US3865585A - Cobalt chromium based alloy - Google Patents

Cobalt chromium based alloy Download PDF

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US3865585A
US3865585A US362867A US36286773A US3865585A US 3865585 A US3865585 A US 3865585A US 362867 A US362867 A US 362867A US 36286773 A US36286773 A US 36286773A US 3865585 A US3865585 A US 3865585A
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percent
alloy
content
carbon
cobalt
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US362867A
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Leo Rademacher
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Edelstahlwerk Witten AG
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Edelstahlwerk Witten AG
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/07Alloys based on nickel or cobalt based on cobalt
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/80Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/84Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys

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  • ABSTRACT A cobalt/chromium based alloy suitable for use in [30] Foreign Application Priority Data making dental prostheses and surgical implants, and May 26, 1972 Germany 2225577 for in making machine Parts which are subject to severe corrosive conditions and mechanical loads at 52] us.
  • c1 75/171, 3/1, 32/2, high temperatures, comprises by Weight 26 Percent to 32/10 A 31 percent chromium, from 4 percent to 6.5 percent 51 1m.
  • Cobalt/chromium alloys are used in machinery construction predominantly for making components which are subjected to severe corrosive conditions and me chanical loadings at high temperatures. They are however equally well known in surgery for the making of implants and in dentistry for making prosthetic struc tures.
  • alloys which, in addition to cobalt as the basic element, also contain by weight from 26 percent to 31 percent chromium, from 4 percent to 6.5 percent molybdenum, up to 1 percent each of silicon, manganese and iron, and from 0.3 percent to 0.5 percent carbon, are of particular importance.
  • alloys are also used which, principally owing to the cost of cobalt content, contain instead up to 20 percent nickel. These may also have the silicon and manganese contents raised up to 6 percent, and may also be provided with additions of copper, aluminium, titanium, niobium, vanadium, zirconium, tantalum, beryllium and boron, either individually or in combination.
  • a disadvantage of these cobalt/chromium alloys is their low capacity for deformation, that is low ductility. This is usually expressed by the elongation at rupture. The published values vary considerably but are predominantly in a range from 2 percent to 6 percent. The highest value published is 8 percent. Because of these low elongation values for the alloys, severe limits are set on the plastic deformations which can be applied to articles made from them, for example straightening operations on the holding braces of dental prosthetic structures, if the risk of breakage is to be avoided.
  • titanium-containing alloys with a cobalt base having improved capacity for deformation for the same or an increased strength have been developed. These alloys contain, by weight, in addition to cobalt, from percent to percent chromium, from 5 percent to percent nickel, up to 3 percent molybdenum, up to 1 percent carbon, silicon, manganese, aluminium and/or iron and from 4 percent to 10 percent titanium.
  • alloys having a cobalt/chromium base which, in addition to cobalt, contain, by
  • an alloy comprises, by weight, from 26 percent to 31 percent chromium, from 4 percent to 6.5 percent molybdenum, up to 2 percent, and preferably only up to 1.5 percent silicon, up to 6 percent and preferably only up to 3 percent manganese, up to 1 percent iron, up to 0.5 percent boron, up to 0.5 percent carbon and from 0.15 percent to 0.5 percent nitrogen the remainder cobalt except for impurities, and the sum of the carbon and nitrogen contents not exceeding 0.7 percent
  • the nitrogen content is preferably from 0.20 percent to 0.35 percent, or advantageously up to a maximum of only 0.30 percent.
  • both the silicon and the manganese contents should not exceed 1 percent each.
  • Example 4 to 6 and 9 the manganese content has been raised to approximately 3 percent, in order to increase the dissolving capacity of the alloys for nitrogen.
  • An addition of boron improves the capacity for casting (Examples 5 and 6).
  • the mechanical properties are not in any way thereby adversely affected.
  • An alloy consisting essentially of from 26 percent to 3l percent chromium, from 4 percent to 6.5 percent molybdenum, up'to 2 percent silicon, up to 6 percent manganese, up to 1 percent iron, up to 0.5 percent boron, up to 0.5 percent carbon, from 0. [5 percent to 0.5 percent nitrogen, with the ,balance being cobalt and impurities, the sum of said carbon content and said nitrogen content not exceeding 0.7 percent.
  • a dental prosthesis made from an alloy as claimed in claim 1.
  • a surgical implant made from an alloy as claimed in claim 1.

Abstract

A cobalt/chromium based alloy suitable for use in making dental prostheses and surgical implants, and also for use in making machine parts which are subject to severe corrosive conditions and mechanical loads at high temperatures, comprises by weight, 26 percent to 31 percent chromium, from 4 percent to 6.5 percent molybdenum, up to 2 percent silicon, up to 6 percent maganese, up to 1 percent iron, up to 0.5 percent boron, up to 0.5 percent carbon, from 0.15 percent to 0.5 percent nitrogen, and the remainder cobalt except for impurities, the sum of the carbon and nitrogen contents not exceeding 0.7 percent.

Description

United States Patent Rademacher Feb. 11, 1975 [54] COBALT CHROMIUM BASED ALLOY 2,381,459 8/1945 Merrick 75/171 3,606,615 9 I97] R d' t l. 75 HI Invent: Rademacher, w'tten'Heven 3,758,299 9i1973 Eh nis e t ..75i171 Germany [73] Assignee: Edelstahlwerk Witten Prim ry ExaminerR. Dean Aktiengesellschaft, Witten, Germany A rn y, Ag n or Fi -T wn, M eady and 221 Filed: May 22, 1973 Stanger [21] Appl. No.: 362,867 [57] ABSTRACT A cobalt/chromium based alloy suitable for use in [30] Foreign Application Priority Data making dental prostheses and surgical implants, and May 26, 1972 Germany 2225577 for in making machine Parts which are subject to severe corrosive conditions and mechanical loads at 52] us. c1 75/171, 3/1, 32/2, high temperatures, comprises by Weight 26 Percent to 32/10 A 31 percent chromium, from 4 percent to 6.5 percent 51 1m. 01 C22c 19/00 molybdenum "P to 2 Permt Silicon, "P to 6 P 581 Field of Search 75/171, 170; 148/32, 32.5; maganese "P 1 Percem P 05 Percent 3/1; 32/], 2 10 A ron, up to 0.5 percent carbon, from 0.15 percent to 0.5 percent nitrogen, and the remainder cobalt except [56] References Cited for impurities, the sum of the carbon and nitrogen contents not exceeding 0.7 percent.
10 Claims, No Drawings 1 COBALT ,CHROMIUM BASED ALLOY This invention relates to cobalt/chromium based alloys suitable for use in making dental prostheses structures and surgical implants.
Cobalt/chromium alloys are used in machinery construction predominantly for making components which are subjected to severe corrosive conditions and me chanical loadings at high temperatures. They are however equally well known in surgery for the making of implants and in dentistry for making prosthetic struc tures.
In these medical fields, alloys which, in addition to cobalt as the basic element, also contain by weight from 26 percent to 31 percent chromium, from 4 percent to 6.5 percent molybdenum, up to 1 percent each of silicon, manganese and iron, and from 0.3 percent to 0.5 percent carbon, are of particular importance. In addition, alloys are also used which, principally owing to the cost of cobalt content, contain instead up to 20 percent nickel. These may also have the silicon and manganese contents raised up to 6 percent, and may also be provided with additions of copper, aluminium, titanium, niobium, vanadium, zirconium, tantalum, beryllium and boron, either individually or in combination.
The use of these alloys in surgery and dentistry is based upon the fact that they are resistant to the corrosive conditions existing in the body and in the oral cavity; are easy to cast to the frequently very complicated shapes required; are easy to work, and possess a high modulus of elasticity and high strength and hardness. The published values are: for the modulus of elasticity an average of 220,000 N/mm and depending upon the strength of the alloy, .for the technical elastic limit (0.01 limit) approximately 390 and 440 N/mm respectively, for the 0.2-limit approximately 600 and 625 N/mm respectively, and for the tensile strength approximately 880 and 910 N/mm respectively. Values for the hardness are 340 and 380 Brinell hardness respectively.
A disadvantage of these cobalt/chromium alloys is their low capacity for deformation, that is low ductility. This is usually expressed by the elongation at rupture. The published values vary considerably but are predominantly in a range from 2 percent to 6 percent. The highest value published is 8 percent. Because of these low elongation values for the alloys, severe limits are set on the plastic deformations which can be applied to articles made from them, for example straightening operations on the holding braces of dental prosthetic structures, if the risk of breakage is to be avoided.
For this reason, titanium-containing alloys with a cobalt base having improved capacity for deformation for the same or an increased strength have been developed. These alloys contain, by weight, in addition to cobalt, from percent to percent chromium, from 5 percent to percent nickel, up to 3 percent molybdenum, up to 1 percent carbon, silicon, manganese, aluminium and/or iron and from 4 percent to 10 percent titanium. The published values of their elastic limit range, for the 0.2-limit from approximately 560 to 800 N/mm for the tensile strength from approximately 845 to 1,110 N/mm for the elongation from 10 to 12.7 percent and for the Brinell hardness from 330 to 380 kp/mm Due to the very high affinity of titanium for oxygen, these alloys suffer from the substantial disadvantage that they must be melted under vacuum or under a protective gas, and that, when manufacturing prostheses and implants, they can be melted only by using an acetylene-oxygen-burner with a flame adjusted absolutely to neutral, and not by the high frequency induction heat sources which are also frequently used.
Finally, alloys having a cobalt/chromium base are also known which, in addition to cobalt, contain, by
weight, from 20 percent to 28 percent chromium, from 10 percent to 20 percent nickel, from 3.7 percent to 4.1 percent molybdenum, and from 0.18 percent to 0.22 percent carbon. As a result of this narrow limitation of the molybdenum and carbon contents, the e1ongation is raised to from 10 percent to 14.5 percent. This advantage is however offset by the substantial disadvantage of an appreciable drop in the elastic limit. The values published are, for the 0.l-limit from 375 to 415 N/mm for the tensile strength from 595 to 715 N/mm and for the Diamond Pyramid hardness from 270 to 310 kp/mm It is the object of this invention to provide an alloy which avoids the disadvantages mentioned above while at the same time exhibiting an adequate or even an improved ductility.
To this end, according to this invention, an alloy comprises, by weight, from 26 percent to 31 percent chromium, from 4 percent to 6.5 percent molybdenum, up to 2 percent, and preferably only up to 1.5 percent silicon, up to 6 percent and preferably only up to 3 percent manganese, up to 1 percent iron, up to 0.5 percent boron, up to 0.5 percent carbon and from 0.15 percent to 0.5 percent nitrogen the remainder cobalt except for impurities, and the sum of the carbon and nitrogen contents not exceeding 0.7 percent The nitrogen content is preferably from 0.20 percent to 0.35 percent, or advantageously up to a maximum of only 0.30 percent.
For some applications, both the silicon and the manganese contents should not exceed 1 percent each. A boron content of preferably from 0.01 percent to 0.15 percent, is advantageous.
Examples of alloys in accordance with the invention are set out in Table 1. Table 11 gives the associated mechanical properties.
Table I Chemical Composition (/0 by Weight) Example C N (C N) Si Mn Co Cr Mo B 3. Table ll Mechanical Properties 0.2- Tensile Elongation Hardness Elastic Strength HV 30 Example limit (Nlmm (N/mm") (7:) (kg/mm) 1 580 735 8.2 3 l6 2 565 795 l4.6 31 l 3 570 845 l7.l 308 4 675 lOOO I20 327 5 685 1005 12.0 316 6 655 960 8.3 326 7 655 940 10.9 332 8 635 895 7.1 339 9 725 1010 8.2 328 .ness is nevertheless somewhat reduced. This suggests that the increase in the tensile strength values in the tensile test is a direct result of the improved deformability. From a comparison of Examples 7 and 9 with Example 8, it is apparent that in the total content of carbon and nitrogen, the carbon should preferably constitute the smaller component and should preferably not exceed approximately 0.2 percent.
In Examples 4 to 6 and 9, the manganese content has been raised to approximately 3 percent, in order to increase the dissolving capacity of the alloys for nitrogen. An addition of boron improves the capacity for casting (Examples 5 and 6). The mechanical properties are not in any way thereby adversely affected.
I claim:
1. An alloy consisting essentially of from 26 percent to 3l percent chromium, from 4 percent to 6.5 percent molybdenum, up'to 2 percent silicon, up to 6 percent manganese, up to 1 percent iron, up to 0.5 percent boron, up to 0.5 percent carbon, from 0. [5 percent to 0.5 percent nitrogen, with the ,balance being cobalt and impurities, the sum of said carbon content and said nitrogen content not exceeding 0.7 percent.
2. An alloy as claimed in claim 1, wherein said silicon content is no more than 1.5 percent.
3. An alloy as claimed in claim 1, wherein said manganese content is no more than 3 percent.
4. An alloy as claimed in claim 1, wherein said nitrogen content is from 0.2 percent to 0.35 percent.
5. An alloy as claimed in claim 1, wherein said carbon content is no more than 0.2 percent.
6. An alloy as claimed in claim 1, wherein said silicon content and said maganese content are each no more than 1 percent.
7. An alloy as claimed in claim 1, wherein said boron content is from 0.01 percent to 0.15 percent.
8. A dental prosthesis made from an alloy as claimed in claim 1.
9. A surgical implant made from an alloy as claimed in claim 1.
10. A machine component made from an alloy as claimed in claim 1.

Claims (10)

1. AN ALLOY CONSISTING ESSENTIALLY OF FROM 26 PERCENT TO 31 PERCENT CHROMIUM, FROM 4 PERCENT TO 6.5 PERCENT MOLYBDENUM, UP TO 2 PERCENT SILICON, UP TO 6 PERCENT MANGANESE, UP TO 1 PERCENT IRON, UP TO 0.5 PERCENT BORON, UP TO 0.5 PERCENT CARBON, FROM 0.15 PERCENT TO 0.5 PERCENT NITROGEN, WITH THE BALANCE BEING COBALT AND IMPURITIES, THE SUM OF SAID CARBON CONTENT AND SAID NITROGEN CONTENT NOT EXCEEDING 0.7 PERCENT.
2. An alloy as claimed in claim 1, wherein said silicon content is no more than 1.5 percent.
3. An alloy as claimed in claim 1, wherein said manganese content is no more than 3 percent.
4. An alloy as claimed in claim 1, wherein said nitrogen content is from 0.2 percent to 0.35 percent.
5. An alloy as claimed in claim 1, wherein said carbon content is no more than 0.2 percent.
6. An alloy as claimed in claim 1, wherein said silicon content and said maganese content are each no more than 1 percent.
7. An alloy as claimed in claim 1, wherein said boron content is from 0.01 percent to 0.15 percent.
8. A dental prosthesis made from an alloy as claimed in claim 1.
9. A surgical implant made from an alloy as claimed in claim 1.
10. A machine component made from an alloy as claimed in claim
US362867A 1972-05-26 1973-05-22 Cobalt chromium based alloy Expired - Lifetime US3865585A (en)

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DE2225577A DE2225577C3 (en) 1972-05-26 1972-05-26 Use of a cobalt-chromium-based alloy as a biomaterial

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Cited By (39)

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US4116724A (en) * 1976-05-15 1978-09-26 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Method of heat treating cobalt-chromium-molybdenum based alloy and product
JPS61501784A (en) * 1984-04-06 1986-08-21 フエルアイニヒテ エ−デルシユタ−ルヴエルケ アクチエンゲゼルシヤフト(フアウエ−ヴエ−) dental alloy
US4668290A (en) * 1985-08-13 1987-05-26 Pfizer Hospital Products Group Inc. Dispersion strengthened cobalt-chromium-molybdenum alloy produced by gas atomization
US4714468A (en) * 1985-08-13 1987-12-22 Pfizer Hospital Products Group Inc. Prosthesis formed from dispersion strengthened cobalt-chromium-molybdenum alloy produced by gas atomization
US4728495A (en) * 1985-03-22 1988-03-01 Thyssen Edelstahlwerke Ag Removable dental appliances
US5002731A (en) * 1989-04-17 1991-03-26 Haynes International, Inc. Corrosion-and-wear-resistant cobalt-base alloy
US5462575A (en) * 1993-12-23 1995-10-31 Crs Holding, Inc. Co-Cr-Mo powder metallurgy articles and process for their manufacture
US5904720A (en) * 1996-11-12 1999-05-18 Johnson & Johnson Professional, Inc. Hip joint prosthesis
US6053729A (en) * 1998-03-02 2000-04-25 Ortho Corporation Unitary substantially nickel free alloy injection molded orthodontic bracket
WO2000074637A1 (en) * 1999-06-02 2000-12-14 Osfix International Ltd Oy Dental implants and method for their coating
US20030019106A1 (en) * 2001-04-22 2003-01-30 Diamicron, Inc. Methods for making bearings, races and components thereof having diamond and other superhard surfaces
US20030154719A1 (en) * 2002-02-21 2003-08-21 Kazuya Nishi High-temperature member for use in gas turbine
US20040129349A1 (en) * 2002-07-13 2004-07-08 Dentaurum J.P. Winkelstroeter Kg Nonprecious dental casting alloy
US6773520B1 (en) * 1999-02-10 2004-08-10 University Of North Carolina At Charlotte Enhanced biocompatible implants and alloys
US20040199260A1 (en) * 2000-01-30 2004-10-07 Pope Bill J. Prosthetic joint component having at least one sintered polycrystalline diamond compact articulation surface and substrate surface topographical features in said polycrystalline diamond compact
US20040236433A1 (en) * 2003-05-23 2004-11-25 Kennedy Richard L. Cobalt alloys, methods of making cobalt alloys, and implants and articles of manufacture made therefrom
US20050087915A1 (en) * 1999-12-08 2005-04-28 Diamicron, Inc. Carbides as a substrate material in prosthetic joints
US20050110187A1 (en) * 1999-12-08 2005-05-26 Diamicron, Inc. Use of Ti and Nb cemented in TiC in prosthetic joints
US20050133277A1 (en) * 2003-08-28 2005-06-23 Diamicron, Inc. Superhard mill cutters and related methods
US20050158200A1 (en) * 1994-08-12 2005-07-21 Diamicron, Inc. Use of CoCrMo to augment biocompatibility in polycrystalline diamond compacts
US20050155679A1 (en) * 2003-04-09 2005-07-21 Coastcast Corporation CoCr alloys and methods for making same
US20050203630A1 (en) * 2000-01-30 2005-09-15 Pope Bill J. Prosthetic knee joint having at least one diamond articulation surface
EP1655384A1 (en) * 2004-11-09 2006-05-10 Cordis Corporation A cobalt-chromium-molybdenum fatigue resistant alloy for intravascular medical devices
US20060185770A1 (en) * 2005-02-24 2006-08-24 Nhk Spring Co., Ltd. Co-Cr-Mo-based alloy and production method therefor
US20060210826A1 (en) * 2005-03-21 2006-09-21 Wu James B C Co-based wire and method for saw tip manufacture and repair
US20060263233A1 (en) * 1999-12-08 2006-11-23 Diamicron, Inc. Use of a metal and Sn as a solvent material for the bulk crystallization and sintering of diamond to produce biocompatbile biomedical devices
US20060278212A1 (en) * 2003-09-11 2006-12-14 Alain Coudurier Easy-to-clean cooking surface and electric household appliance comprising same
US20080154380A1 (en) * 2000-01-30 2008-06-26 Dixon Richard H Articulating diamond-surfaced spinal implants
US20090046967A1 (en) * 2001-04-22 2009-02-19 Pope Bill J Bearings, races and components thereof having diamond and other superhard surfaces
US20090263643A1 (en) * 2005-04-07 2009-10-22 Gardinier Clayton F Use of sn and pore size control to improve biocompatibility in polycrystalline diamond compacts
US20100025898A1 (en) * 2000-01-30 2010-02-04 Pope Bill J USE OF Ti AND Nb CEMENTED TiC IN PROSTHETIC JOINTS
US20100198353A1 (en) * 2000-01-30 2010-08-05 Pope Bill J USE OF Ti and Nb CEMENTED IN TiC IN PROSTHETIC JOINTS
EP2676684A1 (en) 2012-06-18 2013-12-25 Biotronik AG Cobalt alloy for medical implants and stent comprising the alloy
EP2676686A1 (en) 2012-06-18 2013-12-25 Biotronik AG Stent made of a cobalt alloy
US8663359B2 (en) 2009-06-26 2014-03-04 Dimicron, Inc. Thick sintered polycrystalline diamond and sintered jewelry
US20140271317A1 (en) * 2011-10-21 2014-09-18 Kyocera Medical Corporation BIOCOMPATIBLE Co-Cr-Mo ALLOY
EP2853229A1 (en) * 2013-09-27 2015-04-01 Seiko Epson Corporation Dental blank to be machined, metal powder for powder metallurgy, dental metal frame for porcelain bonding, and dental prosthesis
US20150216637A1 (en) * 2014-02-06 2015-08-06 Seiko Epson Corporation Dental component, metal powder for powder metallurgy, and method for producing dental component
US11155904B2 (en) 2019-07-11 2021-10-26 L.E. Jones Company Cobalt-rich wear resistant alloy and method of making and use thereof

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Cited By (62)

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Publication number Priority date Publication date Assignee Title
US4116724A (en) * 1976-05-15 1978-09-26 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Method of heat treating cobalt-chromium-molybdenum based alloy and product
JPS61501784A (en) * 1984-04-06 1986-08-21 フエルアイニヒテ エ−デルシユタ−ルヴエルケ アクチエンゲゼルシヤフト(フアウエ−ヴエ−) dental alloy
US4728495A (en) * 1985-03-22 1988-03-01 Thyssen Edelstahlwerke Ag Removable dental appliances
US4668290A (en) * 1985-08-13 1987-05-26 Pfizer Hospital Products Group Inc. Dispersion strengthened cobalt-chromium-molybdenum alloy produced by gas atomization
US4714468A (en) * 1985-08-13 1987-12-22 Pfizer Hospital Products Group Inc. Prosthesis formed from dispersion strengthened cobalt-chromium-molybdenum alloy produced by gas atomization
AT394397B (en) * 1989-04-17 1992-03-25 Haynes Int Inc CORROSION RESISTANT AND WEAR RESISTANT COBALT BASE ALLOY
US5002731A (en) * 1989-04-17 1991-03-26 Haynes International, Inc. Corrosion-and-wear-resistant cobalt-base alloy
US5462575A (en) * 1993-12-23 1995-10-31 Crs Holding, Inc. Co-Cr-Mo powder metallurgy articles and process for their manufacture
US7396505B2 (en) * 1994-08-12 2008-07-08 Diamicron, Inc. Use of CoCrMo to augment biocompatibility in polycrystalline diamond compacts
US20050158200A1 (en) * 1994-08-12 2005-07-21 Diamicron, Inc. Use of CoCrMo to augment biocompatibility in polycrystalline diamond compacts
US5904720A (en) * 1996-11-12 1999-05-18 Johnson & Johnson Professional, Inc. Hip joint prosthesis
US6053729A (en) * 1998-03-02 2000-04-25 Ortho Corporation Unitary substantially nickel free alloy injection molded orthodontic bracket
US6227849B1 (en) 1998-03-02 2001-05-08 Ortho Organizers, Inc. Unitary substantially nickel free alloy injection molded orthodontic bracket
US6773520B1 (en) * 1999-02-10 2004-08-10 University Of North Carolina At Charlotte Enhanced biocompatible implants and alloys
WO2000074637A1 (en) * 1999-06-02 2000-12-14 Osfix International Ltd Oy Dental implants and method for their coating
US7569176B2 (en) 1999-12-08 2009-08-04 Diamicron, Inc. Method for making a sintered superhard prosthetic joint component
US7678325B2 (en) 1999-12-08 2010-03-16 Diamicron, Inc. Use of a metal and Sn as a solvent material for the bulk crystallization and sintering of diamond to produce biocompatbile biomedical devices
US7556763B2 (en) 1999-12-08 2009-07-07 Diamicron, Inc. Method of making components for prosthetic joints
US20050087915A1 (en) * 1999-12-08 2005-04-28 Diamicron, Inc. Carbides as a substrate material in prosthetic joints
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Also Published As

Publication number Publication date
FR2189526B1 (en) 1976-05-28
GB1413588A (en) 1975-11-12
FR2189526A1 (en) 1974-01-25
CH579635A5 (en) 1976-09-15
DE2225577A1 (en) 1973-12-06
DE2225577B2 (en) 1974-08-29
CA993689A (en) 1976-07-27
DE2225577C3 (en) 1980-01-31
IT985216B (en) 1974-11-30

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