CN-121973475-A - Carbon fiber hybrid composite material plate with different moduli, preparation method thereof and pultrusion device thereof

CN121973475ACN 121973475 ACN121973475 ACN 121973475ACN-121973475-A

Abstract

The invention provides a carbon fiber hybrid composite material plate with different moduli, a preparation method thereof and a pultrusion device thereof, relating to the technical field of composite material manufacture and comprising a fiber supply mechanism, wherein the fiber supply mechanism comprises a fiber conveying component and a porous plate group; the porous plate group is arranged at the downstream of the fiber conveying assembly and used for limiting the positions of carbon fiber bundles with different moduli, the glue spraying die is arranged at the downstream of the porous plate group and used for coating and penetrating resin on the carbon fiber bundles with limited positions, the preforming die is arranged at the downstream of the glue spraying die and used for preforming the glued carbon fiber bundles, the secondary forming die is arranged at the downstream of the preforming die and used for shaping, and the traction cutting mechanism is arranged at the downstream of the secondary forming die and used for carrying out traction and cutting on the formed composite material plate. The invention realizes the balanced distribution of fiber stress, precisely controls the layering structure and fully plays the advantage of material mixing.

Inventors

ZHANG DANDAN
LI FUSHUANG
XIN JING
LIU YANJUN
LI JUN
XUE YAN
YU ZHIMIN

Assignees

中国海洋石油集团有限公司
中海石油炼化有限责任公司
中海油化工与新材料科学研究院(北京)有限公司

Dates

Publication Date: 20260505
Application Date: 20260213

Claims (10)

1. A pultrusion device for a hybrid composite sheet of carbon fibers of different moduli, comprising: the fiber feeding mechanism comprises a fiber conveying assembly (104) and a porous plate group, wherein the fiber conveying assembly (104) can convey at least two continuous carbon fiber bundles with different moduli and apply pretension to each carbon fiber bundle; the glue spraying die (150) is arranged at the downstream of the porous plate group and is used for carrying out resin coating and infiltration on the carbon fiber bundles subjected to position definition; the preforming die (200) is arranged at the downstream of the glue spraying die (150) and is used for preforming the carbon fiber bundles after glue dipping; A secondary molding die (300) arranged at the downstream of the pre-molding die (200) for shaping; and the traction cutting mechanism (400) is arranged at the downstream of the secondary forming die (300) and is used for carrying out traction and cutting on the formed composite material plate.
2. The pultrusion device for the carbon fiber hybrid composite board with different moduli according to claim 1, wherein the fiber conveying assembly (104) comprises at least two independent fiber creels, each creel corresponds to a carbon fiber bundle with one modulus, each spindle on the fiber creel is provided with a tension controller (103), and a fiber guiding path is provided with a ceramic guide wheel group; The porous plate group comprises a first porous plate (105) and a second porous plate (106) which are sequentially arranged along the fiber traction direction, wherein the first porous plate (105) is provided with a plurality of through holes penetrating through the thickness of the porous plate for respectively introducing carbon fiber bundles with different moduli, and the second porous plate (106) is provided with a plurality of through holes penetrating through the thickness of the porous plate for converging the carbon fiber bundles which are led in by the first porous plate (105) in a beam splitting way into hybrid carbon fiber bundles.
3. The pultrusion device of the carbon fiber hybrid composite board according to claim 1, wherein the glue spraying die (150) comprises a glue spraying member, a glue recycling member, and a first chamber (154) and a second chamber (155) sequentially arranged along the fiber pulling direction; the glue solution spraying component is used for spraying resin glue solution to the mixed carbon fiber bundles guided by the porous plate group; the first chamber (154) is used for extruding superfluous glue solution on the surface of the fiber bundle and finishing coating the outer surface; The cross-sectional area of the flow passage of the second chamber (155) is tapered along the fiber drawing direction, so as to promote the penetration of the resin glue solution into the filaments in the fiber bundle.
4. The pultrusion device for the carbon fiber hybrid composite board with different moduli according to claim 1, wherein a preforming zone (201), a homogenizing zone (202) and a heating zone (203) are sequentially arranged in the preforming die (200) along the fiber traction direction, the preforming zone (201) is configured to extrude the hybrid carbon fiber bundles after impregnation, the homogenizing zone (202) is configured to uniformly distribute the fiber bundles treated by the preforming zone (201), the heating zone (203) is configured to heat the fiber bundles treated by the homogenizing zone (202), and the preforming zone (201), the homogenizing zone (202) and the heating zone (203) are respectively configured with independent temperature control systems; The dynamic pressure sensor is arranged in the preforming die (200), and is arranged in the preforming region (201) and/or the homogenizing region (202), and is configured to monitor extrusion force of the fiber bundle in the die, and execute adjustment of traction speed when fluctuation amplitude of the monitored extrusion force exceeds +/-5%, wherein the adjustment precision is +/-0.01 m/min; the secondary forming die (300) is a multi-section heating die, and a curing area (301), a cooling area (302) and a shaping area (303) are sequentially arranged along the fiber traction direction.
5. The pultrusion device of different modulus carbon fiber hybrid composite panels according to claim 1, wherein the traction cutting mechanism (400) comprises a dual crawler tractor (401) and a laser cutter (402).
6. A method for producing a sheet of hybrid composite material of carbon fibers of different modulus based on a pultrusion device according to any of claims 1 to 5, characterized in that it comprises: (a) Respectively carrying out surface treatment on at least two continuous carbon fiber bundles with different moduli; (b) Conveying each carbon fiber bundle through a fiber conveying assembly (104), and applying pretension to each carbon fiber bundle through a tension controller (103); (c) The pretension-controlled carbon fiber bundles are subjected to position limitation by utilizing a porous plate group and are converged into hybrid carbon fiber bundles; (d) Introducing the mixed carbon fiber bundles into a glue spraying mold (150) for coating and penetrating resin glue solution; (e) Introducing the impregnated carbon fiber bundles into a pre-forming die (200), and performing preliminary extrusion, distribution adjustment and heating; (f) Introducing the preformed composite material into a secondary molding die (300), and sequentially solidifying, cooling and shaping; (g) And (3) feeding the shaped composite material into the traction cutting mechanism (400) for traction and fixed-length cutting to obtain the carbon fiber hybrid composite material plate with different moduli.
7. The method of claim 6, wherein in step (a), the surface treatment is a plasma treatment or a surface grafting silane coupling agent; preferably, in the step (c), the pretension control comprises the steps of applying pretension of 50N-80N to the high-modulus carbon fiber bundles, applying pretension of 20N-40N to the medium-modulus carbon fiber bundles, and applying pretension of 10N-50N to other hybrid fibers; preferably, in the step (d), the resin glue solution is a blend of modified epoxy resin and vinyl ester, or is modified epoxy resin; Preferably, the mass ratio of the modified epoxy resin to the vinyl ester is 6-8:3; Preferably, 3 wt% -5% wt% of nano SiO 2 filler is added into the resin glue solution, and 0.5% -wt% -1% wt% of graphene nano sheets are added into the resin glue solution; Preferably, when the resin glue solution comprises a blend of modified epoxy resin and vinyl ester in a mass ratio of 7:3, the temperature of the preforming area (201) is 60-80 ℃, the temperature of the homogenizing area (202) is 80-100 ℃, and the temperature of the heating area (203) is 100-120 ℃; Preferably, in step (e), the preliminary extrusion, the distribution adjustment and the heating are performed in sequence in a pre-forming zone (201), a homogenizing zone (202) and a heating zone (203) of the pre-forming die (200); Preferably, in the step (f), the solidification, cooling and shaping are sequentially completed in a solidification area (301), a cooling area (302) and a shaping area (303) of the secondary forming die (300), wherein the temperature of the solidification area (301) is 120-180 ℃, and the temperature of the cooling area (302) is reduced by 1-5 ℃ per cm; Preferably, after the step (f), before the step (g), the method further comprises post-treatment, wherein the post-treatment comprises post-curing the molded composite material plate obtained in the step (f) in a 110-130 ℃ oven for 2-4 hours; preferably, the carbon fiber bundles conveyed by the fiber conveying assembly (104) comprise high modulus carbon fiber bundles and/or medium modulus carbon fiber bundles; The high-modulus carbon fiber bundle is preferably a continuous filament bundle, the tensile strength is not lower than 2000 MPa, the tensile modulus is not lower than 350 GPa, the breaking elongation is 0.2% -0.8%, the high-modulus carbon fiber comprises one or a combination of at least two of high-modulus pitch-based carbon fiber, high-strength high-modulus pitch-based carbon fiber, high-heat conduction pitch-based carbon fiber, high-modulus polyacrylonitrile-based carbon fiber and high-strength high-modulus polyacrylonitrile-based carbon fiber, the medium-modulus carbon fiber bundle is a continuous filament bundle, the tensile strength is not lower than 3500 MPa, the tensile modulus is 200 GPa-350 GPa, the breaking elongation is 1.5% -2.0%, and the medium-modulus carbon fiber bundle comprises at least one of high-strength polyacrylonitrile-based carbon fiber and high-strength medium-modulus polyacrylonitrile-based carbon fiber.
8. The method according to claim 6, wherein the position defining comprises introducing the high-modulus carbon fiber bundles and the medium-modulus carbon fiber bundles into through holes at different positions of the first porous plate (105) respectively in a predetermined spatial arrangement relationship, and converging the high-modulus carbon fiber bundles and the medium-modulus carbon fiber bundles into the hybrid carbon fiber bundles through the second porous plate (106); the predetermined spatial arrangement relationship is selected from any one of the following: the high-modulus carbon fiber bundles are positioned in the middle area of the first porous plate (105), and the middle-modulus carbon fiber bundles are positioned in the upper side area and the lower side area of the first porous plate (105); the medium-modulus carbon fiber bundles are positioned in the middle area of the first porous plate (105), and the high-modulus carbon fiber bundles are positioned in the upper side area and the lower side area of the first porous plate (105); the high-modulus carbon fiber bundles and the middle-modulus carbon fiber bundles are located in the middle area of the first porous plate (105), and the middle-modulus carbon fiber bundles are located in the upper side area and the lower side area; The high-modulus carbon fiber bundles and the middle-modulus carbon fiber bundles are located in the middle area of the first porous plate (105), and the high-modulus carbon fiber bundles are located in the upper side area and the lower side area; The high modulus carbon fiber bundles and the medium modulus carbon fiber bundles are randomly distributed in all through holes of the first porous plate (105).
9. A carbon fiber hybrid composite board of different moduli, characterized in that it is prepared by the preparation method of any one of claims 6 to 8.
10. The different modulus carbon fiber hybrid composite sheet according to claim 9, wherein the different modulus carbon fiber hybrid composite sheet comprises any one of the following structures: (A) The composite material plate is provided with a core layer and surface layers positioned on the upper side and the lower side of the core layer, wherein the core layer is made of high-modulus carbon fibers, the volume fraction of the core layer is 10% -40%, the surface layers are made of medium-modulus carbon fibers, and the total volume fraction of the surface layers is 60% -90%; (B) The composite material plate is provided with a core layer and surface layers positioned on the upper side and the lower side of the core layer, wherein the core layer is made of medium modulus carbon fibers, the volume fraction of the core layer is 40% -70%, the surface layers are made of high modulus carbon fibers, and the total volume fraction of the surface layers is 30% -60%; (C) The composite material plate is provided with a core layer and surface layers positioned on the upper side and the lower side of the core layer, wherein the core layer is formed by mixing high-modulus carbon fibers and medium-modulus carbon fibers, the volume fraction of the high-modulus carbon fibers in the core layer is 40% -60%, and the balance is the medium-modulus carbon fibers, the surface layers are the medium-modulus carbon fibers, and the volume fraction of the surface layers accounts for 30% -50% of the total volume of the carbon fibers; (D) The composite material plate is provided with a core layer and surface layers positioned on the upper side and the lower side of the core layer, wherein the core layer is formed by mixing high-modulus carbon fibers and medium-modulus carbon fibers, the volume fraction of the high-modulus carbon fibers in the core layer is 10% -40%, and the balance is the medium-modulus carbon fibers; (E) In the composite material plate, high-modulus carbon fibers and medium-modulus carbon fibers are uniformly mixed, wherein the total volume fraction of the high-modulus carbon fibers is 20% -50%, and the total volume fraction of the medium-modulus carbon fibers is 50% -80%.

Description

Carbon fiber hybrid composite material plate with different moduli, preparation method thereof and pultrusion device thereof Technical Field The invention relates to the technical field of composite material manufacturing, in particular to a carbon fiber hybrid composite material plate with different moduli, a preparation method thereof and a pultrusion device thereof. Background The carbon fiber composite material is widely applied to the fields of aerospace, rail transit, new energy, sports equipment and the like due to high specific strength, high specific modulus and excellent fatigue resistance. The pultrusion process is a high-efficiency continuous composite material forming method, and is especially suitable for manufacturing sectional materials with constant cross section, such as bars, tubes, plates, I-beams and the like. The basic principle is that after the continuous fiber is impregnated with resin, the resin is gelled and solidified in a forming die under the pulling force of a tractor through the heated forming die, so that the composite material profile with a specific cross-section shape is obtained. High strength carbon fibers have a large elongation at break but a relatively low modulus, while high modulus carbon fibers have excellent stiffness but a large brittleness. In order to give consideration to the rigidity, strength and toughness of the structural member, the hybrid design is carried out by adopting carbon fibers with different moduli such as high strength, high modulus and the like, and the method has become an important development direction in the field of composite materials. The existing pultrusion technology and device mainly aims at forming single type fibers or random short fibers, and equipment of the existing pultrusion technology and device generally comprises a creel, a gum dipping tank, a preforming device, a heating curing die, a tractor, a cutting machine and the like. However, the prior art pultrusion techniques mostly employ single modulus carbon fibers such as high modulus or standard modulus, which exposes several limitations when applied to hybrid composite plates of different modulus carbon fibers. First, the existing fiber reinforced composite plates have a problem that performance is difficult to optimize. Composite plates prepared by mixing fibers with different moduli are difficult to balance in rigidity, strength and toughness, particularly, the tensile modulus and elongation at break are different, high modulus fibers have high rigidity but high brittleness, while medium and low modulus fibers have good strength but insufficient rigidity, so that stress distribution among the fibers is uneven under the same process tension. Under the combined action of the traction tension in the pultrusion process and the stress generated by the curing shrinkage of the resin, the fibers with higher modulus and lower elongation may first reach their strain limits and break, while the fibers with lower modulus do not fully exert their strength potential. The asynchronous stress state is extremely easy to cause defects in the product, even the whole product fails, and the forward play of the hybrid effect and the mechanical properties of the final product are seriously affected. Secondly, the existing fiber hybrid reinforced composite material plate has the problem of structural design limitation. The existing hybrid composite materials mostly adopt a lamination or braiding mode, the process is complex, the cost is high, and the accurate distribution and interface combination of fibers are difficult to realize. Thirdly, there is a problem that the existing pultrusion device is not suitable for various fiber mixing. The traditional pultrusion device has poor compatibility on multi-fiber mixing, and the problems of uneven fiber distribution, insufficient resin infiltration and the like are easy to occur, so that the product quality is influenced. The difference in bundling and resin wetting of the different fiber bundles during the fiber impregnation and preforming stages can easily lead to uneven distribution or entanglement of the fibers at the die entrance. The existing device lacks a targeted fiber path planning and tension independent control system, and is difficult to ensure that the high-modulus and high-strength carbon fibers can keep preset and ideal spatial arrangement before entering a die, so that the hybrid effect of 'hardness and softness combined' expected by material design cannot be accurately realized. The Chinese patent application with publication number of CN113074090A discloses a preparation method of a carbon-glass hybrid wind power blade girder, which comprises a plurality of carbon fibers and a plurality of glass fibers, wherein the length directions of the carbon fibers and the glass fibers are consistent with the length direction of the blade, and the carbon fibers and the glass fibers are arranged along the width direction of the blade. Further,