EP2776604A1 - Metallmaterialien mit einer oberflächenschicht aus calciumphosphat und verfahren zu ihrer herstellung - Google Patents

Metallmaterialien mit einer oberflächenschicht aus calciumphosphat und verfahren zu ihrer herstellung

Info

Publication number
EP2776604A1
EP2776604A1 EP12791131.1A EP12791131A EP2776604A1 EP 2776604 A1 EP2776604 A1 EP 2776604A1 EP 12791131 A EP12791131 A EP 12791131A EP 2776604 A1 EP2776604 A1 EP 2776604A1
Authority
EP
European Patent Office
Prior art keywords
metal
substrate
layer
calcium phosphate
intermediate layer
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP12791131.1A
Other languages
English (en)
French (fr)
Inventor
Adele CARRADÒ
Geneviève POURROY
Wafa ABDEL-FATTAH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Original Assignee
Centre National de la Recherche Scientifique CNRS
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 Centre National de la Recherche Scientifique CNRS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP2776604A1 publication Critical patent/EP2776604A1/de
Withdrawn legal-status Critical Current

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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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
    • A61C8/0013—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating
    • 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
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A61F2/30771—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth applied in original prostheses, e.g. holes or grooves
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1806—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by mechanical pretreatment, e.g. grinding, sanding
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A61F2002/3093—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth for promoting ingrowth of bone tissue
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • 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
    • A61L2420/02—Methods for coating medical devices
    • 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
    • A61L2420/08—Coatings comprising two or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12104—Particles discontinuous
    • Y10T428/12111—Separated by nonmetal matrix or binder [e.g., welding electrode, etc.]

Definitions

  • the present invention relates to a multilayer material comprising a metal or metal alloy substrate, said metal or alloy substrate being coated with an intermediate layer comprising at least one ceramic or crystal structure, or partially crystalline, including a metal or a metal alloy, said intermediate layer being coated with a calcium phosphate layer having a honeycomb nanometric structure, and uses thereof.
  • the invention also relates to processes for preparing such a material, said method comprising autocatalytic deposition of the calcium phosphate layer, which is optionally followed by a growth phase of the calcium phosphate layer.
  • the invention relates to the field of medical implants (or medical prostheses), and in particular bone implants.
  • Medical implants are usually made of metal or alloy compatible with the human body. However, this compatibility needs to be improved in particular from the point of view of its compatibility with the bone, and in particular to improve the growth of osteoblasts at least at the implant / bone interface.
  • Titanium and its alloys are excellent metallic materials for applications in dental and orthopedic surgery, due to high mechanical strength, low modulus of elasticity, high corrosion resistance and excellent biocompatibility.
  • Hydroxyapatite (HA) is the ceramic generally used as a bioactive layer because it can bind chemically with bone. It makes the implants based on titanium or its alloys more compatible and improves the growth of osteoblasts.
  • bone prostheses are performed by plasma torch to obtain a thick layer of hydroxyapatite.
  • these prostheses suffer from the delamination problem of the hydroxyapatite layer.
  • the present invention aims to provide a new material improving the compatibility of metals or alloys with bone, particularly when it is titanium or a titanium alloy.
  • the present invention aims to provide a porous coating that can be impregnated with drugs (anti-bacterial agents, growth factor, etc.).
  • the present invention aims to improve the preparation of implant materials requiring good bone compatibility.
  • the present invention also aims to improve the mechanical properties of materials used in the medical field as implants or prostheses, and improve the bioactivity of their surface.
  • the present invention also aims to improve the life of such materials.
  • the present invention further aims to provide an inexpensive, reliable, and usable solution on an industrial scale.
  • the present invention relates to a multilayer material comprising a metal substrate or a metal alloy, the metal or alloy substrate being coated with an intermediate layer comprising at least one ceramic or a crystalline structure, or partially crystalline, including a metal or a metal alloy such as an oxide or nitride of a metal or an alloy, said intermediate layer being coated with a calcium phosphate layer comprising at the surface a honeycomb nanometric structure.
  • the term "alveolar nanometric structure” means a structure having apparent pores on the surface (observed in the Electronic Scanning Microscope) with a diameter of less than an average of 1 micrometer. These pores roughly form alveoli resembling the natural structure of a spongy bone. These cells comprise relatively thin and flat walls.
  • the material according to the present invention with a surface honeycomb nanometric structure is obtained without growth treatment of the calcium phosphate layer in the presence of a simulated body fluid (SBF), or before such growth treatment.
  • SBF simulated body fluid
  • the material according to the present invention is therefore very advantageous since it has a cellular nanometric structure similar to the natural structure of a bone-like bone without additional treatment of growth of the calcium phosphate layer. presence of an SBF.
  • the metal or alloy substrate may itself be a layer on another substrate.
  • metal or alloy for the intermediate layer one or more metals identical to at least one of the metals used for the substrate.
  • metals of the invention it is preferred to use a metal selected from titanium or an alloy comprising titanium.
  • Such materials are typically medical alloys, and in particular the following alloys: Ti6Al4V, NiTi (Nitinol®), X2CrNiMo18-15-
  • a substrate comprising or consisting of titanium or an alloy comprising titanium, such as those mentioned above, and an intermediate layer comprising titanium, are used.
  • the metal or alloy substrate advantageously has a roughness of less than 800 nm, and preferably less than 500 nm.
  • the intermediate layer a ceramic or a crystalline structure, or partially crystalline comprising titanium.
  • ceramic or crystalline structure, or partially crystalline, including a metal or a metal alloy is meant in particular the oxides, the nitrides of the metal or alloys of the invention.
  • the intermediate layer comprises or is preferably made of sodium titanate (Na 2 Ti 5 Oii), titanium dioxide, titanium nitride, or one of their combinations. It is preferred that the intermediate layer comprises or is made of titanium nitride, and more preferably it comprises or is constituted of sodium titanate (Na 2 Ti 5 0n).
  • the intermediate layer comprises a honeycomb nanometric structure.
  • this structure comprises average pore diameters of less than 100 nm, observed by scanning electron microscopy.
  • the intermediate layer has alternatively a thickness of 50 nanometers to 10 micrometers.
  • This intermediate layer optionally has substantially spherical agglomerates with a diameter of 1 to 3 microns, however the nanometric layer remains apparent by regions.
  • the intermediate layer has a thickness of 100 to 500 nm.
  • substantially spherical agglomerates are absent or substantially absent.
  • the intermediate layer has a smooth surface that conforms to the morphology of the metal substrate or metal alloy.
  • the calcium phosphate layer advantageously has a porosity of 50 to 400 nm (average pore diameters observed by Scanning Electron Microscope).
  • the calcium phosphate layer typically has a thickness of 100 nm to 100 ⁇ , and preferably 1 to 50 ⁇ .
  • the calcium phosphate layer is advantageously obtained by autocatalytic deposition, which is optionally followed by a growth phase of the calcium phosphate layer.
  • the invention relates to a process for preparing a multilayer material comprising a metal or metal alloy substrate, and an intermediate layer comprising a crystalline or partially crystalline ceramic or structure, including a metal or a metal alloy. , such as an oxide or nitride of a metal or alloy, wherein said process comprises:
  • step (Iv) the deposition on the intermediate layer of the material obtained in step (iii) of a calcium phosphate layer comprising at the surface a honeycomb nanometric structure.
  • the method comprises in steps (ii) and (iii): (a1) chemical etching to remove native surface oxides by contacting the polished surface with an aqueous solution of hydrofluoric acid and nitric acid;
  • the method comprises in steps (ii) and (iii):
  • step (a2) chemical etching to remove native surface oxides, refine porosity and passivate the surface of the substrate, to prepare the substrate surface for step (b2);
  • step (i) is preferably carried out by the use of one or more abrasive compounds, for example silicon carbide, so that the substrate has an arithmetic roughness (Ra) of less than 0.5 ⁇ m. ⁇ , and preferably less than or equal to 0.2 ⁇ - ⁇ .
  • abrasive compounds for example silicon carbide
  • step (iii) Prior to the preparation of the intermediate layer (step (iii)) to improve the cohesion between this intermediate layer and the substrate, it is carried out a treating the surface of the substrate to improve the surface condition of the metal or alloy of the substrate.
  • This treatment makes it possible in particular to eliminate, at least in part, the native surface oxides.
  • the surface treatment of the substrate may be different.
  • the step (a1) of chemical etching comprises the use of a combination of nitric acid and hydrofluoric acid for a period preferably of less than 8 minutes and preferably less than 5 minutes, and even more preferably during 2 to 3 minutes.
  • a Kroll reagent is preferably used.
  • the chemical etching step (a2) is advantageously carried out by bringing the material into contact with an alkaline solution comprising an oxidant, and preferably with a solution of sodium hydroxide and hydrogen peroxide, this step preferably being carried out at a temperature between 60 and 100 ° C, preferably for at least 5 minutes.
  • Step (a2) advantageously comprises contacting the product with a solution of oxalic acid, preferably at a temperature between 70 and 100 ° C, preferably for at least 10 minutes, to produce a microporous surface.
  • Step (a2) preferably comprises passivating the surface of the substrate using nitric acid.
  • the above three treatments are carried out to prepare the substrate for PLD deposition.
  • step (ii) (a1 or a2)
  • one or more washings with water are preferably carried out, and then the material is dried.
  • a chemical preparation purely chemical
  • a preparation including laser ablation deposition PLD
  • This step is intended in particular to improve the cohesion between the substrate and the calcium phosphate layer.
  • This intermediate layer is advantageous for preparing a cellular nanometric alveolar calcium phosphate of a satisfactory thickness, which does not have the disadvantage of the delamination of the prior art.
  • the TiN layer deposited by PLD on titanium is characterized by a nanometric size of crystallites and the columnar growth thereof. It can increase the hardness of the prepared intermediate layer.
  • the adhesion of the films to the substrates was evaluated simply by the adhesive tape test (epoxy type). No peeling (detachment) or crackling was observed for the deposited films.
  • the lack of delamination of the calcium phosphate layer was observed by scanning electron microscopy.
  • This step preferably comprises treatment with an alkaline solution, preferably sodium hydroxide, at a concentration of preferably 5M to 15M, and preferably about 10M.
  • This treatment is preferably carried out at a temperature between 40 and 80 ° C, and preferably at a temperature of about 60 ° C.
  • the material is brought into contact with the alkaline solution typically for 1 to 2 days, and contact is preferably made for 18 to 30 hours, and advantageously for 24 hours.
  • This layer comprises, in a variant, sodium and titanate ions, forming a layer of sodium titanate.
  • the heat treatment of step (c1) is preferably carried out at a temperature between 620 ° C and 650 ° C, preferably between 625 ° C and 635 ° C for a time sufficient to dehydrate and crystallize the layer obtained in fine in step (iii).
  • the treatment according to step (b1) followed by a heat treatment according to step (c1) leads to the formation of a layer, for example of partially crystalline, porous sodium titanate on the surface of the sample.
  • the layer obtained has a heterogeneous structure composed of spherical agglomerates with a diameter of 1 to 2 microns deposited on a porous nanometric porous structure very similar to the structure of a bone with average pore diameters of less than 100 nm.
  • step (b2) comprises producing a layer of 100 to 500 nm of nitride or metal dioxide, preferably nitride or of titanium dioxide by laser ablation deposition (PLD) on the surface of the substrate.
  • PLD laser ablation deposition
  • the temperature can be maintained above 580 ° C, for example 600 ° C.
  • PLD deposition is preferred over chemical deposition because the metal or metal alloy surface is much more homogeneous than by chemical deposition, and has a lower surface roughness, further promoting the deposition and growth of calcium phosphate. (steps (iv) and (v)).
  • the spherules observed by chemical deposition are absent or substantially absent by PLD. However, the cost of PLD treatment is higher.
  • the deposition by PLD allows, according to a variant, the deposition of an intermediate layer of titanium dioxide or of titanium nitride, which has advantageous mechanical properties.
  • titanium nitride makes it possible to improve the mechanical properties of the calcium phosphate layer by improving its adhesion to the titanium nitride layer.
  • the titanium nitride layer provides high resistance to fatigue, hardness, Young's modulus, and very high stiffness, as well as a low mechanical wear coefficient, close to those specific to bone. humans.
  • the titanium dioxide layer has very good bioactive properties and can prevent a bacterial infection.
  • step (iv) is carried out by bringing the material into contact, preferably by immersion, in a solution comprising calcium ions. and phosphates for depositing, by autocatalytic deposit on the intermediate layer, a layer of calcium phosphate comprising at the surface a cellular nanometric structure; or is carried out by depositing a calcium phosphate sol-gel on the intermediate layer to obtain a calcium phosphate layer comprising at the surface a honeycomb nanometric structure.
  • the autocatalytic bath comprises an oxidizing bath, an acid bath or an alkaline bath.
  • step (iv) is carried out at a temperature of between 50 ° C. and 100 ° C., and preferably between 60 ° and 80 ° C.
  • Step (iv) is preferably carried out: (a) at a temperature between
  • Deposition by autocatalytic bath of calcium phosphate makes it possible to improve the growth of the calcium phosphate layer, and in particular to produce a layer having a structure very similar to that of bone. For example, it can be seen in FIGS. 7, 8 and 9.
  • An oxidizing autocatalytic bath preferably contains calcium, pyrophosphate, and an oxidizing agent.
  • An alkaline autocatalytic bath preferably contains pyrophosphate, hypophosphite, and calcium.
  • An acidic autocatalytic bath generally leads to spherical aggregates of the order of a few microns.
  • An acidic autocatalytic bath preferably contains calcium, hypophosphite and an organic acid.
  • An organic acid is preferably chosen from mono-, di- or tri-acids with a linear or branched hydrocarbon chain of 1 to 10 carbon atoms, optionally containing or substituted with one or more functions or substituents.
  • the autocatalytic baths comprise as a palladium catalyst or a palladium compound or as a catalyst for silver or a silver compound, and for example palladium chloride or silver chloride.
  • the oxidizing bath comprises calcium chloride of sodium pyrophosphate, hydrogen peroxide, and palladium chloride or silver chloride.
  • the acid bath comprises calcium chloride, sodium fluoride, succinic acid, sodium hypophosphite, and palladium chloride or silver chloride.
  • the alkaline bath comprises sodium chloride, sodium pyrophosphate, sodium hypophosphite, and palladium chloride or silver chloride.
  • the concentration of calcium chloride is between 1 and 50 g / l.
  • the concentration of sodium pyrophosphate is between 1 and 100 g / l.
  • the concentration of hydrogen peroxide is between 0 and 50 g / l.
  • the concentration of sodium hypophosphite is between 10 and 50 g / l.
  • the concentration of organic acid is between 1 and 20 g / l.
  • the calcium phosphate layer may be prepared by depositing a gel obtained according to a Sol-gel method or method.
  • Sol-gel methods for preparing a calcium phosphate gel from a calcium phosphate solution are known from the prior art.
  • the deposit according to this variant of the invention makes it possible to obtain a calcium phosphate layer generally ranging from 500 nm to ⁇ . More specifically, a deposit of a spin-coating gel makes it possible in general to obtain a calcium phosphate thickness of between 0.5 and 10 ⁇ m; depositing a dip-coating gel generally makes it possible to obtain a calcium phosphate thickness of between 0.5 and 20 ⁇ m. It is easier to control the thickness of the layer formed by spinning while the thickness of the layer obtained is greater by soaking. Growth of calcium phosphate layer - steps (v)
  • the method comprises a step (v) of growth of the calcium phosphate layer by bringing the material into contact with a Simulated Body Fluid (SBF).
  • the simulated body fluid can reproduce (in vitro) human blood plasma (with ion concentrations approximately equal to those of human blood plasma) to measure the bioactivity of the calcium phosphate layer on the substrate.
  • the simulated body fluid advantageously comprises ions: sodium, carbonate, phosphate, magnesium, chloride, calcium and sulfate.
  • the contacting is preferably carried out for at least 1 day, and preferably for 4 to 15 days.
  • the calcium phosphate layer preferably has a thickness of 100 nm to 100 ⁇ m, and more preferably 10 to 10 ⁇ m.
  • the calcium phosphate layer has a porosity of 50 to 100 nm reduced compared with that of step (iv).
  • the formation of phosphate and carbonate is observed (observation by infrared spectrometry).
  • the calcium and phosphorus concentration of the SBF solution increases in the first 2 days. After 7 and 14 days, the calcium and phosphorus concentration of the SBF solution decreases showing an absorption of these cations on the substrate.
  • step (iv) After the autocatalytic bath treatment (step (iv)), in the presence of SBF (step (v)) a growth of the calcium phosphate layer which can range from a few hundred nanometers to a few tens of microns is observed.
  • the process of formation of these deposits is very similar to that which leads to the natural formation of the bone. This is therefore a very important advantage of the present invention.
  • Large thicknesses are obtained, in particular by an inexpensive method adapted to complex geometries of samples (implants, prostheses or others). Growth is by biomimicry of bone growth.
  • the morphology of the calcium phosphate layer is adapted to cell growth and impregnation with active agents.
  • the calcium phosphate layer may contain chemical elements improving the adhesion and / or growth of the cells.
  • the calcium phosphate layer comprises one or more compounds that improve the adhesion and / or growth of osteoblasts.
  • the calcium phosphate layer obtained according to the present invention allows its impregnation with such compounds.
  • These compounds are known to the human job.
  • active agents such as one or more antibacterial agents (for example silver ions Ag + (W. Chen et al., In vitro anti-bacterial and biological properties of magnetron co-sputtered silver-containing hydroxyapatite coating, Biomaterials, 27, 32, 2006, pp 5512-5517), Furanone (JK Baveja et al Furanones as potential anti-bacterial coatings on biomaterials, Biomaterials, 25, 20, September 2004, pp 5003-5012) against Staphylococcus epidermidis and Staphylococcus aureus and / or one or more growth hormones (transforming growth factor (TGF- ⁇ ), parathyroid hormone (PTH) and prostaglandin E2 (PGE2) (K.
  • TGF- ⁇ transforming growth factor
  • PTH parathyroid hormone
  • PGE2 prostaglandin E2
  • the invention also makes it possible to incorporate active agents into the calcium phosphate layer, and for example drugs (antibiotics, etc.), for example to fight against infections. of the skilled person.
  • the invention avoids the delamination problem of the calcium phosphate layer, while having a satisfactory thickness of the calcium phosphate layer.
  • the material of the invention has a lower crystallinity than a thick layer of hydroxyapatite formed by plasma torch, which is more favorable to the adhesion of osteoblasts, proliferation and exchanges with the surrounding environment.
  • the layer is partially amorphous because (1) the deposits were made at low temperatures and (2) there was no recrystallization by heat treatments.
  • the calcium phosphate layer according to the invention comprises, for example, calcium carbonate (CaCO 3 ) combined with hydroxyapatite, monocalcium phosphate Ca (H 2 PO 4 ) 2, or dicalcium phosphate (CaHPO 4 ).
  • the invention also relates to a multilayer material obtainable according to the method of the invention, according to any one of its variants and embodiments, including any combination thereof.
  • the invention also relates to an implant or prosthesis for a bone structure comprising a material as defined in the present description.
  • the invention relates to a bone implant, or a dental implant.
  • the invention also relates to the use of a multilayer material, as defined in the present description, for the preparation of an implant or prosthesis for a bone or dental structure.
  • the invention also relates to an implant composition for a bone structure comprising or consisting of a multilayer material as defined in the present description, and in particular for use in the surgical treatment of a human being.
  • said composition is used for the replacement of an articular bone end, for example for bone surgery of a hip, knee, shoulder, elbow, ankle, wrist, finger, and / or toe or for dental surgery.
  • FIG 1 schematically shows two variants of the method of the invention
  • Figure 2 schematically shows the layers of the material of the invention
  • FIG. 4 represents a schematic view of a device for an alkaline and thermal chemical treatment according to a variant of the invention
  • FIG. 5 represents photographs of an intermediate layer by
  • Figure 6 shows a schematic view of a device for deposition by autocatalytic bath according to a variant of the invention
  • Figure 7 shows photographs by FESEM of layers of calcium phosphate obtained by different autocatalytic baths after chemical treatment
  • FIG. 8 shows photographs by FESEM of calcium phosphate layers obtained by different autocatalytic baths deposited on a layer of titanium nitride deposited by PLD;
  • FIG. 9 represents photographs by FESEM of layers of calcium phosphate obtained by different autocatalytic baths deposited on a layer of titanium dioxide deposited by PLD;
  • FIG. 10 represents a photograph (top) by FESEM of the calcium phosphate layer obtained by spin-coating and (bottom) the graph obtained by EDS-X analysis (energy dispersion analysis). ). ;
  • FIG. 11 represents a photograph (top) by FESEM of the calcium phosphate layer obtained by dipping (dip-coating) and (bottom) the graph obtained by EDS-X analysis;
  • FIGS. 12 and 13 show the cell viability on T6A4V (commercial) substrates treated by auto-catalytic baths (3h) with PdCl 2 ( Figure 12) as a catalyst and by auto-catalytic baths (2h) with AgCl ( Figure 13) as a catalyst.
  • each example has a general scope.
  • Figure 1 shows schematically a block diagram of two variants of the invention.
  • Figure 2 schematically shows two three-layered materials of the invention comprising a calcium phosphate layer (21), an intermediate layer of titanium nitride (22) or titanium oxide (24) and a titanium substrate layer or of titanium alloy (23).
  • titanium in particular T6Al4V alloy
  • Other metals or alloys can be used as a substrate.
  • the preparation consists of four main stages, namely:
  • the substrate is then pretreated with an alkaline solution (NaOH); then undergoes heat treatment; finally
  • the pretreated material is immersed in an oxidizing alkaline or acidic alkaline bath for 2 h under defined temperature and pH conditions (Table 2).
  • a high titanium titanium alloy (T6A4V) commercially available as a cylindrical bar for dental application was cut into small blocks (0-20 mm, height 2 mm).
  • the titanium samples were polished by abrasion under a water jet using an automatic polishing device.
  • the polishing disk of the device was rotated at 250 rpm with a polishing pressure of 10 N to 20 N.
  • the titanium alloy ingot was set in motion at 250 rpm on the disk of polishing.
  • a series of polishing steps were performed by refining the abrasive grain (grit 1000, 1200, 2500, 4000) for 2 minutes, until the surface state has the desired roughness.
  • An amorphous colloidal silica slurry for polishing (MasterMet 2, Buehler, IL, USA) was used for the final polishing of the titanium alloy samples. Finally, the materials were cleaned separately by successive ultrasonic treatments of 15 minutes in acetone, then in 70% ethanol, followed by two treatments with distilled water of 15 minutes each.
  • the substrate had an arithmetic average roughness Ra ( ⁇ ) of 0.16 and a maximum roughness Rmax ( ⁇ ) of 0.73.
  • the titanium alloy materials are pretreated in an alkaline solution of 10M NaOH at 60 ° C for 24 hours in a Teflon® flask.
  • Figure 4 schematically shows the equipment used for this treatment.
  • the samples undergo a heat treatment at a temperature of 630 ° C with a temperature ramp of 10 ° C / min, and a hold for 1 h at 630 ° C.
  • the materials are then allowed to cool to room temperature (about 20 ° C) in the oven, then removed and kept in a desiccator for further analysis.
  • Figure 5 shows the surface condition of the samples with spherical agglomerates of different sizes but leaving visible a honeycomb nanometric structure (a).
  • a highly nano-crosslinked structure is observed in Figure 4 (b).
  • Figure 4 (c) shows a sample examined at a 50 ° angle to show the thickness of the honeycomb nanometer layer.
  • the coating is therefore composed of a heterogeneous surface of spherical agglomerates of about 1-2 ⁇ m diameter (Fig. 5a) deposited on a nano-porous structure similar to that of bone (pore diameter ⁇ 100 nm) ( Fig. 5b).
  • the chemical and thermal treatment allows the formation of a layer with a thickness of about 1.8 ⁇ (Fig. 5c) containing ions Na + and Ti 4+ ions to form a layer of sodium titanate (Na 2 Ti 5 0n).
  • This treatment allows the nucleation and growth of hydroxyapatite on the titanium pretreated with the sodium hydroxide solution.
  • Calcium chloride provides calcium and pyrophosphate and / or sodium hypophosphite provides phosphorus.
  • sodium, pyrophosphate and sodium hypophosphite are reducing agents in an oxidizing or acidic medium, respectively.
  • succinic acid acts as a reaction accelerator while sodium fluoride is an etching agent.
  • the catalyst used for the baths was either palladium chloride (PdCl 2 ) or silver chloride (AgCl).
  • Figure 6 schematically shows the device used for autocatalytic deposition.
  • Electron interaction Scanning Electron Microscopy
  • -material surface to be analyzed
  • charge accumulation effects on the surface. These charges are discharged to the ground in the case of a conductive sample.
  • an insulator as the intermediate layer of the invention
  • their accumulation deforms the electron beam and modifies its effective energy: it is therefore necessary to deposit a thin layer of metallization on the surface (gold or carbon ). Carbon was chosen. This layer is therefore deposited only for the purposes of observation by SEM (FESEM).
  • FIG. 7 represents an example of deposition formed after 2 hours of treatment in an oxidizing (Ox), acid (Ac) or alkaline (Al) bath.
  • Oxidative and alkaline bath deposits have structural surfaces similar to those observed by alkaline and thermal chemical treatment ( Figure 5) indicating a potential to maintain proteins and antibiotics in the structure, beneficial for healing or repair improvement. postsurgical.
  • the surfaces obtained by alkaline bath have large spherical agglomerates deposited on a layer of small spherules formed on the metal substrate (diameter less than 50 nm), thus suggesting a denser structure.
  • the chemical composition of the formed layers analyzed by dispersive energy spectroscopy shows the presence of calcium and phosphorus. They are generated by the composition of the baths.
  • the fluorine detected with the use of the acidic autocatalytic bath should improve bone formation at the interface when implanted at a bone site.
  • Figure 7 shows the surfaces observed FESEM by after 2 hours of treatment in oxidizing bath (a), acid (b), or alkaline (c).
  • the laser source was placed outside the irradiation chamber.
  • the size of the irradiation spot was about 2 mm 2 and the incident fluence was 1.5 J / cm 2 .
  • the titanium alloy sample was mounted on a special support which can be rotated and / or translational during the application of the multi-pulsation laser irradiations to avoid drilling and to continually subject a new zone to the laser exposure.
  • the titanium alloy substrate was maintained at a temperature of about 600 ° C.
  • MW (microwave) + plasma heat treatment with microwave (MW) and "cleaning" by plasma to degas the surface of any organic residues.
  • Example 2 A procedure identical to that of Example 1 was carried out. In order to produce calcium phosphate layers, the samples were immersed in autocatalytic baths of different compositions summarized in Table 2.
  • FIG. 8 illustrates an intermediate layer of titanium nitride and FIG. 9 of titanium dioxide observed by FESEM .
  • Al surface obtained by treatment with an alkaline bath (a);
  • Ox surface obtained by treatment with an oxidizing bath (c).
  • the immersion was done for 2 hours.
  • X-ray EDS spectra are obtained showing the presence of O, Na Ca, P for the acidic and alkaline bath. The presence of Cl and absence of Na for the oxidizing bath.
  • Example 3 Preparation of material of the invention by elaboration of the calcium phosphate layer by sol-gel.
  • sol-gel deposition comprises four main steps that can be summarized as follows:
  • the substrate is prepared according to steps (i), (ii) and (iii) of Example 1.
  • a sol-gel suspension of calcium phosphate is prepared under the following conditions: (according to C. Wen, W. Xu, W. Hu, and P. Hodgson, "Hydroxyapatite / titania sol-gel coatings on titanium-zirconium alloy for biomedical applications, "Acta Biomaterialia, Volume 3, No. 3, pp. 403-410, May 2007):
  • the following components are mixed at temperatures between 20 ° C and 100 ° C.
  • the molar ratio Ca / P is equal to 1.67.
  • a solution of triethyl phosphite of concentration 1.8M is prepared in anhydrous ethanol.
  • a solution of calcium nitrate tetrahydrate in anhydrous ethanol of concentration between 2 and 4 M is added dropwise to the previous solution.
  • the mixture is stirred for 3min to 1h and aged at room temperature for up to 3 days.
  • the preceding mixture is deposited by spin-coating at a speed of 3000 rpm for 15s to 2 min, preferably 15 to 40 s.
  • the substrate is then treated at 400 to 700 ° C for 5 minutes to 1 hour, preferably between 500 ° C and 630 ° C for 20 minutes in an argon / air atmosphere.
  • the calcium phosphate layer obtained has a thickness of about ⁇ ⁇ . The process can be repeated several times to obtain a thicker calcium phosphate layer.
  • the substrates are then ultrasonically cleaned in acetone, then in ethanol and then in distilled water.
  • the dense layer of calcium phosphate in FIG. 10 can be observed by FESEM as well as the composition analysis by EDS-X
  • the substrate is soaked in the above mixture at a rate of between 1 and 20 cm / min (preferably 3-10 cm / min), then treated at 400 to 700 ° C. for 5 min to 1 h, preferably between 500 ° C and 630 ° C for 20 min, in an argon / air atmosphere.
  • the thickness of the calcium phosphate layer obtained is a few micrometers. The process can be repeated several times to obtain a thicker calcium phosphate layer.
  • the substrates are then ultrasonically cleaned in acetone, then in ethanol and then in distilled water.
  • the dense layer of calcium phosphate in FIG. 11 can be observed by FESEM as well as the composition analysis by EDS-X.
  • the control (100%) corresponds to the activity of mitochondrial dehydrogenase cells grown on a conventional plastic used for cell growth and whose area is ideal for cell growth.
  • Human osteosarcoma cells (Human osteosarcoma cells, MG63, ATCC: CRL-1427) were cultured at 37 ° C in a modified minimum essential medium.
  • the samples were deposited in wells of 24-well plates (CellStar, PBI International, Milan, Italy).
  • the cells were inoculated directly onto the surface of the samples according to a defined number (5000 cells / sample) and cultured for 48 h and 72 h.
  • the cells seeded on the polystyrene were used as a control.
  • Cell viability is evaluated by treatment with MTT (3- (4,5-Dimethyl-2-thiazolyl) -2,5-diphenyl-2H-tetrazolium bromide assay (MTT, Sigma-Aldrich St. Louis, MO, USA).
  • MTT 3- (4,5-Dimethyl-2-thiazolyl) -2,5-diphenyl-2H-tetrazolium bromide assay
  • MTT solution (1 mg / ml in PBS) was added to each sample and each plate, and incubated for 4 h in the dark, after which the supernatant was aspirated and the formazan crystals dissolved with 100 mL of dimethyl sulfoxide (DMSO, Sigma-Aldrich) 50 mL was collected, centrifuged for 5 min (12000 rpm) to remove any debris The optical density was measured at a wavelength of 570 nm with a spectrophotometer (Spectra Count, Packard Bell, USA) The optical density of the control samples corresponds to a value of 100% of cell viability.
  • DMSO dimethyl sulfoxide
  • TAV means an alloy of T6-AI-V4.
  • FIGS. 12 and 13 represent the cell viability on TAV (commercial) substrates treated with 3h self-catalytic baths with PdCl 2 as a catalyst (FIG. 12) and of duration 2h with AgCl as catalyst (FIG. 13).
  • Values greater than 100% mean that cells feel better about "implants" than about plastic.
  • osteoblasts there is a very good growth of osteoblasts on the surface of the composite materials of the invention. There is better growth when using an acidic autocatalytic bath regardless of the catalyst used. It is also noted that the AgCl type catalyst makes it possible to obtain better growth results.

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US10537658B2 (en) 2017-03-28 2020-01-21 DePuy Synthes Products, Inc. Orthopedic implant having a crystalline gallium-containing hydroxyapatite coating and methods for making the same
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