WO2003039609A1 - Deposition of coatings on substrates - Google Patents
Deposition of coatings on substrates Download PDFInfo
- Publication number
- WO2003039609A1 WO2003039609A1 PCT/GB2002/004889 GB0204889W WO03039609A1 WO 2003039609 A1 WO2003039609 A1 WO 2003039609A1 GB 0204889 W GB0204889 W GB 0204889W WO 03039609 A1 WO03039609 A1 WO 03039609A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- substrate
- layer
- solution
- calcium phosphate
- Prior art date
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Classifications
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- 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
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- 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
-
- 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
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- 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
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- 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
- A61F2/3094—Designing or manufacturing processes
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- 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
- A61F2/32—Joints for the hip
- A61F2/36—Femoral heads ; Femoral endoprostheses
-
- 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
- A61F2/32—Joints for the hip
- A61F2/36—Femoral heads ; Femoral endoprostheses
- A61F2/3662—Femoral shafts
-
- 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
- A61F2002/30925—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth etched
-
- 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
- A61F2002/30929—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth having at least two superposed coatings
-
- 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
- A61F2/32—Joints for the hip
- A61F2/36—Femoral heads ; Femoral endoprostheses
- A61F2/3609—Femoral heads or necks; Connections of endoprosthetic heads or necks to endoprosthetic femoral shafts
- A61F2002/3611—Heads or epiphyseal parts of femur
-
- 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
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—Metals or alloys
- A61F2310/00023—Titanium or titanium-based alloys, e.g. Ti-Ni alloys
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- 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
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—Metals or alloys
- A61F2310/00029—Cobalt-based alloys, e.g. Co-Cr alloys or Vitallium
-
- 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
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- 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
- A61F2310/0097—Coating or prosthesis-covering structure made of pharmaceutical products, e.g. antibiotics
Definitions
- the invention relates to the deposition of calcium phosphate onto a bone replacement prosthesis and more particularly the deposition of calcium phosphate coated vesicles, or droplets having a hydrophobic core coated with calcium phosphate, onto electrically conducting substrates and in particular metallic bone replacement prostheses or parts thereof.
- Patent specification WO 00/00177 describes a vesicle comprising an inner layer which comprises a phospholipid and an outer layer which comprises calcium phosphate.
- the vesicles may contain pharmaceutically active compounds including compounds which assist the binding of the coating to existing bone (bone growth factors) , treat a specific bone disease or any diseased region adjacent to bone, or relieve pain.
- a droplet comprising a hydrophobic core, an inner layer which comprises a surfactant, and an outer layer which comprises calcium phosphate.
- W0 00/00177 also describes a method for producing such vesicles or hydrophobic droplets and a method for depositing such vesicles or droplets on an electrically conducting substrate. The method is referred to as electrolytic deposition but is perhaps more accurately described as electrophoretic deposition.
- the invention provides in one of its aspects a method for producing an adherent coating of a coating material comprising calcium phosphate on an electrically conducting substrate, which method comprises first exposing the substrate to an electrochemical surface pre- treatment using a solution comprising water for removing contaminants and/or effecting a surface conversion and/or applying a primary coating to form a surface layer or surface compound layer adapted to bond to a subsequently deposited coating, and depositing upon the pre-treated surface the coating material by an electrochemical deposition process from a solution comprising calcium and phosphate ions or a suspension of calcium phosphate particles in liquid.
- the electrochemical surface pre-treatment is a treatment for removing contaminants and/or effecting a surface conversion.
- the pre-treatment comprises effecting a surface conversion.
- the electrically conducting substrate may be any substrate which conducts electricity or which has a conducting surface.
- the substrate is preferably metal, more preferably titanium, a titanium alloy or a cobalt/chromium alloy, most preferably a titanium alloy.
- the electrochemical surface pre-treatment may comprise electrochemical etching to dissolve a thin surface layer of the substrate surface.
- the electrolyte composition and impressed electrical current are selected so as to reveal the micro-structure of the metal by dissolving the grain boundaries at a faster rate and thereby roughen the surface.
- Mineral acid electrolyte will normally be suitable, with a complexant, such as fluoride, where the substrate metal is titanium.
- Application of ultrasound and/or current reversal is effective for creating a suitably rough surface.
- the electrochemical surface pre-treatment takes place using a solution comprising water as a solvent.
- the solution may comprise a mixture of solvents including water.
- the solution comprises at least 20% water, more preferably 50% water, more preferably 70% and most preferably 90% or more of water.
- an aqueous solution is used and water is the only solvent.
- the solution is an aqueous phosphate electrolyte.
- the surface of the electrically conducting substrate may be converted, for example, into an oxide, a metal salt or a mixed oxide and metal salt to form a layer that is integral with the surface of the substrate.
- the oxide is typically a hydrous oxide.
- the surface conversion layer is a mixture of oxide and metal salts, both the oxide and the metal salt are derived from the metal of the substrate.
- the metal salt is typically insoluble in water.
- the surface conversion may convert the surface of the metal to form an oxide film on which calcium phosphate is deposited in the electrochemical deposition step of the process.
- the surface conversion layer may also be a mixed oxide and titanium salt layer where the titanium salt is one that is insoluble in water.
- a mixed oxide and phosphate layer can be formed when phosphoric acid is used in the surface conversion process .
- the surface conversion may be achieved by dissolving the surface of the substrate in a phosphate medium in order to form metal phosphate salts on the surface of the substrate.
- the electrochemical deposition process may comprise electrophoretic deposition of particulate material from a suspension thereof in liquid, or electrocoagulation, or electroprecipitation from a solution of a desired coating material or precursor therefor, or electrolytic deposition from a solution of a desired coating material or precursor therefor.
- More than one electrochemical deposition process may be used to build a series of coating layers chosen, for example, to optimise binding efficiency of one layer upon the immediately preceding layer.
- a pre-treatment surface coating, or the deposited coating, or one or more of the deposited coating layers may be subjected to a plasma fusing action. This is conveniently achieved by allowing the applied voltage to rise as the surface coating or coating layer deposits on the substrate and raises the electrical resistance across the substrate surface, such that plasma forms in pores of the deposited coating and thereby generates heat sufficient to melt and fuse the coating. In this way increased coating density (if wanted) and adhesion to the substrate can be achieved.
- the method according to the invention has particular application to the coating onto a substrate electrically conducting surface of vesicles comprising an inner phospholipid coated with an outer layer of calcium phosphate or of droplets comprising an inner hydrophobic core coated with an outer layer of calcium phosphate.
- one or more interlayers is provided on the cleaned and roughened metal surface.
- the first interlayer is the surface conversion layer.
- the surface conversion coating layer can conveniently be in the form of an adherent oxide film produced by anodic polarisation. Periodic polarity reversal may be applied to increase the thickness of the oxide film layer formed.
- a phosphate conversion layer can be formed in phosphoric acid.
- a suitable protective interlayer on cobalt/chromium alloy can be provided by surface dissolution into a neutral/alkaline phosphate solution which creates an adherent insoluble phosphate layer which forms the surface conversion layer. It is typically advantageous to use polarity reversal when forming a surface conversion layer on a cobalt/chromium alloy.
- a graduation of coating properties through the thickness of the coating may be engineered by appropriate control of coating conditions such as particle size, zeta potential, applied electrical potential, pH, temperature. This may conveniently be achieved by using multiple immersion tanks.
- a hydroxyapatite coating may be laid down on a surface conversion coating, and on this an outer layer of hydroxyapatite vesicles .
- the inner layer of hydroxyapatite may be subjected to a plasma treatment as described above to increase its density and adhesion to the substrate.
- Such an inner layer provides a strongly adherent key onto which hydroxyapatite vesicles (which need to be deposited without significant heating as explained in WO 00/00177) can then be deposited by electrophoresis .
- This process may also be performed for other forms of calcium phosphate or using other forms of calcium phosphate as the coating layer.
- Insoluble Hydroxyapatite is the form of calcium phosphate required when resorption into body fluids is to be avoided. In certain circumstances, it is specifically desired to provide a coating, or part of a coating, which is resorbable into body fluids. In that case conditions of deposition are chosen which deposit calcium phosphate in a different, soluble, form.
- Coating layers grown so as to have columnar pores, with control of the pore diameter and length, may be used to provide a reservoir within the pores for pharmaceutically active compounds, such as antibiotics, pain relief agents, etc.
- Control of the fluid viscosity, surface charge and water solubility can provide for progressive release of an active agent diffusing out of the coating.
- sacrificial component that is a component which is easily reduced at a cathode or oxidised at an anode (whichever is required) to create a water soluble rather than a gaseous product.
- liquids which comprise organic solvents, for example alcohols, glycols or ketones.
- Calcium phosphate is soluble in acidic media. As described in WO 00/00177 calcium phosphate in solution is caused to crystallise around a vesicle or droplet using ultrasonics to disperse a water immiscible solvent phase containing the dissolved pharmaceutically active agent to create dispersed droplets around which the calcium phosphate forms a coating. We have found that calcium phosphate crystal formation is improved in this process by progressively reducing the solution acidity.
- This action to raise the pH of the solution may be achieved by chemical reaction such as introduction at a controlled rate of formaldehyde into nitric acid, or by electrodialytic action in which anions are replaced with hydroxyls, or by electrolytic action such as nitrate reduction at a cathode.
- chemical reaction such as introduction at a controlled rate of formaldehyde into nitric acid, or by electrodialytic action in which anions are replaced with hydroxyls, or by electrolytic action such as nitrate reduction at a cathode.
- the perturbation of pH at the depositing surface encourages the suspended fine particles to coagulate onto the roughened substrate metal surface, thus creating an adherent layer.
- Further improvement of the bond strength between the deposited particles may be achieved by incorporating soluble resins (polycarboxylic acids) in the solution. These may either dry out to create an increased bond strength, or be cross-linked in-situ through reactions occurring at the substrate surface.
- the polymeric materials used would need to be biocompatible for implant applications .
- Organically modified ceramics may also be included as part of the suspension to provide a key onto which the polymer could bind, as well as creating an environment encouraging the formation of a stable structure around the vesicles or droplets .
- the present invention provides a method for producing an adherent coating of a coating material comprising vesicles on an electrically conducting substrate, which method comprises first exposing the substrate to an electrochemical surface pre- treatment for removing contaminants and/or effecting a surface conversion and/or applying a primary coating to form, a surface layer or surface compound layer adapted to bond to a subsequently deposited coating, and depositing upon the pre-treated surface by an electrochemical deposition process a coating material comprising vesicles comprising an inner phospholipid coated with an outer layer of calcium phosphate.
- the electrochemical surface pre-treatment is a treatment for removing contaminants and/or effecting a surface conversion layer or the pre-treatment comprises effecting a surface conversion layer.
- the electrochemical deposition process is electrophoretic deposition.
- the electrochemical pre-treatment may take place in any solvent or solvent mixture, such as an organic solvent including one or more of an alcohol, glycol or ketone, or water or a mixture thereof.
- the invention includes a substrate when provided with a surface coating by a method as aforesaid.
- hip prosthesis 11 is made of titanium and is shown in an electrochemical bath 12 filled with appropriate treatment solution or electrolyte 13.
- the prosthesis 11 is connected via lead 14 to an appropriate source of electrical potential .
- Electrode 15 is connected via lead 16 to the source of electrical potential .
- the membrane 17 may have to be removed when a negative potential is applied to electrode 15.
- Parts of the prosthesis 11, primarily the ball joint 18, which are not to be coated are provided with a protective insulating layer, for example of tape.
- a protective insulating layer for example of tape.
- a surface layer of the metal is electrolytically removed using an acid bath containing fluoride with the prosthesis 11 connected to a positive electrical potential supply and the electrode 15 connected to the negative supply.
- Application of ultrasound to the bath and/or periodic current reversal helps to introduce surface roughness during this process.
- the second stage creation of an adherent oxide film on the titanium prosthesis 11 takes place. This is the surface conversion coating. If phosphoric acid is present in the bath then a mixed phosphate and oxide surface conversion coating is formed.
- the prosthesis 11 is then moved to another bath, or the bath 12 is washed out and its contents replaced, to provide a solution containing calcium and phosphate ions, and a potential applied to deposit a layer of hydroxyapatite on to the clean titanium surface.
- nitrate may be included in the solution as a sacrificial component to prevent the release of gas bubbles from the titanium surface.
- the applied deposition voltage is allowed to rise as the layer thickness increases (and the surface electrical resistance increases correspondingly) , such that plasma forms in the pores of deposited hydroxyapatite and generates sufficient heat to cause melt fusing onto the substrate.
- a treatment suspension 13 which contains vesicles, each of which comprises an inner layer which comprises a phospholipid and an outer layer which comprises calcium phosphate.
- the vesicles may contain pharmaceutically active compounds including compounds which assist the binding of the coating to existing bone (bone growth factors) , treat a specific bone disease or any diseased region adjacent to bone, or relieve pain.
- a potential is applied to deposit a coating layer of hydroxyapatite vesicles which bond to - li ⁇
- the invention is not restricted to the details of the foregoing example.
- the method may be applied to other metal prostheses made, for example of an alloy of cobalt and chromium.
- the prosthesis provided with a simple layer of strongly adherent hydroxyapatite ie without vesicles
- the latter can be deposited directly onto the first conversion layer (titanium oxide) of the prosthesis, if desired.
- the final stage deposition need not necessarily be of vesicles as described, but may be of droplets having any hydrophobic core encased in calcium phosphate.
- the other elements are preferably alkaline earth metals, more preferably magnesium, strontium or barium or a mixture thereof.
- substituted magnesium can act to promote bone growth, or substituted strontium can affect adhesion, or the retention or release of a drug contained in the vesicles.
- the method has application for other electrically conducting substrates and other coating materials.
- a particular advantage of electrophoretic deposition and other electrochemical deposition processes, used for depositing electrically insulating coatings, is that the deposited layer is self levelling. This is because the resistance of thick regions reduces current flow in those regions and thus encourages greater deposition in regions where the coating is thinner.
- the method has particular value for providing a uniform thickness coating on a corrugated, or similar uneven surface, such as a catalyst coating on a corrugated metal (eg FECRALLOY steel) substrate .
- a corrugated metal eg FECRALLOY steel
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GBGB0126467.0A GB0126467D0 (en) | 2001-11-03 | 2001-11-03 | Deposition of coatings on substrates |
GB0126467.0 | 2001-11-03 |
Publications (1)
Publication Number | Publication Date |
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WO2003039609A1 true WO2003039609A1 (en) | 2003-05-15 |
Family
ID=9925128
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/GB2002/004889 WO2003039609A1 (en) | 2001-11-03 | 2002-10-28 | Deposition of coatings on substrates |
Country Status (2)
Country | Link |
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GB (1) | GB0126467D0 (en) |
WO (1) | WO2003039609A1 (en) |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005033371A2 (en) * | 2003-10-03 | 2005-04-14 | Atotech Deutschland Gmbh | Apparatus and method for treatment of metal surfaces by inorganic electrophoretic passivation |
DE102004022768A1 (en) * | 2004-05-05 | 2005-12-08 | Heraeus Kulzer Gmbh | Medical implants with glass-ceramic-like multi-element surface layer |
WO2009000158A1 (en) * | 2007-06-22 | 2008-12-31 | The University Of Hong Kong | Strontium fortified calcium nano- and microparticle compositions and methods of making and using thereof |
WO2009046532A1 (en) * | 2007-10-10 | 2009-04-16 | Miv Therapeutics Inc. | Calcium phosphate coated stents comprising cobalt chromium alloy |
EP2165682A3 (en) * | 2008-09-22 | 2010-04-07 | DePuy Products, Inc. | Medical implant |
DE102009001895A1 (en) * | 2009-03-26 | 2010-09-30 | Biotronik Vi Patent Ag | Medical implant for drug release with porous surface |
US7909876B2 (en) | 2005-10-31 | 2011-03-22 | Depuy Spine, Inc. | Intervertebral disc prosthesis with shear-limiting core |
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