CN116254704A - Modified sizing agent for carbon fiber composite material production and preparation and application methods thereof - Google Patents
Modified sizing agent for carbon fiber composite material production and preparation and application methods thereof Download PDFInfo
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- CN116254704A CN116254704A CN202210041452.9A CN202210041452A CN116254704A CN 116254704 A CN116254704 A CN 116254704A CN 202210041452 A CN202210041452 A CN 202210041452A CN 116254704 A CN116254704 A CN 116254704A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 74
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 74
- 238000004513 sizing Methods 0.000 title claims abstract description 55
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 18
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
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- 239000000463 material Substances 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000001723 curing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910019440 Mg(OH) Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000007596 consolidation process Methods 0.000 claims description 4
- 238000003466 welding Methods 0.000 claims description 4
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000003490 calendering Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000011416 infrared curing Methods 0.000 claims description 3
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- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000001587 sorbitan monostearate Substances 0.000 claims description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 3
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 9
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- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- 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 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 230000008595 infiltration Effects 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920006014 semi-crystalline thermoplastic resin Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 239000011800 void material Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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- 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
- D06M15/59—Polyamides; Polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- 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
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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- Polymers & Plastics (AREA)
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a modified sizing agent for carbon fiber composite material production, a preparation method and an application method thereof, wherein the sizing agent is prepared from silane coupling agent modified polyamide imide (PAI), water, an emulsifying agent and Al (OH) 3 And Mg (OH) 2 Composition, silane coupling agent modified Polyamideimide (PAI), water, emulsifier, al (OH) 3 And Mg (OH) 2 The mass ratio of (2) is 0.5-20%:10-98.8%:0.5-10%:0.1-40%:0.1-20%. The modified sizing agent of the present invention has: excellent heat resistance: the thermoplastic resin requires very high processing temperatures, the sizing agent of the invention can be used stably at 250-450 ℃ and has good interfacial compatibility.
Description
Technical Field
The invention belongs to the field of carbon fiber composite material production, and in particular relates to a modified sizing agent for carbon fiber composite material production and a preparation method and an application method thereof.
Background
At present, the carbon fiber composite material taking semi-crystalline thermoplastic resin PEKK as a matrix is a hot topic in the field of aviation and automobiles at present, and how to prepare light aircraft parts of thermoplastic composite materials with excellent mechanical properties under the condition of guaranteeing mass production becomes an issue for the industry expert and scholars to address.
A large number of practices prove that: the carbon fiber composite material using the thermoplastic resin PEKK as the matrix has the advantages of good toughness, low density, easy repair and strong durability, overcomes the problems of insufficient bonding toughness of each layer and easy delamination caused by impact in the compounding process of the thermosetting composite material, and has simple storage condition of the thermoplastic resin PEKK prepreg, and can be recycled to a certain extent. Therefore, carbon fiber composite materials based on thermoplastic resin PEKK have become a research hotspot material for aerospace components. In order to meet the process and performance requirements of thermoplastic resin composite materials, thermoplastic sizing agents have become a hot spot of research, but due to the limited material performance and molding process, the shortcomings of the existing thermoplastic sizing agents are mainly manifested in the following aspects:
1. binding properties: the main chain structure of the thermoplastic resin lacks active functional groups, is difficult to be chemically bonded with the traditional thermosetting epoxy sizing agent, and has poor fluidity at high temperature, cannot infiltrate fibers well, and has poor interface bonding property.
2. Heat resistance: thermoplastic composites are processed at temperatures typically above 250 ℃, however, conventional thermosetting sizing agents have been used at temperatures less than or equal to 250 ℃ and above the upper temperature limit, which can result in degradation of the sizing agent and affect the interfacial bond strength of the resin and the fibers.
3. Environmental protection: the traditional sizing agent needs to introduce a large amount of organic solvent to cause environmental pollution, the reaction is not easy to control, and the production process is complex.
The invention discloses a composite aqueous emulsion sizing agent for carbon fibers and a preparation method thereof, wherein the composite aqueous emulsion sizing agent for carbon fibers is prepared from aqueous modified epoxy resin emulsion, thermoplastic resin and toughening auxiliary agent according to a proportion, the prepared aqueous composite emulsion sizing agent has good compatibility, strong carbon fiber adsorption and infiltration capability, long storage time, uniform sizing amount after sizing of the carbon fibers, stable glue content, stable hairiness, ductility, hardness, width and friction coefficient, and the shearing strength between spline layers is increased by 10% compared with that of a single sizing agent, and the wet prepreg and woven cloth cover performance is excellent. Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a novel sizing agent, and the interface performance of thermoplastic resin and carbon fiber is well ensured while high-temperature reaction is ensured. The invention discloses a modified sizing agent for carbon fiber composite material production and a preparation and application method thereof, and the specific technical scheme is as follows:
a modified sizing agent for carbon fiber composite material production is prepared from silane coupling agent modified polyamide imide (PAI), water, emulsifier and Al (OH) 3 And Mg (OH) 2 Composition, silane coupling agent modified polyamideimide aqueous slurry (PAI), water, emulsifier, al (OH) 3 And Mg (OH) 2 The mass ratio of (2) is 0.5-20%:10-98.8%:0.5-10%:0.1-40%:0.1-20%.
The emulsifier is composed of sorbitan monostearate, polyoxyethylene sorbitan monooleate and sodium dodecyl benzene sulfonate according to the mass ratio of 1:1:1.
Preferably, the Al (OH) 3 And Mg (OH) 2 The grain size of (2) is 500nm-2 μm.
The preparation method of the modified sizing agent for carbon fiber composite material production comprises the following steps:
s1: preparing aqueous solution of silane coupling agent modified polyamide imide (PAI) and water bath at constant temperature of 60 DEG CContinuously stirring in the pot for 30-120 Min, and sequentially adding Al (OH) 3 And Mg (OH) 2 Stirring at a stirring speed of 5000-10000rpm for 2-6h to obtain silane coupling agent modified Polyamideimide (PAI)/Al (OH) 3 /Mg(OH) 2 Mixing the slurry;
s2: charging the mixed slurry obtained in S1, water and an emulsifier into a vacuum emulsifying machine, wherein the silane coupling agent modifies Polyamideimide (PAI), water, the emulsifier and Al (OH) 3 And Mg (OH) 2 The mass ratio of (2) is 0.5-20%:10-98.8%:0.5-10%:0.1-40%: stirring at 10000-50000rpm for 1-3 hr to obtain final product.
An application method of a modified sizing agent for carbon fiber composite material production comprises the following steps:
step 1: preparation of semi-impregnated prepregs
S1: carbon fiber surface treatment: immersing carbon fibers in an acetone solution, cleaning the carbon fibers for 4 hours by using ultrasonic waves, cleaning the carbon fibers by using isopropanol, and then placing the carbon fibers in an oven at 80 ℃ for drying;
s2: sizing the surface of the carbon fiber: drying the carbon fiber obtained in the step S1 in a drying oven at the temperature of 100 ℃ to constant weight, sizing the carbon fiber by using a modified sizing agent, wherein the gum dipping time is 24 hours, and finally drying in a constant-temperature drying oven at the temperature of 150 ℃ to remove other solvents;
s3: semi-impregnated strip preparation: impregnating the carbon fiber treated by the S2 by adopting a wet powder impregnation method, pouring the prepared PEKK resin suspension into a slurry dipping tank, and continuously stirring; dispersing continuous carbon fibers into parallel monofilaments through a dispersing device under the traction of a traction machine, coating PEKK resin suspension on the carbon fibers through a slurry dipping tank, removing solvent through a drying device to obtain carbon fiber bundles coated with the PEKK resin, marking the carbon fiber bundles as CFPEKK, and obtaining a semi-impregnated strip after melting and calendaring;
step 2: and (3) material laying: laying 18 layers of the material obtained in the step 1 along the radial direction of the carbon fiber to form a template, and solidifying each layer of semi-impregnated strip together in a spot welding mode;
step 3: vacuum consolidation: curing in an infrared curing furnace with vacuum function, wherein the baking temperature is 370-390 ℃, the vacuum pressure is 1Mpa, and the baking time is 15s;
step 4: and (3) curing by a press: compacting the plate obtained in the step 3 on a press, and baking at 370-390 ℃ and 2.5-4Mpa under vacuum pressure for 120-300 s to obtain the final product.
Further, the modified sizing agent in S2 of the step 1 is a modified Polyamideimide (PAI) by a silane coupling agent, water, an emulsifier, and Al (OH) 3 And Mg (OH) 2 Composition, modified polyamideimide aqueous slurry (PAI), water, emulsifier, al (OH) 3 And Mg (OH) 2 The mass ratio of (2) is 0.5-20%:10-98.8%:0.5-10%:0.1-40%:0.1-20%.
The porosity of the carbon fiber composite material prepared by the application method of the modified sizing agent for carbon fiber composite material production is 1.5-2%.
The invention utilizes the polyamide-imide aqueous slurry (PAI) to be well combined with resin functional groups such as PEKK, PEEK, PI, the aqueous slurry has excellent environment-friendly performance, and can be uniformly dispersed in the PAI slurry to form hybrid gel after being modified by a coupling agent, so that on one hand, the surface roughness of the fiber is improved, the diffusion of surface defects of the fiber is prevented, and the mechanical engagement effect of an interface is improved; on the other hand, the nano powder plays a role in steric hindrance, effectively isolates the mutual transfer of heat, and improves the heat resistance of the fiber. At the same time, al (OH) 3 Mg (OH) 2 The heat energy is decomposed and absorbed by heating at high temperature, a large amount of water is generated to play a role in flame retardance and smoke suppression, and the flame retardant is a very good halogen-free flame retardant, namely Al (OH) 3 Mg (OH) 2 The heat resistance of the material can be well improved, and the steric hindrance effect can also effectively enhance the damp-heat resistance of the fiber material.
The modified sizing agent of the present invention has: excellent heat resistance: the thermoplastic resin requires very high processing temperature, the sizing agent of the invention can be stably used at 250-450 ℃, and has good interfacial compatibility: the carbon fiber coated with the sizing agent can be well combined with a resin matrix, so that the surface wettability of a carbon fiber bundle is improved, the chemical bonding between the carbon fiber and the corresponding resin is greatly improved, and the corresponding layer shearing capacity is improved; environmental protection aspect: compared with the traditional sizing agent, a large amount of organic solvent is required to be introduced to cause environmental pollution, the reaction is difficult to control and the production process is complex, the sizing agent disclosed by the invention has the advantages that the solvent is water, various defects caused by the organic solvent are effectively avoided, the process difficulty is greatly reduced, the yield is improved, and the sizing agent is more suitable for industrial production.
The sizing agent of the invention has remarkable enhancement compared with the traditional fiber sizing agent in improving the interfacial effect between resin and fiber and improving the heat resistance of fiber. Compared with the traditional thermoplastic carbon fiber composite material, the composite material has a simpler and more convenient production process, is suitable for the production of aerospace products with large batch, high repeatability and complex structure.
When the method is applied, the sizing agent is used for treating the carbon fibers to prepare the PEKK/CF prepreg tape, and finally the optimized technological parameters are adopted for molding the thermoplastic tape, so that the PEKK/CF carbon fiber laminated plate with low void ratio is prepared.
Drawings
FIG. 1 is a schematic illustration of a process flow of the present invention;
FIG. 2 is a coating of PAI/Al (OH) 3 /Mg(OH) 2 SEM contrast pictures of carbon fiber boards before and after the water-based sizing agent;
fig. 3 is an SEM image of the product before and after vacuum consolidation.
Detailed Description
Example 1
The preparation method of the modified sizing agent for carbon fiber composite material production comprises the following specific steps:
step 1: preparing an aqueous solution of silane coupling agent modified polyamide imide (PAI), continuously stirring for 30-120 Min in a water bath kettle with constant temperature of 60 ℃, and sequentially adding Al (OH) 3 And Mg (OH) 2 Stirring at a stirring speed of 5000-10000rpm for 2-6h to obtain silane coupling agent modified Polyamideimide (PAI)/Al (OH) 3 /Mg(OH) 2 Mixing the slurry;
step 2: loading the mixed slurry obtained in the step 1, water and an emulsifying agent into a vacuum emulsifying machine, whereinMiddle silane coupling agent modified polyamide imide (PAI), water, emulsifying agent and Al (OH) 3 And Mg (OH) 2 The mass ratio of (2) is 0.5-20%:10-98.8%:0.5-10%:0.1-40%: stirring at 10000-50000rpm for 1-3 hr to obtain final product.
The silane coupling agent is H550;
the emulsifier consists of sorbitan monostearate, polyoxyethylene sorbitan monooleate and sodium dodecyl benzene sulfonate according to the proportion of 1:1:1;
said Al (OH) 3 And Mg (OH) 2 The grain size of (2) is 500nm-2 μm.
Example 2
As shown in fig. 1, an application method of the modified sizing agent for carbon fiber composite production comprises the following steps:
step 1: preparing a semi-impregnated strip:
s1: carbon fiber surface treatment: immersing carbon fibers in an acetone solution, cleaning the carbon fibers for 4 hours by using ultrasonic waves, then cleaning the carbon fibers for several times by using isopropanol, and finally drying the carbon fibers in an oven at 80 ℃;
s2: sizing the surface of the carbon fiber: drying the carbon fiber to constant weight in a drying oven at 100 ℃, sizing the carbon fiber by using the sizing agent prepared in the embodiment 1 for 24 hours, and finally drying the carbon fiber in the constant-temperature drying oven at 150 ℃ to remove other solvents for standby, wherein the carbon fiber before and after sizing is shown in figure 2;
s3: semi-impregnated strip preparation:
impregnating the treated carbon fiber by adopting a wet powder impregnation method, pouring the prepared PEKK suspension into a slurry dipping tank, continuously stirring, dispersing continuous CF into parallel monofilaments through a dispersing device under the traction of a tractor, coating the fiber with the PEKK resin suspension through the slurry dipping tank, and continuously removing the solvent through a drying device to obtain CF bundles coated with the PEKK resin, abbreviated as CFPEKK; the prepreg tape is prepared after melting and calendaring;
step 2: and (3) material laying: paving materials into templates by adopting an automatic paving machine according to the [0 degree ]18 paving requirement, and solidifying each layer of paved semi-impregnated strips together by an infrared welding gun in a spot welding mode;
step 3: vacuum consolidation: curing in an infrared curing furnace with vacuum function, wherein the baking temperature is 370-390 ℃, the vacuum pressure is 1Mpa, the baking time is 15s, and SEM images of products before and after vacuum curing are shown in figure 3;
step 4: and (3) curing by a press: compacting the plate obtained in the step 3 on a press, and baking at 370-390 ℃ and 2.5-4Mpa under vacuum pressure for 120-300 s to obtain the final product.
Claims (7)
1. A modified sizing agent for producing carbon fiber composite material is characterized in that polyamide imide (PAI), water, emulsifying agent and Al (OH) are modified by silane coupling agent 3 And Mg (OH) 2 Composition, silane coupling agent modified Polyamideimide (PAI), water, emulsifier, al (OH) 3 And Mg (OH) 2 The mass ratio of (2) is 0.5-20%:10-98.8%:0.5-10%:0.1-40%:0.1-20%.
2. The modified sizing agent for carbon fiber composite production according to claim 1, wherein the emulsifier is composed of sorbitan monostearate, polyoxyethylene sorbitan monooleate and sodium dodecyl benzene sulfonate in a mass ratio of 1:1:1.
3. Modified sizing agent for carbon fiber composite production according to claim 1, characterized in that the Al (OH) 3 And Mg (OH) 2 The grain size of (2) is 500nm-2 μm.
4. A process for preparing a modified sizing agent for carbon fiber composite production according to any one of claims 1 to 3, comprising the steps of:
s1: preparing an aqueous solution of silane coupling agent modified polyamide imide (PAI), continuously stirring for 30-120 Min in a water bath kettle with constant temperature of 60 ℃, and sequentially adding Al (OH) 3 And Mg (OH) 2 Stirring at a stirring speed of 5000-10000rpm for 2-6h to obtain silane couplingAgent modified Polyamideimide (PAI)/Al (OH) 3 /Mg(OH) 2 Mixing the slurry;
s2: charging the mixed slurry obtained in S1, water and an emulsifier into a vacuum emulsifying machine, wherein the silane coupling agent modifies Polyamideimide (PAI), water, the emulsifier and Al (OH) 3 And Mg (OH) 2 The mass ratio of (2) is 0.5-20%:10-98.8%:0.5-10%:0.1-40%: stirring at 10000-50000rpm for 1-3 hr to obtain final product.
5. A method of applying the modified sizing agent for carbon fiber composite production according to any one of claims 1 to 3, comprising the steps of:
step 1: preparation of semi-impregnated prepregs
S1: carbon fiber surface treatment: immersing carbon fibers in an acetone solution, cleaning the carbon fibers for 4 hours by using ultrasonic waves, cleaning the carbon fibers by using isopropanol, and then placing the carbon fibers in an oven at 80 ℃ for drying;
s2: sizing the surface of the carbon fiber: drying the carbon fiber obtained in the step S1 in a drying oven at the temperature of 100 ℃ to constant weight, sizing the carbon fiber by using a modified sizing agent, wherein the gum dipping time is 24 hours, and finally drying in a constant-temperature drying oven at the temperature of 150 ℃ to remove other solvents;
s3: semi-impregnated strip preparation: impregnating the carbon fiber treated by the S2 by adopting a wet powder impregnation method, pouring the prepared PEKK resin suspension into a slurry dipping tank, and continuously stirring; dispersing continuous carbon fibers into parallel monofilaments through a dispersing device under the traction of a traction machine, coating PEKK resin suspension on the carbon fibers through a slurry dipping tank, removing solvent through a drying device to obtain carbon fiber bundles coated with the PEKK resin, marking the carbon fiber bundles as CFPEKK, and obtaining a semi-impregnated strip after melting and calendaring;
step 2: and (3) material laying: laying 18 layers of the material obtained in the step 1 along the radial direction of the carbon fiber to form a template, and solidifying each layer of semi-impregnated strip together in a spot welding mode;
step 3: vacuum consolidation: curing in an infrared curing furnace with vacuum function, wherein the baking temperature is 370-390 ℃, the vacuum pressure is 1Mpa, and the baking time is 15s;
step 4: and (3) curing by a press: compacting the plate obtained in the step 3 on a press, and baking at 370-390 ℃ and 2.5-4Mpa under vacuum pressure for 120-300 s to obtain the final product.
6. The method of claim 5, wherein the modified sizing agent in step S2 is a modified Polyamideimide (PAI) with silane coupling agent, water, emulsifier, and Al (OH) 3 And Mg (OH) 2 Composition, silane coupling agent modified polyamideimide aqueous slurry (PAI), water, emulsifier, al (OH) 3 And Mg (OH) 2 The mass ratio of (2) is 0.5-20%:10-98.8%:0.5-10%:0.1-40%:0.1-20%.
7. The carbon fiber composite material produced by the application method of the modified sizing agent for carbon fiber composite material production according to claim 5, wherein the porosity thereof is 1.5-2%.
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