EP1465945A1 - Rubber composition comprising carbon nanotubes as reinforcing agent and preparation thereof - Google Patents

Rubber composition comprising carbon nanotubes as reinforcing agent and preparation thereof

Info

Publication number
EP1465945A1
EP1465945A1 EP03701911A EP03701911A EP1465945A1 EP 1465945 A1 EP1465945 A1 EP 1465945A1 EP 03701911 A EP03701911 A EP 03701911A EP 03701911 A EP03701911 A EP 03701911A EP 1465945 A1 EP1465945 A1 EP 1465945A1
Authority
EP
European Patent Office
Prior art keywords
rubber
carbon nanotubes
rubbers
rubber composition
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03701911A
Other languages
German (de)
French (fr)
Other versions
EP1465945A4 (en
Inventor
Young-Nam Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KH Chemicals Co Ltd
Original Assignee
KH Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KH Chemicals Co Ltd filed Critical KH Chemicals Co Ltd
Publication of EP1465945A1 publication Critical patent/EP1465945A1/en
Publication of EP1465945A4 publication Critical patent/EP1465945A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B61—RAILWAYS
    • B61D—BODY DETAILS OR KINDS OF RAILWAY VEHICLES
    • B61D17/00—Construction details of vehicle bodies
    • B61D17/04—Construction details of vehicle bodies with bodies of metal; with composite, e.g. metal and wood body structures
    • B61D17/20—Communication passages between coaches; Adaptation of coach ends therefor
    • B61D17/22—Communication passages between coaches; Adaptation of coach ends therefor flexible, e.g. bellows
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/046—Carbon nanorods, nanowires, nanoplatelets or nanofibres
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T30/00—Transportation of goods or passengers via railways, e.g. energy recovery or reducing air resistance

Definitions

  • the present invention relates to a rubber composition comprising carbon nanotubes or graphitic nanofibers (GNF) as a reinforcing agent, and a process for preparation thereof. More particularly, the present invention relates to a process for preparation of a rubber composition, characterized in that carbon nanotubes or GNF, or a mixture of carbon nanotubes or GNF with carbon black or silicone which are conventionally used as a reinforcing agent for rubber, are used as a reinforcement to improve the mechanical, physical, electrical or chemical properties of the rubber composition, and a rubber composition prepared by said process.
  • GNF graphitic nanofibers
  • a carbon nanotube which is an allotrope of carbon black in the aspect of basic structure, is superior to carbon black in strength and has a tensile stress as high as 100 times that of steel. It also has excellent properties such as high elasticity, high conductivity and the like.
  • a carbon nanotube consists of a carbon atom bound to three adjacent carbon atoms, the bonding between those carbon atoms resulting in a hexagonal cyclic structural unit.
  • a number of such units form a plane of repeated hexagonal structures in the form of honeycomb, and the plane rolls into a cylindrical tube to finally constitute a nanotube.
  • Such a carbon nanotube has a diameter in the range of several angstroms to several nanometers, and the ratio of its length to diameter ranges from tens to thousands.
  • Extensive researches on the synthesis of carbon nanotubes are being carried out because the nanotubes have a morphological feature as mentioned above and have good thermal, mechanical and electrical properties resulting from their characteristic chemical bonding. It is expected that utilization of those properties would lead to the development of many new products that are technically limited in the selection of materials, and to the rendering of new properties to existing developed products.
  • carbon nanotubes form composites with polymers, tensile stress as well as the desired properties of the materials such as the electrical and chemical properties would be maximized.
  • the rubber composite materials thus synthesized using carbon nanotubes or GNF as reinforcement may be used in those traditional fields where existing rubber products are used as well as in a variety of new fields such as electromagnetic wave shielding materials.
  • synthetic rubbers such as natural rubber (NR), styrene butadiene rubber (SBR) and polybutadiene rubber (BR) are used with reinforcements like carbon nanotubes or GNF, the products are expected to have improved tensile stress, higher elasticity and higher wear resistance than traditional tires.
  • the inventors of the present invention discovered that rubbers with higher tensile stress and improved properties such as electrical properties, wear resistance and elasticity, compared with traditional rubber products, can be synthesized by substituting all or a part of the carbon black or silicone, which are traditionally used as reinforcement to improve specific properties of rubbers, with carbon nanotubes or graphitic nanofibers (GNF), and attempted to develop a process for preparation of rubbers with improved distribution of carbon nanotubes or GNF in the rubber.
  • GNF graphitic nanofibers
  • the present invention provides a rubber composition containing carbon nanotubes or graphitic nanofibers (GNF) as a reinforcing agent.
  • GNF graphitic nanofibers
  • the rubber composition may be a rubber composite or may have a composite structure.
  • a rubber composition with higher tensile stress and improved properties such as electrical properties, wear resistance and elasticity, compared with traditional rubber products, is provided by replacing all or a part of carbon black or silicone reinforcement with carbon nanotubes or GNF.
  • the type of rubber is not particularly limited, and mention may be made on a rubber selected from the group consisting of natural rubber, synthetic rubbers based on diene polymers or copolymers (e.g., polybutadiene, styrene-butadiene rubber, polyisoprene rubber, etc.), nitrile rubbers, silicone rubbers, neoprene rubbers, butyl rubbers, Thiokol (polyalkylene sulfide), urethane rubbers (polyesters and polyethers), ethylene-propylene rubbers, epichlorohydrin rubbers, epichlorohydrin-ethylene oxide rubbers, chlorosulfonated polyethylene rubber (Hypalon), polyacrylate rubbers, fluorine rubbers, and mixtures thereof.
  • a rubber selected from the group consisting of natural rubber, synthetic rubbers based on diene polymers or copolymers (e.g., polybutadiene, styrene-butadiene
  • the type of carbon nanotubes or graphitic nanofibers is also not particularly limited, and all types of single wall carbon nanotubes, all types of multi-wall carbon nanotubes, all types of GNF, and mixtures thereof may be mentioned.
  • the shapes of carbon nanotubes or GNF (for example, helical, linear, branched types) are not particularly limited, as long as the nanotubes are necessary for improving specific properties of rubbers.
  • carbon nanotubes or graphitic nanofibers when used as a reinforcing agent for rubbers, carbon nanotubes may be doped with H, B, N, O, F, Si, P, S or Cl, or may be reacted with at least one from transition metal atoms or transition metal compounds, or alkaline metal atoms, in order to improve specific properties or the affinity for rubber.
  • the carbon nanotubes or graphitic nanofibers that can be used for the present invention may be prepared by conventional preparation methods, and in particular by the process for preparation of carbon nanotubes or graphitic nanofibers described in
  • the methods of improvement for more uniformly distributing carbon nanotubes or graphitic nanofibers in the rubber are also included in the scope of the present invention.
  • Such role of surfactants is also advantageous in uniformly distributing carbon nanotubes or GNF in rubber.
  • the surfactants used for this purpose may be cationic, anionic or nonionic, and are not limited in type as long as they distribute carbon nanotubes or GNF uniformly in the rubber and improve the properties by strengthening the bonding. Therefore, according to the present invention, surfactants as well as stearic acid or fatty acids may be added.
  • carbon nanotubes or graphitic nanofibers are used in an amount of 0.1 to 150 %, preferably 0.2 to 120 %, and more preferably 0.5 to 100 % by weight of the rubber.
  • carbon nanotubes or graphitic nanofibers may be used in a mixture or compound with carbon black or silicone products that are traditionally used as reinforcements.
  • the amount of carbon nanotubes or graphitic nanofibers may range, with respect to the content of carbon black or silicone product or a mixture of the two, from 0.1 to 99.9 %, preferably from 0.1 to 99 %, and more preferably from 0.5 to 90 % by weight, and if necessary, an amount not more than 50 % by weight can also be used.
  • synthetic rubbers that are prepared by reinforcing synthetic rubbers for automobile tires, such as natural rubber (NR), butadiene rubber (BR), styrene-butadiene rubber (SBR), with carbon nanotubes, may be an advantageous material for tires. Therefore, according to a modification of the present invention, provided are automobile tires and a process for preparation thereof using a rubber composition containing carbon nanotubes or graphitic nanofibers as reinforcement.
  • NR natural rubber
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • Natural rubber was used as the raw material for rubber, and additives that are generally used in the synthesis of rubber for tires were used.
  • the amounts of the additives used in testing the properties of synthetic rubber reinforced with carbon nanotubes were as follows: on the basis of the content of natural rubber, 5 % by weight of carbon nanotubes used as a reinforcing agent
  • the composition was basically similar to the compositions generally used in the synthesis of rubber for tires. Vulcanization was carried out at 150°C for 30 minutes.
  • the tensile stress of thus obtained synthetic rubber was 32.1 MPa, and the stress at 300 % strain was 29.7 MPa. These values, obtained in the case of using a mixture of carbon nanotubes and carbon black, represent increases by about 35 % for tensile stress and about 37 % for the stress at 300 % strain, compared with the case of using carbon black only.
  • composition was the same as that used in Example 1 , except that carbon nanotubes were not used, and included, on the basis of the amount of natural rubber
  • NR carbon black reinforcement
  • N-330 having a particle size of 32 nm
  • elemental sulfur 4 % by weight of zinc oxide
  • the amounts of the additives used in testing the properties of synthetic rubber reinforced with carbon nanotubes were as follows: on the basis of the amount of rubber (NR), 5 % by weight of carbon nanotube reinforcement (multi-wall carbon nanotubes with an average diameter of 60 nm), 25 % by weight of silicone, 2 % by weight of elemental sulfur, 4 % by weight of zinc oxide and 0.4 % by weight of an accelerator.
  • the composition was the same as that used in Comparative Example 2 below, except that 5 % by weight of carbon black was replaced with carbon nanotubes.
  • Vulcanization was carried out at 150°C for 30 minutes.
  • the tensile stress of thus obtained synthetic rubber was 23.8 MPa, and the stress at 300 % strain was 21.7 MPa.
  • Natural rubber (NR) was used as the raw material for rubber, and additives that are generally used in the synthesis of rubber for tires were used.
  • the composition was basically similar to the compositions generally used in the synthesis of rubber for tires, and included, on the basis of the amount of rubber (NR), 30 % by weight of silicone reinforcement having a particle size of 32 nm, 2 % by weight of elemental sulfur, 4 % by weight of zinc oxide and 0.4 % by weight of an accelerator. Vulcanization was carried out at 150°C for 30 minutes.
  • the tensile stress of thus obtained synthetic rubber was 2 MPa, and the stress at 300 % strain was 19.5 MPa.
  • synthesis of composite rubbers by substituting all or a part of carbon black or silicone which is used as reinforcement for rubber, with carbon nanotubes or GNF can result in materials with higher tensile strength and elasticity than conventional products, and which materials are highly resistant to structure deformation or destruction.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a rubber composition in which synthetic rubber or natural rubber, including natural rubber (NR), styrene-butadiene rubber (SBR) and polybutadiene rubber (BR), is reinforced with carbon nanotubes or graphitic nanofibers, and a process for preparation thereof. According to the present invention , application of the physical and mechanical properties of carbon nanotubes or graphitic nanofibers to rubber can result in rubber products which have improved mechanical, physical and chemical properties, compared with existing rubber products reinforced with carbon black or silicone.

Description

RUBBER COMPOSITION COMPRISING CARBON NANOTUBES AS REINFORCING AGENT AND PREPARATION THEREOF
Technical Field The present invention relates to a rubber composition comprising carbon nanotubes or graphitic nanofibers (GNF) as a reinforcing agent, and a process for preparation thereof. More particularly, the present invention relates to a process for preparation of a rubber composition, characterized in that carbon nanotubes or GNF, or a mixture of carbon nanotubes or GNF with carbon black or silicone which are conventionally used as a reinforcing agent for rubber, are used as a reinforcement to improve the mechanical, physical, electrical or chemical properties of the rubber composition, and a rubber composition prepared by said process.
Technical Background Traditionally, rubber products have been synthesized using carbon black or silicone (silane compounds) as a reinforcing agent to enhance the tensile stress or durability of the rubber. However, a carbon nanotube, which is an allotrope of carbon black in the aspect of basic structure, is superior to carbon black in strength and has a tensile stress as high as 100 times that of steel. It also has excellent properties such as high elasticity, high conductivity and the like.
A carbon nanotube consists of a carbon atom bound to three adjacent carbon atoms, the bonding between those carbon atoms resulting in a hexagonal cyclic structural unit. A number of such units form a plane of repeated hexagonal structures in the form of honeycomb, and the plane rolls into a cylindrical tube to finally constitute a nanotube.
Such a carbon nanotube has a diameter in the range of several angstroms to several nanometers, and the ratio of its length to diameter ranges from tens to thousands. Extensive researches on the synthesis of carbon nanotubes are being carried out because the nanotubes have a morphological feature as mentioned above and have good thermal, mechanical and electrical properties resulting from their characteristic chemical bonding. It is expected that utilization of those properties would lead to the development of many new products that are technically limited in the selection of materials, and to the rendering of new properties to existing developed products. Especially, when carbon nanotubes form composites with polymers, tensile stress as well as the desired properties of the materials such as the electrical and chemical properties would be maximized. In particular, formation of composites is expected to contribute in improving tensile stress, elasticity, electrical properties, durability and the like, which are known to be weak points of polymers [Erik T. Thostenson, Zhifeng Ren, Tsu-Wei Chou, Composites Science and Technology 61(2001) 1899-1912].
For a polymer product using carbon nanotubes as a reinforcing agent, it was reported that when polystyrene was added with only 1 % by weight of carbon nanotubes, the tensile stress and elastic stiffness of the product increased by about 25 % and 36-42 %, respectively [Qian D, Dickey EC, Andrews R, Rantell T. Applied Physics Letters, 2000:76(20):2868-2870].
R. Andrews and Y. Chen et al. reported that single wall nanotubes could be used as reinforcement for petroleum pitch fiber. They demonstrated that when even 1 % by weight of carbon nanotubes was used as a reinforcing agent, tensile stress, elastic coefficient and electric conductivity increased greatly, and when 5 % by weight of single wall nanotubes were used, tensile stress, elastic coefficient and electric conductivity increased by 90 %, 150 % and 340 %, respectively. Particularly, they predicted that since the aromatic properties of petroleum pitch are similar to the aromatic properties of nanotubes, the bonding strength would be high [R. Andrews, et al., Applied Physics Letters, 75(1999) 1329-1331]. As such, when fabricating composite structures, addition of even a small amount of carbon nanotubes may maximize the properties of the polymers themselves. However, the results of these researches were obtained by using carbon nanotubes of very high purity, i.e. more than 99 % of purity, since when the purity of the carbon nanotubes used as reinforcement for polymer is low, the carbon black that is formed during the synthesis of carbon nanotubes results in the lowering of the strength. Thus, although a small amount of carbon nanotubes is added as reinforcement, the composite materials become expensive owing to the carbon nanotubes of high purity. Further, in the case of polymers comprising saturated hydrocarbons, their affinity with carbon nanotubes decreases, thereby resulting in the limitation in obtaining desired strength.
However, since most of rubbers are unsaturated hydrocarbons, they show good affinity with carbon black or carbon nanotubes, and also may lead to the production of new composite rubbers having higher tensile stress, wear resistance and durability than the traditional rubbers comprising carbon black only, even though rubbers are synthesized with a mixture of low-purity carbon nanotubes and carbon black. Therefore, it is expected that products stronger than traditional products may be prepared using a relatively inexpensive mixture of low-purity carbon nanotubes and carbon black instead of costly high-purity carbon nanotubes. This is advantageous in that inexpensive, low-purity carbon nanotubes or GNF that are thermally synthesized in conventional carbon black preparation processes, without using various synthesis methods for carbon nanotubes that are known to produce high- purity carbon nanotubes, such as the arc discharge method, laser vaporization, chemical vapor deposition (CVD), catalytic synthesis, plasma synthesis and the like. This is also advantageous in that synthetic rubber materials that use carbon nanotubes as reinforcement can be obtained at relatively low production costs, compared with traditional rubber products.
The rubber composite materials thus synthesized using carbon nanotubes or GNF as reinforcement may be used in those traditional fields where existing rubber products are used as well as in a variety of new fields such as electromagnetic wave shielding materials. Especially, when synthetic rubbers such as natural rubber (NR), styrene butadiene rubber (SBR) and polybutadiene rubber (BR) are used with reinforcements like carbon nanotubes or GNF, the products are expected to have improved tensile stress, higher elasticity and higher wear resistance than traditional tires. Summary of the Invention
The inventors of the present invention discovered that rubbers with higher tensile stress and improved properties such as electrical properties, wear resistance and elasticity, compared with traditional rubber products, can be synthesized by substituting all or a part of the carbon black or silicone, which are traditionally used as reinforcement to improve specific properties of rubbers, with carbon nanotubes or graphitic nanofibers (GNF), and attempted to develop a process for preparation of rubbers with improved distribution of carbon nanotubes or GNF in the rubber.
Accordingly, the present invention provides a rubber composition containing carbon nanotubes or graphitic nanofibers (GNF) as a reinforcing agent.
Detailed Description of the Invention
According to the present invention, the rubber composition may be a rubber composite or may have a composite structure. According to the present invention, a rubber composition with higher tensile stress and improved properties such as electrical properties, wear resistance and elasticity, compared with traditional rubber products, is provided by replacing all or a part of carbon black or silicone reinforcement with carbon nanotubes or GNF.
In the present invention, the type of rubber is not particularly limited, and mention may be made on a rubber selected from the group consisting of natural rubber, synthetic rubbers based on diene polymers or copolymers (e.g., polybutadiene, styrene-butadiene rubber, polyisoprene rubber, etc.), nitrile rubbers, silicone rubbers, neoprene rubbers, butyl rubbers, Thiokol (polyalkylene sulfide), urethane rubbers (polyesters and polyethers), ethylene-propylene rubbers, epichlorohydrin rubbers, epichlorohydrin-ethylene oxide rubbers, chlorosulfonated polyethylene rubber (Hypalon), polyacrylate rubbers, fluorine rubbers, and mixtures thereof.
In the present invention, the type of carbon nanotubes or graphitic nanofibers is also not particularly limited, and all types of single wall carbon nanotubes, all types of multi-wall carbon nanotubes, all types of GNF, and mixtures thereof may be mentioned. The shapes of carbon nanotubes or GNF (for example, helical, linear, branched types) are not particularly limited, as long as the nanotubes are necessary for improving specific properties of rubbers.
Moreover when carbon nanotubes or graphitic nanofibers are used as a reinforcing agent for rubbers, carbon nanotubes may be doped with H, B, N, O, F, Si, P, S or Cl, or may be reacted with at least one from transition metal atoms or transition metal compounds, or alkaline metal atoms, in order to improve specific properties or the affinity for rubber.
The carbon nanotubes or graphitic nanofibers that can be used for the present invention may be prepared by conventional preparation methods, and in particular by the process for preparation of carbon nanotubes or graphitic nanofibers described in
Korean Patent Application No. 2001-43659 (Filing date: July 20, 2001) by the
Applicant of the present invention.
According to a preferred embodiment of the present invention, the methods of improvement for more uniformly distributing carbon nanotubes or graphitic nanofibers in the rubber are also included in the scope of the present invention.
Uniform distribution of additives such as carbon nanotubes in the rubber allows the expression of improved properties that are characteristic to the carbon nanotubes in composite structures such as rubber compositions.
For example, addition of surfactants allows more uniform distribution of carbon nanotubes or GNF in the rubber. Gong, et al. reported that using nonionic surfactants in an epoxy resin reinforced with carbon nanotubes helped to improve uniform distribution of nanotubes in polymers and to strengthen the bonding between polymers and nanotubes [X. gong, et al., Chemistry of Materials 12(2000), 1049-
1052]. Such role of surfactants is also advantageous in uniformly distributing carbon nanotubes or GNF in rubber. The surfactants used for this purpose may be cationic, anionic or nonionic, and are not limited in type as long as they distribute carbon nanotubes or GNF uniformly in the rubber and improve the properties by strengthening the bonding. Therefore, according to the present invention, surfactants as well as stearic acid or fatty acids may be added. In the present invention, carbon nanotubes or graphitic nanofibers are used in an amount of 0.1 to 150 %, preferably 0.2 to 120 %, and more preferably 0.5 to 100 % by weight of the rubber.
These carbon nanotubes or graphitic nanofibers may be used in a mixture or compound with carbon black or silicone products that are traditionally used as reinforcements. In this case, the amount of carbon nanotubes or graphitic nanofibers may range, with respect to the content of carbon black or silicone product or a mixture of the two, from 0.1 to 99.9 %, preferably from 0.1 to 99 %, and more preferably from 0.5 to 90 % by weight, and if necessary, an amount not more than 50 % by weight can also be used.
In the present invention, synthetic rubbers that are prepared by reinforcing synthetic rubbers for automobile tires, such as natural rubber (NR), butadiene rubber (BR), styrene-butadiene rubber (SBR), with carbon nanotubes, may be an advantageous material for tires. Therefore, according to a modification of the present invention, provided are automobile tires and a process for preparation thereof using a rubber composition containing carbon nanotubes or graphitic nanofibers as reinforcement.
Generally, the largest portion in the consumption of rubber is used in the synthesis of rubber for tires. In this regard, when carbon nanotubes are used as reinforcement for rubber, it is found to be possible to produce tires much stronger than conventional tires, with expected increases in tensile stress or elasticity, and improved wear resistance. Further, since carbon nanotubes show good elastic strength or electric conductivity and can achieve desired properties with addition in even smaller amounts, they can be used in more various applications than the conventional rubber products reinforced with carbon black.
Examples
The present invention will be explained in detail with reference to the following examples, which are not intended to limit the present invention. Example 1
Natural rubber was used as the raw material for rubber, and additives that are generally used in the synthesis of rubber for tires were used. The amounts of the additives used in testing the properties of synthetic rubber reinforced with carbon nanotubes were as follows: on the basis of the content of natural rubber, 5 % by weight of carbon nanotubes used as a reinforcing agent
(multi-wall carbon nanotubes of an average diameter of 60 nm), 45'% by weight of carbon black, 2 % by weight of elemental sulfur, 4 % by weight of zinc oxide and 0.4 % by weight of an accelerator. The composition was basically similar to the compositions generally used in the synthesis of rubber for tires. Vulcanization was carried out at 150°C for 30 minutes.
The tensile stress of thus obtained synthetic rubber was 32.1 MPa, and the stress at 300 % strain was 29.7 MPa. These values, obtained in the case of using a mixture of carbon nanotubes and carbon black, represent increases by about 35 % for tensile stress and about 37 % for the stress at 300 % strain, compared with the case of using carbon black only.
Comparative Example 1 Natural rubber (NR) was used as the raw material for rubber, and additives that are generally used in the synthesis of rubber for tires were used.
The composition was the same as that used in Example 1 , except that carbon nanotubes were not used, and included, on the basis of the amount of natural rubber
(NR), 50 % by weight of carbon black reinforcement (N-330 having a particle size of 32 nm), 2 % by weight of elemental sulfur, 4 % by weight of zinc oxide and 0.4 % by weight of an accelerator. Vulcanization was carried out at 150°C for 30 minutes.
The tensile stress of thus obtained synthetic rubber was 23.8 MPa, and the stress at 300 % strain was 21.7 MPa. Example 2
The amounts of the additives used in testing the properties of synthetic rubber reinforced with carbon nanotubes were as follows: on the basis of the amount of rubber (NR), 5 % by weight of carbon nanotube reinforcement (multi-wall carbon nanotubes with an average diameter of 60 nm), 25 % by weight of silicone, 2 % by weight of elemental sulfur, 4 % by weight of zinc oxide and 0.4 % by weight of an accelerator. The composition was the same as that used in Comparative Example 2 below, except that 5 % by weight of carbon black was replaced with carbon nanotubes. Vulcanization was carried out at 150°C for 30 minutes. The tensile stress of thus obtained synthetic rubber was 23.8 MPa, and the stress at 300 % strain was 21.7 MPa. These values, obtained in the case of using a mixture of carbon nanotubes and silicone, represent increases by about 32 % for tensile stress and about 41 % for the stress at 300 % strain, compared with the case of using silicone only.
Comparative Example 2
In this experiment, changes in the properties of rubber composition were observed when a portion of carbon nanotube reinforcement was replaced with silicone reinforcement. Natural rubber (NR) was used as the raw material for rubber, and additives that are generally used in the synthesis of rubber for tires were used. The composition was basically similar to the compositions generally used in the synthesis of rubber for tires, and included, on the basis of the amount of rubber (NR), 30 % by weight of silicone reinforcement having a particle size of 32 nm, 2 % by weight of elemental sulfur, 4 % by weight of zinc oxide and 0.4 % by weight of an accelerator. Vulcanization was carried out at 150°C for 30 minutes.
The tensile stress of thus obtained synthetic rubber was 2 MPa, and the stress at 300 % strain was 19.5 MPa.
From the above Examples, it is found that tensile strength can be remarkably improved with replacement of carbon black or silicone with only a small amount of carbon nanotubes for the reinforcement of rubber.
Industrial Applicability
According to the present invention, synthesis of composite rubbers by substituting all or a part of carbon black or silicone which is used as reinforcement for rubber, with carbon nanotubes or GNF can result in materials with higher tensile strength and elasticity than conventional products, and which materials are highly resistant to structure deformation or destruction.
In particular, when applied to automobile tires, products having better mechanical properties than those reinforced with carbon black or silicone can be obtained.

Claims

WHAT IS CLAIMED IS:
1. A rubber composition containing carbon nanotubes or graphitic nanofibers (GNF) as reinforcement.
2. A rubber composition according to Claim 1, characterized in that the rubber is selected from the group consisting of natural rubber, synthetic rubbers based on diene polymers or copolymers (e.g., polybutadiene, styrene-butadiene rubber, polyisoprene rubber, etc.), nitrile rubbers, silicone rubbers, neoprene rubbers, butyl rubbers, Thiokol (polyalkylene sulfide), urethane rubbers (polyesters and polyethers), ethylene- propylene rubbers, epichlorohydrin rubbers, epichlorohydrin-ethylene oxide rubbers, chlorosulfonated polyethylene rubber (Hypalon), polyacrylate rubbers, fluorine rubbers, and mixtures thereof.
3. A rubber composition according to Claim 1, characterized in that the carbon nanotubes or graphitic nanofibers (GNF) are single wall carbon nanotubes, multi-wall carbon nanotubes, graphitic nano-fiber (GNF), or mixtures thereof.
4. A rubber composition according to Claim 3, characterized in that the carbon nanotubes or graphitic nano-fibers are those representing straight, helical or branched shapes, or mixed shapes, or a mixture of those with different shapes.
5. A rubber composition according to Claim 3 or 4, characterized in that the carbon nanotubes or graphitic nanofibers (GNF) are doped with H, B, N, O, F, Si, P, S, or Cl, or contain at least one from transition metals, transition metal compounds or alkaline metals.
6. A rubber composition according to Claim 1, characterized in that said composition is in the form of composites using surfactants, stearic acid or fatty acids.
7. A rubber composition according to Claim 6, characterized in that the surfactants are cationic, anionic, nonionic or mixtures thereof.
8. A rubber composition according to Claim 1, characterized in that the carbon nanotubes or graphitic nanofibers are contained in an amount of 0.1 - 150 % by weight on the basis of the amount of rubber.
9. A rubber composition according to Claim 1, characterized in that the carbon nanotubes or graphitic nanofibers are used as a mixture or a compound with carbon black or silicone products.
10. A rubber composition according to Claim 9, characterized in that the carbon nanotubes or carbon nanofibers are contained in an amount of 0.1 - 99.9 % by weight on the basis of the amount of carbon black or silicone product, or of a mixture thereof.
11. Automobile tires using a rubber composition according to Claim 1.
EP03701911A 2002-01-17 2003-01-15 Rubber composition comprising carbon nanotubes as reinforcing agent and preparation thereof Withdrawn EP1465945A4 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR2002002686 2002-01-17
KR1020020002686A KR100592527B1 (en) 2002-01-17 2002-01-17 Rubber composition comprising carbon nanotubes as reinforcing agent and preparation thereof
PCT/KR2003/000078 WO2003060002A1 (en) 2002-01-17 2003-01-15 Rubber composition comprising carbon nanotubes as reinforcing agent and preparation thereof

Publications (2)

Publication Number Publication Date
EP1465945A1 true EP1465945A1 (en) 2004-10-13
EP1465945A4 EP1465945A4 (en) 2006-05-10

Family

ID=19718540

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03701911A Withdrawn EP1465945A4 (en) 2002-01-17 2003-01-15 Rubber composition comprising carbon nanotubes as reinforcing agent and preparation thereof

Country Status (6)

Country Link
EP (1) EP1465945A4 (en)
JP (1) JP2005514509A (en)
KR (1) KR100592527B1 (en)
CN (1) CN1615336A (en)
AU (1) AU2003202820A1 (en)
WO (1) WO2003060002A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread

Families Citing this family (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4005048B2 (en) 2003-04-09 2007-11-07 日信工業株式会社 Carbon fiber composite material and method for producing the same
JP4005058B2 (en) 2003-07-23 2007-11-07 日信工業株式会社 Carbon fiber composite material and method for producing the same, carbon fiber composite molded article and method for producing the same
JP4224407B2 (en) 2004-01-29 2009-02-12 日信工業株式会社 Method for producing composite metal material
JP4224445B2 (en) 2004-02-06 2009-02-12 日信工業株式会社 Method for producing carbon black composite material
JP4149413B2 (en) * 2004-05-21 2008-09-10 日信工業株式会社 Carbon fiber composite material and method for producing the same
JP4224428B2 (en) * 2004-05-24 2009-02-12 日信工業株式会社 Method for producing metal material, method for producing carbon fiber composite metal material
CN1328309C (en) * 2004-05-26 2007-07-25 中国科学院金属研究所 Conductive composite materials with positive temperature coefficient effect and process for making same
JP4224438B2 (en) 2004-07-16 2009-02-12 日信工業株式会社 Method for producing carbon fiber composite metal material
JP2006167710A (en) 2004-11-22 2006-06-29 Nissin Kogyo Co Ltd Method of manufacturing thin film, substrate having thin-film, electron emission material, method of manufacturing electron emission material, and electron emission device
JP2007039649A (en) * 2005-06-30 2007-02-15 Nissin Kogyo Co Ltd Composite material
KR100705784B1 (en) * 2005-10-31 2007-04-10 금호타이어 주식회사 Tire apex composition filed carbon nanotube
KR100705783B1 (en) * 2005-10-31 2007-04-10 금호타이어 주식회사 Tire tread composition filed nanofiber
KR100789402B1 (en) * 2005-11-25 2007-12-28 민영혜 Negative ion or ultrared foamy rubber
JP2008143963A (en) * 2006-12-07 2008-06-26 Nissin Kogyo Co Ltd Carbon fiber composite material
KR100827320B1 (en) * 2007-03-22 2008-05-07 금호타이어 주식회사 Belt rubber composition for tire
EP2142589A2 (en) * 2007-05-01 2010-01-13 Dow Corning Corporation Reinforced silicone resin film
KR100833782B1 (en) * 2007-09-18 2008-05-29 금호타이어 주식회사 High thermal conductivity rubber composition
KR100915460B1 (en) * 2007-09-21 2009-09-04 금호타이어 주식회사 Bladder rubber composition comprising carbon nanofiber/carnon black nanocomposites
US20090156740A1 (en) * 2007-12-15 2009-06-18 Annette Lechtenboehmer Tire with component containing polymeric nanofiber
FR2925061B1 (en) * 2007-12-18 2010-01-15 Michelin Soc Tech RUBBER COMPOSITION, IN PARTICULAR FOR THE MANUFACTURE OF TIRES
CN102112299B (en) * 2008-08-08 2015-04-29 埃克森美孚化学专利公司 Graphite nanocomposites
US7923491B2 (en) 2008-08-08 2011-04-12 Exxonmobil Chemical Patents Inc. Graphite nanocomposites
US8725420B2 (en) 2008-10-31 2014-05-13 The Invention Science Fund I, Llc Compositions and methods for surface abrasion with frozen particles
US9050317B2 (en) 2008-10-31 2015-06-09 The Invention Science Fund I, Llc Compositions and methods for therapeutic delivery with frozen particles
US9060926B2 (en) 2008-10-31 2015-06-23 The Invention Science Fund I, Llc Compositions and methods for therapeutic delivery with frozen particles
US9060934B2 (en) 2008-10-31 2015-06-23 The Invention Science Fund I, Llc Compositions and methods for surface abrasion with frozen particles
US8409376B2 (en) 2008-10-31 2013-04-02 The Invention Science Fund I, Llc Compositions and methods for surface abrasion with frozen particles
US9072688B2 (en) 2008-10-31 2015-07-07 The Invention Science Fund I, Llc Compositions and methods for therapeutic delivery with frozen particles
US8793075B2 (en) 2008-10-31 2014-07-29 The Invention Science Fund I, Llc Compositions and methods for therapeutic delivery with frozen particles
US20100111857A1 (en) 2008-10-31 2010-05-06 Boyden Edward S Compositions and methods for surface abrasion with frozen particles
US8762067B2 (en) 2008-10-31 2014-06-24 The Invention Science Fund I, Llc Methods and systems for ablation or abrasion with frozen particles and comparing tissue surface ablation or abrasion data to clinical outcome data
US8721583B2 (en) 2008-10-31 2014-05-13 The Invention Science Fund I, Llc Compositions and methods for surface abrasion with frozen particles
US9072799B2 (en) 2008-10-31 2015-07-07 The Invention Science Fund I, Llc Compositions and methods for surface abrasion with frozen particles
US9050070B2 (en) 2008-10-31 2015-06-09 The Invention Science Fund I, Llc Compositions and methods for surface abrasion with frozen particles
US8731840B2 (en) 2008-10-31 2014-05-20 The Invention Science Fund I, Llc Compositions and methods for therapeutic delivery with frozen particles
US8788211B2 (en) 2008-10-31 2014-07-22 The Invention Science Fund I, Llc Method and system for comparing tissue ablation or abrasion data to data related to administration of a frozen particle composition
US8731841B2 (en) 2008-10-31 2014-05-20 The Invention Science Fund I, Llc Compositions and methods for therapeutic delivery with frozen particles
US8551505B2 (en) 2008-10-31 2013-10-08 The Invention Science Fund I, Llc Compositions and methods for therapeutic delivery with frozen particles
US8852064B2 (en) * 2009-04-14 2014-10-07 Xerox Corporation Reduced feed roll wear using carbon nanotube additives in rubbers
US20110146859A1 (en) * 2009-12-21 2011-06-23 Frank Schmitz Tire with component containing carbon nanotubes
US9085678B2 (en) 2010-01-08 2015-07-21 King Abdulaziz City For Science And Technology Clean flame retardant compositions with carbon nano tube for enhancing mechanical properties for insulation of wire and cable
WO2012080158A1 (en) 2010-12-14 2012-06-21 Styron Europe Gmbh Improved elastomer formulations
CN103619951B (en) * 2011-07-06 2016-11-23 日本瑞翁株式会社 Compositions
US8871019B2 (en) 2011-11-01 2014-10-28 King Abdulaziz City Science And Technology Composition for construction materials manufacturing and the method of its production
KR101422829B1 (en) * 2011-12-27 2014-07-25 한국타이어 주식회사 Tread rubber composition and tire manufactured by using the same
RU2495887C1 (en) * 2012-02-27 2013-10-20 Федеральное государственное унитарное предприятие "Ивановский научно-исследовательский институт плёночных материалов и искусственной кожи технического назначения" Федеральной службы безопасности Российской Федерации (ФГУП "ИвНИИПИК" ФСБ России) Method of producing polymer/carbon nanotube composite
JP6124227B2 (en) * 2012-08-02 2017-05-10 アムリル・アクチェンゲゼルシャフトＡｍｒｉｌ Ａｇ Natural rubber containing nanocarbon
CN102775708A (en) * 2012-08-10 2012-11-14 昆山乔锐金属制品有限公司 Formula of compounded rubber
WO2014032172A1 (en) * 2012-08-31 2014-03-06 Soucy Techno Inc. Rubber compositions and uses thereof
KR101364811B1 (en) * 2012-09-06 2014-02-20 (주)에나인더스트리 Cutting method of carbon nanotubes
US9162530B2 (en) 2013-02-14 2015-10-20 The Goodyear Tire & Rubber Company Tire with rubber tread containing precipitated silica and functionalized carbon nanotubes
US9090757B2 (en) 2013-07-15 2015-07-28 The Goodyear Tire & Rubber Company Preparation of rubber reinforced with at least one of graphene and carbon nanotubes with specialized coupling agent and tire with component
SG11201600608VA (en) * 2013-08-30 2016-02-26 Amril Ag Improved natural rubber compositions
US9840611B2 (en) 2013-10-18 2017-12-12 Soucy Techno Inc. Rubber compositions and uses thereof
CN104672531A (en) * 2013-11-29 2015-06-03 招远市东晟橡胶制品有限公司 Anti-aging rubber for tire
CA2925929C (en) 2013-12-19 2018-12-04 Soucy Techno Inc. Rubber compositions and uses thereof
GB2530526B (en) * 2014-09-25 2017-02-08 Amril Ag Styrene-butadiene rubber (SBR)-CNT filled masterbatch
KR101661155B1 (en) * 2015-08-07 2016-09-29 금호타이어 주식회사 Rubber composite of tyre tread comprising carbon nano tube
RU2697559C1 (en) 2015-10-22 2019-08-15 Бриджстоун Корпорейшн Rubber composition and tire obtained therefrom
US11021581B2 (en) 2016-02-04 2021-06-01 Eastman Chemical Company Durable elastomeric compositions employing cyclododecasulfur as a vulcanizing agent
US10280281B2 (en) 2016-02-04 2019-05-07 Eastman Chemical Company Processes for forming vulcanizable elastomeric formulations and vulcanized elastomeric articles
US10011663B2 (en) 2016-02-04 2018-07-03 Eastman Chemical Company Vulcanizing composition containing cyclododecasulfur and improved cyclododecasulfur compound
US10000380B2 (en) 2016-03-02 2018-06-19 Eastman Chemical Company Method for the manufacture of polymeric sulfur
US11059722B2 (en) 2016-03-02 2021-07-13 Eastman Chemical Company Method for the manufacture of cyclododecasulfur
US9757983B1 (en) 2016-06-07 2017-09-12 The Goodyear Tire & Rubber Company Tire with rubber component containing reinforcement comprised of precipitated silica and functionalized graphene
CN106280736B (en) * 2016-08-24 2018-08-24 无锡宝强工业织造有限公司 A kind of chlorosulfonated polyethylene coating rubber cement and preparation method thereof
CN106626982A (en) * 2016-12-08 2017-05-10 淮安优迪亚橡胶有限公司 Fiber compound rubber
IT201600125806A1 (en) 2016-12-13 2018-06-13 Pirelli Tire for vehicle wheels
CN108299781B (en) * 2018-03-26 2020-07-17 浙江富铭工业机械有限公司 Rubber material for wear-resistant tire and preparation method thereof
US11970610B2 (en) * 2021-12-09 2024-04-30 The Goodyear Tire & Rubber Company Tire rubber composition using pyrazalone-based compound
CN115594887B (en) * 2022-12-13 2023-04-07 广东粤港澳大湾区黄埔材料研究院 Preparation method of modified carbon nanotube and application of modified carbon nanotube in tire tread rubber
CN115850819A (en) * 2023-02-06 2023-03-28 广东粤港澳大湾区黄埔材料研究院 Lower-layer tread rubber composition and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5618875A (en) * 1990-10-23 1997-04-08 Catalytic Materials Limited High performance carbon filament structures
WO2002076888A1 (en) * 2001-03-26 2002-10-03 Ben-Gurion University Of The Negev Method for the preparation of stable suspensions and powders of single carbon nanotubes

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2953996B2 (en) * 1995-05-31 1999-09-27 日本電気株式会社 Metal-coated carbon nanotube and method for producing the same
US6426134B1 (en) * 1998-06-30 2002-07-30 E. I. Du Pont De Nemours And Company Single-wall carbon nanotube-polymer composites
JP3847022B2 (en) * 1999-04-19 2006-11-15 鈴木総業株式会社 Thermally conductive elastomer composition, molded product thereof and laminate thereof
EP1054036A1 (en) * 1999-05-18 2000-11-22 Fina Research S.A. Reinforced polymers
JP3074170B1 (en) * 1999-05-27 2000-08-07 大澤 映二 Manufacturing method of nano-sized spherical graphite
JP4463435B2 (en) * 2000-01-21 2010-05-19 三井化学株式会社 Filler dispersibility improving material, filler-containing resin composition and production method thereof
JP4586251B2 (en) * 2000-09-22 2010-11-24 東レ株式会社 Fuel cell separator
JP3569806B2 (en) * 2001-03-15 2004-09-29 大阪瓦斯株式会社 Iron compound-encapsulated carbon composite and method for producing the same
JP4663187B2 (en) * 2001-09-20 2011-03-30 昭和電工株式会社 Fine carbon fiber mixture and composition containing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5618875A (en) * 1990-10-23 1997-04-08 Catalytic Materials Limited High performance carbon filament structures
WO2002076888A1 (en) * 2001-03-26 2002-10-03 Ben-Gurion University Of The Negev Method for the preparation of stable suspensions and powders of single carbon nanotubes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO03060002A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread

Also Published As

Publication number Publication date
WO2003060002A1 (en) 2003-07-24
KR100592527B1 (en) 2006-06-23
AU2003202820A1 (en) 2003-07-30
CN1615336A (en) 2005-05-11
JP2005514509A (en) 2005-05-19
EP1465945A4 (en) 2006-05-10
KR20030062482A (en) 2003-07-28

Similar Documents

Publication Publication Date Title
WO2003060002A1 (en) Rubber composition comprising carbon nanotubes as reinforcing agent and preparation thereof
JP2005514509A6 (en) Rubber composition containing carbon nanotube as reinforcing agent and method for producing the same
EP1451396B1 (en) Fine carbon fiber mixture and composition thereof
Fakhru’l-Razi et al. Effect of multi-wall carbon nanotubes on the mechanical properties of natural rubber
JP5645090B2 (en) A method for producing a carbon fiber aggregate containing single-walled carbon nanotubes, and a carbon fiber aggregate containing single-walled carbon nanotubes produced by the method.
Tjong Polymer composites with carbonaceous nanofillers: properties and applications
KR100319736B1 (en) Rubber compositions containing carbon fibrils and pneumatic tires
US20120123020A1 (en) Mechanical properties of epoxy filled with functionalized carbon nanotubes
Jung et al. The influence of N-doping types for carbon nanotube reinforced epoxy composites: A combined experimental study and molecular dynamics simulation
Jayalakshmy et al. Applications of carbon-based nanofiller-incorporated rubber composites in the fields of tire engineering, flexible electronics and EMI shielding
JP2005068386A (en) Carbon fiber composite material, method for producing the same, carbon fiber composite molded article and method for producing the same molded article
Zheng et al. Mechanical properties and microstructure characterization of natural rubber reinforced by helical carbon nanofibers
Randjbaran et al. Reasons of Adding Carbon Nanotubes into Composite Systems-Review Paper.
JPH01289843A (en) Rubber composition for tire
Jiang et al. Tensile properties and reinforcement mechanisms of natural rubber/vapor‐grown carbon nanofiber composite
Tang et al. Mechanical properties and oxidation resistance of phenolic formaldehyde interlocking CNTs-Cf/SiC composite
CN112204081A (en) Method for coating fibers containing polar moieties
JP2007277475A (en) Thermoplastic resin composition and thermoplastic resin molded product
JPH01287151A (en) Rubber composition
Pal et al. Rubber blend nanocomposites
KR101918174B1 (en) Tire tread rubber composition using NSBR containing Nano Materials
JPH0361768B2 (en)
Sharma et al. Carbon nanotube composites: critical issues
KR100705784B1 (en) Tire apex composition filed carbon nanotube
JPH0430972B2 (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040712

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KIM, YOUNG-NAM

A4 Supplementary search report drawn up and despatched

Effective date: 20060329

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20060620