CN104328312B - A kind of medical bio degradable kirsite and preparation method thereof - Google Patents
A kind of medical bio degradable kirsite and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000137 annealing Methods 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 25
- 239000011575 calcium Substances 0.000 claims abstract description 25
- 238000005266 casting Methods 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 63
- 239000000956 alloy Substances 0.000 claims description 63
- 238000009413 insulation Methods 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 208000016261 weight loss Diseases 0.000 claims description 7
- 230000004580 weight loss Effects 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000000265 homogenisation Methods 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 238000005275 alloying Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000010792 warming Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 239000007943 implant Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 231100000820 toxicity test Toxicity 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- -1 marmem Inorganic materials 0.000 description 1
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- 238000011587 new zealand white rabbit Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 210000005084 renal tissue Anatomy 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
A kind of medical bio degradable kirsite and preparation method thereof, belongs to field of material technology, and alloying component is by weight percentage containing Mg 0.005 ~ 1%, Ag 0.01 ~ 0.5%, Ca 0.01 ~ 0.5%, Mn 0.01 ~ 0.5%, and inevitable impurity≤0.2%, surplus is Zn；Preparation method is: simple metal zinc is heated to 520 ± 5 DEG C by (1), is sequentially added into manganese metal, argent, calcium metal and magnesium metal after dissolving, and stirring is to mix homogeneously；(2) it is cooled to 460 ± 5 DEG C, is pressed into hexachlorethane, be incubated standing 10 ~ 20min；(3) guarantor is cooled to 440 ± 5 DEG C of casting；(4) it is incubated 100 ~ 200min 300 DEG C ± 5, is warming up to 330 ~ 360 DEG C and is incubated 3 ~ 5 hours, then water-cooled is to room temperature；(5) being incubated 20 ~ 40min at 150 ~ 350 DEG C, then carry out high temperature deformation, air cooling is to room temperature；(6) carrying out repeatedly room temperature deformation intermediate annealing, last air cooling is to room temperature.The kirsite of the present invention can be used for preparing various degradable medical device to meet different Clinical practice requirements.
Description
Technical field
The invention belongs to field of material technology, particularly to a kind of medical bio degradable kirsite and preparation method thereof.
Background technology
Metal material becomes, due to its good mechanical property and processing characteristics, the embedded material that current clinical practice is wide, mainly includes simple metal (tantalum, niobium, zirconium etc.), rustless steel, titanium alloy, cobalt-base alloys, marmem, noble metal etc.；These materials all have good decay resistance, can stable for extended periods of time after implanting human body；But also bring some problems, such as, need second operation to take out；Alloying element is released to human body and brings the harmful effects such as potential hazard.
The problem caused in order to avoid above-mentioned embedded material, it is proposed that use the technology of degradable embedded material.The degradable embedded material of clinical practice at present mainly includes macromolecular material and biological active ceramic material, but this kind of degradation material yet suffers from obvious defect: Polymer Mechanical performance is too low, the sour environment that degraded produces can increase the probability that inflammation produces；Plasticity and the toughness of bioactive ceramics are the most poor, thus limit its range of application.Metal current base degradable embedded material not yet obtains clinical practice, the most underway to its R and D, and focuses primarily upon magnesium alloy and ferrous alloy.But there are some problems with ferrous alloy as degradable embedded material in magnesium alloy in terms of degradation rate, the problem of magnesium alloy maximum is that its degradation speed is too fast, affects its biocompatibility and mechanical property in use；And the problem of ferrous alloy maximum is that degradation speed is the slowest, a series of untoward reaction similar with bio-inert material can be caused.
The chemism of metallic zinc between magnesium and ferrum, so its corrosion rate be expected to can therebetween, such that it is able to prepare the material that degradation rate is suitable.In addition zinc is one of necessary trace element of human body, Zn content in adult body is 1.4 ~ 2.3g, the allowance,dietary of health adult's zinc every day is 15 ~ 40mg, and therefore zinc has certain advantage in the control of degradation rate as degradable embedded material in terms of biological safety.But the mechanical property of pure zinc is poor, intensity and plasticity all can not meet the requirement of embedded material.
Summary of the invention
It is an object of the invention to provide a kind of medical bio degradable kirsite and preparation method thereof, harmless metallic element is selected to carry out alloying, then to alloy by thermal deformation, cold deformation and heat treatment, it is thus achieved that high intensity, good plasticity, degradable kirsite medical degradable material.
The composition of the medical bio degradable kirsite of the present invention is by weight percentage containing Mg 0.005 ~ 1%, Ag 0.01 ~ 0.5%, Ca
0.01 ~ 0.5%, Mn 0.01 ~ 0.5%, inevitable impurity≤0.2%, surplus is Zn.
The tensile strength of above-mentioned medical bio degradable kirsite is 260 ~ 450MPa, and tensile yield strength is 195 ~ 380MPa, elongation percentage 5 ~ 30%.
The preparation method of the medical bio degradable kirsite of the present invention sequentially includes the following steps:
(1) press mentioned component and prepare metallic zinc, magnesium metal, argent, calcium metal and manganese metal as raw material；Simple metal zinc being heated to 520 ± 5 DEG C, is sequentially added into manganese metal, argent, calcium metal and magnesium metal after metallic zinc is dissolved, after whole metal moltens, stirring is to mix homogeneously, it is thus achieved that alloy melt；
(2) alloy melt being cooled to 460 ± 5 DEG C, utilize graphite bell jar to be pressed into hexachlorethane in alloy melt, the hexachlorethane of press-in is the 0.2 ~ 0.3% of alloy melt gross weight, is then incubated standing 10 ~ 20min at 460 ± 5 DEG C；
(3) alloy melt is cooled to after insulation standing terminates 440 ± 5 DEG C cast to mould, die through water cooling in casting cycle, it is thus achieved that ingot casting；
(4) ingot casting carries out Homogenization Treatments, and Homogenization Treatments is to be incubated 100 ~ 200min 300 DEG C ± 5；Then heat to 330 ~ 360 DEG C and be incubated 3 ~ 5 hours, then water-cooled is to room temperature, it is thus achieved that ingot blank；
(5) ingot blank is incubated 20 ~ 40min at 150 ~ 350 DEG C, then carries out high temperature plastic deformation at 150 ~ 350 DEG C, then air cooling is to room temperature, it is thus achieved that heat-altered morphology alloy；Described high temperature plastic is deformed into extruding, rolls or forge, and when extruding, extrusion ratio is 16 ~ 150；When rolling or forge, total deformation is 50 ~ 80%；
(6) heat-altered morphology alloy carrying out repeatedly room temperature deformation-intermediate annealing, the deformation of each room temperature is divided into multi pass drawing or rolling, and the deflection of every time drawing or rolling is 8 ~ 20%, and the total deformation of each room temperature deformation is 60 ~ 80%；Carrying out an intermediate annealing after room temperature deformation, intermediate anneal temperature is 150 ~ 300 DEG C, and the time is 10 ~ 20min every time；When the total deformation of repeatedly room temperature deformation-intermediate annealing reaches 92 ~ 98%, the last time after intermediate annealing air cooling to room temperature, it is thus achieved that medical bio degradable kirsite.
In said method, the tensile strength of heat-altered morphology alloy is 220 ~ 400MPa, and tensile yield strength is 160 ~ 360MPa, elongation percentage 12 ~ 40%.
Above-mentioned medical bio degradable kirsite is sheet material, bar or wire rod.
Above-mentioned step 1 and 2 firing equipments used are resistance furnace.
The cylinder that ingot casting is a diameter of 40 ~ 60mm or the length of side that above-mentioned step 3 obtains are the square of 40 ~ 60mm.
Above-mentioned medical bio degradable kirsite uses weight-loss method, and recording its corrosion rate in 37 DEG C of SBF solution is 0.2 ~ 0.8mm/year.
It is an advantage of the current invention that:
1, in medical bio degradable kirsite, zinc, magnesium, calcium, manganese are the element that human body itself contains, and the silver of trace is harmless to human body, and silver ion can be discharged in its degradation process, play the effect of sterilization, can avoid causing infection after device is implanted, thus alleviate misery and the trouble of patient；
2, medical bio degradable kirsite can be by extruding, roll, forge or the mode such as drawing being processed, it is thus achieved that rod, line, plate and section bar；Its mechanical property can be made significantly to be changed by the small adjustment of alloying element content, yield strength can be reached > 200MPa, elongation percentage > 15% performance requirement, and its degradation rate can be controlled and reach about 0.5mm/year；
3, the rod of medical bio degradable kirsite, line, plate and profile size excursion wider (Φ 0.05 ~ 12mm or t0.1 ~ 20mm), may be used for the preparation of different implant devices, such as nail, hone lamella, angiocarpy bracket, bone tissue engineering scaffold, stitching thread and make composite device etc. with other materials, can be used for preparing various degradable device to meet different Clinical practice requirements.
Accompanying drawing explanation
Fig. 1 is the general toxicity result of the test of the medical bio degradable kirsite of preparation in the embodiment of the present invention 1；Wherein (a) cardiac muscular tissue；(b) liver organization；(c) renal tissue；
Fig. 2 is to extrude the kirsite obtained in the embodiment of the present invention 1 to implant X-ray image after new zealand white rabbit, after wherein (a) implants one week；B () implants one month after；C () implants three months after；
Fig. 3 is the metallographic structure photo figure of heat-altered morphology alloy in the embodiment of the present invention 1；
Fig. 4 is heat-altered morphology Alloy At Room Temperature tensile property curve chart in the embodiment of the present invention 1；
Fig. 5 is macro morphology figure after medical bio degradable kirsite and the pure magnesium of the embodiment of the present invention 1 soaks 8 days in 37 DEG C of SBF solution, wherein (a) medical biodegradable kirsite in being the embodiment of the present invention 1, and (b) is pure magnesium；
Fig. 6 be medical bio degradable kirsite and the pure magnesium of the embodiment of the present invention 1 in 37 DEG C of SBF solution under soaking conditions, corrosion rate is with soak time change curve；In figure, ◆ for pure magnesium, for medical bio degradable kirsite；
Fig. 7 is the alloy microstructure photo figure in the embodiment of the present invention 1 after room temperature deformation；
Fig. 8 is the Alloy At Room Temperature tensile property curve chart in the embodiment of the present invention 1 after room temperature deformation.
Detailed description of the invention
The purity of the metallic zinc used in the embodiment of the present invention is 99.995%, and magnesium metal purity is 99.99%, and argent purity is 99.99%, and calcium metal purity is 99.95%, and manganese metal purity is 99.995%.
In the embodiment of the present invention, the method for testing of general toxicity test is according to GB/T 16886.11-1997 BiologicalEvaluationofMedicalDevice the 11st part: general toxicity test standard.
The embodiment of the present invention is observed the GX71 inversion type system gold phase microscope that equipment is the production of OLYMPUS company that metallographic structure uses.
In the embodiment of the present invention, tension test accepted standard is GB GB/T 228-2002 " metal material room temperature stretching test method ", and equipment is produced AG-X100kN electronic universal material testing machine by being made Co., Ltd. by Shimadzu
In the embodiment of the present invention, test performance accepted standard is standard GB/T/T16545-1996 " removing of corrosion product on the corrosive attack sample of metal and alloy ", and the preparation of SBF solution is according to ISO/FDIS23317:Implants for surgery In
Vitro evaluation for apatite-forming ability of implant materials is carried out.
Ingot casting in the embodiment of the present invention is the square of the cylinder of a diameter of 40 ~ 60mm or the length of side 40 ~ 60mm.
Embodiment 1
Composition is by weight percentage containing Mg 0.05%, Ag
0.5%, Ca 0.1%, Mn
0.1%, inevitable impurity≤0.2%, surplus is Zn；
Metallic zinc, magnesium metal, argent, calcium metal and manganese metal are as raw material；Simple metal zinc being heated to 520 ± 5 DEG C, is sequentially added into manganese metal, argent, calcium metal and magnesium metal after metallic zinc is dissolved, after whole metal moltens, stirring is to mix homogeneously, it is thus achieved that alloy melt；
Alloy melt being cooled to 460 ± 5 DEG C, utilizes graphite bell jar to be pressed into hexachlorethane in alloy melt, the hexachlorethane of press-in is the 0.2% of alloy melt gross weight, then stands 20min 460 ± 5 DEG C of insulations；
Alloy melt is cooled to 440 ± 5 DEG C after terminating and casts to mould by insulation standing, die through water cooling in casting cycle, it is thus achieved that ingot casting；
Ingot casting is incubated 100min 300 DEG C ± 5, then heats to 360 DEG C and is incubated 3 hours, then water-cooled is to room temperature, it is thus achieved that ingot blank；
Ingot blank is incubated 40min at 200 DEG C, then high temperature plastic deformation is carried out at 200 DEG C, air cooling is to room temperature again, obtain heat-altered morphology alloy, tensile strength is 220MPa, and tensile yield strength is 160MPa, elongation percentage 17%, the metallographic structure photo of heat-altered morphology alloy as it is shown on figure 3, room temperature tensile properties curve as shown in Figure 4；
Described high temperature plastic is deformed into extruding, and extrusion ratio is 16；
Heat-altered morphology alloy carries out repeatedly room temperature deformation-intermediate annealing, and the deformation of each room temperature is divided into multi pass drawing, and the deflection of every time drawing is 8 ~ 20%, and the total deformation of each room temperature deformation is 60 ~ 80%；Carrying out an intermediate annealing after room temperature deformation, intermediate anneal temperature is 300 DEG C, and the time is 10min every time；When the total deformation of repeatedly room temperature deformation-intermediate annealing reaches 92%, the last time after intermediate annealing air cooling to room temperature, it is thus achieved that medical bio degradable kirsite, tensile strength is 260MPa, and tensile yield strength is 195MPa, elongation percentage 14%；Use weight-loss method, recording its corrosion rate in 37 DEG C of SBF solution is 0.2mm/year, corrosion rate with soak time change curve as shown in Figure 6, room temperature deformation after alloy microstructure photo as it is shown in fig. 7, room temperature tensile properties curve as shown in Figure 8.
Embodiment 2
Composition is by weight percentage containing Mg 1%, Ag
0.01%, Ca 0.5%, Mn
0.01%, inevitable impurity≤0.2%, surplus is Zn；
Metallic zinc, magnesium metal, argent, calcium metal and manganese metal are as raw material；Simple metal zinc being heated to 520 ± 5 DEG C, is sequentially added into manganese metal, argent, calcium metal and magnesium metal after metallic zinc is dissolved, after whole metal moltens, stirring is to mix homogeneously, it is thus achieved that alloy melt；
Alloy melt being cooled to 460 ± 5 DEG C, utilizes graphite bell jar to be pressed into hexachlorethane in alloy melt, the hexachlorethane of press-in is the 0.25% of alloy melt gross weight, then stands 10min 460 ± 5 DEG C of insulations；
Alloy melt is cooled to 440 ± 5 DEG C after terminating and casts to mould by insulation standing, die through water cooling in casting cycle, it is thus achieved that ingot casting；
Ingot casting is incubated 150min 300 DEG C ± 5, then heats to 330 DEG C and is incubated 5 hours, then water-cooled is to room temperature, it is thus achieved that ingot blank；
At 250 DEG C, ingot blank being incubated 30min, then carries out high temperature plastic deformation at 250 DEG C, then air cooling is to room temperature, it is thus achieved that heat-altered morphology alloy, tensile strength is 400MPa, and tensile yield strength is 60340MPa, elongation percentage 12%；
Described high temperature plastic is deformed into extruding, and extrusion ratio is 150；
Heat-altered morphology alloy carries out repeatedly room temperature deformation-intermediate annealing, and the deformation of each room temperature is divided into multi-pass rolling, and the deflection of every time rolling is 8 ~ 20%, and the total deformation of each room temperature deformation is 60 ~ 80%；Carrying out an intermediate annealing after room temperature deformation, intermediate anneal temperature is 150 DEG C, and the time is 20min every time；When the total deformation of repeatedly room temperature deformation-intermediate annealing reaches 94%, the last time after intermediate annealing air cooling to room temperature, it is thus achieved that medical bio degradable kirsite, tensile strength is 450MPa, and tensile yield strength is 380MPa, elongation percentage 5%；Using weight-loss method, recording its corrosion rate in 37 DEG C of SBF solution is 0.6mm/year.
Embodiment 3
Composition is by weight percentage containing Mg 0.005%, Ag
0.1%, Ca 0.15%, Mn
0.15%, inevitable impurity≤0.2%, surplus is Zn；
Metallic zinc, magnesium metal, argent, calcium metal and manganese metal are as raw material；Simple metal zinc being heated to 520 ± 5 DEG C, is sequentially added into manganese metal, argent, calcium metal and magnesium metal after metallic zinc is dissolved, after whole metal moltens, stirring is to mix homogeneously, it is thus achieved that alloy melt；
Alloy melt being cooled to 460 ± 5 DEG C, utilizes graphite bell jar to be pressed into hexachlorethane in alloy melt, the hexachlorethane of press-in is the 0.3% of alloy melt gross weight, then stands 20min 460 ± 5 DEG C of insulations；
Alloy melt is cooled to 440 ± 5 DEG C after terminating and casts to mould by insulation standing, die through water cooling in casting cycle, it is thus achieved that ingot casting；
Ingot casting is incubated 200min 300 DEG C ± 5, then heats to 340 DEG C and is incubated 3 hours, then water-cooled is to room temperature, it is thus achieved that ingot blank；
At 350 DEG C, ingot blank being incubated 20min, then carries out high temperature plastic deformation at 350 DEG C, then air cooling is to room temperature, it is thus achieved that heat-altered morphology alloy, tensile strength is 270MPa, and tensile yield strength is 200MPa, elongation percentage 40%；
Described high temperature plastic is deformed into extruding, and extrusion ratio is 80；
Heat-altered morphology alloy carries out repeatedly room temperature deformation-intermediate annealing, and the deformation of each room temperature is divided into multi pass drawing, and the deflection of every time drawing is 8 ~ 20%, and the total deformation of each room temperature deformation is 60 ~ 80%；Carrying out an intermediate annealing after room temperature deformation, intermediate anneal temperature is 150 ~ 300 DEG C, and the time is 10 ~ 20min every time；When the total deformation of repeatedly room temperature deformation-intermediate annealing reaches 95%, the last time after intermediate annealing air cooling to room temperature, it is thus achieved that medical bio degradable kirsite, tensile strength is 320MPa, and tensile yield strength is 240MPa, elongation percentage 30%；Using weight-loss method, recording its corrosion rate in 37 DEG C of SBF solution is 0.5mm/year.
Embodiment 4
Composition is by weight percentage containing Mg 0.16%, Ag
0.43%, Ca 0.01%, Mn
0.05%, inevitable impurity≤0.2%, surplus is Zn；
Metallic zinc, magnesium metal, argent, calcium metal and manganese metal are as raw material；Simple metal zinc being heated to 520 ± 5 DEG C, is sequentially added into magnesium metal, argent, calcium metal and manganese metal after metallic zinc is dissolved, after whole metal moltens, stirring is to mix homogeneously, it is thus achieved that alloy melt；
Alloy melt being cooled to 460 ± 5 DEG C, utilizes graphite bell jar to be pressed into hexachlorethane in alloy melt, the hexachlorethane of press-in is the 0.2% of alloy melt gross weight, then stands 15min 460 ± 5 DEG C of insulations；
Alloy melt is cooled to 440 ± 5 DEG C after terminating and casts to mould by insulation standing, die through water cooling in casting cycle, it is thus achieved that ingot casting；
Ingot casting is incubated 100min 300 DEG C ± 5, then heats to 350 DEG C and is incubated 4 hours, then water-cooled is to room temperature, it is thus achieved that ingot blank；
At 150 DEG C, ingot blank being incubated 40min, then carries out high temperature plastic deformation at 150 DEG C, then air cooling is to room temperature, it is thus achieved that heat-altered morphology alloy, tensile strength is 220MPa, and tensile yield strength is 160MPa, elongation percentage 30%；
Described high temperature plastic is deformed into rolling, and total deformation is 80%；
Heat-altered morphology alloy carries out repeatedly room temperature deformation-intermediate annealing, and the deformation of each room temperature is divided into multi-pass rolling, and the deflection of every time rolling is 8 ~ 20%, and the total deformation of each room temperature deformation is 60 ~ 80%；Carrying out an intermediate annealing after room temperature deformation, intermediate anneal temperature is 150 ~ 300 DEG C, and the time is 10 ~ 20min every time；When the total deformation of repeatedly room temperature deformation-intermediate annealing reaches 98%, the last time after intermediate annealing air cooling to room temperature, it is thus achieved that medical bio degradable kirsite, tensile strength is 270MPa, and tensile yield strength is 220MPa, elongation percentage 22%；Using weight-loss method, recording its corrosion rate in 37 DEG C of SBF solution is 0.8mm/year.
Embodiment 5
Composition is by weight percentage containing Mg 0.47%, Ag
0.2%, Ca 0.38%, Mn
0.5%, inevitable impurity≤0.2%, surplus is Zn；
Metallic zinc, magnesium metal, argent, calcium metal and manganese metal are as raw material；Simple metal zinc being heated to 520 ± 5 DEG C, is sequentially added into magnesium metal, argent, calcium metal and manganese metal after metallic zinc is dissolved, after whole metal moltens, stirring is to mix homogeneously, it is thus achieved that alloy melt；
Alloy melt being cooled to 460 ± 5 DEG C, utilizes graphite bell jar to be pressed into hexachlorethane in alloy melt, the hexachlorethane of press-in is the 0.3% of alloy melt gross weight, then stands 10min 460 ± 5 DEG C of insulations；
Alloy melt is cooled to 440 ± 5 DEG C after terminating and casts to mould by insulation standing, die through water cooling in casting cycle, it is thus achieved that ingot casting；
Ingot casting is incubated 200min 300 DEG C ± 5, then heats to 330 DEG C and is incubated 5 hours, then water-cooled is to room temperature, it is thus achieved that ingot blank；
At 350 DEG C, ingot blank being incubated 20min, then carries out high temperature plastic deformation at 350 DEG C, then air cooling is to room temperature, it is thus achieved that heat-altered morphology alloy, tensile strength is 330MPa, and tensile yield strength is 270MPa, elongation percentage 36%；
Described high temperature plastic is deformed into forging, and total deformation is 50%；
Heat-altered morphology alloy carries out repeatedly room temperature deformation-intermediate annealing, and the deformation of each room temperature is divided into multi pass drawing, and the deflection of every time drawing is 8 ~ 20%, and the total deformation of each room temperature deformation is 60 ~ 80%；Carrying out an intermediate annealing after room temperature deformation, intermediate anneal temperature is 150 DEG C, and the time is 20min every time；When the total deformation of repeatedly room temperature deformation-intermediate annealing reaches 96%, the last time after intermediate annealing air cooling to room temperature, it is thus achieved that medical bio degradable kirsite, tensile strength is 380MPa, and tensile yield strength is 300MPa, elongation percentage 26%；Using weight-loss method, recording its corrosion rate in 37 DEG C of SBF solution is 0.35mm/year.
Claims (3)
1. the preparation method of a medical bio degradable kirsite, it is characterised in that sequentially include the following steps:
(1) metallic zinc, magnesium metal, argent, calcium metal and manganese metal are prepared as raw material；Simple metal zinc being heated to 520 ± 5 DEG C, is sequentially added into manganese metal, argent, calcium metal and magnesium metal after metallic zinc is dissolved, after whole metal moltens, stirring is to mix homogeneously, it is thus achieved that alloy melt；
(2) alloy melt being cooled to 460 ± 5 DEG C, utilize graphite bell jar to be pressed into hexachlorethane in alloy melt, the hexachlorethane of press-in is the 0.2 ~ 0.3% of alloy melt gross weight, is then incubated standing 10 ~ 20min at 460 ± 5 DEG C；
(3) alloy melt is cooled to after insulation standing terminates 440 ± 5 DEG C cast to mould, die through water cooling in casting cycle, it is thus achieved that ingot casting；
(4) ingot casting carries out Homogenization Treatments, and Homogenization Treatments is to be incubated 100 ~ 200min 300 DEG C ± 5；Then heat to 330 ~ 360 DEG C and be incubated 3 ~ 5 hours, then water-cooled is to room temperature, it is thus achieved that ingot blank；
(5) ingot blank is incubated 20 ~ 40min at 150 ~ 350 DEG C, then carries out high temperature plastic deformation at 150 ~ 350 DEG C, then air cooling is to room temperature, it is thus achieved that heat-altered morphology alloy；Described high temperature plastic is deformed into extruding, rolls or forge, and when extruding, extrusion ratio is 16 ~ 150；When rolling or forge, total deformation is 50 ~ 80%；
(6) heat-altered morphology alloy carrying out repeatedly room temperature deformation-intermediate annealing, the deformation of each room temperature is divided into multi pass drawing or rolling, and the deflection of every time drawing or rolling is 8 ~ 20%, and the total deformation of each room temperature deformation is 60 ~ 80%；Carrying out an intermediate annealing after room temperature deformation, intermediate anneal temperature is 150 ~ 300 DEG C, and the time is 10 ~ 20min every time；When the total deformation of repeatedly room temperature deformation-intermediate annealing reaches 92 ~ 98%, the last time after intermediate annealing air cooling to room temperature, obtain medical bio degradable kirsite, its composition is by weight percentage containing Mg 0.005 ~ 1%, Ag 0.01 ~ 0.5%, Ca 0.01 ~ 0.5%, Mn 0.01 ~ 0.5%, inevitable impurity≤0.2%, surplus is Zn.
The preparation method of medical bio degradable kirsite the most according to claim 1, it is characterised in that the tensile strength of described heat-altered morphology alloy is 220 ~ 400MPa, tensile yield strength is 160 ~ 360MPa, elongation percentage 12 ~ 40%.
The preparation method of medical bio degradable kirsite the most according to claim 1, it is characterised in that described medical bio degradable kirsite uses weight-loss method, and recording its corrosion rate in 37 DEG C of SBF solution is 0.2 ~ 0.8mm/year.
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| CN102586649B (en) * | 2012-04-01 | 2013-06-05 | 宁波博威合金材料股份有限公司 | Deformation zinc alloy, as well as manufacturing method and application thereof |
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