CN101549170A - Human body absorbable blood vessel support and its manufacturing method - Google Patents
Human body absorbable blood vessel support and its manufacturing method Download PDFInfo
- Publication number
- CN101549170A CN101549170A CNA2009101070602A CN200910107060A CN101549170A CN 101549170 A CN101549170 A CN 101549170A CN A2009101070602 A CNA2009101070602 A CN A2009101070602A CN 200910107060 A CN200910107060 A CN 200910107060A CN 101549170 A CN101549170 A CN 101549170A
- Authority
- CN
- China
- Prior art keywords
- support
- blood vessel
- human body
- body absorbable
- handled
- 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.)
- Granted
Links
Images
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, the invention 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 quickening 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 to cause one of human dead major reason.Percutaneous tranluminal coronary angioplasty is the main means of treatment coronary atherosclerotic heart disease.The coronary heart disease interventional therapy starts from 1977, through nearly 30 years continuous development, perfect, at equipment with technically update and improve.This technology wound is little, instant effect, and mortality rate and complication rate are extremely low, are subjected to patient's favorable comment deeply.Interventional therapy is learned a new branch of science that nowadays also becomes gradually after internal medicine, surgery.
From the balloon expandable treatment stage that begins most to the bare metal stent implanted treatment stage, medicament elution metal rack extensive use till now, again 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 finished, do not take out if do not perform an operation once more, metal rack will forever be retained in the human body, bring a lot of adverse effects even serious consequence.Patient must be for a long time or is taken anticoagulant all the life, 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 secular endothelial function incomplete, endothelialization postpones, thrombosis, permanent physical stimulation, the chronic inflammatory disease of local response, implanted blood vessel and non-implantable intravascular motor behavior do not match, or the like.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 vessel growth after implantation.
In this case, people seek the absorbable material of human body, die away in the hope of finishing after-poppet in task.It is a class support of being badly in need of at present that degradable maybe can absorb support, the potential secular 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 on searching biocompatibility degradation material, run into numerous difficulties,, all do not had well to be approved by market though this anthropoid adsorbable bone section's material and intravascular stent launch is arranged.Subject matter is that macromolecular material intensity is low and must volume big, and the sour environment that the macromolecule degraded causes causes serious problems such as inflammatory reaction.Often degradation material is difficult to the compatibility both satisfied and blood vessel wall, avoids causing simultaneously the inflammatory reaction more serious than metal rack again.Also have some theoretic restrictions in addition, as our not clear how thick support could be after implantation the stable existence certain hour; The degradation speed and the mechanism of biodegradable stent are not very clear; The short-term of the catabolite of degradation material/secular local intracavity biocompatibility and physiological reaction need be done quantitative evaluation in addition.
Ideal degradable embedded material should be able to provide better physiology reparation, the reconstruction of local vascular, and the vertical and radial aligning effect of short-term has growth and angiopoietic again probability of later stage.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 influence blood vessel and reshape art.Last degradable embedded material want can with medicine or gene blend, make biodegradable stent reach the effect of treatment.
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 has only 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 the PLA (321kDa, high molecular), the animal experiment of zigzag support (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 is caused 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-paclitaxel support, can both 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 determined by inherent engineering properties.Polymer can not guarantee and similar radial support power of metallographic phase and little rebound degree.And polymer support is too thick, can not be used in the little blood vessel.
Heublein reports at first and uses the feasibility of magnesium alloy AE21 as the absorbable metal support, carries out industrialization by Biotronik company at last.Magnesium alloy AE21 main component is magnesium (97%), also contain in addition 2% aluminum and 1% rare earth metal (Ce, Pr, Nd).Magnesium alloy AE21 can satisfy biocompatibility, the requirement on mechanical strength and the degradation speed.Animal (pig) test shows very little inflammatory reaction, does not have thrombosis.But also observe endo cell hypertrophy clearly.(Magic Biotronik) contains magnesium and reaches more than 90% second filial generation Absorbale magnesium alloy stent, also contains zirconium, yttrium and rare earth metal in addition.Because aluminum is poisonous to human body, so adopt not aluminiferous magnesium alloy to make support.Animal experiment be implanted with when finding for 4 weeks Absorbale magnesium alloy stent lumen of vessels diameter (1.50mm) bigger than the lumen of vessels diameter (1.26mm) that is implanted with common bare bracket, the lumen of vessels diameter that is implanted with the time Absorbale magnesium alloy stent in 8 weeks 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 owing to timbering material.Before change on the mechanical performance does not take place Absorbale magnesium alloy stent, finished endothelialization on the support.First human trial is finished.63 patients' in each big research center, the world clinical experiment shows, 4 months by a definite date be that main terminal point Follow-up results gets a desired effect with MACE.Do not find dead and thrombosis incident.Mg is as the nutrient of human body, every day intake about 300-400mg, Mg itself can be used as medicament and prevents vascular restenosis and promote new osteogenesis.With the arteria coronaria intravascular stent is example, and its quality has only 3-6mg.International well-known medical apparatus corporation, Ltd as CORDIS, BIOTRONIK etc., is all developing magnesium alloy bracket at present.
Subject matter is that magnesium alloy is too fast in the intravital corrosion rate of people, has limited the application of magnesium alloy bracket.The clinical data of announcing as Biotronik company shows that naked magnesium alloy bracket just disappeared less than 2 months in blood vessel, make the blood vessel restenosis that subsides.Everybody developing process for treating surface to prolong etching time, makes this series products reach practical level.
The biomaterial surface method of modifying of report mainly is a polymeric coating layer at present, contacts with blood by the isolated magnesium alloy of polymeric coating layer, makes the degraded of magnesium alloy occur in after the polymeric coating layer degraded, to prolong the time that magnesium alloy stops in vivo.Another way is that magnesium alloy is carried out surface treatment, with the differential arc oxidation process as optional operation, but the purpose of used technology is the corrosion-inhibiting coating that forms 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 characteristics such as difficult processing cause magnesium alloy to be difficult to the 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 mainly is 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 not find thrombosis, also do not have tangible 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 further research and verify.Nearest report shows that 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 prolonged the time that foreign body stops in blood vessel greatly.Existing to also have a kind of support be that a kind of iron-carbon alloy of high carbon content can absorb support, and this support can improve yield strength (800Mpa) and percentage elongation (20%) behind the DET heat treatment, and corrosion rate is significantly increased.But the percentage elongation of the ferroalloy after handling 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 invention provides a kind of human body absorbable blood vessel support that adopts above-mentioned manufacture method to obtain, the retort stand of described support for handling through surface alloying, described support has the adjustable compound diffusion layer of length of penetration.
The embodiment of the 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 being carried out surface alloying handles;
(4) the described support after the surface treatment is carried out finishing polish.
Support raw material in the described step (1) is a 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 the infiltration rate of support simultaneously, shortens support and absorbs the cycle.After the rack surface alloying, has compound diffusion layer discontinuous, disperse.By changing infiltration source, temperature and time, distribution, shape and the degree of depth of control compound diffusion layer can regulate yield strength and percentage elongation, to reach required intensity of support and absorption cycle within a large range.Compare with the whole alloying 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 invention;
Fig. 2 is the structural representation that the infiltration compound diffusion layer that provides of the embodiment of the invention covers the entire bracket wall thickness;
Fig. 3 is the structural representation that infiltration compound diffusion layer that the embodiment of the 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,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The manufacture method of a kind of human body absorbable blood vessel support that the embodiment of the 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 handles;
(4) the described support after the surface treatment is carried out finishing polish.
Support raw material in the described step (1) is a pure iron, and perhaps the weight of iron ratio content is greater than 99.5% binary or ternary ferroalloy.
Particularly, in the 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, the control oxygen pneumatic is greater than 3atm, and air pressure is greater than 2.5atm, and cooling water pressure is greater than (2.5 kilograms/cm of 20-50psi
2).
In the step (2), the support after cutting carries out pre-polish(ing) to be handled, and this support elder generation water is carried out ultrasonic waves for cleaning, and scavenging period is 1-3 minute, then carries out ultrasonic waves for cleaning 5-30 minute with dehydrated alcohol, then carries out ultrasonic waves for cleaning 1-3 minute with acid solution.On electrochemical polish equipment, polishing is 1-5 minute in the ferrum polishing fluid with the support clamping after cleaning, and polishing voltage is the 5-30 volt.Certain hour is turned holder orientation at interval during electrochemical polish.
Surface alloying in the step (3) is handled 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 the gas that can also infiltrate other in the processing, 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 handled, propping up of cleaning and dehydration is placed on ion oozes in the equipment, support links to each other with the negative electrode of power supply, and furnace shell is connected with anode.Be evacuated down to 2-10Pa, open grid bias power supply, make rack surface keep glow discharge, this moment voltage between 400-700V, treat discharge stability after, feed slowly and contain C gas, as CH
4, C
2H
2, ethanol etc. are kept glow discharge and are made backing temp rise to the 400-900 degree, keep cutting off the power supply behind the certain hour, take out support, carry out next operation.Can adjust the intensity and the corrosive nature of support by the adjustment of temperature and time.
During glow discharge nitriding is handled, propping up of cleaning and dehydration is placed on ion oozes in the equipment, support links to each other with the negative electrode of power supply, and furnace shell is connected with anode.Be evacuated down to 2-10Pa, open grid bias power supply, make rack surface keep glow discharge, this moment, voltage was between 400-700V, treat discharge stability after, feed mist or the ammonia of H and N slowly, keep glow discharge and make backing temp rise to the 400-550 degree, keep cutting off the power supply behind the certain hour, take out support, carry out next operation.Can adjust the intensity and the corrosive nature of support by the adjustment of temperature and time.
During ion carbonitriding is handled, propping up of cleaning and dehydration is placed on ion oozes in the equipment, support links to each other with the negative electrode of power supply, and furnace shell is connected with anode.Be evacuated down to 2-10Pa, open grid bias power supply, make rack surface keep glow discharge, this moment, voltage was between 400-700V, treat discharge stability after, feed H slowly and contain the mist of N, C, keep glow discharge and make backing temp rise to the 400-650 degree, keep cutting off the power supply behind the certain hour, take out support, carry out next operation.Can adjust the intensity and the corrosive nature of support by the adjustment of temperature and time.
Surface alloying in the above-mentioned steps (3) is handled and can also be handled 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 feed different gas, realize that rack surface gas oozes C, N or C+N, concrete parameter sees the following form 1.Can adjust the intensity and the corrosive nature of support by the adjustment of temperature and time.
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 |
| Feed gas | Ethanol+CO 2 | Ammonia | Ammonia+ethanol |
In the intensity of ferroalloy support employing surface-alloying process raising support, accelerate the corrosion rate of support simultaneously, 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.By optimizing distribution, shape and the degree of depth of process of surface treatment parameters of temperature, air pressure and time control disperse phase, to reach required intensity of support and absorption cycle.Support after surface alloying is handled 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 whole alloying 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, quickened 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 finished.
In the 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.The width of rack surface and measurement bracket bar is observed in the polishing back, and rack surface fineness Ra can reach below the 0.1um, and the width after the polishing is 80-120um.
Step (4) can also be carried out drug-carried coat and handle afterwards.Drug-carried coat mainly is to be made by degradable carrier and medicine.Wherein the degradable carrier can comprise polyester macromolecular materials such as polylactic acid, lactic acid-ethanol copolymer, polyethylene glycol, phosphocholine, poly butyric ester, poly butyric ester-hydroxyl pentanoate copolymer, polycaprolactone.Also can be chitosan, modification of chitosan, heparin, phospholipid, biomaterials such as collagen protein.Used medicine is an 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.Used organic solvent has oxolane, dichloromethane, chloroform, methanol, ethanol etc.After the dissolving, on homemade spraying equipment, apply.Pure iron support apparatus after the coating is put into 50 ℃ baking oven drying.The surface compact of the pure iron support apparatus behind the coated medicament, even, solid colour, thickness are about 5 microns.
On the support drug-carried coat, can carry out face coat again and handle, it mainly is the biocompatibility for playing control drug release speed and improving coating surface.This coating can be a chitosan, modification of chitosan, heparin, phospholipid, 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 handled, and product should be kept in the noble gas packing or in the vacuum packaging, the storage life is the 3-24 month.
Above-mentioned retort stand can 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 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 handled depth-adjustment joint that obtain and infiltration by surface alloying, handles through surface alloying, and irony support 1 becomes the ferroalloy support.This irony support 1 can 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 the inner surface and the outer surface (as Fig. 3) of support 1.By regulating the process of surface treatment parameter, the degree of depth that may command is infiltrated is regulated 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 is formed.Particularly, the compound diffusion layer 2 of oozing after C handles when support 1 process 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 handles
4N; Compound diffusion layer 2 after support 1 is handled through carbo-nitriding comprises C and N solid solution, the Fe in Fe
4N and Fe
3C.
Please consult Fig. 1 once more, support 1 is and the corresponding tubulose of vessel size, and it comprises " Z " shape ripple portion 11 and " U " shape connecting rod portion 12, and " U " shape connecting rod portion 12 is connected between adjacent " Z " shape ripple portion 11, and joins end to end into tubular body." Z " shape ripple portion 11 has good bendability and adherent property, and " U " shape connecting rod portion 12 can avoid the cripetura after support 1 is expanded, and guarantees support 1 complete support blood vessels narrow positions.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 constituent 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 the corrosion rate of support 1 simultaneously, 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 support elder generation water 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.Certain hour is turned holder orientation at interval during electrochemical polish.
Support after pre-polish(ing) carries out ion and oozes N.Packing into after this pure iron support 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 the 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 treating that aura is stable, open NH
4Gas cylinder, the adjustments of gas effusion 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, (according to the technology scalable) keeps powered-down after 60 minutes, gas about conditioning chamber internal pressure to 200 handkerchief once more.Treat to take out support after vacuum chamber is cooled to 200 ℃.
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.The width of rack surface and measurement bracket bar is observed in the polishing back, and rack surface fineness Ra can reach below the 0.1um, and the width after the polishing is 80-200um.
Support after the finishing polish can carry out surperficial medicine carrying to be handled.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 a sirolimus, and carrier is a polylactic acid) is accurately added in the container after the weighing,, add in the container by the desired concn required oxolane that weighs with scale.Open magnetic stirring apparatus, dissolve fully until coating material.Surface treated support is placed on the homemade spraying equipment applies.Ferroalloy support after the coating is put into 50 ℃ baking oven drying.The surface compact of the ferroalloy apparatus behind the coated medicament, even, solid colour, thickness are about 5 microns.Drug loading is 140 μ g/cm
2Behind the medicine carrying, can carry out face coat for the thrombosis originality that reduces the surface and handle.Spray earlier electronegative polymeric coating layer, again this support was immersed in chitosan solution 3 seconds, then immersed in the heparin sodium aqua 3 seconds on the surface.Dip-coating chitosan-heparin coating is 8 times so repeatedly.
This support clamping carries out vacuum packaging after on the 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 support elder generation water 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.Certain hour is turned holder orientation at interval during electrochemical polish.
Carry out ion through the support after the 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 the 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 treating that aura is stable, feed ethanol and CO
2The adjustments of gas effusion 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, once more about conditioning chamber internal pressure to 200 handkerchief and electric current (according to the technology scalable) maintenance powered-down, gas after 60 minutes.Treat to take out support after vacuum chamber is cooled to 200 ℃.
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.The width of rack surface and measurement bracket bar is observed in the polishing back, and rack surface fineness Ra can reach below the 0.1um, and the width after the polishing is 80-200um.
Support after the finishing polish can carry out surperficial medicine carrying to be handled.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 a sirolimus, and carrier is a polylactic acid) is accurately added in the container after the weighing,, add in the container by the desired concn required oxolane that weighs with scale.Open magnetic stirring apparatus, dissolve fully until coating material.Surface treated support is placed on the homemade spraying equipment applies.Ferroalloy support after the coating is put into 50 ℃ baking oven drying.The surface compact of the ferroalloy apparatus behind the coated medicament, even, solid colour, thickness are about 5 microns.Drug loading is 140 μ g/cm
2Behind the medicine carrying, can carry out face coat for the thrombosis originality that reduces the surface and handle.Spray earlier electronegative polymeric coating layer, again this support was immersed in chitosan solution 3 seconds, then immersed in the heparin sodium aqua 3 seconds on the surface.Dip-coating chitosan-heparin coating is 8 times so repeatedly.
This support clamping carries out vacuum packaging after on the 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 support elder generation water 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.Certain hour is turned holder orientation at interval during electrochemical polish.
Carry out ion through the support after the 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 the 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 treating that aura is stable, feed ammonia and ethanol, the adjustments of gas effusion 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, once more about conditioning chamber internal pressure to 200 handkerchief and electric current (according to the technology scalable) keep powered-down after 60 minutes, gas.Treat to take out support after vacuum chamber is cooled to 200 ℃.
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.The width of rack surface and measurement bracket bar is observed in the polishing back, and rack surface fineness Ra can reach below the 0.1um, and the width after the polishing is 80-200um.
Support after the finishing polish can carry out surperficial medicine carrying to be handled.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 a sirolimus, and carrier is a polylactic acid) is accurately added in the container after the weighing,, add in the container by the desired concn required oxolane that weighs with scale.Open magnetic stirring apparatus, dissolve fully until coating material.Surface treated support is placed on the homemade spraying equipment applies.Ferroalloy support after the coating is put into 50 ℃ baking oven drying.The surface compact of the ferroalloy apparatus behind the coated medicament, even, solid colour, thickness are about 5 microns.Drug loading is 140 μ g/cm
2Behind the medicine carrying, can carry out face coat for the thrombosis originality that reduces the surface and handle.Spray earlier electronegative polymeric coating layer, again this support was immersed in chitosan solution 3 seconds, then immersed in the heparin sodium aqua 3 seconds on the surface.Dip-coating chitosan-heparin coating is 8 times so repeatedly.
This support clamping carries out vacuum packaging after on the foley's tube.Carried out ethylene oxide sterilizing 8 hours.Storage life is June.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1, a kind of human body absorbable blood vessel support is characterized in that: the retort stand of described support for handling through surface alloying, described support has the adjustable compound diffusion layer of length of penetration.
2, human body absorbable blood vessel support as claimed in claim 1 is characterized in that: described surface alloying is treated to the ion carburizing, glowdischarge carburizing processing or glow discharge nitriding is handled or ion carbonitriding is handled.
3, human body absorbable blood vessel support as claimed in claim 1 is characterized in that: described surface alloying is treated to the gas carburizing processing or gas nitriding is handled or dry cyaniding is handled.
4, as claim 2 or 3 described human body absorbable blood vessel supports, it is characterized in that: when described support comprises the solid solution and the Fe of carbon in ferrum through the described compound diffusion layer after the Carburization Treatment
3C; Described compound diffusion layer after described support is handled through nitriding comprises solid solution and the Fe of nitrogen element in ferrum
4N; Described compound diffusion layer after described support is handled through carbo-nitriding comprises carbon and nitrogen element solid solution, the Fe in ferrum
4N and Fe
3C.
5, human body absorbable blood vessel support as claimed in claim 1, it is characterized in that: described support comprises " Z " shape ripple portion and " U " shape connecting rod portion, described " U " shape connecting rod portion is connected between adjacent described " Z " shape ripple portion, and described support is and the corresponding tubulose of blood vessel.
6, 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 being carried out surface alloying handles;
(4) the described support after the surface treatment is carried out finishing polish.
Support raw material in the described step (1) is a pure iron, and perhaps the weight of iron ratio content is greater than 99.5% binary or ternary ferroalloy.
7, the manufacture method of human body absorbable blood vessel support as claimed in claim 6 is characterized in that: the surface alloying in the described step (3) is treated to ion and oozes processing.
8, the manufacture method of human body absorbable blood vessel support as claimed in claim 7, it is characterized in that: described ion oozes in the processing, when carrying out the ion carburizing, glowdischarge carburizing processing, produce stable glow discharge at described rack surface, feed carbonaceous gas, keep glow discharge and make described backing temp rise to the 400-900 degree; When carrying out the glow discharge nitriding processing, produce stable glow discharge at described rack surface, feed the mist or the ammonia of hydrogen and nitrogen, keep glow discharge and make described backing temp rise to the 400-550 degree; When carrying out the ion carbonitriding processing, produce stable glow discharge at described rack surface, feed hydrogen and mist nitrogenous, carbon, keep glow discharge and make described backing temp rise to the 400-650 degree; The temperature that keeps described support then, described support is taken out in outage again.
9, the manufacture method of human body absorbable blood vessel support as claimed in claim 6, it is characterized in that: described step (4) afterwards, described support is carried out drug-carried coat to be handled, in processing, medicine and degradable carrier are dissolved in organic solvent, described solvent covers described rack surface, forms described drug-carried coat.
10, the manufacture method of human body absorbable blood vessel support as claimed in claim 9 is characterized in that: also carry out face coat on the described drug-carried coat and handle, control described drug releasing rate and improve described biological compatibility of coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101070602A CN101549170B (en) | 2009-05-05 | 2009-05-05 | Human body absorbable blood vessel support and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101070602A CN101549170B (en) | 2009-05-05 | 2009-05-05 | Human body absorbable blood vessel support and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101549170A true CN101549170A (en) | 2009-10-07 |
| CN101549170B CN101549170B (en) | 2013-06-12 |
Family
ID=41153807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101070602A Active CN101549170B (en) | 2009-05-05 | 2009-05-05 | Human body absorbable blood vessel support and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101549170B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2013152728A1 (en) * | 2012-04-12 | 2013-10-17 | 先健科技(深圳)有限公司 | Bioabsorbable medical device or medical device component and preparation method thereof |
| EP2329853A3 (en) * | 2009-11-10 | 2014-01-22 | Biotronik VI Patent AG | Implant and method for manufacturing same |
| CN103614718A (en) * | 2013-10-30 | 2014-03-05 | 西南交通大学 | Method for obtaining bio-functionalized coating with low corrosion speed on pure magnesium surface |
| 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 |
| CN104073868A (en) * | 2014-06-18 | 2014-10-01 | 郑州大学 | Electrochemical treatment method suitable for magnesium alloy interventional device and auxiliary equipment |
| WO2014190908A1 (en) * | 2013-05-30 | 2014-12-04 | 先健科技(深圳)有限公司 | Manufacturing method of iron-based alloy medical apparatus |
| CN105664264A (en) * | 2016-04-11 | 2016-06-15 | 刘国远 | Preparation method of heart and brain intravascular stent |
| CN111101190A (en) * | 2020-02-26 | 2020-05-05 | 山东理工大学 | Electro-polishing device for cardiovascular stent |
| CN113116617A (en) * | 2019-12-31 | 2021-07-16 | 元心科技(深圳)有限公司 | Absorbable peripheral stent and preparation method thereof |
| CN114107881A (en) * | 2021-11-15 | 2022-03-01 | 湖南弘辉科技有限公司 | High-speed fan blade machining process |
| RU2801452C2 (en) * | 2018-11-14 | 2023-08-08 | ВАН, Цзяхао | Method for processing soft magnetic metal materials |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337090B (en) * | 2008-08-29 | 2012-12-12 | 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 |
-
2009
- 2009-05-05 CN CN2009101070602A patent/CN101549170B/en active Active
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2329853A3 (en) * | 2009-11-10 | 2014-01-22 | Biotronik VI Patent AG | Implant and method for manufacturing same |
| US8771783B2 (en) | 2009-11-10 | 2014-07-08 | 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 |
| EP2837359A4 (en) * | 2012-04-12 | 2015-12-09 | Lifetech Scient Shenzhen Co | Bioabsorbable medical device or medical device component and preparation method thereof |
| WO2013152728A1 (en) * | 2012-04-12 | 2013-10-17 | 先健科技(深圳)有限公司 | Bioabsorbable medical device or medical device component and preparation method thereof |
| CN103371876A (en) * | 2012-04-12 | 2013-10-30 | 先健科技(深圳)有限公司 | Bioabsorbable medical instrument or medical instrument part and manufacturing method thereof |
| US9878072B2 (en) | 2012-04-12 | 2018-01-30 | Lifetech Scientific (Shenzhen) Co. Ltd. | Bioabsorbable medical device or medical device component and preparation 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 |
| WO2014190908A1 (en) * | 2013-05-30 | 2014-12-04 | 先健科技(深圳)有限公司 | Manufacturing method of iron-based alloy medical apparatus |
| CN104207866A (en) * | 2013-05-30 | 2014-12-17 | 先健科技(深圳)有限公司 | Manufacturing method for medical apparatus capable of being absorbed by organism or for absorbable part of medical apparatus |
| 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 |
| CN103614718A (en) * | 2013-10-30 | 2014-03-05 | 西南交通大学 | Method for obtaining bio-functionalized coating with low corrosion speed on pure magnesium surface |
| CN104073868A (en) * | 2014-06-18 | 2014-10-01 | 郑州大学 | Electrochemical treatment method suitable for magnesium alloy interventional device and auxiliary equipment |
| 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 |
| CN105664264A (en) * | 2016-04-11 | 2016-06-15 | 刘国远 | Preparation method of heart and brain intravascular stent |
| CN105664264B (en) * | 2016-04-11 | 2018-10-16 | 刘国远 | A kind of preparation method of cardiovascular and cerebrovascular holder |
| RU2801452C2 (en) * | 2018-11-14 | 2023-08-08 | ВАН, Цзяхао | Method for processing soft magnetic metal materials |
| CN113116617A (en) * | 2019-12-31 | 2021-07-16 | 元心科技(深圳)有限公司 | Absorbable peripheral stent and preparation method thereof |
| 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 |
| CN111101190A (en) * | 2020-02-26 | 2020-05-05 | 山东理工大学 | Electro-polishing device for cardiovascular stent |
| CN114107881A (en) * | 2021-11-15 | 2022-03-01 | 湖南弘辉科技有限公司 | High-speed fan blade machining process |
| CN114107881B (en) * | 2021-11-15 | 2023-07-25 | 湖南弘辉科技有限公司 | High-speed fan blade processing technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101549170B (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101549170B (en) | Human body absorbable blood vessel support and its manufacturing method | |
| JP5026422B2 (en) | Surface modification of ePTFE and implant using the same | |
| CN106913916B (en) | Application of degradable zinc-based alloy implant material in preparation of vascular stent | |
| CN201572353U (en) | Human body absorbable intravascular stent | |
| US10058639B2 (en) | Bioresorbable iron-based alloy stent | |
| CN102309368B (en) | Body lumen drug-carrying bracket and preparation method thereof | |
| CN103371876B (en) | The medical apparatus and instruments of biological absorbable or medical device element, and preparation method thereof | |
| CN101496910B (en) | A kind of degradable blood vessel support | |
| CN104857570A (en) | Degradable zinc-based alloy bracket and preparation method thereof | |
| CN102228721A (en) | Degradable coronary stent and manufacturing method thereof | |
| CN105833358B (en) | Intracranial drug eluting stent system and preparation method thereof | |
| JP2013215332A (en) | Bioabsorbable medical instrument and decomposition speed adjusting method for the same | |
| JP2004173770A (en) | In vivo implanting medical appliance | |
| WO2020006882A1 (en) | Degradable spiral coated stent with controllable gradient, preparation method therefor and use thereof | |
| CN111803718B (en) | Anti-fibrosis drug sustained-release coating and preparation method thereof | |
| CN109939271B (en) | Coating structure of medical biodegradable zinc alloy stent and preparation method thereof | |
| CN105457105A (en) | Novel developable magnesium alloy intravascular stent | |
| CN107670121A (en) | A kind of absorbable stent and preparation method thereof | |
| US8231980B2 (en) | Medical implants including iridium oxide | |
| US8771783B2 (en) | Implant and method for manufacturing same | |
| US20140030310A1 (en) | Implant and method for manufacturing same | |
| CN202821735U (en) | Living beings absorbable medical equipment component | |
| CN114652902A (en) | 3D printing intravascular absorbable stent visualized under X-ray and preparation method thereof | |
| CN111676390B (en) | Zn-Ga alloy, preparation method and application thereof | |
| EP3363475A1 (en) | Absorbable iron-based alloy medical instrument implant and manufacturing 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 | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160301 Address after: 518000 Nanshan District high tech Industrial Park in Guangdong Province, North District, Long Hill Road,, the world's top two research building on the south side of the road on the south side of the building on the south side of the 3 Patentee after: Shenzhen Xianjian Biological Material Technology Co., Ltd. Address before: 518000, two Shenzhen Road, Nanshan District science and Technology Park, Guangdong, China Patentee before: Xianjian Scientific (Shenzhen) Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20190613 Address after: 518000 Xianjian Science and Technology Building 1001, 22 South 12 Road, Yuehai Street, Nanshan District, Shenzhen City, Guangdong Province Patentee after: Yuanxin Science and Technology (Shenzhen) Co., Ltd. Address before: 518000 South of 3rd Floor of Saiba Scientific Research Building, Langshan Second Road, North District of Nanshan High-tech Industrial Park, Shenzhen City, Guangdong Province Patentee before: Shenzhen Xianjian Biological Material Technology Co., Ltd. |
|
| TR01 | Transfer of patent right |