CN110306086A - A kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of novel multiple - Google Patents
A kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of novel multiple Download PDFInfo
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Abstract
The present invention relates to a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation methods of novel multiple, its biological medical magnesium alloy prepares the Mg-Zn-Ca-Sn new medical magnesium alloy materials containing graphene first, then its advanced composite material (ACM) is subjected to plastic deformation and prepares the medical implants such as bone plate, finally plating zinc-tin composite membrane prepares the corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel dual on its surface.Present invention employs hydrothermal chemical reaction method synthesizing graphite alkenes, to enhance the corrosion resistance of Mg-Zn-Ca-Sn biological medical magnesium alloy, the Mg-Zn-Ca-Sn biological medical magnesium alloy by graphene enhancing is plastically deformed again, further enhance its corrosion resistance, bone plate is subjected to plating zinc-tin composite membrane by the way of plated film, enhances its corrosion resistance again.For the present invention using Mg-Zn-Ca-Sn alloy as matrix, graphene is hardening constituent, and zinc-tin composite membrane is protective film, realizes the multiple corrosion resistance of Mg-Zn-Ca-Sn biological medical magnesium alloy.
Description
Technical field
The invention belongs to biologic medical surgical implant composite materials preparation technical field, related is a kind of novel more
The corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of weight.
Background technique
Magnesium metal is the second main group alkali earth metal, has the advantages that the small light weight of density.Magnesium resource is very rich,
The distribution mode of the earth's crust is more and mostly exists in a manner of compound.Magnesium energy industry, aerospace, automobile, ship,
The fields such as biologic medical are used widely, and cost is relatively low.
Biological medical magnesium alloy density and elasticity modulus and skeleton are the most close, it is possible to prevente effectively from stress shielding is imitated
It answers.Biological medical magnesium alloy has good biocompatibility, and it is necessary micro member in human body that wherein Mg content, which is only second to K,
Element, bone plate are degraded the Mg of release in human body2+Concentration is very low, will not damage to human body, moreover, Mg, which has, promotes new bone
The effect of generating and healing.Biological medical magnesium alloy is without any side effects to human body as a kind of multifunctional material, and has
There are ideal biological growth-promoting functions.Biological medical magnesium alloy palliates the agonizing sufferings for patient and financial burden, is a kind of good medical treatment
Material.Traditional bio-medical material has non-biodegradable, acts on the resistance that needs to take medicine in human body, causes two to human body
Secondary injury, therefore biological medical magnesium alloy is paid attention to by numerous researchers in recent years, progresses into the visual field of people.
Graphene as bio-medical material biological support, oncotherapy, medicament transport, in terms of apply
Extensively, graphene is combined with biological medical magnesium alloy material, not only enhances its mechanical property and corrosion resistance, but also improve
It the shortcomings that graphene hydrophobicity, poor biocompatibility, it is more advantageous to the adherency and increment of cell, greatly improves graphene material
The biocompatibility of material.
Zinc and tin are also nutrient needed by human.Zinc is primarily present in human muscle and bone, is had good
The liberation of hydrogen rate of biological medical magnesium alloy in human body can be effectively reduced in compatibility, yield strength and corrosion resistance, closes in magnesium
Have the function of strengthening crystal grain in gold.Tin has facilitation to the synthesis of human body internal protein and nucleic acid, in growth and development extremely
It closes important.Tin can form oxidation film, have good corrosion resistance, and enhance Biological magnesium alloy corrosion resistance.In biologic medical magnesium
Alloy material surface layer plating zinc-tin composite membrane further enhances the corrosion resistance of material, and it is intracorporal in people that material product is effectively reduced
Degradation rate.
Summary of the invention
It is an object of the invention to overcome the shortcomings of existing bio-medical material and to provide a kind of novel multiple corrosion resistant
Mg-Zn-Ca-Sn medical bio magnesium alloy preparation method, this method prepares graphene using hydrothermal chemical reaction method, with Mg-Zn-
Ca-Sn medical bio magnesium alloy is matrix, and fusing into graphene and forming graphene hardening constituent enhances the mechanical property of the alloy and resistance to
Corrosive power；The magnesium alloy progress hot extrusion deformation of preparation, which is further refined crystal grain, enhances its corrosion resistance；After cold deformation
Lath-shaped magnesium alloy materials be finish-machined to medical bone plate according to national medical equipment standard, and by the way of plated film will
Bone plate plates zinc-tin composite membrane, plays better antisepsis.Realize the dual corrosion-resistant energy of Mg-Zn-Ca-Sn biological medical magnesium alloy
Power.
A kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of novel multiple, comprising the following steps:
(1) 10ml deionized water dissolving, benefit is added in 50ml reaction kettle polytetrafluoroethylliner liner in the glucose for weighing 1.5g
It is stirred evenly with glass bar；
(2) it is slowly injected into the 10ml concentrated sulfuric acid, while persistently being stirred evenly using glass bar, and the color of solution is from initial
It is colourless to become yellow, eventually become black；
(3) liner is placed in metal reaction kettle autoclave body, lid is close tight, is put into drying box；
(4) reaction time 180min and 200 DEG C of reaction temperature are set, carries out hydrothermal chemical reaction and synthesizes blue-fluorescence graphite
Alkene quantum dot；
(5) by the grapheme material of preparation and magnesium calcium intermediate alloy, pure magnesium, pure tin, pure Zinc smelting, graphene enhancing is obtained
Medical bio magnesium alloy；
(6) the Mg-Zn-Ca-Sn medical bio magnesium alloy for enhancing the graphene of as cast condition carries out hot-pressed, is squeezed into
Lath-shaped；
(7) by lath-shaped Mg-Zn-Ca-Sn medical bio magnesium alloy by the way of machining according to the medical device of country
Tool standard is fabricated to bone plate；
(8) bone plate after processing is beaten on 320 mesh, 800 mesh, 1200 mesh, 2000 mesh, 2500 mesh sand paper after alkali cleaning oil removing
Mill, polishes on polishing cloth, and bone plate is put into the beaker of dress dehydrated alcohol after polishing, dries after supersonic wave cleaning machine cleans；
(9) bone plate is immersed in galvanizing flux and tin plating electrolyte by the way of plated film, plates zinc-tin composite membrane in its outer layer.
A kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of novel multiple is specific according to step (5)
Scheme is as follows:
(1) ready raw material, refining agent, mold and experimental tool are put into baking box before melting and are preheated, preheated
Temperature is 180 DEG C, time 2h；
(2) setting resistance furnace temperature is 350 DEG C, and crucible is put into furnace, and pure magnesium is added after crucible is raised to 350 DEG C,
Logical protective gas, temperature rises to 720 DEG C later；
(3) it is put into melt, keeps the temperature together with pure tin, pure zinc after being completely melt graphene with magnesium such as tinfoil jackets
Electromagnetic agitation 2min after 20min, then keep the temperature 45min；
(4) magnesium calcium intermediate alloy is added, temperature rises to 750 DEG C or so heat preservation 10min, stirs 2min later, then keep the temperature
30min；
(5) refining agent is added after keeping the temperature and stands 5 minutes and is refined, then scrapes slag, then stand 10min；
(6) it stands and temperature is set as 700 DEG C after finishing, exclude dross when melt temperature reaches 700 DEG C and be poured into
In pre-heated mold.
Further, the as cast condition Mg-Zn-Ca-Sn biological medical magnesium alloy that graphene enhances is processed into directly in step (6)
Diameter is the cylindrical bar of 40mm × 30mm, is then hot extruded into the lath-shaped material for being 30mm with a thickness of 5mm wide, hot extrusion temperature
Degree is 350 DEG C.
Further, bone plate superficial oxidation layer cleans up before plated film in the step (9).
Further, the corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of a kind of novel multiple, the step
Suddenly the concrete scheme of (9) is as follows:
(1) the salting liquid pH value of modulation leaching zinc is 10, and the salting liquid pH value of wicking is 6.3, and two kinds of solution temperatures are 90
℃；
(2) by the way of plated film by ready bone plate immerse tin salting liquid in 2min, spent after taking-up from
Sub- water cleaning, then immerse 5min in the salting liquid of zinc, is as above a circulation, repeats above operation 5 times, at this time the plated film of bone plate
The number of plies is 10 layers.
Further, the biological medical magnesium alloy material prepare soda-wash solution ingredient used in bone plate be NaOH and
Na3PO4Mixed solution, the alkali cleaning time be 20min, temperature be 50 DEG C.
Further, the corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of a kind of novel dual,
Magnesium in step (5), zinc, tin purity >=99.95%.
Further, the dosage of refining agent is the 3% of total alloy in the step (5).
Further, magnesium alloy pouring front mold is preheating to 220 DEG C in the step (5), and mold temperature is 200 when casting
DEG C or so.
Further, crucible used in magnesium alloy smelting is graphite crucible in the step (5).
Principle and advantage
The present invention prepares graphene using hydrothermal chemical reaction method, prepares graphene simple process, and environmentally protective,
It is low for equipment requirements.And physical method prepares graphene and many equipment is needed to support, it is at high cost.
The present invention is attempted for the first time by graphene in conjunction with Mg-Zn-Ca-Sn biological medical magnesium alloy, prepares novel graphite
The Mg-Zn-Ca-Sn biological medical magnesium alloy that alkene is strengthened combines.Graphene is applied to biological support, medicine as bio-medical material
Object transport etc., but graphene has hydrophobicity, poor biocompatibility, and graphene and Mg-Zn-Ca-Sn biologic medical magnesium close
Golden material combines, and forms hardening constituent in the magnesium alloy, not only enhances its mechanical property and corrosion resistance, is more advantageous to cell
Adherency and increment, also greatly improve the biocompatibility of grapheme material.
The Mg-Zn-Ca-Sn biological medical magnesium alloy material that the present invention enhances graphene is through Overheating Treatment and hot extrusion
Bone plate is obtained through machining after deformation, tensile strength and corrosion resistance significantly improve.
The present invention is immersed bone plate in the salting liquid of zinc and the salting liquid of tin by the way of plated film respectively, make its
Article topsheet plates zinc-tin composite membrane, according to the corrosion rate for requiring the number of plies for changing film to can control bone plate.Zinc-tin composite membrane surface layer
Oxide layer is formed, the corrosion rate of bone plate is reduced.
In conclusion by graphene using heat treatment, hot extrusion and change in conjunction with Mg-Zn-Ca-Sn biological medical magnesium alloy
The deficiencies of learning the new material for preparing of plated film mode, to solve conventional medical Corrosion Behaviors of Magnesium Alloys rate fast, poor mechanical property.
Detailed description of the invention
Fig. 1 is the corrosion-resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method flow chart of novel multiple of the present invention.
Fig. 2 is the hot-pressed mold pictorial diagram used of the present invention.
Fig. 3 is the lath-shaped Mg-Zn-Ca-Sn biological medical magnesium alloy pictorial diagram after extrusion molding of the present invention.
Specific embodiment
Below according to specific embodiment, the present invention will be further described, but not limitation and this, novel multiple corrosion resistant
It is medical surgical implantation material that the Mg-Zn-Ca-Sn biological medical magnesium alloy of erosion, which prepares finished product, is now only done by taking bone plate as an example with explanation.
Embodiment 1:
A kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation of novel multiple, comprising the following steps:
(1) glucose for weighing 1.5g is added 10ml deionized water dissolving in 50ml reaction kettle polytetrafluoroethylliner liner, uses
Glass bar stirs evenly；
(2) it is slowly injected into the 10ml concentrated sulfuric acid, while being stirred evenly with glass bar, and the color of solution is from initial no discoloration
For yellow, black is eventually become；
(3) liner is placed in metal reaction kettle autoclave body, lid is close tight, is put into drying box；
(4) reaction time 180min and 200 DEG C of reaction temperature are set, carries out hydrothermal chemical reaction and synthesizes blue-fluorescence graphite
Alkene quantum dot；
(5) by the grapheme material of preparation and magnesium calcium intermediate alloy, pure magnesium, pure tin, pure Zinc smelting, graphene enhancing is obtained
Medical bio magnesium alloy, specific steps are as follows: be put into ready raw material, refining agent, mold and experimental tool before melting
It is preheated in baking box, preheating temperature is 180 DEG C, time 2h；It is 350 DEG C that resistance furnace temperature, which is arranged, and crucible is put into furnace,
Pure magnesium is added after crucible is raised to 350 DEG C, leads to protective gas, temperature rises to 720 DEG C later；By the graphene magnesium such as tinfoil jacket
It is put into melt together with pure tin, pure zinc after being completely melt, keeps the temperature electromagnetic agitation 2min after 20min, then keep the temperature 45min；It is added
Magnesium calcium intermediate alloy, temperature rise to 750 DEG C or so heat preservation 10min, stir 2min later, then keep the temperature 30min；Essence is added after heat preservation
It refines agent and stands 5 minutes and refined, then scrape slag, then stand 10min；Temperature is set as 700 DEG C after finishing by standing, when
Melt temperature excludes dross and is poured into pre-heated mold when reaching 700 DEG C.
(6) the as cast condition Mg-Zn-Ca-Sn biological medical magnesium alloy that graphene enhances is processed into diameter is 40mm × 30mm
Cylindrical bar, be then hot extruded into a thickness of 5mm wide be 30mm lath-shaped material, extrusion temperature be 350 DEG C.
(7) by lath-shaped Mg-Zn-Ca-Sn medical bio magnesium alloy by the way of machining according to the medical device of country
Tool standard is fabricated to bone plate；
(8) bone plate after processing is in NaOH and Na3PO4Mixed solution in alkali cleaning, the alkali cleaning time be 20min, temperature 50
℃.It polishes on 320 mesh, 800 mesh, 1200 mesh, 2000 mesh, 2500 mesh sand paper after alkali cleaning oil removing, is polished on polishing cloth, thrown
Bone plate is put into the beaker of dress dehydrated alcohol after light, is dried after supersonic wave cleaning machine cleans；
(9) the salting liquid pH value of modulation leaching zinc is 10, and the salting liquid pH value of wicking is 6.3, and two kinds of solution temperatures are 90
℃；Ready bone plate is immersed into 2min in the salting liquid of tin, is cleaned after taking-up with deionized water, then immerse in the salting liquid of zinc
5min is as above a circulation, repeats above operation 5 times, the coating layers of bone plate are 10 layers at this time.
It finds to form the zinc-tin composite membrane of even compact on bone plate surface layer after tested, film layer completely covers Biological magnesium alloy
Matrix, corrosion potential are -1.063V, corrosion electric current density 2.1162x10-6A/cm2, tensile strength 289MPa.
Embodiment 2:
A kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation of novel multiple, comprising the following steps:
(1) 10ml deionized water dissolving, benefit is added in 50ml reaction kettle polytetrafluoroethylliner liner in the glucose for weighing 1.5g
It is stirred evenly with glass bar；
(2) it is slowly injected into the 10ml concentrated sulfuric acid, while being stirred evenly using glass bar, and the color of solution is from initial nothing
Discoloration is yellow, eventually becomes black；
(3) liner is placed in metal reaction kettle autoclave body, lid is close tight, is put into drying box；
(4) reaction time 180min and 200 DEG C of reaction temperature are set, carries out hydrothermal chemical reaction and synthesizes blue-fluorescence graphite
Alkene quantum dot；
(5) by the grapheme material of preparation and magnesium calcium intermediate alloy, pure magnesium, pure tin, pure Zinc smelting, graphene enhancing is obtained
Medical bio magnesium alloy, specific steps are as follows: be put into ready raw material, refining agent, mold and experimental tool before melting
It is preheated in baking box, preheating temperature is 180 DEG C, time 2h；It is 350 DEG C that resistance furnace temperature, which is arranged, and crucible is put into furnace,
Pure magnesium is added after crucible is raised to 350 DEG C, leads to protective gas, temperature rises to 720 DEG C later；Graphene is complete with tinfoil jacket etc.
It is put into melt together with pure tin, pure zinc after running down, keeps the temperature electromagnetic agitation 2min after 20min, then keep the temperature 45min；Magnesium is added
Calcium intermediate alloy, temperature rise to 750 DEG C or so heat preservation 10min, stir 2min later, then keep the temperature 30min；Refining is added after heat preservation
Agent and standing is refined for 5 minutes, then scrapes slag, then stand 10min；Temperature is set as 700 DEG C after finishing by standing, when molten
Temperature excludes dross and is poured into pre-heated mold when reaching 700 DEG C.
(6) the as cast condition Mg-Zn-Ca-Sn biological medical magnesium alloy that graphene enhances is processed into diameter is 40mm × 30mm
Cylindrical bar, be then hot extruded into a thickness of 5mm wide be 30mm lath-shaped material, extrusion temperature be 350 DEG C.
(7) by lath-shaped Mg-Zn-Ca-Sn medical bio magnesium alloy by the way of machining according to the medical device of country
Tool standard is fabricated to bone plate；
(8) bone plate after processing is in NaOH and Na3PO4Mixed solution in alkali cleaning, the alkali cleaning time be 20min, temperature 50
℃.It polishes on 320 mesh, 800 mesh, 1200 mesh, 2000 mesh, 2500 mesh sand paper after alkali cleaning oil removing, is polished on polishing cloth, thrown
Bone plate is put into the beaker of dress dehydrated alcohol after light, is dried after supersonic wave cleaning machine cleans；
(9) the salting liquid pH value of modulation leaching zinc is 10, and the salting liquid pH value of wicking is 6.3, and two kinds of solution temperatures are 90
℃；Ready bone plate is immersed into 2min in the salting liquid of tin, is cleaned after taking-up with deionized water, then immerse in the salting liquid of zinc
5min is as above a circulation, repeats above operation 5 times, the coating layers of bone plate are 10 layers at this time.
It finds to find to form the zinc-tin composite membrane of even compact on bone plate surface layer after tested after tested, film layer completely covers
Biological magnesium alloy matrix, corrosion potential are -1.003V, corrosion electric current density 2.2034x10-6A/cm2, tensile strength is
296MPa。
Embodiment 3
A kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation of novel multiple, comprising the following steps:
(1) 10ml deionized water dissolving, benefit is added in 50ml reaction kettle polytetrafluoroethylliner liner in the glucose for weighing 1.5g
It is stirred evenly with glass bar；
(2) it is slowly injected into the 10ml concentrated sulfuric acid, while being stirred evenly using glass bar, and the color of solution is from initial colourless
Become yellow, eventually becomes black；
(3) liner is placed in metal reaction kettle autoclave body, lid is close tight, is put into drying box；
(4) reaction time 180min and 200 DEG C of reaction temperature are set, carries out hydrothermal chemical reaction and synthesizes blue-fluorescence graphite
Alkene quantum dot；
(5) by the grapheme material of preparation and magnesium calcium intermediate alloy, pure magnesium, pure tin, pure Zinc smelting, graphene enhancing is obtained
Medical bio magnesium alloy, specific steps are as follows: be put into ready raw material, refining agent, mold and experimental tool before melting
It is preheated in baking box, preheating temperature is 180 DEG C, time 2h；It is 350 DEG C that resistance furnace temperature, which is arranged, and crucible is put into furnace,
Pure magnesium is added after crucible is raised to 350 DEG C, leads to protective gas, temperature rises to 720 DEG C later；Graphene is encased etc. with tinfoil complete
It is put into melt together with pure tin, pure zinc after running down, keeps the temperature electromagnetic agitation 2min after 20min, then keep the temperature 45min；Magnesium is added
Calcium intermediate alloy, temperature rise to 750 DEG C or so heat preservation 10min, stir 2min later, then keep the temperature 30min；Tool is put into baking box
Preheating, preheating temperature are 180 DEG C, time 2h；It is 350 DEG C that resistance furnace temperature, which is arranged, and crucible is put into furnace, when crucible liter
Pure magnesium is added after to 350 DEG C, leads to protective gas, temperature rises to 720 DEG C later；Graphene is completely melt with magnesium such as tinfoil jackets
It is put into melt together with pure tin, pure zinc afterwards, keeps the temperature electromagnetic agitation 2min after 20min, then keep the temperature 45min；It is added among magnesium calcium
Alloy, temperature rise to 750 DEG C or so heat preservation 10min, stir 2min later, then keep the temperature 30min；Refining agent and quiet is added after heat preservation
It sets 5 minutes and is refined, then scrape slag, then stand 10min；Temperature is set as 700 DEG C after finishing by standing, works as melt temperature
Dross is excluded when reaching 700 DEG C to be poured into pre-heated mold.
(6) the as cast condition Mg-Zn-Ca-Sn biological medical magnesium alloy that graphene enhances is processed into diameter is 40mm × 30mm
Cylinder, be then hot extruded into a thickness of 5mm wide be 30mm lath-shaped material, extrusion temperature be 350 DEG C.
(7) by lath-shaped Mg-Zn-Ca-Sn medical bio magnesium alloy by the way of machining according to the medical device of country
Tool standard is fabricated to bone plate；
(8) bone plate after processing is in NaOH and Na3PO4Mixed solution in alkali cleaning, the alkali cleaning time be 20min, temperature 50
℃.It polishes on 320 mesh, 800 mesh, 1200 mesh, 2000 mesh, 2500 mesh sand paper after alkali cleaning oil removing, is polished on polishing cloth, thrown
Bone plate is put into the beaker of dress dehydrated alcohol after light, is dried after supersonic wave cleaning machine cleans；
(9) the salting liquid pH value of modulation leaching zinc is 10, and the salting liquid pH value of wicking is 6.3, and two kinds of solution temperatures are 90
℃；Ready bone plate is immersed into 2min in the salting liquid of tin, is cleaned after taking-up with deionized water, then immerse in the salting liquid of zinc
5min is as above a circulation, repeats above operation 5 times, the coating layers of bone plate are 10 layers at this time.
It finds to find to find after tested after tested to form the zinc-tin composite membrane of even compact, film layer on bone plate surface layer after tested
Biological magnesium alloy matrix is completely covered, corrosion potential is -1.092V, corrosion electric current density 2.1813x10-6A/cm2, tension
Intensity is 283MPa.
The present invention attempted during technical research a variety of different schemes and embodiment 1, embodiment 2 and embodiment 3 into
Row comparison, than 3 kinds embodiments of performance are poor after tested for obtained finished material, and concrete scheme is as follows.
Comparative example 1
Unlike the first embodiment bone plate zinc, tin salting liquid in impregnate two periods, coating layers be 4 layers, through seeing
It examines on discovery Biological magnesium alloy matrix with the presence of scratch, magnesium matrix is not completely covered and is unevenly distributed for film layer, through what is measured
Current potential is -1.295, current density 16.3482x10-6A/cm2, tensile strength 276MPa.
Comparative example 2
As different from Example 2 bone plate zinc, tin salting liquid in impregnate 3 periods, coating layers be 6 layers, through seeing
It examines and can't see scratch on discovery Biological magnesium alloy matrix, film layer covers magnesium matrix substantially but is unevenly distributed, the electricity through measuring
Position is -1.167V, current density 14.2123x10-6A/cm2, tensile strength 283MPa.
Comparative example 3
As different from Example 2 bone plate zinc, tin salting liquid in impregnate 7 periods, coating layers be 14 layers, through seeing
It examines and is covered completely by composite membrane on discovery Biological magnesium alloy matrix, and is very thick and solid, have fine pore appearance in film layer, testing
There is obscission in the process, the current potential through measuring is -1.103V, current density 2.5031x10-6A/cm2, tensile strength is
294MPa。
Claims (11)
1. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of novel multiple, it is characterised in that: use water
Thermo chemical reaction prepares graphene, using Mg-Zn-Ca-Sn biological medical magnesium alloy as matrix, fuses into graphene and forms graphene
Hardening constituent enhances the mechanical property and corrosion resistance of the alloy；The magnesium alloy materials of preparation are thin through hot extrusion deformation crystal grain
Change, further enhances the material corrosion resistance；The Mg-Zn-Ca-Sn bio-medical of lath-shaped graphene enhancing after thermal deformation
Magnesium alloy materials are finish-machined to bone plate according to national medical equipment standard, and are answered bone plate plating zinc-tin by the way of plated film
Film is closed, better antisepsis is played, realizes the multiple corrosion resistance of Mg-Zn-Ca-Sn biological medical magnesium alloy.
2. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy preparation method of novel multiple described in claim 1, special
Sign is, comprising the following steps:
(1) glucose for weighing 1.5g is added 10ml deionized water dissolving in 50ml reaction kettle polytetrafluoroethylliner liner, utilizes glass
Glass stick stirs evenly；
(2) it is slowly injected into the 10ml concentrated sulfuric acid, is persistently stirred evenly using glass bar, and the color of solution colourless becomes from initial
Yellow eventually becomes black；
(3) liner is placed in metal reaction kettle autoclave body, lid is close tight, is put into drying box；
(4) reaction time 180min and 200 DEG C of reaction temperature are set, carries out hydrothermal chemical reaction and synthesizes blue-fluorescence graphene amount
Sub- point；
(5) by the grapheme material of preparation and magnesium calcium intermediate alloy, pure magnesium, pure tin, pure Zinc smelting, graphene enhancing is obtained
Mg-Zn-Ca-Sn medical bio magnesium alloy；
(6) the Mg-Zn-Ca-Sn medical bio magnesium alloy for enhancing the graphene of as cast condition carries out hot-pressed, is squeezed into lath
Shape；
(7) by lath-shaped Mg-Zn-Ca-Sn medical bio magnesium alloy using machining by the way of according to national medical equipment mark
Standard is fabricated to bone plate；
(8) bone plate after processing is polished on 320 mesh, 800 mesh, 1200 mesh, 2000 mesh, 2500 mesh sand paper after alkali cleaning oil removing,
It is polished on polishing cloth, bone plate is put into the beaker of dress dehydrated alcohol after polishing, is dried after supersonic wave cleaning machine cleans；
(9) bone plate is immersed in galvanizing flux and tin plating electrolyte by the way of plated film, plates zinc-tin composite membrane in its outer layer.
3. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 2 preparation side
Method, which is characterized in that the concrete scheme of the step (5) is as follows:
(1) ready raw material, refining agent, mold and experimental tool are put into baking box before melting and are preheated, preheating temperature
It is 180 DEG C, time 2h；
(2) setting resistance furnace temperature is 350 DEG C, and crucible is put into furnace, and pure magnesium is added after crucible is raised to 350 DEG C, is passed through
SF6 and CO2 hybrid protection gas, temperature rise to 720 DEG C；
(3) it by graphene tinfoil jacket, waits and is put into melt together with pure tin, pure zinc after being completely melt, keep the temperature electricity after 20min
Magnetic stirs 2min, then keeps the temperature 45min；
(4) magnesium calcium intermediate alloy is added, temperature rises to 750 DEG C or so heat preservation 10min, then stirs 2min, then keep the temperature 30 min；
(5) refining agent is added after keeping the temperature and stands 5 minutes and is refined, then scrapes slag, then stand 10min；
(6) it stands and resistance furnace temperature is set as 700 DEG C after finishing, dross casting is excluded when melt temperature reaches 700 DEG C
Into pre-heated mold.
4. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 2 preparation side
Method, which is characterized in that be processed into the as cast condition Mg-Zn-Ca-Sn biological medical magnesium alloy that graphene enhances in the step (6)
Diameter is the cylinder of 40mm × 30mm, is then hot extruded into the lath-shaped material for being 30mm with a thickness of 5mm wide, and extrusion temperature is
350℃。
5. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 2 preparation side
Method, which is characterized in that guarantee that bone plate surface layer is not oxidized in the step (9) before plated film.
6. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 2 preparation side
Method, which is characterized in that the concrete scheme of the step (9) is as follows:
(1) the salting liquid pH value of modulation leaching zinc is 10, and the salting liquid pH value of wicking is 6.3, and two kinds of solution temperatures are 90 DEG C；
(2) ready bone plate is immersed into 2min in the salting liquid of tin by the way of plated film, uses deionized water after taking-up
Cleaning, then immerse 5min in the salting liquid of zinc, is as above a circulation, repeats above operation 5 times, at this time the coating layers of bone plate
It is 10 layers.
7. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 2 preparation side
Method, it is characterised in that soda-wash solution ingredient used in bone plate is NaOH and Na3PO4Mixed solution, the alkali cleaning time be 20min, temperature
Degree is 50 DEG C.
8. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 3 preparation side
Method, it is characterised in that magnesium, zinc, tin purity >=99.95%.
9. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 3 preparation side
Method, it is characterised in that the dosage of refining agent is the 3% of total alloy.
10. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 3 preparation side
Method, it is characterised in that magnesium alloy pouring front mold is preheating to 220 DEG C, and mold temperature is at 200 DEG C or so when casting.
11. a kind of corrosion resistant Mg-Zn-Ca-Sn biological medical magnesium alloy of novel multiple according to claim 3 preparation side
Method, it is characterised in that crucible used in magnesium alloy smelting is graphite crucible.
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