CN106492293B - A kind of preparation method of the miniature tubing of biological support titanium - Google Patents
A kind of preparation method of the miniature tubing of biological support titanium Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/048—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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Abstract
The present invention is a kind of preparation method of miniature tubing of biological support titanium, comprising: deposits one layer of conductive metal film in polymeric stent；Electroforming titanium parameter is set again are as follows: Anode-cathode Distance 5-28cm, 45-60 DEG C of electroforming temperature, one layer of titanium of electroforming on conductive metal film；Then polymeric stent is melted；Etching removes conductive metal film, finally the obtained miniature tubing of titanium.The present invention can directly electrotyping forming prepares seamless thin wall microcapillary in macromolecule cylindrical mandrel.The internal diameter of tubule depends on the size of controllable macromolecule cylindrical mandrel, and wall thickness can control even several microns of several hundred a microns.Compared with existing miniature tubing processing technology, the electroforming size of pipe and tubing that the invention provides is more tiny.It is good that method provided by the invention prepares ultra-fine tubing comprehensive mechanical property, and intensity is high, and plasticity is good.
Description
Technical field
The present invention relates to miniature intravascular stent fields, are related to a kind of miniature tubing preparation method of biological support titanium.
Background technique
With the extensive use and development of Minimally Interventional Therapy, intravascular stent implantation is generally acknowledged treatment cardiovascular and cerebrovascular disease
One of most effective means of disease.There is the biomaterial for much meeting human body requirement to be used for the production of intravascular stent at present, most
It commonly include metal material and high molecular material.Compared to high molecular material, metallic support performance is stablized, and can provide more preferable
Support strength, therefore metallic support is inner support product leading at present.Metal material for manufacturing blood vessel internal frame is main
It include: stainless steel, tantalum, cobalt-base alloys, platinum, titanium and new titanium alloy.
Before forming end product, it is necessary to the machining process and technological parameter of strict control metal, it is ensured that miniature
The high precision int of tubing geometric dimension and material micromorphology it is high-homogenized, this just has the processing technology of metallic biomaterial
Very high requirement.Currently, the processing common method of intermetallic composite coating tubing has the forming methods such as drilling, hot extrusion, laser cutting.
In above-mentioned processing method, the miniature tubing of thin footpath thin-walled is still difficult to obtain or pipe workpiece quality obtained is poor, is not able to satisfy blood vessel
Inner support processing uses.In " Hanada K, Matsuzaki K, Huang X, et al.Fabrication of Mg alloy
Tubes for biodegradable stent application [J] .Materials Science&Engineering C,
2013,33 (8): proposing the method for preparing the miniature tubule of magnesium alloy in 4746-4750. " document, can prepare outer diameter and be
1.5~1.8mm, the miniature tubing that wall thickness is 150 μm.However, its method needs the drawing procedure by multi-pass, and drawer
Skill is more complicated, requires mould and die accuracy high, and small-bore drawing mould processing difficulties can not even process that (especially pipe outside diameter is small
When 500 μm, drawing mould sizing part can not sanding and polishing, rough surface), it is thick to drawing lubrication, oxide thickness, surface
Rugosity and properties of product control etc. propose strict demand.Therefore a kind of convenient, accurate processing method is to intravascular metal branch
The finished product production of frame is most important.
Electroforming has been applied to many fields, such as auto industry, manufacturing process product, electricity as a kind of precision machining method
Sub- industry, medical supplies etc..In medical field, galvanoplastic have had relevant research in metal support surface prepares coating,
Prepares coating carries out surface and is modified, and to reach accelerated release in vitro drug, improves the purpose of bracket performance.But do not find electricity consumption also at present
Casting prepares the research of medical stand material.The material grains prepared using electrocasting method are tiny, it might even be possible to reach nanometer
Scale.In traditional metal preparation process, metal is generally cast by blank or steel ingot, during following process, is needed
Product size is gradually reduced to obtain final required thin-wall construction.Compared with electrocasting, traditional method energy consumption is more, and imitates
Rate is lower.Therefore in terms of the bracket for preparing biologic medical, electrocasting has very big potentiality.
From the perspective of material, titanium is nonmagnetic, non-toxic, light, is implanted into human body and human body is greatly reduced
Load；And it has many advantages, such as that corrosion resistance is good, biocompatibility is strong, toughness is good.It is golden with stainless steel, cobalt-base alloys etc.
Symbolic animal of the birth year ratio, has biggish application advantage, and development space is very big.
Summary of the invention
Present invention aims in order to overcome complex process in existing miniature tubing processing technology, mold processing difficulties, determine
Surface shape is irregular at diameter band, rough surface, is also easy to produce the defects of drawing scratch, the vacuum annealing that multi pass drawing needs, modeling
Property poor, the drawing residual stress that eccentric and fold easily occurs, need multiple drawing, being also easy to produce alloy strain erosion and crackle root
The deficiencies of.Provide a kind of method for the miniature tubing preparation of titanium that bore is adjustable, wall thickness is controllable.
As follows using technical solution in order to achieve the object of the present invention: specific preparation step includes:
Step 1, one layer of conductive metal film is deposited in polymeric stent；
Step 2, electroforming titanium parameter is arranged are as follows: Anode-cathode Distance 5- in one layer of titanium of electroforming on conductive metal film
28cm, 45-60 DEG C of electroforming temperature；Use electroforming solution for 60-80g/L meta-titanium perborate, 26-34g/L free sodium hydroxide, 26-
34g/L sodium acetate solution, and match 2-4g/L citric acid and 3-6ml/L hydrogen peroxide；
Step 3, polymeric stent is melted；
Step 4, etching removes conductive metal film, and the miniature tubing of titanium is made.
Further, in step 1 using surface treatment deposition layer of conductive film, specially chemical plating, vacuum evaporation or
Magnetron sputtering.
In step 1, the conductive metal film of deposition is copper, aluminium, zinc.
In step 1, polymeric stent uses polystyrene, polymethyl methacrylate, polyvinyl chloride, poly terephthalic acid
Any one in glycol ester, polypropylene.
Further, in step 3, the heating temperature by polymeric stent fusing is 175 DEG C -280 DEG C.
Wherein, when high molecular material is polystyrene, fusion temperature is 280 DEG C.When high molecular material is poly-
When methyl methacrylate, fusion temperature is 270 DEG C.When high molecular material is polyvinyl chloride, fusion temperature 205
℃.When high molecular material is polyethylene terephthalate, fusion temperature is 280 DEG C.When high molecular material is
When polypropylene, fusion temperature is 175 DEG C.
Compared with prior art, the present invention has remarkable advantage as follows:
(1) method provided by the invention can directly electrotyping forming prepares seamless thin wall in macromolecule cylindrical mandrel
Microcapillary.
(2) internal diameter of tubule depend on controllable macromolecule cylindrical mandrel size, and wall thickness can control it is several hundred
Even several microns of a micron.Compared with existing miniature tubing processing technology, the electroforming size of pipe and tubing that the invention provides is more tiny.
(3) it is good to prepare ultra-fine tubing comprehensive mechanical property for method provided by the invention, and intensity is high, and plasticity is good.
Detailed description of the invention
Fig. 1 is the miniature tubing preparation flow figure of titanium
Specific embodiment
The present invention is further illustrated below by embodiment, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
Electroforming prepares the miniature tubing of titanium, and about 10 μm, 300 μm of wall thickness of pipe internal diameter.
Step 1: pretreating process process being carried out to macromolecule filament are as follows: polystyrene filament ultrasonic cleaning → alkalinity
Oil removing → roughening → sensitization → activation → dipping.
It is cleaned between each step with deionized water.In experiment, temperature needed for controlling each step with thermostat water bath.
Surface degreasing first carried out to 10 μ m diameters, 250 μm of length polystyrene filaments, then with 9g/L CrO3, 600mL/L
H2SO4(p=1.84g/cm3), 60 DEG C, the roughening of 2h chemistry.
Workpiece is impregnated into containing 10g/L SnCl2.H2In 0,40ml/L HCl, 37% solution, under room temperature, 3min,
Its surface is set to adsorb one layer of metal ion for being easy to aoxidize.
In 4g/L AgNO3, 9mL/L NH3.H2O under room temperature, activates 3min.
1min is restored at room temperature with 37% solution of 100mL/L HCHO, then is solved with 40 DEG C of 37% solution of 100mL/L HCL
Glue 3min accelerates subsequent chemical deposition speed to improve the catalytic activity on surface.
Step 2: electroless plating technology is used, to the polystyrene matrix copper-depositing on surface coat of metal.The base of chemical bronze plating liquid
This formula: 8g/L CuSO4.5H2O, 3g/L HCHO, 28g/L EDTA will be put into 50 by the polystyrene filament of each step processing
In DEG C copper plating bath, and pH=12.5 is adjusted with 7.5g/L NaOH solution, constantly stirs sample, after plating 196s, takes out cleaning,
Low temperature drying.
Step 3: using electrocasting method to the one layer of titanium of polystyrene filament electroforming that deposited Copper thin film；Electroforming solution
For 60g/L meta-titanium perborate, 26g/L sodium hydroxide (free), 26g/L sodium acetate solution, and it is furnished with 2g/L citric acid and 3ml/L mistake
Hydrogen oxide.Anode-cathode Distance is 5cm, electroforming temperature 45 C, current density 5A/dm2, the electroforming time is 366min.Obtain 300 μm
Closely knit silver color titanium coating.
Step 4: sample is carried out fusing polystyrene at 280 DEG C.
Step 5: configuration etching solution etches copper coating at room temperature, obtains the miniature tubing of titanium.Etching solution is by 500g/L
FeCl3It is formed with 80mL HCL 36%.Sample bubble is completed etching after room temperature etching liquid, 7s.
Step 6: sample passes through 69% dense HNO3Solution pickling processes, then with deionized water cleaned by ultrasonic vibration
5min, afterwards with the liquor-saturated middle cleaned by ultrasonic vibration 5min of anhydrous second.Obtain the miniature tubing of the good titanium of surface quality, pipe material
Tensile strength be that 644MPa meets the requirement of biomaterial.
Embodiment 2
Electroforming prepares the miniature tubing of titanium, 25 μm of pipe internal diameter about 0.25mm, wall thickness.
Step 1: surface pre-treating process process is carried out to macromolecule filament are as follows:
Polymethyl methacrylate filament polishing → alkaline degreasing → roughening → sensitization → activation → dipping.
It is cleaned between each step with deionized water.In experiment, temperature needed for controlling each step with thermostat water bath.
First 0.25mm diameter, 6.25mm length polymethyl methacrylate filament are carried out with 0.086mm silica sand mechanical thick
Change.Oil removing after mechanical polishing, then remakes hydrophilic treated.Hydrophilic treatment process are as follows: SnCl2.2H2O 20g/L, 85 DEG C of temperature,
8min。
30g/L CrO is used again3, 870mL/L H2SO4(p=1.84g/cm3), chemistry is roughened 2min at room temperature.
Workpiece is impregnated into containing 10g/L SnCl2.H2In 0,40ml/L HCl, 37% solution, under room temperature, 3min,
Its surface is set to adsorb one layer of metal ion for being easy to aoxidize.
In 4g/L AgNO3, 9mL/L NH3.H2O activates 3min under room temperature
1min is restored at room temperature with 37% solution of 100mL/L HCHO, then is solved with 40 DEG C of 37% solution of 100mL/L HCL
Glue 3min accelerates subsequent chemical deposition speed to improve the catalytic activity on surface.
Step 2: electroless plating technology is used, to the polymethylmethacrylate matrix copper-depositing on surface coat of metal.Chemical plating
The basic recipe of copper liquid: 8g/L CuSO4.5H2O, 3g/L HCHO, 28g/L EDTA and a certain amount of stabilizer will pass through each step
The polymethyl methacrylate filament of processing is put into 50 DEG C of copper plating baths, and adjusts pH=12.5 with 7.5g/L NaOH solution, no
Break and stir sample, after plating 196s, takes out cleaning, low temperature drying.
Step 3: using electrocasting method to the one layer of titanium of polymethyl methacrylate filament electroforming that deposited copper coating
Belong to；Electroforming solution is 65g/L meta-titanium perborate, 28g/L sodium hydroxide (free), 28g/L sodium acetate solution, and equipped with 3g/L citric acid
With 4ml/L hydrogen peroxide.Anode-cathode Distance is 10cm, electroforming temperature 50 C, current density 2A/dm2, electroforming time 77min.?
The silver color titanium coating closely knit to 25 μm.
Step 4: sample is carried out fusing polymethyl methacrylate at 270 DEG C.
Step 5: configuration etches copper coating in etching solution at room temperature, obtains the miniature tubing of titanium.
Etching solution is by 500g/L FeCl3It is formed with 80mL HCL 36%.Sample is steeped in room temperature etching liquid, 7s can
To have etched.
Step 6: sample passes through 69% dense HNO3Solution pickling processes, then with deionized water cleaned by ultrasonic vibration
5min, afterwards with the liquor-saturated middle cleaned by ultrasonic vibration 5min of anhydrous second.Obtain the miniature tubing of the good titanium of surface quality, pipe material
Tensile strength be 608MPa, meet the requirement of biomaterial.
Embodiment 3
Electroforming prepares the miniature tubing of titanium, finished product internal diameter about 0.5mm, and 50 μm of wall thickness.
Step 1:0.5mm diameter, 12.5mm length polyvinyl chloride filament basis material first use 1 μm of grinding and polishing cream to polish
It to specular light, after being rinsed with water, is immediately placed in acetone and is cleaned by ultrasonic 15min, then to boil 5min (de- for boiling in dehydrated alcohol
Water), then hot blast drying is carried out with hair dryer.
Step 2: vacuum vapour deposition is utilized, to preparing fine aluminium film on PVC base system.Evaporation source select purity be
99.99% high-purity aluminium flake.Before plating, all substrate clamps and evaporation source are both needed to prior degreasing.Raw material aluminium is firstly placed to acetone
Middle ultrasonic cleaning 30min, then 5min (dehydration) is boiled in boiling in dehydrated alcohol.Before vacuum evaporation, high vacuum coating unit is first opened
In iodine-tungsten lamp baking source toast matrix 15min.When plated film, background vacuum is 3.0 × 10-3Pa, substrate temperature are 40 DEG C, when
Between 1min.
Step 3: using electrocasting method to the one layer of titanium of polyvinyl chloride filament electroforming that deposited aluminium film；Electroforming solution is
70g/L meta-titanium perborate, 30g/L sodium hydroxide (free), 30g/L sodium acetate solution, and it is furnished with 4g/L citric acid and 5ml/L peroxide
Change hydrogen.Anode-cathode Distance is 15cm, 55 DEG C of electroforming temperature, current density 3A/dm2, electroforming time 102min.Obtain 50 μm it is closely knit
Silver color titanium coating.
Step 4: sample is carried out fusing polyvinyl chloride at 205 DEG C.
Step 5: configuration etching liquid etches aluminium film under the conditions of 40 DEG C, obtains the miniature tubing of titanium.
Etching liquid is by H3PO4: HNO3: CH3COOH:H2O=80:5:10:5 composition.Sample is steeped in 40 DEG C of etching solutions,
117s can have been etched.
Step 5: sample passes through 69% dense HNO3Solution pickling processes, then with deionized water cleaned by ultrasonic vibration
5min, afterwards with the liquor-saturated middle cleaned by ultrasonic vibration 5min of anhydrous second.Obtain the miniature tubing of the good titanium of surface quality, pipe material
Tensile strength be 616MPa, meet the requirement of biomaterial.
Embodiment 4
Electroforming prepares the miniature tubing of titanium, finished product internal diameter about 0.8mm, and 80 μm of wall thickness.
Step 1:0.8mm diameter, 20mm length polyethylene terephthalate filament basis material first use 1 μm of grinding
Antiscuffing paste looking-glass finish light, after being rinsed with water, is immediately placed in acetone and is cleaned by ultrasonic 15min, then boil in dehydrated alcohol
It boils 5min (dehydration), then carries out hot blast drying with hair dryer.
Step 2: vacuum vapour deposition is utilized, to preparing fine aluminium film on polyethylene terephthalate matrix.Evaporation
It is 99.99% high-purity aluminium flake that purity is selected in source.Before plating, all substrate clamps and evaporation source are both needed to prior degreasing.Raw material aluminium
It is firstly placed to be cleaned by ultrasonic 30min in acetone, then 5min (dehydration) is boiled in boiling in dehydrated alcohol.Before vacuum evaporation, first open
Toast matrix 15min in iodine-tungsten lamp baking source in high vacuum coating unit.When plated film, background vacuum is 3.0 × 10-3Pa, substrate
Temperature is 40 DEG C, time 1min.
Step 3: using electrocasting method to the one layer of titanium of polyethylene terephthalate filament electroforming that deposited aluminium film
Metal；Electroforming solution is 75g/L meta-titanium perborate, 32g/L sodium hydroxide (free), 32g/L sodium acetate solution, and equipped with 4g/L lemon
Acid and 6ml/L hydrogen peroxide.Anode-cathode Distance is 20cm, electroforming temperature 60 C, current density 4A/dm2, the electroforming time
122min.Obtain 80 μm of closely knit silver color titanium coatings.
Step 4: sample is carried out fusing polyethylene terephthalate at 280 DEG C.
Step 5: configuration etching liquid etches aluminium film under the conditions of 40 DEG C, obtains the miniature tubing of titanium.
Etching liquid is by H3PO4: HNO3: CH3COOH:H2O=80:5:10:5 composition.Sample is steeped in 40 DEG C of etching solutions,
117s can have been etched.
Step 6: sample passes through 69% dense HNO3Solution pickling processes, then with deionized water cleaned by ultrasonic vibration
5min, afterwards with the liquor-saturated middle cleaned by ultrasonic vibration 5min of anhydrous second.Obtain the miniature tubing of the good titanium of surface quality, pipe material
Tensile strength be 628MPa, meet the requirement of biomaterial.
Embodiment 5
Electroforming prepares the miniature tubing of titanium, finished product internal diameter about 1mm, and 1 μm of wall thickness
Step 1: sand paper first being carried out to 1mm diameter, 25mm length polypropylene filament and is polished to 800#, then is clear with deionized water
It washes, in the liquor-saturated middle cleaned by ultrasonic vibration 5min of anhydrous second, removes the pollution of material surface, then carry out hot wind with hair dryer and blow
It is dry.
Step 2: radiofrequency magnetron sputtering technology is used, to preparation metallic zinc film on polypropylene substrate.Test the zinc used
Target purity is 99.9%, and target is under when sputtering, and for sample position upper, the spacing between target and sample is 78mm.Sputtering
Atmosphere is high-purity argon, and sputtering power 80W, Ar Pressure 1Pa, background vacuum pressure is 1.1 × 10-4Pa, 15-20 DEG C of circulating waters,
Sputtering time 1min.
Step 3: using electrocasting method to the one layer of titanium of polypropylene filament electroforming that deposited zinc coating；Electroforming solution is
80g/L meta-titanium perborate, 34g/L sodium hydroxide (free), 34g/L sodium acetate solution, and it is furnished with 2.5g/L citric acid and 4ml/L mistake
Hydrogen oxide.Anode-cathode Distance is 28cm, electroforming temperature 50 C, current density 1A/dm2, electroforming time 366s.Obtain 1 μm it is closely knit
Silver color titanium coating.
Step 4: sample is carried out fusing polypropylene at 175 DEG C.
Step 5: configuration dilute hydrochloric acid etches zinc film at room temperature, obtains the miniature tubing of titanium.
It takes 125mL hydrochloric acid (36%) in beaker, distilled water is added to be settled to 500mL, obtain the salt that mass concentration is 9.0%
Acid solution is diluted to 4.5% into several steps.Sample is steeped in room temperature dilute hydrochloric acid solution, 39s can have been etched.
Step 6: sample passes through 69% dense HNO3Solution pickling processes, then with deionized water cleaned by ultrasonic vibration
5min, afterwards with the liquor-saturated middle cleaned by ultrasonic vibration 5min of anhydrous second.The miniature tubing of the good titanium of surface quality is obtained, biology is met
The requirement of material.
Claims (5)
1. a kind of preparation method of the miniature tubing of biological support titanium, which comprises the steps of:
Step 1, one layer of conductive metal film is deposited in polymeric stent；
Step 2, electroforming titanium parameter is set are as follows: Anode-cathode Distance 5-28cm, 45-60 DEG C of electroforming temperature, in conductive metal film
One layer of titanium of upper electroforming；
Step 3, polymeric stent is melted；
Step 4, etching removes conductive metal film, and the miniature tubing of titanium is made；
In step 3, the heating temperature by polymeric stent fusing is 175 DEG C -280 DEG C.
2. the preparation method of the miniature tubing of biological support titanium as described in claim 1, which is characterized in that in step 1, use
Surface treatment deposition layer of conductive film, specially chemical plating, vacuum evaporation or magnetron sputtering.
3. the preparation method of the miniature tubing of biological support titanium as described in claim 1, which is characterized in that in step 1, deposition
Conductive metal film be copper, aluminium, zinc.
4. the preparation method of the miniature tubing of biological support titanium as described in claim 1, which is characterized in that in step 1, high score
Submounts are using in polystyrene, polymethyl methacrylate, polyvinyl chloride, polyethylene terephthalate, polypropylene
Any one.
5. the preparation method of the miniature tubing of biological support titanium as described in claim 1, which is characterized in that in step 2, use
Electroforming solution be 60-80g/L meta-titanium perborate, 26-34g/L free sodium hydroxide, 26-34g/L sodium acetate solution, and match 2-4g/L lemon
Lemon acid and 3-6ml/L hydrogen peroxide.
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| CN108362147A (en) * | 2018-01-04 | 2018-08-03 | 南通大学 | Micro heat pipe manufacturing method |
| CN109821924B (en) * | 2019-01-18 | 2021-03-02 | 广东工业大学 | Method for preparing amorphous alloy microtube |
| CN114748705A (en) * | 2022-05-12 | 2022-07-15 | 南京浩衍鼎业科技技术有限公司 | Polymer stent plated with metal film and preparation method thereof |
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| CN102605390A (en) * | 2012-03-31 | 2012-07-25 | 大连理工大学 | Method of preparing degradable Fe-Zn alloy pipe for intravascular stent by electroforming |
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| CN1323639A (en) * | 2001-04-19 | 2001-11-28 | 朱琪 | Pure gold blood vessel support and its manufacture process |
| CN102605390A (en) * | 2012-03-31 | 2012-07-25 | 大连理工大学 | Method of preparing degradable Fe-Zn alloy pipe for intravascular stent by electroforming |
| CN105559953A (en) * | 2015-12-11 | 2016-05-11 | 青岛尤尼科技有限公司 | Manufacturing method of magnesium alloy cardiovascular stent, stent and perform of stent |
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