CN109777036B - Polyether ether ketone based wear-resistant composite material and preparation method thereof - Google Patents
Polyether ether ketone based wear-resistant composite material and preparation method thereof Download PDFInfo
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Abstract
A polyether-ether-ketone-based wear-resistant composite material and a preparation method thereof relate to the technical field of functional composite material production, and are characterized in that modified graphene nanoplatelets, polyether-ether-ketone and polytetrafluoroethylene are mixed and then placed in a double-screw extruder, and are subjected to melting, mixing, extrusion and granulation to obtain polyether-ether-ketone-based wear-resistant composite particles. The PEEK-based wear-resistant composite material is characterized in that a compact nano composite transfer membrane surface consisting of PEEK-PTFE-graphene is formed in a friction process through a PTFE phase presenting an island structure in a PEEK matrix and nano flaky graphene micro-sheets uniformly dispersed in the matrix, so that excellent wear resistance is obtained; meanwhile, the 'sea-island' structure appearance and the nano composite microstructure enable the composite material to have excellent mechanical properties, particularly toughness.
Description
Technical Field
The invention belongs to the technical field of functional composite material production.
Technical Field
Polyether ether ketone (PEEK) is used as a high-performance semi-crystalline thermoplastic polymer, has excellent mechanical properties, chemical inertness, wide temperature application range and good thermal stability, and is widely used as a substitute of metal components in the fields of bearing materials, bone implants, piston rings and the like. However, PEEK has limited its wide application due to its high coefficient of friction (greater than 0.4 for dry sliding) and stick-slip behavior.
To improve the tribological properties of PEEK, many researchers have developedBy adding various fillers such as SiO2，Al2O3Carbon Fiber (CF), graphene, PTFE, carbon nanotubes, and the like, as well as various combinations thereof. Of these lubricating fillers, CF and PTFE particles are widely used for their excellent properties. Carbon fibers not only have great advantages in modulus and strength over other fibers, but also have excellent self-lubricating properties due to the graphitic structure of their surface. The research on the tribological properties of the CF reinforced PEEK composite material shows that the addition of CF can greatly improve the wear resistance of PEEK under different application conditions, such as seawater lubrication, water lubrication and dry sliding wear.
PTFE is an important solid lubricant that has been widely used in chemical processing, spacecraft design, and biotechnology industries because of its good physical and chemical properties, such as low coefficient of friction, good thermal and chemical stability. It was found that the addition of PTFE significantly reduced the coefficient of friction of the PEEK composite during the dry sliding wear test. In addition, due to graphene and molybdenum disulfide (MoS)2) Such two-dimensional (2D) materials have been widely studied for reasons such as weak interlayer adhesion (van der waals force) and easy interlayer shear. For example, the addition of graphene to a PEEK matrix can result in a significant reduction in the coefficient of friction due to the formation of a transfer film and the beneficial lubricating effect of graphene.
However, few people research the influence of the compatibility of the PTFE wear-resistant modified material and a PEEK matrix and the synergistic effect of the PTFE wear-resistant modified material and a nanometer two-dimensional material on the friction performance and the mechanical performance of a PEEK composite material. As proved by numerous studies, the formation of a high-performance boundary film on the sliding interface is of great significance for improving the boundary lubrication performance of the friction system. Because the high performance boundary membranes are able to carry the significant loads generated by solid-solid contact. Furthermore, such boundary films may also enhance the wear resistance of the polymer composite by direct friction from separation friction. Therefore, the construction of the friction boundary film with the nano structure has profound significance for improving the friction performance of the PEEK composite material.
Disclosure of Invention
In order to solve the existing problems, the invention aims to provide a novel polyetheretherketone-based wear-resistant composite material.
The polyether-ether-ketone-based wear-resistant composite material is composed of 80-90 parts by mass of polyether-ether-ketone resin, 9.9-19.5 parts by mass of polytetrafluoroethylene and 0.1-0.5 part by mass of modified graphene nanoplatelets in 100 parts by mass of the composite material.
Compared with the traditional polyetheretherketone wear-resistant modified composite material, the PTFE island with the sea-island structure of the composite material can toughen the composite material, and the island-phase PTFE is easier to form an interface film on a sliding interface during friction; meanwhile, the graphene nanoplatelets modified by the spindle-shaped calcium carbonate load can be uniformly dispersed in the PEEK matrix; the invention forms the ternary nanometer interfacial film composed of PEEK, PTFE and graphene, and effectively improves the boundary lubrication performance of a friction system. Due to the fact that the nano transfer film integrating the strength and heat resistance of the PEEK, the low friction coefficient of PTFE and the solid lubricity of graphene is formed, the PEEK composite material shows excellent low friction coefficient and low abrasion loss. Meanwhile, compared with the PEEK, the toughness of the 'sea island' structure in the PEEK composite material is greatly improved. In addition, the composite material has excellent processing performance and is easy to be molded by injection and extrusion.
Another object of the present invention is to propose a process for the preparation of the above composite material.
Mixing the modified graphene nanoplatelets, polyether-ether-ketone and polytetrafluoroethylene, putting the mixture into a double-screw extruder, and performing melt mixing and extrusion granulation to obtain polyether-ether-ketone-based wear-resistant composite particles; the feeding mass of the polyether-ether-ketone resin, the polytetrafluoroethylene and the modified graphene nanoplatelets respectively accounts for 80-90%, 9.9-19.5% and 0.1-0.5% of the total feeding mass. The invention adopts a melt extrusion granulation process, and can improve the uniform mixing degree of the compound.
Furthermore, the polytetrafluoroethylene is extrusion-grade polytetrafluoroethylene, so that the polytetrafluoroethylene cannot be decomposed at the processing temperature of 380-390 ℃.
In addition, the invention also provides a preparation method of the modified graphene nanoplatelets, which comprises the following steps:
1) mixing graphene nanoplatelets, calcium hydroxide and water to obtain a suspension; wherein the mixing mass ratio of the graphene nanoplatelets to the calcium hydroxide is 6.76: 1.
2) Introducing carbon dioxide into the suspension, and carrying out gas-solid reaction at the reaction temperature of 60-70 ℃; and stopping introducing carbon dioxide gas when the pH of the reaction system is reduced to 7 at the end of the gas-solid reaction, filtering to obtain a calcium carbonate loaded graphene filter cake, and drying to obtain the modified graphene nanoplatelets.
The temperature of the gas-solid reaction is 60-70 ℃. The reaction temperature can obtain spindle-shaped calcium carbonate with submicron size, so that the loaded graphene is easily dispersed in a polymer matrix.
The preparation method of the modified graphene nanoplatelets utilizes in-situ generation of inorganic submicron calcium carbonate, can realize high-efficiency isolation of the graphene nanoplatelets and improve the dispersibility of the graphene nanoplatelets.
The heating temperatures of the first zone to the ninth zone of the double-screw extruder are respectively as follows: the temperature of a first area is 375 ℃, the temperature of a second area is 380 ℃, the temperature of a third area is 380 ℃, the temperature of a fourth area is 385 ℃, the temperature of a fifth area is 385 ℃, the temperature of a sixth area is 390 ℃, the temperature of a seventh area is 385 ℃, the temperature of an eighth area is 385 ℃, and the temperature of a ninth area is 380 ℃; the feeding speed is 18-25rps, and the rotating speed of the main machine is 30-38 rps. The temperature design of each zone ensures the polymer to be fully plasticized, and the speed of the feeding and the main machine is mainly set by considering the melt mixing effect and the uniformity and the continuity of the drawing strip.
Drawings
FIG. 1 is a graph comparing the change of friction coefficient with time of the composite materials prepared in the examples of the present invention and the comparative examples.
FIG. 2 is a friction surface energy dispersion spectrum of the composite material prepared by the example of the present invention.
FIG. 3 is a friction surface energy dispersion spectrum of a composite material prepared in comparison with the comparative example.
Detailed Description
The preparation process of the modified graphene nanoplatelets comprises the following steps:
adding 100 g of graphene nanoplatelets and 14.8g of calcium hydroxide into 1000.0 g of water, stirring to form uniform suspension, introducing carbon dioxide, and carrying out gas-solid reaction at the temperature of 60 ℃.
And stopping ventilation when the pH value of the suspension is reduced to 7 after the reaction, performing suction filtration and washing to obtain 120g of calcium carbonate loaded graphene filter cake, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the modified graphene nanoplatelets for later use.
Secondly, a preparation process of the composite material comprises the following steps:
1. example (b):
respectively weighing the following components in parts by weight: 90 parts of polyether-ether-ketone, 9.9 parts of extrusion-grade polytetrafluoroethylene and 0.5 part of modified graphene nanoplatelets.
Adding the raw materials into a high-speed mixer for mechanical mixing, adding the uniformly mixed materials into a double-screw extruder for melt mixing, extruding and granulating.
And (3) placing the granules subjected to melting, mixing and extrusion in an oven at 120 ℃ for 2h, and then performing injection molding by using an injection molding machine. Wherein the parameters of the double-screw extruder are as follows: the temperature of a first area is 375 ℃, the temperature of a second area is 380 ℃, the temperature of a third area is 380 ℃, the temperature of a fourth area is 385 ℃, the temperature of a fifth area is 385 ℃, the temperature of a sixth area is 390 ℃, the temperature of a seventh area is 385 ℃, the temperature of an eighth area is 385 ℃, and the temperature of a ninth area is 380 ℃; the feeding speed is 18-25rps, and the rotating speed of the main machine is 30-38 rps.
2. Comparative example:
respectively weighing the following components in parts by weight: 90 parts of polyether-ether-ketone, 9.9 parts of ethylene-tetrafluoroethylene copolymer and 0.5 part of modified graphene nano-microchip. The ethylene-tetrafluoroethylene copolymer is an extrusion-grade ethylene-tetrafluoroethylene copolymer (F46, DuPont).
The components are added into a high-speed mixer for mechanical mixing, and then the uniformly mixed materials are added into a double-screw extruder for melt mixing and extrusion granulation.
And (3) placing the granules subjected to melting, mixing and extrusion in an oven at 120 ℃ for 2h, and then performing injection molding by using an injection molding machine. Wherein the parameters of the double-screw extruder are set as follows: the temperature of a first area is 375 ℃, the temperature of a second area is 380 ℃, the temperature of a third area is 380 ℃, the temperature of a fourth area is 385 ℃, the temperature of a fifth area is 385 ℃, the temperature of a sixth area is 390 ℃, the temperature of a seventh area is 385 ℃, the temperature of an eighth area is 385 ℃, and the temperature of a ninth area is 380 ℃; the feeding speed is 18-25rps, and the rotating speed of the main machine is 30-38 rps.
Thirdly, product performance verification:
as can be seen from fig. 1, the friction coefficient of the composite material obtained in example was significantly lower than that of the comparative example. With the friction experiment, the composite material obtained in the experimental example can initially form a boundary film on the dual steel ring at about 2000s, and then the friction coefficient is gradually stabilized, which shows that the boundary film in the composite material obtained in the example can continuously and stably exist; the composite material obtained by the comparative example showed a tendency of rising fluctuation in the friction coefficient, because the boundary film was discontinuous and separated during the friction process, and did not exert an effective friction reducing effect.
As can be seen from fig. 2, the composite material obtained in the example has PTFE dispersed in the PEEK matrix in an "island" like structure; in addition, the energy dispersion spectrogram result shows that the content of the fluorine element is obviously increased compared with the bulk. This result shows that the composite material obtained in the examples has an "island" -like structure PTFE which is more easily enriched on the surface during the rubbing process, and forms a dense ternary nanometer boundary film together with the matrix PEEK and the modified graphene. The nano boundary film having a composition of an appropriate ratio has a low friction coefficient and a low abrasion loss (table 1), is not easily detached even under a strong mechanical friction force condition, and exhibits continuous stability.
In the composite material obtained in the comparative example, the ethylene-tetrafluoroethylene copolymer was uniformly dispersed in the PEEK matrix, as shown in fig. 3, and in addition, no fluorine enrichment occurred in the energy dispersion spectrum result, and the formed ternary nano boundary film had a large friction coefficient and a high abrasion loss (table 1).
Table 1: the mechanical properties of the composite materials prepared in the examples of the invention and the comparative examples are shown in the comparative table.
| Item | Coefficient of friction | Abrasion loss/mg | Width of grinding crack/mm | Wear rate/(10)-9cm3/Nm) |
| Examples | 0.266 | 1.9 | 2.90 | 1.01 |
| Comparative example | 0.323 | 3.2 | 3.58 | 3.28 |
As can be seen from table 1, the examples show superior frictional properties compared to the comparative examples.
Table 2: the friction performance of the composite materials prepared in the inventive example and the comparative example are shown in the table.
| Item | Tensile strength/MPa | Elongation at break/% | Flexural Strength/MPa | Impact Strength/KJ/m2 |
| Examples | 87.32 | 7.52 | 96.1 | 13.98 |
| Comparative example | 89.68 | 2.78 | 96.4 | 9.6 |
As can be seen from table 2, the toughness of the examples is significantly improved under the condition of little strength reduction, which is mainly due to the fact that the PTFE is dispersed in the PEEK matrix in the island-shaped structure, which can effectively toughen the PEEK.
Claims (4)
1. The polyether-ether-ketone-based wear-resistant composite material is characterized by comprising 80-90 parts by mass of polyether-ether-ketone resin, 9.9-19.5 parts by mass of polytetrafluoroethylene and 0.1-0.5 part by mass of modified graphene nanoplatelets in 100 parts by mass of the composite material;
the preparation method of the modified graphene nanoplatelets comprises the following steps:
1) mixing graphene nanoplatelets, calcium hydroxide and water to obtain a suspension; wherein the mixing mass ratio of the graphene nanoplatelets to the calcium hydroxide is 6.76: 1;
2) introducing carbon dioxide into the suspension, and carrying out gas-solid reaction at the reaction temperature of 60-70 ℃; and stopping introducing carbon dioxide gas when the pH of the reaction system is reduced to 7 at the end of the gas-solid reaction, filtering to obtain a calcium carbonate loaded graphene filter cake, and drying to obtain the modified graphene nanoplatelets.
2. The method for preparing the polyetheretherketone-based wear-resistant composite material according to claim 1, wherein the modified graphene nanoplatelets, polyetheretherketone and polytetrafluoroethylene are mixed and then placed in a twin-screw extruder, and the mixture is subjected to melt-kneading and extrusion granulation to obtain the polyetheretherketone-based wear-resistant composite particles; the feeding mass of the polyether-ether-ketone resin, the polytetrafluoroethylene and the modified graphene nanoplatelets respectively accounts for 80-90%, 9.9-19.5% and 0.1-0.5% of the total feeding mass.
3. The method for preparing a polyetheretherketone-based abrasion-resistant composite according to claim 2, wherein the polytetrafluoroethylene is an extruded polytetrafluoroethylene.
4. The method for preparing the polyetheretherketone-based wear-resistant composite material according to claim 2, wherein the heating temperatures of the first zone to the ninth zone of the twin-screw extruder are respectively as follows: the temperature of a first area is 375 ℃, the temperature of a second area is 380 ℃, the temperature of a third area is 380 ℃, the temperature of a fourth area is 385 ℃, the temperature of a fifth area is 385 ℃, the temperature of a sixth area is 390 ℃, the temperature of a seventh area is 385 ℃, the temperature of an eighth area is 385 ℃, and the temperature of a ninth area is 380 ℃; the feeding speed is 18-25rps, and the rotating speed of the main machine is 30-38 rps.
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| CN115073880A (en) * | 2022-07-22 | 2022-09-20 | 中国电子科技集团公司第三十八研究所 | Extrudable, toughened and modified polyether-ether-ketone material for aviation liquid cooling pipe system and preparation method thereof |
| CN116751381B (en) * | 2023-03-07 | 2023-12-08 | 江苏君华特种工程塑料制品有限公司 | Preparation method of high-performance carbon fiber reinforced PEEK prepreg and PEEK substrate material |
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