CN116285170A - Polytetrafluoroethylene composite material and preparation method and application thereof - Google Patents
Polytetrafluoroethylene composite material and preparation method and application thereof Download PDFInfo
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 82
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 82
- -1 Polytetrafluoroethylene Polymers 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 28
- 239000004917 carbon fiber Substances 0.000 claims abstract description 28
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 25
- 239000002135 nanosheet Substances 0.000 claims abstract description 24
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 229920006389 polyphenyl polymer Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 235000010216 calcium carbonate Nutrition 0.000 claims abstract description 9
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims abstract 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000009832 plasma treatment Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005461 lubrication Methods 0.000 claims description 4
- 239000002064 nanoplatelet Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polytetrafluoroethylene composite material, a preparation method and application thereof, wherein the polytetrafluoroethylene composite material comprises the following components in parts by weight: 75-95 parts of polytetrafluoroethylene, 10-20 parts of nano CaCO3, 5-10 parts of graphene nano sheets, 2-8 parts of graphite micro powder, 1-5 parts of hydrogen peroxide, 0.1-5 parts of absolute ethyl alcohol, 1-7 parts of sodium dodecyl benzene sulfonate SDBS, 10-15 parts of carbon fiber, 0.1-1 part of antimony trioxide and 12-18 parts of polyphenyl ester. The impact strength, the elastic modulus and the elongation at break of the composite material are obviously improved by filling the nano calcium carbonate and the carbon fiber with the modified PTFE resin, and the composite material has good comprehensive mechanical property and great economic popularization value.
Description
Technical Field
The invention relates to the technical field of lubricating sealing materials, in particular to a polytetrafluoroethylene composite material and a preparation method and application thereof.
Background
Polytetrafluoroethylene, commonly known as "plastic king", is a high molecular polymer prepared by polymerizing tetrafluoroethylene as a monomer, has a chemical formula of (C2F 4) n, has excellent heat resistance and cold resistance, and can be used for a long time at-180-260 ℃. The material has the characteristics of acid resistance, alkali resistance and resistance to various organic solvents, and is almost insoluble in all solvents. Meanwhile, polytetrafluoroethylene has the characteristic of high temperature resistance, and has extremely low friction coefficient, so the polytetrafluoroethylene can be used for lubrication, and also becomes an ideal paint for easily cleaning the inner layer of the water pipe.
Polytetrafluoroethylene (PTFE) has a microstructure of a ribbon-like polycrystal, and relative slip between wafers is easy, so that it has good self-lubricity in both atmosphere and vacuum; in addition, the friction coefficient of PTFE is very low, is the lowest in solid matters, and the dynamic and static friction coefficients of PTFE are close, so that PTFE is a widely used solid lubricating material; in addition, in all polymers, the polytetrafluoroethylene has outstanding high and low temperature resistance and can be used in the temperature range of-190 to 260 ℃. Meanwhile, PTFE is hardly corroded by chemicals, shows excellent chemical stability, and is widely applied to inner wall materials of chemical reaction vessels. The surface energy of PTFE is very low, has excellent non-stick property, and is used for surface coating treatment of other materials; the chemical stability, biological inertia and antithrombotic property can be used for preparing biological materials. PTFE is therefore widely used in the chemical, electro-electrical and mechanical industries.
However, pure PTFE resin has a large expansion coefficient and the dimensional stability of the product is poor; PTFE is also a poor conductor of heat, which makes PTFE articles susceptible to localized overheating during operation; the materials are also low in hardness, poor in abrasion resistance, and often exhibit a large "cold flow" (creep) phenomenon under large loads. These factors greatly limit the further scope of application of PTFE as an engineering plastic, particularly in the field of machining.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a polytetrafluoroethylene composite material, a preparation method and application thereof, wherein the nano calcium carbonate and carbon fiber are used for filling modified PTFE resin, so that the impact strength, the elastic modulus and the elongation at break of the obtained composite material are obviously improved, and the composite material has good comprehensive mechanical properties and great economic popularization value.
The above object of the present invention is achieved by the following technical solutions:
the polytetrafluoroethylene composite material comprises the following components in parts by weight: 75-95 parts of polytetrafluoroethylene and 10-20 parts of nano CaCO 3 5-10 parts of graphene nano-sheets, 2-8 parts of graphite micro powder, 1-5 parts of hydrogen peroxide, 0.1-5 parts of absolute ethyl alcohol, 1-7 parts of sodium dodecyl benzene sulfonate SDBS, 10-15 parts of carbon fibers, 0.1-1 part of antimony trioxide and 12-18 parts of polyphenyl ester.
The present invention may be further configured in a preferred example to: the average lamellar thickness of the graphene nano-sheets is 15-25mm.
The present invention may be further configured in a preferred example to: the volume fraction of the hydrogen peroxide is 25% -35%.
The present invention may be further configured in a preferred example to: the particle diameter d of the graphite micro powder is less than or equal to 30um.
The present invention may be further configured in a preferred example to: the diameter of the carbon fiber is 5-8um.
The present invention may be further configured in a preferred example to: said nano CaCO 3 The particle size distribution is 40-80nm.
A preparation method of a polytetrafluoroethylene composite material comprises the following steps:
s1, performing pre-oxidation treatment on graphene nano sheets by adopting hydrogen peroxide, performing surface activation treatment on the pre-oxidized graphene by adopting a KH550 absolute ethanol solution with the mass fraction of 1% and an SDBS aqueous solution with the mass concentration of 1mg/mL, and performing ultrasonic dispersion, vacuum suction filtration, washing and drying to obtain surface modified graphene nano sheets;
s2, mixing and stirring 75-95 parts of polytetrafluoroethylene, 10-20 parts of nano CaCO3 and 10-15 parts of carbon fiber uniformly, filtering out the carbon fiber, heating to remove water, heating to 350 ℃, removing small molecules in the emulsion, and performing argon plasma treatment. Performing flowing type radio frequency discharge by adopting an external electrode and a 14MHz radio frequency power generator, wherein the argon pressure is 50Pa, the discharge power is 100W, the discharge time is 3-12 min, and the modified carbon fiber and polytetrafluoroethylene resin are uniformly dispersed to form a mixture;
s3, adding 2-8 parts of graphite micro powder, 0.1-1 part of antimonous oxide, 12-18 parts of polyphenyl ester and surface modified graphene nano sheets into the mixture according to a certain proportion, mixing uniformly by adopting a mechanical stirring mode, cold-pressing and molding at room temperature, then placing a pressed and molded sample into a high-temperature sintering furnace, heating to 350-380 ℃ at a heating rate of 40-100 ℃/hour, and carrying out heat preservation and sintering for 2.5 hours; naturally cooling to room temperature to obtain the polytetrafluoroethylene composite material.
The present invention may be further configured in a preferred example to: in step S3, the set value of the applied pressure is 35MPa and the dwell time is 5-15min in the cold press molding process.
The invention also discloses an application of the polytetrafluoroethylene composite material prepared by the technical scheme or the preparation method in the lubrication sealing field.
In summary, the present invention includes at least one of the following beneficial technical effects:
the invention discloses a polytetrafluoroethylene composite material, which comprises the following components in parts by weight: 75-95 parts of polytetrafluoroethylene and 10-20 parts of nano CaCO 3 5-10 parts of graphene nano-sheets, 2-8 parts of graphite micro powder, 1-5 parts of hydrogen peroxide, 0.1-5 parts of absolute ethyl alcohol, 1-7 parts of sodium dodecyl benzene sulfonate SDBS, 10-15 parts of carbon fibers, 0.1-1 part of antimony trioxide and 12-18 parts of polyphenyl ester. The impact strength, the elastic modulus and the elongation at break of the composite material are obviously improved by filling the nano calcium carbonate and the carbon fiber with the modified PTFE resin, and the composite material has good comprehensive mechanical property and great economic popularization value.
The graphene subjected to hydrogen peroxide treatment is subjected to surface activation by Sodium Dodecyl Benzene Sulfonate (SDBS), so that the aggregation phenomenon of the graphene can be effectively improved, and the mechanical properties of the polytetrafluoroethylene sealing material can be obviously improved by a small amount of graphene, wherein the tensile strength, the elongation at break, the compression retraction elastic performance and the creep relaxation resistance of the polytetrafluoroethylene composite sealing material can be obviously improved by the graphene subjected to surface modification by the SDBS. The PI FE composite material prepared from the SDBS modified graphene with the mass fraction of 1% has the best mechanical property and sealing property and has good practical application value.
The interface binding force and the tensile property of the PTFE/CF composite material can be effectively improved by coating carbon fiber with polytetrafluoroethylene emulsion treated by argon plasma; when the treatment time is 9mi < n >, the mechanical property is optimal, the tensile strength is 24.3MPa, the elongation at break is 340%, and the abrasion rate is 2.4 multiplied by 106mm < 3 >/Nm; compared with pure PTFE, the tensile strength and the elongation at break are respectively improved by 48 percent and 100 percent, and the abrasion rate is reduced by 55.6 percent.
By adopting the cold press molding process, the optimal molding pressure is determined to be 35Mpa, the pressing time is 15mi < n >, the heating rate is 60/h, the sintering temperature is 330 ℃ and is kept for 1h, and the temperature is kept for 2h at 375 ℃. Nano CaCO 3 The impact strength, the elastic modulus and the elongation at break of the composite material obtained by filling the modified PTFE resin are obviously improved, and the composite material is prepared by nano CaCO 3 When the filling amount is 1%, the composite material has the best comprehensive mechanical property. Nano CaCO 3 The mechanical property of the modified PTFE composite material is smaller than that of the micron S i N 4 The mechanical property of the modified PTFE composite material is better.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application; it is apparent that the described embodiments are only a part of the embodiments of the present application, not all of the embodiments, and all other embodiments obtained by a person having ordinary skill in the art without making creative efforts based on the embodiments in the present application are within the scope of protection of the present application.
Embodiment one:
the invention discloses a polytetrafluoroethylene composite material, which comprises the following components in parts by weight: 75 parts of polytetrafluoroethylene, 10Nano CaCO in parts by weight 3 5 parts of graphene nanoplatelets, 2 parts of graphite micropowder, 1 part of hydrogen peroxide, 0.1 part of absolute ethyl alcohol, 1 part of sodium dodecyl benzene sulfonate SDBS, 10 parts of carbon fibers, 0.1 part of antimony trioxide and 12 parts of polyphenyl ester.
Wherein, the average lamellar thickness of the graphene nano-sheets is 15mm. The volume fraction of hydrogen peroxide was 25%. The particle diameter d of the graphite micro powder is less than or equal to 30um. The carbon fiber diameter was 5um. Nano CaCO 3 The particle size distribution was 40nm.
Embodiment two:
the invention discloses a polytetrafluoroethylene composite material, which comprises the following components in parts by weight: 95 parts of polytetrafluoroethylene and 20 parts of nano CaCO 3 10 parts of graphene nanoplatelets, 8 parts of graphite micropowder, 5 parts of hydrogen peroxide, 5 parts of absolute ethyl alcohol, 7 parts of sodium dodecyl benzene sulfonate SDBS, 15 parts of carbon fibers, 1 part of antimony trioxide and 18 parts of polyphenyl ester.
Wherein, the average lamellar thickness of the graphene nano-sheets is 25mm. The volume fraction of hydrogen peroxide was 35%. The particle diameter d of the graphite micro powder is less than or equal to 30um. The diameter of the carbon fiber is 8um. Nano CaCO 3 The particle size distribution was 80nm.
Embodiment III:
the invention discloses a polytetrafluoroethylene composite material, which comprises the following components in parts by weight: 85 parts of polytetrafluoroethylene and 15 parts of nano CaCO 3 7 parts of graphene nanoplatelets, 5 parts of graphite micropowder, 3 parts of hydrogen peroxide, 2.5 parts of absolute ethyl alcohol, 4 parts of sodium dodecyl benzene sulfonate SDBS, 12 parts of carbon fibers, 0.5 part of antimony trioxide and 15 parts of polyphenyl ester.
Wherein, the average lamellar thickness of the graphene nano-sheets is 20mm. The volume fraction of hydrogen peroxide was 30%. The particle diameter d of the graphite micro powder is less than or equal to 30um. The diameter of the carbon fiber was 6um. Nano CaCO 3 The particle size distribution was 60nm.
Embodiment four:
the invention also discloses a preparation method of the polytetrafluoroethylene composite material, which comprises the following steps:
s1, performing pre-oxidation treatment on graphene nano sheets by adopting hydrogen peroxide, performing surface activation treatment on the pre-oxidized graphene by adopting a KH550 absolute ethanol solution with the mass fraction of 1% and an SDBS aqueous solution with the mass concentration of 1mg/mL, and performing ultrasonic dispersion, vacuum suction filtration, washing and drying to obtain surface modified graphene nano sheets;
s2, 75 parts of polytetrafluoroethylene and 10 parts of nano CaCO 3 And 10 parts of carbon fiber are uniformly mixed and stirred, the carbon fiber is filtered out, the temperature is raised to 350 ℃ after the water is removed by heating, and the argon plasma treatment is carried out after the micromolecules in the emulsion are removed. Performing flowing radio-frequency discharge by adopting an external electrode and a 14MHz radio-frequency power generator, wherein the argon pressure is 50Pa, the discharge power is 100W, the discharge time is 3min, and uniformly dispersing the modified carbon fiber and polytetrafluoroethylene resin to form a mixture;
s3, adding 2 parts of graphite micro powder, 0.1 part of antimonous oxide, 12 parts of polyphenyl ester and surface modified graphene nano sheets into the mixture according to a certain proportion, mixing uniformly, adopting a mechanical stirring mode to mix materials, cold-press molding at room temperature, then placing a pressed molded sample into a high-temperature sintering furnace, heating to 350 ℃ at a heating rate of 40 ℃/hour, and carrying out heat preservation and sintering for 2.5 hours; naturally cooling to room temperature to obtain the polytetrafluoroethylene composite material.
In step S3, during cold press forming, a pressure set point of 35MPa and a dwell time of 5mi "are applied.
Fifth embodiment:
the invention also discloses a preparation method of the polytetrafluoroethylene composite material, which comprises the following steps:
s1, performing pre-oxidation treatment on graphene nano sheets by adopting hydrogen peroxide, performing surface activation treatment on the pre-oxidized graphene by adopting a KH550 absolute ethanol solution with the mass fraction of 1% and an SDBS aqueous solution with the mass concentration of 1mg/mL, and performing ultrasonic dispersion, vacuum suction filtration, washing and drying to obtain surface modified graphene nano sheets;
S2、95 parts of polytetrafluoroethylene and 20 parts of nano CaCO 3 And 15 parts of carbon fiber are uniformly mixed and stirred, the carbon fiber is filtered out, the temperature is raised to 350 ℃ after the water is removed by heating, and the argon plasma treatment is carried out after the micromolecules in the emulsion are removed. Performing flowing radio-frequency discharge by adopting an external electrode and a 14MHz radio-frequency power generator, wherein the argon pressure is 50Pa, the discharge power is 100W, the discharge time is 12mi, and uniformly dispersing the modified carbon fiber and polytetrafluoroethylene resin to form a mixture;
s3, adding 8 parts of graphite micro powder, 1 part of antimonous oxide, 18 parts of polyphenyl ester and surface-modified graphene nano sheets into the mixture according to a certain proportion, mixing uniformly, adopting a mechanical stirring mode to mix materials, cold-press molding at room temperature, then placing a pressed molded sample into a high-temperature sintering furnace, heating to 380 ℃ at a heating rate of 100 ℃/hour, and carrying out heat preservation and sintering for 2.5 hours; naturally cooling to room temperature to obtain the polytetrafluoroethylene composite material.
In step S3, during cold press forming, a pressure set point of 35MPa and a dwell time of 15mi "are applied.
Example six:
the invention also discloses a preparation method of the polytetrafluoroethylene composite material, which comprises the following steps:
s1, performing pre-oxidation treatment on graphene nano sheets by adopting hydrogen peroxide, performing surface activation treatment on the pre-oxidized graphene by adopting a KH550 absolute ethanol solution with the mass fraction of 1% and an SDBS aqueous solution with the mass concentration of 1mg/mL, and performing ultrasonic dispersion, vacuum suction filtration, washing and drying to obtain surface modified graphene nano sheets;
s2, mixing 85 parts of polytetrafluoroethylene and 15 parts of nano CaCO 3 And mixing and stirring 12 parts of carbon fiber uniformly, filtering out the carbon fiber, heating to remove water, heating to 350 ℃, removing small molecules in the emulsion, and performing argon plasma treatment. Performing flowing radio frequency discharge with external electrode and 14MHz radio frequency power generator under argon pressure of 50Pa, discharge power of 100W and discharge time of 8 min, and mixing modified carbon fiber with polymerAfter the tetrafluoroethylene resin is uniformly dispersed, forming a mixture;
s3, adding 5 parts of graphite micro powder, 0.5 part of antimonous oxide, 15 parts of polyphenyl ester and surface-modified graphene nano sheets into the mixture according to a certain proportion, mixing uniformly, adopting a mechanical stirring mode to mix materials, cold-press molding at room temperature, then placing a pressed molded sample into a high-temperature sintering furnace, heating to 365 ℃ at a heating rate of 70 ℃/hour, and carrying out heat preservation and sintering for 2.5 hours; naturally cooling to room temperature to obtain the polytetrafluoroethylene composite material.
In step S3, during cold press forming, a pressure set point of 35MPa and a dwell time of 10mi "are applied.
Embodiment seven:
the invention also discloses an application of the polytetrafluoroethylene composite material in the lubrication sealing field or the polytetrafluoroethylene composite material prepared by the preparation method of the technical scheme.
The strength and elongation at break of PTFE initially increase with increasing mass fraction of graphene, with the tensile strength being maximum at a mass fraction of around 1%, and then decreasing with increasing filling amount. At the same filling amount, the modification effect of graphite is the worst, the modification effect of graphene treated by SDBS is the best, the tensile strength of the graphene reaches 27.1MPa, and the graphene is improved by about 21.47 percent compared with pure PTFE. The maximum elongation at break of the material of KH550 modified graphene reaches 388% when the mass fraction is 1%, and the maximum elongation at break of the material of SDBS modified graphene is 368% when the mass fraction is 1.5%, which are respectively improved by 38.57% and 31.43% compared with pure PI FE. The decrease in tensile strength and elongation at break is caused after the graphene filling amount exceeds a certain range, and the root cause may be that agglomeration of graphene leads to dispersion and deterioration of bonding in PTFE.
Research shows that the influence of the graphite micro powder on PTFE hardness is obviously smaller than that of graphene under the same content, and the influence of the surface modified graphene on the hardness is obviously higher than that of common graphene, wherein the influence of SDBS modified graphene is the largest, and the PTFE hardness is obviously increased along with the increase of the filling amount. With nano CaCO 3 Increased content, PTFE compositeThe elongation at break of the material is increased and then reduced, and the elongation at break reaches the maximum value when the filler content is 1%. This is due to nano CaCO 3 Physical interaction with the polymer. The physical effect is mainly Van der Waals force, because CaCO 3 The particle size is the same order of magnitude as the size of the macromolecular chain, caCO 3 The particles and the macromolecular chains are dispersed in molecular level, and have stronger binding force, so that the reinforced and toughened effects are achieved. Meanwhile, when the matrix is impacted by external force, the existence of the rigid particles generates stress concentration effect, so that the surrounding resin matrix is easily excited to generate microcracks, and meanwhile, the matrix among the particles also generates yield and plastic deformation to absorb impact energy. In addition, the existence of the rigid particles can prevent and passivate the expansion of the crack of the matrix resin, and finally stop the crack, so that the crack is not developed into destructive crack, thereby having toughening effect.
The implementation principle of the invention is as follows: the invention discloses a polytetrafluoroethylene composite material, which comprises the following components in parts by weight: 75-95 parts of polytetrafluoroethylene and 10-20 parts of nano CaCO 3 5-10 parts of graphene nano-sheets, 2-8 parts of graphite micro powder, 1-5 parts of hydrogen peroxide, 0.1-5 parts of absolute ethyl alcohol, 1-7 parts of sodium dodecyl benzene sulfonate SDBS, 10-15 parts of carbon fibers, 0.1-1 part of antimony trioxide and 12-18 parts of polyphenyl ester. The impact strength, the elastic modulus and the elongation at break of the composite material are obviously improved by filling the nano calcium carbonate and the carbon fiber with the modified PTFE resin, and the composite material has good comprehensive mechanical property and great economic popularization value.
The embodiments of the present invention are all preferred embodiments of the present invention, and are not intended to limit the scope of the present invention in this way, therefore: all equivalent changes in structure, shape and principle of the invention should be covered in the scope of protection of the invention.
Claims (9)
1. A polytetrafluoroethylene composite material characterized by: the polytetrafluoroethylene composite material comprises the following components in parts by weight: 75-95 parts of polytetrafluoroethylene, 10-20 parts of nano CaCO3, 5-10 parts of graphene nano sheets, 2-8 parts of graphite micro powder, 1-5 parts of hydrogen peroxide, 0.1-5 parts of absolute ethyl alcohol, 1-7 parts of sodium dodecyl benzene sulfonate SDBS, 10-15 parts of carbon fiber, 0.1-1 part of antimony trioxide and 12-18 parts of polyphenyl ester.
2. The polytetrafluoroethylene composite according to claim 1, wherein said graphene nanoplatelets have an average platelet thickness of 15-25mm.
3. A polytetrafluoroethylene composite according to claim 1 wherein the hydrogen peroxide is present in a volume fraction of 25% to 35%.
4. The polytetrafluoroethylene composite according to claim 1, wherein the particle diameter d of the graphite micropowder is less than or equal to 30um.
5. A polytetrafluoroethylene composite according to claim 1 wherein said carbon fibers have a diameter of 5-8um.
6. The polytetrafluoroethylene composite according to claim 1, wherein said nano CaCO3 has a particle size distribution of 40-80nm.
7. The preparation method of the polytetrafluoroethylene composite material is characterized by comprising the following steps of:
s1, performing pre-oxidation treatment on graphene nano sheets by adopting hydrogen peroxide, performing surface activation treatment on the pre-oxidized graphene by adopting a KH550 absolute ethanol solution with the mass fraction of 1% and an SDBS aqueous solution with the mass concentration of 1mg/mL, and performing ultrasonic dispersion, vacuum suction filtration, washing and drying to obtain surface modified graphene nano sheets;
s2, uniformly mixing 75-95 parts of polytetrafluoroethylene, 10-20 parts of nano CaCO3 and 10-15 parts of carbon fiber, filtering the carbon fiber, heating to remove water, heating to 350 ℃, removing small molecules in emulsion, and performing argon plasma treatment;
performing flowing type radio frequency discharge by adopting an external electrode and a 14MHz radio frequency power generator, wherein the argon pressure is 50Pa, the discharge power is 100W, the discharge time is 3-12 min, and the modified carbon fiber and polytetrafluoroethylene resin are uniformly dispersed to form a mixture;
s3, adding 2-8 parts of graphite micro powder, 0.1-1 part of antimonous oxide, 12-18 parts of polyphenyl ester and surface modified graphene nano sheets into the mixture according to a certain proportion, mixing uniformly by adopting a mechanical stirring mode, cold-pressing and molding at room temperature, then placing a pressed and molded sample into a high-temperature sintering furnace, heating to 350-380 ℃ at a heating rate of 40-100 ℃/hour, and carrying out heat preservation and sintering for 2.5 hours; naturally cooling to room temperature to obtain the polytetrafluoroethylene composite material.
8. The method according to claim 7, wherein in step S3, the set pressure is applied during the cold press molding at 35MPa and the dwell time is 5-15min.
9. Use of the polytetrafluoroethylene composite according to any one of claims 1 to 6 or the polytetrafluoroethylene composite prepared by the preparation method according to any one of claims 7 to 8 in the field of lubrication sealing.
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| CN112625384A (en) * | 2020-12-18 | 2021-04-09 | 任国峰 | Graphene polytetrafluoroethylene composite material and preparation method thereof |
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