CN100404724C - Ion implantation process method for surface of metal material embedded to human body - Google Patents
Ion implantation process method for surface of metal material embedded to human body Download PDFInfo
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- CN100404724C CN100404724C CNB2004101012981A CN200410101298A CN100404724C CN 100404724 C CN100404724 C CN 100404724C CN B2004101012981 A CNB2004101012981 A CN B2004101012981A CN 200410101298 A CN200410101298 A CN 200410101298A CN 100404724 C CN100404724 C CN 100404724C
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000005468 ion implantation Methods 0.000 title claims abstract description 18
- 239000007769 metal material Substances 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 230000002792 vascular Effects 0.000 claims abstract description 3
- 238000002347 injection Methods 0.000 claims description 25
- 239000007924 injection Substances 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 24
- 239000000919 ceramic Substances 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 19
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- -1 titanium-magnesium-aluminum Chemical compound 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 239000007943 implant Substances 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 240000002853 Nelumbo nucifera Species 0.000 claims description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 2
- 235000006510 Nelumbo pentapetala Nutrition 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
- 229910001285 shape-memory alloy Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 210000000056 organ Anatomy 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000000747 cardiac effect Effects 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 229910052758 niobium Inorganic materials 0.000 abstract 1
- 150000002843 nonmetals Chemical class 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 229910052706 scandium Inorganic materials 0.000 abstract 1
- 229910052721 tungsten Inorganic materials 0.000 abstract 1
- 229910052720 vanadium Inorganic materials 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 4
- 210000001124 body fluid Anatomy 0.000 description 4
- 239000010839 body fluid Substances 0.000 description 4
- 238000002513 implantation Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000010866 blackwater Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 208000017169 kidney disease Diseases 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The present invention discloses a surface processing method for metallic materials transplanted into human bodies. Two or more than two kinds of metallic elements and nonmetallic elements are ionized and accelerated simultaneously into mixed ion beams to treat artificial organs (such as artificial joints, cardiac pacemakers, tooth roots, vascular scaffolds, etc.) made of metallic materials transplanted into the human bodies through ion implantation. The method of the present invention can improve the corrosion resistance, the wear resistance, the adhesion resistance and the fatigue resistance of the metallic organs transplanted into the human bodies, wherein the metals can be chosen from one or more elements of Ti, Zr, V, Nb, Cr, Mo, W, Fe, Co, Ni, Mn, Y, Zn, Sc, etc., and the nonmetals can be chosen from one or more elements of B, C, N, O, etc. The external dimension and the surface accuracy of processed objects are not changed by the method. The method of the present invention has the advantages of stability, reliability, convenience, simplicity and wide application.
Description
Technical Field
The invention relates to a method for processing ion implantation on the surface of a metal material implanted into a human body.
Background
The artificial joint uses titanium alloy metal materials such as: ti6Al 4V; the artificial tooth root implant is made of pure metal titanium material. The specific gravity of titanium and titanium alloy is similar to that of human skeleton, and it has excellent specific strength and certain corrosion resistance. After the human body wears and installs the artificial joint made of the titanium alloy, the recent feeling is more comfortable than the installation of the artificial joint made of the CoCrMo material or the stainless steel material. However, pure metal titanium materials and titanium alloy materials have poor resistance to erosion by body fluids and low wear resistance, compared with CoCrMo materials or stainless steel materials. Especially under the environment of human body fluid, the wear-resisting property is poor. The artificial joint made of titanium alloy cannot meet the standards of the whole life of a person. The titanium alloy joint is worn in the human body to dissolve titanium ions. The body fluid at the joints of the human body turns black, namely 'black water' is generated. The titanium ion dissolved in the body fluid participates in the circulation of the human body. Titanium ions are easily accumulated in the kidney, so that people suffer from nephropathy.
The surface treatment method of metal material human body implantation organ has been nitrogen ion implantation and pure metal ion implantation before, but the artificial joint with pure nitrogen ion implantation or pure metal ion implantation can not be reached, and the artificial joint is accompanied with the standard of human life after being implanted into the human body. Typically only ten to fifteen years. The method of the invention is adopted: multiple ion beams are mixed and injected, a nano-scale ceramic injection layer is formed on the surface of the titanium and titanium alloy material, and compared with the artificial joint which is processed by single nitrogen ion injection or single metal ion injection, the artificial joint has stronger corrosion resistance and wear resistance. The artificial joint prepared by treating the human body implanted titanium and titanium alloy materials by the implantation method has the service life which is estimated to be improved by 3-4 times compared with the artificial joint treated by pure nitrogen ion implantation or pure metal ion implantation.
The mixed implantation of a plurality of ion beams does not have the problem of strippable interface, and the problem of coating stripping of various vacuum coating or brush plating processes is not existed. When the artificial joint is treated by the plating layer, once the plating layer is peeled off, abrasive grains are formed in a joint cavity and abraded, and the damage of the artificial joint is accelerated.
Disclosure of Invention
A surface treating method for metallic material implanted in human body features that the metallic element and non-metallic element are ionized simultaneously, accelerated in electric field and focused in magnetic field to form a uniform layerThe mixed ion beam current is used for carrying out ion implantation on the processed object; wherein, the element combination is as follows: 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 + O, Ti + Cr + Mo + C, Zr + Mo + C + N, Cr + C + N, Cr + Mo + N, Cr + Mo + C, Mo + C + N, Y + C + N, Y + Cr + C, Y + Cr + N, Co + Cr + Mo + C, Co + Cr + C + N, Co + Cr + Mo + N + O; the method for generating the mixed ion beam flow of the metal elements and the nonmetal elements comprises the following steps: the cathode for generating ions by the MEVVA source ion implanter is modified into a cathode capable of generating a plurality of ions from the cathode for generating only single ions; the cathode is manufactured by adopting a solid injection element with the most ion injection to manufacture a cathode shape, manufacturing other injection element or elements into a thin column shape, designing the quantity ratio and the arrangement combination of the elements according to the relationship between the atomic ratio of a ceramic injection layer and the ionization energy ratio of each participating element, manufacturing thin column-shaped metal or nonmetal, arranging and combining the metal or nonmetal in a honeycomb arrangement mode or a lotus arrangement mode, embedding the metal or nonmetal into the cathode made of the solid injection element, and triggering, ionizing and injecting ions by using the cathode in a proper energy distribution mode to obtain a required nano ceramic injection layer; wherein, the ion implantation energy is: 0.5-500 KV; the ion implantation dose is: 1X 1014-5×1020Ion/cm2。
The surface treatment method of the metal material implanted into the human body comprises the following steps: the artificial joint, the artificial implanted tooth root or the vascular stent is made of pure metal titanium, titanium-aluminum alloy, titanium-iron alloy, titanium-magnesium-aluminum alloy, other titanium alloy or nickel-based memory alloy.
The implantation method combines metal ions and non-metal ions according to a certain proportion, a certain incident angle and a proper temperature condition in an ion strong penetration mode, and implants the combined ion beams to the surface of the treated artificial joint with a certain energy distribution. Between the surface of the artificial joint to be treated and the substrate thereof, a transition layer with the concentration of the nano ceramics gradually increasing and reaching the surface is formed. Therefore, no obvious interface exists between the nano ceramic injection layer and the artificial joint body, and the problem of coating stripping of various vacuum coating or brush coating processes does not exist. The nano ceramic injection layer has very good wear resistance and corrosion resistance.
Drawings
FIG. 1 is a schematic view of a metal vapor vacuum arc ion source, namely, an MEVVA source ion implanter, capable of simultaneously generating a plurality of metal ions; FIG. 2 shows the Auger electron energy spectrum of the nano ceramic layer formed by injecting Zr, Gr, C and O into Ti sample at the same time.
Detailed Description
The method for realizing the nano ceramic injection layer comprises the following steps: the required ceramic component can be synthesized by taking a metal or an alloy and only adding proper non-metal elements into the metal or the alloy combination. The non-metallic element may be a gas or a solid.
When the non-metal element is solid, the cathode is made of pure metal or alloy. And solid nonmetal, and 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 nonmetal is made into a thin column shape according to a certain proportion and is embedded into a cathode made of pure metal or alloy in a honeycomb arrangement mode or a shower-shaped arrangement mode. The cathode is used for triggering, ionizing and matching with proper energy distribution to carry out ion implantation. The required nano ceramic injection layer can be obtained. The method for obtaining the nano ceramic injection layer comprises the following steps: TiC, ZrC, YC, CoGrMoC3The pure metal can be replaced by solid nonmetal to generate the following nano ceramic layer: BC. SiC, SiBC, etc. The metal can also be a metal matched with another or several pure metals and then matched with nonmetal or two or more than two kinds of nonmetal to generate a nano ceramic layer, such as: TiZrC, ZrBC, ZrGrC, GrMoC, TiZrVBC, and the like. By this method, a novel special functional ceramic can be produced.
And secondly, when the non-metal element is gas, a gas copper pipe is matched with a needle valve and is arranged in the ion source cathode discharge chamber. And introducing single gas, and adjusting the proper air pressure to keep the ion source in a normal ionization working state. The trigger voltage, the extraction voltage and the components of the extracted ions are adjusted to meet the requirements of the components of the ceramic injection layer. Ion implantation is performed with appropriate energy distribution. And forming a nano ceramic injection layer. Such as: TiN, ZrN, TiO, ZrO, TiZrN; the gas can also be mixed gas or solid plus gas to generate a nano ceramic injection layer, such as: TiNO, ZrNO, TiZrCN, TiZrCNO, GrMoCO, etc.; the metal can be replaced by nonmetal to generate a nano ceramic injection layer, such as: BN, CN, BCN, SiCN, BNO, SiNO and the like. By integrating the first and second methods, scientists can research and produce novel nano ceramics which have not been reached by the former people.
Claims (2)
1. A surface treatment method for a metal material implanted in a human body is characterized in that a metal element and a nonmetal element are ionized simultaneously, accelerated in an electric field and focused in a magnetic field to form a uniformly mixed ion beam current, and the ion implantation is carried out on a processed object; wherein, the element combination is as follows: 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 + O, Ti + Cr + Mo + C, Zr + Mo + C + N, Cr + C + N, Cr + Mo + N, Cr + Mo + C, Mo + C + N, Y + C + N, Y + Cr + C, Y + Cr + N, Co + Cr + Mo + C, Co + Cr + C + N, Co + Cr + Mo + N + O; wherein,the method for generating the mixed ion beam flow of the metal elements and the nonmetal elements comprises the following steps: the cathode for generating ions by the MEVVA source ion implanter is modified into a cathode capable of generating a plurality of ions from the cathode for generating only single ions; the cathode is manufactured by adopting a solid injection element with the most ion injection to manufacture a cathode shape, manufacturing other injection element or elements into a thin column shape, designing the quantity ratio and the arrangement combination of the elements according to the relationship between the atomic ratio of a ceramic injection layer and the ionization energy ratio of each participating element, manufacturing thin column-shaped metal or nonmetal, arranging and combining the metal or nonmetal in a honeycomb arrangement mode or a lotus arrangement mode, embedding the metal or nonmetal into the cathode made of the solid injection element, and triggering, ionizing and injecting ions by using the cathode in a proper energy distribution mode to obtain a required nano ceramic injection layer; wherein, the ion implantation energy is: 0.5-500 KV; the ion implantation dose is: 1X 1014-5×1020Ion/cm2。
2. The surface treatment method of a human body implant metal material as set forth in claim 1, wherein the metal material is: the artificial joint, the artificial implanted tooth root or the vascular stent is made of pure metal titanium, titanium-aluminum alloy, titanium-iron alloy, titanium-magnesium-aluminum alloy, other titanium alloy or nickel-based memory alloy.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101012981A CN100404724C (en) | 2004-12-20 | 2004-12-20 | Ion implantation process method for surface of metal material embedded to human body |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101012981A CN100404724C (en) | 2004-12-20 | 2004-12-20 | Ion implantation process method for surface of metal material embedded to human body |
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| CN1796594A CN1796594A (en) | 2006-07-05 |
| CN100404724C true CN100404724C (en) | 2008-07-23 |
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| CN101337090B (en) * | 2008-08-29 | 2012-12-12 | 乐普（北京）医疗器械股份有限公司 | Composite coating magnesium/magnesium alloy biology device and preparation method thereof |
| CN101496910B (en) * | 2009-03-10 | 2017-06-23 | 成都西南交大研究院有限公司 | A kind of degradable blood vessel support |
| CN103498129B (en) * | 2013-09-03 | 2015-08-19 | 北京航空航天大学 | A kind of iron ion injects deposition carries out surface modification method to biological degradation Magnesium and magnesium alloys |
| CN104726836B (en) * | 2013-12-20 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | The method of surface modification and the titanium metal material of modification are carried out to titanium metal material |
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| CN106637121B (en) * | 2016-10-19 | 2019-04-12 | 中国科学院上海硅酸盐研究所慈溪生物材料表面工程中心 | A kind of medical titanium metal alkyl materials and its manufacturing method |
| CN108677149A (en) * | 2018-06-23 | 2018-10-19 | 西安文理学院 | A kind of high abrasion anti-corrosion PVD coating process |
| CN109234696A (en) * | 2018-09-12 | 2019-01-18 | 杭州联芳科技有限公司 | A kind of intravascular stent nitrogen implantation method |
| 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 |
| CN115181934A (en) * | 2022-06-21 | 2022-10-14 | 广州国显科技有限公司 | Mask plate and preparation method thereof |
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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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2004
- 2004-12-20 CN CNB2004101012981A patent/CN100404724C/en not_active Expired - Fee Related
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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| CN1796594A (en) | 2006-07-05 |
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