CN101249286B - Degradable chemical bitter earth alloy bracket and method of preparing the same - Google Patents
Degradable chemical bitter earth alloy bracket and method of preparing the same Download PDFInfo
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- CN101249286B CN101249286B CN2008101031336A CN200810103133A CN101249286B CN 101249286 B CN101249286 B CN 101249286B CN 2008101031336 A CN2008101031336 A CN 2008101031336A CN 200810103133 A CN200810103133 A CN 200810103133A CN 101249286 B CN101249286 B CN 101249286B
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Abstract
The invention discloses a degradable vascular stent with a composite coating and a preparation method thereof, and comprises a matrix made from pure magnesium or magnesium alloy material; a chemical oxide film layer that is arranged on the surface of the matrix and is used for decreasing the corrosion rate of the matrix and prolonging the service life of the matrix; a degradable polymer material layer that is located at the surface of the chemical oxide film layer and therapeutic drug that are fixed at the degradable polymer material layer. The degradable vascular stent with a composite coating of the invention has excellent mechanical and pharmacological properties, otherwise, the degradation rate of the magnesium material is reduced, and the service life of the stent is prolonged.
Description
Technical field
The invention belongs to the implanted medical device field, relate to a kind of degradable blood vessel bracket that has composite coating and preparation method thereof.
Background technology
Magnesium is the very abundant elements of a kind of reserves, and the composition of magnesium accounts for more than 90% in the magnesium alloy.The density of magnesium alloy is less than 2g/cm
3, in practical metal, the proportion of magnesium alloy is minimum, is 1/4 of ferrum, 2/3 of aluminum; Magnesium alloy has higher specific strength and specific stiffness, damping performance and high-temp plastic, good polishing performance, good advantages such as heat conduction, electric conductivity, electromagnetic wave shielding and environmental protection preferably, is described as " the green engineering material of 21 century ".Therefore the application of magnesium alloy in fields such as automobile making, Aero-Space, Communication Equipment, household electrical appliance, optical instrument and computer manufacturings obtained developing rapidly.
Magnesium alloy still is a kind of very promising bio-medical material; From both at home and abroad the report of magnesium and magnesium alloy each side being not difficult to find in recent ten years; Magnesium is compared with the various metal implant materials that dropped into clinical use at present as embedded material, has very outstanding advantage.Magnesium can promote the formation of bone and cell in life process, catalysis or activation body 300 plurality of enzymes system participate in the energy i (in vivo) metabolism, and in conveying, storage and the utilization of energy, play a crucial role.Magnesium influences proteinic synthesizing through the structure of regulating rDNA (Deoxyribonucleic acid, DNA) and RNA (Ribonucleic acid, ribonucleic acid) in the three big metabolism in vivo.Chemical reaction takes place and changes magnesium ion in magnesium in aqueous medium, magnesium ion comes adjustment through the metabolism of intravital absorption and kidney, thereby magnesium alloy materials is degraded and absorbed in vivo gradually.Magnesium alloy becomes the preferred material of support because of the advantages such as minimal side effect with good mechanical performance and catabolite.Magnesium has good medical science safety as bio-medical material, is particularly useful for the treatment of cardiovascular disease.
But because magnesium is as lively as a cricket metal; Its standard electrode potential is-2.36V (vs.SCE); While is because the oxide-film (mainly being made up of magnesium oxide) that Mg alloy surface forms is generally all loose porous, thereby the decay resistance of magnesium and magnesium alloy materials is relatively poor, and this has seriously restricted the use of magnesium alloy; Therefore must handle Mg alloy surface, to improve the decay resistance of magnesium alloy.At present the surface treatment method of magnesium alloy mainly contains: chemical oxidation, anodic oxidation, overlay coating, differential arc oxidation, ion implantation and Laser Surface Treatment etc.
Chemical oxidation is claimed the chemical conversion processing again, is common a kind of surface treatment method of Mg alloy.Metal and chemical oxidation liquid generation chemical reaction form the passivating film that is made up of oxide or slaine in the metal surface, and magnesium alloy is carried out corrosion protection.Chemical plating has that thickness of coating is even, chemical stability good, any surface finish is smooth; Workable, method simply is easy to control; Can on complex-shaped foundry goods, obtain uniform coating, the performance of coating can be regulated according to different needs, and equipment is simple, low cost and other advantages.Owing in film forming procedure, do not use power supply, thus do not exist because the drawback that the thicknesses of layers that the electric force lines distribution inequality causes is inhomogeneous and the deep hole place can not depositional coating, so long as the surface that electrolyte can arrive can both obtain the uniform conversion film of thickness.
In realizing process of the present invention, the inventor finds to exist at least in the prior art following problem: though traditional chromate treating effect is better, contain hexavalent chromium in the technology, toxicity is big, contaminated environment, and the processing cost of waste liquid is high.The surface treatment of magnesium alloy chromate chemistry all has harm in various degree to human body and environment.Simultaneously, with the chemical oxidation liquid that contains heavy metallic salt magnesium alloy is being carried out the occasion of chemical oxidation, when alloy carried out recycling, heavy metal element can become impurity, influenced the composition of alloy.For the adhesion that improves anticorrosive coat needs preplating, cause technology loaded down with trivial details.Technological requirement is strict, and pH (Potential Hydrogen, hydrogen ion activity index) value excursion is narrow.
Summary of the invention
The problem that the embodiment of the invention will solve provides a kind of degradable blood vessel bracket that has composite coating and preparation method thereof; Chemical oxidation rete on the support can obviously reduce the corrosion rate of support; Prolong the service life of support, the degradable high polymer material layer on the support is in order to carry various curative drugs.
For achieving the above object, the technical scheme of the embodiment of the invention provides a kind of degradable blood vessel bracket that has composite coating, and said support comprises: the matrix that is made up of pure magnesium or magnesium alloy materials; Be positioned at the surface of said matrix, be used to reduce the corrosion rate of said matrix, the chemical oxidation rete that prolongs the service life of said matrix; Be positioned at the degradable high polymer material layer on the surface of said chemical oxidation rete; Be fixed in the curative drug of said degradable high polymer material layer.
Wherein, said magnesium alloy comprises one or more the combination in magnalium series alloy, magnesium manganese series alloy, magnesium zinc series alloy, magnesium zirconium series alloy, magnesium rare earth metal alloy, magnesium lithium series alloy, magnesium calcium series alloy or the magnesium silver series alloy.
Wherein, Said degradable high polymer material comprises: polylactic acid, PLLA, gather Acetic acid, hydroxy-, bimol. cyclic ester, polybutylcyanoacrylate, PCL, gather anhydride, copolymer of poly lactic acid, polyhydroxybutyrate valerate, polyacetylglutamic acid, polyorthoesters, polyethylene glycol oxide/polybutene copolymer, poe, polycaprolactone, polyglycolic acid, polyethylene glycol oxide/polybutylene terephthalate copolymer, methacrylate, methacrylate, polyurethane, silicones, polyvinyl alcohol, allylcarbinol, polyglycolic acid, polyphosphoric acid esterase, and the copolymer between the above-mentioned polymer.
Wherein, said degradable high polymer material also comprises collagen protein, gelatin, chitin.
Wherein, said curative drug comprises one or more in antiproliferative reagent, resisting mitosis reagent, antibiotic, anthracycline antibiotics, bleomycin, mithramycin, enzyme, antiplatelet reagent, antimetabolite, hormone medicine, anticoagulant, solution fibrin medicine, secretion inhibitor medicine, anti-inflammation drugs, the non-steroid medicine.
The technical scheme of the embodiment of the invention also provides a kind of method for preparing that has the degradable blood vessel bracket of composite coating, said method comprising the steps of: through being machined into intravascular stent, said matrix is made up of pure magnesium or magnesium alloy materials with matrix; The pretreatment of matrix, said pretreatment comprise defat, pickling and alkali cleaning step; Chemical oxidation is carried out on surface to said matrix, forms the chemical oxidation rete, and said chemical oxidation rete is used to reduce the corrosion rate of said matrix, prolongs the service life of said matrix; Surface to said chemical oxidation rete applies, and forms the degradable high polymer material layer; Curative drug is fixed to said degradable high polymer material layer.
Wherein, in the pre-treatment step of said matrix, comprising: said matrix is put into degreaser carry out defat, said degreaser consists of: NaOH 5～10g/L, Na
2CO
35～10g/L, Na
2SiO
35～20g/L, surplus is a water, the degreaser temperature is controlled at 293～313K; Degreasing time is 30-40min; Said matrix is put into pickle carry out pickling, said pickle consists of: acetic acid 10～30ml/L, Chile saltpeter 1～10g/L, and surplus is a water, and the pickle temperature is 293～313K, and the pickling time is 0.5～5min; With the said matrix of flushing with clean water; Said matrix is put into alkali wash water carry out alkali cleaning, said alkali wash water consists of sodium hydroxide solution or potassium hydroxide solution 5～20g/L, and the alkali wash water pH value is 12～13, and the alkali wash water temperature is 293～313K, and the alkali cleaning time is 5～10min; With the said matrix of flushing with clean water.
Wherein, Chemical oxidation is carried out on surface to matrix, forms in the step of chemical oxidation rete, comprising: said matrix is put into chemical oxidation liquid carry out chemical oxidation; Said chemical oxidation liquid contains potassium permanganate, sodium permanganate or magnesium permanganate 10～20g/L, rare-earth salts 10～20g/L, coalescents 5～15g/L; Wherein said rare-earth salts is cerous nitrate, Lanthanum (III) nitrate or neodymium nitrate, and said coalescents is magnesium nitrate or Chile saltpeter, and the pH value of said chemical oxidation liquid is between 5～7; The temperature of chemical oxidation liquid is 318～333K, and the chemical oxidation treatment time is 5～10min; With the said matrix of flushing with clean water; Said matrix is dried, and bake out temperature is 303～373K, and drying time is 5～10min.
Wherein, apply on the surface to the chemical oxidation rete, form in the step of degradable high polymer material layer, said coating comprises: dip-coating, thermal spraying, electrostatic coating, collosol and gel, the liquid coating of supercritical.
Wherein, Curative drug is being fixed in the step of degradable high polymer material layer; Comprise: at the uniform velocity rotation after said intravascular stent is fixed; The solution that will contain 1%～15% rapamycin or paclitaxel carries out directional spray to support, and requires to confirm the spraying number of times according to the rack surface medicament contg.
Wherein, Before the pre-treatment step of said matrix, also comprise: said matrix is processed as bone suture, nail, bone connector, vertebra basin, sews up with anchor, mosquito forceps, hemostasis screw, hemostasis plate, hemostatic clamp, tissue adhesive, sealant or artificial bone.
Technique scheme only is an optimal technical scheme of the present invention, has following advantage:
The degradable blood vessel bracket that has composite coating of the present invention has excellent machinery and materia medica performance.The mechanical performance that pure magnesium of controlled degradation that the process surface-coated is handled and magnesium alloy bracket have still kept the excellence that metal material possessed makes the magnesium material implant devices can effectively keep the good mechanical performance in-service; The use of surperficial degradable macromolecule layer simultaneously; Greatly improved required kind and the quantity of carrying medicine of support; Improved medicine fixation stability property; This macromolecular material can fix different drug and dose through the thickness of regulating molecular weight and polymeric layer, and drug loading is generally greater than 30%.
In addition, the magnesium material degradation rate reduces, and support prolongs service life.Because the leakiness of macromolecular material, no matter its thickness how, macromolecular material all is difficult to stop hydrone, and particularly chloride ion arrives Mg alloy surface, so magnesium alloy can begin degraded simultaneously with macromolecular material.The chemical oxidation technical operation is simple, and cost is low, and the time is short.Utilize the chemical reaction of magnesium alloy and oxidation liquid, generate the fine and close oxide-film of one deck, greatly reduced the degradation rate of magnesium alloy, prolonged the service life of support at Mg alloy surface.
Description of drawings
Fig. 1 is the flow chart of the method for preparing of the embodiment of the invention a kind of degradable blood vessel bracket of having composite coating.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment, specific embodiments of the invention describes in further detail.Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
A kind of degradable blood vessel bracket that has composite coating of the present invention; Comprise: the matrix that constitutes by pure magnesium or magnesium alloy materials; Said magnesium alloy comprises one or more the combination in magnalium series alloy, magnesium manganese series alloy, magnesium zinc series alloy, magnesium zirconium series alloy, magnesium rare earth metal alloy, magnesium lithium series alloy, magnesium calcium series alloy or the magnesium silver series alloy; The content of alloying element should satisfy the requirement of bio-medical in this magnesium alloy, makes its degradation amount in degradation process should be in not causing the dosage range of tissue toxicity reaction; Be positioned at the surface of said matrix, be used to reduce the corrosion rate of said matrix, the chemical oxidation rete that prolongs the service life of said matrix; Be positioned at the degradable high polymer material layer on the surface of said chemical oxidation rete; Said degradable high polymer material comprises: polylactic acid, PLLA, gather Acetic acid, hydroxy-, bimol. cyclic ester, polybutylcyanoacrylate, PCL, gather anhydride, copolymer of poly lactic acid, polyhydroxybutyrate valerate, polyacetylglutamic acid, polyorthoesters, polyethylene glycol oxide/polybutene copolymer, poe, polycaprolactone, polyglycolic acid, polyethylene glycol oxide/polybutylene terephthalate copolymer, methacrylate, methacrylate, polyurethane, silicones, polyvinyl alcohol, allylcarbinol, polyglycolic acid, polyphosphoric acid esterase, and the copolymer between the above-mentioned polymer; Said degradable high polymer material also comprises collagen protein, gelatin, chitin.Said curative drug comprises one or more in antiproliferative reagent, resisting mitosis reagent, antibiotic, anthracycline antibiotics, bleomycin, mithramycin, enzyme, antiplatelet reagent, antimetabolite, hormone medicine, anticoagulant, solution fibrin medicine, secretion inhibitor medicine, anti-inflammation drugs, the non-steroid medicine; Nontoxic, nonirritant that degradable high polymer material has; Be prone to machine-shaping, advantage such as drug loading is big; Be fixed in the curative drug of said degradable high polymer material layer.
It is as shown in Figure 1 that the embodiment of the invention a kind of has the flow process of method for preparing of degradable blood vessel bracket of composite coating, may further comprise the steps:
Step s101, matrix is through being machined into intravascular stent, and said matrix is made up of pure magnesium or magnesium alloy materials.Can also said matrix be processed as bone suture, nail, bone connector, vertebra basin, sew up with anchor, mosquito forceps, hemostasis screw, hemostasis plate, hemostatic clamp, tissue adhesive, sealant or artificial bone etc.
Step s102, the pretreatment of matrix, said pretreatment comprise defat, pickling and alkali cleaning step, with impurity such as the oils and fats of removing Mg alloy surface, oxides.The pretreatment of said matrix comprises:
Said matrix is put into degreaser carry out defat, said degreaser consists of: NaOH5～10g/L, Na
2CO
35～10g/L, Na
2SiO
35～20g/L, surplus is a water; The degreaser temperature is controlled at 293～313K; Degreasing time is 30-40min;
Said matrix is put into pickle carry out pickling, said pickle consists of: acetic acid 10～30ml/L, Chile saltpeter 1～10g/L, and surplus is a water; The pickle temperature is 293～313K; The pickling time is 0.5～5min;
With the said matrix of flushing with clean water;
Said matrix is put into alkali wash water carry out alkali cleaning, said alkali wash water consists of sodium hydroxide solution or potassium hydroxide solution 5～20g/L; The alkali wash water pH value is 12～13; The alkali wash water temperature is 293～313K; The alkali cleaning time is 5～10min;
With the said matrix of flushing with clean water.
Step s103 carries out chemical oxidation to the surface of said matrix, forms the chemical oxidation rete, and said chemical oxidation rete is used to reduce the corrosion rate of said matrix, prolongs the service life of said matrix.The said chemical oxidation concrete steps of carrying out comprise:
Said matrix is put into chemical oxidation liquid carry out chemical oxidation; Said chemical oxidation liquid contains potassium permanganate, sodium permanganate or magnesium permanganate 10～20g/L, rare-earth salts 10～20g/L, coalescents 5～15g/L; Wherein said rare-earth salts is cerous nitrate, Lanthanum (III) nitrate or neodymium nitrate, and said coalescents is magnesium nitrate or Chile saltpeter; The pH value of said chemical oxidation liquid is between 5～7; The temperature of chemical oxidation liquid is 318～333K; The chemical oxidation treatment time is 5～10min;
With the said matrix of flushing with clean water;
Said matrix is dried, and bake out temperature is 303～373K, and drying time is 5～10min.
Step s104 applies the surface of said chemical oxidation rete, forms the degradable high polymer material layer.Said painting method comprises: dip-coating, thermal spraying, electrostatic coating, collosol and gel, the liquid coating of supercritical.
Step s105 is fixed to said degradable high polymer material layer with curative drug.Carry out curative drug fixedly the time; With said intravascular stent fixing after at the uniform velocity rotation; The solution that will contain 1%～15% rapamycin or paclitaxel carries out directional spray to this support, and requires to confirm the spraying number of times according to this rack surface medicament contg, generally sprays 1～15 time.The contained drug main of coating of the present invention will comprise antiproliferative reagent, resisting mitosis reagent, antibiotic, anthracycline antibiotics, bleomycin, mithramycin, enzyme etc., also has antiplatelet reagent, antimetabolite, hormone medicine, anticoagulant, solution fibrin medicine, secretion inhibitor medicine, anti-inflammation drugs, non-steroid medicine etc.
Be that example describes with a kind of degradable magnesium alloy support that has composite coating below, oneself can adjust the degradation rate of this support in body fluid and simulated body fluid and control by warp according to the treatment needs.
Embodiment 1: high-purity magnesium becomes intravascular stent with laser engraving after polishing.With the sand papering that attenuates step by step, machinery is removed the oxide on surface earlier.Carry out defat, pickling and alkali cleaning then.Degreaser is NaOH 5g/L, Na
2CO
35g/L and Na
2SiO
35g/L.The degreaser temperature is 303K, and the time is 30min; Pickle is the mixed solution of 20ml/L acetic acid and 5g/L Chile saltpeter.The pickle temperature is 303K, and the pickling time is 3min.Take out the back and use flushing with clean water, then high pure magnesium bracket is soaked in the alkali wash water.Alkali wash water is the sodium hydroxide solution of pH value 12,10g/L, and temperature is 303K, and the alkali cleaning time is 5min.Take out the back and use flushing with clean water, higher pure magnesium bracket is put into chemical oxidation liquid.
Chemical oxidation liquid consists of:
Potassium permanganate 10g/L, cerous nitrate 10g/L, magnesium nitrate 5g/L.The pH value of oxidation liquid is between 5～7.
Magnesium metal rack chemical oxidation process condition:
The temperature of chemical oxidation liquid is 323K, and the chemical oxidation time is 5min.After chemical oxidation is accomplished, take out magnesium bracket and wash, dry.The sample drying temperature is 303K, and the time is 10min.
To put into polylactic acid (PLA) solution (concentration is 1.0g/mL) through the high pure magnesium bracket of chemical oxidation treatment and soak 15 minutes, then support cleaned and put into the vacuum drying oven inner drying.Make solvent with methanol, the rapamycin spraying support with 10ug/ml repeats to spray five times.
Embodiment 2: after polishing, laser engraving becomes intravascular stent with the AZ91D magnesium alloy.With the sand papering that attenuates step by step, remove the oxide on surface earlier.Carry out defat, pickling and alkali cleaning then.Degreaser is NaOH 5g/L, Na
2CO
35g/L and Na
2SiO
35g/L.The degreaser temperature is 303K, and the time is 30min; Pickle is the mixed solution of 20ml/L acetic acid and 5g/L Chile saltpeter.The pickle temperature is 303K, and the pickling time is 3min.Take out the back and use flushing with clean water, then magnesium alloy bracket is soaked in the alkali wash water.Alkali wash water is the sodium hydroxide solution of pH value 12,10g/L, and temperature is 303K, and the alkali cleaning time is 5min.Take out the back and use flushing with clean water, again magnesium alloy bracket is put into chemical oxidation liquid.
The composition of magnesium metal rack chemical oxidation liquid:
Magnesium permanganate 10g/L, neodymium nitrate 10g/L, magnesium nitrate 5g/L.The pH value of oxidation liquid is between 5～7.
Magnesium metal rack chemical oxidation process condition:
The temperature of chemical oxidation liquid is 318K, and the chemical oxidation time is 10min.After chemical oxidation is accomplished, take out magnesium bracket and wash, dry.The sample drying temperature is 303K, and the time is 10min.
Again support is put into 1.0mg/mL polycaprolactone (PCL) solution and soaked 30 minutes, then support is cleaned and put into the vacuum drying oven inner drying.Make organic solvent with oxolane, paclitaxel concentration is 10ug/ml, repeats dip-coating four times.
The degradable blood vessel bracket that has composite coating of the present invention has excellent machinery and materia medica performance.The mechanical performance that pure magnesium of controlled degradation that the process surface-coated is handled and magnesium alloy bracket have still kept the excellence that metal material possessed makes the magnesium material implant devices can effectively keep the good mechanical performance in-service; The use of surperficial degradable macromolecule layer simultaneously; Greatly improved required kind and the quantity of carrying medicine of support; Improved medicine fixation stability property; This macromolecular material can fix different drug and dose through the thickness of regulating molecular weight and polymeric layer, and drug loading is generally greater than 30%;
In addition, the magnesium material degradation rate reduces, and support prolongs service life.Because the leakiness of macromolecular material, no matter its thickness how, macromolecular material all is difficult to stop hydrone, and particularly chloride ion arrives Mg alloy surface, so magnesium alloy can begin degraded simultaneously with macromolecular material.The chemical oxidation technical operation is simple, and cost is low, and the time is short.Utilize the chemical reaction of magnesium alloy and oxidation liquid, generate the fine and close oxide-film of one deck, greatly reduced the degradation rate of magnesium alloy, prolonged the service life of support at Mg alloy surface.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (2)
1. a degradable blood vessel bracket that has composite coating is characterized in that, said support is: high-purity magnesium becomes intravascular stent with laser engraving after polishing; With the sand papering that attenuates step by step, machinery is removed the oxide on surface earlier; Carry out defat, pickling and alkali cleaning then; Degreaser is NaOH 5g/L, Na
2CO
35g/L and Na
2SiO
35g/L; The degreaser temperature is 303K, and the time is 30min; Pickle is the mixed solution of 20ml/L acetic acid and 5g/L Chile saltpeter; The pickle temperature is 303K, and the pickling time is 3min; Take out the back and use flushing with clean water, then high pure magnesium bracket is soaked in the alkali wash water; Alkali wash water is the sodium hydroxide solution of pH value 12,10g/L, and temperature is 303K, and the alkali cleaning time is 5min; Take out the back and use flushing with clean water, higher pure magnesium bracket is put into chemical oxidation liquid;
Chemical oxidation liquid consists of: potassium permanganate 10g/L, cerous nitrate 10g/L, magnesium nitrate 5g/L; The pH value of oxidation liquid is between 5～7;
Magnesium metal rack chemical oxidation process condition: the temperature of chemical oxidation liquid is 323K, and the chemical oxidation time is 5min; After chemical oxidation is accomplished, take out magnesium bracket and wash, dry; The sample drying temperature is 303K, and the time is 10min;
To put into concentration through the high pure magnesium bracket of chemical oxidation treatment is that the polylactic acid solution of 1.0g/mL soaked 15 minutes, then support is cleaned and put into the vacuum drying oven inner drying; Make solvent with methanol, the rapamycin spraying support with 10ug/ml repeats to spray five times.
2. a method for preparing that has the degradable blood vessel bracket of composite coating is characterized in that, said method for preparing is: high-purity magnesium becomes intravascular stent with laser engraving after polishing; With the sand papering that attenuates step by step, machinery is removed the oxide on surface earlier; Carry out defat, pickling and alkali cleaning then; Degreaser is NaOH 5g/L, Na
2CO
35g/L and Na
2SiO
35g/L; The degreaser temperature is 303K, and the time is 30min; Pickle is the mixed solution of 20ml/L acetic acid and 5g/L Chile saltpeter; The pickle temperature is 303K, and the pickling time is 3min; Take out the back and use flushing with clean water, then high pure magnesium bracket is soaked in the alkali wash water; Alkali wash water is the sodium hydroxide solution of pH value 12,10g/L, and temperature is 303K, and the alkali cleaning time is 5min; Take out the back and use flushing with clean water, higher pure magnesium bracket is put into chemical oxidation liquid;
Chemical oxidation liquid consists of: potassium permanganate 10g/L, cerous nitrate 10g/L, magnesium nitrate 5g/L.The pH value of oxidation liquid is between 5～7;
Magnesium metal rack chemical oxidation process condition: the temperature of chemical oxidation liquid is 323K, and the chemical oxidation time is 5min; After chemical oxidation is accomplished, take out magnesium bracket and wash, dry; The sample drying temperature is 303K, and the time is 10min;
To put into concentration through the high pure magnesium bracket of chemical oxidation treatment is that 1.0g/mL is that polylactic acid solution soaked 15 minutes, then support is cleaned and put into the vacuum drying oven inner drying.Make solvent with methanol, the rapamycin spraying support with 10ug/ml repeats to spray five times.
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| US8986369B2 (en) | 2010-12-01 | 2015-03-24 | Zorion Medical, Inc. | Magnesium-based absorbable implants |
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| CN111041265B (en) * | 2019-11-11 | 2021-07-02 | 北京科技大学 | Preparation of degradable magnesium alloy sliding sleeve fracturing ball and method for controlling degradation rate |
| CN113813452B (en) * | 2021-09-22 | 2022-06-14 | 河南科技大学 | Construction method of 3D printing titanium alloy support with photo-thermal and temperature control warning functions |
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