Preparation Method of Light-Resistant Degradable Inorganic Fiber / Polyaryletherketone Composite Material

Abstract

The present invention relates to a preparation method of a light-resistant degradation inorganic fiber / polyaryletherketone composite material, which comprises the following steps: S1, subjecting a metal oxide to dielectric barrier discharge treatment under a protective atmosphere; S2, placing the treated metal oxide in a sulfonated polyetheretherketone solution for impregnation to form a mixed system, adding surface-treated inorganic fibers to the mixed system for blending, and then performing heat treatment to remove the solvent to obtain a modified blended material; S3, mixing the modified blended material with polyaryletherketone and then melt-extruding and granulating or directly molding by pressing to obtain the light-resistant degradation inorganic fiber / polyaryletherketone composite material; the proportion of the metal oxide in the light-resistant degradation inorganic fiber / polyaryletherketone composite material ranges from 0.3 wt% to 3.5 wt%. The material preparation method of the present invention can significantly improve the resistance of the material to light degradation and can effectively delay the speed of the decrease in the bonding force between the fiber and the matrix resin.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and particularly to a preparation method of a light-resistant degradation inorganic fiber / polyaryletherketone composite material. Background Art

[0002] Polyetheretherketone (PEEK) is a super high-performance thermoplastic semi-crystalline engineering plastic with excellent mechanical properties, chemical resistance, high temperature resistance, radiation resistance, hydrolysis resistance, abrasion resistance and high cleanliness. As a high-performance thermoplastic engineering plastic, PEEK can replace some traditional metal materials and be widely used in fields such as automobiles, aerospace, and machinery equipment. Especially in the aerospace field, due to its high heat resistance and low density, PEEK has gradually replaced aluminum products in the manufacture of some components.

[0003] Single PEEK resin can no longer meet the requirements of various complex and extreme environments, and more and more attention has been paid to the reinforcement and modification of PEEK with fibers. Due to the low cost and excellent performance of glass fibers, they have been widely studied and applied. For fiber-reinforced PEEK composites, under light irradiation, affected by molecular chain breakage and molecular weight reduction, the bonding force between glass fibers and the resin matrix weakens, which cannot effectively transfer external stress, thus reducing the mechanical properties of fiber-reinforced PEEK composites. Summary of the Invention

[0004] In order to improve the light-resistant degradation performance of fiber-reinforced polyetheretherketone composites, a preparation method of a light-resistant degradation inorganic fiber / polyaryletherketone composite material is provided. The material preparation method of the present invention can significantly improve the resistance of the material to light degradation and can effectively delay the speed of the decrease in the bonding force between the fiber and the matrix resin.

[0005] In order to achieve the above object, the present invention is realized through the following technical solutions:

[0006] A preparation method of a light-resistant degradation inorganic fiber / polyaryletherketone composite material, comprising the following steps:

[0007] S1. Subjecting the metal oxide to dielectric barrier discharge treatment under a protective atmosphere;

[0008] S2. Placing the treated metal oxide in a sulfonated polyetheretherketone solution for impregnation to form a mixed system, adding surface-treated inorganic fibers to the mixed system for blending, and then removing the solvent by heat treatment to obtain a modified blended material;

[0009] S3. Mixing the modified blended material with polyaryletherketone and then melt-extruding and granulating or directly compression-molding to obtain the light-resistant degradation inorganic fiber / polyaryletherketone composite material;

[0010] The proportion of the metal oxide in the light-resistant degradation inorganic fiber / polyaryletherketone composite material ranges from 0.3 wt% to 3.5 wt%.

[0011] Furthermore, the metal oxide is selected from one or more of cerium oxide, tungsten oxide, copper oxide, zinc oxide, titanium oxide, and tin oxide;

[0012] The polyaryletherketone is selected from one or more of polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), and polyetherketoneetherketoneketone (PEKEKK);

[0013] The inorganic fiber is selected from one or more of glass fiber, carbon fiber, basalt fiber, and ceramic fiber, and is a continuous fiber or a short fiber, and the diameter of the inorganic fiber is less than 15 μm;

[0014] The concentration of the sulfonated polyetheretherketone solution is 15% - 35%, wherein the solvent is one or more of DMF, NMP, DMAc, and DMSO, and the sulfonation degree of the sulfonated polyetheretherketone is 30% - 70%.

[0015] Still further, the metal oxide is selected from cerium oxide, or a mixed configuration of cerium oxide and one or more of tungsten oxide, copper oxide, zinc oxide, and titanium oxide, and the proportion of cerium oxide in the mixed configuration is at least 50 wt%. Preferably, the metal oxide is cerium oxide, and the cerium oxide is preferably cerium dioxide.

[0016] Still further, the surface-treated inorganic fiber is dry-modified or wet-modified by using a silane coupling agent, and the silane coupling agent is selected from one of vinyl silane coupling agents (such as A172), amino silane coupling agents (such as KH550), and methacryloxy silane coupling agents (such as KH570).

[0017] Furthermore, the mass ratio of the metal oxide to the sulfonated polyetheretherketone solution is 1:1 - 5;

[0018] The mass ratio of the metal oxide, the surface-treated inorganic fiber, and the polyaryletherketone is 0.5 - 5:20 - 40:60 - 75.

[0019] Furthermore, the impregnation time of the metal oxide in the sulfonated polyetheretherketone solution is 2 - 36 h; the blending time of the surface-treated inorganic fiber in the mixed system is 10 - 30 min; the heat treatment is carried out at 200 - 280 °C for 2 - 5 h.

[0020] Further, the dielectric barrier discharge treatment is carried out under an argon protection atmosphere and a vacuum degree of 80 - 150 Pa, at a power of 300 - 400 W for 100 - 240 seconds.

[0021] Beneficial technical effects: By pre - treating the metal oxide, the present invention makes it have high activity and uses sulfonated polyether ether ketone as the interfacial binder between the metal oxide and the polyaryletherketone, enabling the metal oxide to be evenly dispersed in the matrix material, improving the light degradation resistance of the composite material. As a reinforcing material for the matrix, the surface - treated metal oxide can slow down the rate of decline in the bonding force between the glass fiber and the matrix resin;

[0022] In addition, the polyaryletherketone matrix resin, especially PEEK, contains a large number of aromatic rings. These aromatic rings can absorb ultraviolet light, reducing the damage to the molecular chain, and the semi - crystalline nature also endows PEEK with good stability. By pre - treating the filler, the resistance to ultraviolet light degradation is improved, and the modification method is green, environmentally friendly, and pollution - free, and is easy for large - scale production. Description of the Drawings

[0023] Figure 1 The left figure of... is the microscopic SEM image of the cross - section of the sample of the product of Example 1 after ultraviolet aging;

[0024] Figure 1 The right figure of... is the microscopic SEM image of the cross - section of the sample of the unmodified control product after ultraviolet aging. Detailed Embodiments

[0025] Hereinafter, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments and drawings of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way limits the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0026] Unless otherwise specifically stated, the numerical values set forth in these embodiments do not limit the scope of the present invention. Technologies and methods known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, such technologies and methods should be regarded as part of the specification. In all examples shown and discussed herein, any specific value should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.

[0027] In the following examples, the experimental methods without specific conditions are usually determined according to national standards; if there is no corresponding national standard, they are carried out according to general standard requirements or general methods.

[0028] In the following, polyaryletherketone is taken as PEEK for example. The raw material of PEEK used is the pure resin PEEK5600G coarse powder. According to needs, other grades such as 3600G, 5601G, 7600G, etc. or other grades of PEEK pure resin, or other types of polyaryletherketone can also be selected as the matrix resin.

[0029] Example 1

[0030] A preparation method of a light-resistant degradation inorganic fiber / polyaryletherketone composite material includes the following steps:

[0031] S1. Place 10 grams of cerium dioxide in a dielectric barrier discharge treatment device, and carry out dielectric barrier discharge treatment for 120 seconds under an argon protection atmosphere, a power of 350 W, and a vacuum degree of 100 Pa;

[0032] S2. Immerse the treated cerium dioxide in a 15g sulfonated polyetheretherketone solution with a solution concentration of 20 wt% (sulfonation degree 60%, solvent is DMAc) for 24h to form a mixed system, then add 300 grams of surface-treated glass fibers (short fibers, fiber diameter less than 15μm) to the mixed system for blending for 18 min, and then carry out heat treatment at 270°C for 4h to obtain a modified blended material;

[0033] Among them, the surface-treated glass fibers are treated by wet modification: KH550 is hydrolyzed with absolute ethanol and water, and the mass ratio of KH550, absolute ethanol, and water is 20:72:8. After complete hydrolysis, a treatment solution is formed. Immerse the glass fibers in the treatment solution (the mass ratio of glass fibers to the treatment solution is 1:3) and stir until completely dispersed, then filter and dry;

[0034] S3. Mix the modified blended material with 690 grams of PEEK5600G coarse powder and then mold it into a plate to obtain a light-resistant degradation inorganic fiber / polyaryletherketone composite material, wherein the proportion of cerium dioxide in the composite material is 1 wt%.

[0035] Example 2

[0036] The preparation method of the composite material in this example is the same as that in Example 1, the difference is that the dosage of cerium dioxide in S1 is 20g.

[0037] The proportion of cerium dioxide in the obtained light-resistant degradation inorganic fiber / polyaryletherketone composite material is about 2 wt%.

[0038] Example 3

[0039] The preparation method of the composite material in this example is the same as that of Example 1, except that the amount of cerium dioxide in S1 is 31 g.

[0040] In the prepared light-resistant degradation inorganic fiber / polyaryletherketone composite material, the proportion of cerium dioxide is about 3.0 wt%.

[0041] Example 4

[0042] A preparation method of a light-resistant degradation inorganic fiber / polyaryletherketone composite material includes the following steps:

[0043] S1. Place 15 g of cerium dioxide and 5 g of zinc oxide in a dielectric barrier discharge treatment device, and perform dielectric barrier discharge treatment for 180 seconds under an argon protection atmosphere, a power of 300 W, and a vacuum degree of 100 Pa;

[0044] S2. Immerse the treated cerium dioxide in a sulfonated polyether ether ketone solution (sulfonation degree 60%, solvent is DMAc) with a mass of 15 g and a solution concentration of 20 wt% for 24 h to form a mixed system. Then add 250 g of surface-treated glass fibers (short fibers, fiber diameter less than 15 μm) to the mixed system for blending for 20 min, and then perform heat treatment at 270 °C for 4 h to obtain a modified blended material;

[0045] The surface-treated glass fibers are treated by wet modification: KH570 is hydrolyzed with absolute ethanol and water, and the mass ratio of KH570, absolute ethanol, and water is 25:70:5. After complete hydrolysis, a treatment solution is formed. Immerse the glass fibers in the treatment solution (the mass ratio of glass fibers to the treatment solution is 1:3) and stir until completely dispersed, then filter and dry;

[0046] S3. Mix the modified blended material with 730 g of PEEK5600G coarse powder and then press and mold it into a plate to obtain a light-resistant degradation inorganic fiber / polyaryletherketone composite material.

[0047] Example 5

[0048] A preparation method of a light-resistant degradation inorganic fiber / polyaryletherketone composite material includes the following steps:

[0049] S1. Place 20 g of cerium dioxide and 10 g of titanium dioxide (rutile type) in a dielectric barrier discharge treatment device, and perform dielectric barrier discharge treatment for 240 seconds under an argon protection atmosphere, a power of 400 W, and a vacuum degree of 100 Pa;

[0050] S2. Place the treated cerium dioxide in a sulfonated polyether ether ketone solution (sulfonation degree 60%, solvent is DMAc) with a solution concentration of 20 wt% and a mass of 45 g, and immerse it for 24 h to form a mixed system. Then, add 350 g of surface-treated glass fibers (short fibers, fiber diameter less than 15 μm) to the mixed system and blend for 25 min. Subsequently, perform heat treatment at 270 °C for 4 h to obtain a modified blended material;

[0051] Among them, the surface-treated glass fibers are treated by wet modification: A172 is hydrolyzed with absolute ethanol and water, and the mass ratio of A172, absolute ethanol, and water is 20:75:5. After complete hydrolysis, a treatment solution is formed. Immerse the glass fibers in the treatment solution (the mass ratio of glass fibers to the treatment solution is 1:3) and stir until completely dispersed, then filter and dry;

[0052] S3. Mix the modified blended material with 620 g of PEEK5600G coarse powder and then mold it into a plate to obtain a light-resistant degradation inorganic fiber / polyaryletherketone composite material.

[0053] Comparative Example 1

[0054] The preparation process of the composite material in this example is the same as that in Example 1. The difference is that instead of using cerium dioxide, surface-treated glass fibers (30 wt% ratio) and PEEK5600G coarse powder (70 wt% ratio) are directly used.

[0055] Comparative Example 2

[0056] The preparation process of the composite material in this example is the same as that in Example 1. The difference is that the cerium dioxide is directly used for S2 and S3 without undergoing the dielectric barrier discharge treatment in S1.

[0057] Comparative Example 3

[0058] The preparation process of the composite material in this example is the same as that in Example 1. The difference is that titanium dioxide (rutile type) is used but without performing S1, and it is directly used for S2 and S3.

[0059] Comparative Example 4

[0060] The preparation process of the composite material in this example is the same as that in Example 1. The difference is that zinc oxide is used but without performing S1, and it is directly used for S2 and S3.

[0061] Perform performance tests on the composite materials of the above examples before and after light aging. The light aging uses ultraviolet light with a wavelength of 340 nm (irradiation intensity 0.9 W / m 2 ) First irradiate at 60 °C for 8 h, then condense at 50 °C for 4 h. 12 h is one cycle, and repeat the aging for 42 cycles. The specific data is shown in Table 1.

[0062] Table 1 Performance of the composite material before and after light aging

[0063]

[0064]

[0065] As can be seen from Table 1, the present invention uses cerium dioxide or a combination of cerium dioxide and other metal oxides, which can improve the degree of light degradation resistance to a certain extent. In particular, in Example 1 where cerium dioxide is used alone, compared with Examples 4 and 5 where it is used in combination with other metal oxides, good light degradation resistance can be achieved with a very small amount of addition, and the decline in various mechanical property indexes is extremely small. The difference between Examples 1 - 3 lies in the amount of cerium dioxide used. As the amount of cerium dioxide increases, the decline in mechanical properties increases; Comparative Example 1 is a composite material of glass fiber and PEEK. As a control group, the composite material systems of Examples 2 - 3 have a higher degree of hybridization compared with the control group, so the impact strength data decreases more significantly compared with the control group, but the elongation at break is still slightly better than that of the control group. In Comparative Example 2, cerium dioxide was not treated by dielectric barrier discharge. Compared with Example 1, after ultraviolet light aging, the mechanical properties deteriorated to a certain extent. Comparative Examples 3 and 4 used untreated titanium dioxide and zinc oxide. After ultraviolet light aging, the mechanical properties deteriorated to a greater extent compared with those of Comparative Example 2. In particular, titanium dioxide has poor ultraviolet light stability. After mixing and formulating titanium dioxide and zinc oxide with cerium dioxide respectively and then performing dielectric barrier discharge treatment, after ultraviolet light aging, the degree of mechanical property deterioration is lighter than that of Comparative Examples 3 and 4 respectively, but still heavier than that when using cerium dioxide alone.

[0066] SEM observations were carried out on the samples after light exposure of Example 1 and the samples after aging of Comparative Example 1. The results are as Figure 1 shown. The left figure is Example 1, and the right figure is Comparative Example 1. By observing the microtopography, there is a certain gap between the filler and the resin matrix in the material of Comparative Example 1 after ultraviolet aging, which is an indication of weakened bonding force. There is no significant change in the bonding force between the filler and the resin matrix in the material of Example 1.

[0067] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes should be covered within the protection scope of the present invention.

Claims

1. A method for preparing a light-resistant degradation inorganic fiber / polyaryletherketone composite material, characterized in that, It includes the following steps: S1. Subject the metal oxide to dielectric barrier discharge treatment under a protective atmosphere; The metal oxide is selected from cerium oxide, or a mixed configuration of cerium oxide and one or more of tungsten oxide, copper oxide, zinc oxide, and titanium oxide, and the cerium oxide accounts for at least 50 wt% in the mixed configuration; S2. Immerse the treated metal oxide in a sulfonated polyether ether ketone solution to form a mixed system, add surface-treated inorganic fibers to the mixed system for blending, and then remove the solvent by heat treatment to obtain a modified blended material; The surface-treated inorganic fibers are dry-modified or wet-modified by using a silane coupling agent, and the silane coupling agent is selected from one of silane coupling agent A172, amino silane coupling agent, and methacryloxy silane coupling agent; S3. Mix the modified blended material with polyaryletherketone and then melt-extrude and pelletize or directly mold it to obtain a light-degradation-resistant inorganic fiber / polyaryletherketone composite material; The proportion of the metal oxide in the light-degradation-resistant inorganic fiber / polyaryletherketone composite material is in the range of 0.3 wt% - 3.5 wt%; 2. The preparation method of the light-resistant degradation inorganic fiber / polyaryletherketone composite material according to claim 1, wherein, The polyaryletherketone is selected from one or more of polyether ether ketone, polyether ketone, polyether ketone ketone, polyether ether ketone ketone, and polyether ketone ether ketone ketone; The inorganic fibers are selected from one or more of glass fibers, carbon fibers, basalt fibers, and ceramic fibers, and are continuous fibers or short fibers, and the diameter of the inorganic fibers is less than 15 μm; The concentration of the sulfonated polyether ether ketone solution is 15% - 35%, and the solvent is one or more of DMF, NMP, DMAc, and DMSO, and the sulfonation degree of the sulfonated polyether ether ketone is 30% - 70%; 3. The preparation method of the light-resistant degradation inorganic fiber / polyaryletherketone composite material according to claim 2, wherein The mass ratio of the metal oxide to the sulfonated polyether ether ketone solution is 1:1 - 5; The mass ratio of the metal oxide, the surface-treated inorganic fibers, and the polyaryletherketone is 0.5 - 5:20 - 40:60 - 75; 4. The preparation method of the light-resistant degradation inorganic fiber / polyaryletherketone composite material according to claim 2, wherein The immersion time of the metal oxide in the sulfonated polyether ether ketone solution is 2 - 36 h; the blending time of the surface-treated inorganic fibers in the mixed system is 10 - 30 min; the heat treatment is carried out at 200 - 280 °C for 2 - 5 h; 5. The preparation method of the light-resistant degradation inorganic fiber / polyaryletherketone composite material according to claim 2, characterized in that, The dielectric barrier discharge treatment is carried out under an argon protective atmosphere and a vacuum degree of 80 - 150 Pa, and at a power of 300 - 400 W for 100 - 240 seconds.

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