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WO1990011852A1 - Methode de traitement de depots de metal coule par pulverisation - Google Patents

Methode de traitement de depots de metal coule par pulverisation Download PDF

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Publication number
WO1990011852A1
WO1990011852A1 PCT/US1990/001737 US9001737W WO9011852A1 WO 1990011852 A1 WO1990011852 A1 WO 1990011852A1 US 9001737 W US9001737 W US 9001737W WO 9011852 A1 WO9011852 A1 WO 9011852A1
Authority
WO
WIPO (PCT)
Prior art keywords
deposit
copper
reduction
alloy containing
base alloy
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.)
Ceased
Application number
PCT/US1990/001737
Other languages
English (en)
Inventor
Brian Mravic
William Gary Watson
Harvey P. Cheskis
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.)
Olin Corp
Original Assignee
Olin Corp
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 Olin Corp filed Critical Olin Corp
Priority to FI914146A priority Critical patent/FI914146A0/fi
Publication of WO1990011852A1 publication Critical patent/WO1990011852A1/fr
Priority to KR1019900702453A priority patent/KR920700078A/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B22D23/003—Moulding by spraying metal on a surface
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • This invention relates generally to the treatment of metal alloys produced by spray casting. More particularly, this invention relates to a method of treating spray cast metal deposits to reduce the porosity thereof.
  • Spray casting is a method of manufacturing metal or metal alloy articles directly to a desired shape.
  • the basic spray casting process comprises the steps of atomizing a fine stream of molten metal, depositing the particles onto a collector where the hot particles solidify to form a preform and then working or directly machining the preform to generate the final shape and/or properties required.
  • One form of such a spray casting process is generally known as the OSPREY process and is more fully disclosed in U.S. Patent Numbers RE 31,767 and 4,804,034 as well as United Kingdom Patent No. 2,172,900. Further details about the process are contained in the publication entitled "The Osprey Preform Process" by R. w. Evans, et al. Powder Metallurgy, Vol. 28, No. 1 (1985) .
  • a controlled stream of molten metal is poured into a gas-atomizing device where it is impacted by high-velocity jets of gas, usually nitrogen or argon.
  • the resulting spray of metal particles is directed onto a "collector" where the hot particles re-coalesce to form a highly dense preform.
  • the collector is fixed to a mechanism which is programmed to form a sequence of movements within the spray, so that the desired preform shape can be generated.
  • the preform can then be further processed, normally by hot working, to form a semi-finished or finished product.
  • the OSPREY process has also been proposed for producing strip or plate or spray-coated strip or plate as disclosed. n U.S. Patent No. 3,775,156 and European Patent Application No. 225,080.
  • a substrate or collector such as a flat substrate or an endless belt is moved continuously through the spray to receive a deposit of uniform thickness across its width.
  • spray cast products have many desirable properties
  • one of the drawbacks to the use of the process, especially in making thin gauge strip material is that the spray cast product has a relatively high degree of porosity.
  • the spray cast product has been found to contain from about 1% to about 10% by volume of pores. It is theorized that most of these pores contain nitrogen gas which has been entrapped during the casting process.
  • the pores or defects Upon cold rolling the material after the spray cast process, the pores or defects are collapsed and elongated in the direction of rolling. These defects may be expected to have a detrimental effect on ductility and such ductility related mechanical properties as lead bend fatigue life and bend formability. These properties are important, especially in the case of copper based alloys which have application in the electrical and electronic industry.
  • a more specific object of the present invention is the provision of a method for treating spray cast strip material which results in a reduction of defects due to porosity.
  • the objects and advantages of the present invention are achieved, in accordance with the present invention, by spray casting a strip of metal by atomizing a molten stream of metal and depositing the atomized particles onto a moving substrate to form a strip.
  • the resulting deposit is then cold worked as by cold rolling to a reduction at which the pores are substantially collapsed and elongated forming planar defects.
  • the strip is then annealed at a temperature and time to heal a significant portion of the planar defects.
  • Such anneal may be from about 1 to about 8 hours at a temperature of at least 450°C. It has been surprisingly found that after the cold working and anneal, the frequency of defects due to the presence of pores is drastically reduced.
  • Figure 1 is a schematic view, partly in section, of a prior art spray-deposition apparatus suitable for producing a thin gauge strip product on a moving substrate;
  • Figure 2 is a photomicrograph taken at a magnification of 250X of a spray cast product showing a typical cross-sectional area as cast
  • Figure 3 is a photomicrograph, taken at 250X magnification, of a longitudinal section of the sample of Figure 2 after the sample has been cold rolled to a 74% reduction
  • Figure 4 is a photomicrograph, taken at 250X magnification, of a transverse section of the sample of Figure 2, after it has been cold rolled to a 74% reduction;
  • Figure 5 is a photomicrograph of a longitudinal section of the sample of Figure 2 magnified 250X, and taken after the sample has been cold rolled to a 74% reduction and subjected to a 500°C/4 hr. anneal.
  • Figure 1 discloses a spray deposition apparatus 10 as known in the art.
  • the system as illustrated produces a continuous strip of a product A.
  • a suitable metal B is a copper alloy.
  • the spray deposition apparatus 10 employs a tundish 12 in which a metal alloy having a desired composition B is held in molten form.
  • the tundish 12 receives the molten alloy B from a tiltable melt furnace 14, via a transfer launder 16.
  • the tundish 12 further has a bottom nozzle 18 through which the molten alloy B issues in a continuous stream C.
  • a gas atomizer 20 is positioned below the tundish bottom nozzle 18 within a spray chamber 22 of the apparatus 10.
  • the atomizer 20 is supplied with a gas under pressure from any suitable source.
  • the gas serves to atomize the molten metal alloy and also supplies a protective atmosphere to prevent oxidation of the atomized droplets.
  • a most preferred gas is nitrogen.
  • the nitrogen should have a low concentration of oxygen to avoid the formation of undesirable oxides.
  • An oxygen concentration of under about 100 ppm and preferably less than about 10 ppm may be used.
  • the atomizer 20 surrounds the molten metal stream C and has a plurality of jets 20A from which the gas exits to impinge on the stream C so as to convert the stream into a spray D comprising a plurality of atomized molten droplets.
  • the droplets are broadcast downwardly from the atomizer 20 in the form of a divergent conical pattern. If desired, more than one atomizer 20 may be used.
  • the atomizer(s) 20 may be moved in a desired pattern for a more uniform distribution of the molten metal particles.
  • a continuous substrate system 24 as employed by the apparatus 10 extends into the spray chamber 22 in generally horizontal fashion and spaced in relation to the gas atomizer 20.
  • the substrate system 24 includes a drive means comprising a pair of spaced rolls 26, and endless substrate 28 in the form of a flexible belt entrained about and extending between the spaced rolls 26 and a series of rollers 30 which underlie and support an upper run 32 of the endless substrate 28.
  • An area 32A of the substrate upper run 32 directly underlies the divergent pattern of spray D.
  • the area 32A receives a deposit E of the atomized metal particles to form the metal strip product A.
  • the metal strip product A of the desired alloy may be milled on its top and bottom surface to remove surface oxides.
  • the milled strip may then be cold rolled to a suitable reduction so that the pores present in the material are substantially collapsed to form planar defects elongated in the directions of cold rolling.
  • Such reduction should be preferably at least 25% up to about 85% and more preferably 50% to about 75%.
  • the strip should be annealed, to heal a substantial portion of such defects.
  • anneal is a bell anneal, at a temperature of from about 450°C and more preferably at least from about 500°C up to about 800°C.
  • the time of the anneal should be sufficient to heal a substantial portion of the planar defects at the temperature of the anneal.
  • the time is from about 1 to about 8 hours and more preferably from about 2 to about 6 hours.
  • the strip may then be further processed in any conventional manner.
  • a suitable type of metal which may be spray cast by the apparatus described above and treated in accordance with the present invention is a copper alloy.
  • copper alloy C19400 is copper alloy C19400.
  • this alloy is a copper based alloy containing from about 1.5 to about 3.5% iron and small amounts of zinc and phosphorous.
  • This alloy is more specifically described in U.S. Patent 3,522,039 to C. D. McLain.
  • the alloy generally comprises 1.5 to 3.5% iron, from 0.01 to 0.15% phosphorous, from 0.03 to 0.20% zinc and the balance essentially copper.
  • strip of this alloy is produced by casting it in molten form into a short rectangularly shaped mold which initially is closed at one end by a plug on a removable ram or starter bar. The metal freezes to the plug and forms a shell against the mold surface. The ram is then steadily withdrawn, pulling the shell with it. As the shell exits from the bottom of the mold, cold water is sprayed on it, cooling it rapidly and causing the contained molten metal to freeze. In this manner a continuously cast slab of the desired length is produced. The cast slab is then hot worked into strip form and further treated to final thickness.
  • copper alloy C19400 was cast as thin gauge strip utilizing a spray casting process as described above. According to the spray cast process, the molten metal was caused to flow through an atomizer where nitrogen gas served to atomize the molten metal alloy into droplets which were broadcast downwardly from the atomizer onto a moving substrate forming a strip of material.
  • compositions - Weight %
  • FIGS 2-5 such Figures are photomicrographs of sample 1 at various stages of treatment taken at a magnification of 250X.
  • the samples were etched to enhance the porosity.
  • the etching solution consisted of 20 ml water, 20 ml ammonium hydroxide and 5 ml hydrogen peroxide.
  • Figure 2 shows a typical longitudinal cross-sectional area of sample 1, in the "as cast" condition, at a magnification of 250X. With the microscopic field view of 115 x 90 mm at a magnification of 250X the actual area shown is about 0.166 mm . As can be seen, there are a substantial number of pores within the magnified area.
  • Figure 3 is a photomicrograph at a magnification of 250X of a typical area of a longitudinal section of sample 1 after the milled sample was annealed at 550°C for 4 hours and then cold rolled to a 74% reduction down to 0.039 inch.
  • Figure 4 is a photomicrograph of a transverse section of sample 1 after the same treatment. As will be noted, even the cold working does not eliminate the defects. However, the defects after cold working are in the form of elongated, generally planar defects. The size and frequency of these defects for the various samples are set forth in Table II.
  • Figure 5 is a photomicrograph at 250X magnification of sample 1 taken through a longitudinal section of a typical area after the sample has been subjected to a 500°C/4 hour anneal after the cold rolling.
  • the frequency of the defects visible at a magnification of 250X is drastically reduced, although there still are a few defects present. This held true for all of the samples.
  • the defect frequency after cold working and the 500°C/4 hour anneal was too low to provide any meaningful measurement, but was at least one to two orders of magnitude lower than those shown in Table II.
  • a control sample having a composition as set forth in Table I was cast and hot worked according to the conventional process.
  • the hot rolled plate was cold rolled 58% to 0.150 inch and then subjected to a 550°C/4 hour anneal followed by a 74% cold rolled reduction to 0.039.
  • the control sample was further annealed at 500°C for 4 hours followed by a 72% cold rolled reduction to 0.011 inch.
  • Table III sets forth the mechanical properties of the spray cast material samples as well as the control sample after the above treatment.
  • Alloy C51000 is a copper base alloy containing from about 3.5 to about 5.8% tin, from about 0.03 to about 0.35% phosphorous, up to about 0.05% lead, up to about 0.30% zinc, up to about 0.10% iron, and the balance essentially copper.
  • Alloy C71300 is a copper base alloy containing from about 23.5 to about 26.5% nickel, up to about 1.0% manganese, up to about 1.0% zinc, up to about 0.20% iron, up to about 0.25% lead, and the balance essentially copper.
  • Table IV below sets forth the nominal composition of various copper base alloys that have been treated in accordance with the present invention.
  • Table V sets forth the mean pore size and frequency of pores of the various Samples set forth in Table IV after spray casting, but before any subsequent treatment.
  • the as-cast porosity size distribution was measured using a magnification of 1620X on the video monitor.
  • Pore or Defect Mean Size Frequency Mircons Sample Number/mm 2 (X Proj/Y Proi . )
  • Samples of the various alloys set forth in Table IV were further processed according to the various conditions set forth in Table VI. As indicated, some of the samples were annealed at 500°C for four hours after being spray cast, while this annealing step was omitted for other samples. All samples were cold rolled to either an 85% or an 82% reduction in the manner indicated in Table VI. Thereafter, some of the samples were further treated by an anneal at 700°C for four hours while this step was omitted for other samples as indicated.
  • Table VII sets forth the pore or defect size and frequencies for the samples tested under the conditions set forth in Table VI. For these measurements a magnification of 672X was used. All samples except Sample 6 were etched with a solution of 44% water, 44% ammonium hydroxide and 12% hydrogen peroxide. Sample 6 was etched with an ASM #4 etchant. TABLE VI
  • Table VIII below sets forth the pore or defect frequency and mean defect size for spray cast samples of Alloy C51000 and C71300, with and without the nominal addition of 0.5% Al, which were subjected to various treatment conditions.
  • the defect frequency and size were measured in the as-cast condition after milling, after being cold rolled 82% (10% per pass), and after being cold rolled (82%, 10%/pass) and annealed at 700°C for four hours, as indicated in the Table.
  • Table VIII shows that in the case of Alloys C51000 and C71300, pore or defect frequency was greatly reduced by cold rolling and annealing, irrespective of whether a nominal Al addition had been made. Thus, the addition of Al does not universally inhibit the healing of the pores. Rather, for reasons not known at this time, it has a detrimental effect only in the case of certain alloys such as C19400.
  • Table IX below sets forth the mechanical properties of spray cast samples, as well as a control sample, of Alloy C71300.
  • the Samples 1 and 2 were spray cast under varying conditions followed by milling of the top and bottom surfaces. The Samples 1 and 2 were then cold rolled to an 87% reduction and annealed at 700°C for three hours.
  • the control sample was conventionally cast using the D.C. (direct chill) casting process and hot rolled after which the top and bottom surfaces were milled. After milling, the control samples were subjected to the same cold roll reduction and anneal as the spray cast samples.
  • yield strength refers to the strength measured at 0.2% offset.
  • ksi' ⁇ is an abbreviation for thousands of pounds per squaje inch.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

L'invention concerne une méthode de traitement d'une bande de métal coulée par pulvérisation, en particulier des alliages de cuivre, en vue de réduire la porosité. La bande déposée (A) est soumise à une réduction par laminage à froid d'au moins 25 % environ puis est recuite à une température comprise entre 450°C et 800°C environ pendant une durée de 1 à 8 heures environ.
PCT/US1990/001737 1989-04-03 1990-04-02 Methode de traitement de depots de metal coule par pulverisation Ceased WO1990011852A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
FI914146A FI914146A0 (fi) 1989-04-03 1990-04-02 Foerfarande foer behandling av metaller som avgjutit medelst sprutning.
KR1019900702453A KR920700078A (ko) 1989-04-03 1990-11-15 분무 주조 금속 침착물을 처리하는 방법

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US33218189A 1989-04-03 1989-04-03
US332,181 1989-04-03
US50158890A 1990-03-30 1990-03-30
USNOTFURNISHED 2002-06-26

Publications (1)

Publication Number Publication Date
WO1990011852A1 true WO1990011852A1 (fr) 1990-10-18

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PCT/US1990/001737 Ceased WO1990011852A1 (fr) 1989-04-03 1990-04-02 Methode de traitement de depots de metal coule par pulverisation

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EP (1) EP0466819A4 (fr)
KR (1) KR920700078A (fr)
AU (1) AU5443290A (fr)
FI (1) FI914146A0 (fr)
WO (1) WO1990011852A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992012272A1 (fr) * 1991-01-02 1992-07-23 Osprey Metals Limited Formage par pulverisation d'un metal au moyen de tuyeres multiples
EP0552479A1 (fr) * 1992-01-17 1993-07-28 Wieland-Werke Ag Procédé pour améliorer la flexibilité de demi-produits en alliage de cuivre
CN1037245C (zh) * 1991-07-05 1998-02-04 张景禄 防沾钢沾渣高温涂料
EP1394277A1 (fr) * 2002-08-05 2004-03-03 Mitsubishi Materials Corporation Matériau fritté et procédé de production

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3663311A (en) * 1969-05-21 1972-05-16 Bell Telephone Labor Inc Processing of copper alloys
US3775156A (en) * 1970-06-20 1973-11-27 Vandervell Products Ltd Method of forming composite metal strip
USRE31767E (en) * 1971-10-26 1984-12-18 Osprey Metals Limited Method and apparatus for making shaped articles from sprayed molten metal or metal alloy
JPS61119660A (ja) * 1984-11-16 1986-06-06 Nippon Mining Co Ltd 高力高導電性銅基合金の製造方法
JPS62177160A (ja) * 1986-01-29 1987-08-04 Sumitomo Metal Mining Co Ltd 析出硬化型銅合金材の製法
JPS62214164A (ja) * 1986-03-15 1987-09-19 Mitsui Mining & Smelting Co Ltd 析出硬化型合金の製造方法
US4738712A (en) * 1985-04-19 1988-04-19 National Research Development Corporation Metal forming
US4804034A (en) * 1985-03-25 1989-02-14 Osprey Metals Limited Method of manufacture of a thixotropic deposit

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3663311A (en) * 1969-05-21 1972-05-16 Bell Telephone Labor Inc Processing of copper alloys
US3775156A (en) * 1970-06-20 1973-11-27 Vandervell Products Ltd Method of forming composite metal strip
USRE31767E (en) * 1971-10-26 1984-12-18 Osprey Metals Limited Method and apparatus for making shaped articles from sprayed molten metal or metal alloy
JPS61119660A (ja) * 1984-11-16 1986-06-06 Nippon Mining Co Ltd 高力高導電性銅基合金の製造方法
US4804034A (en) * 1985-03-25 1989-02-14 Osprey Metals Limited Method of manufacture of a thixotropic deposit
US4738712A (en) * 1985-04-19 1988-04-19 National Research Development Corporation Metal forming
JPS62177160A (ja) * 1986-01-29 1987-08-04 Sumitomo Metal Mining Co Ltd 析出硬化型銅合金材の製法
JPS62214164A (ja) * 1986-03-15 1987-09-19 Mitsui Mining & Smelting Co Ltd 析出硬化型合金の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Metals Handbook, 9th edition, Vol. 2, pp. 354-355, 1979. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992012272A1 (fr) * 1991-01-02 1992-07-23 Osprey Metals Limited Formage par pulverisation d'un metal au moyen de tuyeres multiples
US5343926A (en) * 1991-01-02 1994-09-06 Olin Corporation Metal spray forming using multiple nozzles
CN1037245C (zh) * 1991-07-05 1998-02-04 张景禄 防沾钢沾渣高温涂料
EP0552479A1 (fr) * 1992-01-17 1993-07-28 Wieland-Werke Ag Procédé pour améliorer la flexibilité de demi-produits en alliage de cuivre
EP1394277A1 (fr) * 2002-08-05 2004-03-03 Mitsubishi Materials Corporation Matériau fritté et procédé de production

Also Published As

Publication number Publication date
EP0466819A4 (en) 1993-06-23
AU5443290A (en) 1990-11-05
EP0466819A1 (fr) 1992-01-22
FI914146A7 (fi) 1991-09-03
FI914146A0 (fi) 1991-09-03
KR920700078A (ko) 1992-02-19

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