CN102552973A - Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof - Google Patents
Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and a preparation method thereof. The medical implant is made of a Mg-Sr-Ca series alloy, wherein strontium is 0 to 5 percent (but not 0) of the weight of the Mg-Sr-Ca series alloy; calcium is 0 to 2 percent (but not 0) of the weight of the Mg-Sr-Ca series alloy; a small amount of one or more of trace elements, namely manganese, zirconium, tin, rare earth and yttrium may be contained, and are not more than 2 percent of weight of the Mg-Sr-Ca series alloy; and the balance is magnesium. In-vivo and in-vitro tests prove that the Mg-Sr-Ca series alloy implant is nontoxic, has high histocompatibility, and is a reliable biomedical implant material.
Description
Technical field
The present invention relates to a kind of degradable absorbability Mg-Sr-Ca is alloy medical implant and preparation method thereof.Degradable absorbability Mg-Sr-Ca is the design of alloy, and is nontoxic and possess the favorable tissue compatibility, and mechanical property and degradation speed are adjustable, are suitable as degradable orthopaedics implantation instrument.
Background technology
Medical Biodegradable material is mainly degradable high polymer material and degradable ceramic material at present, and degradable high polymer material comprises polyglycolic acid (PGA), polylactic acid (PLA), gathers acetic acid lactone (PCL) and copolymer, natural polysaecharides material (cellulose, chitin) and native protein material (collagen, fibrin) etc.; The degradable pottery of extensive use comprises hydroxyapatite, type alpha tricalcium phosphate, bata-tricalcium phosphate and phosphoric acid oxygen four calcium.Though degradable high polymer material can be absorbed by the body fully, intensity is low, is difficult to provide the function of support structure, and its vivo degradation product is prone to cause problems such as inflammatory reaction; The shortcoming of degradable pottery is a poor toughness, can't compatible deformation.
The bio-medical metal material is widely used at medical instruments field because of its excellent mechanical property, biocompatibility and corrosion resistance.Widely used biomedical metal material is mainly 316L, 317L, 304V rustless steel, Co-Cr-Mo alloy, pure titanium, Ti-6Al-4V, TiNi alloy.But the shortcoming of bio-medical metal material is a non-degradable, exists with " allosome " form permanent in vivo.Simultaneously, the mechanical property and the osseous tissue of rustless steel, Co-Cr-Mo alloy and titanium alloy do not match, and especially their elastic modelling quantity is about 200GPa like stainless elastic modelling quantity, and titanium alloy is about 100GPa, and the elastic modelling quantity of osseous tissue has only 10-40GPa.Therefore will carry almost all load after causing metal implant to be implanted, cause the stress shielding phenomenon of osseous tissue, be i.e. implant surrounding bone Telatrophy or loose.
From the angle of biocompatibility, magnesium is the indispensable element of human body, is the second important cation (K first) in the body, and normal contents is 25 grams in human body, and half is present in the skeleton.Magnesium has different physiological roles, with the health of the keeping of life, health extremely confidential relation is arranged.And human body is to the about 300-700mg of daily requirement amount of magnesium, and the magnesium that surpasses the psychological need amount can excrete with urine through kidney, so the normal person of renal function, generally can not cause toxic and side effects with 4 ~ 6g magnesium every day.From the materialogy angle, magnesium alloy density (1.75 ~ 1.85g/cm
3) and the dense tissue (1.75g/cm of human body
3) close, elastic modelling quantity is about 45GPa, less than 1/2 of medical titanium alloy elastic modelling quantity (109-112GPa), can effectively alleviate the stress-shielding effect of orthopaedics implant, and possess good comprehensive mechanical properties and machining property.Magnesium alloy chemical character is active, in solution, especially contains Cl
-The human body fluid environment in corrodible degraded, be considered to become a new generation the degradable embedded material.In sum, if adopt magnesium alloy to make orthopaedics implant, the characteristics with the degraded and absorbed of the mechanical property advantage that has " bio-medical metal material " simultaneously concurrently and " degradable high polymer material " have good medical prospect.
Strontium is prevalent in food and the water, is the trace element of human body, and 99% is present in bone and tooth, and wherein Sr content is approximately 100-120mg/kg in the bone, content 300mg/kg in enamel.Sr and Ca belong to II family in the periodic table of elements, in body fluid, all exist with bivalent ions form, and very similarly character is arranged; Its absorption approach, carrier are identical, and Ca and carrier-bound ability are greater than Sr, and both are inversely proportional to by the content in bone; Higher in the ionic concentration of new osteoplastic initial stage Sr; Along with the maturation of bone matrix, by the replacement of Ca ion, the Sr ion keeps certain ratio can keep the normal function of sclerotin in bone matrix to the Sr ion gradually.The report of the toxicity disease that does not cause about excessive Sr so far.
Research at present shows that oral Sr salt can promote osseous tissue to form, and suppresses bone resorption, thereby increases the bone amount and improve bone strength, the treatment osteoporosis.Strontium ranelate (Ou Simei) by the original development of French Les Laboratoires servier shows that through clinical experiment to osteoporosis in postmenopausal women be a reliable medicine.Because Sr is to the facilitation of osseous tissue growth, Sr also is used to prepare the Sr-HA bone cement and contains the Sr coating in the preparation of bio-medical metal material surface.Utilize Sr partly to substitute the Ca among the HA, thereby cause distortion of lattice to influence crystallinity and the dissolubility of HA.Research shows that the Sr-HA bone cement helps osteogenesis and integration, reduces because the danger of the secondary fracture that osteoporosis causes.Contain the Sr coating in the preparation of bio-medical metal material surface, can be through slowly discharging Sr
2+, induce osseous tissue to generate, improve the biological activity of implant.
From the materialogy angle, Sr also is an important alloying element in the magnesium alloy.Sr can produce constitutional supercooling in the enrichment of solid liquid interface forward position, hinder grain growth, thereby crystal grain thinning improves casting properties.Simultaneously, Sr can improve the dissolubility of H in the magnesium alloy, and generates SrH with H
2Cenotype reduces air holes in the process of setting.Since its grain refinement effect and formation contain Sr have mutually high fusing point and and magnesium matrix between less potential difference; An amount of interpolation Sr can improve the room temperature and the elevated temperature strength of magnesium alloy; Improve the high temperature creep property and the hot-cracking resistance of magnesium alloy, improve the decay resistance of magnesium alloy.For example in AZ91D, add 0.6% Sr, its in 3.5% NaCl solution from corrosion electric current density by 16.85A/cm
2Be reduced to 2.01 A/cm
2
Calcium is a kind of essential element, also is the abundantest magnanimity metallic element of content in the human body, and content is only second to C, H, O, N.Become the interior calcium content of human body to be about 1200g under the normal situation, wherein about 99% is present in skeleton and the tooth, and mainly the form with hydroxyapatite crystal exists, and keeps bone and tooth and has hard structure and support.About in addition 1% calcium often is present in outer liquid of soft tissue cells and the blood with free or bonded ionic condition, is referred to as miscible calcium pool.Calcium plays an important role in various physiology of body and biochemical process.From the materialogy angle, calcium is crystal grain thinning significantly, thereby improves the formability and the intensity of magnesium alloy, also can reduce the micro cell effect of magnesium alloy, improves the corrosion resistance of magnesium alloy.
Also not having document and patent to propose Mg-Sr-Ca at present both at home and abroad is that alloy is used as bio-medical material.
Summary of the invention
The object of the invention provides a kind of medical degradable that can be applicable to the orthopaedics medical embedded material and absorbs Mg-Sr-Ca series magnesium alloy implant and preparation method thereof.This alloy implant has excellent biological compatibility and decay resistance, and can satisfy mechanical property requirements.
For realizing above-mentioned purpose, the technical scheme that the present invention adopted is:
A kind of medical degradable absorbs Mg-Sr-Ca series magnesium alloy implant, by weight percentage, mainly contains: strontium (Sr) 0-5%, do not comprise 0, and calcium (Ca) 0-2% does not comprise 0, surplus is a magnesium.
As the further setting of such scheme, also contain in the following trace element one or more, they are manganese (Mn), zirconium (Zr), stannum (Sn), rare earth (RE) and yttrium (Y), by weight percentage, total amount is 0-2%, does not comprise 0% and 2%.
Said manganese content is not more than 1.5%, and zirconium content is not more than 1%, and stannum content is not more than 2%, and content of rare earth is not more than 2%, and yttrium content is not more than 1%.
This programme possibly also contain a small amount of unavoidable impurities element, and they are ferrum (Fe), copper (Cu) and nickel (Ni); By weight percentage, their every kind of content is no more than 0.05%.
Said Mg-Sr-Ca is that alloy is compact texture or loose structure.
A kind of medical degradable absorbs the method for preparing of Mg-Sr-Ca series magnesium alloy implant; With magnesium, strontium, calcium; Perhaps with magnesium, strontium, calcium, after in manganese, zirconium, stannum, rare earth, the yttrium one or more mix, 700-850 ℃ of melting; Making compact texture Mg-Sr-Ca through the vacuum precision casting is alloy, and the medical degradable of processing compact texture through machining process absorbs Mg-Sr-Ca series magnesium alloy implant.Promptly adopting pure Mg, pure Sr and pure Ca is raw material, and perhaps adopting pure Mg, Mg-Sr, Mg-Ca intermediate alloy is raw material, at CO
2+ SF
6Under the atmosphere protection, 700-850 ℃ of melting, making compact texture Mg-Sr-Ca through the vacuum precision casting is alloy, the medical degradable of processing compact texture through machining process absorbs Mg-Sr-Ca series magnesium alloy implant.
This method is prefabricated into the intermediate alloy of Mg-Sr (Ca, Mn, Zr, Sn, RE or Y) with Sr, Ca, Mn, Zr, Sn, RE or Y element, is added into and carries out melting among the fusion Mg.
Said machining process comprises rolling and/or forging and/or extruding and/or rapid solidification;
Wherein, said rolling step for Mg-Sr-Ca be alloy cast ingot 300-500 ℃ solution treatment 2-20 hour, carry out roughing at 400-500 ℃, reduction in pass is 10-15%; In to roll temperature be 350-400 ℃, reduction in pass 30-60%; Final rolling temperature 200-350 ℃, reduction in pass 5-10%;
Said forging step is forged in 200-400 ℃ of scope for being alloy cast ingot 300-500 ℃ of scope solution treatment 2-20 hour with Mg-Sr-Ca then, forges speed and is not less than 350mm/s, and the forging rate is not less than 10%;
Said pressing steps for Mg-Sr-Ca be alloy cast ingot 300-500 ℃ solution treatment 2-20 hour, the extrusion temperature scope is 200-400 ℃, extrusion speed 0.1-30m/min, extrusion ratio 10 ~ 100;
Said rapid solidification is to adopt fine vacuum fast quenching system under the Ar gas shiled, feeding quantity 2-8g, induction heating power 3-7kW; Nozzle and roller spacing 0.8mm, expulsion pressure 0.05-0.2MPa, roller speed are 500-5000r/min; Nozzle slot size 1film * 8mm * 6mm processes rapid coagulation band, then strip is broken into Powderedly, and it is the alloy extruded stock that 200-350 ℃ of vacuum hotpressing 1-24h processes Mg-Sr-Ca; Push extrusion ratio 10-60 in 200-400 ℃ of scope then.
A kind of medical degradable absorbs the another kind of method for preparing of Mg-Sr-Ca series magnesium alloy implant; With magnesium, strontium, calcium; Perhaps with magnesium, strontium, calcium; With in manganese, zirconium, stannum, rare earth, the yttrium one or more as raw material, after adopting powder technique method or prealloy powder sintering process or self propagating high temperature synthetic method to process loose structure Mg-Sr-Ca to be alloy, be processed into degradable and absorb medical implant;
Said powder technique method is that said preparation porous Mg-Sr-Ca is that alloy materials is proportionally prepared; Mix homogeneously; Be pressed into base, vacuum-sintering then is rapidly heated with 30 ℃/min after being warming up to 200-500 ℃ at a slow speed with 2-4 ℃/min; The cold cooling of stove, the Mg-Sr-Ca that obtains loose structure is an alloy;
Said prealloy powder sintering process is to be that the alloy materials powder carries out high-energy ball milling after the mixed as requested with said preparation loose structure Mg-Sr-Ca; Pre-embossed molding subsequently; Heat-treated 10-12 hour for 300-600 ℃, the Mg-Sr-Ca that obtains loose structure is an alloy again;
Said self propagating high temperature synthetic method is to be that alloy materials is mixed and to be pressed into base with preparation porous Mg-Sr-Ca, under the inert gas shielding, and gas pressure 1 * 10
3-1 * 10
5Pa lights that to carry out self propagating high temperature synthetic under 200-700 ℃, and the Mg-Sr-Ca that obtains loose structure is an alloy.
For the degradable that slows down the inventive method preparation absorbs Mg-Sr-Ca is the degradation speed of medical implant, and in above-mentioned two kinds of methods, all also being included in said Mg-Sr-Ca is that alloy surface also is coated with degradable macromolecule coating or degradable ceramic coating;
Said degradable macromolecule coating is polyglycolic acid (PGA), polylactic acid (PLA), L-polylactic acid (PLLA), PCL (PCL), polybutylcyanoacrylate (PACA), gather para-dioxane ketone, gather anhydride, poly phosphazene, amino acids polymer, gather one or more the combination in any in beta-hydroxy-butanoic acid ester and hydroxyl valerate and the copolymer thereof;
Said degradable ceramic coating can be one or more the combination in any in hydroxyapatite, strontium containing hydroxyapatite, fluoridated hydroxyapatite, type alpha tricalcium phosphate, bata-tricalcium phosphate and phosphoric acid oxygen four calcium.
Wherein, the degradable macromolecule coating layer thickness can be 0.01-5mm; The thickness of degradable ceramic coating can be 0.01-5mm.
The method of said coating degradable macromolecule coating is czochralski method and even glue method;
It is to be that alloy carries out pickling with said degradable absorbability Mg-Sr-Ca that said czochralski method applies the degradable macromolecule coating; In organic solvents such as trichloroethane, dissolve the preparation material of said polymeric coating layer then; Then alloy is at the uniform velocity pulled out after the dip-coating in the macromolecular material colloid and carry out centrifugal treating, obtain applying the degradable absorption medical implant of degradable macromolecule coating;
It is to be that alloy carries out pickling with said degradable absorbability Mg-Sr-Ca that said even glue method applies the degradable macromolecule coating; In organic solvents such as trichloroethane, dissolve the preparation material of said polymeric coating layer then; With the macromolecular material colloid drops at alloy surface; Utilize the sol evenning machine high speed rotating that colloid is spread into and form thin layer on the alloy, dry to remove unnecessary solvent, repeatedly apply to reach optimum efficiency.
The method of said coating degradable ceramic coating is plasma spraying, electro-deposition or differential arc oxidation method;
The used plasma gas master of said plasma spray coating degradable ceramic coating gas: Ar 30-100scfh, inferior gas: H
25-20scfh, spraying current: 400-800A, spray voltage: 40-80V, spray distance 100-500mm;
Said electro-deposition degradable ceramic coating is for being negative electrode with the medical implant, in the electrolyte of calcic, phosphorus, fluorine or strontium salt, and electric current density 0.5-30mA/cm
2, temperature 25-85 ℃, behind the processing 10-60min, cleaning-drying obtains said medical implant;
The method of said differential arc oxidation for said medical implant Mg-Sr-Ca be alloy in the electrolyte of calcium, phosphorus, fluorine or strontium salt, oxidation 5-30min under the 200-500V.
Advantage of the present invention and beneficial effect:
Degradable of the present invention absorbs the Mg-Sr-Ca series magnesium alloy; Select the needed by human metallic element for use; Do not contain harmful or potential harmful element, alloy element Sr wherein can promote skeletonization, suppresses bone resorption; Thereby following Mg-Sr-Ca is the alloy degraded, and the common release of local Mg, Sr, Ca can promote organization healing.
Method of the present invention realizes the mechanical property and the degradation speed of regulation and control medical implant through composition design and preparation technology's cooperation (like crimp or face coat), obtains optimum mechanical properties and decay resistance.
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is described further.
Description of drawings
Fig. 1 is an as cast condition Mg-Sr-Ca alloy microscopic structure;
Fig. 2 is for as cast condition and roll attitude Mg-Sr-Ca alloy room temperature tensile performance;
Fig. 3 rolls attitude Mg-Sr-Ca alloy to implant the X ray picture of mouse bone marrow cells chamber after 4 weeks;
Fig. 4 rolls attitude Mg-Sr-Ca alloy to implant the mouse bone marrow cells micro-CT 2D reconstruction figure of chamber after 4 weeks;
Fig. 5 rolls attitude Mg-Sr-Ca alloy to implant the mouse bone marrow cells micro-CT 3D reconstruction figure of chamber after 4 weeks.
The specific embodiment
Used method among the following embodiment if no special instructions, is conventional method.
Used percentage composition among the following embodiment if no special instructions, is the quality percentage composition.
Embodiment 1
Test raw material adopts pure Mg (99.95wt.%), Mg-Sr intermediate alloy and Mg-Ca intermediate alloy, presses Mg-Sr-Ca alloying component (nominal composition by weight percentage: Sr 2%, and Ca 1%, and surplus is Mg) alloyage, at CO
2+ SF
6Atmosphere protection is the fusing pure magnesium ingot down, and temperature is increased to 750 ℃ and adds the Mg-Sr intermediate alloy, treats to stir 10min after its fusing, adds the Mg-Ca intermediate alloy subsequently, stirs 10min, makes alloy element Sr and Ca homogenization.Be incubated 30min after being warming up to 750 ℃, melt cast is carried out gravitational casting to being preheated in 300 ℃ the mould, make the Mg-Sr-Ca ingot casting.The as cast condition Mg-Sr-Ca alloy microscopic structure that adopts the present invention to obtain is as shown in Figure 1.As cast condition Mg-Sr-Ca alloy is processed into the stretching standard sample, carries out tensile tests at room, draw speed 1mm/min.The as cast condition Mg-Sr-Ca alloy room temperature tensile performance that adopts the present invention to obtain is as shown in Figure 2.
Embodiment 2
Alloy smelting process is processed into the 6mm heavy-gauge sheeting with embodiment 1 with the Mg-Sr-Ca alloy cast ingot, and sand papering is to no significant defect, and 400 ℃ are incubated 3 hours, be rolled, and every time volume under pressure 0.2mm, every time melted down 10 minutes, finally was rolled down to 1.2mm thickness plate.To roll attitude Mg-Sr-Ca alloy and be processed into the stretching standard sample, carry out tensile tests at room, draw speed 1mm/min.Adopt that the present invention obtains to roll attitude Mg-Sr-Ca alloy room temperature tensile performance as shown in Figure 2.
Embodiment 3
The attitude Mg-Sr-Ca alloy that rolls that makes is processed into Φ 0.7mm, the bar of long 5mm, sanding and polishing is to 2000# sand paper, oxirane disinfection.Select 83 months C57BL/6 mices, be divided into two groups at random, 4 every group.Wherein anaesthetize and left side knee preserved skin is also sterilized for one group, the DF drill diameter is the 0.7mm circular hole, implants in the hole alloy bar and stitching.The femur boring of other one group of mice left side is as blank.The postoperative routine observation does not find that implant causes foreign body reactions such as surrounding tissue inflammation.4 weeks of postoperative find that osteogenic response is obvious, and bone trabecula density is higher than matched group, and outer periosteum and interior periosteum skeletonization all are higher than matched group.The attitude Mg-Sr-Ca alloy that rolls that adopts that the present invention obtains is implanted mouse bone marrow cells chamber X ray and micro-CT observed result such as Fig. 3, Fig. 4, shown in Figure 5 after 4 weeks.
Embodiment 4
Test raw material adopts pure Mg (99.95wt.%), Mg-Sr intermediate alloy, Mg-Ca intermediate alloy and Mg-Zr intermediate alloy; (nominal composition by weight percentage: Sr 1%, and Ca 1%, and Zr 0.5% to press the Mg-Sr-Ca-Zr alloying component; Surplus is Mg) alloyage, at CO
2+ SF
6Atmosphere protection is the fusing pure magnesium ingot down, and temperature is increased to 750 ℃ and adds the Mg-Sr intermediate alloy, treats to stir 10min after its fusing; Add the Mg-Ca intermediate alloy subsequently, stir 10min, add the Mg-Zr intermediate alloy subsequently; Stir 10-15min, make alloy element Sr, Ca and Zr homogenization.Be incubated 30min after being warming up to 750 ℃, melt cast is carried out gravitational casting to being preheated in 300 ℃ the mould, make the Mg-Sr-Ca-Zr ingot casting.With 400 ℃ of insulations of the ingot casting that makes 3 hours, push extrusion ratio 25:1,270 ℃ of extrusion temperatures.Get extruding attitude Mg-Sr-Ca-Zr alloy that said method makes and be processed into screw and implant 18 NZws left side femurs, offside is implanted pure Ti screw.Postoperative 1,6 and put to death laboratory animal in 12 months respectively, 18 rabbits do not find that all implant causes foreign body reactions such as surrounding tissue inflammation, and 12 months Mg-Sr-Ca-Zr alloys of postoperative implant volume reduces 58%, and degraded place is all filled by new bone.
Is the ratio of 99:5:1 with pure Mg (purity is 99.95%), pure Sr (purity is 99.9%) and pure Ca (purity is 99.9%) in mass ratio, and mix homogeneously is pressed into base; Sintering in vacuum sintering furnace (VSF series (universal) vacuum sintering furnace, Shenyang vacuum technique institute), concrete agglomerating step is: after being warming up to 300 ℃ at a slow speed with 2 ℃/min; Then be rapidly heated to 650 ℃ with 30 ℃/min; At last, the cold cooling of stove obtains the Mg-Sr-Ca alloy of loose structure with the prealloy powder sintering process; Measuring voidage through drainage is 50%, the Mg-Sr-Ca alloy of this loose structure is prepared into through cutting is of a size of 5 * 5 * 5mm
3Cube, promptly obtain medical implant-bone tissue restoration support.
With 12 of the bone tissue restoration support implants for preparing according to the method described above; Utilize operation to be imbedded in the femur of 12 rabbit respectively; At first be in and after the rabbit femoral place holes the left side femur gone in the implant heeling-in with φ=3mm hand drill; Postoperative injection benzylpenicillin potassium 15mg/kg tests with 316L rustless steel (Xibei Inst. of Non-Ferrous Metals) support as contrast; Postoperative was put to death laboratory animal in 1,5 months respectively.Postoperative 1 month, this alloy material of micro-CT observer's rabbit femoral place is because corrosion degraded volume progressively reduces, and bone tissue restoration both injured bones around the material and contact are closely.After bone tissue restoration support implant is implanted May, all degradeds fully, and the inflammation of 316L stainless steel stent surrounding tissue.
Embodiment 6
The preparation technology who rolls attitude Mg-Sr-Ca alloy bone fixing head is with embodiment 1 and 2.Adopt pickling then, dip-coating, drying process prepare PLLA surface modification bone fixing head.Concrete preparation technology is following:
puts into the colloid immersion with the alloy implant after the pickling and at the uniform velocity lifts taking-up, vacuum room temperature dried overnight after 30 minutes.
The PLLA surface modification Mg-Sr-Ca bone fixing head that makes is fixed in the femur of Canis familiaris L..Do not find that through regular observation implant causes foreign body reactions such as surrounding tissue inflammation.Observe to find that PLLA dissolves gradually along with the prolongation of the time of implantation, bone fixing head size decreases, simultaneously with is connected the bone place and connects tight.After 7 months, the implantable bone fixing head is degraded fully.
Embodiment 7
The preparation technology of bone fixing head is with embodiment 1 and 2.Use 800#, 1500#, 2000# sand papering bone fixing head, with 0.04M sodium and 0.2M calcium acetate as electrolyte, pH:10 ~ 11,350V prepares calcic, P anode oxide layer.Anodic oxidation bone fixing head is placed autoclave, and regulating pH value is 13 ~ 14,130 ℃ of insulation 4h, and oven dry gets final product.Concrete preparation technology is following:
After
cleans sample is placed 130 ℃ of insulations of autoclave 4h.
Anodic oxidation that makes and the synthetic common surface modification bone fixing head of hydro-thermal are fixed in the femur of Canis familiaris L..Do not find that through regular observation implant causes foreign body reactions such as surrounding tissue inflammation.Observe the prolongation of finding along with the time of implantation, face coat merges with bone gradually, bone fixing head size decreases.After 10 months, the implantable bone fixing head is degraded fully.
Embodiment 8
A kind of medical degradable absorbs Mg-Sr-Ca series magnesium alloy implant, by weight percentage, contains: strontium 2%, and calcium 1%, manganese 1%, stannum 0.5%, yttrium 0.3%, surplus is a magnesium.
Mg-Sr-Ca is that alloy is a compact texture.
The method for preparing that medical degradable of the present invention absorbs Mg-Sr-Ca series magnesium alloy implant is following: after magnesium, strontium, calcium, manganese, stannum, yttrium are mixed; 800 ℃ of meltings; Making compact texture Mg-Sr-Ca through the vacuum precision casting is alloy, and the medical degradable of processing compact texture through machining process absorbs Mg-Sr-Ca series magnesium alloy implant.
Machining process is extruding, and pressing steps is for being 400 ℃ of solution treatment of alloy cast ingot 16 hours with Mg-Sr-Ca, and the extrusion temperature scope is 400 ℃, extrusion speed 10m/min, extrusion ratio 10 ~ 100.
After extruding is good, be that alloy surface also is coated with the degradable macromolecule coating also at Mg-Sr-Ca.
The degradable macromolecule coating is a polyglycolic acid.
The method that applies the degradable macromolecule coating is a czochralski method.
It is to be that alloy carries out pickling with degradable absorbability Mg-Sr-Ca that czochralski method applies the degradable macromolecule coating; In organic solvents such as trichloroethane, dissolve the preparation material of said polymeric coating layer then; Then alloy is at the uniform velocity pulled out after the dip-coating in the macromolecular material colloid and carry out centrifugal treating, obtain applying the degradable absorption medical implant of degradable macromolecule coating.
Embodiment 9
A kind of medical degradable absorbs Mg-Sr-Ca series magnesium alloy implant, by weight percentage, contains: strontium 4.5%, and calcium 1.8%, manganese 1%, zirconium 0.8%, surplus is a magnesium.
Mg-Sr-Ca is that alloy is a compact texture.
The method for preparing that medical degradable of the present invention absorbs Mg-Sr-Ca series magnesium alloy implant is following: after strontium, calcium, manganese, zirconium, magnesium are mixed; 750 ℃ of meltings; Making compact texture Mg-Sr-Ca through the vacuum precision casting is alloy, and the medical degradable of processing compact texture through machining process absorbs Mg-Sr-Ca series magnesium alloy implant.
Machining process is for forging.
Wherein, forge step for being 500 ℃ of scope solution treatment of alloy cast ingot 10 hours with Mg-Sr-Ca, in 400 ℃ of scopes, forge then, forge speed and be not less than 350mm/s, the forging rate is not less than 10%.
After forging well, be that alloy surface also is coated with the degradable ceramic coating also at Mg-Sr-Ca.
The degradable ceramic coating is phosphoric acid oxygen four calcium.
The method that applies the degradable ceramic coating is a plasma spraying.
The used plasma gas master of plasma spraying degradable ceramic coating gas: Ar 30-100scfh, inferior gas: H
25-20scfh, spraying current: 400-800A, spray voltage: 40-80V, spray distance 100-500mm.
Embodiment 10
A kind of medical degradable absorbs Mg-Sr-Ca series magnesium alloy implant, by weight percentage, contains: strontium 5%, and calcium 2%, manganese 0.5%, zirconium 0.5%, stannum 0.5%, surplus is a magnesium.
Mg-Sr-Ca is that alloy is a compact texture.
The method for preparing that medical degradable of the present invention absorbs Mg-Sr-Ca series magnesium alloy implant is following: with magnesium, strontium, calcium, manganese, zirconium, stannum as raw material; After adopting the powder technique method to process loose structure Mg-Sr-Ca to be alloy, be processed into degradable and absorb medical implant.
The powder technique method is to be that alloy materials is proportionally prepared with preparation porous Mg-Sr-Ca, and mix homogeneously is pressed into base; Vacuum-sintering; Then be rapidly heated after being warming up to 500 ℃ at a slow speed with 4 ℃/min with 30 ℃/min, the cold cooling of stove, the Mg-Sr-Ca that obtains loose structure is an alloy.
Powder technique method gained Mg-Sr-Ca is that alloy surface also is coated with the degradable macromolecule coating.
The degradable macromolecule coating is the combination of polyglycolic acid and polylactic acid.
The method that applies the degradable macromolecule coating is even glue method.
It is to be that alloy carries out pickling with degradable absorbability Mg-Sr-Ca that even glue method applies the degradable macromolecule coating; In organic solvents such as trichloroethane, dissolve the preparation material of said polymeric coating layer then; With the macromolecular material colloid drops at alloy surface; Utilize the sol evenning machine high speed rotating that colloid is spread into and form thin layer on the alloy, dry to remove unnecessary solvent, repeatedly apply to reach optimum efficiency.
Embodiment 11
A kind of medical degradable absorbs Mg-Sr-Ca series magnesium alloy implant, by weight percentage, contains: strontium 3%, and calcium 0.8%, manganese 0.8%, zirconium 0.3%, stannum 0.8%, surplus is a magnesium.
Mg-Sr-Ca is that alloy is a compact texture.
The method for preparing that medical degradable of the present invention absorbs Mg-Sr-Ca series magnesium alloy implant is following: with magnesium, strontium, calcium, manganese, zirconium, stannum as raw material; After adopting the self propagating high temperature synthetic method to process loose structure Mg-Sr-Ca to be alloy, be processed into degradable and absorb medical implant.
The self propagating high temperature synthetic method is to be that alloy materials is mixed and to be pressed into base with preparation porous Mg-Sr-Ca, under the inert gas shielding, and gas pressure 1 * 10
3-1 * 10
5Pa lights that to carry out self propagating high temperature synthetic under 700 ℃, and the Mg-Sr-Ca that obtains loose structure is an alloy.
Gained Mg-Sr-Ca is that alloy surface also is coated with the degradable ceramic coating after the self propagating high temperature synthetic method.
The degradable ceramic coating is the combination of type alpha tricalcium phosphate, bata-tricalcium phosphate and phosphoric acid oxygen four calcium.
The method that applies the degradable ceramic coating is a differential arc oxidation method.
The method of differential arc oxidation for medical implant Mg-Sr-Ca be alloy in the electrolyte of strontium salt, oxidation 15min under the 300V.
Claims (10)
1. a medical degradable absorbs Mg-Sr-Ca series magnesium alloy implant, it is characterized in that: by weight percentage, mainly contain: strontium 0-5%, do not comprise 0, and calcium 0-2% does not comprise 0, surplus is a magnesium.
2. medical degradable according to claim 1 absorbs Mg-Sr-Ca series magnesium alloy implant; It is characterized in that: also contain in the following trace element one or more, they are manganese, zirconium, stannum, rare earth and yttrium, by weight percentage; Total amount is 0-2%, does not comprise 0% and 2%.
3. medical degradable according to claim 2 absorbs Mg-Sr-Ca series magnesium alloy implant, and it is characterized in that: said manganese content is not more than 1.5%, and zirconium content is not more than 1%, and stannum content is not more than 2%, and content of rare earth is not more than 2%, and yttrium content is not more than 1%.
4. medical degradable according to claim 3 absorbs Mg-Sr-Ca series magnesium alloy implant, and it is characterized in that: said Mg-Sr-Ca is that alloy is compact texture or loose structure.
5. a medical degradable absorbs the method for preparing of Mg-Sr-Ca series magnesium alloy implant; It is characterized in that: with magnesium, strontium, calcium; Perhaps with magnesium, strontium, calcium, after in manganese, zirconium, stannum, rare earth, the yttrium one or more mix, 700-850 ℃ of melting; Making compact texture Mg-Sr-Ca through the vacuum precision casting is alloy, and the medical degradable of processing compact texture through machining process absorbs Mg-Sr-Ca series magnesium alloy implant.
6. method according to claim 5 is characterized in that: said machining process comprises rolling and/or forging and/or extruding and/or rapid solidification;
Wherein, said rolling step for Mg-Sr-Ca be alloy cast ingot 300-500 ℃ solution treatment 2-20 hour, carry out roughing at 400-500 ℃, reduction in pass is 10-15%; In to roll temperature be 350-400 ℃, reduction in pass 30-60%; Final rolling temperature 200-350 ℃, reduction in pass 5-10%;
Said forging step is forged in 200-400 ℃ of scope for being alloy cast ingot 300-500 ℃ of scope solution treatment 2-20 hour with Mg-Sr-Ca then, forges speed and is not less than 350mm/s, and the forging rate is not less than 10%;
Said pressing steps for Mg-Sr-Ca be alloy cast ingot 300-500 ℃ solution treatment 2-20 hour, the extrusion temperature scope is 200-400 ℃, extrusion speed 0.1-30m/min, extrusion ratio 10 ~ 100;
Said rapid solidification is to adopt fine vacuum fast quenching system under the Ar gas shiled, feeding quantity 2-8g, induction heating power 3-7kW; Nozzle and roller spacing 0.8mm, expulsion pressure 0.05-0.2MPa, roller speed are 500-5000r/min; Nozzle slot size 1film * 8mm * 6mm processes rapid coagulation band, then strip is broken into Powderedly, and it is the alloy extruded stock that 200-350 ℃ of vacuum hotpressing 1-24h processes Mg-Sr-Ca; Push extrusion ratio 10-60 in 200-400 ℃ of scope then.
7. a medical degradable absorbs the method for preparing of Mg-Sr-Ca series magnesium alloy implant; It is characterized in that: with magnesium, strontium, calcium; Perhaps with magnesium, strontium, calcium; With in manganese, zirconium, stannum, rare earth, the yttrium one or more as raw material, after adopting powder technique method or prealloy powder sintering process or self propagating high temperature synthetic method to process loose structure Mg-Sr-Ca to be alloy, be processed into degradable and absorb medical implant;
Said powder technique method is that said preparation porous Mg-Sr-Ca is that alloy materials is proportionally prepared; Mix homogeneously; Be pressed into base, vacuum-sintering then is rapidly heated with 30 ℃/min after being warming up to 200-500 ℃ at a slow speed with 2-4 ℃/min; The cold cooling of stove, the Mg-Sr-Ca that obtains loose structure is an alloy;
Said prealloy powder sintering process is to be that the alloy materials powder carries out high-energy ball milling after the mixed as requested with said preparation loose structure Mg-Sr-Ca; Pre-embossed molding subsequently; Heat-treated 10-12 hour for 300-600 ℃, the Mg-Sr-Ca that obtains loose structure is an alloy again;
Said self propagating high temperature synthetic method is to be that alloy materials is mixed and to be pressed into base with preparation porous Mg-Sr-Ca, under the inert gas shielding, and gas pressure 1 * 10
3-1 * 10
5Pa lights that to carry out self propagating high temperature synthetic under 200-700 ℃, and the Mg-Sr-Ca that obtains loose structure is an alloy.
8. according to arbitrary described method among the claim 5-7, it is characterized in that: in the said method, comprise that also said Mg-Sr-Ca is that alloy surface also is coated with degradable macromolecule coating or degradable ceramic coating;
Said degradable macromolecule coating is polyglycolic acid, polylactic acid, L-polylactic acid, PCL, polybutylcyanoacrylate, gather para-dioxane ketone, gather anhydride, poly phosphazene, amino acids polymer, gather one or more the combination in any in beta-hydroxy-butanoic acid ester and hydroxyl valerate and the copolymer thereof;
Said degradable ceramic coating can be one or more the combination in any in hydroxyapatite, strontium containing hydroxyapatite, fluoridated hydroxyapatite, type alpha tricalcium phosphate, bata-tricalcium phosphate and phosphoric acid oxygen four calcium.
9. method according to claim 8 is characterized in that: the method for said coating degradable macromolecule coating is czochralski method and even glue method;
It is to be that alloy carries out pickling with said degradable absorbability Mg-Sr-Ca that said czochralski method applies the degradable macromolecule coating; In organic solvents such as trichloroethane, dissolve the preparation material of said polymeric coating layer then; Then alloy is at the uniform velocity pulled out after the dip-coating in the macromolecular material colloid and carry out centrifugal treating, obtain applying the degradable absorption medical implant of degradable macromolecule coating;
It is to be that alloy carries out pickling with said degradable absorbability Mg-Sr-Ca that said even glue method applies the degradable macromolecule coating; In organic solvents such as trichloroethane, dissolve the preparation material of said polymeric coating layer then; With the macromolecular material colloid drops at alloy surface; Utilize the sol evenning machine high speed rotating that colloid is spread into and form thin layer on the alloy, dry to remove unnecessary solvent, repeatedly apply to reach optimum efficiency.
10. method according to claim 8 is characterized in that: the method for said coating degradable ceramic coating is plasma spraying, electro-deposition or differential arc oxidation method;
The used plasma gas master of said plasma spray coating degradable ceramic coating gas: Ar 30-100scfh, inferior gas: H
25-20scfh, spraying current: 400-800A, spray voltage: 40-80V, spray distance 100-500mm;
Said electro-deposition degradable ceramic coating is for being negative electrode with the medical implant, in the electrolyte of calcic, phosphorus, fluorine or strontium salt, and electric current density 0.5-30mA/cm
2, temperature 25-85 ℃, behind the processing 10-60min, cleaning-drying obtains said medical implant;
The method of said differential arc oxidation for said medical implant Mg-Sr-Ca be alloy in the electrolyte of calcium, phosphorus, fluorine or strontium salt, oxidation 5-30min under the 200-500V.
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