CN113073303B - A biomedical pure magnesium surface functional structured ion implantation modified layer and its preparation method and application - Google Patents
A biomedical pure magnesium surface functional structured ion implantation modified layer and its preparation method and application Download PDFInfo
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- CN113073303B CN113073303B CN202110325051.1A CN202110325051A CN113073303B CN 113073303 B CN113073303 B CN 113073303B CN 202110325051 A CN202110325051 A CN 202110325051A CN 113073303 B CN113073303 B CN 113073303B
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- 239000011777 magnesium Substances 0.000 title claims abstract description 103
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 102
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000005468 ion implantation Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 62
- 239000011575 calcium Substances 0.000 claims abstract description 44
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 239000007943 implant Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 99
- 238000002347 injection Methods 0.000 claims description 37
- 239000007924 injection Substances 0.000 claims description 37
- 238000002513 implantation Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002344 surface layer Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002474 experimental method Methods 0.000 claims description 9
- 239000013077 target material Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 47
- 230000007797 corrosion Effects 0.000 abstract description 47
- 229910052791 calcium Inorganic materials 0.000 abstract description 34
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 31
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 239000012890 simulated body fluid Substances 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract description 2
- 150000003018 phosphorus compounds Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 17
- 238000001035 drying Methods 0.000 description 12
- 238000002791 soaking Methods 0.000 description 12
- 230000004580 weight loss Effects 0.000 description 11
- 229910000861 Mg alloy Inorganic materials 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 230000006399 behavior Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical class [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical class [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- -1 calcium-phosphorus compound Chemical class 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052564 epsomite Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract
本发明公开了一种生物医用纯镁表面功能结构化离子注入改性层，包括离子注入并均匀分布于所述纯镁表面的锰改性层，所述锰改性层包括位于内层的锰单质以及位于表层的、从内到外含量递增的氧化锰。本发明还公开了一种生物医用纯镁表面功能结构化离子注入改性层的制备方法。本发明还公开了一种生物医用纯镁表面功能结构化离子注入改性层在可降解骨植入材料中的应用。本发明能使纯镁在模拟体液中浸泡初期形成均匀的电偶腐蚀，促进与人体骨成分相近钙磷化合物的沉积，随时间延长，腐蚀类型转变为均匀腐蚀，达到可控降解，本发明在有效提高生物医用镁耐蚀性能的基础上，也进一步提高了生物相容性，扩大了应用范围。
The invention discloses a functionally structured ion implantation modified layer on the surface of biomedical pure magnesium, comprising a manganese modified layer which is implanted with ions and uniformly distributed on the surface of the pure magnesium, and the manganese modified layer includes manganese in an inner layer. Elemental and surface manganese oxide with increasing content from inside to outside. The invention also discloses a preparation method of a biomedical pure magnesium surface functional structured ion implantation modified layer. The invention also discloses the application of a biomedical pure magnesium surface functional structured ion implantation modified layer in a degradable bone implant material. The invention can enable pure magnesium to form uniform galvanic corrosion in the initial stage of immersion in simulated body fluid, promote the deposition of calcium and phosphorus compounds similar to human bone components, and with time prolonging, the corrosion type changes into uniform corrosion, and controllable degradation is achieved. On the basis of effectively improving the corrosion resistance of biomedical magnesium, it also further improves the biocompatibility and expands the scope of application.
Description
Technical Field
The invention relates to a biomedical pure magnesium surface functional structured ion implantation modified layer, a preparation method and application thereof, belonging to the technical field of biomedical magnesium-based metal material surface modification.
Background
The traditional bone implantation materials mainly comprise stainless steel, titanium alloy and cobalt-chromium alloy, but the materials cause stress shielding effect, are not beneficial to the growth and healing of bone tissues, are not degradable and need to be taken out by secondary operation, and in addition, metal ions dissolved and released after being implanted into a human body have biotoxicity. The density and the elastic modulus of magnesium and magnesium alloy are close to those of natural bones, and meanwhile, the magnesium and magnesium alloy has good biocompatibility and degradability, and degraded magnesium ions can be absorbed by a human body to promote the growth of new bones and participate in metabolism of the human body, so that the magnesium and magnesium alloy is expected to replace the traditional bone implant material in the field of biomedical devices. However, magnesium is too active in chemical property, is very easy to corrode in human electrolyte solution, can degrade within a short time, and leads to early loss of mechanical integrity of the implant, and if serious local corrosion occurs during service of magnesium and magnesium alloy workpieces, the degradation behavior is uncontrollable, so that sudden early fracture failure of the implant apparatus can be caused. Ion implantation is used as an effective surface modification technology, and can improve the corrosion resistance of biomedical magnesium and magnesium alloy. Chu professor team of hong Kong City university Paul K.Chu has carried out a series of researches on ion implantation Surface modification of biomedical magnesium alloy, which can improve the Corrosion resistance of pure magnesium and magnesium alloy in simulated body fluid by ion implantation of Al and elements of rare earth metals Nd, Ce, Pr, etc. (Applied Surface Science,2012,258(19):7651-7657. Corroson Science,2015, 94:142-155.Surface & Coatings Technology,2016,306:6-10.Materials Letters, 2016,163: 85-89.). However, Al element has neurotoxicity and is liable to induce senile dementia, and biotoxicity of rare earth element is not clear yet. Therefore, the biological safety and compatibility of the elements are one of the factors that must be considered. In addition, Liu et al separately inject Ag, Fe, Y into the Mg-1Ca surface, and the results show that Ag and Fe injection accelerates the corrosion rate of the matrix, while Y injection improves the corrosion resistance of the magnesium alloy in the simulated body fluid in a short period of time, but the effect is not obvious, and the Y injection layer does not play a role in long-term protection. (Colloids & Surfaces B biolnterfaces, 2015,133: 99-107.).
Therefore, a biomedical pure magnesium surface functional structural ion implantation modified layer with controllable degradation behavior, and a preparation method and application thereof are needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a biomedical pure magnesium surface functional structural ion injection modified layer which is formed by injecting manganese and/or calcium elements with good biocompatibility into the surface of pure magnesium, improves the corrosion resistance of pure magnesium in body fluid and meets the aim of controlling degradation behaviors.
Meanwhile, the invention provides a preparation method of the biomedical pure magnesium surface functional structural ion implantation modified layer, which is finally prepared and obtained through single/co-implantation and process parameter optimization, and the ion implantation modified layer is compact in structure and contains metal oxide and simple substance.
Meanwhile, the invention provides application of the biomedical pure magnesium surface functional structural ion implantation modified layer in degradable bone implant materials.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention discloses a biomedical pure magnesium surface functional structural ion injection modified layer, which comprises a manganese modified layer which is subjected to ion injection and is uniformly distributed on the surface of pure magnesium, wherein the manganese modified layer comprises a manganese simple substance positioned in an inner layer and a Mn-MnO mixed layer positioned on a surface layer and the content of manganese oxide of which is increased from inside to outside.
The preparation method of the biomedical pure magnesium surface functional structure ion implantation modified layer comprises the following steps:
s1, pretreating the surface of a pure magnesium workpiece to remove a natural oxide film and impurities on the surface;
s2, performing manganese ion implantation on the pretreated pure magnesium workpiece, wherein the purity of the Mn target material is more than 99.9 percent, and the working vacuum degree is less than or equal to 1 multiplied by 10-4Pa, implantation voltage of 50kV, and implantation dose of 2 × 1016～2×1017ions/cm2The temperature of the pure magnesium workpiece is 25-300 ℃ in the injection process;
and S3, after the experiment is finished, cleaning and drying by hot air.
The invention also discloses a biomedical pure magnesium surface functional structure ion implantation modification layer with another structure, which comprises a first calcium modification layer which is ion implanted and uniformly distributed on the surface of the pure magnesium, wherein the first calcium modification layer is a calcium oxide layer, and the content of calcium oxide in the first calcium modification layer is sequentially increased from inside to outside.
The preparation method of the biomedical pure magnesium surface functional structure ion implantation modified layer comprises the following steps:
s1, pretreating the surface of a pure magnesium workpiece to remove a natural oxide film and impurities on the surface;
s2, performing calcium ion implantation on the pretreated pure magnesium workpiece, wherein the purity of the Ca target material is more than 99.9 percent, and the working vacuum degree is less than or equal to 1 multiplied by 10-4Pa, implantation voltage of 50kV, and implantation dose of 2 × 1016～2×1017ions/cm2The temperature of the pure magnesium workpiece is 25-300 ℃ in the injection process;
and S3, after the experiment is finished, cleaning and drying by hot air.
The invention also discloses a biomedical pure magnesium surface functional structured ion implantation modified layer with another structure, which comprises a manganese modified layer which is subjected to ion implantation and is uniformly distributed on the surface of the pure magnesium, wherein the manganese modified layer comprises a manganese simple substance positioned in an inner layer and a Mn-MnO mixed layer positioned on a surface layer and the content of manganese oxide of which is increased from inside to outside. And the surface of the manganese modified layer is subjected to ion implantation and is uniformly distributed with a second calcium modified layer, and the second calcium modified layer comprises a calcium simple substance positioned in an inner layer and a Ca-CaO mixed layer positioned on a surface layer and gradually increased in calcium oxide content from inside to outside.
The preparation method of the biomedical pure magnesium surface functional structure ion implantation modified layer comprises the following steps:
s1, pretreating the surface of a pure magnesium workpiece to remove a natural oxide film and impurities on the surface;
s2, performing first manganese ion implantation on the pretreated pure magnesium workpiece, wherein the purity of the Mn target material is more than 99.9 percent, and the working vacuum degree is less than or equal to 1 multiplied by 10-4Pa, implantation voltage of 50kV, and implantation dose of 2 × 1016～2×1017 ions/cm2The temperature of the pure magnesium workpiece is 25-300 ℃ in the injection process;
after the manganese ion implantation is finished, cleaning, drying by hot air, and then performing secondary calcium ion implantation, wherein the purity of the Ca target material is more than 99.9 percent, and the working vacuum degree is less than or equal to 1 multiplied by 10-4Pa, implantation voltage of 50kV, and implantation dose of 2 × 1016～2×1017ions/cm2The temperature of the pure magnesium workpiece is 25-300 ℃ in the injection process;
and S3, after the experiment is finished, cleaning and drying by hot air.
The pretreatment method comprises the following steps: and (3) grinding and polishing the pure magnesium workpiece by adopting metallographic abrasive paper and a polishing machine, placing the polished pure magnesium workpiece in an absolute ethyl alcohol solution for ultrasonic treatment for 10 minutes, and drying the polished pure magnesium workpiece by hot air.
And after the experiment is finished, taking out, ultrasonically cleaning for 10 minutes by adopting absolute ethyl alcohol, and drying by hot air.
An application of a biomedical pure magnesium surface functional structure ion implantation modified layer in degradable bone implantation materials.
The invention has the following beneficial effects:
(1) manganese element is one of trace elements (0.02g/70kg) necessary for human body, promotes the growth and development of bones, participates in the synthesis of various important physiological enzymes in vivo, and has the effects of promoting the metabolism of sugar and fat and resisting oxidation. Calcium is a major element essential to human body and is vital to human health. Therefore, the manganese and the calcium have good biocompatibility. According to the invention, a small amount of manganese and/or calcium is introduced into the bone implant by optimizing the technological parameters of ion implantation, the modified layer as the bone implant can be degraded in a human body, and the degradation product is harmless to the health of the human body, so that the requirements of biological safety are met, and the biocompatibility can be improved.
(2) Pure magnesium contains impurities (the content is less than 0.05%) such as iron, nickel and copper, and serious local corrosion is formed in simulated body fluid due to the potential difference between magnesium and the impurities. According to the invention, manganese and/or calcium elements are uniformly injected to the surface of pure magnesium under optimized process conditions, oxides in the injected modified layer exist in the surface layer to play a corrosion protection role, and metal simple substances exist in the inner layer, so that the magnesium potential of the inner surface layer is promoted, the potential of an impurity phase is reduced, and the uniform corrosion behavior transformation and the corrosion resistance are facilitated to be improved. In addition, the manganese and calcium are injected into the injection modification layer in a double mode, so that the influence of initial local corrosion is relieved, the corrosion resistance is improved, and the biocompatibility is improved.
(3) The modified layer prepared by the invention is soaked in simulated body fluid to form uniformly distributed micro-couple corrosion at the initial stage, the rapid degradation rate is shown, and the accelerated degradation behavior is beneficial to forming a local slightly alkaline environment and releasing magnesium ions. The local alkalescent environment has the implant bacteriostatic effect in the initial stage of operation and promotes the uniform formation and deposition of similar calcium-phosphorus compounds in human bones in a body fluid environment. At the same time, the rapid release of magnesium ions facilitates cell adhesion, growth and proliferation, and tissue regeneration.
(4) The manganese and calcium elements can refine magnesium alloy grains and play an important role in improving the integrity and the mechanical bearing reliability of the magnesium alloy.
(5) The preparation process is environment-friendly, the process parameters can be accurately controlled, the obtained modified layer has a compact and uniform structure, strong binding force with a magnesium substrate, no obvious interface and stable and reliable performance, and the injection process parameters can be adjusted, so that workpieces with different degradation rates can be manufactured according to different requirements, and the preparation method has wide application prospects.
(6) The preparation method provided by the invention has the advantages of simple process, environmental protection and reliability, manganese and/or calcium exist in the form of oxides and simple substances, the oxides exist on the surface layer, the simple substances exist in the inner layer, the pure magnesium can form uniform galvanic corrosion at the initial stage of soaking in simulated body fluid, the deposition of calcium-phosphorus compounds close to human bone components is promoted, the corrosion type is changed into uniform corrosion along with the time extension, the controllable degradation is achieved, the biocompatibility is further improved on the basis of effectively improving the corrosion resistance of the biomedical magnesium, and the application range is expanded.
Drawings
FIG. 1 is a surface morphology and element distribution diagram of a Mn injection modified layer in example 1;
FIG. 2 is a graph showing the composition analysis of Mn element in the Mn injection modified layer in example 1;
FIG. 3 is a graph showing the corrosion morphology and behavior of the Mn injection modified layer of example 1 immersed in a 37 ℃ SBF solution;
FIG. 4 is a surface morphology and elemental distribution diagram of Ca-infused modified layer of example 4;
FIG. 5 is a diagram showing the analysis of the elemental composition of Ca in the Ca injection-modified layer in example 4;
FIG. 6 is a graph showing the corrosion profile of the Ca injection modified layer of example 4 after being immersed in the SBF solution at 37 ℃ for 7 days;
FIG. 7 is a surface morphology and element distribution map of Mn + Ca co-implantation modified layer in example 7;
FIG. 8 is a graph showing the elemental composition of Mn and Ca in the Mn + Ca co-implantation modified layer in example 7;
FIG. 9 is a corrosion morphology of the Mn + Ca co-implant modified layer of example 7 after soaking in the SBF solution at 37 ℃ for 7 days.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
Example 1:
the biomedical pure magnesium surface functional structured ion injection modified layer comprises a manganese modified layer which is subjected to ion injection and is uniformly distributed on the surface of pure magnesium, wherein the manganese modified layer comprises a manganese simple substance positioned on an inner layer and a Mn-MnO mixed layer positioned on a surface layer and the content of manganese oxide of which is increased from inside to outside. The manganese simple substance and the manganese oxide are both doped in the pure magnesium.
A method for preparing a biomedical pure magnesium surface functional structure ion implantation modified layer comprises the following steps:
(1) pretreatment: polishing pure magnesium by adopting metallographic abrasive paper of different models and a polishing machine, placing the polished pure magnesium in an absolute ethyl alcohol solution for ultrasonic treatment for 10 minutes, and drying the polished pure magnesium by hot air;
(2) performing Mn ion implantation on the pretreated sample (the purity of Mn target material is more than 99.9%), and the working vacuum degree is less than or equal to 1 multiplied by 10-4Pa, implantation voltage of 50kV, and implantation dose of 2 × 1016ions/cm2The temperature of the sample matrix during injection was 25 ℃. And (4) sampling after the experiment is finished, ultrasonically cleaning the sample by adopting absolute ethyl alcohol for 10 minutes, and drying the sample by hot air.
Fig. 1 is a surface morphology and component distribution diagram of the modified layer prepared in this example, where the surface of the modified layer is smooth and flat, and the implanted element Mn is uniformly distributed.
FIG. 2 is a structural composition analysis of the modified ion-implanted layer prepared in this example, wherein the thickness of the modified layer containing manganese is 100 nm. The Mn 2p orbital binding energy spectrum chart can be divided into Mn 2p1/2And Mn 2p3/2Peak of spectrum, wherein, Mn 2p3/2The inclusion of manganese in the metallic state (639eV) and manganese in the oxidized state (640.4eV) indicates that Mn after implantation is present in the modified layer in both the metallic and oxidized states. And as the depth increases, the MnO binding energy peak intensity decreases, and the Mn simple substance peak intensity increases, which indicates that MnO exists in the surface layer and has a thickness of about 50nm, and Mn simple substance exists in the inner layer and has a thickness of about 100 nm.
FIG. 3 shows the simulated body fluid (SBF solution, composition: NaCl (8.0 g. L.) of the ion implantation modified layer prepared in this example-1)，KCl(0.4g·L-1)，NaHCO3(0.35g·L-1)，MgCl2·6H2O(0.1g·L-1)， MgSO4·7H2O(0.06g·L-1)，CaCl2(0.14g·L-1)，Na2HPO4(0.06g·L-1)，KH2PO4(0.06 g·L-1) Glucose (1 g. L)-1) pH 7.4), the corrosion degree of the surface of Mg is accelerated due to the even distribution of galvanic corrosion effect between the injected Mn and Mg, (a) after the injection, pitting pits appear on the surface of pure magnesium, and (b) after the soaking for 3 days, the surface of the graph is covered more densely along with the prolonging of the soaking timeThe corrosion product is a calcium-phosphorus compound similar to human bone components, a compact barrier is gradually formed, corrosion of a corrosion medium can be effectively prevented, meanwhile, corrosion behavior is changed from local corrosion to uniform corrosion, and corrosion resistance is effectively improved.
Meanwhile, a pure magnesium workpiece is placed in the simulated body fluid as a comparative example, after soaking in the SBF solution for 168 hours, the weight loss of unmodified pure magnesium is 11.73mg, and the weight loss of the sample in the embodiment is 5.28mg, which shows that the corrosion resistance of the pure magnesium is obviously improved after modification by the method.
Example 2:
this embodiment differs from embodiment 1 only in that the implantation dose is 2 × 1017ions/cm2The sample temperature during injection was 25 ℃. The weight loss of the modified sample after soaking in SBF solution for 168 hours is 6.25 mg.
Example 3:
this example differs from example 1 only in that the sample temperature during injection was 300 ℃. The weight loss of the modified sample after soaking in SBF solution for 168 hours is 3.84 mg.
Example 4:
the biomedical pure magnesium surface functional structure ion implantation modified layer comprises a first calcium modified layer which is subjected to ion implantation and is uniformly distributed on the surface of pure magnesium, wherein the first calcium modified layer is a calcium oxide layer, and the content of calcium oxide in the first calcium modified layer is sequentially increased from inside to outside.
A method for preparing a biomedical pure magnesium surface functional structure ion implantation modified layer comprises the following steps:
(1) pretreatment: polishing a pure magnesium workpiece by adopting metallographic abrasive paper of different models and a polishing machine, placing the polished pure magnesium workpiece in an absolute ethyl alcohol solution for ultrasonic treatment for 10 minutes, and drying the polished pure magnesium workpiece by hot air;
(2) performing Ca ion implantation (the purity of Ca target material is more than 99.9%) on the pretreated sample, and the working vacuum degree is less than or equal to 1 multiplied by 10-4Pa, implantation voltage of 50kV, and implantation dose of 2 × 1016ions/cm2The temperature of the sample matrix during injection was 25 ℃. And (4) sampling after the experiment is finished, ultrasonically cleaning the sample by adopting absolute ethyl alcohol for 10 minutes, and drying the sample by hot air.
As shown in fig. 4, in this embodiment, calcium is uniformly injected into the surface of pure magnesium, and the surface of the modified layer is smooth and flat.
In addition, fig. 5XPS results show that calcium exists as calcium oxide in the prepared modified layer, and the content gradually decreases as the depth increases, as can be seen from the peak intensity. After being soaked in SBF solution for 168 hours, the weight loss of the modified sample is 6.94mg, more corrosion cracks appear on the surface of the sample, and a large amount of corrosion products are covered, as shown in FIG. 6, the corrosion condition is serious.
Example 5:
this example differs from example 4 only in that the implantation dose is 2X 1017ions/cm 2. The weight loss of the modified sample after soaking in SBF solution for 168 hours is 7.30 mg.
Example 6:
this example differs from example 4 only in that the sample matrix temperature is 300 ℃. The weight loss of the modified sample after soaking in SBF solution for 168 hours is 5.19 mg.
Example 7:
a biomedical pure magnesium surface functional structure ion injection modified layer comprises a manganese modified layer which is subjected to ion injection and is uniformly distributed on the surface of pure magnesium, wherein the manganese modified layer comprises a manganese simple substance positioned in an inner layer and a Mn-MnO mixed layer positioned on a surface layer and the content of manganese oxide of which is increased from inside to outside; and the surface of the manganese modified layer is subjected to ion implantation and is uniformly distributed with a second calcium modified layer, and the second calcium modified layer comprises a calcium simple substance positioned in an inner layer and a Ca-CaO mixed layer positioned on a surface layer and gradually increased in calcium oxide content from inside to outside.
A method for preparing a biomedical pure magnesium surface functional structure ion implantation modified layer comprises the following steps:
(1) pretreatment: polishing a pure magnesium workpiece by adopting metallographic abrasive paper of different models and a polishing machine, placing the polished pure magnesium workpiece in an absolute ethyl alcohol solution for ultrasonic treatment for 10 minutes, and drying the polished pure magnesium workpiece by hot air;
(2) performing ion implantation twice (purity of Mn and Ca target material is more than 99.9%) on the pretreated sample, and working vacuum degree is less than or equal to 1 × 10-4Pa, injection voltage of 50kV, manganese firstIon implantation with a dose of 2 × 1016ions/cm2The temperature of the sample matrix is 25 ℃ in the injection process, the calcium ion injection is carried out for the second time, and the injection dosage is 2 multiplied by 1016ions/cm2The temperature of the sample matrix during injection was 25 ℃. And (4) sampling after the experiment is finished, ultrasonically cleaning the sample by adopting absolute ethyl alcohol for 10 minutes, and drying the sample by hot air.
As shown in fig. 7, manganese and calcium are uniformly injected into the surface of pure magnesium, and the surface is dense and uniform.
As shown in fig. 8, after the double injection of manganese and calcium, the manganese element exists in an oxidized state and in a simple substance, and the calcium element exists in a simple substance form in addition to the oxidized state, as compared with example 4.
The standard electrode potential of the calcium element is-2.76V, which is lower than that of the magnesium element (-2.37V), thus avoiding galvanic corrosion of magnesium and relieving the initial corrosion degree to a certain extent. In addition, more calcium is doped into the magnesium matrix, so that the relative content of magnesium is reduced, and the biocompatibility of the magnesium matrix is improved in the aspect of effectively improving the corrosion resistance of the magnesium matrix.
FIG. 9 shows that after manganese and calcium are injected in a double manner and soaked in SBF solution for 168 hours, the surface of a sample is slightly corroded, obvious corrosion cracks do not exist, the surface is smooth, and the corrosion resistance is effectively improved. The weight loss of the modified sample after soaking in SBF solution for 168 hours is 3.24 mg.
Example 8:
this example differs from example 7 only in that the manganese implant and calcium implant process temperatures are both 300 degrees celsius. The weight loss of the modified sample after soaking in SBF solution for 168 hours is 2.33 mg.
Example 9:
the difference between this example and example 7 is only that the implantation doses of Mn and Ca are 2X 1017ions/cm2. The weight loss of the modified sample after soaking in SBF solution for 168 hours is 4.65 mg.
The method comprises the steps of firstly grinding, polishing and cleaning a pure magnesium workpiece to remove a natural oxide film and impurities on the surface. And then, injecting manganese and/or calcium elements with good biocompatibility into the surface of the pure magnesium to obtain a functional structured ion injection modified layer, and finally preparing the ion injection modified layer which is compact in structure and contains metal oxide and simple substance through single/co-injection and process parameter optimization so as to improve the corrosion resistance of the pure magnesium in simulated body fluid and meet the aim of controllable degradation behavior.
Therefore, according to the biomedical pure magnesium surface functional structural ion implantation modified layer and the preparation method and application thereof, biologically safe manganese and/or calcium elements are uniformly injected onto the pure magnesium surface by optimizing process conditions, so that the deposition of calcium-phosphorus compounds close to human bones is promoted, local corrosion is changed into uniform corrosion, controllable degradation is achieved, and the corrosion rate is effectively delayed. The immersion weight loss data shows that the corrosion resistance of the co-injection modified layer of manganese and calcium prepared in example 7 is the best, and is improved by about 4 times compared with pure magnesium. The preparation process is environment-friendly and can be accurately controlled, workpieces with different degradation rates can be manufactured according to requirements, and the application range of the biomedical magnesium is expanded.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
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