US20150232663A1 - Fiber-based ablative and high temperature pre-preg material - Google Patents
Fiber-based ablative and high temperature pre-preg material Download PDFInfo
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- US20150232663A1 US20150232663A1 US14/636,455 US201514636455A US2015232663A1 US 20150232663 A1 US20150232663 A1 US 20150232663A1 US 201514636455 A US201514636455 A US 201514636455A US 2015232663 A1 US2015232663 A1 US 2015232663A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6269—Curing of mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2631—Coating or impregnation provides heat or fire protection
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
Definitions
- This invention involves composite structures especially for use in hostile high-temperature, ablative applications.
- Structural materials and systems for forming parts for use in hostile high-temperature environments have exhibited deficient properties, in connection with the requirement for high temperature properties, high temperature endurance, low thermal expansion, high stiffness, high thermal conductivity, stiffness, improved thermal dissipation and improved dimensional stability for use in hostile, high-temperature environments.
- a fabric-matrix composite structure for making parts suitable for use in hostile, high-temperature environments, such as rocket exhaust nozzles.
- the structure includes a fabric formed of polyacrylonitrile fiber, especially a polyacrylonitrile fiber that has been oxidized, and especially a combination of polyacrylonitrile fibers that have been oxidized to different degrees.
- the structure also includes a binder that impregnates the fabric.
- the binder might be a phenolic resin.
- the structure is formed, partially cured, formed into a product, and finish cured.
- This invention is a fabric-matrix composite structure for making parts suitable for use in hostile, high-temperature environments, such as rocket exhaust nozzles.
- This embodiment of the composite structure of the present invention showing fabric embedded in the resin.
- the structure includes a fabric formed of polyacrylonitrile fiber, especially a polyacrylonitrile fiber that has been oxidized, and especially a combination of polyacrylonitrile fibers that have been oxidized to different degrees.
- the structure also includes a binder that impregnates the fabric.
- the binder might be a phenolic resin.
- Step 1 involves forming the composite structure by imbedding the fabric with the resin.
- Step 2 involves converting the resin and partially curing it to form a pre-preg.
- Step 4 the structure is formed into a product shape , and, in Step 4 , the product is finish cured.
- One embodiment of this invention is a pre-preg formulation for use in ablative applications such as, but not limited to, rocket or missile exhaust nozzles and high temperature resistant, carbon/carbon applications.
- the pre-preg structure consists of woven fabric based on discontinuous fibers.
- the fibers are typically formed of a hydrocarbon material that is converted to a “pre-ox” fiber, that is, the fibers are oxidized by heating in an oxygen-containing atmosphere, until it achieves the desired level of carbon and oxygen, for example, approximately ten weight percent oxygen content.
- the fabric is then impregnated with a phenolic resin, and can be used in the form of broad goods, molding compound or biased tapes.
- the resultant pre-preg can be molded into various components.
- pre-preg generally refers to a structure including polymer which is not yet completely cured or polymerized. Typically, such polymers are cured to a degree referred to as B stage. At that stage, the polymer is physically stable., but not fully cross-linked.
- the field of the invention relates to a pre-preg formulation and structure with high ablative properties for the use in missile components, rocket nozzles, high temperature resistant parts and carbon/carbon high temperature resistant parts.
- Various embodiments of the present invention provide an improved pre-preg formulation for ablative applications, requiring high temperature resistance, and in other carbon/carbon applications.
- a “carbon/carbon” structure generally refers to a structure having at least two zones, each possessing a different carbon structure.
- Some embodiments of the pre-preg system of the present invention include a fibrous material, either woven or non-woven, impregnated with a thermosetting or thermoplastic matrix resin.
- Some embodiments of the present invention involve a pre-preg formulation that is thermosetting in nature and is cured/molded into rocket/missile components, high temperature components and carbon/carbon preform components at temperatures between 250 F and 425 F.
- a pre-preg formulation might include a fibrous material that is woven, non-woven or aligned unidirectional fibers, pre-impregnated with a thermosetting phenolic matrix resin.
- the pre-preg formulation might include discontinuous fibers.
- the fabric and discontinuous fibers might consist of fibers two different fiber materials.
- the two fiber materials might consist of carbon fiber based on polyacrylonitrile (PAN) at a carbon content of 95+/ ⁇ 3% and polyacrylonitrile (PAN) based pre-ox carbon fiber at a carbon content of 60+/ ⁇ 5%.
- the fibers might be blended into a yarn at a ratio such that the carbon content of the yarn is 82+/ ⁇ 10%.
- the yarn might be manufactured into a substrate that is impregnated with a phenolic resin.
- the substrate might be woven, non-woven or aligned unidirectional fibers.
- the phenolic resin might contains particulate fillers, short fibers, plate shaped fillers and/or nanometer-sized fillers.
- the pre-preg might be used as broad goods, molding compound, straight tapes or biased tapes.
- the pre-preg might be processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave.
- the pre-preg after processing into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave, might be converted from a phenolic impregnated fabric molded structure to a carbon impregnated fabric molded structure (also known as carbon/carbon), via exposure to a minimum of 1200 F in a nitrogen atmosphere.
- the phenolic resin system is capable of being formulated with appropriate solvents for impregnation into fibrous woven fabrics, fibrous nonwoven fabrics or aligned unidirectional fibers.
- the pre-preg might be molded to the required thickness for the intended application and then processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave. Multiple layers of the pre-preg might be used to achieve the required thickness for the final product.
- the phenolic resin used to impregnate the fibrous material can be in applied in solvated form.
- Solvents used for the phenolic resin can include methanol, isopropyl alcohol, denatured alcohol and acetone.
- the pre-preg is manufactured using the fibers/fabrics/nonwovens using conventional solvent-based or non-solvent-based techniques.
- the molding of the pre-preg that is produced is conducted by conventional techniques that utilize heat, pressure, and, in some processes, vacuum. These techniques include compression molding, vacuum-bag molding in an oven, vacuum-bag molding in an autoclave, and vacuum-bag molding in a hydroclave.
- the molding processes convert the pre-preg into a molded, cured (cross-linked) composite.
- the primary application for the pre-preg is in the use of molded components that are subsequently exposed to high temperatures.
- the high-temperature environment can include, but is not be limited to, ablative environments such as rocket and missile nozzles, ablative environments such as heat shields, for high temperature processing such as post-molded carbonization of the phenolic resin to form carbon/carbon structures.
- FIG. 1 is a schematic front elevation view of an embodiment of the present invention showing fabric embedded in resin, and formed into a tolerance part, and
- FIG. 2 is a schematic flow chart of an embodiment of this invention.
- FIG. 1 is a schematic front elevation view of an embodiment of the composite structure.
- This invention is a fabric-matrix composite structure 10 for making parts 13 suitable for use in hostile, high-temperature environments, such as rocket exhaust nozzles.
- This embodiment of the composite structure 10 of the present invention showing fabric 11 embedded in the resin 12 .
- the structure 10 includes a fabric 11 formed of polyacrylonitrile fiber, especially a polyacrylonitrile fiber that has been oxidized, and especially a combination of polyacrylonitrile fibers that have been oxidized to different degrees.
- the structure 10 also includes a binder 12 that impregnates the fabric 11 .
- the binder 12 might be a phenolic resin.
- FIG. 2 is a schematic flow chart of an embodiment of this invention.
- Step 1 (numeral 30 ) involves forming the composite structure by imbedding the fabric with the resin.
- Step 2 (numeral 40 ) involves converting the resin and partially curing it to form a pre-preg.
- Step 4 the structure is formed into a product shape (numeral 50 ), and, in Step 4 , the product is finish cured (numeral 60 ).
- One embodiment of this invention is a pre-preg formulation for use in ablative applications such as, but not limited to, rocket or missile exhaust nozzles and high temperature resistant, carbon/carbon applications.
- the pre-preg structure consists of woven fabric based on discontinuous fibers.
- the fibers are typically formed of a hydrocarbon material that is converted to a “pre-ox” fiber, that is, the fibers are oxidized by heating in an oxygen-containing atmosphere, until it achieves the desired level of carbon and oxygen, for example, approximately ten weight percent oxygen content.
- the fabric is then impregnated with a phenolic resin, and can be used in the form of broad goods, molding compound or biased tapes.
- the resultant pre-preg can be molded into various components.
- pre-preg generally refers to a structure including polymer which is not yet completely cured or polymerized. Typically, such polymers are cured to a degree referred to as B stage. At that stage, the polymer is physically stable., but not fully cross-linked.
- the field of the invention relates to a pre-preg formulation and structure with high ablative properties for the use in missile components, rocket nozzles, high temperature resistant parts and carbon/carbon high temperature resistant parts.
- Various embodiments of the present invention provide an improved pre-preg formulation for ablative applications, requiring high temperature resistance, and in other carbon/carbon applications.
- a “carbon/carbon” structure generally refers to a structure having at least two zones, each possessing a different carbon structure.
- Some embodiments of the pre-preg system of the present invention include a fibrous material, either woven or non-woven, impregnated with a thermosetting or thermoplastic matrix resin.
- Some embodiments of the present invention involve a pre-preg formulation that is thermosetting in nature and is cured/molded into rocket/missile components, high temperature components and carbon/carbon preform components at temperatures between 250 F and 425 F.
- a pre-preg formulation might include a fibrous material that is woven, non-woven or aligned unidirectional fibers, pre-impregnated with a thermosetting phenolic matrix resin.
- the pre-preg formulation might include discontinuous fibers.
- the fabric and discontinuous fibers might consist of fibers two different fiber materials.
- the two fiber materials might consist of carbon fiber based on polyacrylonitrile (PAN) at a carbon content of 95+/ ⁇ 3% and polyacrylonitrile (PAN) based pre-ox carbon fiber at a carbon content of 60+/ ⁇ 5%.
- the fibers might be blended into a yarn at a ratio such that the carbon content of the yarn is 82+/ ⁇ 10%.
- the yarn might be manufactured into a substrate that is impregnated with a phenolic resin.
- the substrate might be woven, non-woven or aligned unidirectional fibers.
- the phenolic resin might contains particulate fillers, short fibers, plate shaped fillers and/or nanometer-sized fillers.
- the pre-preg might be used as broad goods, molding compound, straight tapes or biased tapes.
- the pre-preg might be processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave.
- the pre-preg after processing into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave, might be converted from a phenolic impregnated fabric molded structure to a carbon impregnated fabric molded structure (also known as carbon/carbon), via exposure to a minimum of 1200 F in a nitrogen atmosphere.
- a carbon impregnated fabric molded structure also known as carbon/carbon
- the phenolic resin system is capable of being formulated with appropriate solvents for impregnation into fibrous woven fabrics, fibrous nonwoven fabrics or aligned unidirectional fibers.
- the pre-preg might be molded to the required thickness for the intended application and then processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave. Multiple layers of the pre-preg might be used to achieve the required thickness for the final product.
- the phenolic resin used to impregnate the fibrous material can be in applied in solvated form.
- Solvents used for the phenolic resin can include methanol, isopropyl alcohol, denatured alcohol and acetone.
- the pre-preg is manufactured using the fibers/fabrics/nonwovens using conventional solvent-based or non-solvent-based techniques.
- the molding of the pre-preg that is produced is conducted by conventional techniques that utilize heat, pressure, and, in some processes, vacuum. These techniques include compression molding, vacuum-bag molding in an oven, vacuum-bag molding in an autoclave, and vacuum-bag molding in a hydroclave.
- the molding processes convert the pre-preg into a molded, cured (cross-linked) composite.
- the primary application for the pre-preg is in the use of molded components that are subsequently exposed to high temperatures.
- the high-temperature environment can include, but is not be limited to, ablative environments such as rocket and missile nozzles, ablative environments such as heat shields, for high temperature processing such as post-molded carbonization of the phenolic resin to form carbon/carbon structures.
Abstract
A fabric-matrix composite structure [10] for making parts [13] suitable for use in hostile, high-temperature environments, such as rocket exhaust nozzles. The structure [10] includes a fabric [11] formed of polyacrylonitrile fiber, especially a polyacrylonitrile fiber that has been oxidized, and especially a combination of polyacrylonitrile fibers that have been oxidized to different degrees. The structure [10] also includes a binder [12] that impregnates the fabric [11]. The binder [12] might be a phenolic resin. The structure is formed [30], partially cured [40], formed into a product [50], and finish cured [60].
Description
- This invention involves composite structures especially for use in hostile high-temperature, ablative applications.
- Structural materials and systems for forming parts for use in hostile high-temperature environments, especially for uses such as rocket exhaust nozzles, have exhibited deficient properties, in connection with the requirement for high temperature properties, high temperature endurance, low thermal expansion, high stiffness, high thermal conductivity, stiffness, improved thermal dissipation and improved dimensional stability for use in hostile, high-temperature environments.
- These and other difficulties experienced with the prior art devices have been obviated in a novel manner by the present invention.
- It is, therefore, an outstanding object of some embodiments of the present invention to provide a composite structure for making parts that exhibit superior high temperature properties, superior high temperature endurance, low thermal expansion, high stiffness, high thermal conductivity, stiffness, improved thermal dissipation and improved dimensional stability.
- It is a further object of some embodiments of the invention to provide a composite structure that is easy and economical to produce and use.
- With these and other objects in view, as will be apparent to those skilled in the art, the invention resides in the combination of parts set forth in the specification and covered by the claims appended hereto, it being understood that changes in the precise embodiment of the invention herein disclosed may be made within the scope of what is claimed without departing from the spirit of the invention.
- A fabric-matrix composite structure for making parts suitable for use in hostile, high-temperature environments, such as rocket exhaust nozzles. The structure includes a fabric formed of polyacrylonitrile fiber, especially a polyacrylonitrile fiber that has been oxidized, and especially a combination of polyacrylonitrile fibers that have been oxidized to different degrees. The structure also includes a binder that impregnates the fabric. The binder might be a phenolic resin. The structure is formed, partially cured, formed into a product, and finish cured.
- This invention is a fabric-matrix composite structure for making parts suitable for use in hostile, high-temperature environments, such as rocket exhaust nozzles. This embodiment of the composite structure of the present invention showing fabric embedded in the resin. The structure includes a fabric formed of polyacrylonitrile fiber, especially a polyacrylonitrile fiber that has been oxidized, and especially a combination of polyacrylonitrile fibers that have been oxidized to different degrees. The structure also includes a binder that impregnates the fabric. The binder might be a phenolic resin.
- One embodiment of this invention is a process. Step 1 involves forming the composite structure by imbedding the fabric with the resin. Step 2 involves converting the resin and partially curing it to form a pre-preg. In Step 4, the structure is formed into a product shape , and, in Step 4, the product is finish cured.
- One embodiment of this invention is a pre-preg formulation for use in ablative applications such as, but not limited to, rocket or missile exhaust nozzles and high temperature resistant, carbon/carbon applications. The pre-preg structure consists of woven fabric based on discontinuous fibers. The fibers are typically formed of a hydrocarbon material that is converted to a “pre-ox” fiber, that is, the fibers are oxidized by heating in an oxygen-containing atmosphere, until it achieves the desired level of carbon and oxygen, for example, approximately ten weight percent oxygen content. The fabric is then impregnated with a phenolic resin, and can be used in the form of broad goods, molding compound or biased tapes. The resultant pre-preg can be molded into various components.
- The term “pre-preg” generally refers to a structure including polymer which is not yet completely cured or polymerized. Typically, such polymers are cured to a degree referred to as B stage. At that stage, the polymer is physically stable., but not fully cross-linked.
- The field of the invention relates to a pre-preg formulation and structure with high ablative properties for the use in missile components, rocket nozzles, high temperature resistant parts and carbon/carbon high temperature resistant parts.
- Various embodiments of the present invention provide an improved pre-preg formulation for ablative applications, requiring high temperature resistance, and in other carbon/carbon applications.
- A “carbon/carbon” structure generally refers to a structure having at least two zones, each possessing a different carbon structure.
- Some embodiments of the pre-preg system of the present invention include a fibrous material, either woven or non-woven, impregnated with a thermosetting or thermoplastic matrix resin.
- Some embodiments of the present invention involve a pre-preg formulation that is thermosetting in nature and is cured/molded into rocket/missile components, high temperature components and carbon/carbon preform components at temperatures between 250 F and 425 F. Such a pre-preg formulation might include a fibrous material that is woven, non-woven or aligned unidirectional fibers, pre-impregnated with a thermosetting phenolic matrix resin. The pre-preg formulation might include discontinuous fibers. The fabric and discontinuous fibers might consist of fibers two different fiber materials. The two fiber materials might consist of carbon fiber based on polyacrylonitrile (PAN) at a carbon content of 95+/−3% and polyacrylonitrile (PAN) based pre-ox carbon fiber at a carbon content of 60+/−5%.
- The fibers might be blended into a yarn at a ratio such that the carbon content of the yarn is 82+/−10%. The yarn might be manufactured into a substrate that is impregnated with a phenolic resin. The substrate might be woven, non-woven or aligned unidirectional fibers. The phenolic resin might contains particulate fillers, short fibers, plate shaped fillers and/or nanometer-sized fillers. The pre-preg might be used as broad goods, molding compound, straight tapes or biased tapes. The pre-preg might be processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave.
- The pre-preg, after processing into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave, might be converted from a phenolic impregnated fabric molded structure to a carbon impregnated fabric molded structure (also known as carbon/carbon), via exposure to a minimum of 1200 F in a nitrogen atmosphere. The phenolic resin system is capable of being formulated with appropriate solvents for impregnation into fibrous woven fabrics, fibrous nonwoven fabrics or aligned unidirectional fibers.
- The pre-preg might be molded to the required thickness for the intended application and then processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave. Multiple layers of the pre-preg might be used to achieve the required thickness for the final product.
- The phenolic resin used to impregnate the fibrous material can be in applied in solvated form. Solvents used for the phenolic resin can include methanol, isopropyl alcohol, denatured alcohol and acetone. The pre-preg is manufactured using the fibers/fabrics/nonwovens using conventional solvent-based or non-solvent-based techniques.
- The molding of the pre-preg that is produced is conducted by conventional techniques that utilize heat, pressure, and, in some processes, vacuum. These techniques include compression molding, vacuum-bag molding in an oven, vacuum-bag molding in an autoclave, and vacuum-bag molding in a hydroclave.
- The molding processes convert the pre-preg into a molded, cured (cross-linked) composite. The primary application for the pre-preg is in the use of molded components that are subsequently exposed to high temperatures. The high-temperature environment can include, but is not be limited to, ablative environments such as rocket and missile nozzles, ablative environments such as heat shields, for high temperature processing such as post-molded carbonization of the phenolic resin to form carbon/carbon structures.
- The character of the invention, however, may best be understood by reference to one of its structural forms, as illustrated by the accompanying drawings, in which:
-
FIG. 1 is a schematic front elevation view of an embodiment of the present invention showing fabric embedded in resin, and formed into a tolerance part, and -
FIG. 2 is a schematic flow chart of an embodiment of this invention. -
FIG. 1 is a schematic front elevation view of an embodiment of the composite structure. This invention is a fabric-matrix composite structure 10 for makingparts 13 suitable for use in hostile, high-temperature environments, such as rocket exhaust nozzles. This embodiment of thecomposite structure 10 of the presentinvention showing fabric 11 embedded in theresin 12. Thestructure 10 includes afabric 11 formed of polyacrylonitrile fiber, especially a polyacrylonitrile fiber that has been oxidized, and especially a combination of polyacrylonitrile fibers that have been oxidized to different degrees. Thestructure 10 also includes abinder 12 that impregnates thefabric 11. Thebinder 12 might be a phenolic resin. -
FIG. 2 is a schematic flow chart of an embodiment of this invention. Step 1 (numeral 30) involves forming the composite structure by imbedding the fabric with the resin. Step 2 (numeral 40) involves converting the resin and partially curing it to form a pre-preg. In Step 4, the structure is formed into a product shape (numeral 50), and, in Step 4, the product is finish cured (numeral 60). - One embodiment of this invention is a pre-preg formulation for use in ablative applications such as, but not limited to, rocket or missile exhaust nozzles and high temperature resistant, carbon/carbon applications. The pre-preg structure consists of woven fabric based on discontinuous fibers. The fibers are typically formed of a hydrocarbon material that is converted to a “pre-ox” fiber, that is, the fibers are oxidized by heating in an oxygen-containing atmosphere, until it achieves the desired level of carbon and oxygen, for example, approximately ten weight percent oxygen content. The fabric is then impregnated with a phenolic resin, and can be used in the form of broad goods, molding compound or biased tapes. The resultant pre-preg can be molded into various components.
- The term “pre-preg” generally refers to a structure including polymer which is not yet completely cured or polymerized. Typically, such polymers are cured to a degree referred to as B stage. At that stage, the polymer is physically stable., but not fully cross-linked.
- The field of the invention relates to a pre-preg formulation and structure with high ablative properties for the use in missile components, rocket nozzles, high temperature resistant parts and carbon/carbon high temperature resistant parts.
- Various embodiments of the present invention provide an improved pre-preg formulation for ablative applications, requiring high temperature resistance, and in other carbon/carbon applications.
- A “carbon/carbon” structure generally refers to a structure having at least two zones, each possessing a different carbon structure.
- Some embodiments of the pre-preg system of the present invention include a fibrous material, either woven or non-woven, impregnated with a thermosetting or thermoplastic matrix resin.
- Some embodiments of the present invention involve a pre-preg formulation that is thermosetting in nature and is cured/molded into rocket/missile components, high temperature components and carbon/carbon preform components at temperatures between 250 F and 425 F. Such a pre-preg formulation might include a fibrous material that is woven, non-woven or aligned unidirectional fibers, pre-impregnated with a thermosetting phenolic matrix resin. The pre-preg formulation might include discontinuous fibers. The fabric and discontinuous fibers might consist of fibers two different fiber materials. The two fiber materials might consist of carbon fiber based on polyacrylonitrile (PAN) at a carbon content of 95+/−3% and polyacrylonitrile (PAN) based pre-ox carbon fiber at a carbon content of 60+/−5%.
- The fibers might be blended into a yarn at a ratio such that the carbon content of the yarn is 82+/−10%. The yarn might be manufactured into a substrate that is impregnated with a phenolic resin. The substrate might be woven, non-woven or aligned unidirectional fibers. The phenolic resin might contains particulate fillers, short fibers, plate shaped fillers and/or nanometer-sized fillers. The pre-preg might be used as broad goods, molding compound, straight tapes or biased tapes. The pre-preg might be processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave.
- The pre-preg, after processing into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave, might be converted from a phenolic impregnated fabric molded structure to a carbon impregnated fabric molded structure (also known as carbon/carbon), via exposure to a minimum of 1200 F in a nitrogen atmosphere.
- The phenolic resin system is capable of being formulated with appropriate solvents for impregnation into fibrous woven fabrics, fibrous nonwoven fabrics or aligned unidirectional fibers.
- The pre-preg might be molded to the required thickness for the intended application and then processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave. Multiple layers of the pre-preg might be used to achieve the required thickness for the final product.
- The phenolic resin used to impregnate the fibrous material can be in applied in solvated form. Solvents used for the phenolic resin can include methanol, isopropyl alcohol, denatured alcohol and acetone. The pre-preg is manufactured using the fibers/fabrics/nonwovens using conventional solvent-based or non-solvent-based techniques.
- The molding of the pre-preg that is produced is conducted by conventional techniques that utilize heat, pressure, and, in some processes, vacuum. These techniques include compression molding, vacuum-bag molding in an oven, vacuum-bag molding in an autoclave, and vacuum-bag molding in a hydroclave.
- The molding processes convert the pre-preg into a molded, cured (cross-linked) composite. The primary application for the pre-preg is in the use of molded components that are subsequently exposed to high temperatures. The high-temperature environment can include, but is not be limited to, ablative environments such as rocket and missile nozzles, ablative environments such as heat shields, for high temperature processing such as post-molded carbonization of the phenolic resin to form carbon/carbon structures.
- While it will be apparent that the illustrated embodiments of the invention herein disclosed are calculated adequately to fulfill the object and advantages primarily stated, it is to be understood that the invention is susceptible to variation, modification, and change within the spirit and scope of the subjoined claims. It is obvious that minor changes may be made in the form and construction of the invention without departing from the material spirit thereof. It is not, however, desired to confine the invention to the exact form herein shown and described, but it is desired to include all such as properly come within the scope claimed.
- The invention having been thus described, what is claimed as new and desire to secure by Letters Patent is:
Claims (17)
1. A structure involving a pre-preg formulation that is thermosetting in nature and is cured/molded into rocket/missile components, high temperature components and carbon/carbon preform components at temperatures between 250 F and 425 F.
2. A structure as recited in claim 1 , wherein the pre-preg formulation includes a fibrous material that is woven, non-woven or aligned unidirectional fibers, pre-impregnated with a thermosetting phenolic matrix resin.
3. A structure as recited in claim 1 , wherein the pre-preg formulation includes discontinuous fibers.
4. A structure as recited in claim 3 , wherein the fibrous material or discontinuous fibers consist of fibers of two different fiber materials.
5. A structure as recited in claim 4 , wherein the two fiber materials consist of carbon fiber based on polyacrylonitrile (PAN) at a carbon content of 95+/−3% and polyacrylonitrile (PAN) based pre-ox carbon fiber at a carbon content of 60+/−5%.
6. A structure as recited in claim 5 , wherein the fibrous materials or fibers are blended into a yarn at a ratio such that the carbon content of the yarn is 82+/−10%.
7. A structure as recited in claim 6 , wherein the yarn is manufactured into a substrate that is impregnated with a phenolic resin.
8. A structure as recited in claim 7 , wherein the substrate can be woven, non-woven or aligned unidirectional fibers.
9. A structure as recited in claim 7 , wherein the phenolic resin contains particulate fillers, short fibers, plate shaped fillers and/or nanometer-sized fillers.
10. A structure as recited in claim 1 , wherein the pre-preg can be used as broad goods, molding compound, straight tapes or biased tapes.
11. A structure as recited in claim 1 , wherein the pre-preg can be processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave.
12. A structure as recited in claim 1 , wherein the pre-preg, after processing into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave, can be converted from a phenolic impregnated fabric molded structure to a carbon impregnated fabric molded structure (also known as carbon/carbon), via exposure to a minimum of 1200 F in a nitrogen atmosphere.
13. A structure as recited in claim 7 , wherein the phenolic resin system is capable of being formulated with appropriate solvents for impregnation into fibrous woven fabrics, fibrous nonwoven fabrics or aligned unidirectional fibers.
14. A structure as recited in claim 1 , wherein the pre-preg can be molded to the required thickness for the application as described in claim 1 and then processed into parts via the use of compression molding, vacuum bag molding in oven, vacuum bag molding in autoclave or vacuum bag molding in hydroclave.
15. A structure as recited in claim 14 , wherein multiple layers of the pre-preg can be used to achieve the required thickness.
16. A method of forming a product for use in ablative conditions, comprising the steps of:
a.) forming a composite structure comprised of a polyacrylonitrile or polyacrylonitrile-derivative fabric impregnated with a phenolic polymer,
b.) partially polymerizing the polymer,
c.) forming the structure into the form of the product, and
d.) fully polymerizing the polymer.
17. A method of using a product in ablative conditions, comprising the steps of:
a.) forming a composite structure comprised of a polyacrylonitrile or polyacrylonitrile-derivative fabric impregnated with a phenolic polymer,
b.) partially polymerizing the polymer,
c.) forming the structure into the form of the product,
d.) fully polymerizing the polymer, and
e.) exposing the product to ablative conditions.
Priority Applications (1)
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US14/636,455 US20150232663A1 (en) | 2008-01-28 | 2015-03-03 | Fiber-based ablative and high temperature pre-preg material |
Applications Claiming Priority (4)
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US6265308P | 2008-01-28 | 2008-01-28 | |
PCT/US2009/032299 WO2009097366A1 (en) | 2008-01-28 | 2009-01-28 | Fiber-based ablative and high temperature pre-preg material |
US86465110A | 2010-07-26 | 2010-07-26 | |
US14/636,455 US20150232663A1 (en) | 2008-01-28 | 2015-03-03 | Fiber-based ablative and high temperature pre-preg material |
Related Parent Applications (2)
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PCT/US2009/032299 Continuation WO2009097366A1 (en) | 2008-01-28 | 2009-01-28 | Fiber-based ablative and high temperature pre-preg material |
US12/864,651 Continuation US9045376B2 (en) | 2008-01-28 | 2009-01-28 | Fiber-based ablative and high temperature pre-preg material |
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US20150232663A1 true US20150232663A1 (en) | 2015-08-20 |
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US14/636,455 Abandoned US20150232663A1 (en) | 2008-01-28 | 2015-03-03 | Fiber-based ablative and high temperature pre-preg material |
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US12/864,651 Active 2031-07-21 US9045376B2 (en) | 2008-01-28 | 2009-01-28 | Fiber-based ablative and high temperature pre-preg material |
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WO (2) | WO2009131729A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10780608B2 (en) * | 2015-05-29 | 2020-09-22 | Cytec Industries Inc. | Process for preparing moulded articles from fibre-reinforced composite materials—II |
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CN101913887B (en) * | 2010-08-10 | 2013-05-08 | 烟台凯泊复合材料科技有限公司 | High-temperature resistant carbon fibre product and preparation method thereof |
US8776375B2 (en) * | 2011-05-19 | 2014-07-15 | The Boeing Company | Aircraft structure for high capacity pull off |
CN102560889B (en) * | 2012-01-05 | 2014-04-02 | 黑龙江大学 | Method for producing bead-stringed PAN (polyacrylonitrile)-based carbon fiber electrode materials by electrostatic spinning |
EP3742011A1 (en) * | 2019-05-24 | 2020-11-25 | Aktiebolaget SKF | Liner with improved resistance to wear and plain bearing comprising such a liner |
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US3724386A (en) * | 1970-06-24 | 1973-04-03 | Us Air Force | Ablative nose tips and method for their manufacture |
JPH03150266A (en) * | 1989-11-07 | 1991-06-26 | Akechi Ceramics Kk | Production of carbon/carbon composite material |
US5645219A (en) * | 1993-08-03 | 1997-07-08 | Thiokol Corporation | Addition-polymerization resin systems for fiber-reinforced nozzle ablative components |
US5436042A (en) * | 1994-03-11 | 1995-07-25 | The Carborundum Company | Ceramic fiber-reinforced composite articles and their production |
US5776385A (en) * | 1994-04-15 | 1998-07-07 | Corning Incorporated | Method of making activated carbon composites from supported crosslinkable resins |
US5714419A (en) * | 1994-08-04 | 1998-02-03 | Fiberite, Inc. | Composite material suitable for aircraft interiors |
US5871844A (en) * | 1997-04-02 | 1999-02-16 | Fiberite, Inc. | Carbon--carbon parts having filamentized composite fiber substrates and methods of producing the same |
US6679965B1 (en) * | 1997-06-04 | 2004-01-20 | Alliant Techsystems Inc. | Low density composite rocket nozzle components and process for making the same from standard density phenolic matrix, fiber reinforced materials |
US6309703B1 (en) * | 1998-06-08 | 2001-10-30 | The United States Of America As Represented By The Secretary Of The Air Force | Carbon and ceramic matrix composites fabricated by a rapid low-cost process incorporating in-situ polymerization of wetting monomers |
US6365257B1 (en) * | 1999-04-14 | 2002-04-02 | Bp Corporation North America Inc. | Chordal preforms for fiber-reinforced articles and method for the production thereof |
AU2001277432A1 (en) * | 2000-07-26 | 2002-02-05 | Ballard Power Systems Inc. | Carbon-matrix composites compositions and methods related thereto |
US6537470B1 (en) * | 2000-09-01 | 2003-03-25 | Honeywell International Inc. | Rapid densification of porous bodies (preforms) with high viscosity resins or pitches using a resin transfer molding process |
JP3894035B2 (en) * | 2001-07-04 | 2007-03-14 | 東レ株式会社 | Carbon fiber reinforced substrate, preform and composite material comprising the same |
US6749937B2 (en) * | 2002-03-19 | 2004-06-15 | Honeywell International Inc. | Melt-infiltrated pitch-pan preforms |
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2009
- 2009-01-27 WO PCT/US2009/032174 patent/WO2009131729A2/en not_active Application Discontinuation
- 2009-01-28 WO PCT/US2009/032299 patent/WO2009097366A1/en active Application Filing
- 2009-01-28 US US12/864,651 patent/US9045376B2/en active Active
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2015
- 2015-03-03 US US14/636,455 patent/US20150232663A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10780608B2 (en) * | 2015-05-29 | 2020-09-22 | Cytec Industries Inc. | Process for preparing moulded articles from fibre-reinforced composite materials—II |
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US9045376B2 (en) | 2015-06-02 |
WO2009131729A2 (en) | 2009-10-29 |
WO2009097366A1 (en) | 2009-08-06 |
US20100307163A1 (en) | 2010-12-09 |
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