CN106351058A - High-toughness carbon nanotube modified carbon fiber reinforced paper-based friction material and preparation method thereof - Google Patents

High-toughness carbon nanotube modified carbon fiber reinforced paper-based friction material and preparation method thereof Download PDF

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CN106351058A
CN106351058A CN201611080083.5A CN201611080083A CN106351058A CN 106351058 A CN106351058 A CN 106351058A CN 201611080083 A CN201611080083 A CN 201611080083A CN 106351058 A CN106351058 A CN 106351058A
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parts
friction material
powder
toughness
nano
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胡仲胜
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/149—Antislip compositions
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F13/00—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/10—Composite fibres
    • D21H15/12—Composite fibres partly organic, partly inorganic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Braking Arrangements (AREA)

Abstract

The invention discloses a high-toughness carbon nanotube modified carbon fiber reinforced paper-based friction material. The high-toughness carbon nanotube modified carbon fiber reinforced paper-based friction material is prepared from the following raw materials in parts by weight: 1.1 to 1.4 parts of nano copper powder, 52 to 54 parts of carbon fibers, 27 to 28 parts of bamboo fibers, 3.5 to 4 parts of carbon nanotube, 2.3 to 2.8 parts of full-vulcanized nano powder carboxy terminated nitrile rubber, 5 to 5.5 parts of aramid pulp, 1.3 to 1.5 parts of silane coupling agent kh-550, 3 to 3.5 parts of cerous nitrate, 14 to 15 parts of zirconium boride, 10 to 12 parts of cashew nut shell oil modified phenolic resin with the solid content of 20 percent, 1.2 to 1.5 parts of nano-hydroxyapatite, 3 to 3.5 parts of polyphenylene sulfide micro-grade powder, 2.8 to 3.2 parts of flexible SiO2 nano fibers and a proper amount of water. According to the high-toughness carbon nanotube modified carbon fiber reinforced paper-based friction material disclosed by the invention, by using the polyphenylene sulfide micro-grade powder and the nano-hydroxyapatite, the toughness and the wear resistance of the friction material are improved; by using the flexible SiO2 nano fibers, the toughness and the deformation resistance are improved.

Description

A kind of high tenacity carbon nano-tube modification fibre reinforced paper friction material and its preparation Method
Technical field
The present invention relates to clutch friction material technical field, more particularly, to a kind of high tenacity carbon nano-tube modification carbon fiber Strengthen paper friction material and preparation method thereof.
Background technology
In recent years, developing rapidly with automobile industry and aircraft industry, the research of friction material field also there occurs Growth rapidly.Paper friction material, as the important Wet-type friction material of a class, is mainly used in car transmissions On clutch.The coefficient of friction, friction stability, thermostability and the wearability that how to improve paper friction material remain current The subject matter that paper friction material faces.For this reason, many scholars interface between fiber and resin from raising material Start with conjunction with filler systems two aspect excellent with searching out frictional behaviour, expand research." carbon nano-tube modification carbon fiber increases The preparation of strong paper friction material and research " literary composition first passes through interpolation bamboo fibre and CNT has prepared interfacial bonding property Preferably paper friction material.Research finds, the addition of CNT can improve the boundary of fiber and resin in material well Face binding ability, thus improve the frictional behaviour of material.When content of carbon nanotubes is for 4wt.%, the coefficient of kinetic friction of sample Reach maximum, be 0.1031, now, the friction stability of sample and anti-wear performance are also preferable.Heat analysis result shows, sample During being heated to 1000 DEG C, the mass loss of sample adding 4wt.% CNT is than the sample being not added with CNT Decrease 10%.Sem test result shows, in whole system, bamboo fibre can be good at being attached on carbon fiber, changes It has been apt to the interfacial combined function between carbon fiber and resin, and CNT Preferential adsorption has been on bamboo fibre, this has protected bamboo again Decomposes in friction process for the fiber, improve the heat resistance of sample.In order to further improve the frictional property of material Can, we be separately added in above-mentioned system the fillers such as carborundum, boron carbide, aluminium oxide, zirconium oxide and zirconium boride and Rare earth compound, and have studied the relation between filer content and rare earth species etc. and sample frictional behaviour, different fillers are existed The frictional behaviour of the action mode in system and sample has carried out Primary Study.Result shows, when containing 3wt.%ce in sample (no3) 3 and 15wt.% zirconium boride when, the frictional behaviour of material is optimal, and the coefficient of kinetic friction of material is 0.13285, moves/static friction Coefficient ratio is 0.9010, and the coefficient of variation in 500 friction processes for the coefficient of kinetic friction is 0.75, and wear rate is 0.6 × 10- 8cm3j-1.Finally, have studied with zirconium boride as filler, the compression rebound of carbon nano-tube modification fibre reinforced paper friction material Performance, heat conductivility, heat resistance and dynamic mechanical, and analyze the pass between these performances and sample frictional behaviour System.Result shows, the increase with boronation zirconium content although the compression ratio of sample and heat conductivity are declined slightly, but, dynamically Mechanical test and Thermal Synthetic Analysis result show, the sample containing 15wt.% zirconium boride has higher storage moduluss and thermostability Energy.By the research of the composition-storage moduluss-thermostability-frictional behaviour relation of material, storage moduluss and heat-resisting in discovery system Performance plays a crucial role to the frictional behaviour of material, and the storage moduluss of sample are bigger, and insensitivity is better, and heat resistance is got over Good, friction stability is higher, and the wear rate of material is lower.
Friction material derived above has good performance, but the material being directly mixed to get can be easily separated so that rubbing Wipe unstable properties, braking ability is unstable.Above-mentioned article is modified to CNT using maleic anhydride, improves carbon and receives The dispersibility of mitron, can be dispersed in bamboo fibre surface, form stable combination with bamboo fibre, but the thermostability of bamboo fibre is also It is not fully up to expectations although CNT improves thermostability and the frictional property of bamboo fibre, but in the case of being heated, maleic acid The polymer substance carbonization that acid anhydride is formed, CNT is separated with bamboo fibre, affects frictional behaviour.
Add aramid fiber and can improve the frictional behaviour of friction material, but the thermostability of aramid fiber poor so as to Application in heavy load machinery receives a definite limitation.And aramid fiber surface inertia, crystallization degree are high, are combined with matrix Bad, have impact on the performance of the composite of aramid fiber.With rare earth to carbon fiber and bamboo fibre modifying surface, improve fiber Wearability and thermostability, but the combination of rare earth and fiber insecure, easily separated after friction, cause changing of frictional behaviour Become.Also need to improve the thermostability of friction material, friction stability, ageing resistance, antibiotic property, toughness, static electricity resistance, wear-resisting Property, other performances such as anti-slip, compactness, heat conductivity.
Content of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of high tenacity carbon nano-tube modification carbon fiber Strengthen paper friction material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of high tenacity carbon nano-tube modification fibre reinforced paper friction material, is prepared by the raw materials in: nanometer Copper powder 1.1-1.4, carbon fiber 52-54, bamboo fibre 27-28, CNT 3.5-4, full sulfuration nanometer powder carboxy terminated nitrile rubber 2.3-2.8, Fanglun slurry cake 5-5.5, silane coupler kh-550 1.3-1.5, cerous nitrate 3-3.5, carborundum 10-11, zirconium boride 14-15, solid content are 20% cashew nut oil modified alkyd resin 10-12, nanometer hydroxyapatite 1.2-1.5, polyphenylene sulfide micron Level powder 3-3.5, flexible sio2Nanofiber 2.8-3.2, appropriate amount of water.
The preparation method of described high tenacity carbon nano-tube modification fibre reinforced paper friction material, comprises the following steps:
(1) Fanglun slurry cake is dispersed in water, adds silane coupler kh-550, stir, add copper nanoparticle, stirring 10-15 minute, dry, pulverize, and obtains modifying aramid fiber pulp；
(2) polyphenylene sulfide micron powder is heated to softening, sprays into nanometer hydroxyapatite while stirring, continue to grind 10 points Clock, obtains mixed material；By CNT, full sulfuration nanometer powder carboxy terminated nitrile rubber mixed grinding uniformly, obtain powder, will Bamboo fibre is added to the water, and adds described powder and mixed material while stirring, stirs, ultrasonic disperse 7-10 minute, is dried, In 11-12mpa, 120-125 DEG C, time-triggered protocol 40-50s, obtain modified bamboo fibre；
(3) modifying aramid fiber pulp, modified bamboo fibre and other residual componentss are put in water, discongest uniformly in fluffer, Obtain suspension, in paper molding device suspension being poured into 100-150 mesh sieve, make the thin slice that thickness is 0.7-0.8 μm, will Thin slice is vacuum dried 20-23 minute at 105-108 DEG C, cashew nut oil modified alkyd resin is sprayed on thin slice, naturally dries in the air Dry, place into sulfuration in vulcanizer, conditions of vulcanization is 11-12mpa, 120-125 DEG C, and the time is 250-260s, obtains final product.
The invention has the advantage that the present invention uses copper nanoparticle to adsorb on Fanglun slurry cake surface, improve Fanglun slurry cake , so that friction material is finer and close, coefficient of friction is more stable thermostability, the shortcoming of customer service Fanglun slurry cake heat stability difference.Logical Cross and using CNT, bamboo fibre is modified, improve the thermostability of bamboo fibre, but easy and bamboo fibre after being rubbed Separate so that coefficient of friction is unstable, be used in combination full sulfuration nanometer powder carboxy terminated nitrile rubber, through reacting by heating so that CNT is formed with bamboo fibre and is stably firmly combined, and improves friction stability, improves the stability of bamboo fibre simultaneously, Form the carbonized film of softness when being heated so that coefficient of friction is high and stablize.By using the heating of polyphenylene sulfide micron powder To softening, then adhere to nanometer hydroxyapatite, improve toughness and the wearability of polyphenylene sulfide, improve the toughness of friction material And wearability, by using flexible sio2Nanofiber, improves toughness and the anti-deformation performance of friction material.
Specific embodiment
A kind of high tenacity carbon nano-tube modification fibre reinforced paper friction material, by the raw material of following weight portion (kilogram) Make: copper nanoparticle 1.1, carbon fiber 52, bamboo fibre 27, CNT 3.5, full sulfuration nanometer powder carboxy terminated nitrile rubber 2.3, Fanglun slurry cake 5, silane coupler kh-550 1.3, cerous nitrate 3, carborundum 10, zirconium boride 14, solid content are 20% cashew shell oil Phenol-formaldehyde resin modified 10, nanometer hydroxyapatite 1.2, polyphenylene sulfide micron powder 3, flexible sio2Nanofiber 2.8, water are fitted Amount.
The preparation method of described high tenacity carbon nano-tube modification fibre reinforced paper friction material, comprises the following steps:
(1) Fanglun slurry cake is dispersed in water, adds silane coupler kh-550, stir, add copper nanoparticle, stirring 10 minutes, dry, pulverize, obtain modifying aramid fiber pulp；
(2) polyphenylene sulfide micron powder is heated to softening, sprays into nanometer hydroxyapatite while stirring, continue to grind 10 points Clock, obtains mixed material；By CNT, full sulfuration nanometer powder carboxy terminated nitrile rubber mixed grinding uniformly, obtain powder, will Bamboo fibre is added to the water, and adds described powder and mixed material while stirring, stirs, ultrasonic disperse 7 minutes, is dried, 11mpa, 120 DEG C, time-triggered protocol 40s, obtain modified bamboo fibre；
(3) modifying aramid fiber pulp, modified bamboo fibre and other residual componentss are put in water, discongest uniformly in fluffer, Obtain suspension, in paper molding device suspension being poured into 100 mesh sieves, make the thin slice that thickness is 0.7 μm, by thin slice 105 It is vacuum dried 20 minutes at DEG C, cashew nut oil modified alkyd resin is sprayed on thin slice, naturally dries, place in vulcanizer Sulfuration, conditions of vulcanization is 11mpa, 120 DEG C, and the time is 250s, obtains final product.
Experimental data:
The coefficient of kinetic friction of the thin slice of the present embodiment is 0.1454, move/confficient of static friction ratio for 0.9112, the coefficient of kinetic friction exists The coefficient of variation in 500 friction processes is 0.70, and wear rate is 0.54 × 10-8cm3j-1.

Claims (2)

1. a kind of high tenacity carbon nano-tube modification fibre reinforced paper friction material it is characterised in that: by following weight portion Raw material is made: copper nanoparticle 1.1-1.4, carbon fiber 52-54, bamboo fibre 27-28, CNT 3.5-4, full sulfuration nanometer powder Carboxy terminated nitrile rubber 2.3-2.8, Fanglun slurry cake 5-5.5, silane coupler kh-550 1.3-1.5, cerous nitrate 3-3.5, carborundum 10-11, zirconium boride 14-15, solid content be 20% cashew nut oil modified alkyd resin 10-12, nanometer hydroxyapatite 1.2-1.5, Polyphenylene sulfide micron powder 3-3.5, flexible sio2Nanofiber 2.8-3.2, appropriate amount of water.
2. the preparation method of high tenacity carbon nano-tube modification fibre reinforced paper friction material according to claim 1, its It is characterised by comprising the following steps:
(1) Fanglun slurry cake is dispersed in water, adds silane coupler kh-550, stir, add copper nanoparticle, stirring 10-15 minute, dry, pulverize, and obtains modifying aramid fiber pulp；
(2) polyphenylene sulfide micron powder is heated to softening, sprays into nanometer hydroxyapatite while stirring, continue to grind 10 points Clock, obtains mixed material；By CNT, full sulfuration nanometer powder carboxy terminated nitrile rubber mixed grinding uniformly, obtain powder, will Bamboo fibre is added to the water, and adds described powder and mixed material while stirring, stirs, ultrasonic disperse 7-10 minute, is dried, In 11-12mpa, 120-125 DEG C, time-triggered protocol 40-50s, obtain modified bamboo fibre；
(3) modifying aramid fiber pulp, modified bamboo fibre and other residual componentss are put in water, discongest uniformly in fluffer, Obtain suspension, in paper molding device suspension being poured into 100-150 mesh sieve, make the thin slice that thickness is 0.7-0.8 μm, will Thin slice is vacuum dried 20-23 minute at 105-108 DEG C, cashew nut oil modified alkyd resin is sprayed on thin slice, naturally dries in the air Dry, place into sulfuration in vulcanizer, conditions of vulcanization is 11-12mpa, 120-125 DEG C, and the time is 250-260s, obtains final product.
CN201611080083.5A 2016-11-30 2016-11-30 High-toughness carbon nanotube modified carbon fiber reinforced paper-based friction material and preparation method thereof Pending CN106351058A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020146958A1 (en) * 2019-01-14 2020-07-23 Fastpack S.A. Coating composition of highly wear-resistant nonwoven nanostructured elastomer rubber, comprising short polyparaphenylene terephthalamide fibres, zirconium oxide particles and carbon nanotubes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020146958A1 (en) * 2019-01-14 2020-07-23 Fastpack S.A. Coating composition of highly wear-resistant nonwoven nanostructured elastomer rubber, comprising short polyparaphenylene terephthalamide fibres, zirconium oxide particles and carbon nanotubes

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Application publication date: 20170125