WO2022088704A1 - 带有骨小梁的含氧化层锆铌合金胫骨平台假体及制备方法 - Google Patents

带有骨小梁的含氧化层锆铌合金胫骨平台假体及制备方法 Download PDF

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WO2022088704A1
WO2022088704A1 PCT/CN2021/101287 CN2021101287W WO2022088704A1 WO 2022088704 A1 WO2022088704 A1 WO 2022088704A1 CN 2021101287 W CN2021101287 W CN 2021101287W WO 2022088704 A1 WO2022088704 A1 WO 2022088704A1
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WIPO (PCT)
Prior art keywords
trabecular
bone
intermediate product
zirconium
niobium alloy
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PCT/CN2021/101287
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English (en)
French (fr)
Inventor
刘璐
曹雨
李建宇
张景康
周红秀
Original Assignee
嘉思特华剑医疗器材(天津)有限公司
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Application filed by 嘉思特华剑医疗器材(天津)有限公司 filed Critical 嘉思特华剑医疗器材(天津)有限公司
Priority to US17/916,708 priority Critical patent/US20230338615A1/en
Priority to EP21884445.4A priority patent/EP4094729B1/en
Priority to JP2022549958A priority patent/JP7413554B2/ja
Publication of WO2022088704A1 publication Critical patent/WO2022088704A1/zh

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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00011—Metals or alloys
    • A61F2310/00035—Other metals or alloys
    • A61F2310/00095—Niobium or Nb-based 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention relates to the technical field of medical implant materials, in particular to a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer and a trabecular bone and a preparation method.
  • Total knee arthroplasty is an effective clinical treatment for end-stage knee joint diseases. It replaces the damaged knee joint tissue with artificially designed joint prostheses, thereby relieving the patient's pain, restoring their knee joint function, and improving their life. quality.
  • the components of the knee joint prosthesis include the femoral condyle, the tibial plateau and the platform pad.
  • knee joint prosthesis includes two categories: cement type and biological type (non-cement fixation).
  • cement type the cemented prosthesis relies on the curing and filling of the bone cement to mechanically fix the joint prosthesis and the bone tissue.
  • bone cement fixation can bring many safety and effectiveness problems: the polymerization of bone cement monomer releases heat, causing damage to surrounding tissues; if bone cement particles enter the blood or cause high pressure in the medullary cavity during filling, it will lead to Pulmonary embolism and fat embolism.
  • Biological knee joint prostheses can effectively eliminate the safety and efficacy risks brought by bone cement, and usually use the superficial porous structure to promote bone ingrowth and obtain long-term stability.
  • its surface porous structure is usually obtained by surface treatment processes such as sandblasting, coating, and sintering.
  • these porous structures cannot achieve effective bone ingrowth. According to clinical reports, only 2% to 40% of the tibial plateau of the artificial knee joint has bone ingrowth, which cannot form a strong biological fixation.
  • the patent CN109938888A uses EBM electron beam fusion technology to 3D print the tibial platform with a partitioned trabecular bone structure.
  • the transmission capacity of the force through the discontinuous medium is different.
  • the topology of trabecular bone in different horizontal directions makes the stress/strain of the tibial plateau/bone interface uniform, so as to achieve uniform bone ingrowth. But from the axial inspection of the platform/bone interface, the trabecular bone layer is the only transition layer. Stress shielding occurs between the high elastic modulus of the metal material of the prosthesis and the low elastic modulus of the bone tissue.
  • Zirconium-niobium alloys have excellent corrosion resistance, mechanical properties and good biocompatibility, and are gradually used in the field of medical devices.
  • Zirconium-niobium alloy can react with N, C, O and other elements to form a hard oxide layer on the surface, with excellent wear resistance and low wear rate, which can reduce the wear of soft materials, that is, it has excellent wear resistance of the joint surface interface;
  • the oxide layer can reduce the release of metal ions, and has excellent biocompatibility, that is, excellent biocompatibility with an osseointegrated interface.
  • the articular surface with low wear rate is organically compatible with the osseointegration interface (trabecular bone) with excellent bone ingrowth performance, which enables the prosthesis to achieve the advantages of both interfaces at the same time.
  • a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone by using a zirconium-niobium alloy there is no report on the preparation of a zircon
  • 3D printing technology breaks through the product design concept oriented to the manufacturing process and realizes the product design concept oriented to performance, which not only solves the difficulty of integral molding of complex parts, but also reduces the waste of raw materials and energy caused by machining. .
  • the solid part of the 3D printing product is prone to problems such as uneven microstructure and internal defects, and poor mechanical properties; the powder in the structure of the trabecular bone cannot be well sintered, and the mechanical properties are poor. Therefore, it is of great significance to prepare an oxide-coated zirconium-niobium alloy tibial plateau prosthesis with bone trabeculae with excellent mechanical properties and at the same time realizing the advantages of two interfaces.
  • the main purpose of the present invention is to overcome the deficiencies of the prior art and provide a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with bone trabeculae.
  • the second object of the present invention is to provide a method for preparing a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone.
  • a preparation method of a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone includes the following steps:
  • the first intermediate product of the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone is obtained by 3D printing, and the first intermediate product is placed in a hot isostatic Press furnace, under the protection of inert gas, heat up to 1250°C-1400°C, at 140MPa-180MPa, place at constant temperature for 1h-3h, reduce to normal pressure, cool down to below 200°C with the furnace, take out, and obtain the second intermediate product;
  • the fourth intermediate product is subjected to machining, finishing, polishing, cleaning and drying to obtain a fifth intermediate product, and the roughness Ra of the upper surface of the platform holder of the fifth intermediate product is less than or equal to 0.050 ⁇ m;
  • the fifth intermediate product is placed in the tube furnace, and the atmospheric pressure inert gas with an oxygen-containing mass percentage of 5%-15% is introduced, and heated to 500°C-700°C at 5°C/min-20°C/min, The temperature was lowered to 400°C-495°C at 0.4°C/min-0.9°C/min, and then naturally cooled to below 200°C and taken out to obtain a zirconium-niobium alloy tibial plateau prosthesis with trabecular bone.
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, the fifth intermediate product and the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone The structure of the zirconium-niobium alloy tibial plateau prosthesis is the same;
  • the inert gas is helium or argon
  • the oxide-containing zirconium-niobium alloy tibial platform prosthesis with trabecular bone includes a kidney-shaped platform support 1, and a dovetail-shaped bump 3 is arranged on the upper surface of the inwardly curved part of the kidney-shaped platform support.
  • the outer surfaces of the two oblique branches of The inner side of the block 2 is provided with a front groove 6, the middle part of the kidney-shaped platform supports the lower surface is provided with a handle 4, and other parts of the kidney-shaped platform support lower surface except the connecting handle 4 are provided with trabecular bone 9, trabecular bone 9
  • It is composed of a near-platform bone-supporting trabecular layer 21 and a far-platform bone-supporting trabecular layer 20; the pore diameter and porosity of the near-platform bone-supporting trabecular layer 21 are set uniformly, and the far-platform bone-supporting trabecular layer is set in three zones;
  • the transverse diameter 10 of the kidney-shaped platform holder is divided into a first section 25, a second section 26 and a third section 27 by the first marking point 11 and the second marking point 12, and the first section, the second section and the third section.
  • the length is 25%-38%: 24%-50%: 25%-38% of the transverse diameter of the kidney-shaped platform, the first division line 13 passes the first mark point 11, and the second division line 15 passes the second mark.
  • Point 12; the first partition line 13 and the second partition line 14 are straight lines or arcs, and divide the distal platform trabecular layer 20 of the corresponding kidney-shaped platform support into medial area 15, middle area 16 and lateral area 17 ;
  • the pore size and porosity of the trabecular bone in the medial area 15 are sequentially larger than those in the lateral area 17 and the middle area 16.
  • the chemical composition of the zirconium-niobium alloy powder is 85.6%-96.5% Zr, 1.0%-12.5% Nb by mass percentage, and the rest are inevitable impurities; the particle size of the zirconium-niobium alloy powder is 45-150 ⁇ m.
  • Steps 2), 3) The adjustment temperature is: raise the temperature to -120°C ⁇ -80°C, keep the constant temperature for 3h-5h; then raise the temperature to -40°C ⁇ -20°C, keep the constant temperature for 3h-5h; then raise the temperature to 4°C -8 °C, the constant temperature is maintained for 1h-3h, and the temperature is increased.
  • the bone trabecular diameter of the proximal platform trabecular layer 21 is 0.36mm-0.50mm, the porosity is 55%-65%, the through-porosity is 100%, and the thickness is 0.2mm-1mm.
  • first partition line 13 and the second partition line 14 of the far platform bone support trabecular layer 20 are straight lines, they are arranged in parallel or in a figure-of-eight shape; The degree is 100°-60°, and the degree of the included angle 19 between the second division line 14 and the transverse diameter 10 of the kidney-shaped platform bracket is 80°-120°.
  • the diameter of the trabecular bone in the medial area of the distal platform trabecular layer (20) is 1.00mm-1.10mm, the porosity is 77.6%-85%, and the through-hole rate is 100%; the diameter of the trabecular bone in the middle area is 0.74mm -0.85mm, the porosity is 70.0%-74.7%, and the through porosity is 100%; the diameter of the trabecular bone in the lateral area is 0.86mm-0.99mm, the porosity is 74.8%-77.5%, and the through porosity is 100%; the thickness 0.5mm-3mm.
  • the handle is a reducing pipe connected with a support plate, a reducing pipe with a closed bottom connected with the support plate, a cross-shaped rib plate or a curved cross-shaped rib plate.
  • a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer prepared by the above method is provided.
  • the present invention has the following beneficial effects:
  • the trabecular topological structure of the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with bone trabeculae of the invention is distributed gradiently in three dimensions, which can improve the bonding strength of the tibial plateau bone trabecula and the entity and realize the tibial plateau bone tissue.
  • the microstrain in the 64%-72% area of the finite element model is between the minimum effective strain threshold and the supraphysiological strain threshold, which increases the mechanical adaptability of the prosthesis and has excellent bone ingrowth.
  • the invention adopts 3D printing to form integrally, solves the problem that traditional machining cannot prepare complex structures, and has high bonding strength between trabecular bone and solid body, is not easy to fall off, and prolongs the life of the prosthesis.
  • the bone trabecular part of the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with bone trabeculae prepared by the invention has excellent compressive performance; the compressive yield strength of the solid part is enhanced, and the plasticity is enhanced.
  • the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with bone trabeculae can be integrated to achieve excellent biocompatibility of the osseointegration interface, bone ingrowth, super wear resistance and low wear of the friction interface. Rate.
  • the zirconium-niobium alloy tibial plateau prosthesis with trabecular bone according to the invention has an oxygen-rich layer between the oxide layer and the substrate, and the oxygen-enriched layer has the function of a transition layer to improve the adhesion between the oxide layer and the substrate. Avoid the oxide layer falling off; and the oxide layer has high hardness.
  • the zirconium-niobium alloy tibial plateau prosthesis with trabecular bone according to the invention has low artifact, little interference to nuclear magnetic resonance, and can be detected by nuclear magnetic resonance.
  • Fig. 1 is an axonometric view of a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone according to the present invention (the stem is a curved cross-shaped rib plate).
  • Figure 2 is a schematic diagram of the division of trabecular bone on the lower surface of the oxide-bearing zirconium-niobium alloy tibial plateau prosthesis with bone trabeculae according to the present invention.
  • Fig. 3 is the bottom view of the oxide-coated zirconium-niobium alloy tibial plateau prosthesis with trabecular bone according to the present invention (the stem is a curved cross-shaped rib plate).
  • FIG. 4 is a bottom view of the zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone according to the present invention (the first partition line 13 and the second partition line 14 are arcs).
  • FIG. 5 is a bottom view of the tibial plateau prosthesis with oxide layer of zirconium-niobium alloy with trabecular bone according to the present invention (the first partition line 13 and the second partition line 14 are straight and arranged in a figure-eight shape).
  • Fig. 6 is an axonometric view of a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone according to the present invention (the stem is a reducing tube with a closed bottom).
  • the stem is a reducing tube with a closed bottom, a kidney-shaped platform bracket and a partial section of the trabecular bone layer.
  • the stem is a bottom-closed reducing tube connected with a support plate) (excluding the trabecular bone layer of the distal platform).
  • Fig. 9 is an axonometric view of a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone according to the present invention (the stem is a reducing tube connected with a support plate).
  • Fig. 10 shows the tibial plateau prosthesis of zirconium-niobium alloy containing oxide layer with bone trabeculae (the stem is a curved cross-shaped rib plate) of Example 1.
  • the first partition line 13 and the second partition line 14 are straight lines parallel to the transverse diameter (The length of the tibial plateau) when the angle is 90 degrees, the finite element analysis strain cloud map.
  • Figure 11 shows the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone in Example 2 (the stem is a bottom-closed reducing tube connected with a support plate).
  • the first partition line 13 and the second partition line 14 are:
  • the straight line is a figure-eight finite element analysis strain cloud diagram.
  • Fig. 12 shows the tibial plateau prosthesis of zirconium-niobium alloy containing oxide layer with trabecular bone of Example 3 (the stem is a bottom-sealed reducing tube connected with a support plate).
  • the first partition line 13 and the second partition line 14 are in the shape of Arc Finite Element Analysis Strain Contour.
  • FIG. 13 is the metallographic microstructure diagram of the solid part of the control group 1 (A is the observation at a magnification of 50 times; B is an observation at a magnification of 500 times).
  • FIG. 14 is a metallographic microstructure diagram of the solid part of Example 1 without steps 4) and 5) in the preparation method (A is for observation at a magnification of 50 times; B is for observation at a magnification of 500 times).
  • FIG. 15 is a SEM image of the trabecular bone part of control group 1.
  • FIG. 16 is a SEM image of the bone trabecular portion of Example 1 without steps 4) and 5) in the preparation method.
  • FIG. 17 is a cross-sectional SEM image of the oxide layer and the substrate of Example 1.
  • FIG. 18 is the XRD curve of the surface of the oxide layer of Example 1.
  • Fig. 19 shows the tibial plateau prosthesis of zirconium-niobium alloy containing oxide layer with bone trabeculae (the stem is a curved cross-shaped rib plate) of Example 1.
  • the first partition line 13 and the second partition line 14 are straight lines parallel to the transverse diameter (The length of the tibial plateau) is the equivalent stress contour when the included angle is 90 degrees.
  • a preparation method of a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone includes the following steps:
  • the first intermediate product of the oxide-bearing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone is obtained by 3D printing, and the first intermediate product is placed in a hot isostatic pressing furnace , under the protection of helium, heat up to 1250 °C, at 180 MPa, place at a constant temperature for 3 hours, drop to normal pressure, cool down to below 200 °C with the furnace and take out to obtain the second intermediate product;
  • Steps 2) and 3) The specific steps of adjusting the temperature are as follows: heating to -120°C, maintaining a constant temperature for 5 hours; then heating to -40°C, maintaining a constant temperature for 5 hours; then heating to 4°C, maintaining a constant temperature for 3 hours, and heating up.
  • the fifth intermediate product is placed in the tube furnace, and the normal pressure helium gas containing 5% oxygen-containing mass percentage is introduced, heated to 500°C with 5°C/min, cooled to 400°C with 0.4°C/min, and then Naturally cooled to below 200°C and taken out to obtain a zirconium-niobium alloy tibial plateau prosthesis with trabecular bone.
  • the structure of the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product and the fifth intermediate product of the oxide-bearing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone and the structure of the tibial plateau prosthesis with trabecular bone The structure of the oxide-coated zirconium-niobium alloy tibial plateau prosthesis is the same.
  • the chemical composition of the zirconium-niobium alloy powder is 85.6% Zr, 12.5% Nb, and the rest are inevitable impurities; limited liability company.
  • a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone including a kidney-shaped platform bracket 1, a dovetail-shaped bump 3 is arranged on the upper surface of the inwardly curved part of the kidney-shaped platform bracket, and the dovetail
  • the outer sides of the two oblique branches of the shaped bump 3 are provided with a rear groove 5, and an arc-shaped bump 2 is provided on the upper surface of the kidney-shaped platform support 1 and the outward bend relative to the dovetail-shaped bump 3,
  • the inner side of the arc-shaped bump 2 is provided with a front groove 6, the middle part of the lower surface of the kidney-shaped platform is provided with a handle 4, and other parts of the lower surface of the kidney-shaped platform except the connecting handle 4 are provided with trabecular bone 9.
  • Trabecular 9 is composed of a proximal platform bone supporting trabecular layer 21 and a distal platform bone supporting trabecular layer 20 (see FIG. 7 ); the pore size and porosity of the proximal platform bone supporting trabecular layer 21 are uniformly set (see FIG. 8 ) , the trabecular layer of the distal platform support is arranged in three partitions; the transverse diameter 10 of the corresponding kidney-shaped platform support is divided into the first section 25, the second section 26 and the third section by the first marking point 11 and the second marking point 12 27.
  • the lengths of the first, second and third sections are 30%: 40%: 30% of the transverse diameter of the kidney-shaped platform bracket, the first division line 13 passes the first marking point 11, and the second division line 14 Pass the second marking point 12; the first partition line 13 and the second partition line 14 are straight lines or arcs, and the distal platform trabecular layer 20 of the corresponding kidney-shaped platform support is divided into the medial area 15 and the middle area 16 and outer zone 17 (see Figure 2);
  • the bone trabecular diameter of the near-platform bone support trabecular layer 21 is 0.43 mm, the porosity is 60%, the through-porosity is 100%, and the thickness is 0.6 mm.
  • first partition line 13 and the second partition line 14 of the distal platform trabecular layer 20 are straight lines, they are arranged in parallel; the angle 18 between the first partition line 13 and the kidney-shaped platform support transverse diameter 10 is 90° ( See FIG. 3 ), the angle 19 between the second division line 14 and the transverse diameter 10 of the kidney-shaped platform bracket is 90°.
  • the diameter of the trabecular bone in the medial area of the distal platform trabecular layer 20 is 1.05 mm, the porosity is 80%, and the porosity is 100%; the diameter of the trabecular bone in the middle area is 0.80 mm, and the porosity is 72%.
  • the porosity is 100%; the diameter of the trabecular bone in the lateral area is 0.90mm, the porosity is 75%, and the through porosity is 100%; the thickness is 2mm.
  • the shank is a curved cross-shaped rib (see Figure 3).
  • a side wall 22 can also be arranged on the edge of the lower surface of the kidney-shaped platform, so that the trabecular bone layer is arranged inside the side wall, as shown in FIG. 7 .
  • the preparation method of a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone includes the following steps:
  • the first intermediate product of the oxide-bearing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone is obtained by 3D printing, and the first intermediate product is placed in a hot isostatic pressing furnace , under the protection of helium, heat up to 1325 °C, place at 160 MPa for 2 hours at a constant temperature, reduce to normal pressure, cool down to below 200 °C with the furnace and take out to obtain the second intermediate product;
  • Steps 2) and 3) of adjusting the temperature are as follows: the temperature is raised to -100°C, and kept at a constant temperature for 4 hours; the temperature is then raised to -30°C, and the temperature is kept at a constant temperature for 4 hours; the temperature is raised to 6°C and kept at a constant temperature for 2 hours, and the temperature is raised;
  • the fifth intermediate product is placed in the tube furnace, and the normal pressure helium gas containing 10% oxygen-containing mass percentage is introduced, heated to 600°C at 15°C/min, cooled to 450°C at 0.7°C/min, and then heated to 600°C at 15°C/min.
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, the fifth intermediate product and the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone The structure of the zirconium-niobium alloy tibial plateau prosthesis is the same;
  • the chemical composition of the zirconium-niobium alloy powder is 93.4% Zr, 5.1% Nb, and the rest are inevitable impurities by mass percentage; Metal Materials LLC.
  • a zirconium-niobium alloy tibial plateau prosthesis with an oxide layer with trabecular bone including a kidney-shaped platform bracket 1, a dovetail-shaped bump 3 is arranged on the upper surface of the inwardly curved part of the kidney-shaped platform bracket, and the dovetail
  • the outer sides of the two oblique branches of the shaped bump 3 are provided with a rear groove 5, and an arc-shaped bump 2 is provided on the upper surface of the kidney-shaped platform support 1 and the outward bend relative to the dovetail-shaped bump 3,
  • the inner side of the arc-shaped bump 2 is provided with a front groove 6, the middle part of the lower surface of the kidney-shaped platform is provided with a handle 4, and other parts of the lower surface of the kidney-shaped platform except the connecting handle 4 are provided with trabecular bone 9.
  • the trabecular 9 is composed of a near-platform bone-supporting trabecular layer 21 and a far-platform bone-supporting trabecular layer 20; the pore diameter and porosity of the near-platform bone-supporting trabecular layer 21 are uniformly set, and the far-platform bone-supporting trabecular layer is three-dimensional.
  • the transverse diameter 10 of the corresponding kidney-shaped platform holder is divided into the first section 25, the second section 26 and the third section 27 by the first marking point 11 and the second marking point 12, the first section, the second section and The length of the third segment is 38%: 24%: 38% of the transverse diameter of the kidney-shaped platform, the first division line 13 passes through the first marking point 11, and the second division line 14 passes through the second marking point 12;
  • the line 13 and the second partition line 14 are straight lines, and divide the distal platform trabecular layer 20 of the corresponding kidney-shaped platform bracket into a medial region 15 , a middle region 16 and a lateral region 17 .
  • the trabecular bone diameter of the near-platform bone support trabecular layer 21 is 0.50 mm, the porosity is 65%, and the through porosity is 100%; the thickness of the near-platform bone support trabecular layer 21 is 1 mm.
  • first partition line 13 and the second partition line 14 of the far platform bone support trabecular layer 20 are straight, they are arranged in a figure-eight shape; the angle 18 between the first partition line 13 and the kidney-shaped platform support transverse diameter 10 is 100°, the angle 19 between the second division line 14 and the transverse diameter 10 of the kidney-shaped platform bracket is 80°. (Except for the stem, the trabecular layer of the distal platform is shown in Figure 5)
  • the diameter of the trabecular bone in the medial region of the distal platform trabecular layer 20 is 1.10 mm, the porosity is 85%, and the through porosity is 100%; the diameter of the trabecular bone in the middle region is 0.85 mm, and the porosity is 74.7%. , the porosity is 100%; the trabecular diameter in the lateral area is 0.99mm, the porosity is 77.5%, and the porosity is 100%; the thickness of the distal platform trabecular layer 20 is 0.5mm.
  • the shank is a bottom closed reducer connected to a support plate (see Figure 6 for the shank).
  • the finite element analysis strain cloud diagram of this embodiment is shown in Fig. 11 .
  • a preparation method of a zirconium-niobium alloy tibial plateau prosthesis containing an oxide layer with trabecular bone comprising the following steps:
  • the first intermediate product of the oxide-bearing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone is obtained by 3D printing, and the first intermediate product is placed in a hot isostatic Press furnace, under the protection of argon, heat up to 1400 °C, place at 140 MPa at a constant temperature for 1 hour, reduce to normal pressure, cool down to below 200 °C with the furnace and take out to obtain the second intermediate product;
  • Steps 2) and 3) The specific steps of adjusting the temperature are: heating to -80°C, maintaining a constant temperature for 3 hours; heating to -20°C, maintaining a constant temperature for 3 hours; heating to 8°C, maintaining a constant temperature for 1 hour, and heating up.
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, the fifth intermediate product and the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone The structure of the zirconium-niobium alloy tibial plateau prosthesis is the same;
  • the chemical composition of the zirconium-niobium alloy powder is 96.5% Zr, 1% Nb, and the rest are inevitable impurities by mass percentage; Metal Materials Co., Ltd.;
  • An oxide-containing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone includes a kidney-shaped platform support 1, a dovetail-shaped bump 3 is arranged on the upper surface of the inwardly curved part of the kidney-shaped platform support, and a dovetail-shaped bump 3 is provided on the upper surface of the kidney-shaped platform support.
  • the outer sides of the two oblique branches are provided with a rear groove 5, and an arc-shaped bump 2 is provided on the upper surface of the kidney-shaped platform support 1 and the outward bend relative to the dovetail-shaped bump 3, and the arc-shaped bump 2
  • the inner side of the kidney-shaped platform is provided with a front groove 6, the middle part of the lower surface of the kidney-shaped platform is provided with a handle 4, and the other part of the lower surface of the kidney-shaped platform is provided with trabecular bone 9 except for the connecting handle 4, and the trabecular bone 9 is provided with a trabecular bone.
  • the platform bone support trabecular layer 21 and the distal platform bone support trabecular layer 20 are composed of; the pore diameter and porosity of the near platform bone support trabecular layer 21 are uniformly set, and the far platform bone support trabecular layer is arranged in three zones; corresponding
  • the transverse diameter 10 of the kidney-shaped platform holder is divided into the first section 25, the second section 26 and the third section 27 by the first marking point 11 and the second marking point 12, and the length of the first section, the second section and the third section is The order is 25%-: 50%: 25% of the transverse diameter of the kidney-shaped platform, the first partition line 13 passes through the first marking point 11, the second partition line 14 passes through the second marking point 12;
  • the two-division line 14 is an arc (see FIG. 4 ), and divides the trabecular layer 20 of the distal platform bone support corresponding to the kidney-shaped platform support into a medial area 15, a middle area 16 and a lateral area 17;
  • the trabecular diameter of the trabecular bone layer 21 near the platform is 0.36 mm, the porosity is 55%, the through-porosity is 100%, and the thickness is 0.2 mm.
  • the diameter of the trabecular bone in the medial region of the distal platform trabecular layer 20 is 1.00 mm, the porosity is 77.6%, and the through-porosity is 100%; the diameter of the trabecular bone in the middle region is 0.74 mm, and the porosity is 70.0%. , the porosity is 100%; the trabecular diameter in the lateral area is 0.86mm, the porosity is 74.8%, and the porosity is 100%; the thickness of the distal platform trabecular layer 20 is 3mm.
  • the handle is a bottom-closed reducing tube connected with a support plate.
  • the finite element analysis strain cloud diagram of this embodiment is shown in Fig. 12 .
  • a side wall 22 can also be provided on the edge of the lower surface of the kidney-shaped platform, so that the trabecular bone layer is arranged inside the side wall.
  • Example 1 Using zirconium-niobium alloy powder (same as Example 1) as the raw material, through 3D printing integral molding and machining trimming, the tibial plateau prosthesis with the same structure as Example 1 was obtained.
  • the finite element models of Examples 1, 2, and 3 are subjected to finite element analysis, and the obtained finite element analysis strain cloud map only shows the microstrain (shaded part) in the range of 1000-3000.
  • Examples 1-3 are in the tibial plateau bone
  • the proportion of 1000-3000 microstrain areas on the tissue finite element model in the whole tibial plateau bone tissue finite element model is 65.6%, 64.4% and 68.1% respectively (Figs. 10, 11, 12), suggesting that the The zirconium-niobium alloy tibial plateau prosthesis with trabecular oxide layer can realize the microstrain in most areas of the bone tissue between the minimum effective strain threshold and the supraphysiological strain threshold, which is conducive to bone ingrowth.
  • An electronic universal testing machine (UTM5105, Shenzhen Sansi Zongheng Technology Co., Ltd., China) used a solid compression test piece (the size of the test piece is: 8*8*) without performing steps 4) and 5) of the preparation method in Example 1. 10mm 3 ) and the solid compression test pieces of the control group 1 (specimen size: 8*8*10 mm 3 ) were tested for compression performance, and each of the solid compression test pieces of Example 1 and the control group 1 was 5 pieces. The results are shown in Table 1.
  • Example 1 The compressive yield strength of Example 1 is 546.72MPa, which is better than that of control group 1 (P ⁇ 0.05), indicating that the tibial plateau of zirconium-niobium alloy containing oxide layer with bone trabeculae prepared by the present invention
  • the solid part of the prosthesis has excellent resistance to compression.
  • XRD XRD (D8DISCOVER, Bruker, Germany) analyzed the oxide layer of the oxide-bearing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone in Example 1 (Fig. 18), and the oxide layer contained monoclinic zirconium dioxide and tetragonal Phase zirconium dioxide.
  • a microhardness tester (MHVS-1000 PLUS, Shanghai Aolong Xingdi Testing Equipment Co., Ltd., China) was used to measure the microhardness of the oxide-bearing zirconium-niobium alloy tibial plateau prosthesis with trabecular bone in Examples 1-3 , the test load is 0.05kg, the load time of the specimen is 20s, and 8 points are taken for each specimen.
  • the average hardness values measured in Examples 1-3 are 1948.6Hv, 1923.7Hv and 1967.2Hv, indicating that the oxide-layer zirconium-niobium alloy tibial plateau prosthesis with trabecular bone according to the present invention has high oxide layer hardness.
  • the finite element model of Example 1 is subjected to finite element analysis, and the results are shown in Figure 19.
  • the stress concentration between the bone trabeculae and the solid connection part of the oxide-containing zirconium-niobium alloy tibial plateau prosthesis with bone trabeculae in Example 1 The area is small, indicating that the tibial plateau prosthesis with zirconium-niobium alloy containing oxide layer with trabecular bone of the present invention has excellent bonding strength between the trabecular bone and the solid body.

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Abstract

带有骨小梁的含氧化层锆铌合金胫骨平台假体及制备方法。制备方法包括：以锆铌合金粉为原料，经3D打印一体成型得到中间产物，再经热等静压、深冷和表面氧化，制备出包括近平台托骨小梁层（21）和远平台托骨小梁层（20）的胫骨平台假体，近平台托骨小梁层（21）孔径和孔隙率均匀设置，远平台托骨小梁层（20）孔径和孔隙率分区设置。所制备的胫骨平台假体的骨小梁拓扑结构三个维度梯度分布，有限元模型64％‑72％区域的微应变在最低有效应变阈值和超生理应变阈值之间，增加假体力学适配性，具有优异骨长入性；所形成的氧化层可一体化实现骨整合界面优良生物相容性和摩擦界面的超强耐磨性能、低磨损率。

Description

带有骨小梁的含氧化层锆铌合金胫骨平台假体及制备方法 技术领域
本发明涉及医用植入物材料技术领域，具体涉及带有骨小梁的含氧化层锆铌合金胫骨平台假体及制备方法。
背景技术
全膝关节置换术是目前临床上针对终末期膝关节疾患的有效治疗方式，其通过人工设计的关节假体替代损伤的膝关节组织，从而解除病患疼痛，恢复其膝关节功能，改善其生活质量。与人体解剖结构相对应，膝关节假体的组成包括股骨髁、胫骨平台及平台垫。随着医疗器械技术的飞速发展以及人们对假体产品安全与有效性要求的不断提高，膝关节假体设计和制造技术将需要不断的优化和提升。
目前，临床上应用的膝关节假体包括骨水泥型和生物型(非骨水泥固定)两大类。其中，骨水泥型假体依靠骨水泥的固化和填充，将关节假体与骨组织机械固定。但多年的临床应用发现，骨水泥固定可带来诸多安全与有效性问题：骨水泥单体聚合释放热量，造成周围组织损伤；骨水泥颗粒如果进入血液或在填充时引起髓腔高压，会导致肺栓塞和脂肪栓塞。
生物型膝关节假体可有效消除骨水泥带来的安全与有效性风险，通常利用表面多孔结构促进骨长入，获得长期稳定性。但其表面多孔结构通常采用喷砂、涂层、烧结等表面处理工艺制得，与实体结合强度低，易脱落，降低假体使用寿命。且这些多孔结构并不能实现有效骨长入，临床报道人工膝关节胫骨平台仅有2％～40％骨长入，无法形成有力的生物学固定。
专利CN109938888A通过EBM电子束熔融技术3D打印带有分区骨小梁结构胫骨平台，在人体下肢力线偏移，水平方向受力不均的情况下，通过不连续介质对力的传递能力不同，设计不同水平方向骨小梁分区拓扑结构，使得胫骨平台/骨界面应力/应变均一，从而实现均匀骨长入。但是从轴向考察平台/骨界面，骨小梁层为唯一过渡层。假体金属材质的高弹性模量与骨组织的低弹性模量间会发生应力遮挡。根据Wolff定律：应力只有使骨产生形变(又称微应变)后才能启动原始信号来调节骨的合成与分解代谢，且应变范围只有在最低有效应变阈值和超生理应变阈值之间才能促进骨生长。因此，设计一种膝关节胫骨平台假体，大幅减少应力遮挡，实现骨组织大部分区域微应变在最低有效应变阈值和超生理应变阈值之间，利于骨整合，具有重要意义。
锆铌合金具有优异耐腐蚀性、力学性能和良好生物相容性，被逐渐应用于医疗器械领域。锆铌合金可与N、C、O等元素反应在表面形成坚硬的氧化层，具有优异耐磨性和低磨损率，可降低对软体材料的磨损，即具有关节面界面的优异耐磨性；且氧化层可降低金属离子的释放，具有优异生物相容性，即具有骨整合界面的优异生物相容性。低磨损率的关节面与骨长入性能优异的骨整合界面(骨小梁)有机配伍，可使假体同时实现两界面优 点。但现有技术尚未有采用锆铌合金制备带有骨小梁的的含氧化层锆铌合金胫骨平台假体的报道。
3D打印技术，作为一种增材制造技术，突破面向制造工艺的产品设计概念，实现面向性能的产品设计理念，即解决复杂零件难以整体成型难题，又减少机加工制造带来的原材料和能源浪费。但3D打印产品实体部分易存在显微组织不均匀、内部缺陷等问题，力学性能不佳；骨小梁部分结构中粉末未能得到良好熔结，力学性能差。因此，制备力学性能优异、同时实现两界面优点的带有骨小梁的含氧化层锆铌合金胫骨平台假体具有重要意义。
发明内容
本发明的主要目的在于克服现有技术不足，提供带有骨小梁的含氧化层锆铌合金胫骨平台假体。
本发明的第二个目的是提供带有骨小梁的含氧化层锆铌合金胫骨平台假体的制备方法。
本发明的技术方案概述如下：
带有骨小梁的含氧化层锆铌合金胫骨平台假体的制备方法，包括如下步骤：
1)以锆铌合金粉为原料，经3D打印一体成型得到带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物，将所述第一中间产物放入热等静压炉，在惰性气体保护下，升温至1250℃-1400℃，在140MPa-180MPa，恒温放置1h-3h，降至常压，随炉冷却至200℃以下取出，得到第二中间产物；
2)将第二中间产物放置于程序性降温盒中以1℃/min的速度降温至-80℃～-120℃，恒温放置5h-10h，从程序性降温盒中取出；在液氮中再放置16h-36h，调节温度至室温，得到第三中间产物；
3)将第三中间产物放置于程序性降温盒中以1℃/min的速度降温至-80℃～-120℃，恒温放置5h-10h；从程序性降温盒中取出；在液氮中再放置16h-36h，调节温度至室温；得第四中间产物；
4)将第四中间产物进行机加工修整、抛光、清洗和干燥，得第五中间产物，所述第五中间产物平台托上表面的粗糙度Ra≤0.050μm；
5)将第五中间产物放置于管式炉内，通入含氧质量百分比为5％-15％的常压惰性气体，以5℃/min-20℃/min加热至500℃-700℃，以0.4℃/min-0.9℃/min降温至400℃-495℃，再自然冷却至200℃以下取出，得到带有骨小梁的含氧化层锆铌合金胫骨平台假体；
带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与带有骨小梁的含氧化层锆铌合金胫骨平台假体的结构相同；
所述惰性气体为氦气或氩气；
所述带有骨小梁的含氧化层锆铌合金胫骨平台假体，包括肾形平台托1，在肾形平台 托内向弯处的上表面设置有燕尾形凸块3，在燕尾形凸块3的两个斜向枝的外侧面设置有后凹槽5，在肾形平台托1与相对于燕尾形凸块3的外向弯处的上表面设置有弧形凸块2，在弧形凸块2的内侧面设置有前凹槽6，肾形平台托下表面的中部设置有柄4，肾形平台托下表面除连接柄4以外的其它部分设置有骨小梁9，骨小梁9由近平台托骨小梁层21和远平台托骨小梁层20组成；所述近平台托骨小梁层21的孔径和孔隙率均匀设置，远平台托骨小梁层呈三分区设置；相对应肾形平台托的横径10被第一标注点11和第二标注点12划分为第一段25、第二段26和第三段27，第一段、第二段和第三段的长依次为肾形平台托横径的25％-38％:24％-50％:25％-38％，第一分区线13过第一标注点11，第二分区线15过第二标注点12；第一分区线13和第二分区线14为直线或弧线，并将相对应肾形平台托的远平台托骨小梁层20划分为内侧区15、中间区16和外侧区17；内侧区15骨小梁的孔径和孔隙率依次大于外侧区17和中间区16骨小梁的孔径和孔隙率。
锆铌合金粉的化学成分按质量百分比为85.6％-96.5％的Zr，1.0％-12.5％的Nb，其余为不可避免的杂质；所述锆铌合金粉的粒径为45-150μm。
步骤2)、3)所述调节温度为：升温至-120℃～-80℃，恒温保持3h-5h；再升温至-40℃～-20℃，恒温保持3h-5h；再升温至4℃-8℃，恒温保持1h-3h，升温。
近平台托骨小梁层21的骨小梁孔径为0.36mm-0.50mm，孔隙率为55％–65％，通孔率为100％；厚度为0.2mm-1mm。
远平台托骨小梁层20的第一分区线13和第二分区线14为直线时呈平行设置或呈八字形设置；第一分区线13与肾形平台托横径10的夹角18的度数为100°-60°，第二分区线14与肾形平台托横径10的夹角19的度数为80°-120°。
远平台托骨小梁层(20)的内侧区骨小梁的孔径为1.00mm-1.10mm，孔隙率为77.6％–85％，通孔率为100％；中间区骨小梁孔径为0.74mm-0.85mm，孔隙率为70.0％-74.7％，通孔率为100％；外侧区骨小梁孔径为0.86mm-0.99mm，孔隙率为74.8％-77.5％，通孔率为100％；厚度为0.5mm-3mm。
柄为连接有支撑板的变径管、连接有支撑板的底部封闭的变径管、十字形筋板或弯曲十字形筋板。
上述方法制备的带有骨小梁的含氧化层锆铌合金胫骨平台假体。
与现有技术方案相比，本发明具有以下有益效果：
本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体的骨小梁拓扑结构从三个维度上梯度分布，可提高胫骨平台骨小梁与实体的结合强度和实现胫骨平台骨组织有限元模型64％-72％区域的微应变在最低有效应变阈值和超生理应变阈值之间，增加假体力学适配性，具有优异骨长入性。
本发明采用3D打印一体成型，解决传统机加工无法制备复杂结构的难题，且骨小梁与实体结合强度高，不易脱落，提升假体寿命。
本发明制得的所述带有骨小梁的含氧化层锆铌合金胫骨平台假体的骨小梁部分具有 优异抗压性能；实体部分抗压屈服强度增强，塑性增强。
本发明所述带有骨小梁的含氧化层锆铌合金胫骨平台假体可一体化实现骨整合界面的优良生物相容性、骨长入性和摩擦界面的超强耐磨性、低磨损率。
本发明所述带有骨小梁的含氧化层锆铌合金胫骨平台假体的氧化层与基体之间存在富氧层，富氧层有过渡层作用，提高氧化层与基体之间附着力，避免氧化层脱落；且氧化层硬度高。
本发明所述带有骨小梁的含氧化层锆铌合金胫骨平台假体低伪影，对核磁干扰小，可进行核磁检测。
附图说明
图1为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为弯曲十字形筋板)轴测图。
图2为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体下表面骨小梁分区划分示意图。
图3为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为弯曲十字形筋板)仰视图。
图4为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体(第一分区线13和第二分区线14为弧线)仰视图。
图5为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体(第一分区线13和第二分区线14为直线呈八字形设置)仰视图。
图6为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为底部封闭的变径管)轴测图。
图7为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为底部封闭的变径管、肾形平台托和骨小梁层局剖)轴测图。
图8为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为连接有支撑板的底部封闭的变径管)轴测图(不包括远平台骨小梁层)。
图9为本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为连接有支撑板的变径管)轴测图。
图10为实施例1的带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为弯曲十字形筋板)第一分区线13和第二分区线14为直线平行且与横径(胫骨平台的长)的夹角为90度时有限元分析应变云图。
图11为实施例2的带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为连接有支撑板的底部封闭的变径管)第一分区线13和第二分区线14为直线呈八字形有限元分析应变云图。
图12为实施例3的带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为连接有支撑板的底部封闭的变径管)第一分区线13和第二分区线14呈弧线有限元分析应变云图。
图13为对照组1的实体部分金相显微结构图(A为放大50倍观察；B为放大500倍观察)。
图14为实施例1的未进行制备方法中步骤4)和步骤5)的实体部分金相显微结构图(A为放大50倍观察；B为放大500倍观察)。
图15为对照组1的骨小梁部分SEM图。
图16为实施例1的未进行制备方法中步骤4)和步骤5)的骨小梁部分SEM图。
图17为实施例1的氧化层与基体的横截面SEM图。
图18为实施例1的氧化层表面的XRD曲线。
图19为实施例1的带有骨小梁的含氧化层锆铌合金胫骨平台假体(柄为弯曲十字形筋板)第一分区线13和第二分区线14为直线平行且与横径(胫骨平台的长)的夹角为90度时等效应力云图。
具体实施方式
下面通过具体实施例对本发明作进一步的说明。
实施例1
带有骨小梁的含氧化层锆铌合金胫骨平台假体的制备方法，包括如下步骤：
1)以锆铌合金粉为原料，经3D打印一体成型得到带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物，将第一中间产物放入热等静压炉，在氦气保护下，升温至1250℃，在180MPa，恒温放置3h，降至常压，随炉冷却至200℃以下取出，得到第二中间产物；
2)将第二中间产物放置于程序性降温盒中以1℃/min的速度降温至-80℃，恒温放置10h，从程序性降温盒中取出；在液氮中再放置16h，调节温度至室温，得到第三中间产物；
3)将第三中间产物放置于程序性降温盒中以1℃/min的速度降温至-80℃，恒温放置10h；从程序性降温盒中取出；在液氮中再放置16h，调节温度至室温；得第四中间产物；
步骤2)、3)调节温度具体步骤是：升温至-120℃，恒温保持5h；再升温至-40℃，恒温保持5h；再升温至4℃，恒温保持3h，升温。
4)将第四中间产物进行机加工修整、抛光、清洗和干燥，得第五中间产物，所述第五中间产物平台托上表面的粗糙度Ra＝0.012μm；
5)将第五中间产物放置于管式炉内，通入含氧质量百分比为5％的常压氦气，以5℃/min加热至500℃，以0.4℃/min降温至400℃，再自然冷却至200℃以下取出，得到带有骨小梁的含氧化层锆铌合金胫骨平台假体；
带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物、第二中间产物、第三中间产物、第四中间产物和第五中间产物的结构与带有骨小梁的含氧化层锆铌合金胫骨平台假体的结构相同。
锆铌合金粉的化学成分按质量百分比分别为85.6％的Zr，12.5％的Nb，其余为不可避 免的杂质；所述锆铌合金粉的粒径为45-150μm，购置于西安赛隆金属材料有限责任公司。
带有骨小梁的含氧化层锆铌合金胫骨平台假体(见图1)，包括肾形平台托1，在肾形平台托内向弯处的上表面设置有燕尾形凸块3，在燕尾形凸块3的两个斜向枝的外侧面设置有后凹槽5，在肾形平台托1与相对于燕尾形凸块3的外向弯处的上表面设置有弧形凸块2，在弧形凸块2的内侧面设置有前凹槽6，肾形平台托下表面的中部设置有柄4，肾形平台托下表面除连接柄4以外的其它部分设置有骨小梁9，骨小梁9由近平台托骨小梁层21和远平台托骨小梁层20组成(见图7)；所述近平台托骨小梁层21的孔径和孔隙率均匀设置(见图8)，远平台托骨小梁层呈三分区设置；相对应肾形平台托的横径10被第一标注点11和第二标注点12划分为第一段25、第二段26和第三段27，第一段、第二段和第三段的长依次为肾形平台托横径的30％:40％:30％，第一分区线13过第一标注点11，第二分区线14过第二标注点12；第一分区线13和第二分区线14为直线或弧线，并将相对应肾形平台托的远平台托骨小梁层20划分为内侧区15、中间区16和外侧区17(见图2)；
所述近平台托骨小梁层21的骨小梁孔径为0.43mm，孔隙率为60％，通孔率为100％；厚度为0.6mm。
远平台托骨小梁层20的第一分区线13和第二分区线14为直线时呈平行设置；第一分区线13与肾形平台托横径10的夹角18的度数为90°(见图3)，第二分区线14与肾形平台托横径10的夹角19的度数为90°。
远平台托骨小梁层20的内侧区骨小梁的孔径为1.05mm，孔隙率为80％，通孔率为100％；中间区骨小梁孔径为0.80mm，孔隙率为72％，通孔率为100％；外侧区骨小梁孔径为0.90mm，孔隙率为75％，通孔率为100％；厚度为2mm。
所述柄为弯曲十字形筋板(见图3)。
本实施例的有限元分析应变云图(见图10)。还可以在肾形平台托下表面的边缘设置侧壁22，使骨小梁层设置在侧壁以内见图7。
实施例2
带有骨小梁的含氧化层锆铌合金胫骨平台假体的制备方法，包括如下步骤：
1)以锆铌合金粉为原料，经3D打印一体成型得到带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物，将第一中间产物放入热等静压炉，在氦气保护下，升温至1325℃，在160MPa，恒温放置2h，降至常压，随炉冷却至200℃以下取出，得到第二中间产物；
2)将第二中间产物放置于程序性降温盒中以1℃/min的速度降温至-100℃，恒温放置7h，从程序性降温盒中取出；在液氮中再放置24h，调节温度至室温，得到第三中间产物；
3)将第三中间产物放置于程序性降温盒中以1℃/min的速度降温至-100℃，恒温放置7h；从程序性降温盒中取出；在液氮中再放置24h，调节温度至室温；得第四中间产物；
步骤2)、3)调节温度的步骤为：升温至-100℃，恒温保持4h；再升温至-30℃，恒温保持4h；升温至6℃恒温保持2h，升温；
4)将第四中间产物进行机加工修整、抛光、清洗和干燥，得第五中间产物，所述第五中间产物平台托上表面的粗糙度Ra＝0.035μm；
5)将第五中间产物放置于管式炉内，通入含氧质量百分比为10％的常压氦气，以15℃/min加热至600℃，以0.7℃/min降温至450℃，再自然冷却至200℃以下取出，得到带有骨小梁的含氧化层锆铌合金胫骨平台假体；
带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与带有骨小梁的含氧化层锆铌合金胫骨平台假体的结构相同；
所述锆铌合金粉的化学成分按质量百分比分别为93.4％的Zr，5.1％的Nb，其余为不可避免的杂质；所述锆铌合金粉的粒径为45-150μm，购置于西安赛隆金属材料有限责任公司。
带有骨小梁的含氧化层锆铌合金胫骨平台假体(见图9)，包括肾形平台托1，在肾形平台托内向弯处的上表面设置有燕尾形凸块3，在燕尾形凸块3的两个斜向枝的外侧面设置有后凹槽5，在肾形平台托1与相对于燕尾形凸块3的外向弯处的上表面设置有弧形凸块2，在弧形凸块2的内侧面设置有前凹槽6，肾形平台托下表面的中部设置有柄4，肾形平台托下表面除连接柄4以外的其它部分设置有骨小梁9，骨小梁9由近平台托骨小梁层21和远平台托骨小梁层20组成；所述近平台托骨小梁层21的孔径和孔隙率均匀设置，远平台托骨小梁层呈三分区设置；相对应肾形平台托的横径10被第一标注点11和第二标注点12划分为第一段25、第二段26和第三段27，第一段、第二段和第三段的长依次为肾形平台托横径的38％:24％:38％，第一分区线13过第一标注点11，第二分区线14过第二标注点12；第一分区线13和第二分区线14为直线，并将相对应肾形平台托的远平台托骨小梁层20划分为内侧区15、中间区16和外侧区17。
所述近平台托骨小梁层21的骨小梁孔径为0.50mm，孔隙率为65％，通孔率为100％；所述近平台托骨小梁层21厚度为1mm。
所述远平台托骨小梁层20的第一分区线13和第二分区线14为直线时呈八字形设置；第一分区线13与肾形平台托横径10的夹角18的度数为100°，第二分区线14与肾形平台托横径10的夹角19的度数为80°。(除柄以外，远平台托骨小梁层见图5)
所述远平台托骨小梁层20的内侧区骨小梁的孔径为1.10mm，孔隙率为85％，通孔率为100％；中间区骨小梁孔径为0.85mm，孔隙率为74.7％，通孔率为100％；外侧区骨小梁孔径为0.99mm，孔隙率为77.5％，通孔率为100％；所述远平台托骨小梁层20厚度为0.5mm。
柄为连接有支撑板的底部封闭的变径管(柄参见图6)。
本实施例的有限元分析应变云图见图11。
实施例3
1.带有骨小梁的含氧化层锆铌合金胫骨平台假体的制备方法，包括如下步骤：
(1)以锆铌合金粉为原料，经3D打印一体成型得到带有骨小梁的含氧化层锆铌合金胫骨平台假体第一中间产物，将所述第一中间产物放入热等静压炉，在氩气保护下，升温至1400℃，在140MPa，恒温放置1h，降至常压，随炉冷却至200℃以下取出，得到第二中间产物；
(2)将第二中间产物放置于程序性降温盒中以1℃/min的速度降温至-120℃，恒温放置5h，从程序性降温盒中取出；在液氮中再放置36h，调节温度至室温，得到第三中间产物；
(3)将第三中间产物放置于程序性降温盒中以1℃/min的速度降温至-120℃，恒温放置5h；从程序性降温盒中取出；在液氮中再放置36h，调节温度至室温；得第四中间产物；
步骤2)、3)调节温度具体步骤是：升温至-80℃，恒温保持3h；再升温至-20℃，恒温保持3h；再升温至8℃，恒温保持1h，升温。
(4)将第四中间产物进行机加工修整、抛光、清洗和干燥，得第五中间产物，所述第五中间产物平台托上表面的粗糙度Ra＝0.050μm；
(5)将第五中间产物放置于管式炉内，通入含氧质量百分比为15％的常压氩气，以20℃/min加热至700℃，以0.9℃/min降温至495℃，自然冷却至200℃以下取出，得到带有骨小梁的含氧化层锆铌合金胫骨平台假体；
带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与带有骨小梁的含氧化层锆铌合金胫骨平台假体的结构相同；
所述锆铌合金粉的化学成分按质量百分比分别为96.5％的Zr，1％的Nb，其余为不可避免的杂质；所述锆铌合金粉的粒径为45-150μm，购置于西安赛隆金属材料有限责任公司；
带有骨小梁的含氧化层锆铌合金胫骨平台假体，包括肾形平台托1，在肾形平台托内向弯处的上表面设置有燕尾形凸块3，在燕尾形凸块3的两个斜向枝的外侧面设置有后凹槽5，在肾形平台托1与相对于燕尾形凸块3的外向弯处的上表面设置有弧形凸块2，在弧形凸块2的内侧面设置有前凹槽6，肾形平台托下表面的中部设置有柄4，肾形平台托下表面除连接柄4以外的其它部分设置有骨小梁9，骨小梁9由近平台托骨小梁层21和远平台托骨小梁层20组成；所述近平台托骨小梁层21的孔径和孔隙率均匀设置，远平台托骨小梁层呈三分区设置；相对应肾形平台托的横径10被第一标注点11和第二标注点12划分为第一段25、第二段26和第三段27，第一段、第二段和第三段的长依次为肾形平台托横径的25％-:50％:25％，第一分区线13过第一标注点11，第二分区线14过第二标注点12；第一分区线13和第二分区线14为弧线(见图4)，并将相对应肾形平台托的远平台托骨小梁层20划分为内侧区15、中间区16和外侧区17；
近平台托骨小梁层21的骨小梁孔径为0.36mm，孔隙率为55％，通孔率为100％；厚度为0.2mm。
所述远平台托骨小梁层20的内侧区骨小梁的孔径为1.00mm，孔隙率为77.6％，通孔 率为100％；中间区骨小梁孔径为0.74mm，孔隙率为70.0％，通孔率为100％；外侧区骨小梁孔径为0.86mm，孔隙率为74.8％，通孔率为100％；所述远平台托骨小梁层20厚度为3mm。
柄为连接有支撑板的底部封闭的变径管。
本实施例的有限元分析应变云图见图12。
还可以在肾形平台托下表面的边缘设置侧壁22，使骨小梁层设置在侧壁以内。
对照组1
以锆铌合金粉(同实施例1)为原料，经3D打印一体成型和机加工修整，得到结构同实施例1的胫骨平台假体。
实验验证：
将实施例1、2、3的有限元模型进行有限元分析，得到的有限元分析应变云图只显示范围为1000-3000的微应变(阴影部分)，实施例1-实施例3在胫骨平台骨组织有限元模型上1000-3000微应变区域在整个胫骨平台骨组织有限元模型的占比分别为65.6％、64.4％和68.1％(图10、11、12)，提示本发明所述带有骨小梁的含氧化层锆铌合金胫骨平台假体可实现骨组织大部分区域微应变在最低有效应变阈值和超生理应变阈值之间，利于骨长入。
倒置万能材料显微镜(Axio Vert.A1，德国蔡司zeiss公司，德国)对对照组1的实体部分和实施例1的未进行所述制备方法中步骤4)和步骤5)的实体部分进行金相显微组织观察。结果如图13和14所示，对照组1的金相照片中可以观察到细小α马氏体，组织较细小，易产生应力集中，塑性较差；实施例1金相显示为α相，呈网篮结构，晶粒细化。结果提示，本发明所述带有骨小梁的含氧化层锆铌合金胫骨平台假体的实体部分(不含氧化层)具有优异的强度和塑性。
扫描电子显微镜(Crossbeam340/550，蔡司，德国)对对照组1的骨小梁部分和实施例1的未进行所述制备方法中步骤4)和步骤5)骨小梁部分进行观察分析，结果如图15-16所示，与对照组1相比，实施例1的骨小梁结构中锆铌合金粉发生进一步熔结，提示骨小梁综合性能提高。
电子万能试验机(UTM5105，深圳三思纵横科技股份有限公司，中国)对实施例1未进行所述制备方法中步骤4)和步骤5)的实体压缩试件(试件大小为：8*8*10mm 3)和对照组1的实体压缩试件(试件大小为：8*8*10mm 3)进行压缩性能测试，实施例1和对照组1的实体压缩试件各5个。结果如表1所示，实施例1的抗压屈服强度为546.72MPa，优于对照组1(P＜0.05)，提示本发明制得的带有骨小梁的含氧化层锆铌合金胫骨平台假体的实体部分具有优异抗压缩性能。
表1对照组1和实施例1的实体试件抗压缩实验结果(
Figure PCTCN2021101287-appb-000001
n＝5，*P＜0.05，与对照组1比较)
Figure PCTCN2021101287-appb-000002
电子万能试验机(UTM5105，深圳三思纵横科技股份有限公司，中国)对对照组1的骨小梁压缩试件和实施例1的未进行所述制备方法中步骤4)和步骤5)的孔径为0.80mm，孔隙率为72％，通孔率为100％的骨小梁压缩试件(试件大小为：8*8*10mm 3)进行压缩实验，对照组1和实施例1的骨小梁压缩试件各5个。结果如表2所示，实施例1的骨小梁屈服强度为18.39MPa，显著高于对照组1(P＜0.05)，提示本发明制得的带有骨小梁的含氧化层锆铌合金胫骨平台假体骨小梁部分抗压性能优异。
表2对照组1和实施例1的骨小梁试件抗压缩实验结果(
Figure PCTCN2021101287-appb-000003
n＝5，*P＜0.05，与对照组1比较)
Figure PCTCN2021101287-appb-000004
扫描电子显微镜(Crossbeam340/550，蔡司，德国)对实施例1所述带有骨小梁的含氧化层锆铌合金胫骨平台假体的锆铌合金基体与氧化层的横截面进行观察，(见图17)。并对实施例2、3带有骨小梁的含氧化层锆铌合金胫骨平台假体的锆铌合金基体与氧化层的横截面进行观察，其氧化层厚度分别为10.3μm、17.2μm和20.6μm，且氧化层与锆铌合金基体之间存在富氧层，增强锆铌合金基体与氧化层之间的结合力。
XRD(D8DISCOVER，Bruker，德国)对实施例1的带有骨小梁的含氧化层锆铌合金胫骨平台假体的氧化层进行分析(图18)，氧化层包含单斜相二氧化锆和四方相二氧化锆。
显微硬度仪(MHVS-1000 PLUS，上海奥龙星迪检测设备有限公司，中国)对实施例1-3的带有骨小梁的含氧化层锆铌合金胫骨平台假体进行显微硬度测量，测试载荷为0.05kg，试件载荷时间为20s，每个试件取8个点。实施例1-3测得平均硬度值为1948.6Hv、1923.7Hv和1967.2Hv，提示本发明所述带有骨小梁的含氧化层锆铌合金胫骨平台假体的氧化层硬度高。
实验证明，实施例2、3制备的带有骨小梁的含氧化层锆铌合金胫骨平台假体的骨小梁部分的锆铌合金粉熔结程度、抗压性能，实体部分抗压性能、金相组织，氧化层的晶体结构、厚度和硬度与实施例1制备的带有骨小梁的含氧化层锆铌合金胫骨平台假体相似。
实施例1的有限元模型进行有限元分析，结果如图19所示，实施例1的带有骨小梁的含氧化层锆铌合金胫骨平台假体的骨小梁与实体连接部位的应力集中区域小，提示本发明带有骨小梁的含氧化层锆铌合金胫骨平台假体的骨小梁与实体的结合强度优异。

Claims (8)

  1. 带有骨小梁的含氧化层锆铌合金胫骨平台假体的制备方法，其特征包括如下步骤：
    1)以锆铌合金粉为原料，经3D打印一体成型得到带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物，将所述第一中间产物放入热等静压炉，在惰性气体保护下，升温至1250℃-1400℃，在140MPa-180MPa，恒温放置1h-3h，降至常压，随炉冷却至200℃以下取出，得到第二中间产物；
    2)将第二中间产物放置于程序性降温盒中以1℃/min的速度降温至-80℃～-120℃，恒温放置5h-10h，从程序性降温盒中取出；在液氮中再放置16h-36h，调节温度至室温，得到第三中间产物；
    3)将第三中间产物放置于程序性降温盒中以1℃/min的速度降温至-80℃～-120℃，恒温放置5h-10h；从程序性降温盒中取出；在液氮中再放置16h-36h，调节温度至室温；得第四中间产物；
    4)将第四中间产物进行机加工修整、抛光、清洗和干燥，得第五中间产物，所述第五中间产物平台托上表面的粗糙度Ra≤0.050μm；
    5)将第五中间产物放置于管式炉内，通入含氧质量百分比为5％-15％的常压惰性气体，以5℃/min-20℃/min加热至500℃-700℃，以0.4℃/min-0.9℃/min降温至400℃-495℃，再自然冷却至200℃以下取出，得到带有骨小梁的含氧化层锆铌合金胫骨平台假体；
    带有骨小梁的含氧化层锆铌合金胫骨平台假体的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与带有骨小梁的含氧化层锆铌合金胫骨平台假体的结构相同；
    所述惰性气体为氦气或氩气；
    所述带有骨小梁的含氧化层锆铌合金胫骨平台假体，包括肾形平台托(1)，在肾形平台托内向弯处的上表面设置有燕尾形凸块(3)，在燕尾形凸块(3)的两个斜向枝的外侧面设置有后凹槽(5)，在肾形平台托(1)与相对于燕尾形凸块(3)的外向弯处的上表面设置有弧形凸块(2)，在弧形凸块(2)的内侧面设置有前凹槽(6)，肾形平台托下表面的中部设置有柄(4)，肾形平台托下表面除连接柄(4)以外的其它部分设置有骨小梁(9)，骨小梁(9)由近平台托骨小梁层(21)和远平台托骨小梁层(20)组成；所述近平台托骨小梁层(21)的孔径和孔隙率均匀设置，远平台托骨小梁层呈三分 区设置；相对应肾形平台托的横径(10)被第一标注点(11)和第二标注点(12)划分为第一段(25)、第二段(26)和第三段(27)，第一段、第二段和第三段的长依次为肾形平台托横径的25％-38％:24％-50％:25％-38％，第一分区线(13)过第一标注点(11)，第二分区线(14)过第二标注点(12)；第一分区线(13)和第二分区线(14)为直线或弧线，并将相对应肾形平台托的远平台托骨小梁层(20)划分为内侧区(15)、中间区(16)和外侧区(17)；内侧区(15)骨小梁的孔径和孔隙率依次大于外侧区(17)和中间区(16)骨小梁的孔径和孔隙率。
  2. 根据权利要求1所述的方法，其特征是所述锆铌合金粉的化学成分按质量百分比为85.6％-96.5％的Zr，1.0％-12.5％的Nb，其余为不可避免的杂质；所述锆铌合金粉的粒径为45-150μm。
  3. 根据权利要求1所述的方法，其特征是步骤2)、3)所述调节温度为：升温至-120℃～-80℃，恒温保持3h-5h；再升温至-40℃～-20℃，恒温保持3h-5h；再升温至4℃-8℃，恒温保持1h-3h，升温。
  4. 根据权利要求1所述的方法，其特征是所述近平台托骨小梁层(21)的骨小梁孔径为0.36mm-0.50mm，孔隙率为55％–65％，通孔率为100％；厚度为0.2mm-1mm。
  5. 根据权利要求1所述的方法，其特征是所述远平台托骨小梁层(20)的第一分区线(13)和第二分区线(14)为直线时呈平行设置或呈八字形设置；第一分区线(13)与肾形平台托横径(10)的夹角(18)的度数为100°-60°，第二分区线(14)与肾形平台托横径(10)的夹角(19)的度数为80°-120°。
  6. 根据权利要求1所述的方法，其特征是所述远平台托骨小梁层(20)的内侧区骨小梁的孔径为1.00mm-1.10mm，孔隙率为77.6％–85％，通孔率为100％；中间区骨小梁孔径为0.74mm-0.85mm，孔隙率为70.0％-74.7％，通孔率为100％；外侧区骨小梁孔径为0.86mm-0.99mm，孔隙率为74.8％-77.5％，通孔率为100％；厚度为0.5mm-3mm。
  7. 根据权利要求1所述的方法，其特征是所述柄为连接有支撑板的变径管、连接有支撑板的底部封闭的变径管、十字形筋板或弯曲十字形筋板。
  8. 权利要求1-7之一的方法制备的带有骨小梁的含氧化层锆铌合金胫骨平台假体。
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