CN115122559A - Low-density three-dimensional carbon fiber composite product and production method thereof - Google Patents

Low-density three-dimensional carbon fiber composite product and production method thereof Download PDF

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Publication number
CN115122559A
CN115122559A CN202210711612.6A CN202210711612A CN115122559A CN 115122559 A CN115122559 A CN 115122559A CN 202210711612 A CN202210711612 A CN 202210711612A CN 115122559 A CN115122559 A CN 115122559A
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China
Prior art keywords
foaming
epoxy resin
temperature
carbon fiber
low
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CN202210711612.6A
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Chinese (zh)
Inventor
诸葛磊
张亚刚
巨安奇
郭建忠
王宣
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Zhejiang Haiyue New Material Co ltd
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Zhejiang Haiyue New Material Co ltd
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Priority to CN202210711612.6A priority Critical patent/CN115122559A/en
Publication of CN115122559A publication Critical patent/CN115122559A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/08—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles using several expanding or moulding steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/60—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0872—Prepregs

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

A low-density three-dimensional carbon fiber composite product and a production method thereof comprise the following steps: s1, obtaining an epoxy resin foaming material which can be solidified in sections and foamed in sections; s2, performing first-stage foaming and first-stage curing on the foaming material to obtain a foaming initial blank; s3, wrapping the carbon fiber prepreg sheet on the outer surface of the foaming primary blank, and wrapping and fixing to form a preform; s4, placing the pre-molded body into a full-size mold to perform two-stage foaming and two-stage curing, and performing internal expansion and hot molding on the foaming primary blank in the process; and S5, exhausting or cooling to eliminate the internal expansion force to obtain the finished product. The method can prepare the three-dimensional carbon fiber product with excellent performance and good appearance effect, greatly improves the yield, basically achieves 100% of the yield of simple parts, and achieves 90% of the yield of complex parts.

Description

Low-density three-dimensional carbon fiber composite product and production method thereof
Technical Field
The invention belongs to the technical field of carbon fiber composite products, and particularly relates to a production method of a low-density three-dimensional carbon fiber composite product.
Background
The preparation method of the three-dimensional carbon fiber composite material product mainly adopts a hollow air blowing bag method and a foaming internal expansion supporting method. Chinese patent documents CN113370557A, CN108127938A, CN103331899A, CN101298188A, and the like adopt a hollow air bag blowing method to prepare tubular three-dimensional carbon fiber products with low requirements on texture and a single structure, such as carbon fiber exhaust cylinders, bicycle support frames, missile shells, simple cases, air inlet air knives, and the like. The hollow air blowing bag method is the main production process of the existing three-dimensional carbon fiber product and has the advantages that the product forming process is simple; however, because the interior of the product is hollow, multiple layers of carbon fibers are required to be used as supports, and an angular laying layer is also required to be locally used, the finished product can only be sprayed with colored paint, and a transparent 3K-grain carbon fiber product cannot be produced.
Chinese patent documents cn202111356815.x, CN202011259797.9, and the like adopt a foaming internal expansion support method to prepare a three-dimensional carbon fiber. The method has the advantages that the three-dimensional transparent 3K-grain carbon fiber part with few layers or even a single layer of carbon fiber can be realized; the defects are that when a large and wide carbon fiber composite material product is manufactured (such as a Tesla model 3 large empennage, a tank 300 Saibo edition modified car ultra-large empennage and the like), a large amount of product defects such as grain distortion, yarn separation, yarn clamping, bottom exposure, glue accumulation and material shortage and the like are caused due to the problem of uniform foam support, the deformation and the shake are caused by wind resistance, and the yield of a single-process product is greatly reduced along with the complexity and the large-scale of the shape.
Because the foaming internal expansion supporting method has the defects, when a large carbon fiber composite material product is manufactured, the A-side shell is manufactured by silica gel mould pressing for subsequent compounding. The process is an advanced technology for manufacturing 3K-pattern three-dimensional carbon fiber products at present, but 10 working procedures are needed, and 7 working procedures cannot be automated.
Disclosure of Invention
The invention aims to provide a low-density three-dimensional carbon fiber composite product and a production method thereof, which aim to solve the technical problems in the prior art.
The purpose of the invention is realized by the following technical scheme:
the invention provides a production method of a low-density three-dimensional carbon fiber composite product, which is characterized by comprising the following steps of: s1, obtaining an epoxy resin foaming material capable of being cured in sections and foamed in sections; s2, performing first-stage foaming and first-stage curing on the foaming material to obtain a foaming initial blank; s3, wrapping the carbon fiber prepreg sheet on the outer surface of the foaming primary blank, and wrapping and fixing to form a preform; s4, placing the pre-molded body into a full-size mold to perform two-stage foaming and two-stage curing, and performing internal expansion and hot molding on the foaming primary blank in the process; and S5, removing internal expansion force after exhausting or cooling to obtain the low-density three-dimensional carbon fiber composite product.
More specifically, the invention provides a method for producing a low-density three-dimensional carbon fiber composite product, which is characterized by comprising the following steps of:
s1, preparing the epoxy resin foaming material which is clay-like and has two-section curing and two-section foaming functions at the temperature of 35-60 ℃;
s2, filling the epoxy resin foaming material into a jig with an equal proportion reduced at the temperature of 30-40 ℃ to prepare a blank; cooling to below 25 deg.c and setting in foaming mold; then keeping the mould pressing for 5-30 min at the temperature of 80-110 ℃ and the pressure of 1-5 MPa, and carrying out primary foaming and curing; cooling to 80 ℃ or lower (preferably 40 to 55 ℃) to obtain a density of 0.1 to 0.25g/cm 3 The foamed preform having the shape of an article;
s3, wrapping the carbon fiber prepreg sheet on the outer surface of the foaming primary blank A, and bonding and fixing (including a vacuum preforming process and manual kneading) at 20-50 ℃ (preferably 25-35 ℃) to prepare a preform;
s4, placing the preform into a full-size mold, and performing mold pressing for 5-60 min at the temperature of 120-180 ℃ and under the pressure of 2.0-8.0 MPa in a staged exhaust state to obtain a low-density three-dimensional carbon fiber composite product taking a low-density foam body as an inner core and a three-dimensional carbon fiber reinforcement base as an outer vertical surface;
the Tg of the epoxy resin foaming material after two-stage foaming and curing is 100-150 ℃, the first foaming temperature is 80-110 ℃, and the preferable temperature is 100-110 ℃; the first foaming volume expansion ratio is 2-12 times, and the reaction crosslinking degree of the first curing is less than 60%; the second foaming curing temperature is 120-180 ℃, and preferably 120-160 ℃;
the preparation method of the carbon fiber prepreg sheet comprises the following steps: impregnating carbon fiber cloth in the prepreg, performing prepreg at the temperature of 55-75 ℃, cooling to 20-30 ℃, and cutting into sheets with designed patterns; commercially available products such as carbon fiber prepreg type SYT45 of Zhongshenying hawk, WP-3011 carbon fiber prepreg of Guangwei composite material, and the like; the prepreg is an epoxy resin curing material, and a curing agent and an accelerating agent of the prepreg are consistent with those of the epoxy resin foaming material, so that the prepreg and the blank can be completely combined with each other; the carbon fiber prepreg comprises 38-45 mass percent of epoxy resin and 10000-50000 cP of resin viscosity at 65 ℃.
Further, in the step (2), the foamed parison is a foamed composite body of epoxy resin or modified epoxy resin with a continuous phase of 30-60% of crosslinking degree and a dispersed phase of micro-bubbles and inorganic filler; the overall size of the composite material is 200-800 mu m smaller than that of the preform, and the Shore C hardness at 30 ℃ is 45-90, preferably 60-85; because the foaming primary blank belongs to an incomplete cured body and has post-curing activity, the surface of the foaming primary blank can be sticky at 20-40 ℃, and the foaming primary blank can be bonded with resin in a prepreg, so that the carbon fiber prepreg can be well bonded.
Further, in the step (3), the volume free expansion rate of the preform is 1.05-1.5 times, and the Tg of the molded body is more than or equal to 110 ℃; at the temperature of 120-180 ℃, in the pre-molded body, the semi-crosslinked epoxy resin of the foaming primary blank and the epoxy resin of the pre-impregnated material can be fused and cured together, so that the good composite effect is achieved; at the moment, the high-temperature foaming agent in the foaming primary blank starts to release inert gas or expand by heating, so that the carbon fiber cloth is well attached to the inner surface of the mold, the texture of the carbon fiber is guaranteed, and the problems of glue accumulation, material shortage and the like caused by uneven stress are solved.
The production method of the low-density three-dimensional carbon fiber composite product, which is disclosed by the invention, can be used as long as the application condition requirements of the invention are met.
But more preferably, the invention provides the epoxy resin foaming material, which comprises the following raw materials in percentage by mass: 10-30% of solid epoxy resin, 10-40% of liquid epoxy resin, 0-15% of modified epoxy resin, 0-15% of reactive diluent, 0-5% of reactive coupling agent, 5-20% of nucleating agent, 0-10% of filler, 1-3% of high-temperature foaming agent, 2-8% of high-temperature curing agent, 1-4% of high-temperature accelerator, 1-6% of low-temperature foaming agent and 10-20% of low-temperature curing agent;
the solid epoxy resin is one or more of bisphenol A epoxy resin or hydrogenated bisphenol A epoxy resin, the glass transition temperature Tg of the solid epoxy resin is 12-105 ℃, and the epoxy value is 0.08-0.38 eq/100g, such as the trade marks of E-35, E-31, E-20, E-14 and E-10;
the liquid epoxy resin is one or more of bisphenol A epoxy resin (such as E51, E44, AG-80 and TED-85) with an epoxy value of 0.38-1.0 eq/100g, bisphenol F epoxy resin (such as YDF-161 and YDF162) and phenolic epoxy resin (such as F-44 and F-51);
the modified epoxy resin is one or more of organic silicon modified epoxy resin, polyurethane modified epoxy resin and hydroxyl-terminated liquid nitrile rubber modified epoxy resin, for example: complexing highly and newly produced EPU-133L, EPSI-3266, EPP-175 and the like;
the active diluent is one or more of Allyl Glycidyl Ether (AGE), n-Butyl Glycidyl Ether (BGE), Phenyl Glycidyl Ether (PGE) and epoxy benzene;
the active coupling agent is one or more of an aminosilane coupling agent, an epoxy silane coupling agent and an acryloxy silane coupling agent; preferably an aminosilane coupling agent; the aminosilane coupling agent comprises gamma-aminopropyltrimethoxysilane (trade name A-1110), gamma-aminopropyltriethoxysilane (trade name KH550), N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane (trade name A-1120), N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, anilinomethyltriethoxysilane, anilinomethyltrimethoxysilane, gamma-aminoethylaminoethylaminopropyltrimethoxysilane (trade name A-1130), more preferably KH 550;
the nucleating agent is silicate, carbonate or metal oxide powder with the diameter of 20-500 nanometers; such as one or more of calcium carbonate, precipitated barium sulfate, aluminum hydroxide powder, micro silicon powder, montmorillonite and the like, and more preferably stearate modified hydrophobic nano calcium carbonate and titanate modified hydrophobic nano calcium carbonate;
the filler is one or more of nano carbon black, color paste, nano clay and PVC powder;
the high-temperature foaming agent is a foaming agent capable of releasing gas or expanding heat at the foaming temperature of 120-180 ℃, such as one or more of rubber microspheres, sulfonyl hydrazide foaming agents (OBSH) and modified high-temperature ADC;
the high-temperature curing agent is one or more of dicyandiamide, diaminodiphenyl sulfone and boron trifluoride-monoethylamine;
the high-temperature accelerant is an organic urea accelerant; preferred organic urea accelerators are one or more of 3-phenyl-1, 1-dimethylurea (e.g. german winning ne UR300), N "- (4-methyl-1, 3-phenylene) bis [ N ', N' -dimethylurea (e.g. german winning ne UR500), 3- (4-chlorophenyl) -1, 1-dimethylurea, 3-p-anisyl-1, 1-dimethylurea, complex highly-new dicyandiamide curing accelerator 5050 or dicyandiamide accelerator 5200;
the low-temperature foaming agent is a physical or chemical foaming agent with a foaming temperature of 80-120 ℃, such as one or more of water, 2' -azobisisobutyronitrile, sodium bicarbonate powder, modified low-temperature azodicarbonamide (modified low-temperature ADC), and the like;
the low-temperature curing agent is polyether modified polyamine, such as: polyoxypropylene diamine D400 and polyoxypropylene triamine T403 from henseme; the polyoxypropylene diamine D400 is a bifunctional primary amine which takes propylene oxide as a basic repeating chain segment on a main chain structure, a primary amine group is connected to a second carbon atom of an aliphatic polyether main chain end group, and the average molecular weight is 400-500; the polyoxypropylene triamine T403 is a trifunctional primary amine which takes propylene oxide as a basic repeating chain segment on a main chain structure, has a primary amino group connected with a second carbon atom of an aliphatic polyether main chain end group and has an average molecular weight of 400-500;
preferably, the preparation method of the epoxy resin foaming material comprises the following steps: adding the solid epoxy resin, the liquid epoxy resin, the modified epoxy resin, the reactive diluent, the reactive coupling agent, the nucleating agent and the filler into a heat-insulating kettle according to parts by weight, heating, and stirring and dispersing for 10-80 min at the temperature of 70-90 ℃; cooling to 55-65 ℃, and adding the high-temperature foaming agent, the high-temperature curing agent, the high-temperature accelerator, the low-temperature foaming agent and the low-temperature curing agent; and then grinding at a rotating speed of 50-500 rpm for 10-60 min to obtain the clay-shaped epoxy resin foaming material at the temperature of 35-60 ℃.
The epoxy resin foaming material provided by the invention has basically stable chemical properties within a temperature range of 15-60 ℃, the viscosity of the epoxy resin foaming material gradually decreases from about 50 million centipoise (cP) to about 5 million cP, and the surface hydroxyl is freely exposed along with the temperature rise to cause sticky hand feeling, and the epoxy resin foaming material is specifically characterized in that the epoxy resin foaming material is solid at the temperature below 15 ℃, is asphalt-shaped semisolid at the temperature of 15-35 ℃, and is clay-shaped plastic body at the temperature of 35-60 ℃. The viscosity is reduced to about 15000cP in the range of 60-75 ℃. And starting from about 75 ℃, initially crosslinking the low-temperature curing agent and the epoxy resin to ensure that the viscosity of the foaming agent begins to rise, and the viscosity can reach about 20 ten thousand cP after heat preservation for 20-30 min at about 100 ℃. At this point the low temperature blowing agent begins to react and release gas to foam and expand the entire viscous semi-crosslinked epoxy resin body. Under the action of a high-activity low-temperature curing agent (such as polyether modified polyamine) at the first foaming temperature of 80-120 ℃, 30-60% of epoxy resin active functional groups participate in the reaction, more than 99% of low-temperature foaming agent releases inert gas for foaming, and a foaming primary blank can be prepared. The foaming primary blank is a solid elastomer at normal temperature, and has no reactivity and foamability below 100 ℃, but when the temperature is above 120 ℃, the remaining 40 percent of active functional groups can be subjected to secondary curing under a low-activity curing system, and a small amount of high-temperature foaming agent is also foamed in the secondary curing to provide internal expansion force.
The second purpose of the invention is to provide a low-density three-dimensional carbon fiber composite product prepared by the production method of the low-density three-dimensional carbon fiber composite product.
The low-density three-dimensional carbon fiber composite product is used for automobile parts, such as automobile empennages and exhaust pipes.
Compared with the prior art, the innovation points of the invention are mainly as follows:
the method can prepare the three-dimensional complex carbon fiber transparent 3K-pattern performance part with the length of 2 meters, the width of 0.3 meter and the thickness of 0.3 meter by one-step forming, the product yield can reach 95 percent, the subsequent baking performance at 100 ℃ is stable, and the appearance is good.
At present, the technology of preparing a three-dimensional carbon fiber product by using a foaming body in the market is to prepare the carbon fiber product by using the foaming body as a support after the foaming is finished. Because the foaming body does not have secondary curing activity and secondary self-expansion force, phenomena such as lines collapse, package rising, surface fluctuation, prepreg resin loss and the like often occur, the defective rate reaches more than 10 percent, and the defective rate of carbon fiber products with complex structures can reach 90 percent, which is also an important reason that the carbon fiber products are high in price and cannot be produced in standardized quantity. By adopting the method, the yield of the three-dimensional carbon fiber product is greatly improved, the yield of simple parts is basically 100%, and the yield of complex parts can reach 90%.
The method of the invention adopts low-temperature curing and low-temperature foaming, solves the basic requirement that the primary blank can be used for manufacturing a pre-molded body, and then fully bonds, cross-links and cures the primary blank and the prepreg resin with the Tg of only about 110 ℃ at 120-180 ℃ through secondary curing, so that the secondary blank has good adhesive force.
In addition, when the invention is cured for the second time, along with slight secondary foaming, if the rubber microspheres are used as secondary foaming bodies, the foaming initial blank can be tightly bonded with the prepreg, when the temperature is cooled to be below 110 ℃, the gas in the rubber microspheres is cooled and contracted, and the internal expansion force is eliminated; if OBSH or high-temperature AC foaming is adopted, redundant internal stress can be eliminated by exhausting for many times in the forming process. Finally, the three-dimensional carbon fiber product with good thermal stability and good appearance effect can be prepared.
Detailed Description
It should be understood by those skilled in the art that the present embodiment is only for illustrating the present invention and is not used as a limitation of the present invention.
The raw materials referred to in the examples of the present invention are all commercially available products.
Example 1
A production method of a low-density three-dimensional carbon fiber composite product comprises the following steps:
s1, preparing an epoxy resin foaming material which is clay-like and has two-section curing and two-section foaming functions at the temperature of 35-60 ℃;
the epoxy resin foaming material is self-made and comprises the following raw materials in parts by mass: 20% of solid epoxy resin (bisphenol A epoxy resin E-20), 38% of liquid epoxy resin (bisphenol A epoxy resin E44), 3% of modified epoxy resin (complexing high-new EPU-133L), 10% of reactive diluent (allyl glycidyl ether AGE), 1% of reactive coupling agent (KH550), 5% of nucleating agent (titanate modified hydrophobic nano calcium carbonate), 2% of filler (nano carbon black powder), 3% of high-temperature foaming agent (rubber microsphere), 5% of high-temperature curing agent (dicyandiamide), 1% of high-temperature accelerator (German winning UR300), 2% of low-temperature foaming agent (2, 2' -azobisisobutyronitrile) and 10% of low-temperature curing agent (polyoxypropylene triamine T403);
adding the solid epoxy resin, the liquid epoxy resin, the modified epoxy resin, the reactive diluent, the reactive coupling agent, the nucleating agent and the filler into a heat-preservation kettle according to the parts by weight, heating, and stirring and dispersing at the heat preservation temperature of 80 ℃ for 60 min; cooling to 55 ℃, and adding the high-temperature foaming agent, the high-temperature curing agent, the high-temperature accelerator, the low-temperature foaming agent and the low-temperature curing agent; and then grinding for 30min at the rotating speed of 200rpm to obtain the clay-shaped epoxy resin foaming material at the temperature of 35-60 ℃.
S2, filling the epoxy resin foaming material into a jig with reduced proportion at the temperature of 30 ℃ to prepare a blank; cooling to 20 deg.C, and transferring into foaming mold; then keeping the mould pressing for 10min at the temperature of 110 ℃ and the pressure of 3MPa, and carrying out primary foaming and curing; cooling to 40 deg.C to obtain a density of 0.15g/cm 3 The foamed preform having the shape of an article.
S3, wrapping SYT45 carbon fiber cloth on the outer surface of the foaming primary blank A, and bonding and fixing (including a vacuum preforming process and manual kneading) at 35 ℃ to prepare a preform.
S4, placing the preform into a full-size die, and carrying out die pressing for 30min at the temperature of 150 ℃, under the pressure of 5.0MPa and in a stage exhaust state to obtain the low-density three-dimensional carbon fiber composite product taking the low-density foam body as the inner core and the three-dimensional carbon fiber reinforcement base as the outer vertical surface.
Example 2
A production method of a low-density three-dimensional carbon fiber composite product comprises the following steps:
s1, preparing an epoxy resin foaming material which is clay-like and has two-section curing and two-section foaming functions at the temperature of 35-60 ℃;
the epoxy resin foaming material is self-made and comprises the following raw materials in parts by mass: 30% of solid epoxy resin (bisphenol A epoxy resin E-20), 30% of liquid epoxy resin (bisphenol A epoxy resin E44), 3% of active coupling agent (N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane A-1120), 8% of nucleating agent (titanate modified hydrophobic nano calcium carbonate), 3% of high-temperature foaming agent (rubber microsphere), 4% of high-temperature curing agent (dicyandiamide), 1% of high-temperature accelerator (German Yingchuang UR500), 6% of water and 15% of low-temperature curing agent (polyoxypropylene diamine D400);
adding the solid epoxy resin, the liquid epoxy resin, the modified epoxy resin, the reactive diluent, the reactive coupling agent, the nucleating agent and the filler into a heat-insulating kettle according to parts by weight, heating, and stirring and dispersing for 60min at the temperature of 80 ℃; cooling to 50 ℃, and adding the high-temperature foaming agent, the high-temperature curing agent, the high-temperature accelerator, the low-temperature foaming agent and the low-temperature curing agent; and then grinding for 30min at the rotating speed of 50rpm to obtain the clay-shaped epoxy resin foaming material at the temperature of 35-60 ℃.
S2, filling the epoxy resin foaming material into a jig with reduced proportion at the temperature of 30 ℃ to prepare a blank; cooling to 20 deg.C, and transferring into foaming mold; then keeping the mould pressing for 30min at the temperature of 100 ℃ and the pressure of 1MPa, and carrying out first foaming and curing; cooling to 40 deg.C to obtain a density of 0.25g/cm 3 The foamed preform having the shape of an article.
S3, wrapping WP-3011 carbon fiber cloth on the outer surface of the foaming primary blank A, and bonding and fixing (including a vacuum preforming process and manual kneading) at 35 ℃ to prepare a preform.
S4, placing the preform into a full-size die, and carrying out die pressing for 30min at the temperature of 180 ℃, under the pressure of 5.0MPa and in a stage exhaust state to obtain the low-density three-dimensional carbon fiber composite product taking the low-density foam body as the inner core and the three-dimensional carbon fiber reinforcement base as the outer vertical surface.
Example 3
A production method of a low-density three-dimensional carbon fiber composite product comprises the following steps:
s1, preparing an epoxy resin foaming material which is clay-like and has two-section curing and two-section foaming functions at the temperature of 35-60 ℃;
the epoxy resin foaming material is self-made and comprises the following raw materials in parts by mass: 10% of solid epoxy resin (bisphenol A epoxy resin E-10), 30% of AG-80 liquid epoxy resin, 10% of EPSI-3266 liquid organosilicon modified epoxy resin, 3% of active diluent (epoxy benzene), 5% of active coupling agent (gamma-aminopropyltrimethoxysilane A-1110), 5% of nucleating agent (aluminum hydroxide powder), 9% of filler (SG-2 type PVC resin powder), 2% of high-temperature foaming agent (OBSH foaming agent), 3% of high-temperature curing agent (diaminodiphenyl sulfone), 1% of high-temperature accelerant (3- (4-chlorophenyl) -1, 1-dimethylurea), 1% of 3- (4-chlorophenyl) -1, 1-dimethylurea, 6% of low-temperature modified AC foaming agent foaming at 100-120 ℃, 5% of low-temperature curing agent (polyoxypropylene diamine D400), 10% of low-temperature curing agent (polyoxypropylene triamine T403);
adding the solid epoxy resin, the liquid epoxy resin, the modified epoxy resin, the reactive diluent, the reactive coupling agent, the nucleating agent and the filler into a heat-preservation kettle according to the parts by weight, heating, and stirring and dispersing at the heat preservation temperature of 80 ℃ for 60 min; cooling to 60 ℃, and adding the high-temperature foaming agent, the high-temperature curing agent, the high-temperature accelerator, the low-temperature foaming agent and the low-temperature curing agent; and then grinding for 30min at the rotating speed of 100rpm to obtain the clay-shaped epoxy resin foaming material at the temperature of 35-60 ℃.
S2, filling the epoxy resin foaming material into a jig with reduced proportion at the temperature of 30 ℃ to prepare a blank; cooling to 20 deg.C, and transferring into foaming mold; then keeping the mould pressing for 30min at the temperature of 110 ℃ and the pressure of 3MPa, and carrying out primary foaming and curing; cooling to 40 deg.C to obtain a density of 0.10g/cm 3 The foamed preform having the shape of an article.
S3, impregnating Dongli 3K carbon fiber cloth with epoxy resin (the formula is E-10 resin 40%, AG-80 resin 30%, EPSI-3266 resin 10%, diaminodiphenyl sulfone 13%, 3- (4-chlorophenyl) -1, 1-dimethyl urea 2%, fumed silica 5%, and viscosity is about 1.5 ten thousand cps at 65 ℃) at 65 ℃, and preparing the cloth into the cloth with the gram weight of 195-210 g/cm 2 And pre-impregnated cloth with 40-42 percent of resin content, wrapping the pre-impregnated cloth on the outer surface of the foaming primary blank A, and bonding and fixing at 35 ℃ (comprising a vacuum preforming process and manual kneading) to prepare a preform.
S4, placing the preform into a full-size mold, and performing mold pressing for 30min at the temperature of 165 ℃ and under the pressure of 3.0MPa in a staged exhaust state to obtain the low-density three-dimensional carbon fiber composite product taking the low-density foam body as the inner core and the three-dimensional carbon fiber reinforcement base as the outer vertical surface.
Example 4
A production method of a low-density three-dimensional carbon fiber composite product comprises the following steps:
s1, preparing the epoxy resin foaming material which is clay-like at 35-60 ℃ and has two-stage curing and two-stage foaming functions;
the epoxy resin foaming material is self-made and comprises the following raw materials in parts by mass: 30% of solid epoxy resin (bisphenol A epoxy resin E-31), 10% of YDF-161 liquid epoxy resin, 10% of EPP-175 modified epoxy resin, 5% of active coupling agent (KH550), 10% of nucleating agent (stearate modified hydrophobic nano calcium carbonate), 10% of filler (SG-2 type PVC resin powder), 2% of high-temperature foaming agent (high-temperature AC foaming agent), 5% of high-temperature curing agent (boron trifluoride-monoethylamine), 1% of high-temperature accelerator (3-p-anisyl-1, 1-dimethylurea), 5% of low-temperature foaming agent (sodium bicarbonate), 7% of low-temperature curing agent (polyoxypropylene diamine D400) and 5% of low-temperature curing agent (polyoxypropylene triamine T);
adding the solid epoxy resin, the liquid epoxy resin, the modified epoxy resin, the reactive diluent, the reactive coupling agent, the nucleating agent and the filler into a heat-preservation kettle according to the parts by weight, heating, and stirring and dispersing at the heat preservation temperature of 80 ℃ for 60 min; cooling to 50 ℃, and adding the high-temperature foaming agent, the high-temperature curing agent, the high-temperature accelerator, the low-temperature foaming agent and the low-temperature curing agent; and then grinding for 30min at the rotating speed of 50rpm to obtain the clay-shaped epoxy resin foaming material at the temperature of 35-60 ℃.
S2, filling the epoxy resin foaming material into a jig with reduced proportion at the temperature of 30 ℃ to prepare a blank; cooling to 20 deg.C, and transferring into foaming mold; then keeping the mould pressing for 30min at the temperature of 80 ℃ and the pressure of 5MPa, and carrying out first foaming and curing; cooling to 40 deg.C to obtain a density of 0.12g/cm 3 The foamed preform having the shape of an article.
And S3, wrapping SYT-45 carbon fiber cloth on the outer surface of the foaming primary blank A, and bonding and fixing (including a vacuum preforming process and manual kneading) at 35 ℃ to prepare a preform.
S4, placing the preform into a full-size mold, and performing mold pressing for 30min at the temperature of 170 ℃, under the pressure of 1.0MPa and in a staged exhaust state to obtain the low-density three-dimensional carbon fiber composite product taking the low-density foam body as the inner core and the three-dimensional carbon fiber reinforcement base as the outer vertical surface.
Example 5
A production method of a low-density three-dimensional carbon fiber composite product comprises the following steps:
s1, preparing an epoxy resin foaming material which is clay-like and has two-section curing and two-section foaming functions at the temperature of 35-60 ℃;
the epoxy resin foaming material is self-made and comprises the following raw materials in parts by mass: 30% of solid epoxy resin (bisphenol A epoxy resin E-35), 10% of F-44 liquid epoxy resin, 10% of EPU-133L modified epoxy resin, 20% of nucleating agent (silica fume), 2% of filler (nano carbon black), 3% of high-temperature foaming agent (rubber microsphere), 5% of high-temperature curing agent (dicyandiamide), 1% of high-temperature accelerator (5200), 1% of high-temperature accelerator (5050), 2% of low-temperature foaming agent (2, 2' -azobisisobutyronitrile), 8% of low-temperature curing agent (polyoxypropylene diamine D400) and 8% of low-temperature curing agent (polyoxypropylene triamine T403);
adding the solid epoxy resin, the liquid epoxy resin, the modified epoxy resin, the reactive diluent, the reactive coupling agent, the nucleating agent and the filler into a heat-insulating kettle according to parts by weight, heating, and stirring and dispersing for 30min at the temperature of 70 ℃; cooling to 50 ℃, and adding the high-temperature foaming agent, the high-temperature curing agent, the high-temperature accelerator, the low-temperature foaming agent and the low-temperature curing agent; and then grinding for 30min at the rotating speed of 50rpm to obtain the clay-shaped epoxy resin foaming material at the temperature of 35-60 ℃.
S2, filling the epoxy resin foaming material into a jig with reduced proportion at the temperature of 30 ℃ to prepare a blank; cooling to 20 deg.C, and transferring into foaming mold; then keeping the mould pressing for 30min at the temperature of 80 ℃ and the pressure of 5MPa, and carrying out primary foaming and curing; cooling to 40 deg.C to obtain a density of 0.18g/cm 3 The foamed preform having the shape of an article.
S3, wrapping SYT-45 carbon fiber cloth on the outer surface of the foaming primary blank A, and bonding and fixing (including a vacuum preforming process and manual kneading) at 35 ℃ to prepare a preform.
S4, placing the preform into a full-size mold, and performing mold pressing for 20min at the temperature of 145 ℃ and under the pressure of 2.5MPa in a staged exhaust state to obtain the low-density three-dimensional carbon fiber composite product taking the low-density foam body as the inner core and the three-dimensional carbon fiber reinforcement base as the outer vertical surface.
Example 6
A production method of a low-density three-dimensional carbon fiber composite product comprises the following steps:
s1, preparing an epoxy resin foaming material which is clay-like and has two-section curing and two-section foaming functions at the temperature of 35-60 ℃;
the epoxy resin foaming material is self-made and comprises the following raw materials in parts by mass: 20% of solid epoxy resin (bisphenol A epoxy resin E-20), 15% of TED-85 liquid epoxy resin, 15% of EPSI-3266 modified epoxy resin, 10% of reactive diluent (epoxy benzene), 2% of reactive coupling agent (KH550), 5% of nucleating agent (nano montmorillonite), 5% of filler (SG-2 type PVC resin powder), 3% of high-temperature foaming agent (rubber microsphere), 5% of high-temperature curing agent (dicyandiamide), 1% of high-temperature accelerator (5200), 1% of high-temperature accelerator (5050), 2% of low-temperature foaming agent (2, 2' -azobisisobutyronitrile), 10% of low-temperature curing agent (polyoxypropylene diamine D400) and 6% of low-temperature curing agent (polyoxypropylene triamine T403);
adding the solid epoxy resin, the liquid epoxy resin, the modified epoxy resin, the reactive diluent, the reactive coupling agent, the nucleating agent and the filler into a heat-insulating kettle according to parts by weight, heating, and stirring and dispersing for 30min at the temperature of 70 ℃; cooling to 50 ℃, and adding the high-temperature foaming agent, the high-temperature curing agent, the high-temperature accelerator, the low-temperature foaming agent and the low-temperature curing agent; and then grinding for 30min at the rotating speed of 50rpm to obtain the clay-shaped epoxy resin foaming material at the temperature of 35-60 ℃.
S2, filling the epoxy resin foaming material into a jig with reduced proportion at the temperature of 30 ℃ to prepare a blank; cooling to 20 deg.C, and transferring into foaming mold; then keeping the mould pressing for 30min at the temperature of 80 ℃ and the pressure of 5MPa, and carrying out primary foaming and curing; cooling to 40 deg.C to obtain a density of 0.18g/cm 3 The foamed preform having the shape of an article.
S3, wrapping SYT-45 carbon fiber cloth on the outer surface of the foaming primary blank A, and bonding and fixing (including a vacuum preforming process and manual kneading) at 35 ℃ to prepare a preform.
S4, placing the preform into a full-size mold, and carrying out mold pressing for 20min at the temperature of 180 ℃, under the pressure of 2.5MPa and in a stage exhaust state to obtain the low-density three-dimensional carbon fiber composite product with the low-density foam body as the inner core and the three-dimensional carbon fiber reinforcement base as the outer vertical surface.
The results of testing the 300 Saibobo version of the great wall tank prepared in examples 1-6 with a competitor's brand of finished product are shown in Table 1.
TABLE 1 test results for examples 1-6
Figure BDA0003708267250000151
Note: the automobile tail fin carbon fiber product mainly considers that no cracks appear under the conditions of no wind shaking, high-pressure water gun flushing and broken stone impact when the automobile tail fin carbon fiber product runs at a high speed, and the appearance of the product is integrally good.
As can be seen from table 1, the method of the present invention can prepare a three-dimensional carbon fiber product with excellent performance, the yield of the three-dimensional carbon fiber product is greatly improved, the yield of simple parts is substantially 100%, and the yield of complex parts can reach 90%. Particularly, in the embodiment 5, the polyurethane modified epoxy resin is adopted as the toughness modification, the silica fume with low oil absorption rate is adopted as the filler, the rubber microspheres are adopted as the high-temperature foaming body, the product effect is most stable, the physical properties all meet the requirements of customers, only 26 products are reworked when 1000 products are produced by adopting the technology at present, and the technology is still the first time in the field of processing large-scale appearance performance carbon fiber pieces.
In the embodiment 2, because a completely rigid formula is adopted and water is used as a foaming agent, the air holes are more, so that slight disorder is caused; but the physical properties can meet the refitting requirements, and particularly, the effect is good when the wind resistance is tested; the anti-shaking paint needs to be treated, and the anti-shaking effect is good. The product of the embodiment 3 has better mechanical property, good toughness and good supporting force at lower density, but the PVC powder can be degraded and volatilize HCl during die pressing, so that more product defects exist.
The contrast column adopts a process of once foaming of a polyurethane foam, is a T300 empennage produced by Shenzhen company, and has violent shake at the speed of 90km/h after the product is installed, a large amount of bulges are generated in the paint spraying process, and the product strength cannot reach the standard due to extremely poor performance.

Claims (13)

1. The production method of the low-density three-dimensional carbon fiber composite product is characterized by comprising the following steps of: s1, obtaining an epoxy resin foaming material capable of being cured in sections and foamed in sections; s2, performing first-stage foaming and first-stage curing on the foaming material to obtain a foaming initial blank; s3, wrapping the carbon fiber prepreg sheet on the outer surface of the foaming primary blank, and wrapping and fixing to form a preform; s4, placing the pre-molded body into a full-size mold to perform two-stage foaming and two-stage curing, and performing internal expansion and hot molding on the foaming primary blank in the process; and S5, exhausting or cooling, and then eliminating the internal expansion force to obtain the low-density three-dimensional carbon fiber composite product.
2. The method of producing a low density three dimensional carbon fiber composite article as claimed in claim 1 comprising the steps of:
s1, preparing the epoxy resin foaming material which is clay-like and has two-section curing and two-section foaming functions at the temperature of 35-60 ℃;
s2, filling the epoxy resin foaming material into a jig with an equal proportion reduced at the temperature of 30-40 ℃ to prepare a blank; cooling to below 25 deg.c and setting in foaming mold; then keeping the mould pressing for 5-30 min at the temperature of 80-110 ℃ and the pressure of 1-5 MPa, and carrying out primary foaming and curing; cooling to below 80 ℃ to obtain a product with a density of 0.1-0.25 g/cm 3 The foamed preform having the shape of an article;
s3, wrapping the carbon fiber prepreg sheet on the outer surface of the foaming primary blank A, and bonding and fixing at 20-50 ℃ to prepare a preform;
s4, placing the preform into a full-size mold, and performing mold pressing for 5-60 min at the temperature of 120-180 ℃ and under the pressure of 2.0-8.0 MPa in a staged exhaust state to obtain the low-density three-dimensional carbon fiber composite product.
3. The production method of the low-density three-dimensional carbon fiber composite product according to claim 2, wherein the Tg of the epoxy resin foaming material after two-stage foaming and curing is 100-150 ℃, and the first foaming temperature is 80-110 ℃; the expansion ratio of the first foaming volume is 2-12 times, and the reaction crosslinking degree of the first curing is less than 60%; the second foaming curing temperature is 120-180 ℃.
4. The method for producing a low-density three-dimensional carbon fiber composite material product according to claim 2, wherein the carbon fiber prepreg sheet is prepared by: impregnating carbon fiber cloth in the prepreg, performing prepreg at the temperature of 55-75 ℃, cooling to 20-30 ℃, and cutting into sheets with designed patterns.
5. The method for producing a low-density three-dimensional carbon fiber composite material product according to claim 2, wherein the mass fraction of the epoxy resin in the carbon fiber prepreg is 38-45%, and the resin viscosity at 65 ℃ is 10000-50000 cP.
6. The method for producing a low-density three-dimensional carbon fiber composite product as claimed in claim 2, wherein in the step (2), the foamed preform is a foamed composite body of an epoxy resin or a modified epoxy resin having a crosslinking degree of 30 to 60% in a continuous phase and fine bubbles and an inorganic filler in a dispersed phase; the overall size of the composite material is 200-800 mu m smaller than that of the preform, and the Shore C hardness at 30 ℃ is 45-90; in the step (3), the volume free expansion ratio of the preform is 1.05 to 1.5 times, and the Tg of the molded body is not less than 110 ℃.
7. The method for producing the low-density three-dimensional carbon fiber composite product according to claim 2, wherein the epoxy resin foaming material comprises the following raw materials in percentage by mass: 10-30% of solid epoxy resin, 10-40% of liquid epoxy resin, 0-15% of modified epoxy resin, 0-15% of reactive diluent, 0-5% of reactive coupling agent, 5-20% of nucleating agent, 0-10% of filler, 1-3% of high-temperature foaming agent, 2-8% of high-temperature curing agent, 1-4% of high-temperature accelerator, 1-6% of low-temperature foaming agent and 10-20% of low-temperature curing agent.
8. The production method of the low-density three-dimensional carbon fiber composite material product according to claim 7, wherein the solid epoxy resin is one or more of bisphenol A epoxy resin or hydrogenated bisphenol A epoxy resin, the Tg of the solid epoxy resin is 12-105 ℃, and the epoxy value is 0.08-0.38 eq/100 g; the liquid epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and phenol aldehyde epoxy resin with an epoxy value of 0.38-1.0 eq/100 g; the modified epoxy resin is one or more of organic silicon modified epoxy resin, polyurethane modified epoxy resin and hydroxyl-terminated liquid nitrile rubber modified epoxy resin.
9. The method for producing a low-density three-dimensional carbon fiber composite product according to claim 7, wherein the reactive diluent is one or more of allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether and epoxy benzene; the active coupling agent is one or more of an aminosilane coupling agent, an epoxy silane coupling agent and an acryloxy silane coupling agent; the nucleating agent is silicate, carbonate or metal oxide powder with the diameter of 20-500 nanometers; the filler is one or more of nano carbon black, color paste, nano clay and PVC powder.
10. The method for producing the low-density three-dimensional carbon fiber composite product according to claim 7, wherein the high-temperature foaming agent is a foaming agent capable of releasing gas or thermally expanding at a foaming temperature of 120-180 ℃; the high-temperature curing agent is one or more of dicyandiamide, diaminodiphenyl sulfone and boron trifluoride-monoethylamine; the high-temperature accelerant is an organic urea accelerant; the preferable organic urea accelerator is one or more of 3-phenyl-1, 1-dimethyl urea, N '' - (4-methyl-1, 3-phenylene) bis [ N ', N' -dimethyl urea, 3- (4-chlorophenyl) -1, 1-dimethyl urea, 3-p-anisyl-1, 1-dimethyl urea, complexing highly-new dicyandiamide curing accelerator 5050 or dicyandiamide accelerator 5200; the low-temperature foaming agent is one or more of physical or chemical foaming agents with the foaming temperature of 80-120 ℃; the low-temperature curing agent is polyether modified polyamine.
11. The method for producing the low-density three-dimensional carbon fiber composite product according to any one of claims 1 to 10, wherein the method for preparing the epoxy resin foam material comprises the following steps: adding the solid epoxy resin, the liquid epoxy resin, the modified epoxy resin, the reactive diluent, the reactive coupling agent, the nucleating agent and the filler into a heat-insulating kettle according to parts by weight, heating, and stirring and dispersing at the temperature of 70-90 ℃ for 10-80 min; cooling to 55-65 ℃, and adding the high-temperature foaming agent, the high-temperature curing agent, the high-temperature accelerator, the low-temperature foaming agent and the low-temperature curing agent; and then grinding at a rotating speed of 50-500 rpm for 10-60 min to obtain the clay-shaped epoxy resin foaming material at the temperature of 35-60 ℃.
12. The low-density three-dimensional carbon fiber composite product obtained by the method for producing a low-density three-dimensional carbon fiber composite product according to any one of claims 1 to 10.
13. The low density three dimensional carbon fiber composite article of claim 12, being used in an automotive part.
CN202210711612.6A 2022-06-22 2022-06-22 Low-density three-dimensional carbon fiber composite product and production method thereof Pending CN115122559A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785512B (en) * 2022-11-24 2023-08-25 卡本科技集团股份有限公司 Carbon fiber composite material with three-dimensional open-cell foam structure and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785512B (en) * 2022-11-24 2023-08-25 卡本科技集团股份有限公司 Carbon fiber composite material with three-dimensional open-cell foam structure and preparation method thereof

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