CN102961787A - Iron-based composite material used for full-degradation cardiovascular support and preparation method thereof - Google Patents
Iron-based composite material used for full-degradation cardiovascular support and preparation method thereof Download PDFInfo
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- CN102961787A CN102961787A CN2012105391591A CN201210539159A CN102961787A CN 102961787 A CN102961787 A CN 102961787A CN 2012105391591 A CN2012105391591 A CN 2012105391591A CN 201210539159 A CN201210539159 A CN 201210539159A CN 102961787 A CN102961787 A CN 102961787A
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Abstract
The invention discloses an iron-based composite material used for a full-degradation cardiovascular support and a preparation method thereof. The iron-based composite material comprises Fe and any one of W, Fe2O3, FeS and carbon nano tube, wherein the content of any one of W, Fe2O3, FeS and carbon nano tube is 0-10% and more than 0% in the iron-based composite material in percent by weight. The preparation method of the iron-based composite material comprises the following steps of: mixing iron powder with any one of tungsten powder, Fe2O3 powder, FeS powder and carbon nano tube powder, then carrying out spark plasma sintering or sintering by virtue of powder metallurgy, and cooling, so that the iron-based composite material is obtained. The iron-based composite material used for full-degradation cardiovascular support disclosed by the invention overcomes the defects of the traditional inert metal support such as late thrombosis and restenosis; and a secondary phase harmless to a human body is selected as a strengthening phase of the composite material, so that corrosion rate of an iron base in a body fluid environment is increased, and corrosion of the iron base is more uniform.
Description
Technical field
The present invention relates to a kind of degradable angiocarpy bracket iron base composite material and preparation method thereof.
Background technology
The angiocarpy bracket material of using clinically at present comprises 316L rustless steel, Ti and Ni-Ti alloy, Co-Cr alloy, Pt-Ir alloy and metal Ta etc. take metal material as main.But these timbering materials all are bio-inert material and non-degradable in vivo, can be as the foreign body long-term existence in body behind the implant into body, and the risk that have vascular restenosis, advanced thrombus to occur needs to carry out long-term Antiplatelet therapy simultaneously.In view of above reason, the development trend that to develop biodegradable angiocarpy bracket material be angiocarpy bracket.
The research about degradable angiocarpy bracket material both at home and abroad concentrates on magnesium alloy and the pure iron.But there are some shortcomings in magnesium alloy, compares as the 316L rustless steel, and the mechanical property of magnesium alloy is relatively poor, and the radial support power that provides may be not enough; On the other hand, magnesium alloy corrosion rate in the body fluid environment is too fast, might cause the support graft failure with regard to the corrosion fragmentation by support before vascular remodeling.
From the angle of biocompatibility, ferrum element is the trace element that body weight for humans is wanted, and becomes that iron content is about 4-5g in the human body, wherein 70% is combined with hemoglobin.Ferrum has important physiological function, plays important important function in many biochemical reaction, such as oxygen-sensitive and transmission, electron transfer, catalysis etc.Pure iron can corrosion in the body fluid environment, is expected to become the degradable angiocarpy bracket material of a new generation.Early stage animal experiment study has confirmed also that pure iron has good biocompatibility and as the feasibility of angiocarpy bracket material.But pure iron also exists some problems as the angiocarpy bracket material, mainly is that the mechanical property of pure iron is slightly poor than 316L, needs further to improve its mechanical property; Pure iron corrosion rate in the body fluid environment is slower in addition, is containing Cl
-The body fluid environment in spot corrosion easily occurs, cause that the support part loses mechanical strength and breaks, and causes graft failure.Therefore,, need to accelerate its corrosion rate and make simultaneously the corrosion of pure iron in the body fluid environment more even as the angiocarpy bracket material for pure iron.
From the materialogy angle, the method of improving pure iron corrosion rate and forms of corrosion mainly contains two kinds: the one, and make the easier corrosion of iron-based body by adding some non-noble metal alloy elements, but studies confirm that this kind method is unsatisfactory to the corrosion rate effect of accelerating pure iron; Another kind is to form the middle phase of tiny homodisperse metal by adding the precious metal alloys element, form galvanic corrosion as anode and iron-based body, play the effect of accelerated corrosion, but adopt traditional foundry engieering, the formation of phase and even the distribution are difficult to control in the middle of the metal.Adopt the method for Composite, not only can obtain homodisperse noble metal phase, accelerate the corrosion of iron-based body, see on the macroscopic view that simultaneously can to make the corrosion of iron-based body more even, and because the potentiation of secondary phase can further improve the mechanical property of iron.
Tungsten is the highest element of fusing point outside the de-carbon, and is higher than the standard electrode potential of pure iron.Because its preferably radiation impermeability and thrombogenicity, the pure tungsten mechanicaldetachablecoil is used to Surgery cerebral aneurysm and other hemangioma.Result of study confirms, because the implantation of Tungsten coils, although tungsten ion concentration increase in the serum in the patient body does not cause part or system toxicity.Vascular smooth muscle cell, endotheliocyte and fibroblast all show higher cytoactive on pure tungsten turn surface, and the increase of tungsten ion concentration does not produce significantly impact to cytoactive in the solution.And only has the toxic reaction that when the tungsten ion concentration in the solution is higher than 50 μ g/ml, just can cause vascular smooth muscle cell, endotheliocyte and fibroblast.These have confirmed that tungsten has good biocompatibility.
Ferrum oxide is a kind of magnetic material, has a wide range of applications at biomedical sectors such as targeting transmission, cell signs, and the early stage ferrum oxide that studies confirm that has good biocompatibility.In addition, ferrum oxide is one of catabolite of pure iron.Iron sulfuret. also is a kind of chemical compound of ferrum, does not have cytotoxicity.
CNT is a kind of novel material with carbon element, has special nanostructured and excellent physical and chemical performance, such as low-density, high strength, good electrical conductance and temperature conduction performance, becomes the new study hotspot in biomedical applications field.CNT can improve the intensity of macromolecular material as the enhancing body of polymer composite, also can improve the cell compatibility of matrix material.Can induce and support for Growth of Cells and tissue regeneration provide as tissue engineering bracket through the CNT of finishing.In addition, CNT is in the research that also has a wide range of applications aspect the electro chemical analysis of gas sensor and biomolecule.
Summary of the invention
The purpose of this invention is to provide a kind of degradable angiocarpy bracket iron base composite material and preparation method thereof, this iron base composite material has good biocompatibility, suitable corrosion rate, and can satisfy the mechanical property requirements of angiocarpy bracket material.
A kind of degradable angiocarpy bracket iron base composite material provided by the invention comprises Fe and W;
By weight percentage, in the described iron base composite material, the content of W is 0 ~ 10%, but non-vanishing, the concrete composition of this iron base composite material can be: be that 2% ~ 5% W and the Fe of surplus form by the quality percentage composition, specifically can be W and 95% Fe and 5% the W of 98% Fe and 2%.
Another kind of degradable angiocarpy bracket iron base composite material provided by the invention comprises Fe and Fe
2O
3
By weight percentage, in the described iron base composite material, Fe
2O
3Content be 0 ~ 10%, but non-vanishing, the concrete composition of this iron base composite material can be: be 2% ~ 5% Fe by the quality percentage composition
2O
3Form with the Fe of surplus, specifically can be 98% Fe and 2% Fe
2O
3And the Fe of 95% Fe and 5%
2O
3
Another degradable angiocarpy bracket iron base composite material provided by the invention comprises Fe and FeS;
By weight percentage, in the described iron base composite material, the content of FeS is 0 ~ 10%, but non-vanishing, the concrete composition of this iron base composite material can be: be that 2% ~ 5% FeS and the Fe of surplus form by the quality percentage composition, specifically can be FeS and 95% Fe and 5% the FeS of 98% Fe and 2%.
Another degradable angiocarpy bracket iron base composite material provided by the invention comprises Fe and CNT;
By weight percentage, in the described iron base composite material, the content of CNT is 0 ~ 5%, but non-vanishing, the concrete composition of this iron base composite material can be: be that 0.5% ~ 1% CNT and the Fe of surplus form by the quality percentage composition, specifically can be CNT and 99% Fe and 1% the CNT of 99.5% Fe and 0.5%.
In the above-mentioned iron base composite material, described iron base composite material also may comprise trace element, and described trace element is at least a in manganese, chromium, cobalt and the nickel;
In the described iron base composite material, the quality percentage composition of described trace element is 0 ~ 2%, but non-vanishing;
The content of described manganese, chromium, cobalt and nickel all is not more than 1.5%.
In the above-mentioned iron base composite material, the surface of described iron base composite material also is coated with the degradable macromolecule drug-carried coat;
Macromolecular material in the described degradable macromolecule drug-carried coat is one or more the combination in any in polyglycolic acid (PGA), polylactic acid (PLA), PLLA (PLLA), polycaprolactone (PCL), polybutylcyanoacrylate (PACA), poly-para-dioxane ketone, poly-anhydride, poly phosphazene, polymer-amino-acid, poly-beta-hydroxy-butanoic acid ester and hydroxyl valerate and the copolymer thereof;
Medicine in the described degradable macromolecule drug-carried coat is immunosuppressant (thunderous handkerchief mycin) or cancer therapy drug (such as paclitaxel);
The thickness of described degradable macromolecule drug-carried coat can be 5 ~ 50 μ m.
The invention provides the preparation method of above-mentioned iron base composite material, comprise the steps: iron powder and tungsten powder, Fe
2O
3Any mixes in powder, FeS powder and the carbon nanotube powder, then carries out sintering through discharge plasma sintering or powder metallurgy, namely obtains iron base composite material through cooling.
In the above-mentioned preparation method, described iron powder, tungsten powder, Fe
2O
3Can be 100nm ~ 200 μ m with the particle diameter of FeS powder, such as 100nm ~ 100 μ m, the diameter of described CNT can be 1 ~ 100nm, and such as 10 ~ 30nm, length can be 1 ~ 20 μ m, such as 1 ~ 10 μ m.
In the above-mentioned preparation method, the pressure of described discharge plasma sintering can be 20 ~ 40MPa, and temperature can be 750 ~ 1000 ℃, and the time can be 3 ~ 10min, such as sintering 5min under the condition of 40MPa and 950 ℃.
In the above-mentioned preparation method, the temperature of described powder metallurgy can be 800 ~ 1400 ℃, and the time can be 5 ~ 10h.
In the above-mentioned preparation method, described method also comprises to the step of the described degradable macromolecule drug-carried coat of the surface-coated of described iron base composite material;
Apply described degradable macromolecule drug-carried coat by czochralski method or even glue method;
The step that described czochralski method applies the degradable macromolecule drug-carried coat is: at first described composite is carried out pickling, then in the organic solvents such as trichloroethane, dissolve described macromolecular material and medicine, then described composite is at the uniform velocity pulled out after the dip-coating in described macromolecular material and medicine and carry out centrifugal treating, obtain applying the angiocarpy bracket of degradable macromolecule drug-carried coat.
The step that described even glue method applies the degradable macromolecule drug-carried coat is: at first described composite is carried out pickling, then in the organic solvents such as trichloroethane, dissolve described macromolecular material and medicine, with described macromolecular material and medicine colloid drops at composite material surface, utilize the sol evenning machine high speed rotating that colloid is spread into and form thin layer on the composite, dry to remove unnecessary solvent, repeatedly coated with reaching optimum efficiency.
The present invention also provides the application of above-mentioned iron base composite material in the preparation medical implant, and described medical implant specifically can be angiocarpy bracket.
The present invention has following advantage and beneficial effect:
Degradable angiocarpy bracket iron base composite material provided by the invention has avoided traditional inert metal support problem, the problem includes: problems such as advanced thrombus, stent restenosis.Select harmless secondary phase as the wild phase of composite, improved the corrosion rate of iron-based body in the body fluid environment on the one hand, make the corrosion of iron-based body more even; On the other hand, the adding of secondary phase has also improved the mechanical strength of iron base composite material, more can satisfy the requirement of angiocarpy bracket.
Description of drawings
Fig. 1 is the iron base composite material of embodiment 1 and embodiment 2 preparations and metallographic microstructure and the Fe-2Fe that casts pure iron, SPS pomet
2O
3The EDS of secondary phase and matrix analyzes in the composite.
Fig. 2 is embodiment 1 and the iron base composite material of embodiment 2 preparations and the room temperature compression performance of pure iron.
Fig. 3 is the cell survival rate of VSMC cultivate 1,2 and 4 day in the iron base composite material of embodiment 1 and embodiment 2 preparations and casting pure iron, SPS pomet lixiviating solution after and ECV304, wherein, Fig. 3 (a) and Fig. 3 (b) are respectively the cell survival rate of VSMC and ECV304.
Fig. 4 is the iron base composite material of embodiment 1 and embodiment 2 preparations and the hemolysis rate of casting pure iron, SPS pomet.
The specific embodiment
Employed experimental technique is conventional method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Embodiment 1, preparation Fe-W/Fe
2O
3/ FeS composite
Adopt pure Fe powder (99.9wt.%, particle diameter are 100nm ~ 100 μ m), W powder (99.8%, particle diameter is 100nm ~ 100 μ m), Fe
2O
3Powder (99.0%, particle diameter is 100nm ~ 100 μ m) and FeS powder (99.0%, particle diameter is 100nm ~ 100 μ m) are 2% and 5% preparation according to secondary phase X content (quality) respectively as test raw material.
Through after the mortar hand mix in the batch mixing instrument with the rotating speed mixing 5min of 2000rpm.Mixed-powder is placed graphite jig, under vacuum environment, adopt discharge plasma sintering technology 950 ℃ of sintering under 40MPa pressure, then temperature retention time 5min is cooled to room temperature and namely obtains iron base composite material: be respectively Fe-2W, Fe-5W, Fe-2Fe
2O
3, Fe-5Fe
2O
3, Fe-2FeS and Fe-5FeS.
The metallographic microstructure of the iron base composite material of present embodiment preparation as shown in Figure 1, wherein, Fe-2Fe
2O
3In secondary phase Fe
2O
3With the EDS spectrogram of matrix Fe also as shown in fig. 1, be respectively Fig. 1 (A) and figure (B), also show the metallographic microstructure of casting pure iron and SPS pomet (its sintering process conditions is with the condition in the present embodiment) among Fig. 1.Can be learnt that by this figure the pure iron crystallite dimension of employing SPS method sintering is cast pure iron and obviously reduced W, Fe
2O
3, the secondary phase such as FeS evenly distributes in the iron-based body, major part is distributed on the crystal boundary, fraction is distributed in crystal grain inside, and secondary phase be added in the crystallite dimension that has reduced to a certain extent the iron-based body.
(diameter is 10 ~ 30nm to adopt pure Fe powder and CNT powder, length is 1 ~ 10 μ m) be raw material, be respectively 0.5% and 1% ratio according to adding phase content, with ethanol as dispersant, stainless steel ball ball milling mixing 8h post-drying under the rotating speed of 80r/min with diameter 5mm, then adopt with discharge plasma sintering parameter identical among the embodiment 1 and carry out sintering, obtain the composite sample of Fe-CNT.
The metallographic microstructure of the Fe-CNT composite of present embodiment preparation can be learnt by this figure that as shown in Figure 1 CNT evenly distributes behind the mixing of employing ball milling and the sintering in the iron-based body, the adding of CNT has also obviously reduced the crystallite dimension of iron-based body.
The room temperature compression performance of embodiment 3, iron base composite material
The composite of embodiment 1 and embodiment 2 preparations is carried out the compression performance test according to compression verification standard GB/T 7314-2005 preparation compression sample, and specimen size is Φ 2 * 5mm, and compression strain speed is 2 * 10
-4/ s, because material is plastic material, the stress value when compressive strength pressure shrinkage strain is 40%.
The Compressive Mechanical Properties of the iron base composite material of employing embodiment 1 and embodiment 2 preparations compares with the pure iron of casting (As-cast) pure iron and discharge plasma sintering (SPS) as shown in Figure 2.
The corrosion resistance of embodiment 4, iron base composite material
The composite material line that embodiment 1 and 2 is made cuts into 10 * 10 * 2mm
3Block sample, sanding and polishing is to 2000# sand paper.Then in being 37 ℃ Hank ' s simulated body fluid, temperature carries out the corrosion rate of electro-chemical test and immersion test test material, with pure iron as a comparison.
The electrochemical parameter of the iron base composite material of employing embodiment 1 and embodiment 2 preparations and the corrosion rate that adopts two kinds of detection meanss to calculate are as shown in table 1, can be found out by the data in the table 1, it is fast that Electrochemical results shows that the corrosion rate of the pure iron that adopts the SPS sintering is cast pure iron, the simultaneously adding of second-phase composition significantly improves the corrosion rate of iron, second-phase content is higher, and the corrosion rate of iron is faster.And the Soak Test result shows W, Fe
2O
3, FeS add after corrosion rate and the pure iron of composite suitable, and the adding of CNT significantly provides the corrosion rate of iron.
The electro-chemical test parameter of table 1Fe based composites and the corrosion rate that adopts electrochemistry and Soak Test to calculate
V
Corr: corrosion potential; I
Corr: corrosion current; υ
Corr: corrosion rate
The biocompatibility of embodiment 5, iron base composite material
Method preparation experiment sample according among the embodiment 4 compares with pure iron and SPS pomet, is 1.25cm according to surface area/lixiviating solution volume ratio after ultra-vioket radiation sterilization
2Ml
-1Standard extract lixiviating solution, carry out the cytotoxicity experiment of vascular smooth muscle cell VSMC and endotheliocyte ECV304.In addition sample is added and contain 0.2ml dilution human blood (normal saline: soak 1h in the 10ml normal saline of human blood (volume)=5:4), the hemolysis rate of test material.
The cell survival rate of relative negative control and various composite haemolysis rate result are respectively as shown in Figure 3 and Figure 4 after cultivating, as seen from Figure 3, after iron base composite material and pure iron lixiviating solution are cultivated 1,2 and 4 day, the survival rate of VSMC cell reduces along with the prolongation of cultivating the upper time, and the ECV304 cell still keeps higher survival rate after cultivating 4 days, show all iron base composite materials and pure iron that vascular smooth muscle cell is possessed certain inhibitory action and Human Umbilical Vein Endothelial Cells does not have toxicity, be suitable as vascular stent material and use.As can be seen from Figure 4, the hemolysis rate of all iron base composite materials and pure iron material all about 3%, is lower than the threshold criteria 5% of blood compatibility.
Embodiment 6, be loaded with the preparation of PLLA biodegradable coating iron base composite material
According to embodiment 2 preparation iron base composite materials, then according to following czochralski method in its surface-coated PLLA (PLLA) and taxol drug coating, preparation PLLA and paclitaxel surface modifying material:
(1) uses concentrated nitric acid and Fluohydric acid. configuration pickle, with composite pickling 20min.
(2) dissolving 0.5g PLLA(molecular weight in the 10ml trichloroethane: 200kDa), the 15mg paclitaxel.
(3) composite after the pickling is put into the colloid immersion and at the uniform velocity lifted taking-up after 30 minutes, vacuum room temperature dried overnight is 10 ~ 30 μ m according to the resulting PLLA biodegradable coating of above-described embodiment thickness.
Claims (10)
1. iron base composite material, it is characterized in that: described iron base composite material comprises Fe and W;
By weight percentage, in the described iron base composite material, the content of W is 0 ~ 10%, but non-vanishing.
2. iron base composite material, it is characterized in that: described iron base composite material comprises Fe and Fe
2O
3
By weight percentage, in the described iron base composite material, Fe
2O
3Content be 0 ~ 10%, but non-vanishing.
3. full iron base composite material, it is characterized in that: described iron base composite material comprises Fe and FeS;
By weight percentage, in the described iron base composite material, the content of FeS is 0 ~ 10%, but non-vanishing.
4. iron base composite material, it is characterized in that: described iron base composite material comprises Fe and CNT;
By weight percentage, in the described iron base composite material, the content of CNT is 0 ~ 5%, but non-vanishing, and the CNT diameter is 1 ~ 100nm, and length is 1 ~ 20 μ m.
5. each described iron base composite material according to claim 1-4, it is characterized in that: described iron base composite material also comprises trace element, described trace element is at least a in manganese, chromium, cobalt and the nickel;
In the described iron base composite material, the quality percentage composition of described trace element is 0 ~ 2%, but non-vanishing;
The content of described manganese, chromium, cobalt and nickel all is not more than 1.5%.
6. each described iron base composite material according to claim 1-5, it is characterized in that: the surface of described iron base composite material also is coated with the degradable macromolecule drug-carried coat;
Macromolecular material in the described degradable macromolecule drug-carried coat is one or more the combination in any in polyglycolic acid, polylactic acid, PLLA, polycaprolactone, polybutylcyanoacrylate, poly-para-dioxane ketone, poly-anhydride, poly phosphazene, polymer-amino-acid, poly-beta-hydroxy-butanoic acid ester and hydroxyl valerate and the copolymer thereof;
Medicine in the described degradable macromolecule drug-carried coat is immunosuppressant or cancer therapy drug;
The thickness of described degradable macromolecule drug-carried coat is 5 ~ 50 μ m.
7. the preparation method of each described iron base composite material among the claim 1-6 comprises the steps: iron powder and tungsten powder, Fe
2O
3Any mixes in powder, FeS powder and the carbon nanotube powder, then carries out sintering through discharge plasma sintering or powder metallurgy, namely obtains iron base composite material through cooling.
8. method according to claim 7, it is characterized in that: the pressure of described discharge plasma sintering is 20 ~ 40MPa, and temperature is 750 ~ 1000 ℃, and the time is 3 ~ 10min.
9. method according to claim 7, it is characterized in that: the temperature of described powder metallurgy is 800 ~ 1400 ℃, the time is 5 ~ 10h;
Described method also comprises to the step of the described degradable macromolecule drug-carried coat of the surface-coated of described iron base composite material;
Apply described degradable macromolecule drug-carried coat by czochralski method or even glue method.
10. the application of each described iron base composite material in the preparation medical implant among the claim 1-6.
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| CN108261570A (en) * | 2016-12-30 | 2018-07-10 | 先健科技(深圳)有限公司 | Absorbable iron-based instrument |
| CN109224137A (en) * | 2018-08-10 | 2019-01-18 | 中南大学 | A kind of preparation method of iron-based bone implant that accelerating degradation |
| CN109224137B (en) * | 2018-08-10 | 2021-03-16 | 中南大学 | Preparation method of iron-based bone implant capable of accelerating degradation |
| CN109172860B (en) * | 2018-08-10 | 2021-04-23 | 中南大学 | Degradable iron-based implant and preparation method thereof |
| CN109172860A (en) * | 2018-08-10 | 2019-01-11 | 中南大学 | Degradable iron-based implantation material of one kind and preparation method thereof |
| CN110236749A (en) * | 2019-08-14 | 2019-09-17 | 刘善胤 | A kind of dismountable treating cardio-cerebral vascular disease holder device |
| WO2021203762A1 (en) * | 2020-04-07 | 2021-10-14 | 元心科技(深圳)有限公司 | Zinc-containing medical instrument |
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