CN108047708B - Preparation method of long-chain nylon composite material for 3D printing - Google Patents

Preparation method of long-chain nylon composite material for 3D printing Download PDF

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CN108047708B
CN108047708B CN201711465741.7A CN201711465741A CN108047708B CN 108047708 B CN108047708 B CN 108047708B CN 201711465741 A CN201711465741 A CN 201711465741A CN 108047708 B CN108047708 B CN 108047708B
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zone
coupling agent
wollastonite
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CN108047708A (en
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李振
茅伟华
王立根
颜岩
梁雪娇
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North Berry New Material Technology (suzhou) Co Ltd
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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08K2201/016—Additives defined by their aspect ratio
    • 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
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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

Abstract

The invention relates to a preparation method of a long-chain nylon composite material for 3D printing, which comprises the following steps: preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 5-10 parts of kevlar chopped fiber, 5-15 parts of wollastonite, 0.1-0.3 part of coupling agent, 3-8 parts of toughening agent, 0.5-1 part of hyperbranched resin and 0.2-1 part of antioxidant; spraying a coupling agent solution while stirring wollastonite, drying and cooling; uniformly mixing coupling agent modified wollastonite, long-chain nylon, kevlar chopped fiber, a toughening agent, hyperbranched resin and an antioxidant; adding the premixed raw materials into a double-screw extruder for extrusion granulation to obtain modified particles; and drying the modified particles, adding the dried modified particles into a single-screw extruder to extrude a plastic melt, and treating the plastic melt with hot water and cold water to obtain the wire. The method is suitable for large-scale production, the prepared printed product has no obvious fiber exposure, and the prepared printed product has high tensile strength, bending strength and thermal deformation temperature and stable size.

Description

Preparation method of long-chain nylon composite material for 3D printing
Technical Field
The invention relates to a preparation method of a long-chain nylon composite material for 3D printing, and belongs to the technical field of preparation of materials for 3D printing.
Background
3D printing technology is changing the progress of modern manufacturing industry deeply, and is a technology for constructing objects by printing layer by layer using bondable materials such as powdered metals or plastics based on digital model files without the need for conventional tools, jigs and machines, and is applied to jewelry, footwear, industrial design, construction, engineering and construction (AEC), automotive, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields.
Fused Deposition (FDM) is a common technique for 3D printing, which utilizes thermoplastic polymers extruded from a print head in a molten state, then solidified into a thin profile layer, and then superimposed one on top of another. The FDM technology requires materials with lower condensation shrinkage, steeper viscosity-temperature curve, and higher strength, rigidity, thermal stability, etc., and at present, the polymer materials commonly used in the technology are polylactic acid (PLA), acrylonitrile-butadiene-styrene copolymer (ABS), Polycarbonate (PC), etc., and the nylon composite material has little literature as a 3D printing material.
The nylon material has high strength and certain flexibility, can be used for printing functional final products, can realize one-step forming as long as moving parts and matching parts with complex structures are reasonably designed, and has wide prospects in the field of 3D printing. Compared with nylon 66, nylon 6 and the like, long-chain nylon (such as PA11, PA12, PA1212 and PA1012) has the following outstanding advantages: (1) long chain nylon has low water absorption, while nylon 66 and nylon 6 easily absorb water and have a relatively large degree of crystallinity, so that products printed by the long chain nylon as 3D printing materials have a series of poor problems, such as: the size and the performance of the product caused by water absorption are unstable, the size of the product is smaller than the original design size due to crystallization shrinkage after molding, and the product has larger warping risk and the like; (2) the long-chain nylon has a low melting point (170-. However, the long-chain nylon has the disadvantages of poor strength, low heat-resistant temperature, large shrinkage rate and the like compared with engineering plastics such as nylon 66, nylon 6 or polycarbonate and the like. Therefore, measures are needed to improve the strength, heat resistance and molding shrinkage of the long-chain nylon material, so that the long-chain nylon material has higher performance and printing effect when being applied to 3D printing, and the application field of 3D printing is widened.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the technical problems of poor strength, low heat-resistant temperature and large shrinkage rate of the existing nylon material for 3D printing, a preparation method of a long-chain nylon composite material for 3D printing is provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a long-chain nylon composite material for 3D printing comprises the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 5-10 parts of kevlar chopped fiber, 5-15 parts of wollastonite, 0.1-0.3 part of coupling agent, 3-8 parts of toughening agent, 0.5-1 part of hyperbranched resin and 0.2-1 part of antioxidant;
preparing a coupling agent solution;
spraying a coupling agent solution while stirring wollastonite, drying the wollastonite with the surface soaked with the coupling agent, and cooling to normal temperature to obtain coupling agent modified wollastonite;
uniformly mixing coupling agent modified wollastonite, long-chain nylon, kevlar chopped fiber, a toughening agent, hyperbranched resin and an antioxidant to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder for extrusion granulation to obtain modified particles;
and drying the modified particles to obtain dried particles, adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain the wire.
Preferably, the raw materials comprise the following components in parts by weight: 100 parts of long-chain nylon, 7-8 parts of kevlar chopped fiber, 8-10 parts of wollastonite, 0.2-0.3 part of coupling agent, 5-7 parts of toughening agent, 0.7-1 part of hyperbranched resin and 0.4-0.7 part of antioxidant.
Preferably, said kevlar chopped fibres have a length of 1-3mm and a diameter not exceeding 15 μm.
Preferably, the length-diameter ratio of the wollastonite needle-shaped fiber is more than 15.
Preferably, the long-chain nylon is at least one of PA11, PA12, PA1212, and PA 1012.
Preferably, the coupling agent is a silane coupling agent with the general formula YSiX3X is methoxy or ethoxy, Y contains amino or epoxy.
Preferably, the toughening agent is maleic anhydride grafted ethylene propylene diene monomer or ethylene-acrylate-maleic anhydride copolymer.
Preferably, the hyperbranched resin is of polyester or polyamide type, preferably of the Hyper C100, Hyper HPN202 and Hyper H40 series, the Hyper H40 series comprising Hyper H401, Hyper H402, Hyper H403.
The polyester or polyamide type hyperbranched resin has a highly branched structure (the main chain is short, the branched chains are more), so that the polyester or polyamide type hyperbranched resin cannot be intertwined with other long molecular chains even if the polyester or polyamide type hyperbranched resin has larger molecular weight, is easy to move among macromolecules, can effectively reduce the melt viscosity by a small amount, is difficult to separate out from a solid polymer, and can improve the reduction of the melt flow rate and the reduction of fiber exposure caused by the addition of Kevlar chopped fibers and wollastonite.
Preferably, the antioxidant is a hindered phenol antioxidant or a phosphite antioxidant, the hindered phenol antioxidant is preferably antioxidant 1076, antioxidant 1010, antioxidant 1790, antioxidant 330 and antioxidant 2246, and the phosphite antioxidant is preferably antioxidant 168 and antioxidant 626.
Preferably, the pH of the coupling agent solution is adjusted to between 4 and 5.5.
Preferably, the specific method for preparing the coupling agent modified wollastonite is as follows: and stirring the wollastonite at the speed of 100-600r/min, spraying the atomized coupling agent solution, continuously stirring for 5-10 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface for 2-3 hours at the temperature of 90-120 ℃, and cooling to normal temperature to obtain the coupling agent modified wollastonite.
Preferably, the mixing method for preparing the premixed raw materials comprises the following steps: stirring and mixing for 5-15 minutes at the speed of 100-600 r/min.
Preferably, the temperature of each section of the twin-screw extruder is set as follows: the first zone is 170-182 ℃, the second zone is 183-193 ℃, the third zone is 187-197 ℃, the fourth zone is 190-200 ℃, the fifth zone is 190-200 ℃, the sixth zone is 187-197 ℃, the seventh zone is 187-197 ℃, the eighth zone is 185-195 ℃, the ninth zone is 185-195 ℃, the tenth zone is 183-193 ℃, the eleventh zone is 183-193 ℃, the head is 187-197 ℃, the host rotation speed is 350-450r/min, and the feeding frequency is 7-12 r/min;
preferably, the drying method of the modified particles is as follows: drying at 80-105 deg.C until water content is not more than 0.05%.
Preferably, the temperature of each heating zone of the single-screw extruder is set to 175-185 ℃ in the first zone, 187-198 ℃ in the second zone, 190-200 ℃ in the third zone, 192-202 ℃ in the fourth zone, 188-198 ℃ in the fifth zone, 185-197 ℃ in the sixth zone, 45-55 ℃ for hot water and 20-30 ℃ for cold water.
Preferably, the nylon, the toughening agent, the hyperbranched resin and the antioxidant are mixed to obtain a mixture M1, the kevlar chopped fibers and the coupling agent modified wollastonite are mixed to obtain a mixture M2, the mixture M1 is added from a main feeding port at one area of the double-screw extruder, and the mixture M2 is added from a four-area side feeding port of the double-screw extruder.
The invention has the beneficial effects that:
the preparation method of the long-chain nylon composite material for 3D printing comprises the steps of firstly soaking wollastonite in a coupling agent solution on the surface, drying and cooling to obtain coupling agent modified wollastonite, then mixing the coupling agent modified wollastonite, long-chain nylon, kevlar chopped fiber, a toughening agent, hyperbranched resin and an antioxidant in a certain proportion, adding a premixed raw material into a double-screw extruder to extrude and granulate, then drying the modified granules, adding the dried modified granules into a single-screw extruder to extrude a plastic melt, carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain a wire, wherein the prepared wire and a printed product have no obvious fiber exposure, and the printed product has high tensile strength and bending strength, high thermal deformation temperature and stable size; the method has the following specific beneficial effects:
(1) kevlar chopped fiber is an organic fiber spun by full aromatic polyamide with special high temperature resistance and high strength, and even if special surface treatment and compatibilization are not carried out, the Kevlar chopped fiber with a certain content has good compatibility with long-chain nylon, the heat-resistant temperature and strength of the long-chain nylon can be greatly improved, the molding shrinkage and the like are reduced, but the cost is higher, and the wire rod which is only added with a large amount of Kevlar chopped fiber but not wollastonite and a 3D printed product thereof have the phenomena of fiber exposure and rough surface, and a printing nozzle is easy to block during 3D printing; the microstructure of the wollastonite is needle-shaped with a certain length-diameter ratio, which has great effect on reducing the water absorption of the long-chain nylon material, but has far less effect on enhancing the long-chain nylon material, improving the heat resistance and reducing the molding shrinkage than the kevlar chopped fiber, and has the advantage that the cost is much lower than that of the kevlar chopped fiber. The kevlar chopped fibers and the wollastonite are combined in a reasonable proportion, so that the strength, the thermal stability and the dimensional stability of the long-chain nylon can be effectively improved under the condition of reasonable cost.
(2) The kevlar chopped fibers in combination with the acicular wollastonite have the following advantages over the commonly used glass fiber fillers: the thermal stability is good, the thermal deformation is low, and the dimensional stability is better than that of glass fiber; the acicular mineral filler can solve the problems of surface fiber floating and easy warping of products caused by the glass fiber filler; the reinforced plastic has good melt fluidity and high surface glossiness.
(3) The kevlar chopped fibers with the length of 1-3mm are selected because the kevlar chopped fibers have less influence on the melt flow rate when being applied to 3D printing compared with kevlar long fibers, the high melt flow rate is an important index of 3D printing, and the kevlar chopped fibers with the diameter of not more than 15 mu m can ensure the length-diameter ratio of the fibers, so that the tensile strength, the bending strength and the heat distortion temperature of long-chain nylon can be effectively improved, and similarly, the needle-shaped wollastonite fibers with the length-diameter ratio of more than 15 can effectively improve the strength and the heat distortion temperature of the long-chain nylon.
(4) The compatibility of long-chain nylon and wollastonite can be improved by adding the coupling agent, the improvement effect of the wollastonite on nylon materials can be better exerted, the coupling agent can be more uniform on the surface of the filler by selecting a mode of spraying diluent in an atomizing mode, and the silanol group of the silane coupling agent can be more quickly dissociated by adjusting the diluent to be weakly acidic (the PH is 4-5.5) and can be more quickly combined with the surface of the wollastonite.
(5) The toughening agent can improve the toughness and mechanical property of the nylon composite material, so that the maleic anhydride grafted ethylene propylene diene monomer or the ethylene-acrylate-maleic anhydride copolymer with certain polarity and reaction activity is selected as the toughening agent, the long-chain nylon is a polymer with polarity, the toughening agent can be well dispersed in the long-chain nylon in modification processing, and an amide group in the long-chain nylon and an anhydride group in maleic anhydride have reactivity and the probability of forming a hydrogen bond, so that the compatibility of the long-chain nylon and the toughening agent is greatly improved; such toughening agents may also strengthen the bonding of kevlar fibers, wollastonite modified with coupling agents, and nylon matrix.
(6) The polyester or polyamide type hyperbranched resin selected by the invention can effectively reduce the melt viscosity, is not easy to separate out from solid polymer, can improve the reduction of melt flow rate and the reduction of fiber exposure caused by adding Kevlar chopped fibers and wollastonite, improves the melt fluidity of the composite material, and improves the surface smoothness of the composite material.
(7) The addition of the antioxidant can avoid the oxidation phenomenon of long-chain nylon in the high-temperature processing process and the performance reduction caused by the oxidation phenomenon.
(8) Kevlar chopped fibers and needle-shaped wollastonite belong to fibrous fillers and are easy to break in processing, separate feeding is selected to reduce the breaking probability, side feeding ports of a double-screw extruder are arranged in four regions of the extruder, a mixture M1 is melted, the Kevlar chopped fibers and the wollastonite do not undergo the shearing force of elements in the screws from one region to three regions of the double-screw extruder and the collision with a solid mixture M1, the breaking probability is reduced, and the strength of long-chain nylon can be effectively improved.
Detailed Description
The present invention will now be described in further detail by way of examples.
Example 1
The embodiment provides a preparation method of a long-chain nylon composite material for 3D printing, which comprises the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 5 parts of kevlar chopped fiber, 10 parts of wollastonite, 0.2 part of coupling agent, 3 parts of toughening agent, 0.5 part of hyperbranched resin and 0.2 part of antioxidant; the length of the kevlar chopped fiber is 2mm, and the diameter is 12 μm; the length-diameter ratio of the wollastonite needle-shaped fiber is more than 15; the long-chain nylon is PA 11; the coupling agent is a silane coupling agent with a structural formula of NH2(CH2)3Si(OC2H5)3(ii) a The toughening agent is maleic anhydride grafted ethylene propylene diene monomer; the hyperbranched resin is Hyper C100; the antioxidant is an antioxidant 1076;
preparing a coupling agent solution by using ethanol as a coupling agent, and adjusting the pH value of the coupling agent solution to be 4-5.5;
spraying atomized coupling agent solution into the wollastonite while stirring at the speed of 100r/min, continuing stirring for 5 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface at the temperature of 120 ℃ for 2.5 hours, and cooling to normal temperature to obtain coupling agent modified wollastonite;
stirring and mixing the long-chain nylon, the toughening agent, the hyperbranched resin, the antioxidant, the kevlar chopped fiber and the coupling agent modified wollastonite at the speed of 100r/min for 15 minutes to obtain a premixed raw material;
adding the premixed raw materials from a main feed inlet at the first area of a double-screw extruder, extruding and granulating by the double-screw extruder to obtain modified particles, wherein the temperature of each section of the double-screw extruder is set as follows: the first zone is 176 ℃, the second zone is 188 ℃, the third zone is 191 ℃, the fourth zone is 195 ℃, the fifth zone is 195 ℃, the sixth zone is 192 ℃, the seventh zone is 192 ℃, the eighth zone is 190 ℃, the ninth zone is 190 ℃, the tenth zone is 188 ℃, the eleventh zone is 188 ℃, the machine head is 195 ℃, the main machine rotation speed is 400r/min, and the feeding frequency is 10 r/min;
drying the modified particles at 90 ℃ until the water content is not more than 0.05 percent to obtain dried particles, adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain a wire, wherein the temperatures of heating intervals of the single-screw extruder are set to be 182 ℃ in a first zone, 189 ℃ in a second zone, 195 ℃ in a third zone, 198 ℃ in a fourth zone, 194 ℃ in a fifth zone, 192 ℃ in a sixth zone, the temperature of hot water is 55 ℃ and the temperature of cold water is 25 ℃.
Example 2
The embodiment provides a preparation method of a long-chain nylon composite material for 3D printing, which comprises the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 7 parts of kevlar chopped fiber, 5 parts of wollastonite, 0.1 part of coupling agent, 7 parts of toughening agent, 0.7 part of hyperbranched resin and 0.4 part of antioxidant; the length of the kevlar chopped fiber is 3mm, and the diameter is 10 μm; the length-diameter ratio of the wollastonite needle-shaped fiber is more than 15; the long-chain nylon is PA 1012; the coupling agent is a silane coupling agent with a structural formula of NH2(CH2)3Si(OCH3)3(ii) a The toughening agent is maleic anhydride grafted ethylene propylene diene monomer; the hyperbranched resin is Hyper H402; the antioxidant is antioxidant 330;
preparing a coupling agent solution by using water for the coupling agent, and adjusting the pH value of the coupling agent solution to be between 4 and 5.5;
spraying atomized coupling agent solution into the wollastonite while stirring at the speed of 300r/min, continuing stirring for 8 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface at 110 ℃ for 2.5 hours, and cooling to normal temperature to obtain coupling agent modified wollastonite;
stirring and mixing the long-chain nylon, the toughening agent, the hyperbranched resin, the antioxidant, the kevlar chopped fiber and the coupling agent modified wollastonite at the speed of 300r/min for 10 minutes to obtain a premixed raw material;
adding the premixed raw materials from a main feed inlet at the first area of a double-screw extruder, extruding and granulating by the double-screw extruder to obtain modified particles, wherein the temperature of each section of the double-screw extruder is set as follows: 175 ℃ in the first zone, 193 ℃ in the second zone, 197 ℃ in the third zone, 200 ℃ in the fourth zone, 198 ℃ in the fifth zone, 197 ℃ in the sixth zone, 197 ℃ in the seventh zone, 195 ℃ in the eighth zone, 195 ℃ in the ninth zone, 193 ℃ in the tenth zone, 193 ℃ in the eleventh zone, 195 ℃ in the head, 400r/min in the rotation speed of a main engine and 9r/min in the feeding frequency;
drying the modified particles at 100 ℃ until the water content is not more than 0.05 percent to obtain dried particles, adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating zone of the single-screw extruder is set to be 185 ℃ in a first zone, 195 ℃ in a second zone, 197 ℃ in a third zone, 202 ℃ in a fourth zone, 198 ℃ in a fifth zone, 196 ℃ in a sixth zone, the temperature of hot water is 50 ℃ and the temperature of cold water is 25 ℃.
Example 3
The embodiment provides a preparation method of a long-chain nylon composite material for 3D printing, which comprises the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 8 parts of kevlar chopped fiber, 15 parts of wollastonite, 0.3 part of coupling agent, 3 parts of toughening agent, 0.7 part of hyperbranched resin and 1 part of antioxidant; the length of the kevlar chopped fiber is 2.5mm, and the diameter is 12 μm; the length-diameter ratio of the wollastonite needle-shaped fiber is more than 15; the long-chain nylon is PA 1212; the coupling agent is a silane coupling agent with a structural formula
Figure GDA0002214679560000091
The toughening agent is maleic anhydride grafted ethylene propylene diene monomer; the hyperbranched resin is Hyper H401; the antioxidant is antioxidant 1790;
preparing a coupling agent solution by using ethanol as a coupling agent, and adjusting the pH value of the coupling agent solution to be 4-5.5;
spraying atomized coupling agent solution into the wollastonite while stirring at the speed of 300r/min, continuing stirring for 7 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface at 100 ℃ for 3 hours, and cooling to normal temperature to obtain coupling agent modified wollastonite;
mixing long-chain nylon, a toughening agent, hyperbranched resin and an antioxidant for 15 minutes at the speed of 300r/min to obtain a mixture M1, and stirring and mixing kevlar chopped fibers and wollastonite modified by a coupling agent for 15 minutes at the speed of 300r/min to obtain a mixture M2;
adding the mixture M1 from a main feed opening at one zone of a double-screw extruder, adding the mixture M2 from a side feed opening at four zones, extruding and granulating by the double-screw extruder to obtain modified particles, and setting the temperature of each section of the double-screw extruder as follows: first zone 176 deg.C, second zone 193 deg.C, third zone 196 deg.C, fourth zone 197 deg.C, fifth zone 195 deg.C, sixth zone 195 deg.C, seventh zone 194 deg.C, eighth zone 194 deg.C, ninth zone 192 deg.C, tenth zone 192 deg.C, eleventh zone 193 deg.C, head 194 deg.C, main machine rotation speed 450r/min, and feeding frequency 12 r/min;
drying the modified particles at 95 ℃ until the water content is not more than 0.05 percent to obtain dried particles, then adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating zone of the single-screw extruder is set to be 180 ℃ in a first zone, 192 ℃ in a second zone, 195 ℃ in a third zone, 197 ℃ in a fourth zone, 193 ℃ in a fifth zone, 192 ℃ in a sixth zone, 50 ℃ in hot water and 30 ℃ in cold water.
Example 4
The embodiment provides a preparation method of a long-chain nylon composite material for 3D printing, which comprises the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 10 parts of kevlar chopped fiber, 6 parts of wollastonite, 0.1 part of coupling agent, 8 parts of toughening agent, 1 part of hyperbranched resin and 0.5 part of antioxidant; the length of the kevlar chopped fiber is 1.7mm, and the diameter is 15 mu m; the length-diameter ratio of the wollastonite needle-shaped fiber is more than 15; the long-chain nylon is PA 12; the coupling agent is a silane coupling agent with a structural formula of NH2CH2Si(OCH3)3(ii) a The toughening agent is an ethylene-acrylate-maleic anhydride copolymer; the hyperbranched resin is Hyper HPN 202; the antioxidant is 1010;
preparing a coupling agent solution by using water for the coupling agent, and adjusting the pH value of the coupling agent solution to be between 4 and 5.5;
spraying atomized coupling agent solution into the wollastonite while stirring at the speed of 200r/min, continuing stirring for 10 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface at 90 ℃ for 2 hours, and cooling to normal temperature to obtain coupling agent modified wollastonite;
mixing long-chain nylon, a toughening agent, hyperbranched resin and an antioxidant for 15 minutes at a speed of 200r/min to obtain a mixture M1, and stirring and mixing kevlar chopped fibers and wollastonite modified by a coupling agent for 15 minutes at a speed of 200r/min to obtain a mixture M2;
adding the mixture M1 from a main feed opening at one zone of a double-screw extruder, adding the mixture M2 from a side feed opening at four zones, extruding and granulating by the double-screw extruder to obtain modified particles, and setting the temperature of each section of the double-screw extruder as follows: the first zone is 170 ℃, the second zone is 183 ℃, the third zone is 187 ℃, the fourth zone is 190 ℃, the fifth zone is 190 ℃, the sixth zone is 187 ℃, the seventh zone is 187 ℃, the eighth zone is 185 ℃, the ninth zone is 185 ℃, the tenth zone is 183 ℃, the eleventh zone is 183 ℃, the machine head is 187 ℃, the main machine rotation speed is 350r/min, and the feeding frequency is 7 r/min;
drying the obtained modified particles at 80 ℃ until the water content is not more than 0.05 percent to obtain dried particles, then adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating zone of the single-screw extruder is set to be 175 ℃ in a first zone, 187 ℃ in a second zone, 190 ℃ in a third zone, 192 ℃ in a fourth zone, 188 ℃ in a fifth zone, 185 ℃ in a sixth zone, the temperature of hot water is 45 ℃ and the temperature of cold water is 20 ℃.
Example 5
The embodiment provides a preparation method of a long-chain nylon composite material for 3D printing, which comprises the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 8 parts of kevlar chopped fiber, 10 parts of wollastonite, 0.2 part of coupling agent, 3 parts of toughening agent, 0.7 part of hyperbranched resin and 0.7 part of antioxidant; the length of the kevlar chopped fiber is 1mm, and the diameter is 10 μm; the length-diameter ratio of the wollastonite needle-shaped fiber is more than 15; the long-chain nylon is PA 11; the coupling agent is a silane coupling agent with a structural formula
Figure GDA0002214679560000121
The toughening agent is maleic anhydride grafted ethylene propylene diene monomer; the hyperbranched resin is Hyper H403; the antioxidant is an antioxidant 2246;
preparing a coupling agent solution by using water for the coupling agent, and adjusting the pH value of the coupling agent solution to be between 4 and 5.5;
spraying atomized coupling agent solution into the wollastonite while stirring at the speed of 200r/min, continuing stirring for 5 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface at the temperature of 120 ℃ for 2.5 hours, and cooling to normal temperature to obtain coupling agent modified wollastonite;
mixing long-chain nylon, a toughening agent, hyperbranched resin and an antioxidant for 15 minutes at a speed of 200r/min to obtain a mixture M1, and stirring and mixing kevlar chopped fibers and wollastonite modified by a coupling agent for 15 minutes at a speed of 200r/min to obtain a mixture M2;
adding the obtained mixture M1 from a main feed inlet of a double-screw extruder, adding the mixture M2 from a side feed inlet, extruding and granulating by the double-screw extruder to obtain modified particles, wherein the temperature of each section of the double-screw extruder is set as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 196 ℃, the fourth zone is 199 ℃, the fifth zone is 195 ℃, the sixth zone is 195 ℃, the seventh zone is 194 ℃, the eighth zone is 194 ℃, the ninth zone is 192 ℃, the tenth zone is 192 ℃, the eleventh zone is 192 ℃, the head is 196 ℃, the main machine rotation speed is 400r/min, and the feeding frequency is 8 r/min;
drying the modified particles at 100 ℃ until the water content is not more than 0.05 percent to obtain dried particles, adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating zone of the single-screw extruder is set to be 180 ℃ in a first zone, 194 ℃ in a second zone, 196 ℃ in a third zone, 197 ℃ in a fourth zone, 195 ℃ in a fifth zone, 194 ℃ in a sixth zone, the temperature of hot water is 48 ℃ and the temperature of cold water is 28 ℃.
Example 6
The embodiment provides a preparation method of a long-chain nylon composite material for 3D printing, which comprises the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 6 parts of kevlar chopped fiber, 10 parts of wollastonite, 0.3 part of coupling agent, 5 parts of toughening agent, 0.5 part of hyperbranched resin and 0.2 part of antioxidant; the length of the kevlar chopped fiber is 1.6mm, and the diameter is 10 μm; the length-diameter ratio of the wollastonite needle-shaped fiber is more than 15; the long-chain nylon is PA 11; the coupling agent is a silane coupling agent with a structural formula of NH2(CH2)3Si(OC2H5)3(ii) a The toughening agent is maleic anhydride grafted ethylene propylene diene monomer; the hyperbranched resin is Hyper C100; the antioxidant is antioxidant 168;
preparing a coupling agent solution by using ethanol as a coupling agent, and adjusting the pH value of the coupling agent solution to be 4-5.5;
spraying atomized coupling agent solution into the wollastonite while stirring at the speed of 600r/min, continuing stirring for 5 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface at 120 ℃ for 2.5 hours, and cooling to normal temperature to obtain coupling agent modified wollastonite;
stirring and mixing long-chain nylon, a toughening agent, hyperbranched resin and an antioxidant for 5 minutes at the speed of 600r/min to obtain a mixture M1, and mixing kevlar chopped fibers and wollastonite modified by a coupling agent for 5 minutes at the speed of 600r/min to obtain a mixture M2;
adding the mixture M1 from a main feed inlet at a first area of a double-screw extruder, adding the mixture M2 from a side feed inlet at a fourth area, extruding and granulating by the double-screw extruder to obtain modified particles, and setting the temperature of each section of the double-screw extruder as follows: the first zone is 180 ℃, the second zone is 193 ℃, the third zone is 197 ℃, the fourth zone is 198 ℃, the fifth zone is 196 ℃, the sixth zone is 194 ℃, the seventh zone is 194 ℃, the eighth zone is 195 ℃, the ninth zone is 195 ℃, the tenth zone is 193 ℃, the eleventh zone is 193 ℃, the head is 197 ℃, the main machine rotation speed is 400r/min, and the feeding frequency is 8 r/min;
drying the modified particles at 105 ℃ until the water content is not more than 0.05 percent to obtain dried particles, adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain a wire, wherein the temperature of each heating zone of the single-screw extruder is 185 ℃ in a first zone, 196 ℃ in a second zone, 200 ℃ in a third zone, 200 ℃ in a fourth zone, 196 ℃ in a fifth zone, 195 ℃ in a sixth zone, the temperature of hot water is 50 ℃ and the temperature of cold water is 20 ℃.
Example 7
The embodiment provides a preparation method of a long-chain nylon composite material for 3D printing, which comprises the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 8 parts of kevlar chopped fiber, 10 parts of wollastonite, 0.2 part of coupling agent, 7 parts of toughening agent and hyperbranched tree0.7 part of grease and 0.7 part of antioxidant; the length of the kevlar chopped fiber is 2mm, and the diameter is 10 μm; the length-diameter ratio of the wollastonite needle-shaped fiber is more than 15; the long-chain nylon is PA 11; the coupling agent is a silane coupling agent with a structural formula of NH2(CH2)3Si(OC2H5)3(ii) a The toughening agent is maleic anhydride grafted ethylene propylene diene monomer; the hyperbranched resin is Hyper H401; the antioxidant is 626;
preparing a coupling agent solution by using water for the coupling agent, and adjusting the pH value of the coupling agent solution to be between 4 and 5.5;
spraying atomized coupling agent solution into the wollastonite while stirring at the speed of 400r/min, continuing stirring for 5 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface at the temperature of 120 ℃ for 2.5 hours, and cooling to normal temperature to obtain coupling agent modified wollastonite;
mixing long-chain nylon, a toughening agent, hyperbranched resin and an antioxidant for 10 minutes at the speed of 400r/min to obtain a mixture M1, and stirring and mixing kevlar chopped fibers and wollastonite modified by a coupling agent for 10 minutes at the speed of 400r/min to obtain a mixture M2;
adding the mixture M1 from a main feed inlet of a double-screw extruder, adding the mixture M2 from a side feed inlet, extruding and granulating by the double-screw extruder to obtain modified particles, wherein the temperature of each section of the double-screw extruder is set as follows: the first zone is 182 ℃, the second zone is 193 ℃, the third zone is 197 ℃, the fourth zone is 200 ℃, the fifth zone is 200 ℃, the sixth zone is 197 ℃, the seventh zone is 197 ℃, the eighth zone is 195 ℃, the ninth zone is 195 ℃, the tenth zone is 193 ℃, the eleventh zone is 193 ℃, the head is 197 ℃, the main machine rotation speed is 380r/min, and the feeding frequency is 9 r/min;
drying the modified particles at 100 ℃ until the water content is not more than 0.05 percent to obtain dried particles, adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating zone of the single-screw extruder is 185 ℃ in a first zone, 198 ℃ in a second zone, 200 ℃ in a third zone, 202 ℃ in a fourth zone, 198 ℃ in a fifth zone, 197 ℃ in a sixth zone, the temperature of hot water is 50 ℃ and the temperature of cold water is 25 ℃.
Comparative example 1
The only difference from example 7 is that the kevlar chopped fibres have a length of 2mm and a diameter of 16 μm.
Comparative example 2
The only difference from example 7 is that the kevlar chopped fibres have a length of 2mm and a diameter of 20 μm.
Comparative example 3
The only difference from example 7 is 2 parts kevlar chopped fibres and 16 parts wollastonite.
Comparative example 4
The only difference from example 7 is that the kevlar chopped fibres are 18 parts, without wollastonite.
Comparative example 5
The only difference from example 7 is that there is no toughening agent.
The wires prepared in examples 1 to 7 and comparative examples 1 to 4 were printed with a test sample using an FDM type 3D printer, the printing effect was checked and the sample properties were tested, the tensile strength of the sample was tested with standard ISO 527, and a type a sample in the standard was selected; the bending strength of the sample strip is tested according to the standard ISO 178, and the size of the sample strip is 80mm multiplied by 10mm multiplied by 4 mm; the heat distortion temperature of the sample strip is tested according to the standard ISO 75, the size of the sample strip is 80mm multiplied by 10mm multiplied by 4mm, and the method A (bending stress of 1.80 MPa) is adopted; the linear expansion coefficients of the splines, which are 50mm by 7mm, were tested using the standard GB/T1036. The results obtained are shown in table 1 below:
TABLE 1 Effect and Performance results for wire-printed samples of examples 1-7 and comparative examples 1-4
Figure GDA0002214679560000161
Note: the linear expansion coefficient is in positive correlation with the shrinkage rate, namely the smaller the linear expansion coefficient is, the smaller the material molding shrinkage rate is, and the more stable the size along with the temperature change is.
It can be seen from comparison of comparative example 1, comparative example 2 and example 7 that, under the condition that the length of the kevlar chopped fibers is not changed, the length-diameter ratio of the fibers can be ensured by selecting kevlar chopped fibers with the diameter not more than 15 μm, the tensile strength, the bending strength and the heat distortion temperature of the long-chain nylon can be more effectively improved, the linear expansion coefficient is reduced, and the linear expansion coefficient is gradually increased as the diameter of the kevlar chopped fibers is increased and the tensile strength, the bending strength and the heat distortion temperature of the 3D printed product are gradually reduced.
As can be seen by comparing comparative example 3, comparative example 4 and example 7, in the case that the total content of the kevlar chopped fibers and wollastonite is not changed, when the amount of the kevlar chopped fibers is 2 parts and the amount of the wollastonite is 16 parts, the tensile strength, flexural strength and heat distortion temperature of the 3D printed product are remarkably reduced, and the linear expansion coefficient is remarkably increased, and when the amount of the kevlar chopped fibers is 18 parts and the wollastonite is not present, the 3D printing is not suitable, and it can be seen that the kevlar chopped fibers and the wollastonite must be mixed in a certain proportion to effectively improve the tensile strength, flexural strength and heat distortion temperature of the 3D printed product and reduce the linear expansion coefficient.
As can be seen from comparison between comparative example 5 and examples 1-7, the selection of maleic anhydride grafted ethylene propylene diene monomer or ethylene-acrylate-maleic anhydride copolymer with certain polarity and reactivity as a toughening agent can obviously improve the tensile strength and the bending strength of the nylon composite material.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (9)

1. A preparation method of a long-chain nylon composite material for 3D printing is characterized by comprising the following steps:
preparing the following raw materials in parts by weight: 100 parts of long-chain nylon, 5-10 parts of kevlar chopped fiber, 5-15 parts of wollastonite, 0.1-0.3 part of coupling agent, 3-8 parts of toughening agent, 0.5-1 part of hyperbranched resin and 0.2-1 part of antioxidant; the length of the kevlar chopped fibers is 1-3mm, the diameter is not more than 15 μm, and the length-diameter ratio of the wollastonite needle-shaped fibers is more than 15;
preparing a coupling agent solution;
spraying a coupling agent solution while stirring wollastonite, drying the wollastonite with the surface soaked with the coupling agent, and cooling to normal temperature to obtain coupling agent modified wollastonite;
uniformly mixing coupling agent modified wollastonite, long-chain nylon, kevlar chopped fiber, a toughening agent, hyperbranched resin and an antioxidant to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder for extrusion granulation to obtain modified particles;
and drying the modified particles to obtain dried particles, adding the dried particles into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain the wire.
2. The preparation method of the long-chain nylon composite material for 3D printing according to claim 1, wherein the raw materials comprise the following components in parts by weight: 100 parts of long-chain nylon, 7-8 parts of kevlar chopped fiber, 8-10 parts of wollastonite, 0.2-0.3 part of coupling agent, 5-7 parts of toughening agent, 0.7-1 part of hyperbranched resin and 0.4-0.7 part of antioxidant.
3. The preparation method of the long-chain nylon composite material for 3D printing according to claim 1 or 2, wherein the coupling agent is a silane coupling agent with a general formula of YSiX3X is methoxy or ethoxy, Y contains amino or epoxy, the toughening agent is maleic anhydride grafted ethylene propylene diene monomer or ethylene-acrylate-maleic anhydride copolymer, the hyperbranched resin is polyester or polyamide type hyperbranched resin, and the antioxidant is hindered phenol antioxidant or phosphite antioxidant.
4. The preparation method of the long-chain nylon composite material for 3D printing according to claim 1 or 2, wherein the nylon, the toughening agent, the hyperbranched resin and the antioxidant are mixed to obtain a mixture M1, the kevlar chopped fibers and the coupling agent modified wollastonite are mixed to obtain a mixture M2, the mixture M1 is added from a main feeding port at one area of the double-screw extruder, and the mixture M2 is added from a four-area side feeding port of the double-screw extruder.
5. The preparation method of the long-chain nylon composite material for 3D printing according to claim 1 or 2, wherein the specific method for preparing the coupling agent modified wollastonite is as follows: and stirring the wollastonite at the speed of 100-600r/min, spraying the atomized coupling agent solution, continuously stirring for 5-10 minutes after the coupling agent is sprayed, drying the obtained wollastonite with the coupling agent soaked on the surface for 2-3 hours at the temperature of 90-120 ℃, and cooling to normal temperature to obtain the coupling agent modified wollastonite.
6. The preparation method of the long-chain nylon composite material for 3D printing according to claim 1 or 2, wherein the temperature of each section of the twin-screw extruder is set as follows: the first zone is 170-182 ℃, the second zone is 183-193 ℃, the third zone is 187-197 ℃, the fourth zone is 190-200 ℃, the fifth zone is 190-200 ℃, the sixth zone is 187-197 ℃, the seventh zone is 187-197 ℃, the eighth zone is 185-195 ℃, the ninth zone is 185-195 ℃, the tenth zone is 183-193 ℃, the eleventh zone is 183-193 ℃, the head is 187-197 ℃, the host rotation speed is 350-450r/min and the feeding frequency is 7-12 r/min.
7. The method for preparing a long-chain nylon composite material for 3D printing as claimed in claim 1 or 2, wherein the temperature of each heating zone of the single-screw extruder is set as 175-.
8. The method for preparing a long-chain nylon composite material for 3D printing according to claim 1 or 2, wherein the p H value of the coupling agent solution is adjusted to be between 4 and 5.5.
9. The preparation method of the long-chain nylon composite material for 3D printing according to claim 1 or 2, wherein the mixing method for preparing the premixed raw materials comprises the following steps: stirring and mixing for 5-15 minutes at the speed of 100-600 r/min; the drying method of the modified particles comprises the following steps: drying at 80-105 deg.C until water content is not more than 0.05%.
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CN109049672B (en) * 2018-09-17 2021-03-09 航天特种材料及工艺技术研究所 3D printing material and preparation method and application thereof
CN109280374A (en) * 2018-09-25 2019-01-29 苏州优利金新材料有限公司 A kind of high glass fibre reinforced nylon material and preparation method thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104647760A (en) * 2015-02-12 2015-05-27 华中科技大学 3D printing and manufacturing method of short-fiber reinforced thermosetting resin composite product
CN104861266A (en) * 2015-05-08 2015-08-26 浙江工业大学 High filling polyethylene blend modifier and preparation method thereof and an application
EP2985062A1 (en) * 2014-08-13 2016-02-17 AXAGARIUS GmbH & Co. KG Device for purifying nucleic acids
CN106147214A (en) * 2015-04-16 2016-11-23 黑龙江鑫达企业集团有限公司 A kind of nylon based composites being applicable to 3D printing chest and abdomen fixed band and preparation method thereof
CN106700515A (en) * 2015-11-14 2017-05-24 黑龙江鑫达企业集团有限公司 Preparation method of PA-12/carbon fiber composite material for 3D (three-dimensional) printing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2985062A1 (en) * 2014-08-13 2016-02-17 AXAGARIUS GmbH & Co. KG Device for purifying nucleic acids
CN104647760A (en) * 2015-02-12 2015-05-27 华中科技大学 3D printing and manufacturing method of short-fiber reinforced thermosetting resin composite product
CN106147214A (en) * 2015-04-16 2016-11-23 黑龙江鑫达企业集团有限公司 A kind of nylon based composites being applicable to 3D printing chest and abdomen fixed band and preparation method thereof
CN104861266A (en) * 2015-05-08 2015-08-26 浙江工业大学 High filling polyethylene blend modifier and preparation method thereof and an application
CN106700515A (en) * 2015-11-14 2017-05-24 黑龙江鑫达企业集团有限公司 Preparation method of PA-12/carbon fiber composite material for 3D (three-dimensional) printing

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