阅读说明：本技术 一种采用热塑性树脂上浆三维编织用预浸胶纤维束的方法 (Method for sizing pre-impregnated fiber bundles for three-dimensional weaving by adopting thermoplastic resin ) 是由 许培俊 王临江 张宁 冀有志 雷艳妮 刘亲亲 于 2020-07-16 设计创作，主要内容包括：一种采用热塑性树脂上浆三维编织用预浸胶纤维束的方法,以热固性树脂浸胶液浸渍连续纤维束制得预浸胶纤维束,再使用热塑性树脂上浆剂喷涂或涂刷于预浸胶纤维束表面,制得热塑性树脂上浆三维编织用预浸胶纤维束；这种热塑性树脂上浆三维编织用预浸胶纤维束可用于各种类型的三维编织机编织成不同形状的复合材料预制件,固化后得到树脂含量稳定、分布均匀,纤维体积含量稳定的高质量复合材料制品；本发明针对热固性预浸胶纤维束在用于机器编织复合材料毛坯件时存在的易刮毛、易断纱等问题,采用热塑性树脂对预浸胶纤维束进行上浆,在对预浸胶纤维束起到保护、集束作用的同时,增韧复合材料,制得了可通过机器三维编织制备的高性能连续纤维复合材料,具有易操作、韧性好及强度高的优点。(A method for using thermoplastic resin to size the pre-impregnated fiber bundle for three-dimensional weaving, using thermosetting resin glue dipping solution to dip continuous fiber bundles to prepare pre-dipped fiber bundles, and then using thermoplastic resin sizing agent to spray or brush on the surface of the pre-impregnated fiber bundles to prepare the pre-impregnated fiber bundles for thermoplastic resin sizing three-dimensional weaving; the prepreg fiber bundle for sizing the thermoplastic resin and three-dimensional weaving can be used for various types of three-dimensional weaving machines to weave composite material prefabricated parts with different shapes, and high-quality composite material products with stable resin content, uniform distribution and stable fiber volume content are obtained after solidification; aiming at the problems of easy hair scraping, easy yarn breaking and the like of thermosetting prepreg fiber bundles when used for machine weaving of composite material blank pieces, the invention adopts the thermoplastic resin to carry out sizing on the prepreg fiber bundles, plays the role of protecting and bundling the prepreg fiber bundles, simultaneously toughens the composite material, prepares the high-performance continuous fiber composite material which can be prepared by machine three-dimensional weaving, and has the advantages of easy operation, good toughness and high strength.)

1. A method for using thermoplastic resin to size the pre-impregnated fiber bundle for three-dimensional weaving, firstly preparing the pre-impregnated fiber bundle, then using the thermoplastic resin to size the pre-impregnated fiber bundle, and then carrying out three-dimensional weaving and curing molding; the method is characterized in that: the method specifically comprises the following steps:

The method comprises the following steps: taking thermosetting resin which is solid or semi-solid at room temperature (20 +/-5 ℃) as a raw material, stirring and heating the thermosetting resin to melt by using a magnetic stirrer, wherein the heating temperature is 50-160 ℃, and the stirring speed is 200-1000 rpm, so as to prepare thermosetting resin impregnation liquid;

step two: stirring and heating by using a magnetic stirrer, wherein the heating temperature is 20-150 ℃, the stirring speed is 200-1000 rpm, and dissolving the thermoplastic resin in the organic solvent to prepare the thermoplastic resin sizing agent, wherein the concentration of the thermoplastic resin is 5-25 wt%;

step three: dipping the thermosetting resin dipping solution prepared in the first step into a continuous fiber bundle by using a pre-dipping glue machine at a traction speed of 0.5-2 m/min and a heating temperature of 50-160 ℃, and cooling to room temperature to prepare a pre-dipping glue fiber bundle with the resin content of 28-33 wt%;

step four: coating a thermoplastic resin sizing agent with the solid content of 3-10 wt% on the surface of the pre-dipped fiber bundle by using a spraying or dip-coating process, and after the solvent is completely volatilized, coating the thermoplastic resin sizing agent to form a pre-dipped fiber bundle for three-dimensional weaving, wherein the thickness of the coating is 50-500 micrometers;

step five: sizing thermoplastic resin, weaving the thermoplastic resin into a composite material prefabricated part by using pre-impregnated rubber fiber bundles, wherein the tool is a three-dimensional weaving machine;

Step six: filling the composite material prefabricated part into a forming mold, heating and pressurizing in curing equipment for curing, and cooling to room temperature along with a furnace to prepare the high-performance continuous fiber composite material; wherein the pressurizing pressure is 0-3 MPa, the heating temperature is 20-250 ℃, the heating time is 2-12 hours, and sectional heating is adopted according to the characteristics of different thermosetting resins.

2. The method of claim 1, wherein the method comprises the steps of: the thermosetting resin in the first step is one or a mixed resin prepared from two of epoxy resin, benzoxazine resin, phenolic resin, bismaleimide resin, polyphenylsulfone resin, polybenzimidazole resin, cyanate resin and polyquinoxaline resin in any proportion.

3. The method of claim 1, wherein the method comprises the steps of: the thermoplastic resin in the second step is one of polyether-ether-ketone resin, polycarbonate resin, polyether sulfone resin, polylactic acid resin, polymethyl methacrylate resin, polyphenylene sulfide resin or polyether imide resin.

4. The method of claim 1, wherein the method comprises the steps of: the organic solvent in the second step is one or a mixed solvent prepared from two of N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, chloroform, ethanol, acetone, tetrahydrofuran and ethyl acetate in any proportion.

5. The method of claim 1, wherein the method comprises the steps of: the continuous fiber bundle in the third step is one or a mixed fiber of two of glass fiber, carbon fiber, Kevlar fiber, alumina fiber, silicon carbide fiber and the like mixed in any proportion.

6. The method of claim 1, wherein the method comprises the steps of: and the curing equipment in the sixth step comprises a high-temperature test chamber or an autoclave.

7. A method for sizing a prepreg fiber bundle for three-dimensional weaving by using thermoplastic resin is characterized by comprising the following steps of:

1) weighing epoxy resin and cyanate ester resin according to the mass ratio of 20:80 at room temperature, mixing, and uniformly stirring at the heating temperature of 150 ℃ and the stirring speed of 200rpm to obtain thermosetting resin dipping solution;

2) Preparing 10 wt% of polyether sulfone solution by using N, N-dimethylformamide as a solvent, and stirring and dissolving at a heating temperature of 100 ℃ and a stirring speed of 300rpm to prepare a thermoplastic resin sizing agent;

3) impregnating continuous glass fibers by using the thermosetting resin impregnation liquid prepared in the step 1) at a heating temperature of 150 ℃ and a traction speed of 0.5m/min by using an impregnation machine, cooling to room temperature, and winding to prepare a pre-impregnated glass fiber bundle;

4) spraying the thermoplastic resin sizing agent prepared in the step 2) on the surface of the pre-impregnated glass fiber bundle by using a spraying pot, after the solvent is completely volatilized, the thickness of the coating is 500 micrometers, and winding to prepare the polyether sulfone sized pre-impregnated glass fiber bundle;

5) weaving the polyethersulfone sizing presoaked glass fiber bundles prepared in the step 4) into composite blank parts by using a three-dimensional weaving machine;

6) putting the composite material blank prepared in the step 5) into a mould, integrally putting the mould into a high-temperature experimental box, solidifying the blank by the process of 190 ℃/2h +210 ℃/2h +230 ℃/1h, and then cooling the blank to room temperature along with a furnace to prepare the high-performance resin-based glass fiber composite material product.

8. A method for sizing a prepreg fiber bundle for three-dimensional weaving by using thermoplastic resin is characterized by comprising the following steps of:

1) Weighing benzoxazine resin at room temperature, and stirring the benzoxazine resin to be liquid at the heating temperature of 100 ℃ and the stirring speed of 300rpm to prepare thermosetting resin impregnation liquid;

2) preparing 5 wt% of polyether-ether-ketone solution by using N, N-dimethylacetamide as a solvent, and stirring and dissolving at a heating temperature of 80 ℃ and a stirring speed of 600rpm to prepare a thermoplastic resin sizing agent;

3) impregnating continuous carbon fibers with the thermosetting resin impregnation liquid prepared in the step 1) at a heating temperature of 100 ℃ and a traction speed of 1m/min by using an impregnation machine, cooling to room temperature, and winding to prepare a pre-impregnated carbon fiber bundle;

4) spraying the thermoplastic resin sizing agent prepared in the step 2) on the surface of the pre-impregnated carbon fiber bundle by using a spray can, after the solvent is completely volatilized, the thickness of the coating is 300 microns, and winding to prepare the polyether-ether-ketone sizing pre-impregnated carbon fiber bundle;

5) weaving the polyether-ether-ketone sizing presoaking carbon fiber bundles prepared in the step 4) into composite material blank pieces by using a three-dimensional weaving machine;

6) putting the composite material blank prepared in the step 5) into a mould, integrally putting the mould into a high-temperature experimental box, curing by the process of 180 ℃/2h +200 ℃/2h +230 ℃/1h, and then cooling to room temperature along with a furnace to prepare the high-performance resin-based carbon fiber composite material product.

9. A method for sizing a prepreg fiber bundle for three-dimensional weaving by using thermoplastic resin is characterized by comprising the following steps of:

1) weighing epoxy resin and polyphenylsulfone resin according to the mass ratio of 50:50 at room temperature, mixing, and uniformly stirring at the heating temperature of 90 ℃ and the stirring speed of 500rpm to obtain thermosetting resin impregnation liquid;

2) using trichloromethane as a solvent to prepare 15 wt% of polycarbonate solution, and stirring and dissolving at a heating temperature of 40 ℃ and a stirring speed of 600rpm to prepare a thermoplastic resin sizing agent;

3) impregnating continuous Kevlar fibers by using the thermosetting resin impregnation liquid prepared in the step 1) at a heating temperature of 100 ℃ and a traction speed of 1m/mim by using an impregnator, cooling to room temperature, and winding to prepare a Kevlar pre-impregnated fiber bundle;

4) spraying the thermoplastic resin sizing agent prepared in the step 2) on the surface of the Kevlar prepreg fiber bundle by using a spraying pot, after the solvent is completely volatilized, the thickness of the coating is 50 microns, and winding to prepare the polyether sizing Kevlar prepreg fiber bundle;

5) weaving the polycarbonate sizing presoaked Kevlar fiber bundles prepared in the step 4) into a composite blank by using a three-dimensional weaving machine;

6) putting the composite material blank prepared in the step 5) into a mould, integrally putting the mould into an autoclave, curing the blank at the pressure of 1MPa by the process of 150 ℃/2h +200 ℃/2h, and then cooling the blank to room temperature along with a furnace to prepare the high-performance resin-based Kevlar fiber composite material product.

10. A method for sizing a prepreg fiber bundle for three-dimensional weaving by using thermoplastic resin is characterized by comprising the following steps of:

1) weighing polybenzimidazole resin according to the required amount at room temperature, and stirring the polybenzimidazole resin to be liquid at the heating temperature of 110 ℃ and the stirring speed of 500rpm to prepare thermosetting resin impregnation liquid;

2) preparing 20 wt% polylactic acid solution by taking dichloromethane as a solvent, and stirring and dissolving at a heating temperature of 20 ℃ and a stirring speed of 300rpm to prepare a thermoplastic resin sizing agent;

3) impregnating continuous alumina fibers by using a impregnator with the thermosetting resin impregnation liquid prepared in the step 1) at a heating temperature of 100 ℃ and a traction speed of 1.5m/min, cooling to room temperature, and winding to prepare an alumina fiber pre-impregnated bundle;

4) spraying the thermoplastic resin sizing agent prepared in the step 2) on the surface of the pre-impregnated alumina fiber bundle by using a spraying pot, and after the solvent is completely volatilized, winding to prepare the polylactic acid sizing pre-impregnated alumina fiber bundle, wherein the thickness of the coating is 100 microns;

5) weaving the polylactic acid sizing presoaking alumina fiber bundles prepared in the step 4) into composite material blank parts by using a three-dimensional weaving machine;

6) putting the composite material blank prepared in the step 5) into a mould, integrally putting the mould into an autoclave, curing the blank at the pressure of 1.5MPa by the process of 180 ℃/2h +210 ℃/2h, and then cooling the blank to room temperature along with a furnace to prepare the high-performance resin-based alumina fiber composite material product.

Technical Field

The invention belongs to the technical field of preparation of continuous fiber composite materials, and particularly relates to a method for sizing a prepreg fiber bundle for three-dimensional weaving by using thermoplastic resin.

Technical Field

The three-dimensional braided composite material is a high-performance composite material developed in the last 60 th century by using the braiding principle to replace high-temperature alloy in the field of aviation. The three-dimensional braided composite material can be used for preparing a prefabricated blank part with a complex structure and a near net shape by a braiding technology, so that the raw material consumption, the part processing and the mechanism connection are reduced; meanwhile, the fiber reinforcement is uniformly distributed in the space and has a complete structure, so the three-dimensional braided composite material has extremely excellent mechanical properties. Currently, three-dimensional woven composites are often prepared by vacuum infusion or closed mold molding (RTM) processes.

The RTM process is a process in which a fiber yarn is laid in advance in a mold cavity, after closing the mold, a resin is injected into the cavity to impregnate the fiber yarn, and after curing and molding, the mold is released to obtain a desired product. The product prepared by the RTM process has accurate size and stable performance, and the resin injection and curing of the RTM process are carried out in a die closing state, so that the contact between an operator and harmful substances is reduced, and the requirements of environmental protection are met. However, the RTM process is performed after the mold is closed, and thus there is a problem that the fiber impregnation is insufficient. The problem can be effectively solved by adopting a method of preparing prepreg yarns by impregnating fiber yarns with a resin matrix, then preparing a composite blank by an automatic filament laying technology or dry winding method, and finally curing and forming. The prepreg is a combination of a resin matrix and a reinforcing material, and the prepreg can be classified into a thermosetting prepreg and a thermoplastic prepreg according to the resin matrix. Under the condition of room temperature, the thermosetting resin has high viscosity, so the surface of the thermosetting prepreg yarn is sticky and is not suitable for three-dimensional weaving; thermoplastic resins commonly used in thermoplastic prepregs, such as polypropylene, polyetheretherketone, and polyetherketoneketone, are hard at room temperature and have a high heat distortion temperature, and thus the thermoplastic prepregs are also difficult to be applied to three-dimensional weaving. In order to solve the problem, in the patent application No. CN201811392801.1 'a preparation method of prepreg fiber bundles for three-dimensional weaving', a method for modifying a thermosetting resin matrix is adopted to successfully prepare thermosetting prepreg yarns capable of being three-dimensionally woven by semi-mechanized and semi-manual weaving. However, when the fiber yarn is used for machine knitting, the resin is gradually melted due to frictional heat generated between the yarn and the machine, and the resin is dropped or broken. Therefore, the surface of the thermosetting prepreg yarn needs to be protected, and a thermoplastic resin sizing method which can protect the yarn and play a role in toughening interlamination is proposed.

Thermoplastic resins represented by polyethersulfone and polyetheretherketone have not only excellent ductility and impact resistance but also a certain abrasion resistance at room temperature. Meanwhile, the thermoplastic resin can form a high-toughness layer between thermosetting composite material layers, and an interlayer toughening effect is achieved. Therefore, the thermoplastic sizing agent can be sprayed or brushed on the surface of the thermosetting resin prepreg fiber bundle to coat and bundle the prepreg fiber bundle so as to solve the problems of hair scraping and yarn breaking in the weaving process. Meanwhile, the interlaminar strength of the product is improved and the mechanical property is improved by utilizing the interlaminar toughening characteristic of the thermoplastic resin.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a method for sizing a prepreg fiber bundle for three-dimensional weaving by using thermoplastic resin, which comprises the steps of preparing the prepreg fiber bundle for three-dimensional weaving, sizing the thermoplastic resin on the surface of the prepared fiber bundle, preparing a composite material blank by three-dimensional weaving, solidifying, coating by using the thermoplastic resin, bundling the prepreg fiber bundle, and solving the problems of easy hair scraping and yarn breakage in the machine weaving process in the prior art; meanwhile, the interlayer of the thermosetting three-dimensional braided composite material is toughened through the thermoplastic resin, so that the interlayer strength is improved, and the mechanical property of the three-dimensional braided composite material is improved; has the advantages of easy operation, good toughness and high strength.

In order to achieve the above object, the present invention adopts the following technical solutions.

A method for using thermoplastic resin to size the pre-impregnated fiber bundle for three-dimensional weaving, firstly preparing the pre-impregnated fiber bundle, then using the thermoplastic resin to size the pre-impregnated fiber bundle, and then carrying out three-dimensional weaving and curing molding; the method specifically comprises the following steps:

the method comprises the following steps: taking thermosetting resin which is solid or semi-solid at room temperature (20 +/-5 ℃) as a raw material, stirring and heating the thermosetting resin to melt by using a magnetic stirrer, wherein the heating temperature is 50-160 ℃, and the stirring speed is 200-1000 rpm, so as to prepare thermosetting resin impregnation liquid;

step two: stirring and heating by using a magnetic stirrer, wherein the heating temperature is 20-150 ℃, the stirring speed is 200-1000 rpm, and dissolving the thermoplastic resin in the organic solvent to prepare the thermoplastic resin sizing agent, wherein the concentration of the thermoplastic resin is 5-25 wt%;

step three: dipping the thermosetting resin dipping solution prepared in the first step into a continuous fiber bundle by using a pre-dipping glue machine at a traction speed of 0.5-2 m/min and a heating temperature of 50-160 ℃, and cooling to room temperature to prepare a pre-dipping glue fiber bundle with the resin content of 28-33 wt%;

step four: coating a thermoplastic resin sizing agent with the solid content of 3-10 wt% on the surface of the pre-dipped fiber bundle by using a spraying or dip-coating process, and after the solvent is completely volatilized, coating the thermoplastic resin sizing agent to form a pre-dipped fiber bundle for three-dimensional weaving, wherein the thickness of the coating is 50-500 micrometers;

Step five: sizing thermoplastic resin, weaving the thermoplastic resin into a composite material prefabricated part by using pre-impregnated rubber fiber bundles, wherein the tool is a three-dimensional weaving machine;

step six: filling the composite material prefabricated part into a forming mold, heating and pressurizing in curing equipment for curing, and cooling to room temperature along with a furnace to prepare the high-performance continuous fiber composite material; wherein the pressurizing pressure is 0-3 MPa, the heating temperature is 20-250 ℃, the heating time is 2-12 hours, and sectional heating is adopted according to the characteristics of different thermosetting resins.

The thermosetting resin in the first step is one or a mixed resin prepared from two of epoxy resin, benzoxazine resin, phenolic resin, bismaleimide resin, polyphenylsulfone resin, polybenzimidazole resin, cyanate resin and polyquinoxaline resin in any proportion.

The thermoplastic resin in the second step is one of polyether-ether-ketone resin, polycarbonate resin, polyether sulfone resin, polylactic acid resin, polymethyl methacrylate resin, polyphenylene sulfide resin or polyether imide resin.

The organic solvent in the second step is one or a mixed solvent prepared from two of N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, chloroform, ethanol, acetone, tetrahydrofuran and ethyl acetate in any proportion.

The continuous fiber bundle in the third step is one or a mixed fiber of two of glass fiber, carbon fiber, Kevlar fiber, alumina fiber, silicon carbide fiber and the like mixed in any proportion.

And the curing equipment in the sixth step comprises a high-temperature test chamber or an autoclave.

The invention has the following advantages:

the invention adopts the method that the thermoplastic resin is used for sizing the pre-impregnated fiber bundles for three-dimensional weaving, and then three-dimensional weaving and curing molding are carried out, thus solving the problems of easy hair scraping and yarn breaking of the fiber bundles in machine weaving; meanwhile, the thermoplastic resin toughens the interlayer of the thermosetting three-dimensional braided composite material, so that the mechanical property of a final product is further improved; has the advantages of easy operation, good toughness and high strength.

Detailed Description

The present invention will be described in further detail with reference to examples.