CN108624015A - A kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material - Google Patents
A kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material Download PDFInfo
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- CN108624015A CN108624015A CN201810351992.0A CN201810351992A CN108624015A CN 108624015 A CN108624015 A CN 108624015A CN 201810351992 A CN201810351992 A CN 201810351992A CN 108624015 A CN108624015 A CN 108624015A
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- magnesium granules
- lactic acid
- composite material
- polylactic acid
- acid composite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Manufacturing & Machinery (AREA)
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of increasing material manufacturing methods of medical magnesium granules/lactic acid composite material, the preparation method accesses titanate coupling agent on magnesium granules surface first, then grafted polylactic acid, prepare the mixture of magnesium granules polylactic acid, the mixture is processed into medical magnesium granules/lactic acid composite material of different shapes after mold is squeezed into filiform, by 3D fusion sediment technologies.The present invention improves the binding performance of magnesium granules and polylactic acid surface by accessing metatitanic acid ester bond functional group；The rambling macromolecular chain in polylactic acid inside is changed to realize polylactic acid self-reinforcing effect by fashion of extrusion.
Description
Technical field
The present invention relates to a kind of increasing material manufacturing methods of medical magnesium granules/lactic acid composite material, belong to composite material
Increases material manufacturing technology field.
Background technology
Polylactic acid has good biocompatibility and degradability, and abundant raw material is renewable.Polylactic acid is in human body
It by the decomposition of enzyme, participates in metabolism cycle into the human body, finally with the discharge of carbon dioxide and water, does not cause environment
Pollution, it is nontoxic and without second operation take out, at the same time, there are also deficiencies as inner fixing device for polylactic acid.Main packet
It includes：Polylactic acid poor mechanical property, intensity is low, it is flexible it is big, resist impact energy force difference, and catabolite is be easy to cause in acidity
Tissue local inflammatory reaction.
The density of the density and people's bone of magnesium and magnesium alloy is closer to, and the elasticity modulus of magnesium and magnesium alloy is about 35-
45GPa, compared to titanium alloy and stainless steel, elasticity modulus is greatly lowered, closer to the elasticity modulus (3-20GPa) of people's bone, energy
Enough effective alleviation stress-shielding effects, magnesium usually exist in the form of an ion, and content is only second to calcium, sodium, potassium, can promote the heavy of calcium
Product, it is required element in human body to promote the formation of osteocyte, magnesium, and important influence, but magnesium and its conjunction have been played to vital movement
Gold easily corrodes degradation in human physiological environment, and standard electrode potential (- 2.37V) is easily corroded in use,
It can occur electrochemical corrosion in water, along with H in corrosion process2Generation.
For polylactic acid poor mechanical property, catabolite slant acidity, and magnesium alloy degradation is too fast, it is perishable the shortcomings of, closely
Come, people have been devoted to the two is compound, degradable medical magnesium granules/lactic acid composite material are prepared, to realize material
In comprehensive performance complementary intensity, performance can design, the characteristics such as controllable, catabolite acid-base neutralization of degrading；However magnesium granules
An important factor for polylactic acid binding performance difference being always magnesium granules/lactic acid composite material difficult forming.
Invention content
Technical problem：The object of the present invention is to provide a kind of increasing material manufacturing sides of medical magnesium granules/lactic acid composite material
Method, the invention solve the problems such as magnesium granules are poor with polylactic acid binding performance.
Technical solution：The present invention provides a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material, the party
Method includes the following steps：
1) magnesium granules are surface-treated：Magnesium granules are heat-treated using hydro-thermal method, heating temperature is 180~200 DEG C, is added
The hot time is 1~5h, takes out be dried for standby later；
2) magnesium granules are modified：The magnesium granules that step 1) is dried are mixed with titanate coupling agent aqueous solution, after being sufficiently stirred
On magnesium granules surface, uniform graft has titanate coupling agent, obtains modified magnesium granules；
3) prepared by mixture：By particles of polylactic acid by volume 1:20~1:6 are dissolved in tetrahydrofuran, and stirring makes poly- breast
After granulates are completely dissolved, it is added modified magnesium granules, the volume ratio of magnesium granules and polylactic acid is 1:100~1:3, fully stir
It mixes rear polylactic acid uniform graft and obtains mixture after tetrahydrofuran completely volatilization on magnesium granules surface；
4) at silk：The mixture that step 3) obtains is squeezed into filiform, obtains silk material；
5) increasing material manufacturing：Using silk material as raw material, the medical magnesium of required shape or structure is prepared using the method for increasing material manufacturing
Particle/lactic acid composite material.
Wherein：
It takes out and is dried for standby after described in step 1), refer to heating 1~5h under conditions of temperature is 50~80 DEG C.
The volumetric concentration of titanate coupling agent is 0.5~1.0% in titanate coupling agent aqueous solution described in step 2).
In magnesium granules surface uniform graft titanate coupling agent after being sufficiently stirred described in step 2), stir speed (S.S.) is 8~
10r/s, mixing time are 0.2~1.0h.
Stirring described in step 3) makes particles of polylactic acid be completely dissolved, and the rate of stirring is 10~12r/s, and mixing time is
15~for 24 hours.
The rear polylactic acid that is sufficiently stirred described in step 3) is uniformly grafted on magnesium granules surface, and the rate of stirring is 10~
15r/s, mixing time are 12~15h.
The molecular weight of polylactic acid described in step 3) is 3~1,000,000.
A diameter of 0.2~the 0.6mm of silk material described in step 4).
The method of increasing material manufacturing described in step 5) refers to 3D fused glass pellet technologies：Silk material is heated again by nozzle
It is melted into mixture, under the control of the computer, nozzle is moved to designated position according to the data of 3D models, by the mixed of molten condition
It closes to expect to squeeze and gushes out and finally solidify, successively accumulates the medical magnesium granules/lactic acid composite material for forming final shape or structure.
Advantageous effect：Compared with prior art, the present invention has the advantage that：
1) present invention first by magnesium granules surface access titanate coupling agent, titanate coupling agent improve polylactic acid with
The binding performance of magnesium granules, because containing hydrolyzable functional group RO on titanate coupling agent-And thermoplastic polymer long-chain twines
Around group R, RO-The hydroxyl energy (such as formula one) generated is hydrolyzed to react by the hydroxyl that hydro-thermal method generates with magnesium granules surface
(such as formula two), meanwhile, the long-chain winding group R in titanate coupling agent can be wound with polylactic acid molecule chain, by poly- breast
Acid is grafted on magnesium granules surface, forms firm two-phase interface and combines；
(RO)Ti(OX-R-Y)3+H2O→(HO)Ti(OX-R-Y)3+ ROH formula one
Mg(OH)2+[(HO)Ti(OX-R-Y)3]2→Mg[OTi(OX-R-Y)3]2+2H2O formula two
Wherein, (RO) hydrolyzable, the hydroxyl that the hydroxyl of generation can be generated with magnesium granules surface hydro-thermal react to form chemistry
Key；OX is the group for connecting titanium center, and R is that thermoplastic polymer long-chain winds group, and Y is that thermosetting polymer progress is crosslinked
Reactive group.
2) magnesium granules/lactic acid composite material is squeezed into filamentary material using mold, is changed by fashion of extrusion poly-
Rambling macromolecular chain is to realize polylactic acid self-reinforcing effect inside lactic acid；
3) use 3D fusion sediments technology that can prepare medical magnesium granules/lactic acid composite material of different shapes.
Description of the drawings
Fig. 1 is：A kind of increasing material manufacturing method flow schematic diagram of medical magnesium granules/lactic acid composite material.
Specific implementation mode
The present invention provides a kind of preparation method and applications of medical magnesium granules-lactic acid composite material, the composite woods
The preparation method of material accesses titanate coupling agent by hydro-thermal method and dry method on magnesium granules surface, and titanate coupling agent improves
The binding performance of polylactic acid and magnesium granules；Contain hydrolyzable functional group RO on titanate coupling agent-And thermoplastic polymer is long
Chain winds group R, RO-It is anti-to hydrolyze the hydroxyl that the hydroxyl energy (such as formula one) generated and magnesium granules surface are generated by hydro-thermal method
It answers (such as formula two), meanwhile, the long-chain winding group R in titanate coupling agent can be wound with polylactic acid molecule chain, will be gathered
Lactic acid is grafted on magnesium granules surface, forms firm two-phase interface and combines, and the medical magnesium granules-polylactic acid for obtaining performance stabilization is multiple
Condensation material；Medical magnesium granules-lactic acid composite material is squeezed into filamentary material using mold later, is changed by fashion of extrusion
Rambling macromolecular chain is to realizing polylactic acid self-reinforcing effect inside polylactic acid；It can be made using 3D fusion sediments technology
It is standby go out medical magnesium granules/lactic acid composite material of different shapes.
(RO)Ti(OX-R-Y)3+H2O→(HO)Ti(OX-R-Y)3+ ROH formula one
Mg(OH)2+[(HO)Ti(OX-R-Y)3]2→Mg[OTi(OX-R-Y)3]2+2H2O formula two
Wherein, (RO) hydrolyzable, the hydroxyl that the hydroxyl of generation can be generated with magnesium granules surface hydro-thermal react to form chemistry
Key；OX is the group for connecting titanium center, and R is that thermoplastic polymer long-chain winds group, and Y is that thermosetting polymer progress is crosslinked
Reactive group.
Example 1：
A kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material, includes the following steps：
1) 50gAZ31B magnesium alloy particles are added in 100ml pyroreaction kettles, add 30ml distilled water, be put into baking
In case, 200 DEG C of heating temperature, heat preservation 1h after taking-up is wash with distilled water used in combination hair-dryer to dry up, spare；
2) magnesium alloy particles dried up are added to the titanate coupling agent that titanate coupling agent volumetric concentration is 0.5%
In aqueous solution, be placed on homogenizer, rotating speed be 8r/s under conditions of stir 0.5h, it is equal to obtain titanate coupling agent
The even modification magnesium alloy particles for being grafted on Mg alloy surface；
3) it is 3 × 10 to take molecular weight5Particles of polylactic acid 20g, by volume 1:20 are added to particles of polylactic acid dissolving
In tetrahydrofuran solvent, 15h is stirred under conditions of rotating speed is 10r/s, modified magnesium granules (magnesium granules and polylactic acid are added later
Volume ratio be 1:10) it is, that 10r/s stirs 12h in rotating speed, polylactic acid uniform graft waits for that tetrahydrofuran is waved in titanium alloy surface
After distributing entirely, mixture is obtained；
4) at silk：Obtained mixture is added in extruder, the process for being extruded into silk is as follows：Mixture is at the uniform velocity added
Enter into double screw extruder, and in twin screw extrusion, extruder first segment temperature is 170 DEG C, and second segment temperature is 180
DEG C, third section temperature is 180 DEG C, and head temperature is 170 DEG C；Mold is installed additional in the exit of double screw extruder, limits wire vent
Then diameter uses roller apparatus wrapping wire to collect silk material, obtains the silk material of a diameter of 0.2mm；
5) 3D fused glass pellets：By silk material by nozzle heating and melting, under the control of the computer, nozzle is according to 3D models
Data be moved to designated position, by the mixture of molten condition squeeze gush out and finally solidification, successively accumulation formation most end form
Medical magnesium granules/lactic acid composite material of shape.
Example 2：
A kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material, includes the following steps：
1) the pure magnesium granules of 50gAZ31B are added in 100ml pyroreaction kettles, add 30ml distilled water, is put into baking oven
In, 190 DEG C of heating temperature, heat preservation 2h after taking-up is wash with distilled water used in combination hair-dryer to dry up, spare；
2) magnesium alloy particles dried up are added to the titanate coupling agent water that titanate coupling agent volumetric concentration is 1%
In solution, be placed on homogenizer, rotating speed be 10r/s under conditions of stir 1h, it is uniform to obtain titanate coupling agent
It is grafted on the modification magnesium alloy particles of Mg alloy surface；
3) it is 1.0 × 10 to take molecular weight6Particles of polylactic acid 30g, by volume 1:Particles of polylactic acid is dissolved into tetrahydrochysene by 6
It in THF solvent, is stirred for 24 hours under conditions of rotating speed is 12r/s, modified pure magnesium granules (pure magnesium granules and polylactic acid is added later
Volume ratio be 1：20) 15h, is stirred under conditions of rotating speed is 15r/s, polylactic acid is uniformly grafted on pure magnesium granules surface,
After tetrahydrofuran volatilization completely, mixture is obtained；
4) at silk：Obtained mixture is added in extruder, and the process for being extruded into silk is as follows：Mixture is at the uniform velocity added
Into double screw extruder, and in twin screw extrusion, extruder first segment temperature is 180 DEG C, and second segment temperature is 190
DEG C, third section temperature is 180 DEG C, and head temperature is 190 DEG C；Mold is installed additional in the exit of double screw extruder, limits wire vent
Then diameter uses roller apparatus wrapping wire to collect silk material, obtains a diameter of 0.5mm silk materials；
5) 3D fused glass pellets：By silk material by nozzle heating and melting, under the control of the computer, nozzle is according to 3D models
Data be moved to designated position, the mixture of molten condition is gushed out and is finally solidified, successively accumulation form final shape
Medical magnesium granules/lactic acid composite material.
Example 3：
A kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material, includes the following steps：
1) 50gAZ91D magnesium alloy particles are added in 100ml pyroreaction kettles, add 30ml distilled water, be put into baking
In case, 200 DEG C of heating temperature, heat preservation 2h after taking-up is wash with distilled water used in combination hair-dryer to dry up, spare；
2) magnesium alloy particles dried up are added to the titanate coupling agent that titanate coupling agent volumetric concentration is 0.6%
In aqueous solution, be placed on homogenizer, rotating speed be 9r/s under conditions of stir 0.5h, it is equal to obtain titanate coupling agent
The even modification magnesium alloy particles for being grafted on Mg alloy surface；
3) it is 5.0 × 10 to take molecular weight5Particles of polylactic acid 20g, by volume 1:Particles of polylactic acid is dissolved into tetrahydrochysene by 6
In THF solvent, 20h is stirred under conditions of stir speed (S.S.) 11r/s, be added later modified magnesium alloy particles (magnesium alloy particles with
The volume ratio of polylactic acid is 1:3) 13h, is stirred under conditions of rotating speed is 12r/s, polylactic acid is uniformly grafted on magnesium alloy
Grain surface obtains mixture after tetrahydrofuran volatilization completely；
4) at silk：Obtained mixture is added in extruder, and the process for being extruded into silk is as follows：Mixture is at the uniform velocity added
Into double screw extruder, and in twin screw extrusion, extruder first segment temperature is 190 DEG C, and second segment temperature is 200
DEG C, third section temperature is 190 DEG C, and head temperature is 170 DEG C；Mold is installed additional in the exit of double screw extruder, limits wire vent
Then diameter uses roller apparatus wrapping wire to collect silk material, obtains a diameter of 0.4mm silk materials；
5) 3D fused glass pellets：Silk material is melted into mixture, under the control of the computer, nozzle by nozzle reheating
It is moved to designated position according to the data of 3D models, the mixture of molten condition is squeezed and gushes out and finally solidifies, successively accumulate
Form medical magnesium granules/lactic acid composite material of final shape.
Example 4：
A kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material, includes the following steps：
1) 50gAZ91D magnesium alloy particles are added in 100ml pyroreaction kettles, add 30ml distilled water, be put into baking
In case, 180 DEG C of heating temperature, heat preservation 5h after taking-up is wash with distilled water used in combination hair-dryer to dry up, spare；
2) magnesium alloy particles dried up are added to the titanate coupling agent that titanate coupling agent volumetric concentration is 0.7%
In aqueous solution, be placed on homogenizer, rotating speed be 9r/s under conditions of stir 0.8h, it is equal to obtain titanate coupling agent
The even modification magnesium alloy particles for being grafted on Mg alloy surface；
3) it is 3.0 × 10 to take molecular weight4Particles of polylactic acid 20g, by volume 1:Particles of polylactic acid is dissolved into four by 12
In hydrogen THF solvent, 18h is stirred under conditions of stir speed (S.S.) 12r/s, be added later modified magnesium alloy particles (magnesium alloy with it is poly-
The volume ratio of lactic acid is 1:100) 15h, is stirred under conditions of rotating speed is 12r/s, polylactic acid is uniformly grafted on magnesium alloy
Grain surface obtains mixture after tetrahydrofuran volatilization completely；
4) at silk：Obtained mixture is added in extruder, and the process for being extruded into silk is as follows：Mixture is at the uniform velocity added
Into double screw extruder, and in twin screw extrusion, extruder first segment temperature is 200 DEG C, and second segment temperature is 210
DEG C, third section temperature is 200 DEG C, and head temperature is 200 DEG C；Mold is installed additional in the exit of double screw extruder, limits wire vent
Then diameter uses roller apparatus wrapping wire to collect silk material, obtains a diameter of 0.6mm silk materials；
5) 3D fused glass pellets：By silk material by nozzle heating and melting, under the control of the computer, nozzle is according to 3D models
Data be moved to designated position, by the mixture of molten condition squeeze gush out and finally solidification, successively accumulation formation most end form
Medical magnesium granules/lactic acid composite material of shape.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those skilled in the art within the technical scope disclosed by the invention, can without the variation that creative work is expected or
It replaces, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Subject to fixed protection domain.
Claims (9)
1. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material, it is characterised in that：This method includes following step
Suddenly：
1) magnesium granules are surface-treated：Magnesium granules are heat-treated using hydro-thermal method, heating temperature is 180~200 DEG C, when heating
Between be 1~5h, later take out be dried for standby；
2) magnesium granules are modified：The magnesium granules that step 1) is dried are mixed with titanate coupling agent aqueous solution, in magnesium after being sufficiently stirred
Particle surface uniform graft has titanate coupling agent, obtains modified magnesium granules；
3) prepared by mixture：By particles of polylactic acid by volume 1:20~1:6 are dissolved in tetrahydrofuran, and stirring makes polylactic acid
After grain is completely dissolved, it is added modified magnesium granules, the volume ratio of magnesium granules and polylactic acid is 1:100~1:3, after being sufficiently stirred
Polylactic acid uniform graft obtains mixture on magnesium granules surface after tetrahydrofuran completely volatilization；
4) at silk：The mixture that step 3) obtains is squeezed into filiform, obtains silk material；
5) increasing material manufacturing：Using silk material as raw material, the medical magnesium granules of shape or structure needed for the method preparation using increasing material manufacturing/
Lactic acid composite material.
2. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material as described in claim 1, feature exist
In：It takes out and is dried for standby after described in step 1), refer to heating 1~5h under conditions of temperature is 50~80 DEG C.
3. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material as described in claim 1, feature exist
In：The volumetric concentration of titanate coupling agent is 0.5~1.0% in titanate coupling agent aqueous solution described in step 2).
4. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material as described in claim 1, feature exist
In：It is 8~10r/ to have titanate coupling agent, stir speed (S.S.) in magnesium granules surface uniform graft after being sufficiently stirred described in step 2)
S, mixing time are 0.2~1.0h.
5. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material as described in claim 1, feature exist
In：Stirring described in step 3) makes particles of polylactic acid be completely dissolved, and the rate of stirring is 10~12r/s, and mixing time is 15~
24h。
6. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material as described in claim 1, feature exist
In：The rear polylactic acid that is sufficiently stirred described in step 3) is uniformly grafted on magnesium granules surface, and the rate of stirring is 10~15r/s,
Mixing time is 12~15h.
7. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material as described in claim 1, feature exist
In：The molecular weight of polylactic acid described in step 3) is 3~1,000,000.
8. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material as described in claim 1, feature exist
In：A diameter of 0.2~the 0.6mm of silk material described in step 4).
9. a kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material as described in claim 1, feature exist
In：The method of increasing material manufacturing described in step 5) refers to 3D fused glass pellet technologies：Silk material is melted again by nozzle heating
At mixture, under the control of the computer, nozzle is moved to designated position according to the data of 3D models, by the mixture of molten condition
It squeezes and gushes out and finally solidify, successively accumulates the medical magnesium granules/lactic acid composite material for forming final shape or structure.
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| CN201810351992.0A CN108624015A (en) | 2018-04-19 | 2018-04-19 | A kind of increasing material manufacturing method of medical magnesium granules/lactic acid composite material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111388757A (en) * | 2020-03-21 | 2020-07-10 | 哈尔滨工程大学 | Degradable magnesium-based composite material prepared from spiral magnesium wires |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552993A (en) * | 2011-11-15 | 2012-07-11 | 东南大学 | Magnesium alloy sheet-reinforced absorbable intrabony fixing composite material and preparation method thereof |
| CN103526194A (en) * | 2013-10-17 | 2014-01-22 | 重庆大学 | Method for performing silanization treatment on surfaces of magnesium and magnesium alloy |
| CN107266889A (en) * | 2017-07-31 | 2017-10-20 | 陕西理工大学 | A kind of conductive antibacterial 3D printing PLA silk materials and preparation method thereof of low melting point |
-
2018
- 2018-04-19 CN CN201810351992.0A patent/CN108624015A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552993A (en) * | 2011-11-15 | 2012-07-11 | 东南大学 | Magnesium alloy sheet-reinforced absorbable intrabony fixing composite material and preparation method thereof |
| CN103526194A (en) * | 2013-10-17 | 2014-01-22 | 重庆大学 | Method for performing silanization treatment on surfaces of magnesium and magnesium alloy |
| CN107266889A (en) * | 2017-07-31 | 2017-10-20 | 陕西理工大学 | A kind of conductive antibacterial 3D printing PLA silk materials and preparation method thereof of low melting point |
Non-Patent Citations (2)
| Title |
|---|
| 刘德宝等: ""镁/聚乳酸复合材料的制备与表征"", 《高分子材料科学与工程》 * |
| 卢向雨: ""AZ91D镁合金/环氧富镁涂层体系制备及其耐蚀性的研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111388757A (en) * | 2020-03-21 | 2020-07-10 | 哈尔滨工程大学 | Degradable magnesium-based composite material prepared from spiral magnesium wires |
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Application publication date: 20181009 |