A molybdenum disulfide nanoflower-carbon nanotube-polyether ether ketone composite material and a preparation method thereof

Abstract

The application discloses a molybdenum disulfide nanoflower-carbon nanotube-polyether ether ketone composite material and a preparation method thereof, relates to the technical field of composite materials, and is made of the following components by weight: 97-99 parts of polyether ether ketone and 1-3 parts of molybdenum disulfide nanoflower-carbon nanotube hybrid material. The application improves the compression performance and hardness of the molybdenum disulfide nanoflower-carbon nanotube-polyether ether ketone composite material and improves the friction-reducing and wear-resistant effect at the same time by adding the molybdenum disulfide nanoflower-carbon nanotube hybrid material into the polyether ether ketone.

Description

Technical Field

[0001] This application relates to the field of composite material technology, and in particular to a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material and its preparation method. Background Technology

[0002] Currently, polyetheretherketone (PEEK) is widely used in aerospace, automotive manufacturing, and medical device industries due to its excellent thermal stability, dimensional stability, mechanical strength, chemical stability, and processing performance. However, with the rapid development of modern industrial technology, the requirements for material performance are constantly increasing. For example, when PEEK is used in friction components such as radial bearings and bearing bushings, it is prone to wear under load, resulting in poor friction reduction and wear resistance. Summary of the Invention

[0003] In view of the shortcomings of the above-mentioned related technologies, the purpose of this application is to provide a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material and its preparation method. By adding molybdenum disulfide nanoflower-carbon nanotube hybrid material to polyetheretherketone, the compressive properties and hardness of the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material are improved, while the friction reduction and wear resistance are also improved.

[0004] On the one hand, the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material provided in this application adopts the following technical solution:

[0005] A molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material is made from the following components in parts by weight: 97-99 parts of polyetheretherketone and 1-3 parts of molybdenum disulfide nanoflower-carbon nanotube hybrid material.

[0006] Preferably, the molybdenum disulfide nanoflower-carbon nanotube hybrid material is obtained by a one-step hydrothermal reaction of a precursor and carbon nanotubes.

[0007] Preferably, the precursor includes a molybdenum precursor and a sulfur precursor.

[0008] Preferably, the weight ratio of the molybdenum precursor to the carbon nanotube is 0.2-4:1.

[0009] Preferably, the weight ratio of the molybdenum precursor to the carbon nanotube is 0.268-1.35:1.

[0010] Preferably, the weight ratio of the molybdenum precursor to the carbon nanotube is 0.68:1.

[0011] Preferably, the weight ratio of the molybdenum precursor to the sulfur precursor is 1:1-3.

[0012] Preferably, the weight ratio of the molybdenum precursor to the sulfur precursor is 1:2.

[0013] Preferably, the molybdenum precursor comprises one or both of ammonium molybdate tetrahydrate and ammonium dimolybdate.

[0014] Preferably, the molybdenum precursor is ammonium molybdate tetrahydrate.

[0015] Preferably, the sulfur precursor includes one or more of thiourea, ammonium thiocyanate, and sodium thiosulfate.

[0016] Preferably, the sulfur precursor is thiourea.

[0017] Preferably, the carbon nanotubes include one or both of multi-walled carbon nanotubes and single-walled carbon nanotubes.

[0018] Preferably, the carbon nanotubes are multi-walled carbon nanotubes.

[0019] On the other hand, this application provides a method for preparing a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material, which adopts the following technical solution:

[0020] A method for preparing a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material includes the following steps: mixing a precursor, a surfactant, and carbon nanotubes and performing a one-step hydrothermal reaction to obtain a molybdenum disulfide nanoflower-carbon nanotube hybrid material; mixing the molybdenum disulfide nanoflower-carbon nanotube hybrid material, polyetheretherketone powder, and solvent, ultrasonically dispersing, and drying to obtain a mixture; ball milling the mixture and drying; and finally hot pressing to obtain the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material.

[0021] Preferably, the surfactant comprises one or more of hexadecyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, and octadecyldimethylhydroxyethylammonium nitrate.

[0022] Preferably, the surfactant is hexadecyltrimethylammonium bromide.

[0023] Preferably, the solvent is ethanol, and the ultrasonic dispersion time is 5-40 min.

[0024] Preferably, the solvent is ethanol, and the ultrasonic dispersion time is 15 min.

[0025] Preferably, the hot pressing temperature is 350-370℃, the pressure is 5-10MPa, and the holding time is 0.5-1.5h.

[0026] Preferably, the hot pressing temperature is 360°C, the pressure is 7MPa, and the holding time is 1h.

[0027] In summary, this application includes at least one of the following beneficial technical effects:

[0028] 1. Compared with polyetheretherketone (PEEK), the average friction coefficient of the molybdenum disulfide nanoflower-carbon nanotube-PEEK composite material is reduced by 16.95%-23.73%, the wear is reduced by 82.20%-87.07%, the compressive strength is increased by 12.04%-16.54%, and the surface hardness is increased by 3.17%-3.75%. This improves the compressive performance and hardness of the molybdenum disulfide nanoflower-carbon nanotube-PEEK composite material while enhancing its friction reduction and wear resistance.

[0029] 2. Compared with carbon nanotube-polyetheretherketone composites, molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composites show an average reduction in friction coefficient of 10.26%-17.58%, a reduction in wear amount of 43.71%-59.11%, an increase in compressive strength of 4.92%-9.13%, and an increase in surface hardness of 0.65%-1.22%. This improves the compressive properties and hardness of molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composites while enhancing friction reduction and wear resistance.

[0030] 3. The raw materials for the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material of this application are easy to obtain, the preparation method is simple, the conditions are mild, no special equipment is required, and there is no need for high-concentration chemical reagent modification or coupling agent to improve the dispersibility of additives. It is green and environmentally friendly while reducing the preparation cost. Attached Figure Description

[0031] Figure 1 This is a scanning electron microscope image of the molybdenum disulfide nanoflower-carbon nanotube hybrid material in Example 1 of this application;

[0032] Figure 2 This is a scanning electron microscope image of the molybdenum disulfide nanoflower-carbon nanotube hybrid material in Example 5 of this application. Detailed Implementation

[0033] The present application will be further described in detail below with reference to the embodiments. The following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified, specific conditions in the following embodiments were performed under conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the methods used are conventional methods known in the art, and the consumables and reagents used are commercially available. Unless otherwise stated, the technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be applied to the present invention.

[0034] The raw materials used in the examples and comparative examples are all commercially available.

[0035] Example 1

[0036] Example 1 of this application provides a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material, which is prepared by the following steps: Preparation of molybdenum disulfide nanoflower-carbon nanotube hybrid material: 0.2247g of ammonium molybdate tetrahydrate, 0.4494g of thiourea, and 0.0281g of hexadecyltrimethylammonium bromide were added to 40mL of deionized water as molybdenum precursor, sulfur precursor, and surfactant, respectively, and stirred for 30min. Then, 0.33g of multi-walled carbon nanotubes (MWCNTs) were added, stirred, and ultrasonically treated for 20min to obtain a mixture. The mixture was poured into a 100mL reactor for a hydrothermal reaction with the following parameters: the temperature was increased to 220℃ at a rate of 1℃ / min, and the temperature was maintained for 24h. Then, the temperature was slowly cooled to room temperature at a rate of 0.4℃ / min. After filtration and washing, the molybdenum disulfide nanoflower-carbon nanotube hybrid material was obtained.

[0037] Preparation of molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone (PEEK) composite material: 98g of PEEK powder and 2g of molybdenum disulfide nanoflower-carbon nanotube hybrid material were accurately weighed. The PEEK powder and PEEK hybrid material were added to ethanol, ultrasonically dispersed for 15 min, and then stirred on a magnetic stirrer at 600 rpm for 3 h. The mixture was then dried at 80℃ for 4 h and then at 100℃ for 2 h to obtain a mixture. The mixture was ball-milled at 300 rpm for 4 h, and then dried in a drying oven at 120℃ for 3 h to obtain a final product. The final product was placed in a mold and held under pressure at 360℃ and 7 MPa for 1 h to obtain the molybdenum disulfide nanoflower-carbon nanotube-PEEK composite material.

[0038] Example 2

[0039] Example 2 of this application provides a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material. The difference between Example 2 and Example 1 is that, in the preparation step of the molybdenum disulfide nanoflower-carbon nanotube hybrid material, Example 2 uses 0.3371g of ammonium molybdate tetrahydrate, 0.6742g of thiourea, 0.0421g of hexadecyltrimethylammonium bromide and 0.25g of multi-walled carbon nanotubes.

[0040] Example 3

[0041] Example 3 of this application provides a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material. The difference between Example 3 and Example 1 is that, in the preparation step of the molybdenum disulfide nanoflower-carbon nanotube hybrid material, Example 3 uses 0.1685g of ammonium molybdate tetrahydrate, 0.3371g of thiourea, 0.0211g of hexadecyltrimethylammonium bromide and 0.38g of multi-walled carbon nanotubes.

[0042] Example 4

[0043] Example 4 of this application provides a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material. The difference between Example 4 and Example 1 is that in the preparation step of the molybdenum disulfide nanoflower-carbon nanotube hybrid material, 0.1124g of ammonium molybdate tetrahydrate, 0.2247g of thiourea, 0.0140g of hexadecyltrimethylammonium bromide and 0.42g of multi-walled carbon nanotubes are used.

[0044] Example 5

[0045] Example 5 of this application provides a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material. The difference between Example 5 and Example 1 is that in the preparation step of the molybdenum disulfide nanoflower-carbon nanotube hybrid material, 0.5056g of ammonium molybdate tetrahydrate, 1.0112g of thiourea, 0.0632g of hexadecyltrimethylammonium bromide and 0.13g of multi-walled carbon nanotubes are used.

[0046] Comparative Example 1

[0047] Comparative Example 1 provides a polyetheretherketone (PEEK), prepared by the following steps: 100 g of PEEK powder was accurately weighed. The PEEK powder was added to ethanol, ultrasonically dispersed for 15 min, and then stirred on a magnetic stirrer at 600 rpm for 3 h. It was then dried at 80 °C for 4 h and at 100 °C for 2 h. The PEEK powder was then ball-milled at 300 rpm for 4 h, and then dried in a drying oven at 120 °C for 3 h. The PEEK powder was placed in a mold and held under pressure at 360 °C and 7 MPa for 1 h, hot-pressed to obtain PEEK.

[0048] Comparative Example 2

[0049] Comparative Example 2 provides a carbon nanotube-polyetheretherketone composite material, prepared by the following steps: multi-walled carbon nanotubes are added to 40 mL of deionized water, stirred for 30 min, and then sonicated for 20 min while maintaining stirring to obtain a mixture. The mixture is poured into a 100 mL reactor and heated to 220 °C at a rate of 1 °C / min, maintained at the temperature for 24 h, and then slowly cooled to room temperature at a rate of 0.4 °C / min. The mixture is then filtered and washed, and the treated multi-walled carbon nanotubes are ready for use.

[0050] Accurately weigh 98g of polyetheretherketone (PEEK) powder and 2g of multi-walled carbon nanotubes (MWCNTs). Add the PEEK powder and MWCNTs to ethanol, ultrasonically disperse for 15 min, and then stir on a magnetic stirrer at 600 rpm for 3 h. Dry at 80°C for 4 h, then at 100°C for 2 h to obtain a mixture. Add the mixture to a ball mill and ball mill at 300 rpm for 4 h, then dry in a drying oven at 120°C for 3 h to obtain a composite material. Place the composite material in a mold and hold under pressure at 360°C and 7 MPa for 1 h to obtain a carbon nanotube-PEEK composite material.

[0051] Testing and Inspection

[0052] (1) Scanning electron microscopy (SEM) was performed on the molybdenum disulfide nanoflower-carbon nanotube hybrid materials in Examples 1 and 5, and the SEM images are shown below. Figure 1 and Figure 2 As shown.

[0053] (2) The molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite materials prepared in Examples 1-5, the polyetheretherketone of Comparative Example 1, and the carbon nanotube-polyetheretherketone composite material of Comparative Example 2 were prepared according to ISO standards.

[0054] The compression properties of 604:2002 were tested on a universal testing machine. The sample size was 10×10×4mm, and the test condition was 1mm / min. The test results are shown in Table 1 below.

[0055] (3) The molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite materials prepared in Examples 1-5, the polyetheretherketone of Comparative Example 1, and the carbon nanotube-polyetheretherketone composite material of Comparative Example 2 were prepared according to ISO standards.

[0056] The surface hardness of 868 was tested on a Shore hardness tester with a sample size of 20×10×4mm. The test results are shown in Table 1 below.

[0057] Table 1:

[0058] Example 1 173.99 88.71 Example 2 168.12 88.28 Example 3 169.95 88.35 Example 4 167.28 88.21 Example 5 156.22 86.93 Comparative Example 1 149.3 85.5 Comparative Example 2 159.44 87.64

[0059] (4) The molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite materials prepared in Examples 1-5, the polyetheretherketone of Comparative Example 1, and the carbon nanotube-polyetheretherketone composite material of Comparative Example 2 were subjected to ball-disc reciprocating friction test on an Rtec tribometer. A GCr15 steel ball with a diameter of 6.3 mm was subjected to reciprocating friction with a 20×10×4 mm molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material. The test conditions were: load 80 N, time 30 min, speed 6 Hz (linear velocity 96 mm / s). The test results are shown in Table 2 below.

[0060] Table 2:

[0061] Example 1 0.225 7.09 Example 2 0.233 9.24 Example 3 0.24 8.12 Example 4 0.245 9.76 Example 5 0.237 20.56 Comparative Example 1 0.295 54.83 Comparative Example 2 0.273 17.34

[0062] Results Analysis

[0063] The following combines the experimental data provided in Table 1-2 and Figures 1-2 This application will be described in detail.

[0064] Referring to Table 1, the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone (PEEK) composites of Examples 1-5 showed significant improvements in compressive strength and surface hardness compared to the PEEK of Comparative Example 1 and the carbon nanotube-PEEK composite of Comparative Example 2. This indicates that the addition of the molybdenum disulfide nanoflower-carbon nanotube hybrid material is beneficial to improving the mechanical properties of PEEK and its composites. In particular, when the weight ratio of ammonium molybdate tetrahydrate to multi-walled carbon nanotubes was 0.68:1, the compressive strength of the molybdenum disulfide nanoflower-carbon nanotube-PEEK composite of Example 1 increased by approximately 16.54% (from 149.3 MPa to 173.99 MPa) and the surface hardness also increased by 3.75% (from 85.5 HD to 88.71 HD) compared to the PEEK of Comparative Example 1, and the compressive strength and surface hardness of the carbon nanotube-PEEK composite of Comparative Example 2 were also significantly improved. This indicates that the molybdenum disulfide nanoflower structure and the carbon nanotube structure have a synergistic effect in improving the mechanical properties of polyetheretherketone (PEEK) composite materials prepared by adjusting the ratio of molybdenum precursor to carbon nanotubes in the range of 0.2–4:1.

[0065] Referring to Table 2, the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone (PEEK) composites of Examples 1-5 exhibited lower coefficients of friction and superior wear resistance compared to the PEEK composites of Comparative Example 1 and the carbon nanotube-PEEK composites of Comparative Example 2 in the tribological tests. In particular, when the weight ratio of ammonium molybdate tetrahydrate to multi-walled carbon nanotubes was 0.68:1, the coefficient of friction of the molybdenum disulfide nanoflower-carbon nanotube-PEEK composite of Example 1 decreased by approximately 23.73% (from 0.295 to 0.225) compared to the PEEK composite of Comparative Example 1, and the wear resistance increased by 87.07% (from 54.83 × 10⁻⁶ mm). 3 / N·m decreased to 7.09×10⁻⁶mm 3 The friction reduction and wear resistance of the carbon nanotube-polyetheretherketone composite material in Examples 1-4 were significantly improved compared to Comparative Example 2. This indicates that the molybdenum disulfide nanoflower structure and the carbon nanotube structure in the molybdenum disulfide nanoflower-carbon nanotube hybrid material prepared by controlling the ratio of molybdenum precursor to carbon nanotubes at 0.268-1.35:1 have a synergistic effect in improving the tribological properties of the polyetheretherketone-based composite material. The analysis suggests that the molybdenum disulfide nanotube-carbon nanotube hybrid material forms a lubricating layer on the surface of the molybdenum disulfide nanotube-carbon nanotube-polyetheretherketone composite material. The multi-walled carbon nanotubes connect the molybdenum disulfide nanoflowers, while the molybdenum disulfide nanoflowers also increase the connection points between the multi-walled carbon nanotubes, minimizing agglomeration of both in the composite material and improving the stability of the lubricating layer structure. This combined effect enhances the stability of the lubricating effect of both the molybdenum disulfide nanoflowers and multi-walled carbon nanotubes, thus improving the friction-reducing and wear-resistant properties of the molybdenum disulfide nanotube-carbon nanotube-polyetheretherketone composite material.

[0066] The wear amount of the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material in Example 5 was slightly higher than that of the carbon nanotube-polyetheretherketone composite material in Comparative Example 2. In Examples 1-5, the molybdenum disulfide nanoflower-carbon nanotube hybrid materials all feature a hybrid structure where molybdenum disulfide nanoflowers are grown on multi-walled carbon nanotubes. Figure 1 It can be seen that the preparation of a molybdenum disulfide nanoflower-carbon nanotube hybrid material with molybdenum disulfide nanoflowers grown on multi-walled carbon nanotubes has been successfully achieved. In the molybdenum disulfide nanoflower-carbon nanotube hybrid material of Example 1, the multi-walled carbon nanotubes form a uniform network structure at the bottom of the molybdenum disulfide nanoflowers, providing strong mechanical support, while the molybdenum disulfide nanoflowers grow on the surface of the multi-walled carbon nanotubes, exhibiting good adhesion and dispersion. (Refer to...) Figure 2In Example 5, the molybdenum disulfide nanoflower-carbon nanotube hybrid material has a large number of molybdenum disulfide nanoflowers and a relatively small number of multi-walled carbon nanotubes, forming a structure dominated by molybdenum disulfide nanoflowers. The multi-walled carbon nanotubes are sparsely distributed in the hybrid material. This may be because the network structure formed by the multi-walled carbon nanotubes in Example 5 supports or connects a large number of molybdenum disulfide nanoflowers, resulting in more structural defects. Consequently, the wear resistance of the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material in Example 5 is lower than that of the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite materials in Examples 1-4.

[0067] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material, characterized in that: It is made from the following components in parts by weight: 97-99 parts of polyetheretherketone (PEEK), and 1-3 parts of molybdenum disulfide nanoflower-carbon nanotube hybrid material; the molybdenum disulfide nanoflower-carbon nanotube hybrid material is prepared by the following steps: mixing a precursor, a surfactant, and carbon nanotubes in a one-step hydrothermal reaction; the precursor includes a molybdenum precursor and a sulfur precursor in a weight ratio of 1:1-3; the surfactant includes one or more of hexadecyltrimethylammonium bromide, dodecyl dimethyl benzyl ammonium chloride, and octadecyl dimethyl hydroxyethyl ammonium nitrate; the weight ratio of the molybdenum precursor to the carbon nanotubes is 0.268-1.35:1; the molybdenum precursor includes one or both of ammonium molybdate tetrahydrate and ammonium dimolybdate.

2. The molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material according to claim 1, characterized in that: The sulfur precursor includes one or more of thiourea, ammonium thiocyanate, and sodium thiosulfate.

3. A method for preparing the molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material as described in any one of claims 1-2, characterized in that: Includes the following steps: A molybdenum disulfide nanoflower-carbon nanotube hybrid material is obtained by mixing a precursor, a surfactant, and carbon nanotubes in a one-step hydrothermal reaction. The molybdenum disulfide nanoflower-carbon nanotube hybrid material, polyether ether ketone powder, and solvent are mixed, ultrasonically dispersed, and dried to obtain a mixture. The mixture is then ball-milled and dried, and finally hot-pressed to obtain the molybdenum disulfide nanoflower-carbon nanotube-polyether ether ketone composite material.

4. The method for preparing a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material according to claim 3, characterized in that: The solvent is ethanol, and the ultrasonic dispersion time is 5-40 min.

5. The method for preparing a molybdenum disulfide nanoflower-carbon nanotube-polyetheretherketone composite material according to claim 3, characterized in that: The hot pressing temperature is 350-370℃, the pressure is 5-10MPa, and the holding time is 0.5-1.5h.

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