CN106282710A - Corrosion-resistant biological medical magnesium alloy - Google Patents

Corrosion-resistant biological medical magnesium alloy Download PDF

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CN106282710A
CN106282710A CN201610845752.7A CN201610845752A CN106282710A CN 106282710 A CN106282710 A CN 106282710A CN 201610845752 A CN201610845752 A CN 201610845752A CN 106282710 A CN106282710 A CN 106282710A
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corrosion
magnesium
magnesium alloy
paraffin
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0094—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with organic materials as the main non-metallic constituent, e.g. resin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process

Abstract

The invention discloses a kind of corrosion-resistant biological medical magnesium alloy, corrosion-resistant biological medical magnesium alloy includes the raw material of following weight portion meter: 100 ~ 200 parts of magnesium, 120 ~ 150 parts of zinc, 80 ~ 100 parts of aluminum, molybdenum 60 ~ 90 parts, 100 ~ 200 parts of paraffin, polyacrylate 40 ~ 80 parts, polypropylene 20 ~ 70 parts, hydroxyapatite 10 ~ 40 parts.Preparation method: magnesium, zinc, aluminum, molybdenum, paraffin, polyacrylate, polypropylene, hydroxyapatite mix homogeneously, fusing；Put into model, cool down molding；Put into NaHCO3‑MgCO3Solution soaks 18 ~ 24h, heat treatment 10 ~ 12h.The present invention is by putting into NaHCO3‑MgCO3After solution carries out heat treatment, alloy surface can be made to generate MgO membrane, can well weaken corrosion rate, extend alloy service life.

Description

Corrosion-resistant biological medical magnesium alloy
Technical field
The present invention relates to biological medicine Material Field, particularly relate to a kind of corrosion-resistant biological medical magnesium alloy and preparation side thereof Method.
Background technology
Bio-medical material is called again biomaterial, be respectively from Biomedical Materials and The translated name of Biomaterials.The two topmost academic journals of book subject are Britain " Biomaterials " the most in the world With " the Journal of Biomedical Materials Research " of the U.S., the content involved by two periodicals is identical , it can be seen that Biomedical Materials and Biomaterials two word refers to identical material.Give now biology doctor Definition with material is clear and definite: the disease of biosystem diagnosed, treat, surgical repair, physiotherapy and rehabilitation, replacement organism group Knit or organ (artificial organ), promote or recover its function, and tissue will not be produced dysgenic material.Biological doctor Be not necessarily medicine with material itself, but by with living organism directly in conjunction with and interact and treat.
Magnesium alloy, as bio-medical material, has prominent at mechanical property, biocompatibility and degradability tripartite's mask Advantage.
At present, be widely used in hone lamella, the bio-medical material of nail is mainly titanium or titanium alloy, rustless steel and polylactic acid Deng.But, these materials all have some limitations.Titanium or titanium alloy, stainless steel and other metal materials can occur stress shielding Effect, will implant after human body by metal material, because its people's bone stress not mating generation with the elastic modelling quantity of people's bone material is hidden Gear effect, can make bone strength reduce, heal slow.And the macromolecular material poor mechanical property such as polylactic acid, it is difficult to bear bigger Heavy burden.Accordingly, it would be desirable to develop new bone immobilizing material, i.e. should there is the mechanical property being similar to people's bone, have good again Biocompatibility, and do not produce toxicity.Research show magnesium and magnesium alloy possible as new bone immobilizing material because magnesium and Magnesium alloy has high specific strength and specific stiffness, the specific strength of pure magnesium to be 133GPa/ (g/cm3), and the ratio of superhigh strength magnesium alloy Intensity has reached 480 GPa/ (g/cm3), the specific strength (260 GPa/ (g/cm than Ti6A14V3)) exceed nearly 1 times.Magnesium and magnesium close The Young's modulus of gold is about 45GPa, closer to the elastic modelling quantity (20GPa) of people's bone, can effectively reduce stress-shielding effect.Magnesium with The density of magnesium alloy is about 1.7g/cm3, with people bone density (1.75g/cm3) close, density (4.47g/ far below Ti6A14V cm3), meet the requirement of preferable blade plate.Thus with magnesium and magnesium alloy as bone immobilizing material, it is possible at the initial stage of union of fracture Stable mechanical environment is provided, gradually rather than suddenly reduces its stress force shelter reaction, make fracture site bear to incrementally increase and be To the stress stimulation of physiological level, thus healing acceleration, prevent local osteoporosis and refracture.Therefore, magnesium and magnesium alloy are made For the fixing material after bone injury, there is the performance being much better than other metal bio-medical materials.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that a kind of corrosion-resistant biological medical magnesium alloy and preparation method thereof, resistance to Corrosion biological medical magnesium alloy corrosion rate is little, and service life is long.
In order to solve above-mentioned technical problem, the present invention by the following technical solutions:
Corrosion-resistant biological medical magnesium alloy, including the raw material of following weight portion meter: magnesium 100～200 parts, zinc 120～150 parts, aluminum 80～100 parts, molybdenum 60～90 parts, paraffin 100～200 parts, polyacrylate 40～80 parts, polypropylene 20～70 parts, hydroxyl phosphorus Lime stone 10～40 parts.
As to further improvement of the present invention, corrosion-resistant biological medical magnesium alloy, including the raw material of following weight portion meter: 150 parts of magnesium, 130 parts of zinc, 90 parts of aluminum, molybdenum 70 parts, 150 parts of paraffin, polyacrylate 60 parts, polypropylene 50 parts, hydroxyapatite 20 parts.
As to further improvement of the present invention, paraffin is Tissuemat E, and molecular weight is 2000～4000.
As to further improvement of the present invention, the size of hydroxyapatite is 100～200 μm.
Present invention also offers the preparation method of a kind of corrosion-resistant biological medical magnesium alloy.
The preparation method of a kind of corrosion-resistant biological medical magnesium alloy, comprises the following steps: magnesium, zinc, aluminum, molybdenum, paraffin, poly-third Olefin(e) acid ester, polypropylene, hydroxyapatite mix homogeneously, fusing；Put into model, cool down molding；Put into NaHCO3-MgCO3Solution Middle immersion 18～24h, heat treatment 10～12h.
As to further improvement of the present invention, heat treatment temperature is 773K.
NaHCO3-MgCO3The mass concentration of solution is 10 ~ 20%.
Beneficial effect: the present invention is by putting into NaHCO3-MgCO3After solution carries out heat treatment, alloy surface can be made raw Becoming MgO membrane, through measuring, thickness is between 22～23 μm, so the MgO membrane of alloy surface after heat treatment can well subtract Weak corrosion rate, extends alloy service life.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Corrosion-resistant biological medical magnesium alloy, including the raw material of following weight portion meter: 150 parts of magnesium, 130 parts of zinc, 90 parts of aluminum, molybdenum 70 Part, 150 parts of paraffin, polyacrylate 60 parts, polypropylene 50 parts, hydroxyapatite 20 parts.
Paraffin is Tissuemat E, and molecular weight is 3000.
The size of hydroxyapatite is 150 μm.
The preparation method of a kind of corrosion-resistant biological medical magnesium alloy, comprises the following steps: magnesium, zinc, aluminum, molybdenum, paraffin, poly-third Olefin(e) acid ester, polypropylene, hydroxyapatite mix homogeneously, fusing；Put into model, cool down molding；Put into NaHCO3-MgCO3Solution Middle immersion 20h, heat treatment 11h.
Heat treatment temperature is 773K.
Embodiment 2
Corrosion-resistant biological medical magnesium alloy, including the raw material of following weight portion meter: 100 parts of magnesium, 120 parts of zinc, 80 parts of aluminum, molybdenum 60 Part, 100 parts of paraffin, polyacrylate 40 parts, polypropylene 20 parts, hydroxyapatite 10 parts.
Paraffin is Tissuemat E, and molecular weight is 2000.
The size of hydroxyapatite is 100 μm.
The preparation method of a kind of corrosion-resistant biological medical magnesium alloy, comprises the following steps: magnesium, zinc, aluminum, molybdenum, paraffin, poly-third Olefin(e) acid ester, polypropylene, hydroxyapatite mix homogeneously, fusing；Put into model, cool down molding；Put into NaHCO3-MgCO3Solution Middle immersion 18h, heat treatment 10h.
Heat treatment temperature is 773K.
Embodiment 3
Corrosion-resistant biological medical magnesium alloy, including the raw material of following weight portion meter: 200 parts of magnesium, 150 parts of zinc, 100 parts of aluminum, molybdenum 90 Part, 200 parts of paraffin, polyacrylate 80 parts, polypropylene 70 parts, hydroxyapatite 40 parts.
Paraffin is Tissuemat E, and molecular weight is 4000.
The size of hydroxyapatite is 200 μm.
The preparation method of a kind of corrosion-resistant biological medical magnesium alloy, comprises the following steps: magnesium, zinc, aluminum, molybdenum, paraffin, poly-third Olefin(e) acid ester, polypropylene, hydroxyapatite mix homogeneously, fusing；Put into model, cool down molding；Put into NaHCO3-MgCO3Solution Middle immersion 24h, heat treatment 12h.
Heat treatment temperature is 773K.
Embodiment 4
Corrosion-resistant biological medical magnesium alloy, including the raw material of following weight portion meter: 120 parts of magnesium, 130 parts of zinc, 85 parts of aluminum, molybdenum 70 Part, 120 parts of paraffin, polyacrylate 50 parts, polypropylene 30 parts, hydroxyapatite 20 parts.
Paraffin is Tissuemat E, and molecular weight is 2500.
The size of hydroxyapatite is 120 μm.
The preparation method of a kind of corrosion-resistant biological medical magnesium alloy, comprises the following steps: magnesium, zinc, aluminum, molybdenum, paraffin, poly-third Olefin(e) acid ester, polypropylene, hydroxyapatite mix homogeneously, fusing；Put into model, cool down molding；Put into NaHCO3-MgCO3Solution Middle immersion 22h, heat treatment 11h.
Heat treatment temperature is 773K.
Comparative example 1
Same as in Example 1, difference is: omits and puts into NaHCO3-MgCO3Solution carries out the step of heat treatment.
Performance test
Measure embodiment and the properties of product of comparative example, the results are shown in Table 1.Experimental condition: 30 DEG C, 0.05% hydrochloric acid solution.
Table 1
Conclusion: by putting into NaHCO3-MgCO3Solution carries out the corrosion rate of the alloy after heat treatment 23～26 μm/a, And the corrosion rate of undressed alloy is 56 μm/a, this is because by such heat treatment, alloy surface can be made raw Becoming MgO membrane, through measuring, thickness is between 22～23 μm, so the MgO membrane of alloy surface after heat treatment can well subtract Weak corrosion rate, extends alloy service life.

Claims (1)

  1. The most corrosion-resistant biological medical magnesium alloy, it is characterised in that include the raw material of following weight portion meter: magnesium 100～200 parts, zinc 120～150 parts, aluminum 80～100 parts, molybdenum 60～90 parts, paraffin 100～200 parts, polyacrylate 40～80 parts, polypropylene 20 ～70 parts, hydroxyapatite 10～40 parts；
    The preparation method of described corrosion-resistant biological medical magnesium alloy, comprises the following steps: magnesium, zinc, aluminum, molybdenum, paraffin, polypropylene Acid esters, polypropylene, hydroxyapatite mix homogeneously, fusing；Put into model, cool down molding；Put into NaHCO3-MgCO3In solution Soak 18～24h, heat treatment 10～12h；
    Paraffin is Tissuemat E, and molecular weight is 2000～4000；
    The size of hydroxyapatite is 100～200 μm.
CN201610845752.7A 2014-11-10 2014-11-10 Corrosion-resistant biological medical magnesium alloy Withdrawn CN106282710A (en)

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