JPH05503723A - Composite and its manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Composite and its manufacturing method 〔Technical field〕 The present invention relates to a composite and a method for producing the same.

The present application is filed by Snyder (SBder), who is assigned the same ownership as the present application. “Carbon Fibril” filed on January 28, 1988 by et al. U.S. Patent Application No. 149.5 entitled "Fibrils)" 73 CIP (included here for reference).

[Background technology]

dispensing solid fillers (e.g. fibrous or granular fillers) into a solid or liquid matrix; Various methods exist for dispersing to form composite structures. These methods Root mixer, high shear whirling mixer, roll mill, compaction mixer, or internal Includes blending the filler/matrix mixture using a Brabender type mixer. I'm reading.

Reaction injection molding (RIM) is a molding method as follows.

One or more liquids or mixing reactants are separately metered into the mix head and For example, by first mixing the mixture by high-impact mixing, then pouring the mixture into a mold and weighing it down. Then, a molded part 3 is formed. Often referred to as reinforced reaction injection molding (RRIM) In structural reaction injection molding (SRIM), materials such as shredded glass fibers or particulate mineral fillers are used. A reinforcing agent is added to the mixture before molding. Another type of SRIM method uses low viscosity, In particular, the polymerized RIM composition was poured into a mold filled with fibrous mat/mat, and the resulting Shaping the composition. In both RIM and SRIM methods, the formed part is be coated to provide UV protection and to balance with other components.

A second type of molding process involves premixing. The pre-mixture is processed before the molding operation. A molding composition prepared separately from the molding composition containing all the ingredients necessary for molding, such as Contains fat, reinforcing agent, filler, catalyst, mold release agent, etc. One type of premix is It is called sheet molding compound (SMC). SMC is typically made of shredded glass. A thin, semi-tacky sheet of thermoplastic resin reinforced with glass fibers or continuous glass fiber threads. It is the default. The sheet is formed using, for example, a combination molding method, and various parts are formed. products can be formed. The second type of premix is for bulk molding. It is called compound compound (BMC). BMC is a putty that can be directly molded. prepared into a shape. It can be extruded into a bar or log shape to make it easier to handle. Can be done. Molded premix products are also often used, such as RIM and SRIM molded articles. coated before each use.

Various types of compositions are also known. For example, polymer-based conductive composites (e.g. (in the form of coatings or inks) are known. These compositions contain conductive additives The combination makes it conductive.

Hybrid composites are those in which the matrix is reinforced with two or more reinforcing agents. It is a built-in structure. Reinforcement present in the largest volume fraction (compared to other reinforcements) The reinforcing agent is called the secondary reinforcing agent and the remaining reinforcing agent is called the secondary reinforcing agent.

Elastomers have also been filled with various materials. Such materials are elastomers to improve the mechanical or electrical properties of the matrix or to reduce cost It is used for.

A friction material is a material that converts applied force into heat in order to dissipate it.

Applications for such materials include brakes, automatic transmission discs, and clutches. Ru. Reinforced organic polymers have been used as friction materials.

Carbon fibrils are single carbon fibers with a diameter less than 500 ni. special carbon film Examples of Vibril and its method of manufacture are given by Snyder et al., January 28, 1988. U.S. Patent Application No. 149.573 filed on U.S. Patent No. 4.663.230 by Tennent Issue (carbon fibrils, methods for producing them, and compositions containing them): Tenet et al. U.S. Patent Application Serial No. filed June 6, 1986 by 871.676 (Novel carbon fibrils, methods for producing the same, and compositions containing the same) ), U.S. patent filed June 6, 1986 by Tenet et al.! 5er ialN　o, 871.675 (Novel carbon fibril, method for producing the same, and carbon 1988 by Nandeville et al. US patent application filed on December 16th Serial No. 285.817 (Fibril), and 19 by Manokurthy (hlcCar-thy) and others. US Patent Application No. 151.967 filed on May 15, 1989 (Surface treatment of carbon fine fibers) (All of them are the same as the present application and have been assigned to a person. and they are included here in their entirety for reference).

[Disclosure of the invention]

Blending method The present invention involves introducing one or more fillers and matrix materials into a stirred ball mill. , the filler and the matrix material are combined into particles of aggregates formed by the filler. including sufficient reaction time to reduce the diameter to a value less than a predetermined value. Under reaction conditions, the combined force of shear and impact forces is applied throughout the matrix material. Characterized as an invention is a compounding method for manufacturing a composite including steps of dispersing fillers It is something that can be attached.

In a preferred embodiment, the predetermined value of the aggregate particle size is 100% of the filler particle size. It is 0 times or less, more preferably 100 times or less, even more preferably 10 times or less. Mitsuru The size of one or more of the characteristic axes of the filler (a measure of its particle size) is less than 1 μl. Preferably 0.1μ! It is even more preferable that it be smaller.

Viscosity modifiers (i.e., modifying the inherent viscosity of the matrix/filler mixture to facilitate dispersion) The preferred viscosity adjustment material is preferably added to a stirred ball mill. Moderating agents include materials that are removed after the dispersion process, such as solvents, and materials that are retained after the dispersion process. An example of the latter type of viscosity modifier is the matrix material It is a reactive diluent that chemically reacts with As a more preferable type B, one or more types grinding media (i.e., particulate material that promotes dispersion by applying additional impact force) into a stirred ball mill.

Preferred fillers include whiskers (i.e. single crystal fibers), discontinuous fibers, granular fibers, and carbon fibrils.

Preferably, the fibrils are tubes with graphite layers substantially parallel to the fibril axis. Yes. One M characteristic of substantial parallelism is U.S. patent application S by Snyder et al. As described in Erial No. 149.573, cast onto the fibril axis. The length of the shaded graphite layer extends over a relatively long distance relative to the outer diameter of the fibril. (e.g. at least twice the fibril diameter, preferably less than that diameter) These fibrils have a continuous pyrolytic carbon outer coating (immediately pyrolytically produced from the thermal decomposition of the gas feed used to produce the fibrils. Preferably, it does not contain any attached carbon. Fibrils are 3.5 to 75 nm (both numbers preferably has a length-to-diameter ratio of at least 5.

With this morphology, the outer surface of the graphite layer contains multiple oxygen-containing groups (e.g., carbonyl, Carboxylic acid, carboxylic acid ester, epoxy, vinyl ester, hydroxy, acetic acid hydroxy, isocyanate, or amine groups) or derivatives thereof (e.g. Also preferred are fibrils attached to .

Preferred matrix materials include metal powders, ceramic powders (e.g. glass powders), Thermoplastics, thermosets, and elastomers, and matrices in liquid form. Contains alcoholic materials. Preferred thermoplastic resins include thermoplastic polyesters (e.g. (e.g., polyethylene telecrate), polyurethane, polyether ether ketone polyethersulfone, polyetherimide, polyamide (e.g. nylon) ), and polyurea resins.6 Preferred thermosetting resins include phenolics, Epoxy, thermoset.

thermosetting polyurethane, thermosetting polyester (e.g. alkyd), polyimide, vinyl sumaleimide, polycyclopentadiene, and vinyl acrylimide [Ohio Ashland Chemical Company of Columbus, State such as Arimix resin commercially available from Co., Ltd.). be caught. Preferred elastomers include styrene-butadiene rubber, natural rubber, Tyrene propylene diene monomer (EPDM) rubber, silicone rubber, poly Butadiene (cis and trans 1.4 and 1.2-polybutadiene), polyiso Prene, neoprene, chloroprene, fluoroelastomers (e.g. fluorinated polyethylene), and urethane elastomers.

If the matrix material is a thermoplastic resin, the blending method is based on the contents of the stirred ball mill. is cooled to a temperature at which the matrix material becomes brittle before the dispersion process, and that temperature is then Preferably, the method includes maintaining the temperature during the process.

The present invention also characterizes the composite produced according to the above method as an invention. Ru.

In the present invention, the filler has an average filler diameter of 1 μm or less over the entire matrix material. substantially uniform dispersion even when the temperature is low, resulting in improved composite properties, e.g. Produces composites endowed with gaseous, optical, mechanical, and magnetic properties. uniformity The degree of The composite can be more tailored to the specific intended use.

The present invention simultaneously incorporates various fillers with different diameters and shapes into a matrix. There is no need to process or apply chemical dispersants to enable dispersion. stomach.

- outside, use The present invention also includes a composite containing a matrix mixed with carbon fibrils. The amount of these fibrils is determined by the amount of fibrils that the composite contains directly (i.e., first The amount is sufficient to be electrostatically overcoated (without applying a secondary coating).

In one embodiment, the composite is a reaction injection molded matrix incorporating carbon fibrils. Including Ricks.

Second Ba! As a composite, the resin matrix is mixed with carbon fibrils. The molded product of the pre-mixture containing.

In a preferred embodiment, the premix is a sheet molding compound or a bulk molding compound. It is a compound. The electrical conductivity of the composite is determined by the same amount of carbon brane in the same matrix. The electrical conductivity is preferably greater than the electrical conductivity of the composite material.

The amount of fibrils in the composite is such that it is possible to perform electrostatic coating directly on the surface. Preferably, the amount is sufficient to provide the composite with a high enough electrical conductivity to Yes.

Also preferred are composites in which the amount of fibrils is sufficient to dissipate static electricity. The amount is good preferably less than or equal to 20% by weight (based on resin), more preferably less than or equal to 20% by weight (based on resin). or less than or equal to 4% by weight.

Preferably, the fibrils are tubes with a substantially average layer of graphite on the fibril axis. One feature of new, substantial parallelism is the U.S. patent application S. As described in Erial No. 149,573, cast onto the fibril axis. The length of the shaded graphite layer extends over a relatively long distance relative to the outer diameter of the fibril. (e.g. at least twice the fibril diameter, preferably less than that diameter) These fibrils have a continuous pyrolytic carbon outer coating (immediately pyrolytically produced from the thermal decomposition of the gas feed used to produce the fibrils. Preferably, it does not contain any attached carbon. Fibrils are 3.5 to 75 nm (both numbers preferably has a length-to-diameter ratio of at least 5.

With this morphology, the outer surface of the graphite layer contains multiple oxygen-containing groups (e.g., carbonyl, Carboxylic acid, carboxylic acid ester, epoxy, vinyl ester, hydroxy, acetic acid (alkoxy, incyanate, or amide groups), or derivatives thereof (e.g. fibrils that are attached to (alphahydryl, amino, or imino groups) preferable.

Preferred matrix materials include thermoplastics (e.g. polyamides, polyurethanes). tan, polyurea, or elastomer), and thermosetting resins (e.g. Robe” entadiene, polyester, thermosetting polyurethane, epoxy resin, is a vinyl acrylimide resin (Ashland Chemical, Columbus, Ohio). (such as ant glass resin commercially available from Co., Ltd.). using a resin mixture You can stay there. Any complex in the form of an automotive part for a car, truck or bus Preferably, it is molded.

As a third aspect B, the present invention is polymerized to form a reaction injection molded matrix. A reaction injection compound containing carbon fibrils and one or more liquid reactants that can be It characterizes a complex of shapes suitable for shapes.

In a fourth aspect, the present invention provides a premix comprising a resin mixed with carbon fibrils. It is characterized by

In a preferred embodiment, the liquid reactant is one or more polyols, polyisocyanates, etc. Contains salts or polyamines.

Preferably, the premix is a bulk molding compound or a sheet molding compound.

The amount of fibrils is preferably equal to or less than 20% by weight, more preferably Preferably equal to or less than 4% by weight. Preferred fibrils and resins is as described above.

The present invention also characterizes the method for producing the above-mentioned composite as an invention. .

Reaction injection molded composites are made of a liquid that can polymerize to form a matrix. The reactants and fibrils are mixed, the mixture is introduced into a mold, and the mixture is subjected to pressure. and temperature to produce a composite in the form of a molded part. Manufactured by the following method.

Sheet-shaped molding compound composites are made by mixing fibrils and resin, and then molding the mixture into a sheet. manufactured by a method that includes molding into a sheet. The bulk molding compound composite is , to a method comprising mixing fibrils and resin to form a putty suitable for molding. Manufactured by Both methods require the formation of complexes under reaction conditions including temperature and pressure. Preferably, it includes a molding step for manufacturing into the shape of a shaped part.

Molded parts manufactured by the above method are directly exposed to static electricity once molding is completed. Preferably overridden.

The present invention provides a method for preparing premixes that are electrically conductive with relatively low fibril content, e.g. Reaction injection molded products made from sheet-form molding compounds or bulk molding compounds) A molded composite and a molded composite are provided. This allows for As shown in Figure 2, molded parts made from these composites can be coated electrostatically. , thereby eliminating the need to apply a conductive undercoat as a separate step. Ru. Further advantages offered by fibrils include good mechanical properties (e.g. hardness and impact strength) and the ability to use fewer additives such as flame retardants. be caught. Fibrils also provide inherent EMI shielding.

The use of fibrils ensures good electrical and mechanical properties from batch to batch. It also provides several processing advantages, including better consistency. R.I. In the case of M treatment, the fibrils are smaller in size and the lower fibrils used. The Bryl content will not block the small tubes and holes of the processing equipment. more fib The rills do not need to be in a massively oriented state during processing, so they does not contribute to local distortion. In the case of SMC, the viscosity due to fibrils is The thickening allows the thickening agent needed to form a viscous sheet to be omitted. Become so.

・Air guide cover and ink The present invention is a polymer binder mixed with carbon fibrils.

The invention features an electrically conductive composite in a form suitable for application to the surface of a substrate containing It is something that can be attached.

In a preferred embodiment, the composite is in the form of a powder or liquid coating. Covering The amount of fibrils in is large enough so that the substrate to which the coating is applied is electrostatically coated directly. Preferably, it is of a high quality. The amount is preferably 15% by weight (based on resin) more preferably 0.5 to 10% by weight. Preferred layers are coatings in which the amount of fibrils is 1 to 4% by weight. More than one type of coating May contain the above pigments.

In another preferred embodiment, the coating is applied onto the surface of the substrate to form the electronic component. It is in the form of a resistive ink suitable for screen printing. resistant in When applied to a substrate, the amount of fibrils in the The volume resistivity of the binder (bulk This amount is sufficient to reduce the resistance. Fibril preference A preferred amount is 1 to 30% by weight.

In another preferred embodiment, the coating further includes electrically conductive graphite or metal particles (e.g. (silver foil pieces, metal-coated shredded fibers, or metal powder) printed onto the surface of the substrate It is in the form of a conductive ink suitable for The amount of fibrils in the ink depends on the particle filling. The volume resistivity of the filler (measured without carbon fibrils) is applied to the substrate. It is sufficient to reduce the amount by a predetermined amount when applied. preferably The volume resistivity of the particle-filled binder is greater than 1Ωcx, and the amount of fibrils is This amount is sufficient to reduce the resistivity to less than 1 Ωcx. even more preferable The volume resistivity of the particle-filled binder is greater than 1O-1Ωc1, and the amount of fibrils is is the volume resistivity t! is sufficient to reduce it to a value lower than 0:10-1ΩCj It is a conductive ink. The preferred amount of fibrils is 20-50% by weight.

Preferably, the fibrils are tubes with graphite layers substantially parallel to the fibril axis. 5 One feature of substantial parallelism is the U.S. patent application S. Snyder et al. As described in Erial No. 149.573, cast onto the fibril axis. The length of the shaded graphite layer extends over a relatively long distance relative to the outer diameter of the fibril. (e.g. at least twice the fibril diameter, preferably less than that diameter) (at least 5 times). These fibrils have a continuous pyrolytic carbon outer coating. (i.e., the heat content resulting from the pyrolysis of the gas feed used to produce the fibrils) Preferably, it does not have any chemically attached carbon. Fibrils are 3.5-75nm diameter (inclusive) and preferably has a length-to-diameter ratio of at least 5. Yes.

Preferred polymeric binders include thermoplastics (e.g., polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, or thermoplastic polyester resins, e.g. polyethylene terephthalate), and thermosetting resins (e.g. curable polyester resin or epoxy resin).

The invention also features a substrate coated with a fibril-filled electrically conductive composite. It is something that can be attached. The conductivity of the composite is determined by the direct electrostatic coating on the surface of the coated substrate. It is preferable to have a size large enough to allow for Also, the composite is an electronic component (for example, resistive ink printed onto a substrate in the form of a resistor (for example, a resistor) or printed on a substrate in the form of a conductive trace for electrical connection Preferably, the conductive ink is a substrate for a printed circuit board. Ma Also, for producing coated substrates (they can be electrostatically coated directly) and methods for screen printing fibril-filled inks onto substrates. Law is also characterized as an invention.

Fibril-filled composites are electrically conductive with low fibril content. the result, Has a predetermined resistivity value.

Coatings and inks that are coated with It can be manufactured without any restrictions.

Such increases are undesirable as they make them difficult to apply. The properties of the complex also It does not vary significantly from batch to batch. Because fibrils make composites Good resistance to shear degradation caused by shear mixing used in This is because it shows that Furthermore, the resistivity of the composite is relatively sensitive to temperature fluctuations. Hateful.

As a primer on molded parts (e.g. car parts) for later electrostatic coating of surfaces. These coatings allow direct electrostatic coating of surfaces with low energy. can reduce corona effects and provide uniform coverage. Wear. Additionally, fibril-filled composites ensure that the finished composite does not have a black appearance. Can be over-colored. Coatings can be applied to metal or molded plastic parts. Suitable for use in conjunction with sacrificial anode materials to help prevent corrosion on exposed surfaces It also has good electrical conductivity. When applied to plastic substrates, these coatings have good Demonstrates mechanical adhesion, allowing metal to be plated directly onto plastic.

Fibril-filled composites in the form of resistive or conductive inks offer additional advantages.

When printed onto a substrate, the ink's resistance and ability to adhere to the substrate Not subject to deterioration due to folding or bending of the body. Ink is abrasion and scratch resistant It also has resistance. For conductive inks, fibril-filled inks have a conductive filler. Lighter and less modified than inks that are 100% metal particles (which makes them easier to apply) Shows improved corrosion resistance. Furthermore, conductive ink containing metal particles by fibrils resistivity can now be finely tuned for specific uses and applications; This allows us to obtain resistivity values that cannot be easily obtained using metal particles alone. can be done.

Elastomer one The present invention provides a composite in which carbon fibrils are mixed into an elastomer matrix. It is characteristic. One! As j3-like, those fibrils have continuous heat content. Decarbonized outer coating (i.e., pyrolysis of the gas feed used to produce the fibrils) pyrolytically deposited carbon) and are substantially parallel to the fibril axis. It has the characteristics of being made of a tube with a lead layer. One feature of substantial parallelism is U.S. Patent Application No. 149,573 by Snyder et al. As described in , the length of the graphite layer projected onto the fibril axis is extend a relatively long distance relative to the outer diameter of the fibrils (e.g., at least 2 times the diameter of the rill, preferably at least 5 times that diameter). child These fibrils are preferably smaller than 1 oot+m, more preferably 3. having a diameter of 5 to 75 nm (inclusive) and a length-to-diameter ratio of 5 to 100 It is preferable to do so.

In a second aspect, the fibrils have a crystalline graphite structure and along the fibril axis. It has a characteristic feature that is defined as a fishbone-like arrangement of graphite layers.

Examples of such fibrils are described in U.S. patent application No. 5er by Snyder et al. ial No.]49.573 and Geus et al. 1986 It is described in European Patent Application No. 01911558, published on October 22nd.

Preferably, these fibrils have a diameter of less than 1100n.

The amount of fibrils in the composite is such that the composite can be cured by resistive or induction heating. electrically monitored detection (mo) of at least one physical property of the complex. This amount is preferably sufficient to enable the is preferably less than 25 parts per Cto part of elastomer, more preferably less than 25 parts per Cto part of elastomer. or less than 10 parts per 100 parts of elastomer. However, the master bunch ( i.e., later mixed with additional elastomers to produce the final composite structure. For fibril-filled elastomer precursors), the amount of fibrils in the elastomer Preferably more than 25 parts per 100 parts.

Preferred elastomer matrices include natural rubber, styrene-butadiene rubber (both random and block copolymers), polyimrene, neorene, black Robrene polybutadiene (cis and trans 1,4 and 1,2-polybutadiene) ), fluoroelastomers (e.g. fluorinated polyethylene), silicones rubber, and urethane elastomers. Elastomer outside the fibrils - contains one or more fillers, such as carbon brane, silica, or combinations thereof. Preferably, it includes a combination.

The ratio of the amount of fibrils in the composite to the total amount of filler is at least 61:4 or or more (for example, 1.5.1:6, etc.). The composite is a tire or its parts ( (e.g. tire tread or gauging), in the form of a sealant, solution, or adhesive. Preferably given.

In a third aspect, the present invention provides carbon fibrils in the elastomer matrix. The amount of fibrils is either resistant or attractive. Sufficient to impart electrical conductivity to the composite of sufficient magnitude to allow conductive heating The amount of the composite material to be cured is as follows. This characterizes the lastomer curing method.

In a fourth aspect, the present invention provides electrically conductive additives in the elastomeric matrix. The composite is prepared by incorporating the elastomer, but the amount of additive is electrical conductivity of sufficient magnitude to permit electrical monitoring and detection of physical conditions; is sufficient to impart to the composite the electrical properties of said composite (e.g. intrinsic elastomer resistance) as an indicator of the physical condition of the elastomer. The present invention characterizes a method for monitoring and detecting the physical condition of a streamer. This embodiment is preferable. In a specific example, the electrically conductive additive includes carbon fibrils. Another preferred ingredient As an example, the complex is in the shape of a tire, and the internal pressure of that tire is monitored and detected. be done. The method evaluates the presence of cuts, tears, and pores in elastomers (e.g., composites). It is also preferable to use it for monitoring detection (in the form of bare belts or hoses).

In preferred embodiments of the third and fourth aspects, the amount of fibrils in the composite is less than 25 parts per 100 parts of elastomer, more preferably less than 100 parts of elastomer Less than 10 parts per part. Preferred fibrils are those described above.

In a fifth aspect, the invention provides at least 25 parts per 100 parts of elastomer. producing a masterbatch by dispersing fibrils in an elastomer; A predetermined portion of the masterbatch is filled with a material used for manufacturing the masterbatch. Additional amounts of the same or different elastomer may be incorporated to form a composite. A patent featuring a method of manufacturing an elastomer composite including steps for manufacturing Preferably the amount of fibrils in the final composite is 25 parts per 100 parts of elastomer. parts, more preferably less than 10 parts. Preferred fibrils are described above. It's sticky. During the production of masterbatch or during the compounding process, carbon Lac may be added to the composite.

In a sixth aspect, the present invention provides sufficient elastomer masterbatch. This characterizes the stroma reinforcement method. These fibrils are the and as described above for the second embodiment.

The present invention has good toughness, tensile strength, tear strength, cream and die swelling resistance, and Provides a fibril-reinforced elastomeric composite that exhibits corrosion resistance (i.e., pre-cure strength). Ru.

These composites also have good hardening, stress/strain properties, and wear resistance (relatively soft even when using an elastomeric matrix) and have a low specific gravity. improvement The resulting abrasion resistance provides articles made from these composites with traction and rolling resistance. A favorable balance of drag and tread wear can be achieved. Furthermore, this These advantages are achieved with low fibril content.

Further advantages derive from the electrical properties of fibrils. fibrils are electrically conductive , they reinforce the elastomer matrix and at the same time electrically conduct the matrix. It can be used to perform the dual function of being air conductive. electrical conductivity The composite can be cured by resistive or induction heating, thereby Avoids the heat transfer and cost increase problems often associated with thermal curing . By being able to electrically cure, the fibril-filled composite can be made into a rubber Rubber bonding (for example, when bonding a tire tread to a tire casing), rubber , various bonding operations such as forming metallic bonds, and rubber-ceramic bonds, and Particularly useful as an adhesive in rubber repair systems for products such as tires and conveyor belts. It can be made to stand.

Composite electrical conductivity extrusion of rubber tubes, tires, treads, and related products It is also useful for applications such as.

Additionally, the composites can be partially electrically cured to provide additional shape stability to the composite. can give. The present invention electrically detects physical changes in a complex, such as internal pressure. It also enables products designed to be monitored and detected. For example, tires, air springs Easily and effectively monitor and detect the condition of hoses, hoses or conveyor belts. I can do it.

Izumi Natsu 1 As a first aspect, the present invention uses a matrix mixed with carbon fibrils. It characterizes brakes or parts thereof manufactured from friction materials containing:

In a second aspect, the invention includes a matrix incorporating carbon fibrils. Characterizes clutches or parts thereof manufactured from friction materials.

In a third aspect, the invention includes a matrix incorporating carbon fibrils. Characterizes automatic transmission discs or parts thereof manufactured from friction materials.

As a fourth aspect B, the present invention includes a matrix mixed with carbon fibrils. It characterizes a composite in the form of a friction material.

In a preferred embodiment, the amount of fibrils is equal to 20% by weight (based on resin). or less, more preferably 5 to 10% by weight.

Preferably, the fibrils are tubes with graphite layers substantially parallel to the fibril axis. Yes. One feature of substantial parallelism is the U.S. patent application S. on the fibril axis, as described in ErialN o, 149,573. The length of the projected graphite layer extends over a relatively long distance with respect to the outer diameter of the fibril. (e.g. at least twice the fibril diameter, preferably less than that diameter) (at least 5 times). These fibrils are continuously pyrolyzed carbon on the outside The coating (i.e., the heat generated from the pyrolysis of the gas feed used to make the fibrils) It is preferable that the material has no decompositionally attached carbon. Fibrils are 35-75nm diameter (inclusive) and preferably has a length-to-diameter ratio of at least 5. Yes. It has this morphology, and the outer surface of the graphite layer has multiple oxygen-containing groups (e.g., carboxylic acid). vinyl, carboxylic acid, carboxylic acid ester, epoxy, vinyl ester, hydroxyl cy, alkoxy isocyanate, or amide group>, or derivatives thereof (e.g. for example, fibrils attached to sulfhydryl, amino, or imino groups). It is also preferable to

Preferred matrix materials are carbon and thermosetting resins, such as phenolic resins. , polyester resins, and epoxy resins. It is also preferable to add it in different ways. Examples of preferred fillers include metals, shea, beryllia, Granules such as alumina, silicon carbide, boron carbonate, titanium dioxide, or carbon black This includes things like Examples of preferred applications for friction materials include clutches, automatic transmission discs, and brakes (e.g. linings for brake pads and tubes) .

Articles made from friction materials made from fibril-containing composites exhibit good friction. These properties exhibit rubbing properties and fade resistance at elevated temperatures. 5 Outdoor vehicles, racing cars, and equipment that are frequently exposed to such temperatures. Particularly useful for heavy-duty applications including armored vehicles and automobile disc brakes. It's about quality. Additionally, these friction materials resist delamination and cracking at elevated temperatures. Has resistance.

l belly l emperor o As a first aspect, the present invention provides a secondary fiber reinforcement and a random pattern for the secondary reinforcement. A secondary reinforcing agent is mixed in, which is distributed evenly throughout the matrix. Characterizes a hybrid complex containing a matrix.

In a preferred embodiment, the average diameter of the primary reinforcement is less than the average diameter of the secondary reinforcement. Both are 10 times larger, and preferably at least 100 times larger. matrix Most of the aggregates formed by the secondary reinforcing agent in the or less than 0.5 μm, the secondary reinforcement preferably includes carbon fine fibers (i.e. carbon fibers with a diameter equal to or smaller than 1 μl), whiskers (immediately i.e., single crystal fibers), chopped fibers (i.e., discontinuous fibers with a length of 1/16 to 2 inches) fibers), and particulate materials such as silica or carbon black. carbon fiber Brill, preferably a carbon tube with a layer of graphite substantially parallel to the fibril axis Fibrils are also preferred. One feature of substantial parallelism is that Snyder et al. As described in U.S. Patent Application No. 149,573, The length of the graphite layer projected onto the fibril axis is relatively long compared to the outer diameter of the fibril. extending a distance from each other (e.g., at least twice the fibril diameter, preferably is at least five times its diameter). These fibrils are continuous Thermal content of the gas feed used to produce the pyrolytic carbon overcoat (i.e., the fibrils) It is preferred to have no pyrolytically deposited carbon (derived from the solution). The fibril is having a diameter of 3.5 to 75 nm (inclusive), with a length to diameter of at least 5 It is preferable to have the ratio. The amount of secondary reinforcement incorporated into the matrix is preferably or less than or equal to 20% by volume, and preferably from 1 to 10% by volume. Layer preferred.

Preferred primary reinforcing agents include continuous fibers. Examples of preferred continuous fibers include: carbon, glass, ceramic (e.g. boron, alumina, or silicon carbide), and Real aramid (eg, Kevlar) fibers are included. These fibers Fibers are continuous fibers that may be woven, knitted, crimped, or straight. Also preferred are primary reinforcements comprising discontinuous fibers made from the same type of material as the fibers.

Preferred matrix materials include organic thermosets and thermoplastics. good Examples of preferred thermosetting resins include epoxies, bismaleimides, polyimides, and polymers. Contains polyester resin. Examples of preferred thermoplastic resins include polyethylene, polyethylene, Lipropylene, polyamide (e.g. nylon), polyurethane, polyvinyl chloride , thermoplastic polyester resin, polyether ether ketone, polyether sulfate polyetherimide, oriented polyethylene, liquid crystal polymer, and reaction injection molding Contains resin.

Other preferred matrix materials include inorganic polymers (e.g. polymers such as glass). inorganic oxides), metals (e.g. aluminum or titanium alloys), ceramics (e.g. (for example, Boatland cement or concrete), and carbon.

In a second aspect, the present invention provides that a secondary fiber reinforcement and a secondary fiber reinforcement are mixed; the secondary reinforcement has an average diameter that is at least 1000 times the average diameter of the secondary reinforcement; Characterizes a hybrid composite comprising a matrix with .

In a preferred embodiment of the second embodiment, the secondary reinforcing agent is uniformly dispersed in the matrix. and are randomly oriented with respect to the reinforcing agent. Preferred secondary reinforcing agents are mentioned above. It is a carbon fibril like this. Preferred matrix materials, sub-reinforcing agents, aggregates Particle size and amount of secondary reinforcing agent are as described above.

The present invention also features a method of making a hybrid composite.

The present invention has properties that cannot be obtained with composites containing only secondary reinforcing agents. gives a hybrid complex. The secondary reinforcement is randomly oriented relative to the primary reinforcement and uniformly distributed throughout the matrix (the aggregate particle size is evenly distributed throughout the matrix) (measured by small The normally dominant lateral and internal lamellarity is improved. Furthermore, secondary reinforcement is substantially smaller than the primary reinforcing agent, so it can be incorporated into the matrix without any It does not interfere with the properties of the next reinforcing agent. By dispersing the secondary reinforcement throughout the box, the texture or can avoid destruction or deformation of the laminate.

Other features and advantages will be apparent from the following description of the preferred butterfly and from the claims. It will be something like that.

Description of specific examples First, I will briefly explain the drawings.

The drawing is a schematic cross-sectional view of a two-dimensional hybrid composite embodying the invention.

Blending method Preferably, the composite is produced as follows. Matrix material and one type The above filler is placed in a stirred ball mill of the type conventionally used for powder grinding. It will be done.

In the mill, these materials are subjected to shear forces due to the stirring action of a mechanical rotor and Impact by added granular grinding media of the type conventionally used for powder grinding Apply both power and power. Once the grinding operation is complete, remove the granules. death In the case of oak, metal and ceramic matrices, the matrix itself ( (added in powder form) can generate impact forces, so another grinding medium is No need to add body.

A viscosity modifier is added to a viscous matrix/filler mixture to adjust its inherent viscosity to a powder. Reduce to a low enough value to facilitate comminution. Viscosity modifier matrix Especially if the material is a high molecular weight thermoplastic or partially cured thermoset. It is useful for Examples of suitable viscosity modifiers include water, toluene, acetone, methyl ether. Includes solvents such as methylketone (MEK), isopropanol, or mineral oil. Following the operation, the solution can be removed by, for example, vacuum drying, steam expulsion, or freeze drying. Remove medium. The viscosity modifier is part of the matrix or filler after milling. Any material that can be used as a part may be used. Examples of such modifiers include milling medium matrices. A monomer called a reactive diluent that chemically reacts with the storage material, such as styrene. , triallyl cyanurate, diallyl cyanurate, polyfunctional acrylate, and and divinylbenzene).

Viscosity modifiers may be incorporated into the matrix. In such cases, viscosity control The moderation agent can be obtained during the manufacture of the matrix, for example from the solution and polymerization reaction of solution polymerized SBR. Suitable fillers that may be present in the thermoplastic solution include discontinuous fibers. (e.g. shredded glass or carbon fiber), whiskers (e.g. carbon or silicon carbide) carbon fibers), particulate fibers (e.g. silica or carbon black), carbon fibrils or a combination of any or all of these fillers. Preferably, The average diameter of the filler (i.e. the diameter of the individual particles or fibers that make up the filler) is less than 1 μm. It is at a lower level. Preferred fibrils have a small diameter (preferably 3.5-75 continuous pyrolytic carbon with a graphite layer substantially parallel to the fibril axis It has substantially no coating. About that, Tenet (Tennenj) ), U.S. Patent No. 4.663.230, Tennent et al. Serial N o, g71,675; U.S. license issued by Tefuto et al. 1j serial No. 871,676; U.S. patent comparison by Snyder et al. nSerial No.

149.573, and the United States by Mandeville et al. It is described in patent application 5erial No. 2115.817. These frames Vibril is manufactured as described in earlier patents and patent applications. that The fibrils are US Patent Application No. 5 by Matsukashi et al. 1.967, by introducing oxygen-containing functional groups onto the fibril surface. It may be processed as follows. Preferred matrix materials include those described in the invention disclosure above. As described, metal and ceramic (e.g. glass) powders and organic matrices including thermoplastic resins, thermosetting resins, and elastomeric resins. . The production of carbon fibril-filled elastomers was filed at the same time as the present application, and The same transfer was made by Barber et al. as described in U.S. Patent 5erial No. , it is put here in its entirety for reference. For thermoplastics, composites Place the resin and filler into an agitated ball mill, then add dry ice to the mill The contents must be cooled to or close to the temperature at which the resin turns into a brittle solid. Preferably, it is manufactured by. In this form, the resin is more easily crushed during milling. This results in a more uniform dispersion.

The dry ice evaporates during the milling process, so none remains in the final dispersion.

Milling time determines the final size of the filler agglomerates and therefore the degree of dispersion; It in turn depends on the intended end use of the composite. In electrical applications that require internal particle-particle contact to establish fibers, agglomerates can reduce strength. Larger agglomerates can be tolerated than in mechanical applications where they act as defects.

Carbon fibrils (prepared as described above) are made of styrene-butadiene rubber (S BR) The composite dispersed in the matrix was processed using the stirred whole mill method described above. Fibers produced using conventional internal mixing and roll mill compounding methods compared to a fibril-reinforced SBR matrix. Those results shown in Table ■ The final tensile strength ( M P A> 6.7 10.1 Elongation at break (%) 255 395 Modulus during stretching (MPa) Hardness (IRHD) 64 64 Trousers torn (KN/M) 5.4 6. fl ring fatigue (Kilocycles until failure > 12 40 Table I (continued) 11 Roll mill Ball mill DIN wear: Loss (IIJI'>203 1.89 index 95 102 Heat accumulation ("C) 70 65 Resistivity (Ωcz) 2190 42 The compounding method was filed at the same time as the present application, and the same assignment as the present application has been assigned to a person. U.S. Patent S entitled "Hybrid Complex" by Creehan et al. 　erial　No.

(It is put here in its entirety for reference) of the hybrid complex described in It can also be used to produce prepregs for.

Union for evening The following example shows a carbon fibril incorporated sheet molding compound (SMC). ) composites, drumstick molding compound (BMC) composites, and reaction injection molding (RIM) Describe a complex. Preferred fibrils are disclosed in U.S. Pat. No. 4.66 by Tenet. No. 3.230: U.S. patent ratio 1i1 S area I N by Tenet et al. o, 1t71.675; U.S. Patent Application S erial by Tenet et al. No. 871,676: U.S. patent application filed by Snyder et al. As described in U.S. Patent Application No. 2g5.1117 by et al. small diameter (preferably 3.5 to 75 nm), substantially attached to the fibril axis, so that with parallel graphite layers and substantially no continuous pyrolytic carbon outer coating. Ru. These fibrils are manufactured as described in the aforementioned patents and patent applications. will be built. These fibrils are described in the US patent application Ser. ial No. 351,967, acid on the fibril surface. Treatment may also be performed to introduce a functional group containing an element.

Example 1 - RIM Fibril-containing RIM composites are produced using conventional RIM processing equipment. So Equipment such as material conditioning systems, high pressure metering systems, mix heads, molds, and It has a double-shaped operation table.

The material preparation system consists of a tank that holds the reactants for producing the composite (each reactant is separated). (stored in different tanks), with uniform temperature and composition conditions throughout the tank. A stirrer to maintain and maintain proper levels of dissolved gas in the reactants. It has a temperature control system. Fibrils are present in the final molded product in an amount of 1 to 4% by weight. premixed with one or more reactants in an amount sufficient to provide Preferred additional tanks include any additional tanks, such as shredded glass fibers. Additives such as printing materials and catalysts are preserved. Preferred reactants include polio polyisocyanates (for producing polyurethane matrices) and Polyamines and polyisocyanates (for producing polyurea matrices) is included.

Typically, high pressure piston pumps or lans, e.g. axial or radial, are used. ce) A metering system consisting of a displacement cylinder is used for the reactants, fibrils and additional filling. Meter the appropriate amount of agent into the mix head. The mixing head is, for example, ■500 The reactants and filler are mixed by direct collision at a pressure of ~3500 psi. It has a room where When the mixing is complete, the mixture is transferred to a mold where the reactants are polymerized. to form the final part. Suitable mold structures include machined steel or aluminum. minium, cast aluminum, kirksite, spray gold or electroplated boards, and filled epoxy resins. Typical type during polymerization Internal pressure is 25-100 psi. The molding temperature is easily known to those skilled in the art. However, this will vary depending on the particular reactants used. Place of polyurethane forming reactants When the mold temperature is approximately +30°F (±70°F), the mold control table orients the mold and Provides clamping force that withstands internal pressure, opens and closes molds, removes finished parts, cleans, and positioning the mold to prepare it for the next molding operation.

Fibril-containing RIM composites are useful in a variety of industrial and consumer molded products. Ru. They are automotive parts of cars, trucks, or buses, such as bumpers, interior parts, etc. For parts, instrument panels, integral window sealants, steering wheels, armrests, protective coverings, body panels Particularly useful. The parts are coated before use. carbon fibrils By mixing these parts, they can be electrostatically coated, and their manufacture can be This can be done simultaneously with product processing.

Example 2-3MC The fibril-containing SMC composites are prepared using conventional SMC processing equipment. Continuous This device, which has a belt or belt, is typically used for mixing systems, paste metering installations, etc. It has a press system, a compression system, and a take-out system.

In mixed systems, uncured resin (typically unsaturated thermoset polyester or epoxy resins, which cure by the application of heat) and catalysts, fillers, and thickeners. , mold release agents, pigments, thermoplastic polymers (e.g., polymers to minimize shrinkage during molding). polyvinyl chloride polymers and copolymers, and polyethylene powder), flame retardants, and ultraviolet A soft dough suitable for forming into sheets by adding additives such as line absorbers. Make a paste with the consistency of The paste also contains carbon fibrils.

The mixing system may be batch, batch/continuous, or continuous.

Transfer the paste from the mixing system to the paste reservoir using an adjustable doctor blade and then onto a plastic (e.g. polyethylene) carrier film above and below. Measure and form a paste of a predetermined thickness. The height of the doctor blade is Determine the amount of resin paste in the final SMC composite. 2 paste coatings Apply reinforcement between the sheets, e.g. chopped glass thread or continuous glass roving. Use to form a sandwich. Additional carbon fibrils are added at this stage. You may add Total f of carbon fibrils (i.e., fibrils added during paste formulation) The sum of brill and fibrils applied directly to the paste-coated sheet) is Preferably, it is 1 to 4% by weight.

The pressing machine squeezes the sandwich-like material to form fibrils and resin paste. Make sure to wet all other reinforcements. Typically, the press is a series of serrated steel It consists of a roller or two wire mesh belt compression mechanism.

Next, the sheet that comes out of the press is picked up by a winding turret, for example, and rolled. Form into a shape. Once a complete roll of composite is made, a sheet (typically 2-5 ft wide) and transfer to the second take-up turret. Then the roll unravels the vapor barrier mantle to prevent UV or moisture contamination. Apply. The rolls are stored for about 1 to 78 hours in a ripening chamber maintained at about 85 to 90 degrees Fahrenheit. to provide a uniform and reproducible molding viscosity. Then cut the sheet, e.g. Form into the desired part using compression or mating die molding.

Molded parts produced in this manner are useful in a variety of applications. In the automobile industry , they are parts of heating and ventilation equipment, hoods, trunks, side walls, fenders. -5 For roof panels, front end panels including fender extensions, headlamps and grilles. The installation is useful as a member and cab parts for trucks (e.g. hoods). be. The molded composite is an electrical switchgear container, a manual electric tool such as an electric drill. It is also useful as a container for appliances such as air conditioners and dishwashers. . As in the case of fibril-containing RIM composites, electrostatic coating of these parts can be done.

Example 3 - BMC Fibril-containing BMC composites are produced using conventional 8MC processing equipment. typical Essentially, this device consists of two mixers. First mixer, e.g. simple propeller The resin is (e.g. unsaturated thermosetting polyester or epoxy as in the case of SMC composites) resins), granular fillers, mold release agents, colorants, catalysts, thickeners, low profile (p rofile> Mix with additives. Adding carbon fibrils to the resin mixture is also preferable. Mix the ingredients well to disperse the additives and fibrils throughout the resin. Ru. The resulting mixture is then passed through a second high-load mixer, such as a compaction mixer or a twin-screw mixer. Transfer to a machine and add glass fibers (in the form of chopped yarn or chopped spun roving), Add additional reinforcing agents such as subest, sisal, and organic fibers.

Additional amounts of carbon fibrils may be added at this time.

Total amount of carbon fibrils (i.e. the sum of fibrils added during both mixing stages) is 1-4% by weight based on resin.

A second mixer mixes the ingredients until the resulting mixture has the consistency of a putty. First, the putty is aged (e.g., about 4 hours at 77°F). Maturing is complete When done, form the putty directly or store it in sealed frozen plastic until needed. Store in a bag. Patties are prepared on sticks or logs before ripening for easier handling and storage. It may be extruded into a shape.

The fibril-reinforced BMC premix may be processed by conventional thermosetting molding methods such as squeezing, transfer, or using thermoset injection molding, with sufficient pre-mix to flow into the details of the mold. Shape with pressure. Typical molding pressures range from about 100 to 1500 psi.

Molded parts are useful in many of the same applications as SMC molded parts. additional uses Includes automotive heating vessels and associated conduits. RIM and SMC configuration Similar to shaped parts, BMC molded parts can be pre-applied with an electrically conductive undercoating. It can be electrostatically coated.

Besides the embodiments mentioned above, fibrils can be formed in many types of matrices (e.g. thermoplastics). (such as thermosetting matrices) and directly into the resulting composite. Sufficient electrical conductivity can be provided to enable electrostatic coating of contact surfaces.

Mu, and ink A, r body Both powder and liquid coatings consist of a polymeric binder mixed with carbon fibrils. . Preferred binders for powder coating include the following thermosetting resins. Urethane poly Ester, epoxy, epoxy polyester, polyester triglycidyl socyanurates, and urethane or epoxy type polyesters. Suitable thermoplastic wood Fats include polyethylene, polypropylene, polyamide (e.g. nylon), and polyethylene. vinyl chloride, and thermoplastic polyesters (e.g. polyethylene terephthalate) is included. The molecular weight of the binder must be large enough so that it is solid at room temperature. be. For liquid coatings, preferred resins are thermoplastic polyesters and polyurethanes. It is. The molecular weight of the binder is low enough that it is liquid at room temperature .

To form an electrically conductive coating, 1-4% (based on the weight of the resin) carbon fluoride is added. Preferably, fibril is incorporated into the binder. Such content is applied by coating directly electrostatically forming the outer coating of dielectric components (e.g. plastic) The amount is sufficient. The resistivity of such a coating after application is typically 106ΩCλ The extent is as follows.

Preferred fibrils are disclosed in U.S. Patent No. 4.663.230 by Tenet; U.S. Patent Application No. 1I71,675 by Matt et al. U.S. Patent Application Serial No. 871,676 by Tosonoike; Suna U.S. patent application Serial No. 149.573 by Ider et al.; U.S. Patent Application No. 5erial No. 285.817 by Mandeville et al.; and U.S. Patent Application Serial N oj51 by Ma.7 Carthy et al. Small diameter (preferably 3.5-75 nm) as described in 967 , with a graphite layer substantially parallel to the fibril axis, implementing a continuous pyrolytic carbon outer coating. It is something that you do not have qualitatively. These fibrils are included in the patents and patent applications mentioned above. Manufactured as described. Those fibrils are matsukashi and others. As described in U.S. Patent Application No. 51,967 by The fibril surface may be treated to introduce oxygen-containing functional groups.

These coatings are made by shear mixing together additives such as binders, fibrils, and pigments. Manufactured by

When mixing is complete, apply the coatings directly to the metal or molded plastic parts. or store until needed.

Coatings can be applied to sheet molding compounds (SMC) and bulk moldings such as automotive body panels. The molded compound (BMC) is applied electrostatically in a mold to the press molded part. covered part The article can then be used as is or electrostatically coated with a second coat, e.g. a finish coat. do. In both cases, fibrils are added to the binder to make the coating electrically conductive. By adding it, it is possible to electrostatically coat the surface directly.

B. Ink Preferred polymeric binders for resistive and conductive inks are thermosetting epoxy resins. resins and thermoplastic polyester resins (e.g. polyethylene terephthalate). Ru.

The ink may be provided in the form of a solution or a solvent dispersion.

Preferred fibrils are those mentioned above for powder and liquid coatings. . The amount of fibrils incorporated into the binder is a function of the desired resistivity level; This in turn depends on the intended use of those inks. Generally, 10-2~]0 For resistive inks with resistivities in the range of 6 Ωcw, 1 to 30% by weight fib Lil is mixed in. For example, it already has a relatively low resistivity due to the presence of metal foil. In the case of conductive inks, fibrils are used to finely adjust the resistivity of the ink. However, the resistance cannot be obtained or is impractical by adjusting the amount of silver foil alone. It becomes possible to obtain the value of resistivity. Therefore, the amount of fibrils mixed in is It depends on the resistivity of the filler binder and the desired resistivity value. Generally 20-50% by weight The resistivity of a silver-filled binder with a resistivity greater than 1 part cm is 1Ω. It is mixed in to reduce the value to a value smaller than cx.

The ink is manufactured using the same procedure described above for the conductive powder and liquid coating. be done. They are then attached to a substrate such as a printed circuit board, or for such a substrate. by conventional screen printing onto a disposable donor sheet. screen print to connect resistors (if using resistive ink) or electronic components. A conductive line 118 (in the case of conductive ink) is formed for the conductive ink. ink constant Because of their conductivity, there is no need to perform laser cutting and these inks can be applied to multilayer molded circuit boards. can be used.

elastomer Manufacture composites by dispersing fibrils in an elastomeric matrix do. Preferred fibrils are disclosed in U.S. Pat. No. 4,663,230 by Tenet. 1 U.S. Patent Application No. 871,675 by Tennet et al.; U.S. Patent Application No. 871.676 by Tenet et al. U.S. Patent Application Serial No. 149,573 + by Idar et al. US Patent Application No. 5 by Mandeville et al.

2115.8+7, with a small diameter (preferably from 3.5 to 75 parts m), with a graphite layer parallel to the fibril axis, with a continuous pyrolytic carbon outer layer It has substantially no coating. These fibrils are manufactured as described in the application. Those fibrils are As described in U.S. Patent Application Serial No. 51,967 by et al. The surface of the fibril may be treated to introduce an oxygen-containing functional group. The new elastomer matrix includes natural rubber, styrene-butadiene rubber (both random and block copolymers), polyisoprene, neoprene, chloropropylene Ren, polybutadiene (cis and trans 1.4 and 1.2-polybutadiene) both), fluoroelastomers (e.g. fluorinated polyethylene), silicones Rubber, and urethane elastomer [e.g., spandex (Spar++fe x))) is included.

Low fibril content is preferred. Generally 1 to 10 per 100 parts of elastomer of fibrils are added. Added fillers such as carbon black and silica You may do so.

Hikigami Preferably, for each part of fibril, four parts of y-←da->square' are used.

The special compounding method used to produce fibril-filled elastomer composites is The final properties claimed, the type of elastomeric matrix, the degree of dispersion required, and and the type of filler added outside the fibrils.

For example, it has significant strength values even in the absence of separately added reinforcing agents. In the case of rubber matrices such as natural rubber, Banbury and twin-shaft roll mills are used. The composite can be made using conventional compounding equipment such as a mold.

However, if highly uniform dispersion is desired, methods such as ball milling can be used to First crush the brill. A particularly effective method for obtaining well-dispersed mixtures is described in this book. Creham (Creham), which was filed at the same time as the present application and has been assigned the same assignment as the present application. U.S. Patent Application 5erial entitled "Preparation of Homogeneous Dispersions" by Ehan) No, (the description is included here in its entirety for reference) As such, fibrils, elastomeric matrices, and any other fillers have low viscosity. additives (e.g. oils or liquid solvents) and grinding accelerators (e.g. abrasive particles). - mix together to form a slurry, then mix the slurry at high speed, e.g. with a stirring bowl. This includes stirring in a mill or attritor. The viscosity modifier is also included in the matrix. For example, if the solution weight SBR may be added, once stirring is complete, e.g. For example, the solvent can be removed by vacuum drying, steam expulsion, or freeze drying. Ru. The mixture can then be shaped as is or, for example, in a Banbury or twin-screw roll mill. It may be further subjected to high shear mixing in a mold and then shaped.

During compounding, the amount of fibrils is adjusted to match the desired amount of fibrils in the final composite. selected and may be added directly to the elastomeric matrix. However, fibri A fill-filled composite may be manufactured as follows. Elastomer and large amount (25 parts) fibrils are first brought together to form a masterbatch, and then the final composite Plan to obtain the desired amount of fibrils in the body (for example, 5 to 10 parts). The appropriate amount of masterbatch is mixed with additional elastomer as described above to form the final form a complex.

The composites can be prepared using conventional elastomeric molding techniques by applying heat or resisting or inducing heat. It can be molded into various articles by heating. Particularly useful items include tires; and tire articles such as treads and casings, sealants, and vibration absorbers. It will be done. The uncured composites can be used as adhesives and binders, e.g. in tires and conveyors. It is useful as a repair formulation for. The adhesive is heated in situ by induction or resistance heating. It can be cured with. Articles manufactured from fibril-filled elastomers Physical properties (eg, tire pressure) can be monitored and detected electrically.

In addition to the carbon fibrils mentioned above, for example the 198 carbon fibrils according to Geus et al. Described in European Patent Application No. 0198558, published on 22nd October 2016 A crystalline graphite structure with graphite layers arranged like a fishbone along the fibril axis. Also suitable are fibrils having a morphology defined as . These fibrils hydrocarbons on a single crystal metal particle catalyst (e.g. iron) with a diameter of at least 5 nm. It is manufactured by vapor depositing elementary gas at a temperature of 250 to 800°C.

1 Toyomame 1 A preferred friction material is an organic resin bond mixed with carbon fibrils and other fillers. The relative amounts of ingredients, including agents, depend on the particular use for which the friction material is intended. example For example, brake systems for large trucks where fade resistance and stopping power are issues. In the case of high-load applications such as use, it is more effective than disc brake pads for automobiles. A large amount of fibril may be used; typically the amount of fibril is Up to 20% by weight of the composition based on fat.

The resin binder must be able to withstand the elevated temperatures encountered during use. No, phenolic resins have better resistance to thermal degradation and are relatively low cost. Preferred fillers outside the fibrils include metal (e.g. brass) fibers. , polyaramid fibers (e.g. E.

■ Kevlar commercially available from DuPont de Numer & Company ! fiber), mineral fillers such as diatomaceous earth and barium sulfate, graphite, and shredded carbon fiber. included. By incorporating fibrils, the amount of these additives can be reduced by conventional friction. The amount can be reduced compared to the material composition.

Preferred fibrils are those disclosed in U.S. Pat. No. 4,663,230 by Tenet; U.S. Patent Application No. 871,675 by Matt et al. U.S. Patent Application by Others Serial No. 871,676 + Sunai U.S. Patent Application Serial No. 149.573 by Der et al. U.S. Patent Application Serial No. 285 by Mandeville et al. H7 As described in having a graphite layer substantially parallel to the Brill axis and having a substantially continuous pyrolytic carbon outer coating. It is worthless. These fibrils are described in said patents and patent applications. Manufactured as follows. These fibrils were developed by Matsukashi et al. As described in patent application Serial No. 351.967, The Brill surface may be treated to introduce oxygen-containing functional groups.

Friction materials are made by dry mixing resins, fibrils, and other additives under shear forces, and then The resulting mixture is subjected to conventional thermosetting molding techniques such as pressing or assembly at elevated temperatures. Manufactured by molding using mating die molding. 8 layers in phenolic resin % of carbon fibrils (as described above), metal fibers, diatomaceous earth, barium sulfate A friction material also containing Kevlar polyaramid am, graphite, and carbon m fibres, Manufactured in the form of a disc brake backing plate. These brakes are fibril-free. Low fade compared to synthetic products [Dynoo + meter] ) as measured by tests] and showed improved friction at elevated temperatures.

They also have improved resistance to cracking and delamination at high temperatures (750'F). Indicated.

Wataburi dispatch Preferred hybrid composites include chains in which the secondary reinforcement has an average diameter on the order of about 1 to 10 microns. Composite consisting of continuous or discontinuous fibers, with secondary reinforcement consisting of carbon fibrils. . Preferred fibrils are disclosed in U.S. Pat. No. 4.663.230 by Tenet: U.S. Patent Application Serial N.O. by Nenoto et al.

871.675: U.S. Patent Application SerialN o by Tenet et al. No. 871,676: U.S. Patent Application Serial No. 871,676 by Snyder et al. , 149,573, and U.S. patent application Serial by Mandeville et al. Small diameter (preferably (3.5-75 nm), has a graphite layer substantially parallel to the fibril axis, and has a continuous thermal It is substantially free of a decomposed carbon outer coating. These fibrils are manufactured as described in the patent and patent application. Those fibrils are In U.S. Patent Application Serial N oj51.967 by Tukashi et al. Treated to introduce oxygen-containing functional groups onto the fibril surface as described You may.

The composite is a unidirectional composite (i.e., where the reinforcing agent is individual continuous fibers and their All are arranged parallel to each other so that they are mainly (composite reinforced in only one direction), two-dimensional layering of unidirectional tape or fabric body or laminate (i.e., where the reinforcing agent is continuous fibers and covers the matrix in a single plane) composites reinforced in two or more directions), multidimensional layers or laminates, i.e. composites in which continuous fiber reinforcement is not confined to a single surface), and discontinuous fiber reinforcement Isotropic composites (i.e. discontinuous fibers as secondary reinforcement, e.g. chopped glass or carbon fibers or carbon whiskers are randomly distributed throughout the matrix; A composite material providing homogeneous reinforcement may also be used. Thermosetting resin has a continuous reinforcing agent. Discontinuous fibers are preferable, but thermoplastics and thermosetting resins are preferable for discontinuous fibers. appropriate for the case.

The drawing shows an epoxy matrix with layers of reinforcing fibers 14 and carbon fibrils 16. A two-dimensional woven fabric laminate with reinforced base 12! It shows 0. -Next fiber 12 is poly Acrylonitrile carbon fiber. - Each layer of next fiber has two mutual layers in a single plane. The fibers are woven in a direction perpendicular to the epoxy matrix 12 to reinforce the epoxy matrix 12. carbon fib The rills 16 are evenly distributed throughout the matrix 12 and are arranged in the secondary fibers 14. It is randomly oriented.

The composite is manufactured as follows. Resin (viscous liquid for easy mixing, pre-prepared with fibrils dispersed throughout (in the form of a paste or melt) form a group. The majority of fibril aggregates have an average diameter smaller than 0.5 μl. A particularly effective method for obtaining well-dispersed prepregs is disclosed in a patent application filed concurrently with the present application. and the same assignment as the present application is made by Creamham, which is assigned to a person. U.S. patent application entitled ``Manufacturing'' Serial N.

As stated in (the entire description is included here for reference): fibrils, matrix, and any other fillers with low viscosity additives (e.g., oil). or liquid solvent) and a grinding accelerator (e.g., abrasive particles such as grid particles); to form a slurry, which is then heated at high speed, e.g., in a stirred ball mill. This includes stirring in a mill or attritor. Once stirring is complete, e.g. The solvent can be removed by vacuum drying, steam expulsion, or freeze drying.

If the reinforcing agents are discontinuous fibers, add them to the resin along with the fibrils. Can be added. If the reinforcing agent is a continuous fiber, the resin filament The Brill mixture is applied to the primary reinforcement using conventional impregnation methods to form a resin-fibril mixture. Care is taken to ensure that the compound properly wets the primary reinforcement.

The composite is then molded and cured using conventional molding techniques.

The composite shown in the drawings was manufactured as follows.

9 parts of N,N,N',N'-tetraglycidyl-4,4'-methylenebisbenze amine (commercially available as MY720 epoxy from Ciba Geigy), 1 part bisphenol A and epichlorohydrin (GY60 from Ciba Geigy) 10 epoxy), and 5 parts of 4°4'-diaminodiphenylene Lusulfone curing agent (commercially available as HT 976 curing agent from Ciba Geigy) carbon fibrils (as described in Snyder et al., supra). (manufactured as described above), the fibrils are evenly distributed throughout the resin. using a stirred ball mill until dispersed (as described in the Creamham application, supra). Mixed (as shown). The volume fraction of fibrils in the prepared samples is the total resin content. It was in the range of 0.01 to 0.05 based on . Next, mix the mixture into a woven polyacrylic Lonitrile carbon fiber fabric (: 24 x 23 (±1) yarn count and 10.7 on Celion 3K with an areal density of Yar's Techn iweave 8 Harness Satin Fabric (Harness 5atin 1 leave) 8 HS style 3 -17 5-8H) was applied by hand to a 6-ply laminate. Volume fraction of composite fabric 0.6 It was 0+0.02.

The resulting composite is then shaped, cured, and fibrillated to form the final composite structure. The properties of a composite with a fibril volume fraction of 0.025 were measured, and the composite was free of fibrils. compared with a fresh control sample. Their results show that randomly oriented, uniformly distributed filaments Brill measures properties such as compressive strength, short distance shear strength, in-plane shear strength, and translayer resistivity. Matrix-driven properties and matrix components such as flexural strength and modulus inhibits continuous fiber-driven properties such as tensile strength and modulus. It showed that it could be improved without any problems.

Other aspects are within the following claims.

Pσt/U39010421 engineering λττλC5 to ΣHte 5m1t INT, CL, (51: HOIB lfo, 6; B52B 910o; D O2G 37oo; B29B'710J cos, y 5P00 BO5D 04; C08K 3104; C08L 6310J B41y 31100I-1, -^-4-1 Go 13ηl axis 211

Claims (1)

[Claims] 1. A composite consisting of a reaction injection molded matrix mixed with carbon fibrils. 2. A composite consisting of a molded product of a premix containing a resin matrix mixed with carbon fibrils. 3. 3. A composite according to claim 2, wherein the premix is a sheet molding compound. 4. 3. A composite according to claim 2, wherein the premix is a bulk molding compound. 5. 3. A composite according to claim 1 or 2, wherein the amount of fibrils is sufficient to impart to the composite an electrical conductivity of sufficient magnitude for direct electrostatic coating of the surface. 6. The electrical conductivity of the composite is similar to that of the same matrix filled with the same amount of carbon black. The composite according to claim 1 or 2, which has an electrical conductivity higher than that of the composite of carbon dioxide. 7. 3. A composite according to claim 1, wherein the amount of fibrils is less than or equal to 20% by weight. 8. 8. A composite according to claim 7, wherein the amount of fibrils is less than or equal to 4% by weight. 9. 3. The amount of fibrils is less than or equal to 4% by weight and is sufficient to impart electrical conductivity to the composite of sufficient magnitude for direct electrostatic coating of surfaces. complex. 10. The amount of fibrils increases the electrical conductivity large enough to dissipate static electricity. 3. A complex according to claim 1 or 2, which is sufficient to impart coalescence. 11. 3. A composite according to claim 1 or 2, wherein the amount of fibrils is equal to or less than 4% by weight and is sufficient to impart to the composite an electrical conductivity of sufficient magnitude to dissipate static electricity. . 12. 3. A composite according to claim 1 or 2, wherein the fibrils consist of tubes with graphite layers substantially parallel to the fibril axis. 13. 13. The composite of claim 12, wherein the fibrils have a length-to-diameter ratio of at least 5. 14. The composite according to claim 12, wherein the fibrils have a diameter of 3.5 to 75 nm (inclusive). 15. 13. The composite of claim 12, wherein the fibrils are substantially free of a continuous pyrolytic carbon overcoat. 16. 13. The composite of claim 12, wherein the outer surface of the graphite layer is bonded to a plurality of oxygen-containing groups, or derivatives thereof. 17. 3. A composite according to claim 1 or 2, wherein the matrix consists of a thermoplastic material. 18. 18. A composite according to claim 17, wherein the matrix consists of polyamide, polyurethane, polyurea, or elastomer, or mixtures thereof. 19. 3. A composite according to claim 1 or 2, wherein the matrix consists of a thermosetting material. 20. If the matrix is polydicyclopentadiene, polyester, or thermosetting polyester, 20. The composite according to claim 19, comprising urethane, vinyl acrylimide, or epoxy resin, or a mixture thereof. 21. 3. A composite according to claim 1 or 2, wherein the composite is shaped into an automobile part. 22. A composite in a form suitable for reaction injection molding comprising carbon fibrils and one or more liquid reactants capable of polymerizing to form a reaction injection molding matrix. 23. A premix consisting of a resin mixed with carbon fibrils. 24. 24. The premix according to claim 23, wherein the premix is in the form of a sheet molding compound. Compound. 25. 24. The premix according to claim 23, wherein the premix is in the form of a bulk molding compound. thing. 26. Claim 22 or Claim 22, wherein the amount of fibrils is less than or equal to 20% by weight. is the composition described in 23. 27. 27. The amount of fibrils is less than or equal to 4% by weight. composition. 28. 24. A composition according to claim 22 or 23, wherein the fibrils consist of tubes with graphite layers substantially parallel to the fibril axis. 29. 29. The composition of claim 28, wherein the fibrils have a length-to-diameter ratio of at least 5. 30. 29. The composition according to claim 28, wherein the fibrils have a diameter of 3.5 to 75 nm (inclusive). 31. 29. The composition of claim 28, wherein the fibrils are substantially free of a continuous pyrolytic carbon overcoat. 32. 29. The outer layer of claim 28, wherein the outer surface of the graphite layer is associated with a plurality of oxygen-containing groups, or derivatives thereof. 33. The liquid reactant is one or more polyols, polyisocyanates, or polyamines. 23. The composition of claim 22. 34. 24. The composition according to claim 23, wherein the resin comprises a thermosetting resin. 35. Fabrication of composites containing reaction injection molded matrices incorporating carbon fibrils In the method of manufacturing, the fibrils are mixed with one or more liquid reactants capable of polymerizing to form the matrix, the mixture is introduced into a mold, and the and molding the mixture under reaction conditions including pressure and temperature to produce the composite in the form of a molded part. 35. Manufacturing composites containing sheet molding compounds mixed with carbon fibrils A method for producing a composite body comprising the steps of: mixing the fibrils and a resin; and forming the mixture into a sheet. 37. 36. The method of claim 35, further comprising molding the composite under reaction conditions including pressure and temperature to produce a composite in the form of a shaped part. 38. A method of producing a composite comprising a bulk molding compound incorporating carbon fibrils, comprising mixing the fibrils with a resin to form a putty suitable for molding. A method for manufacturing a composite comprising: 39. 39. The method of claim 38, further comprising molding the composite under reaction conditions including pressure and temperature to produce a composite in the form of a molded part. 40. 40. The method of any one of claims 35, 37, and 39, further comprising electrostatically coating the surface of the molded part directly. 41. A composite produced by the method according to any one of claims 35-39. 42. A composite consisting of a matrix mixed with sufficient carbon fibrils to enable direct electrostatic coating of the composite surface. 43. In the compounding process for producing the composite, one or more fillers and matrices are added. the filler and the matrix material for a reaction time sufficient to reduce the particle size of the aggregates formed by the filler to a value below a predetermined value. anti- A method of compounding comprising the steps of subjecting the filler to a combined shear and impact force under stress conditions to disperse the filler throughout the matrix material. 44. 44. The compounding method according to claim 43, wherein the predetermined value of the aggregate particle size is 1000 times or less the particle size of the filler. 45. The predetermined value of the aggregate particle size must be less than 100 times the particle size of the filler. The compounding method according to claim 44. 46. 46. The compounding method according to claim 45, wherein the predetermined value of the aggregate particle size is not more than 10 times the particle size of the filler. 47. 47. A compounding method according to any one of claims 44 to 46, wherein one or more of the characteristic axes of the filler are smaller than 1μ. 48. 5. The method of claim 4, wherein one or more of the characteristic axes of the filler are smaller than 0.1μ. 49. 44. The method of claim 43, further comprising adding a viscosity modifier to the stirred ball mill. 50. 50. The compounding method according to claim 49, wherein the viscosity modifier is removed after the dispersion step. 51. 51. The compounding method of claim 50, wherein the viscosity modifier is a solvent. 52. 50. The method of claim 49, wherein the viscosity modifier is retained after the dispersion step. 53. 53. The formulation method of claim 52, wherein the viscosity modifier is a reactive diluent that chemically reacts with the matrix material. 54. 44. The compounding method of claim 43, further comprising adding one or more grinding media to the stirred ball mill. 55. 44. The method of claim 43, wherein the filler comprises whiskers. 56. 44. The method of claim 43, wherein the filler comprises discontinuous fibers. 57. 44. The method of claim 43, wherein the filler comprises a particulate filler. 58. 44. The method of claim 43, wherein the filler comprises carbon fibrils. 59. 59. The composite of claim 58, wherein the fibrils consist of tubes with graphite layers substantially parallel to the fibril axis. 60. 59. The composite of claim 58, wherein the fibrils have a length-to-diameter ratio of at least 5. 61. 60. The composite according to claim 58, wherein the fibrils have a diameter of 3.5 to 75 nm (inclusive). 62. 59. The composite of claim 58, wherein the fibrils are substantially free of a continuous pyrolytic carbon overcoat. 63. 59. The composite of claim 58, wherein the outer surface of the graphite layer is bonded to a plurality of oxygen-containing groups, or derivatives thereof. 64. 44. A composite according to claim 43, wherein the matrix material comprises a metal powder. 65. 44. A composite according to claim 43, wherein the matrix material comprises a ceramic powder. 66. 66. The composite of claim 65, wherein the ceramic powder comprises a glass powder. 67. 44. The composite according to claim 43, wherein the matrix material comprises a thermoplastic resin. 68. Thermoplastic resin is thermoplastic polyester, polyurethane, polyether ester 68. The composite according to claim 67, which is a polyetherketone, a polyether sulfone, a polyetherimide, a polyamide, or a polyurea resin. 69. 44. The compounding method of claim 43, wherein the matrix material comprises a thermosetting resin. 70. Thermosetting resins include phenolic, epoxy, and thermosetting polyurethane. thermohard Kasumi polyester, polyimide, bismaleimide, polycyclopentadiene, or The compounding method according to claim 69, wherein is a vinyl acrylimide resin. 71. 44. The method of claim 43, wherein the matrix material comprises an elastomer. 72. Elastomers include styrene-butadiene rubber, natural rubber, and ethylene plastic. Pyrene/diene monomer rubber, silicone rubber, polybutadiene, polyisoprene, neoprene, chloroprene, fluoroelastomer, or urethane elastomer - The compounding method according to claim 71. 73. 44. The method of claim 43, wherein the matrix material is in liquid form. 74. The matrix material is a thermoplastic and the contents of the stirred ball mill are 44. The method of claim 43, further comprising cooling the matrix material to a temperature at which it becomes brittle and maintaining that temperature during the dispersion step. 75. The matrix material is a thermoplastic or thermosetting resin and the filler is carbon fibre. 44. The method of claim 43, wherein the viscosity modifier and the grinding media are added to a stirred ball mill. 76. 44. A composite made according to claim 43. 77. a primary fiber reinforcement and a randomly oriented matrix with respect to the primary reinforcement; A hybrid composite consisting of a matrix with a secondary reinforcing agent dispersed uniformly throughout the box. 78. The average diameter of the primary reinforcement is at least 10 times the average diameter of the secondary reinforcement. 78. The composite of claim 77. 79. 79. The composite of claim 78, wherein the average diameter of the primary reinforcement is at least 100 times the average diameter of the secondary reinforcement. 80. comprising a matrix mixed with a primary fiber reinforcement and a secondary fiber reinforcement, wherein said primary reinforcement is at least 1000 times the average diameter of said secondary reinforcement. A hybrid complex with an average diameter of 81. 81. The hybrid composite of claim 80, wherein the secondary reinforcement is randomly oriented relative to the primary reinforcement and is uniformly distributed throughout the matrix. 82. 81. A composite according to claim 77 or 80, wherein the majority of aggregates formed by the secondary reinforcing agent in the matrix are less than or equal to 10 microns. 83. 83. The composite of claim 82, wherein the majority of the aggregates are 0.5 microns or less. 84. 78. The composite of claim 77, wherein the secondary reinforcement comprises carbon microfibers. 85. The composite of claim 77, wherein the secondary reinforcement comprises whiskers. 86. 78. The composite of claim 77, wherein the secondary reinforcement comprises chopped fibers. 87. 78. The composite of claim 77, wherein the secondary reinforcement comprises a particulate reinforcement. 38. 81. A composite according to claim 77 or 80, wherein the secondary reinforcing agent comprises carbon fibrils. 89. 89. The composite of claim 88, wherein the carbon fibrils consist of tubes having graphite layers substantially parallel to the fibril axis. 90. 89. The composite of claim 88, wherein the fibrils have a length-to-diameter ratio of at least 5. 91. 84. The composite according to claim 83, wherein the fibrils have a diameter of 3.5 to 75 nm (inclusive). 92. 89. The composite of claim 88, wherein the fibrils are substantially free of a continuous pyrolytic carbon overcoat. 93. 81. A composite according to claim 77 or 80, wherein the primary reinforcement comprises continuous fibres. 94. The continuous fibers are made of carbon, glass, ceramic, or polyaramid fibers. 94. The composite of claim 93. 95. Continuous fibers may be woven, knitted, crimped, or straight. 94. The complex according to claim 93. 96. 81. A composite according to claim 77 or 80, wherein the primary reinforcement comprises discontinuous fibers. 97. 81. The composite according to claim 77 or 80, wherein the matrix is made of an organic thermosetting resin. Combined. 98. The thermosetting resin is epoxy, bismaleimide, polyimide, or polyester. 98. The composite of claim 97, which is a terresin. 99. 81. The composite according to claim 77 or 80, wherein the matrix is made of an organic thermoplastic resin. Combined. 100. Claims where the thermoplastic resin is polyethylene, oriented polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, thermoplastic polyester resin, polyetheretherketone, polyethersulfone, polyetherimide, liquid crystal polymer, or reaction injection molding resin. The complex according to item 99. 101. 81. The composite according to claim 77 or 80, wherein the matrix comprises an inorganic polymer. 102. 81. A composite according to claim 77 or 80, wherein the matrix is metal. 103. 81. A composite according to claim 77 or 80, wherein the matrix is a ceramic material. 104. 81. A composite according to claim 77 or 80, wherein the matrix is carbon. 105. The amount of secondary reinforcement incorporated into the matrix is equal to 20% by volume or 81. The composite according to claim 77 or 80, wherein: is less than that. 106. The amount of secondary reinforcing agent mixed into the matrix is 1 to 10% by volume. The complex according to claim 105. 107. The secondary reinforcement is a tube with a graphite layer substantially parallel to the fibril axis. Carbon fibrils having a length-to-diameter ratio of at least 5 and a diameter of 3.5 to 75 nm (inclusive). , a carbon fib with substantially no continuous pyrolytic carbon outer coating 81. A composite according to claim 77 or 80, wherein the composite comprises rills and the primary reinforcement comprises continuous carbon fibres. 108. A matrix, a fibrous primary reinforcing agent, and a secondary reinforcing agent are mixed, and the secondary reinforcing agent is randomly oriented with respect to the primary reinforcing agent and uniformly dispersed throughout the matrix. A method for producing a hybrid composite consisting of. 109. a matrix, a fibrous secondary reinforcement, and a small average diameter of the secondary reinforcement; a fibrous primary reinforcement having an average diameter of at least 100 times A method for producing a synthetic composite. 110. 10. A primary and secondary reinforcing agent are mixed with a matrix in such a manner that said secondary reinforcing agent is randomly oriented relative to said primary reinforcing agent and is uniformly dispersed throughout said matrix. 109. 111. 110. The method according to claim 108 or 109, wherein the fine fibers are carbon fibrils. 112. A brake with a friction material containing a matrix mixed with carbon fibrils. key or its parts. 113. Clamps with friction material containing a matrix mixed with carbon fibrils switch or parts thereof. 114. Automatic transmission disc or parts thereof having a friction material containing a matrix mixed with carbon fibrils. 115. 115. An article according to any one of claims 112 to 114, wherein the amount of fibrils is less than or equal to 20% by weight. 116. 116. The article of claim 115, wherein the amount of fibrils is 5-10% by weight. 117. The fibrils consist of tubes with graphite layers substantially parallel to the fibril axis. 115. The article of any one of claims 112-114. 118. 120. The article of claim 117, wherein the fibrils have a length-to-diameter ratio of at least 5. 119. 18. The article of claim 1 17, wherein the fibrils have a diameter of 3.5 to 75 nm, inclusive. 120. 118. The article of claim 117, wherein the fibrils are substantially free of a continuous pyrolytic carbon overcoat. 121. The outer surface of the graphite layer is combined with a plurality of oxygen-containing groups or derivatives thereof. 118. The article of claim 117. 122. The article according to any one of claims 112 to 114, wherein the matrix is a thermosetting resin. 123. The matrix is phenolic resin, polyester, or epoxy resin. 123. The article of claim 122. 124. According to any one of claims 112 to 114, the matrix is made of carbon. Articles listed. 125. 115. The article of any one of claims 112-114, further comprising one or more fillers. 126. The filler is metal, glass, ceramic, carbon, or polyaramid fiber. 126. The article of claim 125. 127. 126. The article of claim 125, wherein the filler is a particulate filler. 128. Fillers include graphite, clay, barium sulfate, diatomaceous earth, silica, and magnesia. 126. The article of claim 125, comprising one or more of A, beryllia, alumina, silicon carbide, titanium dioxide, or carbon black. 129. A composite in the form of a friction material consisting of a matrix mixed with carbon fibrils. 130. The fibrils consist of tubes with graphite layers substantially parallel to the fibril axis. 30. The fibrils of claim 129, wherein the fibrils have a length-to-diameter ratio of at least 5, a diameter of 3.5 to 75 nm, inclusive, and are substantially free of a continuous pyrolytic carbon outer coating. complex. 131. Contains a polymeric binder mixed with carbon fibrils and is applied to the surface of a substrate. An electrically conductive composite in a form suitable for use. 132. 132. The composite of claim 131, wherein the composite is in the form of a powder coating. 133. 132. The composite of claim 131, wherein the composite is in the form of a liquid coating. 134. The amount of fibrils is directly electrostatically coated onto the surface of the substrate to which the coating is applied. 134. A coating according to claim 132 or 133, in sufficient amount to enable 135. 134. A coating according to claim 132 or 133, wherein the amount of fibrils is less than or equal to 15% by weight. 136. 136. The coating of claim 135, wherein the amount of fibrils is from 0.5 to 10% by weight. 137. 136. The coating of claim 135, wherein the amount of fibrils is 1-4% by weight. 138. The amount of fibrils is less than or equal to 15% by weight and the coating is suitable. 134. A coating according to claim 132 or 133, in sufficient quantity to be able to be electrostatically coated directly onto the surface of the substrate in which it is used. 139. 132. The composite of claim 131, wherein the composite is in the form of a resistive ink suitable for screen printing onto the surface of a substrate to form an electronic component. 140. 140. The resistive ink of claim 139, wherein the amount of fibrils is sufficient to reduce the volume resistivity of the binder to a value of 10@-2 to 10@6 Ωc when applied to a substrate. 141. 141. The resistive type according to claim 140, having a resistivity of 10-1 to 104 Ωc■. Nku. 142. 140. The resistive material according to claim 139, wherein the amount of fibrils is 1 to 30% by weight. Nku. 143. 140. The resistivity of claim 139, wherein the amount of fibrils is between 1 and 30% by weight and is sufficient to reduce the volume resistivity of the binder to a value between 10 and 106 Ωc when applied to the substrate. ink. 144. The composite further includes electrically conductive graphite or metal particles and is coated on the surface of the substrate. It is in the form of a conductive ink suitable for 132. The composite of claim 131, which is sufficient to reduce the volume resistivity of the particle-filled binder by a predetermined value when used. 145. 145. The conductive ink of claim 144, wherein the particle-filled binder has a volume resistivity greater than 1 Ωc and the amount of fibrils is sufficient to reduce the volume resistivity to less than 1 Ωc. 146. 145. The conductive ink of claim 144, wherein the volume resistivity of the particle-filled binder is greater than 10-1 Ωc, and the amount of fibrils is sufficient to reduce the volume resistivity to less than 10-1 Ωc. 147. 145. The conductive ink of claim 144, wherein the amount of fibrils is less than or equal to 30% by weight. 148. 145. The particle-filled binder has a volume resistivity greater than 1 Ωc and the amount of fibrils is less than or equal to 30% by weight and is sufficient to reduce the volume resistivity to a value less than 1 Ωc. conductive ink. 149. 145. The conductive ink of claim 144, wherein the metal particles consist of silver foil. 150. The fibrils consist of tubes with graphite layers substantially parallel to the fibril axis. 132. The composite of claim 131. 151. 151. The composite of claim 150, wherein the fibrils have a length-to-diameter ratio of at least 5. 152. 51. The composite according to claim 150, wherein the fibrils have a diameter of 3.5 to 75 nm, inclusive. 153. 51. The composite of claim 150, wherein the fibrils are substantially free of a continuous pyrolytic carbon overcoat. 154. 132. The composite of claim 131, wherein the binder comprises a thermoplastic resin. 155. 155. The composite of claim 154, wherein the binder comprises polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, or thermoplastic polyester resin. 156. 132. The composite of claim 131, wherein the binder comprises a thermosetting resin. 157. 157. The composite of claim 156, wherein the binder comprises a saturated polyester, alkyd, or epoxy resin. 158. The coating according to claim 132 or 133, further comprising at least one pigment. Cover. 159. coated with an electrically conductive composite containing a polymer binder mixed with carbon fibrils. overturned substrate. 160. 160. The substrate of claim 159, wherein the conductivity of the composite is sufficient to permit surface electrostatic coating of the surface of the substrate. 161. 160. The substrate of claim 159, wherein the substrate comprises a substrate for a printed circuit board, and the composite is a resistive ink printed onto the substrate in the form of an electronic component. 162. 162. The substrate of claim 161, wherein the electronic component is a resistor. 163. The substrate consists of a substrate for a printed circuit board, and the composite carries electronic components. A conductor printed on said substrate in the form of a conductive line for electrical connection. 160. The substrate of claim 159, which is a conductive ink. 164. A method of coating a substrate comprising the steps of: preparing an electrically conductive coating by incorporating carbon fibrils into a polymeric binder; and applying the coating to the substrate. 165. 165. The method of claim 164, further comprising electrostatically applying the surface coating directly to the coated substrate. 166. A method of printing on a substrate comprising the steps of: preparing an ink by incorporating carbon fibrils into a polymeric binder; and screen printing said ink onto said substrate. 167. A composite consisting of an elastomeric matrix incorporated with carbon fibrils, characterized in that said fibrils have the form of tubes without a continuous pyrolytic carbon overcoat and with a graphite layer substantially parallel to the fibril axis. complex Combined. 168. 168. The composite of claim 167, wherein the fibrils have a diameter of less than 100 nm. 169. 179. The composite of claim 168, wherein the fibrils have a diameter of 3.5 to 75 nm, inclusive. 170. 168. The composite of claim 167, wherein the fibrils have a length-to-diameter ratio of 5 to 100. Combined. 171. A composite comprising an elastomeric matrix mixed with carbon fibrils, characterized in that the fibrils have a crystalline graphite structure and a morphology defined as a fishbone-like arrangement of graphite layers along the fibril axis. body. 172. 172. The composite of claim 171, wherein the fibrils have a diameter of less than 100 nm. 173. Elastomer matrices include natural rubber, styrene-butadiene rubber, polyisoprene, neoprene, chloroprene, polybutadiene, and fluoroelastomer. 172. The composite according to claim 167 or 171, wherein the composite is selected from the group consisting of tomer, silicone rubber, and urethane elastomer. 174. 172. A composite according to claim 167 or 171, further comprising at least one filler. 175. 175. The composite of claim 174, wherein the filler is carbon black, silica, or a combination thereof. 176. 175. The composite of claim 174, wherein the ratio of the amount of fibrils to the total amount of filler is at least 1:4. 177. The amount of fibrils in the composite is less than 25 parts per 100 parts of elastomer. 172. The composite according to claim 167 or 171, wherein 178. The amount of fibrils in the composite is less than 10 parts per 100 parts of elastomer. 178. The conjugate of claim 177. 179. The amount of fibrils in the composite is greater than 25 parts per 100 parts of elastomer 179. The composite according to claim 178. 180. The amount of fibrils in the composite is such that the composite can be cured by resistance or induction heating. 172. The complex of claim 167 or 171, wherein the complex is in sufficient amount to allow 181. The amount of fibrils in the composite is less than 25 parts per 100 parts of elastomer The quantity must be sufficient to allow the composite to be cured by heating, resistance or induction heating. The complex according to claim 167 or 171. 182. 172. The composite of claim 167 or 171, wherein the amount of fibrils in the composite is sufficient to enable electrical monitoring and detection of at least one physical property of the composite. 183. 172. The amount of fibrils in the composite is less than 25 parts per 100 parts of elastomer and is sufficient to enable electrical monitoring and detection of at least one physical property of the composite. The complex described. 184. Claim 167 or 171, wherein the composite is in the form of an elastomer solution. complex. 185. 172. A composite body according to claim 167 or 171, wherein the composite body is in the form of a tire or a part thereof. 186. 172. A composite according to claim 167 or 171, wherein the composite is in the form of a sealant. 187. 172. A composite according to claim 167 or 171, wherein the composite is in the form of an adhesive. 188. In a method of curing an elastomer, a composite is prepared by incorporating carbon fibrils into an elastomer matrix, and wherein the amount of said fibrils provides said electrical conductivity of sufficient magnitude to provide resistive or inductive heating. given to the complex and curing the composite by resistive or induction heating. 189. In a method of monitoring and detecting the physical state of an elastomer, a conjugate is prepared by incorporating an electrically conductive additive into an elastomer matrix, wherein the amount of said additive electrically changes the physical state of said elastomer. supervised by sufficient to provide the composite with electrical conductivity of sufficient magnitude to be visually detectable. A monitoring and detection method comprising the steps of monitoring and detecting the electrical properties of the composite as an indicator of the physical state of the elastomer. 190. 200. The method of claim 189, wherein the electrically conductive additive comprises carbon fibrils. 191. The elastomer is shaped like a tire, and the tire pressure is monitored and detected. 191. The method of claim 189 or 190. 192. 191. The method of claim 189 or 190, wherein the elastomer is monitored for the presence of cuts, tears or holes. 193. 191. The method of claim 188 or 190, wherein the amount of fibrils is less than 25 parts per 100 parts of elastomer. 194. 194. The method of claim 193, wherein the amount of fibrils is less than 10 parts per 100 parts of elastomer. 195. The fibrils consist of tubes with graphite layers substantially parallel to the fibril axis. 191. A method according to claim 188 or 190, characterized in that the method has the form of: 196. 196. The composite of claim 195, wherein the fibrils have a length-to-diameter ratio of 5 to 100. Combined. 197. 196. The composite of claim 195, wherein the fibrils have a diameter of 3.5 to 75 nm, inclusive. 198. 196. The composite of claim 195, wherein the fibrils are substantially free of a continuous pyrolytic carbon overcoat. 199. 191. A composite according to claim 188 or 190, characterized in that the fibrils have a crystalline graphite structure and a morphology defined as a fishbone-like arrangement of graphite layers along the fibril axis. 200. In a method for producing an elastomer composite, the elastomer contains at least 25 parts of fibrils per 100 parts of elastomer. A method for producing an elastomer composite comprising the steps of: producing a masterbatch by dispersing the masterbatch; and blending an additional amount of elastomer into a predetermined portion of the masterbatch to form a composite. 201. The amount of fibrils in the composite is less than 25 parts per 100 parts of elastomer. 201. The method of claim 200, wherein: 202. The amount of fibrils in the composite is less than 10 parts per 100 parts of elastomer. 202. The method of claim 201, wherein: 203. The fibrils consist of tubes with graphite layers substantially parallel to the fibril axis. 201. The method of claim 200, having the form of: 204. 204. The composite of claim 203, wherein the fibrils have a length-to-diameter ratio of 5 to 100. Combined. 205. 204. The composite of claim 203, wherein the fibrils have a diameter of 3.5 to 75 nm, inclusive. 206. 204. The composite of claim 203, wherein the fibrils are substantially free of a continuous pyrolytic carbon overcoat. 207. 201. A composite according to claim 200, characterized in that the fibrils have a crystalline graphite structure and have a morphology defined as a bone-like arrangement of graphite layers along the fibril axis. 208. 201. The method of claim 200, further comprising incorporating carbon black into the composite. 209. incorporating carbon fibrils into an elastomer matrix in an amount sufficient to improve the mechanical properties of the elastomer, said fibrils having a continuous pyrolytic carbon outer coating qualitatively parallel to the fibril axis; An elastomer reinforcement method characterized by having a graphite layer. 210. 210. The method of claim 209, wherein the fibrils have a diameter less than 100 nm. 211. The borohydride according to claim 21, wherein the fibrils have a diameter of 3.5 to 75 nm (inclusive). 212. 210. The borohydride of claim 209, wherein the fibrils have a length-to-diameter ratio of 5 to 100. 213. It consists of incorporating into the elastomer matrix a sufficient amount of carbon fibrils to improve the mechanical properties of the elastomer, the fibrils having a crystalline graphite structure and a fishbone-shaped layer of graphite along the fibril axis. defined as an array A method for reinforcing an elastomer, the method comprising: 214. 214. The method of claim 213, wherein the fibrils have a diameter of less than 100 nm.