WO2008011765A1 - Stratifié de matériaux composites renforcé et son procédé de préparation - Google Patents

Stratifié de matériaux composites renforcé et son procédé de préparation Download PDF

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Publication number
WO2008011765A1
WO2008011765A1 PCT/CN2006/002972 CN2006002972W WO2008011765A1 WO 2008011765 A1 WO2008011765 A1 WO 2008011765A1 CN 2006002972 W CN2006002972 W CN 2006002972W WO 2008011765 A1 WO2008011765 A1 WO 2008011765A1
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resin
layer
thermoplastic
toughened
carbon fiber
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PCT/CN2006/002972
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English (en)
Chinese (zh)
Inventor
Xiaosu Yi
Xuefeng An
Bangming Tang
Ming Zhang
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Beijing Institute of Aeronautical Materials, AVIC I
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Application filed by Beijing Institute of Aeronautical Materials, AVIC I filed Critical Beijing Institute of Aeronautical Materials, AVIC I
Publication of WO2008011765A1 publication Critical patent/WO2008011765A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material

Definitions

  • the invention relates to a toughened resin-based composite material laminate and a preparation method thereof.
  • Fiber reinforced resin-based composite laminates are increasingly used in a wide range of applications, especially in the aerospace industry, where a variety of aircraft are heavily carbon fiber composite structures.
  • the general defect of such materials is that the toughness is low, and the performance of the low-speed impact damage is not good, which restricts the further expansion of its application range.
  • various improvements have been proposed, such as development of a new high-toughness matrix, toughening modification of existing material systems, and the like, and thus, some high-toughness composite laminates have been produced.
  • the development of new resin systems not only involves huge investment, high risk, but also convincing the industry to abandon existing mature materials and switch to new material systems, which is neither economical nor quite difficult. Therefore, toughening based on the existing system is the most realistic choice.
  • the conventional toughening technique is to introduce a high toughness component such as a rubber or a thermoplastic resin into a low-toughness matrix (mostly a thermosetting resin) to form a two-phase or multi-phase structure to improve the toughness of the resin as a whole.
  • a high toughness component such as a rubber or a thermoplastic resin
  • a low-toughness matrix mostly a thermosetting resin
  • toughening with a rubber phase affects the temperature resistance of a multiphase system, so a high performance matrix resin is usually toughened with a thermoplastic resin.
  • a large number of studies have shown that if the volume fraction ratio of the thermoplastic toughening resin is increased, and the thermodynamic "phase separation" is formed to form a bicontinuous, oppositely rotating granular "roughening" structure in which the thermoplastic phase is wrapped with the thermosetting phase, the toughening is obtained.
  • the traditional toughening technique is a toughening technique that is "integral" in the spatial position.
  • the technical basis is to use “phase separation” and “roughening” on the basis of thermodynamics and dynamics of the two-component material system. The mechanism, and “phase separation” and “roughening” all occur in any spatial position of the system. Therefore, this toughening technique is "in situ".
  • this will bring two problems: First, after the introduction of a large amount of thermoplastic components, the processability of the toughened matrix is significantly degraded, which brings many difficulties to the construction of the composite material; Second, the chemical composition changes and the phase structure after solidification The changes that make the control of the new structure very complex are tantamount to developing a new material. Moreover, both of these problems inevitably increase material costs and process costs.
  • separation of functional components Separation of the toughener component from the resin matrix component, but giving full play to the functional properties of the respective components, allowing the toughener component to be sufficiently toughened and the resin matrix component to maintain its high strength
  • the high modulus property does not change, and does not cause intermediate properties between the two due to direct mixing (the necessary link of traditional toughening techniques).
  • the separation of the layer structure function Make full use of the periodic nature of the overall laminate material in the thickness direction, and in the selection of the type and properties of the component materials, the material structure and the toughness determining layer of the specific stiffness and specific strength are determined.
  • the materials are separated in function, and the respective structures correspond to the most suitable resin component materials.
  • periodic or “non-periodic” structural optimization: on the basis of functional optimization design of the separated components and layer structures, the “periodic” or “non-periodic” of layer materials and layer structures Re-integration.
  • the "periodicity” herein is embodied in a layered material system composed of a carbon fiber reinforcement, a resin matrix component and a toughener component having a periodicity in the thickness direction. Among them, if the laminate system composed of the toughening component and the matrix component has a very large number of "frequency" in the thickness direction, it is defined as a “non-periodic” laminated material system. This is "structural optimization.”
  • prefabrication integration Elimination of the preparation and preparation of traditional multi-component resin matrix, and the integration of toughening modification into a prefabrication process in the composite lamination process.
  • there is no toughened matrix resin system (traditional toughening technique) in advance, and then it is used to wet the carbon fiber layer and recombine, but to obtain a "cycle” or "non-periodic” prefabricated layer.
  • compositely prepared into a composite laminate That is to say, there is no need to have a homogeneous window of the two-component material on the phase diagram as in the conventional toughening technique, and then "phase separation" and "thickness” in thermodynamics and kinetics of the two-component material.
  • the above technical solution belongs to a kind of "off-position, toughening technology, for a selective, full play on the basis of structural design. Toughening technology optimized for multi-layered, multi-scale components and structures of composite materials.
  • an object of the present invention is to provide a composite laminate comprising at least one carbon fiber reinforced matrix resin layer and at least one toughening resin layer, wherein the toughening resin layer comprises at least one The following components: polyether ketone, polysulfone, polyether sulfone, thermoplastic polyimide, polyetherimide, polycarbonate, polyphenylene ether, polyamide and other thermoplastic resins, or epoxy resin, bismales A mixed resin system of a thermosetting resin such as an imide resin, a thermosetting polyimide resin, a phenol resin, a cyanate resin, or an unsaturated polyester resin, and at least one of the above thermoplastic resins.
  • a thermosetting resin such as an imide resin, a thermosetting polyimide resin, a phenol resin, a cyanate resin, or an unsaturated polyester resin, and at least one of the above thermoplastic resins.
  • Another object of the present invention is to provide a method of preparing a composite laminate comprising at least one carbon fiber reinforced matrix resin layer and at least one tough resin layer, the method comprising:
  • a preformed material comprising at least one component selected from the group consisting of polyether ketone, polysulfone, polyether sulfone, thermoplastic polyimide, polyetherimide, polycarbonate, poly a thermoplastic resin such as phenyl ether or polyamide, or a thermosetting resin such as an epoxy resin, a bismaleimide resin, a thermosetting polyimide resin, a phenol resin, a cyanate resin, or an unsaturated polyester resin, and at least one of the above a mixed resin system of a thermoplastic resin;
  • the structural material is composited to a carbon fiber reinforced matrix resin and cured in accordance with the curing process of the original carbon fiber reinforced matrix resin.
  • Figure 1 illustrates the comparison of the basic idea of "in situ” toughening and "off-site” toughening.
  • Figure 2 illustrates the "in situ" toughening and "off-site” toughening process technology, where TS is heat A solid resin, TP is a thermoplastic resin.
  • Figure 3 shows the morphological distribution of the typical resin matrix phase of the "off-site" toughened composite.
  • Figure 4 shows the typical interlayer morphology of an "off-site" composite.
  • the present invention provides a composite laminate comprising at least one carbon fiber reinforced matrix resin layer and at least one toughened resin layer, wherein the toughened resin layer comprises at least one of the following components: polyether ketone, polysulfone, polyether sulfone, Thermoplastic polyimide, polyetherimide, polycarbonate, polyphenylene ether, polyamide, etc., or epoxy resin, bismaleimide resin, thermosetting polyimide resin, phenolic resin, cyanide A mixed resin system of a thermosetting resin such as an acid ester resin or an unsaturated polyester resin and at least one of the above thermoplastic resins.
  • the toughened resin layer comprises at least one of the following components: polyether ketone, polysulfone, polyether sulfone, Thermoplastic polyimide, polyetherimide, polycarbonate, polyphenylene ether, polyamide, etc., or epoxy resin, bismaleimide resin, thermosetting polyimide resin, phenolic resin, cyanide
  • the toughening resin layer is formed in a thermoplastic phase or a thermoplastic phase (the thermoplastic component phase is between 10% and 75% by weight of the toughened resin layer, preferably between 10% and 50% More preferably between 15% and 35%) is a continuous or double-continuous structure of the continuous phase and forms a physical interpenetration and connection with adjacent matrix resin layers (eg IPN, Semi- IPN, etc., having a thickness of 0.1 ⁇ m - 25 ⁇ m, preferably 0.5 ⁇ m - 20 ⁇ m ⁇ , more preferably 1 ⁇ - 10 ⁇ .
  • the thermoplastic component phase is between 10% and 75% by weight of the toughened resin layer, preferably between 10% and 50% More preferably between 15% and 35
  • adjacent matrix resin layers eg IPN, Semi- IPN, etc., having a thickness of 0.1 ⁇ m - 25 ⁇ m, preferably 0.5 ⁇ m - 20 ⁇ m ⁇ , more preferably 1 ⁇ - 10 ⁇ .
  • the carbon fiber reinforced matrix resin layer comprises at least one resin selected from the group consisting of epoxy resins, bismaleimide resins, thermosetting polyimide resins, phenolic resins, cyanic acid Ester resin, unsaturated polyester resin, etc., using a thermoplastic component such as polyether ketone, or polysulfone, or polyether sulfone, or thermoplastic polyimide, or polyetherimide, or polycarbonate, or polyphenylene Ether, or polyamide, etc., even using an epoxy resin, or a bismaleimide resin, or a thermosetting polyimide resin, or a phenolic resin, or a cyanate resin, or an unsaturated polyester resin, etc.
  • the toughened resin layer is a preformed structural material composed of at least one component selected from the group consisting of polyether ketone, polysulfone, polyether sulfone, thermoplastic polyimide, poly Thermoplastic resin such as etherimide, polycarbonate, polyphenylene ether, polyamide, or epoxy resin, bismaleimide resin, thermosetting polyimide resin, phenolic resin, cyanate resin, unsaturated poly A mixed resin system of a thermosetting resin such as an ester resin and at least one of the above thermoplastic resins.
  • the preformed structural material of the toughened resin layer is a film, a glue, a felt or a powder, in the form of a separate structural material, a loose toughened layer attached to the paper base, or a woven structure. Toughened material.
  • the toughening agent further includes other functional components, such as a binder, a styling agent, an electromagnetic wave reflector, an absorbent, or a conductive agent, a thermal conductive agent, a magnetic conductive agent, etc., to achieve compounding. Multifunctionalization of materials.
  • the specific form of the composite laminate of the present invention may be "a layer of carbon fiber reinforced matrix resin layer - a toughened resin layer" or a layer of carbon fiber reinforced matrix resin layer - a toughened resin layer A layer of carbon fiber reinforced matrix resin layer, or "a layer of carbon fiber reinforced matrix resin layer - a layer of toughened resin layer - a surface layer", and any repeated repetition of the above three forms.
  • the present invention also provides a method of preparing a composite laminate comprising a carbon fiber reinforced matrix resin layer and at least one toughened resin layer, the method comprising:
  • a preformed material comprising at least one component selected from the group consisting of polyether ketone, polysulfone, polyether sulfone, thermoplastic polyimide, polyetherimide, polycarbonate, poly a thermoplastic resin such as phenyl ether or polyamide, or a thermosetting resin such as an epoxy resin, a bismaleimide resin, a thermosetting polyimide resin, a phenol resin, a cyanate resin, or an unsaturated polyester resin, and at least one of the above a mixed resin system of a thermoplastic resin;
  • the structural material is composited to a carbon fiber reinforced matrix resin and cured in accordance with the curing process of the original carbon fiber reinforced matrix resin.
  • the carbon fiber reinforced matrix resin layer comprises at least one resin selected from the group consisting of epoxy resins, bismaleimide resins, thermosetting polyimide resins, phenolic resins, cyanogens An acid ester resin, an unsaturated polyester resin or the like, using a thermoplastic component such as polyether ketone, or polysulfone, or polyether sulfone, or thermoplastic polyimide, or polyetherimide, or polycarbonate, or poly Phenylene ether, or polyamide, etc., even using an epoxy resin, or a bismaleimide resin, or a thermosetting polyimide resin, or a phenolic resin, or a cyanate resin, or an unsaturated polyester resin, etc.
  • a thermoplastic component such as polyether ketone, or polysulfone, or polyether sulfone, or thermoplastic polyimide, or polyetherimide, or polycarbonate, or poly Phenylene ether, or polyamide, etc.
  • the toughening resin layer is a preformed structural material composed of at least one component selected from the group consisting of polyether ketone, polysulfone, polyether sulfone, thermoplastic polyimide, Thermoplastic resin such as polyetherimide, polycarbonate, polyphenylene ether, polyamide, or epoxy resin, bismaleimide resin, thermosetting polyimide resin, phenolic resin, cyanate resin, unsaturated A mixed resin system of a thermosetting resin such as a polyester resin and one of the above thermoplastic resins.
  • At least one of the following methods is employed in the step of "preforming a material comprising at least one component selected from the group consisting of:” , hot melt coating, cast film formation, spray film formation, film formation, fluidized bed sedimentation, electrostatic powder adsorption, to obtain film, glue, felt or powder, as an independent structural material, loose attached to the paper base Toughening material in the form of a toughened layer or a fabric structure.
  • the structural material is composited to the matrix resin using at least one of the following methods: spraying, sedimentation, electrostatic adsorption or printing means that the toughening material forms a toughened layer on the substrate material
  • spraying, sedimentation, electrostatic adsorption or printing means that the toughening material forms a toughened layer on the substrate material
  • a RTM (Resin Transfer Molding) / RFI (Resin Film Infusion) liquid forming system is employed.
  • various methods and methods such as solution film formation, or hot melt coating, or casting film formation, or spray film formation, or printing film formation, or fluidized bed sedimentation, or electrostatic powder adsorption, are added in the dry state.
  • a thin layer of toughened resin is obtained on the sheet of tough material.
  • the injection molding is carried out, and the curing is carried out according to the original curing system to obtain a toughened composite material.
  • a material comprising at least one component selected from the group consisting of: a structural material
  • a thermoplastic component phase or a thermoplastic component phase thermoplastic component phase
  • an adjacent matrix resin layer for example, IPN.Semi-IPN, etc.
  • the toughened resin layer when preparing the toughened resin layer, it further includes adding other functional components such as a binder, a styling agent, an electromagnetic wave reflecting agent, an absorbent, or a conductive agent, a thermal conductive agent, A magnetic permeability agent or the like to achieve multifunctionalization of the composite material.
  • a binder a styling agent, an electromagnetic wave reflecting agent, an absorbent, or a conductive agent, a thermal conductive agent, A magnetic permeability agent or the like to achieve multifunctionalization of the composite material.
  • the toughening component can be formed into various forms such as a film, a powder, a glue, a felt, etc., and can be applied by a plurality of means such as paving, spraying, painting, printing, etc.
  • Prefabricated composites of the reinforcement layer including composite prepregs or dry reinforcement sheets.
  • the carbon fiber reinforced matrix resin layer may be any carbon fiber reinforced resin layer, and as long as the matrix resin meets the needs of the present invention, the reinforcing method may also employ a method known in the art.
  • the curing process of the carbon fiber reinforced composite material may employ any known curing method for such a resin.
  • a preferred carbon fiber reinforced matrix resin layer comprises at least the following resins: an epoxy resin, a bismaleimide resin, a polyimide resin, a cyanate resin, a polyamide resin and the like.
  • the toughening layer includes at least one of the following resins: polyether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polyamide, and the like.
  • a more preferred combination of the carbon fiber reinforced matrix resin layer-toughening layer is: a carbon fiber reinforced epoxy resin layer - a polyether ketone layer, a carbon fiber reinforced epoxy resin layer - a polysulfone layer, and a carbon fiber reinforced layer.
  • the off-site toughening method and the product thereof of the invention do not greatly adjust the chemical composition, the process system and the product structure of the original composite material, and The toughness is greatly improved only by selectively introducing a toughened structure at its relatively weak interlayer region, while other indicators (such as static mechanical properties, wet/heat properties, preparation processes, etc.) remain substantially unchanged. Therefore, the off-site toughening method pursues a phase-separated structure that is limited to layers and has a periodicity and design. The structure is located between the designated layers and forms an integral layer with the adjacent laminate layers rather than a separate resin layer.
  • the structure appears as a reverse-transformed morphology in which the thermoplastic resin phase or the thermoplastic-rich resin phase is a continuous phase; this reverse-transformation may penetrate into adjacent layups, but is preferably limited to a very shallow range.
  • the thickness of the toughened structure is preferably as thin as possible to prevent adverse effects on the thickness and weight loss efficiency of the composite material.
  • the method of the present invention is applicable to both a conventional prepreg system and a liquid forming technique such as RTM/RF I; it may be a post-treatment step of a composite material raw material, or may be a stage of a preparation process of a composite material structure.
  • the method of the invention is used in prepreg recombination.
  • the use of off-site toughening technology in prepreg composites basically eliminates the need to make major adjustments to the original production regulations.
  • the prepreg is still produced according to the original process.
  • the off-site toughening is Post-treatment of existing prepregs, or additional steps in the preparation of composites. The following two cases are explained.
  • the toughening agent is wound after being fixed on the surface of the prepreg.
  • the obtained prepreg can be
  • the composite material is prepared directly according to the original process.
  • the method of the invention is used in RTM/RFI preform compounding.
  • the off-site toughening technique is applied, and the pre-formed fabric needs to be pre-treated before injection/impregnation, which can be implemented as follows:
  • the treated fabric is made into a preform, and injection/impregnation is carried out according to the original process.
  • a composite article is obtained after curing.
  • the resulting composite material has a typical resin matrix phase morphology distribution as shown in FIG. That is, in the position where the toughening effect is required, there is a phase structure which is advantageous for the improvement of the toughness (inter-layer portion in Fig. 3); and for other parts, the original composition and the phase structure should be maintained without introducing any new changes.
  • the product of the invention can be used as an aerospace composite material, can also be used to upgrade a low-toughness composite material for active toughness to a high-toughness composite material, can also realize an optimized design and selective toughening of the toughened structure, and even add a composite material when necessary.
  • the method does not substantially change the basic component system of existing low toughness composites, and the preparation The process and its parameters, the design structure of the corresponding parts, etc., while maintaining the in-plane mechanical properties and wet/heat properties of the original low-toughness material, greatly improving the interlayer toughness and impact damage resistance, and low-cost Achieve high performance of low-performance composite materials.
  • the heating rate was 1.0 ° C / min - 2.0. C/min.
  • a toughened film was prepared: Polyethersulfone (PBS) was dissolved in tetrahydrofuran to give a ratio of 5 ° /. The solution was uniformly applied to the upper surface of the horizontally placed industrial film, and the toughened film was obtained after the solvent was naturally volatilized, and the toughness of the toughened film was about 20 g/m 2 . The toned toughened film is removed from the industrial film and taken up on a paper tube for use.
  • PBS Polyethersulfone
  • the uncomforted basic composite has a CAI strength of 142 MPa, while the CAI strength of the composite toughened by the off-site method is 314 MPa. After comparison, it can be seen that the toughness of the material is significant. Improve, up to 2.2 times the original.
  • the molding process vacuuming to 0.095 MPa throughout the whole process, heating from room temperature to 80 °C, after 0.5 h of heat preservation Pressurize 130 °C to 0.55 MPa ⁇ 0.6 MPa, continue to heat for 0.5 h, then heat up to 130 for 1 h, then The temperature is raised to 180 ⁇ for 2 h, then the temperature is raised to 200 ⁇ for 2 h, and finally cooled to below 60 ° C.
  • the heating rate is 1. 0 O /min ⁇ 2. 0 ⁇ / ⁇
  • the polyaryletherketone ( ⁇ ) was dissolved in a tetrahydrofuran/dimercaptocarboxamide mixed solvent to prepare 20 ° /.
  • the solution was cast-coated on a base paper to form a resin film having a specified thickness.
  • the gravure depth and the number of printing were controlled, and the areal density of the toughened layer was controlled to 20 g/m 2 .
  • the obtained paper-based continuous toughening material has a width of 700 faces and a length without limitation, and is directly received after being dried in the line during the production process.
  • the low toughness composite prepreg provided by the manufacturer, and also use the [45/0/-45/90] «method quasi-isotropic layup.
  • the toughened material is cut to the same size as the prepreg, placed on the surface of the prepreg and heated slightly. After the paper base is removed, the toughening layer has been completely adhered to the prepreg. Continue the paving operation and repeat the insertion process. Curing is carried out in an autoclave according to the aforementioned process of low toughness composite.
  • the prepared composite laminates were tested for static mechanical properties and impact damage resistance.
  • the test results are summarized in Table 1.
  • Table 1 Material test results before and after toughening Performance
  • the present invention Low toughness Test standard
  • a low-toughness bismaleimide composite was prepared as a matrix material: wrapped with TB-1 T700/Bismaleimide prepreg prepared by wet prepreg, according to [45/0/-45/90] 2S mode, isotropically layered, autoclave curing, molding process: from room temperature
  • the temperature is raised to 180 ⁇ .
  • the pressure is 0.4 MPa.
  • the temperature is raised to 160 , the pressure is increased to 0.7 MPa.
  • the temperature is raised to 180 ⁇ , the temperature is kept for 3 hours. The temperature is further increased to 200 ° C for 5 hours.
  • the prepared composite sheet is cut into 89 mm x 55 mm specimens, after the impact compression test ( The test specification refers to QMW CAI), the impact energy is 2 J/mm, and the CAI value is 180 MPa.
  • the modified composite sheet is cut into 89 mm ⁇ 55 mm specimens for post-impact compression test (test specification refers to QMW CAI), impact energy 2 J/leg, CAI value is 290 MPa D CAI value is 1.61 before modification Times.
  • test specification refers to QMW CAI
  • impact energy 2 J/leg impact energy 2 J/leg
  • CAI value is 290 MPa
  • D CAI value is 1.61 before modification Times.
  • a low-toughness polyimide composite material was prepared as a matrix material: T300/polyimide prepreg was prepared by wet method using a TB-1 winding prepreg, according to [45/0/-45/90] 2S mode. Quasi-isotropically layered, molded and solidified on a hot press, forming process: from room temperature to 205 ° C ⁇ 210 V, after 2 h of heat preservation, heat up to 240 ° C ⁇ 250 ° C for 1 h, pressurize to 1.5 MPa ⁇ 2 MPa, and then warmed to 300 ° C for 2 h, then heated to 325 ° C for 1 h, and finally cooled to below 60 to open the mold. The heating rate is from 1.0 ° C / min to 2.0 ° C / min.
  • the prepared composite sheet was cut into 55 mm ⁇ 89 mm specimens for post-impact compression test (test specification with reference to QMW CAI), impact energy 4 J, and impact damage area was examined with SM2000 C-scanner, perpendicular to loading
  • the projection width in the direction is 40 mm, and the CAI value is 212 MPa.
  • the modified prepreg was uniformly isotropically laminated according to the [45/0/- 45/90] 2s method, and was molded and molded on a hot press according to the process of the comparative example.
  • Modified composite sheet cut into 55 mm 89 legs Specimen, compression test after impact (test specification refers to QMW CAI), impact energy 4 J, inspection of impact damage area with SM2000 C-scanner, projection width perpendicular to the loading direction is 18 legs, CAI value ⁇ Before the modification was 1.46 times.
  • the bismaleimide (BMI) resin of the RTM molding process is toughened.
  • the main ingredients are shown in the table
  • BMI Diphenylnonane Bismaleimide 60
  • the B component was pre-dispersed (brushed) onto the surface of a T300 carbon fiber solid preform (Hexcel 827). Only the liquid resin A is pressed into the closed mold to complete the filling. In the closed mold, simultaneous infiltration, impregnation, and contact with the B component adhered to the surface of the preform are caused by the liquid resin A.
  • the mold is kept closed, and the curing reaction of the two components A and B in the mold is initiated by heating.
  • Curing conditions to 1. 5.
  • the heating rate of C / min is raised from room temperature to 130 ° C under normal pressure, and kept for one hour while maintaining pressure of 0.22 MPa - hour.
  • the temperature is raised from 130 ° C to 190 ° C at the same rate, while increasing from 0. 20 MPa to 0. 40 MPa, and then holding for 3 h; finally, at a cooling rate of about 2 ° C / min
  • the temperature is lowered, but the pressure is kept constant during the cooling process until it is cooled to room temperature, thereby completing the entire curing process.
  • the mold is opened, and the product is taken out.
  • Nylon chopped fiber 10 Dissolve DDS of solid phase B component in tetrahydrofuran, add nylon chopped fiber, mix and mix, spray and disperse on dry T300 carbon fiber, and heat it slightly to make nylon chopped fiber.
  • the carbon fiber preform sprayed with the B phase component is placed in a mold, and the temperature is raised to 40 ° C ⁇ 5 (TC, and only the liquid resin component A is pressed into the closed mold to complete the filling. In the closed mold, at the same time The infiltration, impregnation, and contact of the B component adhered to the surface of the preform or the bundle of fibers in the in-mold reinforcing material by the liquid resin A occurs.
  • a toughened RFI composite system was prepared.
  • a resin film was prepared by a continuous doctor blade method.
  • the Al, A2, A3, and A4 components were uniformly melted and melted, and the resin film A was prepared by a continuous doctor blade method.
  • a solution of B in tetrahydrofuran was formed, and the solution was used to form a sheet-like fiber preform D (without a cloth) on the TB-1 type wound prepreg and the fiber C.
  • the resin film A and the fiber preform D are laid up in a mold to form a flat plate shape Forming the assembly E.
  • the resin was melted and impregnated with the fiber preform (D) under heating (120 ° C) (0 ⁇ 5 MPa), and then heated under pressure (0.5 MPa) until the resin was cured for 2 h. Cooling to 60 ⁇ . Release the mold.
  • polyaryl ether ketone is a polymer thermoplastic fine powder resin with a molecular weight of about 30,000.
  • the viscosity of the resin mixture increases sharply when the content of the components is too high. If the dislocation operation is not performed, the resin mixture is difficult to be uniformly formed by the continuous doctor film method. Stable resin film.
  • the toughened layer was also prepared in the same manner as in Example 2 using the commercial prepreg of Example 2. Similarly, a toughening layer was added between the composite layers in the same manner as in Example 2, but not every layer was added, but only the middle 20 layers were toughened, and the upper and lower surfaces of each layer remained unchanged.
  • Compressive strength after impact 1 MPa 245 SACMA SRM2-88 Polyaryletherketone resin acts as a styling agent, accomplishes the intended function of unidirectional fibers, and at the same time acts as a toughening effect in the composite system.
  • the CAI value (the control system uses RTM resin as a styling agent, the same process is shaped and cured.
  • the composite material has a CAI value of 156 MPa).
  • a T800/5228 (toughened epoxy) open-cell laminate was prepared with a stress concentration at the opening. During the lamination process, a 16 ⁇ m thick PAEK film was added between each prepreg near the opening to form a localized off-center toughened structure with a diameter of about 30 mm.
  • the un-toughened open-cell laminate and the toughened open-cell laminate were subjected to a compression test, and the loading was stopped when the load reached approximately 80% of the maximum compressive strength.
  • the SM2000 C-scanner was used to inspect the damage of the laminate, and it was found that the untoughened laminate showed a large delamination near the opening, while the toughened laminate had only a very small delamination.

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Abstract

L'invention concerne un stratifié de matériaux composites et un procédé de préparation de ce stratifié. Ce stratifié comprend au moins une matrice formée d'une couche de résine renforcée de fibres de carbone et au moins une couche de résine durcie. la couche de résine durcie comprend au moins un des composants suivants: résine thermoplastique de polyéther cétone, polysulfone, polyéther sulfone, polyimide thermoplastique, polyether imide, polycarbonate, polyphényl éther, polyamide et analogues, ou un mélange d'au moins une des résines termoplastiques ci-dessus avec une résine thermodurcissable époxyde, une résine bismaléimide, une résine polyimide thermodurcissable, une résine phénolique, une résine cyanate, une résine polyester insaturé et analogues.
PCT/CN2006/002972 2006-07-19 2006-11-07 Stratifié de matériaux composites renforcé et son procédé de préparation WO2008011765A1 (fr)

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WO2018206939A1 (fr) * 2017-05-09 2018-11-15 Applied Graphene Materials Uk Limited Matériaux de moulage composites
JP2020519500A (ja) * 2017-05-09 2020-07-02 アプライド グラフェン マテリアルズ ユーケー リミテッド コンポジット成形材料
US11820872B2 (en) 2017-05-09 2023-11-21 Applied Graphene Materials Uk Limited Composite moulding materials
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CN114425891A (zh) * 2022-02-25 2022-05-03 中国船舶重工集团公司第十二研究所 高渗透性插层增韧材料及其制备方法
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CN114806447A (zh) * 2022-04-15 2022-07-29 中国航空制造技术研究院 一种长室温储存期环氧胶膜的制备方法
CN114773844A (zh) * 2022-06-21 2022-07-22 北京玻钢院复合材料有限公司 一种聚酰亚胺增韧邻苯二甲腈树脂组合物、复合材料以及其制备方法
CN115581815B (zh) * 2022-10-12 2023-07-28 江苏君华特种工程塑料制品有限公司 连续碳纤维cf/paek热塑性复合材料股骨接骨板及其制备方法
CN115581815A (zh) * 2022-10-12 2023-01-10 江苏君华特种工程塑料制品有限公司 连续碳纤维cf/paek热塑性复合材料股骨接骨板及其制备方法
CN115678275A (zh) * 2022-11-09 2023-02-03 航天特种材料及工艺技术研究所 一种热压罐零吸胶成型预浸料用双马树脂及其制备方法

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