CN110305464A - A kind of continuous nitride silica fibre reinforced resin base composite wire and preparation method thereof - Google Patents

Abstract

The invention discloses a continuous silicon nitride fiber-reinforced resin-based composite wire and a preparation method thereof, belonging to the technical field of composite materials. The composite wire is made of silicon nitride fiber, lubricant, resin, coupling agent, softener and solvent. The purpose of the present invention is to reduce the damage of fibers in the process of three-dimensional weaving, and the bundled and wear resistance of the composite wires produced are significantly improved, and at the same time, they also have good flexibility, which can meet the needs of fabrics in different warp densities, weft densities and The bending deformation requirement under the thickness significantly reduces the breakage of fibers during the three-dimensional weaving process, reduces the broken yarn and defects in the fabric, and ensures the performance of the fabric.

Description

A continuous silicon nitride fiber reinforced resin-based composite wire and its preparation method

technical field

The invention belongs to the technical field of composite materials, in particular to a continuous silicon nitride fiber reinforced resin-based composite wire and a preparation method thereof.

Background technique

Silicon nitride fiber is a ceramic fiber material with excellent properties such as high strength, high hardness, good oxidation resistance, thermal stability, excellent creep resistance, good thermal shock resistance and high electrical insulation. Compared with quartz fiber, silicon nitride fiber has better high temperature resistance, and is an ideal material for preparing fiber reinforcement of ceramic matrix composites, so it has great application potential in aerospace, defense industry and other fields.

As a reinforcement, three-dimensional fabric has the advantages of good thickness direction performance and strong shape design, and its application in the aerospace field has reached a certain scale. As the main preparation method of three-dimensional fabrics, three-dimensional weaving is relatively mature in technology, but in the preparation process, the interweaving movement of fibers is more frequent than that of flat fabrics, which makes the fibers more prone to stretching, bending, Friction, shearing, torsion and other damages, at the same time, due to the high hardness and brittleness of the silicon nitride fiber itself, these damages are more serious. After the fiber is damaged, it is easy to break, which reduces the continuity of the fiber in the fabric, increases the number of broken yarns and defects inside the fabric, causes great damage to the performance of the fabric, and even affects the preparation efficiency of the fabric. Therefore, improving the damage resistance of silicon nitride fibers and reducing the damage of silicon nitride fibers in the three-dimensional weaving process is of great significance to speed up the preparation of silicon nitride fiber fabric reinforcements.

In order to improve weaving adaptability and fiber damage resistance, fiber sizing or surface treatment is often required. However, due to the relatively late start of research on silicon nitride fibers, and the high content of silicon and nitrogen elements in silicon nitride fibers, the affinity for organic polymeric substrates is weak, resulting in difficulties in the preparation of sizing agents and surface treatment agents for silicon nitride fibers. Although there are some reports on sizing agents or surface treatment agents for silicon nitride fibers, there are still some problems. For example, the patent application number CN201710182433 proposes a silicon nitride fiber sizing agent, which improves the strength of the tow, reduces hairiness and broken filaments, but when the fiber sizing rate is low, the protection of the fiber by the size film is very weak. With the passage of the weaving process, the fibers will still be damaged in a large area, and when the sizing rate increases, the brittleness of the fibers will be increased and the flexibility of the fibers will be reduced. When the warp and weft density or thickness of the fabric increases, it is easy to break; A nitride fiber sizing agent proposed in the patent No. CN201710887481 has a certain protective effect and performance improvement on the fiber, but the production efficiency is low and it is not suitable for large-scale production. Therefore, from the perspective of sizing agents or surface treatment agents, it is still difficult to reduce the damage of silicon nitride fibers and improve the three-dimensional weaving adaptability of silicon nitride fibers.

Contents of the invention

Aiming at the existing technical problems, the technical problem to be solved by the present invention is to provide a continuous silicon nitride fiber reinforced resin-based composite wire and its preparation method, and use the composite wire as a three-dimensional weaving yarn to prepare a three-dimensional fabric to solve the problem of nitriding The problem of large damage of silicon fiber in the process of manufacturing reinforced three-dimensional fabric.

The technical problem to be solved in the present invention adopts the following technical solutions to realize:

A continuous silicon nitride fiber-reinforced resin-based composite wire is made of components comprising the following parts by weight:

60-80 parts of modified resin solution;

Lubricant 0.5-2 parts;

Silicon nitride fiber 25-45 parts.

Preferably, the modified resin solution is made of resin, softening agent, silane coupling agent, solvent, and each component by weight is as follows:

Wherein, the lubricant is simethicone.

Preferably, the viscosity of the simethicone oil is not higher than 300.

Wherein, the resin is one of thermoplastic polyurethane and polylactic acid.

Wherein, the softening agent is one or more of ethylene glycol, polyethylene glycol, polypropylene glycol, and polyvinylpyrrolidone.

Preferably, in order to ensure the stability of the solution, the molecular weight of polyethylene glycol is not greater than 3000.

Wherein, the solvent is one or two of dimethylformamide, ethyl acetate, acetone, butanone.

Wherein, the coupling agent is a silane coupling agent.

In order to reduce the friction during three-dimensional weaving, it is necessary to lubricate the composite wire, and because the solubility of the lubricant in the solution system used is low, the lubricant of the present invention is impregnated after the fibers are impregnated with the resin solution .

The invention also introduces a method for preparing continuous silicon nitride fiber reinforced resin-based composite wires, which includes the following steps:

(1) Take raw materials according to the following components by weight:

(2) Add 10-20 parts by weight of solvent and 0.3-2 parts by weight of coupling agent into the preparation container, heat in a water bath to 20-30°C, and stir for 5-10 minutes to prepare a coupling agent dilution;

(3) Add 60-70 parts by weight of solvent, 2-15 parts by weight of softener and 8-20 parts by weight of resin to the coupling agent dilution prepared in step (2), and heat it in a water bath to 30-45 °C, stir until the resin is completely dissolved to obtain a modified resin solution;

(4) Add the modified resin solution made by steps (1)-(3) into the solution tank, add 0.5-2 parts by weight of lubricant into the lubricant tank, and add 25-45 parts by weight of silicon nitride fiber Placed on the creel, the fibers are drawn sequentially through the solution tank, drying pipe I, lubricant tank, drying pipe II equipped with a pipeline fan, and then wound and collected by a winding machine to obtain the unidirectional Continuous silicon nitride fiber reinforced resin composite wire.

Further, in order to accelerate the evaporation of the solvent and avoid the softening of the polymer due to excessive temperature, the drying area is divided into two sections with different temperatures. Preferably, the temperature of the drying pipe 1 is 120-150°C, and the drying The temperature of tube II is 50-80°C.

Further, in order to speed up the drying of the composite wire and reduce the disturbance of the airflow to the fibers, preferably, the airflow rate of the duct fan is in the range of 5-10m ³ /min.

Furthermore, considering the production rate and quality stability of the composite wire, preferably, the winding speed of the winding machine is 5-12 m/min.

It should be noted that the main purpose of the present invention is to improve the damage resistance of fibers when preparing silicon nitride fiber reinforced fabrics, so in the pretreatment process for the preparation of silicon nitride fiber reinforced ceramic matrix composites, it is necessary to When the silicon nitride reinforced fabric is calcined at a high temperature, all the organic components in the fiber bundle will be decomposed, so the method of the present invention does not affect the next step of the preparation process of the silicon nitride fiber reinforced ceramic matrix composite material.

Based on the background of solving the problem of three-dimensional weaving of silicon nitride fibers, the present invention prepares unidirectional continuous silicon nitride fiber reinforced resin-based composite wires. Compared with the prior art, the beneficial effects of the present invention are reflected in:

First, the continuous silicon nitride fiber-reinforced resin-based composite wire of the present invention can be prepared without complex chemical reactions, and the production process is relatively simple, which can be applied to production;

Second, the continuous silicon nitride fiber-reinforced resin-based composite wire of the present invention helps to reduce breakage during the three-dimensional weaving process, thereby reducing yarn breakage and defects inside the fabric, and ensuring the stability of fabric performance and production continuity;

Third, the continuous silicon nitride fiber-reinforced resin-based composite wire prepared by the present invention can effectively coat the fiber, reduce hairiness on the surface of the fiber, significantly improve wear resistance and clustering, and reduce friction on the fiber during three-dimensional weaving , fiber damage is reduced;

Fourth, the continuous silicon nitride fiber-reinforced resin-based composite wire prepared by the present invention can maintain good flexibility even with the increase of the resin content, and will not become brittle and hard, which can meet the requirements of the wire in the preparation of larger Bending deformation requirements in the case of fabrics with warp density, weft density or thickness;

Fifth, the continuous silicon nitride fiber-reinforced resin-based composite wire prepared by the present invention can not only be used for three-dimensional weaving, but also be used as suture thread and braided wire for suture.

Description of drawings

Fig. 1 is a schematic diagram of the preparation process and device of a method for preparing a continuous silicon nitride fiber reinforced resin-based composite wire according to the present invention.

Fig. 2 is an electron microscope image of the composite wire prepared in Example 3 of the present invention.

Detailed ways

Specific examples of the present invention are given below. The specific embodiments are only used to further describe the present invention in detail, and do not limit the protection scope of the claims of the present application.

Some raw materials used in the embodiment are as follows:

Simethicone oil, the product brand is Dow Corning PMX-200, 50 viscosity; the softener is PEG-400, PE6-600, from Petronas Malaysia; the coupling agent is KH-550, from Nanjing Chuangshi Chemical Auxiliary Co., Ltd. ; The resin is thermoplastic polyurethane, and the grade is Bayer's F165A.

In the following examples, all fibers are single-strand fibers.

Example 1

A continuous silicon nitride fiber reinforced resin-based composite wire, prepared according to the following method:

(1) Take raw materials according to the following parts by weight:

Wherein solvent selects acetone for use;

(2) Add 10 parts by weight of solvent and 1 part by weight of coupling agent into the preparation container, heat in a water bath to 20° C., and stir for 5 minutes to prepare a coupling agent dilution;

(3) Add 76 parts by weight of solvent, 5 parts by weight of softener PEG-400 and 8 parts by weight of resin to the coupling agent diluent obtained in step (2), and heat it in a water bath to 40°C, and stir until the resin Dissolve completely to obtain a modified resin solution;

(4) Add the modified resin solution made by steps (1)-(3) into the solution tank, add 1 part by weight of lubricant into the lubricant tank, and place 40 parts by weight of silicon nitride fiber on the creel above, the fibers are pulled through the solution tank, drying pipe I, lubricant tank, drying pipe II equipped with a pipeline fan in sequence, and then wound and collected by a winding machine to obtain the continuous silicon nitride fiber-reinforced Resin-based composite wire.

The temperature of the drying pipe I is 130°C, the air flow rate of the pipeline fan is 6m ³ /min, the temperature of the drying pipe II is 50°C, and the winding speed of the winding machine is 10m/min.

Example 2

A continuous silicon nitride fiber reinforced resin-based composite wire, prepared according to the following method:

(1) Take raw materials according to the following parts by weight:

Wherein solvent selects acetone for use;

(2) Add 10 parts by weight of solvent and 1 part by weight of coupling agent into the preparation container, heat in a water bath to 20° C., and stir for 5 minutes to prepare a coupling agent dilution;

(3) Add 70 parts by weight of solvent, 4 parts by weight of PEG-400 and 4 parts by weight of PEG-800 mixed softener, 12 parts by weight of resin to the coupling agent diluent obtained in step (2), and water bath Heat to 40°C and stir until the resin is completely dissolved to obtain a modified resin solution;

(4) Add the modified resin solution made by steps (1)-(3) into the solution tank, add 2 parts by weight of lubricant into the lubricant tank, and place 30 parts by weight of silicon nitride fiber on the creel above, the fibers are pulled through the solution tank, drying pipe I, lubricant tank, drying pipe II equipped with a pipeline fan in sequence, and then wound and collected by a winding machine to obtain the continuous silicon nitride fiber reinforced Resin-based composite wire.

The temperature of the drying pipe I is 130°C, the air flow rate of the pipeline fan is 8m ³ /min, the temperature of the drying pipe II is 50°C, and the winding speed of the winding machine is 8m/min.

Example 3

A continuous silicon nitride fiber reinforced resin-based composite wire, prepared according to the following method:

(1) Take raw materials according to the following parts by weight:

Wherein solvent selects acetone for use;

(2) Add 20 parts by weight of solvent and 1 part by weight of coupling agent into the preparation container, heat in a water bath to 20° C., and stir for 5 minutes to prepare a coupling agent dilution;

(3) Add 54 parts by weight of solvent, 10 parts by weight of softener PEG-800 and 15 parts by weight of resin to the coupling agent diluent obtained in step (2), and heat to 40°C in a water bath, and stir until the resin Dissolve completely to obtain a modified resin solution;

(4) Add the modified resin solution made by steps (1)-(3) into the solution tank, add 2 parts by weight of lubricant into the lubricant tank, and place 25 parts by weight of silicon nitride fiber on the creel above, the fibers are pulled through the solution tank, drying pipe I, lubricant tank, drying pipe II equipped with a pipeline fan in sequence, and then wound and collected by a winding machine to obtain the continuous silicon nitride fiber reinforced Resin-based composite wire.

The temperature of the drying pipe I is 140°C, the air flow rate of the pipeline fan is 8m ³ /min, the temperature of the drying pipe II is 60°C, and the winding speed of the winding machine is 5m/min.

comparative example

In order to further illustrate the flexibility of the composite wire of the present invention, a comparative example is provided on the basis of the above examples. The composite wires of Comparative Examples 1-3 are made on the basis of Examples 1-3, after removing the softening agent in Preparation Step 1 and Preparation Step 3.

test case

Embodiment 1-3 and comparative example 1-3 are carried out the test of stiffness and abrasion resistance, and stiffness is a reference value illustrating the flexibility of composite wire, and the larger the value of stiffness, shows that the flexibility of composite wire is lower and can The weaker the ability to adapt to the bending deformation of three-dimensional weaving, the easier it is to damage during three-dimensional weaving. Abrasion resistance is the reference value of the wear resistance of the composite wire during three-dimensional weaving by testing the number of times the composite wire is rubbed to break. The test results are shown in Table 1.

The test basis for stiffness is: GB/T 7690.4-2013 Test methods for reinforcing material yarns Part 4: Determination of stiffness

The test basis for abrasion resistance is: FZ/T 01058-1999 Yarn Abrasion Resistance Test Method Reciprocating Grinding Roller Method

Table 1 Test results of different composite wires

From the test results of stiffness, it can be seen that compared with the composite wire made by Comparative Example 1-3 without adding softener, the stiffness of the composite wire made by Example 1-3 after adding softener decreases, and the flexibility The performance is improved, which helps the composite wire adapt to the bending deformation during three-dimensional weaving and reduces fiber damage.

As can be seen from the test results of the wear resistance, the wear resistance of the composite wire is stronger than that of the untreated fiber. From the comparison of Examples 1-3 and Comparative Examples 1-3, it can be seen that the addition of the softener does not make the composite wire The abrasion resistance is significantly reduced, and the enhancement of abrasion resistance can further protect the fibers during three-dimensional weaving.

Claims (6)

1. a kind of continuous nitride silica fibre reinforced resin base composite wire, which is characterized in that be made of the component of following parts by weight:

60-80 parts of modified resin solution；

0.5-2 parts of lubricant；

25-45 parts of silicon nitride fiber；

The modified resin solution is made of the component of following parts by weight:

2. a kind of continuous nitride silica fibre reinforced resin composite wire as described in claim 1, which is characterized in that the lubrication Agent is dimethicone, and the coupling agent is silane coupling agent, and the solvent is dimethylformamide, ethyl acetate, acetone, fourth One or both of ketone.

3. a kind of continuous nitride silica fibre reinforced resin base composite wire as described in claim 1, which is characterized in that the tree Rouge is one of thermoplastic polyurethane, polylactic acid.

4. a kind of continuous nitride silica fibre reinforced resin base composite wire as described in claim 1, which is characterized in that described soft Soft dose is one of ethylene glycol, polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone or a variety of.

5. such as a kind of preparation side of continuous nitride silica fibre reinforced resin base composite wire of any of claims 1-4 Method, which comprises the following steps:

(1) raw material is weighed according to following parts by weight of component:

(2) solvent of 10-20 parts by weight and the coupling agent of 0.3-2 parts by weight are added in preparing container, and heating water bath is to 20- It 30 DEG C, stirs 5-10 minutes, coupling agent dilution is made；

(3) solvent of 60-70 parts by weight, the softening agent of 2-15 parts by weight are added in the coupling agent dilution made from step (2) With the resin of 8-20 parts by weight, and heating water bath is to 30-45 DEG C, and stirring to resin is completely dissolved, and modified resin solution is made；

(4) the modified resin solution made of step (1)-(3) is added in solution tank, the lubricant of 0.5-2 parts by weight is added Enter in lubricant tank, the silicon nitride fiber of 25-45 parts by weight is placed on bobbin cradle, fiber is made successively to be drawn through solution Slot, drying pipe I, lubricant tank, the drying pipe II equipped with pipeline fan, wind using up- coiler and collect, and obtain described Continuous nitride silica fibre reinforced resin base composite wire.

6. a kind of preparation method of continuous nitride silica fibre reinforced resin base composite wire as claimed in claim 5, feature It is, in the step (5), the temperature of drying pipe I is 120-150 DEG C, and the temperature of drying pipe II is 50-80 DEG C, pipeline fan Throughput be 5-10m³/ min, the winding rate of up- coiler are 5-12m/min.