CN101721742A - Biological coating and dental arch wire coated with same - Google Patents
Biological coating and dental arch wire coated with same Download PDFInfo
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- CN101721742A CN101721742A CN200910243794A CN200910243794A CN101721742A CN 101721742 A CN101721742 A CN 101721742A CN 200910243794 A CN200910243794 A CN 200910243794A CN 200910243794 A CN200910243794 A CN 200910243794A CN 101721742 A CN101721742 A CN 101721742A
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Abstract
The invention discloses a biological coating and a dental arch wire coated with the same, and belongs to the technical fields of surface modification of biomedical metal materials and medical equipment. The biological coating comprises Ti and Nb serving as main components, and also comprises at least one of tin, aluminum, silicon, zirconium, tantalum, hafnium, palladium, gallium, nickel and oxygen. The invention provides the dental arch wire which uses a TiNbAl titanium alloy serving as a base material and is coated by the coating. Medical equipment products coated by the coating have good biocompatibility and good corrosion resistance and great improvement on superelasticity, shape memory effect, fatigue performance and other composite properties, and can be used in the field of medical treatment serving as functional coatings on surfaces of super-elastic stents, orthodontic dental arch wires, orthopedic implant equipment and the like. The dental arch wire has lower elastic modulus, excellent biocompatibility and mechanical compatibility; and the base material of the dental arch wire has excellent mechanical performance, corrosion resistance, and can be subjected to large deformation cold machining, such as cold rolling, cold wire drawing and the like.
Description
Technical field
The invention belongs to bio-medical metal surface properties modification and technical field of medical instruments, particularly a kind of biological coating and apply the dental arch filament of this biological coating.
Background technology
Ti-Ni marmem (TiNi), Ti-6Al-4V, Ti-6Al-7Nb, rustless steel are that bio-medical metal material such as alloy has been widely used as medical instruments field, but are faced with the danger that use Ni, Al, V harmful ion discharge simultaneously.The Ti-Ni alloy support is by extensive clinical practice, but Nitinol contains genotoxic potential elements such as Ni, and the nickel of alloy surface is escaped still troubling.Ti-6Al-4V, Ti-6Al-7Nb alloy are widely used in biological and medicinal implant material owing to have highly corrosion resistant, proper mechanical capacity and super-elasticity, substitute the sclerous tissues of corrupted.The Ti-6Al-4V alloy has good characteristic as embedded material, owing to contain V, the clinical nontoxic new titanium alloy that waits in expectation.The no V-Ti of development comprises at present: Ti-15Mo-5Zr-3Al, Ti-6Al-2Nb-1Ta, Ti-6Al-7Nb, Ti-6Al-6Nb-1Ta, Ti-5Al-2.5Fe etc.The mechanical performance of some of them alloy is better than the Ti-6Al-4V titanium alloy.As the influence that implant produces human body, Ni has potential teratogenecity and carcinogenecity, and Al has the suspection of teratogenecity.In recent years, the research of bio-medical metal material and application have obtained increasing concern, mainly concentrate on the following aspects: NiTi marmem and titanium alloy surface modification technology and Study on biocompatibility thereof; The development and the application of no Ni low elastic modulus titanium alloy; The research of (inner support degradable) magnesium (base) alloy bio-medical material; POROUS TITANIUM, the preparation of NiTi alloy, surface modification and study on biocompatibility; Contain Ni, Al, V bio-medical metal material harmful ion releasing mechanism, pathogenesis, protection and application facet research.
China bio-medical metal material market is huge, and the NiTi marmem is occupied an leading position at endovascular stent and non-vessel stent application facet at present, still is faced with implantation initial stage Ni ion and discharges obviously, implants danger such as fatigue fracture for a long time.It is remarkable that the NiTi alloy is implanted initial stage Ni ion burst size, eliminates implantation initial stage Ni ion fully and discharge, and will improve the adaptability of health to implant, reduces to implant and repel and infection chance.The difficulty of NiTi alloy surface modifying design is the dynamic characteristic of marmem.When improving NiTi alloy biocompatibility, can not take into account the dynamic characteristic of NiTi alloy fully, occur so lose that situation by process for modifying surface.Surface modification forms the titanium compound on new surface, causes the variation of outer surface subgrade chemical constituent, and Ni concentration increases, thereby influences martensitic phase transformation, shape memory effect and performances such as super-elasticity and biocompatibility, brings some negative results.Widely used NiTi alloy surface modifying technology comprises: and laser and plasma treatment, ion implantation, hydroxyapatite (Hydroxylapatite, HAP), chemical vapor deposition (CVD) etc.Ion implantation and laser treatment causes that usually the surface is decrystallized, improves resistance to corrosion.Yet surface layer is inhomogeneous, and enrichment of N i, surface layer become harder than matrix.Can improve resistance to corrosion at NiTi surface-coated TiN and TiCN, cause the cracking of the surface layer different with matrix but Kimura points out distortion that shape memory effect causes.Hydroxyapatite coating layer has excellent biocompatibility, but because it can fuse with body fluid, causes it to be easy to dissolve.The natural calcium phosphate coating that the NiTi alloy immerses physiological solution formation may replace hydroxyapatite coating layer.Form the direction that active coating is the surface modification development at the NiTi alloy surface.NiTi is exposed to the metal-protein surface complex that forms in the human plasma fiber adhesion albumen and has reduced alloy corrosion speed, can reduce by 50% in solutions of chlorine and cell culture fluid.Clearly, the NiTi alloy surface modifying depends on the characteristic of apparatus.It is to improve biocompatibility by carbon coating that of NiTi alloy surface modifying has developing direction.
This shows, suppress the release of bio-medical metal material harmful ion, improve its biocompatibility, increase its safety in utilization, to the extensive use of bio-medical metal material, significant the Application and Development of new material by process for modifying surface.
Plasma spraying is the process for modifying surface that is applicable to the comparative maturity that improves the medical metal material biocompatibility.Adopt plasma spraying technology to carry out titanium niobium alloy coating and pure titanium on the NiTi surface and modify, in the hope of the super-elasticity and the shape-memory properties of maintenance NiTi uniqueness, and the shielding nickel element, prevent Ni
2+Discharge, improve biology safety.People's such as Li Yongbin experimental result shows, and is not remarkable though phase transition temperature slightly raises after surface spraying Ti and the TiNb coating, shielded the Ni element behind the spray-on coating, and coating is smooth, smooth, evenly, and the about 3.25 μ m of thickness.External normal saline soak test shows, has prevented that Ni2+ from separating out after NiTi surface process Ti and the TiNb coating; After NiTi group body is implanted into 1 year, detect unusual high Ni2+ content at implant surrounding bone tissue and muscular tissue, relevant with wearing and tearing; Ti group and TiNb group muscular tissue biocompatibility are better than the NiTi group, and do not have significant difference between the former two, and osseous tissue biocompatibility TiNb organizes best.Experiment in vitro shows that three groups of implants all have good anti-corrosion, but NiTi group body after being implanted into 1 year obvious corrosion phenomenon has taken place, and is mainly tarnishing and composition and changes; TiNb group and Ti group then do not have obviously corrosion, and erosion corrosion has in various degree all taken place all implant surfaces.
Double ion beam sputtered deposition (DIBSD) film process possesses exclusive sputter and deposition parameter and control device, is the method that has the manufacturing thin film of innovation ability most.The DIBSD method claims ion beam-assisted sputtering sedimentation or ion beam enhanced film deposition again.Typical application is Zr-Nb film system and the FCC Cr-Au film system mutually of Fe-Ni plural layers, BCC phase.The Nb alloying element has best biocompatibility, belongs to body-centered cubic structure, with the β titanium be isomorphous elements, niobium and titanium atom semidiameter are little, infinitely dissolve each other with the β titanium, dissolve in titanium and form displaced type solid solution, this shows that it is fully feasible from thermodynamics that the DIBSD method prepares the TiNb coating.By main source emission Ar+ ion beam sputtering TiNb alloys target or Nb target, the auxiliary bombardment growth of auxilliary source ion bundle TiNb thin film can change or adjust composition, structure and the character of thin film.Existing research concentrates on adopts the DIBSD method to prepare the corrosion resisting property that the TiNb alloy coat improves titanium alloy at titanium alloy surface.Double ion beam sputtered deposition (DIBSD) film process is at the bio-medical metal material, especially a kind of potential Perfected process of preparation TiNb alloy biological coating on the marmem.
United States Patent (USP) 5399088 has been reported a kind of just abnormal dental arch filament of coating, and substrate metal is a kind of in rustless steel, Nitinol, chromium cobalt-nickel alloy, nichrome, billon, the beta-titanium alloy.The coating material is a kind of in titanium, titanium alloy, niobium, the niobium alloy.For example, base material is a Nitinol, and coating is a niobium titanium alloy.Patent does not have clear and definite proposition coating chemical constituent scope, therefore can't effectively protect the intellectual property.United States Patent (USP) 6752882 has been reported a kind of medical binary titanium niobium alloy, contains the Nb of 10-30%, and the nonmetal inclusion element that may contain comprises carbon, oxygen and nitrogen, and total content is less than 1%.Have low elastic modulus and high intensity, can be used for plastic surgery and dental implant.United States Patent (USP) 6409852 has been reported a kind of medical implant material-titanium alloy, has good biocompatibility, characteristics that elastic modelling quantity is low.This alloy contains 6-9%Mo, the alloy element of 0-1% (among Nb, the Zr a kind of).United States Patent (USP) 5685306 has been reported a kind of TiNbZr alloy of low elastic modulus, is used for medical implants such as cardiovascular, contains 10-20%Nb or 35-50%Nb, contains 0.5-20%Zr.United States Patent (USP) 5509933 and 5871595 has been reported two kinds of titanium niobium-base alloys, all has excellent biological compatibility and low elastic modelling quantity, and its composition range the former be: zirconium is less than 20%, niobium 10～20% or 35～50%; The latter is a zirconium 2.5～13%, niobium 20～40%, and tantalum 4.5～25%, tantalum+niobium are 35～42%, the weight ratio of niobium and tantalum is 2～13.Other is about the United States Patent (USP) of low elastic modulus, and content of niobium is about 10～20%, and as 5545227,5573401,5169597, content of niobium is about 35～50%, as 5169597.
Chinese patent CN 1696329A invents a kind of binary noble coatings and preparation method of stainless surface modification, the thickness that it is characterized by coating and stainless metallurgical binding is the alloy film coating of the Pd of 3～6 μ m, Fe film and transition composition thereof, adopt filtered cathode vacuum arc technology, at Pd, the Fe film of 316L stainless steel surfaces deposite gradually, behind vacuum diffusion heat treatments diffusion reaction, obtain a kind of PdFe alloy surface modifying coating.The coating biology compatibility is good, has certain magnetic property; CN 101437978A relates to the biocompatible coating of the nanostructured on a kind of Ti-Ni alloy surface, the composition that it is characterized in that each subgrade changes, promptly, innermost layer is the pseudo-diffusion layer of pure titanium layer and Ti-Ni alloy composition, the intermediate layer is the mixed layer of alternative pure titanium layer and titanium and titanium nitride, and skin is the purity nitrogen titanium layer.Making step comprises that heat treatment, surface preparation, ion sputtering clean, pseudo-diffusion layer deposition, subgrade film are coated with, being coated with etc. of purity nitrogen titanium layer.Coating can suppress the stripping of nickel, and good biocompatibility can not come off with the matrix distortion and ftracture; Resistance to matrix is little.CN 101229395A relates to a kind of AlTiN coating of Ti6Al4V alloy surface, by height ionizing pulse prepared, is used for intravital artificial bone of orthopedics's implantable bioartificial or apparatus, as hip joint, knee joint and root of the tooth.The CN201168029Y utility model patent relates to a kind of metal coating formula TiNi alloy skoliosis orthotic device.The metal type coating is selected titanium or titanium niobium coating for use, reducing the release of nickel ion in the orthopedic rod of Ti-Ni marmem, and corrosion-resistant, endurance, anti-wear, answer mechanics superior performance.Adopt plasma technology spray metal formula coating.This utility model patent does not have chemical constituent, preparation technology and the coating of clear and definite metal type coating to characterize, and can not effectively protect.
Summary of the invention
The purpose of this invention is to provide a kind of biological coating and apply the dental arch filament of this biological coating.
At first the invention provides a kind of biological coating, it is characterized in that, the component of biological coating and each composition weight percentage composition are: niobium (Nb): 18%～32%; At least a in the following column element: stannum (Sn): aluminum (Al) 0.001%～8%: silicon (Si) 0.001%～5%: zirconium (Zr) 0.001%～6%: 0.001～6%, tantalum (Ta): 0.001～6%, hafnium (Hf): 0.001～8%, palladium (Pd): gallium (Ga) 0.001%～3%: 0.001～6%, germanium (Ge): 0.001～6%, nickel (Ni): 0.001～0.05%, oxygen (O): 0.001%～0.2%; Surplus is titanium (Ti).
A kind of optimized technical scheme, described biological coating contains at least a in stannum (Sn), aluminum (Al), silicon (Si), zirconium (Zr), tantalum (Ta), hafnium (Hf), palladium (Pd), gallium (Ga), germanium (Ge), the nickel (Ni) and above-mentioned element wt percentage composition sum≤8%.
Also contain in carbon (C), hydrogen (H), nitrogen (N), the argon (Ar) one or more in the described biological coating, wherein, weight percentage sum≤0.05% of carbon (C), hydrogen (H), three kinds of components of nitrogen (N), weight percentage≤0.03% of argon (Ar).
The thickness of described biological coating between 0.01 μ m～80 μ m, preferred 0.05 μ m～50 μ m.
Described biological coating is used for the coat metal substrates material, comprises titanium-base alloy, Ti-Ni alloy and rustless steel.
Secondly, the present invention also provides a kind of dental arch filament, it is characterized in that, this dental arch filament has applied aforesaid biological coating on matrix, the matrix component of dental arch filament and each composition weight percentage composition are: niobium (Nb): stannum (Sn) 24%～42%: aluminum (Al) 0.35%～5.5%: silicon (Si) 0.3%～5.5%: 0.5%～5.5%, and surplus is titanium (Ti) and unavoidable impurities.
Can also contain zirconium (Zr) in the matrix of dental arch filament, be that matrix component and each composition weight percentage composition are: niobium (Nb): stannum (Sn) 24%～42%: aluminum (Al) 0.35%～5.5%: silicon (Si) 0.3%～5.5%: 0.5%～5.5%,, zirconium (Zr): 0.2%～5.5%, surplus is titanium (Ti) and unavoidable impurities; A kind of optimized technical scheme is weight percentage sum≤12% of stannum in the matrix (Sn), aluminum (Al), silicon (Si) and four kinds of components of zirconium (Zr).
In the described matrix, weight percentage sum≤45% of niobium (Nb) and aluminum (Al).
Unavoidable impurities is one or more in carbon (C), hydrogen (H), oxygen (O), the nitrogen (N) in the described matrix, percentage composition by weight, carbon containing (C) amount≤0.05%; Hydrogeneous (H) amount≤0.005%; Contain oxygen (O) amount≤0.05%; Nitrogenous (N) amount≤0.05% wherein, contains oxygen (O) amount and nitrogenous (N) amount sum≤0.07%.
Beneficial effect of the present invention is: coating of the present invention can adopt plasma spraying or the preparation of double ion beam sputtered deposition (DIBSD) film process, can be coated in and contain on Ni, Al, the V harmful ion bio-medical metal material base material, can be applicable to complicated medical apparatus and instruments, can be widely used in medical field, as the super functional coating that plays surfaces such as support, just abnormal dental arch filament and orthopaedics implantation instrument;
Have following advantage:
1, biological coating of the present invention contains toxicity elemental nickel (Ni), aluminum (Al), vanadium (V) and seldom or not contains, and can effectively reduce the release of matrix toxic element ion, has reduced human body harm, and biocompatibility is good;
2, biological coating of the present invention has good mechanical compatibility, corrosion resistance, endurance, has super-elasticity and shape-memory properties;
3, the composition protection domain of the clear and definite binary TiNb coating of the present invention, alloying elements such as a small amount of Al, the Sn that contains in the clear and definite TiNb alloy, Si, Zr, Sn, Ta, Pd, Hf, Ge, Ga, O, coating has specific composition range, is easy to protection of Intellectual Property Rights;
4, the biocompatibility and the decay resistance of the medical apparatus and instruments goods of coating coating of the present invention significantly improve, and the composite attribute function of the martensitic phase transformation of alloy base material, super-elasticity and dynamic characteristics such as shape memory effect, fatigue behaviour improves;
5, coating of the present invention can promote the exploitation and the application of nickeliferous (Ni), aluminum (Al), vanadium (V) ion biomedical metal material, can be widely used in medical field.
Dental arch filament of the present invention has low elastic modelling quantity, has excellent biological compatibility and mechanical compatibility, does not contain or contain less poisonous element; Have favorable mechanical performance, corrosion resisting property; Have excellent cold-forming property and very low cold work hardening rate, can carry out the cold working of aximal deformation values such as cold rolling and hand-drawn wire.
The specific embodiment
Biological coating of the present invention is the TiNb alloy, and coating has specific composition range and specific functional characteristic.The composition protection domain of the clear and definite binary TiNb coating of the present invention; alloying elements such as a small amount of Al, the Sn that contains in the clear and definite TiNb alloy, Si, Zr, Sn, Ta, Pd, Hf, Ge, Ga, O; the TiNb coating has good biocompatibility and corrosion resistance, shape-memory properties and elastic performance, can improve the composite attribute of martensitic phase transformation, super-elasticity and the dynamic characteristics such as shape memory effect, fatigue behaviour of alloy substrate.
Coating of the present invention can be coated in and contain on Ni, Al, the V harmful ion bio-medical metal material matrix, be used to improve its biocompatibility, corrosion resisting property, can improve the composite attribute of martensitic phase transformation, super-elasticity and the dynamic characteristics such as shape memory effect, fatigue behaviour of alloy substrate simultaneously.
The matrix of dental arch filament of the present invention adds a small amount of Al, Sn, Si, the formation of Zr alloying element on TiNb alloy basis, design super-elasticity and shape memory titanium niobium-base alloy with good biocompatibility and low elastic modulus.This novel beta-titanium alloy good processability, cost is low.Form by the vacuum consumable electrode arc furnace vacuum induction melting, prepare plate, rod, silk material through cold or hot-working and heat treatment.The prepared dental arch filament of the present invention can be used for orthodontic.
Because coating and matrix are with basic alloy, the preparation method of coating of the present invention adopts with Technologies such as basic alloy plasma coating technology and double ion beam sputtered deposition (DIBSD) thin film.
Dental arch filament matrix preparation method of the present invention is as follows: with the raw material mix homogeneously, suppress 1～3 kilogram electrode, be smelted into the cylinder ingot casting through the secondary vacuum consumable electroarc furnace, the melting useful vacuum degree all is not more than 5Pa, hammer cogging in 850 ℃～1050 ℃ temperature ranges, behind 950 ℃～1050 ℃ homogenization insulation 30～180min, through swaging, cold rolling, bar is processed in cold-drawns etc., total deformation is controlled between 65%～95%, every time deflection is controlled between 20%～30%, bar is heat-treated, and heat treatment temperature is between 950 ℃～1050 ℃, between insulation 30～180min.Above-mentioned dental arch filament matrix processing technique is carried out by the prior art file and is got final product.
The invention will be further described below in conjunction with embodiment:
Embodiment 1
With titanium sponge, niobium titanium intermediate alloy is raw material, takes by weighing 2.3 kilograms of titanium sponges, 2.7 kilograms of niobium titanium intermediate alloys, and wherein, the weight percentage of Nb is 50% in the niobium titanium intermediate alloy.
Electrode with 3 kilograms of compactings behind above-mentioned titanium sponge, the niobium titanium intermediate alloy mix homogeneously, be smelted into the cylinder ingot casting through the secondary vacuum consumable electroarc furnace, the melting useful vacuum degree all is not more than 5Pa, the gained ingot casting is adopted mechanical alloying powder process, gained grain end particle diameter adopts the low-power plasma spraying method to apply biological coating less than 50 μ m on TiNi dental arch filament (weight percentage of Ni is 55.8%) surface, and spray power is 10Kw, spray distance is 45mm, powder sending quantity 45g/min.
The biological coating thickness that goes out in TiNi dental arch filament surface preparation is 40 μ m, and it is 0.05% that biological coating contains oxygen (O) amount, and nickeliferous (Ni) amount is 0.005%, and containing niobium (Nb) amount is 25%, and surplus is titanium (Ti).
Embodiment 2
With titanium sponge, niobium titanium intermediate alloy is raw material, takes by weighing 2.3 kilograms of titanium sponges, 2.7 kilograms of niobium titanium intermediate alloys, and wherein, the weight percentage of Nb is 50% in the niobium titanium intermediate alloy.
With above-mentioned titanium sponge, suppress 3 kilograms electrode behind the niobium titanium intermediate alloy mix homogeneously, be smelted into the cylinder ingot casting through the secondary vacuum consumable electroarc furnace, the melting useful vacuum degree all is not more than 5Pa, forge, rolling processing TiNb alloy target material, after the annealed processing, the target crystallite dimension is less than 150 μ m, adopt double ion beam sputtered deposition process to prepare biological coating on TiNi dental arch filament (weight percentage of Ni is 55.8%) surface, main source emission Ar ion beam sputtering TiNb alloys target, the auxiliary bombardment growth of auxilliary source ion bundle TiNb thin film changes or adjusts the composition of thin film, structure and character, main source power is 10Kw, auxilliary source power is 10Kw, spray distance is 45mm, powder sending quantity 45g/min.
The biological coating thickness that goes out in TiNi dental arch filament surface preparation is 15 μ m, and it is 0.02% that biological coating contains oxygen (O) amount, and nickeliferous (Ni) amount is 0.001%, and containing niobium (Nb) amount is 23%, and surplus is titanium (Ti).
Embodiment 3
Biological coating of the present invention is coated on the dental arch filament matrix of the present invention forms the dental arch filament that has applied biological coating, wherein, matrix is the TiNbAl series titanium alloy, and coating is that TiNb is with the based component coating;
At first, preparation dental arch filament matrix:
With titanium sponge, sponge zirconium, niobium titanium intermediate alloy, aluminum titanium intermediate alloy, aluminum silicon intermediate alloy, titanium stannum intermediate alloy is a raw material, take by weighing 2.5 kilograms of titanium sponges, 0.03 kilogram of sponge zirconium, 2.2 kilograms of niobium titanium intermediate alloys (columbic weight percentage is 80% in the niobium titanium intermediate alloy), 0.1 kilogram of aluminum titanium intermediate alloy (weight percentage of aluminum is 52% in the aluminum titanium intermediate alloy), 0.075 kilogram of aluminum silicon intermediate alloy (weight percentage of aluminum is 50% in the aluminum silicon intermediate alloy), 0.1 kilogram of titanium stannum intermediate alloy (weight percentage of titanium is 80% in the titanium stannum intermediate alloy), with the above-mentioned raw materials mix homogeneously, suppress 3 kilograms electrode, be smelted into the cylinder ingot casting through the secondary vacuum consumable electroarc furnace, the melting useful vacuum degree all is not more than 5Pa, hammer cogging in 900 ℃ of temperature ranges, behind 900 ℃ of homogenization insulation 100min, through swaging, cold rolling, bar is processed in cold-drawns etc., total deformation is controlled between 65%～95%, every time deflection is controlled at 30%, bar is heat-treated, heat treatment temperature is incubated 150min at 1000 ℃.Above-mentioned processing technique is carried out by the prior art file and is got final product.Processing dental arch filament silk material diameter is 0.31mm.Gained dental arch filament matrix component and each composition weight percentage composition are: niobium (Nb): stannum (Sn) 35%: aluminum (Al) 0.36%: silicon (Si) 1.5%: zirconium (Zr) 0.65%: 0.50%; Surplus is titanium (Ti).
Then, applying coating on the dental arch filament matrix:
With titanium sponge, niobium titanium intermediate alloy is raw material, takes by weighing 2 kilograms of titanium sponges, 3 kilograms of niobium titanium intermediate alloys, and wherein, the weight percentage of Nb is 50% in the niobium titanium intermediate alloy.
With above-mentioned titanium sponge, suppress 3 kilograms electrode behind the niobium titanium intermediate alloy mix homogeneously, be smelted into the cylinder ingot casting through the secondary vacuum consumable electroarc furnace, the melting useful vacuum degree all is not more than 5Pa, forge, rolling processing TiNb alloy target material, after the annealed processing, the target crystallite dimension is less than 150 μ m, adopt double ion beam sputtered deposition to prepare biological coating, main source emission Ar ion beam sputtering TiNb alloys target, the auxiliary bombardment growth of auxilliary source ion bundle TiNb thin film changes or adjusts the composition of thin film, structure and character, main source power are 10Kw, and auxilliary source power is 10Kw, spray distance is 45mm, powder sending quantity 45g/min.
The biological coating thickness of preparing at the dental arch filament matrix surface for preparing is 6 μ m, and it is 0.02% that biological coating contains oxygen (O) amount, and containing aluminum (Al) amount is 0.005%, and containing niobium (Nb) amount is 29%, and surplus is titanium (Ti).
Embodiment 4
Biological coating of the present invention is coated on the dental arch filament matrix of the present invention forms the dental arch filament that has applied biological coating, wherein, matrix is the TiNbAl series titanium alloy, and coating is that TiNb is with the based component coating;
At first, preparation dental arch filament matrix:
With titanium sponge, niobium titanium intermediate alloy, aluminum titanium intermediate alloy, aluminum silicon intermediate alloy, titanium stannum intermediate alloy is a raw material, take by weighing 2.67 kilograms of titanium sponges, 2.0 kilograms of niobium titanium intermediate alloys (columbic weight percentage is 80% in the niobium titanium intermediate alloy), 0.1 kilogram of aluminum titanium intermediate alloy (weight percentage of aluminum is 52% in the aluminum titanium intermediate alloy), 0.08 kilogram of aluminum silicon intermediate alloy (weight percentage of aluminum is 50% in the aluminum silicon intermediate alloy), 0.15 kilogram of titanium stannum intermediate alloy (weight percentage of titanium is 80% in the titanium stannum intermediate alloy), with the above-mentioned raw materials mix homogeneously, suppress 3 kilograms electrode, be smelted into the cylinder ingot casting through the secondary vacuum consumable electroarc furnace, the melting useful vacuum degree all is not more than 5Pa, at 850 ℃ of hammer coggings, behind 950 ℃ of homogenization insulation 60min, through swaging, cold rolling, bar is processed in cold-drawns etc., total deformation is controlled at 70%, every time deflection is controlled at 20%, bar is heat-treated, heat treatment temperature is incubated 60min at 950 ℃.Above-mentioned processing technique is carried out by the prior art file and is got final product.Processing dental arch filament silk material diameter is 0.31mm.Gained dental arch filament matrix component and each composition weight percentage composition are: niobium (Nb): stannum (Sn) 30%: aluminum (Al) 0.50%: silicon (Si) 1.8%: 0.7%, surplus is titanium (Ti).
Then, applying coating on the dental arch filament matrix:
With titanium sponge, niobium titanium intermediate alloy is raw material, takes by weighing 2 kilograms of titanium sponges, 3 kilograms of niobium titanium intermediate alloys, and wherein, the weight percentage of Nb is 50% in the niobium titanium intermediate alloy.
With above-mentioned titanium sponge, niobium titanium intermediate alloy mix homogeneously, suppress 3 kilograms electrode, be smelted into the cylinder ingot casting through the secondary vacuum consumable electroarc furnace, the melting useful vacuum degree all is not more than 5Pa, and ingot casting is adopted mechanical alloying powder process, and gained grain end particle diameter is less than 50 μ m, adopt the low-power plasma spraying method to prepare coating, spray power is 10Kw, and spray distance is 45mm, powder sending quantity 45g/min;
The biological coating thickness of preparing at the dental arch filament matrix surface for preparing is 35 μ m, and it is 0.03% that biological coating contains oxygen (O) amount, and containing aluminum (Al) amount is 0.008%, and containing niobium (Nb) amount is 27.5%, and surplus is titanium (Ti).
Dental arch filament performance behind the dental arch filament matrix of embodiment 3 and embodiment 4 gained and the coating biological coating is as shown in table 1, and as can be seen from the table: the elastic modelling quantity of the dental arch filament of dental arch filament of the present invention and coating biological coating is low, all is lower than 50MPa.Intensity increased after the dental arch filament matrix applied biological coating, and plasticity and elastic modulus change are little.Because the TiNb biological compatibility of coating is good, therefore can improve matrix greatly is TiNbAl alloy dental arch filament safety in utilization.
The mechanical property of the dental arch filament behind the dental arch filament matrix of table 1 embodiment 3,4 and the coating biological coating
Claims (10)
1. a biological coating is characterized in that, the component of biological coating and each composition weight percentage composition are: niobium (Nb): 18%～32%; At least a in the following column element: stannum (Sn): aluminum (Al) 0.001%～8%: silicon (Si) 0.001%～5%: zirconium (Zr) 0.001%～6%: 0.001～6%, tantalum (Ta): 0.001～6%, hafnium (Hf): 0.001～8%, palladium (Pd): gallium (Ga) 0.001%～3%: 0.001～6%, germanium (Ge): 0.001～6%, nickel (Ni): 0.001～0.05%, oxygen (O): 0.001%～0.2%; Surplus is titanium (Ti).
2. a kind of biological coating according to claim 1, it is characterized in that, described biological coating contains at least a in stannum (Sn), aluminum (Al), silicon (Si), zirconium (Zr), tantalum (Ta), hafnium (Hf), palladium (Pd), gallium (Ga), germanium (Ge), the nickel (Ni) and above-mentioned element wt percentage composition sum≤8%.
3. a kind of biological coating according to claim 1, it is characterized in that, also contain in carbon (C), hydrogen (H), nitrogen (N), the argon (Ar) one or more in the described biological coating, wherein, weight percentage sum≤0.05% of carbon (C), hydrogen (H), three kinds of components of nitrogen (N), weight percentage≤0.03% of argon (Ar).
4. a kind of biological coating according to claim 1 is characterized in that, the thickness of described biological coating is between 0.01 μ m～80 μ m.
5. biological coating according to claim 1 is characterized in that described biological coating is used to apply titanium-base alloy, Ti-Ni alloy and rustless steel.
6. dental arch filament, it is characterized in that, this dental arch filament has applied biological coating as claimed in claim 1 on matrix, wherein, the matrix component of dental arch filament and each composition weight percentage composition are: niobium (Nb): stannum (Sn) 24%～42%: aluminum (Al) 0.35%～5.5%: silicon (Si) 0.3%～5.5%: 0.5%～5.5%, and surplus is titanium (Ti) and unavoidable impurities.
7. dental arch filament according to claim 6 is characterized in that, also contains zirconium (Zr) in the described matrix, and the weight percentage of zirconium (Zr) is 0.2%～5.5%.
8. according to claim 6 or 7 described dental arch filaments, it is characterized in that, in the described matrix, weight percentage sum≤45% of niobium (Nb) and aluminum (Al).
9. dental arch filament according to claim 7 is characterized in that, weight percentage sum≤12% of stannum in the described matrix (Sn), aluminum (Al), silicon (Si) and four kinds of components of zirconium (Zr).
10. according to claim 6,7,8 or 9 described dental arch filaments, it is characterized in that unavoidable impurities is one or more in carbon (C), hydrogen (H), oxygen (O), the nitrogen (N) in the described matrix, percentage composition by weight, carbon containing (C) amount≤0.05%; Hydrogeneous (H) amount≤0.005%; Contain oxygen (O) amount≤0.05%; Nitrogenous (N) amount≤0.05% wherein, contains oxygen (O) amount and nitrogenous (N) amount sum≤0.07%.
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| CN101988182A (en) * | 2010-12-08 | 2011-03-23 | 沈阳工业大学 | Surface modification method for wear-resisting orthodontic arch wire and obtained wear-resisting arch wire |
| CN102179353A (en) * | 2011-04-14 | 2011-09-14 | 南昌航空大学 | Method for preparing coating for hiding surface of orthodontic metallic tooth arc wire |
| CN102191481A (en) * | 2011-04-12 | 2011-09-21 | 哈尔滨工程大学 | Medical magnesium alloy with surface carrying Hf-Si-N gradient coating and preparation method thereof |
| CN103041449A (en) * | 2012-12-19 | 2013-04-17 | 北京固圣生物科技有限公司 | Composite bioactivity functional coating |
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| US6752882B2 (en) * | 1999-01-07 | 2004-06-22 | Jiin-Huey Chern Lin | Medical implant made of biocompatible low modulus high strength titanium-niobium alloy and method of using the same |
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| US6752882B2 (en) * | 1999-01-07 | 2004-06-22 | Jiin-Huey Chern Lin | Medical implant made of biocompatible low modulus high strength titanium-niobium alloy and method of using the same |
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| CN102191481A (en) * | 2011-04-12 | 2011-09-21 | 哈尔滨工程大学 | Medical magnesium alloy with surface carrying Hf-Si-N gradient coating and preparation method thereof |
| CN102191481B (en) * | 2011-04-12 | 2012-07-11 | 哈尔滨工程大学 | Medical magnesium alloy with surface carrying Hf-Si-N gradient coating and preparation method thereof |
| CN102179353A (en) * | 2011-04-14 | 2011-09-14 | 南昌航空大学 | Method for preparing coating for hiding surface of orthodontic metallic tooth arc wire |
| WO2013143857A1 (en) * | 2012-03-30 | 2013-10-03 | Dentsply Ih Ab | A medical device having a surface comprising antimicrobial metal |
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| CN103041449B (en) * | 2012-12-19 | 2015-01-14 | 北京固圣生物科技有限公司 | Composite bioactivity functional coating |
| CN106999630A (en) * | 2014-11-17 | 2017-08-01 | 海洋纳米技术有限公司 | It is used as the coated layer with morphogenic activity and the amorphous inorganic polyphosphate calcium phosphate and calcium carbonate granule of support |
| CN111918680A (en) * | 2018-04-04 | 2020-11-10 | 百多力两合公司 | Coated implantable medical devices and coating methods |
| CN114959696A (en) * | 2022-04-29 | 2022-08-30 | 清华大学 | Hard coating and preparation method and application thereof |
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