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WO2008146113A2 - Procédé pour le revêtement d'une surface d'un élément métallique pour augmenter l'ostéointégration de celui-ci et dispositif prothétique comprenant ledit élément - Google Patents

Procédé pour le revêtement d'une surface d'un élément métallique pour augmenter l'ostéointégration de celui-ci et dispositif prothétique comprenant ledit élément Download PDF

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Publication number
WO2008146113A2
WO2008146113A2 PCT/IB2008/001229 IB2008001229W WO2008146113A2 WO 2008146113 A2 WO2008146113 A2 WO 2008146113A2 IB 2008001229 W IB2008001229 W IB 2008001229W WO 2008146113 A2 WO2008146113 A2 WO 2008146113A2
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WO
WIPO (PCT)
Prior art keywords
collagen
deposition
process according
electrolytic bath
electrolytic
Prior art date
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PCT/IB2008/001229
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English (en)
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WO2008146113A3 (fr
Inventor
Francesco Paolucci
Massimo Marcaccio
Norberto Roveri
Silvia Manara
Anna Tampieri
Daniele Pressato
Claudio De Luca
Sergio Di Fede
Original Assignee
Fin-Ceramica Faenza S.P.A.
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Publication date
Application filed by Fin-Ceramica Faenza S.P.A. filed Critical Fin-Ceramica Faenza S.P.A.
Publication of WO2008146113A2 publication Critical patent/WO2008146113A2/fr
Publication of WO2008146113A3 publication Critical patent/WO2008146113A3/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • 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
    • 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
    • A61L27/34—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases

Definitions

  • the present invention relates to a process for coating at least one metal element of a prosthetic device, in order to obtain a high bone integration between the
  • Prosthetic device are for instance: implants, synthetic means, external fastening systems, stabilizing systems, melting cages, dental implants, screws, to be used to clinical/surgical purposes in orthopedics, maxillo- facial surgery and neurosurgery.
  • the human bone is one of the most complex examples of biomineralized material existing in nature. It is mainly made up of inorganic components such as hy- droxyapatite (HA) and water (70-80%), and of organic components such as type I collagen, proteoglycanes and other non-collagenous proteins (20-30%) .
  • HA hy- droxyapatite
  • organic components such as type I collagen, proteoglycanes and other non-collagenous proteins (20-30%) .
  • hydroxyapatite nanocrystals get in close contact with fibrils of type I collagen and generate a nanostructured, regular set with hierarchical struc- ture having given mechanic and elastic properties that "are able to support all organs of the human body.
  • Such deposition mechanism of hydroxyapatite nanocrystals in close contact within collagen fibrils is mediated by competent cells such as fibroblasts and osteoblasts.
  • competent cells such as fibroblasts and osteoblasts.
  • the loss of bone substance with consequent need of restoring the lacking volume or the request of increasing the existing bone volume is one of the most relevant problems in orthopedics, maxillo- facial surgery and neurosurgery.
  • Several solutions were proposed to face the lack of bone volume, in particular various substances of natural, inorganic synthetic or merely synthetic origin were used as bone substitute.
  • the extraordinary mechanical behavior of natural bone due to its nanocomposite hierarchical structure has been shown by many authors to be hardly achievable with any other type of biomaterial . Therefore, the ideal bone substitute is still autologous bone taken from the patient himself from a donor site.
  • complementary metal structures in bone reconstruction procedures is not limited only to reconstructions without an immediate mechanical load, but are very often an integral part of bone regeneration such as for instance in dental/maxillo-facial surgery, wherein the positioning of titanium screws becomes in time a single body with the recipient bone, giving rise to an anatomical system that can house artificial dental elements for recovering the loss of dental elements .
  • osteointegration a concept introduced by Branemark at the end of the 60s and later developed in the 80s with the oncoming of new histological techniques
  • osteointegration refers to the direct, structural and functional union between the recipient vital bone and the surface of a prosthetic device subjected to load.
  • the implementation and preservation of bone integration depend on bone healing, repairing and remodeling capacity. It is clear that a complete osteointegration of metal with the recipient bone is extremely important, since anatomical and morpho- functional results of many bone reconstruction surgical operations depend on it. For instance, if a complete bone integration with the healthy bone is not obtained in dental surgery, there is the risk of mobilization of prosthetic implants.
  • Titanium alloys (mainly Ti ⁇ Al 4 V alloys and Ti 6 Al 7 Nb alloys) are preferred with respect to other metal alloys not only thanks to their easy processing, but especially thanks to their high biocompatibility, high me- chanical resistance, resistance to corrosion, low tendency to induce bone resorption and to their elastic properties which, if compared with other metal alloys, are more similar to those of human bone (relatively low elastic modulus of 100 GPa with respect to over 200 GPa of alternative materials, stainless steels and cobalt alloys) .
  • implant surface begins with a cell chemotaxis towards the interface bone-implant and migrations of other factors (macromolecules, chemical mediators, proteins, nutrients etc.) with the formation first of a coagulum and then of granulation tissue that can prepare an ideal bed for the transformation of undifferentiated parent cells (mesenchymal cells present in bone marrow) into mature cells that can synthesize the mineral bone matrix in the final neoossification stage.
  • undifferentiated parent cells mesenchymal cells present in bone marrow
  • the result of a good bone integration is inevitably determined by a perfect quality of the recipient bone.
  • metal implants housed in patients suffering from both senile and secondary osteoporosis or from other degenerative ill- nesses of the skeletal structure very often fail.
  • these coatings are obtained by chemical-physical processes such as CVD (Chemical Vapor Deposition) and PVD (Physical Vapor Deposition) , which allow to obtain ultrathin (size of some tens of run) and resistant coatings that are able to damp mechanical stresses due to friction between adjacent joint surfaces, thus preventing the release of ions that may induce inflammatory reactions on adjacent tissues. If on one side these techniques can ensure a faster primary bone integration (e.g.
  • HA hydroxyapatite
  • HA nucleation inside collagen fibers induces the carbonatation of HA nanocrystals in B position with replacement of PO 4 3" ion with CO 3 2' ion, similarly to what occurs in the process of deposition of human apatite, preventing the deposition in A position wherein CO 3 2" ion would replace OH " group as occurs in synthetic carbonate- apatite.
  • the close analogy in terms of microstructure and chemical composition of the nanocomposite colla- gen-apatite with human bone can result in a bioactive structure which, once deposited onto a metal surface, is able to modulate the kinetics of new bone formation and bone remodeling.
  • Nanostructured composites of cal- cium phosphates/collagen are apt to be deposited onto metal surfaces.
  • traditional coating methods such as plasma spray, CVD (Chemical Vapor Deposition) and PVD (Physical Vapor Deposition) cannot be applied to this type of material, especially due to the fi- brous shape of collagen.
  • the electrolytic deposition was carried out in a solution of Ca(NO 3 ) 2 and NH 4 H 2 PO 4 added with a solution of 1 M NaOH so as to ob- tain a pH of 4.8-5.3, which was later added with type I collagen in acid solution, followed by a post- adjustment of pH to the values referred to above.
  • the electrolytic deposition was carried out at a constant potential at the cathode of -1, -2 or -3V with respect to the reference cathode (saturated calomelane electrode, SCE) .
  • the Applicant aims at increasing the bone integration capacity of prosthetic devices including at least one metal element by way of a coating process of the element surface with at least one layer of a highly biocompatible material, so as to obtain an interface with the bone structure that enables a faster new bone formation and a bone integration strengthening in time.
  • the Applicant has found that this problem can be solved by means of a process according to the following claims, wherein a composite of collagen with a calcium phosphate is deposited electrochemically onto the surface of the metal element designed to come in contact with the bone structure, under such process conditions that collagen fibers self-assemble with the inorganic calcium phosphate ⁇ component near the metal surface, precipitating onto the latter in one mineral phase based on HA, without the addition of alkaline compounds into the electrolytic bath.
  • the present invention therefore relates to a process for coating a surface of a metal element, comprising: providing an electrolytic bath comprising at least one collagen, calcium ions and phosphate ions; immersing into said electrolytic bath at least one cathode and at least one anode, said at least one cathode comprising the metal element to be coated; applying electric direct current to said electrolytic bath so as to obtain on said surface an electrolytic co-deposition of collagen with a calcium-phosphate compound comprising hydroxyapatite .
  • the present invention relates to a prosthetic device comprising at least one metal element, said metal element having at least one surface coated with at least one layer that can be obtained by electrolytic co-deposition of a collagen with a calcium phosphate compound comprising hydroxyapatite.
  • the electrolytic bath has a pH of from 3.0 to 4.5, preferably from 3.5 to 4.0, said pH rising in proximity to the cathode .-to a value above 8, generally from 10 to 12, during the co-deposition process without addition of any alkaline compound.
  • the electrolytic bath At the end of the electrolytic co-deposition process, generally has a pH of from 4.0 to 6.0, preferably from 4.5 to 5.5.
  • the electrolytic co-deposition is carried out with a substantially constant direct current.
  • the direct current is kept at relatively low values so as to avoid the removal of deposited material due to an excessive development of gaseous hydrogen at the cathode.
  • the direct current has a value of from 10 to 60 T ⁇ A, more preferably from 30 to 40 mA.
  • collagen is type I collagen.
  • collagen undergoes a preliminary step of enzymatic digestion in order to remove telopeptides present on collagen molecules, which might prevent the self- assembly of the protein on the metal surface.
  • collagen is present in the electrolytic bath as a suspension and has in general an initial concentration of from 0.005 to 0.05% weight/volume, preferably from 0.01 to 0.02% weight/volume .
  • calcium ions are added to the electrolytic bath as a soluble salt under reaction conditions, e.g. calcium nitrate.
  • the initial concentration of phosphate ions in the electrolytic bath is generally of 0.01 to 0.1 moles/liter, preferably 0.02 to 0.06 moles/liter .
  • phosphate ions are added to the electrolytic bath as a soluble salt under reaction condi- tions, e.g. ammonium dihydrogenophosphate .
  • the initial concentration of phosphate ions in the electrolytic bath is generally of from 0.01 to 0.10 moles/liter, preferably from 0.02 to 0.04 moles/liter.
  • phosphate ions includes both phosphate PO 4 3"" ions and hydrogenophosphate HPO 4 2" as well as dihydrogenophosphate H 2 PO 4 " ions that might be present in equilibrium with PO 4 3" ions in variable amounts depending on pH.
  • the metal element comprises titanium or an alloy thereof, e.g.
  • the thickness of the collagen and hydroxya- patite layer can be varied within wide intervals, from a thickness of few nm, e.g. from 10 nm to 500 nm, up to higher thickness values, generally from 50 ⁇ m to 500 ⁇ m, preferably from 100 ⁇ m to 200 ⁇ m.
  • the thickness of the collagen and hydroxyapatite layer is preferably not higher than 500 ⁇ m, since higher thickness values may cause delamination phenomena that would result in surface irregularities jeopardizing the bone integration capacity of the treated surface.
  • the calcium phosphate compound comprises at least 90% by weight, more preferably at least 95% by weight, of hydroxyapatite.
  • hydroxyapa- tite is present as lanceolate, flat crystals (biomi- metic morphology) with an average size of the longest side below 300 nm, more preferably from 100 to 200 nm.
  • the layer obtained by electrolytic co-deposition according to the present invention generally comprises: from 10 to 90% by weight of hydroxyapatite and from 10 to 90% by weight of collagen. More preferably, said layer comprises: from 60 to 70% by weight of hydroxyapatite and from 30 to 40% by weight of collagen.
  • Fig. 1 a schematic representation of a device for implementing the electrolytic co-deposition according to the present invention
  • Fig. 2 SEM image of the coating obtained by co- deposition of collagen and hydroxyapatite according to the invention after 5 min. of electrodeposition
  • Fig. 3 TEM images of the coating obtained by co- deposition of collagen and hydroxyapatite according to the invention; (a) and (b) after 5 min. of electrode- position, (c) and (d) after 30 min. of electrodeposition;
  • Fig. 4 FTIR spectrum of the coating obtained by co- deposition of collagen and hydroxyapatite according to the invention after 30 min. of electrodeposition (spectrum A) , compared with the FTIR spectrum of a bone tissue (spectrum B) ;
  • Fig. 5 X-ray diffractogram obtained by co-deposition of collagen and hydroxyapatite according to the invention after 30 min. of electrodeposition; the supplement contains a portion of a X-ray diffractogram of a bone tissue by way of comparison;
  • Fig. 6 SEM images of self-assembled collagen fibers according to the invention, after decalcification with EDTA/glutaraldehyde .
  • Type I collagen used in the experiments was extracted from horse tendon using a standard manufacturing method wherein animal tissues and the derived raw tissue were subjected to strict medical-veterinary controls. After completely removing the synovial mem- brane, the tissue was finely cut up and suspended in an. aqueous HCl solution at pH 2.5, then digested with pepsin for 24 h. After enzymatic digestion collagen was precipitated raising pH to 5.5 by addition of a NaOH solution and then subjected to washing cycles with distilled water, then treated with 1 M NaOH for 1 h so as to remove any glycoside residue and ensure a complete viral deactivation. At the end of the procedure, it was treated in an ambient at pH 5.5 by addition of HCl. Short before the deposition process, col- lagen fibers were homogeneously resuspended (1% w/w) in 0.3% acetic acid (w/w) .
  • the electrolytic deposition processes described below were carried out with a two-electrode electrochemical system schematically shown in Figure 1, comprising an electrolytic bath (1) in which calcium ions, phosphate ions and collagen as suspension in the aqueous medium are present; a cathode (2) and an anode (3) are immersed in the electrolytic bath (1) , between the latter an electric direct current is applied, which is controlled by means of a potentiostat (4) used as gal- vanostat (Amel model 552-Potentiostat/Amel model 721- Integrator) .
  • the cathode was made up of a titanium foil sized 15 mm x 25 mm. Before electrolytic deposition, the titanium foil was cleaned by ultrasonic treatment in acetone bath and then in distilled water 5 till every residue was removed.
  • the electrolytic bath was prepared by dissolving in distilled water Ca (NO 3 ) 2 and NH 4 H 2 PO 4 until a concentration of 42 mM of [Ca 2+ ] and 25 mM of PO 4 3" was achieved.
  • a suspension of type I collagen prepared as
  • I 0 described above was added to the electrolytic bath in a concentration of 0.012% w/v.
  • the initial pH of the electrolytic bath was of about 4.0.
  • the pH of the electrolytic bath was of about 5.0-5.5.
  • the electrochemical cell containing the electrolytic bath was kept at room temperature while applying a basically constant current of 34 mA.
  • the duration of the deposition process of the composite coating of collagen/HA was fixed0 at 5 seconds, 30 seconds, 5 minutes, 30 minutes.
  • the collagen begins to self-assemble only near the cathode, where a local rise of pH is obtained by effect of the electrochemical process, and not in the whole mass of the bath as a result of the addition of 0H ⁇ ions.
  • the initial pH of the electrolytic bath is adjusted to a value below the isoelectric point of collagen, so as to enable the migration of the positively charged molecule to the cathode.
  • Example 1 Various samples obtained according to Example 1 were characterized as follows.
  • FTIR Infrared microscopy spectra
  • Perkin-Elmer infrared spectrophotometer mod.
  • Spectrum One FT-IR with an associated Perkin-Elmer microscope Perkin-Elmer Autoimage microscope
  • Spectral resolution was of 4 cm "1
  • spatial resolution was of 100x100 ⁇ m
  • the spectrum was the result of 32 scans.
  • the basic line of the spectrum was obtained from a region without sample. The specific areas to be analyzed were identified by vision with a camera located on the microscope.
  • Scanning electron microscope (SEM) images were obtained with a Philips 515 microscope.
  • the titanium foil subjected to electrochemical coating was suitably placed and treated with a coating of colloidal gold in a time range of from 30 to 180 seconds at a voltage of 30 mV.
  • the analysis with transmission electron microscope (TEM) was carried out with a Philips 420T microscope.
  • a sample of pulverized coating was suspended in bi- distilled water and a drop of the suspension thus obtained was deposited onto a perforated carbon foil supported by a copper microgrid.
  • X-ray diffractometry was employed for determining the crystallinity degree by using an Analytical X' Pert Pro diffTactometer and a ⁇ CuK radiation generated at 40 kV and 40 ⁇ iA.
  • the instrument was configured at 1° of divergence and 0.2 mm of receiving slit.
  • the crystallinity degree was evaluated by applying the following formula:
  • Crystallinity [%] 100 X ⁇ I net ./( ⁇ Itot. - Bgr. const . ).
  • the size of the single crystal was determined by ap- plying Scherrer's formula:
  • ⁇ represent the angle of diffraction
  • the hydroxyapatite crystals take a needle-like shape with a length of 160 ⁇ 20 nm and a width 60+10 nm (images (c) e (d) ) .
  • images (c) e (d) images (c) e (d) ) .
  • crystals seem to be located inside the collagenous fibrils in the less mineralized area of the sample, whereas in the more mineralized area there occurs the opposite phenomenon, i.e. mineralization takes place outside collagenous fibrils. This phenomenon lets us assume that the self-assembly stage of collagen I molecules deprived of telopeptides, so as to later precipitate in fibril form, occurs simultaneously to the nanocrys- tallization stage of carbonate-hydroxyapatite .
  • the insert shows a portion of the diffractogram of a bone tissue, so as to point out a development that is wholly similar to the one of the sample obtained according to the invention.
  • some samples were decalcified in 10% EDTA solution for 24 hours. This process enables to completely remove the mineral phase surrounding the fibers and improves the characterization and quantification thereof.
  • SEM images concerning the coating on the titanium foil subjected to decalcification are shown in Figure 6. Collagen fibers are shown as deposited homogeneously on the titanium surface without any preferential orientation; this may lead to believe that the mineralization process does not significantly modify the typical morphology of this molecule.

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

Abstract

L'invention concerne un procédé pour le revêtement d'une surface d'un élément métallique, en particulier un élément métallique d'un dispositif prothétique, comprenant les opérations consistant à : se procurer un bain électrolytique comprenant : au moins un collagène, des ions calcium et des ions phosphate ; immerger dans ledit bain électrolytique au moins une cathode et au moins une anode, ladite au moins une cathode comprenant l'élément métallique devant être revêtu ; appliquer un courant électrique continu audit bain électrolytique de façon à obtenir sur ladite surface un co-dépôt électrolytique de collagène avec un composé de phosphate de calcium comprenant de l'hydroxyapatite. La couche de revêtement ainsi obtenue a une biocompatibilité élevée, de façon à obtenir une interface entre un élément métallique et une structure osseuse, ce qui permet une formation osseuse nouvelle plus rapide et un renforcement de l'intégration osseuse au cours du temps.
PCT/IB2008/001229 2007-05-28 2008-05-19 Procédé pour le revêtement d'une surface d'un élément métallique pour augmenter l'ostéointégration de celui-ci et dispositif prothétique comprenant ledit élément WO2008146113A2 (fr)

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ITMI2007A001083 2007-05-28
IT001083A ITMI20071083A1 (it) 2007-05-28 2007-05-28 Processo per rivestire una superficie di un elemento metallico per aumentarne l'osteointegrazione e dispositivo protesico che include detto elemento

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WO2008146113A2 true WO2008146113A2 (fr) 2008-12-04
WO2008146113A3 WO2008146113A3 (fr) 2009-02-05

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011049915A3 (fr) * 2009-10-19 2013-01-03 Biomet Manufacturing Corp. Procédés de dépôt de régions individuelles d'hydroxyapatite sur des implants médicaux
CN103074659A (zh) * 2013-01-29 2013-05-01 浙江大学 医用金属植入体表面嵌入壳聚糖微球胶原涂层的制备方法
CN103726089A (zh) * 2012-10-10 2014-04-16 电子科技大学 一种镍钛合金表面制备含硅羟基磷灰石纳米复合涂层的电化学方法
CN104790007A (zh) * 2015-04-21 2015-07-22 浙江大学 医用金属植入体表面的矿化胶原涂层的制备方法
CN106283160A (zh) * 2016-08-05 2017-01-04 宁波江东仑斯福环保科技有限公司 一种医用金属基生物涂层的制备方法
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
CN114752982A (zh) * 2022-04-15 2022-07-15 攀枝花学院 具有时序降解功能的生物医用镁合金及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5330826A (en) * 1990-08-13 1994-07-19 Mcdonnell Douglas Corporation Preparation of ceramic-metal coatings
US5205921A (en) * 1991-02-04 1993-04-27 Queen's University At Kingston Method for depositing bioactive coatings on conductive substrates
US5258044A (en) * 1992-01-30 1993-11-02 Etex Corporation Electrophoretic deposition of calcium phosphate material on implants
CA2073781A1 (fr) * 1992-07-13 1994-01-14 Morteza Shirkhanzadeh Procede de formation de revetements bioactifs composes sur les implants
WO2002059395A2 (fr) * 2000-12-28 2002-08-01 The Board Of Regents Of The University Of Nebraska Depot electrolytique de revetements pour des metaux et alliages destines a servir de protheses
AU2003228587A1 (en) * 2002-04-18 2003-11-03 University Of Florida Biomimetic organic/inorganic composites, processes for their production, and methods of use

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011049915A3 (fr) * 2009-10-19 2013-01-03 Biomet Manufacturing Corp. Procédés de dépôt de régions individuelles d'hydroxyapatite sur des implants médicaux
CN103726089A (zh) * 2012-10-10 2014-04-16 电子科技大学 一种镍钛合金表面制备含硅羟基磷灰石纳米复合涂层的电化学方法
CN103074659A (zh) * 2013-01-29 2013-05-01 浙江大学 医用金属植入体表面嵌入壳聚糖微球胶原涂层的制备方法
CN103074659B (zh) * 2013-01-29 2015-11-04 浙江大学 医用金属植入体表面嵌入壳聚糖微球胶原涂层的制备方法
CN104790007A (zh) * 2015-04-21 2015-07-22 浙江大学 医用金属植入体表面的矿化胶原涂层的制备方法
CN106283160A (zh) * 2016-08-05 2017-01-04 宁波江东仑斯福环保科技有限公司 一种医用金属基生物涂层的制备方法
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
CN114752982A (zh) * 2022-04-15 2022-07-15 攀枝花学院 具有时序降解功能的生物医用镁合金及其制备方法
CN114752982B (zh) * 2022-04-15 2023-09-29 攀枝花学院 具有时序降解功能的生物医用镁合金及其制备方法

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