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WO1998013539A1 - Procede pour recouvrir un materiau metallique a l'aide d'un compose de phosphate de calcium - Google Patents

Procede pour recouvrir un materiau metallique a l'aide d'un compose de phosphate de calcium Download PDF

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Publication number
WO1998013539A1
WO1998013539A1 PCT/GB1997/002527 GB9702527W WO9813539A1 WO 1998013539 A1 WO1998013539 A1 WO 1998013539A1 GB 9702527 W GB9702527 W GB 9702527W WO 9813539 A1 WO9813539 A1 WO 9813539A1
Authority
WO
WIPO (PCT)
Prior art keywords
calcium
ions
phosphate
phosphate compound
aqueous solution
Prior art date
Application number
PCT/GB1997/002527
Other languages
English (en)
Inventor
William Bonfield
Serena Michelle Best
Nobuyuki Asaoka
Original Assignee
Abonetics Limited
Mitsubishi Materials Corporation
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 Abonetics Limited, Mitsubishi Materials Corporation filed Critical Abonetics Limited
Priority to AU43096/97A priority Critical patent/AU4309697A/en
Publication of WO1998013539A1 publication Critical patent/WO1998013539A1/fr

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00Electrolytic coating other than with metals
    • C25D9/04Electrolytic coating other than with metals with inorganic materials
    • C25D9/08Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389The prosthesis being coated or covered with a particular material
    • A61F2310/00592Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00796Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite

Definitions

  • the present invention relates to a method for coating a calcium phosphate compound onto a medical implant metallic material such as an artificial articulation, an artificial bone, or an artificial root of a tooth.
  • titanium, titanium alloys, cobalt-chromium alloys, stainless steel and the like have hitherto been employed.
  • these metallic materials do not bind directly to the tissue of the organism, thus raising problems of low initial bonding strength, and loosening over longer periods of time.
  • a method for improving the initial bonding strength of the implant material As a method for improving the initial bonding strength of the implant material, a method has been developed in which a bone cement including poly methyl methacrylate (PMMA) is injected into a site to be treated and solidified.
  • PMMA poly methyl methacrylate
  • a method has been proposed utilizing a metal implant material on which a calcium phosphate compound such as hydroxyapatite is coated on its surface.
  • a method by connecting the implant material directly with hard tissue such as bone via a bioactive coating layer, the initial bond strength and stability for a prolonged time may be improved.
  • plasma spraying As methods for forming such a coating layer, plasma spraying, sputtering, dip coating and sol-gel coating methods have hitherto been employed.
  • the plasma spraying method is a relatively practical method, but has problems such as the formation of soluble by-products or amorphous components, which results in the dissolution of the coating layer after implantation, and ablation at a gap between a substrate and the coating layer.
  • the methods for forming the coating layer other than the plasma spraying method also encounter problems such as an insufficient bonding strength and nonuniformity of the coating layer, and therefore are not sufficiently practical.
  • a method for coating a calcium phosphate compound onto a metallic material comprises electrodepositing the calcium phosphate compound from an aqueous solution containing calcium ions, phosphate ions and a complex forming agent onto an electrode comprising the metallic material.
  • the present invention provides a method as described above wherein the calcium phosphate compound is hydroxyapatite, and the pH of the aqueous solution is controlled to be not less than 4.0 for the electrodepositing.
  • the present invention provides a method wherein the calcium phosphate compound salt is other than hydroxyapatite, and the method further comprises the step of immersing the material having the calcium phosphate compound electrodeposited thereon in an aqueous solution having pH of not less than 4.0, whereby the calcium phosphate compound salt is converted to hydroxyapatite.
  • a calcium phosphate compound salt is electrodeposited onto a metallic material from an aqueous solution containing calcium ions, phosphate ions and a complex forming agent.
  • the material to be coated is not limited as long as it is made of metal and does not spoil the effect of the present invention.
  • Metals which are superior in anti-corrosive properties and do not exhibit toxicity in having organisms such as titanium, a titanium alloy, stainless steel or a cobalt-chromium alloy may be employed.
  • any configurations may be employed including a plate, a sphere, a cylinder, a prism, a circular cone, a pyramid, and a variety of other forms imitating a tooth or a bone.
  • the aqueous solution containing calcium ions, phosphate ions and a complex forming agent may be prepared by dissolving in water a compound containing calcium ions, a compound containing phosphate ions, and a complex forming agent.
  • the compound containing calcium ions may include, e.g. Ca(OH) 2 , Ca(N0 3 ) 2 , CaC 12 , Ca (CH 3 COO) -., calcium citrate or calcium lactate.
  • the compound containing phosphate ions may include, e.g. H 3 P0 4 , Na 3 P0 4 , (NH 4 ) 3 P0 4 , j PO ⁇ , or a salt in which a part of the cation in these salts is substituted by hydrogen (e.g. (NH 4 ) 2 HP0 4 ).
  • a compound containing both phosphate ions and calcium ions such as hydroxyapatite, calcium tertiary phosphate, calcium quaternary phosphate or calcium hydrogen phosphate, may be employed.
  • the concentration of the calcium ions and the phosphate ions in the above aqueous solution is preferably 0.01 to 2.0 mol/1, and the concentration of [P0 4 3" ] is preferably 0.005 to 2.0 mol/1.
  • the Ca/P molar ratio is preferably 1.0 to 3.0.
  • the complex forming agent may include citric acid, ethylenediaminetetraacetic acid (EDTA) , lactic acid or nitrilotriacetic acid (NTA) .
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • the preferable concentration of the complex forming agent in the aqueous solution is 0.01 to 1.0 mol/1.
  • a calcium phosphate compound salt is electrodeposited on the metallic material to be coated as an electrode.
  • the counter electrode is not limited as long as it does not reduce the effect of the present invention, and may include the same metals as the material to be coated, and electrically conductive plastic materials.
  • the distance between the electrodes in the aqueous solution is preferably 1 to 50mm.
  • the voltage for the electrodeposition is preferably 1 to 100V/cm 2 . By suitably regulating the voltage, the film forming rate and construction of the coating layer may be controlled.
  • the duration of the electrodeposition is preferably from 3 to 120 minutes. By suitably adjusting the duration of the electrodeposition, the thickness of the coating layer may be controlled.
  • the temperature of the aqueous solution is preferably maintained at a constant temperature within a range of from 15° to 100°C.
  • the time for the electrodeposition may be shortened.
  • a coating layer having a larger particle size may be obtained, while if it is maintained at a lower temperature, a coating layer having a smaller particle size may be obtained.
  • hydroxyapatite may be electrodeposited as the coating layer.
  • the aqueous solution may be regulated at a pH of not less than 4.0 by adding a pH regulating agent to the aqueous solution. It is not required to dissolve all of the pH regulating agent before beginning the electrodeposition.
  • the agent may be added little by little after beginning the electrodeposition. That is, if the pH of the aqueous solution is not less than 4.0 when the calcium ions, phosphate ions and the complex forming agent are dissolved therein, the pH regulating agent is not required to be added before beginning the electro-deposition, and may be added little by little after beginning the electrodeposition in order to prevent the pH value dropping below 4.0 during the electrodeposition, so that hydroxyapatite may be electrodeposited.
  • the pH regulating agent As the pH regulating agent, ammonia, sodium hydroxide or potassium hydroxide may be employed. In terms of preventing contamination by undesired metal ions, ammonia is particularly preferred.
  • the pH regulating agent is preferably prepared as an alkaline solution by dissolving the agent in water. The preferred concentration of the alkaline solution is, for example, in the case of employing ammonia, 0.03 to 0.5 mol/1, and in the case of employing sodium hydroxide, 0.01 to 0.1 mol/1.
  • the calcium phosphate compound in the coating layer obtained by the coating method of the present invention may include calcium hydrogen phosphate dihydrate (CaHPO 4 .2H20) , monetite (CaHP0 4 ) , calcium tertiary phosphate (Ca 3 (P0 4 ) 2 ), or the aforementioned hydroxyapatite .
  • the layer of the calcium phosphate compound other than hydroxyapatite obtained by the electrodeposition may be converted into the more stable hydroxyapatite by immersing the coated material having the calcium phosphate compound salt electrodeposited thereon in an aqueous solution having pH of not less than 4.0, preferably 4.0 to 12.0.
  • the step may be performed by, but is not limited to, adjusting the pH of the aforementioned aqueous solution employed upon the electrodeposition to the desired pH value by, e.g.
  • the coating layer of the calcium phosphate compound obtained by the method of the present invention may further be subjected to a heat treatment for improving bonding strength. Even the heat treatment at relatively low temperature at which the coated material is not damaged, e.g.
  • the bonding strength of the coating layer can be improved at such a relatively low temperature since the aqueous solution as a coating bath has an electrophoresis effect so that the coating layer is formed of finer particles on the material to be coated as the electrode, than that of a conventional layer.
  • a coating layer of a calcium phosphate compound is formed by electrodeposition, and thus a calcium phosphate compound composed of fine and uniform particles may be coated even on the surface of a metal material having a complicated configuration. Therefore, the present invention is useful as a method for improving the biological compatibility of implant materials.
  • 0.1 mol of calcium nitrate, 0.06 mol of ammonium phosphate and 0.1 mol of EDTA were dissolved in 1 litre of distilled water.
  • This aqueous solution was poured into a vessel in a water bath, and controlled at a temperature of 95°C.
  • a pure platinum plate anode, 50 x 20 x 0.1 mm
  • a stainless-steel SUS316L plate cathode, 50 x 20 x 1 mm
  • electrodeposition was performed at DC 10V for 30 minutes.
  • a coating layer of monetite (CaHP0 4 ) having a thickness of lO ⁇ m was obtained on the surface of the cathode.
  • the coated alloy plate obtained in Example 3 with a 30 ⁇ m thick coating layer was subjected to a heat treatment at 750°C for 60 minutes. Bonding strengths before and after the heat treatment were measured according to JIS H8666 "ceramic spraying test method" for comparison. As a result, the bonding strength was improved from 13MPa to 22MPa while the alloy plate, i.e. the coated material, was not damaged.
  • the bonding strength of the layer measured by the same method as Example 5 was 5MPa.
  • Electrodeposition was then performed at DC 5V for 10 minutes while the aqueous ammonia solution was added dropwise using a low-speed motor with monitoring of the pH to be maintained at 4.5.
  • dense coating layers of hydroxyapatite having thicknesses of 5 ⁇ m, 20 ⁇ m and 30 ⁇ m, respectively, were obtained on the surface of each cathode.
  • the pH was maintained at 4.5 ⁇ 0.2.
  • the coated alloy plate obtained in Example 7 with a 25 ⁇ m coating layer was subjected to a heat treatment at 750°C for 60 minutes. Bonding strengths before and after the heat treatment were measured by the same method as in Example 5 and compared. As a result, the bonding strength was improved from 15MPa to 25MPa while the alloy plate, i.e. the coated material, was not damaged.
  • hydroxyapatite was sprayed by a plasma spray gun manufactured by METCO Co. under the trade name of METCO 9MB to give a film thickness of 25 ⁇ m.
  • the spraying was carried out under the conditions of 500A, 40V, spraying distance of 50mm, using a mixed gas of Ar:H 2 of 100:3.
  • the bonding strength of the layer measured by the same method as in Example 5 was 6MPa.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Dermatology (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

La présente invention concerne un procédé pour recouvrir un matériau métallique à l'aide d'un composé de phosphate de calcium. Ce procédé consiste à déposer par électrolyse le composé de phosphate de calcium à partir d'une solution aqueuse contenant des ions de calcium, des ions de phosphate et un agent formant complexe sur une électrode comportant le matériau métallique. La couche de revêtement obtenue par ce procédé comprend des particules fines et uniformes d'un composé de phosphate de calcium et présente une forte résistance d'adhésion.
PCT/GB1997/002527 1996-09-24 1997-09-16 Procede pour recouvrir un materiau metallique a l'aide d'un compose de phosphate de calcium WO1998013539A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43096/97A AU4309697A (en) 1996-09-24 1997-09-16 Method for coating a calcium phosphate compound onto a metallic material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8252012A JPH10102288A (ja) 1996-09-24 1996-09-24 リン酸カルシウム化合物のコーティング方法
JP8/252012 1996-09-24

Publications (1)

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WO1998013539A1 true WO1998013539A1 (fr) 1998-04-02

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JP (1) JPH10102288A (fr)
AU (1) AU4309697A (fr)
WO (1) WO1998013539A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002078759A1 (fr) * 2001-04-02 2002-10-10 Stratec Medical Ag Couche superficielle bioactive, notamment pour protheses et implants medicaux
AU2001244109B2 (en) * 2000-01-26 2004-12-02 Werner Lubitz Closure of bacterial ghosts
DE10006992B4 (de) * 2000-02-16 2006-10-12 Aesculap Ag & Co. Kg Verfahren zur Beschichtung eines Implantats und Implantat mit Beschichtung
WO2009147045A1 (fr) * 2008-06-03 2009-12-10 Königsee Implantate und Instrumente zur Osteosynthese GmbH Procédé d'immersion électrochimique dans un électrolyte aqueux pour produire une couche de surface biologiquement stable à la dégradation, sur des corps de base en titane ou en alliages à base de titane
WO2010112044A1 (fr) * 2009-04-02 2010-10-07 Smith & Nephew Orthopaedics Ag Procédé de traitement de surface d'un implant, implant traité par ledit procédé et solution électrolytique destinée à être utilisée dans ledit procédé
DE102009041248A1 (de) * 2009-09-04 2011-05-05 Innotere Gmbh Bioaktiv beschichtete Metallimplantate und Verfahren zu deren Herstellung
ITMI20102071A1 (it) * 2010-11-09 2012-05-10 Chemical Ct S R L Elettrodeposizione di idrossiapatite nanometrica su impianti protesici e processo elettrolitico per la sua realizzazione
CN102560604A (zh) * 2012-02-09 2012-07-11 哈尔滨工业大学 一种提高钙磷-壳聚糖在泡沫金属中电泳沉积均匀性的方法
WO2011049915A3 (fr) * 2009-10-19 2013-01-03 Biomet Manufacturing Corp. Procédés de dépôt de régions individuelles d'hydroxyapatite sur des implants médicaux
CN108508077A (zh) * 2018-05-29 2018-09-07 四川维思达医疗器械有限公司 一种确定磷酸钙电化学涂层中电极工作条件的方法
CN108982565A (zh) * 2018-05-29 2018-12-11 四川维思达医疗器械有限公司 一种确定磷酸钙涂层形貌的电解液浓度条件的方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6921544B2 (en) * 2001-03-06 2005-07-26 Rutgers, The State University Magnesium-substituted hydroxyapatites
JP2006501887A (ja) * 2002-09-13 2006-01-19 ザ ユニバーシティ オブ ブリティッシュ コロンビア リン酸カルシウムで被覆された埋込型医用デバイスおよびその製作方法
JP2005245800A (ja) * 2004-03-05 2005-09-15 Hosoda Denki:Kk 助長剤入り酸性水、インプラント入り酸性水及び洗口液
JP5356653B2 (ja) * 2007-03-09 2013-12-04 国立大学法人北見工業大学 骨適合性チタン材料の製造方法
JP6134140B2 (ja) * 2009-12-11 2017-05-24 ラティテュード・18,インコーポレイテッド 無機リン酸塩組成物および方法
US20130139930A1 (en) 2009-12-18 2013-06-06 Latitude 18, Inc. Inorganic phosphate corrosion resistant coatings
CN108760966A (zh) * 2018-05-29 2018-11-06 四川维思达医疗器械有限公司 一种确定磷酸钙电化学涂层中电解液条件的方法

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US5205921A (en) * 1991-02-04 1993-04-27 Queen's University At Kingston Method for depositing bioactive coatings on conductive substrates
JPH05285212A (ja) * 1991-11-19 1993-11-02 Ishifuku Metal Ind Co Ltd インプラント材の表面処理方法
US5413693A (en) * 1991-01-04 1995-05-09 Redepenning; Jody G. Electrocrystallization of strongly adherent brushite coatings on prosthetic alloys
DE19504386A1 (de) * 1995-02-10 1996-08-22 Univ Dresden Tech Verfahren zur Herstellung einer gradierten Beschichtung aus Calciumphosphatphasen und Metalloxidphasen auf metallischen Implantaten

Patent Citations (4)

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US5413693A (en) * 1991-01-04 1995-05-09 Redepenning; Jody G. Electrocrystallization of strongly adherent brushite coatings on prosthetic alloys
US5205921A (en) * 1991-02-04 1993-04-27 Queen's University At Kingston Method for depositing bioactive coatings on conductive substrates
JPH05285212A (ja) * 1991-11-19 1993-11-02 Ishifuku Metal Ind Co Ltd インプラント材の表面処理方法
DE19504386A1 (de) * 1995-02-10 1996-08-22 Univ Dresden Tech Verfahren zur Herstellung einer gradierten Beschichtung aus Calciumphosphatphasen und Metalloxidphasen auf metallischen Implantaten

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CHEMICAL ABSTRACTS, vol. 120, no. 10, 7 March 1994, Columbus, Ohio, US; abstract no. 116877, INOE, KYOSHI ET AL: "Surface treatment of prosthetic implants" XP002049280 *
DATABASE WPI Section Ch Week 9348, Derwent World Patents Index; Class D22, AN 93-382264, XP002049281 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2001244109B2 (en) * 2000-01-26 2004-12-02 Werner Lubitz Closure of bacterial ghosts
AU2001244109B9 (en) * 2000-01-26 2005-05-26 Werner Lubitz Closure of bacterial ghosts
DE10006992B4 (de) * 2000-02-16 2006-10-12 Aesculap Ag & Co. Kg Verfahren zur Beschichtung eines Implantats und Implantat mit Beschichtung
WO2002078759A1 (fr) * 2001-04-02 2002-10-10 Stratec Medical Ag Couche superficielle bioactive, notamment pour protheses et implants medicaux
AU2001244019B2 (en) * 2001-04-02 2004-09-30 Stiftung, Robert Mathys Bioactive surface layer, particularly for medical implants and prosthesis
CN1296101C (zh) * 2001-04-02 2007-01-24 斯恩蒂斯有限公司 用于医用植入体和假牙的生物活性表面层
DE102008026558B4 (de) * 2008-06-03 2010-04-01 Königsee Implantate und Instrumente zur Osteosynthese GmbH Elektrochemisches Tauchverfahren in einem wässrigen Elektrolyt zur Erzeugung einer biologisch degradationsstabilen Oberflächenschicht auf Grundkörpern aus Titan oder Titanbasislegierungen
DE102008026558A1 (de) * 2008-06-03 2010-01-14 Königsee Implantate und Instrumente zur Osteosynthese GmbH Elektrochemisches Tauchverfahren in einem wässrigen Elektrolyt zur Erzeugung einer biologisch degradationsstabilen Oberflächenschicht auf Grundkörpern aus Titan oder Titanbasislegierungen
WO2009147045A1 (fr) * 2008-06-03 2009-12-10 Königsee Implantate und Instrumente zur Osteosynthese GmbH Procédé d'immersion électrochimique dans un électrolyte aqueux pour produire une couche de surface biologiquement stable à la dégradation, sur des corps de base en titane ou en alliages à base de titane
WO2010112044A1 (fr) * 2009-04-02 2010-10-07 Smith & Nephew Orthopaedics Ag Procédé de traitement de surface d'un implant, implant traité par ledit procédé et solution électrolytique destinée à être utilisée dans ledit procédé
DE102009041248A1 (de) * 2009-09-04 2011-05-05 Innotere Gmbh Bioaktiv beschichtete Metallimplantate und Verfahren zu deren Herstellung
WO2011049915A3 (fr) * 2009-10-19 2013-01-03 Biomet Manufacturing Corp. Procédés de dépôt de régions individuelles d'hydroxyapatite sur des implants médicaux
ITMI20102071A1 (it) * 2010-11-09 2012-05-10 Chemical Ct S R L Elettrodeposizione di idrossiapatite nanometrica su impianti protesici e processo elettrolitico per la sua realizzazione
CN102560604A (zh) * 2012-02-09 2012-07-11 哈尔滨工业大学 一种提高钙磷-壳聚糖在泡沫金属中电泳沉积均匀性的方法
CN108508077A (zh) * 2018-05-29 2018-09-07 四川维思达医疗器械有限公司 一种确定磷酸钙电化学涂层中电极工作条件的方法
CN108982565A (zh) * 2018-05-29 2018-12-11 四川维思达医疗器械有限公司 一种确定磷酸钙涂层形貌的电解液浓度条件的方法
CN108508077B (zh) * 2018-05-29 2020-04-03 四川维思达医疗器械有限公司 一种确定磷酸钙电化学涂层中电极工作条件的方法

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Publication number Publication date
JPH10102288A (ja) 1998-04-21
AU4309697A (en) 1998-04-17

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