WO2022088701A1 - 含氧化层锆铌合金髋关节假体系统及制备方法 - Google Patents

含氧化层锆铌合金髋关节假体系统及制备方法 Download PDF

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Publication number
WO2022088701A1
WO2022088701A1 PCT/CN2021/101277 CN2021101277W WO2022088701A1 WO 2022088701 A1 WO2022088701 A1 WO 2022088701A1 CN 2021101277 W CN2021101277 W CN 2021101277W WO 2022088701 A1 WO2022088701 A1 WO 2022088701A1
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Prior art keywords
bone
trabecular bone
type
trabecular
intermediate product
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PCT/CN2021/101277
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English (en)
French (fr)
Inventor
刘念
叶金铎
提浩强
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 JP2022545925A priority Critical patent/JP7470194B2/ja
Priority to EP21884442.1A priority patent/EP4082696A4/en
Priority to US17/907,795 priority patent/US20230248527A1/en
Publication of WO2022088701A1 publication Critical patent/WO2022088701A1/zh

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    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/32—Joints for the hip
    • A61F2/34—Acetabular cups
    • A61F2002/3401—Acetabular cups with radial apertures, e.g. radial bores for receiving fixation screws
    • A61F2002/3403—Polar aperture
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/32—Joints for the hip
    • A61F2/36—Femoral heads ; Femoral endoprostheses
    • A61F2/3609—Femoral heads or necks; Connections of endoprosthetic heads or necks to endoprosthetic femoral shafts
    • A61F2002/3611—Heads or epiphyseal parts of femur
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/32—Joints for the hip
    • A61F2/36—Femoral heads ; Femoral endoprostheses
    • A61F2/3609—Femoral heads or necks; Connections of endoprosthetic heads or necks to endoprosthetic femoral shafts
    • A61F2002/365—Connections of heads to necks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00395—Coating or prosthesis-covering structure made of metals or of alloys
    • A61F2310/00419—Other metals
    • A61F2310/00485—Coating made of zirconium or Zr-based alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00395—Coating or prosthesis-covering structure made of metals or of alloys
    • A61F2310/00419—Other metals
    • A61F2310/00491—Coating made of 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
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    • 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
    • B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning 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
    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • 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 artificial joints, in particular, to an oxide layer-containing zirconium-niobium alloy hip joint prosthesis system and a preparation method.
  • the artificial hip joint prostheses currently used clinically include cemented prostheses and non-cemented prostheses.
  • cementless prostheses have been widely used due to their good bone ingrowth properties.
  • the osseointegration interface of cementless hip prosthesis usually adopts the following two methods: the first is to spray hydroxyapatite coating or titanium coating on the surface of the femoral stem, and the second is to print trabecular bone-like pores on the surface. Structure of the cuff, and then assemble the femoral stem with the cuff. However, the surface coating in the first method has the risk of falling off, which affects the use effect.
  • the cuff in the second method is an assembly structure with the femoral stem. Clinical studies have shown that in order to combine the femoral stem with the cuff in the structural design, the head and neck of the bone stem in the structural design has a problem of sudden change in cross-section. There is a very serious stress concentration.
  • the main risks faced by the combined stem in clinical practice include the severe stress concentration of the bone stem in the head and neck, and the risk of failure of the bone stem and the cuff.
  • the existence of the above-mentioned risks may lead to the failure of the entire hip prosthetic system.
  • the trabecular cups prepared by many domestic medical equipment companies all adopt the uniform trabecular design method, which is affected by the uneven distribution of contact pressure between the cup and the pelvis.
  • the compressive strain distribution on the pelvis is not uniform, and the main problem is that only a few areas of the pelvis close to the upper part of the cup meet the conditions for bone growth, and most of the bone tissue in contact with the cup does not meet the conditions for bone growth, In clinical practice, it is easy to cause short bone growth or bone resorption due to excessive or small compressive strain.
  • the trabecular bone structure on the outer surface of the femoral stem is mostly distributed evenly.
  • Clinical data show that the femoral stem with uniform trabecular bone structure has the bone tissue on the upper and outer sides of the femoral stem, and the bone ingrowth at the lower medial and lower lateral sides is not ideal.
  • Further studies have shown that the main reasons for the unsatisfactory bone ingrowth in the upper lateral and lower medial is that the contact pressure between the femoral stem and the bone tissue is small, and the compressive strain value of the bone tissue combined with the upper lateral and lower medial of the femoral stem is small and low. At 1000 microstrain, it does not meet the conditions for the growth of bone tissue.
  • the contact pressure between the femoral stem and the bone tissue is too large, and the compressive strain of the bone tissue combined with the femoral stem is too large, which is higher than 3000 microstrain. It also does not meet the conditions for bone tissue growth. Therefore, if the overall printed femoral stem adopts uniform trabecular bone, although it can overcome the problem of coating stem falling off and the failure of the assembled stem and cone connection, it cannot guarantee the uniform ingrowth of bone tissue on the bone trabecular structure.
  • the current assembling methods of the femoral head and the inner lining are mainly titanium alloy ball head and high cross-linked polyethylene, as well as ceramic ball head and ceramic inner lining.
  • the problem with the combination of titanium alloy ball head and high cross-linked lining is that the debris formed by the wear of high cross-linked polyethylene easily causes osteolysis.
  • the ability of ceramic ball head and ceramic lining to resist impact is relatively poor, which will cause the prosthesis to fail due to impacting the porcelain.
  • 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, so that the prosthesis can achieve the advantages of both interfaces at the same time.
  • 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 hip prosthesis system with excellent mechanical properties and at the same time realizing the advantages of two interfaces.
  • the purpose of the present invention is to overcome the deficiencies of the prior art and provide an oxide layer-containing zirconium-niobium alloy hip joint prosthesis system.
  • the second object of the present invention is to provide a preparation method of a zirconium-niobium alloy hip joint prosthesis system containing an oxide layer.
  • a preparation method of a zirconium-niobium alloy hip joint prosthesis system containing an oxide layer comprising the following steps:
  • the first intermediate product of the cup and the first intermediate product of the femoral stem are respectively obtained by 3D printing integral molding, and the two first intermediate products are put into a hot isostatic pressing furnace, Under the protection of helium or argon, the temperature is raised to 1250°C-1400°C, at 140MPa-180MPa, placed at a constant temperature for 1h-3h, lowered to normal pressure, cooled to below 200°C with the furnace, and taken out to obtain two second intermediate products;
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, and the fifth intermediate product of the mortar cup have the same structure as the mortar cup;
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, and the fifth intermediate product of the femoral stem have the same structure as the femoral stem;
  • the oxide-containing zirconium-niobium alloy hip joint prosthesis system includes a femoral stem 1, a femoral head 2, an inner lining 3 and a acetabular cup 4;
  • the femoral stem includes a cylindrical head 11, a neck 12 and a stem 13; the stem 13 includes a proximal end 14 and a distal end 15; the proximal outer surface of the stem is provided with a femoral stem Trabecular bone 16, femoral stem trabecular bone 16 is divided into lateral upper zone 1101, lateral lower zone 1102, medial upper zone 191 and medial lower zone 192; the trabecular bone set in lateral upper zone 1101 and medial lower zone 192 is the first trabecular bone 112; the trabecular bone set in the upper medial area 191 is the second type trabecular bone 113; the trabecular bone set in the lower lateral area 1102 is the trabecular bone 114 of the third type; the first type trabecular bone
  • the pore size and porosity of 112 are sequentially smaller than the second type of bone trabecular 113 and the third type of bone trabecular 114;
  • the structure of the cup includes a hemispherical body 49, the middle of the hemispherical body is provided with a first circular hole 41 with an internal thread, and the outer surface of the hemispherical body is provided with a cup bone trabecular 43.
  • the cup bone trabecular 43 is partitioned, the first partition line 46 and the second partition line 45 intersect, and the intersection point passes through the center of the first circular hole 41 with internal thread, and the third partition line 44 is circular and is located in the hemispherical body.
  • the first partition line, the second partition line and the third partition line divide the outer surface of the hemispherical body into: a first upper area 471, a first lower area 472, a second upper area 473, and a second lower area 474 , the third upper area 475, the third lower area 476, the fourth upper area 477 and the fourth lower area 478; the first upper area, the second upper area, the third upper area and the fourth upper area are equal in area;
  • One side of the hemispherical body is provided with a second circular hole 42 with an internal thread, and the number of the second circular hole 42 with an internal thread is 3, of which 2 are respectively arranged in the first upper area 471 and the third upper area 475 Inside, the other one is arranged at the junction of the first upper area 471 and the third upper area 475;
  • the third upper region and the fourth upper region are provided with a fourth type of trabecular bone 481
  • the third lower region and the fourth lower region are provided with a fifth type of bone trabecular 482
  • the first upper region is provided with a sixth type of bone trabecula 483
  • the first lower zone is provided with the seventh type of trabecular bone 484
  • the second upper zone is provided with the eighth type of trabecular bone 485
  • the second lower zone is provided with the ninth type of trabecular bone 486
  • the fourth type of trabecular bone is provided
  • the pore size and porosity of the trabeculae are smaller than the fifth, sixth, seventh, eighth, and ninth trabecular.
  • the chemical composition of the zirconium-niobium alloy powder includes 85.6%-96.5% of Zr, 1.0%-12.5% of Nb by mass percentage, and the rest are inevitable impurities; the particle size of the zirconium-niobium alloy powder is 45 ⁇ m-150 ⁇ m.
  • the chemical composition of the zirconium-niobium alloy forging includes 85.6%-96.5% of Zr, 1.0%-12.5% of Nb by mass percentage, and the balance is inevitable impurities.
  • steps 1-2) and 1-3) are as follows: heating to -120°C ⁇ -80°C, keeping at constant temperature for 3h-5h; heating to -40°C ⁇ -20°C, keeping at constant temperature for 3h-5h; The temperature was raised to 4°C-8°C and kept at a constant temperature for 1h-3h.
  • the diameter of the first trabecular bone 112 is 700 ⁇ m-770 ⁇ m, and the porosity is 65%-75%; the diameter of the second trabecular bone 113 is 780 ⁇ m-850 ⁇ m, and the porosity is 76%-80%; the third trabecular bone 114 The pore diameter is 860 ⁇ m-950 ⁇ m, and the porosity is 81%-85%; the thickness of the first trabecular bone, the second trabecular bone and the third trabecular bone are equal, ranging from 1.2 mm to 1.5 mm;
  • the fourth type of trabecular bone 481 has a diameter of 700 ⁇ m-740 ⁇ m and a porosity of 65%-70%; the fifth type of bone trabecular 482 has a diameter of 750 ⁇ m-770 ⁇ m and a porosity of 71%-75%; the The sixth type of trabecular bone 483 has a pore size of 780 ⁇ m-810 ⁇ m and a porosity of 76%-78%; the seventh type of bone trabecular 484 has a pore size of 820 ⁇ m-850 ⁇ m and a porosity of 79%-80%; The diameter of the trabecular bone 485 is 860 ⁇ m-900 ⁇ m, and the porosity is 81%-83%; the diameter of the trabecular bone 486 of the ninth type is 910 ⁇ m-950 ⁇ m, and the porosity is 84%-85%; The trabeculae, the fifth type of bone trabeculae, the sixth type of bone
  • the trabecular bone hip joint prosthesis system prepared by the above method is zirconium-niobium alloy partitioned with oxide layer.
  • the present invention has the following beneficial effects:
  • the femoral stem and the acetabular cup of the oxide-containing zirconium-niobium alloy hip joint prosthesis system of the present invention are integrally formed by 3D printing, which solves the problems that the traditional machining cannot prepare complex structures and the connection and cooperation between the sleeve and the femoral stem body fail, and the bone is small.
  • the beam and the entity have high bonding strength, are not easy to fall off, and prolong the life of the prosthesis.
  • the femoral stem of the oxide-containing zirconium-niobium alloy hip joint prosthesis system of the present invention solves the possible occurrence of uniform trabecular bone in the lateral and medial lower regions of the trabecular bone due to too small or too large compressive strain of the femur. question.
  • Most of the compressive strain values of the femoral bone tissue are between 1000-3000 microstrain, which is in line with the theory of bone growth and ensures the uniform growth of bone in the trabecular bone area.
  • the acetabular cup of the oxide layer-containing zirconium-niobium alloy hip joint prosthesis system of the present invention adopts the method of partitioning the trabecular bone to provide a suitable environment for bone growth. According to the results of finite element analysis, the area that meets the bone growth conditions in the finite element model of bone tissue can reach 40%, and the osseointegration of the cup and the host bone can be achieved.
  • the oxide layer-containing zirconium-niobium alloy hip joint prosthesis system of the present invention is integrated to realize the excellent biocompatibility of the osseointegration interface, the bone ingrowth and the super-strong wear resistance and low wear rate of the friction interface.
  • the surface of the femoral head and the inner lining are oxidized to form a ceramic surface, which realizes the super wear resistance and low wear rate of the friction interface; the femoral stem and the cup realize the excellent bone ingrowth and biocompatibility of the osseointegration interface.
  • the zirconium-niobium alloy hip joint prosthesis system containing the oxide layer of the invention has low artifacts, has little interference to nuclear magnetic resonance, and can perform nuclear magnetic detection.
  • FIG. 1 is a schematic diagram of the structure dispersion of the oxide layer-containing zirconium-niobium alloy hip joint prosthesis system of the present invention.
  • Figure 2 is a schematic diagram of the structure of the femoral stem.
  • Figure 3 is a schematic diagram of the proximal zoning of the femoral stem.
  • Figure 4 is a schematic diagram of the proximal structure of the femoral stem.
  • Figure 5 is an axonometric view of the acetabular cup.
  • Figure 6 is an axonometric view of the cup (without trabecular bone).
  • Figure 7 is a schematic diagram of the structure of the acetabular cup.
  • Figure 8 is a top view of the cup.
  • Figure 9 is a schematic diagram of the structure of the femoral head.
  • Figure 10 is a schematic diagram of the lining structure.
  • FIG. 11 is a cloud map of the femoral stem strain distribution of control group 1.
  • FIG. 12 is a cloud map of the strain distribution of the femoral stem in Example 1.
  • FIG. 12 is a cloud map of the strain distribution of the femoral stem in Example 1.
  • FIG. 13 is a cloud map of the cup strain distribution of control group 1.
  • FIG. 14 is a cloud diagram of the strain distribution of the cup of Example 1.
  • FIG. 15 is a metallographic microstructure diagram of the solid part of the femoral stem of control group 2.
  • 16 is a metallographic microstructure diagram of the solid part of the femoral stem of Example 1 without steps 1-4) and 1-5) in the preparation method.
  • FIG. 17 is the SEM image of the femoral stem trabecular bone of control group 2.
  • FIG. 19 is a cross-sectional SEM image of the oxide layer and the base of the femoral stem of Example 1.
  • FIG. 20 is the XRD curve of the surface of the oxide layer of the femoral stem of Example 1.
  • a preparation method of a zirconium-niobium alloy hip joint prosthesis system containing an oxide layer comprising the following steps:
  • the first intermediate product of the cup and the first intermediate product of the femoral stem are respectively obtained by 3D printing integral molding, and the two first intermediate products are put into a hot isostatic pressing furnace, Under the protection of helium, the temperature was raised to 1250°C, placed at a constant temperature of 180MPa for 3 hours, lowered to normal pressure, cooled to below 200°C with the furnace, and taken out to obtain two second intermediate products;
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, and the fifth intermediate product of the mortar cup have the same structure as the mortar cup;
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, and the fifth intermediate product of the femoral stem have the same structure as the femoral stem;
  • the oxide-containing zirconium-niobium alloy hip joint prosthesis system (see Fig. 1 ) includes a femoral stem 1, a femoral head 2 (see Fig. 9), an inner lining 3 (see Fig. 10) and a cup 4;
  • the femoral stem (see FIGS. 2-4 ) includes a cylindrical head 11, a neck 12 and a handle 13; the handle 13 includes a proximal end 14 and a distal end 15; the handle
  • the femoral stem bone trabecular 16 is arranged on the outer surface of the proximal end, and the femoral stem bone trabecular 16 is divided into a lateral upper zone 1101, a lateral lower zone 1102, a medial upper zone 191 and a medial lower zone 192; the lateral upper zone 1101 and the medial lower zone 192
  • the set bone trabeculae is the first type of bone trabecular 112; the bone trabecula set in the inner upper region 191 is the second type of bone trabecular 113;
  • the structure of the cup includes a hemispherical body 49, the middle of the hemispherical body is provided with a first circular hole 41 with an internal thread, and the outer surface of the hemispherical body is provided with a cup.
  • Bone trabecular 43, the cup bone trabecular 43 is partitioned, the first partition line 46 and the second partition line 45 intersect, and the intersection point passes through the center of the first circular hole 41 with internal thread, and the third partition line 44
  • the circle is located at the near edge of the hemispherical body; the first partition line, the second partition line and the third partition line divide the outer surface of the hemispherical body into: the first upper area 471, the first lower area 472, the second upper area zone 473, second lower zone 474, third upper zone 475, third lower zone 476, fourth upper zone 477 and fourth lower zone 478; first upper zone, second upper zone, third upper zone and fourth The area of the upper area is equal; a second circular hole 42 with an internal thread is provided on one side of the hemispherical body, and the number of the second circular hole 42 with an internal thread is 3, of which 2 are respectively arranged on the first upper In the area 471 and the third upper area 475, the other one is arranged at the junction of the
  • the third upper region and the fourth upper region are provided with a fourth type of trabecular bone 481
  • the third lower region and the fourth lower region are provided with a fifth type of bone trabecular 482
  • the first upper region is provided with a sixth type of bone trabecula 483
  • the first lower area is provided with the seventh type of trabecular bone 484
  • the second upper area is provided with the eighth type of trabecular bone 485, and the second lower area is provided with the ninth type of trabecular bone 486;
  • the chemical composition of the zirconium-niobium alloy powder includes 85.6% of Zr, 12.5% of Nb by mass percentage, and the rest are inevitable impurities; the particle size of the zirconium-niobium alloy powder is 45 ⁇ m-150 ⁇ m.
  • the chemical composition of the zirconium-niobium alloy forging includes 85.6% of Zr, 12.5% of Nb by mass percentage, and the balance is inevitable impurities.
  • steps 1-2) and 1-3) are as follows: heating to -120°C, maintaining a constant temperature for 5 hours; heating to -40°C, maintaining a constant temperature for 5 hours; heating to 4°C, maintaining a constant temperature for 3 hours, and heating.
  • the diameter of the first trabecular bone 112 is 700 ⁇ m and the porosity is 65%; the diameter of the second trabecular bone 113 is 780 ⁇ m and the porosity is 76%; the diameter of the third trabecular bone 114 is 860 ⁇ m and the porosity is 81%;
  • the thickness of the first trabecular bone, the second trabecular bone and the third trabecular bone are equal to 1.2 mm;
  • the fourth type of trabecular bone 481 has a diameter of 700 ⁇ m and a porosity of 65%; the fifth type of trabecular bone 482 has a diameter of 750 ⁇ m and a porosity of 71%; the sixth type of trabecular bone 483 has a diameter of 780 ⁇ m , the porosity is 76%; the seventh type of trabecular bone 484 has a pore size of 820 ⁇ m and a porosity of 79%; the eighth type of bone trabecular 485 has a pore size of 860 ⁇ m and a porosity of 81%; the ninth type The trabecular bone 486 has a pore size of 910 ⁇ m and a porosity of 84%; the fourth, fifth, sixth, seventh, and eighth bone trabeculae The thickness of the ninth trabecular bone is equal to 1.2mm.
  • a preparation method of a zirconium-niobium alloy hip joint prosthesis system containing an oxide layer comprising the following steps:
  • the first intermediate product of the cup and the first intermediate product of the femoral stem are respectively obtained by 3D printing integral molding, and the two first intermediate products are put into a hot isostatic pressing furnace, Under the protection of argon, the temperature was raised to 1325°C, placed at a constant temperature of 160MPa for 2h, lowered to normal pressure, cooled to below 200°C with the furnace, and taken out to obtain two second intermediate products;
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, and the fifth intermediate product of the mortar cup have the same structure as the mortar cup;
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, and the fifth intermediate product of the femoral stem have the same structure as the femoral stem;
  • the oxide-containing zirconium-niobium alloy hip joint prosthesis system includes a femoral stem 1, a femoral head 2, an inner lining 3 and a acetabular cup 4;
  • the femoral stem includes a cylindrical head 11, a neck 12 and a stem 13; the stem 13 includes a proximal end 14 and a distal end 15; the proximal outer surface of the stem is provided with a femoral stem Trabecular bone 16, femoral stem trabecular bone 16 is divided into lateral upper zone 1101, lateral lower zone 1102, medial upper zone 191 and medial lower zone 192; the trabecular bone set in lateral upper zone 1101 and medial lower zone 192 is the first
  • the seed bone trabeculae 112; the bone trabeculae set in the upper medial region 191 is the second type of bone trabecula 113; the bone trabeculae set in the lateral lower region 1102 is the third bone trabecula 114;
  • the structure of the cup includes a hemispherical body 49, the middle of the hemispherical body is provided with a first circular hole 41 with an internal thread, and the outer surface of the hemispherical body is provided with a cup bone trabecular 43.
  • the cup bone trabecular 43 is partitioned, the first partition line 46 and the second partition line 45 intersect, and the intersection point passes through the center of the first circular hole 41 with internal thread, and the third partition line 44 is circular and is located in the hemispherical body.
  • the first partition line, the second partition line and the third partition line divide the outer surface of the hemispherical body into: a first upper area 471, a first lower area 472, a second upper area 473, and a second lower area 474 , the third upper area 475, the third lower area 476, the fourth upper area 477 and the fourth lower area 478; the first upper area, the second upper area, the third upper area and the fourth upper area are equal in area;
  • One side of the hemispherical body is provided with a second circular hole 42 with an internal thread, and the number of the second circular hole 42 with an internal thread is 3, of which 2 are respectively arranged in the first upper area 471 and the third upper area 475 Inside, the other one is arranged at the junction of the first upper area 471 and the third upper area 475;
  • the third upper region and the fourth upper region are provided with a fourth type of trabecular bone 481
  • the third lower region and the fourth lower region are provided with a fifth type of bone trabecular 482
  • the first upper region is provided with a sixth type of bone trabecula 483
  • the first lower area is provided with the seventh type of trabecular bone 484
  • the second upper area is provided with the eighth type of trabecular bone 485, and the second lower area is provided with the ninth type of trabecular bone 486;
  • the chemical composition of the zirconium-niobium alloy powder includes 93.4% of Zr, 5.1% of Nb by mass percentage, and the rest are inevitable impurities; the particle size of the zirconium-niobium alloy powder is 45 ⁇ m-150 ⁇ m.
  • the chemical composition of the zirconium-niobium alloy forging includes 93.4% of Zr, 5.1% of Nb by mass percentage, and the balance is inevitable impurities.
  • steps 1-2) and 1-3) are as follows: heating to -100°C, maintaining a constant temperature for 4 hours; heating to -30°C, maintaining a constant temperature for 4 hours; heating to 6°C, maintaining a constant temperature for 2 hours, and heating.
  • the diameter of the first trabecular bone 112 is 740 ⁇ m and the porosity is 70%; the diameter of the second trabecular bone 113 is 810 ⁇ m and the porosity is 78%; the diameter of the third trabecular bone 114 is 900 ⁇ m and the porosity is 83%;
  • the thickness of the first trabecular bone, the second trabecular bone and the third trabecular bone are equal to 1.3 mm;
  • the fourth type of trabecular bone 481 has a diameter of 720 ⁇ m and a porosity of 67%; the fifth type of trabecular bone 482 has a diameter of 760 ⁇ m and a porosity of 73%; the sixth type of trabecular bone 483 has a diameter of 800 ⁇ m , the porosity is 77%; the seventh type of trabecular bone 484 has a pore size of 840 ⁇ m and a porosity of 79.5%; the eighth type of bone trabecular 485 has a pore size of 880 ⁇ m and a porosity of 82%; the ninth type The trabecular bone 486 has a pore size of 930 ⁇ m and a porosity of 84.5%; the fourth, fifth, sixth, seventh, and eighth types of trabecular bone The thickness of the ninth trabecular bone is equal to 1.3mm.
  • the first intermediate product of the cup and the first intermediate product of the femoral stem are respectively obtained by 3D printing integral molding, and the two first intermediate products are put into a hot isostatic pressing furnace, Under the protection of argon, the temperature was raised to 1400°C, placed at a constant temperature of 140MPa for 1 h, lowered to normal pressure, cooled to below 200°C with the furnace, and taken out to obtain two second intermediate products;
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, and the fifth intermediate product of the mortar cup have the same structure as the mortar cup;
  • the first intermediate product, the second intermediate product, the third intermediate product, the fourth intermediate product, and the fifth intermediate product of the femoral stem have the same structure as the femoral stem;
  • the oxide-containing zirconium-niobium alloy hip joint prosthesis system includes a femoral stem 1, a femoral head 2, an inner lining 3 and a acetabular cup 4;
  • the femoral stem includes a cylindrical head 11, a neck 12 and a stem 13; the stem 13 includes a proximal end 14 and a distal end 15; the proximal outer surface of the stem is provided with a femoral stem Trabecular bone 16, femoral stem trabecular bone 16 is divided into lateral upper zone 1101, lateral lower zone 1102, medial upper zone 191 and medial lower zone 192; the trabecular bone set in lateral upper zone 1101 and medial lower zone 192 is the first
  • the seed bone trabeculae 112; the bone trabeculae set in the upper medial region 191 is the second type of bone trabeculae 113; the bone trabeculae set in the lateral lower region 1102 is the third bone trabecula 114;
  • the structure of the cup includes a hemispherical body 49, the middle of the hemispherical body is provided with a first circular hole 41 with an internal thread, and the outer surface of the hemispherical body is provided with a cup bone trabecular 43.
  • the cup bone trabecular 43 is partitioned, the first partition line 46 and the second partition line 45 intersect, and the intersection point passes through the center of the first circular hole 41 with internal thread, and the third partition line 44 is circular and is located in the hemispherical body.
  • the first partition line, the second partition line and the third partition line divide the outer surface of the hemispherical body into: a first upper area 471, a first lower area 472, a second upper area 473, and a second lower area 474 , the third upper area 475, the third lower area 476, the fourth upper area 477 and the fourth lower area 478; the first upper area, the second upper area, the third upper area and the fourth upper area are equal in area;
  • One side of the hemispherical body is provided with a second circular hole 42 with an internal thread, and the number of the second circular hole 42 with an internal thread is 3, of which 2 are respectively arranged in the first upper area 471 and the third upper area 475 Inside, the other one is arranged at the junction of the first upper area 471 and the third upper area 475;
  • the third upper region and the fourth upper region are provided with a fourth type of trabecular bone 481
  • the third lower region and the fourth lower region are provided with a fifth type of bone trabecular 482
  • the first upper region is provided with a sixth type of bone trabecula 483
  • a seventh type of trabecular bone 484 is provided in the first lower region
  • an eighth type of trabecular bone 485 is provided in the second upper region
  • a ninth type of trabecular bone 486 is provided in the second lower region.
  • the chemical composition of the zirconium-niobium alloy powder includes 96.5% of Zr, 1.0% of Nb by mass percentage, and the rest are inevitable impurities; the particle size of the zirconium-niobium alloy powder is 45 ⁇ m-150 ⁇ m.
  • the chemical composition of the zirconium-niobium alloy forging includes 96.5% of Zr, 1.0% of Nb by mass percentage, and the balance is inevitable impurities.
  • steps 1-2) and 1-3) are as follows: 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.
  • the first trabecular bone 112 has a diameter of 770 ⁇ m and a porosity of 75%; the second trabecular bone (113) has a diameter of 850 ⁇ m and a porosity of 80%; the third trabecular bone (114) has a diameter of 950 ⁇ m and a porosity of 80%. is 85%; the thickness of the first trabecular bone, the second trabecular bone and the third trabecular bone are equal to 1.5mm;
  • the fourth type of trabecular bone 481 has a diameter of 740 ⁇ m and a porosity of 70%; the fifth type of trabecular bone 482 has a diameter of 770 ⁇ m and a porosity of 75%; the sixth type of trabecular bone 483 has a diameter of 810 ⁇ m , with a porosity of 78%; the seventh type of trabecular bone 484 has a pore size of 850 ⁇ m and a porosity of 80%; the eighth type of trabecular bone 485 has a pore size of 900 ⁇ m and a porosity of 83%; the ninth type The trabecular bone 486 has a pore size of 950 ⁇ m and a porosity of 85%; the fourth, fifth, sixth, seventh, and eighth bone trabeculae The thickness of the ninth trabecular bone is equal to 1.5mm.
  • Example 1 Homogeneous trabecular hip joint prosthesis system, the structure is different from Example 1,
  • the first type of bone trabecula, the second type of bone trabecula and the third type of bone trabeculae of the femoral stem are the same type of bone trabeculae, the diameter of which is 780 ⁇ m, the porosity is 76%, and the thickness of the bone trabecula is 1.2 mm.
  • the fourth, fifth, sixth, seventh, eighth and ninth types of trabecular bone in the cup are the same type of trabecular bone. , with a pore size of 780 ⁇ m, a porosity of 76%, and a thickness of 1.2 mm of trabecular bone. Others are the same as in Example 1.
  • Example 1 zirconium-niobium alloy powder (same as Example 1) as the raw material, through 3D printing integral molding and machining trimming, the femoral stem and acetabular cup with the same structure as Example 1 were obtained.
  • the finite element model of the femoral stem of Example 1 and the finite element model of the femoral stem of control group 1 are subjected to finite element analysis, and the obtained finite element analysis strain cloud map only shows the micro-strain (shaded part) in the range of 1000-3000.
  • Example 1 On the bone tissue finite element model, the 1000-3000 microstrain area accounted for 75% of the entire bone tissue finite element model (Fig. 12), which was greater than that of the control group 1 (Fig. 11, and the 1000-3000 microstrain area accounted for 20%) ), suggesting that the femoral stem of the oxide-containing zirconium-niobium alloy hip joint prosthesis system of the present invention is beneficial to bone ingrowth.
  • the finite element model of the cup of Example 1 and the finite element model of the cup of the control group 1 are subjected to finite element analysis, and the obtained finite element analysis strain cloud map only shows the micro-strain (shaded part) in the range of 1000-3000, Example 1
  • the proportion of the 1000-3000 microstrain area of the acetabular cup on the bone tissue finite element model in the entire bone tissue finite element model is 40% (Fig. 14), which is greater than that of the control group 1 (Fig. 13, the proportion of the 1000-3000 microstrain area 15%), suggesting that the cup of the oxide-containing zirconium-niobium alloy hip joint prosthesis system of the present invention can realize micro-strain in most areas of bone tissue, which is suitable for bone growth and facilitates bone ingrowth.
  • the finite element analysis results prove that the strain distribution cloud map of the femoral stem of Examples 2 and 3 on the bone tissue finite element model is similar to the strain distribution cloud map of the femoral stem of Example 1 on the bone tissue finite element model; Examples 2 and 3 The strain distribution cloud map of the acetabular cup on the bone tissue finite element model is similar to the strain distribution cloud map of the acetabular cup in Example 1 on the bone tissue finite element model.
  • Example 1 The compressive yield strength of Example 1 is 546.72 MPa, which is better than that of control group 2 (P ⁇ 0.05), indicating that the femoral stem of the oxide-coated zirconium-niobium alloy hip joint prosthesis system made by the present invention
  • the solid part has excellent resistance to compression.
  • Table 1 The results of the anti-compression test of the solid specimens of the control group 2 and Example 1 ( *P ⁇ 0.05, compared with control group 2)
  • the yield strength of the trabecular bone in Example 1 was 17.94 MPa, which was significantly higher than that in the control group 2 (P ⁇ 0.05), indicating that the oxide-containing zirconium-niobium alloy hip joint prosthesis system prepared by the present invention had better performance.
  • the trabecular part of the femoral stem has excellent compressive performance.
  • the oxide layer of the femoral stem of Example 1 was analyzed by XRD (D8DISCOVER, Bruker, Germany) (FIG. 20), and the oxide layer contained monoclinic zirconium dioxide and tetragonal zirconium dioxide.
  • a microhardness tester (MHVS-1000 PLUS, Shanghai Aolong Xingdi Testing Equipment Co., Ltd., China) was used to measure the microhardness of the femoral stems of Examples 1-3.
  • the test load was 0.05kg, and the test piece load time was 20s. Eight points were taken from each specimen.
  • the average hardness values measured in Examples 1-3 are 1948.6Hv, 1923.7Hv and 1967.2Hv, indicating that the oxide layer of the femoral stem of the oxide-coated zirconium-niobium alloy hip prosthesis system of the present invention has high hardness.

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Abstract

含氧化层锆铌合金髋关节假体系统及制备方法，该系统包括股骨柄（1）、股骨头（2）、内衬（3）和臼杯（4）；臼杯（4）和股骨柄（1）以锆铌合金粉为原料采用3D打印一体成型、热等静压、深冷和表面氧化制备；内衬（3）和股骨头（2）将锆铌合金锻件进行机加工、修整、抛光、清洗、干燥、表面氧化处理；并且假体系统各部分由具有不同孔隙率、孔径的分区骨小梁组成。采用3D打印一体成型及后续热处理步骤，解决了机加工无法制备复杂结构和袖套与股骨柄柄体连接配合失效的问题，股骨头和内衬表面经氧化后形成氧化层，实现摩擦界面的超强耐磨性、低磨损率。

Description

含氧化层锆铌合金髋关节假体系统及制备方法 技术领域
本发明涉及人工关节技术领域，具体而言，尤其涉及含氧化层锆铌合金髋关节假体系统及制备方法。
背景技术
人工髋关节置换手术是治疗股骨头坏死、髋关节发育不良、退行性髋骨关节炎、类风湿性关节炎等疾病终末期病变最重要和最有效的手术之一，随着人口老龄化的加剧，该类患者逐年增加。
目前临床上使用的人工髋关节假体包括骨水泥固定型假体和非骨水泥固定型假体。其中非骨水泥固定型假体由于良好的骨长入性能，因此得到了越来越广泛的应用。
非骨水泥固定型髋关节假体的骨整合界面通常采用以下两种方式：第一种为股骨柄表面喷涂羟基磷灰石涂层或钛涂层，第二种为表面打印骨小梁样多孔结构的袖套，然后将股骨柄与袖套进行组配。但第一种方式中的表面涂层存在脱落风险，影响使用效果。第二种方式中的袖套由于与股骨柄为装配结构，临床研究显示，股骨柄在结构设计中为了与袖套结合，结构设计中骨柄的头颈部存在截面突然变化的问题，在该位置存在十分严重的应力集中。组配柄在临床中面临的主要风险包括骨柄在头颈部存在严重的应力集中，而且也容易发生骨柄与袖套出现配合失效的风险。上述风险的存在有可能导致整个髋关节假体系统失效。
在骨小梁臼杯设计及应用方面，目前国内多家医疗器材公司制备的骨小梁臼杯均采用均匀骨小梁设计方法，其结果是受臼杯与骨盆的接触压力分布不均匀的影响，骨盆上的压应变分布也不均匀，存在的主要问题是骨盆上只有靠近臼杯上方的少数区域骨组织符合骨生长的条件，与臼杯接触的大部分骨组织不符合骨生长的条件，在临床上容易造成骨不长或因为压应变过大或过小造成骨吸收。
目前股骨柄外表面的骨小梁结构多采用均匀分布方式，临床资料显示，采用均匀骨小梁结构的股骨柄，骨组织在股骨柄上外侧，下内侧和下外侧的骨长入还不理想。进一步的研究显示，在上外侧和下内侧骨长入不理想的主要原因是股骨柄和骨组织的接触压力小，而且与股骨柄上外侧和下内侧结合骨组织的压缩应变数值偏小，低于1000微应变，不满足骨组织的生长的条件，同时在下外侧区域，股骨柄和骨组织的接触压力过大，与股骨柄结合的骨组织的压缩应变数值偏大，高于3000微应变，也不满足骨组织生长的条件。因此，整体打印的股骨柄如果采用均匀骨小梁虽然可以克服涂层柄脱落问题和组配柄锥连接失效问题，但是无法保证骨组织在骨小梁结构上的均匀长入。
在股骨头和内衬的制备方面，目前股骨头与内衬的组配方法主要为钛合金球头和高交联聚乙烯以及陶瓷球头和陶瓷内衬。钛合金球头与高交联内衬组配存在的问题是高交联聚乙烯磨损形成的碎屑容易造成骨溶解。此外，陶瓷球头和陶瓷内衬抵抗冲击的能力相对较差，会因冲击掉瓷造成假体失效。
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。
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含氧化层锆铌合金髋关节假体系统具有重要意义。
发明内容
本发明的目的在于克服现有技术不足，提供含氧化层锆铌合金髋关节假体系统。
本发明的第二个目的是提供含氧化层锆铌合金髋关节假体系统的制备方法。
本发明的技术方案概述如下：
含氧化层锆铌合金髋关节假体系统的制备方法，包括如下步骤：
1)臼杯和股骨柄的制备：
1-1)以锆铌合金粉为原料，经3D打印一体成型分别得到臼杯的第一中间产物和股骨柄的第一中间产物，将两种第一中间产物放入热等静压炉，在氦气或氩气保护下，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，得到两种第二中间产物；
1-2)将两种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，得到两种第三中间产物；
1-3)将两种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；得到两种第四中间产物；
1-4)将两种第四中间产物进行机加工修整、抛光、清洗和干燥，得到两种第五中间产物；
1-5)将两种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％的常压氦气或氩气，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，分别得到臼杯和股骨柄；
2)内衬和股骨头的制备：
2-1)将锆铌合金锻件进行机加工、修整、抛光、清洗和干燥，分别得到内衬或股骨头的中间产物，内衬的中间产物的内、外表面的粗糙度为Ra≤0.050μm；股骨头的中间产 物的外表面的粗糙度为Ra≤0.050μm；
2-2)分别将内衬的中间产物和股骨头的中间产物放置于管式炉内，通入含氧质量百分比为5％-15％的常压氦气或氩气，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，得到内衬和股骨头；
臼杯的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与臼杯的结构相同；
股骨柄的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与股骨柄的结构相同；
所述含氧化层锆铌合金髋关节假体系统，包括股骨柄1、股骨头2、内衬3和臼杯4；
所述股骨柄，包括圆柱形头部11、颈部12和柄部13；所述柄部13包括柄部近端14和柄部远端15；所述柄部近端外表面设置有股骨柄骨小梁16，股骨柄骨小梁16分区为外侧上区1101、外侧下区1102、内侧上区191和内侧下区192；外侧上区1101和内侧下区192设置的骨小梁为第一种骨小梁112；内侧上区191设置的骨小梁为第二种骨小梁113；外侧下区1102设置的骨小梁为第三种骨小梁114；所述第一种骨小梁112的孔径和孔隙率依次小于第二种骨小梁113和第三种骨小梁114；
所述臼杯的结构，包括半球面本体49，所述半球面本体的中部设置有带内螺纹的第一圆孔41，半球面本体的外表面设置有臼杯骨小梁43，所述臼杯骨小梁43进行分区设置，第一分区线46和第二分区线45相交，交点过带内螺纹的第一圆孔41的中心，第三分区线44呈圆形，位于半球面本体的近边缘处；第一分区线、第二分区线和第三分区线将半球面本体外表面分为：第一上区471、第一下区472、第二上区473、第二下区474、第三上区475、第三下区476、第四上区477和第四下区478；第一上区、第二上区、第三上区和第四上区面积相等；在所述半球面本体的一侧设置有带内螺纹的第二圆孔42，所述带内螺纹的第二圆孔42为3个，其中2个分别设置在第一上区471和第三上区475内，另1个设置在第一上区471和第三上区475的交界处；
第三上区和第四上区设置有第四种骨小梁481，第三下区和第四下区设置有第五种骨小梁482，第一上区设置有第六种骨小梁483，第一下区设置有第七种骨小梁484，第二上区设置有第八种骨小梁485，第二下区设置有第九种骨小梁486；第四种骨小梁的孔径和孔隙率依次小于第五种骨小梁、第六种骨小梁、第七种骨小梁、第八种骨小梁、第九种骨小梁。
所述锆铌合金粉的化学成分按质量百分比包括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45μm-150μm。
所述锆铌合金锻件化学成分按质量百分比包括85.6％-96.5％的Zr，1.0％-12.5％的Nb，余量为不可避免的杂质。
步骤1-2)和1-3)所述调节温度的步骤为：升温至-120℃～-80℃，恒温保持3h-5h；升温至-40℃～-20℃，恒温保持3h-5h；升温至4℃-8℃恒温保持1h-3h，升温。
所述第一骨小梁112孔径为700μm-770μm，孔隙率为65％-75％；第二骨小梁113孔径为780μm-850μm，孔隙率为76％-80％；第三骨小梁114孔径为860μm-950μm，孔隙率为81％-85％；所述第一骨小梁、第二骨小梁和第三骨小梁厚度相等，为1.2mm-1.5mm；
所述第四种骨小梁481孔径为700μm-740μm，孔隙率为65％-70％；所述第五种骨小梁482孔径为750μm-770μm，孔隙率为71％-75％；所述第六种骨小梁483孔径为780μm-810μm，孔隙率为76％-78％；所述第七种骨小梁484孔径为820μm-850μm，孔隙率为79％-80％；所述第八种骨小梁485孔径为860μm-900μm，孔隙率为81％-83％；所述第九种骨小梁486孔径为910μm-950μm，孔隙率为84％-85％；所述第四种骨小梁、第五种骨小梁、第六种骨小梁、第七种骨小梁、第八种骨小梁和第九种骨小梁厚度相等，为1.2mm-1.5mm。
上述方法制备的含氧化层锆铌合金分区骨小梁髋关节假体系统。
与现有技术方案相比，本发明具有以下有益效果：
本发明含氧化层锆铌合金髋关节假体系统的股骨柄和臼杯采用3D打印一体成型，解决传统机加工无法制备复杂结构和袖套与股骨柄柄体连接配合失效的难题，且骨小梁与实体结合强度高，不易脱落，提升假体寿命。
本发明含氧化层锆铌合金髋关节假体系统的股骨柄解决了均匀骨小梁可能发生的骨小梁在外侧和内侧下区因为股骨的压应变数值过小或过大产生的骨吸收等问题。使股骨骨组织的大部分压应变数值位于1000-3000微应变之间，符合骨生长理论，保证骨在骨小梁区域的均匀长入。
本发明含氧化层锆铌合金髋关节假体系统的臼杯，采用分区骨小梁方式，为骨生长提供适合的环境。根据有限元分析结果，骨组织有限元模型中符合骨生长条件的区域可达40％，实现臼杯与宿主骨的骨整合。
本发明含氧化层锆铌合金髋关节假体系统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。股骨头和内衬表面经氧化后形成陶瓷化表面，实现摩擦界面的超强耐磨性、低磨损率；股骨柄和臼杯实现骨整合界面的优异骨长入性和生物相容性。
本发明含氧化层锆铌合金髋关节假体系统低伪影，对核磁干扰小，可进行核磁检测。
附图说明
图1为本发明含氧化层锆铌合金髋关节假体系统的结构分散示意图。
图2为股骨柄结构示意图。
图3为股骨柄的近端分区示意图。
图4为股骨柄的近端结构示意图。
图5为臼杯轴测图。
图6为臼杯(无骨小梁)轴测图。
图7为臼杯结构示意图。
图8为臼杯俯视图。
图9为股骨头结构示意图。
图10为内衬结构示意图。
图11为对照组1的股骨柄应变分布云图。
图12为实施例1的股骨柄应变分布云图。
图13为对照组1的臼杯应变分布云图。
图14为实施例1的臼杯应变分布云图。
图15为对照组2的股骨柄实体部分金相显微结构图。
图16为实施例1的股骨柄未进行制备方法中步骤1-4)和步骤1-5)实体部分金相显微结构图。
图17为对照组2的股骨柄骨小梁SEM图。
图18为实施例1的股骨柄未进行制备方法中步骤1-4)和步骤1-5)骨小梁SEM图。
图19为实施例1的股骨柄的氧化层与基体的横截面SEM图。
图20为实施例1的股骨柄氧化层表面的XRD曲线。
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
含氧化层锆铌合金髋关节假体系统的制备方法，包括如下步骤：
1)臼杯和股骨柄的制备：
1-1)以锆铌合金粉为原料，经3D打印一体成型分别得到臼杯的第一中间产物和股骨柄的第一中间产物，将两种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，得到两种第二中间产物；
1-2)将两种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，得到两种第三中间产物；
1-3)将两种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；得到两种第四中间产物；
1-4)将两种第四中间产物进行机加工修整、抛光、清洗和干燥，得到两种第五中间产物；
1-5)将两种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，分别得到臼杯和股骨柄；
2)内衬和股骨头的制备：
2-1)将锆铌合金锻件进行机加工、修整、抛光、清洗和干燥，分别得到内衬或股骨头的中间产物，内衬的中间产物的内、外表面的粗糙度为Ra＝0.012μm；股骨头的中间产物的外表面的粗糙度为Ra＝0.012μm；
2-2)分别将内衬的中间产物和股骨头的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，得到内衬和股骨头；
臼杯的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与臼杯的结构相同；
股骨柄的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与股骨柄的结构相同；
所述含氧化层锆铌合金髋关节假体系统(见图1)，包括股骨柄1、股骨头2(见图9)、内衬3(见图10)和臼杯4；
所述股骨柄(见图2-图4)，包括圆柱形头部11、颈部12和柄部13；所述柄部13包括柄部近端14和柄部远端15；所述柄部近端外表面设置有股骨柄骨小梁16，股骨柄骨小梁16分区为外侧上区1101、外侧下区1102、内侧上区191和内侧下区192；外侧上区1101和内侧下区192设置的骨小梁为第一种骨小梁112；内侧上区191设置的骨小梁为第二种骨小梁113；外侧下区1102设置的骨小梁为第三种骨小梁114；
所述臼杯的结构(见图5-图8)，包括半球面本体49，所述半球面本体的中部设置有带内螺纹的第一圆孔41，半球面本体的外表面设置有臼杯骨小梁43，所述臼杯骨小梁43进行分区设置，第一分区线46和第二分区线45相交，交点过带内螺纹的第一圆孔41的中心，第三分区线44呈圆形，位于半球面本体的近边缘处；第一分区线、第二分区线和第三分区线将半球面本体外表面分为：第一上区471、第一下区472、第二上区473、第二下区474、第三上区475、第三下区476、第四上区477和第四下区478；第一上区、第二上区、第三上区和第四上区面积相等；在所述半球面本体的一侧设置有带内螺纹的第二圆孔42，所述带内螺纹的第二圆孔42为3个，其中2个分别设置在第一上区471和第三上区475内，另1个设置在第一上区471和第三上区475的交界处；
第三上区和第四上区设置有第四种骨小梁481，第三下区和第四下区设置有第五种骨小梁482，第一上区设置有第六种骨小梁483，第一下区设置有第七种骨小梁484，第二上区设置有第八种骨小梁485，第二下区设置有第九种骨小梁486；
所述锆铌合金粉的化学成分按质量百分比包括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45μm-150μm。
所述锆铌合金锻件化学成分按质量百分比包括85.6％的Zr，12.5％的Nb，余量为不可避免的杂质。
步骤1-2)和1-3)所述调节温度的步骤为：升温至-120℃，恒温保持5h；升温至-40℃，恒温保持5h；升温至4℃恒温保持3h，升温。
所述第一骨小梁112孔径为700μm，孔隙率为65％；第二骨小梁113孔径为780μm，孔隙率为76％；第三骨小梁114孔径为860μm，孔隙率为81％；所述第一骨小梁、第二骨小梁和第三骨小梁厚度相等，为1.2mm；
所述第四种骨小梁481孔径为700μm，孔隙率为65％；所述第五种骨小梁482孔径为750μm，孔隙率为71％；所述第六种骨小梁483孔径为780μm，孔隙率为76％；所述第七种骨小梁484孔径为820μm，孔隙率为79％；所述第八种骨小梁485孔径为860μm，孔隙率为81％；所述第九种骨小梁486孔径为910μm，孔隙率为84％；所述第四种骨小梁、第五种骨小梁、第六种骨小梁、第七种骨小梁、第八种骨小梁和第九种骨小梁厚度相等，为1.2mm。
实施例2
含氧化层锆铌合金髋关节假体系统的制备方法，包括如下步骤：
1)臼杯和股骨柄的制备：
1-1)以锆铌合金粉为原料，经3D打印一体成型分别得到臼杯的第一中间产物和股骨柄的第一中间产物，将两种第一中间产物放入热等静压炉，在氩气保护下，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，得到两种第二中间产物；
1-2)将两种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，得到两种第三中间产物；
1-3)将两种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；得到两种第四中间产物；
1-4)将两种第四中间产物进行机加工修整、抛光、清洗和干燥，得到两种第五中间产物；
1-5)将两种第五中间产物放置于管式炉内，通入含氧质量百分比为10％的常压氩气，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，分别得到臼杯和股骨柄；
2)内衬和股骨头的制备：
2-1)将锆铌合金锻件进行机加工、修整、抛光、清洗和干燥，分别得到内衬或股骨头的中间产物，内衬的中间产物的内、外表面的粗糙度为Ra＝0.035μm；股骨头的中间产物的外表面的粗糙度为Ra＝0.035μm；
2-2)分别将内衬的中间产物和股骨头的中间产物放置于管式炉内，通入含氧质量百分比为10％的常压氩气，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，得到内衬和股骨头；
臼杯的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物 与臼杯的结构相同；
股骨柄的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与股骨柄的结构相同；
所述含氧化层锆铌合金髋关节假体系统，包括股骨柄1、股骨头2、内衬3和臼杯4；
所述股骨柄，包括圆柱形头部11、颈部12和柄部13；所述柄部13包括柄部近端14和柄部远端15；所述柄部近端外表面设置有股骨柄骨小梁16，股骨柄骨小梁16分区为外侧上区1101、外侧下区1102、内侧上区191和内侧下区192；外侧上区1101和内侧下区192设置的骨小梁为第一种骨小梁112；内侧上区191设置的骨小梁为第二种骨小梁113；外侧下区1102设置的骨小梁为第三种骨小梁114；
所述臼杯的结构，包括半球面本体49，所述半球面本体的中部设置有带内螺纹的第一圆孔41，半球面本体的外表面设置有臼杯骨小梁43，所述臼杯骨小梁43进行分区设置，第一分区线46和第二分区线45相交，交点过带内螺纹的第一圆孔41的中心，第三分区线44呈圆形，位于半球面本体的近边缘处；第一分区线、第二分区线和第三分区线将半球面本体外表面分为：第一上区471、第一下区472、第二上区473、第二下区474、第三上区475、第三下区476、第四上区477和第四下区478；第一上区、第二上区、第三上区和第四上区面积相等；在所述半球面本体的一侧设置有带内螺纹的第二圆孔42，所述带内螺纹的第二圆孔42为3个，其中2个分别设置在第一上区471和第三上区475内，另1个设置在第一上区471和第三上区475的交界处；
第三上区和第四上区设置有第四种骨小梁481，第三下区和第四下区设置有第五种骨小梁482，第一上区设置有第六种骨小梁483，第一下区设置有第七种骨小梁484，第二上区设置有第八种骨小梁485，第二下区设置有第九种骨小梁486；
所述锆铌合金粉的化学成分按质量百分比包括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45μm-150μm。
所述锆铌合金锻件化学成分按质量百分比包括93.4％的Zr，5.1％的Nb，余量为不可避免的杂质。
步骤1-2)和1-3)所述调节温度的步骤为：升温至-100℃，恒温保持4h；升温至-30℃，恒温保持4h；升温至6℃恒温保持2h，升温。
所述第一骨小梁112孔径为740μm，孔隙率为70％；第二骨小梁113孔径为810μm，孔隙率为78％；第三骨小梁114孔径为900μm，孔隙率为83％；所述第一骨小梁、第二骨小梁和第三骨小梁厚度相等，为1.3mm；
所述第四种骨小梁481孔径为720μm，孔隙率为67％；所述第五种骨小梁482孔径为760μm，孔隙率为73％；所述第六种骨小梁483孔径为800μm，孔隙率为77％；所述第七种骨小梁484孔径为840μm，孔隙率为79.5％；所述第八种骨小梁485孔径为880μm，孔隙率为82％；所述第九种骨小梁486孔径为930μm，孔隙率为84.5％；所述第四种骨小梁、第五种骨小梁、第六种骨小梁、第七种骨小梁、第八种骨小梁和第九种骨小梁厚度相等， 为1.3mm。
实施例3
含氧化层锆铌合金髋关节假体系统的制备方法，其特征是包括如下步骤：
1)臼杯和股骨柄的制备：
1-1)以锆铌合金粉为原料，经3D打印一体成型分别得到臼杯的第一中间产物和股骨柄的第一中间产物，将两种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，得到两种第二中间产物；
1-2)将两种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，得到两种第三中间产物；
1-3)将两种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；得到两种第四中间产物；
1-4)将两种第四中间产物进行机加工修整、抛光、清洗和干燥，得到两种第五中间产物；
1-5)将两种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℃，再自然冷却至200℃以下取出，分别得到臼杯和股骨柄；
2)内衬和股骨头的制备：
2-1)将锆铌合金锻件进行机加工、修整、抛光、清洗和干燥，分别得到内衬或股骨头的中间产物，内衬的中间产物的内、外表面的粗糙度为Ra＝0.050μm；股骨头的中间产物的外表面的粗糙度为Ra＝0.050μm；
2-2)分别将内衬的中间产物和股骨头的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℃，再自然冷却至200℃以下取出，得到内衬和股骨头；
臼杯的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与臼杯的结构相同；
股骨柄的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与股骨柄的结构相同；
所述含氧化层锆铌合金髋关节假体系统，包括股骨柄1、股骨头2、内衬3和臼杯4；
所述股骨柄，包括圆柱形头部11、颈部12和柄部13；所述柄部13包括柄部近端14和柄部远端15；所述柄部近端外表面设置有股骨柄骨小梁16，股骨柄骨小梁16分区为外侧上区1101、外侧下区1102、内侧上区191和内侧下区192；外侧上区1101和内侧下区192设置的骨小梁为第一种骨小梁112；内侧上区191设置的骨小梁为第二种骨小梁113； 外侧下区1102设置的骨小梁为第三种骨小梁114；
所述臼杯的结构，包括半球面本体49，所述半球面本体的中部设置有带内螺纹的第一圆孔41，半球面本体的外表面设置有臼杯骨小梁43，所述臼杯骨小梁43进行分区设置，第一分区线46和第二分区线45相交，交点过带内螺纹的第一圆孔41的中心，第三分区线44呈圆形，位于半球面本体的近边缘处；第一分区线、第二分区线和第三分区线将半球面本体外表面分为：第一上区471、第一下区472、第二上区473、第二下区474、第三上区475、第三下区476、第四上区477和第四下区478；第一上区、第二上区、第三上区和第四上区面积相等；在所述半球面本体的一侧设置有带内螺纹的第二圆孔42，所述带内螺纹的第二圆孔42为3个，其中2个分别设置在第一上区471和第三上区475内，另1个设置在第一上区471和第三上区475的交界处；
第三上区和第四上区设置有第四种骨小梁481，第三下区和第四下区设置有第五种骨小梁482，第一上区设置有第六种骨小梁483，第一下区设置有第七种骨小梁484，第二上区设置有第八种骨小梁485，第二下区设置有第九种骨小梁486。
所述锆铌合金粉的化学成分按质量百分比包括96.5％的Zr，1.0％的Nb，其余为不可避免的杂质；所述锆铌合金粉的粒径为45μm-150μm。
所述锆铌合金锻件化学成分按质量百分比包括96.5％的Zr，1.0％的Nb，余量为不可避免的杂质。
步骤1-2)和1-3)所述调节温度的步骤为：升温至-80℃，恒温保持3h；升温至-20℃，恒温保持3h；升温至8℃恒温保持1h，升温。
所述第一骨小梁112孔径为770μm，孔隙率为75％；第二骨小梁(113)孔径为850μm，孔隙率为80％；第三骨小梁(114)孔径为950μm，孔隙率为85％；所述第一骨小梁、第二骨小梁和第三骨小梁厚度相等，为1.5mm；
所述第四种骨小梁481孔径为740μm，孔隙率为70％；所述第五种骨小梁482孔径为770μm，孔隙率为75％；所述第六种骨小梁483孔径为810μm，孔隙率为78％；所述第七种骨小梁484孔径为850μm，孔隙率为80％；所述第八种骨小梁485孔径为900μm，孔隙率为83％；所述第九种骨小梁486孔径为950μm，孔隙率为85％；所述第四种骨小梁、第五种骨小梁、第六种骨小梁、第七种骨小梁、第八种骨小梁和第九种骨小梁厚度相等，为1.5mm。
对照组1
均匀骨小梁髋关节假体系统，结构与实施例1不同的是，
股骨柄的第一种骨小梁、第二种骨小梁和第三种骨小梁为同一种骨小梁，其孔径为780μm，孔隙率为76％，骨小梁的厚度为1.2mm。
臼杯的第四种骨小梁、第五种骨小梁、第六种骨小梁、第七种骨小梁、第八种骨小梁和第九种骨小梁为同一种骨小梁，其孔径为780μm，孔隙率为76％，骨小梁的厚度为1.2mm。其它同实施例1。
对照组2
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的股骨柄和臼杯。
实验验证：
将实施例1的股骨柄有限元模型与对照组1的股骨柄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在骨组织有限元模型上1000-3000微应变区域在整个骨组织有限元模型的占比为75％(图12)，大于对照组1(图11，1000-3000微应变区域占比为20％)，提示本发明含氧化层锆铌合金髋关节假体系统的股骨柄利于骨长入。
将实施例1的臼杯有限元模型与对照组1的臼杯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的臼杯在骨组织有限元模型上1000-3000微应变区域在整个骨组织有限元模型的占比为40％(图14)，大于对照组1(图13，1000-3000微应变区域占比为15％)，提示本发明含氧化层锆铌合金髋关节假体系统的臼杯可实现骨组织大部分区域微应变适合骨生长，利于骨长入。
有限元分析结果证明，实施例2、3的股骨柄在骨组织有限元模型上的应变分布云图与实施例1的股骨柄在骨组织有限元模型上的应变分布云图相似；实施例2、3的臼杯在骨组织有限元模型上的应变分布云图与实施例1的臼杯在骨组织有限元模型上的应变分布云图相似。
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2的股骨柄实体部分和实施例1的股骨柄未进行所述制备方法中步骤1-4)和步骤1-5)的实体部分进行金相显微组织观察。结果如图15-16所示，对照组2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，本发明含氧化层锆铌合金髋关节假体系统的股骨柄实体部分(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2的股骨柄骨小梁部分和实施例1的股骨柄未进行所述制备方法中步骤1-4)和步骤1-5)骨小梁部分进行观察分析，结果如图17-18所示，与对照组2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的股骨柄未进行所述制备方法中步骤1-4)和步骤1-5)的实体压缩试件(试件大小为：8*8*10mm 3)和对照组2的股骨柄实体压缩试件(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2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2(P＜0.05)，提示本发明制得的含氧化层锆铌合金髋关节假体系统的股骨柄实体部分具有优异抗压缩性能。
表1对照组2和实施例1的实体试件抗压缩实验结果(
Figure PCTCN2021101277-appb-000001
*P＜0.05，与对照组2比较)
Figure PCTCN2021101277-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2股骨柄的孔径为780μm，孔隙率为76％的骨小梁压缩试件和实施例1股骨柄的未进行所述制备方法中步骤1-4)和步骤1-5)的孔径为780μm，孔隙率为76％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2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17.94MPa，显著高于对照组2(P＜0.05)，提示本发明制得的含氧化层锆铌合金髋关节假体系统的股骨柄骨小梁部分抗压性能优异。
表2对照组2和实施例1的骨小梁试件抗压缩实验结果(
Figure PCTCN2021101277-appb-000003
n＝5，*P＜0.05，与对照组2比较)
Figure PCTCN2021101277-appb-000004
扫描电子显微镜(Crossbeam340/550，蔡司，德国)对实施例1股骨柄的锆铌合金基体与氧化层的横截面进行观察，(见图19)。并对实施例2、3股骨柄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股骨柄的氧化层进行分析(图20)，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的股骨柄进行显微硬度测量，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，提示本发明含氧化层锆铌合金髋关节假体系统的股骨柄的氧化层硬度高。
实验证明，实施例2、3制备的臼杯和股骨柄和实施例1制备的臼杯，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制备的股骨柄相似；实施例1、2、3制备的股骨头和内衬的氧化层晶体结构、厚度和硬度与实施例1制备的股骨柄相似。

Claims (6)

  1. 含氧化层锆铌合金髋关节假体系统的制备方法，其特征是包括如下步骤：
    1)臼杯和股骨柄的制备：
    1-1)以锆铌合金粉为原料，经3D打印一体成型分别得到臼杯的第一中间产物和股骨柄的第一中间产物，将两种第一中间产物放入热等静压炉，在氦气或氩气保护下，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，得到两种第二中间产物；
    1-2)将两种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，得到两种第三中间产物；
    1-3)将两种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；得到两种第四中间产物；
    1-4)将两种第四中间产物进行机加工修整、抛光、清洗和干燥，得到两种第五中间产物；
    1-5)将两种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％的常压氦气或氩气，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，分别得到臼杯和股骨柄；
    2)内衬和股骨头的制备：
    2-1)将锆铌合金锻件进行机加工、修整、抛光、清洗和干燥，分别得到内衬或股骨头的中间产物，内衬的中间产物的内、外表面的粗糙度为Ra≤0.050μm；股骨头的中间产物的外表面的粗糙度为Ra≤0.050μm；
    2-2)分别将内衬的中间产物和股骨头的中间产物放置于管式炉内，通入含氧质量百分比为5％-15％的常压氦气或氩气，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，得到内衬和股骨头；
    所述含氧化层锆铌合金髋关节假体系统，包括股骨柄(1)、股骨头(2)、内衬(3)和臼杯(4)；
    所述股骨柄，包括圆柱形头部(11)、颈部(12)和柄部(13)；所述柄部(13)包括柄部近端(14)和柄部远端(15)；所述柄部近端外表面设置有股骨柄骨小梁(16)， 股骨柄骨小梁(16)分区为外侧上区(1101)、外侧下区(1102)、内侧上区(191)和内侧下区(192)；外侧上区(1101)和内侧下区(192)设置的骨小梁为第一种骨小梁(112)；内侧上区(191)设置的骨小梁为第二种骨小梁(113)；外侧下区(1102)设置的骨小梁为第三种骨小梁(114)；所述第一种骨小梁(112)的孔径和孔隙率依次小于第二种骨小梁(113)和第三种骨小梁(114)；
    臼杯的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与臼杯的结构相同；
    股骨柄的第一中间产物、第二中间产物、第三中间产物、第四中间产物、第五中间产物与股骨柄的结构相同；
    所述臼杯的结构，包括半球面本体(49)，所述半球面本体的中部设置有带内螺纹的第一圆孔(41)，
    半球面本体的外表面设置有臼杯骨小梁(43)，所述臼杯骨小梁(43)进行分区设置，第一分区线(46)和第二分区线(45)相交，交点过带内螺纹的第一圆孔(41)的中心，第三分区线(44)呈圆形，位于半球面本体的近边缘处；第一分区线、第二分区线和第三分区线将半球面本体外表面分为：第一上区(471)、第一下区(472)、第二上区(473)、第二下区(474)、第三上区(475)、第三下区(476)、第四上区(477)和第四下区(478)；第一上区、第二上区、第三上区和第四上区面积相等；在所述半球面本体的一侧设置有带内螺纹的第二圆孔(42)，所述带内螺纹的第二圆孔(42)为3个，其中2个分别设置在第一上区(471)和第三上区(475)内，另1个设置在第一上区(471)和第三上区(475)的交界处；
    第三上区和第四上区设置有第四种骨小梁(481)，
    第三下区和第四下区设置有第五种骨小梁(482)，
    第一上区设置有第六种骨小梁(483)，
    第一下区设置有第七种骨小梁(484)，
    第二上区设置有第八种骨小梁(485)，
    第二下区设置有第九种骨小梁(486)；
    第四种骨小梁的孔径和孔隙率依次小于第五种骨小梁、第六种骨小梁、第七种骨小梁、第八种骨小梁、第九种骨小梁。
  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包括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45μm-150μm。
  3. 根据权利要求1所述的方法，其特征是所述锆铌合金锻件化学成分按质量百分比包括85.6％-96.5％的Zr，1.0％-12.5％的Nb，余量为不可避免的杂质。
  4. 根据权利要求1所述的方法，其特征是步骤1-2)和1-3)所述调节温度的步骤为：升温至-120℃～-80℃，恒温保持3h-5h；升温至-40℃～-20℃，恒温保持3h-5h；升温至4℃-8℃恒温保持1h-3h，升温。
  5. 根据权利要求1所述的方法，其特征是所述
    第一骨小梁(112)孔径为700μm-770μm，孔隙率为65％-75％；
    第二骨小梁(113)孔径为780μm-850μm，孔隙率为76％-80％；
    第三骨小梁(114)孔径为860μm-950μm，孔隙率为81％-85％；所述第一骨小梁、第二骨小梁和第三骨小梁厚度相等，为1.2mm-1.5mm；
    所述第四种骨小梁(481)孔径为700μm-740μm，孔隙率为65％-70％；
    所述第五种骨小梁(482)孔径为750μm-770μm，孔隙率为71％-75％；
    所述第六种骨小梁(483)孔径为780μm-810μm，孔隙率为76％-78％；
    所述第七种骨小梁(484)孔径为820μm-850μm，孔隙率为79％-80％；
    所述第八种骨小梁(485)孔径为860μm-900μm，孔隙率为81％-83％；
    所述第九种骨小梁(486)孔径为910μm-950μm，孔隙率为84％-85％；
    所述第四种骨小梁、第五种骨小梁、第六种骨小梁、第七种骨小梁、第八种骨小梁和第九种骨小梁厚度相等，为1.2mm-1.5mm。
  6. 权利要求1-5之一的方法制备的含氧化层锆铌合金分区骨小梁髋关节假体系统。
PCT/CN2021/101277 2020-10-30 2021-06-21 含氧化层锆铌合金髋关节假体系统及制备方法 WO2022088701A1 (zh)

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