WO2013058339A1 - 生体用Co-Cr-Mo合金 - Google Patents
生体用Co-Cr-Mo合金 Download PDFInfo
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- WO2013058339A1 WO2013058339A1 PCT/JP2012/076999 JP2012076999W WO2013058339A1 WO 2013058339 A1 WO2013058339 A1 WO 2013058339A1 JP 2012076999 W JP2012076999 W JP 2012076999W WO 2013058339 A1 WO2013058339 A1 WO 2013058339A1
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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
-
- 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 biological Co alloy, and more particularly, to a Co—Cr—Mo alloy having excellent mechanical properties such as proof stress and tensile strength.
- Co-Cr-Mo alloys are widely used around the world as biomaterials.
- ASTM F75 standard Co-28% Cr-6% Mo alloy (casting material) is known.
- ASTM F75 standard material is difficult to sufficiently suppress solidification defects and segregation as it is cast, and there is room for improvement in strength and ductility.
- Patent Document 1 proposes a casting material of Co—Cr—Mo alloy in which the contents of Cr and nitrogen are higher than those of the standard material.
- a Co casting alloy containing Cr: more than 30%, 36% or less, Mo: 5 to 8%, and N: 0.20 to 0.65% by mass% is a conventional ASTM. It describes that the yield strength, tensile strength, and elongation were improved as compared with F75 standard materials.
- Patent Document 1 a Co—Cr—Mo alloy ingot is produced by die casting, and its mechanical properties are measured.
- the mechanical material disclosed in Reference Document 1 is not necessarily used. It was thought that the characteristics could not be realized.
- it is generally effective to perform hot working such as hot rolling or hot forging.
- the Co—Cr—Mo alloy having the composition described in Patent Document 1 is effective. Has poor hot workability, it is difficult to increase the strength by hot working, and it was difficult to obtain a Co—Cr—Mo alloy having excellent yield strength and tensile strength.
- an object of the present invention is to provide a Co—Cr—Mo alloy having excellent mechanical properties such as yield strength (0.2% yield strength) and tensile strength.
- the present invention that has achieved the above-mentioned problems contains, in mass%, Cr: more than 30%, 36% or less, Mo: 5-8%, and N: 0.20-0.65%, with the balance being Co and inevitable It is a biological Co—Cr—Mo alloy characterized by being a typical impurity and manufactured by additive manufacturing.
- the solidified structure is preferably a dendrite structure, and the branch interval of the primary arms of the dendrite structure is preferably 5 ⁇ m or less.
- the biomedical Co—Cr—Mo alloy of the present invention has, for example, a 0.2% proof stress of 700 MPa or more and a tensile strength of 980 MPa or more.
- the present invention includes a powder used for producing the above-described biomedical Co—Cr—Mo alloy, and this powder has a gist in that the particle size is 100 ⁇ m or less.
- the present invention also includes a method for producing a biomedical Co—Cr—Mo alloy characterized by laminating a Co—Cr—Mo alloy powder having the chemical composition described above.
- the laser beam having an output of 50 W or more is irradiated and the layered modeling is performed with the scan pitch in the surface direction being 0.1 mm or more.
- the scan pitch in the surface direction means the laser irradiation interval.
- FIG. 1 is a graph showing the relationship between the scan pitch in the surface direction and the 0.2% proof stress.
- FIG. 2 is a graph showing the relationship between laser output, tensile strength and elongation.
- FIG. 3 is an optical micrograph observing the structure of the Co alloy produced in the examples described later.
- the Co—Cr—Mo alloy of the present invention contains Cr: more than 30%, 36% or less, Mo: 5 to 8%, and N: 0.20 to 0.65% by mass.
- the Cr content is more than 30% (meaning mass%, hereinafter the same for the chemical composition), thereby further improving mechanical properties and N.
- the amount of solid solution can be increased.
- the amount of Cr is preferably 31% or more, and more preferably 32% or more.
- the Cr content is set to 36% or less.
- the amount of Cr is preferably 35% or less, and more preferably 34% or less.
- Mo is an element effective for improving corrosion resistance and wear resistance. Therefore, the Mo amount is set to 5% or more. The amount of Mo is preferably 6% or more. On the other hand, when the amount of Mo becomes excessive, workability is deteriorated. Therefore, the Mo amount is determined to be 8% or less. The amount of Mo is preferably 7% or less.
- N is an element that has a function of forming a stable ⁇ phase and improving ductility. N is an element that also has the effect of improving the 0.2% yield strength. Therefore, in the present invention, the N amount is set to 0.20% or more. The N amount is preferably 0.25% or more, and more preferably 0.30% or more. On the other hand, when the amount of N becomes excessive, Cr 2 N precipitates and the mechanical properties deteriorate. Therefore, the N amount is set to 0.65% or less. The N amount is preferably 0.60% or less, and more preferably 0.55% or less.
- the composition of the Co alloy of the present invention is as described above, and the balance is substantially Co.
- Co is an element having corrosion resistance and wear resistance.
- the Co alloy of the present invention includes inevitable impurities brought in depending on the situation of raw materials, materials, manufacturing facilities, and the like.
- the Co alloy of the present invention is manufactured by additive manufacturing.
- the Co alloy produced by additive manufacturing exhibits a finely solidified structure, and usually the solidified structure is a dendrite structure, and the branch interval of the primary arm of the dendrite structure is, for example, 5 ⁇ m or less, preferably 1.5 ⁇ m. It is as follows.
- the lower limit of the branch interval is usually about 0.5 ⁇ m.
- Laminated modeling is described in, for example, Japanese Patent No. 4054075, and is solidified after melting the material powder by laying the material powder in layers and irradiating electromagnetic radiation such as a laser beam or particle radiation such as an electron beam. And producing a molded body.
- electromagnetic radiation such as a laser beam or particle radiation such as an electron beam.
- the Co alloy having the above composition is layered, a Co alloy having 0.2% proof stress and tensile strength and excellent elongation can be provided. Further, according to the layered modeling, since the radiation irradiation pattern can be precisely controlled, a complicated shape can be formed.
- the mechanical properties (0.2% proof stress, tensile strength and elongation) of the Co alloy are correlated with the conditions of the layered manufacturing, and the scan pitch in the surface direction is increased.
- the 0.2% proof stress can be further improved, and in particular, the tensile strength and elongation can be further improved by increasing the radiation output.
- the scan pitch in the surface direction is preferably 0.1 mm or more, more preferably 0.2 mm or more, and further preferably 0.3 mm or more.
- the upper limit of the scan pitch in the surface direction is, for example, 0.5 mm or less in order not to form pores.
- the radiation output is preferably 50 W or more, more preferably 100 W or more, and still more preferably 150 W or more.
- the upper limit of the radiation output depends on the device that outputs the radiation, but is, for example, 400 W or less.
- the radiation diameter (for example, the radius of the circle) is about 0.1 to 1 mm
- the distance between the radiation source and the material powder is about 100 to 10,000 mm
- the thickness of the stack The thickness (the thickness of one layer of the powder) may be about 0.01 to 0.1 mm.
- the atmosphere at the time of layered modeling is not particularly limited, but it is preferably performed in an inert gas atmosphere such as argon gas or nitrogen gas.
- the material powder used for additive manufacturing can be prepared by an atomizing method (water atomizing method or gas atomizing method), a rotating electrode method, a ball mill method, or the like.
- the powder prepared by the above method is preferably subjected to sieving or the like as necessary to obtain a particle size of 100 ⁇ m or less (preferably 70 ⁇ m or less, more preferably 50 ⁇ m or less).
- the particle size of the material powder is usually not less than 5 ⁇ m. In this specification, the particle size means the maximum diameter.
- the type of radiation in additive manufacturing is not particularly limited, but in the present invention, a laser in electromagnetic radiation is used.
- the laser include YAG laser, excimer laser, semiconductor laser, and CO 2 laser.
- the Co alloy of the present invention produced by the layered modeling of the Co alloy having the above composition is excellent in mechanical properties such as 0.2% proof stress, tensile strength and elongation.
- the 0.2% proof stress is, for example, 700 MPa or more (preferably 730 MPa or more, more preferably 760 MPa or more), and the tensile strength is, for example, 980 MPa or more (preferably 1000 MPa or more, more preferably 1020 MPa or more).
- the elongation (total elongation) is, for example, 8.0% or more (preferably 10.0% or more, more preferably 15.0% or more).
- the structure of the Co alloy of the present invention is usually a dendrite structure, and the mechanical properties differ depending on the direction of the Co alloy (direction with respect to the stacking direction) due to the influence of the structure having anisotropy.
- the 0.2% proof stress and the tensile strength are higher in the direction perpendicular to the stacking direction, and the elongation is higher in the direction parallel to the stacking direction. Therefore, it is preferable to manufacture by appropriately adjusting the direction in which the load is mainly applied and the stacking direction according to the use of the biomaterial.
- the Co alloy of the present invention is formed by layering so that the loading direction and the stacking direction when using a biomaterial are perpendicular. What is necessary is just to manufacture, and in the use for which expansion
- a Co alloy melt having the chemical composition shown in Table 1 was prepared, a Co alloy powder was produced by a water atomization method, and then sieved to produce a Co alloy powder having a particle size of 45 ⁇ m or less.
- the powder was formed into a dumbbell-shaped tensile test piece shape in accordance with JIS T6115, a cobalt chromium alloy for dental casting, using a laser additive manufacturing apparatus (EOSINT M250 xtended) with the laser output and scan pitch (surface direction) shown in Table 1.
- Co alloys were prepared (Test Nos. 1-7, 9, and 11-15).
- Test No. For Nos. 1 to 5, 9, and 11 to 14, layered modeling was performed so that the tensile test direction and the lamination direction were parallel, and test no. 6, 7, and 15 were layered so that the tensile test direction and the stacking direction were perpendicular to each other.
- the layered modeling was performed in an argon atmosphere, the laser irradiation diameter was 0.4 mm (400 micron), and the layer thickness was 0.05 mm.
- each test piece 0.2% yield strength, tensile strength, and elongation (total elongation) were measured according to JIS T6115. Each test No. The number of tests was 3 in all cases.
- test No. 8 For comparison, a sample (test No. 8) produced by centrifugal casting using a room temperature sand mold with Co-33% by mass Cr-5% by mass Mo-0.34% by mass N satisfying the composition of the present invention.
- Table 1 also shows the results of a sample (test No. 10) produced by centrifugal casting using a room temperature sand mold with Co-29 mass% Cr-6 mass% Mo which is an ASTM F75 standard material.
- As-Cast is shown in the laser output column to indicate that the product was manufactured by centrifugal casting.
- test No. which is the Co alloy of the present invention. 1 to 7 and 11 to 15 were all excellent in mechanical properties of 0.2% proof stress, tensile strength and elongation.
- FIG. 1 is a graph showing the relationship between the scan pitch in the surface direction and the 0.2% proof stress
- FIG. 2 shows the relationship between the radiation output (laser output in this embodiment), tensile strength and elongation. It is a graph. 1 and 2, it can be seen that 0.2% proof stress is improved as the scan pitch is increased, and tensile strength and elongation are improved as the laser output is increased.
- test no. Comparing 3 and 6 it can be seen that the elongation is excellent when the tensile direction is parallel to the laminating direction, and 0.2% proof stress and tensile when the tensile direction is perpendicular to the laminating direction. It turns out that it is excellent in strength.
- Test No. 4 and 7, or test no. It can be read by comparing 13 and 15.
- test no. 3 A structural photograph of No. 3 observed with an optical microscope is shown in FIG. 3A is a structural photograph of a cross section perpendicular to the stacking direction, and FIG. 3B is a structural photograph of a cross section parallel to the stacking direction.
- FIG. 3 shows that a fine dendrite structure is formed.
- the Co—Cr—Mo alloy of the present invention can be suitably used as a biomaterial for, for example, dental use and orthopedic use.
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- Oral & Maxillofacial Surgery (AREA)
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- Transplantation (AREA)
- Automation & Control Theory (AREA)
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Abstract
Description
Claims (6)
- 質量%で、
Cr:30%超、36%以下、
Mo:5~8%、及び
N :0.20~0.65%を含有し、残部はCo及び不可避的不純物であり、
積層造形によって製造されたことを特徴とする生体用Co-Cr-Mo合金。 - 凝固組織がデンドライト組織であり、
該デンドライト組織の一次アームの枝間隔が5μm以下である請求項1に記載の生体用Co-Cr-Mo合金。 - 0.2%耐力が700MPa以上、引張強さが980MPa以上である請求項1又は2に記載の生体用Co-Cr-Mo合金。
- 請求項1~3の何れかに記載の生体用Co-Cr-Mo合金を製造するために用いる粉末であって、
粒径が100μm以下であることを特徴とする生体用Co-Cr-Mo合金粉末。 - 請求項4に記載のCo-Cr-Mo合金粉末を積層造形することを特徴とする生体用Co-Cr-Mo合金の製造方法。
- 出力50W以上のレーザーを照射するとともに、面方向のスキャンピッチを0.1mm以上として積層造形する請求項5に記載の生体用Co-Cr-Mo合金の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12842425.6A EP2770070A4 (en) | 2011-10-21 | 2012-10-18 | CO-CR-MO ALLOY FOR IMPLANTS |
JP2013539690A JP6143227B2 (ja) | 2011-10-21 | 2012-10-18 | 生体用Co−Cr−Mo合金 |
CN201280051075.1A CN103890207A (zh) | 2011-10-21 | 2012-10-18 | 生物体用Co-Cr-Mo合金 |
US14/352,216 US20140271317A1 (en) | 2011-10-21 | 2012-10-18 | BIOCOMPATIBLE Co-Cr-Mo ALLOY |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-231703 | 2011-10-21 | ||
JP2011231703 | 2011-10-21 |
Publications (1)
Publication Number | Publication Date |
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WO2013058339A1 true WO2013058339A1 (ja) | 2013-04-25 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2012/076999 WO2013058339A1 (ja) | 2011-10-21 | 2012-10-18 | 生体用Co-Cr-Mo合金 |
Country Status (5)
Country | Link |
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US (1) | US20140271317A1 (ja) |
EP (1) | EP2770070A4 (ja) |
JP (1) | JP6143227B2 (ja) |
CN (1) | CN103890207A (ja) |
WO (1) | WO2013058339A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015151610A (ja) * | 2014-02-18 | 2015-08-24 | 国立大学法人東北大学 | Co−Cr−Mo基合金粉末組成物 |
JP2015190004A (ja) * | 2014-03-28 | 2015-11-02 | 国立大学法人東北大学 | 機械部品 |
JP2017137568A (ja) * | 2015-12-28 | 2017-08-10 | ゼネラル・エレクトリック・カンパニイ | 酸素を含有するガス混合気を用いた金属付加製造 |
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 |
WO2020144924A1 (ja) * | 2019-01-08 | 2020-07-16 | 日立Geニュークリア・エナジー株式会社 | 流体接触部材及び流体接触部材の製造方法 |
Families Citing this family (2)
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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 |
CN111992721B (zh) * | 2020-08-03 | 2022-11-29 | 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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2012
- 2012-10-18 WO PCT/JP2012/076999 patent/WO2013058339A1/ja active Application Filing
- 2012-10-18 CN CN201280051075.1A patent/CN103890207A/zh active Pending
- 2012-10-18 US US14/352,216 patent/US20140271317A1/en not_active Abandoned
- 2012-10-18 JP JP2013539690A patent/JP6143227B2/ja active Active
- 2012-10-18 EP EP12842425.6A patent/EP2770070A4/en not_active Withdrawn
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ATSUSHI TAKAICHI ET AL.: "Anisotropic Mechanical Properties of Co- 29Cr-6Mo Alloy Fabricated by Selective Laser Melting Process", THE JOURNAL OF THE JAPANESE SOCIETY FOR DENTAL MATERIALS AND DEVICES, vol. 30, no. 5, 25 September 2011 (2011-09-25), pages 293, XP008173550 * |
ATSUSHI TAKAICHI ET AL.: "Application to dentistry of selective laser melting : Microstructures and mechanical properties of Co-Cr-Mo alloys fabricated by selective laser meltin", THE JOURNAL OF THE JAPANESE SOCIETY FOR DENTAL MATERIALS AND DEVICES, vol. 29, no. 5, 20 September 2010 (2010-09-20), pages 445, XP008173845 * |
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See also references of EP2770070A4 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015151610A (ja) * | 2014-02-18 | 2015-08-24 | 国立大学法人東北大学 | Co−Cr−Mo基合金粉末組成物 |
JP2015190004A (ja) * | 2014-03-28 | 2015-11-02 | 国立大学法人東北大学 | 機械部品 |
JP2017137568A (ja) * | 2015-12-28 | 2017-08-10 | ゼネラル・エレクトリック・カンパニイ | 酸素を含有するガス混合気を用いた金属付加製造 |
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 |
WO2020144924A1 (ja) * | 2019-01-08 | 2020-07-16 | 日立Geニュークリア・エナジー株式会社 | 流体接触部材及び流体接触部材の製造方法 |
JP2020111768A (ja) * | 2019-01-08 | 2020-07-27 | 日立Geニュークリア・エナジー株式会社 | 流体接触部材及び流体接触部材の製造方法 |
JP7160694B2 (ja) | 2019-01-08 | 2022-10-25 | 日立Geニュークリア・エナジー株式会社 | 流体接触部材及び流体接触部材の製造方法 |
US11946554B2 (en) | 2019-01-08 | 2024-04-02 | Hitachi-Ge Nuclear Energy, Ltd. | Fluid contact member and method of manufacturing fluid contact member |
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EP2770070A1 (en) | 2014-08-27 |
US20140271317A1 (en) | 2014-09-18 |
CN103890207A (zh) | 2014-06-25 |
EP2770070A4 (en) | 2015-08-12 |
JPWO2013058339A1 (ja) | 2015-04-02 |
JP6143227B2 (ja) | 2017-06-07 |
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