WO2022063243A1 - 具有多孔膜的骨骼植入物及其制备方法 - Google Patents

具有多孔膜的骨骼植入物及其制备方法 Download PDF

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WO2022063243A1
WO2022063243A1 PCT/CN2021/120407 CN2021120407W WO2022063243A1 WO 2022063243 A1 WO2022063243 A1 WO 2022063243A1 CN 2021120407 W CN2021120407 W CN 2021120407W WO 2022063243 A1 WO2022063243 A1 WO 2022063243A1
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Prior art keywords
tantalum
film
porous
matrix
niobium
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PCT/CN2021/120407
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English (en)
French (fr)
Inventor
刘寓中
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Beijing Huayu Chuangxin Science & Trade Co Ltd
Beijing Huayu Chuangxin Ta-Nb Science & Technology Co Ltd
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Beijing Huayu Chuangxin Science & Trade Co Ltd
Beijing Huayu Chuangxin Ta-Nb Science & Technology Co Ltd
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Application filed by Beijing Huayu Chuangxin Science & Trade Co Ltd, Beijing Huayu Chuangxin Ta-Nb Science & Technology Co Ltd filed Critical Beijing Huayu Chuangxin Science & Trade Co Ltd
Priority to EP21871612.4A priority Critical patent/EP4218841A4/en
Priority to KR1020237013798A priority patent/KR20230110494A/ko
Priority to US18/246,635 priority patent/US20230364309A1/en
Priority to CN202180007239.XA priority patent/CN114867498B/zh
Priority to JP2023519352A priority patent/JP2023544553A/ja
Publication of WO2022063243A1 publication Critical patent/WO2022063243A1/zh
Anticipated expiration legal-status Critical
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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
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • 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
    • 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
    • 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
    • A61C8/0015—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 being a conversion layer, e.g. oxide layer
    • 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
    • A61C8/0018—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 shape
    • 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
    • A61C8/0018—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 shape
    • A61C8/0022—Self-screwing
    • 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
    • A61F2/28—Bones
    • 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
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04M—TELEPHONIC COMMUNICATION
    • H04M1/00—Substation equipment, e.g. for use by subscribers
    • H04M1/02—Constructional features of telephone sets
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

Definitions

  • the present invention relates to a skeletal implant (implant) with a porous membrane and a method for producing the skeletal implant.
  • Metal materials have excellent comprehensive mechanical properties and anti-fatigue properties, and are especially suitable for orthopaedic implant materials.
  • orthopaedic implant materials With the rapid development of materials science, orthopaedic implant materials have experienced the development process from stainless steel, cobalt-chromium alloy to titanium alloy, and achieved good results.
  • the complex internal environment of the human body can cause material corrosion and lead to the release of toxic elements, resulting in reduced biocompatibility of some metal materials.
  • the materials in the prior art such as stainless steel, cobalt-chromium alloys and titanium alloys, are dark in color, even black, which affects the aesthetic properties of the materials and limits the application range.
  • the above shortcomings have a certain negative impact on the application of metal materials as biomedical materials.
  • Porous tantalum is an ideal orthopedic implant material that has appeared in recent years. It is a refractory metal with a melting point of nearly 3000 °C, dark gray in appearance and smooth surface. Compared with existing medical metal materials, tantalum mainly has Two advantages: (1) Tantalum has better corrosion resistance; (2) Tantalum has better biocompatibility, and porous tantalum has a lower elastic modulus. However, due to its dark grey color, tantalum can affect the aesthetic appearance when used especially in dental implants.
  • porous tantalum is an ideal orthopedic implant material
  • the elastic modulus of orthopedic materials made of tantalum recorded in the literature is between cortical bone and cancellous bone.
  • the elastic modulus of porous tantalum is closer to that of human cancellous bone.
  • the elastic modulus is significantly lower than the elastic modulus of cortical bone, and the bone tissue bearing human load is mainly cortical bone. From the effect of animal experiments and clinical applications, the elastic modulus of bone implants should be closer to the human cortex Bone, too high is easy to produce stress shielding, and too low is also unfavorable for force transmission.
  • the present invention can provide elastic modulus from low to high for selection under different coating conditions.
  • the elastic modulus of the dental implant has an impact on the stress distribution of the bone interface.
  • the higher the elastic modulus of the dental implant the smaller the intra-bony stress around the neck. , and the greater the intraosseous stress at the root end; the lower the elastic modulus of the dental implant, the greater the relative displacement movement between the dental implant and the bone interface; when the elastic modulus of the dental implant is similar to cortical bone and cancellous bone, Biomechanical compatibility is good.
  • the dental implant is made of titanium alloy or other materials into a cylinder or a cone, and then a thread is formed on the outer surface, the purpose is to enable the human bone to grow into the thread and combine the implant with the human bone to strengthen the implant. Compatibility and firmness with the human body, but the depth of the threaded rib is limited, too deep will affect the strength of the implant.
  • the present invention provides a bone implant or composite comprising:
  • the matrix is selected from a tantalum matrix, a niobium matrix, a tantalum-niobium alloy matrix, and a titanium matrix, and
  • porous film is selected from porous lithium tantalate film, porous lithium niobate film, porous lithium tantalate and lithium niobate mixture film and porous titanium oxide film.
  • a skeletal implant or composite comprising:
  • a tantalum matrix, a niobium matrix, a tantalum-niobium alloy matrix, or a titanium matrix A tantalum matrix, a niobium matrix, a tantalum-niobium alloy matrix, or a titanium matrix;
  • Porous titanium oxide film on a titanium substrate Porous titanium oxide film on a titanium substrate.
  • the present invention also provides a method for preparing the bone implant or composite, comprising:
  • the matrix is selected from a tantalum matrix, a niobium matrix, a tantalum-niobium alloy matrix, and a titanium matrix, and
  • porous film is selected from porous lithium tantalate film, porous lithium niobate film, porous lithium tantalate and lithium niobate mixture film and porous titanium oxide film.
  • the present invention provides a method for preparing the bone implant or composite, comprising:
  • the lithium tantalate film contains tantalum oxide
  • lithium niobate film contains niobium oxide
  • the mixture film contains tantalum oxide and niobium oxide.
  • the invention also relates to the use of the composite in medical materials such as dental implants.
  • the bone implant of the present invention has one or more of the following beneficial effects:
  • the bone implant of the present invention has one or more of the following beneficial effects: (1)
  • the provided metal compound film is porous, which is conducive to guiding Human bone enters the implant, enhancing the compatibility and firmness of the implant. At the same time, the compound film layer seems to be close to the ceramic body, which has the effect of insulation and heat insulation, and reduces the stimulation of the rapid heat to the human body.
  • the film layer is not formed by ion deposition in the solution, but the metal of the implant participates in the electrochemical reaction to form, and has a performance transition layer, the film layer is firmly combined with the matrix, and the bone implant has excellent resistance to Corrosion performance;
  • the elastic modulus of the bone implant can be adjusted according to the process conditions, so that it has higher biocompatibility with the elastic modulus of human or animal bones (such as alveolar bone);
  • the white color of the bone implant is close to the color of the bone itself, and has an aesthetic appearance;
  • the bone implant has excellent antibacterial properties due to the film layer after coating treatment at high temperature (above 400°C). sex.
  • Figures 1a-1c show SEM images of pure tantalum flakes without porous lithium tantalate films.
  • FIGS. 2a-2d show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • 3a-3c show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 4a-4c show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 5a-5c show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • 6a-6c show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • FIG. 7a-7d show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • FIG 9 shows a photograph of the appearance of a tantalum sheet coated with a porous lithium tantalate film according to an embodiment of the present invention.
  • FIG. 10 shows a photograph of the appearance of a tantalum sheet coated with a porous lithium tantalate film according to an embodiment of the present invention.
  • FIG. 11 shows a photograph of the appearance of a tantalum sheet coated with a porous lithium tantalate film according to an embodiment of the present invention.
  • FIG. 12 shows a photograph of the appearance of a tantalum sheet coated with a porous lithium tantalate film according to an embodiment of the present invention.
  • FIG. 13 shows a photograph of the appearance of a tantalum sheet and a tantalum dental implant coated with a porous lithium tantalate film according to an embodiment of the present invention.
  • FIG. 14 shows a photograph of the appearance of a tantalum sheet and a tantalum dental implant coated with a porous lithium tantalate film according to an embodiment of the present invention.
  • Figure 14a shows a photograph of the appearance of a porous tantalum dental implant coated with a porous lithium tantalate membrane according to an embodiment of the present invention.
  • Figures 15a-15g show photographs of the appearance of a tantalum sheet coated with a porous lithium tantalate film according to one embodiment of the present invention.
  • Figures 16a-16b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • 17a-17b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 18a-18b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 19a-19b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • 20a-20b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 21a-21b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 22a-22b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 23a-23i show photographs of the appearance of a tantalum sheet coated with a porous lithium tantalate film according to one embodiment of the present invention.
  • Figures 24a-24b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 25a-25b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 26a-26b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • 27a-27b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 28a-28b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 29a-29b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 30a-30b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figures 31a-31b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • 32a-32b show SEM electron micrographs of tantalum flakes coated with porous lithium tantalate films according to one embodiment of the present invention.
  • Figure 33a shows a photograph of the appearance of a tantalum cranial bone coated with a porous lithium tantalate film according to one embodiment of the present invention.
  • Figure 33b shows a schematic cross-sectional view of a tantalum cranial bone coated with a porous lithium tantalate film according to one embodiment of the present invention.
  • Figure 33c shows a schematic top view of a tantalum cranial bone coated with a porous lithium tantalate film according to one embodiment of the present invention.
  • FIG. 34 shows a photograph of the appearance of a tantalum-niobium alloy sheet coated with a film of a mixture of porous lithium tantalate and lithium niobate according to one embodiment of the present invention.
  • Figures 35a-35b show SEM electron micrographs of tantalum-niobium alloy sheets coated with a film of a mixture of porous lithium tantalate and lithium niobate according to one embodiment of the present invention.
  • FIG. 36 shows a photograph of the appearance of a tantalum-niobium alloy sheet coated with a film of a mixture of porous lithium tantalate and lithium niobate according to one embodiment of the present invention.
  • Figures 37a-37b show SEM electron micrographs of tantalum-niobium alloy sheets coated with a film of a mixture of porous lithium tantalate and lithium niobate according to one embodiment of the present invention.
  • FIG. 38 shows a photograph of the appearance of a niobium sheet coated with a porous lithium niobate film according to an embodiment of the present invention.
  • Figures 39a-39b show SEM electron micrographs of niobium flakes coated with porous lithium niobate films according to one embodiment of the present invention.
  • FIG 40 shows a photograph of the appearance of a niobium sheet coated with a porous lithium niobate film according to an embodiment of the present invention.
  • FIG. 41 shows a photograph of the appearance of a niobium cranial bone coated with a porous lithium niobate film according to an embodiment of the present invention.
  • Figures 42a-42b show SEM electron micrographs of niobium flakes coated with porous lithium niobate films according to one embodiment of the present invention.
  • FIG 43 shows a photograph of the appearance of a niobium sheet coated with a porous lithium niobate film according to an embodiment of the present invention.
  • Figures 44a-44b show SEM images of niobium flakes coated with porous lithium niobate films according to one embodiment of the present invention
  • the present invention provides a bone implant or tantalum composite comprising:
  • the present invention provides a bone implant or niobium composite comprising:
  • the present invention provides a bone implant or tantalum-niobium alloy composite comprising:
  • the present invention provides a bone implant or titanium composite comprising:
  • the bone implant or tantalum composite comprises: (1) a tantalum matrix; and (2) a porous lithium tantalate film on at least a portion of the surface of the tantalum matrix, wherein the porous lithium tantalate
  • the membrane has a pore size of 0.1-1 ⁇ m.
  • the length can be up to about 40 ⁇ m.
  • the bone implant or niobium composite comprises: (1) a niobium matrix; and (2) a porous lithium niobate film on at least a portion of the surface of the niobium matrix, wherein the porous lithium niobate
  • the membrane has a pore size of 0.1-1 ⁇ m. For crack-like pores, the length can be up to about 40 ⁇ m.
  • the bone implant or tantalum-niobium alloy composite comprises: (1) a tantalum-niobium alloy matrix; and (2) porous lithium tantalate and niobate on at least a portion of the surface of the tantalum-niobium alloy matrix A lithium mixture membrane, wherein the mixture membrane has a pore size of 0.1-1 ⁇ m. For crack-like pores, the length can be up to about 40 ⁇ m.
  • the bone implant or titanium composite comprises: (1) a titanium matrix; and (2) a porous titanium oxide film on at least a portion of the surface of the titanium matrix, wherein the porous titanium oxide
  • the membrane has a pore size of 0.1-1 ⁇ m.
  • the length can be up to about 40 ⁇ m.
  • the holes are not limited to circular holes, but may be holes with irregular shapes, such as crack-like holes.
  • the bone implant or composite has a porosity of more than 30%, eg, a porosity of 50-80%, or a porosity of 60-90%.
  • bone implants In the context of the present invention, bone implants, composites and composite materials can be used interchangeably.
  • Tantalum substrates suitable for the present invention include pure tantalum substrates and tantalum alloy substrates, wherein the tantalum alloy substrate is preferably a tantalum-niobium alloy substrate.
  • the bone implant eg a dental implant, has an elastic modulus of at least 150 GPa.
  • the bone implant eg, a dental implant
  • the bone implant such as a dental implant, has an elastic modulus of 150-200 GPa.
  • the bone implant eg, a dental implant
  • the skeletal implant such as a cranial (cranial) implant, has an elastic modulus of 10-160 GPa, as measured by nanoindentation.
  • the skeletal implant eg, a cranial (cranial) implant
  • the skeletal implant such as a cranial (cranial) implant, has an elastic modulus of 30-140 GPa, as measured by nanoindentation.
  • the skeletal implant eg, a cranial (cranial) implant
  • the skeletal implant eg, a cranial (cranial) implant
  • the skeletal implant eg, a cranial (cranial) implant
  • the skeletal implant eg, a cranial (cranial) implant
  • the skeletal implant such as a cranium (cranium) implant, has an elastic modulus of 80-90 GPa, as measured by nanoindentation.
  • the entire surface of the tantalum substrate is covered with a porous lithium tantalate film.
  • the entire surface of the niobium matrix is covered with a porous lithium niobate film.
  • the entire surface of the tantalum-niobium alloy substrate is covered with a mixture film of porous lithium tantalate and lithium niobate.
  • the entire surface of the titanium substrate is covered with a porous titanium oxide film.
  • the elastic modulus of dental implants has an impact on the stress distribution of the bone interface.
  • the higher the elastic modulus of dental implants the smaller the intra-osseous stress around the neck, while the root-end intraosseous stress is smaller.
  • the larger the dental implant elastic modulus the greater the relative displacement movement between the dental implant and the bone interface; when the elastic modulus of the dental implant is similar to that of cortical bone and cancellous bone, the biomechanical compatibility is poor.
  • the suitable elastic modulus of dental implants is above 70GPa.
  • the skeletal implants of the present invention, including dental implants have an elastic modulus of at least 150 GPa, so the dental implants of the present invention have a very suitable elastic modulus and have excellent biomechanical compatibility.
  • the skeletal implant comprises skeletal prostheses such as cranium and dental implants.
  • the cranium is porous, such as the tantalum cranium shown in Figure 33a and the niobium cranium shown in Figure 41 .
  • the dental implant includes a prosthetic abutment portion, a main body portion, and a neck portion connecting the prosthetic abutment portion and the main body portion.
  • the preparation methods of dental implants are known to those skilled in the art, for example, reference can be made to CN109758245A, CN109965996A and CN110610046A.
  • the dental implant comprises a denture abutment part, a main body part and a neck connecting the denture abutment part and the main body part, wherein the outer surface of the main body part is provided with External thread in contact with alveolar bone.
  • the bone implant has a color similar to bone.
  • the bone implant is white, especially for prosthetic abutments.
  • the matrix is porous.
  • the porous matrix has excellent mechanical properties and histocompatibility. Reconstruction of human tissue, bone grafting, and replacement can all use porous materials to implant bone defects. After being implanted into the human body as a scaffold material, due to its excellent tissue compatibility, the porous material does not need to be degraded in the human body, so it does not need to be removed by a second operation. Porous metal has firm texture, wear resistance and fatigue resistance better than cancellous bone, ceramic products and freeze-dried bone chips, and can provide sufficient physiological load.
  • Tantalum, niobium, tantalum-niobium alloy and titanium are refractory metals, and the above porous metals are usually prepared by the method of refractory metals.
  • porous tantalum can be prepared by powder sintering using known methods, and porous tantalum can also be prepared by vapor deposition method, and other methods of preparing porous tantalum in the art can also be used.
  • the tantalum used is dense.
  • porous tantalum is used as a medical orthopedic material, and there is no mention of using dense tantalum metal as a medical orthopedic material.
  • the elastic modulus of dental implants has an impact on the stress distribution of the bone interface. Generally, the higher the elastic modulus of dental implants, the smaller the internal stress around the neck.
  • One embodiment of the present invention is to coat a porous tantalum dental implant with a porous lithium tantalate film and thereby improve the mechanical properties of the dental implant, such as tensile strength and elastic modulus.
  • One embodiment of the present invention is to coat a porous niobium dental implant with a porous lithium niobate film, and thereby improve the mechanical properties of the dental implant, such as tensile strength and elastic modulus.
  • One embodiment of the present invention is to coat a porous tantalum niobium dental implant with a film of a mixture of porous lithium tantalate and lithium niobate, and thereby improve the mechanical properties of the dental implant, such as tensile strength and elastic modulus.
  • Another embodiment of the present invention is to coat a layer of porous lithium tantalate film on the dense metal tantalum, which not only makes its tensile strength and elastic modulus larger, but also better meets the tensile strength and elasticity of dental implants Modulus requirements, and because of the porous lithium tantalate film on the surface of the tantalum matrix, the dental implant can be better compatible with human biological tissue, so that human biological tissue can be combined with the tantalum matrix through the porous lithium tantalate film , so that the tantalum material is fully integrated and integrated with human tissues such as alveolar bone.
  • the non-leakage part of a bone implant such as a dental implant may not be plated with a lithium tantalate film layer, and only pure tantalum material is used. Lithium tantalate coating is preferred for denture abutments and necks to increase the aesthetic appearance.
  • the preparation method of dense tantalum material is known to those skilled in the art, for example, it can be obtained by casting, rolling and other methods.
  • a method of preparing the bone implant comprises: (1) providing a tantalum substrate; and (2) forming a porous lithium tantalate film on the tantalum substrate.
  • a method of preparing the bone implant comprises: (1) providing a niobium matrix; and (2) forming a porous lithium niobate film on the niobium matrix.
  • a method of making the bone implant comprises: (1) providing a tantalum-niobium alloy matrix; and (2) forming a layer of porous lithium tantalate and lithium niobate on the tantalum-niobium alloy matrix mixture film.
  • the method of preparing the bone implant comprises: (1) providing a titanium substrate; and (2) forming a porous titanium oxide film on the titanium substrate.
  • the matrix has the desired shape for a bone implant, such as the shape of a dental implant and a cranial bone.
  • a porous lithium tantalate film is plated on a tantalum substrate having the desired shape of the bone implant.
  • a porous lithium tantalate film is plated on the tantalum substrate having the desired shape of the bone implant, and the unwanted pores on the bone implant are removed by cutting or grinding.
  • the lithium tantalate film was removed, leaving the porous lithium tantalate film only on part of the surface of the bone implant.
  • a plurality of manufactured assemblies with qualified external dimensions but unprocessed inner holes are first plated with lithium tantalate film, and then the inner holes are processed, so that the inner holes can be kept uncoated.
  • a porous lithium tantalate film is coated on part of the surface of the tantalum substrate having the desired bone implant shape.
  • the porous membrane has a thickness of 1-20 ⁇ m, preferably 2-10 ⁇ m, more preferably 3-5 ⁇ m.
  • step (2) the porous lithium tantalate film is formed by a molten salt electrochemical method.
  • the tantalum substrate in step (2), is placed in an oxygen-containing inorganic lithium salt (such as LiNO 3 ) or a mixed melt of an oxygen-containing inorganic lithium salt and lithium hydroxide at 250° C. to 650° C. , or in the mixed melt of salt and lithium hydroxide or the mixed melt of lithium salt and oxygen-containing salt, apply an anode voltage of 1 to 66V, constant pressure for 0.01 to 200 hours, and the boost current density is 1 to 1000 milliliters A/ cm2 to form a porous lithium tantalate film.
  • an oxygen-containing inorganic lithium salt such as LiNO 3
  • a mixed melt of an oxygen-containing inorganic lithium salt and lithium hydroxide at 250° C. to 650° C.
  • the boost current density is 1 to 1000 milliliters A/ cm2 to form a porous lithium tantalate film.
  • the tantalum substrate in step (2), is placed in an oxygen-containing inorganic lithium salt (such as LiNO 3 ) or a mixed melt of an oxygen-containing inorganic lithium salt and lithium hydroxide at 440° C. to 600° C. , or in the mixed melt of salt and lithium hydroxide or the mixed melt of lithium salt and oxygen-containing salt, apply an anode voltage of 10 to 30 V, constant pressure for 5 minutes to 10 hours, and the boost current density is 1 to 1000 mA/ cm2 to form a porous lithium tantalate film.
  • an oxygen-containing inorganic lithium salt such as LiNO 3
  • a mixed melt of an oxygen-containing inorganic lithium salt and lithium hydroxide at 440° C. to 600° C.
  • the tantalum substrate in step (2), is placed in an oxygen-containing inorganic lithium salt (such as LiNO 3 ) or a mixed melt of an oxygen-containing inorganic lithium salt and lithium hydroxide at 570° C. to 598° C. , or in the mixed melt of salt and lithium hydroxide or the mixed melt of lithium salt and oxygen-containing salt, apply an anode voltage of 10 to 20 V, constant pressure for 8 to 30 minutes, and the boost current density is 5 to 20 mA/ cm2 to form a porous lithium tantalate film.
  • an oxygen-containing inorganic lithium salt such as LiNO 3
  • a mixed melt of an oxygen-containing inorganic lithium salt and lithium hydroxide at 570° C. to 598° C.
  • an ultrasonic generator may be provided in the mixed melt or the mixed melt in step (2).
  • the molten salt electrochemical method is a molten lithium salt electrochemical method.
  • step (2) the step of anodizing the tantalum substrate may be performed.
  • a Ta 2 O 5 film such as an amorphous Ta 2 O 5 film, is formed on the tantalum substrate.
  • Non-porous ones are suitable for use on tantalum capacitors.
  • the Ta 2 O 5 film can also be porous, which is more advantageous for the fabrication of porous lithium tantalate films.
  • the implant is placed in concentrated sulfuric acid at 190°C to 245°C (ie, a porous Ta 2 O 5 film is formed in 98% concentrated sulfuric acid).
  • an amorphous Ta 2 O 5 film is formed on the tantalum substrate by anodizing in the anodizing step.
  • the tantalum substrate is placed in an oxygen-containing electrolyte solution at room temperature to 380° C., preferably at room temperature to 300° C., and an anode voltage of 3 to 800 V is applied for a constant voltage of 0.01 to 2 hours, wherein the pressure is increased.
  • the current density is 1-200 mA/cm 2 to form an amorphous Ta 2 O 5 film.
  • the applied voltage should be low, and vice versa. For example, for a 0.01% H3PO4 solution at room temperature, a voltage of up to 600V can be applied. Regardless of the solution, the applied voltage should be below the flash voltage of the solution.
  • the oxygen-containing electrolyte solution may be an aqueous solution, a non-aqueous solution, or a mixture of an aqueous electrolyte and an organic compound.
  • the aqueous oxygen-containing electrolyte can be, for example, an aqueous solution of an acid, a base, or a salt.
  • the solution temperature is from room temperature (about 25° C.) to 95° C.
  • the anode voltage is from 5 to 600 V
  • the constant voltage time is within 60 to 90 minutes. If the temperature is too high, the water volatilization rate is too fast. When the solution temperature is higher, the anode voltage should be lower.
  • the non-aqueous oxygen-containing electrolyte can be anhydrous concentrated sulfuric acid or molten salt or a mixture of molten salt and alkalis, such as potassium nitrate, sodium nitrate, lithium nitrate, or their mixtures with alkalis such as lithium, sodium, potassium, etc.
  • alkalis such as potassium nitrate, sodium nitrate, lithium nitrate, or their mixtures with alkalis such as lithium, sodium, potassium, etc.
  • Another class of oxygen-containing electrolyte solutions may be mixtures of aqueous electrolytes with organic compounds such as ethanol, ethylene glycol, n-butanol, and the like.
  • the temperature of the aqueous solution should be below 95°C, otherwise the volatilization of water will be rapid and difficult to control.
  • the preparation method of the present invention includes pre-nitriding or carburizing the tantalum substrate.
  • nitriding or carburizing may not be performed.
  • nitriding or carburizing can be used.
  • a method of preparing a dental implant comprising:
  • Electrochemical coating treatment is carried out in the molten lithium-containing salt.
  • tantalum, niobium, and tantalum-niobium alloy implants can produce white lithium tantalate film, lithium niobate film, or a mixture film of lithium tantalate and lithium niobate, and a porous titanium oxide film can be formed on the surface of titanium implants.
  • the present invention proposes to replace the threaded rib with a suitable hole, which can penetrate deep into the inner wall of the implant, that is, perforation, without affecting the strength of the implant. compatibility and robustness.
  • the outer hole can also not be perforated, and a certain thickness can be reserved so that the inner hole of the implant can be threaded to facilitate the fixation of the connector or the abutment.
  • a method of preparing a dental implant comprising:
  • punch holes according to the design requirements by the method of punching the spinneret plate or by laser punching;
  • the extra material on the surface should be removed by polishing. For example, if the hole is punched with a laser, there will be no extra material around the hole, and polishing is easier;
  • a method of perforating an implant comprising:
  • the perforated entrance that is, the hole on the side that is to be in contact with the human bone.
  • the diameter of the hole is controlled at 0.08-0.30mm, preferably 0.16-0.22mm;
  • the outlet that is, the end hole where the hole is protected by the hole in the implanted body.
  • the diameter is controlled at 0.28-0.06, preferably 0.22-0.13 mm.
  • the hole shape can be a tapered hole or a straight hole. Tapered holes may be more advantageous for guiding human bone into the implant.
  • a design of a non-perforated implant is provided, which ensures that the inner wall of the central hole of the dental implant needs to be processed in order to install the abutment connector. mm, otherwise it is not perforated so that the inner hole can be threaded.
  • niobium and tantalum-niobium alloy substrates apply equally to the embodiments concerning tantalum substrates.
  • a bone implant comprising:
  • the matrix is selected from tantalum matrix, niobium matrix, tantalum-niobium alloy matrix and titanium matrix, preferably said matrix is selected from tantalum matrix, niobium matrix and tantalum-niobium alloy matrix, and
  • the porous film is selected from porous lithium tantalate film, porous lithium niobate film, mixture film of porous lithium tantalate and lithium niobate and porous titanium oxide film, preferably the porous film is selected from porous lithium tantalate film, Porous lithium niobate films and mixture films of porous lithium tantalate and lithium niobate.
  • the bone implant of embodiment 1, comprising:
  • a tantalum matrix, a niobium matrix, a tantalum-niobium alloy matrix, or a titanium matrix A tantalum matrix, a niobium matrix, a tantalum-niobium alloy matrix, or a titanium matrix;
  • Porous titanium oxide film on a titanium substrate Porous titanium oxide film on a titanium substrate.
  • porous lithium tantalate film, porous lithium niobate film, mixture film of porous lithium tantalate and lithium niobate, or porous titanium oxide film has 0.1 -1 ⁇ m pore size.
  • porous lithium tantalate film, porous lithium niobate film, mixture film of porous lithium tantalate and lithium niobate, or porous titanium oxide film has 1 -20 ⁇ m, preferably 2-10 ⁇ m, more preferably 3-5 ⁇ m in thickness.
  • skeletal implant of embodiment 1 or 2 wherein the skeletal implant comprises a skeletal prosthesis, a dental implant, and a cranium.
  • the dental implant comprises a prosthetic abutment portion, a main body portion, and a neck portion connecting the prosthetic abutment portion and the main body portion.
  • the matrix is selected from tantalum matrix, niobium matrix, tantalum-niobium alloy matrix and titanium matrix, preferably said matrix is selected from tantalum matrix, niobium matrix and tantalum-niobium alloy matrix, and
  • the porous film is selected from porous lithium tantalate film, porous lithium niobate film, mixture film of porous lithium tantalate and lithium niobate and porous titanium oxide film, preferably the porous film is selected from porous lithium tantalate film, Porous lithium niobate films and mixture films of porous lithium tantalate and lithium niobate.
  • the lithium tantalate film contains tantalum oxide
  • lithium niobate film contains niobium oxide
  • the mixture film contains tantalum oxide and niobium oxide.
  • step (2) the porous membrane is formed by a molten salt electrochemical method.
  • the tantalum substrate is placed in an oxygen-containing electrolyte solution at room temperature to 380°C, preferably room temperature to 300°C, and applied for 3 Anode voltage to 800V, constant voltage for 0.01 to 2 hours, with a boost current density of 1-200 mA/cm 2 , to form an amorphous Ta 2 O 5 film.
  • the niobium substrate is placed in an oxygen-containing electrolyte solution at room temperature to 380°C, preferably room temperature to 300°C, applying 3 Anode voltage to 800V, constant voltage for 0.01 to 2 hours, with a boost current density of 1-200 mA/cm 2 , to form an amorphous Nb 2 O 5 film.
  • step (2) the tantalum matrix, niobium matrix or tantalum-niobium alloy matrix is placed in an oxygen-containing inorganic lithium salt or oxygen-containing inorganic lithium salt and hydrogen at 440°C to 600°C
  • an anode voltage of 10 to 30 V is applied, and the pressure is kept constant for 5 minutes to 10 hours.
  • the current density is 5-20 mA/cm 2 to form a film layer containing the lithium-containing compound.
  • step (2) the tantalum matrix, niobium matrix or tantalum-niobium alloy matrix is placed in an oxygen-containing inorganic lithium salt or oxygen-containing inorganic lithium salt and hydrogen at 570°C to 598°C
  • an anode voltage of 10 to 20 V is applied, and the pressure is kept constant for 8 to 30 minutes, wherein the pressure is increased.
  • the current density is 5-20 mA/cm 2 to form a film layer containing the lithium-containing compound.
  • step (c) a sonotrode is disposed in the mixed melt or the mixed melt.
  • Step 1 Process tantalum metal into dense tantalum flakes.
  • Step 2 For the tantalum sheet, a 10V anode voltage is applied in a molten lithium nitrate solution at 570° C., and a constant voltage reaction is performed for 30 minutes to form a porous lithium tantalate film layer on the tantalum sheet.
  • Figures 2a-2d show SEM electron micrographs of the sample of Example 1.
  • FIG. 9 shows a photograph of the appearance of the sample of Example 1.
  • Step 1 Process tantalum metal into dense tantalum flakes.
  • Step 2 For the tantalum sheet, a 10V anode voltage was applied in a molten lithium nitrate solution at 580° C., and a constant voltage reaction was performed for 25 minutes to form a porous lithium tantalate film layer on the tantalum sheet.
  • Figures 3a-3c show SEM electron micrographs of the Example 2 sample.
  • Figure 10 shows a photograph of the appearance of the sample of Example 2.
  • Step 1 Process tantalum metal into dense tantalum flakes.
  • Step 2 For the tantalum sheet, a 10V anode voltage is applied in a molten lithium nitrate solution at 598° C., and a constant voltage reaction is performed for 10 minutes to form a porous lithium tantalate film layer on the tantalum sheet.
  • Figures 4a-4c show SEM electron micrographs of the Example 3 sample.
  • Figure 11 shows a photograph of the appearance of the Example 3 sample.
  • Step 1 Process tantalum metal into dense tantalum flakes.
  • Step 3 For the tantalum sheet obtained in step (2), a 10V anode voltage was applied in a molten lithium nitrate solution at 598° C., and a constant voltage reaction was performed for 8 minutes to form a porous lithium tantalate film layer on the tantalum sheet.
  • Figures 5a-5c show SEM electron micrographs of the Example 4 sample.
  • Figure 12 shows a photograph of the appearance of the Example 4 sample.
  • Step 1 Process tantalum metal into dense tantalum flakes.
  • Step 3 For the tantalum sheet obtained in step (2), a 28V anode voltage was applied in a molten lithium nitrate solution at 482° C., and a constant voltage reaction was performed for 6.5 hours to form a porous lithium tantalate film layer on the tantalum sheet.
  • Figures 6a-6c show SEM electron micrographs of the Example 5 sample.
  • Step 1 Process tantalum metal into dense tantalum flakes.
  • Step 2 For the tantalum sheet, a 33V anode voltage was applied in a molten lithium nitrate solution at 440° C., and a constant voltage reaction was performed for 12 hours to form a porous lithium tantalate film layer on the tantalum sheet.
  • Figures 7a-7d show SEM electron micrographs of the Example 6 sample.
  • Step 1 Process tantalum metal into dense tantalum flakes.
  • Step 3 For the tantalum sheet obtained in step (2), a 10V anode voltage was applied in a molten lithium nitrate solution at 598° C., and a constant voltage reaction was performed for 10 minutes to form a porous lithium tantalate film layer on the tantalum sheet.
  • Figures 8a-8c show SEM electron micrographs of the Example 7 sample.
  • Step 1 The metal tantalum is processed into dense tantalum sheets and tantalum dental implants, respectively.
  • Step 2 Apply 10V in molten lithium nitrate:potassium nitrate (weight ratio 1:1) solution at 580°C for the tantalum sheet and the tantalum dental implant (threaded tantalum rod 6mm in diameter with holes 2mm in diameter), respectively Anode voltage, constant voltage reaction for 30 minutes, forming porous lithium tantalate film layer on tantalum sheet and tantalum dental implant.
  • Figure 13 shows a photograph of the appearance of the Example 8 sample.
  • Step 1 The metal tantalum was processed into dense tantalum sheets and tantalum dental implants (threaded tantalum rods with a diameter of 6 mm with holes of 2 mm in diameter), respectively.
  • Step 2 For the tantalum sheet and the tantalum dental implant, respectively, firstly, an anode voltage of 60V was applied in a 0.05 wt% H 3 PO 4 aqueous solution at 90° C. for 1.5 hours, and then cleaned.
  • Step 3 For the tantalum sheet and tantalum dental implant obtained in step (2), apply 10V anode voltage in molten lithium nitrate:potassium nitrate (weight ratio 1:1) at 598°C, and react under constant pressure for 8 minutes. A porous lithium tantalate film layer is formed on the sheet and tantalum dental implants.
  • Figure 14 shows a photograph of the appearance of the Example 9 sample.
  • Figure 14a shows a photograph of the appearance of the sample of Example 9a.
  • the metal tantalum is processed into a dense tantalum sheet without the step of forming a porous lithium tantalate film layer on the tantalum sheet.
  • Figures 1a-1c show SEM electron micrographs of the sample of Comparative Example 1.
  • the tantalum sheet coated with the porous lithium tantalate film of the present invention has a larger pore size about Open pores in the range of 1-30 microns, and rough surface, these pores and uneven rough surface are conducive to cell adhesion and tissue chimera, and can enhance the connection strength of bone implants such as dental implants and bone tissue,
  • the bone implant can be better combined with human biological tissue through the porous lithium tantalate film and the tantalum matrix, so that the tantalum matrix can be fully combined with human tissue such as alveolar bone and integrated into one.
  • the tantalum sheet without the porous lithium tantalate film has relatively few pores, and the surface is smooth and flat, which is not conducive to the close bonding of the tantalum matrix with human tissues such as alveolar bone.
  • the pores of the tantalum sheet coated with the porous lithium tantalate film have a size in the range of about 10 nanometers to 1 micrometer in the smallest dimension, which is much smaller than the size of bacteria (usually greater than 5 micrometers). ), therefore, the bone implant coated with the porous lithium tantalate film of the present invention can well inhibit the entry of bacteria and play a certain antibacterial effect.
  • FIGs 9-12 show that the tantalum sheet coated with the porous lithium tantalate membrane appears white, has an aesthetic appearance, and is particularly suitable for making dental implants.
  • a lithium tantalate film is formed in a molten lithium nitrate: potassium nitrate (weight ratio 1:1) solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 15a shows a photograph of the appearance of the Example 10 sample.
  • Figures 16a-16b show SEM electron micrographs of the Example 10 sample.
  • Lithium tantalate film layers were formed in molten lithium nitrate: potassium nitrate (weight ratio 1:1) solution on tantalum sheets and tantalum brain bases respectively, and the process conditions for forming lithium tantalate film layers are shown in Table 3.
  • Figure 15b (tantalum sheet) and Figure 33a (brain bone) show the appearance photos of the sample of Example 11.
  • Figures 17a-17b show SEM electron micrographs of the Example 11 sample.
  • a lithium tantalate film is formed in a molten lithium nitrate: potassium nitrate (weight ratio 1:1) solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 15c shows a photograph of the appearance of the Example 12 sample.
  • Figures 18a-18b show SEM electron micrographs of the Example 12 sample.
  • Figure 15d shows a photograph of the appearance of the Example 13 sample.
  • Figures 19a-19b show SEM electron micrographs of the Example 13 sample.
  • Figure 15e shows a photograph of the appearance of the Example 14 sample.
  • Figures 20a-20b show SEM electron micrographs of the Example 14 sample.
  • Figure 15f shows a photograph of the appearance of the Example 15 sample.
  • Figures 21a-22b show SEM electron micrographs of the Example 15 sample.
  • a lithium tantalate film layer is formed in a molten lithium nitrate: potassium nitrate (weight ratio 1:1) solution, and the process conditions are shown in Table 3.
  • Figure 15g shows a photograph of the appearance of the Example 16 sample.
  • Figures 22a-22b show SEM electron micrographs of the Example 16 sample.
  • the temperature is: 220 ° C, apply 150V anode voltage, constant pressure for 30 minutes, then wash and dry; then in molten lithium nitrate: potassium nitrate (weight ratio 1: 1)
  • the lithium tantalate film is formed in the solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 23a shows a photograph of the appearance of the Example 17 sample.
  • Figures 24a-24b show SEM electron micrographs of the Example 17 sample.
  • the temperature is: 220 ° C, apply 150V anode voltage, constant pressure for 30 minutes, then wash and dry; then in molten lithium nitrate: potassium nitrate (weight ratio 1: 1)
  • the lithium tantalate film is formed in the solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 23b shows a photograph of the appearance of the Example 18 sample.
  • Figures 25a-25b show SEM electron micrographs of the Example 18 sample.
  • the temperature is: 220 ° C, apply 150V anode voltage, constant pressure for 30 minutes, then wash and dry; then in molten lithium nitrate: potassium nitrate (weight ratio 1: 1)
  • the lithium tantalate film is formed in the solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 23c shows a photograph of the appearance of the Example 19 sample.
  • Figures 26a-26b show SEM electron micrographs of the Example 19 sample.
  • the temperature is: 220 ° C, apply 82V anode voltage, constant pressure 30 minutes, then wash and dry; Then in molten lithium nitrate: potassium nitrate (weight ratio 1: 1)
  • the lithium tantalate film is formed in the solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 23d shows a photograph of the appearance of the Example 20 sample.
  • Figures 27a-27b show SEM electron micrographs of the Example 20 sample.
  • the temperature is: 210° C., apply 82V anode voltage, constant voltage for 30 minutes, then wash and dry; then in molten lithium nitrate: potassium nitrate (weight ratio 1: 1)
  • the lithium tantalate film is formed in the solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 23e shows a photograph of the appearance of the Example 21 sample.
  • Figures 28a-28b show SEM electron micrographs of the Example 21 sample.
  • the temperature is: 210° C., apply 82V anode voltage, constant voltage for 30 minutes, then wash and dry; then in molten lithium nitrate: potassium nitrate (weight ratio 1: 1)
  • the lithium tantalate film is formed in the solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 23f shows a photograph of the appearance of the Example 22 sample.
  • Figures 29a-29b show SEM electron micrographs of the Example 22 sample.
  • the temperature is: 210° C., apply 82V anode voltage, constant voltage for 30 minutes, then wash and dry; then in molten lithium nitrate: potassium nitrate (weight ratio 1: 1)
  • the lithium tantalate film is formed in the solution, and the process conditions for forming the lithium tantalate film are shown in Table 3.
  • Figure 23g shows a photograph of the appearance of the Example 23 sample.
  • Figures 30a-30b show SEM electron micrographs of the Example 23 sample.
  • Figure 23h shows a photograph of the appearance of the Example 24 sample.
  • Figures 31a-31b show SEM electron micrographs of the Example 24 sample.
  • Figure 23i shows a photograph of the appearance of the Example 25 sample.
  • Figures 32a-32b show SEM electron micrographs of the Example 25 sample.
  • the tantalum sheet coated with the porous lithium tantalate film of the present invention has a larger pore size about Openings in the range of 0.1-30 microns, even honeycomb-like openings, and rough surfaces, these pores and uneven rough surfaces are conducive to cell adhesion and tissue chimeric, and can strengthen bone implants such as dental implants
  • the strength of the connection between the body and the bone tissue, such as the cranium (cranium) enables the bone implant to better combine with the human biological tissue and the tantalum matrix through the porous lithium tantalate membrane, so that the tantalum matrix can fully combine with the human tissue more closely and integrated.
  • the tantalum sheet without the porous lithium tantalate film has relatively few pores and a smooth and flat surface, which is not conducive to the close integration of the tantalum matrix with human tissues such as alveolar bone and cranium
  • the titanium sheet with a titanium oxide film layer prepared in Example 25 showed a suitable elastic modulus, and its SEM photograph showed that the film layer had a fibrous porous interactive network (see Figure 32b), which was beneficial to cell adhesion and organization. It can enhance the connection strength of bone implants such as bone tissue (for example, the cranium (cranium)), so that the bone implant can be better combined with human biological tissue through the porous titanium oxide film layer and the titanium matrix , so that the titanium matrix is fully integrated and integrated with human tissue more closely.
  • bone implants such as bone tissue (for example, the cranium (cranium)
  • the pores of the tantalum sheet coated with the porous lithium tantalate film have a size in the range of about 10 nanometers to 1 micrometer in the smallest dimension, which is much smaller than the size of bacteria (usually greater than 5 micrometers). ), therefore, the bone implant coated with the porous lithium tantalate film of the present invention can well inhibit the entry of bacteria and play a certain antibacterial effect.
  • a mixture film of lithium tantalate and lithium niobate is formed in molten lithium nitrate: potassium nitrate (weight ratio 1:1) solution on a tantalum-niobium alloy sheet, and the process conditions for forming a mixture film of lithium tantalate and lithium niobate are shown in table 3.
  • Figure 34 shows a photograph of the appearance of the Example 26 sample.
  • Figures 35a-35b show SEM electron micrographs of the Example 26 sample.
  • Figure 36 shows a photograph of the appearance of the Example 27 sample.
  • Figures 37a-37b show SEM electron micrographs of the Example 27 sample.
  • a lithium niobate film is formed in molten lithium nitrate: potassium nitrate (weight ratio 1:1) solution, and the process conditions for forming the lithium niobate film are shown in Table 3.
  • Figure 38 shows a photograph of the appearance of the Example 28 sample.
  • Figures 39a-39b show SEM electron micrographs of the Example 28 sample.
  • a lithium niobate film layer was formed on the niobium sheet and the niobium brain cap in molten lithium nitrate: potassium nitrate (weight ratio 1:1) solution, and the process conditions for forming the lithium niobate film layer are shown in Table 3.
  • Figures 40 (niobium flakes) and 41 (niobium cranial bones) show photographs of the appearance of the Example 29 sample.
  • Figures 42a-42b show SEM electron micrographs of the Example 29 sample.
  • a lithium niobate film is formed in molten lithium nitrate: potassium nitrate (weight ratio 1:1) solution, and the process conditions for forming the lithium niobate film are shown in Table 3.
  • Figure 43 shows a photograph of the appearance of the Example 30 sample.
  • Figures 44a-44b show SEM electron micrographs of the Example 31 sample.
  • the elastic moduli in Table 3 were measured by a nanoindenter TI-950, NHT of Hysitron, US.

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Abstract

一种具有多孔膜的骨骼植入物及其制备方法。所述骨骼植入物包括：基体；和位于基体上的多孔膜，其中所述基体选自钽基体、铌基体、钽铌合金基体和钛基体，和其中所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜和多孔钛氧化物膜。所述骨骼植入物具有优异的耐腐蚀性能，骨骼植入物的弹性模量可以根据工艺条件调控，使得与人体或动物骨骼的弹性模量具有更高的生物相容性，所述骨骼植入物的白色与骨骼本身的颜色接近，具有美学外观，所述骨骼植入物具有优异的抑菌性。

Description

具有多孔膜的骨骼植入物及其制备方法 技术领域
本发明涉及一种具有多孔膜的骨骼植入物(种植体)以及制备所述骨骼植入物的方法。
背景技术
金属材料具有优异的综合力学性能和抗疲劳特性，特别适用作骨科植入材料。随着材料学日新月异的发展，骨科植入材料经历了从不锈钢、钴铬合金到钛合金的发展历程，并且取得了较好的效果。但是，复杂的人体内环境会引起材料腐蚀而导致有毒元素的释放，从而导致某些金属材料的生物相容性降低。此外，现有技术中的材料例如不锈钢、钴铬合金到钛合金颜色较深，甚至为黑色，影响材料美观性能和限制了应用范围。以上这些不足对于金属材料作为生物医用材料的应用产生了一定负面影响。
多孔钽是近年来出现的一种较理想的骨科植入材料，其是一种难熔金属，熔点近3000℃，外观呈深灰色，表面光洁，与现有医用金属材料相比，钽主要有两方面的优势：(1)钽具有更优异的耐腐蚀性能；(2)钽的生物相容性更好，多孔钽的弹性模量较低。但是，由于钽呈深灰色，当特别用于牙植入体时，会影响美学外观。
尽管多孔钽是比较理想的骨科植入材料，文献记载的钽制作的骨科材料的弹性模量介于皮质骨和松质骨之间，但是，多孔钽的弹性模量更接近人体松质骨的弹性模量，但明显低于皮质骨的弹性模量，而承受人体载荷的骨组织主要是皮质骨，从动物实验和临床应用效果来看，骨骼植入物的弹性模量更应接近人体皮质骨，过高容易产生应力屏蔽，过低也不利于力的传递本发明可在不同镀膜条件下提供从低到高的弹性模量供选择。
但是，对于牙种植体，从生物力学的观点出发，牙种植体的弹性模量对骨界面的应力分布是有影响的，通常牙种植体的弹性模量越高，颈周骨内应力越小，而根端骨内应力越大；牙种植体弹性模量越低，牙种植体与 骨界面的相对位移运动就越大；牙种植体的弹性模量与皮质骨、松质骨相近时，生物力学相容性较好，有学者提出认为高弹性模量更好，适宜牙种植体的弹性模量是在70～200GPa为好，有资料报道皮质骨的弹性模量是18GPa左右。
但是，对于脑盖骨(头盖骨)种植体，对弹性模量的要求会有所不同。
牙种植体无论是用钛合金或其他材料做成柱体或锥体，然后在外表面形成螺纹，目的是为了使人体骨能长入螺纹中使种植体与人体骨结合到一起，以加强种植体与人体的相容性及牢固性，但螺纹肋的深度是有限的，太深会影响种植体的强度。
因此，仍需要寻找一种具有美学外观和/或更高生物相容性的骨骼植入物，特别是牙种植体和脑盖骨(头盖骨)种植体。
发明内容
为此，本发明提供一种骨骼植入物或复合物，其包括：
(1)基体；和
(2)位于基体上的多孔膜，
其中所述基体选自钽基体、铌基体、钽铌合金基体和钛基体，和
其中所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜和多孔钛氧化物膜。
进一步地，本发明提供一种骨骼植入物或复合物，其包括：
(1)钽基体、铌基体、钽铌合金基体、或钛基体；和
(2)位于钽基体上的多孔钽酸锂膜，其中钽酸锂膜含有钽氧化物，
位于铌基体上的多孔铌酸锂膜，其中铌酸锂膜含有铌氧化物，
位于钽铌合金基体上的多孔钽酸锂和铌酸锂的混合物膜，其中混合物膜含有钽氧化物和铌氧化物，或
位于钛基体上的多孔钛氧化物膜。
本发明还提供一种制备所述骨骼植入物或复合物的方法，其包括：
(1)提供基体；和
(2)在基体上形成多孔膜，
其中所述基体选自钽基体、铌基体、钽铌合金基体和钛基体，和
其中所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜和多孔钛氧化物膜。
进一步地，本发明提供一种制备所述骨骼植入物或复合物的方法，其包括：
(1)提供钽基体、铌基体、钽铌合金基体、或钛基体；和
(2)在钽基体、铌基体、或钽铌合金基体上形成多孔钽酸锂膜、多孔铌酸锂膜、或多孔钽酸锂和铌酸锂的混合物膜，或在钛基体上形成多孔钛氧化物膜，
其中钽酸锂膜含有钽氧化物，
其中铌酸锂膜含有铌氧化物，和
其中混合物膜含有钽氧化物和铌氧化物。
本发明还涉及所述复合物在医用材料例如牙种植体中的用途。
本发明的骨骼植入物具有以下一项或多项有益效果：本发明的骨骼植入物具有以下一项或多项有益效果：(1)所提供的金属化合物膜是多孔的，有利于引导人体骨骼进入种植体，增强种植体的相容性和牢固性。同时，该化合物膜层像是接近于陶瓷体，有绝缘隔热效果，减轻急热对人体的刺激。(2)所述膜层不是溶液中的离子沉积生成，而是种植体的金属参加电化学反应生成，并有性能过渡层，膜层与基体结合牢固，所述骨骼植入物具有优异的耐腐蚀性能；(3)所述骨骼植入物的弹性模量可以根据工艺条件调控，使得与人体或动物骨骼(例如牙槽骨)的弹性模量具有更高的生物相容性；(4)所述骨骼植入物的白色与骨骼本身的颜色接近，具有美学外观；(5)由于镀膜处理均在高温下(400℃以上)后的膜层，所述骨骼植入物具有优异的抑菌性。
附图说明
图1a-1c显示未镀有多孔钽酸锂膜的纯钽片的SEM电镜照片。
图2a-2d显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图3a-3c显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图4a-4c显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图5a-5c显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图6a-6c显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图7a-7d显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图8a-8c显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图9显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的外观照片。
图10显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的外观照片。
图11显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的外观照片。
图12显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的外观照片。
图13显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片和钽牙种植体的外观照片。
图14显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片和钽牙种植体的外观照片。
图14a显示根据本发明一个实施方案的镀有多孔钽酸锂膜的多孔钽牙种植体的外观照片。
图15a-15g显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的外观照片。
图16a-16b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图17a-17b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图18a-18b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图19a-19b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图20a-20b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图21a-21b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图22a-22b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图23a-23i显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的外观照片。
图24a-24b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图25a-25b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图26a-26b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图27a-27b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图28a-28b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图29a-29b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图30a-30b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图31a-31b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图32a-32b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽片的SEM电镜照片。
图33a显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽脑盖骨的外观照片。
图33b显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽脑盖骨的截面示意图。
图33c显示根据本发明一个实施方案的镀有多孔钽酸锂膜的钽脑盖骨的俯视示意图。
图34显示根据本发明一个实施方案的镀有多孔钽酸锂和铌酸锂的混合物膜的钽铌合金片的外观照片。
图35a-35b显示根据本发明一个实施方案的镀有多孔钽酸锂和铌酸锂的混合物膜的钽铌合金片的SEM电镜照片。
图36显示根据本发明一个实施方案的镀有多孔钽酸锂和铌酸锂的混合物膜的钽铌合金片的外观照片。
图37a-37b显示根据本发明一个实施方案的镀有多孔钽酸锂和铌酸锂的混合物膜的钽铌合金片的SEM电镜照片。
图38显示根据本发明一个实施方案的镀有多孔铌酸锂膜的铌片的外观照片。
图39a-39b显示根据本发明一个实施方案的镀有多孔铌酸锂膜的铌片的SEM电镜照片。
图40显示根据本发明一个实施方案的镀有多孔铌酸锂膜的铌片的外观照片。
图41显示根据本发明一个实施方案的镀有多孔铌酸锂膜的铌脑盖骨的外观照片。
图42a-42b显示根据本发明一个实施方案的镀有多孔铌酸锂膜的铌片的SEM电镜照片。
图43显示根据本发明一个实施方案的镀有多孔铌酸锂膜的铌片的外观照片。
图44a-44b显示根据本发明一个实施方案的镀有多孔铌酸锂膜的铌片的SEM电镜照片
具体实施方式
在一个实施方案中，本发明提供一种骨骼植入物或钽复合物，其包括：
(1)钽基体；和
(2)位于钽基体上的多孔钽酸锂膜，其中铌酸锂膜含有铌氧化物。
在一个实施方案中，本发明提供一种骨骼植入物或铌复合物，其包括：
(1)铌基体；和
(2)位于铌基体上的多孔铌酸锂膜，其中铌酸锂膜含有铌氧化物。
在一个实施方案中，本发明提供一种骨骼植入物或钽铌合金复合物，其包括：
(1)钽铌合金基体；和
(2)位于钽铌合金基体上的多孔钽酸锂和铌酸锂的混合物膜，其中混合物膜含有钽氧化物和铌氧化物。
在一个实施方案中，本发明提供一种骨骼植入物或钛复合物，其包括：
(1)钛基体；和
(2)位于钛基体上的多孔钛氧化物膜。
在一个实施方案中，所述骨骼植入物或钽复合物包括：(1)钽基体；和(2)位于钽基体的至少一部分表面上的多孔钽酸锂膜，其中所述多孔钽酸锂膜具有0.1-1μm的孔径。对于裂纹状的孔，其长度可达约40μm。
在一个实施方案中，所述骨骼植入物或铌复合物包括：(1)铌基体；和(2)位于铌基体的至少一部分表面上的多孔铌酸锂膜，其中所述多孔铌酸锂膜具有0.1-1μm的孔径。对于裂纹状的孔，其长度可达约40μm。
在一个实施方案中，所述骨骼植入物或钽铌合金复合物包括：(1)钽 铌合金基体；和(2)位于钽铌合金基体的至少一部分表面上的多孔钽酸锂和铌酸锂的混合物膜，其中所述混合物膜具有0.1-1μm的孔径。对于裂纹状的孔，其长度可达约40μm。
在一个实施方案中，所述骨骼植入物或钛复合物包括：(1)钛基体；和(2)位于钛基体的至少一部分表面上的多孔钛氧化物膜，其中所述多孔钛氧化物膜具有0.1-1μm的孔径。对于裂纹状的孔，其长度可达约40μm。
在本发明上下文中，所述孔不限于圆孔，其可以是具有不规则形状的孔，例如裂纹状的孔。
在本发明的一个实施方案中，所述骨骼植入物或复合物具有30％以上的孔隙率，例如具有50-80％的孔隙率，或具有60-90％的孔隙率。
在本发明上下文中，骨骼植入物、复合物和复合材料可以相互替换使用。
适用于本发明的钽基体包括纯钽基体和钽合金基体，其中钽合金基体优选钽铌合金基体。
在本发明的一个实施方案中，所述骨骼植入物例如牙种植体具有至少150GPa的弹性模量。
在本发明另一个实施方案中，所述骨骼植入物例如牙种植体具有至少170GPa的弹性模量。
在本发明再一个实施方案中，所述骨骼植入物例如牙种植体具有150-200GPa的弹性模量。
在本发明仍另一个实施方案中，所述骨骼植入物例如牙种植体具有170-190GPa的弹性模量。
在本发明的一个实施方案中，所述骨骼植入物例如脑盖骨(头盖骨)种植体具有10-160GPa的弹性模量，由纳米压痕法测量。
在本发明的另一个实施方案中，所述骨骼植入物例如脑盖骨(头盖骨)种植体具有20-150GPa的弹性模量，由纳米压痕法测量。
在本发明的再一个实施方案中，所述骨骼植入物例如脑盖骨(头盖骨)种植体具有30-140GPa的弹性模量，由纳米压痕法测量。
在本发明的又一个实施方案中，所述骨骼植入物例如脑盖骨(头盖骨) 种植体具有40-130GPa的弹性模量，由纳米压痕法测量。
在本发明的仍又一个实施方案中，所述骨骼植入物例如脑盖骨(头盖骨)种植体具有50-120GPa的弹性模量，由纳米压痕法测量。
在本发明的仍又一个实施方案中，所述骨骼植入物例如脑盖骨(头盖骨)种植体具有60-110GPa的弹性模量，由纳米压痕法测量。
在本发明的仍又一个实施方案中，所述骨骼植入物例如脑盖骨(头盖骨)种植体具有70-100GPa的弹性模量，由纳米压痕法测量。
在本发明的仍又一个实施方案中，所述骨骼植入物例如脑盖骨(头盖骨)种植体具有80-90GPa的弹性模量，由纳米压痕法测量。
在本发明的一个实施方案中，所述钽基体的全部表面均覆盖多孔钽酸锂膜。
在本发明的一个实施方案中，所述铌基体的全部表面均覆盖多孔铌酸锂膜。
在本发明的一个实施方案中，所述钽铌合金基体的全部表面均覆盖多孔钽酸锂和铌酸锂的混合物膜。
在本发明的一个实施方案中，所述钛基体的全部表面均覆盖多孔钛氧化物膜。
从生物力学的观点出发，牙种植体的弹性模量对骨界面的应力分布是有影响的，通常牙种植体的弹性模量越高，颈周骨内应力越小，而根端骨内应力越大；牙种植体弹性模量越低，牙种植体与骨界面的相对位移运动就越大；牙种植体的弹性模量与皮质骨、松质骨相近时，生物力学相容性较差；适宜的牙种植体弹性模量是在70GPa以上。本发明的骨骼植入物，包括牙种植体，具有至少150GPa的弹性模量，因此本发明的牙种植体非常合适的弹性模量，具有优异的生物力学相容性。
在本发明的一个实施方案中，所述骨骼植入物包括骨骼假体例如脑盖骨和牙种植体。
在本发明的一个实施方案中，脑盖骨是多孔的，如图33a所示的钽脑盖骨和图41所示的铌脑盖骨。
在本发明的一个实施方案中，所述牙种植体包括假牙基台部、主体部 和连接所述假牙基台部与所述主体部的颈部。关于牙种植体的制备方法是本领域技术人员已知的，可以例如参考CN109758245A、CN109965996A以及CN110610046A。
在本发明一个优选的实施方案中，所述牙种植体包括假牙基台部、主体部和连接所述假牙基台部与所述主体部的颈部，其中所述主体部的外表面设有与牙槽骨接触的外螺纹。
在本发明的一个实施方案中，所述骨骼植入物具有与骨骼相似的颜色。在本发明一个优选实施方案中，所述骨骼植入物为白色的，特别是对于假牙基台部。
在本发明的一个实施方案中，其中所述基体为多孔的。多孔基体具有优良的力学性能和组织相容性。人体组织的再造、植骨及置换术等都可应用多孔材料植入骨缺损部位，骨质会沿着多孔孔隙及与宿主界面长入，使多孔材料充分与骨组织紧密结合并融为一体。作为支架材料植入人体后，由于其优良的组织相容性使得多孔材料不需要在人体内降解，因此也不需要二次手术取出。多孔金属质地坚固，抗磨损，抗疲劳能力均优于骨松质、陶瓷制品、冻干骨片，可以提供足够的生理负荷。
钽、铌、钽铌合金和钛属于难熔金属，上述多孔金属通常采用难熔金属的制备方法。例如，可以采用已知的方法通过粉末烧结制备多孔钽，也可以通过气相沉积方法制备多孔钽，本领域制备多孔钽的其它方法也是可以用的。
在本发明的一个实施方案中，使用的钽为致密的。现有技术均是使用多孔钽作为医用骨科材料，没有提到使用致密钽金属作为医用骨科材。对于牙种植体，从生物力学的观点出发，牙种植体的弹性模量对骨界面的应力分布是有影响的，通常牙种植体的弹性模量越高，颈周骨内应力越小，而根端骨内应力越大；牙种植体弹性模量越低，牙种植体与骨界面的相对位移运动就越大；牙种植体的弹性模量与皮质骨、松质骨相近时，生物力学相容性较差；适宜的牙种植体弹性模量是在70GPa以上。由于牙种植体经常承担咀嚼的功能，负荷非常大，多孔钽的抗拉强度和弹性模量无法满足该负荷要求。致密金属钽的抗拉强度和弹性模量均较大，更适合用于 牙种植体。
本发明的一个实施方案是在多孔钽牙种植体上镀一层多孔钽酸锂膜，并因此提高牙种植体的机械性能，例如抗拉强度和弹性模量。
本发明的一个实施方案是在多孔铌牙种植体上镀一层多孔铌酸锂膜，并因此提高牙种植体的机械性能，例如抗拉强度和弹性模量。
本发明的一个实施方案是在多孔钽铌牙种植体上镀一层多孔钽酸锂和铌酸锂的混合物膜，并因此提高牙种植体的机械性能，例如抗拉强度和弹性模量。
本发明的另一个实施方案是在致密金属钽上镀一层多孔钽酸锂膜，不仅使其抗拉强度和弹性模量变得更大，更好地满足牙种植体的抗拉强度和弹性模量要求，而且由于在钽基体的表面上具有多孔钽酸锂膜，使得该牙种植体能够与人体生物组织更好地相容，使得人体生物组织能够通过多孔钽酸锂膜与钽基体结合，使钽材料充分与人体组织例如牙槽骨更紧密结合并融为一体。
在本发明的一个实施方案中，对于骨骼植入物例如牙种植体的不外漏的部分也可以不镀钽酸锂膜层，仅采用纯钽材料。对于假牙基台部和颈部优选镀钽酸锂膜，以增加美学外观。
致密钽材料的制备方法对于本领域技术人员来说是已知的，例如可以通过铸造、轧制等方法获得。
在本发明的一个实施方案中，制备所述骨骼植入物的方法包括：(1)提供钽基体；和(2)在钽基体上形成一层多孔钽酸锂膜。
在本发明的一个实施方案中，制备所述骨骼植入物的方法包括：(1)提供铌基体；和(2)在铌基体上形成一层多孔铌酸锂膜。
在本发明的一个实施方案中，制备所述骨骼植入物的方法包括：(1)提供钽铌合金基体；和(2)在钽铌合金基体上形成一层多孔钽酸锂和铌酸锂的混合物膜。
在本发明的一个实施方案中，制备所述骨骼植入物的方法包括：(1)提供钛基体；和(2)在钛基体上形成一层多孔钛氧化物膜。
在本发明的一个实施方案中，所述基体具有骨骼植入物所需的形状，例如牙种植体和脑盖骨的形状。
在本发明的一个优选实施方案中，在具有所需骨骼植入物形状的钽基体上镀一层多孔钽酸锂膜。
在本发明的另一个实施方案中，在具有所需骨骼植入物形状的钽基体上镀一层多孔钽酸锂膜，并且用切削或磨削的方法将骨骼植入物上不需要的多孔钽酸锂膜除掉，而只在该骨骼植入物的部分表面上保留多孔钽酸锂膜。具体而言，先将制造的多个外观尺寸合格的但内孔还未加工的联合体进行镀钽酸锂膜处理，然后再加工内孔，这样就能保持内孔不镀膜处理。
在本发明的一个优选实施方案中，在具有所需骨骼植入物形状的钽基体的部分表面上镀一层多孔钽酸锂膜。
在本发明的一个实施方案中，所述多孔膜具有1-20μm，优选2-10μm，更优选3-5μm的厚度。
在步骤(2)中，所述多孔钽酸锂膜通过熔盐电化学方法形成。
在本发明的一个实施方案中，在步骤(2)中将钽基体置于250℃～650℃的含氧无机锂盐(如LiNO 3)或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加1～66V的阳极电压，恒压0.01～200小时，其中升压电流密度为1～1000毫安/厘米 2，以形成多孔钽酸锂膜。
在本发明另一个实施方案中，在步骤(2)中将钽基体置于440℃～600℃的含氧无机锂盐(如LiNO 3)或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加10～30V的阳极电压，恒压5分钟～10小时，其中升压电流密度为1～1000毫安/厘米 2，以形成多孔钽酸锂膜。
在本发明又一个实施方案中，在步骤(2)中将钽基体置于570℃～598℃的含氧无机锂盐(如LiNO 3)或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加10～20V的阳极电压，恒压8分钟～30分钟，其中升压电流密度为5～20毫安/厘米 2，以形成多孔钽酸锂膜。
在一个优选实施方案中，在步骤(2)中可将超声波发生器设置于所述混合熔融物或所述混合熔融液中。
优选地，在步骤(2)中熔盐电化学方法为熔融锂盐电化学方法。
在步骤(2)之前，可以对钽基体进行阳极氧化的步骤。
在所述阳极氧化步骤中，在钽基体上形成Ta 2O 5膜，例如无定型Ta 2O 5膜。无孔的适用于钽电容器上使用。
Ta 2O 5膜也可以是多孔的，对多孔钽酸锂膜的制作更有优势。具体的是将植入体置入浓硫酸，在190℃～245℃下(即98％的浓硫酸内形成多孔的Ta 2O 5膜)进行。
在本发明的一个实施方案中，在所述阳极氧化步骤中通过阳极氧化在钽基体上形成一层无定型Ta 2O 5膜。特别地，在所述阳极氧化步骤中将钽基体置于室温至380℃，优选室温至300℃的含氧电解质溶液中，施加3至800V的阳极电压，恒压0.01至2小时，其中升压电流密度为1～200毫安/厘米 2，以形成一层无定型Ta 2O 5膜。
在所述阳极氧化步骤中，如果溶液温度高，施加的电压应低，反之可高。例如，对于在室温下的0.01％H 3PO 4溶液，最高可施加600V的电压。无论何种溶液，所加电压应在该溶液的闪火电压以下。
在所述阳极氧化步骤中，所述含氧电解质溶液可以是水溶液、非水溶液、或水溶液电解质与有机化合物的混合物。
水溶液含氧电解质可以是例如酸、碱、盐的水溶液。溶液温度为室温(大约25℃)至95℃，阳极电压为5至600V，恒压时间在60～90分钟以内。温度过高，水分挥发速度过快。溶液温度较高时，阳极电压应较低。
非水溶液含氧电解质可以是无水浓硫酸或熔融盐或熔融盐与碱类的混合物，如硝酸钾、硝酸钠、硝酸锂，或它们与锂，钠、钾等碱的混合物。
另一类含氧电解质溶液可以是水溶液电解质与有机化合物如乙醇、乙二醇、正丁醇等的混合物。水溶液的温度应在95℃以下，否则水的挥发迅速，不易控制。
在本发明的一个实施方案中，本发明的制备方法包括预先对钽基体进行渗氮或渗碳处理。但是，也可以不进行渗氮或渗碳处理。为了获得较高 的硬度，可采用渗氮或渗碳处理。
在一个优选的实施方案中，使用离子渗氮炉，用钽基体为阴极，炉温为500-1000℃，炉压为20-2000Pa，充入气体为氮气、氢气，氮气：氢气＝2:1至1:10，渗氮0.5-6小时，使钽基体表面形成渗氮层，并使钽基体渗氮后的硬度控制在HV180～480之间。
根据本发明的一个实施方案，提供一种制备牙种植体的方法，其包括：
1)选择直径大小合适的钽棒，或铌棒，钽铌合金棒，或钛棒，
2)提供加工好的圆柱体或圆锥形种植体(包括加工外螺纹和内孔螺纹等，提供与种植体配合的连接体及机台)。
3)在含锂盐熔融中进行电化学镀膜处理。
其中钽，铌，钽铌合金种植体表面可以生成白色的钽酸锂膜，铌酸锂膜，或钽酸锂与铌酸锂的混合物膜，钛种植体表面生成一层多孔氧化钛膜。
本发明提出用合适的孔代替螺纹肋，该孔可一直深入到种植体内壁，即穿孔，而不影响种植体强度，该方案的优点是能增加种植体与人体骨的接触面，增加种植体的相容性和牢固性。
当然外孔也可以不穿孔，留一定厚度，以便种植体内孔能加工螺纹，以利连接体或基台的固定。
根据本发明的一个实施方案，提供一种制备牙种植体的方法，其包括：
1)提供牙植入体坯料，并设计打孔参数；
即，确定圆柱或圆锥种植体的尺寸，包括圆柱外直径和内孔直径，然后将有孔圆柱体展开成平面图，设计确定孔的大小，孔间距或孔的分布，及孔的打入深度，孔形，即直孔或锥孔；
2)打孔；
即，用喷丝头板打孔的方法或激光打孔的按设计要求打孔；
3)抛光；
即，打孔后要用抛光的方法去掉表面多出的材料，如用激光打孔一般不会有在孔周围多出材料，抛光较易；
4)将打孔后抛光好的钽片用氩弧焊或激光焊接成原设计好的圆柱或圆锥种植体，并进行必要的修理及加工内螺纹等；
5)用电化学方法在多孔体种植体及机台进行所述表面处理，以生成与种植体金属相对应的复合物多孔膜，得到带孔的镀膜牙种植体。
根据本发明的一个实施方案，提供一种穿孔种植体的方法，其包括：
1)穿孔入口，即准备与人体骨接触的那一面的孔。孔的直径大小控制在0.08～0.30mm，优选0.16～0.22mm；
2)出口，即孔与植入体内孔相护接的那一端孔。直径控制在0.28～0.06，优选0.22～0.13mm。孔形可是锥孔或直孔。锥孔可能更有利引导人体骨长入植入体。
根据本发明的一个实施方案，提供一种不穿孔种植体的设计，保证牙植入体中心孔内壁为了安装基台连接体需加工的螺纹等的加工，植入体上的孔留0.6～0.8mm，否则不穿孔，以便内孔加工螺纹。
在本发明上下文中，铌和钽铌合金基体同样适用于关于钽基体的实施方案。
除非另有明确指出，抗拉强度和弹性模量按GB/T22315—2008标准测试。
下面描述的具体实施方案有助于本领域技术人员理解本发明，但是不用于限制本发明的范围。
1.一种骨骼植入物，其包括：
(1)基体；和
(2)位于基体上的多孔膜，
其中所述基体选自钽基体、铌基体、钽铌合金基体和钛基体，优选所述基体选自钽基体、铌基体和钽铌合金基体，和
其中所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜和多孔钛氧化物膜，优选所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜以及多孔钽酸锂和铌酸锂的混合物膜。
2.根据实施方案1所述的骨骼植入物，其包括：
(1)钽基体、铌基体、钽铌合金基体、或钛基体；和
(2)位于钽基体上的多孔钽酸锂膜，其中钽酸锂膜含有钽氧化物，
位于铌基体上的多孔铌酸锂膜，其中铌酸锂膜含有铌氧化物，
位于钽铌合金基体上的多孔钽酸锂和铌酸锂的混合物膜，其中混合物膜含有钽氧化物和铌氧化物，或
位于钛基体上的多孔钛氧化物膜。
3.根据实施方案1或2所述的骨骼植入物，其中所述多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜或多孔钛氧化物膜具有0.1-1μm的孔径。
4.根据实施方案1或2所述的骨骼植入物，其中所述多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜或多孔钛氧化物膜具有1-20μm，优选2-10μm，更优选3-5μm的厚度。
5.根据实施方案1或2所述的骨骼植入物，其中所述骨骼植入物具有至少150GPa的弹性模量。
6.根据实施方案1或2所述的骨骼植入物，其中所述骨骼植入物具有至少170GPa的弹性模量。
7.根据实施方案1或2所述的骨骼植入物，其中所述骨骼植入物具有150-200GPa的弹性模量。
8.根据实施方案7所述的骨骼植入物，其中所述骨骼植入物具有170-190GPa的弹性模量。
9.根据实施方案1或2所述的骨骼植入物，其中所述骨骼植入物具有与骨骼相似的颜色。
10.根据实施方案1或2所述的骨骼植入物，其中所述骨骼植入物包括骨骼假体、牙种植体和脑盖骨。
11.根据实施方案10所述的骨骼植入物，其中所述牙种植体包括假牙基台部、主体部和连接所述假牙基台部与所述主体部的颈部。
12.根据实施方案1或2所述的骨骼植入物，其中所述骨骼植入物具有10-160GPa的弹性模量，优选20-150GPa的弹性模量，更优选30-140GPa的弹性模量。
13.根据实施方案1或2所述的骨骼植入物，其中所述钽基体、铌基体或钽铌合金基体为多孔的。
14.根据实施方案1或2所述的骨骼植入物，其中所述钽基体、铌基 体或钽铌合金基体为致密的。
15.一种制备实施方案1-14中任一项所述的骨骼植入物的方法，其包括：
(1)提供基体；和
(2)在基体上形成多孔膜，
其中所述基体选自钽基体、铌基体、钽铌合金基体和钛基体，优选所述基体选自钽基体、铌基体和钽铌合金基体，和
其中所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜和多孔钛氧化物膜，优选所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜以及多孔钽酸锂和铌酸锂的混合物膜。
16.根据实施方案15所述的方法，其包括：
(1)提供钽基体、铌基体、钽铌合金基体、或钛基体；和
(2)在钽基体、铌基体、或钽铌合金基体上形成多孔钽酸锂膜、多孔铌酸锂膜、或多孔钽酸锂和铌酸锂的混合物膜，或在钛基体上形成多孔钛氧化物膜，
其中钽酸锂膜含有钽氧化物，
其中铌酸锂膜含有铌氧化物，和
其中混合物膜含有钽氧化物和铌氧化物。
17.根据实施方案15或16所述的方法，其中在步骤(2)中通过熔盐电化学方法形成多孔膜。
18.根据实施方案15或16所述的方法，其中在步骤(2)之前在钽基体上形成Ta 2O 5膜。
19.根据实施方案18所述的方法，其中通过阳极氧化在钽基体上形成无定型Ta 2O 5膜。
20.根据实施方案19所述的方法，其中在钽基体上形成Ta 2O 5膜的步骤中，将钽基体置于室温至380℃，优选室温至300℃的含氧电解质溶液中，施加3至800V的阳极电压，恒压0.01至2小时，其中升压电流密度为1～200毫安/厘米 2，以形成无定型Ta 2O 5膜。
21.根据实施方案15或16所述的方法，其中在步骤(2)之前在铌基体 上形成Nb 2O 5膜。
22.根据实施方案21所述的方法，其中通过阳极氧化在铌基体上形成无定型Nb 2O 5膜。
23.根据实施方案22所述的方法，其中在铌基体上形成Nb 2O 5膜的步骤中，将铌基体置于室温至380℃，优选室温至300℃的含氧电解质溶液中，施加3至800V的阳极电压，恒压0.01至2小时，其中升压电流密度为1～200毫安/厘米 2，以形成无定型Nb 2O 5膜。
24.根据实施方案15或16所述的方法，其中在步骤(2)之前在钽铌合金基体上形成Ta 2O 5和Nb 2O 5的混合物膜。
25.根据实施方案24所述的方法，其中通过阳极氧化在钽铌合金基体上形成无定型Ta 2O 5和Nb 2O 5的混合物膜。
26.根据实施方案25所述的方法，其中在钽铌合金基体上形成Ta 2O 5和Nb 2O 5的混合物膜的步骤中，将钽铌合金基体置于室温至380℃，优选室温至300℃的含氧电解质溶液中，施加3至800V的阳极电压，恒压0.01至2小时，其中升压电流密度为1～200毫安/厘米 2，以形成无定型Ta 2O 5和Nb 2O 5的混合物膜。
27.根据实施方案20、23和26中任一项所述的方法，其中所述含氧电解质溶液为水溶液、非水溶液、或水溶液电解质与有机化合物的混合物。
28.根据实施方案27所述的方法，其中熔盐电化学方法为熔融锂盐电化学方法。
29.根据实施方案15或16所述的方法，其中将钽基体、铌基体或钽铌合金基体置于250℃～650℃的含氧无机锂盐或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加1～66V的阳极电压，恒压0.01～200小时，其中升压电流密度为1～1000毫安/厘米 2，以形成含有含锂化合物的膜层。
30.根据实施方案29所述的方法，其中在步骤(2)中将钽基体、铌基体或钽铌合金基体置于440℃～600℃的含氧无机锂盐或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加10～30V的阳极电压，恒压5分钟～10小时，其 中升压电流密度为5～20毫安/厘米 2，以形成含有含锂化合物的膜层。
31.根据实施方案29所述的方法，其中在步骤(2)中将钽基体、铌基体或钽铌合金基体置于570℃～598℃的含氧无机锂盐或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加10～20V的阳极电压，恒压8分钟～30分钟，其中升压电流密度为5～20毫安/厘米 2，以形成含有含锂化合物的膜层。
32.根据实施方案29所述的方法，其中含氧无机锂盐为LiNO 3。
33.根据实施方案29所述的方法，其中在步骤(c)中将超声波发生器设置于所述混合熔融物或所述混合熔融液中。
34.根据实施方案15或16所述的方法，其中对钽基体、铌基体或钽铌合金基体进行渗氮处理或渗碳处理。
35.骨骼植入物在医用材料中的用途，其中所述骨骼植入物如实施方案1-14中任一项所述或根据实施方案15-34中任一项所述的方法制备。
36.根据实施方案35的用途，其中所述医用材料为牙种植体或脑盖骨。
实施例
下面通过实施例并结合附图进一步理解本发明的性质和目的，应理解这些实施例仅用于示例的目的，不用于限定本发明的范围。
实施例1
步骤1：将金属钽加工成致密的钽片。
步骤2：对于该钽片，在570℃熔融硝酸锂溶液中施加10V阳极电压，恒压反应30分钟，在钽片上形成多孔钽酸锂膜层。
图2a-2d显示了实施例1样品的SEM电镜照片。
图9显示了实施例1样品的外观照片。
实施例2
步骤1：将金属钽加工成致密的钽片。
步骤2：对于该钽片，在580℃熔融硝酸锂溶液中施加10V阳极电压，恒压反应25分钟，在钽片上形成多孔钽酸锂膜层。
图3a-3c显示了实施例2样品的SEM电镜照片。
图10显示了实施例2样品的外观照片。
实施例3
步骤1：将金属钽加工成致密的钽片。
步骤2：对于该钽片，在598℃熔融硝酸锂溶液中施加10V阳极电压，恒压反应10分钟，在钽片上形成多孔钽酸锂膜层。
图4a-4c显示了实施例3样品的SEM电镜照片。
图11显示了实施例3样品的外观照片。
实施例4
步骤1：将金属钽加工成致密的钽片。
步骤2：对于该钽片，采用体积比例为乙二醇：0.01％H 3PO 4＝2：1的溶液，溶液温度为90℃，施加60V阳极电压，恒压3小时，然后清洗。
步骤3：对于步骤(2)中得到的钽片，在598℃熔融硝酸锂溶液中施加10V阳极电压，恒压反应8分钟，在钽片上形成多孔钽酸锂膜层。
图5a-5c显示了实施例4样品的SEM电镜照片。
图12显示了实施例4样品的外观照片。
实施例5
步骤1：将金属钽加工成致密的钽片。
步骤2：对于该钽片，采用体积比例为乙二醇：0.01％H 3PO 4＝2：1的溶液，溶液温度为90℃，施加143V阳极电压，恒压3小时，然后清洗。
步骤3：对于步骤(2)中得到的钽片，在482℃熔融硝酸锂溶液中施加28V阳极电压，恒压反应6.5小时，在钽片上形成多孔钽酸锂膜层。
图6a-6c显示了实施例5样品的SEM电镜照片。
实施例6
步骤1：将金属钽加工成致密的钽片。
步骤2：对于该钽片，在440℃熔融硝酸锂溶液中施加33V阳极电压，恒压反应12小时，在钽片上形成多孔钽酸锂膜层。
图7a-7d显示了实施例6样品的SEM电镜照片。
实施例7
步骤1：将金属钽加工成致密的钽片。
步骤2：对于该钽片，采用体积比例为乙二醇：0.01％H 3PO 4＝2：1的溶液，溶液温度为90℃，施加60V阳极电压，恒压3小时，然后清洗。
步骤3：对于步骤(2)中得到的钽片，在598℃熔融硝酸锂溶液中施加10V阳极电压，恒压反应10分钟，在钽片上形成多孔钽酸锂膜层。
图8a-8c显示了实施例7样品的SEM电镜照片。
实施例8
步骤1：分别将金属钽加工成致密的钽片和钽牙种植体。
步骤2：分别对于该钽片和钽牙种植体(直径为6mm的螺纹钽棒，具有直径2mm的孔)，在580℃的熔融硝酸锂:硝酸钾(重量比1:1)溶液中施加10V阳极电压，恒压反应30分钟，在钽片和钽牙种植体上形成多孔钽酸锂膜层。
图13显示了实施例8样品的外观照片。
实施例9
步骤1：分别将金属钽加工成致密的钽片和钽牙种植体(直径为6mm的螺纹钽棒，具有直径2mm的孔)。
步骤2：分别对于该钽片和钽牙种植体，首先在90℃下在0.05重量％H 3PO 4水溶液中施加60V阳极电压，恒压1.5小时，然后清洗。
步骤3：对于步骤(2)中得到的钽片和钽牙种植体，在598℃的熔融硝酸锂:硝酸钾(重量比1:1)中施加10V阳极电压，恒压反应8分钟，在钽片和钽牙种植体上形成多孔钽酸锂膜层。
图14显示了实施例9样品的外观照片。
实施例9a
在多孔的钽牙种植体上在580℃的熔融硝酸锂:硝酸钾(重量比1:1)中施加10V阳极电压，恒压反应25分钟。
图14a显示了实施例9a样品的外观照片。
比较例1
将金属钽加工成致密的钽片，而不在钽片上进行形成多孔钽酸锂膜层的步骤。
图1a-1c显示了比较例1样品的SEM电镜照片。
表1 样品的抗拉强度
Figure PCTCN2021120407-appb-000001
表2 样品的弹性模量
Figure PCTCN2021120407-appb-000002
Figure PCTCN2021120407-appb-000003
注：在表2中，由于各样品镀膜后的膜厚大约10μm左右，膜下过渡层也大约在30um左右，可见其在粗大的钽测试样中所占比重很小，因此测量出的数据与纯钽很接近，表2检测数据基本接近纯钽弹性模量，不能代表本发明样品镀膜表层的弹性模量，而以纳米压痕法例如仪器型号TI-950测得的值是能代表本发明不同镀膜工艺的弹性模量的变化。
表1和表2的数据表明，镀有多孔钽酸锂膜的钽片相比于未镀有多孔钽酸锂膜的钽片，其抗拉强度和弹性模量都得到很大提高，特别是其弹性模量远大于制作牙种植体所要求的70GPa的弹性模量，这是非常有利的。
通过比较镀有多孔钽酸锂膜的钽片与未镀有多孔钽酸锂膜的钽片的SEM电镜照片，可以看出本发明镀有多孔钽酸锂膜的钽片具有较多孔径大约在1-30微米范围的开孔，且表面粗糙，这些孔隙和凹凸不平的粗糙表面有利于细胞的粘附和组织的嵌合，能够增强骨骼植入物如牙种植体与骨组织的连接强度，使得骨骼植入物能够与人体生物组织更好地通过多孔钽酸锂膜与钽基体结合，使钽基体充分与人体组织例如牙槽骨更紧密结合并融为一体。而未镀有多孔钽酸锂膜的钽片相对具有很少的孔，表面光洁平坦，不利于钽基体与人体组织例如牙槽骨紧密结合一起。
另外，从SEM电镜照片来看，镀有多孔钽酸锂膜的钽片的孔隙在最小维度上的尺寸大约在10纳米至1微米的范围，该尺寸远远小于细菌的尺寸(通常大于5微米)，因此，本发明镀有多孔钽酸锂膜的骨骼植入物能够很好地抑制细菌的进入，起到一定抑菌的作用。
图9-12表明镀有多孔钽酸锂膜的钽片显示白色，具有美学外观，特别适合于制作牙种植体。
实施例10
在钽片上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图15a显示了实施例10样品的外观照片。
图16a-16b显示了实施例10样品的SEM电镜照片。
实施例11
分别在钽片和钽脑盖骨基体上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图15b(钽片)、图33a(脑盖骨)显示了实施例11样品的外观照片。
图17a-17b显示了实施例11样品的SEM电镜照片。
实施例12
在钽片上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图15c显示了实施例12样品的外观照片。
图18a-18b显示了实施例12样品的SEM电镜照片。
实施例13
在钽片上先采用体积比例为乙二醇:0.01重量％H 3PO 4＝2:1的溶液，溶液温度为90℃，施加60V阳极电压，恒压1.5小时，然后清洗。然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图15d显示了实施例13样品的外观照片。
图19a-19b显示了实施例13样品的SEM电镜照片。
实施例14
在钽片上先采用体积比例为乙二醇:0.01重量％H 3PO 4＝2:1的溶液，溶液温度为90℃，施加60V阳极电压，恒压1.5小时，然后清洗。然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图15e显示了实施例14样品的外观照片。
图20a-20b显示了实施例14样品的SEM电镜照片。
实施例15
在钽片上先采用体积比例为乙二醇:0.0重量1％H 3PO 4＝2:1的溶液，溶液温度为90℃，施加143V阳极电压，恒压1.5小时，然后清洗。然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图15f显示了实施例15样品的外观照片。
图21a-22b显示了实施例15样品的SEM电镜照片。
实施例16
在钽片上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，工艺条件见表3。
图15g显示了实施例16样品的外观照片。
图22a-22b显示了实施例16样品的SEM电镜照片。
实施例17
在钽片上先在98％浓H 2SO 4的溶液中，温度为：220℃，施加150V阳极电压，恒压30分钟，然后清洗烘干；然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图23a显示了实施例17样品的外观照片。
图24a-24b显示了实施例17样品的SEM电镜照片。
实施例18
在钽片上先在98％浓H 2SO 4的溶液中，温度为：220℃，施加150V阳极电压，恒压30分钟，然后清洗烘干；然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图23b显示了实施例18样品的外观照片。
图25a-25b显示了实施例18样品的SEM电镜照片。
实施例19
在钽片上先在98％浓H 2SO 4的溶液中，温度为：220℃，施加150V阳极电压，恒压30分钟，然后清洗烘干；然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图23c显示了实施例19样品的外观照片。
图26a-26b显示了实施例19样品的SEM电镜照片。
实施例20
在钽片上先在98％浓H 2SO 4的溶液中，温度为：220℃，施加82V阳极电压，恒压30分钟，然后清洗烘干；然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图23d显示了实施例20样品的外观照片。
图27a-27b显示了实施例20样品的SEM电镜照片。
实施例21
在钽片上先在98％浓H 2SO 4的溶液中，温度为：210℃，施加82V阳极电压，恒压30分钟，然后清洗烘干；然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图23e显示了实施例21样品的外观照片。
图28a-28b显示了实施例21样品的SEM电镜照片。
实施例22
在钽片上先在98％浓H 2SO 4的溶液中，温度为：210℃，施加82V阳极电压，恒压30分钟，然后清洗烘干；然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图23f显示了实施例22样品的外观照片。
图29a-29b显示了实施例22样品的SEM电镜照片。
实施例23
在钽片上先在98％浓H 2SO 4的溶液中，温度为：210℃，施加82V阳极电压，恒压30分钟，然后清洗烘干；然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂膜层，形成钽酸锂膜层的工艺条件见表3。
图23g显示了实施例23样品的外观照片。
图30a-30b显示了实施例23样品的SEM电镜照片。
实施例24
在钽片上在98％浓H 2SO 4的溶液中进行阳极氧化，温度为：220℃，施加150V阳极电压，恒压30分钟，见表3。
图23h显示了实施例24样品的外观照片。
图31a-31b显示了实施例24样品的SEM电镜照片。
实施例25
在钛片上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中进行阳极氧化形成钛氧化物膜层，形成钛氧化物膜层的工艺条件见表3。
图23i显示了实施例25样品的外观照片。
图32a-32b显示了实施例25样品的SEM电镜照片。
表3的数据表明，镀有多孔钽酸锂膜的钽复合物具有合适的弹性模量，其例如适合于制作脑盖骨(头盖骨)种植体。
通过比较镀有多孔钽酸锂膜的钽片与未镀有多孔钽酸锂膜的钽片的SEM电镜照片，可以看出本发明镀有多孔钽酸锂膜的钽片具有较多孔径大约在0.1-30微米范围的开孔，甚至是蜂窝状的开孔，且表面粗糙，这些孔隙和凹凸不平的粗糙表面有利于细胞的粘附和组织的嵌合，能够增强骨骼植入物如牙种植体与骨组织例如脑盖骨(头盖骨)的连接强度，使得骨骼植入物能够与人体生物组织更好地通过多孔钽酸锂膜与钽基体结合，使钽基体充分与人体组织更紧密结合并融为一体。而未镀有多孔钽酸锂膜的钽片相对具有很少的孔，表面光洁平坦，不利于钽基体与人体组织例如牙槽骨和脑盖骨(头盖骨)等紧密结合一起。
实施例25制备的具有钛氧化物膜层的钛片显示了合适的弹性模量，且其SEM照片显示膜层具有纤维状的多孔交互网络(见图32b)，有利于细胞的粘附和组织的嵌合，能够增强骨骼植入物如骨组织(例如脑盖骨(头盖骨))的连接强度，使得骨骼植入物能够与人体生物组织更好地通过多孔钛氧化物膜层与钛基体结合，使钛基体充分与人体组织更紧密结合并融为一体。
另外，从SEM电镜照片来看，镀有多孔钽酸锂膜的钽片的孔隙在最小维度上的尺寸大约在10纳米至1微米的范围，该尺寸远远小于细菌的尺寸(通常大于5微米)，因此，本发明镀有多孔钽酸锂膜的骨骼植入物能够很好地抑制细菌的进入，起到一定抑菌的作用。
实施例26
在钽铌合金片上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸 锂和铌酸锂的混合物膜层，形成钽酸锂和铌酸锂的混合物膜层的工艺条件见表3。
图34显示了实施例26样品的外观照片。
图35a-35b显示了实施例26样品的SEM电镜照片。
实施例27
在钽铌合金片上先采用体积比例为乙二醇:0.01重量％H 3PO 4＝2:1的溶液，溶液温度为90℃，施加143V阳极电压，恒压1.5小时，然后清洗。然后在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成钽酸锂和铌酸锂的混合物膜层，形成钽酸锂和铌酸锂的混合物膜层的工艺条件见表3。
图36显示了实施例27样品的外观照片。
图37a-37b显示了实施例27样品的SEM电镜照片。
实施例28
在铌片上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成铌酸锂膜层，形成铌酸锂膜层的工艺条件见表3。
图38显示了实施例28样品的外观照片。
图39a-39b显示了实施例28样品的SEM电镜照片。
实施例29
在铌片和铌脑盖骨基体上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成铌酸锂膜层，形成铌酸锂膜层的工艺条件见表3。
图40(铌片)和图41(铌脑盖骨)显示了实施例29样品的外观照片。
图42a-42b显示了实施例29样品的SEM电镜照片。
实施例30
在铌片上在熔融硝酸锂:硝酸钾(重量比1:1)溶液中形成铌酸锂膜层，形成铌酸锂膜层的工艺条件见表3。
图43显示了实施例30样品的外观照片。
图44a-44b显示了实施例31样品的SEM电镜照片。
表3 样品的制备和弹性模量(由纳米压痕仪TI-950,NHT，来自Hysitron，US测量)
Figure PCTCN2021120407-appb-000004
表3中的弹性模量由US，Hysitron的纳米压痕仪TI-950,NHT测得。
表3的数据表明，镀有多孔钽酸锂和铌酸锂的混合物膜的复合物以及具有多孔铌酸锂膜的复合物具有合适的弹性模量，其例如适合于制作脑盖骨(头盖骨)种植体。
尽管显示和描述了本发明的具体实施方案，应当理解其它改进、替代和可选方案是本领域技术人员所了解的。这类改进、替代和可选实施方案可不偏离应由所附权利要求书决定的本发明的精神和范围而作出。本发明的各个特征描述于所附权利要求书中。

Claims (36)

  1. 一种骨骼植入物，其包括：
    (1)基体；和
    (2)位于基体上的多孔膜，
    其中所述基体选自钽基体、铌基体、钽铌合金基体和钛基体，优选所述基体选自钽基体、铌基体和钽铌合金基体，和
    其中所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜和多孔钛氧化物膜，优选所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜以及多孔钽酸锂和铌酸锂的混合物膜。
  2. 根据权利要求1所述的骨骼植入物，其包括：
    (1)钽基体、铌基体、钽铌合金基体、或钛基体；和
    (2)位于钽基体上的多孔钽酸锂膜，其中钽酸锂膜含有钽氧化物，
    位于铌基体上的多孔铌酸锂膜，其中铌酸锂膜含有铌氧化物，
    位于钽铌合金基体上的多孔钽酸锂和铌酸锂的混合物膜，其中混合物膜含有钽氧化物和铌氧化物，或
    位于钛基体上的多孔钛氧化物膜。
  3. 根据权利要求1或2所述的骨骼植入物，其中所述多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜或多孔钛氧化物膜具有0.1-1μm的孔径。
  4. 根据权利要求1或2所述的骨骼植入物，其中所述多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜或多孔钛氧化物膜具有1-20μm，优选2-10μm，更优选3-5μm的厚度。
  5. 根据权利要求1或2所述的骨骼植入物，其中所述骨骼植入物具有至少150GPa的弹性模量。
  6. 根据权利要求1或2所述的骨骼植入物，其中所述骨骼植入物具有至少170GPa的弹性模量。
  7. 根据权利要求1或2所述的骨骼植入物，其中所述骨骼植入物具有150-200GPa的弹性模量。
  8. 根据权利要求7所述的骨骼植入物，其中所述骨骼植入物具有170 -190GPa的弹性模量。
  9. 根据权利要求1或2所述的骨骼植入物，其中所述骨骼植入物具有与骨骼相似的颜色。
  10. 根据权利要求1或2所述的骨骼植入物，其中所述骨骼植入物包括骨骼假体、牙种植体和脑盖骨。
  11. 根据权利要求10所述的骨骼植入物，其中所述牙种植体包括假牙基台部、主体部和连接所述假牙基台部与所述主体部的颈部。
  12. 根据权利要求1或2所述的骨骼植入物，其中所述骨骼植入物具有10-160GPa的弹性模量，优选20-150GPa的弹性模量，更优选30-140GPa的弹性模量。
  13. 根据权利要求1或2所述的骨骼植入物，其中所述钽基体、铌基体或钽铌合金基体为多孔的。
  14. 根据权利要求1或2所述的骨骼植入物，其中所述钽基体、铌基体或钽铌合金基体为致密的。
  15. 一种制备权利要求1-14中任一项所述的骨骼植入物的方法，其包括：
    (1)提供基体；和
    (2)在基体上形成多孔膜，
    其中所述基体选自钽基体、铌基体、钽铌合金基体和钛基体，优选所述基体选自钽基体、铌基体和钽铌合金基体，和
    其中所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜、多孔钽酸锂和铌酸锂的混合物膜和多孔钛氧化物膜，优选所述多孔膜选自多孔钽酸锂膜、多孔铌酸锂膜以及多孔钽酸锂和铌酸锂的混合物膜。
  16. 根据权利要求15所述的方法，其包括：
    (1)提供钽基体、铌基体、钽铌合金基体、或钛基体；和
    (2)在钽基体、铌基体、或钽铌合金基体上形成多孔钽酸锂膜、多孔铌酸锂膜、或多孔钽酸锂和铌酸锂的混合物膜，或在钛基体上形成多孔钛氧化物膜，
    其中钽酸锂膜含有钽氧化物，
    其中铌酸锂膜含有铌氧化物，和
    其中混合物膜含有钽氧化物和铌氧化物。
  17. 根据权利要求15或16所述的方法，其中在步骤(2)中通过熔盐电化学方法形成多孔膜。
  18. 根据权利要求15或16所述的方法，其中在步骤(2)之前在钽基体上形成Ta 2O 5膜。
  19. 根据权利要求18所述的方法，其中通过阳极氧化在钽基体上形成无定型Ta 2O 5膜。
  20. 根据权利要求19所述的方法，其中在钽基体上形成Ta 2O 5膜的步骤中，将钽基体置于室温至380℃，优选室温至300℃的含氧电解质溶液中，施加3至800V的阳极电压，恒压0.01至2小时，其中升压电流密度为1～200毫安/厘米 2，以形成无定型Ta 2O 5膜。
  21. 根据权利要求15或16所述的方法，其中在步骤(2)之前在铌基体上形成Nb 2O 5膜。
  22. 根据权利要求21所述的方法，其中通过阳极氧化在铌基体上形成无定型Nb 2O 5膜。
  23. 根据权利要求22所述的方法，其中在铌基体上形成Nb 2O 5膜的步骤中，将铌基体置于室温至380℃，优选室温至300℃的含氧电解质溶液中，施加3至800V的阳极电压，恒压0.01至2小时，其中升压电流密度为1～200毫安/厘米 2，以形成无定型Nb 2O 5膜。
  24. 根据权利要求15或16所述的方法，其中在步骤(2)之前在钽铌合金基体上形成Ta 2O 5和Nb 2O 5的混合物膜。
  25. 根据权利要求24所述的方法，其中通过阳极氧化在钽铌合金基体上形成无定型Ta 2O 5和Nb 2O 5的混合物膜。
  26. 根据权利要求25所述的方法，其中在钽铌合金基体上形成Ta 2O 5和Nb 2O 5的混合物膜的步骤中，将钽铌合金基体置于室温至380℃，优选室温至300℃的含氧电解质溶液中，施加3至800V的阳极电压，恒压0.01至2小时，其中升压电流密度为1～200毫安/厘米 2，以形成无定型Ta 2O 5和Nb 2O 5的混合物膜。
  27. 根据权利要求20、23和26中任一项所述的方法，其中所述含氧电解质溶液为水溶液、非水溶液、或水溶液电解质与有机化合物的混合物。
  28. 根据权利要求27所述的方法，其中熔盐电化学方法为熔融锂盐电化学方法。
  29. 根据权利要求15或16所述的方法，其中将钽基体、铌基体或钽铌合金基体置于250℃～650℃的含氧无机锂盐或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加1～66V的阳极电压，恒压0.01～200小时，其中升压电流密度为1～1000毫安/厘米 2，以形成含有含锂化合物的膜层。
  30. 根据权利要求29所述的方法，其中在步骤(2)中将钽基体、铌基体或钽铌合金基体置于440℃～600℃的含氧无机锂盐或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加10～30V的阳极电压，恒压5分钟～10小时，其中升压电流密度为5～20毫安/厘米 2，以形成含有含锂化合物的膜层。
  31. 根据权利要求29所述的方法，其中在步骤(2)中将钽基体、铌基体或钽铌合金基体置于570℃～598℃的含氧无机锂盐或含氧无机锂盐与氢氧化锂的混合熔融物中，或盐与氢氧化锂的混合熔融液或锂盐与含氧盐的混合熔融液中，施加10～20V的阳极电压，恒压8分钟～30分钟，其中升压电流密度为5～20毫安/厘米 2，以形成含有含锂化合物的膜层。
  32. 根据权利要求29所述的方法，其中含氧无机锂盐为LiNO 3。
  33. 根据权利要求29所述的方法，其中在步骤(c)中将超声波发生器设置于所述混合熔融物或所述混合熔融液中。
  34. 根据权利要求15或16所述的方法，其中对钽基体、铌基体或钽铌合金基体进行渗氮处理或渗碳处理。
  35. 骨骼植入物在医用材料中的用途，其中所述骨骼植入物如权利要求1-14中任一项所述或根据权利要求15-34中任一项所述的方法制备。
  36. 根据权利要求35的用途，其中所述医用材料为牙种植体或脑盖骨。
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