CN100404724C - Ion implantation treatment method for the surface of metal material implanted in human body - Google Patents
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- 238000005468 ion implantation Methods 0.000 title claims abstract description 19
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- 239000002184 metal Substances 0.000 claims abstract description 21
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- 238000010884 ion-beam technique Methods 0.000 claims abstract description 7
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- 238000002347 injection Methods 0.000 claims description 20
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- 150000002500 ions Chemical class 0.000 claims description 17
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- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- -1 titanium-magnesium-aluminum Chemical compound 0.000 claims description 5
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
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- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 3
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- 239000007943 implant Substances 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 2
- 230000005684 electric field Effects 0.000 claims description 2
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 claims description 2
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- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
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Abstract
人体植入金属材料表面离子注入处理方法。本发明属材料科学领域，其公开了一种人体植入金属材料表面处理方法。该方法采用两种或两种以上的金属元素与非金属元素同时电离、加速成混合离子束流，对植入人体的金属材料制成的人工器官(牙根、人工关节、心脏起搏器、血管支架等)进行离子注入处理。本发明方法可提高人体植入金属器官的耐腐蚀性、耐磨性、抗黏附性和抗疲劳性。其中所述金属选自：Ti.Zr.V.Nb.Ta.Cr.Mo.W.Fe.Co.Ni.Mn.Y.Zn.Sc.等两种或多种元素；其非金属选自：B.C.N.O.S.Si一种或多种元素。此工艺不改变被加工对象的外形尺寸及表面精度。本发明方法稳定可靠，方便易行，具有很好的应用性。
A method for treating the surface of a metal material implanted in a human body by ion implantation. The invention belongs to the field of material science and discloses a method for treating the surface of a metal material implanted in a human body. This method uses two or more metal elements and non-metal elements to simultaneously ionize and accelerate into a mixed ion beam, which is used to treat artificial organs (tooth roots, artificial joints, cardiac pacemakers, blood vessels) made of metal materials implanted in the human body. stents, etc.) for ion implantation. The method of the invention can improve the corrosion resistance, wear resistance, adhesion resistance and fatigue resistance of the metal organs implanted in the human body. Wherein said metal is selected from two or more elements such as Ti.Zr.V.Nb.Ta.Cr.Mo.W.Fe.Co.Ni.Mn.Y.Zn.Sc.; its non-metal is selected from : BCNOSSi one or more elements. This process does not change the dimensions and surface precision of the processed object. The method of the invention is stable and reliable, convenient and easy to implement, and has good applicability.
Description
技术领域 technical field
本发明涉及一种人体植入金属材料表面离子注入处理方法。The invention relates to a treatment method for ion implantation on the surface of a metal material implanted in a human body.
背景技术 Background technique
人工关节使用钛合金金属材料如：Ti6Al4V；人造牙根植入体，使用纯金属钛材料。钛及钛合金的比重与人体骨骼的比重近似，有很好的比强度，有一定的耐蚀性。人体配戴安装钛合金制成的人工关节后，近期感觉比安装CoCrMo材料或不锈钢材料制成的人工关节舒适。但是，纯金属钛材料及钛合金材料比起CoCrMo材料或不锈钢材料，存在耐人体体液溶蚀性差，耐磨性低。尤其是在人体体液环境情况下，耐磨性能差。由钛合金制成的人工关节，不能达到伴随人一生的标准。钛合金关节，在人体体内磨损，溶解出钛离子。人体关节处体液变黑，即产生“黑水”。溶入体液的钛离子，参加人的体内循环。钛离子容易聚集在肾脏，使人患肾病。Artificial joints use titanium alloy metal materials such as: Ti6Al4V; artificial tooth root implants use pure metal titanium materials. The specific gravity of titanium and titanium alloys is similar to that of human bones, with good specific strength and certain corrosion resistance. After the human body wears artificial joints made of titanium alloy, it feels more comfortable than artificial joints made of CoCrMo or stainless steel in the near future. However, compared with CoCrMo materials or stainless steel materials, pure metal titanium materials and titanium alloy materials have poor corrosion resistance to human body fluids and low wear resistance. Especially in the environment of human body fluid, the wear resistance is poor. Artificial joints made of titanium alloy cannot meet the standard of accompanying people for a lifetime. Titanium alloy joints wear out in the human body and dissolve titanium ions. The body fluid at the joints of the human body turns black, that is, "black water" is produced. Titanium ions dissolved in body fluids participate in human body circulation. Titanium ions are easy to gather in the kidneys, causing people to suffer from kidney disease.
金属材料人体植入器官表面处理方法，此前曾有氮离子注入、单纯金属离子注入，但是，单纯氮离子注入或单纯金属离子注入的人工关节还不能达到，其植入人体后，伴随人一生的标准。一般只能使用十至十五年。而采用本发明方法：多重离子束混合注入，在钛及钛合金材料表面形成纳米级陶瓷注入层，比单纯氮离子注入或单纯金属离子注入，处理的人工关节，有更强的耐蚀性和耐磨性能。用本注入方法处理人体植入钛及钛合金材料，制成的人工关节，比单纯氮离子注入或单纯金属离子注入处理的人工关节使用寿命预计提高3-4倍。There have been nitrogen ion implantation and simple metal ion implantation methods for the surface treatment of metal materials implanted in the human body. standard. Generally, it can only be used for ten to fifteen years. And adopt the method of the present invention: the mixed implantation of multiple ion beams forms nano-scale ceramic implantation layer on the surface of titanium and titanium alloy materials, has stronger corrosion resistance and stronger corrosion resistance than the artificial joint treated by simple nitrogen ion implantation or simple metal ion implantation. wear resistance. The artificial joint made by implanting titanium and titanium alloy materials into the human body with this injection method is expected to increase the service life by 3-4 times compared with the artificial joint treated with simple nitrogen ion implantation or simple metal ion implantation.
多种离子束混合注入不存在可剥离界面问题，既不存在各种真空镀膜或刷镀工艺的镀膜剥层问题。使用镀层处理的人工关节，镀层一旦剥落，在关节腔内会形成磨粒磨损，加速人工关节的损坏。Mixed implantation of various ion beams does not have the problem of peelable interface, nor does it have the problem of peeling off of various vacuum coating or brush plating processes. With the artificial joint treated with coating, once the coating peels off, abrasive wear will be formed in the joint cavity, which will accelerate the damage of the artificial joint.
发明内容 Contents of the invention
一种人体植入金属材料的表面处理方法，其特征在于采用金属元素和非金属元素同时电离，在电场中加速，在磁场中聚焦，形成均匀混合的离子束流，对被加工物体进行离子注入；其中，元素组合为：Ti+C+N、Zr+C+N、Ti+Zr+C+N、Ti+C、Zr+C、Ti+C+O、Zr+C+O、Ti+N+O、Zr+N+O、Zr+O、Ti+V+C、Ti+Nb+C、Zr+Cr+B、Zr+Cr+C+O、Ti+Cr+Mo+C、Zr+Mo+C+N、Cr+C+N、Cr+Mo+C+N、Cr+Mo+C、Mo+C+N、Y+C+N、Y+Cr+C、Y+Cr+C+N、Co+Cr+Mo+C、Co+Cr+Mo+C+N、Co+Cr+Mo+N+O；其中，金属元素和非金属元素混合离子束流产生方法为：将MEVVA源离子注入机产生离子的阴极由只产生单一离子改造成能产生多种离子的阴极；此阴极制造采用离子注入最多的一种固体注入元素制成阴极形状，将其他一种或多种注入元素制成细柱状，按陶瓷注入层原子比和各参与元素的电离能比关系，设计各元素的量比及排列组合，将制成细柱状金属或非金属，按蜂巢排列方式或莲蓬状排列方式排列组合，镶嵌到上述固体注入元素制成的阴极中，用此阴极触发、电离、配以适当能量分布进行离子注入，可得到所需的纳米陶瓷注入层；其中，离子注入能量为：0.5-500KV；离子注入剂量为：1×1014-5×1020Ion/cm2。A surface treatment method for implanting metal materials in the human body, which is characterized in that metal elements and non-metal elements are simultaneously ionized, accelerated in an electric field, focused in a magnetic field, and a uniformly mixed ion beam is formed to perform ion implantation on the processed object ; Among them, the element combination is: Ti+C+N, Zr+C+N, Ti+Zr+C+N, Ti+C, Zr+C, Ti+C+O, Zr+C+O, Ti+N +O, Zr+N+O, Zr+O, Ti+V+C, Ti+Nb+C, Zr+Cr+B, Zr+Cr+C+O, Ti+Cr+Mo+C, Zr+Mo +C+N, Cr+C+N, Cr+Mo+C+N, Cr+Mo+C, Mo+C+N, Y+C+N, Y+Cr+C, Y+Cr+C+N . The cathode of machine-generated ions is transformed from only producing a single ion to a cathode capable of producing multiple ions; this cathode is made of a solid implanted element with the most ion implantation to make the cathode shape, and other one or more implanted elements are made into fine Columnar, according to the relationship between the atomic ratio of the ceramic injection layer and the ionization energy ratio of each participating element, the amount ratio and arrangement of each element are designed, and the thin columnar metal or non-metal will be made into a honeycomb arrangement or a lotus arrangement. Embedded in the cathode made of the above-mentioned solid implanted elements, using this cathode to trigger, ionize, and carry out ion implantation with appropriate energy distribution, the desired nano-ceramic implanted layer can be obtained; wherein, the ion implantation energy is: 0.5-500KV; The injection dose is: 1×10 14 -5×10 20 Ion/cm 2 .
如上所述人体植入金属材料表面处理方法，其中，金属材料为：纯金属钛、钛铝合金、钛铁合金、钛镁铝合金、其它钛合金或镍基记忆合金制成的人工关节、人工植入牙根或血管支架。The method for surface treatment of metal materials implanted in the human body as described above, wherein the metal materials are: artificial joints, artificial implants made of pure titanium, titanium-aluminum alloys, titanium-iron alloys, titanium-magnesium-aluminum alloys, other titanium alloys, or nickel-based memory alloys. into dental roots or vascular stents.
本注入方法以离子强渗透的方式，将金属和非金属离子按一定的比例组合、一定的入射角度及适当的温度条件下，以一定的能量分布将组合离子束，注入到被处理人工关节表面。在被处理人工关节表面与其基体之间，形成纳米陶瓷浓度逐渐增加，及至表面的过渡层。因此，纳米陶瓷注入层与人工关节机体之间没有明显的界面，不存在各种真空镀膜或刷镀工艺的镀膜剥层问题。此纳米陶瓷注入层，有着非常良好的耐磨损性能和耐腐蚀性能。In this implantation method, metal and non-metal ions are combined in a certain proportion, under a certain incident angle and appropriate temperature conditions, and a certain energy distribution is used to inject the combined ion beam into the surface of the artificial joint to be treated by means of strong ion penetration. . Between the treated artificial joint surface and its substrate, a transition layer with gradually increasing concentration of nano-ceramics is formed, reaching the surface. Therefore, there is no obvious interface between the nano-ceramic injection layer and the artificial joint body, and there is no problem of peeling of the coating film in various vacuum coating or brush coating processes. This nano-ceramic injection layer has very good wear resistance and corrosion resistance.
附图说明 Description of drawings
图1.为能同时产生多种金属离子的，金属蒸汽真空弧离子源即MEVVA源离子注入机示意图；图2.为Zr、Gr、C、O同时注入Ti试样，形成纳米陶瓷层，其俄歇电子能谱。Fig. 1. is a schematic diagram of a metal vapor vacuum arc ion source, namely MEVVA source ion implanter, which can produce multiple metal ions simultaneously; Fig. 2. is the simultaneous injection of Zr, Gr, C, O into a Ti sample to form a nano-ceramic layer. Auger Electron Spectroscopy.
具体实施方式 Detailed ways
实现上述纳米陶瓷注入层的方法：取一种金属或合金，此金属或合金组合只要再配以适当的非金属元素，即可合成所需的陶瓷成分。上述非金属元素可以是气体、也可以是固体。The method for realizing the above-mentioned nano-ceramic injection layer: take a metal or alloy, and the combination of this metal or alloy can be combined with appropriate non-metallic elements to synthesize the desired ceramic composition. The above-mentioned non-metallic elements may be gases or solids.
一、非金属元素是固体时，用纯金属或合金制成阴极。固体非金属，按陶瓷注入层原子比和各参与元素的电离能比关系，设计各元素的量比。将固体非金属依比量制成细柱状，按蜂巢排列方式或莲蓬状排列方式镶嵌到纯金属或合金制成的阴极中。用此阴极触发、电离、配以适当能量分布进行离子注入。可得到所需的纳米陶瓷注入层。采用此方法获取纳米陶瓷注入层的有：TiC、ZrC、YC、CoGrMoC3、纯金属也可以换成固体非金属，生成如下纳米陶瓷层：BC、SiC、SiBC等。上述金属也可以是一种金属配以另一种或几种纯金属，再配以非金属或两种及种两种以上非金属，生成纳米陶瓷层如：TiZrC、ZrBC、ZrGrC、GrMoC、TiZrVBC等。用此种方法可以生成新型特殊功能陶瓷。1. When the non-metal element is solid, the cathode is made of pure metal or alloy. For solid non-metals, the quantity ratio of each element is designed according to the relationship between the atomic ratio of the ceramic injection layer and the ionization energy ratio of each participating element. The solid non-metal is made into thin columns according to the proportion, and embedded in the cathode made of pure metal or alloy according to the arrangement of honeycomb or lotus. Use this cathode to trigger, ionize, and perform ion implantation with proper energy distribution. The required nano-ceramic injection layer can be obtained. Nano-ceramic injection layers obtained by this method include: TiC, ZrC, YC, CoGrMoC 3 , and pure metals can also be replaced by solid non-metals to generate the following nano-ceramic layers: BC, SiC, SiBC, etc. The above metals can also be one kind of metal with another or several pure metals, and then with non-metals or two or more kinds of non-metals to form nano-ceramic layers such as: TiZrC, ZrBC, ZrGrC, GrMoC, TiZrVBC wait. This method can generate new special functional ceramics.
二、非金属元素是气体时，用通气铜管配以针阀，安装在离子源阴极放电室。通入单一气体，调整适当气压，使离子源保持正常电离工作状态。调整触发电压、引出电压、引出离子的成分，达到陶瓷注入层成分的要求。配以适当能量分布进行离子注入。形成纳米陶瓷注入层。如：TiN、ZrN、TiO、ZrO、TiZrN；上述气体也可以是混合气体或固体加气体，生成纳米陶瓷注入层，如：TiNO、ZrNO、TiZrCN、TiZrCNO、GrMoCO等；上述金属也可换成非金属，生成纳米陶瓷注入层，如：BN、CN、BCN、SiCN、BNO、SiNO等。综合方法一、二，科学家可以研究生产，前人未曾触及的新型纳米陶瓷。2. When the non-metallic element is a gas, use a ventilation copper tube with a needle valve and install it in the cathode discharge chamber of the ion source. Introduce a single gas and adjust the proper air pressure to keep the ion source in normal ionization working condition. Adjust the trigger voltage, extraction voltage, and the composition of the extracted ions to meet the requirements of the composition of the ceramic injection layer. Ion implantation with proper energy distribution. A nano-ceramic injection layer is formed. Such as: TiN, ZrN, TiO, ZrO, TiZrN; the above-mentioned gases can also be mixed gases or solid plus gas to form nano-ceramic injection layers, such as: TiNO, ZrNO, TiZrCN, TiZrCNO, GrMoCO, etc.; the above-mentioned metals can also be replaced by non- Metal to generate nano-ceramic injection layer, such as: BN, CN, BCN, SiCN, BNO, SiNO, etc.
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| CN112171530B (en) * | 2020-09-25 | 2024-05-03 | 江苏瑞和磨料磨具有限公司 | Ceramic corundum abrasive coated grinding tool and preparation method thereof |
| CN112321880B (en) * | 2020-11-27 | 2021-06-01 | 中国科学院兰州化学物理研究所 | Method for modifying polyether-ether-ketone surface by injecting bimetallic ions |
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| CN1122380A (en) * | 1995-08-25 | 1996-05-15 | 北京有色金属研究总院 | Composite surface treatment method for steel die |
| DE19830530A1 (en) * | 1998-07-08 | 2000-01-13 | Merck Patent Gmbh | Production of titanium surfaces coated with calcium phosphate, especially for making medical prostheses or implants |
| WO2001048262A1 (en) * | 1999-12-23 | 2001-07-05 | Southwest Jiaotong University | Method for forming a tio2-x film on a material surface by using plasma immersion ion implantation and the use thereof |
| AU2003279406A1 (en) * | 2003-11-13 | 2004-06-06 | Lifenova Biomedical, S.A. | Method of producing endosseous implants or medical prostheses by means of ionic implantation, and endosseous implant or medical prosthesis thus produced |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122380A (en) * | 1995-08-25 | 1996-05-15 | 北京有色金属研究总院 | Composite surface treatment method for steel die |
| DE19830530A1 (en) * | 1998-07-08 | 2000-01-13 | Merck Patent Gmbh | Production of titanium surfaces coated with calcium phosphate, especially for making medical prostheses or implants |
| WO2001048262A1 (en) * | 1999-12-23 | 2001-07-05 | Southwest Jiaotong University | Method for forming a tio2-x film on a material surface by using plasma immersion ion implantation and the use thereof |
| AU2003279406A1 (en) * | 2003-11-13 | 2004-06-06 | Lifenova Biomedical, S.A. | Method of producing endosseous implants or medical prostheses by means of ionic implantation, and endosseous implant or medical prosthesis thus produced |
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