US20140271317A1 - BIOCOMPATIBLE Co-Cr-Mo ALLOY - Google Patents

BIOCOMPATIBLE Co-Cr-Mo ALLOY Download PDF

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Publication number
US20140271317A1
US20140271317A1 US14/352,216 US201214352216A US2014271317A1 US 20140271317 A1 US20140271317 A1 US 20140271317A1 US 201214352216 A US201214352216 A US 201214352216A US 2014271317 A1 US2014271317 A1 US 2014271317A1
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Prior art keywords
alloy
biocompatible
less
present
layered
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Abandoned
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US14/352,216
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English (en)
Inventor
Naoyuki Nomura
Takao Hanawa
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.)
Tokyo Medical and Dental University NUC
Kyocera Medical Corp
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Tokyo Medical and Dental University NUC
Kyocera Medical Corp
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Assigned to KYOCERA MEDICAL CORPORATION, NATIONAL UNIVERSITY CORPORATION TOKYO MEDICAL AND DENTAL UNIVERSITY reassignment KYOCERA MEDICAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HANAWA, TAKAO, NOMURA, NAOYUKI
Publication of US20140271317A1 publication Critical patent/US20140271317A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/045—Cobalt or cobalt alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • B22F10/366—Scanning parameters, e.g. hatch distance or scanning strategy
    • B22F3/1055—
    • 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
    • C22C1/0433—Nickel- or cobalt-based alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present invention relates to a biocompatible Co alloy, and particularly to a Co—Cr—Mo alloy excellent in mechanical properties, particularly, proof stress, tensile strength, and the like.
  • Co—Cr—Mo alloys have been used widely all over the world as a biocompatible material and, for example, a Co-28% Cr-6% Mo alloy (casting material) standardized as ASTM F75 has been known.
  • the cast material standardized as ASTM F75 is difficult to sufficiently suppress solidification defects and segregation as it is and there is room for improvement of strength and ductility.
  • Patent Document 1 proposes a casting material of a Co—Cr—Mo alloy with increased contents of Cr and nitrogen as compared with the above-mentioned standardized material.
  • Patent Document 1 JP-A-2009-114477
  • Patent Document 1 it is described that a cast Co alloy containing, in mass %, more than 30% and not more than 36% of Cr, 5 to 8% of Mo, and 0.20 to 0.65% of N has improved yield strength, tensile strength, and elongation as compared with the material standardized as ASTM F75.
  • Patent Document 1 an ingot of a Co—Cr—Mo type alloy is produced by metal mold casting and mechanical properties thereof are measured.
  • the mechanical properties as disclosed in Cited Document 1 cannot necessarily be realized.
  • it is generally effective to carry out hot processing such as hot rolling or hot forging.
  • the Co—Cr—Mo alloy with the composition described in Patent Document 1 is poor in the hot processability and difficult to have high strength by hot processing and thus it is difficult to obtain a Co—Cr—Mo alloy excellent in yield strength, tensile strength and the like.
  • the present invention aims to provide a Co—Cr—Mo alloy excellent in mechanical properties such as yield strength (0.2% proof stress) and tensile strength.
  • the present invention which has achieved the above-mentioned problem is a biocompatible Co—Cr—Mo alloy comprising, in mass %,
  • the biocompatible Co—Cr—Mo alloy of the present invention preferably has a solidification structure of a dendrite structure and the primary arm spacing of the dendrite structure is not more than 5 ⁇ m.
  • the biocompatible Co—Cr—Mo alloy of the present invention has the 0.2% proof stress of not less than 700 MPa and the tensile strength of not less than 980 MPa, for example.
  • the present invention also comprises a powder to be used for producing the biocompatible Co—Cr—Mo alloy.
  • the powder has a gist for having a particle diameter of not more than 100 ⁇ m.
  • the present invention also comprises a process for producing a Co—Cr—Mo alloy wherein the Co—Cr—Mo alloy having the above-described chemical composition is layered-manufactured.
  • layered manufacturing is preferably carried out by irradiating laser of an output power of not less than 50 W and adjusting the scan pitch in the plane direction to be not less than 0.1 mm.
  • the scan pitch in the plane direction means a irradiation spacing of laser.
  • a Co—Cr—Mo alloy excellent in 0.2% proof stress, tensile strength, and elongation is provided since a Co—Cr—Mo alloy with high Cr and high N is produced by layered manufacturing.
  • FIG. 1 is a graph illustrating a relationship between the scan pitch in the plane direction and 0.2% proof stress.
  • FIG. 2 is a graph illustrating a relationship between the output power of laser, and tensile strength and elongation.
  • FIG. 3 is an optical microscope photograph obtained by observing the structure of a Co alloy produced in the Examples described later.
  • the inventors of the present invention repeatedly made investigations to provide a Co—Cr—Mo alloy excellent in mechanical properties such as yield strength and tensile strength and found that a Co—Cr—Mo alloy excellent in 0.2% proof stress, tensile strength and elongation is obtained by powdering a Co—Cr—Mo alloy with a composition described in Patent Document 1 and carrying out layered manufacturing of the powder, and the finding now lead to completion of the present invention.
  • the alloy composition of the present invention and layered manufacturing will be described in order.
  • a Co—Cr—Mo alloy of the present invention contains, in mass %, more than 30% and not more than 36% of Cr, 5 to 8% of Mo, and 0.20 to 0.65% of N.
  • Cr is an element indispensable for surely attaining corrosion resistance.
  • the mechanical properties are further improved and the amount of dissolved N is increased by adjusting the Cr amount to be more than 30% (it means mass %, hereinafter the same in the chemical composition).
  • the Cr amount is preferably not less than 31% and more preferably not less than 32%.
  • the Cr amount is determined to be not more than 36% in the present invention.
  • the Cr amount is preferably not more than 35% and more preferably not more than 34%.
  • Mo is an element effective for improvement of corrosion resistance and wear resistance. Therefore, the Mo amount is determined to be not less than 5%. The Mo amount is preferably not less than 6%. On the other hand, if the Mo amount is excessive, it results in deterioration of processability. Therefore, the Mo amount is determined to be not more than 8%. The Mo amount is preferably not more than 7%.
  • N is an element for forming a stable ⁇ phase and having an action of improving ductility. N is an element also having an action of improving the 0.2% proof stress. Therefore, the N amount is determined to be not less than 0.20% in the present invention. The N amount is preferably not less than 0.25% and more preferably not less than 0.30%. On the other hand, if the N amount is excessive, Cr 2 N is precipitated and mechanical properties are deteriorated. Therefore, the N amount is determined to be not more than 0.65%. The N amount is preferably not more than 0.60% and more preferably not more than 0.55%.
  • the composition of the Co alloy of the present invention is as described above and the balance is made up by substantially Co.
  • Co is an element having corrosion resistance and wear resistance.
  • the Co alloy of the present invention may contain at least one element selected from the group consisting of not more than 0.2% of C, not more than 1.00% of Ni, not more than 1.00% of Si, and not more than 1.00% of Mn.
  • the Co alloy of the present invention is characterized by being produced by layered manufacturing.
  • the Co alloy produced by layered manufacturing has a fine solidification structure and in general, the solidification structure is a dendrite structure, and the primary arm spacing of the dendrite structure is, for example, not more than 5 ⁇ m and preferably not more than 1.5 ⁇ m.
  • the lower limit of the arm spacing is generally around 0.5 ⁇ m.
  • the layered manufacturing is described in, for example, Japanese Patent No. 4054075, and is a method for producing a compact by spreading a material powder in a layer form, melting and thereafter solidifying the material powder by irradiating the powder with electromagnetic radiation such as laser beam or corpuscular radiation such as electron beam.
  • electromagnetic radiation such as laser beam or corpuscular radiation such as electron beam.
  • the Co alloy with the above-mentioned composition is obtained by layered manufacturing, it is made possible to provide the Co alloy excellent in elongation in addition to 0.2% proof stress, tensile strength. Further, by layered manufacturing, the irradiation pattern of the radial rays is precisely controlled and therefore, shaping into a complicated shape is made possible.
  • the scan pitch in the plane direction is preferably adjusted to be not less than 0.1 mm, more preferably not less than 0.2 mm, and even more preferably not less than 0.3 mm.
  • the upper limit of the scan pitch in the plane direction is, for example, not more than 0.5 mm for preventing pore formation.
  • the output power of the radial rays is preferably not less than 50 W, more preferably not less than 100 W, and even more preferably not less than 150 W. Although it depends on the apparatus for outputting the radial rays, the upper limit of the output power of the radial rays is, for example, not more than 400 W.
  • the radiation diameter (e.g., radius of circle) of radial rays may be adjusted to be about 0.1 to 1 mm; the distance from the radial ray source to the material powder may be adjusted to be about 100 to 10000 mm; and the layer thickness (thickness of one layer of the powder) may be adjusted to be about 0.01 to 0.1 mm.
  • the atmosphere at the time of the layered manufacturing is also not particularly limited, and it is preferable to carry out the layered manufacturing in an atmosphere of an inert gas such as argon gas or nitrogen gas.
  • the material powder used for the layered manufacturing can be prepared by an atomization method (water atomization method or gas atomization method), a rotating electrode process, a ball mill method, and the like. It is preferable that the powder prepared by the above-mentioned method is sieved if necessary to have a particle diameter of not more than 100 ⁇ m (preferably not more than 70 ⁇ m, and more preferably not more than 50 ⁇ m). In addition, the particle diameter of the material powder is generally not below 5 ⁇ m. In this description, the particle diameter means the maximum diameter.
  • the type of radial rays in the layered manufacturing is not particularly limited, but laser of electromagnetic radiation is employed in the present invention.
  • laser of electromagnetic radiation examples include YAG laser, excimer laser, semiconductor laser, and CO 2 laser.
  • the Co alloy of the present invention produced by layered-manufacturing the Co alloy with the above-mentioned composition is excellent in mechanical properties such as 0.2% proof stress, tensile strength, and elongation.
  • the 0.2% proof stress is, for example, not less than 700 MPa (preferably not less than 730 MPa and more preferably not less than 7 60 MPa) and the tensile strength is, for example, not less than 980 MPa (preferably not less than 1000 MPa and more preferably not less than 1020 MPa).
  • the elongation (total elongation) is, for example, not less than 8.0% (preferably not less than 10.0% and more preferably not less than 15.0%).
  • the structure of the Co alloy of the present invention is generally a dendrite structure. Because of the effect of the anisotropy of the structure, the mechanical properties of the Co alloy are different depending on the directions (directions to the layer direction). Concretely, the 0.2% proof stress and tensile strength show higher values in the direction perpendicular to the layered direction and the elongation shows a higher value in the direction parallel to the layered direction. Consequently, it is preferable to produce a biocompatible material while properly adjusting the direction to which a load is mainly applied at the time of use of the material and the layered direction, in accordance with the use application of the biocompatible material.
  • the Co alloy of the present invention in the case of a use application in which the 0.2% proof stress and tensile strength are mainly required, it is proper to produce the Co alloy of the present invention by layered manufacturing in a manner that the load direction at the time of use of the biocompatible material and the layered direction are perpendicular to each other. Also, in the case of a use application in which elongation is mainly required, it is proper to produce the Co alloy of the present invention by layered manufacturing in a manner that the load direction at the time of use of the biocompatible material and the layered direction are parallel to each other.
  • a molten Co alloy with the chemical composition described in Table 1 was prepared and a Co alloy powder was produced by a water atomization method. Thereafter, the powder was sieved to produce a Co alloy powder with a particle diameter of not more than 45 ⁇ m.
  • Each Co alloy in form of a dumbbell type tensile test specimen according to JIS T6115, the dentistry casting cobalt-chromium alloy, was produced from the above-mentioned powder by a layered manufacturing apparatus (EOSINT M250 xtended) with the laser output power and scan pitch (in plane direction) as described in Table 1 (test Nos. 1 to 7, 9 and 11 to 15).
  • Test Nos. 1 to 5, 9, and 11 to 14 were layered-manufactured in a manner that the tensile test direction and the layered direction were to be parallel to each other and test Nos. 6, 7, and 15 were layered-manufactured in a manner that the tensile test direction and the layered direction were to be perpendicular to each other.
  • the layered manufacturing was carried out in an argon atmosphere, the irradiation diameter of laser was 0.4mm (400 microns), and the layered thickness was 0.05 mm.
  • Table 1 also shows the results of a specimen (test No. 8) produced from Co-33 mass% Cr-5 mass % Mo-0.34 mass % N satisfying the composition of the present invention by a centrifugal casting method using a room temperature sand mold and a specimen (test No. 10) produced from Co-29 mass% Cr-6 mass % Mo, a material standardized as ASTM F75, by a centrifugal casting method using a room temperature sand mold.
  • “As-Cast” is written in the column of laser output power.
  • FIG. 1 is a graph illustrating a relationship between the scan pitch in the plane direction and 0.2% proof stress
  • FIG. 2 is a graph illustrating a relationship between the output power of the radial rays (output power of laser in the examples) and tensile strength and elongation.
  • FIG. 3 shows a photograph of a structure of the specimen of test No. 3 observed by an optical microscope.
  • FIG. 3( a ) is a photograph of a structure of a cross section perpendicular to the layered direction
  • FIG. 3( b ) is a photograph of a structure of a cross section parallel to the layered direction. According to FIG. 3 , it can be understood that a fine dendrite structure is formed.
  • the Co—Cr—Mo alloy of the present invention can be used suitably as an biocompatible material, for example, for dentistry, orthopedics, and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Manufacturing & Machinery (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Medicinal Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Physics & Mathematics (AREA)
  • Surgery (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Plasma & Fusion (AREA)
  • Vascular Medicine (AREA)
  • Powder Metallurgy (AREA)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)
US14/352,216 2011-10-21 2012-10-18 BIOCOMPATIBLE Co-Cr-Mo ALLOY Abandoned US20140271317A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2011-231703 2011-10-21
JP2011231703 2011-10-21
PCT/JP2012/076999 WO2013058339A1 (ja) 2011-10-21 2012-10-18 生体用Ｃｏ－Ｃｒ－Ｍｏ合金

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US (1) US20140271317A1 (de)
EP (1) EP2770070A4 (de)
JP (1) JP6143227B2 (de)
CN (1) CN103890207A (de)
WO (1) WO2013058339A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111992721A (zh) * 2020-08-03 2020-11-27 Oppo广东移动通信有限公司 壳体、电子设备及其壳体的制作方法
US11946554B2 (en) 2019-01-08 2024-04-02 Hitachi-Ge Nuclear Energy, Ltd. Fluid contact member and method of manufacturing fluid contact member

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6198062B2 (ja) * 2014-02-18 2017-09-20 国立大学法人東北大学 Ｃｏ基合金粉末
JP6306393B2 (ja) * 2014-03-28 2018-04-04 国立大学法人東北大学 機械部品
US10583532B2 (en) * 2015-12-28 2020-03-10 General Electric Company Metal additive manufacturing using gas mixture including oxygen
CN107177769B (zh) * 2016-03-09 2019-02-12 中国科学院金属研究所 一种抗感染不锈钢植入物制备方法
JP2018040028A (ja) * 2016-09-06 2018-03-15 国立大学法人 東京医科歯科大学 金属積層造形用ジルコニウム合金粉末、及びそれを使用したインプラントの製造方法

Citations (6)

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Publication number Priority date Publication date Assignee Title
US3865585A (en) * 1972-05-26 1975-02-11 Witten Edelstahl Cobalt chromium based alloy
US4668290A (en) * 1985-08-13 1987-05-26 Pfizer Hospital Products Group Inc. Dispersion strengthened cobalt-chromium-molybdenum alloy produced by gas atomization
US5462575A (en) * 1993-12-23 1995-10-31 Crs Holding, Inc. Co-Cr-Mo powder metallurgy articles and process for their manufacture
US20080195214A1 (en) * 2005-03-28 2008-08-14 Akihiko Chiba Co-Cr-Mo Alloy for Artificial Joint Having Excellent Wear Resistance
US20080251163A1 (en) * 2004-11-19 2008-10-16 Iwate University Bio-Co-Cr-Mo Alloy With Ion Elution Suppressed by Structure Control, And Process For Producing Same
US20110036468A1 (en) * 2009-07-31 2011-02-17 Avio S.P.A Process for manufacturing components obtained by sintering of Co-Cr-Mo alloys having improved ductility at high temperatures

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DE19511772C2 (de) 1995-03-30 1997-09-04 Eos Electro Optical Syst Vorrichtung und Verfahren zum Herstellen eines dreidimensionalen Objektes
JP5164144B2 (ja) * 2007-11-02 2013-03-13 国立大学法人岩手大学 生体用Ｃｏ−Ｃｒ−Ｍｏ鋳造合金
WO2010026996A1 (ja) * 2008-09-05 2010-03-11 国立大学法人東北大学 窒素添加Ｃｏ－Ｃｒ－Ｍｏ合金の結晶粒微細化方法および窒素添加Ｃｏ－Ｃｒ－Ｍｏ合金

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865585A (en) * 1972-05-26 1975-02-11 Witten Edelstahl Cobalt chromium based alloy
US4668290A (en) * 1985-08-13 1987-05-26 Pfizer Hospital Products Group Inc. Dispersion strengthened cobalt-chromium-molybdenum alloy produced by gas atomization
US5462575A (en) * 1993-12-23 1995-10-31 Crs Holding, Inc. Co-Cr-Mo powder metallurgy articles and process for their manufacture
US20080251163A1 (en) * 2004-11-19 2008-10-16 Iwate University Bio-Co-Cr-Mo Alloy With Ion Elution Suppressed by Structure Control, And Process For Producing Same
US20080195214A1 (en) * 2005-03-28 2008-08-14 Akihiko Chiba Co-Cr-Mo Alloy for Artificial Joint Having Excellent Wear Resistance
US20110036468A1 (en) * 2009-07-31 2011-02-17 Avio S.P.A Process for manufacturing components obtained by sintering of Co-Cr-Mo alloys having improved ductility at high temperatures

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
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English translation of the Written Opinion of the International Search Authority mailed November 20, 2012 for PCT/JP2012/076999; 5 pages. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11946554B2 (en) 2019-01-08 2024-04-02 Hitachi-Ge Nuclear Energy, Ltd. Fluid contact member and method of manufacturing fluid contact member
CN111992721A (zh) * 2020-08-03 2020-11-27 Oppo广东移动通信有限公司 壳体、电子设备及其壳体的制作方法

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WO2013058339A1 (ja) 2013-04-25
EP2770070A1 (de) 2014-08-27
JP6143227B2 (ja) 2017-06-07
JPWO2013058339A1 (ja) 2015-04-02
CN103890207A (zh) 2014-06-25
EP2770070A4 (de) 2015-08-12

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