WO2014149391A1 - Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation - Google Patents
Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation Download PDFInfo
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- WO2014149391A1 WO2014149391A1 PCT/US2014/018026 US2014018026W WO2014149391A1 WO 2014149391 A1 WO2014149391 A1 WO 2014149391A1 US 2014018026 W US2014018026 W US 2014018026W WO 2014149391 A1 WO2014149391 A1 WO 2014149391A1
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- WIPO (PCT)
- Prior art keywords
- prepreg
- elevated temperature
- glass
- fiber
- reduced pressure
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/12—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
-
- 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.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
Definitions
- a prepreg curing process for preparing composites having superior surface finish and high fiber consolidation is provided .
- Prepreg curing is ordinarily conducted in autoclave in which elevated temperature and pressure conditions are used to create composites having relatively smooth surface finishes.
- a process is provided for curing a prepreg
- thermosetting resin composition and fiber Providing a prepreg comprising a thermosetting resin composition and fiber
- the first elevated temperature is in the range of about 120°F to about 350°.
- the second elevated temperature is greater than the first elevated temperature.
- the third elevated temperature is greater than the first and/or second elevated temperature.
- the fourth elevated temperature is less than the first and/or second and/or third elevated
- thermosetting resin composition and fiber Providing a prepreg comprising a thermosetting resin composition and fiber
- the reduced pressure should be greater than 258 mm Hg (5 psi) , desirably greater than 517 mm Hg ⁇ 10 psi) , such as greater than 686 mm Hg (13.3 psi) .
- the first elevated temperature is in the range of about 120°F to about 350°F, such as about 200°F and the time is about 2 hours.
- the second elevated temperature is about 290°F and the time is about 3 hours.
- the third elevated temperature is
- the fourth elevated temperature may be about
- the time should be about 2 hours.
- the fourth elevated temperature is less than the first and/or second and/or third elevated
- the fourth elevated temperature may be about 90°F.
- towpregging processes are also provided.
- thermosetting resin composition are issues for composite or laminate formation.
- Consolidation pressure is ordinarily provided by autoclave or a press, with pressures reaching in the range of up to 100 psi. Even when such external pressure is increased beyond 100 psi, the resin may not see such pressure as the fibers begin to bear the load. And resin fluid pressure can further reduce as the resin cures and begins to shrink.
- low fluid pressure at and/or during cure can occur at the temperature lagging areas, resulting in poor wetting and poor composite properties.
- matrix resins include resins that have low viscosity and high volatility, resin volatilization may create imperfection/microvoids in the composite or laminate.
- compositions are also provided.
- the fiber may be constructed from unidirectional fibers, woven fibers, chopped fibers, non-woven fibers or long, discontinuous fibers .
- the fiber chosen may be selected from carbon, glass, aramid, boron, polyalkylene, guartz, polybenzimidazole ,
- polyetheretherketone polyphenylene sulfide, poly p-phenylene benzobisoaxazole, silicon carbide, poly p-phenylene
- the carbon is selected from polyacrylonitrile , pitch, rayon and acrylic
- the glass is selected from S glass, S2 glass, E glass, R glass, A glass, AR glass, C glass, D glass, ECR glass, glass filament, staple glass, T glass and zirconium oxide glass.
- thermosetting resin composition should have a viscosity in the range of 100 to 400,000 cps at an impregnation temperature of 140°F to 300°F.
- time within which the viscosity of the thermosetting resin composition increases by 100% under the process conditions is in the range of 10 minutes to 10 hours.
- thermosetting resin composition may include oxazine, oxazoline, epoxy, episulfide, cyanate ester, maleimide, nadimide, itaconimide, phenolic, thiophenolic and combinations thereof .
- thermosetting resin composition includes as at least a portion thereof an oxazine component
- the oxazine component may be embraced by the following structure:
- X is selected from a direct bond (when o is 2 ⁇ , alkyl (when o is 1), alkylene ⁇ when o is 2-4), carbonyl (when o is 2), thiol (when o is 1), thioether (when o is 2), sulfoxide (when o is 2), and sulfone (when o is 2), and Ri is selected from hydrogen, alkyl and aryl.
- oxazine may be embraced by the following structure:
- Ri and R 2 are the same or different and are selected from hydrogen, alkyl, such as methyl, ethyl, propyls and butyls, and aryl.
- the oxazine thus may be selected from any of the following exemplified structures:
- Ri are R 2 are as defined above, and R 3 is defined as Ri or 2-
- the oxazine component may include the combination multifunctional oxazines and monofunctional oxazines.
- R is aryl or alkyl, such as methyl, ethyl, propyls and butyls .
- R 1 , R 2 , R 3 , R 4 , and X are hydrogen or as regards x a direct bond to a divalent organic radical, and m is 1.
- Exemplary oxazoline compounds have the structure
- R 1 to R s are each independently selected from Ci-if) alkyl, C 2 ⁇ o alkenyl, each of which being optionally substituted or interrupted by one or more -0—, -NH—, —S—, -CO-, -C ⁇ 0)0-, -NHC(O)-, and C 6 - 20 aryl groups.
- the oxazoline compounds include 4, 4', 5,5'- tetrahydro-2, 2 ' -bis-oxazole, 2 , 2 ' -bis ( 2-oxazoline ) ; a 2,2'-
- alkanediyl bis [4 , 4-dihydrooxazole] , e.g., 2, 2'- (2,4- butanediyl) bis [ 4 , 5-dihydrooxazole] and 2,2 '-(1,2- ethanediyl) bis [ 4 , 5-dihydrooxazole] ; a 2 , 2 ' - ( arylene ) bis
- [ 4 , 5-dihydrooxazole] e.g., 2 , 2 ' - ( 1 , 4-phenylene) bis (4,5- dihydrooxazole] , 2 , ' - ( 1 , 5-naphthalenyl ) bis (4,5- dihydrooxazole] , 2 , 2 ' - ( 1 , 3-phenylene) bis [4,5- dihydrooxazole) , and 2 , 2 ' - ( 1 , 8-anthracenyl ) bis [4,5- dihydrooxazole ; a sulfonyl, oxy, thio or alkylene bis 2-
- (arylene) [ , 5-dihydrooxazole e.g., sulfonyl bis 2-(l,4- phenylene) [4, -dihydrooxazole] , thio bis 2,2'-(l, 4- phenylene) [ 4 , 5-dihydrooxazole ] and methylene bis 2,2'- (1,4- phenylene) [ 4 , 5-dihydrooxazole] ; a 2, 2 ' , 2"- (1, 3, 5-arylene) tris [ 4 , 5-dihydrooxazole ] , e.g., 2,2',2"-tris (4,5- dihydrooxazole ] 1 , 3 , 5-benzene ; a poly [ (2-alkenyl) 4,5- hydrooxazole] , e.g., poly [2- (2-propenyl ) , 5-dihydrooxazol and of course combinations thereof
- the oxazoline compounds may have any one or more he following structures:
- polyepoxides having at least about two 1,2-epoxy groups per molecule are suitable for use herein.
- the polyepoxides may be saturated,
- polyepoxides include the polyglycidyl ethers, which are prepared by reaction of epichlorohydrin or epibromohydrin with a polyphenol in the presence of alkali.
- suitable polyphenols therefor are, for example, resorcinol,
- pyrocatechol hydroquinone , bisphenol A (bis (4- hydroxyphenyl ⁇ -2 , 2-propane) , bisphenol F (bis (4- hydroxyphenyl ) -methane) , bisphenol S, biphenol, bis (4- hydroxyphenyl ) -1, 1-isobutane, 4,4' -dihydroxy-benzophenone, bis ⁇ -hydroxyphenyl ) -1, 1-ethane, and 1 , 5-hydroxy-naphthalene .
- Other suitable polyphenols as the basis for the polyglycidyl ethers are the known condensation products of phenol and formaldehyde or acetaldehyde of the novolak resin-type.
- polyepoxides that are in principle suitable for use herein are the polyglycidyl ethers of polyalcohols or diamines. Such polyglycidyl ethers are derived from
- polyalcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1 , 2-propylene glycol, 1,4-butylene glycol, triethylene glycol, 1 , 5-pentanediol , 1, 6-hexanediol or trimethylolpropane .
- Still other polyepoxides are polyglycidyl esters of polycarboxylic acids, for example, reaction products of glycidol or epichlorohydrin with aliphatic or aromatic polycarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, terephthalic acid or a dimeric fatty acid.
- liquid epoxy resins derived from the reaction of bisphenol A or bisphenol F and epichlorohydrin.
- the epoxy resins that are liquid at room temperature generally have epoxy equivalent weights of from 125 to about 480.
- the thermosetting resin composition may contain from about 10 to about 90 percent by weight, such as from about 20 to about 40 percent by weight, of epoxy resin. Ordinarily, the thermosetting resin composition may contain from about 40 to about 70 percent by weight benzoxazine.
- the composition may include as at least a portion of the epoxy component a reactive diluent such as a mono- epoxide (e.g., monoglycidyl ethers of alkyl- and alkenyl- substituted phenols) .
- a reactive diluent such as a mono- epoxide (e.g., monoglycidyl ethers of alkyl- and alkenyl- substituted phenols) .
- episulfide is desirable as well, whether they are full or partial episulfides, provided that they are in the solid state.
- Episulfides may be
- the resin component may also include one or more of cyanate ester, maleimide, nadimide, itaconimide, phenolic and/or thiophenolic .
- the resin component should be present in the
- thermosetting resin composition in an amount in the range of about 5 to about 60 percent by weight, such as about 10 to about 50 percent by weight, desirably about 15 to about 35 percent by weight, based on the total weight of the composition.
- thermosetting resin composition may also include a toughener.
- a toughener is an
- tougheners may include
- poly (propylene) oxide polyether sulfone, such as PES 5003P, available commercially from Sumitomo Chemical Company, Japan; carboxy-terminated acrylonitrile butadienes; hydroxy- terminated acrylonitrile butadienes; core shell polymers; and BLENDEX 338, SILTE STM 1500 and ULTE 2000, which are
- ULTEM 2000 (CAS Reg. No. 61128-46-9) is a polyetherimide having a molecular weight ("Mw") of about 30,000 ⁇ 10,000. Those
- NIPOL tradename NIPOL are also desirable. Of the NIPOL branded rubbers, acrylonitrile polybutadiene rubbers are particularly desirable .
- the toughener component should be present in the thermosetting resin component in an amount in the range of about 1 to about 90 percent by weight, such as about 10 to about 70 percent by weight, desirably about 15 to about 30 percent by weight, based on the total weight of the composition.
- the curing agent may be selected from nitrogen- containing compounds such as amine compounds, amide compounds, imidazole compounds, guanidine compounds, urea compounds and derivatives and combinations thereof.
- the amine compounds may be selected from, aliphatic polyamines, aromatic polyamines, alicyclic polyamines and combinations thereof.
- the amine compounds may be selected from
- diethylaminopropylamine diethylaminopropylamine, xylenediamine, diaminodiphenylamine, isophoronediamine, menthenediamine and combinations thereof.
- modified amine compounds may be used, which include epoxy amine additives formed by the addition of an amine compound to an epoxy compound, for instance, novolac-type resin modified through reaction with aliphatic amines.
- the imidazole compounds may be selected from:
- imidazole isoimidazole, alkyl-substituted imidazoles, and combinations thereof. More specifically, the imidazole
- compounds are selected from 2-methyl imidazole, 2-ethyl-4- methylimidazole, 2 , 4-dimethylimidazole, butylimidazole, 2- heptadecenyl-4 -methylimidazole , 2 -undecenylimidazole, l-vinyl-2- methylimidazole, 2-n-heptadecylimidazole, 2-undecylimidazole , 1- benzyl-2-methylimidazole, l-propyl-2-methylimidazole, 1- cyanoethyl-2-methylimidazole, l-cyanoethyl-2-ethyl-4- methylimidazole, l-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-phenylimidazole, l-guanaminoethyl-2-methylimidazole and addition products of an imidazole
- Modified imidazole compounds may be used as well, which include imidazole adducts formed by the addition of an imidazole compound to an epoxy compound.
- Guanidines substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, cyclic tertiary amines, aromatic amines and/or mixtures thereof.
- the hardeners may be involved stoichiometrically in the hardening reaction; they may, however, also be catalytically active.
- substituted guanidines are methyl-guanidine, dimethylguanidine,
- trimeth lguanidine trimeth lguanidine, tetra-methylguanidine, methylisobiguanidine, dimethylisobiguanidine, tet amethyliso-biguanidine,
- guanamine derivatives include alkylated benzoguanamine resins,
- catalytically-active substituted ureas may be used.
- p-chlorophenyl-N, N-dimethylurea (monuron) , 3- phenyl-1 , 1-dimethylurea (fenuron) or 3, -dichlorophenyl-N, N- dimethylurea (diuron) are representative examples.
- Benzoxazine polymerization can also be initiated by cationic initiators, such as Lewis acids, and other known cationic initiators, such as metal halides; organometallic derivatives; metallophorphyrin compounds such as aluminum phthalocyanine chloride; methyl tosylate, methyl triflate, and triflic acid; and oxyhalides, and appropriate salts thereof.
- cationic initiators such as Lewis acids, and other known cationic initiators, such as metal halides; organometallic derivatives; metallophorphyrin compounds such as aluminum phthalocyanine chloride; methyl tosylate, methyl triflate, and triflic acid; and oxyhalides, and appropriate salts thereof.
- compositions may also include coreactants,
- Lewis acids such as phenols and derivatives thereof
- strong acids such as alkylenic acids and cationic catalysts .
- the amount of curing agent may depend upon a number of factors, including whether the curing agent acts as a catalyst or participates directly in crosslinking of the composition, the concentration of epoxy groups and other reactive groups in the composition, the desired curing rate and the like.
- the curing agent should be present in an amount in the range of about 0.01 to about 40 percent by weight, such as about 0.5 to about 20 percent by weight, desirably about 1 to about 15 percent by weight, based on the total weight of the composition.
- a resin for use in a prepregging process with fiber with the noted components in the specified amount is set forth in the table below.
- the cured prepreg is storage stable at room
- the cured prepreg shows using c-scan substantially no detectable voids larger than approximately 1/8 inch.
- the cured prepreg shows total void content of less than about 2% by volume determined by acid digestion using ASTM 3171-11.
- ASTM 3171-11 Standard Test Methods for Constitiuent Content of Composite Materials, determines the constituent content of composite by either of two approaches.
- Method I uses acid digestion or ignition to remove matrix resin while leaving the fiber reinforcement unaffected and provides for calculation of resin matrix and reinforcement content plus void volume percent.
- Method II uses physical dimensions of the cured prepreg sample, its density and the previously determined fiber areal weight, resin matrix density and fiber density to
- the procedure described in this test method requires cutting approximately 1 to 2 gram samples of the cured prepreg, drying to an equilibrium condition and determining the density using weight difference protocol.
- the sample is weighed, placed into beaker and immersed in 70% nitric acid heated to 80°C until digestion of the matrix resin is complete.
- the beaker contents are then filtered through a tared sintered glass filter using vacuum and finally washed with 3 passes with distilled water and one pass with acetone.
- the filter is then dried in a 100°C oven for up to 1 hour, cooled in a dessicator and weighed.
- Combustion may be used for fiber reinforcements, like glass or quartz, that do not degrade at high temperatures.
- test procedure follows the digestion method except the sample is placed in a preweighed crucible, exposed to a temperature in the 500 °C range until all resin matrix is removed, cooled to ambient and weighed. Determination of the void volume requires calculation of matrix resin volume percent and fiber reinforcement volume percent.
- Fiber reinforcement volume percent uses the following formula :
- Matrix resin volume percent uses the following
- V m (Mi-M f )/Mi x p c /p m x 100
- Void volume percent uses the following formula:
- V v 100- (V E + VJ .
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210372775.6A CN114714642A (en) | 2013-03-15 | 2014-02-24 | Prepreg curing process for preparing composites with excellent surface finish and high fiber consolidation |
CN201480016257.4A CN105121113A (en) | 2013-03-15 | 2014-02-24 | Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation |
BR112015023426-7A BR112015023426B1 (en) | 2013-03-15 | 2014-02-24 | pre-impregnated curing process to prepare composites having superior surface finish and high fiber consolidation |
CA2906374A CA2906374C (en) | 2013-03-15 | 2014-02-24 | Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation |
JP2016500362A JP6585027B2 (en) | 2013-03-15 | 2014-02-24 | Pre-preg curing method for preparing composite materials with excellent surface finish and high fiber compaction |
EP14768260.3A EP2969447A4 (en) | 2013-03-15 | 2014-02-24 | Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US13/838,164 US9427943B2 (en) | 2013-03-15 | 2013-03-15 | Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation |
US13/838,164 | 2013-03-15 |
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WO2014149391A1 true WO2014149391A1 (en) | 2014-09-25 |
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PCT/US2014/018026 WO2014149391A1 (en) | 2013-03-15 | 2014-02-24 | Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation |
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US (1) | US9427943B2 (en) |
EP (1) | EP2969447A4 (en) |
JP (2) | JP6585027B2 (en) |
CN (2) | CN105121113A (en) |
BR (1) | BR112015023426B1 (en) |
CA (1) | CA2906374C (en) |
WO (1) | WO2014149391A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US9427943B2 (en) * | 2013-03-15 | 2016-08-30 | Henkel IP & Holding GmbH | Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation |
US9205633B2 (en) * | 2013-03-15 | 2015-12-08 | Henkel IP & Holding GmbH | Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation |
CN104761897B (en) * | 2015-03-20 | 2017-07-28 | 西北工业大学 | A kind of modified pbo fiber/cyanate ester resin wave-penetrating composite material and preparation method thereof |
KR102644665B1 (en) * | 2015-12-16 | 2024-03-07 | 디아이씨 가부시끼가이샤 | Oxazine compounds, compositions and cured products |
EP3508459A1 (en) | 2018-01-09 | 2019-07-10 | OCV Intellectual Capital, LLC | Fiber reinforced materials with improved fatigue performance |
JP7114367B2 (en) * | 2018-06-28 | 2022-08-08 | 三菱重工業株式会社 | Forming method for composite structure |
CN113248935B (en) * | 2021-05-17 | 2021-12-31 | 广州市市维新材料科技有限公司 | Reactive liquid asphalt, preparation method and application thereof, water reactive normal-temperature asphalt mixture and preparation method thereof |
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Also Published As
Publication number | Publication date |
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JP2016510833A (en) | 2016-04-11 |
CN114714642A (en) | 2022-07-08 |
CA2906374C (en) | 2021-07-06 |
CA2906374A1 (en) | 2014-09-25 |
CN105121113A (en) | 2015-12-02 |
BR112015023426A2 (en) | 2017-07-18 |
BR112015023426B1 (en) | 2020-12-08 |
US20140273694A1 (en) | 2014-09-18 |
JP2019166843A (en) | 2019-10-03 |
EP2969447A4 (en) | 2016-12-14 |
US9427943B2 (en) | 2016-08-30 |
EP2969447A1 (en) | 2016-01-20 |
JP6585027B2 (en) | 2019-10-02 |
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