CN103276361B - A kind of at magnesium base composite material surface preparation Ti/TiO 2or the method for TiN biocompatibility rete - Google Patents
A kind of at magnesium base composite material surface preparation Ti/TiO 2or the method for TiN biocompatibility rete Download PDFInfo
- Publication number
- CN103276361B CN103276361B CN201310169315.4A CN201310169315A CN103276361B CN 103276361 B CN103276361 B CN 103276361B CN 201310169315 A CN201310169315 A CN 201310169315A CN 103276361 B CN103276361 B CN 103276361B
- Authority
- CN
- China
- Prior art keywords
- magnesium
- composite material
- tio
- base composite
- rete
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000011777 magnesium Substances 0.000 title claims abstract description 116
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 36
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 3
- 239000010936 titanium Substances 0.000 claims abstract description 54
- 239000011159 matrix material Substances 0.000 claims abstract description 40
- 238000000151 deposition Methods 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 238000010891 electric arc Methods 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 18
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 17
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 239000001506 calcium phosphate Substances 0.000 claims description 15
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 15
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 15
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 15
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000004137 magnesium phosphate Substances 0.000 claims description 13
- 229960002261 magnesium phosphate Drugs 0.000 claims description 13
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 13
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007733 ion plating Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 230000003019 stabilising effect Effects 0.000 claims description 7
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 229910052774 Proactinium Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005240 physical vapour deposition Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- 210000001124 body fluid Anatomy 0.000 abstract description 7
- 239000010839 body fluid Substances 0.000 abstract description 7
- 239000012530 fluid Substances 0.000 abstract description 6
- 238000002513 implantation Methods 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 38
- 238000002474 experimental method Methods 0.000 description 18
- 229910000861 Mg alloy Inorganic materials 0.000 description 14
- 210000001519 tissue Anatomy 0.000 description 12
- 241001465754 Metazoa Species 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 241000283973 Oryctolagus cuniculus Species 0.000 description 8
- 230000007170 pathology Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000007541 cellular toxicity Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- -1 poly(lactic acid) Polymers 0.000 description 4
- 231100000820 toxicity test Toxicity 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 210000003205 muscle Anatomy 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of at magnesium base composite material surface acquisition Ti/TiO
2or the method for TiN rete, this rete has good biocompatibility, is combined closely with magnesium matrix material, can stop or delay the corrosion of magnesium matrix material in body fluid.If need to plate Ti/TiO
2layer, be then evacuated down to 3 × 10
-3the vacuum tightness of more than Pa, the pure titanium target that ignites plays arc discharge, and depositing time is 2 ~ 10min.If need to plate TiN layer, be then filled with nitrogen in a vacuum chamber, striking current controls at 50 ~ 100A, and depositing time is 8 ~ 12min.By the Ti/TiO that the method obtains
2or when TiN rete is on active service under biological environment, the slow degraded of magnesium matrix material can be realized, effectively delay magnesium matrix and fluid environment generation chemical reaction, being conducive to organism discharging degraded product in tolerance range, is the operable superficial film with biocompatibility of a kind of magnesium base biological implantation material.
Description
Technical field
The present invention relates to a kind of surface at magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material, the Ti/TiO obtained by vacuum PVD technology
2or the method for TiN protectiveness rete, this rete has good biocompatibility.
Background technology
Biocompatibility evaluates various bio-medical material to be on active service under human body environment the key of behavior, the medical material implanted should meet biological safety, the tissue of human body and the physiological environment requirement of organ can be adapted to, and the reparation realized disease damage tissue and organ or reconstruction.Magnesium base composite material is the medical metal implanted material with good biocompatibility, possess the physics of applicable bone tissue growth, mechanics, chemical synthesis feature performance benefit, compared with the medical metal materials such as existing titanium, stainless steel, cobalt, the content of magnesium in human body is higher, and can metabolism be there is in magnesium under the fluid environment of organism, after body fluid decomposes, form magnesium ion, participate in the catalytic process of body endoenzyme, and excreted by body fluid.Magnesium ion can also promote the deposition of calcium and the formation of osteocyte, and accelerated bone growth closes process, is the bio-medical metal implant material that a class has development prospect.
But in the process that magnesium base composite material is on active service and is degraded under human body fluid environment, can produce various chemical reaction, wherein topmost chemical reaction is:
Mg+2H
2O→M
g(OH)
2+H
2↑。
This reaction can alkalogenic corrosion product and separate out hydrogen, causes tissue local pH value near the magnesium base composite material that implants to change formation alkaline environment, and forms the infringement that subsurface bubble etc. is unfavorable for organized renewing.For the corrosion resistance nature when body material improving magnesium base composite material is on active service under fluid environment, an effective means carries out surface modification to the surface of magnesium base composite material, slow down the corrosion process of magnesium matrix material, the chemical reaction product of organism to magnesium matrix material is made to have the time of an enough adaptation and degraded excretion, thus reduce magnesium substrates to the disadvantageous effect of organism, meet the requirement of biological tissue to embedded material better.
At present, there is the various different surface treatment method for medical magnesium alloy, comprise the broad variety such as chemical conversion film or physical transformations film coating.Patent CN200710159044.9 provides a kind of method of Magnesiumalloy surface modifying, magnesium alloy is immersed in chemical conversion solution chemical reaction occurs, Mg alloy surface first forms one deck chemical conversion film, then prepare again at the skin of this tunic and there is bioactive ceramic layer, play and both improve magnesium matrix corrosion resistance nature, the problem combined between implant and organism can be improved again.Under the thinking of this method, some related art method obtain development & application, patent CN201110361137.6 adopts the method for differential arc oxidization technique and infiltration, inside and outside double-layered compound film is formed at Mg alloy surface, object is internal layer differential arc oxidation layer improves erosion resistance while, outer hydroxyl phosphatic rock, plays the effect improving biocompatibility.Patent CN201210184704.X is also the technique adopting a kind of micro-arc anodic oxidation film and poly(lactic acid) coating, obtain the compound coating of internal layer oxide compound, outer poly(lactic acid), regulate and control the corrosion degradation speed of magnesium alloy and the pH value of ambient body fluid, make coating have well anti-corrosion and biocompatibility.In addition, some other is also had to improve the method for magnesium material surface property.As formed one deck unitary film at Mg alloy surface to improve the technology of corrosion resistance of magnesium alloy energy, patent CN201210381065.6 provides a kind of at Mg alloy surface employing sol-gel process, the method of bio-vitric coating is prepared in thermal treatment after drying, this coating consists of CaO-P2O5-Na2O-AO-BO, and wherein A, B are Zn or Sr.This bio-vitric coating has fine and close corrosion resistant feature, effectively can reduce the degradation rate of magnesium alloy, improves the solidity to corrosion of magnesium alloy.Patent CN201110034306.5 provides a kind of at magnesium surface formation and one or more component alloy amorphous films in Zn, Ca, Mn, Fe, Al, Y or rare earth.Although these unitary films improve the corrosion resistance nature on magnesium material surface, consider as biomaterial, the biocompatibility of its rete is not improved significantly.Other technology additionally provides the method forming multilayer film at magnesium surface, if patent CN200510100004.8 is in the method for the multiple layer metal films such as Mg alloy surface plating aluminium, copper, chromium, nickel, titanium, cobalt, zinc, vanadium or stainless steel.Patent CN201110090572.X forms Mg-Hf by Assisted by Ion Beam CVD (Chemical Vapor Deposition) method at Mg alloy surface, the preparation method of Hf-N, Hf-Si-N Gradient coating, to improve its corrosion-resistant, abrasion resistance properties, and improves its biocompatibility further.
The present invention is directed to the superficial film modification technology of the magnesium base composite material such as magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material exploitation, object it can be used as medical embedded material to be applied in organism environment.According to biological implantation material medically clinical experiment time the Special Circumstances that run into and early stage experimentation on animals basis on, the rete that the present invention designs has two important features: first, rete and magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material realize metallurgical binding, guarantee that the matrix of rete and magnesium base composite material has enough bonding strengths, reach more than 3 months active times; Second, rete can be degraded under arms slowly in interim realization, but can effectively stop or delay magnesium matrix and fluid environment generation chemical reaction, the accumulation the reducing corrosion product especially precipitation of hydrogen in chemical reaction, slows down producing subsurface bubble and be beneficial to organism can be discharged by metabolism in tolerance range.Based on the above biological handling characteristics implanting magnesium base composite material superficial film, present invention employs well in advance magnesium base composite material embedded material exemplar, then plate a layer thickness at the Ti/TiO of 0.1 μm ~ 10 μm by the physical gas phase deposition technology under vacuum condition at material surface
2or TiN rete; metal titanium and oxide compound thereof or layer of nitride film be the clinical middle material with good biocompatibility and resistance to fluid environment characteristic obtaining ripe application originally; be plated in the surface of magnesium substrates; both can not affect the biocompatibility of material, can be implemented in again the protection to magnesium substrates in certain active time.Simultaneously, because the rete thickness obtained through physical gas phase deposition technology can artificial adjustment, therefore can according to requirement duration of service, determine the thickness of the upper layer of different medical embedded magnesium substrates by experiment, time range interior surface layers can slow down the degradation rate of base material under arms, the general active time guaranteeing more than 3 months, makes the degradation behavior of magnesium substrates become the process that can control.
Summary of the invention
It is short that technical problem to be solved by this invention is to provide a kind of technical process, and what feasibility was strong obtains Ti/TiO at magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material surface
2or the method for TiN rete.
In order to solve the problems of the technologies described above, provided by the invention at magnesium base composite material surface acquisition Ti/TiO
2or the method for TiN rete, it is characterized in that: comprise following steps:
(1) magnesium base composite material, in vacuum arc deposition （VAD） equipment after effects on surface cleaning carries out surface coating, and vacuum multi-arc ion plating machine is evacuated down to 6.0 × 10
-3the vacuum tightness of more than Pa, be then heated to 200 DEG C ~ 220 DEG C, be filled with argon gas, partial pressure of ar gas controls at 0.4Pa ~ 0.6Pa, and connect magnesium base composite material grid bias power supply, bias value is 100V ~ 250V, tentatively bombards 2min ~ 3min to magnesium base composite material;
(2) if need to plate Ti/TiO
2layer, then, after step (1), be evacuated down to 3 × 10 again
-3the vacuum tightness of more than Pa, magnesium alloy or magnesium base composite material bias voltage are adjusted to 150V ~ 400V, and meanwhile, the pure titanium target that ignites plays arc discharge, and striking current controls at 30A ~ 80A, and depositing time is 2min ~ 10min, now obtains pure Ti rete; Place in an atmosphere after being taken out from vacuum chamber by the product having plated Ti layer, on Ti layer surface, natural oxidation obtains TiO
2layer, thus obtain Ti/TiO
2layer;
(3) if need to plate TiN layer, then after step (1), be filled with nitrogen in a vacuum chamber, keep nitrogen partial pressure at 0.5Pa ~ 1Pa, take up space volume ratio 45% ~ 50%, magnesium base composite material bias value is at 50V ~ 250V, and striking current controls at 50A ~ 100A, and depositing time is 8min ~ 12min;
(4), other correlation parameters used in coating process are set as: arc source working current: 30A ~ 100A, target quantity 4 ~ 8, target diameter 60mm ~ 100mm, target current scope 30A ~ 100A, during work, stabilising arc electric current is 50A ~ 60A, target current potential-18V ~-20V, magnesium base composite material Heating temperature is 400 DEG C ~ 450 DEG C.
Above-mentioned steps refers to the surface cleaning of magnesium base composite material in (1): first by magnesium base composite material grinding and polishing on abrasive paper for metallograph, remove surface oxidation film, then put into raw spirit to clean, or adopt ultrasonic cleaning apparatus to clean, guarantee magnesium matrix material surface cleaning oxide-free.
What adopt technique scheme obtains Ti/TiO on magnesium base composite material surface
2or the method for TiN rete, Ti/TiO can be obtained at magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material surface
2the rete of layer or TiN layer.Without plated film and the magnesium matrix material contrast after plated film, as seen after plated film, originally the magnesium matrix material on silvery white surface changes into golden yellow rete completely.Find that the erosion resistance in human body simulation body fluid of the magnesium base composite material after plated film obtains through overtesting to increase substantially, liberation of hydrogen speed reduces more than 70%.By the observation of cell toxicity test, animal Implantation Test, this Ti/TiO
2the rete of layer or TiN layer, to organism nontoxicity, can use completely in organism.
Advantage of the present invention and positively effect are: the present invention adopts vacuum arc deposition （VAD） method, and the feature for magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material sets suitable coating process, obtains the Ti/TiO with biocompatibility
2layer or TiN layer rete, technical process is short, and feasibility is strong.This rete is combined closely with magnesium matrix material, magnesium matrix material after plated film can obtain the active time of more than 16 weeks under biological fluid environment, within 3 ~ 4 weeks, extend more than 4 times to active time than non-Coating Materials, reach biological bone embedded material military service phase requirement.The slow degraded of magnesium matrix material can be realized under arms in process simultaneously, magnesium matrix and fluid environment generation chemical reaction are effectively delayed, decrease the precipitation of hydrogen in chemical reaction, be conducive to organism bubble can be discharged in tolerance range, being suitable as biomaterial surface Coating Materials to use, is the operable top coat of magnesium base biological implantation material of a kind of advanced person.
Accompanying drawing explanation
Fig. 1 is the silvery white surface magnesium matrix material without plated film in the present invention.
Fig. 2 is the golden surface magnesium matrix material in the present invention after plated film.
Fig. 3 is the Ti/TiO that the embodiment of the present invention 1 obtains
2the electron micrograph of rete side.
Fig. 4 is the electron micrograph in the TiN rete front that the embodiment of the present invention 2 obtains.
Fig. 5 is that coating cell toxicity test in 10%, 50% and 100% nutrient solution that the embodiment of the present invention 1 obtains obtains negative experimental result.
Fig. 6 is the embodiment of the present invention 2 after animal body experiment, to the experiment heart of the rabbit tissue slice without pathology.
Fig. 7 is the embodiment of the present invention 2 after animal body experiment, to the experiment liver of the rabbit tissue slice without pathology.
Fig. 8 is the embodiment of the present invention 2 after animal body experiment, to the experiment kidney of the rabbit tissue slice without pathology.
Fig. 9 is the embodiment of the present invention 2 after animal body experiment, to the experiment muscle of the rabbit tissue slice without pathology.
Embodiment
What the present invention adopted obtains Ti/TiO on magnesium base composite material surface
2or the method for TiN rete, at the Ti/TiO that the surface of magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material is obtained by vacuum PVD technology
2or TiN rete, its film coating method comprises following steps:
(1), the cleaning of magnesium base composite material, first by magnesium base composite material grinding and polishing on sand paper, remove surface oxidation film, then put into raw spirit and clean, also ultrasonic cleaning apparatus can be adopted to clean, guarantee magnesium base composite material surface cleaning oxide-free;
(2), in vacuum arc deposition （VAD） equipment surface coating is carried out to the magnesium base composite material through above-mentioned steps (1) surface cleaning, vacuum multi-arc ion plating machine is evacuated down to 6.0 × 10
-3the vacuum tightness of more than Pa, be then heated to 200 DEG C ~ 220 DEG C, be filled with argon gas, partial pressure of ar gas controls at 0.4Pa ~ 0.6Pa, and connect magnesium base composite material grid bias power supply, bias value is 100V ~ 250V, tentatively bombards 2min ~ 3min to magnesium substrates;
(3) if need to plate Ti/TiO
2layer, then, after step (2), be evacuated down to 3 × 10 again
-3the vacuum tightness of more than Pa, magnesium base composite material bias voltage is adjusted to 150V ~ 400V, simultaneously, the pure titanium target that ignites plays arc discharge, striking current controls at 30A ~ 80A, and depositing time is 2min ~ 10min, now obtains pure Ti rete, place in an atmosphere after the product having plated Ti layer is taken out from vacuum chamber, just can obtain TiO at Ti layer surface natural oxidation
2layer, thus obtain Ti/TiO
2layer;
(4) if need to plate TiN layer, then after step (2), be filled with nitrogen in a vacuum chamber, keep nitrogen partial pressure at 0.5Pa ~ 1Pa, take up space volume ratio 45% ~ 50%, magnesium base composite material bias value is at 50 ~ 250V, and striking current controls at 50A ~ 100A, and depositing time is 8min ~ 12min;
(5), other correlation parameters used in coating process are set as: arc source working current: 30A ~ 100A, target quantity 4 ~ 8, target diameter 60mm ~ 100mm, target current scope 30A ~ 100A, during work, best stabilising arc electric current is 50A ~ 60A, target current potential-18V ~-20V, magnesium matrix heating materials temperature is 400 DEG C ~ 450 DEG C.
What adopt technique scheme obtains Ti/TiO on magnesium base composite material surface
2or the method for TiN rete, Ti/TiO can be obtained at magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material surface
2the rete of layer or TiN layer.See Fig. 1 and Fig. 2 without plated film and the magnesium matrix material contrast after plated film, as seen after plated film, originally the magnesium matrix material on silvery white surface changes into golden yellow rete completely.Find that the erosion resistance in human body simulation body fluid of the magnesium base composite material after plated film obtains through overtesting to increase substantially, liberation of hydrogen speed reduces more than 70%.By the observation of cell toxicity test, animal Implantation Test, this Ti/TiO
2the rete of layer or TiN layer, to organism nontoxicity, can use completely in organism.
Below in conjunction with the drawings and specific embodiments, the present invention is elaborated.
Embodiment 1:
Adopt in magnesium matrix and add the matrix material of hydroapatite particles as body material, first by the polishing on sand paper of magnesium matrix material, remove surface oxidation film, then put into raw spirit to clean, then in ultrasonic cleaning apparatus, add raw spirit clean further, guarantee magnesium matrix material surface cleaning oxide-free.In vacuum arc deposition （VAD） equipment, surface coating is carried out to magnesium/hydroxyapatite composite material.Vacuum multi-arc ion plating machine is evacuated down to 6.0 × 10
-3pa vacuum tightness, is then heated to 200 DEG C, is filled with argon gas, and partial pressure of ar gas controls at 0.5Pa, and connect magnesium matrix material grid bias power supply, bias value is 100V, tentatively bombards 2min to magnesium substrates.Again be evacuated down to 3 × 10
-3the vacuum tightness of more than Pa, magnesium/hydroxyapatite composite material bias voltage is adjusted to 150V, and the pure titanium target that ignites plays arc discharge, and striking current controls at 30A, and depositing time is 2min, obtains pure Ti rete.Place in an atmosphere after the product having plated Ti layer is taken out from vacuum chamber, just can obtain the TiO of Ti layer surface natural oxidation
2layer, thus obtain Ti/TiO on magnesium/hydroxyapatite composite material surface
2layer.In the present embodiment, arc source working current is 30A, target quantity 4, target diameter 60mm, and target current controls at 30A, and during work, best stabilising arc electric current is 50A, and target current potential-20V, magnesium/hydroxyapatite composite material Heating temperature is 400 DEG C.The Ti/TiO that the present embodiment obtains
2layer electron photomicrograph is shown in Fig. 3.See the experimental result that Fig. 5, Fig. 5 are coating cell toxicity test acquisition feminine genders in 10%, 50% and 100% nutrient solution that the embodiment of the present invention 1 obtains.
Embodiment 2:
Adopt in magnesium matrix and add the matrix material of tricalcium phosphate particle as body material, first by magnesium base composite material polishing on sand paper, remove surface oxidation film, then put into raw spirit to clean, then in ultrasonic cleaning apparatus, add raw spirit clean further, guarantee magnesium matrix material surface cleaning oxide-free.In vacuum arc deposition （VAD） equipment, surface coating is carried out to magnesium/tricalcium phosphate composite material.Vacuum multi-arc ion plating machine is evacuated down to 6.0 × 10
-3the vacuum tightness of more than Pa, is then heated to 200 DEG C, is filled with argon gas, and partial pressure of ar gas controls at 0.5Pa, and connect magnesium matrix material grid bias power supply, bias value is 250V, tentatively bombards 3min to magnesium substrates; Be filled with nitrogen in a vacuum chamber, keep nitrogen partial pressure at 1Pa, take up space volume ratio 45%, magnesium matrix material 250V, and striking current controls at 100A, and depositing time is 12min, obtains TiN rete.In the present embodiment, arc source working current: 100A, target quantity 8, target diameter 100mm, target current is 100A, and during work, best stabilising arc electric current is 60A, and target current potential-20V, magnesium/tricalcium phosphate composite material Heating temperature is 450 DEG C.The TiN rete electron photomicrograph that the present embodiment obtains is shown in Fig. 4.Fig. 6 is the embodiment of the present invention 2 after animal body experiment, to the experiment heart of the rabbit tissue slice without pathology.Fig. 7 is the embodiment of the present invention 2 after animal body experiment, to the experiment liver of the rabbit tissue slice without pathology.Fig. 8 is the embodiment of the present invention 2 after animal body experiment, to the experiment kidney of the rabbit tissue slice without pathology.Fig. 9 is the embodiment of the present invention 2 after animal body experiment, to the experiment muscle of the rabbit tissue slice without pathology.
Embodiment 3:
Adopt in magnesium matrix and add the matrix material of hydroapatite particles as body material, first by the polishing on sand paper of magnesium matrix material, remove surface oxidation film, then put into raw spirit to clean, then in ultrasonic cleaning apparatus, add raw spirit clean further, guarantee magnesium/hydroxyapatite composite material surface cleaning oxide-free.Surface coating is carried out in vacuum arc deposition （VAD） equipment.Vacuum multi-arc ion plating machine is evacuated down to 6.0 × 10
-3the vacuum tightness of more than Pa, is then heated to 210 DEG C, is filled with argon gas, and partial pressure of ar gas controls at 0.4Pa, and connect magnesium/hydroxyapatite composite material grid bias power supply, bias value is 250V, tentatively bombards 3min to magnesium substrates; Again be evacuated down to 3 × 10
-3the vacuum tightness of more than Pa, magnesium/hydroxyapatite composite material bias voltage is adjusted to 400V, and meanwhile, the pure titanium target that ignites plays arc discharge, and striking current controls at 80A, and depositing time is 10min, obtains pure Ti rete.Place in an atmosphere after the product having plated Ti layer is taken out from vacuum chamber, just can obtain TiO at Ti layer surface natural oxidation
2layer, thus obtain Ti/TiO
2layer.In the present embodiment, arc source working current is 100A, target quantity 8, target diameter 100mm, target current scope 100A, and during work, best stabilising arc electric current is 60A, and target current potential-18V, magnesium/hydroxyapatite composite material Heating temperature is 450 DEG C.
Embodiment 4:
Adopt in magnesium matrix and add the matrix material of tricalcium phosphate particle as body material, first by magnesium base composite material polishing on sand paper, remove surface oxidation film, then put into raw spirit to clean, then in ultrasonic cleaning apparatus, add raw spirit clean further, guarantee magnesium matrix material surface cleaning oxide-free.In vacuum arc deposition （VAD） equipment, surface coating is carried out to magnesium/tricalcium phosphate composite material.Vacuum multi-arc ion plating machine is evacuated down to 6.0 × 10
-3the vacuum tightness of more than Pa, is then heated to 220 DEG C, is filled with argon gas, and partial pressure of ar gas controls at 0.6Pa, and connect magnesium matrix material grid bias power supply, bias value is 100V, tentatively bombards 2min to magnesium substrates; Be filled with nitrogen in a vacuum chamber, keep nitrogen partial pressure at 0.5Pa, take up space volume ratio 50%, and magnesium matrix material bias value is at 50V, and striking current controls at 50A, and depositing time is 8min, obtains TiN rete.Arc source working current: 30A in the present embodiment, target quantity 4, target diameter 60mm, target current scope 30A, during work, best stabilising arc electric current is 50A, and target current potential-18V, magnesium/tricalcium phosphate composite material Heating temperature is 400 DEG C.
Claims (2)
1. one kind obtains Ti/TiO on magnesium base composite material surface
2or the method for TiN rete, at the Ti/TiO that the surface of magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material is obtained by vacuum PVD technology
2or TiN rete, is characterized in that: comprise following steps:
(1) magnesium base composite material, in vacuum arc deposition （VAD） equipment after effects on surface cleaning carries out surface coating, and vacuum multi-arc ion plating machine is evacuated down to 6.0 × 10
-3the vacuum tightness of more than Pa, be then heated to 200 DEG C ~ 220 DEG C, be filled with argon gas, partial pressure of ar gas controls at 0.4Pa ~ 0.6Pa, and connect magnesium base composite material grid bias power supply, bias value is 100V ~ 250V, tentatively bombards 2min ~ 3min to magnesium base composite material;
(2) if need to plate Ti/TiO
2layer, then, after step (1), be evacuated down to 3 × 10 again
-3the vacuum tightness of more than Pa, magnesium base composite material bias voltage is adjusted to 150V ~ 400V, and meanwhile, the pure titanium target that ignites plays arc discharge, and striking current controls at 30A ~ 80A, and depositing time is 2min ~ 10min, now obtains pure Ti rete; Place in an atmosphere after being taken out from vacuum chamber by the product having plated Ti layer, on Ti layer surface, natural oxidation obtains TiO
2layer, thus obtain Ti/TiO
2layer;
(3) if need to plate TiN layer, then after step (1), be filled with nitrogen in a vacuum chamber, keep nitrogen partial pressure at 0.5Pa ~ 1Pa, the volume ratio that takes up space is 45% ~ 50%, magnesium base composite material bias value is at 50V ~ 250V, and striking current controls at 50A ~ 100A, and depositing time is 8min ~ 12min;
(4), other correlation parameters used in coating process are set as: arc source working current: 30A ~ 100A, target quantity 4 ~ 8, target diameter 60mm ~ 100mm, target current scope 30A ~ 100A, during work, stabilising arc electric current is 50A ~ 60A, target current potential-18V ~-20V, magnesium base composite material Heating temperature is 400 DEG C ~ 450 DEG C.
2. according to claim 1 at magnesium base composite material surface acquisition Ti/TiO
2or the method for TiN rete, it is characterized in that: above-mentioned steps refers to the surface cleaning of magnesium base composite material in (1): first by magnesium base composite material grinding and polishing on sand paper, remove surface oxidation film, then put into raw spirit to clean, or adopt ultrasonic cleaning apparatus to clean, guarantee magnesium matrix material surface cleaning oxide-free.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310169315.4A CN103276361B (en) | 2013-05-09 | 2013-05-09 | A kind of at magnesium base composite material surface preparation Ti/TiO 2or the method for TiN biocompatibility rete |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310169315.4A CN103276361B (en) | 2013-05-09 | 2013-05-09 | A kind of at magnesium base composite material surface preparation Ti/TiO 2or the method for TiN biocompatibility rete |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103276361A CN103276361A (en) | 2013-09-04 |
| CN103276361B true CN103276361B (en) | 2015-08-05 |
Family
ID=49058972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310169315.4A Active CN103276361B (en) | 2013-05-09 | 2013-05-09 | A kind of at magnesium base composite material surface preparation Ti/TiO 2or the method for TiN biocompatibility rete |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103276361B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107723680B (en) * | 2017-08-28 | 2019-10-29 | 南昌大学 | A kind of preparation method of the regulatable Mg alloy surface multi-stage nano coating of corrosion resistance |
| CN109731134A (en) * | 2018-12-26 | 2019-05-10 | 中南大学湘雅二医院 | A kind of modified magnesium alloy bone implant material in surface and preparation method |
| CN111378942A (en) * | 2018-12-28 | 2020-07-07 | 芜湖美的厨卫电器制造有限公司 | Anti-corrosion treatment process for metal surface, metal workpiece, electric heating pipe and electric water heater |
| CN114807839B (en) * | 2022-04-25 | 2023-03-14 | 南昌大学 | Stepped degradation magnesium alloy barrier film for dentistry and preparation method thereof |
| CN115006601A (en) * | 2022-06-13 | 2022-09-06 | 上海锐畅医疗科技有限公司 | Antibacterial nano composite coating and preparation method thereof |
| CN115478274A (en) * | 2022-10-10 | 2022-12-16 | 西安工业大学 | Protection method and protection coating for avoiding galvanic corrosion of titanium alloy and dissimilar metal |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0663087B2 (en) * | 1987-12-23 | 1994-08-17 | 工業技術院長 | Method for forming titanium nitride film |
-
2013
- 2013-05-09 CN CN201310169315.4A patent/CN103276361B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| AZ91C镁合金表面Ti-TiN复合镀层的阴极多弧离子镀法制备与表征;王成龙等;《腐蚀与防护》;20080430;第29卷(第4期);第182-184页 * |
| 镁合金电弧离子镀镀金属氮化物薄膜的研究;熊光连;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20120715(第7期);第B022-187页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103276361A (en) | 2013-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103276361B (en) | A kind of at magnesium base composite material surface preparation Ti/TiO 2or the method for TiN biocompatibility rete | |
| Li et al. | Corrosion resistance of glucose-induced hydrothermal calcium phosphate coating on pure magnesium | |
| Ali et al. | Surface modification and cytotoxicity of Mg-based bio-alloys: An overview of recent advances | |
| Narayanan et al. | Electrochemical nano-grained calcium phosphate coatings on Ti–6Al–4V for biomaterial applications | |
| CN101461964B (en) | Bioactivity surface modification method of biological medical degradable magnesium alloy | |
| CN102618829B (en) | Medical magnesium alloy material with amorphous film and preparation method thereof | |
| CN101244291B (en) | Magnesium or magnesium alloy material with complex gradient layer and preparation thereof | |
| Lee et al. | The biocompatibility of HA thin films deposition on anodized titanium alloys | |
| Wang et al. | Biodegradable shape memory alloys: Progress and prospects | |
| CN107119260B (en) | A kind of bone implant magnesium-copper coating and preparation method thereof | |
| CN102286767B (en) | Composite coating on surface of magnesium alloy biological implant material and preparation method thereof | |
| CN103911644A (en) | Micro-arc oxidation electrolyte and micro-arc oxidation method for titanium alloys | |
| CN106902391A (en) | A kind of magnesium alloy is implanted into composite material and its preparation and application | |
| CN103372232A (en) | Micro-arc oxidation self-sealing hole active coating of magnesium-based implant material and preparation method of micro-arc oxidation self-sealing hole active coating | |
| CN107829123B (en) | Aluminum alloy with double-layer coating on surface and preparation method and application thereof | |
| CN102181842A (en) | Method for modifying titanium surface | |
| Dou et al. | Effects of calcium salts on microstructure and corrosion behavior of micro-arc oxidation coatings on Mg-2Zn-1Ca-0.8 Mn alloy | |
| JP6154884B2 (en) | Strontium-containing coating for body implants | |
| Wu et al. | Microstructural evolution and biological properties of PEO coating on SLM-prepared NiTi alloy | |
| CN105200413B (en) | A kind of preparation method of magnesium alloy surface calcium phosphor tin composite coating | |
| Baigonakova et al. | Structure, cytocompatibility and biodegradation of nanocrystalline coated Mg–Ca–Zn alloys | |
| CN108103546B (en) | A kind of controlled degradation magnesium-based functionally graded material and preparation method thereof | |
| CN104178765A (en) | Method for preparing controlled degradation metal composite coating on surface of medical magnesium alloy | |
| Oladijo et al. | An Overview of Sputtering Hydroxyapatite for BiomedicalApplication | |
| Bai et al. | Microwave plasma oxidation of near-equiatomic NiTi alloy for obtaining low-Ni TiO2 coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240522 Address after: Room 140, Building 1, R&D Headquarters, Central South University Science and Technology Park, Yingzuo Road, Yuelu Street, Yuelu District, Changsha City, Hunan Province, 410006 Patentee after: Changsha magnesium New Material Technology Co.,Ltd. Country or region after: China Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: CENTRAL SOUTH University Country or region before: China |