CN102605390B - Method of preparing degradable Fe-Zn alloy pipe for intravascular stent by electroforming - Google Patents
Method of preparing degradable Fe-Zn alloy pipe for intravascular stent by electroforming Download PDFInfo
- Publication number
- CN102605390B CN102605390B CN201210091212.6A CN201210091212A CN102605390B CN 102605390 B CN102605390 B CN 102605390B CN 201210091212 A CN201210091212 A CN 201210091212A CN 102605390 B CN102605390 B CN 102605390B
- Authority
- CN
- China
- Prior art keywords
- electroforming
- alloy
- negative electrode
- intravascular stent
- pipe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a method of preparing a degradable Fe-Zn alloy pipe for an intravascular stent by electroforming, belonging to the field of biological materials and electrochemical processing. The method is characterized in that a Fe-Zn alloy material is prepared by mutual-competition and codeposition processes of Fe ions and Zn ions, and the obtained alloy is fine in crystal grain and good in comprehensive mechanical performance; the thickness of an electroforming layer can be up to 7-150 microns, and the electroforming layer is served as an individual to be used independently after separating from a substrate, so that a seamless microcapillary pipe for a stent is directly obtained, and a regular pressure shaping procedure of a metal superfine pipe for laser-cutting of the stent is avoided; and a component ratio of a Fe-Zn alloy is changed by regulation of electroforming parameters, thermal treatment changes a microstructure of the Fe-Zn alloy, and the synergistic effect of both sides can regulate the degrading speed of the Fe-Zn alloy material in human body fluid or blood and improve the mechanical performance of the Fe-Zn alloy material. Therefore, according to the method provided by the invention, the Fe-Zn alloy pipe for the intravascular stent, with good biocompatibility, biological corrosion degradation performance and comprehensive mechanical performance is prepared.
Description
Technical field
The present invention relates to a kind of in acidic solution electroforming prepare the method for biodegradable Fe-Zn alloy pipe, specifically refer to anode dissolved ferric iron, ferrous ion in solution and zine ion are made the method for iron-zinc alloy section bar in cathode surface deposition, belong to bio-medical material and electro-chemical machining field.
Background technology
At present a lot of Implantable Medical Devices are all permanent, and this class apparatus tends to cause many complication, and for example, permanent stainless steel intravascular stent can cause the restenosis of implant site blood vessel, long-term local inflammatory response etc.And the device of being made by biological medical degradable material completes after function mission in human body, can be degraded and absorbed along with people's metabolic processes, can not cause long-term impact to human body, can in infant waits the patient who grows in Fast Growth, use in addition yet.Biodegradable metals material, owing to having good comprehensive mechanical property, is an important development direction of following Biodegradable material.Iron is the requisite trace element of human body, and the hematopoiesis of human body is played an important role, and plays the effect of transportation oxygen and nutritive substance in blood, can promote the synthetic of cytopigment and various enzymes, is a kind of safe and absorbable metallic substance.
Through the retrieval of existing document is found, the people such as Peuster have reported " A novel approach to temporary stenting:degradable cardiovascular stents produced from corrodible metal---results6-18months after implantation into New Zealand white rabbits " (a kind of novel method of temporary supporting blood vessel: the degradable angiocarpy bracket being made by corrodible metal---support is implanted the result of New Zealand white rabbit 6-18 month) in < < Heart > > (heart) impurity calendar year 2001s 86 volume 563-569 page, they have tested the reliability and security of degradable retort stand (iron content >99.8%).Result demonstration, between the follow-up period of 6-18 month, rack mechanical is functional, without Cardioversion, occurs.And along with the prolongation of time, the content of Fe is on the increase in body fluid, illustrate that degradation process has occurred support.But within the tracking phase of 18 months, support does not still have degradable, also can as stainless steel stent, cause intimal hyperplasia, therefore need to consider pure iron material alloys, to accelerate its corrosion degradation speed.
The standard potential of Zn element is-0.76V, the standard potential of Fe is-0.44V, Zn joins in pure iron as alloying element, can form sosoloid to reduce the electropotential of alloy substrate with Fe on the one hand, can form intermetallic compound to increase the quantity of micro cathode in alloy with Fe on the other hand, thereby accelerate the degradation speed of Fe base alloy.Aspect biology, Zn is also trace element necessary in human body, and the content in human body is only second to Fe.Its important that grows to cell, is the main component of tens of kinds of enzymes in human body, and relevant with brain development and intelligence.So the alloy that Zn adds Fe to form also has good biomedical security.But pure Fe fusing point is 1534 ℃, the boiling point of pure Zn is 907 ℃, and at room temperature, the solubleness of Zn in Fe is very little, while wanting to prepare the poor alloy of this high-melting-point by conventional smelting process, there will be the problems such as the gasification of low melting point constituent element, evaporation, be difficult to control composition and the quality of alloy.
Electroforming is on the surface of conductor material, prepares the working method of the metal level that one deck is thin by the method for electrolysis.Its principle and electroplating technology are similar, and different is electroforming metal layer and Matrix separation, can be used as a separate component and use.In Iron And Steel Industry, widespread use electroplating technology is prepared Zn-Fe anodic protection coating (content of Fe is mainly distributed between 0.4%～25%).But so far there are no, utilize galvanoplastics preparation to take the report of Fe as main bio-medical Fe-Zn binary alloy tubing.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides a kind of galvanoplastics of using and prepare the method for degradable Fe-Zn alloy pipe for intravascular stent.The method should utilize Fe, the Zn positive ion in ionogen to the process of the mutual competing codeposition of negative electrode, to prepare biodegradable Fe-Zn alloy under electric field action; And can be by adjusting electrochemical parameter, the ionic concn proportioning in electrolytic solution, and pH, temperature, change the composition proportion of Fe-Zn alloy, and the mass ratio of Zn is changed between 1～40%; Also can control the heterogeneous microstructure of alloy by solid solution and Precipitation thermal treatment subsequently, thereby reach this material of regulation and control degradation rate in human body fluid or blood, improve the object of material mechanical performance.
The technical solution used in the present invention is: a kind of electroforming is prepared intravascular stent and adopted following steps by the method for degradable Fe-Zn alloy pipe:
A. prepare electroforming solution, electroforming solution component is: deionized water 1000g, iron protochloride 200～300g, zinc chloride 1～50g, sodium lauryl sulphate 0.01～0.5g, Trisodium Citrate 5～30g, xitix 1～2g, sodium-chlor 10～20g, Manganous chloride tetrahydrate 1～5g;
B. with sodium hydroxide and hydrochloric acid, carry out the pH of regulator solution, make pH remain on 3.0～4.0;
C. electroforming negative electrode carried out pre-treatment before energising, comprised oil removing, cleaned weak etch;
D. adopt direct supply or the pulse power to carry out electroforming, guarantee that cathode current density is 1.0～3.0A/dm
2, the temperature of electroforming solution remains on 30～40 ℃, mechanical stirring in addition in electroforming process;
E. after electroforming completes, the low melting point negative electrode core heat fused with electromolding alloy layer is fallen, obtained the Fe-Zn alloy pipe that Zn element mass percent is 1～40%.
In technique scheme, described electroforming negative electrode core is fusing point lower than the wire of 400 ℃, and its diameter matches with the diameter of preparing intravascular stent; Electroforming anode shape is ring-type, and axle is placed centered by negative electrode core, and its material is pure iron, and purity is not less than 99.9%.
The invention has the beneficial effects as follows: this electroforming is prepared intravascular stent and compared with the existing method of preparing Biodegradable material by the method for degradable Fe-Zn alloy pipe, is characterized in:
1) avoided two kinds of element physical propertiess of Fe and Zn brought conventional alloying that differs greatly to prepare problem, utilize the mutual competing codeposition process of Fe and Zn ion to prepare Fe-Zn alloy material, and the alloy obtaining has tiny crystal grain, and comprehensive mechanical property is good.
2) thickness of electroformed layer can reach 70 microns to 150 microns, uses separately with conduct after Matrix separation is individual, therefore can directly make seamless fine tubing for support, has avoided the conventional pressure forming operation of laser cut stent with metal superfine pipe.
3) by regulating the composition proportion of electroforming parameter change Fe-Zn alloy, thermal treatment changes the heterogeneous microstructure of Fe-Zn alloy, this two aspects synergy can regulate and control the degradation rate of Fe-Zn alloy material in human body fluid or blood, and improves its mechanical property.Therefore adopt the technology of the present invention to prepare to have the intravascular stent Fe-Zn alloy pipe of good biocompatibility, biological corrosion degradation property and comprehensive mechanical property.
Accompanying drawing explanation
Fig. 1 is that the equipment schematic diagram of degradable Fe-Zn alloy pipe for intravascular stent is prepared in electroforming.
In figure: 1, electrotyping bath; 2, electroforming solution; 3, annular pure iron anode; 4, negative electrode core; 5, Fe-Zn alloy electroformation layer.
Embodiment
With specific embodiment, the present invention is described in further detail by reference to the accompanying drawings below, but and do not mean that any restriction of the present invention being protected to content.
Embodiment 1
A. in electrotyping bath 1, prepare electroforming solution 2, electroforming solution 2 comprises: deionized water 1000g, iron protochloride 300g, zinc chloride 10g, sodium lauryl sulphate 0.02g, Trisodium Citrate 20g, xitix 1.5g, sodium-chlor 15g, Manganous chloride tetrahydrate 5g;
B. with sodium hydroxide and hydrochloric acid, carry out the pH of regulator solution, make pH remain on 3.5;
C. adopt direct supply to carry out electroforming.What connect power cathode is negative electrode core 4, and its material therefor is metallic tin silk, and the diameter of silk is 1.8mm, and it submerges in electrolytic solution, and the useful length that can generate even Fe-Zn alloy electroformation layer 5 is 40mm.What connect positive source is annular pure iron anode 3, and its purity is 99.9%.Negative electrode core 4 is placed on the central shaft of annular pure iron anode 3, to guarantee the homogeneity of electroforming tube wall thickness.Negative electrode core 4 carried out pre-treatment before energising, comprised oil removing, cleaned weak etch;
D. guarantee that negative electrode constant current density is 1.5A/dm
2, the temperature of electroforming solution 2 remains on 35 ℃, in electroforming process, adopts mechanical stirring, electroforming time 4h;
E. after electroforming completes, the negative electrode core 4 with Fe-Zn alloy electroformation layer 5 is utilized to heating unit heating, the molten negative electrode core 4 that goes, finally by cleaning polishing, obtaining zinc content is 15%, length is 40mm, and internal diameter is 1.8mm, the fine tubing of Fe-Zn alloy thin-wall that wall thickness is 0.1mm.
This alloy pipe is again through 750 ℃ of solution treatment 10min, shrend, 250 ℃ of timeliness 5h.The alloy material finally obtaining, its tensile strength is 350MPa, elongation after fracture is 20%.In simulated body fluid, through 90 days Soak Tests, obtaining its corrosion degradation speed is 0.7mmy
-1.
Embodiment 2
A. in electrotyping bath 1, prepare electroforming solution 2, electroforming solution 2 comprises: deionized water 1000g, iron protochloride 300g, zinc chloride 7g, sodium lauryl sulphate 0.02g, Trisodium Citrate 20g, xitix 1.5g, sodium-chlor 15g, Manganous chloride tetrahydrate 5g;
B. with sodium hydroxide and hydrochloric acid, carry out the pH of regulator solution, make pH remain on 3.5;
C. adopt direct supply to carry out electroforming.What connect power cathode is negative electrode core 4, and its material therefor is metallic tin silk, and the diameter of silk is 1.8mm, and it submerges in electrolytic solution, and the useful length that can generate even Fe-Zn alloy electroformation layer 5 is 40mm.What connect positive source is annular pure iron anode 3, and its purity is 99.9%.Negative electrode core 4 is placed on the central shaft of annular pure iron anode 3, to guarantee the homogeneity of electroforming tube wall thickness.Negative electrode core 4 carried out pre-treatment before energising, comprised oil removing, cleaned weak etch;
D. guarantee that negative electrode constant current density is 1.5A/dm
2, the temperature of electroforming solution 2 remains on 35 ℃, in electroforming process, adopts mechanical stirring, electroforming time 4h;
E. after electroforming completes, the negative electrode core 4 with Fe-Zn alloy electroformation layer 5 is utilized to heating unit heating, the molten negative electrode core 4 that goes, finally by cleaning polishing, obtaining zinc content is 10%, length is 40mm, and internal diameter is 1.8mm, the fine tubing of Fe-Zn alloy thin-wall that wall thickness is 0.1mm.
This alloy pipe is again through 680 ℃ of solution treatment 10min, shrend, 250 ℃ of timeliness 5h.The alloy material finally obtaining, its tensile strength is 320MPa, elongation after fracture is 23%.In simulated body fluid, through 90 days Soak Tests, obtaining its corrosion degradation speed is 0.58mmy
-1.
Claims (2)
1. a method for degradable Fe-Zn alloy pipe for intravascular stent is prepared in electroforming, it is characterized in that: adopt following steps:
A. prepare electroforming solution, electroforming solution component is: deionized water 1000g, iron protochloride 200～300g, zinc chloride 1～50g, sodium lauryl sulphate 0.01～0.5g, Trisodium Citrate 5～30g, xitix 1～2g, sodium-chlor 10～20g, Manganous chloride tetrahydrate 1～5g;
B. with sodium hydroxide and hydrochloric acid, carry out the pH of regulator solution, make pH remain on 3.0～4.0;
C. electroforming negative electrode carried out pre-treatment before energising, comprised oil removing, cleaned weak etch;
D. adopt direct supply or the pulse power to carry out electroforming, guarantee that cathode current density is 1.0～3.0A/dm
2, the temperature of electroforming solution remains on 30～40 ℃, mechanical stirring in addition in electroforming process;
E. after electroforming completes, the low melting point negative electrode core heat fused with electromolding alloy layer is fallen, obtained the Fe-Zn alloy pipe that Zn element mass percent is 1～40%.
2. the method for degradable Fe-Zn alloy pipe for intravascular stent is prepared in electroforming according to claim 1, it is characterized in that: described electroforming negative electrode core is fusing point lower than the wire of 400 ℃, and its diameter matches with the diameter of preparing intravascular stent; Electroforming anode shape is ring-type, and axle is placed centered by negative electrode core, and its material is pure iron, and purity is not less than 99.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210091212.6A CN102605390B (en) | 2012-03-31 | 2012-03-31 | Method of preparing degradable Fe-Zn alloy pipe for intravascular stent by electroforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210091212.6A CN102605390B (en) | 2012-03-31 | 2012-03-31 | Method of preparing degradable Fe-Zn alloy pipe for intravascular stent by electroforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102605390A CN102605390A (en) | 2012-07-25 |
| CN102605390B true CN102605390B (en) | 2014-08-13 |
Family
ID=46523138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210091212.6A Active CN102605390B (en) | 2012-03-31 | 2012-03-31 | Method of preparing degradable Fe-Zn alloy pipe for intravascular stent by electroforming |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102605390B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10137014B2 (en) | 2013-12-24 | 2018-11-27 | Nipro Corporation | Stent |
| CN104689369B (en) * | 2015-03-13 | 2017-06-30 | 西安爱德万思医疗科技有限公司 | A kind of tough Zn-Fe systems kirsite of the degradable corrosion-proof and high-strength of human body and its application |
| CN106492293B (en) * | 2016-11-18 | 2019-08-30 | 南京理工大学 | A kind of preparation method of the miniature tubing of biological support titanium |
| CN106757198B (en) * | 2016-12-16 | 2019-09-27 | 中色科技股份有限公司 | A method of preparing porous aluminum has homogeneous coating and flawless generation in the process |
| CN109200342A (en) * | 2017-07-06 | 2019-01-15 | 先健科技(深圳)有限公司 | Implantable device |
| CN109234769A (en) * | 2018-10-09 | 2019-01-18 | 福建夜光达科技股份有限公司 | A kind of preparation method of ultra-thin metal layer |
| CN109321955B (en) * | 2018-12-14 | 2020-01-24 | 大连理工大学 | Electroplating solution for electrodepositing Fe-Zn alloy |
| DE102020121729B4 (en) | 2020-08-19 | 2023-11-02 | Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden e.V. (IFW Dresden e.V.) | Implant material and its use |
| CN112914538A (en) * | 2021-03-29 | 2021-06-08 | 重庆科技学院 | Blood vessel blood flow volume acquisition device and method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5772864A (en) * | 1996-02-23 | 1998-06-30 | Meadox Medicals, Inc. | Method for manufacturing implantable medical devices |
| CN101085377A (en) * | 2007-06-11 | 2007-12-12 | 沈阳工业大学 | Process for forming magnesium alloy ultra-fine thin-wall tube used for degradable blood vessel bracket |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8268382B2 (en) * | 2010-07-12 | 2012-09-18 | Medtronic Vascular, Inc. | Method of making a stent with hollow struts |
| JP5713336B2 (en) * | 2010-08-12 | 2015-05-07 | 株式会社オプトニクス精密 | Stent |
-
2012
- 2012-03-31 CN CN201210091212.6A patent/CN102605390B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5772864A (en) * | 1996-02-23 | 1998-06-30 | Meadox Medicals, Inc. | Method for manufacturing implantable medical devices |
| CN101085377A (en) * | 2007-06-11 | 2007-12-12 | 沈阳工业大学 | Process for forming magnesium alloy ultra-fine thin-wall tube used for degradable blood vessel bracket |
Non-Patent Citations (2)
| Title |
|---|
| Electroformed iron as new biomaterial for degradable stents: Development process and structure–properties relationship;M. Moravej等;《Acta Biomaterialia》;20101231(第6期);1726-1735 * |
| M. Moravej等.Electroformed iron as new biomaterial for degradable stents: Development process and structure–properties relationship.《Acta Biomaterialia》.2010,(第6期),1726-1735. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102605390A (en) | 2012-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102605390B (en) | Method of preparing degradable Fe-Zn alloy pipe for intravascular stent by electroforming | |
| Hernández-Escobar et al. | Current status and perspectives of zinc-based absorbable alloys for biomedical applications | |
| Moravej et al. | Effect of electrodeposition current density on the microstructure and the degradation of electroformed iron for degradable stents | |
| CN106676604B (en) | Preparation method and applications with the porous titanium of lattice structure or the antibacterial bioactive ceramics film of titanium alloy surface | |
| WO2018216321A1 (en) | Metal porous body and method for producing metal porous body | |
| EP1494729B3 (en) | Metal implants | |
| CN102505089B (en) | Biodegradable magnesium-lithium alloy material and preparation method thereof | |
| CN110029383B (en) | Degradable zinc-copper foam biological material | |
| He et al. | A study of degradation behaviour and biocompatibility of Zn—Fe alloy prepared by electrodeposition | |
| CN107130279B (en) | A kind of HA nanotube bioactivity coatings preparation method | |
| CN105821247B (en) | A kind of high-strength low-modulus beta-titanium alloy raw material for being directly used in 3D printing and its preparation method and application | |
| CN103882497A (en) | Method for preparing composite ceramic membrane on surface of magnesium alloy intravascular stent by micro-arc oxidation | |
| CN102634725A (en) | Biomedical corrodible degradation bi-component Fe-Zn alloy material | |
| CN101988182A (en) | Surface modification method for wear-resisting orthodontic arch wire and obtained wear-resisting arch wire | |
| CN108815589A (en) | A kind of medical degradable zinc-containing alloy intravascular stent product | |
| Shuai et al. | Rod-like Eutectic Structure in Biodegradable Zn–Al–Sn Alloy Exhibiting Enhanced Mechanical Strength | |
| Du et al. | The influence of porous structure on the corrosion behavior and biocompatibility of bulk Ti-based metallic glass | |
| Xu et al. | The enhancement of mechanical properties and uniform degradation of electrodeposited Fe-Zn alloys by multilayered design for biodegradable stent applications | |
| CN108543118B (en) | Magnesium alloy fixing screw capable of being degraded controllably in vivo | |
| Wang et al. | Degradable Magnesium Corrosion Control for Implant Applications | |
| CN108714252B (en) | Preparation method of magnesium alloy fixing screw capable of being degraded controllably in vivo | |
| KR20170023799A (en) | Method for the surface treatment of a biocorrodable implant | |
| Wang et al. | Microstructure and in vitro biodegradable properties of Fe-Zn alloys prepared by electroforming | |
| He et al. | Corrosion behavior and biocompatibility of Na2EDTA-induced nacre coatings on AZ91D alloys prepared via hydrothermal treatment | |
| CN108560036B (en) | Surface-carried Zn2+Magnesium alloy material and preparation method and application thereof |
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 |