CN109731134A - A kind of modified magnesium alloy bone implant material in surface and preparation method - Google Patents
A kind of modified magnesium alloy bone implant material in surface and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of modified magnesium alloy bone implant materials in surface, the composite coating including matrix alloy and coated on described matrix surface；Described matrix alloy includes following component, is based on mass fraction Zn:0.05%-1%, Ca:0.1%-2%, Sr:0.01%-2%, Ag:1%-3%, Y:1%-5%, Zr:0.5%-7%；Surplus is Mg；The composite coating includes following material component, based on parts by weight are as follows: 50-80 parts of l-lactic acid, 60-90 parts of chitosan, 40-60 parts of gelatin, 20-40 parts of polycaprolactone, 30-40 parts of ethyl cellulose, 50-60 parts of silicate compound, 50-60 parts of four water-calcium nitrate, 80-100 parts of solvent, 60-110 parts of ethyl alcohol, 5-20 parts of surfactant.The present invention prepares composite coating, during the preparation process, passes through high-temperature calcination, the composite coating surface made generates a large amount of gap, the specific surface area of coating is increased, good synostosis can be formed with biological tissue, there is the alloy material to implant excellent biological.
Description
Technical field
The invention belongs to magnesium alloy technical fields, and in particular to a kind of modified magnesium alloy bone implant material in surface and preparation side
Method.
Background technique
Magnesium alloy has a kind of emerging biodegradable material, has preferable biocompatibility and degradability.Make
For the magnesium alloy to implant, need to have certain intensity, moulding ability, elasticity modulus and suitable degradation rate, but existing
Corrosion resistance in the body fluid of some magnesium alloy implant materials is poor, and degradation speed is too fast, so that perienchyma generates inflammation,
It can also cause perienchyma downright bad when serious, in the prior art, have and add rare earth element in the magnesium alloy to improve the resistance to of alloy
Corrosivity improves the corrosion resistance of alloy although the addition of rare earth element, but influences the biocompatibility of alloy.
Patent 200710012204.7 " magnesium alloy/calcium phosphate composite material " proposes the combination of a variety of magnesium alloys and calcium salt
Biomaterial is prepared, main technology of preparing is the method using melting and casting, this is the routine for preparing composite material for industry
Technology, is difficult to meet that complicated for the type of Biocomposite material, ingredient is uniform, the accurate requirement of content.And magnesium exists
It is easy to oxidize during melting and casting, and bring various impurity into, cause the defect on the composite property of preparation.
What patent 200910103351.4 " Biodegradable hydroxylapatite-magnesium and calcium metallic based composites " proposed is one
For kind using composite material made of nanometer hydroxyapatite and magnesium calcium alloy, hydroxyapatite can be well on biocompatibility
Meet bone tissue growth, but the material does not have biodegradation character.
Summary of the invention
It is an object of the present invention to: deficiency in the prior art is solved, provides that a kind of corrosion resistance is strong, bio-compatible
Property good surface modified magnesium alloy bone implant material.
The second object of the present invention is, provides a kind of method for preparing the modified magnesium alloy bone implant material in the surface.
To achieve the goals above, the technical solution adopted by the present invention are as follows: a kind of modified magnesium alloy bone implant material in surface,
Composite coating including matrix alloy and coated on described matrix surface；
Described matrix alloy includes following component, based on mass fraction are as follows:
Zn:0.05%-1%, Ca:0.1%-2%, Sr:0.01%-2%, Ag:1%-3%, Y:1%-5%, Zr:
0.5%-7%；Surplus is Mg；
The composite coating includes following material component, based on parts by weight are as follows:
50-80 parts of l-lactic acid, 60-90 parts of chitosan, 40-60 parts of gelatin, 20-40 parts of polycaprolactone, ethyl cellulose
It is 30-40 parts plain, 50-60 parts of silicate compound, 50-60 parts of four water-calcium nitrate, 80-100 parts of solvent, 60-110 parts of ethyl alcohol, surface
5-20 parts of activating agent.
Further, described matrix alloy includes following component, based on mass fraction are as follows:
Zn:0.5%-0.7%, Ca:1.5%-1.8%, Sr:0.8%-1%, Ag:1%-1.2%, Y:1%-2%, Zr:
3%-4%；Surplus is Mg.
Further, the composite coating includes following material component, based on parts by weight are as follows:
60-70 parts of l-lactic acid, 80-85 parts of chitosan, 35-40 parts of ethyl cellulose, 55-60 parts of silicate compound,
50-55 parts of four water-calcium nitrate, 40-50 parts of gelatin, 30-40 parts of polycaprolactone, 80-90 parts of solvent, 80-100 parts of ethyl alcohol, surface is living
5-10 parts of agent of property.
Further, the silicate compound is ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, butyl silicate
One of or a variety of mixing.
Further, the solvent is one of tetrahydrofuran, methylene chloride, dimethyl sulfoxide or a variety of mixing.
A method of preparing the modified magnesium alloy in surface, which comprises the following steps:
S1: in proportion by zinc source, calcium source, barium source, Yin Yuan, yttrium source, zirconium source and magnesium source mixed melting at aluminium alloy, by alloy
Liquid is cast into mold, and alloy pig is obtained；
S2: the alloy pig is placed in high temperature furnace, under an inert atmosphere, in-furnace temperature is warming up to 400-500 DEG C,
60-120min is kept the temperature, cools to 200-300 DEG C with the furnace, then keep the temperature 20-30min, then cooled to room temperature in air；
S3: the alloy pig after above-mentioned steps S2 heat treatment is cut, extrusion forming, preform is made；
S4: the solvent, l-lactic acid, chitosan, gelatin and polycaprolactone being added into container, at 80-90 DEG C
It stirs evenly, the preform made from the step S3 is soaked in the container, container is placed in ultrasonic wave and is shaken clearly
In device, ultrasonic vibration 30-60min dries spare；
S5: taking another container, and the ethyl alcohol and surfactant is added, stirs evenly, and adds ethyl cellulose, silicic acid
Compound and four water-calcium nitrate, stir evenly, and obtain mixed solution, by above-mentioned steps S4 treated preform in mixed solution
Middle immersion 10-30min takes out, dry at 70-90 DEG C, repeats immersion-drying；
S6: preform of the above-mentioned steps S5 after dry being placed in Muffle furnace, at 400-500 DEG C, calcines 5-6h, from
So it is cooled to room temperature.
Further, in the step S1, the zinc source is magnesium-zinc alloy, magnesium zinc zircaloy, magnesium zinc strontium alloy, pure
One of zinc or a variety of mixing；The calcium source is the mixing of one or both of magnesium zinc calcium alloy, magnesium calcium alloy；It is described
Barium source is the mixing of one or both of magnesium zinc strontium alloy, magnesium strontium intermediate alloy；The silver source is fine silver, in magnesium silver alloy
One or two kinds of mixing；The yttrium source is the mixing of one or both of magnesium zinc yittrium alloy, magnesium yttrium intermediate alloy；The zirconium
Source is the mixing of one or both of Mg-Zr alloys, magnesium zinc zircaloy；The magnesium source is pure magnesium, magnesium-zinc alloy, the conjunction of magnesium zinc zirconium
One in gold, magnesium zinc strontium alloy, magnesium zinc calcium alloy, magnesium strontium intermediate alloy, magnesium zinc yittrium alloy, magnesium yttrium intermediate alloy, Mg-Zr alloys
Kind or a variety of mixing.
Further, in the step S3, the temperature of the extrusion deformation is 200-300 DEG C.
It further, in the step S3, further include that the preform surface is polished with sand paper to light, then it will be described
Preform impregnates spare in ethanol water；Wherein, the quality volume fraction of the ethanol water is 20-50%.
Further, in the step S6, in calcination process, heating rate in the Muffle furnace is 5-10 DEG C/
min。
By adopting the above-described technical solution, the beneficial effects of the present invention are:
In the modified magnesium alloy in surface of the invention, the composite coating including matrix alloy and coated in matrix alloy surface；
L-lactic acid and chitosan in composite coating are degradation material, and polycaprolactone has good biocompatibility,
The surface of matrix alloy coats one layer of composite coating, and body fluid is directly contacted with composite coating, and body fluid first corrodes composite layer, when compound
After layer degradation, then start matrix alloy of degrading；Matrix alloy corrosion resistance can be effectively improved, and composite coating and matrix close
Gold mutually acts synergistically in body fluid, controls the degradation rate of alloy.
The present invention prepares composite coating, and during the preparation process, by high-temperature calcination, the composite coating surface made generates a large amount of
Gap, increase the specific surface area of coating, good synostosis can be formed with biological tissue, make the alloy material to implant
Expect to have excellent biological.
Detailed description of the invention
Fig. 1 is that magnesium alloy substrate and coating SEM scheme in the embodiment of the present invention 1；
Fig. 2 is 1 floating coat surface SEM of the embodiment of the present invention figure.
Specific embodiment
With the alloying element proportion in table 1, matrix alloy is prepared
1 matrix alloy composition table of table
| Zn (%) | Ca (%) | Sr (%) | Ag (%) | Y (%) | Zr (%) | Mg (%) | |
| Embodiment 1 | 0.05 | 1.0 | 0.5 | 3.0 | 1.0 | 7.0 | Surplus |
| Embodiment 2 | 0.05 | 0.5 | 1.0 | 1.5 | 5.0 | 0.5 | Surplus |
| Embodiment 3 | 0.1 | 1.0 | 0.2 | 2.0 | 3.5 | 1.0 | Surplus |
| Embodiment 4 | 0.1 | 2.0 | 0.01 | 1.2 | 2.0 | 2.0 | Surplus |
| Embodiment 5 | 0.5 | 0.1 | 2.0 | 0.5 | 1.5 | 4.0 | Surplus |
| Embodiment 6 | 0.5 | 1.8 | 0.5 | 1.0 | 2.0 | 1.5 | Surplus |
| Embodiment 7 | 1.0 | 0.5 | 0.8 | 0.2 | 5.0 | 4.5 | Surplus |
| Embodiment 8 | 0.7 | 1.5 | 0.01 | 3.0 | 1.5 | 3.0 | Surplus |
Embodiment 1:
S1: by the composition proportion in above-mentioned table 1, by magnesium zinc zircaloy, magnesium zinc calcium alloy, magnesium zinc strontium alloy, fine silver and magnesium
Yttrium intermediate alloy mixed melting casts aluminium alloy into mold at aluminium alloy, obtains alloy pig；
S2: the alloy pig is placed in high temperature furnace, under an inert atmosphere, with the rate of 10 DEG C/min by in-furnace temperature
500 DEG C of heating keeps the temperature 60min, after cooling to 300 DEG C with the furnace, in heat preservation 30min, then takes out magnesium ingot, naturally cold in air
But to room temperature；
S3: the alloy pig after above-mentioned steps S2 heat treatment is cut, the extrusion forming at 200 DEG C, is made
The matrix alloy item of 10cmX20cmX2cm 1；It is closed with the surface of sand paper polishing matrix alloy item to light, then by described matrix
Gold bar is immersed in the ethanol water that volume fraction is 20%, spare；
S4: 90 parts of dimethyl sulfoxides of addition, 60 parts of l-lactic acid, 60 parts of chitosans, 40 parts of gelatin and 20 parts into container
Polycaprolactone stirs evenly at 80 DEG C, matrix alloy item made from the step S3 is soaked in the container, by container
It is placed in the clear oscillator of ultrasonic wave, after ultrasonic vibration 30min, preform is dried spare；
S5: taking another container, and 80 parts of ethyl alcohol and 5 parts of surfactants are added, stirs evenly, adds 30 parts of ethyls
Cellulose, 55 parts of butyl silicates and 50 parts of four water-calcium nitrates, stir evenly, obtain mixed solution, above-mentioned steps S4 is handled
After preform afterwards impregnates 30min in mixed solution, take out, it is dry at 70 DEG C, then 20min is impregnated in mixed solution,
It is dry at 70 DEG C, it is repeated 3 times immersion-drying process；
S6: preform of the above-mentioned steps S5 last time after dry is placed in Muffle furnace, with the rate liter of 5 DEG C/min
Temperature calcines 5h to 500 DEG C at such a temperature, and the modified magnesium alloy in surface is made in subsequent cooled to room temperature.It obtains being coated with multiple
Close the modified magnesium alloy item 1 in surface of coating
Embodiment 2:
S1: by the composition proportion in above-mentioned table 1, by magnesium zinc zircaloy, magnesium zinc calcium alloy, magnesium zinc strontium alloy, fine silver, magnesium zinc
Aluminium alloy is cast into mold at aluminium alloy, obtains alloy pig by yittrium alloy, pure magnesium mixed melting；
S2: the alloy pig is placed in high temperature furnace, under an inert atmosphere, with the rate of 10 DEG C/min by in-furnace temperature
450 DEG C of heating keeps the temperature 120min, after cooling to 300 DEG C with the furnace, in heat preservation 30min, then takes out magnesium ingot, natural in air
It is cooled to room temperature；
S3: the alloy pig after above-mentioned steps S2 heat treatment is cut, the extrusion forming at 300 DEG C, is made
The matrix alloy item of 10cmX20cmX2cm 2；It is closed with the surface of sand paper polishing matrix alloy item to light, then by described matrix
Gold bar is immersed in the ethanol water that volume fraction is 50%, spare；
S4: 80 parts of tetrahydrofurans of addition, 50 parts of l-lactic acid, 70 parts of chitosans, 50 parts of gelatin and 40 parts into container
Polycaprolactone stirs evenly at 80 DEG C, matrix alloy item made from the step S3 is soaked in the container, by container
It is placed in the clear oscillator of ultrasonic wave, after ultrasonic vibration 60min, preform is dried spare；
S5: taking another container, and 100 parts of ethyl alcohol and 8 parts of surfactants are added, stirs evenly, adds 35 parts of second
Base cellulose, 60 parts of methyl orthosilicate compounds and 60 parts of four water-calcium nitrates, stir evenly, obtain mixed solution, by above-mentioned step
Treated by rapid S4 after matrix alloy item impregnates 20min in mixed solution, takes out, dries at 90 DEG C, then in mixed solution
Middle immersion 30min, it is dry at 90 DEG C, it is repeated 5 times immersion-drying process；
S6: matrix alloy item of the above-mentioned steps S5 last time after dry is placed in Muffle furnace, with the speed of 8 DEG C/min
Rate is warming up to 500 DEG C, calcines 6h at such a temperature, and the modified magnesium alloy in surface is made in subsequent cooled to room temperature.It is coated
There is the modified magnesium alloy item 2 in the surface of composite coating
Embodiment 3:
S1: by the composition proportion in above-mentioned table 1, by magnesium zinc zircaloy, magnesium zinc calcium alloy, magnesium zinc strontium alloy, fine silver, magnesium yttrium
Aluminium alloy is cast into mold at aluminium alloy, obtains alloy pig by intermediate alloy and pure magnesium mixed melting；
S2: the alloy pig is placed in high temperature furnace, under an inert atmosphere, with the rate of 5 DEG C/min by in-furnace temperature
400 DEG C of heating keeps the temperature 100min, after cooling to 200 DEG C with the furnace, then keeps the temperature 30min, then take out magnesium ingot, natural in air
It is cooled to room temperature；
S3: the alloy pig after above-mentioned steps S2 heat treatment is cut, the extrusion forming at 250 DEG C, is made
The matrix alloy item of 10cmX20cmX2cm；With the surface of sand paper polishing matrix alloy item to light, then by described matrix alloy bar
It is immersed in the ethanol water that volume fraction is 50%, it is spare；
S4: 100 parts of methylene chloride of addition, 80 parts of l-lactic acid, 90 parts of chitosans, 40 parts of gelatin and 30 parts into container
Polycaprolactone stirs evenly at 90 DEG C, matrix alloy item made from the step S3 is soaked in the container, by container
It is placed in the clear oscillator of ultrasonic wave, after ultrasonic vibration 30min, matrix alloy item is dried spare；
S5: taking another container, and 900 parts of ethyl alcohol and 20 parts of surfactants are added, stirs evenly, adds 40 parts of second
Base cellulose, 55 parts of ethyl orthosilicates and 60 parts of four water-calcium nitrates, stir evenly, obtain mixed solution, at above-mentioned steps S4
After matrix alloy item after reason impregnates 30min in mixed solution, take out, it is dry at 70 DEG C, then impregnated in mixed solution
20min, it is dry at 70 DEG C, it is repeated 3 times immersion-drying process；
S6: matrix alloy item of the above-mentioned steps S5 last time after dry is placed in Muffle furnace, with 10 DEG C/min's
Rate is warming up to 500 DEG C, calcines 5h at such a temperature, and the modified magnesium alloy in surface is made in subsequent cooled to room temperature.It is applied
It is covered with the modified magnesium alloy item 3 in surface of composite coating.
Embodiment 4:
S1: by the composition proportion in above-mentioned table 1, by Mg-Zr alloys, magnesium zinc calcium alloy, magnesium-zinc alloy, magnesium zinc strontium alloy, pure
Aluminium alloy is cast into mold at aluminium alloy, obtains alloy pig by silver, magnesium yttrium intermediate alloy and pure magnesium mixed melting；
S2: the alloy pig is placed in high temperature furnace, under an inert atmosphere, with the rate of 10 DEG C/min by in-furnace temperature
500 DEG C of heating keeps the temperature 60min, after cooling to 300 DEG C with the furnace, in heat preservation 20min, then takes out magnesium ingot, naturally cold in air
But to room temperature；
S3: the alloy pig after above-mentioned steps S2 heat treatment is cut, the extrusion forming at 300 DEG C, is made
The matrix alloy item of 10cmX20cmX2cm 4；It is closed with the surface of sand paper polishing matrix alloy item to light, then by described matrix
Gold bar is immersed in the ethanol water that volume fraction is 300%, spare；
S4: 100 parts of dimethyl sulfoxides of addition, 85 parts of l-lactic acid, 80 parts of chitosans, 35 parts of gelatin and 25 parts into container
Polycaprolactone stirs evenly at 80 DEG C, matrix alloy item made from the step S3 is soaked in the container, by container
It is placed in the clear oscillator of ultrasonic wave, after ultrasonic vibration 30min, matrix alloy item is dried spare；
S5: taking another container, and 80 parts of ethyl alcohol and 15 parts of surfactants are added, stirs evenly, adds 40 parts of second
Base cellulose, 20 parts of methyl orthosilicates, 30 parts of ethyl orthosilicates and 50 parts of four water-calcium nitrates, stir evenly, obtain mixed solution,
By above-mentioned steps S4, treated after matrix alloy item impregnates 30min in mixed solution, takes out, dry at 90 DEG C, then
10min is impregnated in mixed solution, it is dry at 90 DEG C, it is repeated 8 times immersion-drying process；
S6: matrix alloy item of the above-mentioned steps S5 last time after dry is placed in Muffle furnace, with 10 DEG C/min's
Rate is warming up to 500 DEG C, calcines 5.5h at such a temperature, and the modified magnesium alloy in surface is made in subsequent cooled to room temperature.It obtains
The modified magnesium alloy item 4 in surface coated with composite coating.
Embodiment 5:
In the present embodiment, the element component content of matrix alloy is as shown in table 1；The preparation side being related in the present embodiment
Method, Parameter Conditions are identical as embodiment 1, the difference is that, in the present embodiment, in S2 step, 30 are added into container
Part tetrahydrofuran and 60 methylene chloride replace 90 part of two methylene sulfone in embodiment 1；In S5 step, with 10 parts of positive silicic acid propyl esters and 45
Part methyl orthosilicate replaces 55 parts of butyl silicates in embodiment 1, remaining is identical with embodiment 1.Respectively obtain matrix
The modified magnesium alloy item 5 of magnesium alloy item 5 and surface coated with composite coating.
Embodiment 6: the preparation method, parameter, raw material and content of the present embodiment are identical as embodiment 2, and difference exists
In in the present embodiment, the component content of matrix alloy is different.It respectively obtains matrix magnesium alloy item 6 and is coated with compound painting
The modified magnesium alloy item 6 in the surface of floor.
Embodiment 7: the preparation method, parameter, raw material and content of the present embodiment are identical as embodiment 3, and difference exists
In in the present embodiment, the component content of matrix alloy is different.It respectively obtains matrix magnesium alloy item 7 and is coated with compound painting
The modified magnesium alloy item 7 in the surface of floor.
Embodiment 8: the preparation method, parameter, raw material and content of the present embodiment are identical as embodiment 4, and difference exists
In in the present embodiment, the component content of matrix alloy is different.It respectively obtains matrix magnesium alloy item 8 and is coated with compound painting
The modified magnesium alloy item 8 in the surface of floor.
Under identical testing conditions, the modified magnesium alloy of the matrix magnesium alloy prepared in test implementation 1-8 and surface
Corrosion potential and corrosion current, result is as shown in the following table 2 and table 3:
2 matrix magnesium alloy corrosion resistance test result of table
3 composite magnesium alloy corrosion resistance test result of table
It can be concluded that, the good corrosion resistance of matrix alloy coats compound on matrix alloy surface from above-mentioned table 2 and table 3
After coating, the corrosion potential of composite alloy is improved, and corrosion current becomes smaller, by the surface coatings in matrix alloy,
Significantly improve the corrosion resistance of alloy.
To the mechanical property of modified alloy item in surface obtained in above-described embodiment 1-8, result such as table 4,
The mechanical experimental results of 4 surface modified alloy of table
The yield strength of the surface modified alloy of embodiment 1-8 preparation is between 233-270MPa, and tensile strength is in 240-
Between 284MPa, for elongation percentage between 13%-17%, elasticity modulus meets the performance of positioning magnesium alloy between 38-47GPa.
The bond strength of the coating of modified alloy item in surface obtained and matrix alloy in above-described embodiment 1-8 is tested,
As a result as shown in table 5 below:
5 coating of table and matrix alloy bond strength
The associativity of the surface modified alloy of the embodiment of the present invention 1-8 preparation, coating and matrix alloy is strong, exists in alloy
During degradation, coating is first degraded, and stronger bond strength makes coating be not easy to fall off from matrix in degradation process, can
The degradation rate of effective control matrix alloy；By the corrosion resistance and mechanical property that modification magnesium alloy of the invention is excellent,
Bone fixation etc. can will be used as material implanted to use.
Claims (10)
1. a kind of modified magnesium alloy bone implant material in surface, it is characterised in that: including matrix alloy and be coated on described matrix table
The composite coating in face；
Described matrix alloy includes following component, based on mass fraction are as follows:
Zn:0.05%-1%, Ca:0.1%-2%, Sr:0.01%-2%, Ag:1%-3%, Y:1%-5%, Zr:0.5%-
7%；Surplus is Mg；
The composite coating includes following material component, based on parts by weight are as follows:
50-80 parts of l-lactic acid, 60-90 parts of chitosan, 40-60 parts of gelatin, 20-40 parts of polycaprolactone, ethyl cellulose 30-
40 parts, 50-60 parts of silicate compound, 50-60 parts of four water-calcium nitrate, 80-100 parts of solvent, 60-110 parts of ethyl alcohol, surfactant
5-20 parts.
2. the modified magnesium alloy bone implant material in surface according to claim 1, it is characterised in that: described matrix alloy includes
Following component, based on mass fraction are as follows:
Zn:0.5%-0.7%, Ca:1.5%-1.8%, Sr:0.8%-1%, Ag:1%-1.2%, Y:1%-2%, Zr:3%-
4%；Surplus is Mg.
3. the modified magnesium alloy bone implant material in surface according to claim 1, it is characterised in that: the composite coating includes
Following material component, based on parts by weight are as follows:
60-70 parts of l-lactic acid, 80-85 parts of chitosan, 35-40 parts of ethyl cellulose, 55-60 parts of silicate compound, four water
50-55 parts of calcium nitrate, 40-50 parts of gelatin, 30-40 parts of polycaprolactone, 80-90 parts of solvent, 80-100 parts of ethyl alcohol, surfactant
5-10 parts.
4. the modified magnesium alloy bone implant material in surface according to claim 1, it is characterised in that: the silicate compound is
One of ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, butyl silicate or a variety of mixing.
5. the modified magnesium alloy bone implant material in surface according to claim 1, it is characterised in that: the solvent is tetrahydro furan
It mutters, one of methylene chloride, dimethyl sulfoxide or a variety of mixing.
6. a kind of preparation method of the modified magnesium alloy bone implant material in any surface claim 1-5, which is characterized in that
The following steps are included:
S1: zinc source, calcium source, barium source, Yin Yuan, yttrium source, zirconium source and magnesium source mixed melting are poured aluminium alloy at aluminium alloy in proportion
Casting obtains alloy pig into mold；
S2: the alloy pig is placed in high temperature furnace, under an inert atmosphere, in-furnace temperature is warming up to 400-500 DEG C, heat preservation
60-120min, keeps the temperature 20-30min, then cooled to room temperature in air by 200-300 DEG C of furnace cooling；
S3: the alloy pig after above-mentioned steps S2 heat treatment is cut, extrusion forming, preform is made；
S4: the solvent, l-lactic acid, chitosan, gelatin and polycaprolactone being added into container, stir at 80-90 DEG C
Uniformly, the preform made from the step S3 is soaked in the container, container is placed in the clear oscillator of ultrasonic wave,
Ultrasonic vibration 30-60min dries spare；
S5: taking another container, and the ethyl alcohol and surfactant is added, stirs evenly, and adds ethyl cellulose, silicic acid chemical combination
Object and four water-calcium nitrate, stir evenly, and obtain mixed solution, and by above-mentioned steps S4, treated that preform is immersed in mixed solution
Middle immersion 10-30min takes out, dry at 70-90 DEG C, repeats immersion-drying；
S6: preform of the above-mentioned steps S5 after dry is placed in Muffle furnace, at 400-500 DEG C, calcines 5-6h, naturally cold
But to room temperature.
7. the preparation method of the modified magnesium alloy bone implant material in surface according to claim 6, it is characterised in that: described
Step S1 in, the zinc source be one of magnesium-zinc alloy, magnesium zinc zircaloy, magnesium zinc strontium alloy, pure zinc or a variety of mixing；
The calcium source is the mixing of one or both of magnesium zinc calcium alloy, magnesium calcium alloy；The barium source is magnesium zinc strontium alloy, in magnesium strontium
Between one or both of alloy mixing；The silver source is the mixing of one or both of fine silver, magnesium silver alloy；The yttrium
Source is the mixing of one or both of magnesium zinc yittrium alloy, magnesium yttrium intermediate alloy；The zirconium source is Mg-Zr alloys, magnesium zinc zircaloy
One or both of mixing；The magnesium source is pure magnesium, magnesium-zinc alloy, magnesium zinc zircaloy, magnesium zinc strontium alloy, the conjunction of magnesium zinc calcium
One of gold, magnesium strontium intermediate alloy, magnesium zinc yittrium alloy, magnesium yttrium intermediate alloy, Mg-Zr alloys or a variety of mixing.
8. the preparation method of the modified magnesium alloy bone implant material in surface according to claim 6, it is characterised in that: described
Step S3 in, the temperature of the extrusion deformation is 200-300 DEG C.
9. the preparation method of the modified magnesium alloy bone implant material in surface according to claim 6, it is characterised in that: described
It further include the preform surface being polished with sand paper to light, then the preform is impregnated in ethanol water in step S3
It is spare；Wherein, the quality volume fraction of the ethanol water is 20-50%.
10. the preparation method of the modified magnesium alloy bone implant material in surface according to claim 6, it is characterised in that: in institute
It states in step S6, in calcination process, the heating rate in the Muffle furnace is 5-10 DEG C/min.
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