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 PDFInfo
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 30
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 30
- -1 calcium phosphate compound Chemical class 0.000 title claims abstract description 30
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 30
- 239000007769 metal material Substances 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 title claims abstract description 12
- 239000011248 coating agent Substances 0.000 title claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 238000004070 electrodeposition Methods 0.000 claims description 26
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 19
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical class [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960005069 calcium Drugs 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 2
- 239000001354 calcium citrate Substances 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000001527 calcium lactate Substances 0.000 claims description 2
- 229960002401 calcium lactate Drugs 0.000 claims description 2
- 235000011086 calcium lactate Nutrition 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 235000013337 tricalcium citrate Nutrition 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims 1
- 239000011247 coating layer Substances 0.000 abstract description 30
- 239000002245 particle Substances 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000001105 regulatory effect Effects 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007943 implant Substances 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007750 plasma spraying Methods 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS 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
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00389—The prosthesis being coated or covered with a particular material
- A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
- A61F2310/00796—Coating 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.
Landscapes
- 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
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)
Publication Number | Publication Date |
---|---|
WO1998013539A1 true WO1998013539A1 (fr) | 1998-04-02 |
Family
ID=17231350
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1997/002527 WO1998013539A1 (fr) | 1996-09-24 | 1997-09-16 | Procede pour recouvrir un materiau metallique a l'aide d'un compose de phosphate de calcium |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPH10102288A (fr) |
AU (1) | AU4309697A (fr) |
WO (1) | WO1998013539A1 (fr) |
Cited By (11)
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 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
1996
- 1996-09-24 JP JP8252012A patent/JPH10102288A/ja active Pending
-
1997
- 1997-09-16 AU AU43096/97A patent/AU4309697A/en not_active Abandoned
- 1997-09-16 WO PCT/GB1997/002527 patent/WO1998013539A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Non-Patent Citations (2)
Title |
---|
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 * |
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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 |
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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 |
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AU4309697A (en) | 1998-04-17 |
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