluminum alloy
US9080225B2 (en) Aluminum alloy and manufacturing method thereof
US9657372B2 (en) Manufacturing method of aluminum alloy in which Al—Fe—Si compound is refined
KR101241426B1 (en) Method of manufacturing aluminium alloy
US9901981B2 (en) Alloy production method and alloy produced by the same
WO2010055897A1 (en) Magnesium alloy and magnesium alloy casting
US20100166595A1 (en) Phosphor-bronze alloy as raw materials for semi solid metal casting
US20100172791A1 (en) Aluminum-bronze alloy as raw materials for semi solid metal casting
US20040151613A1 (en) Heat-resistant magnesium alloy for casting and heat-resistant magnesium alloy cast product
KR101591629B1 (en) Method for manufacturing Al-Mg alloy under the melting point of magnesium
JP2624302B2 (en) Mg-Sr alloy for A1-Si casting alloy modification
KR20120129720A (en) Filler metal for welding aluminum and manufacturing method thereof
CN109072359B (en) Aging heat treatment type high-strength magnesium alloy and preparation method thereof
JP2024132243A (en) Eutectic Al-Si alloy for casting and eutectic Al-Si alloy casting
JPS591647A (en) Manufacture of zinc alloy for bearing

Legal Events

Date Code Title Description
AS Assignment

Owner name: MITSUBISHI SHINDOH CO., LTD.,JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:OISHI, KEIICHIRO;REEL/FRAME:021363/0494

Effective date: 20080530

Owner name: MITSUBISHI MATERIALS CORPORATION,JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:OISHI, KEIICHIRO;REEL/FRAME:021363/0494

Effective date: 20080530

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION