Resin composite material part based on ultrasonic curing and manufacturing method thereof
By adopting a combined process of heating, ultrasonic and thermal convection curing in composite material manufacturing, combined with pultrusion or 3D printing, the problems of uneven curing and temperature gradient in composite material molding are solved, and product accuracy and stability are improved. Achieved designs with different performances.
Patent Information
- Application Number
- CN202411228663.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-03
- Publication Date
- 2024-12-06
AI Technical Summary
In the manufacturing process of composite materials, especially in the molding technology of continuous fiber reinforced composite materials, the prior art is difficult to effectively cure with ultrasonic waves, resulting in uneven curing and temperature gradient problems, affecting product accuracy and stability.
A method of manufacturing resin composite material is adopted, including preparing liquid materials according to a predetermined ratio, preparing reinforcement materials with a predetermined shape, applying liquid materials around the reinforcement materials, and performing heating curing, ultrasonic curing and thermal convection curing after forming an intermediate The sequence of the three processes is determined according to the type of resin and curing agent, combined with pultrusion, prepreg or 3D printing process, and curing is performed using ultrasonic waves of 20-40KHz.
It realizes efficient curing of composite materials, solves the temperature gradient problem, improves product accuracy and stability, simplifies process steps, reduces process complexity, and achieves different crosslinking structures and performances through different ultrasonic frequencies and resin combinations.
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Figure CN119078053A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of composite materials, and in particular, to a resin composite material and a manufacturing method thereof. Background Art
[0002] At present, with the growing needs of aviation, new energy and daily necessities, the processing and manufacturing of composite materials has entered a stage of rapid development. Composite materials have a large application space in improving product performance, such as weight reduction and mechanical properties. In terms of processing and manufacturing technology, higher requirements are also put forward for the control of product precision and stability. Curing is the most important process in the processing and manufacturing of composite materials, which has a great influence on the control of product precision and stability.
[0003] In terms of the curing process of composite materials, there are currently two mainstream curing methods. The first is through heat conduction, mainly direct contact heating of the mold to achieve the purpose of molding. This method has a high thermal efficiency, but the cost of the mold is high, especially for products with complex cross-sections; the second is through radiation, including light radiation or electron beam curing processes. The latter has certain requirements for equipment, and there are problems such as the attenuation of radiation on the surface and a certain depth of the material during the curing process, which leads to different curing degrees.
[0004] Ultrasonic curing is as efficient as thermal conduction curing and can achieve simultaneous curing of the composite surface and a certain depth, solving the problem of temperature gradient during the curing process and improving product performance such as precision and stability. Different curing speeds / structures can be achieved according to different resins and different ultrasonic combinations, improving the flexibility of the process.
[0005] In the method for producing epoxy resin-based composite materials using ultrasonic mixing (patent application publication CN110815619A), ultrasonic waves are mainly applied to the preparation of resin components, the preparation of curing agent components, and the mixing of two components in a certain proportion. The invention can avoid the generation of bubbles due to stirring through the use of ultrasonic waves, reducing the operation steps of removing bubbles from materials in the existing production process, and the reduction of bubbles can further improve the curing effect and avoid the vacuum on the surface of the material formed after curing; on the other hand, the invention patent application also discloses that ultrasonic waves can make the materials mix evenly, shortening the mixing time while ensuring the mixing uniformity of the materials. However, in the curing process, the invention patent application does not fully explain the advantages of ultrasonic application, but only mentions that the use of ultrasonic waves in the front-end mixing process can improve the subsequent curing effect, but the curing method still uses the traditional process mentioned above.
[0006] In Mechanochemical unzipping of insulating polyladderene to semiconductor polyacetylene (SCIENCE, 4Aug 2017, Vol 357, Issue 6350, pp.475-479), it is disclosed that ultrasound is a common way to apply mechanical force to polymers, which will create cavities in the solution, sucking the polymers in at high speed, and then causing tension in the middle of the polymer chain. The polymer solution was treated with ultrasound, and after only 20 seconds, the colorless polymer solution turned light blue.
[0007] In Direct sound printing (Mohsen Habibi, Shervin Foroughi, Vahidkaramzadeh, Muthukumaran Packirisamy, Nature communications, 06Apr 2022), a technical solution is disclosed for filling a cylindrical, opaque-shelled chamber with a resin mixed with a curing agent (polydimethylsiloxane, PDMS). After filling the chamber, the chamber is immersed in a water tank, which serves as a medium for the propagation of sound waves into the chamber (the focus of the ultrasound beam is traced along a calculated path, 18 mm deep into the liquid polymer precursor. Tiny bubbles begin to appear in the liquid on the path of the focus, and solidified polymer soon follows.
[0008] Despite advances in the art, particularly in utilizing the focusable properties of ultrasound and its associated applications, further improvements are still needed in many areas, including the more general molding techniques for composite materials, particularly continuous fiber reinforced composite materials. Summary of the invention
[0009] The technical problem to be solved by the present application is how to solidify a resin composite material by applying ultrasound and combining it with other processes during the manufacturing process of the resin composite material.
[0010] To solve the above technical problems, according to one aspect of the present application, a method for manufacturing a resin composite material is provided, wherein the resin composite material comprises a resin and a reinforcing material sandwiched between the resins in layers, and the manufacturing method comprises the following steps: 1) preparing a liquid material comprising a resin and a curing agent according to a predetermined ratio; 2) preparing a reinforcing material having a predetermined shape and layers, and applying the liquid material around the reinforcing material; 3) moving the resin composite material intermediate formed after the reinforcing material is impregnated with the liquid material to a heating mold; 4) heating and curing the resin composite material intermediate formed after the reinforcing material is impregnated with the liquid material; 5) ultrasonically curing the resin composite material intermediate formed after the reinforcing material is impregnated with the liquid material; 6) thermal convection curing the resin composite material intermediate formed after the reinforcing material is impregnated with the liquid material. The order of implementing the above steps 4) heating and curing, 5) ultrasonically curing, and 6) thermal convection curing is determined according to the resin, curing agent and their ratio used in the resin composite material.
[0011] According to an embodiment of the present application, the method for manufacturing a resin composite material may further include adding an auxiliary agent to the liquid material.
[0012] According to an embodiment of the present application, the manufacturing process of the resin composite material intermediate may include a pultrusion process, a prepreg process or a 3D printing process.
[0013] According to an embodiment of the present application, the frequency of the ultrasonic wave may be 20-40 KHz, preferably 20 KHz, 28 KHz, or 40 KHz.
[0014] According to an embodiment of the present application, the resin may be a vinyl resin, an epoxy resin, a polyurethane resin or a polydicyclopentadiene resin.
[0015] According to an embodiment of the present application, the reinforcing material may include glass fiber, carbon fiber, aramid fiber, ultra-molecular weight polyethylene fiber, and grids or fabrics thereof.
[0016] According to an embodiment of the present application, the ultrasonic curing may include ultrasonic curing of the entire resin composite intermediate, and may also include ultrasonic curing of a selected region of the resin composite intermediate.
[0017] According to an embodiment of the present application, the resin composite material intermediate may include different resin materials in different regions, and ultrasonic curing is performed using ultrasonic waves of the same frequency.
[0018] According to an embodiment of the present application, performing ultrasonic curing on the resin composite intermediate includes performing ultrasonic curing at different frequencies on different regions of the resin composite intermediate.
[0019] According to an embodiment of the present application, the heating curing may include segmented thermal curing, and the segmented thermal curing may adopt length partitioning and corresponding temperature partitioning. The length partitioning may include equal division in length, and the temperature partitioning may include temperature gradient distribution in the length partitioning.
[0020] According to an embodiment of the present application, the temperature of the heating and curing may be 90° C. to 130° C.
[0021] According to an embodiment of the present application, the oven temperature used for thermal convection curing may be 60°C.
[0022] According to an embodiment of the present application, the curing agent may include a catalyst containing ruthenium and nitrogen heterocyclic carbene (see Chinese invention patent application publication CN201280036442) or an amine curing agent.
[0023] According to an embodiment of the present application, the resin composite material may include a plate, a profile having a predetermined cross-section, and a member having a predetermined shape.
[0024] According to another aspect of the present application, a resin composite board is provided, which is produced by the manufacturing method as described above.
[0025] According to another aspect of the present application, a resin composite profile is provided, which is produced by the manufacturing method as described above.
[0026] According to still another aspect of the present application, there is provided a resin composite structural member produced by the manufacturing method as described above.
[0027] Compared with the prior art, the resin composite material and the manufacturing method thereof according to the embodiment of the present application have at least the following beneficial effects:
[0028] 1. In the manufacturing method of the resin composite material according to the embodiment of the present application, after the reinforcing material is sandwiched in the resin, three curing processes of thermal curing, ultrasonic curing and thermal convection curing are carried out, and the order of the three curing processes can be arranged in a sequence of implementation according to the different resins, or the three curing processes can be implemented simultaneously, so as to selectively arrange and combine the three curing processes according to the requirements of the physical and chemical performance indicators of the produced products, and apply them appropriately to achieve the expected effect.
[0029] 2. Ultrasonic curing has a curing efficiency that is no less than that of thermal conduction curing, and can achieve simultaneous curing of the composite material surface and a certain depth, solving the problem of temperature gradient during the curing process and improving product performance such as precision and stability.
[0030] 3. Using the same ultrasonic wave, different curing speeds / structures can be achieved based on different resins.
[0031] 4. Using the same resin, different curing speeds / structures can be achieved based on different ultrasonic wavelengths.
[0032] 5. Different resins can be cured by ultrasound, which can be formed in one step, greatly reducing the process steps and reducing the process complexity.
[0033] 6. Ultrasonic waves can act on the resin through the medium or directly install the ultrasonic transducer on the mold to cure the resin, form a corresponding cross-linked structure, complete the combination between the resin and the spacing medium, and achieve the corresponding functional requirements.
[0034] 7. Based on different resins, the same ultrasonic wave can be used to achieve different cured cross-linking structures. Different resins are injected into the corresponding molds according to different application requirements. By applying ultrasonic waves of a certain frequency, different resins produce corresponding cross-linking reactions, generate different cross-linking structures, and ultimately lead to different hardness and corresponding different performance. In this way, under the action of the same ultrasonic wave, the final product can achieve different hardness / elasticity designs for different parts. BRIEF DESCRIPTION OF THE DRAWINGS
[0035] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings of the embodiments will be briefly introduced below. Obviously, the drawings in the following description only relate to some embodiments of the present application, rather than limiting the present application.
[0036] Figure 1 It is a process flow chart for manufacturing fiber-reinforced resin composite parts according to an embodiment of the present application. DETAILED DESCRIPTION
[0037] In order to make the purpose, technical scheme and advantages of the embodiment of the present application clearer, the technical scheme of the embodiment of the present application will be clearly and completely described in conjunction with the drawings of the embodiment of the present application. Obviously, the described embodiment is a part of the embodiment of the present application, not all of the embodiments. Based on the described embodiment of the present application, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of this application.
[0038] Unless otherwise defined, the technical or scientific terms used herein shall have the usual meanings understood by persons with ordinary skills in the field to which this application belongs. The words "first", "second" and similar words used in this patent application specification and claims do not indicate any order, quantity or importance, but are only used to distinguish different components. Similarly, words such as "one" or "an" do not indicate a quantity limitation, but indicate the existence of at least one.
[0039] Figure 1It is a process flow chart for manufacturing fiber-reinforced resin composite parts according to an embodiment of the present application.
[0040] According to the embodiments of the present application, the resin composite material refers to a resin composite plate, profile and component that is formed by compounding resin and reinforcing material and undergoing a specific process.
[0041] Therefore, the resin composite material includes a resin and a reinforcing material layered and sandwiched between the resins.
[0042] The manufacturing method includes the following steps: 1) preparing a liquid material containing a resin and a curing agent according to a predetermined ratio; 2) preparing a reinforcing material with a predetermined shape and layering, and applying the liquid material around the reinforcing material; 3) moving the resin composite intermediate formed by the reinforcing material being impregnated with the liquid material to a heated mold; 4) heating and curing the resin composite intermediate formed by the reinforcing material being impregnated with the liquid material; 5) ultrasonically curing the resin composite intermediate formed by the reinforcing material being impregnated with the liquid material; 6) thermal convection curing the resin composite intermediate formed by the reinforcing material being impregnated with the liquid material. The order of implementing the above steps 4) heating and curing, 5) ultrasonically curing, and 6) thermal convection curing is determined according to the resin, curing agent, and their ratio used in the resin composite.
[0043] According to an embodiment of the present application, the method for manufacturing a resin composite material may further include adding an auxiliary agent to the liquid material, the auxiliary agent including but not limited to HPMA (2-Hydroxypropyl methacrylate).
[0044] According to an embodiment of the present application, the manufacturing process of the resin composite material intermediate may include a pultrusion process, a prepreg process or a 3D printing process.
[0045] According to an embodiment of the present application, the frequency of the ultrasonic wave may be 20 KHz to 40 KHz, and preferably, the ultrasonic wave of commonly used industrial frequencies of 20 KHz, 28 KHz, and 40 KHz is adopted.
[0046] Based on different resins, the same ultrasound can be used to achieve different cured cross-linking structures. Different resins are injected into the corresponding mold according to different application requirements. By applying ultrasound of a certain frequency, different resins produce corresponding cross-linking reactions, generate different cross-linking structures, and ultimately lead to different hardness and corresponding different performance. In this way, under the action of the same ultrasound, the hardness design of different parts of the final product can be achieved. Usually, this kind of one-piece design is currently achieved by bonding different products, and by curing different resins with ultrasound, it can be formed in one step, which greatly reduces the process steps and reduces the process complexity.
[0047] Considering that ultrasound can act on the resin in a non-contact manner, the resin can also be injected into the cavity. The ultrasound and the resin are separated by other media, but the ultrasound can directly act on the resin through the medium to solidify the resin, form a corresponding cross-linking structure, complete the combination between the resin and the spacing medium, and achieve the corresponding functional requirements.
[0048] The same resin can use different ultrasonic frequencies to achieve different curing speeds / structures. Take epoxy resin as an example. Different curing speeds can be achieved by using three ultrasonic waves with the more common working frequencies in the industry, namely 20kHz, 28kHz and 40kHz. However, the embodiments of the present application are not limited to this, but any frequency in a certain frequency range, such as 20-40kHz, may become an industrial standard working frequency and thus be utilized.
[0049] According to an embodiment of the present application, the resin may be vinyl resin, epoxy resin, polyurethane resin, polydicyclopentadiene resin, or the like.
[0050] According to an embodiment of the present application, the reinforcing material may include glass fiber, carbon fiber, aramid fiber, ultra-molecular weight polyethylene fiber and its mesh or fabric. However, for manufacturing a dedicated component, various fibers are made into different shapes to meet the shape and strength requirements of the component, and the properties of the fiber can adopt a combination of various local shapes.
[0051] According to an embodiment of the present application, the ultrasonic curing may include ultrasonic curing of the entire resin composite intermediate, and may also include ultrasonic curing of a selected region of the resin composite intermediate.
[0052] According to an embodiment of the present application, the resin composite material intermediate may include different resin materials in different regions, and ultrasonic curing is performed using ultrasonic waves of the same frequency.
[0053] According to an embodiment of the present application, performing ultrasonic curing on the resin composite intermediate includes performing ultrasonic curing at different frequencies on different regions of the resin composite intermediate.
[0054] According to an embodiment of the present application, the heating curing may include segmented thermal curing, and the segmented thermal curing may adopt length partitioning and corresponding temperature partitioning. The length partitioning may include equal division in length, and the temperature partitioning may include temperature gradient distribution in the length partitioning.
[0055] According to an embodiment of the present application, the temperature of the heating and curing may be 90° C. to 130° C.
[0056] According to an embodiment of the present application, the oven temperature used for thermal convection curing may be 60°C.
[0057] According to an embodiment of the present application, the curing agent may include a catalyst containing ruthenium and nitrogen heterocyclic carbene or an amine curing agent.
[0058] In the process of ultrasonic curing, the catalyst plays a vital role. The advantage of latent catalyst is that it makes the timing of mixing the resin components (including catalyst) more flexible, rather than just before curing. Before the polymerization reaction starts, it is necessary to trigger the dissociation of some groups in the catalyst precursor dispersed in the resin to stimulate its catalytic activity. In addition to the common thermal initiation and chemical initiation, mechanical initiation is also a feasible means, and ultrasound is one of the efficient mechanical initiation methods. Ultrasound has also been proven in previous work as an effective means of activating catalysts and initiating catalytic reactions. Taking the ring-opening metathesis polymerization (ROMP) catalyzed by ruthenium-carbene complexes and the ring-closing metathesis (RCM) of olefins as examples, the polymer segment introduced in the side chain of the carbene ligand can effectively transmit the shear force provided by ultrasound to the coordination bond between carbene and ruthenium, weakening the interaction between the ligand and the metal atom (catalytic active center) so that the carbene dissociates, thereby forming active reaction sites on the ruthenium atom and initiating the catalytic reaction.
[0059] According to an embodiment of the present application, the resin composite material may include a plate, a profile having a predetermined cross-section, and a member having a predetermined shape.
[0060] Next, application examples 1 to 5 of the present application are described.
[0061] Example 1
[0062] Raw materials table 1
[0063] Raw material name Manufacturer information Brand Glass Fiber Jushi Group Co., Ltd. E6DR24-2400-386H Dicyclopentadiene Cymetech ULTRENE99DCPD Second generation Grubbs catalyst Umicore Grubbs Catalyst M204
[0064] In the case of pultrusion, the manufacturing process includes the following steps:
[0065] In the first step, the required fibers are threaded manually through the mixing tank / die, and the production line tension is established by winding;
[0066] The second step is the preparation of resin and curing agent components: both components are stored in a buffer tank with insulation, and a metering pump is used to ensure that the two components enter the mixing tank in a certain proportion;
[0067] The third step is to evenly arrange the fibers, layer them, and immerse them in a mixed glue tank through a separator rod;
[0068] In the fourth step, the fiber impregnated with the two components continues to pass through a separator rod of a certain specification into a heated mold for preliminary forming;
[0069] In the fifth step, the initially formed composite material is ultrasonically cured;
[0070] In the sixth step, the composite material after ultrasonic curing is cured by thermal convection to finally be formed.
[0071] The specific process parameters are: pultrusion line speed 20cm / min, dicyclopentadiene feed flow rate 40ml / min, second-generation Grubbs catalyst feed flow rate 0.4ml / min, stirring evenly in the mixing tank, the production line is in a continuous state, the initial stirring time is 5 minutes, and the subsequent stirring function is always maintained. In the fourth step, the mold is heated, the total length of the mold is 90cm, the length partition is set to 30cm / 30cm / 30cm, and the temperature partition is set to 100℃ / 120℃ / 120℃. In the fifth step, the ultrasonic curing has an ultrasonic frequency of 40KHz and a length of 30cm. In the sixth step, the thermal convection curing has a length of 60cm and an oven temperature of 60℃. The required sample is obtained.
[0072] Example 2
[0073] The raw materials used in Example 2 are the same as those in Example 1, see Raw Materials Table 1 for details.
[0074] In the case of pultrusion, the manufacturing process includes the following steps:
[0075] In the first step, the required fibers are threaded manually through the mixing tank / die, and the production line tension is established by winding;
[0076] The second step is the preparation of resin and curing agent components: both components are stored in a buffer tank with insulation, and a metering pump is used to ensure that the two components enter the mixing tank in a certain proportion;
[0077] The third step is to evenly arrange the fibers, layer them, and immerse them in a mixed glue tank through a separator rod;
[0078] In the fourth step, the fiber impregnated with the two components continues to pass through a separator rod of a certain specification into a heated mold for preliminary forming;
[0079] In the fifth step, the initially formed composite material is cured by thermal convection;
[0080] In the sixth step, the composite material cured by thermal convection is ultrasonically cured to finally be formed.
[0081] The specific process parameters are: pultrusion line speed 20cm / min, dicyclopentadiene feed flow rate 40ml / min, second-generation Grubbs catalyst feed flow rate 0.4ml / min, stirring evenly in the mixing tank, the production line is in a continuous state, the initial stirring time is 5 minutes, and the subsequent stirring function is always maintained. In the fourth step, the mold heating, the total length of the mold is 90cm, the length partition is set to 30cm / 30cm / 30cm, and the temperature partition is set to 100℃ / 120℃ / 120℃. In the fifth step, the thermal convection curing, the length is 30cm, and the oven temperature is 90℃. In the sixth step, the ultrasonic curing, the ultrasonic frequency is 40KHz. Length 30cm. The required sample is obtained.
[0082] Example 3
[0083] The raw materials used in Example 3 are the same as those in Example 1, see Raw Materials Table 1 for details.
[0084] In the case of pultrusion, the manufacturing process includes the following steps:
[0085] In the first step, the required fibers are threaded manually through the mixing tank / die, and the production line tension is established by winding;
[0086] The second step is the preparation of resin and curing agent components: both components are stored in a buffer tank with insulation, and a metering pump is used to ensure that the two components enter the mixing tank in a certain proportion;
[0087] The third step is to evenly arrange the fibers, layer them, and immerse them in a mixed glue tank through a separator rod;
[0088] In the fourth step, the fiber impregnated with the two components continues to pass through a separator rod of a certain specification into a heated mold, which also has the function of ultrasonic curing, and is initially formed;
[0089] In the fifth step, the initially formed composite material is cured by thermal convection to finally be formed.
[0090] The specific process parameters are: pultrusion line speed 20cm / min, dicyclopentadiene feed flow rate 40ml / min, second-generation Grubbs catalyst feed flow rate 0.4ml / min, stirring evenly in the mixing tank, the production line is in a continuous state, the initial stirring time is 5 minutes, and the subsequent stirring function is always maintained. In the fourth step, the mold is heated, the total length of the mold is 90cm, the length partition is set to 30cm / 30cm / 30cm, and the temperature partition is set to 80℃ / 80℃ / 100℃. Ultrasonic curing, the ultrasonic frequency is 40KHz. The layout is 30cm in length interval corresponding to 100℃. In the fifth step, the thermal convection curing is 30cm in length and the oven temperature is 60℃. The required sample is obtained.
[0091] An example of molding by pultrusion process is given above, however, the embodiments of the present application are not limited thereto, and the molding of resin and reinforcing materials can also be achieved by prepreg process, 3D printing process, etc., and technicians in this field can select and apply according to actual needs of design and production.
[0092] Example 4
[0093] Raw materials table 2
[0094] Raw material name Manufacturer information Brand Standard bisphenol A epoxy resin Dow Chemical DER330 Amine curing agent Evonik China ANCAMINE2689 Methylene diphenyl diisocyanate Wanhua Chemical WANNATE MDI-100A Polyols BASF Lupraphen 1608 / 4
[0095] In Example 4, ultrasonic wave 40kHz is used as an example. Two resins, epoxy resin and polyurethane resin, are used as examples. Under the same ultrasonic wave frequency and power, and with similar designs of other process parameters, the curing speed of polyurethane resin is significantly faster than that of epoxy resin.
[0096] The specific process parameters are:
[0097] Add 1.2 kg of standard bisphenol A epoxy resin and 0.8 kg of amine curing agent into the reactor, stir evenly at a stirring speed of 40 r / min for 10 min. Then use ultrasonic curing at a frequency of 40 kHz for 12 min to obtain the desired sample.
[0098] Add 0.4 kg of diphenylmethane diisocyanate and 1.6 kg of polyol to the reactor and stir evenly at a stirring speed of 40 r / min for 10 min. Then use ultrasonic curing at a frequency of 40 kHz for 9 min to obtain the desired sample.
[0099] When using ultrasound with a frequency of 40kHz, the curing speed of epoxy resin and polyurethane resin is shown in Table 3.
[0100] Table 3
[0101] Ultrasonic 40kHz Resin Type Curing speed (min) 1 Epoxy resin 12 2 Polyurethane resin 9
[0102] Example 5
[0103] In Example 5, the raw materials used are the same as those of Example 4, see Table 2 for details.
[0104] In Example 5, epoxy resin is used as an example. Two ultrasonic waves with common working frequencies of 20kHz and 40kHz are used in the industry to achieve different curing speeds. Under the ultrasonic wave of 20kHz, the curing speed is significantly faster than that of 40kHz.
[0105] The specific process parameters are as follows: add 1.2 kg of standard bisphenol A epoxy resin and 0.8 kg of amine curing agent into the reactor, stir evenly, the stirring speed is 40 r / min, and the stirring time is 10 min. Then use ultrasonic curing at a frequency of 40 kHz and the action time is 12 min to obtain the desired sample.
[0106] Add 1.2 kg of standard bisphenol A epoxy resin and 0.8 kg of amine curing agent into the reactor, stir evenly at a stirring speed of 40 r / min for 10 min. Then use ultrasonic curing at a frequency of 28 kHz for 10 min to obtain the desired sample.
[0107] In the case of epoxy resin, different frequencies of ultrasound achieve different curing speeds, as shown in Table 4.
[0108] Table 4
[0109] Epoxy resin Ultrasonic frequency (kHz) Curing speed (min) 1 28 10 2 40 12
[0110] According to another aspect of the present application, a resin composite board is provided, which is produced by the manufacturing method as described above.
[0111] According to another aspect of the present application, a resin composite profile is provided, which is produced by the manufacturing method as described above.
[0112] According to still another aspect of the present application, there is provided a resin composite structural member produced by the manufacturing method as described above.
[0113] Compared with the prior art, the resin composite material and the manufacturing method thereof according to the embodiment of the present application have at least the following beneficial effects:
[0114] 1. In the manufacturing method of the resin composite material according to the embodiment of the present application, after the reinforcing material is sandwiched in the resin, three curing processes of thermal curing, ultrasonic curing and thermal convection curing are carried out, and the order of the three curing processes can be arranged in a sequence of implementation according to the different resins, or the three curing processes can be implemented simultaneously, so as to selectively arrange and combine the three curing processes according to the requirements of the physical and chemical performance indicators of the produced products, and apply them appropriately to achieve the expected effect.
[0115] 2. Ultrasonic curing has a curing efficiency that is no less than that of thermal conduction curing, and can achieve simultaneous curing of the composite material surface and a certain depth, solving the problem of temperature gradient during the curing process and improving product performance such as precision and stability. In addition, ultrasonic curing is a non-contact curing method that applies external force, which can protect the surface of the resin composite material from contact damage.
[0116] 3. Using the same ultrasonic wave, different curing speeds / structures can be achieved based on different resins.
[0117] 4. Using the same resin, different curing speeds / structures can be achieved based on different ultrasonic wavelengths.
[0118] 5. Different resins can be cured by ultrasound, which can be formed in one step, greatly reducing the process steps and reducing the process complexity.
[0119] 6. Ultrasonic waves can act on the resin through the medium or directly install the ultrasonic transducer on the mold to cure the resin, form a corresponding cross-linked structure, complete the combination between the resin and the spacing medium, and achieve the corresponding functional requirements.
[0120] 7. Based on different resins, the same ultrasonic wave can be used to achieve different cured cross-linking structures. Different resins are injected into the corresponding molds according to different application requirements. By applying ultrasonic waves of a certain frequency, different resins produce corresponding cross-linking reactions, generate different cross-linking structures, and ultimately lead to different hardness and corresponding different performance. In this way, the hardness design of different parts of the final product can be achieved under the action of the same ultrasonic wave.
[0121] The above description is merely an exemplary embodiment of the present application and is not intended to limit the protection scope of the present application. The protection scope of the present application is determined by the appended claims.
Claims
1. A method for manufacturing a resin composite material based on ultrasonic curing, wherein the resin composite material comprises a resin and a reinforcing material sandwiched between the resins in layers, and the manufacturing method comprises the following steps: 1) preparing a liquid material containing a resin and a curing agent according to a predetermined ratio; 2) preparing a reinforcing material having a predetermined shape and layering, and applying the liquid material around the reinforcing material; 3) moving the resin composite material intermediate formed by the reinforcing material being infiltrated with the liquid material into a heated mold; 4) heating and curing the resin composite material intermediate formed by the reinforcing material being infiltrated with the liquid material; 5) ultrasonically curing a resin composite material intermediate formed by the reinforcing material being infiltrated with the liquid material; 6) performing thermal convection curing on a resin composite intermediate formed by the reinforcing material being infiltrated with the liquid material; The order of implementing the heating curing, the ultrasonic curing and the thermal convection curing in sequence or simultaneously is determined according to the resin, curing agent and their ratio used in the resin composite material.
2. The method for manufacturing a resin composite part based on ultrasonic curing as claimed in claim 1, further comprising adding an auxiliary agent to the liquid material.
3. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The manufacturing process of the resin composite material intermediate includes a pultrusion process, a prepreg process or a 3D printing process.
4. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The frequency of the ultrasonic wave is 20KHz to 40KHz.
5. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 2, in, The frequency of the ultrasonic wave is 20KHz, 28KHz or 40KHz.
6. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The resin is vinyl resin, epoxy resin, polyurethane resin or polydicyclopentadiene resin.
7. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The reinforcing material includes glass fiber, carbon fiber, aramid fiber, ultra-molecular weight polyethylene fiber and grids or fabrics thereof.
8. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The ultrasonic curing includes the entire ultrasonic curing of the resin composite material intermediate.
9. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The ultrasonic curing includes ultrasonic curing of a selected area of the resin composite intermediate.
10. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The resin composite material intermediate includes different resin materials in different regions and is ultrasonically cured using ultrasonic waves of the same frequency.
11. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The ultrasonic curing of the resin composite intermediate includes performing ultrasonic curing of different frequencies on different regions of the resin composite intermediate.
12. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The heating curing includes segmented thermal curing, and the segmented thermal curing adopts length partitions and corresponding temperature partitions.
13. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 12, in, The length partition includes an equal division in length, and the temperature partition includes a temperature gradient distribution in the length partition.
14. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The temperature of the heating and curing is 90°C to 130°C.
15. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The oven temperature used for the thermal convection curing is 60°C.
16. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The curing agent includes a catalyst containing ruthenium and nitrogen heterocyclic carbene or an amine curing agent.
17. The method for manufacturing a resin composite material based on ultrasonic curing according to claim 1, in, The resin composite material comprises a plate, a profile with a predetermined cross section and a component with a predetermined shape.
18. A resin composite board produced by the manufacturing method according to any one of claims 1 to 17.
19. A resin composite profile produced by the manufacturing method according to any one of claims 1 to 17.
20. A resin composite member produced by the manufacturing method according to any one of claims 1 to 17.