WO2018221810A1 - Procédé de fabrication d'un support métallique poreux recouvert d'un film d'oxyde poreux et support métallique poreux ainsi fabriqué - Google Patents

Procédé de fabrication d'un support métallique poreux recouvert d'un film d'oxyde poreux et support métallique poreux ainsi fabriqué Download PDF

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WO2018221810A1
WO2018221810A1 PCT/KR2017/014539 KR2017014539W WO2018221810A1 WO 2018221810 A1 WO2018221810 A1 WO 2018221810A1 KR 2017014539 W KR2017014539 W KR 2017014539W WO 2018221810 A1 WO2018221810 A1 WO 2018221810A1
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porous
metal support
porous metal
freezing
oxide film
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PCT/KR2017/014539
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English (en)
Korean (ko)
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정현도
이진아
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한국생산기술연구원
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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • 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
    • 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
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B22D25/005—Casting metal foams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising

Definitions

  • the present invention relates to a method for producing a porous metal support coated with a porous oxide film and a porous metal support prepared thereby. More particularly, the present invention relates to a method for forming a porous oxide film on the surface of a metal porous body produced by a freeze casting process by an anodizing process, and a porous metal support prepared thereby.
  • 'bio implant implants such as titanium, stainless steel alloys, metal materials such as cobalt-chromium alloys, bioinert ceramic materials such as alumina, zirconia and hydroxyapatite Bioactive ceramic materials such as) are widely used.
  • titanium has high biocompatibility, high physical properties, high fatigue resistance, and in particular about half the low modulus of elasticity compared to cobalt-chromium alloys or stainless steel alloys. It is widely used as a material for implant implants.
  • titanium has a low modulus of elasticity
  • stress shielding may occur when titanium is used as a implant for implantation because of the difference in modulus of elasticity with bone.
  • the material used as a living implant is required to be able to withstand loads over a long period of time with sufficient strength and to have good affinity with surrounding tissues. Therefore, from this point of view, there is an active research to develop a porous support for application to hard tissue in recent years.
  • Freeze casting is a technology that freezes ceramic slurry, removes ice and heat-treats the ceramic porous body, which is a typical ceramic wet process, which is environmentally friendly and very economical. .
  • the metal itself is not used as a precursor, but only ceramic powder, a polymer material, and a ceramic such as titanium hydride (TiH 2 ), which becomes a metal such as titanium after heat treatment, have been used.
  • a coating process is used to prevent oxidation of the implant for implantation and to improve biocompatibility.
  • the implant for living implants is a porous body, a wet coating process has been applied to coat the interior of the pores.
  • the anodizing process is a process of oxidizing the surface of a component with oxygen generated from the anode when the treated object is electrolyzed to the anode.
  • the porous body can be coated efficiently and effectively, but the precipitates after the reaction have pores. There was a problem that can be adversely affected by stacking inside the pores.
  • Patent Document 1 Republic of Korea Patent No. 10-1070341
  • the technical problem to be achieved by the present invention is to form a porous oxide film on the surface of the metal porous body prepared by freezing casting using a metal powder as a precursor for producing a slurry by an anodizing process, wherein the alcohol in the electrolyte in the anodic oxidation process
  • an embodiment of the present invention comprises the steps of preparing a slurry by mixing a metal powder, a freezing medium and a dispersing agent, freezing casting the slurry to prepare a metal porous body and the metal porous body in the electrolyte After immersion and anodizing to form a porous oxide film on the surface of the metal porous body, the electrolyte solution provides a method for producing a porous metal support, characterized in that it comprises an alcohol solvent.
  • the preparing of the slurry may be a method of preparing a porous metal support, characterized in that performed at a temperature higher than the freezing temperature of the freezing medium.
  • the metal powder may be a porous metal support manufacturing method comprising at least one pure metal or alloy selected from the group consisting of titanium, magnesium, iron, aluminum and copper.
  • the freezing medium includes one or more selected from the group consisting of water, camphor, camphor, naphthalene and terpenoid-based materials. It may be a method for producing a porous metal support characterized in that.
  • the content of the metal powder may be a porous metal support manufacturing method, characterized in that 10% by volume to 40% by volume relative to the content of the freezing medium.
  • the dispersant may be a method for producing a porous metal support, characterized in that it comprises an oligomeric polyester (oligomeric polyester).
  • the content of the dispersant may be a method for producing a porous metal support, characterized in that 0.1 to 10% by weight relative to the content of the metal powder.
  • the step of preparing the slurry may be a method for producing a porous metal support, characterized in that is carried out with the grinding of the metal powder by ball-milling (Ball-milling) or stirring.
  • the step of preparing the porous metal body, freezing casting the slurry to produce a freezing molded body, removing the freezing medium from the freezing molded body to prepare a porous structure and the porous structure Sintering may be a method for producing a porous metal support comprising the step of preparing a porous body.
  • the step of preparing the freezing molded body may be a method for producing a porous metal support, characterized in that performed at a temperature below the freezing temperature of the freezing medium.
  • the slurry in the step of preparing the freezing molded body, may be injected into a mold to be a porous metal support manufacturing method, characterized in that the rotation and cooling.
  • the freezing molded body after the step of manufacturing the freezing molded body, it may be a porous metal support manufacturing method characterized in that it further comprises the step of growing the granules of the freezing medium.
  • the freezing medium may be a method for producing a porous metal support, characterized in that the freeze-dried, sublimation and dissolution to remove from the freezing molded body by any one or more methods.
  • the sintering may be a method for producing a porous metal support, characterized in that carried out in a temperature range of 1100 °C to 1400 °C.
  • the alcohol solvent may be a porous metal support manufacturing method comprising an alcohol solvent having 1 to 6 carbon atoms.
  • the content of the alcohol solvent may be a porous metal support manufacturing method, characterized in that 1% by volume to 50% by volume relative to the content of the electrolyte.
  • the electrolyte may be a method for producing a porous metal support, characterized in that it comprises one or more selected from the group consisting of calcium solution, phosphoric acid solution and calcium phosphate solution.
  • another embodiment of the present invention provides a porous metal support prepared by a method for producing a porous metal support.
  • another embodiment of the present invention provides an implant comprising a porous metal support.
  • another embodiment of the present invention includes a metal porous substrate and a porous oxide film coated on the surface of the metal porous base material, the porous oxide film of calcium (Ca) and phosphorus (P) It provides a porous metal support comprising any one or more.
  • the metal porous base material may be a porous metal support, characterized in that it comprises at least one pure metal or alloy selected from the group consisting of titanium, magnesium, iron, aluminum and copper.
  • a freeze casting process may be performed using a metal powder, and a porous metal support coated with a porous oxide film may be prepared by performing an anodizing process on the metal porous body manufactured by the freeze casting process.
  • the porous metal support is manufactured using the metal powder itself rather than the ceramic, the porous metal support may be manufactured using various metals as well as titanium, and the content of impurities may be very small and the purity may be high.
  • the porous oxide film formed through the anodic oxidation process may include any one or more of calcium and phosphorus. Therefore, the porous metal support may have high biocompatibility, thereby facilitating the proliferation of cells, and may be applied as an implant.
  • FIG. 1 is a flow chart showing a method of manufacturing a porous metal support according to an embodiment of the present invention.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a porous metal body according to an embodiment of the present invention.
  • Figure 3 is a schematic diagram showing a simple process of manufacturing a porous metal body according to an embodiment of the present invention.
  • Figure 4 is a schematic diagram showing the anodic oxidation of the step of forming a porous oxide film according to an embodiment of the present invention.
  • FIG. 5 is an XRD graph showing a phase of a porous metal support with or without a porous oxide film according to an embodiment of the present invention.
  • Figure 6 is an image showing the shape of the porous metal support coated with a porous oxide film according to an embodiment of the present invention by magnification.
  • FIG. 7 is an image (Fig. 7 (a)) to Fig. 7 (b) according to the magnification of the shape of the porous metal film coated with a porous oxide film according to an embodiment of the present invention, EDS analysis graph (Fig. 7 (c)) ) And the weight table according to the components (Fig. 7 (d)).
  • Figure 8 is a graph showing the results of EDS analysis showing the components of the porous metal support with or without a porous oxide film according to an embodiment of the present invention.
  • Figure 9 is an image showing the shape of the porous metal support coated with a porous oxide film is not added ethanol in the electrolyte according to an embodiment of the present invention.
  • FIG. 10 is an image showing the shape of a porous metal support coated with a porous oxide film in which ethanol is added to an electrolyte solution according to an embodiment of the present invention.
  • FIG. 11 is an image showing cells attached to a porous metal support coated with a porous oxide film according to Comparative Example 2 (FIG. 11 (A)) and Preparation Example 1 (FIG. 7 (B)) according to an embodiment of the present invention. .
  • FIG. 12 is a graph showing cell proliferation results of a porous metal support coated with a porous oxide film according to an embodiment of the present invention.
  • the method of preparing a porous metal support includes preparing a slurry by mixing a metal powder, a freezing medium, and a dispersant (S100), preparing a porous metal body by freezing casting the slurry (S200), and the metal. It may include a step (S300) to form a porous oxide film on the surface of the metal porous body by anodizing the porous body in the electrolyte solution.
  • the slurry is preferably performed at a temperature higher than the freezing temperature of the freezing medium because the slurry should be prepared in a good fluidity state.
  • the type of the metal powder is not particularly limited, but the metal powder preferably includes at least one pure metal or alloy selected from the group consisting of titanium, magnesium, iron, aluminum and copper.
  • titanium powder is more preferably used because titanium has excellent properties as a material for implantable implants. This metal powder will be formed into the porous metal support as a final result.
  • the freezing medium is not particularly limited as long as the energy required for removing the freezing medium in step S220 of preparing the porous structure to be described later is not excessive.
  • the freezing medium may include one or more selected from the group consisting of water, camphor, camphor, naphthalene, and terpenoid-based materials, but is not limited thereto. It doesn't happen.
  • the camping is a freezing temperature of 35 °C to 45 °C, can be easily evaporated to remove at room temperature can be used as a freezing medium can be improved energy efficiency in producing the porous metal support of the present invention.
  • the dispersant serves to disperse the metal powder in the freezing medium, and may be used without limitation as long as the material can be easily dry evaporated. Specifically, oligomeric polyester may be used as the dispersant.
  • the dispersant serves to disperse the metal powder in the freezing medium. If no dispersant is used, layer separation between the metal powder and the freezing medium can occur at a high rate. Therefore, it is necessary to appropriately adjust the amount of dispersant used.
  • step (S100) it is possible to adjust the content ratio of the metal powder and the freezing medium in order to control the mechanical properties such as porosity, pore size and thereby compressive strength of the porous metal support to be produced later.
  • the content of the metal powder may be 10% by volume to 40% by volume relative to the content of the freezing medium.
  • the content of the metal powder is less than 10% by volume relative to the content of the freezing medium, it is difficult to form a porous metal support structure to be manufactured later due to the lack of the amount of metal in the process of removing the freezing medium after freezing casting.
  • the content of the metal powder is more than 40% by volume relative to the content of the freezing medium, the slurry is difficult to have an appropriate viscosity, so that the porous metal support produced later may not sufficiently grow in three-dimensionally connected pores. not. Accordingly, the porosity of the porous metal support after removing the freezing medium can be adjusted in the range of about 60% to about 90%.
  • step (S100) it is possible to use a dispersant and to adjust the amount of the dispersant to help the metal powder is dispersed in the freezing medium.
  • the content of the dispersant may be 0.1 to 10% by weight of the content of the dispersant compared to the content of the metal powder.
  • the content of the dispersant is less than 0.1% by weight relative to the content of the metal powder, the metal powders are not preferable because they coagulate with each other and do not uniformly disperse in the freezing medium.
  • the content of the dispersant is more than 10% by weight relative to the content of the metal powder, it will not be enough to evaporate in the step of preparing a porous structure to be described later (S220), furthermore in the step of preparing a porous body to be described later (S230) It is not preferable because it may interfere with the sintering of the porous body.
  • Ball-miling or agitation may be performed to more uniformly mix the metal powder, freezing medium and dispersant.
  • the slurry may be prepared by the ball milling, wherein the ball milling is finely pulverizing the metal powder, and in the step (S200) of preparing a porous metal body to be described later, the wall of the metal powder has a more dense density. It can be carried out to ensure that the porous metal support can maintain its shape.
  • the step of freezing casting the slurry to produce a porous metal body (S200), as shown in Figure 2, the step of freezing casting the slurry to produce a freezing molded body (S210), the freezing in the freezing molded body Removing the medium may include preparing a porous structure (S220) and sintering the porous structure to prepare a porous body (S230).
  • Figure 3 is a schematic diagram showing a process for producing a porous metal body, freeze-casting the slurry prepared by mixing a metal powder, a freezing medium and a dispersing agent (Fig. 3 (B), and after the granules of the freezing medium of the freezing molded body are grown (FIG. 3 (C)), the freezing medium is removed and sintered to prepare a porous metal body (FIG. 3 (D)). ).
  • the step of producing the freezing molded body by freezing casting the slurry may include the step of rotating and cooling the slurry is injected into the mold, the temperature below the freezing temperature of the freezing medium Preference is given to performing at.
  • the slurry prepared in the above-mentioned step (S100) is injected into a mold having a predetermined shape, rotated together with the mold in the mold, and cooled to manufacture a freezing molded body.
  • the mold into which the slurry is injected may be manufactured in various shapes according to the field in which the porous metal support is used.
  • the mold may be manufactured using polyethylene or aluminum.
  • step (S210) it is possible to prevent the precipitation of the metal powder in the slurry by rotating the slurry in a mold in a constant speed range, it is possible to manufacture a freezing molded body by cooling the slurry in this state.
  • This utilizes the principle of forcibly distributing uniformly on the freezing medium by applying a constant driving force from the outside to the metal powder to be precipitated in the freezing medium.
  • the rotational speed of the mold is preferably in the range of the first rotational speed to the second rotational speed.
  • the first rotational speed means a rotational speed for generating an external driving force equal to the force to precipitate the metal powder in the freezing medium
  • the second rotational speed is an external driving force equal to the force to separate the metal powder due to the centrifugal effect. It means the rotation speed to generate.
  • the rotational speed of the mold is slower than a specific first rotational speed, the separation of the metal between the freezing medium and the metal powder is undesirable because the force to precipitate the metal powder in the freezing medium is greater than the external driving force caused by the rotation of the mold.
  • the rotational speed of the mold is faster than the specific second rotational speed, the external driving force generated by the rotation becomes larger than the force to precipitate the metal powder in the freezing medium, so that the metal powder and the freezing medium having density difference are separated by the centrifugal effect Is undesirable because it can happen.
  • step (S210) it is possible to control the porosity and pore size of the porous metal support produced by controlling the freezing temperature. That is, by varying the freezing temperature while the slurry is rotated and cooled, it is possible to control the porosity and pore size by adjusting the spacing of the condensation phase of the freezing medium.
  • This principle is generally that the lower the freezing temperature, the faster the nucleation rate, so that the gap between the condensation phases of the freezing medium is narrowed.
  • the pores of small size are formed, and in the case of relatively high freezing temperature, the pores of large size are controlled to control the porosity, pore size, etc. of the porous metal support.
  • the freezing temperature is preferably controlled in the range below the freezing temperature of the freezing medium.
  • the freezing medium is camphor
  • the freezing temperature of the camping fin is 51 ° C to 52 ° C
  • the temperature may be about 42 ° C.
  • the freezing medium in order to secure the pore characteristics as a porous metal support, such as porosity, pore size, space three-dimensional connectivity, the freezing medium It may further comprise the step of growing granules. More specifically, the method may include growing the granules of the condensation freezing medium by rotating the freezing molded body while maintaining the temperature in a predetermined temperature range near the freezing temperature.
  • Growing the granules of the freezing medium may utilize local remelting of the condensed freezing medium.
  • the freezing molded body is maintained for a predetermined time in the freezing temperature of the freezing medium to -20 °C range of the freezing temperature to grow the condensation phase.
  • the freezing medium melts as a whole and the freezing molded body collapses, which is undesirable.
  • it is not preferable because there is a problem that the time required for increasing the pore size is long because granule growth does not occur or proceeds very slowly.
  • the condensed phase is grown by maintaining the freezing molded body at a temperature of 25 ° C. to 45 ° C. for a predetermined time.
  • a porous structure is manufactured by removing the freezing medium from the freezing molded body (S220).
  • the freezing medium may be removed from the freezing molded body using any one or more of freeze drying, sublimation and dissolution. That is, by sublimation of the freezing medium by rapid drying by vacuum treatment in the frozen state, or by dissolving the frozen medium in the frozen state, portions in which the freezing medium was present in the freezing molded body are formed as pores in the porous structure. Will be.
  • the heat treatment temperature may be variously applied depending on the metal powder used.
  • the metal powder is titanium
  • heat treatment may be performed at a temperature range of 1100 ° C. to 1400 ° C.
  • the heat treatment temperature is less than 1100 ° C., grains constituting the porous body may not be properly formed, and thus it is difficult to obtain a desired strength.
  • the heat treatment temperature is higher than 1400 ° C., a part of the heat treated porous body may be It is not preferable because it may cause a problem of melting and flowing down.
  • the step (S230) may be carried out in a vacuum state to fundamentally block the problem that the porous structure is oxidized by the side reactions such as oxygen and unnecessary impurities are incorporated into the porous body.
  • the degree of vacuum in the vacuum state it is not particularly necessary to limit the degree of vacuum in the vacuum state, but more preferably a range of 0.5 ⁇ 10 -6 Torr to 1.0 ⁇ 10 -6 Torr may be suitable. If the vacuum degree is less than 0.5 ⁇ 10 -6 Torr, the porous structure can be oxidized because there is no effect of vacuum, and if the vacuum degree is greater than 1.0 ⁇ 10 -6 Torr, unnecessary manufacturing costs due to high vacuum may be increased. Not desirable
  • the metal porous body is immersed in an electrolyte and then anodized to form a porous oxide film on the surface of the metal porous body (S300).
  • FIG. 4 is a schematic diagram showing the anodic oxidation of the step (S300) of forming the porous oxide film.
  • the electrolyte solution 30 is injected into the electrolytic cell, and the anode electrode 10 and the cathode electrode 20 are immersed.
  • the metal porous body may be used as the anode electrode 10, and a conventional auxiliary electrode may be used for the cathode electrode 20.
  • the auxiliary electrode sound platinum may be platinum (Pt), silver (Ag), titanium (Ti), or carbon (C).
  • the voltage applied in the anodic oxidation may be 270 V to 350 V. If the applied voltage is less than 270 V, it may be insufficient to coat the porous oxide film on the surface of the metal porous body, and if the applied voltage exceeds 350 V, The discharge of electrons is so large that defects such as cracks may occur on the porous metal surface, which is not preferable.
  • the electrolyte solution in which the anode electrode and the cathode electrode may be immersed may include an alcohol solvent.
  • the alcohol solvent may increase the fluidity of the electrolyte to facilitate the movement of ions that may be anodized to the inside of the metal porous body, thereby forming a porous oxide film up to the inside of the pores.
  • the decrease in porosity may be controlled.
  • the carbon number of the alcohol solvent is too high, it is difficult to show the fluidity increasing effect, it is preferable to use an alcohol solvent having 1 to 6 carbon atoms of the alcohol solvent.
  • the content of the alcohol solvent may be 1% by volume to 50% by volume relative to the content of the electrolyte solution.
  • the content of the alcohol solvent is less than 1% by volume relative to the content of the electrolyte, the effect of increasing the fluidity of the electrolyte is insignificant, and not preferable.
  • the content of the alcohol solvent is more than 50% by volume relative to the content of the electrolyte, the alcohol It is not preferable because the solvent may act as an impurity.
  • the electrolyte may not be limited as long as the electrolyte contains any one or more of calcium (Ca) and phosphorus (P). Since calcium (Ca) and phosphorus (P) are included, the anodization process is finally manufactured. It is possible to improve the biocompatibility of the porous metal support.
  • the electrolyte solution may include one or more selected from the group consisting of calcium solution, phosphoric acid solution and calcium phosphate solution.
  • the calcium solution is calcium chloride, calcium nitrate, calcium acetate, calcium acetate monohydrate, calcium acetate monohydrate, calcium gluconate, calcium benzo Calcium benzoate or calcium malate.
  • the phosphoric acid solution may be potassium dihydrogen phosphate, sodium phosphate, or ammonium phosphate.
  • the calcium phosphate solution is calcium glycerophosphate (Calcium glycerophosphate), hydroxyapatite (Hydroxyapatite), ⁇ -tricalcium phosphate ( ⁇ -tricalcium phosphate, ⁇ -TCP), ⁇ -tricalcium phosphate ( ⁇ -tricalcium phosphate, ⁇ - TCP), tetracalcium phosphate (TTCP), amorphous calcium phosphate (ACP), monocalcium phosphate anhydrate (MCPA), dicalcium phosphate anhydrate (DCPD), octacalcium phosphate (octacalcium phosphate, OCP), monocalcium phosphate monohydrate (MCPM) or dicalcium phosphate dehydrate (DCPD).
  • CaCP calcium glycerophosphate
  • MCPA monocalcium phosphate anhydrate
  • DCPD dicalcium phosphate anhydrate
  • octacalcium phosphate octacalcium phosphate
  • the porous metal support may be manufactured by forming a porous oxide film by an anodizing process on the surface of the metal porous body prepared by freezing casting.
  • the porous oxide film may be uniformly coated to the inside of the pores by increasing the fluidity of the electrolyte by introducing an alcohol solvent into the electrolyte in the anodic oxidation process.
  • the porous metal support is manufactured using the metal powder itself rather than the ceramic, the porous metal support may be manufactured using various metals as well as titanium, and the content of impurities may be very small and the purity may be high.
  • the porous metal support has mechanical properties such as elastic modulus and stiffness similar to that of biological bone tissue, is chemically stable, has excellent biocompatibility and bone conductivity, and may include pores capable of differentiation and growth of bone tissue. It may be suitable for use as.
  • the porous metal support may include a metal porous base material and a porous oxide film coated on the metal porous base material surface.
  • the metal porous base material may include one or more pure metals or alloys selected from the group consisting of titanium, magnesium, iron, aluminum, and copper, but is not limited thereto, and particularly, titanium has excellent properties as a material for implantable implants. It is preferable to include titanium because it has.
  • the porous oxide film may include any one or more of calcium (Ca) and phosphorus (P) because the porous metal support should exhibit biocompatibility characteristics.
  • a porous body was prepared by maintaining the temperature at ⁇ 60 ° C. in a vacuum atmosphere of 5.0 ⁇ 10 ⁇ 3 Torr to remove the freezing medium from the freezing molded body.
  • the porous body was sintered at about 1300 ° C. for about 2 hours to prepare a porous metal support.
  • X-ray diffraction (XRD) of Preparation Example 1 and Comparative Example 1 was conducted to analyze the phase of the porous metal support with or without the porous oxide film.
  • FIG. 5 is an XRD graph showing a phase of a porous metal support with and without a porous oxide film.
  • Preparation Example 1 was observed using a scanning electron microscope (Scanning Electron Microscopy, SEM).
  • Figure 6 is an image showing the shape of the porous metal support coated with a porous oxide film by magnification.
  • Preparation Example 1 of the porous metal support coated with the porous oxide film confirmed that a plurality of pores existed on the surface thereof, and that the porous oxide film was uniformly coated inside the pores.
  • Preparation Example 1 and Comparative Example 1 were analyzed using an energy dispersive spectroscopy (EDS) to analyze the components of the porous metal support coated with a porous oxide film with or without a porous oxide film.
  • EDS energy dispersive spectroscopy
  • FIG. 7 (a) and 7 (b) are images showing the shape of the porous metal support coated with a porous oxide film according to the magnification
  • FIG. 7 (c) is a graph showing the results of EDS analysis on the image of FIG. 7 (b). The graph is shown in the table of FIG.
  • Figure 8 is a graph showing the results of EDS analysis showing the components of the porous metal support with or without a porous oxide film.
  • calcium (Ca) and phosphorus (P) components may be coated, and in particular, calcium (Ca) and phosphorus (P) may be coated. It can be determined that it can be adjusted to include a bone-like component in a ratio of 1.6: 1, so that it can exhibit bone-like biocompatibility.
  • Preparation Example 1 and Comparative Example 2 were observed using a scanning electron microscope (Scanning Electron Microscopy, SEM) to analyze the shape of the porous metal support coated with a porous oxide film according to the presence or absence of ethanol in the electrolyte.
  • SEM scanning Electron Microscopy
  • FIG. 9 is an image showing the shape of a porous metal support coated with a porous oxide film not added with ethanol in an electrolyte, and shows an enlarged image of a, b, c, and d in the image.
  • FIG. 10 is an image showing the shape of a porous metal support coated with a porous oxide film in which ethanol is added to an electrolyte, and images of a magnification of an enlarged portion a are shown in a-1 and a-2.
  • Figures b-1 and b-2 show images according to magnification.
  • the coating of the porous oxide film proceeds uniformly to the inside of the pores due to the increased fluidity of the electrolyte due to the addition of ethanol in the electrolyte.
  • the cells were attached onto Preparation Example 1 and Comparative Example 2, and then the porous metal support was observed using a scanning electron microscope. The extent of cell proliferation after 1, 4, and 7 days was analyzed.
  • FIG. 11 is an image showing cells attached to a porous metal support coated with a porous oxide film according to Comparative Example 2 (FIG. 7A) and Preparation Example 1 (FIG. 7B), and FIG. 12 is a comparative example 2 and FIG. It is a graph showing the cell proliferation results of Preparation Example 1.

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Abstract

La présente invention concerne un procédé de fabrication d'un support métallique poreux recouvert d'un film d'oxyde poreux et un support métallique poreux ainsi fabriqué. La présente invention concerne plus précisément un procédé de fabrication permettant de former un film d'oxyde poreux sur la surface d'un corps métallique poreux, fabriqué selon un processus de moulage par congélation, au moyen d'un processus d'anodisation utilisant une solution d'électrolyte à laquelle un solvant alcoolique a été ajouté. Dans la présente invention, la fluidité de la solution d'électrolyte augmente donc du fait de la présence du solvant alcoolique dans la solution d'électrolyte, ce qui permet de former le film d'oxyde poreux même à l'intérieur de pores. De plus, les précipités ne s'accumulent pas à l'intérieur des pores, même après le processus d'anodisation. Une diminution de la porosité peut donc être contrôlée. En outre, le support métallique poreux présente une grande biocompatibilité, de sorte qu'une prolifération de cellules peut se produire sans difficulté. Le support métallique poreux peut donc faire office d'implant.
PCT/KR2017/014539 2017-05-31 2017-12-12 Procédé de fabrication d'un support métallique poreux recouvert d'un film d'oxyde poreux et support métallique poreux ainsi fabriqué WO2018221810A1 (fr)

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