CN101549170B - Human body absorbable blood vessel support and its manufacturing method - Google Patents
Human body absorbable blood vessel support and its manufacturing method Download PDFInfo
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Abstract
The present invention provides a method for manufacturing human body absorbable blood vessel support, including the following steps: (1) support forming; (2) cleaning and pre-polishing the support; (3) performing surface alloying treatment to the support; (4) performing fine finish to the support after surface treatment. The invention also provides a human body absorbable blood vessel support, theinvention adopts a surface alloying technique so that the support has a compound diffusion layer with adjustable penetration depth, thereby improving the support intensity and simultaneously quickeni ng the corrosion speed of the support and shortening the support absorption cycle. The yield strength and elongation rate can be modulated in a prodigious scope by controlling the distribution, shape and depth of the composite diffusion layer, to reach the intensity and absorption cycle required by the support.
Description
Technical field
The invention belongs to medical instruments field, relate in particular to a kind of human body absorbable blood vessel support and preparation method thereof.
Background technology
Coronary atherosclerotic heart disease is one of major reason that causes mankind's death.Percutaneous tranluminal coronary angioplasty is the Main Means for the treatment of coronary atherosclerotic heart disease.Coronary Artery Disease Intervention Treatment starts from 1977, through the developments of nearly 30 years, perfect, at equipment with technically update and improve.This technology wound is little, instant effect, and mortality rate and complication rate are extremely low, deeply are subjected to patient's favorable comment.Interventional therapy is learned a new branch of science that nowadays also becomes gradually after internal medicine, surgery.
From balloon angioplasty stage of beginning most to the bare metal stent implanted treatment stage, medicament elution metal rack extensive use till now, then to the biodegradable stent interventional therapy of studying, correlation technique is in development progressively.The medicament elution metal rack can reduce the vascular restenosis rate of short-term, but the inherent defect of permanent implanted metal has limited the use widely of bracket for eluting medicament.After the blood vessel plastotype is completed, do not take out if again do not perform an operation, metal rack will forever be retained in human body, bring even serious consequence of a lot of adverse effects.Patient must be for a long time or is taken all the life anticoagulant, not only increases patient's financial burden, also often causes nagiopasthyrosis, even angiorrhexis.When restenosis occurring, can not the secondary implant frame, the later stage blood vessel is reshaped the unfavorable of operation.The interaction of support and main body, the restriction of biocompatibility comes from, and causes long-term endothelial dysfunction, endothelialization postpones, thrombosis, permanent physical stimulation, the chronic inflammatory disease of local response, implanted blood vessel and non-implantable intravascular motor behavior do not mate, etc.The existence of metal rack makes patient can not carry out some necessary medical inspection and treatments, as MRI, magnetic therapy etc.The child growth stage can not be carried out the blood vessel plastotype by support when angiostenosis occurring, because metal rack can become the blockage of blood flow along with the growth of blood vessel after implantation.
In this case, people seek the absorbable material of human body, die away to completing after-poppet in task.Degradable or bioabsorbable stent are class supports of being badly in need of at present, the potential long-term complexity that this support can avoid existing metal rack to bring.Although this idea is not a new idea, when metal rack occurred, people had begun to test the high molecular degradable support.But run into numerous difficulties on searching biocompatibility degradation material, though this anthropoid adsorbable bone section's material and intravascular stent launch is arranged, all do not had well to be approved by market.Subject matter is that macromolecular material intensity is low and must volume large, and the sour environment that the macromolecule degraded causes causes the serious problems such as inflammatory reaction.Often degradation material is difficult to both to satisfy the compatibility with blood vessel wall, avoids again causing simultaneously the inflammatory reaction more serious than metal rack.Also have in addition some theoretic restrictions, support as not clear how thick in us could be after implantation the stable existence certain hour; Degradation speed and the mechanism of biodegradable stent are not very clear; The short-term of the catabolite of degradation material/long-term local intracavity biocompatibility and physiological reaction need to be done quantitative evaluation in addition.
Desirable degradable embedded material should be able to provide better physiology reparation, the reconstruction of local vascular, short-term vertically and straightening function radially, growth and later stage angiopoietic probability is again arranged.The degradable embedded material is wanted and can be detected by MRI and IVUS when following up a case by regular visits to, and can not affect blood vessel and reshape art.Last degradable embedded material want can with medicine or gene blend, make biodegradable stent reach the effect for the treatment of.
First degradable self expandable PLA support is by the Stacks of Duke University development.Animal (Canis familiaris L.) test shows that degradable self expandable PLA support only has very little inflammatory reaction.But other degradable polymer (polyglycolic acid/polylactic acid, polycaprolactone, polyhydroxybutyratevalerate, polyorthoester, and polyethyleneoxide/polybutylene terephthalate) after the experiment of the animal (pig) of support, very serious inflammatory reaction and vascular cell hypertrophy are arranged.These reactions may be by material itself, and catabolite or support moulding cause.Afterwards, obtain acceptable less inflammatory reaction and vascular cell hypertrophy after PLA (321kDa, high molecular), the animal experiment of Z-shaped supporting frame (Igaki-Tamai).But someone for this support slowly the caused problem of degradation process query has been proposed.The blood vessel injury that initial support expansion causes might cause thrombosis, and may cause later stage vascular cell hypertrophy in the process of expansion of the persistence of support.The biodegradable stent of medicine carrying thing also has been developed and has carried out animal experiment.Two kinds of supports comprise ST638 (tyrosine kinase antagonist) support (Igaki-Tamai) and Double helix PLA-effect after Taxus DES implantation, can reduce the in-stent restenosis rate, but the inflammation problem exist still.The commercialization of part degradable polymer support, include balloon expandable and self expandable PLA support (Guidant), everolimus coating self expandable PLA support (Biosensors) and tyrosine-derived polycarbonate support (containing radiopaque iodine trunk, Reva Medical).However, the most outstanding shortcoming of degradable polymer support is to be determined by intrinsic engineering properties.Polymer can not guarantee and the similar radial support power of metallographic phase and little rebound degree.And polymer support is too thick, can not be used in little blood vessel.
Heublein reports at first and uses magnesium alloy AE21 as the feasibility of absorbable metal support, carries out industrialization by Biotronik company at last.Magnesium alloy AE21 main component is magnesium (97%), also contains in addition 2% aluminum and 1% rare earth metal (Ce, Pr, Nd).Magnesium alloy AE21 can satisfy biocompatibility, the requirement on mechanical strength and degradation speed.Animal (pig) test shows very little inflammatory reaction, there is no thrombosis.But also observe endo cell hypertrophy clearly.Second filial generation Absorbale magnesium alloy stent (Magic, Biotronik) contains magnesium and reaches more than 90%, also contains in addition zirconium, yttrium and rare earth metal.Because aluminum is poisonous to human body, so adopt the magnesium alloy that does not contain aluminum to make support.Animal experiment be implanted with when finding for 4 week Absorbale magnesium alloy stent lumen of vessels diameter (1.50mm) larger than the lumen of vessels diameter (1.26mm) that is implanted with common bare bracket, the lumen of vessels diameter that is implanted with Absorbale magnesium alloy stent in 8 whens week is 1.55mm, and the lumen of vessels diameter that is implanted with common bare bracket is 1.09mm.The endo cell hypertrophy reduces a lot, and this may be the reason due to timbering material.Before change on mechanical performance does not occur Absorbale magnesium alloy stent, completed endothelialization on support.First human body test is completed.63 patients' in each large research center, the world clinical experiment shows, 4 months by a definite date get a desired effect take MACE as main terminal point Follow-up results.Do not find death and Cardioversion.Mg is as the nutrient of human body, every day intake in the 300-400mg left and right, Mg itself can be used as medicament and prevents vascular restenosis and promote new osteogenesis.Take the coronary blood pipe holder as example, its quality only has 3-6mg.International well-known medical apparatus corporation, Ltd, as CORDIS, BIOTRONIK etc., all developing magnesium alloy bracket at present.
Subject matter is that the corrosion rate of magnesium alloy in human body is too fast, has limited the application of magnesium alloy bracket.The clinical data of announcing as Biotronik company shows, naked magnesium alloy bracket just disappeared less than 2 months in blood vessel, makes the blood vessel restenosis that subsides.Everybody developing process for treating surface to extend etching time, makes this series products reach practical level.
At present the biomaterial surface method of modifying of report is mainly polymeric coating layer, completely cut off magnesium alloy by polymeric coating layer and contacts with blood, makes the degraded of magnesium alloy occur in after polymeric coating layer degrades, the time that stops in vivo with the prolongation magnesium alloy.Another way is that magnesium alloy is carried out surface treatment, with the differential arc oxidation process as optional operation, but the purpose of technique used is to form the corrosion-inhibiting coating of aluminum on the surface, but because Al is the neurotoxicity element, it introduces the biocompatibility that can reduce the Mg alloy product.
Magnesium alloy is low because of intensity, and plasticity is poor, and the characteristics such as difficult processing cause magnesium alloy to be difficult to high strength and the high-ductility of the requirement of acquisition support.For obtaining the magnesium alloy of high strength and high-ductility, conventional pressure processing can't satisfy the support mechanical property requirements, and superplasticforming processing technique complexity also is difficult to reach.
Ferrum is the needed by human micronutrient element, is the important composition composition of many enzymes.Ferrum is mainly conveying and the Tissue respiration process that participates in the inner oxygen of human body to the physiological function of human body.Body metabolism needs 1～2mg ferrum every day, but because human body is low to the absorbance of ferrum, the ferrum that need to absorb 60～110mg every day from food just can be satisfied the demand.Lack ferrum, can cause iron deficiency anemia.Peuster is that first investigates the feasibility of absorbable metal support in angiopoiesis and the people of safety.The available iron support of his research and development be according to commercialization the design of permanent support (PUVA-AS16), form with laser engraving pure iron (＞99.8%).Show in 6-18 month follow up a case by regular visits at the animal experiment on 16 New Zealand white rabbits and do not find thrombosis, also there is no obvious inflammatory reaction and vascular cell hypertrophy.Any systemic toxicity is not found in the organ inspection.Can use safely although initial animal experiment shows the available iron support, still need to have further research to verify.Nearest report shows, retort stand is used for intravascular stent, good biocompatibility, and iron ion helps to suppress smooth muscle and the growth that promotes endotheliocyte.The difficulty that ferroalloy is made does not exist the intensity of magnesium alloy low much smaller than the Mg alloy, and plasticity is poor, and elastic modelling quantity is low, and difficult processing absorbs too fast problem.But pure iron props up corrosion slowly, has greatly extended the time that foreign body stops in blood vessel.Existing to also have a kind of support be a kind of iron-carbon alloy bioabsorbable stent of high carbon content, and this support can improve yield strength (800Mpa) and percentage elongation (20%) after the DET heat treatment, and corrosion rate is significantly increased.But the percentage elongation of the ferroalloy after processing like this is still not high enough, can not satisfy the instructions for use of support.
Summary of the invention
Technical problem to be solved by this invention is, a kind of human body absorbable blood vessel support and preparation method thereof is provided, and can accelerate the corrosion rate of support, and have good percentage elongation.
In order to solve the problems of the technologies described above, the embodiment of the present invention provides a kind of human body absorbable blood vessel support that adopts above-mentioned manufacture method to obtain, described support is the retort stand through rack forming, cleaning and pre-polish(ing), surface alloying processing and the finishing polish after surface alloying is processed, and described support has the adjustable compound diffusion layer of length of penetration; Described retort stand is pure iron, and perhaps the weight of iron ratio content is greater than 99.5% binary or ternary ferroalloy; Described surface alloying is treated to the ion carburizing, glowdischarge carburizing processing or glow discharge nitriding is processed or ion carbonitriding is processed; Perhaps, described surface alloying is treated to gas carburizing processing or gas nitriding processing or dry cyaniding processing.
The embodiment of the present invention also provides a kind of manufacture method of human body absorbable blood vessel support, comprises the steps:
(1) rack forming;
(2) described support is cleaned and pre-polish(ing);
(3) described support is carried out surface alloying and process, described surface alloying is treated to the ion carburizing, glowdischarge carburizing processing or glow discharge nitriding is processed or ion carbonitriding is processed; Perhaps, described surface alloying is treated to gas carburizing processing or gas nitriding processing or dry cyaniding processing;
(4) the described support after surface treatment is carried out finishing polish;
Support raw material in described step (1) is pure iron, and perhaps the weight of iron ratio content is greater than 99.5% binary or ternary ferroalloy.
Technique scheme adopts surface-alloying process, forms the adjustable compound diffusion layer of length of penetration on support, thereby has improved the intensity of support, accelerates simultaneously the infiltration rate of support, shortens support and absorbs the cycle.After the rack surface alloying, has compound diffusion layer discontinuous, disperse.By changing infiltration source, temperature and time, control distribution, shape and the degree of depth of compound diffusion layer, yield strength and percentage elongation can be regulated within a large range, to reach the required intensity of support and absorption cycle.Compare with the Integral alloy of prior art, surface alloying can guarantee when improving bending strength that there is enough plasticity the inside of supporting structure, can not rupture when support is strutted by sacculus.
Description of drawings
Fig. 1 is the structural representation of a kind of human body absorbable blood vessel support of providing of the embodiment of the present invention;
Fig. 2 is the structural representation that the infiltration compound diffusion layer that provides of the embodiment of the present invention covers whole support wall thickness;
Fig. 3 is the structural representation that infiltration compound diffusion layer that the embodiment of the present invention provides is confined to support inner surface and outer surface.
The specific embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The manufacture method of a kind of human body absorbable blood vessel support that the embodiment of the present invention provides comprises the steps:
(1) rack forming;
(2) described support is cleaned and pre-polish(ing);
(3) described support being carried out surface alloying processes;
(4) the described support after surface treatment is carried out finishing polish.
Support raw material in described step (1) is pure iron, and perhaps the weight of iron ratio content is greater than 99.5% binary or ternary ferroalloy.
Particularly, in step (1), setting laser cutting machine operating frequency (300-1000Hz), running voltage (200-300V), pulse width (0.02-0.18us), cutting speed are 0.05-0.3inch/s.The cutting of retort stand tubing: in the tubing cutting, monitor the support cutting process, control oxygen pneumatic greater than 3atm, air pressure is greater than 2.5atm, and cooling water pressure is greater than (2.5 kilograms/cm of 20-50psi
2).
In step (2), support after cutting carries out pre-polish(ing) to be processed, and the first water of this support is carried out ultrasonic waves for cleaning, and scavenging period is 1-3 minute, then carried out ultrasonic waves for cleaning 5-30 minute with dehydrated alcohol, then carried out ultrasonic waves for cleaning 1-3 minute with acid solution.On electrochemical polish equipment, in the ferrum polishing fluid polishing 1-5 minute, polishing voltage was the 5-30 volt with the support clamping after cleaning.The interval certain hour is turned holder orientation during electrochemical polish.
Surface alloying in step (3) is processed and can be adopted ion to ooze processing, and this ion oozes and is treated to ion carburizing, glowdischarge carburizing processing or glow discharge nitriding processing or ion carbonitriding processing.Certainly ion oozes in processing and can also infiltrate other gas, as long as after can making rack surface carry out the surface alloying processing, has accelerated the corrosion rate of support, has improved the percentage elongation of support, all within protection scope of the present invention.
During ion carburizing, glowdischarge carburizing is processed, will clean and propping up of dewatering is placed on ion and oozes in equipment, support is connected with the negative electrode of power supply, and furnace shell and anodic bonding.Be evacuated down to 2-10Pa, open grid bias power supply, make rack surface keep glow discharge, this moment voltage between 400-700V, after discharge stability, pass into slowly and contain C gas, as CH
4, C
2H
2, ethanol etc. are kept glow discharge and are made backing temp rise to 400-900 degree centigrade, keep cutting off the power supply after certain hour, take out support, carry out next operation.Can come by the adjustment of temperature and time intensity and the corrosive nature of adjusting pole.
During glow discharge nitriding is processed, will clean and propping up of dewatering is placed on ion and oozes in equipment, support is connected with the negative electrode of power supply, and furnace shell and anodic bonding.Be evacuated down to 2-10Pa, open grid bias power supply, make rack surface keep glow discharge, voltage between 400-700V, after discharge stability, passes into mist or the ammonia of H and N slowly at this moment, keep glow discharge and make backing temp rise to 400-550 degree centigrade, keep cutting off the power supply after certain hour, take out support, carry out next operation.Can come by the adjustment of temperature and time intensity and the corrosive nature of adjusting pole.
During ion carbonitriding is processed, will clean and propping up of dewatering is placed on ion and oozes in equipment, support is connected with the negative electrode of power supply, and furnace shell and anodic bonding.Be evacuated down to 2-10Pa, open grid bias power supply, make rack surface keep glow discharge, voltage between 400-700V, after discharge stability, passes into H and the mist that contains N, C slowly at this moment, keep glow discharge and make backing temp rise to 400-650 degree centigrade, keep cutting off the power supply after certain hour, take out support, carry out next operation.Can come by the adjustment of temperature and time intensity and the corrosive nature of adjusting pole.
Surface alloying in above-mentioned steps (3) is processed and can also be processed or gas nitriding processing or dry cyaniding processing by gas carburizing.
In atmosphere controlled heat treatment furnace, put into support, be warmed up to suitable temperature and pass into different gas, realize that rack surface gas oozes C, N or C+N, design parameter sees the following form 1.Can come by the adjustment of temperature and time intensity and the corrosive nature of adjusting pole.
The parameter range of choice of table 1 gas with various infiltration method
| Processing method | Ooze C | Ooze N | Ooze C+N |
| Temperature (℃) | 600-900 | 500-570 | 500-620 |
| Pass into gas | Ethanol+CO 2 | Ammonia | Ammonia+ethanol |
Adopt the intensity of surface-alloying process raising support at the ferroalloy support, accelerate simultaneously the corrosion rate of support, shorten the method that support absorbs the cycle.The key of the surface alloying of support is to form by Fe on the surface of support
4N, Fe
3That C forms is discontinuous, the compound diffusion layer of disperse.Control distribution, shape and the degree of depth of disperse phase by optimizing surface treatment process parameters of temperature, air pressure and time, to reach the required intensity of support and absorption cycle.Support after surface alloying is processed can be regulated within a large range in yield strength and percentage elongation, makes it to meet the instructions for use of support.Compare with the Integral alloy of prior art, surface alloying can guarantee when improving bending strength that there is enough plasticity the inside of supporting structure, can not rupture when support is strutted by sacculus.And by surface treatment, accelerated the corrosion rate of support in blood vessel, by the adjusting of surface treatment parameter, controlled change depth of penetration is regulated corrosion rate, guarantees to be absorbed by the body as early as possible after the blood vessel plastotype is completed.
In step (4), the support after surface treatment is put into the alcoholic solution that contains perchloric acid, and solution temperature is cooled to-7 ℃～1 ℃, applies voltage 5-30V on anode, and the time is 1-3 minute.Then, the taking-up support is put into after ultrasonic washing with clean water 1-3 minute and is used dehydration of alcohol.Observe the width of rack surface and measurement bracket bar after polishing, rack surface fineness Ra can reach below 0.1um, and the width after polishing is 80-120um.
Step (4) can also be carried out drug-carried coat and process afterwards.Drug-carried coat is mainly to be made by degradable carrier and medicine.Wherein the degradable carrier can comprise the polyester macromolecular materials such as polylactic acid, lactic acid-ethanol copolymer, polyethylene glycol/polylactic acid, phosphocholine, poly butyric ester, Polyhydroxybutyrate-co-hydroxyvalerate copolymer, polycaprolactone.Can be also chitosan, modification of chitosan, heparin, phospholipid, the biomaterials such as collagen protein.Medicine used is anti-inflammatory, suppresses propagation or promotes endothelium to climb the medicine that covers.these medicines comprise sirolimus (sirolimus), tacrolimus (tacrolimus), everolimus (everolimus), supralimus, zotarolimus, pimecrolimus, micophenolic acid, ABT-578, biolimus, paclitaxel (paclitaxel), tyxane, QP2, CD34, dexamethasone, 17-beta-estradiol, batimastat, actinomycin D, methotrexate, angiopeptin, tyrosine kinase inhibitors, vincristine, mitomycin, and cyclosporin etc.
Concrete operations are: in organic solvent, the mixing quality ratio is 1: 4 to 4: 1 (medicine: carrier) with medicine and carrier prorate mixed dissolution.Organic solvent used has oxolane, dichloromethane, chloroform, methanol, ethanol etc.After dissolving, apply on homemade spraying equipment.Pure iron support apparatus after coating is put into the baking oven drying of 50 ℃.The surface compact of the pure iron support apparatus after coated medicament, even, solid colour, thickness are about 5 microns.
On the support drug-carried coat, can carry out face coat again and process, it is mainly the biocompatibility of controlling drug releasing rate and improving coating surface for playing.This coating can be chitosan, modification of chitosan, heparin, phospholipid, the biomaterial such as collagen protein or improve the hydrophilic high polymer of rack surface.Be coated with layer manufacturing method thereof and can be spraying, dip-coating.
The support product also can carry out oxirane or radiation sterilization to be processed, and product should be kept in the noble gas packing or in vacuum packaging, the storage life is the 3-24 month.
Above-mentioned retort stand can be for pure iron or weight of iron ratio content greater than 99.5% binary or ternary ferroalloy.The pure iron support has higher bending strength, can adopt thinner frame structure, so have the ability by minor diameter more or more crooked lesion vessels.
See also Fig. 1, the embodiment of the present invention also provides a kind of human body absorbable blood vessel support that adopts above-mentioned manufacture method to obtain, and this support 1 is for having the ferroalloy support of infiltration compound diffusion layer 2.Infiltration compound diffusion layer 2 is that irony support 1 is processed degree of depth scalable that obtain and infiltration by surface alloying, processes through surface alloying, and irony support 1 becomes the ferroalloy support.This irony support 1 can be for pure iron or weight of iron ratio content greater than 99.5% binary or ternary ferroalloy.
This infiltration compound diffusion layer 2 can cover the wall thickness (as Fig. 2) of whole described support 1, perhaps only is positioned at inner surface and the outer surface (as Fig. 3) of support 1.By regulating the process of surface treatment parameter, can control the degree of depth of infiltration, regulate corrosion rate.Surface treatment can be oozed C, N or C+N, and infiltration compound diffusion layer 2 is by C, N element solid solution and the Fe in Fe
4N, Fe
3The compound diffusion layer discontinuous, disperse that C forms forms.The compound diffusion layer 2 of oozing after C processes when support 1 process particularly, comprises solid solution and the Fe of C in Fe
3C； When support 1 comprises solid solution and the Fe of N in Fe through the compound diffusion layer 2 of oozing after N processes
4N； Compound diffusion layer 2 after support 1 is processed through carbo-nitriding comprises C and N solid solution, the Fe in Fe
4N and Fe
3C。
Please again consult Fig. 1, support 1 is and the corresponding tubulose of vessel size, and it comprises " Z " shape ripple section 11 and " U " shape connecting rod section 12, and " U " shape connecting rod section 12 is connected between adjacent " Z " shape ripple section 11, and joins end to end into tubular body." Z " shape ripple section 11 has good bendability and adherent property, and " U " shape connecting rod section 12 can avoid the cripetura after support 1 expansion, guarantees the complete support blood vessels narrow positions of support 1.Clinically, support can be used for coronary artery, peripheral blood vessel.According to the difference of implanting lesion vessels, support 1 can design different waveform quantity and size.
In the present embodiment, support adopts purity greater than 99.5% smelting raw material pure iron tubing, and its chemical composition meets the requirement of GB/T9971-2004, and tube outer diameter is 1.6-4.0mm, and wall thickness is 0.15-0.35mm.
So the intravascular stent that the technical program provides adopts surface-alloying process, support 1 is processed as has the ferroalloy support that permeates compound diffusion layer 2, thereby improved the intensity of support 1, accelerated simultaneously the corrosion rate of support 1, shortened the method that support absorbs the cycle.
Specific embodiment 1
The pure iron pipe (external diameter 2.8mm, wall thickness 0.2mm) that will meet the GB/T9971-2004 requirement is laser-cut into the tubular structure of hollow out by pre-set decorative pattern.The first water of the support of well cutting is carried out ultrasonic waves for cleaning, and scavenging period is 10 minutes, then carries out ultrasonic waves for cleaning 10 minutes with dehydrated alcohol, then carries out ultrasonic waves for cleaning 2 minutes with acid solution.On electrochemical polish equipment, polishing is 2 minutes in the ferrum polishing fluid with the support clamping after cleaning, and polishing voltage is 16 volts.The interval certain hour is turned holder orientation during electrochemical polish.
Support after pre-polish(ing) carries out nitriding.Packing into after this pure iron support is cleaned up contacts fully with the thermometric workpiece on the cathode disc of glow ion stove, closes vacuum chamber.Start vacuum pump and be evacuated to below 6 handkerchiefs, open grid bias power supply, regulation voltage makes and produces glow discharge in vacuum chamber to 450V, and this moment, electric current should be turned down in order to avoid because of arc discharge ablation support as far as possible.After aura is stable, open NH
4Gas cylinder, the adjusting gas flow meter remains on about 30 handkerchiefs vacuum chamber pressure, improve voltage and current and make support be warming up to 520-560 ℃ to 600V and 20A, conditioning chamber internal pressure to 200 handkerchief left and right (according to the technique scalable) keeps powered-down after 60 minutes, gas again.After being cooled to 200 ℃, vacuum chamber takes out support.
Support after surface treatment is put into the electrochemical polish solution that contains n-butyl alcohol, perchloric acid and methanol (4: 1: 2), and solution temperature is cooled to 0 ℃, applies voltage 16V on anode, and the time is 3 minutes.Then, the taking-up support is put into ultrasonic washing with clean water and is used dehydration of alcohol after 3 minutes.Observe the width of rack surface and measurement bracket bar after polishing, rack surface fineness Ra can reach below 0.1um, and the width after polishing is 80-200um.
Support after finishing polish can carry out surperficial medicine carrying to be processed.The preparation of coated medicament solution should be used glass container with cover.Magnetic stirring apparatus and politef stirrer provide good stirring.Coating material (medicine is sirolimus, and carrier is polylactic acid) is accurately added in container after weighing, by the desired concn required oxolane that weighs with scale, add in container.Open magnetic stirring apparatus, until coating material dissolves fully.Surface treated stentplacement is applied on homemade spraying equipment.Ferroalloy support after coating is put into the baking oven drying of 50 ℃.The surface compact of the ferroalloy apparatus after coated medicament, even, solid colour, thickness are about 5 microns.Drug loading is 140 μ g/cm
2After medicine carrying, can carry out face coat for the thrombosis originality that reduces the surface and process.First at the electronegative polymeric coating layer of surface spraying, then this support was immersed in chitosan solution 3 seconds, then immersed in heparin sodium aqua 3 seconds.Dip-coating chitosan-heparin coating is 8 times so repeatedly.
This support clamping carries out vacuum packaging after on foley's tube.Carried out ethylene oxide sterilizing 8 hours.Storage life is June.
The pure iron pipe (external diameter 2.8mm, wall thickness 0.2mm) that will meet the GB/T9971-2004 requirement is laser-cut into the tubular structure of hollow out by pre-set decorative pattern.The first water of the support of well cutting is carried out ultrasonic waves for cleaning, and scavenging period is 10 minutes, then carries out ultrasonic waves for cleaning 10 minutes with dehydrated alcohol, then carries out ultrasonic waves for cleaning 2 minutes with acid solution.On electrochemical polish equipment, polishing is 2 minutes in the ferrum polishing fluid with the support clamping after cleaning, and polishing voltage is 16 volts.The interval certain hour is turned holder orientation during electrochemical polish.
Carry out ion through the support after pre-polish(ing) and ooze C: contact fully with the thermometric workpiece on the cathode disc of the glow ion stove of packing into after this pure iron support is cleaned up, close vacuum chamber.Start vacuum pump and be evacuated to below 6 handkerchiefs, open grid bias power supply, regulation voltage makes and produces glow discharge in vacuum chamber to 450V, and this moment, electric current should be turned down in order to avoid because of arc discharge ablation support as far as possible.After aura is stable, pass into ethanol and CO
2The adjusting gas flow meter remains on about 30 handkerchiefs vacuum chamber pressure, improve voltage and current and make support be warming up to 520-560 ℃ to 600V and 20A, conditioning chamber internal pressure to 200 handkerchief left and right and electric current (according to the technique scalable) keep powered-down, gas after 60 minutes again.After being cooled to 200 ℃, vacuum chamber takes out support.
Support after surface treatment is put into the electrochemical polish solution that contains n-butyl alcohol, perchloric acid and methanol (4: 1: 2), and solution temperature is cooled to 0 ℃, applies voltage 16V on anode, and the time is 3 minutes.Then, the taking-up support is put into ultrasonic washing with clean water and is used dehydration of alcohol after 3 minutes.Observe the width of rack surface and measurement bracket bar after polishing, rack surface fineness Ra can reach below 0.1um, and the width after polishing is 80-200um.
Support after finishing polish can carry out surperficial medicine carrying to be processed.The preparation of coated medicament solution should be used glass container with cover.Magnetic stirring apparatus and politef stirrer provide good stirring.Coating material (medicine is sirolimus, and carrier is polylactic acid) is accurately added in container after weighing, by the desired concn required oxolane that weighs with scale, add in container.Open magnetic stirring apparatus, until coating material dissolves fully.Surface treated stentplacement is applied on homemade spraying equipment.Ferroalloy support after coating is put into the baking oven drying of 50 ℃.The surface compact of the ferroalloy apparatus after coated medicament, even, solid colour, thickness are about 5 microns.Drug loading is 140 μ g/cm
2After medicine carrying, can carry out face coat for the thrombosis originality that reduces the surface and process.First at the electronegative polymeric coating layer of surface spraying, then this support was immersed in chitosan solution 3 seconds, then immersed in heparin sodium aqua 3 seconds.Dip-coating chitosan-heparin coating is 8 times so repeatedly.
This support clamping carries out vacuum packaging after on foley's tube.Carried out ethylene oxide sterilizing 8 hours.Storage life is June.
Specific embodiment 3
The pure iron pipe (external diameter 2.8mm, wall thickness 0.2mm) that will meet the GB/T9971-2004 requirement is laser-cut into the tubular structure of hollow out by pre-set decorative pattern.The first water of the support of well cutting is carried out ultrasonic waves for cleaning, and scavenging period is 10 minutes, then carries out ultrasonic waves for cleaning 10 minutes with dehydrated alcohol, then carries out ultrasonic waves for cleaning 2 minutes with acid solution.On electrochemical polish equipment, polishing is 2 minutes in the ferrum polishing fluid with the support clamping after cleaning, and polishing voltage is 16 volts.The interval certain hour is turned holder orientation during electrochemical polish.
Carry out ion through the support after pre-polish(ing) and ooze C+N: contact fully with the thermometric workpiece on the cathode disc of the glow ion stove of packing into after this pure iron support is cleaned up, close vacuum chamber.Start vacuum pump and be evacuated to below 6 handkerchiefs, open grid bias power supply, regulation voltage makes and produces glow discharge in vacuum chamber to 450V, and this moment, electric current should be turned down in order to avoid because of arc discharge ablation support as far as possible.After aura is stable, pass into ammonia and ethanol, the adjusting gas flow meter remains on about 30 handkerchiefs vacuum chamber pressure, improving voltage and current makes support be warming up to 520-560 ℃ to 600V and 20A, conditioning chamber internal pressure to 200 handkerchief left and right and electric current (according to the technique scalable) keep powered-down after 60 minutes, gas again.After being cooled to 200 ℃, vacuum chamber takes out support.
Support after surface treatment is put into the electrochemical polish solution that contains n-butyl alcohol, perchloric acid and methanol (4: 1: 2), and solution temperature is cooled to 0 ℃, applies voltage 16V on anode, and the time is 3 minutes.Then, the taking-up support is put into ultrasonic washing with clean water and is used dehydration of alcohol after 3 minutes.Observe the width of rack surface and measurement bracket bar after polishing, rack surface fineness Ra can reach below 0.1um, and the width after polishing is 80-200um.
Support after finishing polish can carry out surperficial medicine carrying to be processed.The preparation of coated medicament solution should be used glass container with cover.Magnetic stirring apparatus and politef stirrer provide good stirring.Coating material (medicine is sirolimus, and carrier is polylactic acid) is accurately added in container after weighing, by the desired concn required oxolane that weighs with scale, add in container.Open magnetic stirring apparatus, until coating material dissolves fully.Surface treated stentplacement is applied on homemade spraying equipment.Ferroalloy support after coating is put into the baking oven drying of 50 ℃.The surface compact of the ferroalloy apparatus after coated medicament, even, solid colour, thickness are about 5 microns.Drug loading is 140 μ g/cm
2After medicine carrying, can carry out face coat for the thrombosis originality that reduces the surface and process.First at the electronegative polymeric coating layer of surface spraying, then this support was immersed in chitosan solution 3 seconds, then immersed in heparin sodium aqua 3 seconds.Dip-coating chitosan-heparin coating is 8 times so repeatedly.
This support clamping carries out vacuum packaging after on foley's tube.Carried out ethylene oxide sterilizing 8 hours.Storage life is June.
The above is only preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. human body absorbable blood vessel support, it is characterized in that: described support is the retort stand through rack forming, cleaning and pre-polish(ing), surface alloying processing and the finishing polish after surface alloying is processed, and described support has the adjustable compound diffusion layer of length of penetration; Described retort stand raw material is pure iron, and perhaps the weight of iron ratio content is greater than 99.5% binary or ternary ferroalloy; Described surface alloying is treated to the ion carburizing, glowdischarge carburizing processing or glow discharge nitriding is processed or ion carbonitriding is processed; Perhaps, described surface alloying is treated to gas carburizing processing or gas nitriding processing or dry cyaniding processing.
2. human body absorbable blood vessel support as claimed in claim 1 is characterized in that: process through ion carburizing, glowdischarge carburizing when described support or the described compound diffusion layer of gas carburizing after processing comprises solid solution and the Fe of carbon in ferrum
3C； Described compound diffusion layer after described support is through glow discharge nitriding processing or gas nitriding processing comprises solid solution and the Fe of nitrogen element in ferrum
4N； Described compound diffusion layer after described support is through ion carbonitriding processing or dry cyaniding processing comprises carbon and nitrogen element solid solution, the Fe in ferrum
4N and Fe
3C。
3. human body absorbable blood vessel support as claimed in claim 1, it is characterized in that: described support comprises " Z " shape ripple section and " U " shape connecting rod section, described " U " shape connecting rod section is connected between adjacent described " Z " shape ripple section, and described support is and the corresponding tubulose of blood vessel.
4. the manufacture method of a human body absorbable blood vessel support, is characterized in that, described manufacture method comprises the steps:
(1) rack forming;
(2) described support is cleaned and pre-polish(ing);
(3) described support is carried out surface alloying and process, described surface alloying is treated to the ion carburizing, glowdischarge carburizing processing or glow discharge nitriding is processed or ion carbonitriding is processed; Perhaps, described surface alloying is treated to gas carburizing processing or gas nitriding processing or dry cyaniding processing;
(4) the described support after surface treatment is carried out finishing polish;
Support raw material in described step (1) is pure iron, and perhaps the weight of iron ratio content is greater than 99.5% binary or ternary ferroalloy.
5. the manufacture method of human body absorbable blood vessel support as claimed in claim 4, it is characterized in that: described ion oozes in processing, when carrying out the ion carburizing, glowdischarge carburizing processing, produce stable glow discharge at described rack surface, pass into carbonaceous gas, keep glow discharge and make described backing temp rise to 400-900 degree centigrade; When carrying out the glow discharge nitriding processing, produce stable glow discharge at described rack surface, pass into mist or the ammonia of hydrogen and nitrogen, keep glow discharge and make described backing temp rise to 400-550 degree centigrade; When carrying out the ion carbonitriding processing, produce stable glow discharge at described rack surface, pass into hydrogen and mist nitrogenous, carbon, keep glow discharge and make described backing temp rise to 400-650 degree centigrade; Then the temperature that keeps described support, more described support is taken out in outage.
6. the manufacture method of human body absorbable blood vessel support as claimed in claim 4, it is characterized in that: described step (4) afterwards, described support is carried out drug-carried coat to be processed, in processing, medicine and degradable carrier are dissolved in organic solvent, described solvent covers described rack surface, forms described drug-carried coat.
7. the manufacture method of human body absorbable blood vessel support as claimed in claim 6, is characterized in that: also carry out face coat on described drug-carried coat and process, control the biocompatibility of described drug releasing rate and the described coating of raising.
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| EP2329853B1 (en) | 2009-11-10 | 2015-07-22 | Biotronik VI Patent AG | Implant and method for manufacturing same |
| CN102228721A (en) * | 2011-06-09 | 2011-11-02 | 中国科学院金属研究所 | Degradable coronary stent and manufacturing method thereof |
| CN103371876B (en) * | 2012-04-12 | 2016-01-20 | 先健科技(深圳)有限公司 | The medical apparatus and instruments of biological absorbable or medical device element, and preparation method thereof |
| CN104207866B (en) * | 2013-05-30 | 2016-12-07 | 深圳市先健生物材料技术有限公司 | The medical apparatus and instruments of biological absorbable or the manufacture method of its absorbable parts |
| CN103614718B (en) * | 2013-10-30 | 2016-02-03 | 西南交通大学 | A kind of method obtaining the coating of biological functional and low corrosion speed at pure magnesium surface |
| CN104073868B (en) * | 2014-06-18 | 2016-08-31 | 郑州大学 | A kind of electrochemical process for treating being applicable to magnesium alloy intervention apparatus and auxiliary equipment |
| CN104047046A (en) * | 2014-06-20 | 2014-09-17 | 重庆望江工业有限公司 | Nitrided electrolytic corrosion liquid and electrolytic testing method for depth of steel part nitriding layer |
| CN105664264B (en) * | 2016-04-11 | 2018-10-16 | 刘国远 | A kind of preparation method of cardiovascular and cerebrovascular holder |
| CN113116617B (en) * | 2019-12-31 | 2022-08-19 | 元心科技(深圳)有限公司 | Absorbable peripheral stent and preparation method thereof |
| CN111101190B (en) * | 2020-02-26 | 2022-07-05 | 山东理工大学 | Electro-polishing device for cardiovascular stent |
| CN114107881B (en) * | 2021-11-15 | 2023-07-25 | 湖南弘辉科技有限公司 | High-speed fan blade processing technology |
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| CN101337090A (en) * | 2008-08-29 | 2009-01-07 | 乐普（北京）医疗器械股份有限公司 | Composite coating magnesium/magnesium alloy biology device and preparation method thereof |
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