CN114409934A - Fiber hybrid filled polytetrafluoroethylene composite material and preparation method thereof - Google Patents

Fiber hybrid filled polytetrafluoroethylene composite material and preparation method thereof Download PDF

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CN114409934A
CN114409934A CN202210278948.8A CN202210278948A CN114409934A CN 114409934 A CN114409934 A CN 114409934A CN 202210278948 A CN202210278948 A CN 202210278948A CN 114409934 A CN114409934 A CN 114409934A
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fiber
glass fiber
temperature
molybdenum disulfide
hybrid
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严云峰
王云霞
王建章
阎逢元
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/011—Nanostructured additives

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Abstract

The invention provides a polytetrafluoroethylene composite material filled with a fiber hybrid and a preparation method thereof, belonging to the field of polymer composite materials. According to the invention, nano-scale molybdenum disulfide is self-assembled on the surface of glass fiber through a hydrothermal reaction to obtain a glass fiber-molybdenum disulfide fiber hybrid, the glass fiber-molybdenum disulfide fiber hybrid has higher surface roughness and specific surface area compared with untreated glass fiber, and then the glass fiber-molybdenum disulfide fiber hybrid is added into polytetrafluoroethylene suspension powder for cold press molding and sintering, the polytetrafluoroethylene suspension powder is fully melted and undergoes a crosslinking reaction, and a polytetrafluoroethylene polymer composite material is formed after sintering is finished.

Description

Fiber hybrid filled polytetrafluoroethylene composite material and preparation method thereof
Technical Field
The invention relates to the field of polymer composite materials, in particular to a polytetrafluoroethylene composite material filled with a fiber hybrid and a preparation method and application thereof.
Background
With the rapid development of aviation and aerospace industries, more rigorous requirements are put forward on the tribological properties of polymer composite materials under extreme conditions of high speed, high temperature, heavy load and the like. The polymer composite material taking the fiber as the reinforcing phase can greatly improve the mechanical property of the material, thereby expanding the application range and the use temperature of the composite material. However, fiber reinforced polymer composites tend to have low abrasion resistance, and the failure mechanism during frictional wear is mainly the pulling out and flaking of the hard fibers, which then undergoes the process of thinning, breaking and removing the fibers. In order to improve the tribological properties of such materials, it is common practice to add solid lubricants.
In the prior art, a mechanical mixing mode is generally adopted, and two fillers, namely a reinforcing phase and a lubricating phase, are utilized to modify a polymer material. In the modification process, the problem of poor interface compatibility exists in a multiple interface formed between the two fillers and the polymer matrix, the improvement of the performance of the polymer material by the two fillers is obviously hindered, and the effect of adding one to less than two is often obtained. Therefore, how to improve the interfacial compatibility between the two fillers (i.e., the reinforcing phase and the lubricating phase) and the polymer matrix, so as to fully exert the synergistic effect between the two fillers, and simultaneously improve the mechanical properties and the lubricity (i.e., the friction and wear resistance) of the polymer composite material, thereby expanding the application range of the polymer composite material is a problem to be solved in the prior art.
Disclosure of Invention
The invention aims to provide a polytetrafluoroethylene composite material filled with a fiber hybrid and a preparation method thereof. The method provided by the invention obviously improves the interface compatibility between the lubricating phase molybdenum disulfide and the reinforcing phase glass fiber and the polymer matrix, the synergistic effect between the two fillers is fully exerted, and the prepared polytetrafluoroethylene composite material filled with the fiber hybrid has good mechanical property and excellent lubricity (namely antifriction and wear-resistant properties).
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a polytetrafluoroethylene composite material filled with a fiber hybrid, which comprises the following steps:
(1) mixing a sulfur source, a molybdenum source, water and glass fiber, and then carrying out hydrothermal reaction to obtain a glass fiber-molybdenum disulfide fiber hybrid;
(2) mixing the glass fiber-molybdenum disulfide fiber hybrid obtained in the step (1) with polytetrafluoroethylene suspension powder to obtain a mixture;
(3) and (3) sequentially carrying out cold press molding and sintering on the mixture obtained in the step (2) to obtain the polytetrafluoroethylene composite material filled with the fiber hybrid.
Preferably, the temperature of the hydrothermal reaction in the step (1) is 200-240 ℃, and the time of the hydrothermal reaction is 20-26 h.
Preferably, the mass ratio of the glass fiber to the molybdenum disulfide in the glass fiber-molybdenum disulfide fiber hybrid in the step (1) is (0.5-5): 1.
preferably, the step (2) further comprises, after mixing: drying the mixed product; the drying temperature is 100-140 ℃, and the drying time is 1-3 h.
Preferably, the mass fraction of the glass fiber-molybdenum disulfide fiber hybrid in the mixture in the step (2) is less than or equal to 30%.
Preferably, the pressure of the cold press molding in the step (3) is 25-60 MPa.
Preferably, the sintering temperature in the step (3) is 350-400 ℃, and the sintering time is 150-400 min.
Preferably, the temperature raising manner of the sintering in the step (3) is a stepwise temperature programming
Preferably, the staged temperature programming mode is a first stage, and the temperature is raised to 270-290 ℃ from room temperature at the speed of 2-3 ℃/min; in the second stage, the temperature is increased from 270 to 290 ℃ to 330 to 350 ℃ at the speed of 1 ℃/min; and in the third stage, the temperature is increased from 330 ℃ to 350 ℃ to the sintering temperature at the speed of 0.5 ℃/min.
The invention also provides the polytetrafluoroethylene composite material filled with the fiber hybrid prepared by the preparation method in the technical scheme. In the invention, the fiber hybrid filled polytetrafluoroethylene composite material comprises polytetrafluoroethylene, glass fiber and molybdenum disulfide loaded on the surface of the glass fiber.
The invention provides a preparation method of a polytetrafluoroethylene composite material filled with a fiber hybrid, which takes a sulfur source and a molybdenum source as precursors, self-assembles (in-situ synthesizes) nano-grade molybdenum disulfide on the surface of glass fiber through hydrothermal reaction, realizes the combination of hardness and hardness of lubricating phase molybdenum disulfide and reinforcing phase glass fiber, greatly improves the surface roughness and specific surface area of the glass fiber at the same time, obtains the fiber hybrid with a micro-nano structure, namely the glass fiber-molybdenum disulfide fiber hybrid, and has higher surface roughness and specific surface area compared with untreated glass fiber, then adds the fiber hybrid as a binary composite filler into a polytetrafluoroethylene suspension powder matrix for cold press molding, and fully melts and carries out crosslinking reaction on polytetrafluoroethylene suspension powder in the subsequent sintering process to form the polytetrafluoroethylene polymer composite material, compared with the traditional mechanical mixed molybdenum disulfide and glass fiber, the synthesized fiber hybrid has higher surface roughness and larger specific surface area, and can obviously improve the interface bonding strength between the fiber hybrid and the polymer resin matrix, thereby obviously improving the interface compatibility between the fiber hybrid and the polymer resin matrix and fully exerting the synergistic effect between the two fillers. The prepared polytetrafluoroethylene composite material filled with the fiber hybrid has good mechanical properties, excellent antifriction and wear resistance and high heat resistance, so that the application range of the composite material is expanded. The results of the examples show that the polytetrafluoroethylene composite material filled with fiber hybrid with optimal surface grafting amount prepared by the method provided by the invention has the advantages of 149.7MPa of tensile strength, 263 percent of elongation at break, 0.186 percent of friction coefficient at room temperature and 2.41 multiplied by 10 of wear rate-6mm3Nm, low friction coefficient at 200 deg.C to 0.163, and low wear rate to 3.81X 10-6mm3Nm, the composite material has betterThe bearing performance, the antifriction and wear-resisting properties are good, and the friction coefficient is stable in a wider temperature range.
Drawings
FIG. 1 is an XRD spectrum of a fiber hybrid-filled polytetrafluoroethylene composite material prepared in example 2 of the present invention;
FIG. 2 is an infrared spectrum of a polytetrafluoroethylene composite filled with a hybrid fiber prepared in example 2 of the present invention;
FIG. 3 is an SEM photograph of glass fibers in step (1) described in example 2 of the present invention;
FIG. 4 is an SEM image of the glass fiber-molybdenum disulfide fiber hybrid prepared in example 3 of the present invention;
FIG. 5 is an SEM image of a fibrous hybrid-filled polytetrafluoroethylene composite prepared in example 2 of the invention.
Detailed Description
The invention provides a preparation method of a polytetrafluoroethylene composite material filled with a fiber hybrid, which comprises the following steps:
(1) mixing a sulfur source, a molybdenum source, water and glass fiber, and then carrying out hydrothermal reaction to obtain a glass fiber-molybdenum disulfide fiber hybrid;
(2) mixing the glass fiber-molybdenum disulfide fiber hybrid obtained in the step (1) with polytetrafluoroethylene suspension powder to obtain a mixture;
(3) and (3) sequentially carrying out cold press molding and sintering on the mixture obtained in the step (2) to obtain the polytetrafluoroethylene composite material filled with the fiber hybrid.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
The invention mixes the sulfur source, the molybdenum source, the water and the glass fiber and then carries out hydrothermal reaction to obtain the glass fiber-molybdenum disulfide fiber hybrid.
In the present invention, the sulfur source is preferably one or more of thiourea, sodium sulfide, potassium sulfide and ammonium sulfide. In the present invention, the molybdenum source is preferably ammonium molybdate.
In the present invention, the glass fiber is preferably subjected to acid treatment and washing in this order before use.
In the present invention, the acid treatment is preferably performed by washing with a mixed solution of 37% by mass hydrochloric acid and 68% by mass nitric acid aqueous solution at a volume ratio of 1: 1. In the invention, in the acid treatment process, impurities on the surface of the glass fiber are removed, so that the surface of the glass is smooth, and the subsequent hydrothermal reaction is facilitated.
In the present invention, the washing is preferably performed by washing with distilled water to neutrality.
In the invention, the sulfur source, the molybdenum source, the water and the glass fiber are preferably mixed and stirred to obtain a mixed solution; mixing the mixed solution with glass fibers.
In the invention, the stirring time is preferably 15-30 min. The stirring speed is not specially limited, and the components are dissolved and uniformly mixed.
In the invention, the temperature of the hydrothermal reaction is preferably 200-240 ℃, and more preferably 210-230 ℃. The invention controls the temperature of the hydrothermal reaction within the range, is favorable for controlling the pressure of the hydrothermal reaction system, and avoids the phenomenon that the synthesized MoS is caused by overhigh reaction temperature2The growth is too fast, can't obtain nanometer size's molybdenum disulfide, avoids simultaneously that reaction temperature is crossed lowly and can make the molybdenum disulfide of production breakable, is unfavorable for collecting to realize improving glass fiber surface roughness and specific surface area.
In the invention, the time of the hydrothermal reaction is preferably 20-26 h, and more preferably 22-25 h. According to the invention, the time of the hydrothermal reaction is controlled within the range, so that the growth process of the molybdenum disulfide formed by the hydrothermal reaction is controlled, and the nano-sized molybdenum disulfide is obtained, thereby realizing the purpose of improving the surface roughness and the specific surface area of the glass fiber.
After the hydrothermal reaction is finished, the product of the hydrothermal reaction is preferably washed and dried in sequence to obtain the glass fiber-molybdenum disulfide fiber hybrid.
The invention has no special limitation on the washing mode, and the aim of removing impurities and obtaining a purer glass fiber-molybdenum disulfide fiber hybrid is fulfilled. In the invention, the drying temperature is preferably 80-120 ℃, and more preferably 90-110 ℃. In the invention, the drying time is preferably 22-26 h, and more preferably 23-25 h.
In the invention, the mass ratio of the glass fiber to the molybdenum disulfide in the glass fiber-molybdenum disulfide fiber hybrid is preferably (0.5-5): 1, more preferably (0.8 to 4.5): 1. in the embodiment of the invention, the mass ratio of the glass fiber and the molybdenum disulfide in the glass fiber-molybdenum disulfide fiber hybrid can be specifically 4:1, 2:1 or 1: 1. According to the invention, the mass ratio of the glass fiber to the molybdenum disulfide in the glass fiber-molybdenum disulfide fiber hybrid is controlled in the above range, so that the distribution state of the molybdenum disulfide on the surface of the glass fiber can be adjusted, and the glass fiber-molybdenum disulfide fiber hybrid with a micro-nano structure, which is formed by combining the molybdenum disulfide on the soft lubricating layer and the glass fiber on the hard fiber layer and has high surface roughness and specific surface area, can be obtained.
After the glass fiber-molybdenum disulfide fiber hybrid is obtained, the glass fiber-molybdenum disulfide fiber hybrid and polytetrafluoroethylene suspension powder are mixed to obtain a mixture.
In the present invention, the mixing is preferably performed by mechanical stirring. In the invention, the mixing temperature is preferably 0-20 ℃, and more preferably 0-10 ℃. The invention controls the mixing temperature within the range, is beneficial to more uniformly mixing all the components, and avoids the agglomeration of the polytetrafluoroethylene caused by overhigh temperature.
After the mixing is finished, the mixed product is preferably dried to obtain a mixture.
In the invention, the drying temperature is preferably 100-140 ℃, and more preferably 110-130 ℃. In the invention, the drying time is 1-3 h, and more preferably 1.5-2.5 h. The invention controls the temperature and time of drying in the above range, which is beneficial to removing excessive moisture.
In the invention, the mass fraction of the glass fiber-molybdenum disulfide fiber hybrid in the mixture is preferably less than or equal to 30%, more preferably 5-25%, and further preferably 8-15%. According to the invention, the mass fraction of the glass fiber-molybdenum disulfide fiber hybrid in the mixture is controlled within the range, so that the better modification effect of the glass fiber-molybdenum disulfide fiber hybrid on the subsequently formed polytetrafluoroethylene polymer resin is favorably realized, the condition that the modification effect is not obvious due to too low mass fraction of the hybrid is avoided, and the condition that the subsequent cold press molding cannot be carried out due to too high mass fraction is also avoided.
After a mixture is obtained, the mixture is sequentially subjected to cold press molding and sintering to obtain the polytetrafluoroethylene composite material filled with the fiber hybrid.
In the present invention, the temperature of the cold press molding is preferably room temperature. In the invention, the pressure of the cold press molding is preferably 25-60 MPa, and more preferably 30-55 MPa. According to the invention, the pressure of cold press molding is controlled within the range, so that the composite material with good mechanical property can be obtained subsequently, and the phenomenon that the density of the composite material is too low and the mechanical property is reduced due to too low pressure is avoided. In the present invention, the cold-press forming mold is preferably selected according to the size of the sample.
In the invention, the sintering temperature is preferably 350-400 ℃, and more preferably 355-390 ℃. In the invention, the sintering time is preferably 150-400 min, and more preferably 170-350 min. In the present invention, the time for the sintering is preferably adjusted according to the size of the sample. According to the invention, the sintering temperature and time are controlled within the above ranges, which is beneficial to the full melting and crosslinking reaction of the polytetrafluoroethylene suspended powder in the mixture, and meanwhile, the molecular weight and the crystallinity of the polytetrafluoroethylene polymer resin formed by recrystallization after sintering are adjusted, and the mechanical property, the lubricity (namely the antifriction and wear-resistant properties) and the heat resistance of the polytetrafluoroethylene composite material filled with the fiber hybrid are obviously improved by cooperating with the synergistic effect between the two fillers, so that the application range of the composite material is expanded.
In the present invention, the temperature raising method of the sintering is a stepwise temperature programming. In the present invention, the stepwise temperature programming is preferably performed in a manner that: in the first stage, the temperature is increased from room temperature to 270-290 ℃ at the speed of 2-3 ℃/min; in the second stage, the temperature is increased from 270 to 290 ℃ to 330 to 350 ℃ at the speed of 1 ℃/min; and in the third stage, the temperature is increased from 330 ℃ to 350 ℃ to the sintering temperature at the speed of 0.5 ℃/min. In the sintering process, a staged temperature programming mode is adopted, so that the temperature control is facilitated, the temperature flushing is avoided, the full melting and the cross-linking reaction of the polytetrafluoroethylene suspended powder in the mixture are facilitated, the molecular weight and the crystallinity of the polytetrafluoroethylene polymer resin formed by recrystallization after the sintering is finished are adjusted, the synergistic effect between two fillers is exerted to the maximum extent, the mechanical property, the lubricity (namely the antifriction and wear-resistant properties) and the heat resistance of the polytetrafluoroethylene composite material filled with the fiber hybrid are obviously improved, and the application range of the composite material is expanded.
After sintering is finished, the sintered product is preferably sequentially cooled and demoulded to obtain the polytetrafluoroethylene composite material filled with the fiber hybrid.
In the present invention, the cooling method is preferably natural cooling. The demolding mode is not particularly limited, and the technical scheme known in the field can be adopted.
The method provided by the invention obviously improves the interface compatibility between the two fillers of molybdenum disulfide and glass fiber and the polymer matrix, and the synergistic effect between the two fillers is fully exerted,
the invention also provides the polytetrafluoroethylene composite material filled with the fiber hybrid prepared by the preparation method in the technical scheme. In the invention, the polytetrafluoroethylene composite material filled with the fiber hybrid comprises glass fibers dispersed in polytetrafluoroethylene, and molybdenum disulfide loaded on the surfaces of the glass fibers.
The polytetrafluoroethylene composite material filled with the fiber hybrid provided by the invention has good mechanical properties and excellent lubricity (namely antifriction and wear-resistant properties).
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation method of polytetrafluoroethylene composite material filled with fiber hybrid
(1) Dissolving 0.85g of thiourea and 0.99g of ammonium molybdate by using 100mL of distilled water under magnetic stirring, stirring for 20min to obtain a mixed solution, then mixing the mixed solution with 3.57g of glass fiber, transferring to a 250mL reaction kettle, carrying out hydrothermal reaction at 220 ℃ for 24h, washing black products of the hydrothermal reaction for a plurality of times, and drying at 100 ℃ for 24h to obtain a glass fiber-molybdenum disulfide fiber hybrid;
the glass fiber is obtained by washing a commercially available glass fiber product with a mixed solution of hydrochloric acid with the mass fraction of 37% and nitric acid aqueous solution with the mass fraction of 68% in a volume ratio of 1:1, and then washing the glass fiber product with distilled water to be neutral;
the mass ratio of the glass fiber to the molybdenum disulfide in the glass fiber-molybdenum disulfide fiber hybrid is 4: 1;
(2) mechanically stirring and mixing the glass fiber-molybdenum disulfide fiber hybrid obtained in the step (1) and polytetrafluoroethylene suspension powder at 0 ℃, and drying for 2 hours at 120 ℃ to obtain a mixture;
the mass fraction of the glass fiber-molybdenum disulfide fiber hybrid in the mixture is 10%;
(3) cold-pressing and molding the mixture obtained in the step (2) under 30MPa by using different molds according to the size of a sample, then placing the mixture into a sintering furnace, raising the temperature to the sintering temperature of 360 ℃ according to a staged procedure, carrying out heat preservation and sintering for 180min according to the size of the sample, then naturally cooling a sintered product, and then demoulding to obtain the polytetrafluoroethylene composite material filled with the fiber hybrid; the density of the composite material was 2.25g/cm as measured by a drainage method using an analytical balance with a density accessory3；
The staged temperature programming mode is as follows: in the first stage, the temperature is raised to 280 ℃ from room temperature at the speed of 2 ℃/min; in the second stage, the temperature is increased from 280 ℃ to 340 ℃ at the speed of 1 ℃/min; in the third stage, the temperature is increased from 340 ℃ to 360 ℃ of sintering temperature at the speed of 0.5 ℃/min.
Detecting one: mechanical properties
The polytetrafluoroethylene composite material filled with the fiber hybrid prepared in example 1 is mechanically processed into a national standard specified size, and is subjected to mechanical property test on a universal testing machine to detect the tensile strength and the elongation at break, wherein the tensile sample is a dumbbell-shaped sample with the length of 80mm, and specific results are shown in table 1.
And (2) detecting: tribological properties
The fiber hybrid-filled polytetrafluoroethylene composite material prepared in example 1 was used as a friction partner with a steel pin of GCr15(AISI52100), a sliding linear speed of 0.5m/s, a sliding distance of 2KM, an additional load of 10N, and a friction coefficient automatically recorded by a friction tester as an average value of the entire sliding process. The wear rate K is calculated as follows, where Δ V is the wear volume (mm) (. DELTA.V)/(F · S)3) F is the load (N) and S is the total sliding distance (m). The friction coefficient and the wear rate of the fiber hybrid filled polytetrafluoroethylene composite material prepared in example 1 at room temperature and 200 ℃ were respectively tested, and the specific results are shown in table 1.
Example 2
Preparation method of polytetrafluoroethylene composite material filled with fiber hybrid
(1) Dissolving 1.71g of thiourea and 1.98g of ammonium molybdate by using 100mL of distilled water under magnetic stirring, stirring for 20min to obtain a mixed solution, then mixing the mixed solution with 3.57g of glass fiber, transferring to a 250mL reaction kettle, carrying out hydrothermal reaction at 220 ℃ for 24h, washing black products of the hydrothermal reaction for several times, and drying at 100 ℃ for 24h to obtain a glass fiber-molybdenum disulfide fiber hybrid;
the glass fiber is obtained by washing a commercially available glass fiber product with a mixed solution of hydrochloric acid with the mass fraction of 37% and nitric acid aqueous solution with the mass fraction of 68% in a volume ratio of 1:1, and then washing the glass fiber product with distilled water to be neutral;
the mass ratio of the glass fiber to the molybdenum disulfide in the glass fiber-molybdenum disulfide fiber hybrid is 2: 1;
(2) mechanically stirring and mixing the glass fiber-molybdenum disulfide fiber hybrid obtained in the step (1) and polytetrafluoroethylene suspension powder at 0 ℃, and drying for 2 hours at 120 ℃ to obtain a mixture;
the mass fraction of the glass fiber-molybdenum disulfide fiber hybrid in the mixture is 10%;
(3) cold-pressing and molding the mixture obtained in the step (2) under 40MPa by using different molds according to the size of a sample, then placing the mixture into a sintering furnace, raising the temperature to 370 ℃ according to a staged procedure, carrying out heat preservation and sintering for 240min according to the size of the sample, then naturally cooling a sintered product, and then demoulding to obtain the polytetrafluoroethylene composite material filled with the fiber hybrid; the density of the composite material was 2.25g/cm as measured by a drainage method using an analytical balance with a density accessory3；
The staged temperature programming mode is as follows: in the first stage, the temperature is raised to 280 ℃ from room temperature at the speed of 2 ℃/min; in the second stage, the temperature is increased from 280 ℃ to 340 ℃ at the speed of 1 ℃/min; in the third stage, the temperature is increased from 340 ℃ to 370 ℃ of sintering temperature at the rate of 0.5 ℃/min.
The mechanical properties and tribological properties of the polytetrafluoroethylene composite filled with the hybrid fiber prepared in example 2 were measured in the same manner as in example 1, and the specific results are shown in table 1.
FIG. 1 is an XRD spectrum of a polytetrafluoroethylene composite filled with a hybrid fiber prepared in example 2. As can be seen from FIG. 1, the diffraction peaks of the composite prepared in example 2 are almost the same as those of pure polytetrafluoroethylene, and are all around 18 degrees, and no diffraction peaks of other crystals are detected, which indicates that the composite prepared in example 2 does not contain other organic components.
FIG. 2 is an IR spectrum of a polytetrafluoroethylene composite filled with a hybrid fiber prepared in example 2, which is shown in FIG. 2 and located at 1201cm-1And 1148cm-1The characteristic peak of (a) is attributed to the asymmetric stretching vibration and the symmetric stretching vibration peak of C-F, which are characteristic absorption peaks of polytetrafluoroethylene, and it is demonstrated that the composite material prepared in example 2 contains polytetrafluoroethylene.
Fig. 3 is an SEM image of the glass fiber in the step (1) in example 2, and it can be seen from fig. 3 that the surface of the glass fiber raw material in the step (1) in example 2 is very smooth.
FIG. 5 is an SEM image of the fiber hybrid-filled PTFE composite prepared in example 2, wherein the glass fiber-molybdenum disulfide fiber hybrid in the composite prepared in example 2 is tightly adhered to the matrix polymer, as can be seen from the white circle portion shown in FIG. 5.
Example 3
Preparation method of polytetrafluoroethylene composite material filled with fiber hybrid
(1) Dissolving 3.41g of thiourea and 3.95g of ammonium molybdate by using 100mL of distilled water under magnetic stirring, stirring for 20min to obtain a mixed solution, then mixing the mixed solution with 3.57g of glass fiber, transferring to a 250mL reaction kettle, carrying out hydrothermal reaction at 220 ℃ for 24h, washing black products of the hydrothermal reaction for a plurality of times, and drying at 100 ℃ for 24h to obtain a glass fiber-molybdenum disulfide fiber hybrid;
the glass fiber is obtained by washing a commercially available glass fiber product with a mixed solution of hydrochloric acid with the mass fraction of 37% and nitric acid aqueous solution with the mass fraction of 68% in a volume ratio of 1:1, and then washing the glass fiber product with distilled water to be neutral;
the mass ratio of the glass fiber to the molybdenum disulfide in the glass fiber-molybdenum disulfide fiber hybrid is 1: 1;
(2) mechanically stirring and mixing the glass fiber-molybdenum disulfide fiber hybrid obtained in the step (1) and polytetrafluoroethylene suspension powder at 0 ℃, and drying for 2 hours at 120 ℃ to obtain a mixture;
the mass fraction of the glass fiber-molybdenum disulfide fiber hybrid in the mixture is 10%;
(3) selecting different dies for the mixture obtained in the step (2) according to the size of the sample under 50MPaCold press molding, then placing into a sintering furnace, raising the temperature to 380 ℃ according to a staged procedure, carrying out heat preservation sintering for 300min according to the size of a sample, then naturally cooling a sintered product, and then demoulding to obtain the polytetrafluoroethylene composite material filled with the fiber hybrid; the density of the composite material was 2.26g/cm as measured by a drainage method using an analytical balance with a density accessory3；
The staged temperature programming mode is as follows: in the first stage, the temperature is raised to 280 ℃ from room temperature at the speed of 2 ℃/min; in the second stage, the temperature is increased from 280 ℃ to 340 ℃ at the speed of 1 ℃/min; in the third stage, the temperature is raised from 340 ℃ to 380 ℃ of sintering temperature according to the speed of 0.5 ℃/min.
Fig. 4 is an SEM image of the glass fiber-molybdenum disulfide fiber hybrid prepared in example 3, and comparing fig. 3 and 4, it can be seen that the glass fiber in the glass fiber-molybdenum disulfide fiber hybrid prepared in example 3 is completely covered with synthetic molybdenum disulfide, which allows the fiber hybrid in example 3 to have a larger specific surface area and surface roughness than the glass fiber raw material.
The mechanical properties and tribological properties of the polytetrafluoroethylene composite filled with the hybrid fiber prepared in example 3 were measured in the same manner as in example 1, and the specific results are shown in table 1.
TABLE 1 mechanical and tribological Properties of Polytetrafluoroethylene composites filled with hybrid fibers prepared in examples 1 to 3
Figure BDA0003552836030000101
Figure BDA0003552836030000111
As can be seen from the examples and Table 1, the tensile strength of the composite material prepared by the invention can reach 149.7MPa, the elongation at break can reach 263%, the friction coefficient at room temperature is as low as 0.186, and the wear rate is as low as 2.41 x 10-6mm3Nm, coefficient of friction as low as 0.1 at 200 DEG C63, the wear rate is as low as 3.81X 10-6mm3The composite material has excellent bearing performance, good friction and wear resistance and stable friction coefficient in a wide temperature range. The method provided by the invention obviously improves the interface compatibility between the two fillers of molybdenum disulfide and glass fiber and the polymer matrix, the synergistic effect between the two fillers is fully exerted, and the prepared polytetrafluoroethylene composite material filled with the fiber hybrid has good mechanical property and excellent lubricity (namely antifriction and wear-resistant property).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a polytetrafluoroethylene composite material filled with a fiber hybrid comprises the following steps:
(1) mixing a sulfur source, a molybdenum source, water and glass fiber, and then carrying out hydrothermal reaction to obtain a glass fiber-molybdenum disulfide fiber hybrid;
(2) mixing the glass fiber-molybdenum disulfide fiber hybrid obtained in the step (1) with polytetrafluoroethylene suspension powder to obtain a mixture;
(3) and (3) sequentially carrying out cold press molding and sintering on the mixture obtained in the step (2) to obtain the polytetrafluoroethylene composite material filled with the fiber hybrid.
2. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction in the step (1) is 200 to 240 ℃ and the time of the hydrothermal reaction is 20 to 26 hours.
3. The preparation method according to claim 1, wherein the mass ratio of the glass fiber to the molybdenum disulfide in the glass fiber-molybdenum disulfide fiber hybrid in the step (1) is (0.5-5): 1.
4. the method according to claim 1, wherein the step (2) further comprises, after mixing: drying the mixed product; the drying temperature is 100-140 ℃, and the drying time is 1-3 h.
5. The preparation method according to claim 1, wherein the mass fraction of the glass fiber-molybdenum disulfide fiber hybrid in the mixture in the step (2) is less than or equal to 30%.
6. The preparation method according to claim 1, wherein the pressure for cold press molding in the step (3) is 25 to 60 MPa.
7. The method according to claim 1, wherein the sintering temperature in the step (3) is 350-400 ℃, and the sintering time is 150-400 min.
8. The production method according to claim 1 or 7, wherein the temperature raising manner for the sintering in the step (3) is a stepwise temperature programming.
9. The method of claim 8, wherein the stepwise temperature programming is performed by: in the first stage, the temperature is increased from room temperature to 270-290 ℃ at the speed of 2-3 ℃/min; in the second stage, the temperature is increased from 270 to 290 ℃ to 330 to 350 ℃ at the speed of 1 ℃/min; and in the third stage, the temperature is increased from 330 ℃ to 350 ℃ to the sintering temperature at the speed of 0.5 ℃/min.
10. The polytetrafluoroethylene composite material filled with the fiber hybrid prepared by the preparation method of any one of claims 1 to 9, which comprises polytetrafluoroethylene, glass fibers dispersed in the polytetrafluoroethylene, and molybdenum disulfide loaded on the surfaces of the glass fibers.
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