CN114425872A - Method for manufacturing high-flame-retardant-grade composite part - Google Patents
Method for manufacturing high-flame-retardant-grade composite part Download PDFInfo
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- CN114425872A CN114425872A CN202011178992.9A CN202011178992A CN114425872A CN 114425872 A CN114425872 A CN 114425872A CN 202011178992 A CN202011178992 A CN 202011178992A CN 114425872 A CN114425872 A CN 114425872A
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- Prior art keywords
- flame
- retardant
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- resin
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003063 flame retardant Substances 0.000 claims abstract description 39
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000004744 fabric Substances 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 16
- 239000004917 carbon fiber Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000006835 compression Effects 0.000 claims abstract description 6
- 238000007906 compression Methods 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract description 5
- 238000001721 transfer moulding Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000005096 rolling process Methods 0.000 claims abstract description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- 150000004645 aluminates Chemical class 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 238000009755 vacuum infusion Methods 0.000 abstract description 2
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
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- 238000009940 knitting Methods 0.000 description 9
- 238000007602 hot air drying Methods 0.000 description 8
- 238000003892 spreading Methods 0.000 description 7
- 230000007480 spreading Effects 0.000 description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 6
- 238000007603 infrared drying Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009745 resin transfer moulding Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
- B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
-
- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B21/20—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes specially adapted for knitting articles of particular configuration
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
- D10B2101/06—Glass
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2403/00—Details of fabric structure established in the fabric forming process
- D10B2403/02—Cross-sectional features
- D10B2403/024—Fabric incorporating additional compounds
- D10B2403/0242—Fabric incorporating additional compounds enhancing chemical properties
- D10B2403/02421—Fabric incorporating additional compounds enhancing chemical properties containing particulate matter, e.g. powder or granulate
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2403/00—Details of fabric structure established in the fabric forming process
- D10B2403/03—Shape features
- D10B2403/033—Three dimensional fabric, e.g. forming or comprising cavities in or protrusions from the basic planar configuration, or deviations from the cylindrical shape as generally imposed by the fabric forming process
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a method for manufacturing a composite material part with high flame retardant grade, which comprises the following steps: a, preparing inorganic flame-retardant powder suspension from flame-retardant powder; b, introducing the inorganic flame-retardant powder suspension into a feeding tank; c, spraying the suspension on the surface of the fiber through a spraying pipe after the fiber is laid with weft; d, moving the fiber forwards, pressing and removing excessive water by using a compression roller after weft laying is finished, and uniformly dispersing the inorganic flame-retardant powder to a fiber laying layer; e, drying by adopting infrared rays; f, stitch-bonding; g, continuously drying residual moisture by using hot air and rolling; h, cutting the laying layer; i, injecting, molding and curing a resin system; and j, demolding. The flame retardant performance of RTM parts is improved by adding the flame retardant auxiliary agent, and the combustion-supporting resistance agent is tightly combined with the fibers by the binder. The carbon fiber fabric woven by the process can be used for composite material forming processes such as RTM (resin transfer molding), vacuum infusion and the like, and can be used in combination with flame-retardant resin, so that the flame-retardant grade of a final product can be greatly improved.
Description
Technical Field
The invention belongs to the field of polymer composite material manufacturing, and particularly relates to a manufacturing method of a high-flame-retardant-grade composite material part.
Background
The RTM forming process is developed rapidly in the composite material forming process, and has the advantages of high surface quality, high precision, low porosity, forming of complex components and the like, so that the RTM forming process is widely applied to multiple fields of military products and civil products. However, the resin matrix used as the high molecular organic material has the same life disadvantage of being flammable and generating a large amount of harmful gas and smoke during combustion. Because the rail transit field personnel are intensive, the space is airtight, so not only consider in being suitable for the fire-protection rating standard to control the degree of fuming, but also implement strict regulation to the harmful substance that contains in the flue gas, this degree that the flue gas caused the secondary damage to the passenger under the condition of can greatly reduced conflagration. Therefore, the halogen-free high-flame-retardant resin-based carbon fiber composite material is very important in popularization and application of the carbon fiber composite material.
The multiaxial warp knitting fabric has higher gram weight which can reach more than 800 g/square meter at most, has lower production cost compared with other textile reinforced structures, is an ideal three-dimensional structure reinforced material, is the most effective and economic pre-designed reinforced fabric at present, has the greatest advantage of simple ply, is suitable for manufacturing large-sized thick-wall workpieces, and is applied to the fields of aerospace, wind power generation, transportation, construction and the like.
With the introduction of the latest EN45545 standard, rail traffic fire protection requirements have addressed a new height, and in order to reduce the risk of fire when the vehicle is in operation, it is desirable that the railway vehicle upholstery material all fall within the EN45545 HL3 category. Conventional unsaturated resins and partial epoxy resin composites have not fully met the EN45545 HL 3-grade fire rating requirement.
Flame retardant (aluminum hydroxide, antimony oxide and liquid flame retardant) is generally added into resin for mixing, but because carbon fiber warp-knitted fabrics are generally used for manufacturing thick-wall large-sized parts and are compact, the flame retardant auxiliary agent is high in flame retardant content at the front end and low in flame retardant content at the tail end due to blocking of the fabrics when the resin is injected, so that the flame retardant performance of the parts is uneven.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a manufacturing method of a composite material with high flame retardant rating, which can solve the problems.
The purpose of the invention is realized by adopting the following technical scheme:
a method for manufacturing a high flame-retardant grade composite material part comprises the following steps: a, preparing inorganic flame-retardant powder suspension from flame-retardant powder; b, introducing the inorganic flame-retardant powder suspension into a feeding tank; c, spraying the suspension on the surface of the fiber through a spraying pipe after the fiber is laid with weft; d, moving the fiber forwards, pressing and removing excessive water by using a compression roller after weft laying is finished, and uniformly dispersing the inorganic flame-retardant powder to a fiber laying layer; e, drying by adopting infrared rays; f, stitch-bonding; g, continuously drying residual moisture by using hot air and rolling; h, cutting the laying layer; i, injecting, molding and curing a resin system; and j, demolding.
Preferably, in step c, the suspension is sprayed between several layers of fabrics from bottom to top, respectively, depending on the fabric texture.
Preferably, the fabric weave structure is a warp knitting fabric with angles of 0 degree, 90 degrees and +/-45 degrees from bottom to top respectively.
Preferably, in a and b, the liquid base in the suspension powder body fluid adopts a modified epoxy resin sizing agent aqueous solution.
Preferably, the fibers are carbon fibers or glass fibers.
Preferably, the preparation of the inorganic flame-retardant powder suspension comprises the following steps: firstly, adding a modified epoxy resin sizing agent into deionized water at the temperature of 40-60 ℃; secondly, adding a defoaming agent and an aluminate coupling agent, wherein the adding proportion of the aluminate coupling agent is 0.4-3% of the mass of the flame-retardant powder; and finally, starting stirring to prepare an aqueous solution, wherein the concentration of the sizing agent is 2-5%, and the solid volume concentration of the finally prepared suspension is 30-40%.
Preferably, the content of the inorganic flame-retardant powder in the fabric dried and rolled in the step g is 20-50% of the weight of the fiber warp-knitted fabric.
Preferably, the resin system used in step i is an epoxy resin system, and comprises 100 parts of resin, 3-30 parts of flame retardant, 0.2-0.8 part of dispersant, 0.3-0.5 part of accelerator and 10-80 parts of curing agent.
Preferably, the resin system further comprises an inorganic flame retardant with a synergistic flame retardant effect, wherein the inorganic flame retardant comprises but is not limited to antimony trioxide, so as to enhance the flame retardant effect of the product.
Preferably, the forming technology in step i adopts one of vacuum assisted forming, resin transfer molding, derivative process of RTM, vacuum assisted RTM forming, lightweight RTM forming and resin film infiltration forming.
Compared with the prior art, the invention has the beneficial effects that: the flame retardant performance of RTM parts is improved by adding a flame retardant auxiliary agent in the weaving process of carbon fibers, the main component of the auxiliary agent is aluminum hydroxide, magnesium hydroxide or a mixture thereof, and a binder is added in proportion to enable the auxiliary agent to be tightly combined with the carbon fibers, so that the uneven flame retardant effect caused by scattering in the resin injection process is ensured. The carbon fiber fabric woven by the process can be used for composite material forming processes such as RTM (resin transfer molding), vacuum infusion and the like, and can be used in combination with flame-retardant resin, so that the flame-retardant grade of a final product can be greatly improved.
Drawings
FIG. 1 is a schematic view of a multi-axial warp knitting machine according to the present invention;
fig. 2 is a schematic diagram of an RTM process according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
A method for manufacturing a composite material part with high flame-retardant rating for resin transfer molding comprises the following steps.
The preparation of inorganic flame-retardant powder suspension liquid is that firstly, modified epoxy resin sizing agent is added into deionized water at the temperature of 40-60 ℃, a small amount of defoaming agent and a certain amount of aluminate coupling agent, and the aluminate coupling agent is added into the flame-retardant powder in a proportion of 0.4-3%. Starting stirring to prepare an aqueous solution, wherein the concentration of the sizing agent is 2-5%. Slowly pouring the mixture of aluminum hydroxide and magnesium hydroxide into a feeding tank for multiple times, stirring and continuously starting in the pouring process, and promoting the mixture to be dispersed more uniformly by a circulating pump. The ratio of the aluminum hydroxide to the magnesium hydroxide is 20-80: 80-20. The solid volume concentration of the finally obtained suspension is 30-40%. In a preferred embodiment, first, 3 parts of modified epoxy resin sizing agent and 1 part of aluminate coupling agent are added into 100 parts of deionized water at 50 ℃, and stirring is started to prepare an aqueous solution. A mixture of 42 parts of aluminum hydroxide powder (3000 mesh) and 35 parts of magnesium hydroxide powder is slowly poured into the feed tank 15 several times, with stirring being continuously turned on during pouring, and is caused to disperse more uniformly by the circulation pump 17. The final suspension had a solid volume concentration of 32%. The blending may be performed in a supply tank.
Referring to fig. 1, the illustrated multi-axial warp knitting machine includes an upstream creel 1, a plurality of sets of yarn feeding assemblies, a plurality of spraying pipes with the same number as the yarn feeding assemblies, a first yarn spreading console 11, a feeding tank 15, a feeding pump 16, a circulating pump 17, a feeding pipe 18, a pressing roller 19, a liquid receiving tank 20, an infrared drying box 21, infrared exhaust air 22, a hot air drying box 23, hot air drying exhaust air 24, a knitting head 25 and a winding machine 26, wherein the upstream creel 1 and the yarn spreading console 11 are arranged upstream of the yarn spreading console (i.e., a smuggling platform), a stirring head is arranged in the feeding tank 15, and the circulating pump 17 is arranged on a tank body of the feeding tank 15; the bottom of the feed tank 15 is connected with a feed pump 16 through a feed pipe 18; the tail end of the feeding pipe 18 is provided with a plurality of spraying pipes in parallel, and the spraying pipes are arranged above the filament spreading table at intervals; a press roller 19 is arranged above the tail end of the silk exhibition platform, and a liquid receiving groove 20 is arranged below the tail end of the silk exhibition platform; an infrared drying box 21, a hot air drying box 23, hot air drying exhaust 24, a weaving machine head 25 and a winding machine 26 are sequentially arranged at the downstream of the silk exhibition platform, the top of the infrared drying box 21 is provided with the infrared exhaust 22, and the top of the hot air drying box 23 is provided with the hot air drying exhaust 24.
Further, the equipment comprises three groups of wire supply assemblies and three spray pipes, wherein the first yarn supply assembly is formed by a first creel 2, a first weft laying device 8 and a first wire spreading component 12, the second yarn supply assembly is formed by a second creel 3, a second weft laying device 9 and a second wire spreading component 13, and the third yarn supply assembly is formed by a third creel 4, a third weft laying device 10 and a third wire spreading component 14; the tail end of the feeding pipe 18 is provided with three spray pipes, namely a first spray pipe 5, a second spray pipe 6 and a third spray pipe 7 in parallel.
And starting the multi-axial warp knitting machine, performing warp inserting and weft laying operation according to the setting after the starting step is completed, and uniformly and gaplessly laying the carbon fibers on the yarn travelling platform. After normal operation, the feeding pump 16 is started, the spraying pipes (5, 6 and 7) positioned above the yarn walking platform are respectively opened, the suspension is uniformly sprayed on the surface of the carbon fiber, and the spraying amount of the suspension in a single spraying pipe is controlled according to 80ml per square meter. The amount of suspension sprayed is determined by the speed of the warp knitting machine, the set solid content of the flame retardant on the final fabric. Starting the multi-axial warp knitting machine to complete the starting step. Wherein the angles of the warp knitting fabric from bottom to top are respectively 0 degree, 90 degrees and +/-45 degrees, and the density of a single-layer surface is 150 g/square meter. And carrying out warp inserting and weft laying operation according to the setting, and then uniformly laying the carbon fibers on the yarn travelling platform without gaps.
The carbon fiber cloth cover moves forward, after weft laying is finished, the excess water is pressed and removed by a compression roller 19 at the outlet of a yarn walking platform, the pressure of the compression roller is controlled to be 0.1MPa, and the flame-retardant suspension powder can be uniformly dispersed to the carbon fiber laying layer by the compression roller 19; the pressed moisture is discharged into the waste liquid tank through the liquid receiving tank 20 below the press roller. The pressing-off of the redundant moisture can greatly reduce the subsequent drying load.
Moisture was removed using an infrared drying device 21, and the infrared drying temperature was set to 150 ℃. The infrared device has the advantages of high drying efficiency, stability, reliability and the like, and water vapor is exhausted through the upper infrared exhaust 22, such as an exhaust device.
And continuously drying residual moisture by using hot air at the temperature of 120 ℃ in the hot air drying oven 23. The water vapor is exhausted through hot air drying exhaust 24, such as an exhaust port.
Looping and stitching: the edge sewing is carried out at the weaving head 25, and the coil length is controlled to be 1-2mm, preferably 2mm, in order to ensure that the inorganic flame retardant powder is not easy to scatter during the subsequent molding.
And (4) winding, namely winding the fabric by using a winding machine 26.
Cutting and layering multiaxial fabric according to design, cutting and shaping multiaxial fabric, layering according to design requirements, setting the thickness of the layering to be 20mm, and laying 8 layers.
And (5) injecting resin. Referring to a and b in fig. 2, different normal temperature curing resins or medium and high temperature curing resins can be selected according to the requirements of the product. The selection range of the injection pressure and the injection rate is wide when the resin is injected.
Curing and demolding, see c and d in fig. 2, the curing temperature ranges from room temperature to 160 ℃.
There are different examples for the resin system, which are specified below.
Example 1: in the resin introducing step, the resin system is RZ-2 of China Shanghai petrochemical institute of petrochemical engineering, wherein 40 parts of bisphenol A epoxy resin, 40 parts of bisphenol F epoxy resin, 20 parts of ethylene glycol diglycidyl ether, 8 parts of isophorone diamine, 23025 parts of polyetheramine D, 5 parts of antimony trioxide, the glue injection pressure is 0.3MPa, and the glue injection temperature is 40 ℃. The curing temperature was 80 degrees 2 hours +120 degrees 1 hour.
And (3) respectively testing the glue injection position 1 and the corner 3 of the workpiece, wherein the flame retardant property is close to and meets the flame retardant grade requirement of EN45545-2HL 3.
Example 2: the introduced resin system comprises 40 parts of bisphenol A epoxy resin, 40 parts of bisphenol F epoxy resin, 20 parts of ethylene glycol diglycidyl ether, 23036 parts of polyether amine D, 10 parts of antimony trioxide, the glue injection pressure is 0.3MPa, and the glue injection temperature is 40 ℃. The curing temperature was 80 degrees 2 hours +120 degrees 2 hours.
Comparative example 1: the common multi-axial warp without flame retardant is directly used to be spread, and the introduced resin components are 40 parts of bisphenol A type epoxy resin, 40 parts of bisphenol F type epoxy resin, 20 parts of ethylene glycol diglycidyl ether, 8 parts of isophorone diamine, 23025 parts of polyether amine D, 5 parts of antimony trioxide, 60 parts of aluminum hydroxide powder, 40 parts of magnesium hydroxide, the glue injection pressure is 0.3MPa, and the glue injection temperature is 40 ℃. The curing temperature was 80 degrees 2 hours +120 degrees 1 hour.
Comparative example 2: the introduced resin components comprise 40 parts of bisphenol A epoxy resin, 40 parts of bisphenol F epoxy resin, 20 parts of ethylene glycol diglycidyl ether, 23036 parts of polyetheramine D, 10 parts of antimony trioxide, 60 parts of aluminum hydroxide powder and 40 parts of magnesium hydroxide, the glue injection pressure is 0.5MPa, and the glue injection temperature is 40 ℃. The curing temperature was 80 degrees 2 hours +120 degrees 2 hours.
Table-Performance verification
Testing: referring to trademarks, the carbon fiber composite material obtained by the method can reach a high-grade flame retardant grade and can meet the data requirement of EN 45545-2R 3 danger grade HL 3: the CFE flame extension test is more than or equal to 20; the heat release amount is less than or equal to 60; the smoke density of Ds (4) is less than or equal to 150; the smoke density of the VOF (4) is less than or equal to 300; the toxicity test is less than or equal to 0.75. The carbon fiber composite material prepared by the method has better mechanical property.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A manufacturing method of a high flame-retardant grade composite material part is characterized by comprising the following steps:
a, preparing inorganic flame-retardant powder suspension from flame-retardant powder;
b, introducing the inorganic flame-retardant powder suspension into a feeding tank;
c, spraying the suspension on the surface of the fiber through a spraying pipe after the fiber is laid with weft;
d, moving the fiber forwards, pressing and removing excessive water by using a compression roller after weft laying is finished, and uniformly dispersing the inorganic flame-retardant powder to a fiber laying layer;
e, drying by adopting infrared rays;
f, stitch-bonding;
g, continuously drying residual moisture by using hot air and rolling;
h, cutting the laying layer;
i, injecting, molding and curing a resin system;
and j, demolding.
2. The method of claim 1, wherein: in step c, the suspension is sprayed between several layers of fabric from bottom to top, respectively, depending on the fabric weave structure.
3. The method according to claim 1 or 2, characterized in that: the fabric weave structure is that the angles of the warp knitted fabric from bottom to top are respectively 0 degree, 90 degrees and +/-45 degrees.
4. The method of claim 1, wherein: in a and b, the liquid base in the suspension powder body liquid adopts a modified epoxy resin sizing agent aqueous solution.
5. The method of claim 1, wherein: the fiber is carbon fiber or glass fiber.
6. The method according to claim 1 or 4, characterized in that: the preparation of the inorganic flame-retardant powder suspension comprises the following steps: firstly, adding a modified epoxy resin sizing agent into deionized water at the temperature of 40-60 ℃; secondly, adding a defoaming agent and an aluminate coupling agent, wherein the adding proportion of the aluminate coupling agent is 0.4-3% of the mass of the flame-retardant powder; and finally, starting stirring to prepare an aqueous solution, wherein the concentration of the sizing agent is 2-5%, and the solid volume concentration of the finally prepared suspension is 30-40%.
7. The method of claim 1, wherein: and g, the content of the inorganic flame-retardant powder in the fabric dried and rolled in the step g is 20-50% of the weight of the fiber warp-knitted fabric.
8. The method of claim 1, wherein: the resin system matched with the epoxy resin in the step i is an epoxy resin system and comprises 100 parts of resin, 3-30 parts of flame retardant, 0.2-0.8 part of dispersing agent, 0.3-0.5 part of accelerator and 10-80 parts of curing agent.
9. The method of claim 8, wherein: the resin system also contains an inorganic flame retardant with a synergistic flame-retardant effect, wherein the inorganic flame retardant comprises but is not limited to antimony trioxide so as to enhance the flame-retardant effect of the product.
10. The method of claim 1, wherein: the forming technology in the step i adopts one of vacuum auxiliary forming, resin transfer molding forming, derivative technology of RTM vacuum auxiliary RTM forming, light RTM forming and resin film infiltration forming.
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