CN110240779B - High-precision non-plug straw FDM 3D printing consumable and preparation method thereof - Google Patents
High-precision non-plug straw FDM 3D printing consumable and preparation method thereof Download PDFInfo
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- CN110240779B CN110240779B CN201910573122.2A CN201910573122A CN110240779B CN 110240779 B CN110240779 B CN 110240779B CN 201910573122 A CN201910573122 A CN 201910573122A CN 110240779 B CN110240779 B CN 110240779B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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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- 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
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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Abstract
The invention discloses a high-precision non-plug straw FDM 3D printing consumable and a preparation method thereof, wherein the consumable consists of the following components: 25-85 parts of high molecular raw materials; 15-75 parts of straw powder; 0-5 parts of a toughening agent; 0-5 parts of a compatilizer; 0.1-1 part of antioxidant; 0-1 part of a lubricant; 0-1 part of toner; the preparation method comprises the following steps: (1) soaking selected straws in alkaline solution, centrifuging, drying, adding ethanol solution dispersed by compatilizer, and drying; (2) weighing raw materials according to the proportion, and uniformly mixing the raw materials by using a mixer; (3) putting the mixed materials into a double-screw extruder to be extruded into strips, and cooling, air-drying and granulating the strips to prepare granules; (4) and (3) putting the granules into a 3D printing consumable single-screw extruder to be extruded into filaments, cooling, drying by a fan, pulling strips, and winding into a disc by a winding machine to obtain the finished product. The invention has the advantages of wide raw material source, precise wire diameter, smooth surface, stable discharge and no plugging phenomenon in the printing process in the extrusion and wire drawing process of the prepared consumable material, and no burr and raised edge of the printed product.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a high-precision plug-free FDM 3D printing consumable and a preparation method thereof.
Background
The 3D printing technique is a method of manufacturing a solid part by stacking materials layer by layer based on data information of a three-dimensional model. The 3D printing technology available at present has nearly 20, wherein Fused Deposition Modeling (FDM) is the most commonly used, and is invented by Americans in 1988, and the printer has the advantages of simple structure, convenience in operation, high molding speed, abundant material types, low cost, environmental friendliness and the like, so that the printer is applied to the fields of automobile manufacturing, aviation, medical treatment, food processing, biomedicine, teaching, artware, buildings and the like, and is one of the 3D printing technologies which have the widest application field, the highest maturity, the largest application value and the widest prospect at present.
The FDM technology, as a non-laser-formed manufacturing system, has the greatest advantage that almost all common plastics, mainly ABS, PLA, PC/ABS, paraffin and polyester, can be used for printing. FDM uses filiform thermoplastic material as raw material, and can use powdered metal or adhesive material such as crop straw, etc. to make filiform material supply, and the material is heated and melted in the spray head. The spray head moves along the section profile and the filling track of the part, and simultaneously extrudes the molten material, and the material is quickly solidified and bonded with the surrounding material.
The foreign FDM technology is more mature than the domestic technology, the precision of a formed part is high, the thinnest wall thickness of the formed part can reach 0.4mm, the industrial requirement can be met, the application field is wider, the equipment cost is higher and is almost 4 times of that of domestic equipment, the price of printing materials is both customized and researched aiming at the equipment, and the price of the materials is more than 10 times of that of the domestic materials. Domestic industrial grade 3D printing apparatus has all needed further promotion in many aspects such as material quality, printing precision except that the cost is lower. At present, although the FDM 3D printing technology is popularized fast in China, the FDM 3D printing technology is mainly used for experimental teaching and handicraft manufacturing, and large-scale practical application is difficult to carry out. Raw materials, quality and price are still major factors that restrict the development of 3D printing.
The crop straw is a crop residue rich in fiber components left after the harvest of seeds, mainly comprises beans, hemps, potatoes, cereals, oil plants, straws of crops such as sugarcane, cotton, melons, fruits, tobacco and the like, is a main byproduct of the crops, is large in quantity, and is a renewable biological resource with multiple purposes. The crop straw resources in China are basically in the current situations of high pollution, high consumption and low yield, most of the crop straws are discarded or burned, and reasonable development and utilization cannot be achieved. The comprehensive application of the crop straw resources has important significance for protecting the environment, saving the resources, increasing the income, promoting the sustainable development of agriculture and the like. The new material of straw in 3D prints not only can solve peasant income problem of peasant, the environmental protection, can also obtain the new material that 3D printed after processing is retrieved, can show the cost that reduces 3D and print like this. The daily necessities such as wood grain tableware and flower vase can be printed by processing the raw materials such as the straws, the product produced by 3D printing of the crop straws has the texture of natural plant color and the unique faint scent of the straws, so that the printed product has more wood texture, is not only practical, but also has ornamental value, and the crop straws are used as the 3D printed material, are green and environment-friendly, and have very wide application prospect in the future.
However, the existing straw 3D printing material mainly solves the problems of corrosion resistance, size, mechanical properties and mechanical properties, such as high bending strength, high heat deformation temperature, high elongation at break and the like, and is a single straw, and most materials still have the problems of easy breakage, end blockage, low precision and the like of extruded materials in the printing process.
Disclosure of Invention
Aiming at the defects of the existing problems, the invention aims to provide a high-precision 3D printing consumable which has no broken line in the extrusion process and has no warping, burr and plug in the printing process. In the extrusion and wire drawing process of the prepared consumable, the wire diameter is accurate, the surface is smooth, and the high polymer straws are uniformly mixed; in the printing process, the discharging is stable without the phenomenon of an end cap, and the printed product has no burr and edge warping; tests show that the prepared consumable material has improved impact strength, tensile strength and bending strength.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high-precision non-plug straw FDM 3D printing consumable consists of the following components in parts by mass:
25-85 parts of high molecular raw materials;
15-75 parts of straw powder;
0.1-5 parts of a toughening agent;
0.1-5 parts of a compatilizer;
0.1-1 part of antioxidant;
0.1-1 part of lubricant;
0-1 part of toner.
In a preferred embodiment of the present invention, the polymer material is polyvinyl alcohol, polylactic acid (PLA), polyethylene, polypropylene (PP), acrylonitrile-styrene copolymer, acrylonitrile-acrylate-styrene, acrylonitrile-butadiene-styrene (ABS), polyphenylsulfone, polyethersulfone, polyimide, liquid crystal polymer, polyetheretherketone, polyphenylene sulfide, polyethylene terephthalate-1, 4-cyclohexanedimethanol, polymethyl methacrylate, polybutylene succinate, polycaprolactone, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polyamide-imide, polyetherimide, polysulfone, polyetherketoneketone, polyetherketone, polyphenylene oxide, polyethylene terephthalate-1, 4-cyclohexanedimethanol, polyvinyl chloride, polyalkyl acrylate, poly (vinyl acetate), poly (vinyl ether-co-styrene), poly (vinyl ether-co-styrene), poly (ethylene-co-styrene), poly (ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co-ethylene-co, At least one of polyformaldehyde, polybutylene terephthalate, nylon and polystyrene.
As a preferred technical solution of the present application, the toughening agent is at least one of EVA, PU, TPO, TPE, TPV, TPU, TPEE, TPR, acrylate bifunctional ethylene-based elastomer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, silicone rubber, ACR, ABS high rubber powder, SEPS, SBS, PBE, grafted POE, ethylene-methyl acrylate-glycidyl methacrylate random copolymer, EMA, MBS, SOE, SIS, SEBS, EPDM, and POE.
As a preferred technical scheme of the application, the compatilizer is at least one of an aluminate coupling agent, a silane coupling agent, a titanate coupling agent and a maleic anhydride graft.
As a preferable technical scheme of the application, the antioxidant is at least one of sulfuric acid esters, hindered amines, phosphorous acid esters and hindered phenols.
In a preferred embodiment of the present invention, the lubricant is at least one of waxes, silicones, amides, and stearic acid.
As a preferred technical scheme of the application, the straw powder needs to be processed by the following steps: the straw is dried, ground, crushed and screened to obtain straw powder with the size of more than 200 meshes.
The preparation method of the high-precision non-plug straw FDM 3D printing consumable comprises the following steps:
(1) crushing and sieving selected straws, soaking the straws in an alkaline solution, centrifugally drying the straws, adding an ethanol solution dispersed by a compatilizer, and drying the straws to obtain straw powder;
(2) weighing the raw materials of each component according to the proportion, and uniformly mixing the raw materials by using a mixer;
(3) putting the mixed materials into a double-screw extruder to be extruded into strips, and preparing high-precision non-plug straw FDM 3D printing consumable material granules through cooling, air drying and grain cutting;
(4) the cut granules are put into a single-screw extruder of the 3D printing supplies to be extruded into wires, the wires are cooled by a water tank, a fan is dried, a pulling strip is pulled, a winding machine is wound into a disc, and the high-precision non-plug straw type FDM 3D printing supplies are manufactured.
As a preferred technical scheme of the application, the specific steps of the step (1) are as follows: crushing and grinding selected straws through a 200-mesh and 300-mesh sieve to prepare powder, soaking the powder in a strong base solution with the concentration of 3% for 0.5h, centrifugally washing, adding a mixed solution prepared from a compatilizer and a 95% ethanol-water solution, stirring for 0.5h, drying in a 120 ℃ oven for 5h, and grinding to obtain straw powder; and (3) mixing the weighed raw materials at a high speed for 5-10min to obtain the experimental raw materials with uniform components.
As a preferred technical scheme of the application, in the step (3), the machine temperature zone of the double-screw extruder is set to be 190-240 ℃.
As a preferred technical scheme of the application, in the step (4), the temperature of the melting extrusion of the single-screw extruder for the 3D printing consumables is 190-240 ℃.
As a preferable technical scheme of the application, in the step (4), the diameter of the wire rod is adjusted through the processes of traction, diameter measurement and wire storage of the cooled and solidified wire rod through the rotating speed of the screw rod and the running speed of the traction machine, and the diameter range of the wire rod is 1.73-1.77 mm; the screw rotating speed is 90-200rpm, and the traction machine rotating speed is 120-250 rpm.
Advantageous effects
Compared with the prior art, the invention has the following beneficial effects: 3D printing is combined with straw materials, so that waste of crop straw biomass resources and environmental pollution are reduced, the cost of the materials is reduced, the environment is protected, and high-valued, cyclic and renewable and comprehensive utilization of the crop straw biomass resources are improved; in the aspect of 3D printing, the raw and other materials sources are extensive, reduce overall manufacturing cost to the extrusion wire drawing process of the consumptive material of preparing, the line footpath is accurate, and the surface is smooth, and polymer straw misce bene prints the stable no choke plug phenomenon of process ejection of compact, prints the product burr-free, the condition on stick up the limit, and the consumptive material of preparing all improves to some extent in impact, tensile and bending strength performance.
Usually, the addition of straw powder inevitably affects the printing smoothness of the high polymer material: straw particles are easy to accumulate at the spray head, so that the printer cannot print, and when straw fusion materials are uneven, the situation that the material is unevenly spouted by the printing head to cause burrs and faults can be caused. According to the invention, the elastomer toughening agent is selected, so that the straw 3D printing consumable material is not broken in the wire drawing process, the toughening agent and the base material uniformly wrap straw particles by blending the proportion of the toughening agent and the compatilizer, the melt flow rate of the material is stabilized at 10-30g/10min, a better printing range is provided, the product made of the 3D printing consumable material has no burr and fault choke plug, and high-precision printing is realized.
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instruments used are not indicated by manufacturers, and are regarded as conventional products which can be purchased in the market.
Example 1
(1) The experimental materials are prepared according to the following component ratio: ABS 757: 25kg, antioxidant 1010: 0.025Kg, antioxidant 168: 0.05kg, lubricant TAS-2A: 0.075kg, aluminate coupling agent: 0.15Kg, straw powder: 5kg, SBS: 3Kg, red toner: 0.1 kg.
(2) The straw powder is pretreated: crushing and grinding selected straws, sieving the crushed straws with a 200-mesh sieve to obtain powder, soaking the powder in a 3% NaOH solution for 0.5h, centrifugally washing, adding a mixed solution prepared from an aluminate coupling agent and a 95% ethanol-water solution, stirring for 0.5h, drying in a 120 ℃ oven for 5h, and grinding to obtain straw powder. And (3) mixing the weighed raw materials at a high speed for 10min to obtain the experimental raw materials with uniform components.
(3) And (3) extruding the obtained raw materials by a double-screw high-temperature melting extruder, setting the temperature of a machine temperature zone to be 210 plus 240 ℃, drawing the experimental materials into strips, cooling with cold water, drying with a blower, and pelletizing by a machine to obtain uniform and full pellets.
(4) And (3) placing the obtained granules into a 3D printing single-screw consumable extruder for melt extrusion, wherein the temperature of 6 sections of temperature zones is 235 ℃, 240 ℃, 235 ℃, 230 ℃.
(5) And cooling the material strips extruded, mixed and melted by the machine head through a cold water tank.
(6) And (3) the cooled and solidified material wire is subjected to the processes of traction, diameter measurement and wire storage, the diameter of the wire is adjusted through the rotating speed of the screw and the running speed of the traction machine, and the diameter range of the wire is 1.73-1.77 mm. The screw speed was 200rpm and the tractor speed was 250 rpm.
(7) And winding the consumables with qualified wire diameter into a disc, wherein the winding length is 225m, and the weight of each disc of wire is 1 kg.
(8) And carrying out vacuum packaging on the wound consumable material by using a vacuum packaging machine to obtain the consumable material.
Example 2
(1) The experimental materials are prepared according to the following component ratio: PLA 4032D: 50kg, antioxidant 1076: 0.05Kg, antioxidant 1098: 0.1kg, silane coupling agent KH 560: 0.5Kg, straw: 10kg, TPU: 8Kg, lubricant EBS: 0.5 Kg.
(2) The straw powder needs to be pretreated: crushing selected straws, grinding the straws to pass through a 250-mesh sieve to obtain powder, putting the powder into a 3% KOH solution, soaking for 0.5h, centrifugally washing, putting a mixed solution prepared from a compatilizer KH560 and a 95% ethanol-water solution, stirring for 0.5h, putting the mixed solution into a 120 ℃ oven, drying for 5h, and grinding to obtain straw powder. And (3) mixing the weighed raw materials at a high speed for 5min to obtain the experimental raw materials with uniform components.
(3) And (3) putting the uniformly mixed materials into a double-screw extruder for extrusion, setting the heating area at 200-210 ℃, extruding at the temperature, cooling by cooling water, air-drying by a fan, and granulating by a machine to prepare the straw PLA material particles.
(4) And (3) placing the obtained granules into a 3D printing single-screw consumable extruder for melt extrusion, wherein the temperature of the 6-section temperature zone is 190 ℃, 200 ℃, 205 ℃, 200 ℃ and 200 ℃.
(5) Cooling the extruded strand, drawing, measuring the diameter and storing the strand, setting the rotation speed of a screw at 120rpm, setting the rotation speed of a drawing machine at 160rpm, and controlling the diameter of the strand to be 1.74-1.76 mm.
(6) And winding the consumables with qualified wire diameter into a disc, wherein the winding length is 225m, and the weight of each disc of wire is 1 kg.
(7) And carrying out vacuum packaging on the wound consumable material by using a vacuum packaging machine to obtain the consumable material.
Example 3
(1) The experimental materials are prepared according to the following component ratio: PP CJS-700: 50kg, antioxidant 616: 0.06Kg, antioxidant 317: 0.1kg, lubricant EBS: 0.15kg, silane coupling agent KH 550: 0.3Kg, straw: 15kg, EVA 630: 8 Kg.
(2) The straw powder is pretreated: crushing selected straws, grinding the straws to pass through a 300-mesh sieve to obtain powder, soaking the powder in a 3% KOH solution for 0.5h, centrifugally washing, adding a mixed solution prepared from a compatilizer KH550 and a 95% ethanol-water solution, stirring for 0.5h, drying in a 120 ℃ oven for 5h, and grinding to obtain straw powder. And (3) mixing the weighed raw materials at a high speed for 5min to obtain the experimental raw materials with uniform components.
(3) Extruding the obtained raw materials by a double-screw high-temperature melting extruder, setting the temperature of a machine temperature zone to be 190-.
(4) And melting and extruding the obtained granules in a 3D printing single-screw consumable extruder, wherein the temperature of 6 sections of temperature zones is 190 ℃, 190 ℃ and 190 ℃.
(5) And cooling the material strips which are extruded, mixed and melted by the machine head through a cold water tank, wherein the temperature of cooling water is set to be 25 ℃.
(6) And (3) the cooled and solidified material wire is subjected to the processes of traction, diameter measurement and wire storage, the diameter of the wire is adjusted through the rotating speed of the screw and the running speed of the traction machine, and the diameter range of the wire is 1.74-1.76 mm. The screw speed was 90rpm and the tractor speed was 120 rpm.
(7) And (3) winding the consumables with qualified wire diameter into a disc, wherein the winding length is 222m, and the weight of each disc of wire is 1 kg.
(8) And (5) carrying out vacuum packaging on the wound consumable material by using a vacuum packaging machine to obtain the consumable material finally.
Effect testing
The 3D printing consumables of examples 1-3 were tested for performance and the results are shown in the following table:
TABLE 1 3D printing supplies Performance testing of examples 1-3
| Item | Test standard | Unit | Test conditions | Number 123 |
| Tensile strength | ISO527 | MPa | 50mm/min | 50.3，34.7，25.8 |
| Bending strength | ISO178 | MPa | 50mm/min | 67.6，43.3，32.4 |
| Impact strength | ISO180 | KJ/m 2 | 4.0mm,23 ℃ | 28.5，5.9，13.2 |
| Melt index | ISO1133 | g/10min | 2.16kg | 16.4，14.6，16.1 |
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art are intended to be included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is to be protected by the following claims.
Claims (1)
1. A preparation method of high-precision non-blocking straw FDM 3D printing supplies is characterized by comprising the following steps:
(1) the experimental materials are prepared according to the following component ratio: ABS 757: 25kg, antioxidant 1010: 0.025Kg, antioxidant 168: 0.05kg, lubricant TAS-2A: 0.075kg, aluminate coupling agent: 0.15Kg, straw powder: 5kg, SBS: 3Kg, red toner: 0.1 kg;
(2) the straw powder is pretreated: crushing selected straws, grinding the straws through a 200-mesh sieve to prepare powder, putting the powder into a 3% NaOH solution to be soaked for 0.5h, centrifugally washing the powder, putting a mixed solution prepared from an aluminate coupling agent and a 95% ethanol-water solution, stirring the mixed solution for 0.5h, putting the mixed solution into a 120 ℃ oven to be dried for 5h, grinding the mixed solution to obtain straw powder, and mixing the weighed raw materials at a high speed for 10min to obtain an experimental raw material with uniform components;
(3) extruding the obtained raw materials by a double-screw high-temperature melting extruder, setting the temperature of a machine temperature zone to be 210-240 ℃, drawing strips on experimental materials, cooling with cold water, drying by a blower, and granulating by the machine to obtain uniform and full granules;
(4) melting and extruding the obtained granules in a 3D printing single-screw consumable extruder, wherein the temperature of 6 sections of temperature zones is 235 ℃, 240 ℃, 235 ℃ and 230 ℃;
(5) cooling the material strips extruded, mixed and melted by the machine head through a cold water tank;
(6) after the cooled and solidified material wires are subjected to the processes of traction, diameter measurement and wire storage, the diameter of the wire is adjusted through the rotating speed of a screw and the operating speed of a traction machine, the diameter range of the wire is 1.73-1.77mm, the rotating speed of the screw is 200rpm, and the rotating speed of the traction machine is 250 rpm;
(7) winding the consumables with qualified wire diameter into a disc, wherein the winding length is 225m, and the weight of each disc of wire is 1 kg;
(8) and carrying out vacuum packaging on the wound consumable material by using a vacuum packaging machine to obtain the consumable material.
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| CN112123620B (en) * | 2020-09-15 | 2021-07-16 | 瑞年科技(广东)有限公司 | Preparation process of polypropylene composite material film based on bio-based wheat straw |
| CN112300552A (en) * | 2020-11-11 | 2021-02-02 | 深圳市华海天贸科技有限公司 | Degradable 3D printing consumable and preparation method thereof |
| CN112670879B (en) * | 2020-12-28 | 2023-12-08 | 国网河南省电力公司超高压公司 | SF6 gas plugging process for high-voltage combined electrical apparatus |
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| CN110240779A (en) | 2019-09-17 |
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