CN114181493B - PEEK-based composite material with low abrasion and high comprehensive performance and preparation method thereof - Google Patents
PEEK-based composite material with low abrasion and high comprehensive performance and preparation method thereof Download PDFInfo
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 58
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000005299 abrasion Methods 0.000 title claims abstract description 19
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 title claims abstract 14
- 239000000314 lubricant Substances 0.000 claims abstract description 96
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical group S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000009830 intercalation Methods 0.000 claims abstract description 31
- 230000002687 intercalation Effects 0.000 claims abstract description 31
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 13
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 13
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 13
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims abstract description 9
- 239000004137 magnesium phosphate Substances 0.000 claims abstract description 9
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims abstract description 9
- 229960002261 magnesium phosphate Drugs 0.000 claims abstract description 9
- 235000010994 magnesium phosphates Nutrition 0.000 claims abstract description 9
- 230000008878 coupling Effects 0.000 claims abstract description 8
- 238000010168 coupling process Methods 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims abstract description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000005253 cladding Methods 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 28
- 239000011162 core material Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/326—Magnesium phosphate
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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)
- Lubricants (AREA)
Abstract
The invention relates to a PEEK-based composite material with low abrasion and high comprehensive performance and a preparation method thereof, wherein the PEEK-based composite material comprises the following raw materials in parts by weight: 50-80 parts of PEEK, 3-10 parts of PTFE, 3-20 parts of modified lubricant and 10-40 parts of PBI; the modified lubricant is of a shell-core structure, the core is an intercalation compound of a lamellar structure lubricant and a granular structure lubricant, and the shell layer is a coupling coating; the lamellar structure lubricant is tungsten disulfide, and the particle size is 1-15 mu m; the granular structure lubricant is a mixture of phosphate and stannous sulfide, and the particle size is 500nm-5 mu m; the phosphate comprises one or more of calcium phosphate, magnesium phosphate and zinc phosphate; the mass ratio of the tungsten disulfide to the stannous sulfide to the phosphate is 4:1 (0.4-0.8). The PEEK-based composite material has the advantages of low wear rate, low friction coefficient, high heat resistance and high mechanical property.
Description
Technical Field
The invention relates to the technical field of polymer material processing, in particular to a PEEK-based composite material with low abrasion and high comprehensive performance and a preparation method thereof.
Background
Polyether ether ketone (PEEK) is one of the most representative varieties of polyaryletherketone polymers, and is thermoplastic resin with the best comprehensive performance. The composite material has outstanding mechanical properties and has very good performances in the aspects of high temperature resistance, corrosion resistance, flame retardance, irradiation resistance, electrical insulation and the like. Although PEEK resin has excellent high temperature resistance, the glass transition temperature (143 ℃) is relatively low, the thermal deformation temperature of pure resin is only about 160 ℃, the wide application is limited, and the PEEK material can be modified by using glass fiber, carbon fiber, various whiskers or inorganic compounds, so that the use temperature, modulus, strength, dimensional stability and the like of the PEEK material can be improved. Along with the continuous development of science and technology, the requirements for high-performance materials are continuously expanded, the global yield of PEEK materials is rapidly expanded, and the PEEK materials are widely applied to the fields of automobiles, machining, aerospace, biomedical treatment and electronic appliances.
In order to further improve the comprehensive performance of PEEK, most of practical applications are to blend PEEK materials with other inorganic particles or fibers to prepare composite materials, and common PEEK composite materials are prepared by the following processes: melt blending, solution blending, in situ polymerization, and the like.
PEEK has abrasion resistance and self-lubricating property and is widely applied to various parts such as gears, bearings, gaskets, piston rings and the like. However, under the severe conditions of high load/speed combination, the pure PEEK material still cannot meet the use requirements, and PEEK needs to be modified to reduce the friction coefficient, improve the wear resistance and improve the tribological performance.
Disclosure of Invention
In order to improve the technical problem of PEEK wear resistance, a PEEK-based composite material with low wear and high comprehensive performance and a preparation method thereof are provided. The PEEK-based composite material has the advantages of low wear rate, low friction coefficient, high heat resistance and high mechanical property.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
A PEEK-based composite material with low abrasion and high comprehensive performance comprises the following raw materials in parts by weight: 50-80 parts of PEEK, 3-10 parts of PTFE, 3-20 parts of modified lubricant and 10-40 parts of PBI; the modified lubricant is of a shell-core structure, the core is an intercalation compound of a lamellar structure lubricant and a granular structure lubricant, and the shell layer is a coupling coating.
Further, the lamellar structure lubricant is tungsten disulfide, and the particle size is 1-15 mu m; the granular structure lubricant is a mixture of phosphate and stannous sulfide, and the particle size is 500nm-5 mu m. The particles with small particle size are easy to intercalate in the lamellar material, and compared with common blending, the lamellar material has better synergistic effect of improving the wear resistance.
Still further, the phosphate comprises one or more of calcium phosphate, magnesium phosphate and zinc phosphate; the mass ratio of the tungsten disulfide to the stannous sulfide to the phosphate is 4:1 (0.4-0.8).
Still further, the preparation method of the modified lubricant comprises the following steps:
(1) And (3) core preparation: dispersing the lamellar structure lubricant in absolute ethyl alcohol to prepare dispersion liquid, carrying out ultrasonic treatment, and then drying to obtain lamellar peeled lamellar structure lubricant; then mixing the obtained lamellar structure lubricant and granular structure lubricant which are subjected to lamellar stripping and ball milling solvent, and then performing ball milling intercalation;
(2) Coating a shell layer: and (3) adding a coupling agent into the material system in the step (1) after adjusting the pH value to be 7.5-9.5 for ball milling coating, and drying after the ball milling coating is completed to obtain the modified lubricant.
Further, the concentration of the dispersion in the above process is 8-30mg/mL, preferably 20mg/mL; the time of the ultrasonic treatment is 0.5-5h, preferably 1-2h; the coupling agent is a silane coupling agent with double bonds, preferably one of KH570, A171, KH-A172 and A151; zirconia grinding beads are also added in the ball milling intercalation compounding process, and the ball milling speed of the ball milling intercalation is 200-400rpm and the time is 1-5h; the ball milling speed of the ball milling coating is 200-400rpm, the ball milling temperature is 45-80 ℃ and the time is 1-5h.
Still further, the ratio of the total mass of the lamellar structure lubricant to the particulate structure lubricant to the mass of the coupling agent is (20-25): 1; the ball milling solvent is prepared from distilled water and ethanol according to a mass ratio of 9:1; the ratio of the total weight of the lamellar structure lubricant and the granular structure lubricant to the weight of the ball milling solvent is 5-7:10.
The invention also provides a preparation method of the PEEK-based composite material with low abrasion and high comprehensive performance, which comprises the following steps: PEEK is fed from a main feeding port and a side feeding port of the double-screw extruder, PTFE, a modified lubricant and PBI which are uniformly mixed in advance are fed, and the PEEK-based composite material is obtained after double-screw extrusion and granulation.
Further, the feeding frequency of the main feeding port is 4 Hz-10 Hz, the feeding frequency of the side feeding port is 1 Hz-5 Hz, and the screw rotating speed of the double screw extruder is 300 rpm-480 rpm; the temperature control of each zone of the double-screw extruder is as follows: the temperature of the first region is 250+/-10 ℃, the temperature of the second region is 300+/-10 ℃, the temperature of the third region is 340+/-10 ℃, the temperatures of the fourth region to the eighth region are 370+/-10 ℃, and the temperatures of the ninth region to the tenth region and the die are 350+/-20 ℃.
The beneficial technical effects are as follows:
Firstly, opening a lamellar lubricant by adopting ultrasonic treatment, then, adopting ball milling to intercalate a granular lubricant into the lamellar lubricant to form an intercalated compound, then, adopting a double-bond-containing silane coupling agent to coat the intercalated compound, adopting alkaline hydrolysis heating conditions in the coating process, firstly, carrying out hydrogen bond bonding on the hydrophilic end of a double-bond-containing silane coupling agent hydrolysate with the surface hydroxyl of the intercalated compound, grafting the hydrolysate onto the surface of the intercalated compound, and then, carrying out self-condensation polymerization on the hydrolysate on the surface of a substance to generate film coating, thus obtaining the modified lubricant with a shell-core structure; the surface coating of the modified lubricant is a hydrolytic polycondensation product containing double bonds, and compared with other coupling agent coatings without double bonds, the modified lubricant has better dispersing effect in the PEEK matrix, so that the modified lubricant can be more uniformly dispersed in the PEEK matrix, and the friction coefficient is reduced. Compared with common materials, the modified lubricant with the intercalation structure can exert more excellent lubricity, is more beneficial to forming a microcosmic continuous thin transfer film with high adhesion strength on a grinding surface of the PEEK-based composite material when friction occurs, and further reduces the friction coefficient by cooperating with the lubrication effect of PTFE on the macroscopic scale, so that the abrasion proportion of the composite material is lower. To improve the heat resistance and mechanical strength of the composite, PBI is added. The composite material has better heat resistance, mechanical strength and lower wear rate. The material is suitable for various wear-resistant parts such as gears, bearings, gaskets, piston rings and the like.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods in the following examples, for which specific conditions are not noted, are generally determined according to national standards; if the national standard is not corresponding, the method is carried out according to the general international standard or the standard requirements set by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
A PEEK-based composite material with low abrasion and high comprehensive performance comprises the following raw materials in parts by weight: 59 parts of PEEK, 5 parts of PTFE, 11 parts of modified lubricant and 25 parts of PBI; the modified lubricant is of a shell-core structure, the core is an intercalation compound of lamellar structure lubricant tungsten disulfide (particle size is 1-15 mu m) and granular structure lubricant stannous sulfide and calcium phosphate (particle size of granular structure lubricant is 500nm-5 mu m), and the shell is KH570 coupling coating; the mass ratio of the tungsten disulfide to the stannous sulfide to the calcium phosphate is 4:1:0.5;
the preparation method of the modified lubricant comprises the following steps:
(1) And (3) core preparation: dispersing tungsten disulfide in absolute ethyl alcohol to prepare a dispersion liquid with the concentration of 20mg/mL, carrying out ultrasonic treatment for 5 hours, and then drying to obtain layered stripping tungsten disulfide; mixing the obtained layered stripped tungsten disulfide, stannous sulfide, calcium phosphate and a ball milling solvent (distilled water: ethanol=9:1, mass ratio), wherein the solid-liquid mass ratio is 6:10, adding zirconia grinding beads (the ratio of the grinding beads to the total mass of the materials is 5:1), and performing ball milling intercalation, wherein the ball milling intercalation speed is 380rpm, and the time is 5 hours;
(2) Coating a shell layer: adding weak base (such as ammonia water) into the material system after ball milling intercalation in the step (1) to adjust the pH value to 8, adding KH570 for ball milling cladding, wherein the mass ratio of the dosage of KH570 to the total mass of tungsten disulfide, stannous sulfide and calcium phosphate is 1:24, the ball milling speed of ball milling cladding is 380rpm, the ball milling temperature is 60 ℃, the time is 3h, and drying to obtain the modified lubricant.
The preparation method of the PEEK-based composite material comprises the following steps: feeding PEEK from a main feeding port and a side feeding port of a double-screw extruder, and feeding PTFE, a modified lubricant and PBI which are uniformly mixed in advance, and carrying out double-screw extrusion granulation to obtain a PEEK-based composite material; the feeding frequency of the main feeding port is 5Hz, the feeding frequency of the side feeding port is 2Hz, the screw rotating speed of the double screw extruder is 360rpm, and the temperature of each zone is controlled during extrusion: the temperature of the first area is 250 ℃, the temperature of the second area is 300 ℃, the temperature of the third area is 340 ℃, the temperature of the fourth area to the eighth area is 370 ℃, and the temperature of the ninth area to the tenth area is 350 ℃ for the mouth mold.
Example 2
A PEEK-based composite material with low abrasion and high comprehensive performance comprises the following raw materials in parts by weight: 55 parts of PEEK, 8 parts of PTFE, 17 parts of modified lubricant and 20 parts of PBI; the modified lubricant is of a shell-core structure, the core is an intercalation compound of lamellar structure lubricant tungsten disulfide (particle size is 1-15 mu m) and granular structure lubricant stannous sulfide and magnesium phosphate (particle size of granular structure lubricant is 500nm-5 mu m), and the shell is an A171 coupling coating; the mass ratio of the tungsten disulfide to the stannous sulfide to the magnesium phosphate is 4:1:0.67;
the preparation method of the modified lubricant comprises the following steps:
(1) And (3) core preparation: dispersing tungsten disulfide in absolute ethyl alcohol to prepare a dispersion liquid with the concentration of 20mg/mL, carrying out ultrasonic treatment for 5 hours, and then drying to obtain layered stripping tungsten disulfide; mixing the obtained layered stripped tungsten disulfide, stannous sulfide, magnesium phosphate and a ball milling solvent (distilled water: ethanol=9:1, mass ratio), wherein the solid-liquid mass ratio is 6:10, adding zirconia grinding beads (the ratio of the grinding beads to the total mass of the materials is 5:1), and performing ball milling intercalation, wherein the ball milling intercalation speed is 360rpm, and the time is 5h;
(2) Coating a shell layer: adding weak base (such as ammonia water) into the material system after ball milling intercalation in the step (1) to adjust the pH value to 9, adding A171 for ball milling cladding, wherein the mass ratio of the dosage of the A171 to the total mass of tungsten disulfide, stannous sulfide and calcium phosphate is 1:24, the ball milling speed of ball milling cladding is 360rpm, the ball milling temperature is 55 ℃, the time is 4 hours, and drying to obtain the modified lubricant.
The preparation method of the PEEK-based composite material is the same as that of the embodiment 1.
Example 3
A PEEK-based composite material with low abrasion and high comprehensive performance comprises the following raw materials in parts by weight: 62.5 parts of PEEK, 3 parts of PTFE, 6.5 parts of modified lubricant and 28 parts of PBI; the modified lubricant is of a shell-core structure, the core is an intercalation compound of lamellar structure lubricant tungsten disulfide (particle size is 1-15 mu m) and granular structure lubricant stannous sulfide and zinc phosphate (particle size of granular structure lubricant is 500nm-5 mu m), and the shell is an A151 coupling coating; the mass ratio of the tungsten disulfide to the stannous sulfide to the zinc phosphate is 4:1:0.42;
the preparation method of the modified lubricant comprises the following steps:
(1) And (3) core preparation: dispersing tungsten disulfide in absolute ethyl alcohol to prepare a dispersion liquid with the concentration of 20mg/mL, carrying out ultrasonic treatment for 5 hours, and then drying to obtain layered stripping tungsten disulfide; mixing the obtained layered stripped tungsten disulfide, stannous sulfide, magnesium phosphate and a ball milling solvent (distilled water: ethanol=9:1, mass ratio), wherein the solid-liquid mass ratio is 6:10, adding zirconia grinding beads (the ratio of the grinding beads to the total mass of the materials is 5:1), and performing ball milling intercalation, wherein the ball milling intercalation speed is 360rpm, and the time is 5h;
(2) Coating a shell layer: adding weak base (such as ammonia water) into the material system after ball milling intercalation in the step (1) to adjust the pH value to 7.5, adding A151 for ball milling cladding, wherein the mass ratio of the A151 to the total mass of tungsten disulfide, stannous sulfide and calcium phosphate is 1:24, the ball milling speed of ball milling cladding is 360rpm, the ball milling temperature is 65 ℃ and the time is 3 hours, and drying to obtain the modified lubricant.
The preparation method of the PEEK-based composite material is the same as that of the embodiment 1.
Example 4
A PEEK-based composite material with low abrasion and high comprehensive performance comprises the following raw materials in parts by weight: 58.5 parts of PEEK, 6 parts of PTFE, 13.5 parts of modified lubricant and 22 parts of PBI; the modified lubricant is of a shell-core structure, the core is an intercalation compound of lamellar structure lubricant tungsten disulfide (particle size is 1-15 mu m) and granular structure lubricant stannous sulfide and calcium phosphate (particle size of granular structure lubricant is 500nm-5 mu m), and the shell is KH570 coupling coating; the mass ratio of the tungsten disulfide to the stannous sulfide to the calcium phosphate is 4:1:0.65;
The preparation method of the modified lubricant is the same as in example 1.
Example 5
A PEEK-based composite material with low abrasion and high comprehensive performance comprises the following raw materials in parts by weight: 61 parts of PEEK, 4 parts of PTFE, 9 parts of modified lubricant and 26 parts of PBI; the modified lubricant is of a shell-core structure, the core is an intercalation compound of lamellar structure lubricant tungsten disulfide (particle size is 1-15 mu m) and granular structure lubricant stannous sulfide and calcium phosphate (particle size of granular structure lubricant is 500nm-5 mu m), and the shell is KH570 coupling coating; the mass ratio of the tungsten disulfide to the stannous sulfide to the calcium phosphate is 4:1:0.65;
The preparation method of the modified lubricant is the same as in example 1.
Comparative example 1
The raw material ratio and the preparation method of the PEEK-based composite of this comparative example are the same as those of example 1, except that the modified lubricant is prepared: the tungsten disulfide, stannous sulfide, magnesium phosphate and ball milling solvent are directly mixed without peeling the tungsten disulfide, zirconia is added for ball milling after ball milling, and KH570 coating is carried out after ball milling.
Comparative example 2
The raw material ratio and the preparation method of the PEEK-based composite of this comparative example are the same as those of example 1, except that the modified lubricant is prepared: after the peeling of the tungsten disulfide sheet layer is completed, no intercalation is carried out, and stannous sulfide, magnesium phosphate, a ball milling solvent, zirconia grinding balls and KH570 are directly added for ball milling cladding after the pH value is regulated.
Comparative example 3
The raw material ratio and the preparation method of the PEEK-based composite of this comparative example are the same as those of example 1, except that the modified lubricant is prepared: after ball milling intercalation, KH570 coating is not carried out.
Comparative example 4
The raw material ratio and the preparation method of the PEEK-based composite of this comparative example are the same as those of example 1, except that no phosphate is added (the mass of the missing phosphate increases to that of stannous sulfide) in the preparation process of the modified lubricant.
Comparative example 5
The raw material ratio and the preparation method of the PEEK-based composite of this comparative example are the same as those of example 1, except that stannous sulfide is not added (the mass of the deleted stannous sulfide increases to the mass of the phosphate) in the preparation process of the modified lubricant.
Comparative example 6
The raw material ratio and the preparation method of the PEEK-based composite of this comparative example are the same as those of example 1, except that tungsten disulfide is not added (the mass of the deleted tungsten disulfide is increased to that of stannous sulfide) in the preparation process of the modified lubricant, and the process of delamination and intercalation does not exist due to the absence of tungsten disulfide, and stannous sulfide and phosphate are directly dispersed in a ball milling solvent to coat KH 570.
The weight part ratios of the components of the above examples are shown in Table 1.
TABLE 1 examples 1-5 weight part ratio of the respective components
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| PEEK | 59 | 55 | 62.5 | 58.5 | 61 |
| PTFE | 5 | 8 | 3 | 6 | 4 |
| Modified lubricant | 11 | 17 | 6.5 | 13.5 | 9 |
| PBI | 25 | 20 | 28 | 22 | 26 |
The composite materials prepared in the above examples and comparative examples were subjected to performance tests, including wear rate, coefficient of friction, tensile strength, flexural strength, impact strength, compressive strength. The performance data for examples 1-5 are shown in Table 2, and the data for examples 1 and comparative examples 1-6 are shown in Table 3.
TABLE 2 performance number of the composites of examples 1-5
TABLE 3 Performance data for the composites of example 1, comparative examples 1-6
| Wear rate (μm/h) | Coefficient of friction | |
| Example 1 | 4.4 | 0.13 |
| Comparative example 1 | 6.1 | 0.18 |
| Comparative example 2 | 5.8 | 0.17 |
| Comparative example 3 | 6.3 | 0.18 |
| Comparative example 4 | 5.0 | 0.15 |
| Comparative example 5 | 5.2 | 0.16 |
| Comparative example 6 | 6.7 | 0.19 |
As can be seen from tables 1 and 2, the PEEK-based composite material provided by the invention has higher mechanical properties and better wear resistance and heat resistance. Comparative example 1 the intercalation and coating effect of the subsequent particulate matter was affected without peeling the tungsten disulfide sheet, comparative example 1 corresponds to blending of materials, and the change in microstructure of the core material would result in a greater decrease in wear resistance with an increase in wear rate of about 38%. Comparative example 2 although the tungsten disulfide sheet was peeled off, the intercalation step and the coating step were combined into one step, so that the intercalation process could not be uniformly achieved, and thus the abrasion resistance was lowered and the abrasion rate was increased by about 32%. In comparative example 3, the core material (the particulate lubricant intercalation layer lubricant) was not coated with the coupling agent, and the abrasion rate was increased by about 43%, and it was found that the lubricant material was unevenly dispersed in the PEEK matrix without using the coupling agent, resulting in a decrease in abrasion resistance. The absence of phosphate in the modified lubricant of comparative example 4 resulted in an increase in wear rate of about 13.6%; the modified lubricant of comparative example 5 was free of stannous sulfide, resulting in an increase in wear rate of about 18%; the modified lubricant of comparative example 6 was free of lamellar tungsten disulfide, resulting in an increase in wear rate of about 52%. It can be seen that the lamellar tungsten disulfide plays a main role in wear resistance in the action of wear resistance, phosphate and stannous sulfide are inserted into the lamellar tungsten disulfide, and the coating silane coupling agent can play a more excellent role in lubricity, so that a continuous thin transfer film with high adhesion strength is formed on microcosmic scale, and the wear resistance is further improved in cooperation with the lubrication action of PTFE on macroscopic scale.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. The PEEK-based composite material with low abrasion and high comprehensive performance is characterized by comprising the following raw materials in parts by weight: 50-80 parts of PEEK, 3-10 parts of PTFE, 3-20 parts of modified lubricant and 10-40 parts of PBI; the modified lubricant is of a shell-core structure, the core is an intercalation compound of a lamellar structure lubricant and a granular structure lubricant, and the shell layer is a coupling coating;
the preparation method of the modified lubricant comprises the following steps:
(1) And (3) core preparation: dispersing the lamellar structure lubricant in absolute ethyl alcohol to prepare dispersion liquid, carrying out ultrasonic treatment, and then drying to obtain lamellar peeled lamellar structure lubricant; then mixing the obtained lamellar structure lubricant and granular structure lubricant which are subjected to lamellar stripping and ball milling solvent, and then performing ball milling intercalation;
(2) Coating a shell layer: adding a coupling agent into the material system in the step (1) after adjusting the pH value to be 7.5-9.5 for ball milling cladding, and drying after the ball milling cladding is completed to obtain the modified lubricant;
The granular structure lubricant is a mixture of phosphate and stannous sulfide.
2. The low-wear high-comprehensive-performance PEEK-based composite material according to claim 1, wherein the lamellar structure lubricant is tungsten disulfide and has a particle size of 1-15 μm; the particle size of the granular structure lubricant is 500nm-5 mu m.
3. The PEEK based composite of claim 2, wherein said phosphate comprises one or more of calcium phosphate, magnesium phosphate, and zinc phosphate; the mass ratio of the tungsten disulfide to the stannous sulfide to the phosphate is 4:1 (0.4-0.8).
4. A low wear, high integrity PEEK based composite according to claim 1, wherein said dispersion has a concentration of 8-30mg/mL; the ultrasonic treatment time is 0.5-5h; the coupling agent is a silane coupling agent with double bonds; zirconia grinding beads are also added in the ball milling intercalation compounding process, and the ball milling speed of the ball milling intercalation is 200-400rpm and the time is 1-5h; the ball milling speed of the ball milling coating is 200-400rpm, the ball milling temperature is 45-80 ℃ and the time is 1-5h.
5. The PEEK-based composite of low wear, high overall performance according to claim 1, wherein the ratio of the total mass of lamellar structured lubricant to particulate structured lubricant to the mass of coupling agent is (20-25): 1; the ball milling solvent is prepared from distilled water and ethanol according to a mass ratio of 9:1; the ratio of the total weight of the lamellar structure lubricant and the granular structure lubricant to the weight of the ball milling solvent is 5-7:10.
6. The method for preparing the PEEK-based composite material with low abrasion and high comprehensive performance according to any one of claims 1 to 5, wherein PEEK is fed from a main feeding port of a double-screw extruder, PTFE, a modified lubricant and PBI which are uniformly mixed in advance are fed from a side feeding port, and the PEEK-based composite material is obtained after double-screw extrusion granulation.
7. The method according to claim 6, wherein the feeding frequency of the main feeding port is 4Hz to 10Hz, the feeding frequency of the side feeding port is 1Hz to 5Hz, and the screw speed of the twin-screw extruder is 300rpm to 480rpm; the temperature control of each zone of the double-screw extruder is as follows: the temperature of the first region is 250+/-10 ℃, the temperature of the second region is 300+/-10 ℃, the temperature of the third region is 340+/-10 ℃, the temperatures of the fourth region to the eighth region are 370+/-10 ℃, and the temperatures of the ninth region to the tenth region and the die are 350+/-20 ℃.
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