A high-toughness polyether ether ketone composite material and a preparation method and application thereof

Abstract

The application discloses a high-toughness polyether ether ketone composite material and a preparation method and application thereof, belongs to the field of polyether ether ketone composite materials, and aims to solve the technical problem that the existing polyether ether ketone composite material cannot simultaneously have high strength and high toughness. The method comprises the following steps: mixing graphene oxide, silicone rubber and polyether ether ketone resin powder to obtain mixed powder; then, the mixed powder is pressed at room temperature, and then sintering is performed to obtain the high-toughness polyether ether ketone composite material. The polyether ether ketone is modified by the silicone rubber and the graphene oxide in cooperation, the selection and matching of the modified materials are fully used to give full play to the synergistic effect of the silicone rubber and the graphene oxide, the toughness is greatly improved without reducing the strength and thermal stability of the base material, the obtained polyether ether ketone composite material has high strength, high thermal stability and high toughness, and can be applied to fields, such as aerospace, automobile industry and biomedicine, which have high requirements on comprehensive performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of polyether ether ketone composite materials, and particularly relates to a high-strength and high-toughness polyether ether ketone composite material and a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the rapid development of the fields of aerospace, aviation, automobile industry, biological medicine and the like, the demand for high-performance materials is increasing, and especially the emergence of high-performance fiber reinforced thermoplastic composite materials fills the urgent demand for high-performance materials in the tip field. Polyether ether ketone (PEEK) is a high polymer composed of a repeating unit containing a ketone bond and two ether bonds in the main chain structure, and belongs to a special high polymer material. Compared with other special engineering plastics, it has more significant advantages, such as resistance to positive high temperature 260℃, excellent mechanical properties, good self-lubricating property, chemical corrosion resistance, flame retardation, peel resistance, wear resistance, radiation resistance and the like. The super-strong mechanical properties enable it to be used in high-end mechanical, automobile, nuclear engineering and aviation fields.

[0003] Polyether ether ketone has rigidity and flexibility, and in particular, the fatigue resistance under alternating stress is very outstanding, which is comparable to alloy materials. The traditional rubber toughening material has good toughening effect, but at the same time, the strength and heat resistance of the material are often sacrificed, which cannot meet the demand of the strength and toughness and high-temperature resistance of polyether ether ketone material. In addition, although the rigid particle toughening can improve the toughness and strength of the plastic polymer, the improvement range of the toughness is limited. Therefore, how to greatly improve the toughness of polyether ether ketone while not reducing the original strength and heat resistance of polyether ether ketone is a problem to be solved. SUMMARY

[0004] The purpose of the present application is to solve the technical problem that the existing polyether ether ketone composite material cannot simultaneously have high strength and high toughness, and to provide a high-strength and high-toughness polyether ether ketone composite material and a preparation method and application thereof.

[0005] One of the purposes of the present application is to provide a preparation method of a high-strength and high-toughness polyether ether ketone composite material, which is carried out according to the following steps:

[0006] S1: mixing and grinding graphene oxide, silicone rubber and polyether ether ketone resin powder, and then putting them into a centrifuge tube to mix by a vortex mixer to obtain a mixed powder;

[0007] S2: pressing the mixed powder at room temperature, and then sintering to obtain a high-strength and high-toughness polyether ether ketone composite material.

[0008] Further limited, the mass ratio of graphene oxide, silicone rubber and polyether ether ketone resin powder in S1 is 0.1:(0.1-0.15):(8-10).

[0009] Further limit, the mixing and grinding in S1 is for 15-20 minutes.

[0010] Further limit, the oscillation mixing in S1 is for 3-5 times, each time for 5-8 minutes.

[0011] Further limit, the pressure for the pressing in S2 is 3-6 MPa, and the time is 3-5 minutes.

[0012] Further limit, the sintering temperature in S2 is 390-400℃, and the time is 40-45 minutes.

[0013] Further limit, after the sintering in S2, the mold is cooled with the temperature of the oven, and the oven temperature is reduced to 140-160℃ before the opening of the oven, and the mold is cooled to room temperature.

[0014] The second object of the present application is to provide a high-toughness polyether ether ketone composite material prepared by the above method, wherein the tensile strength is not less than 100 MPa, and the breaking energy is ≥500 J / m 3 .

[0015] Further limit, the crystallinity of the polyether ether ketone composite material is ≤25%.

[0016] The third object of the present application is to provide an application of the high-toughness polyether ether ketone composite material prepared by the above method in the fields of aerospace, automobile industry and biomedical.

[0017] Compared with the prior art, the present application has the following remarkable effects:

[0018] The present application modifies the polyether ether ketone by using the silicon rubber and the graphene oxide in cooperation, fully plays the synergistic effect of the silicon rubber and the graphene oxide through the selection and matching of the modified materials, greatly improves the toughness without reducing the strength and thermal stability of the base material, and the tensile strength is not less than 100 MPa, and the breaking energy is ≥500 J / m 3 , T d5 is 575.46℃, and the residual amount at 800℃ is 50.8%, so the obtained polyether ether ketone composite material has high strength, high thermal stability and high toughness, and can be applied in the fields of aerospace, automobile industry and biomedical which have high comprehensive performance requirements. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is the XRD spectrum of the pure PEEK and the composite material obtained from Example 1 and Comparative Examples 1-3;

[0020] Figure 2Flexural strength of the pure PEEK and its composite material obtained from Example 1 and Comparative Examples 1-3 according to ASTM D790 standard;

[0021] Figure 3 Tensile strength of the pure PEEK and its composite material obtained from Example 1 and Comparative Examples 1-3 according to ASTM D638 standard;

[0022] Figure 4 Tensile fracture energy absorption of the pure PEEK and its composite material obtained from Example 1 and Comparative Examples 1-3;

[0023] Figure 5 Thermogravimetric curve of the pure PEEK and its composite material obtained from Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0024] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and should not be used to limit the present application.

[0025] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art unless otherwise specified, which can be obtained by commercial channels by those skilled in the art.

[0026] The terms "comprising", "including", "having", "containing", or any other similar words used in the following examples are intended to cover non-exclusive inclusion. For example, a composition, step, method, article or device that comprises the listed elements does not necessarily limit to those elements only, but can include other elements not explicitly listed or inherent to such composition, step, method, article or device.

[0027] The "one embodiment" or "an embodiment" described in the present application means that the specific features, structures or characteristics can be included in at least one implementation of the present application. The "in one embodiment" appearing in different places in the specification does not mean the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments.

[0028] The endpoints of the ranges and any values disclosed in the present application are not limited to the precise values stated. The ranges or values should be construed to be roughly around the ranges or values. For numerical ranges, the endpoints of the various ranges, the endpoints of the various ranges and individual point values between the endpoints of the various ranges, and the individual point values can be combined to form one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] The silicone rubber SR used in the following examples was purchased from Wacker Silicone Resin 604, Germany.

[0030] The polyether ether ketone resin powder used in the following examples was purchased from Jilin Zhongyan High Polymer Material.

[0031] Example 1: The method for preparing the high-toughness polyether ether ketone composite material of the present example was carried out according to the following steps:

[0032] 0.1 g of graphene oxide GO, 0.1 g of silicone rubber SR, and 9.8 g of polyether ether ketone resin powder were put into a mortar and mixed and ground for 15 min, and then the ground blend was put into a centrifuge tube and mixed by a vortex mixer for 3 times, 5 min each time. Then the powder mixture was filled into a mold coated with a release agent, and a small flat vulcanizing machine was used to press at room temperature with a pressure of 5 MPa for 5 min. Finally, the mold was put into an electric heating oven and heated to 395 °C for 40 min, then the power was turned off and the mold was cooled with the temperature of the oven, and when the temperature of the oven dropped to 150 °C, the oven was opened, and when the mold cooled to room temperature, it was demolded, and a high-toughness polyether ether ketone composite material was obtained, which was recorded as GO / SR / PEEK.

[0033] Comparative Example 1: The method for preparing the polyether ether ketone of the present comparative example was carried out according to the following steps:

[0034] 10 g of polyether ether ketone resin powder was filled into a mold coated with a release agent, and a small flat vulcanizing machine was used to press at room temperature with a pressure of 5 MPa for 5 min. Finally, the mold was put into an electric heating oven and heated to 395 °C for 40 min, then the power was turned off and the mold was cooled with the temperature of the oven, and when the temperature of the oven dropped to 150 °C, the oven was opened, and when the mold cooled to room temperature, it was demolded, and a polyether ether ketone was obtained, which was recorded as pure PEEK.

[0035] Comparative Example 2: The method for preparing the polyether ether ketone composite material of the present comparative example was carried out according to the following steps:

[0036] 0.2 g of graphene oxide GO and 9.8 g of polyether ether ketone resin powder were put into a mortar and mixed and ground for 15 min, and then the ground blend was put into a centrifuge tube and mixed by a vortex mixer for 3 times, 5 min each time. Then the powder mixture was filled into a mold coated with a release agent, and a small flat vulcanizing machine was used to press at room temperature with a pressure of 5 MPa for 5 min. Finally, the mold was put into an electric heating oven and heated to 395 °C for 40 min, then the power was turned off and the mold was cooled with the temperature of the oven, and when the temperature of the oven dropped to 150 °C, the oven was opened, and when the mold cooled to room temperature, it was demolded, and a polyether ether ketone composite material was obtained, which was recorded as GO / PEEK.

[0037] Comparative Example 3: The method for preparing the polyether ether ketone composite material of the present comparative example was carried out according to the following steps:

[0038] Put 0.2 g of silicone rubber SR and 9.8 g of polyether ether ketone resin powder into a mortar and mix and grind for 15 min, then put the ground blend into a centrifuge tube and mix by vortex mixer for 3 times, 5 min each time. Then fill the powder mixture into a mold coated with release agent, pressurize to 5 MPa at room temperature with a small flat vulcanizing machine, and keep pressure for 5 min. Finally, put the mold into an electric oven, heat to 395℃ and keep for 40 min, then turn off the power and let the mold cool with the temperature of the oven, open the oven when the oven temperature cools down to 150℃, and the mold cools to room temperature and is demolded, to obtain a polyether ether ketone composite, denoted as SR / PEEK.

[0039] Figure 1 The XRD spectra of pure PEEK and its composites. Pure PEEK has four main diffraction peaks at (110), (111), (200) and (211), corresponding to 2θ positions of 18.88°, 20.87°, 22.86° and 28.90°, respectively, indicating its orthorhombic structure. All composites show main diffraction peaks similar to the orthorhombic phase of PEEK, and there is no obvious change in position, indicating that the crystal structure of PEEK remains unchanged with the addition of GO and SR. Through calculation and analysis of the curve, the crystallinity of pure PEEK, GO / PEEK, SR / PEEK and GO / SR / PEEK composite is 28.82%, 26.33%, 25.99% and 24.64%, respectively.

[0040] The obtained composites were sampled and tested according to ASTM D790 standard, Figure 2 For comparison of the bending strength of pure PEEK and its composites, the bending strength of PEEK is 173.0 MPa, the bending strength of GO / PEEK is 189.0 MPa, the bending strength of SR / PEEK is 176.1 MPa, and the bending strength of GO / SR / PEEK is 179.2 MPa.

[0041] The obtained composites were sampled and tested according to ASTM D638 standard, Figure 3 For comparison of the tensile strength of pure PEEK and its composites, the tensile strength of PEEK is 83.8 MPa, the tensile strength of GO / PEEK is 89.8 MPa, the tensile strength of SR / PEEK is 91.01, and the tensile strength of GO / SR / PEEK increases from 83.8 MPa to 104.7 MPa.

[0042] Figure 4 The fracture energy of the composite obtained by calculation based on the tensile specimen, which is used to judge the toughness of the material. The fracture energy of pure PEEK is 176.9 J / m 3In comparison, the fracture energy of GO / PEEK and SR / PEEK are 248.4 J / m 3 and 438.6 J / m 3 , respectively. The fracture energy of GO / SR / PEEK is 501.9 J / m 3 , which is increased by 35.9%, 129.1% and 174.53% compared to pure PEEK. It is proved that the toughness of GO / SR / PEEK composite is improved while the strength of the matrix material is not reduced. GO and SR have a synergistic effect.

[0043] High thermal stability is the main reason why PEEK resin becomes a popular candidate material for composite polymer matrix. Therefore, it is most important not to sacrifice thermal performance to improve mechanical properties. Therefore, the material was subjected to thermal gravimetric analysis (TGA) under nitrogen conditions at 25-800℃, with a heating rate of 10℃ / min. Figure 5 The TGA curves of pure PEEK and GO / SR / PEEK composite are shown. The temperature at which 5% weight loss of pure PEEK (T d5 ) is 566.5℃, and the residual amount at 800℃ is 48.0%. After adding GO and SR in PEEK, T d5 is 575.46℃, and the residual amount at 800℃ is 50.8%, which is 2.8% higher than PEEK. This shows that the composite still has high thermal stability.

[0044] The above only describes the preferred specific embodiments of the present application, these specific embodiments are different implementations based on the overall concept of the present application, and the protection scope of the present application is not limited thereto, any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for preparing a high-strength and tough polyetheretherketone composite material, characterized in that, The method is performed according to the following steps: S1: Mix and grind graphene oxide, silicone rubber and polyetheretherketone resin powder, then put them into a centrifuge tube and mix them by vortex mixer to obtain mixed powder; S2: The mixed powder is pressed at room temperature and then sintered to obtain a high-strength and tough polyether ether ketone composite material; The mass ratio of graphene oxide, silicone rubber, and polyetheretherketone resin powder in S1 is 0.1:(0.1-0.15):(8-10). The pressing pressure in S2 is 3-6 MPa, and the time is 3-5 min; the sintering temperature in S2 is 390-400℃, and the time is 40-45 min.

2. The method according to claim 1, characterized in that, Mix and grind in S1 for 15-20 minutes.

3. The method according to claim 1, characterized in that, Oscillate and mix in S1 3-5 times, each time for 5-8 minutes.

4. The method according to claim 1, characterized in that, After sintering in S2, the mold is cooled along with the temperature of the oven. After the oven temperature drops to 140-160℃, the mold is opened and cooled to room temperature along with the oven.

5. The high-strength and high-toughness polyetheretherketone composite material prepared by the method according to any one of claims 1-4, characterized in that, When preparing samples according to ASTM D638 standard, the tensile strength should not be less than 100 MPa, and the rupture energy should be ≥500 J / m. 3 .

6. The composite material according to claim 5, characterized in that, Crystallinity ≤25%.

7. The application of the high-strength and tough polyether ether ketone composite material prepared by the method according to any one of claims 1-4 in the fields of aerospace, automotive industry, and biomedicine.

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