CN114836006B

CN114836006B - Fiber-reinforced thermosetting/thermoplastic resin matrix composite material for splicing and preparation method and application thereof

Info

Publication number: CN114836006B
Application number: CN202210307530.5A
Authority: CN
Inventors: 刘新; 武湛君; 陈铎; 尹文轩; 孙涛; 李世超
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2022-03-25
Filing date: 2022-03-25
Publication date: 2023-05-09
Anticipated expiration: 2042-03-25
Also published as: CN114836006A

Abstract

The invention discloses a novel fiber reinforced thermosetting/thermoplastic resin matrix composite material capable of being spliced and used, and a preparation method and application thereof. The composite material is formed by splicing a plurality of units, the units are made of reinforced fiber materials, the middle of the units is made of thermosetting resin materials, the edges of the units are made of thermoplastic resin materials, and the edges of the units are at least one edge of the units; the thermoplastic resin materials spliced at the edges of each unit are mutually spliced through processing treatment. The preparation method disclosed by the invention is simple to operate and low in cost, and can realize the simultaneous exertion of the advantages of the fiber reinforced thermoplastic resin matrix composite material and the fiber reinforced thermosetting resin matrix composite material.

Description

Fiber-reinforced thermosetting/thermoplastic resin matrix composite material for splicing and preparation method and application thereof

Technical Field

The invention relates to a novel composite material structure and a forming technology, in particular to a novel fiber reinforced thermosetting/thermoplastic resin matrix composite material capable of being spliced for use, and a preparation method and application thereof.

Background

The fiber reinforced resin matrix composite materials are the earliest developed, the fastest developed and most widely applied high-performance composite materials, and are mainly divided into two main types according to different types of resin, namely fiber reinforced thermosetting resin matrix composite materials and fiber reinforced thermoplastic resin matrix composite materials.

Because the thermosetting resin has better manufacturability (such as low viscosity), the fiber reinforced thermosetting resin matrix composite material has a plurality of molding process methods, and because the thermosetting resin is cured and has a three-dimensional network structure at a microcosmic level, the mechanical property and the like of the thermosetting resin are very excellent, the fiber reinforced thermosetting resin matrix composite material is widely applied in the fields of aviation, aerospace, navigation, transportation, electronics, machinery and the like. However, after curing, the material cannot be reprocessed and repaired, and certain waste and pollution are caused.

The thermoplastic resin has a long-chain macromolecular structure, can be reprocessed and repaired according to the requirement after being heated and molded, and has better thermal performance, chemical performance and the like, so that the fiber reinforced thermoplastic resin matrix composite material is widely valued and applied. However, the thermoplastic resin has poorer manufacturability than the thermosetting resin, and is mainly characterized by high viscosity, the fiber reinforced thermoplastic resin matrix composite material is relatively difficult to mold, and the mechanical property of the molded composite material is generally lower than that of the thermosetting resin matrix composite material.

It can be seen that the fiber reinforced thermosetting resin matrix composite material and the fiber reinforced thermoplastic resin matrix composite material have advantages and disadvantages, and if one composite material can have the advantages of both, the composite material can be conveniently molded, has good mechanical properties, can be repeatedly used and repaired, and reduces waste and pollution, the composite material has a very promising development prospect.

Disclosure of Invention

Based on the problems existing in the prior art, the invention provides a fiber reinforced thermosetting/thermoplastic resin matrix composite material for splicing and a preparation method and application thereof. The invention firstly selects a thermosetting resin system, prepares thermoplastic resin with the same system, impregnates the thermoplastic resin around the reinforcing fiber, impregnates the thermosetting resin with the same system in the reinforcing fiber, and is heated and cured, and the thermoplastic resin around the reinforcing fiber is spliced for use according to the size requirement, so that the internal thermosetting composite material plays a main bearing role.

Aiming at the defects of the fiber-reinforced thermoplastic resin matrix composite material and the fiber-reinforced thermosetting resin matrix composite material, the invention provides a novel fiber-reinforced thermosetting/thermoplastic resin matrix composite material capable of being spliced for use, and a preparation method and application thereof.

The invention provides a fiber reinforced thermosetting/thermoplastic resin matrix composite material for splicing, which is formed by splicing a plurality of units, wherein the units are made of thermosetting resin materials in the middle of reinforced fiber materials, the edges are made of thermoplastic resin materials, and the edges are at least one edge of the units; the thermoplastic resin materials spliced at the edges of each unit are mutually spliced through processing treatment.

Further, in the above technical solution, the reinforcing fiber material includes carbon fiber material, glass fiber, and aramid fiber.

Further, in the above technical solution, the number of the units is at least 2.

Further, in the above technical solution, the thermosetting resin material includes epoxy resin, bismaleimide resin, phenolic resin; the thermoplastic resin material comprises corresponding thermoplastic epoxy resin, thermoplastic bismaleimide resin, thermoplastic phenolic resin and other system resins.

Further, in the above technical solution, the splicing mode includes butt joint, joggle joint, lap joint and splicing.

Further, in the above technical solution, the processing treatment includes laser welding, ultrasonic welding, hot-melt welding, and pulse current welding.

The invention also provides a preparation method of the novel spliced fiber reinforced thermosetting/thermoplastic resin matrix composite material, which comprises the following steps:

1) Preparing a thermoplastic resin which is in the same system as the thermosetting resin;

2) Designing a repeated spliced structure form on the reinforced fiber layer;

3) Dissolving a thermoplastic resin into a low-viscosity liquid by using a volatile solvent;

4) Impregnating a thermoplastic resin solution with a certain width at the edge of the repeating unit according to the pattern design;

5) Drying the edge thermoplastic resin solvent for later use;

6) Laying the repeated units according to the designed layer number;

7) The reinforced fiber material of the middle part of the repeating unit which is not impregnated with the thermoplastic resin is fully impregnated with the thermosetting resin by adopting a thermosetting resin molding process, and is heated and cured, wherein the curing temperature is not higher than the decomposition temperature of the thermoplastic resin of the edge part of the repeating unit, and the edge is not influenced;

because the thermoplastic resin at the edge of the unit and the thermosetting resin at the middle part are the same-system resin, the thermoplastic resin and the thermosetting resin have good compatibility on the contact surface, thus stabilizing the performance of the unit

8) Edge splicing is carried out on the cured units according to the required area (large-area components can be spliced infinitely according to the required area);

9) And (3) adopting a thermoplastic resin processing technology to carry out secondary processing on thermoplastic resin at the spliced edges of the units, so that all the units are integrated, and obtaining the fiber reinforced thermosetting/thermoplastic resin matrix composite material.

10 If a certain unit is damaged in the using process, the replacement of a new unit can be carried out by repeatedly processing the edge of the unit, so that the local repair work which cannot be realized by the thermosetting composite material can be completed

11 After the member is used, the thermoplastic resin at the edge of the unit can be processed according to the use condition to realize the disassembly of the unit

12 The units are stacked and stored, the space is saved, and the steps 1) to 13) can be repeated when the unit is reused.

Further, in the above technical scheme, the volatile solvent includes ethanol, acetone, toluene, butanol, and dibutyl ester, and the viscosity of the low-viscosity solution is 300-800mpa.s.

Further, in the above technical solution, the thermosetting resin molding process includes vacuum infusion, hand lay-up, and spray coating; the temperature of the heating and curing is 60-80 ℃ 0.5-3h+100-140 ℃ 0.5-3h+150-180 ℃ 1-4h. The specific heat cure temperature and time will be determined by the nature of the different resins.

The invention also provides an application of the composite material or the composite material prepared by the preparation method, which is applied to structural components of aerospace aircrafts, ships, submarines, automobile trains and mechanical and electrical appliances.

The invention adopts the unit structure made of the T300 carbon fiber fabric, the bending strength of the spliced composite material plate can reach 879MPa, the tensile strength is 693MPa, the tensile modulus is 60GPa, and the performance of the spliced composite material plate is similar to that of a common composite material plate.

Drawings

Fig. 1 is a molecular formula of a thermoplastic epoxy resin, wherein n=10-100.

Fig. 2 is a fiber cloth impregnated with thermoplastic epoxy resin of example 1.

Fig. 3 is a carbon fiber cloth unit impregnated with thermoplastic epoxy resin of example 1.

FIG. 4 is a 6-layer unit laid down in example 1.

Fig. 5 is a cured cell plate of example 1.

Fig. 6 is a composite panel after splice according to example 1.

Fig. 7 is a fiber cloth impregnated with thermoplastic epoxy resin of example 2.

Fig. 8 is a carbon fiber cloth unit impregnated with thermoplastic epoxy resin of example 2.

Fig. 9 is a 6-layer unit laid down in example 2.

Fig. 10 is a cured cell plate of example 2.

Fig. 11 is a composite panel after example 2 has been spliced.

Detailed Description

The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.

Example 1

A preparation method of a novel spliced fiber reinforced thermosetting/thermoplastic resin matrix composite material comprises the following steps:

1) E51 epoxy resin is selected as a matrix material, and a T300 carbon fiber woven cloth with the thickness of 900mm multiplied by 0.2mm is selected as a reinforcing material;

2) Thermoplastic epoxy resins are prepared. 100g of E51 epoxy resin is taken, 150ml of N, N-Dimethylformamide (DMF) is added, then 35g of aniline is added, the reaction is carried out for 8 hours at 150 ℃, the temperature is reduced to room temperature, the product after the reaction is poured into 300ml of distilled water, the white gelatinous product is obtained, and the unreacted aniline and the epoxy resin are removed by repeated washing with acetone. Then, vacuum-dried at 80℃for 48 hours to obtain a thermoplastic epoxy resin having a chemical formula shown in FIG. 1.

3) Dissolving the prepared thermoplastic epoxy resin in 100ml of ethanol to prepare a solution with the viscosity of 400mpa.s, and respectively longitudinally dipping the carbon fiber cloth at the positions of 290mm-300mm, 590mm-600mm and 890mm-900mm in the transverse direction of the fiber cloth for 10mm width to serve as a lap joint part of the repeating units;

4) Meanwhile, thermoplastic epoxy resin with the width of 2mm-5mm is transversely impregnated at the position of 300mm and 600mm in the longitudinal direction of the carbon fiber cloth, so that the integrity of the unit can be maintained when the edge of the repeated unit is cut, and the unit is shown in figure 2.

5) And (3) arranging the impregnated fibers in an oven, drying at 80 ℃, removing ethanol, and cooling to room temperature to impregnate the edge position of the thermoplastic epoxy resin to be in a hard state.

6) The carbon fiber cloth was cut along the edges of the unit impregnated thermoplastic epoxy to obtain 9 identical thermoplastic epoxy impregnated carbon fiber cloth units as shown in fig. 3.

7) Repeating the steps 3) -6), and making 18 identical carbon fiber cloth units impregnated with thermoplastic epoxy resin.

8) The middle dry fiber portions (non-impregnated areas) of the 6 carbon fiber cloth units impregnated with the thermoplastic epoxy resin are superposed and laid, and the thermoplastic epoxy resin impregnated portions of two adjacent carbon fiber cloths are respectively arranged on two sides of the layer, as shown in fig. 4.

9) And wrapping the laid 6 layers of units in a vacuum bag by adopting a vacuum infusion process, dipping the thermosetting epoxy resin solution mixed with the m-phenylenediamine curing agent into the carbon fiber cloth of the middle dry fiber part by vacuum negative pressure, and curing in the vacuum curing furnace by a curing system of 60 ℃ 0.5h+120 ℃ 1h+160 ℃ 2 h.

10 Cooling the cured unit board to room temperature along with a furnace, and taking out for standby. The cured cell plate is shown in FIG. 5

11 Repeating steps 8) -10) 2 times to produce 3 identical unit plates.

12 When the heat-insulation composite material is used, the edges of the three unit plates are spliced and fixed, laser welding is carried out on the edge parts impregnated with thermoplastic epoxy resin, so that 6 layers of edge parts of each two unit plates which are lapped are welded together and are equal to the main bearing part of the middle thermosetting epoxy resin-based composite material in height, and a large-area flat plate (fiber content is 60%) with the thickness of 900mm multiplied by 300mm multiplied by 2mm is formed after the 3 unit plates are spliced, as shown in figure 6.

13 If a certain unit plate is damaged in the using process, the thermoplastic resin at the edge of the unit plate can be heated, softened and removed to replace a new unit plate for splicing, and the unit plates are welded together through the edges, so that the whole composite plate can be continuously used.

14 After the spliced composite material plates are used, thermoplastic resin at the edge of each unit plate can be heated, softened and removed, and after the unit plates are restored to room temperature, the unit plates are collected and stored, so that the space can be saved and the unit plates can be reused.

15 According to the requirement, thermoplastic epoxy resin can be impregnated around the fiber cloth units, so that the unit plates can be spliced and used in the transverse and longitudinal directions at the same time.

Example 2

1) E51 epoxy resin is selected as a matrix material, and 600mm multiplied by 0.2mm T300 carbon fiber woven cloth is selected as a reinforcing material;

2) Thermoplastic epoxy resins are prepared. The procedure is as in 2) of example 1.

3) The prepared thermoplastic epoxy resin was dissolved in 100ml of ethanol to prepare a solution 400mpa.s, and carbon fiber cloth was impregnated at 295mm to 305mm in the transverse and longitudinal directions of the fiber cloth by 10mm width, respectively, as a spliced portion of the repeating unit, as shown in fig. 7.

4) And (3) arranging the impregnated fibers in an oven, drying at 80 ℃, removing ethanol, and cooling to room temperature to impregnate the edge position of the thermoplastic epoxy resin to be in a hard state.

5) The carbon fiber cloth was cut along the edges of the unit impregnated thermoplastic epoxy resin to obtain 4 identical thermoplastic epoxy resin impregnated carbon fiber cloth units, as shown in fig. 8.

6) Repeating the steps 3) -6) for 6 times to manufacture 24 identical carbon fiber cloth units impregnated with thermoplastic epoxy resin.

7) 6 carbon fiber cloth units impregnated with thermoplastic epoxy resin were laid one over the other as shown in fig. 9.

8) And wrapping the laid 6 layers of units in a vacuum bag by adopting a vacuum infusion process, dipping the thermosetting epoxy resin solution mixed with the m-phenylenediamine curing agent into the carbon fiber cloth at the middle part by vacuum negative pressure, and curing in a vacuum curing furnace by a curing system of 60 ℃ 0.5h+120 ℃ 1h+160 ℃ 2 h.

9) And cooling the cured unit plate to room temperature along with a furnace, and taking out for later use. The cured cell plate is shown in fig. 10.

10 Repeating 8) -10) steps 4 times to produce 4 identical unit plates.

11 4 unit plates are spliced and fixed at the edges, laser welding is carried out on the edge parts impregnated with thermoplastic epoxy resin, so that 6 layers of edge parts of each two unit plates which are lapped are welded together, and 4 unit plates are spliced to form a large-area flat plate (fiber content is 60%) with 600mm multiplied by 2mm, as shown in figure 11

12 If a certain unit plate is damaged in the using process, the thermoplastic resin at the edge of the unit plate can be heated, softened and removed to replace a new unit plate for splicing, and the unit plates are welded together through the edges, so that the whole composite plate can be continuously used.

13 After the spliced composite material plates are used, thermoplastic resin at the edge of each unit plate can be heated, softened and removed, and after the unit plates are restored to room temperature, the unit plates are collected and stored, so that the space can be saved and the unit plates can be reused.

14 According to the requirement, thermoplastic epoxy resin can be impregnated around the fiber cloth units, so that the unit plates can be spliced and used in the transverse and longitudinal directions at the same time.

Claims

1. The fiber reinforced thermosetting/thermoplastic resin matrix composite material for splicing is characterized in that the composite material is formed by splicing a plurality of units, the units are made of thermosetting resin materials in the middle of reinforced fiber materials, the edges are made of thermoplastic resin materials, and the edges are at least one edge of the units; the thermoplastic resin materials which are spliced into the edges of each unit are mutually spliced through processing treatment;

the thermosetting resin material comprises epoxy resin, bismaleimide resin and phenolic resin; the thermoplastic resin material comprises corresponding thermoplastic epoxy resin, thermoplastic bismaleimide resin and thermoplastic phenolic resin co-system resin.

2. The composite material of claim 1, wherein the reinforcing fiber material comprises a carbon fiber material, a glass fiber, an aramid fiber.

3. The composite material of claim 1, wherein the number of units is at least 2.

4. The composite material of claim 1, wherein the means of splicing comprises butt-joint, joggle-joint, lap-joint, plug-in.

5. The composite material of claim 1, wherein the processing comprises laser welding, ultrasonic welding, hot melt welding, pulse current welding.

6. A method of preparing a fiber reinforced thermosetting/thermoplastic resin based composite for use in splicing according to any one of claims 1 to 5, comprising the steps of:

2) Designing a repeated spliced structure form on the reinforced fiber material;

5) Drying the edge thermoplastic resin solvent for later use;

6) Laying the repeated units according to the designed layer number;

7) The reinforcing fiber material of the middle part of the repeating unit which is not impregnated with the thermoplastic resin is completely impregnated with the thermosetting resin by adopting a thermosetting resin molding process, and is heated and cured;

8) Performing edge splicing on the cured units according to the required area;

7. The method according to claim 6, wherein the volatile solvent comprises ethanol, acetone, toluene, butanol, dibutyl ester, and the low viscosity solution has a viscosity of 300 to 800mpa.s.

8. The method of claim 6, wherein the thermosetting resin molding process comprises vacuum infusion, hand lay-up, spray coating; the temperature of the heating and curing is 60-80 ℃ 0.5-3h+100-140 ℃ 0.5-3h+150-180 ℃ 1-4h.

9. Use of a composite material according to any one of claims 1 to 5 or a composite material prepared by a method according to any one of claims 6 to 8, for a structural component of an aerospace vehicle, a marine submarine, an automotive train, a mechanical electrical appliance.