CN112300552A - Degradable 3D printing consumable and preparation method thereof - Google Patents
Degradable 3D printing consumable and preparation method thereof Download PDFInfo
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- CN112300552A CN112300552A CN202011254306.1A CN202011254306A CN112300552A CN 112300552 A CN112300552 A CN 112300552A CN 202011254306 A CN202011254306 A CN 202011254306A CN 112300552 A CN112300552 A CN 112300552A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The invention relates to a degradable 3D printing consumable and a preparation method thereof. The degradable 3D printing consumable material comprises 60-99 parts of plastic raw materials, 10-20 parts of plant fiber powder, 2-10 parts of toughening agent, 2-5 parts of melt reinforcing agent, 0.5-3 parts of plastic foaming agent and 0.1-1 part of diffusion oil; the plant fiber powder is prepared by crushing plant fibers and then soaking the crushed plant fibers in a sodium hydroxide solution. The preparation method of the degradable 3D printing consumable comprises the following steps: and mixing the components according to a ratio, adding the components into an extruder to extrude and cut granules, drying the cut granules, and adding the dried cut granules into the extruder to extrude to obtain the degradable 3D printing consumable material. This degradable 3D printing consumables is guaranteeing easy degradation on the good basis of 3D printing consumables physical properties.
Description
Technical Field
The invention relates to the field of 3D printing consumables, in particular to a degradable 3D printing consumable and a preparation method thereof.
Background
3D prints one kind of rapid prototyping technique, can be based on digital model, and the technique of applying materials successive layer printing mode such as metal powder or plastics to construct the object is mature gradually, but along with natural environment is destroyed day by day, and renewable resource petroleum coal as the main source of polymer is more and more lost, and no plastify process is promoted, and degradable environmental protection material is becoming more and more important. At present, various different auxiliaries are added to various 3D printing consumables for compounding different plant fibers in the market, except for the fact that PLA (polylactic acid) as a main material can be degraded in a composting manner, the environment-friendly effect of the auxiliaries and the degradation of the compounded and added plant fibers is not considered. 3D printing consumables have the difficult problem of degrading. The plant fiber is mainly divided into three components, namely lignin, hemicellulose and cellulose, and a large number of hydrogen bonds exist in the three main components. Cellulose and lignin in the plant fiber are tightly bonded together, and the solvent can not be smoothly soaked into the plant fiber, so that the plant fiber is difficult to degrade.
Disclosure of Invention
When the plant fiber powder is used as a plastic polymer filler, the plant fiber powder has the advantages of high strength, natural and simple surface texture, bright color and novel texture, but the plant fiber is mainly divided into three main components, namely lignin, hemicellulose and cellulose, and the three main components all have a large number of hydrogen bonds. Cellulose and lignin in the plant fiber are tightly bonded together, and foreign substances cannot be smoothly immersed into the plant fiber, so that the 3D printing consumable material has the technical problem of difficult degradation.
In order to solve the technical problems, the invention provides a degradable 3D printing consumable and a preparation method thereof.
The invention provides a degradable 3D printing consumable, which comprises the following components in parts by weight: 60-99 parts of plastic raw material, 10-20 parts of plant fiber powder, 2-10 parts of toughening agent, 2-5 parts of melt reinforcing agent, 0.5-3 parts of plastic foaming agent and 0.1-1 part of diffusion oil; the plant fiber powder is prepared by crushing plant fibers and then soaking the crushed plant fibers in a sodium hydroxide solution.
Further, 0.1-2 parts of toner is also included.
Furthermore, the plastic raw material is one or more of polylactic acid, polybutylene succinate, polybutylene adipate/terephthalate and polycaprolactone.
Further, the toughening agent is one or more of polybutylene adipate/terephthalate, polybutylene succinate and ethylene-methyl acrylate-glycidyl methacrylate copolymer.
Further, the melt reinforcing agent is an acrylic copolymer containing epoxy functional groups.
Further, the plastic foaming agent is azodicarbonamide.
Further, the diffusion oil is silicone oil; and/or the toner is titanium dioxide.
Further, the plant fiber is pulverized to 10-200 μm.
Further, soaking the crushed plant fibers in a sodium hydroxide solution with the concentration of 1-2% according to the solid-liquid mass ratio of 3: 7-8.
The invention also provides a preparation method of the degradable 3D printing consumable, which comprises the following steps: and mixing the components according to a ratio, adding the components into an extruder to extrude and cut granules, drying the cut granules, and adding the dried cut granules into the extruder to extrude to obtain the degradable 3D printing consumable material.
Compared with the prior art, the invention has the advantages that: the invention comprises 60-99 parts of plastic raw material, 10-20 parts of plant fiber powder, 2-10 parts of toughening agent, 2-5 parts of melt reinforcing agent, 0.5-3 parts of plastic foaming agent and 0.1-1 part of diffusion oil; the plant fiber powder is prepared by crushing plant fibers and then soaking the crushed plant fibers in a sodium hydroxide solution; the toughening agent increases the toughness and viscosity of the composite material, the melt strength of the material is improved by the melt reinforcing agent, the mechanical property of the composite material is ensured, the diffusion oil has the function of lubricating the dispersion of plant fibers, the plant fiber powder is prepared by crushing the plant fibers, then soaking the plant fibers in a sodium hydroxide solution, crushing the plant fibers to enable the connection of cellulose, hemicellulose and lignin to become loose or even break, reducing the crystallinity of the cellulose, then soaking the plant fibers in the sodium hydroxide solution to enable the lignin to be decomposed into small molecules which can be dissolved by the solution, enabling hydrogen bonds of the cellulose, the hemicellulose and the lignin to break, greatly reducing the bonding between the cellulose and the lignin, enabling the cellulose to be exposed and better degraded, and combining other components, so that the material is easy to degrade on the basis of ensuring the good physical property of the 3D printing consumable.
Drawings
The features and advantages of the present invention will be more clearly understood by reference to the accompanying drawings, which are illustrative and not to be construed as limiting the invention in any way, and in which:
fig. 1 is a 3D printing consumable manufactured in embodiment 1 of the present invention.
Fig. 2 is a sample printed by the 3D printing consumable manufactured in embodiment 1 of the present invention.
FIG. 3 is a graph showing the degradation of example 1, comparative example 3 and example 2 of the present invention in a soil environment for 1 to 4 months.
Detailed Description
This embodiment provides a degradable 3D printing consumables, calculates according to part by weight, including the component: 60-99 parts of plastic raw material, 10-20 parts of plant fiber powder, 2-10 parts of toughening agent, 2-5 parts of melt reinforcing agent, 0.5-3 parts of plastic foaming agent, 0.1-1 part of diffusion oil and 0.1-2 parts of toner; the plant fiber powder is prepared by crushing plant fibers and then soaking the crushed plant fibers in a sodium hydroxide solution; the plastic raw material is one or more of polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate/terephthalate (PBAT) and Polycaprolactone (PCL); the toughening agent is one or more of poly (butylene adipate)/butylene terephthalate (preferably Flex-64D synthesized by Guangdong gold technology or C1200 of Basff), poly (butylene succinate) and ethylene-methyl acrylate-glycidyl methacrylate copolymer; the plastic foaming agent is azodicarbonamide; the melt reinforcing agent is an acrylic copolymer containing epoxy functional groups; the diffusion oil is silicone oil; the toner is titanium dioxide.
The degradable multi-plant fiber 3D printing supplies are printed with vivid plant effects and good mechanical properties after the toner is matched with colors. The amino in the azodicarbonamide provides amino under the environment of a certain temperature of compost and performs amination with plant fibers in the 3D printing consumable to accelerate the decomposition speed of the plant fibers in the natural environment, and the amino in the azodicarbonamide continues to destroy ester bonds between lignin and cellulose in the linear plant fibers through amination under the environment of the compost to form amine salts. The ammonium salt is a mycoprotein which can synthesize oil with non-protein compounds and microorganisms, and the degradation speed is improved by 50-70%.
Further, the plant fiber powder in the present embodiment is obtained by treating plant fibers as follows: flax, jute, bamboo fibre, coir, abaca, chaff, corn stalk, wheat straw, straw and fruit shell. The 3D printing consumable prepared from the plant fiber powder mainly containing straws is mostly yellow and black in color.
Furthermore, in the embodiment, the plant fiber is crushed to 10-200 μm, and then the crushed plant fiber is soaked in 1-2% sodium hydroxide solution for 24-28h according to the solid-liquid mass ratio of 3:7-8, and then the plant fiber powder is obtained by washing and drying.
The specific embodiment further comprises a preparation method of the degradable 3D printing consumable, which comprises the following steps: the components are mixed and added into a preheated double-screw extruder according to the proportion to be extruded and cut into granules at the temperature of 190 ℃ at 170 ℃, then the cut granules are dried and then added into a single-screw extruder to be extruded at the temperature of 200 ℃ at 180 ℃ at the temperature of 200 ℃ to obtain the degradable 3D printing consumable material, wherein the temperature of the single-screw extruder is higher than the temperature of the double-screw extruder.
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
Example 1
The embodiment provides a degradable multi-plant fiber 3D printing consumable, which is prepared from the following components in parts by weight:
50 parts of PLA and 20 parts of PBAT, then adding 0.5 part of diffusion oil for mixing, then adding 1 part of azodicarbonamide (azodicarbonamide purchased from Sumitomo corporation, Japan), 10 parts of plant fiber powder, 0.1 part of toner, 2 parts of polybutylene succinate and 2 parts of melt reinforcing agent (acrylic copolymer containing epoxy functional groups) for uniform mixing, then adding a preheated double-screw extruder, and carrying out extrusion and grain cutting at 190 ℃; and then drying the obtained particles in a dehumidifying dryer for 4H, adding the dried particles into a single-screw extruder, and drawing at 200 ℃ to obtain the 3D printed line, wherein the 3D printed line is shown in figure 1.
The plant fiber powder in the embodiment is obtained by processing a mixture of flax, jute, chaff and straw, and specifically, the flax, jute, chaff and straw are crushed to 10-200 mu m by a crusher, and then the crushed mixture is soaked in a sodium hydroxide solution with the concentration of 1-2% for 24h according to the solid-liquid mass ratio of 3:7 to obtain the plant fiber powder.
The resulting sample printed by the 3D printer through the 3D printed lines in this example is shown in fig. 2.
Example 2
The embodiment provides a degradable multi-plant fiber 3D printing consumable, which is prepared from the following components in parts by weight:
60 parts of PCL and 10 parts of PBS (the PBS in the example is FD92 synthesized by Mitsubishi), 1 part of diffusion oil is added for mixing, 2 parts of azodicarbonamide (purchased from Sumitomo corporation), 20 parts of plant fiber, 0.1 part of color, 5 parts of poly (adipic acid)/butylene terephthalate (Flex-64D synthesized by Guangdong gold technology and 4 parts of melt reinforcing agent (acrylic copolymer containing epoxy functional group) are added for uniform mixing, then a preheated double-screw extruder is added for extrusion and granulation at 70 ℃, the obtained particles are dried for 2H in a dehumidifying dryer, then a single-screw extruder is added, and the wires are drawn at 80 ℃ to prepare the 3D printed wire.
The plant fiber powder in the embodiment is obtained by processing flax, specifically, the flax is crushed to 10-200 μm by a crusher, and then the crushed flax is soaked in a sodium hydroxide solution with the concentration of 1% for 26h according to the solid-liquid mass ratio of 3:7 to obtain the plant fiber powder.
Example 3
The embodiment provides a degradable multi-plant fiber 3D printing consumable, which is prepared from the following components in parts by weight:
60 parts of PCL and 10 parts of PBS (the PBS in this example is FD92 synthesized by Mitsubishi), 1 part of diffusion oil is added and mixed, then 2 parts of azodicarbonamide (purchased from Sumitomo corporation), 20 parts of vegetable fiber, 0.1 part of toner, 10 parts of ethylene-methyl acrylate-glycidyl methacrylate copolymer and 5 parts of melt reinforcing agent (acrylic copolymer containing epoxy functional group) are added and mixed uniformly, and then a preheated double screw extruder is added and extrusion granulation is carried out at 170 ℃; and then drying the obtained particles in a dehumidifying dryer for 2H, adding the particles into a single-screw extruder, and drawing at 180 ℃ to obtain the 3D printing line.
The plant fiber powder in the embodiment is obtained by treating flax, specifically, a mixture of coconut fiber, abaca, chaff and corn stalk is crushed to 10-200 μm by a crusher, and then the crushed mixture is soaked in a sodium hydroxide solution with the concentration of 2% for 24h according to the solid-liquid mass ratio of 3:8 to obtain the plant fiber powder.
Comparative example 1
The 3D printing consumable prepared by this comparative example is substantially the same as the composition and preparation method of example 1, except that: the plant fiber is crushed to more than 400 mu m and is not soaked by sodium hydroxide.
Comparative example 2
The 3D printing consumable prepared by this comparative example is substantially the same as the composition and preparation method of example 1, except that: no component azodicarbonamide was added.
Comparative example 3
The 3D printing consumable prepared by this comparative example is substantially the same as the composition and preparation method of example 1, except that: crushing the plant fiber to over 400 mu m without soaking in sodium hydroxide; in addition, no azodicarbonamide is added as a component.
The 3D printing consumables prepared in example 2 and comparative example 3 of example 1 were placed in soil and naturally degraded by fungi in the soil for 4 months, and as a result, as shown in fig. 3, the degradation rates of the 3D printing consumables prepared in example 1, comparative example 3 and example 2 were shown from top to bottom, respectively, and it was found that the degradation rates of example 1 and example 2 were significantly faster than that of comparative example 3, and the 3D printing consumables prepared in example 1 and example 2 were significantly completely degraded after 4 months of degradation, while the 3D printing consumables prepared in comparative example 3 were hardly degraded.
Physical property tests were conducted on the above examples 1 to 3 and comparative examples 1 to 3, and the test results are shown in tables 1 and 2.
TABLE 1 Performance test results of 3D printing consumables prepared in examples 1 to 3
TABLE 2 Performance test results of 3D printing consumables prepared in comparative examples 1 to 3
In the performance tests of the above examples and comparative examples, which were both performed in the same open room temperature, the printing temperatures using the same 3D printer were all: 190-200 ℃, the temperature of the bottom plate is 60 ℃, the printing speed is 55mm/s, and the idle running speed of the nozzle is 150 mm/s. The bottom plate of the printer is a glass bottom plate, the size of a printed object is 20CM by 20CM, and the printed object is filled with 40% of cubes. The height of the plane of the four sides and corners of the cube touching the glass substrate is averaged and the substrate adhesion is rated as good if the average is less than 0.5 MM. If the face of the cube adhered to the bottom plate has a gap, the cube cracks, and the cube is determined to be layered regardless of the size. As can be seen from tables 1 and 2, the physical properties of the 3D printing consumables proposed by the present invention are significantly superior to those of the 3D printing consumables in the comparative examples.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The degradable 3D printing consumable is characterized by comprising the following components in parts by weight: 60-99 parts of plastic raw material, 10-20 parts of plant fiber powder, 2-10 parts of toughening agent, 2-5 parts of melt reinforcing agent, 0.5-3 parts of plastic foaming agent and 0.1-1 part of diffusion oil; the plant fiber powder is prepared by crushing plant fibers and then soaking the crushed plant fibers in a sodium hydroxide solution.
2. The degradable 3D printing consumable of claim 1, further comprising 0.1-2 parts of toner.
3. The degradable 3D printing consumable of claim 1, wherein the plastic material is one or more of polylactic acid, polybutylene succinate, polybutylene adipate/terephthalate and polycaprolactone.
4. The degradable 3D printing consumable of claim 1, wherein the toughening agent is one or more of polybutylene adipate/terephthalate, polybutylene succinate, and ethylene-methyl acrylate-glycidyl methacrylate copolymer.
5. The degradable 3D printing consumable of claim 1, wherein the melt enhancer is an acrylic copolymer containing epoxy functional groups.
6. The degradable 3D printing consumable of claim 1, wherein the plastic foaming agent is azodicarbonamide.
7. The degradable 3D printing consumable of claim 1, wherein the diffusion oil is silicone oil.
8. The degradable 3D printing consumable according to claim 1, wherein the plant fiber is pulverized to 10-200 μm.
9. The degradable 3D printing consumable according to claim 1, wherein the crushed plant fiber is soaked in a sodium hydroxide solution with a concentration of 1% -2% according to a solid-liquid mass ratio of 3: 7-8.
10. A method of preparing a degradable 3D printing consumable according to any one of claims 1 to 9, comprising: and mixing the components according to a ratio, adding the components into an extruder to extrude and cut granules, drying the cut granules, and adding the dried cut granules into the extruder to extrude to obtain the degradable 3D printing consumable material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672616A (en) * | 2015-03-16 | 2015-06-03 | 深圳市光华伟业实业有限公司 | Woody 3D printing line |
| CN105907069A (en) * | 2016-07-06 | 2016-08-31 | 威海两岸环保新材料科技有限公司 | Plant powder modified polylactic acid 3d printing material and preparation method thereof |
| CN110240779A (en) * | 2019-06-28 | 2019-09-17 | 盐城工学院 | A kind of high-precision is without plug type stalk FDM 3D printing consumptive material and preparation method thereof |
| CN111574813A (en) * | 2019-06-11 | 2020-08-25 | 南京林业大学 | Polylactic acid-based biomass composite material and 3D printing forming thereof |
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2020
- 2020-11-11 CN CN202011254306.1A patent/CN112300552A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672616A (en) * | 2015-03-16 | 2015-06-03 | 深圳市光华伟业实业有限公司 | Woody 3D printing line |
| CN105907069A (en) * | 2016-07-06 | 2016-08-31 | 威海两岸环保新材料科技有限公司 | Plant powder modified polylactic acid 3d printing material and preparation method thereof |
| CN111574813A (en) * | 2019-06-11 | 2020-08-25 | 南京林业大学 | Polylactic acid-based biomass composite material and 3D printing forming thereof |
| CN110240779A (en) * | 2019-06-28 | 2019-09-17 | 盐城工学院 | A kind of high-precision is without plug type stalk FDM 3D printing consumptive material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 雷文编著: "《材料成型与加工实验教程（第1版）》", 31 May 2017, 东南大学出版社 * |
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