CN103276361A - Method for preparing Ti/TiO2 or TiN biocompatible film on surface of magnesium matrix composite - Google Patents
Method for preparing Ti/TiO2 or TiN biocompatible film on surface of magnesium matrix composite Download PDFInfo
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- CN103276361A CN103276361A CN2013101693154A CN201310169315A CN103276361A CN 103276361 A CN103276361 A CN 103276361A CN 2013101693154 A CN2013101693154 A CN 2013101693154A CN 201310169315 A CN201310169315 A CN 201310169315A CN 103276361 A CN103276361 A CN 103276361A
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000011777 magnesium Substances 0.000 title claims abstract description 115
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000011159 matrix material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 34
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 10
- 239000010936 titanium Substances 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000008021 deposition Effects 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 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
- 238000000151 deposition Methods 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 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
- 230000003647 oxidation Effects 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
- 238000010891 electric arc Methods 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000010839 body fluid Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 210000001124 body fluid Anatomy 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- 239000007943 implant Substances 0.000 abstract description 6
- 239000012620 biological material Substances 0.000 abstract description 3
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 239000007857 degradation product Substances 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 34
- 239000000463 material Substances 0.000 description 21
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 16
- 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 description 16
- 229910000861 Mg alloy Inorganic materials 0.000 description 14
- 239000001506 calcium phosphate Substances 0.000 description 14
- 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 description 14
- 229940078499 tricalcium phosphate Drugs 0.000 description 14
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 14
- 235000019731 tricalcium phosphate Nutrition 0.000 description 14
- 239000004137 magnesium phosphate Substances 0.000 description 12
- 229960002261 magnesium phosphate Drugs 0.000 description 12
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 12
- 235000010994 magnesium phosphates Nutrition 0.000 description 12
- 210000001519 tissue Anatomy 0.000 description 12
- 241001465754 Metazoa Species 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 241000283973 Oryctolagus cuniculus Species 0.000 description 8
- 230000007170 pathology Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 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
- 238000002513 implantation 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
- 239000000126 substance Substances 0.000 description 4
- 231100000820 toxicity test Toxicity 0.000 description 4
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 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
- 210000000988 bone and bone Anatomy 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000013495 cobalt Nutrition 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
- 239000012567 medical material Substances 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
- 238000002360 preparation method Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 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 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
- 239000013060 biological fluid 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
- 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
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001727 in vivo Methods 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
- 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
- 230000002035 prolonged effect Effects 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
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000008467 tissue growth Effects 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
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- Physical Vapour Deposition (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a method for preparing a Ti/TiO2 or TiN biocompatible film on the surface of a magnesium matrix composite. The film has excellent biocompatibility, is tightly combined with the magnesium matrix material and can be used for stopping or delaying the corrosion of the magnesium matrix material in body fluid. If a Ti/TiO2 layer needs to be plated, the vacuum degree is above 3*10<-3> Pa through vacuumization, a pure titanium target is ignited for arc striking and discharging, and the deposition time is 2-10 minutes. If a TiN layer needs to be plated, nitrogen is introduced into a vacuum chamber, the arc striking current is controlled to be 50-100A, and the deposition time is 8-12 minutes. When the Ti/TiO2 or TiN film obtained by using the method is on service under a living body environment, the purpose of slowly degrading the magnesium matrix material can be reached, a chemical reaction between the magnesium matrix and the body fluid environment is effectively delayed, and the living body can discharge degradation products within a sustainable range; and the Ti/TiO2 or TiN film is a surface film which can be applied to magnesium matrix implant biomaterials and has biocompatibility.
Description
Technical field
The present invention relates to a kind of surface at magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material, by the Ti/TiO of physical vacuum gas phase deposition technology acquisition
2Or the method for TiN protectiveness rete, this rete has excellent biological compatibility.
Background technology
Biocompatibility is the key of estimating the military service behavior under the human body environment of various bio-medical materials, the medical material that implants should satisfy biological safety, the physiological environment requirement of tissue and the organ of human body be can adapt to, and reparation or the reconstruction of tissue and organ realized disease is decreased.Magnesium base composite material is the medical metal embedded material with good biocompatibility, the physics, mechanics, the chemical over-all properties advantage that possess suitable bone tissue growth, compare with medical metal materials such as existing titanium, stainless steel, cobalts, the content of magnesium in human body is higher, and metabolism can take place in magnesium under the body fluid environment of organism, after body fluid decomposes, form magnesium ion, participate in the catalytic process of body endoenzyme, and excrete by body fluid.Magnesium ion can also promote the deposition of calcium and the formation of osteocyte, and accelerated bone growth is closed 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, can produce various chemical reactions under the human body fluid environment, wherein topmost chemical reaction is:
Mg+2H
2O→M
g(OH)
2+H
2↑。
The alkalogenic corrosion product of this reaction meeting and separate out hydrogen causes near the magnesium base composite material that implants the tissue local pH value formation alkaline environment that changes, and formation subsurface bubble etc. is unfavorable for the infringement of organized renewing.Corrosion resistance nature when being on active service under the body fluid environment for the body material that improves magnesium base composite material, an effective means is that surface modification is carried out on the surface of magnesium base composite material, slow down the corrosion process of magnesium matrix material, make organism that the time of enough adaptation and degraded drainage be arranged the chemical reaction product of magnesium matrix material, thereby reduce magnesium substrates to the disadvantageous effect of organism, satisfy biological tissue better to the requirement of embedded material.
At present, various surface treatment method at medical magnesium alloy is arranged, comprise broad varietys such as chemical conversion film or physics conversion film coating.Patent CN200710159044.9 provides a kind of method of Magnesiumalloy surface modifying, magnesium alloy immersed chemical reaction takes place in the chemical conversion solution, on Mg alloy surface, form one deck chemical conversion film earlier, then at the ceramic layer of the outer refabrication biologically active of this tunic, play and both improve the magnesium matrix corrosion resistance nature, can improve the problem of combination between implant and the organism again.Under the thinking of this method, some related art method have obtained exploitation and have used, patent CN201110361137.6 adopts the method for differential arc oxidization technique and infiltration, form inside and outside double-layered compound film at Mg alloy surface, purpose is when internal layer differential arc oxidation layer improves erosion resistance, outer hydroxyl phosphatic rock plays the effect that improves biocompatibility.Patent CN201210184704.X also is the technology that adopts 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 rate of magnesium alloy and the pH value of ambient body fluid, make coating have good anti-corrosion and biocompatibility.In addition, also have some other to improve the method for magnesium material surface property.As forming the technology that one deck unitary film improves the corrosion resistance of magnesium alloy energy at Mg alloy surface, patent CN201210381065.6 provides a kind of and has adopted sol-gel process at Mg alloy surface, thermal treatment prepares the method for bio-vitric coating 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, can effectively reduce the degradation rate of magnesium alloy, improves the solidity to corrosion of magnesium alloy.Patent CN201110034306.5 provides a kind of one or more component alloy amorphous films in magnesium surface formation and Zn, Ca, Mn, Fe, Al, Y or rare earth.Though these unitary films have improved the corrosion resistance nature on magnesium material surface, consider that as biomaterial the biocompatibility of its rete is not improved significantly.The other technology also provides the method that forms multilayer film at magnesium surface, as the method for patent CN200510100004.8 at multiple layer metal films such as Mg alloy surface plating aluminium, copper, chromium, nickel, titanium, cobalt, zinc, vanadium or stainless steels.Patent CN201110090572.X forms Mg-Hf by the Assisted by Ion Beam CVD (Chemical Vapor Deposition) method at Mg alloy surface, Hf-N, and the preparation method of Hf-Si-N multi-gradient coating improving its corrosion-resistant, abrasion resistance properties, and further improves its biocompatibility.
The present invention is directed to the superficial film modification technology of magnesium base composite materials such as magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material exploitation, purpose is it will be used in vivo in the environment as medical embedded material.On the Special Circumstances that run into when the clinical experiment medically according to biological implantation material and the early stage experimentation on animals basis, the rete of the present invention's design has two important features: first, rete and magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material is realized metallurgical binding, the matrix of guaranteeing rete and magnesium base composite material has enough bonding strengths, reaches active time more than 3 months; Second, rete interim realization is under arms degraded slowly, but can stop or delay magnesium matrix and body fluid environment generation chemical reaction effectively, the accumulation that reduces corrosion product is the separating out of hydrogen in the chemical reaction especially, produces subsurface bubble and be beneficial to organism and discharge by metabolism in tolerance range but slow down.Based on the above biological handling characteristics of implanting the magnesium base composite material superficial film, the present invention has adopted and has carried out magnesium base composite material embedded material exemplar in advance, plates a layer thickness at the Ti/TiO of 0.1 μ m～10 μ m by the physical gas phase deposition technology under the vacuum condition at material surface then
2Perhaps TiN rete; metal titanium and oxide compound thereof or layer of nitride film were exactly the clinical middle ripe material of using with good biocompatibility and the environmental characteristics of anti-body fluid that obtains originally; it is plated in the surface of magnesium substrates; neither can influence the biocompatibility of material, can be implemented in the interior protection to magnesium substrates of certain active time again.Simultaneously, because the rete thickness that obtains through physical gas phase deposition technology can artificial adjustment, therefore can be according to requirement duration of service, come to determine the thickness of the upper layer of different medical embedded magnesium substrates by experiment, the time range interior surface layers can be slowed down the degradation rate of base material under arms, generally can guarantee the active time more than 3 months, make the degradation behavior of magnesium substrates become the process that to control.
Summary of the invention
It is short that technical problem to be solved by this invention provides 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), in vacuum arc deposition equipment, the magnesium base composite material after the surface cleaning is carried out surface coating, vacuum arc deposition film machine is evacuated down to 6.0 * 10
-3The vacuum tightness that Pa is above is heated to 200 ℃～220 ℃ then, charges into argon gas, and partial pressure of ar gas is controlled at 0.4Pa～0.6Pa, connects the magnesium base composite material grid bias power supply, and bias value is 100V～250V, and magnesium base composite material is tentatively bombarded 2min～3min;
(2), plate Ti/TiO if desired
2Layer then in step (1) afterwards, is evacuated down to 3 * 10 again
-3The vacuum tightness that Pa is above, magnesium alloy or magnesium base composite material bias voltage are adjusted to 150V～400V, and simultaneously, the pure titanium target that ignites plays arc discharge, and striking current is controlled at 30A～80A, and depositing time is 2min～10min, obtains pure Ti rete this moment; The product that has plated the Ti layer is taken out the back in atmosphere, place from vacuum chamber, obtain TiO at Ti laminar surface natural oxidation
2Layer, thus Ti/TiO obtained
2Layer;
(3), plate the TiN layer if desired, then in step (1) afterwards, in vacuum chamber, charge into nitrogen, keep nitrogen partial pressure at 0.5Pa～1Pa, volume ratio 45%～50% takes up space, the magnesium base composite material bias value is at 50V～250V, and striking current is controlled at 50A～100A, and depositing time is 8min～12min;
(4), other correlation parameters that use in coating process are set at: arc source working current: 30A～100A, 4～8 of target quantity, target diameter 60mm～100mm, target range of current 30A～100A, the stabilising arc electric current is 50A～60A during work, target current potential-18V～-20V, the magnesium base composite material Heating temperature is 400 ℃～450 ℃.
Surface cleaning to magnesium base composite material in the above-mentioned steps (1) refers to: earlier with magnesium base composite material grinding and polishing on abrasive paper for metallograph, remove surface oxidation film, putting into raw spirit then cleans, or adopt ultrasonic cleaning apparatus to clean, guarantee magnesium matrix material surface cleaning oxide-free.
That adopts technique scheme obtains Ti/TiO on the magnesium base composite material surface
2Or the method for TiN rete, can obtain Ti/TiO at magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material surface
2The rete of layer or TiN layer.Without plated film with through the magnesium matrix material contrast after the plated film, as seen pass through plated film after, originally silvery white surperficial magnesium matrix material has changed into golden yellow rete fully.Magnesium base composite material after overtesting is found plated film erosion resistance in human body simulation body fluid obtains to increase substantially, and 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 can use in organism fully to the organism nontoxicity.
Advantage of the present invention and positively effect are: the present invention adopts the vacuum arc deposition method, sets suitable coating process at the characteristics of magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material, has obtained to have the Ti/TiO of biocompatibility
2Layer or TiN tunic layer, technical process is short, and feasibility is strong.This rete is combined closely with the magnesium matrix material, magnesium matrix material behind the plated film can be in the active time that obtains under the biological fluid environment more than 16 weeks, than not prolonged more than 4 times to active time in 3～4 weeks of Coating Materials, reach biological bone implant material military service phase requirement.Can realize simultaneously the slow degraded of magnesium matrix material under arms in the process, magnesium matrix and body fluid environment generation chemical reaction have been delayed effectively, reduced separating out of hydrogen in the chemical reaction, but be conducive to organism and in tolerance range, discharge bubble, being suitable as the biomaterial surface Coating Materials and using, is a kind of advanced person's the operable top coat of magnesium base biological implantation material.
Description of drawings
Fig. 1 is without the silvery white surperficial magnesium matrix material of plated film among the present invention.
Fig. 2 is through the golden yellow surperficial magnesium matrix material behind the plated film among the present invention.
Fig. 3 is the Ti/TiO that the embodiment of the invention 1 obtains
2The electron micrograph of rete side.
Fig. 4 is the electron micrograph in the TiN rete front of the embodiment of the invention 2 acquisitions.
Fig. 5 is that coating cell toxicity test in 10%, 50% and 100% nutrient solution that the embodiment of the invention 1 obtains obtains negative experimental result.
Fig. 6 is that the embodiment of the invention 2 is after the animal body experiment, to testing the tissue slice that does not have pathology with the heart of rabbit.
Fig. 7 is that the embodiment of the invention 2 is after the animal body experiment, to testing the tissue slice that does not have pathology with the liver of rabbit.
Fig. 8 is that the embodiment of the invention 2 is after the animal body experiment, to testing the tissue slice that does not have pathology with the kidney of rabbit.
Fig. 9 is that the embodiment of the invention 2 is after the animal body experiment, to testing the tissue slice that does not have pathology with the muscle of rabbit.
Embodiment
What the present invention adopted obtains Ti/TiO on the magnesium base composite material surface
2Or the method for TiN rete, the Ti/TiO that obtains by the physical vacuum gas phase deposition technology on the surface of magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material
2Perhaps TiN rete, its film coating method comprises following steps:
(1), the cleaning of magnesium base composite material, with magnesium base composite material grinding and polishing on sand paper, remove surface oxidation film earlier, put into raw spirit then and clean, also can adopt ultrasonic cleaning apparatus to clean, guarantee magnesium base composite material cleaning surfaces oxide-free;
(2), in vacuum arc deposition equipment, the magnesium base composite material through above-mentioned steps (1) surface cleaning is carried out surface coating, vacuum arc deposition film machine is evacuated down to 6.0 * 10
-3The vacuum tightness that Pa is above is heated to 200 ℃～220 ℃ then, charges into argon gas, and partial pressure of ar gas is controlled at 0.4Pa～0.6Pa, connects the magnesium base composite material grid bias power supply, and bias value is 100V～250V, and magnesium substrates is tentatively bombarded 2min～3min;
(3), plate Ti/TiO if desired
2Layer then in step (2) afterwards, is evacuated down to 3 * 10 again
-3The vacuum tightness that Pa is above, the magnesium base composite material bias voltage is adjusted to 150V～400V, simultaneously, the pure titanium target that ignites plays arc discharge, striking current control is at 30A～80A, and depositing time is 2min～10min, obtains pure Ti rete this moment, the product that has plated the Ti layer is taken out the back in atmosphere, place from vacuum chamber, just can obtain TiO at Ti laminar surface natural oxidation
2Layer, thus Ti/TiO obtained
2Layer;
(4), plate the TiN layer if desired, then in step (2) afterwards, in vacuum chamber, charge into nitrogen, keep nitrogen partial pressure at 0.5Pa～1Pa, volume ratio 45%～50% takes up space, the magnesium base composite material bias value is at 50～250V, and striking current is controlled at 50A～100A, and depositing time is 8min～12min;
(5), other correlation parameters that use in coating process are set at: arc source working current: 30A～100A, 4～8 of target quantity, target diameter 60mm～100mm, target range of current 30A～100A, best stabilising arc electric current is 50A～60A during work, target current potential-18V～-20V, magnesium matrix material Heating temperature is 400 ℃～450 ℃.
That adopts technique scheme obtains Ti/TiO on the magnesium base composite material surface
2Or the method for TiN rete, can obtain Ti/TiO at magnesium/hydroxyapatite or magnesium/tricalcium phosphate composite material surface
2The rete of layer or TiN layer.Without plated film with see Fig. 1 and Fig. 2 through the magnesium matrix material contrast after the plated film, as seen pass through plated film after, originally silvery white surperficial magnesium matrix material has changed into golden yellow rete fully.Magnesium base composite material after overtesting is found plated film erosion resistance in human body simulation body fluid obtains to increase substantially, and 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 can use in organism fully to the organism nontoxicity.
Below in conjunction with the drawings and specific embodiments the present invention is elaborated.
Embodiment 1:
Adopt the matrix material that adds hydroapatite particles in the magnesium matrix as body material, earlier the magnesium matrix material is polished at sand paper, remove surface oxidation film, putting into raw spirit then cleans, in ultrasonic cleaning apparatus, add raw spirit then and further clean, guarantee magnesium matrix material surface cleaning oxide-free.In vacuum arc deposition equipment, magnesium/hydroxyapatite composite material is carried out surface coating.Vacuum arc deposition film machine is evacuated down to 6.0 * 10
-3Pa vacuum tightness is heated to 200 ℃ then, charges into argon gas, and partial pressure of ar gas is controlled at 0.5Pa, connects magnesium matrix material grid bias power supply, and bias value is 100V, and magnesium substrates is tentatively bombarded 2min.Be evacuated down to 3 * 10 again
-3The vacuum tightness that Pa is above, magnesium/hydroxyapatite composite material bias voltage is adjusted to 150V, and the pure titanium target that ignites plays arc discharge, and striking current is controlled at 30A, and depositing time is 2min, obtains pure Ti rete.The product that has plated the Ti layer is taken out the back in atmosphere, place from vacuum chamber, just can obtain the TiO of Ti laminar surface natural oxidation
2Layer, thus Ti/TiO obtained on magnesium/hydroxyapatite composite material surface
2Layer.In the present embodiment, the arc source working current is 30A, 4 of target quantity, and target diameter 60mm, the target current control is at 30A, and best stabilising arc electric current is 50A during work, target current potential-20V, magnesium/hydroxyapatite composite material Heating temperature is 400 ℃.The Ti/TiO that present embodiment obtains
2Layer electron photomicrograph seen Fig. 3.Referring to Fig. 5, Fig. 5 is that coating cell toxicity test in 10%, 50% and 100% nutrient solution that the embodiment of the invention 1 obtains obtains negative experimental result.
Embodiment 2:
Adopt the matrix material that adds the tricalcium phosphate particle in the magnesium matrix as body material, earlier magnesium base composite material is polished at sand paper, remove surface oxidation film, putting into raw spirit then cleans, in ultrasonic cleaning apparatus, add raw spirit then and further clean, guarantee magnesium matrix material surface cleaning oxide-free.In vacuum arc deposition equipment, magnesium/tricalcium phosphate composite material is carried out surface coating.Vacuum arc deposition film machine is evacuated down to 6.0 * 10
-3The vacuum tightness that Pa is above is heated to 200 ℃ then, charges into argon gas, and partial pressure of ar gas is controlled at 0.5Pa, connects magnesium matrix material grid bias power supply, and bias value is 250V, and magnesium substrates is tentatively bombarded 3min; In vacuum chamber, charge into nitrogen, keep nitrogen partial pressure at 1Pa, the volume ratio 45% that takes up space, magnesium matrix material 250V, striking current is controlled at 100A, and depositing time is 12min, obtains the TiN rete.In the present embodiment, arc source working current: 100A, 8 of target quantity, target diameter 100mm, the target electric current is 100A, best stabilising arc electric current is 60A during work, target current potential-20V, magnesium/tricalcium phosphate composite material Heating temperature is 450 ℃.The TiN rete electron photomicrograph that present embodiment obtains is seen Fig. 4.Fig. 6 is that the embodiment of the invention 2 is after the animal body experiment, to testing the tissue slice that does not have pathology with the heart of rabbit.Fig. 7 is that the embodiment of the invention 2 is after the animal body experiment, to testing the tissue slice that does not have pathology with the liver of rabbit.Fig. 8 is that the embodiment of the invention 2 is after the animal body experiment, to testing the tissue slice that does not have pathology with the kidney of rabbit.Fig. 9 is that the embodiment of the invention 2 is after the animal body experiment, to testing the tissue slice that does not have pathology with the muscle of rabbit.
Embodiment 3:
Adopt the matrix material that adds hydroapatite particles in the magnesium matrix as body material, earlier the magnesium matrix material is polished at sand paper, remove surface oxidation film, putting into raw spirit then cleans, in ultrasonic cleaning apparatus, add raw spirit then and further clean, guarantee magnesium/hydroxyapatite composite material cleaning surfaces oxide-free.In vacuum arc deposition equipment, carry out surface coating.Vacuum arc deposition film machine is evacuated down to 6.0 * 10
-3The vacuum tightness that Pa is above is heated to 210 ℃ then, charges into argon gas, and partial pressure of ar gas is controlled at 0.4Pa, connects magnesium/hydroxyapatite composite material grid bias power supply, and bias value is 250V, and magnesium substrates is tentatively bombarded 3min; Be evacuated down to 3 * 10 again
-3The vacuum tightness that Pa is above, magnesium/hydroxyapatite composite material bias voltage is adjusted to 400V, and simultaneously, the pure titanium target that ignites plays arc discharge, and striking current is controlled at 80A, and depositing time is 10min, obtains pure Ti rete.The product that has plated the Ti layer is taken out the back in atmosphere, place from vacuum chamber, just can obtain TiO at Ti laminar surface natural oxidation
2Layer, thus Ti/TiO obtained
2Layer.The arc source working current is 100A in the present embodiment, 8 of target quantity, and target diameter 100mm, target range of current 100A, best stabilising arc electric current is 60A during work, target current potential-18V, magnesium/hydroxyapatite composite material Heating temperature is 450 ℃.
Embodiment 4:
Adopt the matrix material that adds the tricalcium phosphate particle in the magnesium matrix as body material, earlier magnesium base composite material is polished at sand paper, remove surface oxidation film, putting into raw spirit then cleans, in ultrasonic cleaning apparatus, add raw spirit then and further clean, guarantee magnesium matrix material surface cleaning oxide-free.In vacuum arc deposition equipment, magnesium/tricalcium phosphate composite material is carried out surface coating.Vacuum arc deposition film machine is evacuated down to 6.0 * 10
-3The vacuum tightness that Pa is above is heated to 220 ℃ then, charges into argon gas, and partial pressure of ar gas is controlled at 0.6Pa, connects magnesium matrix material grid bias power supply, and bias value is 100V, and magnesium substrates is tentatively bombarded 2min; Charge into nitrogen in vacuum chamber, keep nitrogen partial pressure at 0.5Pa, the volume ratio 50% that takes up space, magnesium matrix material bias value are at 50V, and striking current is controlled at 50A, and depositing time is 8min, obtains the TiN rete.Arc source working current: 30A in the present embodiment, 4 of target quantity, target diameter 60mm, target range of current 30A, best stabilising arc electric current is 50A during work, target current potential-18V, magnesium/tricalcium phosphate composite material Heating temperature is 400 ℃.
Claims (2)
1. one kind obtains Ti/TiO on magnesium base composite material surface
2Or the method for TiN rete, it is characterized in that: comprise following steps:
(1), in vacuum arc deposition equipment, the magnesium base composite material after the surface cleaning is carried out surface coating, vacuum arc deposition film machine is evacuated down to 6.0 * 10
-3The vacuum tightness that Pa is above is heated to 200 ℃～220 ℃ then, charges into argon gas, and partial pressure of ar gas is controlled at 0.4Pa～0.6Pa, connects the magnesium base composite material grid bias power supply, and bias value is 100V～250V, and magnesium base composite material is tentatively bombarded 2min～3min;
(2), plate Ti/TiO if desired
2Layer then in step (1) afterwards, is evacuated down to 3 * 10 again
-3The vacuum tightness that Pa is above, the magnesium base composite material bias voltage is adjusted to 150V～400V, and simultaneously, the pure titanium target that ignites plays arc discharge, and striking current is controlled at 30A～80A, and depositing time is 2min～10min, obtains pure Ti rete this moment; The product that has plated the Ti layer is taken out the back in atmosphere, place from vacuum chamber, obtain TiO at Ti laminar surface natural oxidation
2Layer, thus Ti/TiO obtained
2Layer;
(3), plate the TiN layer if desired, then in step (1) afterwards, in vacuum chamber, charge into nitrogen, keep nitrogen partial pressure at 0.5Pa～1Pa, the volume ratio that takes up space is 45%～50%, the magnesium base composite material bias value is at 50V～250V, and striking current is controlled at 50A～100A, and depositing time is 8min～12min;
(4), other correlation parameters that use in coating process are set at: arc source working current: 30A～100A, 4～8 of target quantity, target diameter 60mm～100mm, target range of current 30A～100A, the stabilising arc electric current is 50A～60A during work, target current potential-18V～-20V, the magnesium base composite material Heating temperature is 400 ℃～450 ℃.
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: the surface cleaning to magnesium base composite material in the above-mentioned steps (1) refers to: earlier with magnesium base composite material grinding and polishing on sand paper, remove surface oxidation film, putting into raw spirit then cleans, or adopt ultrasonic cleaning apparatus to clean, guarantee magnesium matrix material surface cleaning oxide-free.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107723680A (en) * | 2017-08-28 | 2018-02-23 | 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 |
| CN114807839A (en) * | 2022-04-25 | 2022-07-29 | 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01168857A (en) * | 1987-12-23 | 1989-07-04 | Agency Of Ind Science & Technol | Formation of titanium nitride film |
-
2013
- 2013-05-09 CN CN201310169315.4A patent/CN103276361B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01168857A (en) * | 1987-12-23 | 1989-07-04 | Agency Of Ind Science & Technol | Formation of titanium nitride film |
Non-Patent Citations (2)
| Title |
|---|
| 熊光连: "镁合金电弧离子镀镀金属氮化物薄膜的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 王成龙等: "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", 《腐蚀与防护》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107723680A (en) * | 2017-08-28 | 2018-02-23 | 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 |
| CN114807839A (en) * | 2022-04-25 | 2022-07-29 | 南昌大学 | Stepped degradation magnesium alloy barrier film for dentistry and preparation method thereof |
| 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 |
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