Three-dimensional printing consumable material of continuous fiber-reinforced composite material and preparation method therefor, three-dimensional printing method, and three-dimensional printed article

Abstract

The present application relates to the technical field of additive manufacturing, and in particular to a three-dimensional printing consumable material of a continuous fiber-reinforced composite material and a preparation method therefor, a three-dimensional printing method, and a three-dimensional printed article. In the present application, a woven tube structure is used, and a continuous fiber core is embedded into a skin-layer fiber woven tube in a wrapping or interlacing mode, so that the interface bonding force of fibers can be improved, and a three-dimensional printing consumable material having excellent mechanical properties can be obtained. In addition, by adjusting the types, proportions, weaving structures, relative positions, contents, and the like of continuous fibers and skin-layer fibers, the three-dimensional printing consumable material having excellent mechanical properties, thermal properties, special functionalities, and processing properties can be obtained, the strength, stiffness, heat resistance, and other properties of the printed article can be significantly improved, and the manufacturing requirements of high-performance structural members and special functional members are met. The present application solves the problems of difficult continuous fiber supply, poor interface bonding force, etc. in the prior art, and has wide application prospects.

Description

A continuous fiber reinforced composite material 3D printing consumable, its preparation method, 3D printing method, and product thereof. Technical Field

[0001] This application belongs to the field of additive manufacturing technology, specifically relating to a continuous fiber reinforced composite material 3D printing consumable, its preparation method, 3D printing method, and product. Background Technology

[0002] 3D printing technology, also known as additive manufacturing technology, can directly generate objects with complex shapes from digital models by adding materials layer by layer. This significantly shortens product development cycles and reduces manufacturing costs, and has become one of the revolutionary technologies in the manufacturing industry.

[0003] Currently, the mainstream consumables for 3D printing are mainly thermoplastic polymers, which have limited mechanical and heat resistance properties, making it difficult to meet the requirements of high-performance structural components. To improve the performance of 3D printed products, researchers have begun to try adding fillers as reinforcing phases to the polymer matrix, commonly used fillers such as short fibers, glass microspheres, and carbon nanotubes. However, the dispersion and orientation of fillers such as short fibers in the matrix are difficult to control, resulting in limited reinforcing effects and failing to significantly improve the mechanical properties of the products.

[0004] Compared to short fibers, continuous fibers possess higher strength and modulus, exhibiting superior mechanical properties along the fiber direction. However, the smooth and inert surface of inorganic continuous fibers makes it difficult to form strong interfacial bonds with the polymer matrix, hindering the full realization of the composite material's performance. Existing continuous fiber printing processes employ two routes: one involves pre-impregnating the continuous fibers to form printing filaments; the other involves feeding the continuous and polymer fibers through separate channels during printing, followed by lamination at the printer head. However, directly using pre-impregnated continuous fibers for printing filaments is limited by the insufficient amount of polymer material adhering to the continuous fibers, leading to cracking of directly printed components. Furthermore, printing with continuous and polymer fibers through a dual-channel approach suffers from limited bonding between the continuous fibers and the polymer matrix due to the single-sided contact between the two sides, also impacting the overall mechanical properties of the printed parts. Summary of the Invention

[0005] The purpose of this application is to provide a continuous fiber reinforced composite material 3D printing consumable, its preparation method, 3D printing method, and the resulting product. The 3D printing consumable provided by this application improves the bonding force between the continuous fiber and the polymer fiber, thereby enhancing the mechanical properties of the 3D printed product, while also enabling stable supply and precise positioning of the continuous fiber.

[0006] To achieve the above objectives, this application provides the following technical solution:

[0007] A continuous fiber reinforced composite material 3D printing consumable includes a continuous fiber core and a sheath fiber woven tube; the continuous fiber core is wrapped in the cavity of the sheath fiber woven tube, and / or the continuous fiber core is interwoven in the tube wall of the sheath fiber woven tube;

[0008] The continuous fiber core material includes one or more of carbon fiber, glass fiber, basalt fiber, polymer fiber, metal fiber, ceramic fiber, and bio-based fiber;

[0009] The lining fiber used in the woven tube is a polymer fiber.

[0010] Preferably, the dermis fiber includes one or more of the following: polyamide fiber, polypropylene fiber, polyethylene fiber, polylactic acid fiber, polycaprolactone fiber, polyvinyl alcohol fiber, polyetheretherketone fiber, polyimide fiber, polyphenylene sulfide fiber, polycarbonate fiber, polyethylene terephthalate fiber, polyvinyl chloride fiber, blended polymer fiber, and modified polymer fiber.

[0011] The number of tube wall layers of the corrugated fiber tube is ≥1; the mass ratio of the continuous fiber core layer to the corrugated fiber tube is 1~80:20~99.

[0012] Preferably, the polymer fibers used in the continuous fiber core material include one or more of aramid fibers, poly(p-phenylenebenzodioxazole) fibers, polyethylene fibers, polyester fibers, polyimide fibers, and polyamide fibers.

[0013] The metal fibers include one or more of copper fibers, aluminum fibers, and tungsten fibers;

[0014] The ceramic fibers include alumina fibers and / or silicon carbide fibers;

[0015] The bio-based fibers include bamboo fiber and / or flax fiber;

[0016] The continuous fiber core material is a single fiber filament or a fiber bundle; the number of the continuous fiber core material is ≥1.

[0017] Preferably, the continuous fiber core material comprises functional polymer fibers; the functional polymer fibers include one or more of conductive fibers, flame-retardant fibers, antibacterial fibers, and fluorescent fibers.

[0018] Preferably, when the continuous fiber core material is wrapped in the cavity of the sheath fiber weaving tube, the distribution of the continuous fiber core material in the cross section of the three-dimensional printing consumable is a central distribution, an eccentric distribution, or a multi-core distribution.

[0019] When the distribution pattern is eccentric, the continuous fiber reinforced composite material 3D printing consumable also includes auxiliary positioning fibers; the auxiliary positioning fibers and the continuous fiber core are together wrapped in the cavity of the skin fiber weaving tube; the positional relationship between the auxiliary positioning fibers and the continuous fiber core is that they are arranged in parallel or intertwined.

[0020] This application also provides a method for preparing the continuous fiber reinforced composite material 3D printing consumable described in the above scheme, including the following steps:

[0021] Using cortex fibers and continuous fiber core materials as raw materials, the materials are woven according to a preset structure to obtain the continuous fiber reinforced composite material three-dimensional printing consumables;

[0022] Alternatively, the dermal fiber, continuous fiber core material, and auxiliary positioning fiber can be used as raw materials and woven according to a preset structure to obtain the continuous fiber reinforced composite material three-dimensional printing consumable.

[0023] The weaving method is either braiding or knitting.

[0024] Preferably, the number of spindles in the weaving is 4 to 200, the number of needles in the knitting is 4 to 200, the weaving or knitting angle is 5 to 85°, and the arrangement of the dermal fibers is circular or spiral.

[0025] Preferably, after weaving, the resulting fabric is further subjected to a setting treatment and / or surface treatment; the setting treatment method includes heat treatment, solvent treatment, steam fumigation treatment or ultraviolet curing treatment;

[0026] The surface treatment method is plasma treatment or preparation of a functional layer on the surface of the woven fabric; the functional layer includes one or more of the following: a lubricating layer, an antioxidant layer, an antistatic layer, a flame retardant layer, a conductive layer, and an antibacterial layer.

[0027] This application also provides a three-dimensional printing method, comprising the following steps: performing three-dimensional printing using the continuous fiber reinforced composite material three-dimensional printing consumables described in the above scheme or the continuous fiber reinforced composite material three-dimensional printing consumables prepared by the preparation method described in the above scheme.

[0028] This application also provides three-dimensional printed articles obtained by the three-dimensional printing method described above.

[0029] This application provides a continuous fiber reinforced composite material 3D printing consumable, comprising a continuous fiber core and a sheath fiber woven tube; the continuous fiber core is wrapped within the cavity of the fiber woven tube, and / or the continuous fiber core is interwoven within the tube wall of the sheath fiber woven tube; the continuous fiber core includes one or more of carbon fiber, glass fiber, basalt fiber, polymer fiber, metal fiber, ceramic fiber, and bio-based fiber; the sheath fiber used in the sheath fiber woven tube is polymer fiber. The beneficial effects of this application are as follows:

[0030] Improving interfacial bonding and enhancing mechanical properties: This application is the first to apply woven tube technology to the preparation of 3D printing consumables. This application embeds continuous fibers into the interior of the cortex fiber woven tube in a wrapping or interlacing manner, realizing the stable embedding of continuous fibers and the effective coating of continuous fibers by cortex fibers, thereby improving the interfacial bonding between continuous fibers and cortex fibers and enhancing the mechanical properties of 3D printing consumables, including tensile strength, flexural strength and impact toughness.

[0031] Preventing fiber breakage and achieving stable supply and precise positioning of continuous fibers: In this field, the stable supply and precise positioning of continuous fibers during 3D printing is a technical challenge. Traditional methods using continuous fibers for 3D printing are prone to fiber breakage, entanglement, and displacement, affecting print quality. This application addresses this by encasing the continuous fiber core material inside the sheath fiber manufacturing tube or weaving it within the tube wall of the sheath fiber weaving tube. This provides a certain displacement margin, allowing it to adapt to minute stress changes during printing, preventing fiber breakage, entanglement, and displacement, and improving print quality.

[0032] Improved material compatibility and reduced internal stress: Furthermore, by selecting a corrugated fiber material that matches the continuous fiber, this application can optimize the thermal expansion coefficient and melting characteristics of the continuous fiber and the matrix, reduce internal stress during processing and use, and prevent product deformation and cracking.

[0033] Flexible structural design: Furthermore, this application is applicable to a combination of various continuous fibers and sheath fibers, and the sheath fiber woven tube can be a multi-layer structure, and there can also be multiple continuous fiber core layers. The number of sheath fiber woven tube layers, the number of continuous fiber core layers, fiber types and arrangement can be adjusted according to actual needs, resulting in a high degree of customization, meeting the performance requirements of different application scenarios, and broadening the application range of the material.

[0034] This application also provides a method for preparing the continuous fiber reinforced composite 3D printing consumables described above. The preparation method provided by this application is simple, easy to control, suitable for mass production, and has low cost, which contributes to the widespread application of continuous fiber reinforced composite 3D printing consumables. Furthermore, this application also achieves uniform distribution and directional arrangement of fibers by precisely controlling weaving or knitting parameters, reducing anisotropy of mechanical properties, and improving the reliability and consistency of the products.

[0035] This application also provides a 3D printing method, specifically using the continuous fiber-reinforced composite material 3D printing consumables described above for 3D printing. The 3D printing consumables provided by this application possess appropriate flexibility and stable dimensions, resulting in a smooth printing process without frequent equipment adjustments or printing interruptions, thus improving printing speed and efficiency and meeting the needs of industrial production. Furthermore, traditional methods using continuous fibers for 3D printing require specially designed printheads, fiber supply systems, and control software, leading to high equipment costs and complex processes. In contrast, this application pre-embeds continuous fibers into the consumables, eliminating the need for an additional fiber supply system and allowing direct use in existing FDM 3D printers without special modifications, thus lowering the application threshold and reducing equipment costs and process complexity. Attached Figure Description

[0036] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0037] Figure 1 is a schematic diagram of the preparation process and structure of the continuous fiber reinforced composite material three-dimensional printing consumable with braided tube structure provided in this application;

[0038] Figure 2 is a schematic diagram of the three-dimensional printing consumable structure of the continuous fiber reinforced composite material with knitted tube structure provided in this application;

[0039] Figure 3 is a schematic diagram of the preparation process and structure of the three-dimensional printing consumable of continuous fiber reinforced composite material with multi-layer woven tube structure provided in this application, wherein 1 is the continuous fiber core material, 3 is the braided tube layer (which can be multi-layered), and 4 is the knitted tube layer (which can be multi-layered).

[0040] Figure 4 is a schematic diagram of the structure of the three-dimensional printing consumable of the continuous fiber reinforced composite material with eccentric distribution of continuous fiber core material provided in this application, wherein 1 is the continuous fiber core material, 2 is the auxiliary positioning fiber for auxiliary eccentric positioning, 3 is the braided tube layer, and 4 is the knitted tube layer.

[0041] Figure 5 is a schematic diagram of the structure of the three-dimensional printing consumable of the continuous fiber reinforced composite material with different weaving angles or pitches provided in this application. The grid density in the figure is the pitch.

[0042] Figure 6 is a schematic diagram of the heat treatment process, where 5 is the insulation layer, 6 is the heating layer, and 7 is the mold opening. Detailed Implementation

[0043] This application provides a continuous fiber reinforced composite material 3D printing consumable, including a continuous fiber core and a sheath fiber woven tube; the continuous fiber core is wrapped in the cavity of the fiber woven tube, and / or the continuous fiber core is interwoven in the tube wall of the sheath fiber woven tube;

[0044] The continuous fiber core material includes one or more of carbon fiber, glass fiber, basalt fiber, polymer fiber, metal fiber, ceramic fiber, and bio-based fiber;

[0045] The lining fiber used in the woven tube is a polymer fiber.

[0046] Unless otherwise specified, all raw material components in this application are commercially available products well known to those skilled in the art.

[0047] In this application, the sheath fiber used in the woven tube is a polymer fiber; specifically, the sheath fiber preferably includes polyamide (PA) fiber, polypropylene (PP) fiber, polyethylene (PE) fiber, polylactic acid (PLA) fiber, polycaprolactone (PCL) fiber, polyvinyl alcohol (PVA) fiber, polyetheretherketone (PEEK) fiber, polyimide (PI) fiber, polyphenylene sulfide (PPS) fiber, polycarbonate (PC) fiber, polyethylene terephthalate (PET) fiber, polyvinyl chloride (PVC) fiber, and blended polymers. The fiber is selected from one or more of polyamide fibers and modified polymer fibers, wherein the polyamide fiber is preferably polyamide 6 fiber; the blended polymer fiber is specifically a fiber formed from a blend of at least two of polyamide, polypropylene, polyethylene, polylactic acid, polycaprolactone, polyvinyl alcohol, polyetheretherketone, polyimide, polyphenylene sulfide, polycarbonate, polyethylene terephthalate, and polyvinyl chloride; the modified polymer fiber is preferably obtained by modifying the polymer fiber matrix with a modifier; the polymer fiber matrix specifically includes polyamide, polypropylene, polyethylene, polylactic acid, polycaprolactone, poly... The modifier comprises one or more of vinyl alcohol, polyetheretherketone, polyimide, polyphenylene sulfide, polycarbonate, polyethylene terephthalate, and polyvinyl chloride; the modifier preferably comprises one or more of inorganic fillers, short fibers, nanomaterials, magnetic particles, and antioxidants; the inorganic fillers preferably comprise one or more of carbon black, metal oxide powder, and mineral powder; the short fibers preferably comprise one or more of glass fiber, carbon fiber, and aramid fiber; the nanomaterials preferably comprise one or more of carbon nanotubes, graphene, and metal nanowires; this application does not have special requirements for the magnetic particles and antioxidants, and those well known to those skilled in the art can be used; in this application, the use of inorganic fillers as modifiers can enhance the mechanical properties, thermal stability, and wear resistance of the polymer matrix; the use of short fibers as modifiers can enhance the tensile strength, impact resistance, and fatigue resistance of the polymer matrix; the use of nanomaterials as modifiers can enhance the mechanical, wear resistance, electrical, and thermal properties of the polymer matrix; the addition of magnetic particles can impart magnetic properties to the polymer matrix; and the addition of antioxidants can improve the anti-aging properties of the polymer matrix. In specific embodiments of this application, specific polymer fibers can be selected according to process requirements and performance requirements. For example, polypropylene fibers (melting point 145°C) and polycaprolactone fibers (melting point about 65°C) with low melting points are suitable for low-temperature processing; polyetheretherketone (PEEK) fibers (melting point 343°C) with high melting points are suitable for high-temperature applications; and a combination of polylactic acid fibers (melting point 170°C) and polyamide 6 fibers (melting point 220°C) can balance processing temperature and material properties.

[0048] In this application, the diameter of the cortex fiber is 10-300 μm, and in specific embodiments, it can be 15 μm, 25 μm, 50 μm, 100 μm, or 200 μm; the number of tube wall layers of the cortex fiber woven tube is ≥1 layer, that is, the cortex fiber woven tube can be a single-layer structure or a multi-layer nested structure. Specifically, the number of tube wall layers of the cortex fiber woven tube is preferably 1-20 layers, and in specific embodiments, it can be 2 layers, 3 layers, 5 layers, 10 layers, or 15 layers; in this application, when the number of tube wall layers of the cortex fiber woven tube is greater than 1 layer, the type of cortex fiber in each layer and the type of continuous fiber core material interwoven therein can be the same or different, in order to achieve specific performance combinations and functional requirements.

[0049] In this application, the mass ratio of the continuous fiber core material to the sheath fiber woven tube is 1-80:20-99. In specific embodiments, it can be 10:90, 20:80, 25:75, 30:70, 50:50, 55:45, 70:30 or 80:20.

[0050] In this application, the corrugated fiber woven tube can specifically be a braided tube and / or a knitted tube. When the number of wall layers of the corrugated fiber woven tube is greater than one, this application does not have special requirements for the specific weaving form of each layer of the woven tube; the weaving methods of each layer can be the same or different. Furthermore, when the continuous fiber core material is interwoven in the corrugated fiber woven tube, the type of continuous fiber, the type of corrugated fiber, the weaving angle, and the weaving or knitting density used in each layer can be different to achieve specific performance combinations and functional requirements. For example, in a specific embodiment of this application, when the number of wall layers of the corrugated fiber woven tube is two, and the continuous fiber core... When the layers are interwoven in the tube wall, the inner tube wall can be interwoven with carbon fiber bundles and PLA fibers, and the outer tube wall can be interwoven with glass fibers and PA fibers. The weaving angle of the inner tube wall can be 30°, and the weaving angle of the outer fibers can be 60°. Figure 1 is a schematic diagram of the preparation process and structure of the continuous fiber reinforced composite material 3D printing consumable with braided tube structure of this application. Figure 2 is a schematic diagram of the structure of the continuous fiber reinforced composite material 3D printing consumable with knitted tube structure of this application. Figure 3 is a schematic diagram of the preparation process and structure of the continuous fiber reinforced composite material 3D printing consumable with multi-layer braided tube structure.

[0051] In this application, the continuous fiber core material includes one or more of carbon fiber, glass fiber, basalt fiber, polymer fiber, metal fiber, ceramic fiber, and bio-based fiber; when the continuous fiber core material includes polymer fiber, the polymer fiber includes one or more of aramid fiber, poly(p-phenylenebenzodioxazole) fiber, polyethylene fiber, polyester fiber, polyimide fiber, and polyamide fiber; the metal fiber includes one or more of copper fiber, aluminum fiber, and tungsten fiber; the ceramic fiber includes alumina fiber and / or silicon carbide fiber; the bio-based fiber includes bamboo fiber and / or flax fiber. In a specific embodiment of this application, the continuous fiber core material is preferably carbon fiber, glass fiber, carbon fiber-glass fiber hybrid fiber, or basalt-aramid hybrid fiber; the weight ratio of carbon fiber to glass fiber in the carbon fiber-glass fiber hybrid fiber is 1:1; the weight ratio of basalt fiber to aramid fiber in the basalt-aramid hybrid fiber is 1:1.

[0052] In this application, the continuous fiber core material preferably comprises functional polymer fibers; the functional polymer fibers preferably include one or more of conductive fibers, flame-retardant fibers, antibacterial fibers, and fluorescent fibers. By employing functional polymer fibers, this application can endow the 3D printing consumables with specific functional properties. In the embodiments of this application, the functional polymer fibers can be distributed in different fiber layers of the woven tube wall to achieve a functional gradient. The continuous fiber reinforced composite 3D printing consumables provided by this application are suitable for combinations of various continuous fibers and skin fibers, and the appropriate material system can be selected according to requirements, resulting in a high degree of customization and broadening the application range of the material.

[0053] In this application, the continuous fiber core material is a single fiber filament or a fiber bundle; the diameter of the single fiber filament is 2 to 800 μm, and in a specific embodiment, it can be 5 μm, 7 μm, 10 μm, 100 μm, 300 μm or 500 μm; the number of single fibers in the fiber bundle is 1K to 50K, and in a specific embodiment, it can be 2K, 5K, 10K, 20K, 30K or 40K.

[0054] In this application, the number of continuous fiber core materials is preferably ≥1, more preferably 1 to 100, specifically 1, 2, 5, 10, 30, 50 or 80.

[0055] In this application, when the continuous fiber core material is wrapped in the cavity of the sheath fiber weaving tube, the distribution of the continuous fiber core material in the cross section of the consumable is central distribution, eccentric distribution, or multi-core distribution. In a specific embodiment of this application, by multi-core distribution, that is, by introducing multiple bundles of continuous fibers in the same filament through stranding or plying, the performance and functional diversity of the 3D printing consumable can be further improved.

[0056] In this application, when the distribution is eccentric, the composite material 3D printing consumable also includes auxiliary positioning fibers; the auxiliary positioning fibers and the continuous fiber core are wrapped together in the cavity of the sheath fiber weaving tube; the positional relationship between the auxiliary positioning fibers and the continuous fiber core is that they are arranged in parallel or intertwined; the material of the auxiliary positioning fibers can be selected from the material of the continuous fiber core or the sheath fiber, which will not be elaborated here; the diameter of the auxiliary positioning fibers is 2 to 800 μm, and in specific embodiments, it can be 5 μm, 10 μm, 100 μm, 300 μm or 500 μm; the structural schematic diagram of the continuous fiber core eccentrically distributed continuous fiber reinforced composite material 3D printing consumable provided in this application is shown in Figure 4.

[0057] In this application, the diameter of the continuous fiber reinforced composite material 3D printing consumable is 0.1 to 10 mm, and in a specific embodiment, it can be 1.75 mm or 2.85 mm.

[0058] This application also provides a method for preparing the continuous fiber reinforced composite material 3D printing consumables described in the above technical solution, including the following steps:

[0059] Using cortex fibers and continuous fiber core materials as raw materials, the materials are woven according to a preset structure to obtain the continuous fiber reinforced composite material three-dimensional printing consumables;

[0060] Alternatively, the dermal fiber, continuous fiber core material, and auxiliary positioning fiber can be used as raw materials and woven according to a preset structure to obtain the continuous fiber reinforced composite material three-dimensional printing consumable.

[0061] The weaving method is either braiding or knitting.

[0062] In this application, the number of spindles for knitting is 4 to 200, and in specific embodiments, it can be 10, 30, 50, 100, or 150; the number of needles for knitting is 4 to 200, and in specific embodiments, it can be 10, 30, 50, 100, or 150; the knitting or knitting speed is 10 to 800 rpm, and in specific embodiments, it can be 20 rpm, 30 rpm, 100 rpm, 300 rpm, or 500 rpm; the knitting or knitting angle is 5 to 85°, and in specific embodiments, it can be 10°, 30°, 50°, 60°, or 70°; the knitting pitch is preferably 0.1 to 10 mm. In this application, the flexibility, strength, and surface quality of the filament can be controlled by changing the weaving angle and weaving density to achieve specific performance combinations and functional requirements. For example, when the weaving angle is set to 30°, 45°, and 60°, a smaller weaving angle (30°) makes the fibers more parallel in the axial direction, increasing the flexibility of the material, which is suitable for applications requiring bending. A larger weaving angle (60°) makes the fibers more tightly interwoven in the radial direction, improving the strength and stability of the material, which is suitable for applications requiring high strength. Figure 5 is a schematic diagram of the structure of continuous fiber reinforced composite material 3D printing consumables with different weaving angles or pitches.

[0063] In this application, the sheath fibers are arranged in a ring or spiral pattern; during weaving, the tension of the continuous fiber core material is 0.1–10 N, and in specific embodiments, it can be 0.5 N, 1 N, 3 N, 5 N, or 8 N; the tension of the sheath fibers is 0.1–10 N, and in specific embodiments, it can be 0.5 N, 1 N, 3 N, 5 N, or 8 N. During weaving or knitting, the continuous fiber core material and sheath fibers are introduced with appropriate tension to ensure stable fiber supply and arrangement; by adjusting the fiber guiding device of the weaving or knitting machine, the continuous fibers can be distributed at any position in the cross-section of the filament, meeting special requirements such as functional gradient and local reinforcement.

[0064] This application does not have specific requirements for the specific weaving method. Weaving can be carried out according to the structure of the target 3D printing consumable. Specifically, when the continuous fiber core material is wrapped in the cavity of the sheath fiber weaving tube, the sheath fiber is woven or knitted on the surface of the continuous fiber core material; when the continuous fiber core material is interwoven in the tube wall of the sheath fiber weaving tube, the sheath fiber and the continuous fiber core material are woven or knitted into a tube; when the distribution of the continuous fiber core material is eccentric, the sheath fiber is woven or knitted on the surface of the continuous fiber core material and the auxiliary positioning fiber.

[0065] In this application, during the weaving or knitting process, the distribution position of the continuous fiber core material is adjusted by core yarn configuration methods such as single strand, parallel strand, and combined strand to achieve central distribution, eccentric distribution, or multi-core distribution, thereby meeting the needs of functional gradient and local reinforcement.

[0066] In this application, the weaving process further includes setting and / or surface treatment of the resulting fabric; these will be described in detail below.

[0067] In this application, the shaping treatment method preferably includes heat treatment, solvent treatment, steam fumigation treatment or ultraviolet curing treatment; in specific embodiments of this application, the corresponding shaping treatment method is preferably selected according to the characteristics of the polymer fiber used in the corrugated fiber tube.

[0068] In this application, the heat treatment is applicable to thermoplastic polymer fibers; the heat treatment temperature is preferably 50°C below the melting point of the polymer fiber to 10°C above the melting point of the polymer fiber, specifically preferably 50–400°C; the heat treatment time is 0.1–60 min, and in specific embodiments, it can be 10 s, 1 min, 5 min, 10 min, 30 min, or 50 min; in this application, when multiple different polymers are used in the sheath fiber, the heat treatment can be carried out in stages, with heat treatment performed sequentially according to the melting points of different polymers. In a specific embodiment of this application, the heat treatment is preferably carried out using a tubular furnace, the tube wall of which consists of a heating layer and an insulation layer from the inside out, and a die is provided at the outlet end of the tubular furnace; the woven material is passed through the tubular furnace at a uniform speed for heat treatment, and the speed at which the material passes through the tubular furnace can be controlled according to the target heat treatment time, specifically 0.1–10 m / min. Figure 6 is a schematic diagram of the heat treatment process in this application.

[0069] In specific embodiments of this application, in order to avoid material degradation or performance decline due to over-treatment, it is necessary to strictly control the temperature and time of heat treatment. Specifically, an appropriate heat treatment temperature and time are selected according to the melting point of the selected polymer fiber. For example, when the lining fiber is PP fiber, the heat treatment temperature is preferably 180°C and the heat treatment time is preferably 5 min; when the lining fiber is PEEK fiber, the heat treatment temperature is preferably 370°C and the heat treatment time is preferably 10 min.

[0070] In this application, the solvent treatment is applicable to soluble polymer fibers; the solvent for the solvent treatment is water and / or an organic solvent; the organic solvent includes one or more of ethanol, acetone, dichloromethane, toluene, and cyclohexanone; when the solvent is a mixture of water and an organic solvent, the volume fraction of the organic solvent in the mixture is preferably greater than or equal to 0.1% and less than 100%, specifically 1%, 5%, 20%, 50%, 80%, or 90%; the temperature of the solvent treatment is from room temperature to 100°C, and in specific embodiments, it can be 30°C, 50°C, or 80°C; the time of the solvent treatment is 0.1 to 60 minutes, and in specific embodiments, it can be 1 minute, 5 minutes, 10 minutes, 30 minutes, or 50 minutes. In a specific embodiment of this application, when the sheath fiber is PVA fiber, pure water is preferably used for solvent treatment, the solvent treatment temperature is preferably 85°C, and the time is preferably 5 minutes, ensuring that the PVA fiber is adequately dissolved.

[0071] In this application, the steam fumigation treatment is applicable to polymer fibers that need to be softened, specifically PLA fibers; the steam used for steam fumigation is water vapor; the temperature of the steam fumigation is 50-300℃, and in a specific embodiment, it can be 100℃ or 200℃; the time is 0.1-60min, and in a specific embodiment, it can be 1min, 5min, 10min, 30min or 50min.

[0072] In this application, the ultraviolet curing treatment is applicable to photosensitive polymer fibers; the irradiation time of the ultraviolet curing treatment is 0.1 to 60 min, and in specific embodiments, it can be 1 min, 5 min, 10 min, 30 min or 50 min.

[0073] In this application, when heat treatment or steam fumigation is used for shaping, the resulting material is preferably cooled after shaping. The cooling method is air cooling, water cooling, or segmented cooling. The cooling rate can be adjusted according to the material properties to avoid internal stress and deformation. When solvent treatment is used for shaping, the resulting material is preferably dried after shaping. The drying temperature is 20–150°C, and in specific embodiments, it can be 40°C, 70°C, 100°C, or 130°C. The drying time is 0.1–24 hours, and in specific embodiments, it can be 1 hour, 5 hours, 10 hours, 15 hours, or 20 hours. Drying ensures complete solvent evaporation and improves the dimensional stability of the 3D printing consumables.

[0074] This application uses a shaping process to partially melt, soften, or dissolve the outer fibers, which then coat the continuous fibers to form a dense structure, thereby improving the structural stability of 3D printing consumables.

[0075] In this application, the surface treatment method is plasma treatment or preparation of a functional layer on the surface of the woven fabric; the functional layer includes one or more of the following: a lubricating layer, an antioxidant layer, an antistatic layer, a flame-retardant layer, a conductive layer, and an antibacterial layer; the method for preparing the functional layer includes spraying, dipping, brushing, or chemical plating. In this application, the surface treatment can be performed after a setting treatment; when a setting treatment is not required, the surface treatment can be performed directly on the woven material. This application, through surface treatment, can improve the feeding performance, weather resistance, and functional characteristics of 3D printing consumables.

[0076] In this application, after obtaining the 3D printing consumable, the process further includes winding; the winding is performed using an automatic winding machine; the tension of the 3D printing consumable during winding is 0.1–100 N, and in specific embodiments, it can be 1 N, 5 N, 10 N, 30 N, 50 N, or 80 N; this application uses an automatic winding machine to wind the prepared 3D printing consumable into a spool for easy storage and use. During the winding process, the tension of the 3D printing consumable should be kept stable to avoid slack or excessive stretching; the storage environment for the 3D printing consumable is a dry, light-proof environment, with a storage temperature of -20–50°C, and in specific embodiments, it can be 0°C, 20°C, or 40°C; the relative humidity is 0%–90%, and in specific embodiments, it can be 10%, 30%, 50%, or 70%; storage under the above environment can prevent the 3D printing consumable from aging or performance degradation.

[0077] The preparation method of the 3D printing consumables provided in this application has the characteristics of wide material selection, flexible and controllable process, and excellent performance. The specific parameters of the fiber, such as diameter, tension, and weight ratio, have a large adjustment range and can be selected according to actual needs. The types of continuous fibers and skin fibers are fully covered, which can meet the diverse needs of different fields and application scenarios for 3D printing consumables.

[0078] This application also provides a three-dimensional printing method, comprising the following steps: performing three-dimensional printing using the continuous fiber reinforced composite material three-dimensional printing consumables described in the above scheme or the continuous fiber reinforced composite material three-dimensional printing consumables prepared by the preparation method described in the above scheme.

[0079] In this application, the conditions for 3D printing include: a nozzle temperature of 100–400°C, which in a specific embodiment can be 200°C or 300°C; a printing speed of 1–100 mm / s, which in a specific embodiment can be 5 mm / s, 10 mm / s, 30 mm / s, 50 mm / s, or 80 mm / s; and a layer thickness of 0.1–5 mm, which in a specific embodiment can be 0.5 mm, 1 mm, 2 mm, or 3 mm. By rationally setting the printing parameters, this application can achieve a stable and efficient printing process, producing 3D printed products with excellent properties such as high strength, high rigidity, heat resistance, and corrosion resistance. Furthermore, by controlling the distribution and orientation of fibers in the 3D printing consumables, directional design of product performance can be achieved, meeting special requirements such as multi-axial stress, localized strengthening, and functional gradient.

[0080] In a specific embodiment of this application, the 3D printing consumable is preferably installed into the feeding system of the 3D printing equipment. Then, printing parameters are set to control the feeding speed and direction of the 3D printing consumable, ensuring smooth feeding and maintaining the stability and continuity of the continuous fibers during the printing process. Following a preset printing path and model, 3D printing is performed to prepare 3D printed products with enhanced mechanical properties and specific functions. In a specific embodiment of this application, the obtained 3D printed products can also be subjected to annealing, surface treatment, or other post-processing processes as needed to improve product performance.

[0081] The continuous fiber reinforced composite material 3D printing consumables provided in this application can be widely used in the preparation of 3D printed products requiring high performance and lightweight materials. For example: in the aerospace field, it can manufacture high-strength, lightweight structural components, such as drone fuselages, satellite components, and rocket sections; in the automotive manufacturing field, it can produce high-performance automotive parts, such as body structural components, suspension system components, and interior parts, improving vehicle performance and fuel efficiency; in the medical device field, it can prepare biodegradable and biocompatible medical supplies, such as orthopedic implants, tissue engineering scaffolds, and drug delivery systems; in the industrial manufacturing field, it can produce high-strength, wear-resistant industrial parts, such as gears, bearings, and pump housings, extending service life and reducing maintenance costs; in the electronic device field, it can print conductive electronic components, sensors, and antennas, achieving structural and functional integration of electronic devices; in the sports equipment field, it can manufacture high-performance sports equipment, such as bicycle frames, skis, and rackets, improving athletic performance; and in the construction engineering field, it can produce building components with special properties, such as seismic bracing, insulation boards, and decorative materials.

[0082] This application also provides three-dimensional printed articles obtained by the three-dimensional printing method described above.

[0083] In this application, the 3D printed product has the characteristics of high strength, high modulus, high temperature resistance, flame retardancy, impact resistance, conductivity, and antibacterial properties. It can be used for a long time in high temperature (-50~400℃), high humidity, and high corrosive environments with stable performance. It is suitable for aerospace, automobile manufacturing, medical devices, industrial manufacturing, electronic devices, sports equipment, construction engineering, national defense and military industries.

[0084] In this application, the 3D printed articles specifically include one or more of the following: aerospace equipment, automotive parts, medical devices, industrial machinery parts, electronic components, sports equipment, building components, and military equipment.

[0085] In this application, the 3D printed product can be further processed as needed, such as machining, coating, electroplating, welding, etc., to further expand its application scope.

[0086] To further illustrate this application, the technical solutions of this application are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of this application.

[0087] Example 1

[0088] 3K continuous carbon fiber was selected as the core material. The single filament diameter of the continuous carbon fiber is 7μm, exhibiting high strength and high modulus. The sheath fiber is polyamide 6 (PA6) fiber, with a melting point of 220℃ and a fiber diameter of 230μm, used as the braiding material. The braiding machine is equipped with 16 braiding spindles and a braiding speed of 30 rpm. The continuous carbon fiber is introduced from the center of the braiding machine, with the fiber tension controlled at 1N to ensure stable fiber delivery. The PA6 fibers are cross-braided at a 45° angle to form a tubular structure, tightly wrapping around the continuous carbon fiber. The tension of the PA6 fibers is controlled at 0.5N, resulting in a continuous fiber-reinforced composite wire.

[0089] The continuous fiber-reinforced composite filament was heat-treated in a tubular furnace at 230°C for 10 seconds at a speed of 2 m / min. This temperature, slightly higher than the melting point of PA6, ensures that the polymer fibers melt on the surface and adhere to each other, forming a dense composite structure. After exiting the furnace, it immediately enters a cooling zone for rapid shaping using air cooling. The cooled 3D printing filament is then wound onto a spool using an automatic winding machine, with the winding speed synchronized with the heat treatment speed to maintain constant tension and prevent filament loosening or deformation. The final 3D printing filament has a uniform surface, free of obvious bubbles or defects, and a uniform diameter of approximately 1.75 mm, with a continuous fiber core and sheath fiber woven tube mass ratio of 20:80.

[0090] Mechanical property test results show that the tensile strength of the obtained 3D printing consumables reaches 1500MPa and the flexural strength reaches 1200MPa, which are significantly higher than those of pure polyamide materials.

[0091] This 3D printing filament was applied to a commercial FDM 3D printer, where the printhead temperature reached a maximum of 280℃. Printing parameters were set as follows: nozzle temperature 250℃, printing speed 2–50 mm / s, and layer thickness 0.2–3 mm. During printing, the filament feed was smooth, without clogging or fiber breakage. The resulting printed products exhibited high strength and rigidity, with excellent surface quality, meeting the requirements for high-performance structural components.

[0092] Example 2

[0093] 1K continuous glass fiber was selected as the core material, with a single filament diameter of 9μm. Water-soluble PVA fiber with a diameter of 15μm was chosen as the sheath fiber for weaving. Eight spindles were used for weaving at a speed of 20 rpm. The continuous glass fiber was introduced from the center of the weaving machine, with fiber tension controlled at 0.8N to ensure stable fiber transport. The PVA fibers were cross-woven at a 30° angle to form a tubular structure, tightly wrapping around the glass fiber. The PVA fiber tension was controlled at 0.4N, resulting in a continuous fiber-reinforced composite wire.

[0094] Continuous fiber-reinforced composite filaments were immersed in a solvent bath of pure water at 85°C for 5 minutes. The PVA fibers partially dissolved in the pure water, becoming viscous and tightly bonded to the surface of the continuous glass fibers. The filaments were then removed from the solvent and placed in a ventilated environment to allow the residual solvent to evaporate naturally. To ensure complete solvent evaporation and setting, the filaments were dried in a forced-air drying oven at 50°C for 2 hours. The resulting 3D printing filament had a smooth surface, a uniform diameter of approximately 2 mm, and a mass ratio of continuous fiber core to sheath fiber woven tube of 25:75.

[0095] Mechanical performance test results show that the tensile strength of the obtained 3D printing consumables reaches 800MPa and the flexural strength is 600MPa.

[0096] The 3D printing consumables were applied to an FDM 3D printer with a 1.2mm nozzle diameter. The print head was suitable for water-soluble materials. The printing parameters were set as follows: nozzle temperature 220℃, printing speed 30mm / s, and layer thickness 0.25mm. The printing process was smooth, and the product formed well. After printing, it can be washed with water to remove residual PVA, improving the purity and performance of the product.

[0097] Example 3

[0098] The continuous fiber core material is a 12K basalt-aramid blend fiber bundle, with a basalt fiber to aramid fiber weight ratio of 1:1 and a single filament diameter of 10μm. The sheath fiber is PLA fiber, with a melting point of 170℃ and a fiber diameter of 25μm, used as the braiding material, with two braided layers. The braiding machine has 16 spindles for the inner layer and 24 spindles for the outer layer, with a braiding speed of 30 rpm. The basalt-aramid blend fiber is introduced from the center of the braiding machine, with fiber tension controlled at 0.6N to ensure stable fiber transport. The inner layer PLA fiber is braided at a 40° angle to form an inner braided tube, tightly wrapping the core material. Then, PLA fiber is braided again at a 50° angle outside the inner braided tube to form an outer braided tube, further enhancing the structural stability and resulting in a continuous fiber-reinforced composite thread.

[0099] The continuous fiber-reinforced composite filament was placed in a steam fumigation chamber at a steam temperature of 180℃ for 10 minutes. Under the action of high-temperature steam, the PLA fibers softened and melted, encapsulating and penetrating between the continuous fibers to form a dense composite structure. After fumigation, the filament was removed and allowed to cool naturally at room temperature to complete the setting process. The final 3D printing filament had a uniform surface and color, with a diameter of approximately 2.5 mm, and the mass ratio of the continuous fiber core to the sheath fiber woven tube was 55:45.

[0100] Mechanical performance test results show that the tensile strength of the obtained 3D printing consumables reaches 1000MPa and the bending strength is 800MPa.

[0101] This 3D printing consumable was applied to a commercial FDM 3D printer with the following printing parameters set: nozzle temperature 200℃, printing speed 35mm / s, and layer thickness 0.6mm. The printing process was stable, producing high-precision products with high strength and heat resistance. It combines the excellent properties of basalt fiber and aramid fiber, making it suitable for high-performance applications.

[0102] Example 4

[0103] All other conditions are the same as in Example 1, except that:

[0104] The continuous fiber core was replaced with 12K carbon fiber (7μm monofilament diameter, 4900MPa tensile strength) and 24K glass fiber (13μm monofilament diameter, 3450MPa tensile strength), with a carbon fiber to glass fiber weight ratio of 1:1; the PA6 fiber was braided at a 60° angle. The resulting 3D printing filament exhibited a tensile strength of 1600MPa, a flexural strength of 1300MPa, and an impact strength of 85kJ / m. 2 It combines high strength and high toughness.

[0105] Example 5

[0106] All other conditions are the same as in Example 1, except that:

[0107] The continuous fiber core material was replaced with 16K basalt fiber (fiber monofilament diameter of 11μm, tensile strength of 4800MPa) and Kevlar aramid fiber (fiber monofilament diameter of 12μm, tensile strength of 3600MPa), with a weight ratio of basalt fiber to Kevlar aramid fiber of 1:1.

[0108] The outer layer fiber is PEEK fiber with a diameter of 50μm and a weaving angle of 45°; the heat treatment temperature is 370℃ and the treatment time is 10min.

[0109] The resulting 3D printing filament has a heat distortion temperature of 280℃ and an impact strength of 90kJ / m. 2 It exhibits outstanding heat resistance and also has high impact resistance.

[0110] Example 6

[0111] All other conditions are the same as in Example 1, except that:

[0112] By changing the weaving angle of PA6 fibers to 30° or 60°, the results showed that a weaving angle of 30° could improve the flexibility of the 3D printing consumables, making it suitable for applications that require bending.

[0113] When the weaving angle is 60°, the fibers can be more tightly interwoven in the radial direction, which improves the strength and stability of the 3D printing consumables and is suitable for applications that require high strength.

[0114] Example 7

[0115] All other conditions are the same as in Example 1, except that:

[0116] The cortex fiber was replaced with PCL fiber with a diameter of 75μm, and the heat treatment temperature was 60℃ for 5 minutes.

[0117] The resulting 3D printing consumables only require a printing temperature of 70°C and can be combined with continuous fiber core materials that cannot withstand high-temperature processing for printing.

[0118] Example 8

[0119] All other conditions are the same as in Example 2, the only difference being:

[0120] The step of using water for shaping was omitted, and the woven continuous fiber-reinforced composite filament was directly used as consumable for 3D printing. The results showed that the obtained consumable could be used directly for printing, but the feeding stability was slightly reduced, which was manifested in a slightly lower surface smoothness of the printed product compared with Example 2, and occasional material jamming occurred, but it was still fully capable of meeting the printing requirements.

[0121] Example 9

[0122] This embodiment prepares an eccentric continuous fiber reinforced composite material 3D printing consumable, that is, the continuous fiber core material is deviated from the center position in the cross section of the consumable to meet specific functional requirements, such as improving the local performance of the product or realizing functional gradient.

[0123] 3K continuous carbon fiber was selected as the core material, with a single filament diameter of 7μm, exhibiting excellent properties of high strength and high modulus. The polymer fiber for the sheath, PA6 fiber, with a melting point of 220℃ and a fiber diameter of 20μm, was used as the braiding material. To achieve the eccentric structure, the braiding machine was modified, moving the core material inlet from the center to an eccentric position. Specifically, by adjusting the angle and position of the core material inlet tube to be closer to the edge of the braiding area, the continuous carbon fiber was introduced to the side of the braiding tube during the braiding process. Additionally, a PA6 fiber was incorporated into the core material to help maintain the eccentric position of the continuous carbon fiber. The braiding machine is equipped with 16 braiding spindles, and the braiding speed is set to 30 rpm. The continuous carbon fiber is introduced from the eccentric inlet tube with a constant tension of 1N. The PA6 fiber is cross-braided at a 45° braiding angle, with the fiber tension controlled at 0.5N, forming a tubular structure that tightly wraps around the carbon fiber, resulting in a continuous fiber-reinforced composite 3D printing consumable. Due to the offset of the core material introduction position, the continuous carbon fibers are located in the edge region of the braided tube, forming an eccentric fiber-reinforced structure.

[0124] The woven material is heat-treated in a tubular furnace at 230°C for 10 seconds at a speed of 2 m / min. This temperature is slightly higher than the melting point of PA6 to ensure complete melting of the polymer fibers. The molten PA6 fibers coat and penetrate the carbon fibers and surrounding areas, forming a dense composite structure. After exiting the furnace, the material immediately enters the cooling zone and is cooled by air to rapidly set the material. Because the continuous carbon fibers are off-center in the cross-section of the material, the molten PA6 fibers, after cooling and setting, form a 3D printing material with an asymmetrical fiber distribution across the cross-section.

[0125] After cooling, the 3D printing filament is wound onto a spool using an automatic winding machine. The winding speed is synchronized with the heat treatment speed to maintain constant tension and prevent the filament from loosening or deforming. The final 3D printing filament has a smooth surface, a uniform diameter of approximately 1.75 mm, and a continuous fiber core to sheath fiber woven tube mass ratio of 35:65. The cross-section shows an eccentric distribution of fibers.

[0126] Mechanical property test results show that the tensile strength of the obtained eccentric 3D printing consumable along the fiber-reinforced region reaches 1400MPa, which is slightly lower than that of the 3D printing consumable reinforced with continuous fibers distributed in the center, but still significantly higher than that of pure polyamide material; the bending properties show anisotropy, and the stiffness and strength of the fiber-reinforced region are higher.

[0127] This eccentric 3D printing filament was applied to a commercial FDM 3D printer, where the printhead temperature reached a maximum of 280°C. Printing parameters were set as follows: nozzle temperature 250°C, printing speed 40 mm / s, and layer thickness 0.6 mm. During printing, attention must be paid to the filament feed direction to ensure the fiber-reinforced area faces the direction requiring reinforcement in the product. The 3D printing filament feed was smooth, without blockage or fiber breakage. The final printed product exhibited higher strength and stiffness in the fiber-reinforced area, suitable for structural components requiring localized reinforcement. By adjusting the printing path and the filament feed direction, directional design of the product's mechanical properties can be achieved. This embodiment successfully prepared an eccentrically continuous fiber-reinforced 3D printing filament through modification of the weaving equipment and adjustment of process parameters. This method broadens the application scope of this application, providing new possibilities for the performance design and optimization of 3D printed products, and has significant application value.

[0128] Example 10

[0129] This embodiment describes the fabrication of a multi-layered, nested, continuous fiber-reinforced composite 3D printing filament. The inner continuous fiber core material uses 12K carbon fiber bundles, specifically T700S carbon fibers with a single filament diameter of 7 μm, exhibiting a tensile strength of 4900 MPa, a tensile modulus of 230 GPa, and an elongation at break of 2.1%. The outer continuous fiber core material uses 24K glass fiber bundles with a single filament diameter of 13 μm, supplied by Owens Corning alkali-free glass fiber, exhibiting a tensile strength of 3450 MPa, a tensile modulus of 73 GPa, and an elongation at break of 4.7%. The inner polymer fiber is PLA fiber with a diameter of 20 μm and a melting point of 170°C. The outer polymer fiber is PA6 fiber with a diameter of 20 μm and a melting point of 220°C.

[0130] Using a multi-layer braiding machine, 12K carbon fiber bundles are introduced into the inner core position of the braiding machine at a tension of 1N through a fiber guide device. Subsequently, PLA fibers are braided at a tension of 0.5N through 16 braiding spindles at a braiding angle of 30° to form a tubular structure, interweaving the carbon and PLA fibers to form an inner embedded structure. Next, the outer layer is braided. Based on the completed inner layer braiding, 24K glass fiber bundles are introduced into the outer braiding area at a tension of 1N through a fiber guide device, advancing synchronously with the inner layer filaments. Then, PA6 fibers are braided at a tension of 0.5N through 24 braiding spindles at a braiding angle of 60°, covering the outer layer, interweaving the glass and PA6 fibers to form an outer embedded structure, resulting in a composite wire.

[0131] A phased heat treatment process was employed for shaping. The woven composite filament was passed through a tubular furnace at a speed of 1 m / min. The first stage heating temperature was set at 180℃ (10℃ above the PLA melting point), with a heating length of 1 m and a heating time of approximately 1 minute. The purpose was to melt the inner PLA fibers, coating and penetrating them between the carbon fibers. The second stage heating temperature was raised to 230℃ (10℃ above the PA6 melting point), with a heating length of 1 m and a heating time of approximately 1 minute. The purpose was to melt the outer PA6 fibers, coating and penetrating them between the glass fibers. Immediately afterwards, the filament entered a segmented cooling system. The first cooling stage reduced the temperature from 230℃ to 150℃, with a length of 1 m and a cooling time of approximately 1 minute. The second cooling stage reduced the temperature from 150℃ to room temperature, with a length of 1 m and a cooling time of approximately 1 minute. The purpose of segmented cooling was to gradually reduce the temperature, decrease internal stress, and prevent filament deformation. Surface treatment was performed to impart flame-retardant properties to the 3D printing filament. After cooling, the wire is passed through a dip-coating device to coat its surface with a flame-retardant coating. The coating material is a halogen-free flame retardant solution (solvent is deionized water, flame retardant concentration is 10%), and the dip-coating time is 5 seconds. Subsequently, the coated wire is placed in a tunnel drying oven at a temperature of 100°C for 30 minutes to ensure complete solvent evaporation and uniform coating adhesion.

[0132] Finally, the processed multi-layer nested 3D printing filament is wound into a spool using an automatic winding machine, with the winding tension controlled at 20N. The spool is then placed in a dry, light-protected storage environment at 20°C and relative humidity below 50% to prevent material aging or performance degradation. The finished multi-layer nested 3D printing filament has a diameter of 2.5mm, and the fiber weight ratio is as follows: carbon fiber 20%, glass fiber 30%, PLA polymer 25%, and PA6 polymer 25%.

[0133] Mechanical property test results show that the tensile strength of the obtained multi-layer nested 3D printing consumable reaches 1800 MPa, the tensile modulus is 150 GPa, the flexural strength is 1500 MPa, the flexural modulus is 120 GPa, and the impact strength is 80 kJ / m. 2 Thermal performance testing showed that the heat distortion temperature (HDT) of the 3D printing consumable was 200℃, and the glass transition temperature (T0) was... g The temperature is 85℃. In terms of functional characteristics, the flame retardant performance reaches UL94V-0 level, and the corrosion resistance is excellent. There is no significant performance degradation after soaking in acid and alkali solutions for 24 hours.

[0134] In this 3D printing application, an FDM 3D printer was used with a nozzle diameter of 1.5mm, a heating nozzle temperature set to 240℃, a print bed temperature of 80℃, a printing speed of 30mm / s, and a layer thickness of 0.8mm. The prepared multi-layer nested 3D printing filament was installed into the printer's feeding system, ensuring smooth filament feeding. Printing parameters were set to suit the characteristics of the multi-layer nested 3D printing filament, the printing model was loaded, and printing began. Due to the high strength and high modulus of the multi-layer nested 3D printing filament, the printing speed and nozzle temperature were adjusted during printing to prevent warping caused by overheating or rapid cooling. After printing, the product was allowed to cool to room temperature before being removed. The printed product exhibited excellent mechanical properties, with a tensile strength exceeding 1500MPa, meeting the requirements of high-strength applications. In terms of thermal performance, the product maintained dimensional stability at high temperatures of 150–200℃, making it suitable for manufacturing high-temperature resistant components. It also demonstrated good flame retardant properties, making it suitable for applications with high fire protection requirements.

[0135] As can be seen from the above embodiments, the combination of materials and the adjustment of process parameters have a significant impact on the performance of the final product. In terms of materials, the type and combination of fibers can effectively control the strength, toughness, and heat resistance of the filaments.

[0136] Although the above embodiments have provided a detailed description of this application, they are only some embodiments of this application, not all embodiments. Other embodiments can be obtained based on these embodiments without creative intent, and these embodiments all fall within the protection scope of this application.

Claims

1. A continuous fiber-reinforced composite 3D printing consumable, characterized in that, It includes a continuous fiber core and a sheath fiber woven tube; the continuous fiber core is wrapped in the cavity of the sheath fiber woven tube, and / or the continuous fiber core is interwoven in the tube wall of the sheath fiber woven tube; The continuous fiber core material includes one or more of carbon fiber, glass fiber, basalt fiber, polymer fiber, metal fiber, ceramic fiber, and bio-based fiber; The lining fiber used in the woven tube is a polymer fiber.

2. The continuous fiber-reinforced composite 3D-printing consumable according to claim 1, characterized in that, The dermis fiber includes one or more of the following: polyamide fiber, polypropylene fiber, polyethylene fiber, polylactic acid fiber, polycaprolactone fiber, polyvinyl alcohol fiber, polyetheretherketone fiber, polyimide fiber, polyphenylene sulfide fiber, polycarbonate fiber, polyethylene terephthalate fiber, polyvinyl chloride fiber, blended polymer fiber, and modified polymer fiber. The number of tube wall layers of the corrugated fiber tube is ≥1; the mass ratio of the continuous fiber core layer to the corrugated fiber tube is 1~80:20~99.

3. The continuous fiber-reinforced composite 3D printing consumable of claim 2, wherein, The blended polymer fiber is a fiber formed from a blend of at least two of the following: polyamide, polypropylene, polyethylene, polylactic acid, polycaprolactone, polyvinyl alcohol, polyether ether ketone, polyimide, polyphenylene sulfide, polycarbonate, polyethylene terephthalate, and polyvinyl chloride.

4. The continuous fiber-reinforced composite 3-dimensional printing consumable of claim 2, wherein, The modified polymer fiber is obtained by modifying the polymer fiber matrix with a modifier; the polymer fiber matrix includes one or more of polyamide, polypropylene, polyethylene, polylactic acid, polycaprolactone, polyvinyl alcohol, polyetheretherketone, polyimide, polyphenylene sulfide, polycarbonate, polyethylene terephthalate, and polyvinyl chloride; the modifier includes one or more of inorganic fillers, short fibers, nanomaterials, magnetic particles, and antioxidants; the inorganic fillers include one or more of carbon black, metal oxide powder, and mineral powder; the short fibers include one or more of glass fiber, carbon fiber, and aramid fiber; the nanomaterials include one or more of carbon nanotubes, graphene, and metal nanowires.

5. The continuous fiber-reinforced composite 3-dimensional printing consumable of claim 1, wherein, The diameter of the cortical fibers is 10–300 μm.

6. The continuous fiber-reinforced composite 3-dimensional printing consumable of claim 1, wherein, The polymer fibers used in the continuous fiber core material include one or more of aramid fibers, poly(p-phenylenebenzodioxazole) fibers, polyethylene fibers, polyester fibers, polyimide fibers, and polyamide fibers. The metal fibers include one or more of copper fibers, aluminum fibers, and tungsten fibers; The ceramic fibers include alumina fibers and / or silicon carbide fibers; The bio-based fibers include bamboo fiber and / or flax fiber; The continuous fiber core material is a single fiber filament or a fiber bundle; the number of the continuous fiber core material is ≥1.

7. The continuous-fiber-reinforced composite 3-dimensional printing consumable of claim 1, wherein, The continuous fiber core material includes functional polymer fibers; the functional polymer fibers include one or more of conductive fibers, flame-retardant fibers, antibacterial fibers, and fluorescent fibers.

8. The continuous fiber-reinforced composite 3-dimensional printing consumable of claim 6, wherein, The diameter of the fiber monofilament is 2 to 800 μm, and the number of fiber monofilaments in the fiber bundle is 1K to 50K.

9. The continuous-fiber-reinforced composite 3-dimensional printing consumable of claim 1, wherein, When the continuous fiber core material is wrapped in the cavity of the sheath fiber woven tube, the distribution of the continuous fiber core material in the cross section of the three-dimensional printing consumable is central distribution, eccentric distribution, or multi-core distribution. When the distribution pattern is eccentric, the continuous fiber reinforced composite material 3D printing consumable also includes auxiliary positioning fibers; the auxiliary positioning fibers and the continuous fiber core are together wrapped in the cavity of the skin fiber weaving tube; the positional relationship between the auxiliary positioning fibers and the continuous fiber core is that they are arranged in parallel or intertwined.

10. The continuous fiber-reinforced composite 3-dimensional printing consumable of claim 9, wherein, The diameter of the auxiliary positioning fiber is 2 to 800 μm.

11. The continuous-fiber-reinforced composite 3-dimensional printing consumable according to claim 1, characterized in that, The diameter of the continuous fiber reinforced composite material 3D printing consumable is 0.1 to 10 mm.

12. The method of producing a continuous fiber-reinforced composite 3D printing consumable according to any one of claims 1 to 11, characterized in that, Includes the following steps: Using cortex fibers and continuous fiber core materials as raw materials, the materials are woven according to a preset structure to obtain the continuous fiber reinforced composite material three-dimensional printing consumables; Alternatively, the dermal fiber, continuous fiber core material, and auxiliary positioning fiber can be used as raw materials and woven according to a preset structure to obtain the continuous fiber reinforced composite material three-dimensional printing consumable. The weaving method is either braiding or knitting.

13. The method of claim 12, wherein, The number of spindles in the weaving is 4 to 200, the number of needles in the knitting is 4 to 200, the weaving or knitting angle is 5 to 85°, and the arrangement of the dermal fibers is circular or spiral.

14. The method of claim 12, wherein, The speed of the weaving or knitting is 10 to 800 rpm; the pitch of the weaving is 0.1 to 10 mm.

15. The method of claim 12, wherein, In the weaving process, the tension of the continuous fiber core material is 0.1–10 N, and the tension of the sheath fiber is 0.1–10 N.

16. The preparation method according to claim 12, characterized in that, After weaving, the process further includes setting and / or surface treatment of the resulting fabric; the setting method includes heat treatment, solvent treatment, steam fumigation treatment or ultraviolet curing treatment. The surface treatment method is plasma treatment or preparation of a functional layer on the surface of the woven fabric; the functional layer includes one or more of the following: a lubricating layer, an antioxidant layer, an antistatic layer, a flame retardant layer, a conductive layer, and an antibacterial layer.

17. A method of three-dimensional printing, characterized by The method includes the following steps: performing three-dimensional printing using the continuous fiber reinforced composite material three-dimensional printing consumables as described in any one of claims 1 to 11 or the continuous fiber reinforced composite material three-dimensional printing consumables prepared by the preparation method described in any one of claims 12 to 16.

18. The method of three-dimensional printing according to claim 17, wherein, The conditions for the 3D printing include: nozzle temperature of 100-400℃, printing speed of 1-100mm / s, and layer thickness of 0.1-5mm.

19. A three-dimensional printed article obtained by the three-dimensional printing method of claim 17 or 18.

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