CN106633734A - Preparation method for magnetic light-weight degradable material applied to three-dimension printing - Google Patents
Preparation method for magnetic light-weight degradable material applied to three-dimension printing Download PDFInfo
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- CN106633734A CN106633734A CN201710005806.3A CN201710005806A CN106633734A CN 106633734 A CN106633734 A CN 106633734A CN 201710005806 A CN201710005806 A CN 201710005806A CN 106633734 A CN106633734 A CN 106633734A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a preparation method for a magnetic light-weight degradable material applied to three-dimension printing. The method comprises the following steps: adding magnetic nano-sheets into epoxidized soybean oil, and conducting blending; under a nitrogen atmosphere of 40 DEG C, performing magnetic stirring and ultrasonic dispersion to form uniform magnetic nano-seriflux; mixing the magnetic nano-seriflux, polylactic acid, polyurethane elastomer rubber, epoxidized soybean oil acrylate and stearic acid in proportion, and extruding the mixture into filaments, so as to prepare a light-weight magnetic filament material. The material is light in weight, good in mechanical properties, and is a good magnetic material, and can meet the requirements of magnetic materials for a three-dimension printing design.
Description
Technical field
The invention belongs to 3D printing material manufacture technical field, relate to a kind of magnetic lightweight suitable for 3D printing can drop
The preparation method of solution material.
Technical background
3D printing technique is also called rapid shaping technique, and the technology does not need traditional Dao Ju ﹑ fixtures and lathe, with numeral
Based on model file, successively print to manufacture arbitrary shape article using the material with cohesive such as metal dust or plastics
Technology.The field that 3D printer can be manufactured is extensive, including Fei Hang Qi ﹑ weapons, and building Mo Xing ﹑ human organs and children play
Tool etc..However, the development of 3D printing technique is limited to a great extent the exploitation of 3D printing material.Therefore exploitation is more various
Multi-functional 3D printing material becomes the focus and key of future studies and application.The 3D printing material of the present invention is a kind of green wood
Material, has the performance of magnetic metal and plastics concurrently, with light weight, good toughness and degradable compared with traditional magnetic material
Advantage, prints for 3D desktops and provides more material materials.
Melted extrusion modeling shaping (FDM) technology is a kind of conventional technology of 3D printing, and this technology is polymerized using thermoplasticity
Thing in the molten state, from printing head extrusion, is then frozen into profile thin layer, then being formed by stacking in layer.Although light
Curing technology can also be used for the shaping of the associated materials comprising plastics, but its high cost, technique are complex, and can not beat
Print dark material；Thus at present FDM be most widely used, cheapest forming technique, the 3D printing prepared by the present invention
Magnetic lightweight silk material can be widely applied to FDM techniques.
At present, the technology for preparing silk material on market using composite is still less, and this is primarily due to as reinforcement
The fiber of agent or inorganic filler viscosity change larger due to size and melt easily cause greatly FDM type 3D printer spinning nozzles
Blocking and the coarse and defect on silk material surface.
The content of the invention
In order to solve problem present in background technology, the present invention proposes a kind of magnetic lightweight suitable for 3D printing can
The preparation method of degradable material so that the article for printing not only has good mechanical property and apparent property but also has
Magnetic, to meet various 3D printing demands.The present invention coats nano lamellar material using epoxidized soybean oil, using nano lubricating machine
Reason, significantly reduces the plug wire probability of material, reduces the possibility of the surface defect of printing silk material.
The technical solution adopted for the present invention to solve the technical problems is to comprise the steps of：
Step one：Magnetic Nano sheet material is added in epoxidized soybean oil and is mixed, under 40 DEG C of nitrogen atmospheres, passed through
Magnetic agitation and ultrasonic disperse form uniform magnetic Nano somaplasm liquid, and magnetic Nano sheet material and epoxidized soybean oil are according to mass ratio
For 1:2 ratio, magnetic Nano sheet material is mainly by nano nickel and nanometer ferrite with mass ratio 1:1 composition；Add epoxy big
The special ratios that soya-bean oil is adopted are prevented from the dispersion and oxidation of nano nickel and nanometer ferrite.
Step 2：By magnetic Nano somaplasm liquid, PLA, elastic polyurethane body rubber, epoxy soybean oil acrylate and
Stearic acid is proportionally put in three-dimensional material mixer carries out just mixing, is extruded into silk by screw extruder and prepares lightweight magnetic silk
Material, obtains product as magnetic lightweight degradation material of the present invention.
The PLA is serial from the PLA of Naturework, and the elastic polyurethane body rubber selects Bayer Bitterfeld GmbH
DP3491A。
In the step 2, the quality of magnetic Nano somaplasm liquid is the 2～5% of total prescription quality.
In the step 2, the quality of PLA is the 80～85% of total prescription quality.
In the step 2, elastic polyurethane body rubber be used for system toughness reinforcing, content be total prescription quality 5～
10%.
In the step 2, the quality of epoxy soybean oil acrylate is the 5～8% of total prescription quality, stearic acid ratio
For 2～5%.
By screw extruder in the step 2 be extruded into silk be 180～200 DEG C of temperature and screw speed be 75～
Carry out under the process conditions of 90r/min, so that magnetic of the epoxy soybean oil acrylate in magnetic Nano somaplasm liquid is received
Coating and interface transition layer are formed on rice sheet material.
It is embodied as prepares and be analyzed after test according to national standard after material of the present invention, is put into FDM types 3D and beats
Printed in print machine.
Existing magnetic 3D printing material on the market is only applicable to the laser sintering process of higher level in 3D printing technique,
The technology it is relatively costly and higher to printing technical requirements, and be not applied for FDM melt extruded technologies.And present invention system
Standby 3D printing material can be applied to the FDM melt extruded technologies that cost is lower, technical requirements are lower, and solve similar material
The problem of material easy plug wire in print procedure.
The present invention from stratified nano materials as filler, the dimensionally far smaller than size of spinning nozzle, stratiform in addition
Nano material may also function as lubrication in the forming process of 3D printing, reduce the generation of plug wire phenomenon.The present invention is by epoxy
Soybean oil acrylate is effectively introduced in material preparation process, for reducing the reunion of stratified nano materials and strengthening its boundary
Surface intensity.
The present invention, as matrix material, is had steady Wu Wei ﹑ heat Wu Du ﹑ using PLA (PLA) mainly due to PLA
Qualitative good, easy processing all meets requirement of the 3D printing technique to polymeric material, and polylactic acid raw material the advantages of transparent easy dyeing
It is degradable, it is generally acknowledged environment-friendly material.However, PLA fragility is stronger, elastic polyurethane body rubber is added in the present invention
Toughness reinforcing is carried out, to prepare the 3D printing material of good strength.
By selecting suitable degradable high polymer material, the magnetic nano sheet-shaped material to adding carries out pre- anti-the present invention
Should improve its Interface adhesive strength with macromolecular material, compound double screw extruder carry out response type Ji Chu ﹑ La Si ﹑ around
Disk, obtains the excellent degradable 3D printing material of mechanical property and hot property.
The magnetic lightweight degradation material prepared by the method is only passed than the weight of metal oxide magnetic material
30% or so of system ferrite magnetic material, its tensile strength is more than 40MPa, and elongation at break reaches 20～30%；Impact is strong
Degree is more than 30KJ/m2；Reach the mechanical property requirements of 3D printing material；Its magnetic strength 120～150kA/m of coercivity；Remanent magnetism 0.168
～0.281T；Maximum magnetic flux product can 9～13KJ/m3；It is good magnetic material, disclosure satisfy that the magnetic material that 3D printing is designed
Require, be especially adapted for use in the requirement of FDM melt extruded technologies.
The invention has the beneficial effects as follows：
(1) present invention is using conventional PLA, can natural degradation in the environment, be environment friendly material.
(2) 3D printing material made by the present invention has good toughness and impact strength, is printed by 3D printing technique
Product appearance high-quality out, impact strength are high, it is good to draw high intensity.
(3) present invention is mixed and made into magnetic material using magnetic Nano somaplasm liquid and PLA, makes product have magnetic, can
It is used in the multiple fields such as print magnetic instrument and toy.
(4) present invention can be applied to the FDM melt extruded technologies that cost is lower, technical requirements are lower.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into this
Bright scope is only limitted to example.In the case of without departing from said method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiments of the invention are as follows：
The magnetic Nano somaplasm liquid that below example is adopted is made in the following ways：
Will be mainly by nano nickel and nanometer ferrite with mass ratio 1:The magnetic Nano sheet material of 1 composition is according to mass ratio 1:
2 are added in epoxidized soybean oil and are mixed, and under 40 DEG C of nitrogen atmospheres, are formed uniformly by magnetic agitation and ultrasonic disperse
Magnetic Nano somaplasm liquid, it is standby.
Embodiment 1
Its component is calculated as by weight：
Specific implementation step is as follows,
Step 1：PLA is dried 8 hours under 50 degree, polyurethane elastomer is dried 8 hours at 80 DEG C.
Step 2:By batch mixer by PLA, elastic polyurethane body rubber, magnetic Nano somaplasm liquid, epoxidized soybean oil propylene
Acid esters, stearic acid are put in three-dimensional material mixer according to aforementioned proportion carries out just mixing.
Step 3：Just mixed material is added in the hopper of double screw extruder, is 90r/min in 185 DEG C and rotating speed
Under conditions of extrude the silk material of a diameter of 1.75mm.
Step 4：Above-mentioned silk material is put in FDM type 3D printers and is printed.Above-mentioned material is carried out into performance detection, is tied
Fruit is as follows：
| Detection project | Execution standard | Numerical value |
| Density (g/cm3) | GB4472-84 | 2.38 |
| Tensile strength (MPa) | GB/T1040-92 | 43 |
| Elongation at break (%) | GB/T 1040-92 | 30 |
| Impact strength (KJ/m2) | GB/T 1843-2008 | 38 |
| Magnetic strength coercivity (kA/m) | GB 11209-1989 | 120 |
| Remanent magnetism (T) | GB 11209-1989 | 0.168 |
| Maximum magnetic flux product can (KJ/m3) | GB 11209-1989 | 9 |
| 60 days degradation rates (%) | GB/T 29646-2013 | 30.3 |
Embodiment 2
Its component is calculated as by weight：
Specific implementation step is as follows,
Step 1：PLA is dried 8 hours under 50 degree, polyurethane elastomer is dried 8 hours at 80 DEG C.
Step 2:By batch mixer by PLA, elastic polyurethane body rubber, magnetic Nano somaplasm liquid, epoxidized soybean oil propylene
Acid esters, stearic acid are put in three-dimensional material mixer according to aforementioned proportion carries out just mixing.
Step 3：Just mixed material is added in the hopper of double screw extruder, is 90r/min in 200 DEG C and rotating speed
Under conditions of extrude the silk material of a diameter of 1.75mm.
Step 4：Above-mentioned silk material is put in FDM type 3D printers and is printed.Above-mentioned material is carried out into performance detection, is tied
Fruit is as follows：
Material is carried out into performance detection, it is as a result as follows：
| Detection project | Execution standard | Numerical value |
| Density (g/cm3) | GB4472-84 | 3.58 |
| Tensile strength (MPa) | GB/T1040-92 | 42 |
| Elongation at break (%) | GB/T 1040-92 | 20 |
| Impact strength (KJ/m2) | GB/T 1843-2008 | 31 |
| Magnetic strength coercivity (kA/m) | GB 11209-1989 | 150 |
| Remanent magnetism (T) | GB 11209-1989 | 0.281 |
| Maximum magnetic flux product can (KJ/m3) | GB 11209-1989 | 13 |
| 60 days degradation rates (%) | GB/T 29646-2013 | 31.4 |
Embodiment 3
Its component is calculated as by weight：
Specific implementation step is as follows,
Step 1：PLA is dried 8 hours under 50 degree, polyurethane elastomer is dried 8 hours at 80 DEG C.
Step 2:By batch mixer by PLA, elastic polyurethane body rubber, magnetic Nano somaplasm liquid, epoxidized soybean oil propylene
Acid esters, stearic acid are put in three-dimensional material mixer according to aforementioned proportion carries out just mixing.
Step 3：Just mixed material is added in the hopper of double screw extruder, is 85r/min in 190 DEG C and rotating speed
Under conditions of extrude the silk material of a diameter of 1.75mm.
Step 4：Above-mentioned silk material is put in FDM type 3D printers and is printed.Above-mentioned material is carried out into performance detection, is tied
Fruit is as follows：
Embodiment 4
Its component is calculated as by weight：
Specific implementation step is as follows,
Step 1：PLA is dried 8 hours under 50 degree, polyurethane elastomer is dried 8 hours at 80 DEG C.
Step 2:By batch mixer by PLA, elastic polyurethane body rubber, magnetic Nano somaplasm liquid, epoxidized soybean oil propylene
Acid esters, stearic acid are put in three-dimensional material mixer according to aforementioned proportion carries out just mixing.
Step 3：Just mixed material is added in the hopper of double screw extruder, is 75r/min in 180 DEG C and rotating speed
Under conditions of extrude the silk material of a diameter of 1.75mm.
Step 4：Above-mentioned silk material is put in FDM type 3D printers and is printed.Above-mentioned material is carried out into performance detection, is tied
Fruit is as follows：
| Detection project | Execution standard | Numerical value |
| Density (g/cm3) | GB4472-84 | 3.18 |
| Tensile strength (MPa) | GB/T1040-92 | 42 |
| Elongation at break (%) | GB/T 1040-92 | 21 |
| Impact strength (KJ/m2) | GB/T 1843-2008 | 30 |
| Magnetic strength coercivity (kA/m) | GB 11209-1989 | 126 |
| Remanent magnetism (T) | GB 11209-1989 | 0.183 |
| Maximum magnetic flux product can (KJ/m3) | GB 11209-1989 | 11 |
| 60 days degradation rates (%) | GB/T 29646-2013 | 34.2 |
Embodiment 5
Its component is calculated as by weight：
Specific implementation step is as follows,
Step 1：PLA is dried 8 hours under 50 degree, polyurethane elastomer is dried 8 hours at 80 DEG C.
Step 2:By batch mixer by PLA, elastic polyurethane body rubber, magnetic Nano somaplasm liquid, epoxidized soybean oil propylene
Acid esters, stearic acid are put in three-dimensional material mixer according to aforementioned proportion carries out just mixing.
Step 3：Just mixed material is added in the hopper of double screw extruder, is 75r/min in 190 DEG C and rotating speed
Under conditions of extrude the silk material of a diameter of 1.75mm.
Step 4：Above-mentioned silk material is put in FDM type 3D printers and is printed.Above-mentioned material is carried out into performance detection, is tied
Fruit is as follows：
| Detection project | Execution standard | Numerical value |
| Density (g/cm3) | GB4472-84 | 2.68 |
| Tensile strength (MPa) | GB/T1040-92 | 47 |
| Elongation at break (%) | GB/T 1040-92 | 28 |
| Impact strength (KJ/m2) | GB/T 1843-2008 | 36 |
| Magnetic strength coercivity (kA/m) | GB 11209-1989 | 122 |
| Remanent magnetism (T) | GB 11209-1989 | 0.170 |
| Maximum magnetic flux product can (KJ/m3) | GB 11209-1989 | 10 |
| 60 days degradation rates (%) | GB/T 29646-2013 | 30.9 |
Embodiment 6
Its component is calculated as by weight：
Specific implementation step is as follows,
Step 1：PLA is dried 8 hours under 50 degree, polyurethane elastomer is dried 8 hours at 80 DEG C.
Step 2:By batch mixer by PLA, elastic polyurethane body rubber, magnetic Nano somaplasm liquid, epoxidized soybean oil propylene
Acid esters, stearic acid are put in three-dimensional material mixer according to aforementioned proportion carries out just mixing.
Step 3：Just mixed material is added in the hopper of double screw extruder, is 85r/min in 185 DEG C and rotating speed
Under conditions of extrude the silk material of a diameter of 1.75mm.
Step 4：Above-mentioned silk material is put in FDM type 3D printers and is printed.Above-mentioned material is carried out into performance detection, is tied
Fruit is as follows：
| Detection project | Execution standard | Numerical value |
| Density (g/cm3) | GB4472-84 | 3.24 |
| Tensile strength (MPa) | GB/T1040-92 | 47 |
| Elongation at break (%) | GB/T 1040-92 | 29 |
| Impact strength (KJ/m2) | GB/T 1843-2008 | 37 |
| Magnetic strength coercivity (kA/m) | GB 11209-1989 | 134 |
| Remanent magnetism (T) | GB 11209-1989 | 0.248 |
| Maximum magnetic flux product can (KJ/m3) | GB 11209-1989 | 12 |
| 60 days degradation rates (%) | GB/T 29646-2013 | 32 |
As seen from the above-described embodiment, the present invention by selecting suitable degradable high polymer material, receive by the magnetic to adding
Rice flaky material carries out pre-reaction and improves its Interface adhesive strength with macromolecular material, and then obtains mechanical property and hot property
Excellent degradable 3D printing material.The magnetic lightweight degradation material prepared by the method and metal oxide magnetic material
Compare lightweight and flexible, be good magnetic material, the 3D printing requirement of FDM melt extruded technologies can be met.
Claims (8)
1. a kind of preparation method of the magnetic lightweight degradation material suitable for 3D printing, it is characterised in that comprise the steps of：
Step one：Magnetic Nano sheet material is added in epoxidized soybean oil and is mixed, under 40 DEG C of nitrogen atmospheres, by magnetic force
Stirring and ultrasonic disperse form uniform magnetic Nano somaplasm liquid, and magnetic Nano sheet material and epoxidized soybean oil are 1 according to mass ratio:
2 ratio, magnetic Nano sheet material is mainly by nano nickel and nanometer ferrite with mass ratio 1:1 composition；
Step 2：By magnetic Nano somaplasm liquid, PLA, elastic polyurethane body rubber, epoxy soybean oil acrylate and tristearin
Acid is put in three-dimensional material mixer according to special ratios carries out just mixing, then is extruded into silk preparation lightweight magnetic by screw extruder
Silk material.
2. the preparation method of a kind of magnetic lightweight degradation material suitable for 3D printing according to claim 1, it is special
Levy and be：The PLA is serial from the PLA of Naturework, and the elastic polyurethane body rubber selects Bayer Bitterfeld GmbH
DP3491A。
3. the preparation method of a kind of magnetic lightweight degradation material suitable for 3D printing according to claim 1, it is special
Levy and be：Composition quality percentage in the step 2 is respectively：PLA be 80～85%, polyurethane elastomer be 5～
10%, magnetic Nano somaplasm liquid is 2～5%, and epoxy soybean oil acrylate is 5～8%, and stearic acid is 2～5%.
4. the preparation method of a kind of magnetic lightweight degradation material suitable for 3D printing according to claim 1, it is special
Levy and be：By screw extruder in the step 2 be extruded into silk be 180～200 DEG C of temperature and screw speed be 75～
Carry out under the process conditions of 90r/min.
5. the preparation method of a kind of magnetic lightweight degradation material suitable for 3D printing according to claim 1, it is special
Levy and be：Before the mixing of the step 2, PLA is dried 8 hours at 50 DEG C, polyurethane elastomer is dried 8 at 80 DEG C
Hour.
6. a kind of magnetic lightweight degradation material suitable for 3D printing, it is characterised in that：The main quality hundred by following component
Fraction is mixed：PLA is 80～85%, and polyurethane elastomer is 5～10%, and magnetic Nano somaplasm liquid is 2～5%, ring
Oxygen soybean oil acrylate is 5～8%, and stearic acid is 2～5%.
7. a kind of magnetic lightweight degradation material suitable for 3D printing according to claim 6, it is characterised in that：Using
The arbitrary methods described of claim 1-5 is prepared from.
8. a kind of magnetic lightweight degradation material suitable for 3D printing according to claim 6, it is characterised in that：It is described
Material is used for the 3D printing technique of FDM melt extrudeds.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628192A (en) * | 2019-09-30 | 2019-12-31 | 苏州戴文勒斯新材料科技有限公司 | Electromagnetic shielding material based on 3D printing and preparation method thereof |
| CN111138833A (en) * | 2019-12-20 | 2020-05-12 | 东莞深圳清华大学研究院创新中心 | 3D printing magnetic thermoplastic polyurethane elastomer material and preparation method and application thereof |
| CN112194885A (en) * | 2020-10-10 | 2021-01-08 | 福建师范大学泉港石化研究院 | PLA3D printing composite material with paramagnetic performance and preparation method thereof |
| CN112375355A (en) * | 2020-11-23 | 2021-02-19 | 横店集团东磁股份有限公司 | Biodegradable magnetic sheet and preparation method thereof |
| CN114953248A (en) * | 2022-05-12 | 2022-08-30 | 华中科技大学 | Antibacterial type magnetic composite wire for 4D printing and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104441667A (en) * | 2015-01-06 | 2015-03-25 | 彭晓领 | 3D printing magnetic field orientation preparing method of plastic magnets |
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2017
- 2017-01-04 CN CN201710005806.3A patent/CN106633734B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104441667A (en) * | 2015-01-06 | 2015-03-25 | 彭晓领 | 3D printing magnetic field orientation preparing method of plastic magnets |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628192A (en) * | 2019-09-30 | 2019-12-31 | 苏州戴文勒斯新材料科技有限公司 | Electromagnetic shielding material based on 3D printing and preparation method thereof |
| CN111138833A (en) * | 2019-12-20 | 2020-05-12 | 东莞深圳清华大学研究院创新中心 | 3D printing magnetic thermoplastic polyurethane elastomer material and preparation method and application thereof |
| CN112194885A (en) * | 2020-10-10 | 2021-01-08 | 福建师范大学泉港石化研究院 | PLA3D printing composite material with paramagnetic performance and preparation method thereof |
| CN112375355A (en) * | 2020-11-23 | 2021-02-19 | 横店集团东磁股份有限公司 | Biodegradable magnetic sheet and preparation method thereof |
| CN114953248A (en) * | 2022-05-12 | 2022-08-30 | 华中科技大学 | Antibacterial type magnetic composite wire for 4D printing and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN106633734B (en) | 2018-09-28 |
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