WO2022198965A1 - 一种骨修复钛钼基羟基磷灰石复合材料及其制备方法 - Google Patents

一种骨修复钛钼基羟基磷灰石复合材料及其制备方法 Download PDF

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WO2022198965A1
WO2022198965A1 PCT/CN2021/121174 CN2021121174W WO2022198965A1 WO 2022198965 A1 WO2022198965 A1 WO 2022198965A1 CN 2021121174 W CN2021121174 W CN 2021121174W WO 2022198965 A1 WO2022198965 A1 WO 2022198965A1
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titanium
powder
molybdenum
preparation
composite material
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French (fr)
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颉芳霞
黄家兵
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江南大学
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass

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  • the invention relates to the technical field of biomedical material preparation, in particular to a titanium-molybdenum-based hydroxyapatite composite material for bone repair and a preparation method thereof.
  • titanium and titanium alloys have excellent properties and are considered to be the preferred materials for the replacement and repair of hard tissues such as artificial joints, spinal orthopedic internal fixation systems, and dental implants.
  • Pure titanium (Ti) and Ti-6Al-4V are currently the most widely used titanium alloys for bone repair, but aluminum (Al) and vanadium (V) have been proven to be toxic to the human body, and their elastic modulus does not match human bone. lead to the "stress shielding phenomenon".
  • Adding Nb, Ta, Zr, Mo and other non-toxic elements to develop a new type of ⁇ -type biomedical titanium alloy can effectively reduce the elastic modulus and has great development prospects.
  • molybdenum (Mo) element as a trace element necessary for human body, animals and plants, helps to regulate the acid-base balance in the human body, and can be used as a cofactor for some enzymes.
  • Human affinity element Human affinity element.
  • Mo and Ti belong to the isomorphic structure and can form an infinite solid solution with Ti, which not only reduces the elastic modulus, but also improves the wear resistance and strength of Ti. Therefore, Ti-Mo alloys have broad application prospects in biomedical applications.
  • Titanium alloy has good mechanical properties, and can be used as a human implant material to carry larger parts, but as a biologically inert material, the surface has no biological activity, and it is difficult to form a strong chemical bond with the body tissue, resulting in long-term use. Loose and fail.
  • Hydroxyapatite (HA) as a bone-like bioceramic, has a similar composition and structure to human bones, and can osseointegrate with bone tissue when implanted into the body, and has excellent biological activity.
  • its mechanical properties are poor and cannot be used in parts with large bearing capacity. Therefore, combining the excellent mechanical properties of titanium-molybdenum alloy and the excellent biological activity of hydroxyapatite to prepare biocomposite materials with both properties is an important direction for the development of biomedical materials.
  • press sintering can realize customized molds, and only a small amount of machining is required for subsequent processing.
  • the sintering process is carried out under the protection of flowing argon, and the process is clean and low-cost.
  • the applicant of the present invention provides a titanium-molybdenum-based hydroxyapatite composite material and a preparation method thereof.
  • the present invention uses harmless titanium-molybdenum alloy and adds hydroxyapatite powder, prepares high-fine powder by means of high-energy ball milling, and adopts high-temperature tube furnace to realize gradient heating degreasing and sintering, so as to further improve the biological activity of artificial implants and solve the The mechanical properties of the implant and bone tissue do not match.
  • the prepared composite material has uniform composition, low elastic modulus (30-50GPa), high compressive strength (500-1550MPa), and high hardness (300-520HV). It has excellent comprehensive mechanical properties, excellent biological activity and biocompatibility, and can be used as the preferred material for bone replacement or bone repair.
  • a titanium-molybdenum-based hydroxyapatite composite material for bone repair the raw material types of the composite material and the dosage of each raw material are:
  • Each raw material is in parts by weight
  • the mass percentage of each element powder in the titanium-molybdenum alloy metal powder is Ti: 80%-90%, Mo: 10%-20%.
  • a preparation method of a titanium-molybdenum-based hydroxyapatite composite material for bone repair comprising the following steps:
  • step (1) grinding the raw material weighed in step (1) to obtain titanium-molybdenum metal powder with fine particle size;
  • step (3) adding 3-20 parts of hydroxyapatite powder to the titanium-molybdenum metal powder obtained in step (2), and continuing to grind to obtain a titanium-molybdenum-based hydroxyapatite mixed powder;
  • step (3) (4) loading the titanium-molybdenum-based hydroxyapatite mixed powder obtained in step (3) into a steel mold, and using a tablet press or a hydraulic press for bidirectional compression, and demoulding to obtain a compact;
  • the purity of the Ti powder is 99.99% and the particle size is 325-500 mesh; the purity of the Mo powder is 99.99% and the particle size is 400-500 mesh; the process control agent is stearic acid, stearic acid One of zinc, vinyl bis-stearamide and polyethylene glycol.
  • steps (2) and (3) a planetary ball mill is used for grinding.
  • the ball mill comprises a stainless steel ball mill tank, the ball milling medium is a stainless steel grinding ball with a diameter of 4-10 mm, the mass ratio of the balls is 3:1-20:1, the ball-milling speed is 300-600r/min, and the ball-milling time is 6-24h.
  • the hydroxyapatite powder is a spherical micron-sized powder with a purity of 99.99% and an average particle size of 15 ⁇ m or a needle-shaped nano-sized powder with a length of 100 nm.
  • step (2) the particle size of the titanium-molybdenum metal powder is 5-50 ⁇ m; in step (3), the particle size of the titanium-molybdenum-based hydroxyapatite mixed powder is 2-50 ⁇ m.
  • step (4) the pressure of the two-way pressing process is 300-800 MPa, and the pressure holding time is 1-12 minutes.
  • step (5) the stepped heating-up sintering is performed in a tube furnace.
  • step (5) the stepped sintering process is as follows: the temperature is raised to 300-500°C at a rate of 1-3°C/min, kept for 1-2 hours, and then heated to 800-1000°C at a rate of 3-5°C/min, Incubate for 2h; continue to heat up to 1100-1500°C at a rate of 5-10°C/min, and keep for 1-3h.
  • the preparation process is simple. After mixing powder, bidirectional pressing is adopted, and the pressure distribution of the compact is uniform, so as to avoid the cracking of the structure during the sintering process; the sintering is carried out by a stepped heating method, and the sintering is performed at one time, and there is no need for secondary sintering after degreasing.
  • step sintering and heat preservation can promote the transformation of ⁇ -Ti into ⁇ -Ti, and the structure of the final composite material is based on ⁇ + ⁇ type Ti alloy, and the prepared material
  • the tissue contains a large number of bioactive ceramic phases (such as CaTiO 3 , Ca 3 (PO 4 ) 2 , HA, etc.), which can improve the chemical bonding force between the material and the collective tissue, and enable the implanted material to be more compatible with bone tissue. good combination.
  • the preparation process is easy to adjust the material composition of the composite material, the material utilization rate is high, the preparation process is simple, clean, and the cost is low.
  • the molding method can realize the complex customization of the shape of the sintered body, with strong operability and low equipment requirements. .
  • FIG. 1 SEM picture of the microstructure of the Ti-10Mo/10HA composite material obtained in Example 1.
  • a preparation method of a titanium-molybdenum-based hydroxyapatite composite material for bone repair comprising the following steps:
  • the raw material weighed in step (1) is ground in the stainless steel ball mill tank of the planetary ball mill (the ball milling medium is a stainless steel grinding ball with a diameter of 4 ⁇ 10mm, and the mass ratio of the ball to the material is 10:1)
  • the ball milling speed is 400r/min
  • the ball milling time is 6h
  • the titanium-molybdenum metal powder with fine particle size is obtained, and the particle size is 5-50 ⁇ m;
  • step (3) adding 2.00 g of hydroxyapatite powder (a spherical micron powder with a purity of 99.99% and an average particle size of 15 ⁇ m) to the titanium-molybdenum metal powder obtained in step (2), and continuing to grind to obtain a titanium-molybdenum-based hydroxyl group Apatite mixed powder, particle size is 2 ⁇ 50 ⁇ m;
  • step (3) The titanium-molybdenum-based hydroxyapatite mixed powder obtained in step (3) is loaded into a steel mold, and a tableting machine is used for bidirectional compression.
  • the pressure of the bidirectional compression process is 600MPa, and the pressure holding time is 12min. After demolding get a compact;
  • step (5) carrying out stepped heating and sintering of the compact obtained in step (4) in a tube furnace under the protection of flowing argon gas, and cooling to room temperature to obtain a titanium-molybdenum-based hydroxyapatite composite material, Ti-10Mo/10HA;
  • the step-type sintering process is as follows: heating to 450°C at a rate of 2°C/min, holding for 1 hour, then heating to 1000°C at a rate of 3°C/min, holding for 2 hours; continuing to heat up to 1300°C at a rate of 5°C/min °C, keep warm for 2h.
  • the powder is uniformly mixed and the particle size is fine.
  • the composite material is guaranteed to have a titanium alloy matrix with uniform structure and low elastic modulus; the microstructure of the composite material prepared in this example is shown in Figure 1.
  • ⁇ -Ti, ⁇ -Ti and ceramic phases (CaTiO 3 , Ca 3 (PO 4 ) 2 , CaO, HA, Ti x P y ), and has excellent biological activity;
  • the density of Ti-10Mo/10HA composite is 4.22g/cm 3
  • the elastic modulus is 42.81GPa, which is much lower than that of pure Ti (101GPa) and Ti-6Al-4V (110GPa)
  • the compressive strength is 812MPa, which is greater than that of human bone (100GPa).
  • ⁇ 230MPa) and pure Ti the comprehensive mechanical properties meet the requirements of implants.
  • hydroxyapatite powder a spherical micron powder with a purity of 99.99% and an average particle size of 15 ⁇ m
  • Ti-10Mo/7HA a titanium-molybdenum-based hydroxyapatite composite material
  • the Ti-10Mo/7HA composite material prepared in this example has a density of 4.39 g/cm 3 , an elastic modulus of 46.46 GPa and a compressive strength of 1153 MPa.
  • the in vitro biomimetic mineralization experiment is used to determine the biological activity of the composite material prepared in this embodiment. The evaluation was carried out, and the samples were soaked in simulated body fluid at a temperature of 37 °C, the solution was changed every 2 days, and the soaking time was 7 days. Has better biological activity. The experimental results are shown in Figure 2. A large number of spherical bone-like apatites are deposited on the surface, indicating that the composite material has excellent biological activity.
  • hydroxyapatite powder a spherical micron powder with a purity of 99.99% and an average particle size of 15 ⁇ m
  • Ti-10Mo/5HA a titanium-molybdenum-based hydroxyapatite composite material
  • the Ti-10Mo/5HA composite material prepared in this embodiment has a density of 4.51 g/cm 3 , an elastic modulus of 48.69 GPa, and a compressive strength of 1486 MPa.
  • hydroxyapatite powder a spherical micron powder with a purity of 99.99% and an average particle size of 15 ⁇ m
  • Ti-10Mo/3HA a titanium-molybdenum-based hydroxyapatite composite material
  • the Ti-10Mo/3HA composite material prepared in this example has a density of 4.57 g/cm 3 , an elastic modulus of 47.74 GPa and a compressive strength of 1511 MPa.
  • a preparation method of a titanium-molybdenum-based hydroxyapatite composite material for bone repair comprising the following steps:
  • step (2) the raw material weighed in step (1) is ground in the stainless steel ball mill tank of the planetary ball mill (the ball milling medium is a stainless steel grinding ball with a diameter of 4 ⁇ 10mm, and the mass ratio of the ball to the material is 3:1)
  • the ball milling speed is 300r/min
  • the ball milling time is 24h
  • the titanium-molybdenum metal powder with fine particle size is obtained, and the particle size is 5-50 ⁇ m;
  • step (3) Add 1.00 g of hydroxyapatite powder (acicular nano-scale powder with a purity of 99.99% and a length of 100 nm) to the titanium-molybdenum metal powder obtained in step (2), and continue grinding to obtain titanium-molybdenum-based hydroxyphosphorus Limestone mixed powder with a particle size of 2 to 50 ⁇ m;
  • step (3) The titanium-molybdenum-based hydroxyapatite mixed powder obtained in step (3) was loaded into a steel mold, and two-way pressing was carried out by using a tablet press.
  • the pressure of the two-way pressing process was 300 MPa, and the pressure holding time was 6 minutes. get a compact;
  • step (4) carrying out stepped heating and sintering of the compact obtained in step (4) in a tube furnace under the protection of flowing argon gas, and cooling to room temperature to obtain a titanium-molybdenum-based hydroxyapatite composite material, Ti-15Mo/15HA;
  • the stepped sintering process is as follows: heating to 300°C at a rate of 3°C/min, holding for 1 hour, then heating to 800°C at a rate of 5°C/min, holding for 2 hours; continuing to heat up to 1200°C at a rate of 8°C/min °C, keep warm for 1h.
  • a preparation method of a titanium-molybdenum-based hydroxyapatite composite material for bone repair comprising the following steps:
  • the raw material weighed in step (1) is ground in the stainless steel ball mill tank of the planetary ball mill (the ball milling medium is a stainless steel grinding ball with a diameter of 4 ⁇ 10mm, and the mass ratio of the ball to the material is 20:1)
  • the ball mill rotation speed is 600r/min
  • the ball milling time is 6h
  • the titanium-molybdenum metal powder with fine particle size is obtained, and the particle size is 5-50 ⁇ m;
  • step (3) adding 4.00 g of hydroxyapatite powder (a spherical micron powder with a purity of 99.99% and an average particle size of 15 ⁇ m) to the titanium-molybdenum metal powder obtained in step (2), and continuing to grind to obtain a titanium-molybdenum-based hydroxyl group Apatite mixed powder, particle size is 2 ⁇ 50 ⁇ m;
  • step (3) The titanium-molybdenum-based hydroxyapatite mixed powder obtained in step (3) is loaded into a steel mold, and a hydraulic press is used to carry out two-way pressing.
  • the pressure of the two-way pressing process is 800MPa, and the pressure holding time is 1min. blank;
  • step (4) carrying out stepped heating and sintering of the compact obtained in step (4) in a tube furnace under the protection of flowing argon gas, and cooling to room temperature to obtain a titanium-molybdenum-based hydroxyapatite composite material, Ti-20Mo/20HA;
  • the stepwise sintering process is as follows: heating to 500°C at a rate of 1°C/min, holding for 2 hours, then heating to 900°C at a rate of 4°C/min, holding for 2 hours; continuing to heat up to 1500°C at a rate of 10°C/min °C, keep warm for 3h.
  • the remaining steps in this example are the same as those in Example 1, except that no hydroxyapatite powder is added to prepare a composite material, a Ti-10Mo alloy.
  • the Ti-10Mo alloy was used as a comparison material, with a density of 4.70 g/cm 3 , an elastic modulus of 45.80 GPa and a compressive strength of 1526 MPa.
  • Table 1 shows the performance parameters of the composite materials and human bones prepared in Examples 1-6 and Comparative Example 1. It can be seen from Table 1 that the titanium-molybdenum-based hydroxyapatite composite material and the titanium-molybdenum alloy have similar mechanical properties, which meet the requirements of orthopaedic materials. Mechanical compatibility requirements.

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Abstract

本发明公开了一种骨修复钛钼基羟基磷灰石复合材料及其制备方法。本发明所述的复合材料是由钛钼合金、过程控制剂与羟基磷灰石混合制得。本发明制备的复合材料的弹性模量低(30～50GPa)、抗压强度高(500～1550MPa)、硬度高(300～520HV)，含有大量的生物活性陶瓷相(CaTiO 3、Ca 3(PO 4) 2、HA等)，有利于诱导骨结合，兼具优良的力学性能和生物活性，可用于骨修复和骨替代。

Description

一种骨修复钛钼基羟基磷灰石复合材料及其制备方法 技术领域
本发明涉及生物医用材料制备技术领域，尤其是涉及一种骨修复钛钼基羟基磷灰石复合材料及其制备方法。
背景技术
目前临床应用的人造生物医用材料中，钛及钛合金性能优异，被认为是人工关节、脊柱矫形内固定系统、牙种植体等硬组织替代和修复的首选材料。纯钛(Ti)及Ti-6Al-4V是目前应用最广泛的骨修复钛合金，但铝(Al)和钒(V)被证实会对人体产生毒害，且其弹性模量与人骨不匹配，导致“应力屏蔽现象”。添加Nb、Ta、Zr、Mo等无毒元素来研制新型的β型生物医用钛合金，可以有效降低弹性模量，具有极大的发展前景。与其它β-Ti添加元素相比，钼(Mo)元素作为人体及动植物所必需的微量元素，有助于调节人体内的酸碱平衡度，并可以作为一些酶的辅助因子，是一种人体亲和元素。此外，Mo与Ti属于同晶型结构，能与Ti形成无限固溶体，不仅降低弹性模量，且能够提高Ti的耐磨性及强度。因此，Ti-Mo系合金在生物医用方面具有广泛的应用前景。
钛合金具有良好的力学性能，作为人体植入材料可用于承载较大的部位，但作为一种生物惰性材料，表面无生物活性，难以与机体组织形成强有力的化学键合，导致长期使用时的松动、失效。羟基磷灰石(HA)作为一种类骨生物陶瓷，与人体骨骼具有相似的成分和结构，在植入生物体内时能与骨组织发生骨性结合，具有优异的生物活性。但是其力学性能较差，不能应用于承载力较大的部位。因此综合钛钼合金优良的力学性能与羟基磷灰石优良的生物活性，制备两者性能兼备的生物复合材料，是开发生物医用材料的一个重要方向。
目前，利用生物陶瓷的生物活性改善钛合金生物惰性的研究较多。其中制备生物活性涂层尤为常见，主要是通过等离子喷涂、电化学沉积、激光熔覆、仿生矿化等技术实现。但是所制备的涂层与金属材料性质差异较大，涂层的术后稳定性较差且容易脱落，导致骨结合性能下降和植入的失败。为了解决涂层较薄和结合力不强的问题，国内外学者研究了钛及钛合金与生物陶瓷混合制备生物活性复合材料。其中文献(Davoud Bovanda，Mardali Yousefpoura，Sousan Rasouli，et al.Characterization of Ti-HA composite fabricated by mechanical alloying[J].Materials and Design，2015，65:447-453)报道了一种Ti-HA复合材料的制备方法，其能够改善材料的生物活性，但是因基体中大量α-Ti存在，力学性能难以满足要求。文献(刘凯歌，胡树兵.放电等离子烧结技术制备(Ti-35Nb-7Zr-5Ta)-15HA复合材料微观组织的演变及生物活性[J].中国有色金属学报，2020，30(01):112-121.)报道了一种(Ti-35Nb-7Zr-5Ta)-15HA生物复合材料的制备方法，但Ta的熔点较高，不利于复合材料的制备，且放电等离子烧结机理易受烧结过程中产生的陶瓷相的影响，导致材料组织存在较多缺陷。SPS技术因烧结机理和石墨模具的限制，制备样品通常为简单圆柱体，难以制备复杂形状工件，且石墨模具的强度低、寿命短、容易对烧结材料造成污染。模压烧结作为一种近净成形工艺，能够实现定制化模具，后续处理只需要少量机加工，烧结过程在流动氩气保护下进行，过程清洁且低成本。
技术问题
针对现有技术存在的上述问题，本发明申请人提供了一种钛钼基羟基磷灰石复合材料及其制备方法。本发明使用无危害的钛钼合金并添加羟基磷灰石粉末，借助高能球磨制备高精细粉末，采用高温管式炉实现梯度升温脱脂烧结，目的在于进一步提高人工植入物的生物活性，解决因植入物与骨组织的力学性能不匹配等问题，制备得到的复合材料成分组织均匀、弹性 模量低(30～50GPa)、抗压强度高(500～1550MPa)、硬度高(300～520HV)，综合力学性能优异，具有优良的生物活性及生物相容性，可以作为骨替代或骨修复的首选材料。
技术解决方案
本发明的技术方案如下：
一种骨修复钛钼基羟基磷灰石复合材料，该复合材料的原料种类及各原料的用量为：
钛钼金属粉末    100份
过程控制剂粉末  0.5～5份
羟基磷灰石粉末  3～20份；
各原料以重量份数计；
所述钛钼合金金属粉末中各元素粉末的质量百分数为Ti：80％～90％、Mo：10％～20％。
一种骨修复钛钼基羟基磷灰石复合材料的制备方法，所述制备方法包括以下步骤：
(1)按Ti：80％～90％、Mo：10％～20％的质量百分比，分别称取Ti、Mo粉末，合计100份；同时称取0.5～5份过程控制剂粉末；
(2)将步骤(1)称取的原料进行研磨，得到粒径细小的钛钼金属粉末；
(3)在步骤(2)制得的钛钼金属粉末中加入3～20份的羟基磷灰石粉末，继续研磨，得到钛钼基羟基磷灰石混合粉末；
(4)将步骤(3)得到的钛钼基羟基磷灰石混合粉末装入钢制模具中，利用压片机或液压机进行双向压制，脱模后得到压坯；
(5)将步骤(4)所得的压坯在流动氩气保护下进行阶梯式升温烧结，冷却至室温，得到钛钼基羟基磷灰石复合材料。
步骤(1)中所述Ti粉末纯度为99.99％、粒度为325～500目；所述Mo粉末纯度为99.99％、粒度为400～500目；所述过程控制剂为硬脂酸、硬脂酸锌、乙烯基双硬脂酰胺、聚乙二醇中的一种。
步骤(2)、(3)中，研磨采用行星式球磨机。
所述球磨机包含不锈钢球磨罐，球磨介质是直径4～10mm的不锈钢研磨球，球料质量比为3:1～20:1，球磨转速为300～600r/min，球磨时间为6～24h。
步骤(3)中，羟基磷灰石粉末为纯度99.99％、平均粒径为15μm的球状微米级粉末或长度为100nm的针状纳米级粉末。
步骤(2)中，钛钼金属粉末的粒径为5～50μm；步骤(3)中，钛钼基羟基磷灰石混合粉末的粒径为2～50μm。
步骤(4)中，双向压制工艺的压力为300～800MPa，保压时间1～12min。
步骤(5)中，阶梯式升温烧结在管式炉中进行。
步骤(5)中，阶梯式烧结工艺为：以1～3℃/min的速度升温至300～500℃，保温1～2h，之后以3～5℃/min的速度升温至800～1000℃，保温2h；继续以5～10℃/min的速度升温至1100～1500℃，保温1～3h。
有益效果
本发明有益的技术效果在于：
(1)使用球磨罐对加入了HA的Ti、Mo粉末进行高能球磨，制得的混合粉末分布均匀、粒径细小；HA粉末的添加使烧结后的复合材料中弥散分布大量具有生物活性的陶瓷相(如CaTiO 3、Ca 3(PO 4) 2、HA等)，提高了材料的骨诱导能力；添加Mo元素制备的复合材料的弹性模量低(30～50GPa)、抗压强度高(500～1550MPa)、硬度高(300～520HV)，综合力学性能优异。
(2)制备工艺步骤简单，混粉后采用双向压制，压坯压力分布均匀，避免烧结过程中的组织 开裂；采用阶梯式的升温方式进行烧结，一次性烧结成形，无需脱脂后进行二次烧结，工艺便捷，避免污染，减少组织缺陷；阶梯烧结、保温可以促进α-Ti转变为β-Ti，是最终制得的复合材料的组织以α+β型Ti合金为基体，且制得的材料组织中含有大量的生物活性陶瓷相(如CaTiO 3、Ca 3(PO 4) 2、HA等)，可以在提高材料与集体组织化学键合力的同时，使植入生物体的材料能够与骨组织更好的结合。
(3)制备过程易于调节复合材料的材料成分、材料利用率高，制备工艺简单、清洁，成本低廉，采用模压方式能够实现烧结体形状的复杂化定制，可操作性强，对设备要求不高。
附图说明
图1实施例1所得Ti-10Mo/10HA复合材料的微观组织SEM图片。
图2实施例2所得Ti-10Mo/7HA复合材料的生物活性评估结果(SEM图)。
本发明的实施方式
下面将结合实施例和附图对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。
实施例1
一种骨修复钛钼基羟基磷灰石复合材料的制备方法，所述制备方法包括以下步骤：
(1)按Ti(纯度为99.99％、粒度为500目)：90％、Mo(纯度为99.99％、粒度为400目)：10％的质量百分比，分别称取18.00g Ti和2.00g Mo粉末，同时称取0.40g硬脂酸粉末；
(2)将步骤(1)称取的原料在行星式球磨机的不锈钢球磨罐中研磨(球磨介质为直径4～10mm的不锈钢研磨球，球料质量比为10:1)球磨转速为400r/min，球磨时间为6h，得到粒径细小的钛钼金属粉末，粒径为5～50μm；
(3)在步骤(2)制得的钛钼金属粉末中加入2.00g的羟基磷灰石粉末(纯度99.99％、平均粒径为15μm的球状微米级粉末)，继续研磨，得到钛钼基羟基磷灰石混合粉末，粒径为2～50μm；
(4)将步骤(3)得到的钛钼基羟基磷灰石混合粉末装入钢制模具中，利用压片机进行双向压制，双向压制工艺的压力为600MPa，保压时间12min，脱模后得到压坯；
(5)将步骤(4)所得的压坯在流动氩气保护下在管式炉中进行阶梯式升温烧结，冷却至室温，得到钛钼基羟基磷灰石复合材料，Ti-10Mo/10HA；所述阶梯式烧结工艺为：以2℃/min的速度升温至450℃，保温1h，之后以3℃/min的速度升温至1000℃，保温2h；继续以5℃/min的速度升温至1300℃，保温2h。
本实施例中粉末经过高能球磨后，粉末混合均匀、粒径细小，在后续烧结中保证复合材料具有组织均匀、低弹性模量的钛合金基体；本实施例制备的复合材料微观组织如图1所示，主要由α-Ti、β-Ti以及陶瓷相(CaTiO 3、Ca 3(PO 4) 2、CaO、HA、Ti xP y)组成，具有优良的生物活性；本实施例制备得到的Ti-10Mo/10HA复合材料密度为4.22g/cm 3，弹性模量为42.81GPa，远低于纯Ti(101GPa)和Ti-6Al-4V(110GPa)，抗压强度为812MPa，大于人骨(100～230MPa)和纯Ti，综合力学性能满足植入物要求。
实施例2
本实施例其余步骤与实施例1相同，不同之处在于加入1.4g羟基磷灰石粉末(纯度99.99％、平均粒径为15μm的球状微米级粉末)，得到钛钼基羟基磷灰石复合材料，Ti-10Mo/7HA。
本实施例制备得到的Ti-10Mo/7HA复合材料密度为4.39g/cm 3，弹性模量为46.46GPa，抗压强度为1153MPa，采用体外仿生矿化实验对本实施方式制备的复合材料的生物活性进行了评估，将样品在模拟体液中进行浸泡，温度为37℃，每2天更换一次溶液，浸泡时间为7 天，若表面沉积生成图2所示的类骨磷灰石层，则表明材料具有较好的生物活性。实验结果如图2所示，表面沉积生成大量的球状类骨磷灰石，表明复合材料具有优异的生物活性。
实施例3
本实施例其余步骤与实施例1相同，不同之处在于加入1.00g羟基磷灰石粉末(纯度99.99％、平均粒径为15μm的球状微米级粉末)得到钛钼基羟基磷灰石复合材料，Ti-10Mo/5HA。
本实施方式制备得到的Ti-10Mo/5HA复合材料密度为4.51g/cm 3，弹性模量为48.69GPa，抗压强度为1486MPa。
实施例4
本实施例其余步骤与实施例1相同，不同之处在于加入0.6g羟基磷灰石粉末(纯度99.99％、平均粒径为15μm的球状微米级粉末)，得到钛钼基羟基磷灰石复合材料，Ti-10Mo/3HA。
本实施例制备得到的Ti-10Mo/3HA复合材料密度为4.57g/cm 3，弹性模量为47.74GPa，抗压强度为1511MPa。
实施例5
一种骨修复钛钼基羟基磷灰石复合材料的制备方法，所述制备方法包括以下步骤：
(1)按Ti(纯度为99.99％、粒度为325目)：85％、Mo(纯度为99.99％、粒度为400目)：15％的质量百分比，分别称取17.00g Ti和3.00g Mo粉末，同时称取0.10g乙烯基双硬酯酰胺粉末；
(2)将步骤(1)称取的原料在行星式球磨机的不锈钢球磨罐中研磨(球磨介质为直径4～10mm的不锈钢研磨球，球料质量比为3:1)球磨转速为300r/min，球磨时间为24h，得到粒径细小的钛钼金属粉末，粒径为5～50μm；
(3)在步骤(2)制得的钛钼金属粉末中加入1.00g的羟基磷灰石粉末(纯度99.99％、长度为100nm的针状纳米级粉末)，继续研磨，得到钛钼基羟基磷灰石混合粉末，粒径为2～50μm；
(4)将步骤(3)得到的钛钼基羟基磷灰石混合粉末装入钢制模具中，利用压片机进行双向压制，双向压制工艺的压力为300MPa，保压时间6min，脱模后得到压坯；
(5)将步骤(4)所得的压坯在流动氩气保护下在管式炉中进行阶梯式升温烧结，冷却至室温，得到钛钼基羟基磷灰石复合材料，Ti-15Mo/15HA；所述阶梯式烧结工艺为：以3℃/min的速度升温至300℃，保温1h，之后以5℃/min的速度升温至800℃，保温2h；继续以8℃/min的速度升温至1200℃，保温1h。
实施例6
一种骨修复钛钼基羟基磷灰石复合材料的制备方法，所述制备方法包括以下步骤：
(1)按Ti(纯度为99.99％、粒度为400目)：80％、Mo(纯度为99.99％、粒度为500目)：20％的质量百分比，分别称取16.00g Ti和4.00g Mo粉末，同时称取1.00g硬脂酸锌粉末；
(2)将步骤(1)称取的原料在行星式球磨机的不锈钢球磨罐中研磨(球磨介质为直径4～10mm的不锈钢研磨球，球料质量比为20:1)球磨转速为600r/min，球磨时间为6h，得到粒径细小的钛钼金属粉末，粒径为5～50μm；
(3)在步骤(2)制得的钛钼金属粉末中加入4.00g的羟基磷灰石粉末(纯度99.99％、平均粒径为15μm的球状微米级粉末)，继续研磨，得到钛钼基羟基磷灰石混合粉末，粒径为2～50μm；
(4)将步骤(3)得到的钛钼基羟基磷灰石混合粉末装入钢制模具中，利用液压机进行双向压制，双向压制工艺的压力为800MPa，保压时间1min，脱模后得到压坯；
(5)将步骤(4)所得的压坯在流动氩气保护下在管式炉中进行阶梯式升温烧结，冷却至室温，得到钛钼基羟基磷灰石复合材料，Ti-20Mo/20HA；所述阶梯式烧结工艺为：以1℃/min的速度升温至500℃，保温2h，之后以4℃/min的速度升温至900℃，保温2h；继续以10℃/min的速度升温至1500℃，保温3h。
对比例1
本实施例其余步骤与实施例1相同，不同之处在于未加入羟基磷灰石粉末，制得复合材料，Ti-10Mo合金。Ti-10Mo合金作为对比材料，密度为4.70g/cm 3，弹性模量为45.80GPa，抗压强度为1526MPa。
表1为实施例1-6、对比例1制备的复合材料及人骨的性能参数，由表1可知，钛钼基羟基磷灰石复合材料与钛钼合金具有相近的力学性能，满足骨科材料的力学相容性要求。
表1 Ti-Mo/HA复合材料及对比材料的性能参数。
Figure PCTCN2021121174-appb-000001

Claims (10)

  1. 一种骨修复钛钼基羟基磷灰石复合材料，其特征在于：所述复合材料的原料种类及各原料的用量为：
    钛钼金属粉末          100份
    过程控制剂粉末        0.5～5份
    羟基磷灰石粉末        3～20份；
    各原料以重量份数计；
    所述钛钼金属粉末中各元素粉末的质量百分数为Ti：80％～90％、Mo：10％～20％。
  2. 一种权利要求1所述骨修复钛钼基羟基磷灰石复合材料的制备方法，其特征在于：所述制备方法包括以下步骤：
    (1)按Ti：80％～90％、Mo：10％～20％的质量百分比，分别称取Ti、Mo粉末，合计100份；同时称取0.5～5份过程控制剂粉末；
    (2)将步骤(1)称取的原料进行研磨，得到粒径细小的钛钼金属粉末；
    (3)在步骤(2)制得的钛钼金属粉末中加入3～20份的羟基磷灰石粉末，继续研磨，得到钛钼基羟基磷灰石混合粉末；
    (4)将步骤(3)得到的钛钼基羟基磷灰石混合粉末装入钢制模具中，利用压片机或液压机进行双向压制，脱模后得到压坯；
    (5)将步骤(4)所得的压坯在流动氩气保护下进行阶梯式升温烧结，冷却至室温，得到钛钼基羟基磷灰石复合材料。
  3. 根据权利要求2所述的制备方法，其特征在于：步骤(1)中所述 Ti粉末纯度为99.99％、粒度为325～500目；所述Mo粉末纯度为99.99％、粒度为400～500目；所述过程控制剂为硬脂酸、硬脂酸锌、乙烯基双硬脂酰胺、聚乙二醇中的一种。
  4. 根据权利要求2所述的制备方法，其特征在于：步骤(2)、(3)中，研磨采用行星式球磨机。
  5. 根据权利要求4所述的制备方法，其特征在于：所述球磨机包含不锈钢球磨罐，球磨介质是直径4～10mm的不锈钢研磨球，球料质量比为3:1～20:1，球磨转速为300～600r/min，球磨时间为6～24h。
  6. 根据权利要求2所述的制备方法，其特征在于：步骤(3)中，羟基磷灰石粉末为纯度99.99％、平均粒径为15μm的球状微米级粉末或长度为100nm的针状纳米级粉末。
  7. 根据权利要求2所述的制备方法，其特征在于：步骤(2)中，钛钼金属粉末的粒径为5～50μm；步骤(3)中，钛钼基羟基磷灰石混合粉末的粒径为2～50μm。
  8. 根据权利要求2所述的制备方法，其特征在于：步骤(4)中，双向压制工艺的压力为300～800MPa，保压时间1～12min。
  9. 根据权利要求2所述的制备方法，其特征在于：步骤(5)中，阶梯式升温烧结在管式炉中进行。
  10. 根据权利要求2所述的制备方法，其特征在于：步骤(5)中，阶梯式烧结工艺为：以1～3℃/min的速度升温至300～500℃，保温1～2h，之后以3～5℃/min的速度升温至800～1000℃，保温2h；继续以5～10℃/min的速度升温至1100～1500℃，保温1～3h。
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