CN108381908B - 3D printing process for continuous fiber reinforced thermosetting resin matrix composite material - Google Patents
3D printing process for continuous fiber reinforced thermosetting resin matrix composite material Download PDFInfo
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- CN108381908B CN108381908B CN201810130086.8A CN201810130086A CN108381908B CN 108381908 B CN108381908 B CN 108381908B CN 201810130086 A CN201810130086 A CN 201810130086A CN 108381908 B CN108381908 B CN 108381908B
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 82
- 239000011347 resin Substances 0.000 title claims abstract description 72
- 229920005989 resin Polymers 0.000 title claims abstract description 72
- 239000000835 fiber Substances 0.000 title claims abstract description 66
- 238000010146 3D printing Methods 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000011159 matrix material Substances 0.000 title claims abstract description 21
- 238000001723 curing Methods 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000007639 printing Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000016 photochemical curing Methods 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 239000000805 composite resin Substances 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000005243 fluidization Methods 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920000271 Kevlar® Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229920006240 drawn fiber Polymers 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000004761 kevlar Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 238000003303 reheating Methods 0.000 claims description 2
- 238000001029 thermal curing Methods 0.000 claims description 2
- 238000004017 vitrification Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
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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
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- 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
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/314—Preparation
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
Abstract
A3D printing process for a continuous fiber reinforced thermosetting resin matrix composite material comprises the steps of selecting a thermosetting resin prepolymer, a high-temperature curing agent, a photo-curing resin prepolymer and a photoinitiator as pre-dipping raw materials, heating and uniformly mixing the pre-dipping raw materials, pre-dipping a resin prepolymer system by using continuous dry fiber tows, and cooling the pre-dipped material to obtain a continuous fiber reinforced thermosetting resin matrix composite material wire; conveying the composite material wire into a 3D printing head, heating again, drawing out the molten wire from a printing nozzle, immediately ventilating and cooling the drawn wire after drawing out the wire, and irradiating by a follow-up ultraviolet source to finish pre-curing; printing layer by layer in a circulating manner to obtain a preformed component; and finally, placing the preformed component in a temperature environment capable of initiating a thermosetting reaction for curing and forming to finally prepare the 3D printing forming component.
Description
Technical Field
The invention relates to the technical field of 3D printing of composite materials, in particular to a 3D printing process of a continuous fiber reinforced thermosetting resin matrix composite material.
Background
The 3D printing technique is a rapid additive manufacturing technique that constructs a solid body by using bondable materials such as linear wires of metal powder or plastic, based on a digital model, in a layer-by-layer printing or layer-by-layer selective bonding manner. The 3D printing supplies are the material basis of 3D printing and are also the bottleneck limiting the further development and application of 3D printing. At present, 3D printing consumables are mainly divided into four types, namely ceramics, metals, composite materials and polymers, and commonly used 3D printing consumables are mainly pure thermoplastic wires and comprise acrylonitrile-butadiene-styrene copolymer (ABS), polylactic acid (PLA) and the like. The drawbacks are evident: weak bearing capacity, extremely poor interlayer performance, insufficient tensile strength and the like, which seriously limit further application and development.
According to the latest literature, colleges and universities at home and abroad and research and development teams of well-known enterprises begin to try to perform 3D printing tests by using fibers as reinforcement composite common 3D printing consumables. At present, the 3D printing technology of the chopped fiber reinforced thermoplastic resin matrix composite material is realized, but the mechanical property of a final composite material molding member is enhanced only in a limited way due to the fact that the addition amount, the length-diameter ratio and the like of the chopped fibers are always limited, and the thermoplastic resin has the defects of shrinkage cracking, warping deformation, poor heat resistance and corrosion resistance, low strength and hardness and the like. In order to thoroughly solve the problems and greatly improve the mechanical property of a fiber reinforced resin matrix composite 3D printing forming component so as to meet the requirements of the engineering field, the existing mechanisms begin to develop chopped fiber reinforced thermosetting resin matrix composite 3D printing and continuous fiber reinforced thermoplastic resin matrix composite 3D printing from a thermosetting resin matrix and a continuous fiber reinforcement.
In summary, 3D printing of continuous fiber reinforced thermosetting resin based composite materials is not achieved in the prior art.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a 3D printing process for a continuous fiber reinforced thermosetting resin-based composite material, which is used for realizing 3D printing and rapid molding of a continuous fiber reinforced thermosetting resin-based composite material component.
In order to achieve the purpose, the invention adopts the following technical scheme:
A3D printing process for a continuous fiber reinforced thermosetting resin-based composite material comprises the following steps:
step one, selecting thermosetting resin prepolymer, high-temperature curing agent, photo-curing resin prepolymer and photoinitiator which are in glass state at normal temperature as prepreg raw materials, heating the prepreg raw materials to a temperature above the viscous fluidization temperature of the thermosetting resin prepolymer and below the critical temperature at which the high-temperature curing agent starts to initiate thermosetting reaction, mixing uniformly, directly adopting continuous dry fiber tows to prepreg the resin prepolymer system, and cooling the impregnated system to a temperature below the vitrification temperature of the thermosetting resin prepolymer through dipping to prepare the continuous fiber reinforced thermosetting resin matrix composite wire which is added with the curing agent but is not cured and is suitable for 3D printing;
conveying the continuous fiber reinforced thermosetting resin-based composite material wire prepared in the step one into a 3D printing head, heating the continuous fiber reinforced thermosetting resin-based composite material wire to a temperature above the viscous fluidization temperature of a thermosetting resin prepolymer, enabling a high-temperature curing agent to start to be below the critical temperature of a thermosetting reaction, enabling the molten wire to pass through the printing head and be attached to a fiber tow on a printing platform, and immediately ventilating and cooling the fiber tow after the fiber tow is pulled out, so that the fiber tow is rapidly attached to the printing platform to be solidified and shaped, and meanwhile, carrying out follow-up ultraviolet light source irradiation to finish precuring; printing layer by layer in the circulating process to prepare a fiber reinforced thermosetting resin matrix composite 3D printing preforming component;
and step three, placing the preformed component prepared in the step two in a temperature environment capable of initiating a thermosetting reaction, and exciting a high-temperature curing agent to initiate a thermosetting polymerization crosslinking reaction for complete curing and forming to finally prepare the fiber reinforced thermosetting resin matrix composite 3D printing forming component with excellent comprehensive performance.
In the first step, the glass transition temperature of the selected thermosetting resin prepolymer is higher than 30 ℃ and lower than the critical temperature at which the high-temperature curing agent starts to initiate a thermosetting reaction, the thermosetting resin prepolymer is in a glass state at normal temperature, and the thermosetting resin prepolymer is in a viscous state with low viscosity and strong fluidity after being heated; the mass fraction of the selected photo-curing resin prepolymer is between 0 and 50 percent, and the mixing temperature of the two resin prepolymers, the high-temperature curing agent and the photoinitiator and the pre-dipping temperature of the dry fiber tows are in the temperature interval.
The dry fiber tows selected in the step one are one or more of carbon fibers, glass fibers and Kevlar fibers.
The temperature of the temperature environment in the third step is higher than the critical temperature of the thermocuring reaction initiated by the high-temperature curing agent, and the additional environment attributes of high pressure, inert gas atmosphere, infrared irradiation or microwave irradiation are set according to the requirement.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention can meet the requirement of pre-dipping silk making of a plurality of fiber tows, is suitable for a plurality of high-performance thermosetting resins and mixtures thereof, prepares the 3D printing silk material in advance by a step method, independently controls the silk making link, and can control the resin content and the resin distribution of the prepared tows.
2) According to the invention, the raw materials directly adopt the continuous dry fiber tows, and the continuous fiber reinforced thermosetting resin matrix composite material wire suitable for 3D printing is obtained by pre-impregnating the thermosetting resin prepolymer system, so that the advantages of the thermosetting resin and the continuous fiber tows are integrated, the defects of short fibers and thermoplastic resin are made up, and various performances of a formed member are greatly improved; more importantly, the wire is suitable for 3D printing forming based on the layered manufacturing principle, is different from the forming mode of the traditional composite material, and can be widely popularized and expand the application field of composite material members through the wide application of the current 3D printing technology.
3) The invention effectively applies the continuous fiber reinforced thermosetting resin-based composite material to the technical field of 3D printing, adopts high-strength continuous fiber tows and thermosetting resin with superior performance to replace common 3D printing thermoplastic wire materials, directly simplifies the complex composite material forming process into a simple and convenient method which can be used by people through the 3D printing technology, and solves the defects of low strength, large deformation, unstable size, poor heat resistance, poor corrosion resistance and the like of common 3D printing forming members, so that the continuous fiber reinforced thermosetting resin-based composite material can meet the requirements of the engineering field, and has great economic value and development potential.
Detailed Description
The present invention is further described below with reference to examples.
A3D printing process for a continuous fiber reinforced thermosetting resin-based composite material comprises the following steps:
firstly, selecting a thermosetting resin prepolymer, a high-temperature curing agent, a light-cured resin prepolymer and a photoinitiator which are in glass state at normal temperature as prepreg raw materials, heating the prepreg raw materials to a temperature above the viscous flow temperature of the thermosetting resin prepolymer, wherein the high-temperature curing agent starts to initiate a thermosetting reaction to be below the critical temperature, the two resin prepolymers are both in a viscous flow state with low viscosity and strong fluidity, after being uniformly mixed with the high-temperature curing agent and the photoinitiator, directly adopting a continuous dry fiber tow to prepreg the resin prepolymer system, and cooling the resin prepolymer system to a temperature below the glass transition temperature of the thermosetting resin prepolymer after impregnation, wherein the resin prepolymer system recovers the glass state, so that the continuous fiber reinforced thermosetting resin matrix composite wire which is added with the curing agent but is not cured and is suitable for 3D printing is prepared;
conveying the continuous fiber reinforced thermosetting resin-based composite material wire prepared in the step one into a 3D printing head, reheating the continuous fiber reinforced thermosetting resin-based composite material wire to a temperature above the viscous fluidization temperature of a thermosetting resin prepolymer, enabling a high-temperature curing agent to start to initiate a thermosetting reaction to be below the critical temperature, enabling the molten wire to pass through the printing head and be attached to a fiber tow on a printing platform, drawing the fiber tow out of a printing nozzle, immediately ventilating and cooling the drawn fiber tow to be rapidly attached to the printing platform for solidification and shaping, and simultaneously enabling the drawn fiber tow to be irradiated by a follow-up ultraviolet light source to activate a photoinitiator to initiate a photocuring polymerization crosslinking reaction to complete precuring; printing layer by layer according to the model requirement in the circulation process to prepare a fiber reinforced thermosetting resin matrix composite 3D printing preforming component;
and step three, placing the preformed component prepared in the step two in a temperature environment capable of initiating a thermosetting reaction, and exciting a high-temperature curing agent to initiate a thermosetting polymerization crosslinking reaction for complete curing and forming to finally prepare the fiber reinforced thermosetting resin matrix composite 3D printing forming component with excellent comprehensive performance.
In the first step, the glass transition temperature of the selected thermosetting resin prepolymer is higher than 30 ℃ and lower than the critical temperature at which the high-temperature curing agent starts to initiate a thermosetting reaction, the thermosetting resin prepolymer is in a glass state at normal temperature, and the thermosetting resin prepolymer is in a viscous state with low viscosity and strong fluidity after being heated; the selected photo-curing resin prepolymer is added according to the adhesion shaping requirement, the pre-curing requirement and the performance requirement after final curing in the third step, the mass fraction is between 0% and 50%, the mixing temperature of the two resin prepolymers, the high-temperature curing agent and the photoinitiator and the pre-dipping temperature of the dry fiber tows are both in the temperature interval, so that the resin prepolymers and the curing agent are uniformly mixed under the heating condition of low viscosity and strong fluidity, the dry fiber tows are pre-dipped uniformly, the tows are cooled after being fully dipped, the temperature is reduced to be below the glass transition temperature of the thermosetting resin prepolymers, the resin prepolymer system recovers the glass state, the tows are not adhered to each other after the pre-dipped tows are wound, and the process has certain strength, hardness and toughness, and no curing reaction is generated in the process.
The dry fiber tows selected in the step one are one or more of carbon fibers, glass fibers and Kevlar fibers.
In the second step, the tows need to pass through the printing head in advance, then the temperature of the printing head is heated to be higher than the viscous fluidization temperature of the thermosetting resin prepolymer, the high-temperature curing agent starts to initiate the thermosetting reaction to be lower than the critical temperature, the resin prepolymer system impregnated in the tows is changed into the viscous state again, the viscous state is drawn to pass through the nozzle and then contacts the printing plane, and the viscous state is pre-cured through cooling solidification and ultraviolet illumination, so that the traction force, the adhesive force and the shaping force for maintaining the shape of the component required in the printing process are provided.
The temperature of the temperature environment in the third step is higher than the critical temperature of the thermosetting reaction initiated by the high-temperature curing agent, the thermosetting polymerization crosslinking reaction is initiated by the high-temperature curing agent to completely cure and form the preformed component, at the moment, the uncured resin in the preformed component is changed into a viscous state with low viscosity and strong fluidity due to the high-temperature environment while the polymerization crosslinking reaction is carried out, but the fluidity of the pre-formed component is restrained after the pre-curing by the ultraviolet irradiation in the step two, the pre-formed component is ensured to always keep the shape intact and not to generate deformation or resin loss in the curing process, besides the heating, additional environmental attributes such as high pressure, inert gas atmosphere, infrared irradiation or microwave irradiation can be set according to requirements, the resin flow is enhanced, the pores are filled, the curing effect is improved, and finally obtaining the fiber reinforced thermosetting resin matrix composite material 3D printing forming member with excellent comprehensive performance after deep polymerization crosslinking reaction and curing forming.
Claims (4)
1. A3D printing process for a continuous fiber reinforced thermosetting resin-based composite material is characterized by comprising the following steps:
step one, selecting thermosetting resin prepolymer, high-temperature curing agent, photo-curing resin prepolymer and photoinitiator which are in glass state at normal temperature as prepreg raw materials, heating the prepreg raw materials to a temperature above the viscous fluidization temperature of the thermosetting resin prepolymer and below the critical temperature at which the high-temperature curing agent starts to initiate thermosetting reaction, mixing uniformly, directly adopting continuous dry fiber tows to prepreg the resin prepolymer system, and cooling the impregnated system to a temperature below the vitrification temperature of the thermosetting resin prepolymer through dipping to prepare the continuous fiber reinforced thermosetting resin matrix composite wire which is added with the curing agent but is not cured and is suitable for 3D printing;
conveying the continuous fiber reinforced thermosetting resin-based composite material wire prepared in the step one into a 3D printing head, reheating the continuous fiber reinforced thermosetting resin-based composite material wire to a temperature above the viscous fluidization temperature of a thermosetting resin prepolymer, enabling a high-temperature curing agent to start to be below the critical temperature of a thermosetting reaction, enabling the molten wire to pass through the printing head and be attached to a fiber tow on a printing platform, drawing the fiber tow out of a printing nozzle, immediately ventilating and cooling the drawn fiber tow, and then rapidly attaching to the printing platform for solidification and shaping, and simultaneously completing precuring through follow-up ultraviolet light source irradiation; printing layer by layer in the circulating process to prepare a fiber reinforced thermosetting resin matrix composite 3D printing preforming component;
and step three, placing the preformed component prepared in the step two in a temperature environment capable of initiating a thermosetting reaction, and exciting a high-temperature curing agent to initiate a thermosetting polymerization crosslinking reaction for complete curing and forming to finally prepare the fiber reinforced thermosetting resin matrix composite 3D printing forming component with excellent comprehensive performance.
2. The 3D printing process of the continuous fiber reinforced thermosetting resin based composite material as claimed in claim 1, wherein: in the first step, the glass transition temperature of the selected thermosetting resin prepolymer is higher than 30 ℃ and lower than the critical temperature at which the high-temperature curing agent starts to initiate a thermosetting reaction, the thermosetting resin prepolymer is in a glass state at normal temperature, and the thermosetting resin prepolymer is in a viscous state with low viscosity and strong fluidity after being heated; the mass fraction of the selected photo-curing resin prepolymer is between 0 and 50 percent, and the mixing temperature of the two resin prepolymers, the high-temperature curing agent and the photoinitiator and the pre-dipping temperature of the dry fiber tows are in the temperature interval.
3. The 3D printing process of the continuous fiber reinforced thermosetting resin based composite material as claimed in claim 1, wherein: the dry fiber tows selected in the step one are one or more of carbon fibers, glass fibers and Kevlar fibers.
4. The 3D printing process of the continuous fiber reinforced thermosetting resin based composite material as claimed in claim 1, wherein: the temperature of the temperature environment in the third step is higher than the critical temperature of the thermocuring reaction initiated by the high-temperature curing agent, and the additional environment attributes of high pressure, inert gas atmosphere, infrared irradiation or microwave irradiation are set according to the requirement.
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| CN201810130086.8A CN108381908B (en) | 2018-02-08 | 2018-02-08 | 3D printing process for continuous fiber reinforced thermosetting resin matrix composite material |
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| CN201810130086.8A CN108381908B (en) | 2018-02-08 | 2018-02-08 | 3D printing process for continuous fiber reinforced thermosetting resin matrix composite material |
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| US11331854B2 (en) * | 2018-03-26 | 2022-05-17 | Arevo, Inc. | System and method for dispensing composite filaments for additive manufacturing |
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| CN110355995B (en) * | 2019-08-19 | 2021-07-06 | 航天特种材料及工艺技术研究所 | 3D printing forming method by adopting continuous fibers, target structure obtained by forming and application |
| CN110667114B (en) * | 2019-10-17 | 2022-01-28 | 吉林大学 | Integrated printing device and printing method for continuous fiber embedded material |
| CN111117103B (en) * | 2019-12-22 | 2021-12-31 | 同济大学 | Reinforced wire rod for fused deposition molding and preparation method thereof |
| CN111607217B (en) * | 2020-07-07 | 2021-06-25 | 四川大学 | 3D printing continuous fiber amidourea polymer composite material and preparation method thereof |
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| CN114478947B (en) * | 2021-12-23 | 2023-12-08 | 山东华夏神舟新材料有限公司 | Novel photo-curing 3D printing resin material and preparation method thereof |
| CN114474711A (en) * | 2022-01-07 | 2022-05-13 | 上海大学 | 3D printing method and device for thermosetting material or photosensitive material |
| CN115781536B (en) * | 2022-12-13 | 2024-04-16 | 昆明理工大学 | Retired carbon fiber reinforced resin sheet grinding wheel uniformly solidified by microwaves and preparation method |
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| CN107254015A (en) * | 2017-06-23 | 2017-10-17 | 东华大学 | A kind of thermosetting resin base fibrous composite and preparation method thereof |
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Effective date of registration: 20231121 Address after: 710075 Zone 306, Industrial Incubation Base Office Building B, Chongwen Town, Jinghe New City, Xixian New District, Xi'an City, Shaanxi Province Patentee after: Xi'an Huasheng composite material technology Co.,Ltd. Address before: Beilin District Xianning West Road 710049, Shaanxi city of Xi'an province No. 28 Patentee before: XI'AN JIAOTONG University |