CN117736784A - MXene-h-BN hybrid and preparation and application thereof, self-lubricating reinforced fabric composite material and preparation thereof - Google Patents
MXene-h-BN hybrid and preparation and application thereof, self-lubricating reinforced fabric composite material and preparation thereof Download PDFInfo
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
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- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
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- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to the technical field of composite materials and lubricating materials, and provides an MXene-h-BN hybrid and preparation and application thereof, a self-lubricating reinforced fabric composite material and preparation thereof. According to the invention, the functionalized h-BN and the silanized MXene are subjected to mercapto-ene click reaction under the action of a thermal initiator, so as to obtain the MXene-h-BN hybrid. The MXene-h-BN hybrid prepared by the method has the advantages of good thermal conductivity, high strength and good dispersibility, and the MXene-h-BN hybrid prepared by the method is used as a reinforcing modifier to modify the self-lubricating fiber fabric, so that the thermal conductivity and tribological property of the self-lubricating fiber fabric are obviously improved, and the service stability and service life of the self-lubricating fiber fabric serving as a moving part of a lubricating layer are prolonged.
Description
Technical Field
The invention relates to the technical field of composite materials and lubricating materials, in particular to an MXene-h-BN hybrid and preparation and application thereof, a self-lubricating reinforced fabric composite material and preparation thereof.
Background
The self-lubricating joint bearing has the advantages of small volume, light weight, no maintenance, high reliability and the like, and replaces the traditional oil and fat lubricating bearings on important parts of the solar sailboard unfolding mechanism of the spacecraft, the landing gear of the airplane, the screw propeller of the helicopter, the hinge joint of large-scale hydraulic equipment and the like. The excellent performance of self-lubricating knuckle bearings depends largely on the self-lubricating lining material between the inner and outer rings of the bearing, mainly including metal and ceramic matrix composites, solid self-lubricating films, polymers and their filled composites and self-lubricating fibrous fabric composites. The self-lubricating fiber fabric composite material has the characteristics of high tensile strength, high modulus, excellent wear resistance, good fatigue performance, strong designability and the like, has a large number of applications in key parts such as engines, landing gears, flap and the like of aviation aircrafts at home and abroad, and has very wide application prospects.
However, conventional fabric composites tend to accumulate a significant amount of frictional heat during the rubbing process, which can result in significant wear and premature failure of the friction material. In general, the incorporation of nanofillers (e.g., inorganic nanoparticles, nanowires, graphene oxide) into textile composites is a promising approach to enhance polymer composite properties. Unlike conventional fillers, the nano-effect of the nanoparticles can exhibit higher interactions with the matrix, providing unique properties. MXene is favored in all respects because of its high thermal conductivity, abundant surface functionality, and excellent mechanical properties. Interestingly, MXene is also a promising alternative lubricant in composites, enhancing tribological properties. However, van der Waals interactions between the original MXene nanoplatelets make the MXene prone to aggregation during collection and processing, further resulting in poor dispersion of the MXene in the resin matrix, limiting its inherent mechanical properties. In addition, the weak interfacial compatibility between MXene and resin increases the interfacial thermal resistance, thereby reducing the potential thermal conductivity of MXene. Thus, it is often desirable to surface modify MXene nanoplatelets that contain rich functional groups to overcome their inherent drawbacks.
Compared with the chemical functionalization of MXene and large/small molecules, the introduction of inorganic materials (forming hybrids) on the surface of MXene is also an effective strategy for further improving the performance of MXene. Hexagonal boron nitride has similar structural and physicochemical characteristics to graphene and exhibits excellent mechanical strength, biocompatibility, and thermal conductivity. The support of nano boron nitride on the MXene sheet not only can prevent the agglomeration of MXene and nano particles, but also can exert the advantages of the nano boron nitride on the MXene sheet to realize special performance.
A great deal of literature reports that hybrids can be prepared by sol-gel methods, in-situ grafting, electrostatic self-assembly and other methods, but the complex conditions, pollution and the like limit the application of the hybrids in various fields. Among them, the sol-gel method is a method of solidifying a compound containing a high chemical active component through a solution, sol, gel, and then performing a heat treatment to obtain an oxide or other compound solid. It is widely used for preparing heat insulating materials, acoustic impedance coupling materials, dielectric materials, organic-inorganic hybrid materials, metal ceramic coating corrosion resistant materials and the like. However. It has mainly the following disadvantages: the price of the used raw materials is relatively high, and some raw materials are organic matters and are harmful to health; usually the whole experimental process requires a long time, often days or weeks; the gel has a plurality of micropores, and a lot of gas and organic matters can escape during the drying process, and shrink. Thus, the mechanical and thermal properties of the hybrids synthesized using the above method may be affected.
Disclosure of Invention
In view of the above, the invention aims to provide an MXene-h-BN hybrid and preparation and application thereof, a self-lubricating reinforced fabric composite material and preparation thereof. The MXene-h-BN hybrid prepared by the method has the advantages of good thermal conductivity, high strength and good dispersibility.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an MXene-h-BN hybrid, which comprises the following steps:
mixing sulfuric acid, hydrogen peroxide and hexagonal boron nitride, and carrying out hydroxylation to obtain hydroxylated hexagonal boron nitride;
functionalizing the hydroxylated hexagonal boron nitride by using a first silane reagent to obtain functionalized h-BN; the first silane reagent is a silane reagent containing double bonds;
ti is treated by LiF+HCl system 3 AlC 2 Etching to obtain an MXene nano-sheet;
mixing the MXene nano-sheet with a second silane reagent, and performing hydrolysis reaction to obtain silanized MXene; the second silane reagent is a sulfhydryl-containing silane reagent;
dispersing the silanized MXene and the functionalized h-BN in a solvent, and performing a sulfhydryl-alkene clicking reaction under the action of a thermal initiator to obtain the MXene-h-BN hybrid.
Preferably, the dosage ratio of the sulfuric acid to the hydrogen peroxide to the hexagonal boron nitride is 5-20 mL: 20-60 mL: 1-8 g; the mass concentration of the sulfuric acid is 60-98%, and the mass concentration of the hydrogen peroxide is 20-30%;
the hydroxylation temperature is 40-80 ℃ and the hydroxylation time is 6-18 h;
the double bond-containing silane reagent comprises gamma-methacryloxypropyl trimethoxysilane and/or vinyl triethoxysilane;
the dosage ratio of the first silane reagent to the hydroxylated hexagonal boron nitride is 2-40 mL: 0.2-6 g;
the temperature of the functionalization is 40-200 ℃ and the time is 4-22 h.
Preferably, the mercapto group-containing silane reagent comprises gamma-mercaptopropyl triethoxysilane and/or gamma-mercaptopropyl trimethoxysilane; the dosage ratio of the MXene nano-sheet to the second silane reagent is 0.4-8 g: 4-60 mL;
the temperature of the hydrolysis reaction is 60-220 ℃ and the time is 4-22 h.
Preferably, the mass ratio of the silanized MXene to the functionalized h-BN is 0.06-2: 0.08 to 4;
the thermal initiator is azodiisobutyronitrile and/or benzoyl peroxide;
the mass ratio of the silanized MXene to the thermal initiator is 0.06-2: 0.002-0.8;
the temperature of the sulfhydryl-alkene clicking reaction is 20-160 ℃ and the time is 2-16 h.
The invention also provides the MXene-h-BN hybrid prepared by the preparation method.
The invention also provides application of the MXene-h-BN hybrid in the self-lubricating reinforced fabric composite material.
The invention also provides a self-lubricating reinforced fabric composite material, which is prepared from the following raw materials: MXene-h-BN hybrids, adhesives and self-lubricating fiber fabrics;
the adhesive is resin;
the self-lubricating fiber fabric is PPS/PTFE self-lubricating liner material;
the mass of the MXene-h-BN hybrid is 0.8-16% of the mass of the adhesive.
Preferably, the resin is one or two of phenolic resin, polyimide resin, epoxy resin and polyamideimide;
the weave structure of the PPS/PTFE self-lubricating liner material is one of plain weave, twill, satin weave or evolutionary weave structure;
the PPS/PTFE self-lubricating lining material has the warp density of 240-400 and the weft density of 220-360.
The invention also provides a preparation method of the self-lubricating reinforced fabric composite material, which comprises the following steps:
dispersing the MXene-h-BN hybrid in the adhesive to obtain filler dispersion glue solution;
carrying out surface activation on the self-lubricating fiber fabric by utilizing air plasma etching to obtain an activated self-lubricating fiber fabric;
and immersing the activated self-lubricating fiber fabric in the filler dispersion glue solution, fishing out, and curing to obtain the self-lubricating reinforced fabric composite material.
Preferably, the power of the air plasma etching is 40-220W, and the time is 6-40 min;
the curing temperature is 100-240 ℃, the pressure is 0.1-1 MPa, the time is 80-200 min, and the rate of heating to the curing temperature is 2-26 ℃/min.
The invention provides a preparation method of an MXene-h-BN hybrid, which comprises the following steps: mixing sulfuric acid, hydrogen peroxide and hexagonal boron nitride, and carrying out hydroxylation to obtain hydroxylated hexagonal boron nitride; functionalizing the hydroxylated hexagonal boron nitride by using a first silane reagent to obtain functionalized h-BN; the first silane reagent is a silane reagent containing double bonds; ti is treated by LiF+HCl system 3 AlC 2 Etching to obtain an MXene nano-sheet; mixing the MXene nano-sheet with a second silane reagent, and performing hydrolysis reaction to obtain silanized MXene; the second silane reagent is a sulfhydryl-containing silane reagent; dispersing the silanized MXene and the functionalized h-BN in a solvent, and performing a sulfhydryl-alkene clicking reaction under the action of a thermal initiator to obtain the MXene-h-BN hybrid.
The method comprises the steps of hydroxylating the h-BN nano-sheet by sulfuric acid and hydrogen peroxide to obtain h-BN-OH; use of LiF+HCl System for Ti 3 AlC 2 Etching to obtainMXene(Ti 3 C 2 ) A nanosheet; functionalizing the hydroxylated h-BN by using a first silane reagent to prepare functionalized h-BN; functionalizing the MXene by using a second silane reagent to prepare silanized MXene; and (3) carrying out sulfhydryl-alkene clicking reaction on the functionalized h-BN and the silanized MXene under the action of a thermal initiator to obtain the MXene-h-BN hybrid. The MXene-h-BN hybrid prepared by the method has the advantages of good thermal conductivity, high strength, good dispersibility and the like, and the MXene-h-BN hybrid prepared by the method is used as a reinforcing modifier to modify the self-lubricating fiber fabric, so that the thermal conductivity and tribological property of the self-lubricating fiber fabric are obviously improved, and the service stability and service life of the self-lubricating fiber fabric serving as a moving part of a lubricating layer are prolonged.
Drawings
FIG. 1 is a graph of h-BN, h-BN-MPS, MXene nanoplatelets (Ti 3 C 2 )、MXene-MPTEs(Ti 3 C 2 -MPTEs) and MXene-h-BN (Ti) 3 C 2 -h-BN);
FIG. 2 is a graph of h-BN, hydroxylated hexagonal boron nitride (h-BN-OH), MXene nanoplatelets (Ti 3 C 2 ) MXene-h-BN (Ti) 3 C 2 -h-BN);
FIG. 3 is the frictional wear data of the self-lubricating textile composites obtained in examples and comparative examples, wherein (a) is the wear rate of the self-lubricating textile composites obtained in examples and comparative examples, and (b) is the coefficient of friction of the self-lubricating textile composites obtained in examples and comparative examples;
FIG. 4 is a wear surface topography of the self-lubricating fabric composite obtained in comparative example 1 and example 1;
FIG. 5 is a graph showing the tensile strength of the self-lubricating fabric composites obtained in the comparative examples and examples;
fig. 6 is a graph of thermal conductivity of the fabric composites of the self-lubricating fabric composites obtained in the comparative examples and examples at room temperature and 150 ℃.
Detailed Description
The invention provides a preparation method of an MXene-h-BN hybrid, which comprises the following steps:
mixing sulfuric acid, hydrogen peroxide and hexagonal boron nitride, and carrying out hydroxylation to obtain hydroxylated hexagonal boron nitride;
functionalizing the hydroxylated hexagonal boron nitride by using a first silane reagent to obtain functionalized h-BN; the first silane reagent is a silane reagent containing double bonds;
ti is treated by LiF+HCl system 3 AlC 2 Etching to obtain an MXene nano-sheet;
mixing the MXene nano-sheet with a second silane reagent, and performing hydrolysis reaction to obtain silanized MXene; the second silane reagent is a sulfhydryl-containing silane reagent;
dispersing the silanized MXene and the functionalized h-BN in a solvent, and performing a sulfhydryl-alkene clicking reaction under the action of a thermal initiator to obtain the MXene-h-BN hybrid.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
Sulfuric acid, hydrogen peroxide and hexagonal boron nitride are mixed and hydroxylated to obtain hydroxylated hexagonal boron nitride.
In the present invention, the mass concentration of the sulfuric acid is preferably 60 to 98%. In the present invention, the mass concentration of the hydrogen peroxide is preferably 20 to 30%.
In the invention, the dosage ratio of the sulfuric acid, the hydrogen peroxide and the hexagonal boron nitride is preferably 5-20 mL: 20-60 mL: 1-8 g.
In the present invention, the temperature of the hydroxylation is preferably 40 to 80℃and the time is preferably 6 to 18 hours.
In the present invention, the mixing of sulfuric acid, hydrogen peroxide and hexagonal boron nitride for hydroxylation preferably comprises: mixing sulfuric acid and hydrogen peroxide to obtain a hydroxylation reagent; dispersing hexagonal boron nitride in water to obtain hexagonal boron nitride dispersion liquid; and adding the hydroxylation reagent into the hexagonal boron nitride dispersion liquid to carry out hydroxylation.
After the hydroxylation, the present invention preferably further comprises: and (3) carrying out solid-liquid separation on the obtained hydroxylation system, and washing and drying the obtained filter residues in sequence. In the present invention, the washing reagent preferably includes water, preferably deionized water, and ethanol, preferably absolute ethanol. In the present invention, the temperature of the drying is preferably 60℃and the time is preferably 2 hours.
After obtaining the hydroxylated hexagonal boron nitride, the invention utilizes a first silane reagent to functionalize the hydroxylated hexagonal boron nitride to obtain functionalized h-BN.
In the present invention, the first silane reagent is a silane reagent containing a double bond; the double bond-containing silane reagent preferably includes gamma-methacryloxypropyl trimethoxysilane (MPS) and/or vinyltriethoxysilane, more preferably gamma-methacryloxypropyl trimethoxysilane (MPS).
In the invention, the dosage ratio of the first silane reagent to the hydroxylated hexagonal boron nitride is preferably 2-40 mL:0.2 g to 6g.
In the present invention, the temperature of the functionalization is preferably 40 to 200℃and the time is preferably 4 to 22 hours. In the present invention, the pH of the functionalization is preferably 2 to 6, more preferably 4. In the present invention, the functionalization is preferably performed under reflux and stirring conditions.
In the present invention, the functionalizing the hydroxylated hexagonal boron nitride with a first silane reagent preferably comprises the steps of: dispersing hydroxylated hexagonal boron nitride in a solvent to obtain hydroxylated hexagonal boron nitride dispersion; and adding a first silane reagent to the hydroxylated hexagonal boron nitride dispersion liquid to perform functionalization. In the present invention, the solvent is preferably ethanol and water; the volume ratio of the ethanol to the water is preferably 2-6: 0.5 to 2, more preferably 3:1, a step of; the ethanol is preferably absolute ethanol and the water is preferably deionized water. In the present invention, the dispersion is preferably performed under ultrasonic conditions, and the time of the dispersion is preferably 40 to 120 minutes.
After the functionalization, the present invention preferably further includes: and (3) carrying out solid-liquid separation on the obtained functionalized system, and washing and drying the obtained filter residues in sequence. In the present invention, the washed reagent is preferably absolute ethanol. In the present invention, the temperature of the drying is preferably 80 ℃.
The invention utilizes LiF+HCl system to process Ti 3 AlC 2 And etching to obtain the MXene nano-sheet.
In the present invention, the concentration of HCl is preferably 6 to 12mol/L. In the present invention, the ratio of LiF to HCl is preferably 1 to 6g: 40-100 mL. In the present invention, the LiF and Ti 3 AlC 2 The dosage ratio of (2) is preferably 1-6 g: 1-8 g.
In the invention, the etching temperature is preferably 30-50 ℃ and the etching time is preferably 24-48 h.
In the present invention, the LiF+HCl system is used for preparing Ti 3 AlC 2 The etching preferably comprises the steps of: carrying out first mixing on lithium fluoride and hydrochloric acid to obtain a first mixed system; ti is mixed with 3 AlC 2 And adding the mixture into the first mixed system to etch. In the present invention, the first mixing is preferably performed under stirring for a period of preferably 5 to 20 minutes.
After the etching, the method preferably comprises the following steps: centrifuging the obtained crude product in deionized water until the pH value of the supernatant is 5-7; dispersing the lower layer precipitate in deionized water, ultrasonic treating and centrifuging to separate Ti 3 C 2 A nanosheet; finally, the obtained dark green supernatant is freeze-dried to obtain single-layer and less-layer Ti 3 C 2 . In the present invention, the rotational speed of the centrifugation is preferably 2000 to 4000rpm, and the time is preferably 1 to 6 minutes.
After the MXene nano-sheets are obtained, the MXene nano-sheets and a second silane reagent are mixed for hydrolysis reaction, so that the silanized MXene is obtained.
In the present invention, the second silane reagent is a mercapto group-containing silane reagent; the mercapto group-containing silane reagent preferably includes γ -mercaptopropyl triethoxysilane (MPTEs) and/or γ -mercaptopropyl trimethoxysilane, and more preferably γ -mercaptopropyl triethoxysilane (MPTEs).
In the invention, the dosage ratio of the MXene nano-sheet to the second silane reagent is preferably 0.4-8 g: 4-60 mL.
In the present invention, the temperature of the hydrolysis reaction is preferably 60 to 220℃and the time is preferably 4 to 22 hours. In the present invention, the pH of the hydrolysis is preferably 2 to 6, more preferably 4. In the present invention, the hydrolysis is preferably performed under reflux and stirring.
In the present invention, the MXene nanoplatelets and the second silane reagent are mixed to perform a hydrolysis reaction preferably comprising: dispersing the MXene nano-sheets in a solvent to obtain MXene nano-sheet dispersion liquid; and adding a second silane reagent into the MXene nano-sheet dispersion liquid to perform hydrolysis reaction. In the present invention, the solvent is preferably ethanol and water, and the volume ratio of the ethanol to the water is preferably 2 to 6:0.5 to 2, more preferably 3:1, a step of; the ethanol is preferably absolute ethanol and the water is preferably deionized water. In the present invention, the dispersion is preferably performed under ultrasonic conditions, and the time of the dispersion is preferably 40 to 120 minutes.
After the hydrolysis reaction, the present invention preferably further comprises: and (3) carrying out solid-liquid separation on the obtained hydrolysis reaction system, and washing and drying the obtained filter residues in sequence. In the present invention, the washed reagent is preferably absolute ethanol. In the present invention, the drying temperature is preferably 60 to 80 ℃.
After the functionalized h-BN and the silanized MXene are obtained, the silanized MXene and the functionalized h-BN are dispersed in a solvent, and a sulfhydryl-alkene clicking reaction is carried out under the action of a thermal initiator, so that the MXene-h-BN hybrid is obtained.
In the present invention, the solvent is preferably N, N-Dimethylformamide (DMF). In the present invention, the ratio of the amount of the silylated MXene to the solvent is preferably 06 to 2g: 80-400 mL.
In the invention, the mass ratio of the silanized MXene to the functionalized h-BN is preferably 0.06-2: 0.08 to 4.
In the present invention, the dispersion is preferably performed under ultrasonic conditions, and the time of the dispersion is preferably 20 to 140 minutes.
In the present invention, the thermal initiator is preferably azobisisobutyronitrile and/or benzoyl peroxide, and more preferably Azobisisobutyronitrile (AIBN). In the invention, the mass ratio of the silylated MXene to the thermal initiator is preferably 0.06-2: 0.002-0.8.
In the invention, the temperature of the mercapto-ene click reaction is preferably 20-160 ℃ and the time is preferably 2-16 h. In the present invention, the mercapto-ene click reaction is preferably performed under stirring.
After the mercapto-ene click reaction, the present invention preferably further comprises: and (3) carrying out solid-liquid separation on the obtained sulfhydryl-alkene click reaction system, and washing and drying the obtained filter residues in sequence. In the present invention, the washed reagent is preferably absolute ethanol. In the present invention, the drying temperature is preferably 40 to 100 ℃.
The invention also provides the MXene-h-BN hybrid prepared by the preparation method.
The invention also provides application of the MXene-h-BN hybrid in the self-lubricating reinforced fabric composite material.
The invention also provides a self-lubricating reinforced fabric composite material, which is prepared from the following raw materials: MXene-h-BN hybrids, adhesives and self-lubricating fiber fabrics.
The preparation raw materials of the self-lubricating reinforced fabric composite material provided by the invention comprise MXene-h-BN hybrid. In the invention, the mass of the MXene-h-BN hybrid is 0.8 to 16 percent of the mass of the adhesive.
The preparation raw materials of the self-lubricating reinforced fabric composite material provided by the invention comprise an adhesive, wherein the adhesive is resin. In the present invention, the resin is preferably one or two of a phenol resin, a polyimide resin, an epoxy resin, and a polyamideimide.
The preparation raw materials of the self-lubricating reinforced fabric composite material provided by the invention comprise self-lubricating fiber fabrics, wherein the self-lubricating fiber fabrics are PPS/PTFE self-lubricating liner materials. In the invention, the weave structure of the PPS/PTFE self-lubricating gasket material is preferably one of plain weave, twill weave, satin weave or evolutionary weave; the evolving structure preferably comprises a plain evolving structure, a twill evolving structure, a satin evolving structure, a plain-twill evolving structure, a plain-satin evolving structure, a twill-satin evolving structure or a plain-twill-satin evolving structure. In the present invention, the PPS/PTFE self-lubricating liner material preferably has a warp density of 240 to 400 and a weft density of 220 to 360. In the present invention, the reinforcing fibers of the PPS/PTFE self-lubricating liner material are preferably PPS fibers, and the lubricating fibers are preferably PTFE fibers.
The invention also provides a preparation method of the self-lubricating reinforced fabric composite material, which comprises the following steps:
dispersing the MXene-h-BN hybrid in the adhesive to obtain filler dispersion glue solution;
carrying out surface activation on the self-lubricating fiber fabric by utilizing air plasma etching to obtain an activated self-lubricating fiber fabric;
and immersing the activated self-lubricating fiber fabric in the filler dispersion glue solution, fishing out, and curing to obtain the self-lubricating reinforced fabric composite material.
The invention disperses the MXene-h-BN hybrid in the adhesive to obtain filler dispersed glue solution.
In the present invention, the types and amounts of the MXene-h-BN hybrid and the adhesive are the same as those of the above technical solutions, and will not be described herein.
The invention utilizes air plasma etching to perform surface activation on the self-lubricating fiber fabric to obtain the activated self-lubricating fiber fabric.
The invention preferably further comprises a pretreatment prior to the surface activation of the self-lubricating fiber fabric, wherein the pretreatment preferably comprises desizing, cleaning and drying. In the present invention, the cleaning is capable of washing off the finish of the self-lubricating fiber fabric.
In the invention, the power of the air plasma etching is preferably 40-220W, and the time is preferably 6-40 min.
After the activated self-lubricating fiber fabric is obtained, the activated self-lubricating fiber fabric is immersed in the filler dispersion glue solution, fished out and cured, and the self-lubricating reinforced fabric composite material is obtained.
After the impregnation, the invention preferably further comprises drying; the temperature of the drying is preferably 35-80 ℃; the drying is preferably carried out in an oven.
In the invention, after the impregnation is carried out until the impregnation is dried, the PPS/PTFE fiber fabric accounts for 50 to 80 weight percent.
In the present invention, the curing temperature is preferably 100 to 240 ℃, the pressure is preferably 0.1 to 1MPa, the time is preferably 80 to 200min, and the rate of heating to the curing temperature is preferably 2 to 26 ℃/min.
The MXene-h-BN hybrids and their preparation and use, the self-lubricating reinforced fabric composites and their preparation provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Comparative example 1
(1) PPS fiber and PTFE fiber are adopted to weave PPS/PTFE fiber fabric grey cloth (the warp density is 326, the weft density is 290, and the weave structure is twill), and the grey cloth is dried for standby after desizing and cleaning with fiber surface oiling agent; then, the fiber fabric grey cloth is subjected to fiber surface activation treatment in air plasma, the plasma treatment power is 200W, and the time is 10min, so that the activated self-lubricating fiber fabric is obtained.
(2) And repeatedly dipping the activated self-lubricating fiber fabric in a phenolic resin solution until the mass fraction of the fabric reaches 75+/-5 wt%, obtaining an uncured PPS/PTFE fiber fabric (Pure FC), bonding the uncured PPS/PTFE fiber fabric on the surface of a metal substrate by adopting a phenolic resin adhesive, and curing for 2 hours at 184 ℃ to obtain a lubricating fiber fabric composite material test piece.
(3) Under the room temperature environment, the dynamic load of 30MPa and the rotating speed of 760 revolutions per minute, the friction test is carried out for 2 hours, and the average friction coefficient and the wear rate of the self-lubricating fabric composite material are respectively as follows: 0.0479,2.79 ×10 -14 m 3 /N·m。
Comparative example 2
(1) PPS fiber and PTFE fiber are adopted to weave PPS/PTFE fiber fabric grey cloth (the radial density is 326, the weft density is 290, and the weave structure is twill), and the grey cloth is dried for standby after desizing and cleaning with fiber surface oiling agent; then, the fiber fabric grey cloth is subjected to fiber surface activation treatment in air plasma, the plasma treatment power is 200W, and the time is 10min, so that the activated self-lubricating fiber fabric is obtained.
(2) Repeatedly dipping the activated self-lubricating fiber fabric in a phenolic resin solution containing h-BN (the mass fraction of the h-BN relative to the phenolic resin is 1 wt%) until the mass fraction of the fabric reaches 75+/-5 wt%, obtaining an uncured PPS/PTFE fiber fabric (h-BN/FC), bonding the uncured PPS/PTFE fiber fabric on the surface of a metal substrate by adopting a phenolic resin adhesive, and curing for 2 hours at 184 ℃ to obtain a self-lubricating fiber fabric composite material test piece.
(3) Under the room temperature environment, the dynamic load of 30MPa and the rotating speed of 760 revolutions per minute, the friction test is carried out for 2 hours, and the average friction coefficient and the wear rate of the self-lubricating fabric composite material are respectively as follows: 0.0457,2.09 ×10 -14 m 3 /N·m。
Comparative example 3
(1) PPS fiber and PTFE fiber are adopted to weave PPS/PTFE fiber fabric grey cloth (the warp density is 326, the weft density is 290, and the weave structure is twill), and the grey cloth is dried for standby after desizing and cleaning with fiber surface oiling agent; then, the fiber fabric grey cloth is subjected to fiber surface activation treatment in air plasma, the plasma treatment power is 200W, and the time is 10min, so that the activated self-lubricating fiber fabric is obtained.
(2) To functionalize h-BN, 0.5g h-BN-OH is added to a volume ratio of 3:1 and carrying out ultrasonic treatment for 60min to obtain the h-BN-OH dispersion liquid. Then 6mL of MPS was added to the h-BN-OH dispersion and the pH of the solution was adjusted to 4 with acetic acid to further promote hydrolysis. The mixture was reacted at 80℃under magnetic stirring for 6h under reflux. Finally, the product was washed with absolute ethanol several times and dried at 80℃to give vinyl-functionalized h-BN, designated h-BN-MPS.
(3) Repeatedly dipping the activated self-lubricating fiber fabric in a phenolic resin solution of h-BN-MPS (the mass fraction of the h-BN-MPS relative to phenolic resin is 1 wt%) until the mass fraction of the fabric reaches 75+/-5 wt%, obtaining an uncured PPS/PTFE fiber fabric (h-BN-MPS/FC), bonding the uncured PPS/PTFE fiber fabric on the surface of a metal substrate by adopting a phenolic resin adhesive, and curing for 2 hours at 184 ℃ to obtain a self-lubricating fiber fabric composite material test piece.
(4) Under the room temperature environment, the dynamic load of 30MPa and the rotating speed of 760 revolutions per minute, the friction test is carried out for 2 hours, and the average friction coefficient and the wear rate of the self-lubricating fabric composite material are respectively as follows: 0.0467,1.75 ×10 -14 m 3 /N·m。
The preparation method of the h-BN-OH comprises the following steps: 2g h-BN was placed in a beaker containing 200mL of ethanol and sonicated at room temperature for 1h to disperse it uniformly. Subsequently, 10mL of sulfuric acid (98% by mass) and 30mL of hydrogen peroxide (30% by mass) were mixed according to 1:3 was added dropwise to the h-BN dispersion. The mixture was stirred continuously at 60℃for about 12h. After the reaction was completed, the hydroxylated h-BN was collected by centrifugation and washed several times with deionized water and ethanol. Finally, the product was dried at 60℃for 2h, and the material prepared was labeled as h-BN-OH.
Comparative example 4
(1) PPS fiber and PTFE fiber are adopted to weave PPS/PTFE fiber fabric grey cloth (the warp density is 326, the weft density is 290, and the weave structure is twill), and the grey cloth is dried for standby after desizing and cleaning with fiber surface oiling agent; then, the fiber fabric grey cloth is subjected to fiber surface activation treatment in air plasma, the plasma treatment power is 200W, and the time is 10min, so that the activated self-lubricating fiber fabric is obtained.
(2) Incorporating activated self-lubricating fiber fabrics in Ti 3 C 2 Is contained in the phenolic resin solution (Ti) 3 C 2 The impregnation was repeated until the mass fraction of the fabric reached 75.+ -. 5wt% with respect to the mass fraction of the phenolic resin of 1wt%, to obtain an uncured PPS/PTFE fiber fabric (Ti) 3 C 2 And (FC), bonding the fiber to the surface of a metal substrate by adopting a phenolic resin adhesive, and curing the fiber at 184 ℃ for 2 hours to obtain the self-lubricating fiber fabric composite material test piece.
(3) Under the room temperature environment, the dynamic load of 30MPa and the rotating speed of 760 revolutions per minute, the friction test is carried out for 2 hours, and the average friction coefficient and the wear rate of the self-lubricating fabric composite material are respectively as follows: 0.0476,1.84 ×10 -14 m 3 /N·m。
Wherein Ti is 3 C 2 The preparation method of the (C) comprises the following steps: will be2g of lithium fluoride was stirred in 60mL of hydrochloric acid (9 mol/L) for 10min. Subsequently 2g of Ti 3 AlC 2 Slowly add to the mixed solution and stir the mixture at 45 ℃ for 36 hours. After the etching reaction was completed, the crude product was centrifuged (3500 rpm,3 min) in deionized water until the supernatant pH was 7. Then, the lower precipitate was dispersed in deionized water, sonicated and centrifuged to exfoliate Ti 3 C 2 A nano-sheet. Finally, the obtained dark green supernatant is freeze-dried to obtain single-layer and less-layer Ti 3 C 2 。
Comparative example 5
(1) PPS fiber and PTFE fiber are adopted to weave PPS/PTFE fiber fabric grey cloth (the warp density is 326, the weft density is 290, and the weave structure is twill), and the grey cloth is dried for standby after desizing and cleaning with fiber surface oiling agent; then, the fiber fabric grey cloth is subjected to fiber surface activation treatment in air plasma, the plasma treatment power is 200W, and the time is 10min, so that the activated self-lubricating fiber fabric is obtained.
(2) To at Ti 3 C 2 Surface acquisition of-SH groups, ti 3 C 2 Nanoplatelets (access mode same as comparative example 4) were MPTEs functionalized: in a typical process, 0.5g Ti is used 3 C 2 Added into the mixture with the volume ratio of 3:1 in a mixed solution of absolute ethanol and deionized water and performing ultrasonic dispersion for 1h to obtain Ti 3 C 2 And (3) a dispersion. Then 6mL of MPTEs was added to Ti 3 C 2 In the dispersion, to further promote hydrolysis, the pH of the solution was adjusted to 4 with acetic acid, and the dispersion was refluxed for 6 hours at 80℃under magnetic stirring. Finally, washing the product with absolute ethyl alcohol for multiple times and drying at 80 ℃ to obtain the mercapto-functionalized Ti 3 C 2 Designated as MXene-MPTEs.
(3) Incorporating activated self-lubricating fiber fabrics in Ti 3 C 2 In phenolic resin solution of MPTEs (Ti 3 C 2 -MPTEs 1wt% relative to phenolic resin, repeatedly impregnating until the fabric mass fraction reaches 75+ -5 wt%, to obtain uncured PPS/PTFE fiber fabric (Ti 3 C 2 MPTEs/FC) bonded to metal substrates using phenolic resin adhesivesAnd (3) curing the surface at 184 ℃ for 2 hours to obtain the self-lubricating fiber fabric composite material test piece.
(4) Under the room temperature environment, the dynamic load of 30MPa and the rotating speed of 760 revolutions per minute, the friction test is carried out for 2 hours, and the average friction coefficient and the wear rate of the self-lubricating fabric composite material are respectively as follows: 0.0482,1.45 ×10 -14 m 3 /N·m。
Example 1
(1) PPS fiber and PTFE fiber are adopted to weave PPS/PTFE fiber fabric grey cloth (the warp density is 326, the weft density is 290, and the weave structure is twill), and the grey cloth is dried for standby after desizing and cleaning with fiber surface oiling agent; then, the fiber fabric grey cloth is subjected to fiber surface activation treatment in air plasma, the plasma treatment power is 200W, and the time is 10min, so that the activated self-lubricating fiber fabric is obtained.
(2) And (3) grafting h-BN on the surface of the MXene rapidly by adopting a sulfhydryl-alkene click reaction, so that a novel three-dimensional point plane structure is constructed.
First, 0.2g of MXene-MPTEs (obtained in the same manner as comparative example 5) and 0.2. 0.2g h-BN-MPS (obtained in the same manner as comparative example 3) were dissolved in 200mL of DMF and dispersed by ultrasound for 60min. Then, 0.008g of AIBN was added to the mixed solution as a thermal initiator of the click reaction, and the mixture was reacted at 80℃under magnetic stirring for 4 hours. Finally, washing the product with a large amount of absolute ethyl alcohol, removing ungrafted substances, and drying at 80 ℃ to obtain Ti 3 C 2 -h-BN nanohybrids.
(3) Incorporating activated self-lubricating fiber fabrics in Ti 3 C 2 In the phenolic resin solution of-h-BN (Ti 3 C 2 -h-BN with respect to the phenolic resin, 1 wt.% and repeatedly impregnating until the fabric mass fraction reached 75.+ -. 5 wt.% to obtain an uncured PPS/PTFE fiber fabric (Ti) 3 C 2 And (3) h-BN/FC), bonding the fiber fabric composite material on the surface of a metal substrate by adopting a phenolic resin adhesive, and curing the fiber fabric composite material at 184 ℃ for 2 hours to obtain a self-lubricating fiber fabric composite material test piece.
(4) Under the room temperature environment, the dynamic load of 30MPa and the rotating speed of 760r/min are adopted, the friction test is carried out for 2 hours, and the average friction coefficient and the wear rate of the self-lubricating fabric composite material are respectively as follows: 0.0475,1.02 ×10 -14 m 3 /N·m。
FIG. 1 is a graph of h-BN, h-BN-MPS, MXene nanoplatelets (Ti 3 C 2 )、MXene-MPTEs(Ti 3 C 2 -MPTEs) and MXene-h-BN (Ti) 3 C 2 -h-BN), as can be seen from figure 1: h-BN shows a good crystalline structure and distinct characteristic peaks appear at the (002) and (004) planes. The characteristic peak of MXene at 6.1 ° corresponds to the (002) crystal plane. For Ti 3 C 2 Two typical strong diffraction peaks were observed around 6.2℃and 27.3℃indicating that h-BN was grafted onto the MXene surface.
FIG. 2 is a graph of h-BN, hydroxylated hexagonal boron nitride (h-BN-OH), MXene nanoplatelets (Ti 3 C 2 ) MXene-h-BN (Ti) 3 C 2 -h-BN), as can be seen from figure 2: the spectrum of h-BN shows that B1s, N1s and O1s are unimodal and the binding energy is 192.3eV, 396.4eV and 524.6eV, respectively. At Ti 3 C 2 In the h-BN hybrids Ti2p, S2p and Si2p are present. The characterization analysis proves that the MXene-h-BN nano functional material with the three-dimensional point plane structure is successfully prepared.
The frictional wear performance of the self-lubricating fabric composites obtained in examples and comparative examples was evaluated by using a Xuanwu No. three frictional wear tester (contact mode: pin-disc, rotation speed 760r/min, load 30 MPa), and the results are shown in FIG. 3, wherein FIG. 3 shows the frictional wear data of the self-lubricating fabric composites obtained in examples and comparative examples, and (a) shows the wear rate of the self-lubricating fabric composites obtained in examples and comparative examples, and (b) shows the friction coefficient of the self-lubricating fabric composites obtained in examples and comparative examples; as shown in fig. 3, the pure PPS/PTFE self-lubricating material has a higher wear rate, and the PTFE fibers directly contact the dual, reducing the coefficient of friction. After nano material is added, the abrasion rate of PPS/PTFE self-lubricating material is obviously reduced, ti 3 C 2 h-BN/FC exhibit minimal wear rates.
FIG. 4 shows the wear surface topography of the self-lubricating textile composites obtained in comparative example 1 and example 1, wherein (a) is the wear surface topography of the self-lubricating textile composite obtained in comparative example 1 and (b) is the wear surface topography of the self-lubricating textile composite obtained in example 1; as is apparent from fig. 4: pure PPS-The wear surface of the PTFE self-lubricating material has numerous cracks, and the resin falls off causing many fibers to pull out and become severed, the primary wear mechanism being abrasive wear. For Ti 3 C 2 h-BN/FC, the wear surface of which is the smoothest, the fibers are tightly protected by the resin, and only some abrasive dust and tiny grooves appear, which indicates that the addition of MXene-h-BN helps to increase the bearing capacity of the PPS/PTFE self-lubricating fiber fabric composite material and increases the shearing resistance of the resin.
Fig. 5 shows the tensile strength of the self-lubricating textile composites obtained in the comparative examples and examples. Compared with pure PPS/PTFE fabric composite material (123.42 MPa), ti is added 3 C 2 The tensile strength of the fabric composite material of-h-BN reaches the maximum 165.69MPa, which is increased by 34.25%. This suggests that h-BN particles, in combination with MXene sheets, can form a specific three-dimensional point-plane structure, can be better dispersed in a resin matrix and form a gradient modulus with the resin interface, and effectively transfer stress.
Fig. 6 is a graph of thermal conductivity of the fabric composites of the self-lubricating fabric composites obtained in the comparative examples and examples at room temperature and 150 ℃. The thermal conductivity of the additive-added fabric composite is improved compared to pure FC. It was found that the thermal conductivity of the original FC was about 0.179W/mK at room temperature and about 0.201W/mK at 150 ℃. In contrast, ti 3 C 2 The thermal conductivity of the h-BN/FC is highest and is 0.286W/mK and 0.288W/mK at room temperature and 150℃respectively. This result indicates Ti having a three-dimensional point-plane structure 3 C 2 The h-BN provides a unique heat transfer network path for phonons and electrons, improves the movement speed of the phonons and slows down the scattering of the phonons. In addition, ti with a large specific surface area 3 C 2 h-BN is capable of forming continuous, interconnected heat conducting channels and plays an important role in reducing interfacial thermal resistance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the MXene-h-BN hybrid is characterized by comprising the following steps of:
mixing sulfuric acid, hydrogen peroxide and hexagonal boron nitride, and carrying out hydroxylation to obtain hydroxylated hexagonal boron nitride;
functionalizing the hydroxylated hexagonal boron nitride by using a first silane reagent to obtain functionalized h-BN; the first silane reagent is a silane reagent containing double bonds;
ti is treated by LiF+HCl system 3 AlC 2 Etching to obtain an MXene nano-sheet;
mixing the MXene nano-sheet with a second silane reagent, and performing hydrolysis reaction to obtain silanized MXene; the second silane reagent is a sulfhydryl-containing silane reagent;
dispersing the silanized MXene and the functionalized h-BN in a solvent, and performing a sulfhydryl-alkene clicking reaction under the action of a thermal initiator to obtain the MXene-h-BN hybrid.
2. The method according to claim 1, wherein the ratio of sulfuric acid, hydrogen peroxide and hexagonal boron nitride is 5-20 mL: 20-60 mL: 1-8 g; the mass concentration of the sulfuric acid is 60-98%, and the mass concentration of the hydrogen peroxide is 20-30%;
the hydroxylation temperature is 40-80 ℃ and the hydroxylation time is 6-18 h;
the double bond-containing silane reagent comprises gamma-methacryloxypropyl trimethoxysilane and/or vinyl triethoxysilane;
the dosage ratio of the first silane reagent to the hydroxylated hexagonal boron nitride is 2-40 mL: 0.2-6 g;
the temperature of the functionalization is 40-200 ℃ and the time is 4-22 h.
3. The preparation method according to claim 1, wherein the mercapto group-containing silane reagent comprises γ -mercaptopropyl triethoxysilane and/or γ -mercaptopropyl trimethoxysilane;
the dosage ratio of the MXene nano-sheet to the second silane reagent is 0.4-8 g: 4-60 mL;
the temperature of the hydrolysis reaction is 60-220 ℃ and the time is 4-22 h.
4. The preparation method according to claim 1, wherein the mass ratio of the silylated MXene to the functionalized h-BN is 0.06-2: 0.08 to 4;
the thermal initiator is azodiisobutyronitrile and/or benzoyl peroxide;
the mass ratio of the silanized MXene to the thermal initiator is 0.06-2: 0.002-0.8;
the temperature of the sulfhydryl-alkene clicking reaction is 20-160 ℃ and the time is 2-16 h.
5. An MXene-h-BN hybrid produced by the production process according to any one of claims 1 to 4.
6. Use of an MXene-h-BN hybrid as defined in claim 5 in a self-lubricating reinforced fabric composite.
7. The self-lubricating reinforced fabric composite material is characterized by comprising the following preparation raw materials: MXene-h-BN hybrids, adhesives and self-lubricating fiber fabrics;
the adhesive is resin;
the self-lubricating fiber fabric is PPS/PTFE self-lubricating liner material;
the mass of the MXene-h-BN hybrid is 0.8-16% of the mass of the adhesive.
8. The self-lubricating reinforced fabric composite of claim 7, wherein the resin is one or two of phenolic resin, polyimide resin, epoxy resin, and polyamideimide;
the weave structure of the PPS/PTFE self-lubricating liner material is one of plain weave, twill, satin weave or evolutionary weave structure;
the PPS/PTFE self-lubricating lining material has the warp density of 240-400 and the weft density of 220-360.
9. A method of making a self-lubricating reinforced fabric composite as claimed in claim 7 or 8, comprising the steps of:
dispersing the MXene-h-BN hybrid in the adhesive to obtain filler dispersion glue solution;
carrying out surface activation on the self-lubricating fiber fabric by utilizing air plasma etching to obtain an activated self-lubricating fiber fabric;
and immersing the activated self-lubricating fiber fabric in the filler dispersion glue solution, fishing out, and curing to obtain the self-lubricating reinforced fabric composite material.
10. The method according to claim 9, wherein the power of the air plasma etching is 40-220W for 6-40 min;
the curing temperature is 100-240 ℃, the pressure is 0.1-1 MPa, the time is 80-200 min, and the rate of heating to the curing temperature is 2-26 ℃/min.
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