WO2021248260A1 - Metal material, preparation method therefor and application thereof - Google Patents

Metal material, preparation method therefor and application thereof Download PDF

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Publication number
WO2021248260A1
WO2021248260A1 PCT/CN2020/094850 CN2020094850W WO2021248260A1 WO 2021248260 A1 WO2021248260 A1 WO 2021248260A1 CN 2020094850 W CN2020094850 W CN 2020094850W WO 2021248260 A1 WO2021248260 A1 WO 2021248260A1
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parts
metal material
mixed powder
niobium
tantalum
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PCT/CN2020/094850
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French (fr)
Chinese (zh)
Inventor
徐春娟
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南京江东工贸有限公司
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Priority to CN202080005302.1A priority Critical patent/CN113166854A/en
Priority to PCT/CN2020/094850 priority patent/WO2021248260A1/en
Publication of WO2021248260A1 publication Critical patent/WO2021248260A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/06Titanium or titanium alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0433Nickel- or cobalt-based alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104Silver, e.g. silver sulfadiazine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/12Materials or treatment for tissue regeneration for dental implants or prostheses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/24Materials or treatment for tissue regeneration for joint reconstruction
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/38Materials or treatment for tissue regeneration for reconstruction of the spine, vertebrae or intervertebral discs

Definitions

  • the invention relates to the field of metal composite material preparation, in particular, to a composite metal material preparation and a preparation method and application thereof.
  • Titanium-based alloy materials are mainly used in aerospace and biomedical fields due to their unique chemical and mechanical properties and good biocompatibility. They are alloy materials commonly used in technology, but titanium alloys have poor oxidation resistance at high temperatures. , The forming atmosphere needs to be strictly controlled; at the same time, the thermal conductivity of titanium alloy is poor, and there are strict requirements for energy input during the forming process.
  • the biological materials used in the orthopedics field include metal materials, polymer materials, bioceramics and composite materials.
  • Metal materials are widely used in joint, spine and trauma diseases due to their high mechanical strength and fatigue resistance. Treatment has played a huge role in the reconstruction of bone stability and the replacement of joint function.
  • the most commonly used metal materials in clinical practice include stainless steel, cobalt-based alloys and titanium-based alloys. Others such as shape memory alloys and stable metals (tantalum, niobium, ho, etc.) have also been used more and more widely.
  • the present invention provides a metal material.
  • the alloy material has a relatively high Good fatigue resistance and strong corrosion resistance increase its comprehensive mechanical properties.
  • appropriate amount of silver is added to ensure its basic mechanical properties At the same time of performance, it has a certain broad-spectrum sterilization or antibacterial effect, effectively solves the bacterial infection problem of titanium alloy surgical implants, and can be widely used in medical fields such as joints, spine and trauma.
  • the technical solution of the present invention includes a metal material comprising the following components in parts by weight: 35-42 parts of nickel, 15-20 parts of cobalt, 1-3 parts of silver, 25-30 parts of titanium, 0.5-3 parts of tantalum, 0.1-0.3 parts of niobium.
  • niobium contains the following components in parts by weight: 38 parts of nickel, 17 parts of cobalt, 1.8 parts of silver, 26.5 parts of titanium, 0.8 parts of tantalum, and 0.1 parts of niobium.
  • the technical scheme of the present invention also includes a method for preparing a metal material, including the following steps:
  • Step 1 The ingredients are prepared according to the following parts by weight: 35-42 parts of nickel, 15-20 parts of cobalt, 1-3 parts of silver, 25-30 parts of titanium, 0.5-3 parts of tantalum, and 0.1-0.3 parts of niobium. Place the mixed powder in a stainless steel ball mill tank, fill it with absolute ethanol, and seal it. Use argon gas to protect and mix in a planetary ball mill for 4 hours. Take out the ball-milled mixed powder and place it on filter paper for 6-8 minutes to obtain mixed powder. ;
  • Step 2 Put a certain amount of polyvinyl alcohol into deionized distilled water and heat it until it dissolves. After cooling, add a certain proportion of polyvinyl alcohol solution to the mixed powder, and stir thoroughly to make it have a proper degree The slurry is naturally air-dried and cooled, then dried in a vacuum drying oven at a temperature of 70-80°C, and finally taken out for natural cooling.
  • Step 3 Keep the vacuum always below 8 ⁇ 10 -2 Pa for sintering, first heat to 200°C-300°C for debinding and decomposition; heat to sintering temperature 1400-1500°C°, keep for 2-4h, then heat to Keep the temperature at 1700°C-1800°C for 1-2h, cool to room temperature along with the furnace, take the sintered body out of the furnace, clean it in an ultrasonic water bath for 15-20min, and then dry it.
  • the ball-to-material ratio used in the ball milling in the step 1 is 10:1.
  • the rotation speed of the ball mill in the step 1 is 400-500 r/min.
  • the ratio of the mixed powder to the polyvinyl alcohol solution in step 2 is: each 100 g of the mixed powder is mixed with 20 ml of the polyvinyl alcohol solution.
  • heating is performed to a sintering temperature of 1400-1500°C° at a rate of 5-10°C/min.
  • step 3 heating to 1700°C-1800°C at a rate of 10-15°C/min.
  • the technical solution of the present invention also includes a metal material product, which is characterized in that it is made of the metal material described in any one of the above solutions, and is used in medical fields such as oral restorations, joints, spine, and trauma.
  • the beneficial effects of the present invention are: by adding cobalt, tantalum and niobium, the alloy material has good fatigue resistance and strong corrosion resistance, and its comprehensive mechanical properties are increased. At the same time, it has good biocompatibility. Performance, high mechanical strength and fatigue resistance; the method of combining colloidal dipping and powder metallurgy can be used to prepare porous materials, through the design and construction of the porous structure, the connection between the implant and the bone is obtained, thereby providing a good Biologically fixed, the porous structure can improve the compatibility of the implant and bone tissue on the one hand, and on the other hand can promote the deposition of vitronectin and fibronectin on the surface and inside of the alloy, thereby increasing the adhesion of osteoblasts, Proliferation and differentiation; can be widely used in medical fields such as joints, spine and trauma.
  • adding a proper amount of silver to the titanium alloy can make the titanium alloy have a certain broad-spectrum bactericidal or antibacterial effect while ensuring its basic mechanical properties, effectively solving the bacterial infection problem of titanium alloy surgical implants.
  • a metal material comprising the following components in parts by weight: 35 parts of nickel, 15 parts of cobalt, 1 part of silver, 30 parts of titanium, 0.5 part of tantalum, and 0.1 part of niobium.
  • a metal material comprising the following components in parts by weight: 38 parts of nickel, 17 parts of cobalt, 1.8 parts of silver, 26.5 parts of titanium, 0.8 parts of tantalum, and 0.1 parts of niobium.
  • a metal material comprising the following components in parts by weight: 42 parts of nickel, 20 parts of cobalt, 3 parts of silver, 25 parts of titanium, 3 parts of tantalum, and 0.3 parts of niobium.
  • the metal material in Example 1 was prepared according to the following steps:
  • Step 1 The ingredients are prepared according to the following parts by weight: 35 parts of nickel, 15 parts of cobalt, 1 part of silver, 30 parts of titanium, 0.5 part of tantalum, and 0.1 part of niobium. Put the mixed powder in a stainless steel ball mill tank, fill it with absolute ethanol, and seal it. Use argon gas to protect and mix in the planetary ball mill for 4 hours. The speed of the ball mill is 400r/min. Take out the ball milled mixed powder and place it on the filter paper. 6 minutes to get mixed powder;
  • Step 2 Put a certain amount of polyvinyl alcohol into deionized distilled water and heat it until it dissolves. After cooling, add a certain proportion of polyvinyl alcohol solution to the mixed powder, and stir thoroughly to make it have a proper degree The slurry is naturally air-dried and cooled, then dried in a vacuum drying oven at a temperature of 80 °C, and finally taken out to be naturally cooled.
  • Step 3 Keep the vacuum always below 8 ⁇ 10 -2 Pa for sintering, first heat to 200°C for debinding and decomposition; heat to sintering temperature 1400°C for 2h, then heat to 1700°C for 2h, then The furnace is cooled to room temperature, and the sintered body is taken out of the furnace, cleaned in an ultrasonic water bath for 15 minutes, and then dried to obtain it.
  • the metal material in Example 3 was prepared according to the following steps:
  • Step 1 The ingredients are prepared according to the following parts by weight: 42 parts of nickel, 20 parts of cobalt, 3 parts of silver, 25 parts of titanium, 3 parts of tantalum, and 0.3 parts of niobium.
  • the planetary ball mill uses argon gas to protect and mix for 4 hours.
  • the ball-to-material ratio used in the ball mill is 10:1, and the speed of the ball mill is 500r/min. .
  • Step 2 Put a certain amount of polyvinyl alcohol into deionized distilled water and heat it to dissolve. After cooling, mix 100g of the mixed powder with 20ml polyvinyl alcohol solution and stir thoroughly to make it have a proper degree of consistency The slurry is naturally air-dried and cooled, then dried in a vacuum drying oven at a temperature of 70°C, and finally taken out for natural cooling.
  • Step 3 Keep the vacuum always below 8 ⁇ 10 -2 Pa for sintering, first heat to 300°C for debinding and decomposition; heat it to the sintering temperature of 1460°C at a rate of 5-10°C/min, and hold for 2 hours. Heat to 1780°C at a rate of 10-15°C/min, keep it for 2h, cool to room temperature along with the furnace, take the sintered body out of the furnace, clean it in an ultrasonic water bath for 20 minutes, and dry it to get it.
  • An artificial joint made of composite metal materials prepared in Examples 1-5 can be applied to joint replacement surgery.
  • a dental implant made of composite metal materials prepared in Examples 1-5 can be applied to denture implant surgery.

Abstract

A metal material, a preparation method therefor and a metal material product thereof, the metal material comprising the following components in parts by weight: 35-42 parts of nickel, 15-20 parts of cobalt, 1-3 parts of silver, 25-30 parts of titanium, 0.5-3 parts of tantalum, and 0.1-0.3 parts of niobium. The preparation method for the metal material uses a combination of a colloid dipping method and a powder metallurgy method, thus improving the defects in which a titanium alloy has poor oxidation resistance and poor thermal conductivity at high temperatures and has strict requirements for energy input during a formation process; in addition, by adding cobalt, tantalum and niobium, the metal material has relatively good fatigue resistance, corrosion resistance and comprehensive mechanical properties. Meanwhile, as the metal material has good biocompatibility, relatively high mechanical strength and fatigue resistance, adding an appropriate amount of silver element ensures the basic mechanical properties thereof, and the metal material also has a certain broad-spectrum sterilization or antibacterial effect, thus effectively solving the problem of bacterial infections of titanium alloy surgical implantation instruments. Furthermore, metal material products made of said metal material can be widely applied to medical fields such as oral prostheses, joints, spine, trauma and so on.

Description

一种金属材料及其制备方法与应用A metal material and its preparation method and application 技术领域Technical field
本发明涉及金属复合材料制备领域,具体地,涉及一种复合金属材料制备及其制备方法与应用。The invention relates to the field of metal composite material preparation, in particular, to a composite metal material preparation and a preparation method and application thereof.
背景技术Background technique
随着科学技术的不断进步,单一材料已经很难满足现代工业对材料综合性能的需求,复合材料由于其性能可设计性,越来越受到业界的关注。With the continuous advancement of science and technology, it is difficult for a single material to meet the needs of modern industry for the comprehensive performance of materials. Composite materials have received more and more attention from the industry due to their performance and designability.
钛基合金材料因其独特的化学、机械性能及良好的生物相容性,主要应用于航空航天和生物医学领域,是技术中较常采用的合金材料,但钛合金在高温下抗氧化能力差,需要严格控制成形气氛;同时,钛合金的导热性差,成形过程中对能量的输入也有严格的要求。Titanium-based alloy materials are mainly used in aerospace and biomedical fields due to their unique chemical and mechanical properties and good biocompatibility. They are alloy materials commonly used in technology, but titanium alloys have poor oxidation resistance at high temperatures. , The forming atmosphere needs to be strictly controlled; at the same time, the thermal conductivity of titanium alloy is poor, and there are strict requirements for energy input during the forming process.
目前,在骨科领域应用的生物材料包括金属材料、高分子材料、生物陶瓷及复合材料,其中金属材料因具有较高的机械强度和抗疲劳性能而广泛应用于关节、脊柱及创伤等领域疾病的治疗,在骨骼稳定性重建及关节功能替代方面发挥了巨大的作用。目前,临床上最为常用的金属材料包括不锈钢、钴基合金与钛基合金,其他如形状记忆合金、稳定金属(钽、铌、浩等)也得到了越来越广泛的应用。但作为生物医用材料,传统的金属材料仍在以下方面存在不可回避的不足,金属假体-骨界面结合问题,假体表面光滑,远期固定效果不佳;大多数表面改性层一般比表面涂层厚且性能呈梯度逐渐改变,具有高于表面涂层的载荷承载能力。但改性层的孔隙率、覆盖厚度还不能尽如人意,表面改性后的假体-骨界面也并非理想的骨整合,合金与纯金属相比往往具有制备工艺简单、力学性能及延展性好的特点,这一点从钛合金的广泛应用可以得到验证,从这个角度出发,我们选择了钛钴镍与钽铌一起制备合金,以期获得具有良好的生物相容性,并且耐 疲劳性好、抗腐烛性强、综合力学性能高和抗氧化能力强,流动性好的金属材料。并通过加入适量银元素,使其具有一定的广谱杀菌或抑菌功效,有效解决钛合金外科植入器械细菌感染问题。At present, the biological materials used in the orthopedics field include metal materials, polymer materials, bioceramics and composite materials. Metal materials are widely used in joint, spine and trauma diseases due to their high mechanical strength and fatigue resistance. Treatment has played a huge role in the reconstruction of bone stability and the replacement of joint function. At present, the most commonly used metal materials in clinical practice include stainless steel, cobalt-based alloys and titanium-based alloys. Others such as shape memory alloys and stable metals (tantalum, niobium, ho, etc.) have also been used more and more widely. However, as biomedical materials, traditional metal materials still have unavoidable deficiencies in the following aspects: the problem of metal prosthesis-bone interface bonding, the prosthesis surface is smooth, and the long-term fixation effect is not good; most surface modification layers are generally more surface The coating is thick and the performance changes gradually, and it has a higher load carrying capacity than the surface coating. However, the porosity and covering thickness of the modified layer are still not satisfactory, and the prosthesis-bone interface after surface modification is not ideal osseointegration. Compared with pure metal, the alloy often has simple preparation process, mechanical properties and ductility. Good characteristics, this can be verified by the wide application of titanium alloys. From this point of view, we have selected titanium, cobalt, nickel and tantalum niobium to prepare alloys, in order to obtain good biocompatibility, and good fatigue resistance. Metal materials with strong corrosion resistance, high comprehensive mechanical properties, strong oxidation resistance and good fluidity. And by adding an appropriate amount of silver element, it has a certain broad-spectrum sterilization or antibacterial effect, which effectively solves the bacterial infection problem of titanium alloy surgical implants.
发明内容Summary of the invention
为解决钛合金在高温下抗氧化能力差,导热性差,及其用于医疗材料存在不可回避的不足,本发明提供了一种金属材料,通过添加钴、钽和铌,使该合金材料具有较好的耐疲劳性和抗腐烛性强,使其综合力学性能增加高,同时由于其具有良好的生物相容性、较高的机械强度和抗疲劳性能,加入适量银元素,保证其基本力学性能的同时,具有一定的广谱杀菌或抑菌功效,有效解决钛合金外科植入器械细菌感染问题,可以广泛应用于关节、脊柱及创伤等医疗领域。In order to solve the problem of titanium alloy's poor oxidation resistance and thermal conductivity at high temperatures, and its unavoidable deficiencies in its use as medical materials, the present invention provides a metal material. By adding cobalt, tantalum and niobium, the alloy material has a relatively high Good fatigue resistance and strong corrosion resistance increase its comprehensive mechanical properties. At the same time, due to its good biocompatibility, high mechanical strength and fatigue resistance, appropriate amount of silver is added to ensure its basic mechanical properties At the same time of performance, it has a certain broad-spectrum sterilization or antibacterial effect, effectively solves the bacterial infection problem of titanium alloy surgical implants, and can be widely used in medical fields such as joints, spine and trauma.
为实现上述目的,本发明技术方案为:In order to achieve the above-mentioned objective, the technical scheme of the present invention is as follows:
本发明技术方案包括一种金属材料,包含按重量份计的下列组分:镍35-42份、钴15-20份、银1-3份、钛25-30份、钽0.5-3份、铌0.1-0.3份。The technical solution of the present invention includes a metal material comprising the following components in parts by weight: 35-42 parts of nickel, 15-20 parts of cobalt, 1-3 parts of silver, 25-30 parts of titanium, 0.5-3 parts of tantalum, 0.1-0.3 parts of niobium.
具体的,包含按重量份计的下列组分:镍38份、钴17份、银1.8份、钛26.5份、钽0.8份、铌0.1份。Specifically, it contains the following components in parts by weight: 38 parts of nickel, 17 parts of cobalt, 1.8 parts of silver, 26.5 parts of titanium, 0.8 parts of tantalum, and 0.1 parts of niobium.
本发明技术方案还包括一种金属材料的制备方法,包括如下步骤:The technical scheme of the present invention also includes a method for preparing a metal material, including the following steps:
步骤1:配料按照按以下重量份配制混合粉:镍35-42份、钴15-20份、银1-3份、钛25-30份、钽0.5-3份、铌0.1-0.3份。将混合粉置于不锈钢球磨罐中,注满无水乙醇后密封,在行星球磨机采用氩气保护混合4h,将球磨好的混合粉取出并置于滤纸上静置6-8分钟,得到混合粉;Step 1: The ingredients are prepared according to the following parts by weight: 35-42 parts of nickel, 15-20 parts of cobalt, 1-3 parts of silver, 25-30 parts of titanium, 0.5-3 parts of tantalum, and 0.1-0.3 parts of niobium. Place the mixed powder in a stainless steel ball mill tank, fill it with absolute ethanol, and seal it. Use argon gas to protect and mix in a planetary ball mill for 4 hours. Take out the ball-milled mixed powder and place it on filter paper for 6-8 minutes to obtain mixed powder. ;
步骤2:将一定量的聚乙稀醇放入去离子蒸饱水中加热至其溶解,冷却后,按一定比例取聚乙烯醇溶液加入混合粉中,充分搅拌均勾使之成为具有适当點度的浆状物,自然风干冷却,再放到温度为70-80℃的真空干燥箱里干燥,最后取出自然冷却。Step 2: Put a certain amount of polyvinyl alcohol into deionized distilled water and heat it until it dissolves. After cooling, add a certain proportion of polyvinyl alcohol solution to the mixed powder, and stir thoroughly to make it have a proper degree The slurry is naturally air-dried and cooled, then dried in a vacuum drying oven at a temperature of 70-80℃, and finally taken out for natural cooling.
步骤3:保持真空度始终在8×10 -2Pa以下进行烧结,先加热至200℃-300℃进行排胶和分解;加热至烧结温度1400-1500℃°,保温2-4h后,加热至1700℃-1800℃,保温1-2h,随炉冷却至室温,将烧结体从炉内取出,置于超声波水浴中清洗15-20min后烘干,即得。 Step 3: Keep the vacuum always below 8×10 -2 Pa for sintering, first heat to 200℃-300℃ for debinding and decomposition; heat to sintering temperature 1400-1500℃°, keep for 2-4h, then heat to Keep the temperature at 1700°C-1800°C for 1-2h, cool to room temperature along with the furnace, take the sintered body out of the furnace, clean it in an ultrasonic water bath for 15-20min, and then dry it.
具体的,所述步骤1中球磨中采用的球料比为10:1。Specifically, the ball-to-material ratio used in the ball milling in the step 1 is 10:1.
具体的,所述步骤1中球磨机的转速为400-500r/min。Specifically, the rotation speed of the ball mill in the step 1 is 400-500 r/min.
具体的,所述步骤2中混合粉与聚乙稀醇溶液比例为:每100g混合粉与20ml聚乙稀醇溶液混合。Specifically, the ratio of the mixed powder to the polyvinyl alcohol solution in step 2 is: each 100 g of the mixed powder is mixed with 20 ml of the polyvinyl alcohol solution.
具体的,所述步骤3中以5-10℃/min的速率加热至烧结温度1400-1500℃°。Specifically, in the step 3, heating is performed to a sintering temperature of 1400-1500°C° at a rate of 5-10°C/min.
具体的,所述步骤3中以10-15℃/min的速率加热至1700℃-1800℃。Specifically, in the step 3, heating to 1700°C-1800°C at a rate of 10-15°C/min.
本发明技术方案还包括一种金属材料制品,其特征在于,利用上述方案中任一项所述的金属材料制成,应用于口腔修复体、关节、脊柱及创伤等医疗领域。The technical solution of the present invention also includes a metal material product, which is characterized in that it is made of the metal material described in any one of the above solutions, and is used in medical fields such as oral restorations, joints, spine, and trauma.
本发明的有益效果是:通过添加钴、钽和铌,使该合金材料具有较好的耐疲劳性和抗腐烛性强,使其综合力学性能增加高,同时由于其具有良好的生物相容性、较高的机械强度和抗疲劳性能;通过胶体浸渍法与粉末冶金法相结合的方法可制备得到多孔材料,通过多孔结构的设计和构建,获得植入物和骨的连接,从而提供良好的生物学固定,多孔结构一方面可以改善植入物和骨组织的相容性,另一方面能促进玻连蛋白和纤连蛋白在合金表面及内部的沉积,从而增加成骨细胞的粘附、增殖和分化;可以广泛应用于关节、脊柱及创伤等医疗领域。The beneficial effects of the present invention are: by adding cobalt, tantalum and niobium, the alloy material has good fatigue resistance and strong corrosion resistance, and its comprehensive mechanical properties are increased. At the same time, it has good biocompatibility. Performance, high mechanical strength and fatigue resistance; the method of combining colloidal dipping and powder metallurgy can be used to prepare porous materials, through the design and construction of the porous structure, the connection between the implant and the bone is obtained, thereby providing a good Biologically fixed, the porous structure can improve the compatibility of the implant and bone tissue on the one hand, and on the other hand can promote the deposition of vitronectin and fibronectin on the surface and inside of the alloy, thereby increasing the adhesion of osteoblasts, Proliferation and differentiation; can be widely used in medical fields such as joints, spine and trauma.
尤其是在钛合金中适量加入银元素,可使钛合金在保证其基本力学 性能的同时,具有一定的广谱杀菌或抑菌功效,有效解决钛合金外科植入器械细菌感染问题。In particular, adding a proper amount of silver to the titanium alloy can make the titanium alloy have a certain broad-spectrum bactericidal or antibacterial effect while ensuring its basic mechanical properties, effectively solving the bacterial infection problem of titanium alloy surgical implants.
具体实施方式detailed description
实施例1Example 1
一种金属材料,包含按重量份计的下列组分:镍35份、钴15份、银1份、钛30份、钽0.5份、铌0.1份。A metal material comprising the following components in parts by weight: 35 parts of nickel, 15 parts of cobalt, 1 part of silver, 30 parts of titanium, 0.5 part of tantalum, and 0.1 part of niobium.
实施例2Example 2
一种金属材料,包含按重量份计的下列组分:镍38份、钴17份、银1.8份、钛26.5份、钽0.8份、铌0.1份。A metal material comprising the following components in parts by weight: 38 parts of nickel, 17 parts of cobalt, 1.8 parts of silver, 26.5 parts of titanium, 0.8 parts of tantalum, and 0.1 parts of niobium.
实施例3Example 3
一种金属材料,包含按重量份计的下列组分:镍42份、钴20份、银3份、钛25份、钽3份、铌0.3份。A metal material comprising the following components in parts by weight: 42 parts of nickel, 20 parts of cobalt, 3 parts of silver, 25 parts of titanium, 3 parts of tantalum, and 0.3 parts of niobium.
实施例4Example 4
实施例1中的金属材料,按照以下步骤进行制备:The metal material in Example 1 was prepared according to the following steps:
步骤1:配料按照按以下重量份配制混合粉:镍35份、钴15份、银1份、钛30份、钽0.5份、铌0.1份。将混合粉置于不锈钢球磨罐中,注满无水乙醇后密封,在行星球磨机采用氩气保护混合4h,球磨机的转速为400r/min,将球磨好的混合粉取出并置于滤纸上静置6分钟,得到混合粉;Step 1: The ingredients are prepared according to the following parts by weight: 35 parts of nickel, 15 parts of cobalt, 1 part of silver, 30 parts of titanium, 0.5 part of tantalum, and 0.1 part of niobium. Put the mixed powder in a stainless steel ball mill tank, fill it with absolute ethanol, and seal it. Use argon gas to protect and mix in the planetary ball mill for 4 hours. The speed of the ball mill is 400r/min. Take out the ball milled mixed powder and place it on the filter paper. 6 minutes to get mixed powder;
步骤2:将一定量的聚乙稀醇放入去离子蒸饱水中加热至其溶解,冷却后,按一定比例取聚乙烯醇溶液加入混合粉中,充分搅拌均勾使之成为具有适当點度的浆状物,自然风干冷却,再放到温度为80℃的真空干燥箱里干燥,最后取出自然冷却。Step 2: Put a certain amount of polyvinyl alcohol into deionized distilled water and heat it until it dissolves. After cooling, add a certain proportion of polyvinyl alcohol solution to the mixed powder, and stir thoroughly to make it have a proper degree The slurry is naturally air-dried and cooled, then dried in a vacuum drying oven at a temperature of 80 ℃, and finally taken out to be naturally cooled.
步骤3:保持真空度始终在8×10 -2Pa以下进行烧结,先加热至200℃进行排胶和分解;加热至烧结温度1400℃°,保温2h后,加热至1700℃,保温2h,随炉冷却至室温,将烧结体从炉内取出,置于超声波水浴中清洗15min后烘干,即得。 Step 3: Keep the vacuum always below 8×10 -2 Pa for sintering, first heat to 200°C for debinding and decomposition; heat to sintering temperature 1400°C for 2h, then heat to 1700°C for 2h, then The furnace is cooled to room temperature, and the sintered body is taken out of the furnace, cleaned in an ultrasonic water bath for 15 minutes, and then dried to obtain it.
实施例5Example 5
实施例3中的金属材料,按照以下步骤进行制备:The metal material in Example 3 was prepared according to the following steps:
步骤1:配料按照按以下重量份配制混合粉:镍42份、钴20份、银3份、钛25份、钽3份、铌0.3份。将混合粉置于不锈钢球磨罐中,注满无水乙醇后密封,在行星球磨机采用氩气保护混合4h,球磨中采用的球料比为10:1,球磨机的转速为500r/min。。将球磨好的混合粉取出并置于滤纸上静置8分钟,得到混合粉;Step 1: The ingredients are prepared according to the following parts by weight: 42 parts of nickel, 20 parts of cobalt, 3 parts of silver, 25 parts of titanium, 3 parts of tantalum, and 0.3 parts of niobium. Put the mixed powder in a stainless steel ball mill tank, fill it with absolute ethanol, and seal it. The planetary ball mill uses argon gas to protect and mix for 4 hours. The ball-to-material ratio used in the ball mill is 10:1, and the speed of the ball mill is 500r/min. . Take out the ball-milled mixed powder and place it on the filter paper and let it stand for 8 minutes to obtain the mixed powder;
步骤2:将一定量的聚乙稀醇放入去离子蒸饱水中加热至其溶解,冷却后,每100g混合粉与20ml聚乙稀醇溶液混合,充分搅拌均勾使之成为具有适当點度的浆状物,自然风干冷却,再放到温度为70℃的真空干燥箱里干燥,最后取出自然冷却。Step 2: Put a certain amount of polyvinyl alcohol into deionized distilled water and heat it to dissolve. After cooling, mix 100g of the mixed powder with 20ml polyvinyl alcohol solution and stir thoroughly to make it have a proper degree of consistency The slurry is naturally air-dried and cooled, then dried in a vacuum drying oven at a temperature of 70°C, and finally taken out for natural cooling.
步骤3:保持真空度始终在8×10 -2Pa以下进行烧结,先加热至300℃进行排胶和分解;以5-10℃/min的速率加热至烧结温度1460℃°,保温2h后,以10-15℃/min的速率加热至1780℃,保温2h,随炉冷却至室温,将烧结体从炉内取出,置于超声波水浴中清洗20min后烘干,即得。 Step 3: Keep the vacuum always below 8×10 -2 Pa for sintering, first heat to 300°C for debinding and decomposition; heat it to the sintering temperature of 1460°C at a rate of 5-10°C/min, and hold for 2 hours. Heat to 1780°C at a rate of 10-15°C/min, keep it for 2h, cool to room temperature along with the furnace, take the sintered body out of the furnace, clean it in an ultrasonic water bath for 20 minutes, and dry it to get it.
实施例6Example 6
一种利用实施例1-5所制备得到复合金属材料制成的人工关节,可应用于关节置换手术。An artificial joint made of composite metal materials prepared in Examples 1-5 can be applied to joint replacement surgery.
实施例7Example 7
一种利用实施例1-5所制备得到复合金属材料制成的牙种植体,可应用于义齿种植手术。A dental implant made of composite metal materials prepared in Examples 1-5 can be applied to denture implant surgery.
以上所述仅是本发明的优选实施方式,应当指出:对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications are also It should be regarded as the protection scope of the present invention.

Claims (9)

  1. 一种金属材料,其特征在于,包含其组分按重量份计的下列组分:镍35-42份、钴15-20份、银1-3份、钛25-30份、钽0.5-3份、铌0.1-0.3份。A metal material, characterized in that it contains the following components in parts by weight: 35-42 parts of nickel, 15-20 parts of cobalt, 1-3 parts of silver, 25-30 parts of titanium, 0.5-3 parts of tantalum Parts, 0.1-0.3 parts of niobium.
  2. 根据权利要求1所述的一种金属材料,其特征在于,包含其组分按重量份计的下列组分:镍38份、钴17份、银1.8份、钛26.5份、钽0.8份、铌0.1份。A metal material according to claim 1, characterized in that it contains the following components in parts by weight: 38 parts of nickel, 17 parts of cobalt, 1.8 parts of silver, 26.5 parts of titanium, 0.8 parts of tantalum, and niobium 0.1 part.
  3. 一种金属材料的制备方法,其特征在于,包括如下步骤:A method for preparing a metal material is characterized in that it comprises the following steps:
    步骤1:配料按照按以下重量份配制混合粉:镍35-42份、钴15-20份、银1-3份、钛25-30份、钽0.5-3份、铌0.1-0.3份。将混合粉置于不锈钢球磨罐中,注满无水乙醇后密封,在行星球磨机采用氩气保护混合4h,将球磨好的混合粉取出并置于滤纸上静置6-8分钟,得到混合粉;Step 1: The ingredients are prepared according to the following parts by weight: 35-42 parts of nickel, 15-20 parts of cobalt, 1-3 parts of silver, 25-30 parts of titanium, 0.5-3 parts of tantalum, and 0.1-0.3 parts of niobium. Place the mixed powder in a stainless steel ball mill tank, fill it with absolute ethanol, and seal it. Use argon gas to protect and mix in a planetary ball mill for 4 hours. Take out the ball-milled mixed powder and place it on filter paper for 6-8 minutes to obtain mixed powder. ;
    步骤2:将一定量的聚乙稀醇放入去离子蒸饱水中加热至其溶解,冷却后,按一定比例取聚乙烯醇溶液加入混合粉中,充分搅拌均勾使之成为具有适当點度的浆状物,自然风干冷却,再放到温度为70-80℃的真空干燥箱里干燥,最后取出自然冷却。Step 2: Put a certain amount of polyvinyl alcohol into deionized distilled water and heat it until it dissolves. After cooling, add a certain proportion of polyvinyl alcohol solution to the mixed powder, and stir thoroughly to make it have a proper degree The slurry is naturally air-dried and cooled, then dried in a vacuum drying oven at a temperature of 70-80℃, and finally taken out for natural cooling.
    步骤3:保持真空度始终在8×10 -2Pa以下进行烧结,先加热至200℃-300℃进行排胶和分解;加热至烧结温度1400-1500℃°,保温2-4h后,加热至1700℃-1800℃,保温1-2h,随炉冷却至室温,将烧结体从炉内取出,置于超声波水浴中清洗15-20min后烘干,即得。 Step 3: Keep the vacuum always below 8×10 -2 Pa for sintering, first heat to 200℃-300℃ for debinding and decomposition; heat to sintering temperature 1400-1500℃°, keep for 2-4h, then heat to Keep the temperature at 1700°C-1800°C for 1-2h, cool to room temperature along with the furnace, take the sintered body out of the furnace, clean it in an ultrasonic water bath for 15-20min, and then dry it.
  4. 根据权利要求3所述的一种金属材料的制备方法,其特征在于,所述步骤1中球磨中采用的球料比为10:1。The method for preparing a metal material according to claim 3, wherein the ball-to-material ratio used in the ball milling in the step 1 is 10:1.
  5. 根据权利要求3所述的一种金属材料的制备方法,其特征在于,所述步骤1中球磨机的转速为400-500r/min。The method for preparing a metal material according to claim 3, wherein the rotation speed of the ball mill in the step 1 is 400-500 r/min.
  6. 根据权利要求3所述的一种金属材料的制备方法,其特征在于,所述步骤2中混合粉与聚乙稀醇溶液比例为:每100g混合粉与20ml 聚乙稀醇溶液混合。The method for preparing a metal material according to claim 3, wherein the ratio of the mixed powder to the polyvinyl alcohol solution in the step 2 is: each 100 g of the mixed powder is mixed with 20 ml of the polyvinyl alcohol solution.
  7. 根据权利要求3所述的一种金属材料的制备方法,其特征在于,所述步骤3中以5-10℃/min的速率加热至烧结温度1400-1500℃°。The method for preparing a metal material according to claim 3, characterized in that, in the step 3, heating is performed to a sintering temperature of 1400-1500° C. at a rate of 5-10° C./min.
  8. 根据权利要求3所述的一种金属材料的制备方法,其特征在于,所述步骤3中以10-15℃/min的速率加热至1700℃-1800℃。The method for preparing a metal material according to claim 3, characterized in that, in the step 3, heating to 1700°C-1800°C at a rate of 10-15°C/min.
  9. 一种金属材料制品,其特征在于,利用权利要求1-8任一项所述的金属材料制成,应用于口腔修复体、关节、脊柱及创伤等医疗领域。A metal material product, characterized in that it is made of the metal material according to any one of claims 1-8, and is used in medical fields such as oral restorations, joints, spine and trauma.
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