CN102973342B - Preparation method of degradable magnesium alloy interventional stent - Google Patents
Preparation method of degradable magnesium alloy interventional stent Download PDFInfo
- Publication number
- CN102973342B CN102973342B CN201210543704.4A CN201210543704A CN102973342B CN 102973342 B CN102973342 B CN 102973342B CN 201210543704 A CN201210543704 A CN 201210543704A CN 102973342 B CN102973342 B CN 102973342B
- Authority
- CN
- China
- Prior art keywords
- magnesium alloy
- intervention support
- blasting treatment
- treatment
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a preparation method of a degradable magnesium alloy interventional stent, and the method comprises the following steps of A, selecting a magnesium alloy capillary tube; B, forming through a laser engraving way; C, removing slag; D, primary sand blasting, and vacuum drying after the ultrasonic washing for 3min to 10min in weak-acid washing agent after the sand blasting treatment; E, heat treatment: the heat treatment is carried by adopting a vacuum furnace or a heat treatment furnace under the argon protection, the heat treatment time is 5min to 20min, and the heat treatment temperature is 200DEG C to 400DEG C; F, secondary sand blasting and vacuum drying after the ultrasonic washing of 3min to 10min in weak-acid washing agent after the secondary sand blasting treatment; and G, electrolysis polishing. The method is simple in steps, reasonable in design, convenient to realize, good in application effect and capable of effectively preventing the oxidation of the stent in the machining process; and moreover, the prepared interventional stent is high in dimensional precision, high in surface smoothness and excellent in mechanical property.
Description
Technical field
The present invention relates to the preparation method of intervention support for the human organ interventional therapys such as a kind of blood vessel, bile duct, especially relate to a kind of preparation method of degradable magnesium alloy intervention support.
Background technology
Blood vessel intervention support is applied to the treatment of the undesirable or damaged blood vessels of percutaneous transluminal angioplasty effect at first, and repairs the compound damage that bypass is put up a bridge and caused.Compare with simple PTCA, the acute occlusion causing after intravascular stent implant into body and the incidence rate of restenosis obviously reduce.Because support contacts with blood for a long time, the blood compatibility of material and the quality of biomechanical property, will directly affect clinical application effect.
At present, be applied to the clinical support overwhelming majority and be made of metal, comprised 316L rustless steel, titanium alloy, cobalt-base alloys, tantalum-base alloy, magnesium alloy etc.The most mechanical property of metallic stent material is better, but As time goes on, metal material is aging, corrosion gradually, discharges metal ion in body fluid, to body, may produce harmful effect.In addition, support is subject to the effect of body internal stress in vivo for a long time, after using, fatigue fracture may occur in the long period.Thereby current research and development trend are the degradable intervention supports of research.
Low and the specific strength of the density of magnesium alloy, specific stiffness are high, particularly have good biocompatibility, elastic modelling quantity low, can progressively degrade and by the effective feature such as absorption of human body in vivo, in recent years, increasing magnesium alloy materials is used to exploitation and the application of Srgery grafting apparatus (as blade plate, bone screw etc.) and internal medicine intervention apparatus (as products such as endovascular stents).Magnesium alloy as intravascular stent generally contains more than 90% magnesium, mechanical property is suitable with 316L rustless steel, be unique a kind of biodegradation absorption metallic stent material of doing, within after its implant into body about about two months, can be absorbed, the Mg ion pair human body discharging has no side effect.
Owing to being absorbed by blood dissolves, magnesium alloy bracket can carry out repeatedly interventional therapy at same vascular lesion position, and not having the overlapping problem of bringing of support, this has positive effect to improving lesion vessels compliance, can adopt noninvasive test to follow up a case by regular visits to after the more important thing is Stent.2004, magnesium alloy coronary artery bracket tested and has obtained success first for human clinical.Recently, have again a kind of new magnesium alloy biodegradable stent to be developed, its composition is Mg-3A1-1Re, and research shows it is safely and effectively.
As a kind of absorbable metal support, magnesium alloy bracket has the potentiality as New-support, and catabolite is nontoxic, is an important directions of metal rack development.But magnesium alloy plasticity is at room temperature very poor, in processing preparation process, be very easily oxidized, so dark, the polish of the high-end product of magnesium alloy have become restriction magnesium alloy at the bottleneck of the high-tech area application such as biomedical engineering and development.
Early stage intravascular stent partly forms with B alloy wire braiding, and the support that particularly TiNi B alloy wire is made is all woven into mostly.Afterwards; support precision and the mechanical property of clinical discovery braiding are poor; processed finished products rate is low, so developed the laser-engraving technique of tubing, adopts the structure of thin footpath thin-wall Mg alloy tubing laser engraving support more stable; not yielding; radial support power is stronger, and working (machining) efficiency is higher, and can effectively control the oxidation of surface of the work with gas protection in the course of processing; the figure of processing easily changes, and then can reduce the cost of manufacture of support.Magnesium alloy is very active, and surface is atmospheric oxidn easily, and corrosion dissolution easily occurs most polar solvents such as water, for the post processing of magnesium alloy bracket has brought very large difficulty.Therefore, be necessary to develop processing and the post-processing technology of biodegradable magnesium alloy intravascular stent.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned deficiency of the prior art, a kind of preparation method of degradable magnesium alloy intervention support is provided, its method step is simple, reasonable in design, realization is convenient and result of use is good, can effectively avoid support to be oxidized in the course of processing, and the dimensional accuracy of prepared intervention support be high, surface smoothness is high and good mechanical performance.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of degradable magnesium alloy intervention support, is characterized in that the method comprises the following steps:
Step 1, magnesium alloy capillary tube are selected: selected magnesium alloy capillary tube is external diameter Φ 1.5mm～Φ 19mm, wall thickness 0.2mm～1mm, the magnesium alloy seamless pipe of length 20mm～100mm and linearity≤1mm/m; The material of described magnesium alloy seamless pipe is can biodegradable medical magnesium alloy material;
Step 2, laser engraving molding: first the intervention support pattern that designs in advance also drawn required engraving molding is imported to laser engraving machine; Afterwards, under inert gas shielding, adopt described laser engraving machine to carry out precision engraving to selected described magnesium alloy capillary tube in step 1, and make the intervention support through the molding of precision engraving;
The laser output power of described laser engraving machine is 20W～50W, and laser output frequency is 1500Hz～9000Hz, and the pulsewidth of institute's Output of laser is 0.1ms～0.5ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the described magnesium alloy distance being etched between surface capillaceous is 2mm～3mm, and cutting speed is 70mm/min～150mm/min;
Step 3, the processing of removing slag: by described in step 2 through the intervention support of precision engraving molding, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry;
Step 4, a blasting treatment, its processing procedure is as follows:
Step 401, blasting treatment: adopt sandblasting machine to carry out blasting treatment to the intervention support removing slag in step 3 after processing, the sand grains adopting during blasting treatment is mixed to form by bead and white corundum pearl, and in described sand grains, the percentage by volume of bead is 10%～30%; The granularity of described bead and white corundum pearl is-180 orders;
Step 402, ultrasonic cleaning: by the intervention support after blasting treatment in step 401, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry;
Step 5, heat treatment: adopt vacuum drying oven or adopt heat-treatment furnace under argon shield, the intervention support after vacuum drying in step 402 is heat-treated, heat treatment time is 5min～20min, and heat treatment temperature is 200 ℃～400 ℃;
Step 6, secondary blasting treatment, its processing procedure is as follows:
Step 601, blasting treatment: the intervention support after adopting sandblasting machine to heat treatment in step 5 carries out blasting treatment, the sand grains adopting during blasting treatment is mixed to form by bead and white corundum pearl, and in described sand grains, the percentage by volume of bead is 10%～30%; The granularity of described bead and white corundum pearl is-180 orders;
Step 602, ultrasonic cleaning: by the intervention support after blasting treatment in step 601, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry;
Step 7, electrobrightening are processed, and its processing procedure is as follows:
Step 701, electrobrightening are processed: using in step 602 intervention support after vacuum drying as anode, the aluminium bar of take carries out electrobrightening processing as negative electrode; And while carrying out electrobrightening processing, electrolysis temperature is-25 ℃～20 ℃, and decomposition voltage is that voltage is 8V～15V DC voltage, and electrolysis time is 30s～2min; The electrolyte adopting is uniformly mixed to form by phosphoric acid and organic solvent, and in described electrolyte, the volume ratio of phosphoric acid is 10%～20%;
Step 702, ultrasonic cleaning: the intervention support after electrobrightening in step 701 is processed, put into dehydrated alcohol ultrasonic cleaning 3min～10min final vacuum dry.
The preparation method of above-mentioned a kind of degradable magnesium alloy intervention support, is characterized in that: the material of medical magnesium alloy described in step 1 is AZ31 magnesium alloy or WE43 magnesium alloy.
The preparation method of above-mentioned a kind of degradable magnesium alloy intervention support, is characterized in that: the noble gas described in step 2 is argon or nitrogen.
The preparation method of above-mentioned a kind of degradable magnesium alloy intervention support, it is characterized in that: described in step 3, step 402 and step 602, being weakly acidic abluent, is that ((ratio of 70～75) ︰ (10～20) evenly mixes 20～10) ︰ by nitric acid, dehydrated alcohol and water according to volume ratio.
The preparation method of above-mentioned a kind of degradable magnesium alloy intervention support, is characterized in that: the granularity of bead described in step 401 and step 601 and white corundum pearl is-180 order～+ 250 orders.
The preparation method of above-mentioned a kind of degradable magnesium alloy intervention support, is characterized in that: organic solvent described in step 701 is methanol and/or ethanol.
The preparation method of above-mentioned a kind of degradable magnesium alloy intervention support, is characterized in that: organic solvent described in step 701 is preferably the mixed solvent evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 50%～80%.
The preparation method of above-mentioned a kind of degradable magnesium alloy intervention support, it is characterized in that: while carrying out blasting treatment in step 401, sandblast distance is 25cm～30cm, and sandblast angle is 30 °～45 °, blasting pressure is 0.4MPa ± 0.02Mpa, and the sandblast time is 40s～55s; While carrying out blasting treatment in step 601, sandblast distance is 35cm～40cm, and sandblast angle is 30 °～45 °, and blasting pressure is 0.4MPa ± 0.02Mpa, and the sandblast time is 20s～35s.
The preparation method of above-mentioned a kind of degradable magnesium alloy intervention support, is characterized in that: while carrying out blasting treatment in step 401, blasting pressure is preferably 0.4MPa, and the sandblast time is preferably 50s; While carrying out blasting treatment in step 601, blasting pressure is preferably 0.4MPa, and the sandblast time is preferably 30s.
The present invention compared with prior art has the following advantages:
1, preparation method step is simple, realization is convenient and machining accuracy is high, can obtain the magnesium alloy intervention support that dimensional accuracy is high.
2, the pattern that endovascular stent is prepared in required processing is convenient to global design, in the easy change of designed pattern and preparation technology, control is accurate, precision is high, thin footpath that selected raw material is good biocompatibility and biodegradable thin-wall Mg alloy seamless metal tubing.
3, preparation method is reasonable in design, and its preparation process mainly comprises the following steps: one, magnesium alloy capillary tubes is selected; Two,, under inert gas shielding, by laser engraving machine, magnesium alloy pipe is carried out to precision engraving; Three, in mixed solution, carry out ultrasonic cleaning, remove residue, not only easy to clean and remove slag effective; Four, a blasting treatment, removes machined burrs and oxide skin; Five, heat treatment: eliminate the stress that magnesium alloy materials inside and the laser engraving course of processing produce; Six, secondary blasting treatment, the surface strength of increase support; Seven, electrobrightening is processed, and removes oxide layer, reduces rack surface roughness value, improves anticoagulation function, now just obtains degradable intervention support.
4, in processing preparation, the matrix of intervention support guarantees not oxidized, makes the surperficial aftertreatment technology of intervention support matrix simple.
5, according to the different size of thin footpath used thin-wall Mg alloy tubing, reasonably select the machined parameters of laser engraving machine, make the endovascular stent surface quality that cuts out better, dimensional accuracy is higher, and mechanical property is better.
6, because magnesium alloy is very active; its surface is easily by atmospheric oxidn; thereby easily there is corrosion dissolution in most polar solvents such as itself and water; therefore adopt the organic solvent of weak acid to carry out surface treatment to support; and according to the different size of laser engraving molding after-poppet, rationally adjust ratio and the processing time of solution in solvent, can reach better treatment effect.
7, result of use is good, and prepared intervention support craft precision is high, and the pattern of required processing easily changes and controls accurately, and in processing preparation, support matrix also can guarantee not oxidized.Thereby the present invention can avoid support to be oxidized, obtain the degradable magnesium alloy intervention support that dimensional accuracy is high, surface strength is high and mechanical property is good in the course of processing.
8, applied widely, the subsequent treatment process on intervention support surface after its magnesium alloy laser engraving precise forming capillaceous and engraving molding, not only can be used for preparation clinical middle treatment angiostenosis and the biodegradable magnesium alloy blood vessel inner bracket of energy, can be used for equally the preparation that all kinds of blood vessels of human body such as arteria coronaria, intracranial vessel and non-blood vessel are got involved inner support.
In sum, the inventive method step is simple, reasonable in design, realization is convenient and result of use is good, can effectively avoid support to be oxidized in the course of processing, and the dimensional accuracy of prepared intervention support is high, surface strength is high and good mechanical performance.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the FB(flow block) of preparation method of the present invention.
The specific embodiment
As shown in Figure 1 a kind of preparation method of degradable magnesium alloy intervention support, comprise the following steps:
Step 1, magnesium alloy capillary tube are selected: selected magnesium alloy capillary tube is the magnesium alloy seamless pipe of external diameter Φ 1.5mm～Φ 19mm, wall thickness 0.2mm～1mm, length 20mm～100mm and linearity≤1mm/m; The material of described magnesium alloy seamless pipe is can biodegradable medical magnesium alloy material.
Step 2, laser engraving molding: first the intervention support pattern that designs in advance also drawn required engraving molding is imported to laser engraving machine; Afterwards, under inert gas shielding, adopt described laser engraving machine to carry out precision engraving to selected described magnesium alloy capillary tube in step 1, and make the intervention support through the molding of precision engraving.
The laser output power of described laser engraving machine is 20W～50W, and laser output frequency is 1500Hz～9000Hz, and the pulsewidth of institute's Output of laser is 0.1ms～0.5ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the described magnesium alloy distance being etched between surface capillaceous is 2mm～3mm, and cutting speed is 70mm/min～150mm/min.
Described pattern on the intervention support of precision engraving molding is for being between two by a plurality of the pipe network structure that mirror symmetry figure forms, and the single mesh on described pipe network structure be circle, ellipse, rhombus or swallow-tail form.
Step 3, the processing of removing slag: by described in step 2 through the intervention support of precision engraving molding, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry.
Step 4, a blasting treatment, its processing procedure is as follows:
Step 401, blasting treatment: adopt sandblasting machine to carry out blasting treatment to the intervention support removing slag in step 3 after processing, the sand grains adopting during blasting treatment is mixed to form by bead and white corundum pearl, and in described sand grains, the percentage by volume of bead is 10%～30%; The granularity of described bead and white corundum pearl is-180 orders.
Step 402, ultrasonic cleaning: by the intervention support after blasting treatment in step 401, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry.
Step 5, heat treatment: adopt vacuum drying oven or adopt heat-treatment furnace under argon shield, the intervention support after vacuum drying in step 402 is heat-treated, heat treatment time is 5min～20min, and heat treatment temperature is 200 ℃～400 ℃.
Step 6, secondary blasting treatment, its processing procedure is as follows:
Step 601, blasting treatment: the intervention support after adopting sandblasting machine to heat treatment in step 5 carries out blasting treatment, the sand grains adopting during blasting treatment is mixed to form by bead and white corundum pearl, and in described sand grains, the percentage by volume of bead is 10%～30%; The granularity of described bead and white corundum pearl is-180 orders.
Step 602, ultrasonic cleaning: by the intervention support after blasting treatment in step 601, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry.
Step 7, electrobrightening are processed, and its processing procedure is as follows:
Step 701, electrobrightening are processed: using in step 602 intervention support after vacuum drying as anode, the aluminium bar of take carries out electrobrightening processing as negative electrode; And while carrying out electrobrightening processing, electrolysis temperature is-25 ℃～20 ℃, and decomposition voltage is that voltage is 8V～15V DC voltage, and electrolysis time is 30s～2min; The electrolyte adopting is uniformly mixed to form by phosphoric acid and organic solvent, and in described electrolyte, the volume ratio of phosphoric acid is 10%～20%.
Step 702, ultrasonic cleaning: the intervention support after electrobrightening in step 701 is processed, put into dehydrated alcohol ultrasonic cleaning 3min～10min final vacuum dry.
In actual fabrication process, being weakly acidic abluent described in step 3, step 402 and step 602, is that ((ratio of 70～75) ︰ (10～20) evenly mixes 20～10) ︰ by nitric acid, dehydrated alcohol and water according to volume ratio.During concrete cleaning, also can adopt the weak acid pickling agent of other type.
While carrying out blasting treatment in step 401, sandblast distance is 25cm～30cm, and sandblast angle is 30 °～45 °, and blasting pressure is 0.4MPa ± 0.02Mpa, and the sandblast time is 40s～55s; While carrying out blasting treatment in step 601, sandblast distance is 35cm～40cm, and sandblast angle is 30 °～45 °, and blasting pressure is 0.4MPa ± 0.02Mpa, and the sandblast time is 20s～35s.
The actual electrobrightening that carries out is when process, and organic solvent described in step 701 is methanol and/or ethanol, also can adopt the organic solvent of other type.
Embodiment 1
In the present embodiment, the preparation method of the degradable magnesium alloy intervention support adopting, comprises the following steps:
Step 1, magnesium alloy capillary tube are selected: selected magnesium alloy capillary tube is the magnesium alloy seamless pipe of external diameter 2mm, wall thickness 0.2mm, length 30mm and linearity 1mm/m; The material of described magnesium alloy seamless pipe is AZ31 magnesium alloy materials.
Step 2, laser engraving molding: first the intervention support pattern that designs in advance also drawn required engraving molding is imported to laser engraving machine; Afterwards, under inert gas shielding, adopt described laser engraving machine to carry out precision engraving to selected described magnesium alloy capillary tube in step 1, and make the intervention support through the molding of precision engraving.
In the present embodiment, described noble gas is argon.
The laser output power of described laser engraving machine is 25W, and laser output frequency is 1500Hz, and the pulsewidth of institute's Output of laser is 0.1ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the described magnesium alloy distance being etched between surface capillaceous is 2mm, and cutting speed is 70mm/min.
Step 3, the processing of removing slag: by described in step 2 through the intervention support of precision engraving molding, put into that to be weakly acidic abluent ultrasonic cleaning 3min final vacuum dry.
Step 4, a blasting treatment, its processing procedure is as follows:
Step 401, blasting treatment: adopt sandblasting machine to carry out blasting treatment to the intervention support removing slag in step 3 after processing, the sand grains adopting during blasting treatment is mixed to form by bead and white corundum pearl, and in described sand grains, the percentage by volume of bead is 10%; The granularity of described bead and white corundum pearl is-180 order～+ 250 orders.
Actual while carrying out blasting treatment, the granularity of described bead and white corundum pearl is all crossed 180 mesh sieves and just can.
In this step, while carrying out blasting treatment, sandblast distance is 25cm, and sandblast angle is 30 °, and blasting pressure is 0.4MPa, and the sandblast time is 50s.
Step 402, ultrasonic cleaning: by the intervention support after blasting treatment in step 401, put into that to be weakly acidic abluent ultrasonic cleaning 3min final vacuum dry.
Step 5, heat treatment: the intervention support after adopting vacuum drying oven to vacuum drying in step 402 carries out vacuum heat, and heat treatment time is 20min, and heat treatment temperature is 200 ℃.
Step 6, secondary blasting treatment, its processing procedure is as follows:
Step 601, blasting treatment: the intervention support after adopting sandblasting machine to heat treatment in step 5 carries out blasting treatment, and the sand grains adopting during blasting treatment is mixed to form by bead and white corundum pearl, and in described sand grains, the percentage by volume of bead is 10%; The granularity of described bead and white corundum pearl is-180 order～+ 250 orders.
In this step, while carrying out blasting treatment, sandblast distance is 35cm, and sandblast angle is 30 °, and blasting pressure is 0.4MPa, and the sandblast time is 30s.
Step 602, ultrasonic cleaning: by the intervention support after blasting treatment in step 601, put into that to be weakly acidic abluent ultrasonic cleaning 3min final vacuum dry.
Step 7, electrobrightening are processed, and its processing procedure is as follows:
Step 701, electrobrightening are processed: using in step 602 intervention support after vacuum drying as anode, the aluminium bar of take carries out electrobrightening processing as negative electrode; And while carrying out electrobrightening processing, electrolysis temperature is-25 ℃, and decomposition voltage is that voltage is 8V DC voltage, and electrolysis time is 30s.The electrolyte adopting is uniformly mixed to form by phosphoric acid and organic solvent, and in described electrolyte, the volume ratio of phosphoric acid is 10%.The mixed solvent of described organic solvent for evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 60%.
Step 702, ultrasonic cleaning: the intervention support after electrobrightening in step 701 is processed, put into dehydrated alcohol ultrasonic cleaning 3min final vacuum dry.
In the present embodiment, the ratio that weakly acidic abluent is 20 ︰ 70 ︰ 10 by nitric acid, dehydrated alcohol and water according to volume ratio that is adopting in step 3, step 402 and step 602 evenly mixes, and the water that wherein adopted is deionized water.
Embodiment 2
In the present embodiment, as different from Example 1: in step 1, selected magnesium alloy capillary tube is the magnesium alloy seamless pipe that external diameter Φ 19mm, wall thickness 1mm, length 100mm and linearity are 1mm/m; The material of described magnesium alloy seamless pipe is WE43 magnesium alloy materials; While carrying out laser engraving in step 2, the laser output power of described laser engraving machine is 50W, and laser output frequency is 9000Hz, and the pulsewidth of institute's Output of laser is 0.5ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the distance being etched between surface are 3mm, and cutting speed is 150mm/min; While carrying out blasting treatment in step 401, sandblast distance is 30cm, and sandblast angle is 45 °, and blasting pressure is 0.38MPa, and the sandblast time is 55s; While heat-treating in step 5, adopt vacuum drying oven or adopt heat-treatment furnace to heat-treat under argon shield, heat treatment time is 20min, and heat treatment temperature is 400 ℃; While carrying out blasting treatment in step 601, sandblast distance is 40cm, and sandblast angle is 45 °, and blasting pressure is 0.38MPa, and the sandblast time is 35s; In step 401 and step 601, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 30%; The ratio that weakly acidic abluent is 15 ︰ 75 ︰ 10 by nitric acid, dehydrated alcohol and water according to volume ratio that is adopting in step 3, step 402 and step 602 evenly mixes, the water that wherein adopted is deionized water, and the ultrasonic cleaning time is 10min; While carrying out electrobrightening processing in step 701, electrolysis temperature is 20 ℃, and decomposition voltage is that voltage is 15V DC voltage, and electrolysis time is 2min.The volume ratio of the phosphoric acid in electrolyte that adopts is 15%, the mixed solvent of described organic solvent for evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 50%; In step 702, the ultrasonic cleaning time is 10min.
In the present embodiment, all the other method steps and technological parameter are all identical with embodiment 1.
Embodiment 3
In the present embodiment, as different from Example 1: in step 1, selected magnesium alloy capillary tube is the magnesium alloy seamless pipe that external diameter Φ 10mm, wall thickness 0.5mm, length 50mm and linearity are 1mm/m; The material of described magnesium alloy seamless pipe is AZ 31 magnesium alloy materials; While carrying out laser engraving in step 2, under nitrogen protection, carry out, and the laser output power of described laser engraving machine is 40W, laser output frequency is 7000Hz, and the pulsewidth of institute's Output of laser is 0.4ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the distance being etched between surface are 3mm, and cutting speed is 100mm/min; While carrying out blasting treatment in step 401, sandblast distance is 28cm, and sandblast angle is 35 °, and blasting pressure is 0.42MPa, and the sandblast time is 40s; While heat-treating in step 5, adopt vacuum drying oven or adopt heat-treatment furnace to heat-treat under argon shield, heat treatment time is 10min, and heat treatment temperature is 300 ℃; While carrying out blasting treatment in step 601, sandblast distance is 38cm, and sandblast angle is 35 °, and blasting pressure is 0.42MPa, and the sandblast time is 20s; In step 401, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 15%; In step 601, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 20%; The ratio that weakly acidic abluent is 15 ︰ 75 ︰ 10 by nitric acid, dehydrated alcohol and water according to volume ratio that is adopting in step 3, step 402 and step 602 evenly mixes, in step 3 and step 602, the ultrasonic cleaning time is 6min, and in step 402, the ultrasonic cleaning time is 7min; While carrying out electrobrightening processing in step 701, electrolysis temperature is 0 ℃, and decomposition voltage is that voltage is 10V DC voltage, and electrolysis time is 30s; The volume ratio of the phosphoric acid in electrolyte that adopts is 15%, the mixed solvent of described organic solvent for evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 70%; In step 702, the ultrasonic cleaning time is 4min.
In the present embodiment, all the other method steps and technological parameter are all identical with embodiment 1.
Embodiment 4
In the present embodiment, as different from Example 1: in step 1, selected magnesium alloy capillary tube is the magnesium alloy seamless pipe that external diameter Φ 10mm, wall thickness 0.4mm, length 30mm and linearity are 1mm/m; The material of described magnesium alloy seamless pipe is WE43 magnesium alloy materials; While carrying out laser engraving in step 2, under argon shield, carry out, and the laser output power of described laser engraving machine is 35W, laser output frequency is 5000Hz, and the pulsewidth of institute's Output of laser is 0.3ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the distance being etched between surface are 2mm, and cutting speed is 90mm/min; While carrying out blasting treatment in step 401, sandblast distance is 26cm, and sandblast angle is 38 °, and blasting pressure is 0.4MPa, and the sandblast time is 45s; While heat-treating in step 5, adopt vacuum drying oven or adopt heat-treatment furnace to heat-treat under argon shield, heat treatment time is 20min, and heat treatment temperature is 400 ℃; While carrying out blasting treatment in step 601, sandblast distance is 36cm, and sandblast angle is 38 °, and blasting pressure is 0.4MPa, and the sandblast time is 25s; In step 401, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 30%; In step 601, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 25%; The ratio that weakly acidic abluent is 15 ︰ 75 ︰ 10 by nitric acid, dehydrated alcohol and water according to volume ratio that is adopting in step 3, step 402 and step 602 evenly mixes, in step 3 and step 402, the ultrasonic cleaning time is 5min, and in step 602, the ultrasonic cleaning time is 4min; While carrying out electrobrightening processing in step 701, electrolysis temperature is-20 ℃, and decomposition voltage is that voltage is 10V DC voltage, and electrolysis time is 30s; The volume ratio of the phosphoric acid in electrolyte that adopts is 15%, the mixed solvent of described organic solvent for evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 80%; In step 702, the ultrasonic cleaning time is 3min, and the abluent that also can adopt other and magnesium not to react carries out ultrasonic cleaning.
In the present embodiment, all the other method steps and technological parameter are all identical with embodiment 1.
Embodiment 5
In the present embodiment, as different from Example 1: in step 1, selected magnesium alloy capillary tube is the magnesium alloy seamless pipe that external diameter Φ 10mm, wall thickness 0.4mm, length 40mm and linearity are 1mm/m; The material of described magnesium alloy seamless pipe is AZ 31 magnesium alloy materials; While carrying out laser engraving in step 2, under nitrogen protection, carry out, and the laser output power of described laser engraving machine is 35W, laser output frequency is 6000Hz, and the pulsewidth of institute's Output of laser is 0.2ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the distance being etched between surface are 2mm, and cutting speed is 100mm/min; While heat-treating in step 5, adopt vacuum drying oven or adopt heat-treatment furnace to heat-treat under argon shield, heat treatment time is 10min, and heat treatment temperature is 300 ℃; In step 401, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 20%; In step 601, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 10%; The ratio that weakly acidic abluent is 10 ︰ 70 ︰ 20 by nitric acid, dehydrated alcohol and water according to volume ratio that is adopting in step 3, step 402 and step 602 evenly mixes, in step 3 and step 602, the ultrasonic cleaning time is 5min, and in step 402, the ultrasonic cleaning time is 4min; While carrying out electrobrightening processing in step 701, electrolysis temperature is-10 ℃, and decomposition voltage is that voltage is 10V DC voltage, and electrolysis time is 50s; The volume ratio of the phosphoric acid in electrolyte that adopts is 13%, the mixed solvent of described organic solvent for evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 80%; In step 702, the ultrasonic cleaning time is 4min, and the abluent that also can adopt other and magnesium not to react carries out ultrasonic cleaning.
In the present embodiment, all the other method steps and technological parameter are all identical with embodiment 1.
Embodiment 6
In the present embodiment, as different from Example 1: in step 1, selected magnesium alloy capillary tube is the magnesium alloy seamless pipe that external diameter Φ 12mm, wall thickness 0.6mm, length 60mm and linearity are 1mm/m; The material of described magnesium alloy seamless pipe is AZ31 magnesium alloy materials; While carrying out laser engraving in step 2, under nitrogen protection, carry out, and the laser output power of described laser engraving machine is 20W, laser output frequency is 1700Hz, and the pulsewidth of institute's Output of laser is 0.2ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the distance being etched between surface are 2.5mm, and cutting speed is 120mm/min; While heat-treating in step 5, adopt vacuum drying oven or adopt heat-treatment furnace to heat-treat under argon shield, heat treatment time is 5min, and heat treatment temperature is 300 ℃; In step 401, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 25%; In step 601, during blasting treatment, the percentage by volume of the bead in sand grains that adopts is 15%; The ratio that weakly acidic abluent is 12 ︰ 72 ︰ 16 by nitric acid, dehydrated alcohol and water according to volume ratio that is adopting in step 3, step 402 and step 602 evenly mixes; While carrying out electrobrightening processing in step 701, electrolysis temperature is 10 ℃, and decomposition voltage is that voltage is 12V DC voltage, and electrolysis time is 90s; The volume ratio of the phosphoric acid in electrolyte that adopts is 18%, the mixed solvent of described organic solvent for evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 62%.
In the present embodiment, all the other method steps and technological parameter are all identical with embodiment 1.
Embodiment 7
In the present embodiment, as different from Example 1: in step 1, selected magnesium alloy capillary tube is the magnesium alloy seamless pipe that external diameter Φ 1.5mm, wall thickness 0.3mm, length 20mm and linearity are 1mm/m; The material of described magnesium alloy seamless pipe is AZ31 magnesium alloy materials; While carrying out laser engraving in step 2, under nitrogen protection, carry out, and the laser output power of described laser engraving machine is 22W, laser output frequency is 2000Hz, and the pulsewidth of institute's Output of laser is 0.2ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the distance being etched between surface are 2.5mm, and cutting speed is 85mm/min; While heat-treating in step 5, adopt vacuum drying oven or adopt heat-treatment furnace to heat-treat under argon shield, heat treatment time is 15min, and heat treatment temperature is 350 ℃; The ratio that weakly acidic abluent is 18 ︰ 75 ︰ 7 by nitric acid, dehydrated alcohol and water according to volume ratio that is adopting in step 3, step 402 and step 602 evenly mixes; While carrying out electrobrightening processing in step 701, electrolysis temperature is 15 ℃, and decomposition voltage is that voltage is 10V DC voltage, and electrolysis time is 70s; The volume ratio of the phosphoric acid in electrolyte that adopts is 20%, the mixed solvent of described organic solvent for evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 75%.
In the present embodiment, all the other method steps and technological parameter are all identical with embodiment 1.
Embodiment 8
In the present embodiment, as different from Example 1: in step 1, selected magnesium alloy capillary tube is the magnesium alloy seamless pipe that external diameter Φ 16mm, wall thickness 0.8mm, length 85mm and linearity are 1mm/m; The material of described magnesium alloy seamless pipe is AZ31 magnesium alloy materials; While carrying out laser engraving in step 2, under nitrogen protection, carry out, and the laser output power of described laser engraving machine is 45W, laser output frequency is 8000Hz, and the pulsewidth of institute's Output of laser is 0.2ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the distance being etched between surface are 2.5mm, and cutting speed is 90mm/min; While heat-treating in step 5, adopt vacuum drying oven or adopt heat-treatment furnace to heat-treat under argon shield, heat treatment time is 10min, and heat treatment temperature is 350 ℃; The ratio that weakly acidic abluent is 16 ︰ 72 ︰ 12 by nitric acid, dehydrated alcohol and water according to volume ratio that is adopting in step 3, step 402 and step 602 evenly mixes; While carrying out electrobrightening processing in step 701, electrolysis temperature is 10 ℃, and decomposition voltage is that voltage is 12V DC voltage, and electrolysis time is 90s; The volume ratio of the phosphoric acid in electrolyte that adopts is 18%, and described organic solvent is methanol.
In the present embodiment, all the other method steps and technological parameter are all identical with embodiment 1.
Embodiment 9
In the present embodiment, as different from Example 1: in step 1, selected magnesium alloy capillary tube is the magnesium alloy seamless pipe that external diameter Φ 18mm, wall thickness 0.9mm, length 90mm and linearity are 1mm/m; The material of described magnesium alloy seamless pipe is AZ31 magnesium alloy materials; While carrying out laser engraving in step 2, under nitrogen protection, carry out, and the laser output power of described laser engraving machine is 45W, laser output frequency is 3000Hz, and the pulsewidth of institute's Output of laser is 0.2ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the distance being etched between surface are 2.5mm, and cutting speed is 80mm/min; While heat-treating in step 5, adopt vacuum drying oven or adopt heat-treatment furnace to heat-treat under argon shield, heat treatment time is 15min, and heat treatment temperature is 250 ℃; While carrying out electrobrightening processing in step 701, electrolysis temperature is-5 ℃, and decomposition voltage is that voltage is 9V DC voltage, and electrolysis time is 40s; The volume ratio of the phosphoric acid in electrolyte that adopts is 15%, and described organic solvent is ethanol.
In the present embodiment, all the other method steps and technological parameter are all identical with embodiment 1.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every any simple modification of above embodiment being done according to the technology of the present invention essence, change and equivalent structure change, and all still belong in the protection domain of technical solution of the present invention.
Claims (8)
1. a preparation method for degradable magnesium alloy intervention support, is characterized in that the method comprises the following steps:
Step 1, magnesium alloy capillary tube are selected: selected magnesium alloy capillary tube is external diameter Φ 1.5mm～Φ 19mm, wall thickness 0.2mm～1mm, the magnesium alloy seamless pipe of length 20mm～100mm and linearity≤1mm/m; The material of described magnesium alloy seamless pipe is can biodegradable medical magnesium alloy material;
Step 2, laser engraving molding: first the intervention support pattern that designs in advance also drawn required engraving molding is imported to laser engraving machine; Afterwards, under noble gas or nitrogen protection, adopt described laser engraving machine to carry out precision engraving to selected described magnesium alloy capillary tube in step 1, and make the intervention support through the molding of precision engraving;
The laser output power of described laser engraving machine is 20W～50W, and laser output frequency is 1500Hz～9000Hz, and the pulsewidth of institute's Output of laser is 0.1ms～0.5ms; And while carrying out laser engraving, the Laser emission mouth of described laser engraving machine and the described magnesium alloy distance being etched between surface capillaceous is 2mm～3mm, and cutting speed is 70mm/min～150mm/min;
Step 3, the processing of removing slag: by described in step 2 through the intervention support of precision engraving molding, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry;
Step 4, a blasting treatment, its processing procedure is as follows:
Step 401, blasting treatment: adopt sandblasting machine to carry out blasting treatment to the intervention support removing slag in step 3 after processing, the sand grains adopting during blasting treatment is mixed to form by bead and white corundum pearl, and in described sand grains, the percentage by volume of bead is 10%～30%; The granularity of described bead and white corundum pearl is-180 order～+ 250 orders;
Step 402, ultrasonic cleaning: by the intervention support after blasting treatment in step 401, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry;
Step 5, heat treatment: adopt vacuum drying oven or adopt heat-treatment furnace under argon shield, the intervention support after vacuum drying in step 402 is heat-treated, heat treatment time is 5min～20min, and heat treatment temperature is 200 ℃～400 ℃;
Step 6, secondary blasting treatment, its processing procedure is as follows:
Step 601, blasting treatment: the intervention support after adopting sandblasting machine to heat treatment in step 5 carries out blasting treatment, the sand grains adopting during blasting treatment is mixed to form by bead and white corundum pearl, and in described sand grains, the percentage by volume of bead is 10%～30%; The granularity of described bead and white corundum pearl is-180 order～+ 250 orders;
Step 602, ultrasonic cleaning: by the intervention support after blasting treatment in step 601, put into that to be weakly acidic abluent ultrasonic cleaning 3min～10min final vacuum dry;
Step 7, electrobrightening are processed, and its processing procedure is as follows:
Step 701, electrobrightening are processed: using in step 602 intervention support after vacuum drying as anode, the aluminium bar of take carries out electrobrightening processing as negative electrode; And while carrying out electrobrightening processing, electrolysis temperature is-25 ℃～20 ℃, and decomposition voltage is that voltage is 8V～15V DC voltage, and electrolysis time is 30s～2min; The electrolyte adopting is uniformly mixed to form by phosphoric acid and organic solvent, and in described electrolyte, the volume ratio of phosphoric acid is 10%～20%;
Step 702, ultrasonic cleaning: the intervention support after electrobrightening in step 701 is processed, put into dehydrated alcohol ultrasonic cleaning 3min～10min final vacuum dry;
Organic solvent described in step 701 is methanol and/or ethanol.
2. according to the preparation method of a kind of degradable magnesium alloy intervention support claimed in claim 1, it is characterized in that: the material of medical magnesium alloy described in step 1 is AZ31 magnesium alloy or WE43 magnesium alloy.
3. according to the preparation method of a kind of degradable magnesium alloy intervention support described in claim 1 or 2, it is characterized in that: the noble gas described in step 2 is argon.
4. according to the preparation method of a kind of degradable magnesium alloy intervention support described in claim 1 or 2, it is characterized in that: described in step 3, step 402 and step 602, being weakly acidic abluent, is that ((ratio of 70～75) ︰ (10～20) evenly mixes 20～10) ︰ by nitric acid, dehydrated alcohol and water according to volume ratio.
5. according to the preparation method of a kind of degradable magnesium alloy intervention support described in claim 1 or 2, it is characterized in that: the granularity of bead described in step 401 and step 601 and white corundum pearl is-180 orders.
6. according to the preparation method of a kind of degradable magnesium alloy intervention support claimed in claim 1, it is characterized in that: organic solvent described in step 701 is preferably the mixed solvent evenly being mixed by methanol and ethanol, and in described electrolyte, the percent by volume of methanol is 50%～80%.
7. according to the preparation method of a kind of degradable magnesium alloy intervention support described in claim 1 or 2, it is characterized in that: while carrying out blasting treatment in step 401, sandblast distance is 25cm～30cm, sandblast angle is 30 °～45 °, blasting pressure is 0.4MPa ± 0.02Mpa, and the sandblast time is 40s～55s; While carrying out blasting treatment in step 601, sandblast distance is 35cm～40cm, and sandblast angle is 30 °～45 °, and blasting pressure is 0.4MPa ± 0.02Mpa, and the sandblast time is 20s～35s.
8. according to the preparation method of a kind of degradable magnesium alloy intervention support claimed in claim 7, it is characterized in that: while carrying out blasting treatment in step 401, blasting pressure is preferably 0.4MPa, and the sandblast time is preferably 50s; While carrying out blasting treatment in step 601, blasting pressure is preferably 0.4MPa, and the sandblast time is preferably 30s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210543704.4A CN102973342B (en) | 2012-12-08 | 2012-12-08 | Preparation method of degradable magnesium alloy interventional stent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210543704.4A CN102973342B (en) | 2012-12-08 | 2012-12-08 | Preparation method of degradable magnesium alloy interventional stent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102973342A CN102973342A (en) | 2013-03-20 |
| CN102973342B true CN102973342B (en) | 2014-10-08 |
Family
ID=47847886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210543704.4A Active CN102973342B (en) | 2012-12-08 | 2012-12-08 | Preparation method of degradable magnesium alloy interventional stent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102973342B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105012000A (en) * | 2014-04-29 | 2015-11-04 | 爱派司生技股份有限公司 | Clavicle bone plate with smooth surface and special curvature |
| CN105395298A (en) * | 2014-09-04 | 2016-03-16 | 汤敬东 | Partially degradable blood vessel stent and preparation method thereof |
| CN105154963A (en) * | 2015-08-17 | 2015-12-16 | 奚廷斐 | Electrolytic polishing solution for magnesium alloy medical heart stent and surface polishing processing technology of medical heart stent |
| CN105816215A (en) * | 2015-12-10 | 2016-08-03 | 北京泰杰伟业科技有限公司 | Regional blood flow guiding device as well as preparation method and use method thereof |
| CN106048707B (en) * | 2016-06-29 | 2018-09-28 | 西北有色金属研究院 | A kind of surface treatment method of medical degradable metal intervention support |
| CN109366013A (en) * | 2018-11-26 | 2019-02-22 | 辽宁垠艺生物科技股份有限公司 | Narrow tube decorative pattern cutting method |
| CN111451944A (en) * | 2020-05-18 | 2020-07-28 | 东莞立德生物医疗有限公司 | Biomedical degradable magnesium alloy bone nail and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357089A (en) * | 2008-09-12 | 2009-02-04 | 西北有色金属研究院 | Production method of biology degradable magnesium alloy vascular inner rack |
| CN101543437A (en) * | 2009-04-29 | 2009-09-30 | 乐普（北京）医疗器械股份有限公司 | Method for preparing intravascular stent |
| CN102505104A (en) * | 2011-12-27 | 2012-06-20 | 中国兵器工业第五二研究所 | Magnesium alloy surface pretreatment method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07173635A (en) * | 1993-12-20 | 1995-07-11 | Suzuki Motor Corp | Method for surface treatment of metal |
-
2012
- 2012-12-08 CN CN201210543704.4A patent/CN102973342B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357089A (en) * | 2008-09-12 | 2009-02-04 | 西北有色金属研究院 | Production method of biology degradable magnesium alloy vascular inner rack |
| CN101543437A (en) * | 2009-04-29 | 2009-09-30 | 乐普（北京）医疗器械股份有限公司 | Method for preparing intravascular stent |
| CN102505104A (en) * | 2011-12-27 | 2012-06-20 | 中国兵器工业第五二研究所 | Magnesium alloy surface pretreatment method |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平7-173635A 1995.07.11 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102973342A (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102973342B (en) | Preparation method of degradable magnesium alloy interventional stent | |
| CN101357089A (en) | Production method of biology degradable magnesium alloy vascular inner rack | |
| US6375826B1 (en) | Electro-polishing fixture and electrolyte solution for polishing stents and method | |
| Yang et al. | Corrosion and passivation of annealed Ti–20Zr–6.5 Al–4V alloy | |
| CN105925949B (en) | A kind of preparation method of titanium or titanium alloy surface micro-nano porous structure | |
| US20020092583A1 (en) | Medical devices, particularly stents, and methods for their manufacture | |
| Kathuria | The potential of biocompatible metallic stents and preventing restenosis | |
| CN105559953A (en) | Manufacturing method of magnesium alloy cardiovascular stent, stent and perform of stent | |
| EP2885074B1 (en) | Surface oxide removal methods | |
| JP6560193B2 (en) | Magnesium alloy tube material and manufacturing method thereof, and stent using the same and manufacturing method thereof | |
| Maffia et al. | Selective laser melting of NiTi stents with open-cell and variable diameter | |
| US7357854B1 (en) | Process for electropolishing a device made from cobalt-chromium | |
| CN102988119B (en) | Manufacture method of titanium or titanium alloy laryngotracheal interventional stent | |
| TWI526202B (en) | Methods of processing vascular stents | |
| Demir et al. | Fiber laser micromachining of magnesium alloy tubes for biocompatible and biodegradable cardiovascular stents | |
| US20130092555A1 (en) | Removal of an island from a laser cut article | |
| Catalano et al. | Use of sheet material for rapid prototyping of cardiovascular stents | |
| CN108543118A (en) | The magnesium alloy fixing screws of internal controlled degradation | |
| Petrini et al. | Development of biodegradable magnesium alloy stents with coating | |
| Kathuria | Laser microprocessing of stent for medical therapy | |
| CN108213704B (en) | Method for manufacturing human body implantation stent by using ultrashort pulse laser | |
| Sojitra et al. | Surface enhancement and characterization of L-605 cobalt alloy cardiovascular stent by novel electrochemical treatment | |
| CN105664264A (en) | Preparation method of heart and brain intravascular stent | |
| RU2620428C1 (en) | Method of obtaining coating on implants from titanium and its alloys | |
| CN109267054B (en) | Method for improving corrosion resistance of magnesium alloy by using ultrasonic fluorination coating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |