[go: up one dir, main page]

WO2009038971A1 - Systèmes et composites de résine d'imprégnation résistants à l'érosion - Google Patents

Systèmes et composites de résine d'imprégnation résistants à l'érosion Download PDF

Info

Publication number
WO2009038971A1
WO2009038971A1 PCT/US2008/075101 US2008075101W WO2009038971A1 WO 2009038971 A1 WO2009038971 A1 WO 2009038971A1 US 2008075101 W US2008075101 W US 2008075101W WO 2009038971 A1 WO2009038971 A1 WO 2009038971A1
Authority
WO
WIPO (PCT)
Prior art keywords
erosion resistance
composite article
modified nanoparticles
cured
impregnating resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2008/075101
Other languages
English (en)
Inventor
James M. Nelson
Ryan E. Marx
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of WO2009038971A1 publication Critical patent/WO2009038971A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the present disclosure relates to the use of surface modified nanoparticles in impregnating resin systems to improve the erosion resistance of composite articles.
  • the present disclosure also relates to methods of improving the erosion resistance of composite articles.
  • Composite articles having improved erosion resistance are also disclosed.
  • the present disclosure provides an erosion resistant composite article comprising a fibrous layer impregnated with a curable resin and surface modified nanoparticles comprising a core, a surface, and a surface modifying agent attached to the surface.
  • the fibrous layer comprises two or more fibrous plies.
  • the fibrous layer comprises at least one of glass fibers, inorganic fibers, organic fibers, natural fibers, or carbon fibers.
  • the curable resin is a thermosetting resin.
  • the resin is selected from the group consisting of epoxy resins, polyester resins, acrylic resins, and vinyl esters.
  • the fibrous layer is impregnated with a reactive diluent.
  • the reactive diluent is styrene.
  • the surface modified nanoparticles comprise silica. In some embodiments, the surface modified nanoparticles comprise an inorganic surface. In some embodiments, the inorganic surface comprises a metal oxide.
  • the surface modifying agent is a reactive surface modifying agent.
  • the present disclosure provides an impregnating resin system comprising a curable resin and surface modified nanoparticles.
  • the erosion resistance of the impregnating resin as measure according to the Rain Erosion Resistance Test is at least 2 times (in some embodiments, 5 times, and in some embodiments, 10 times) greater than the erosion resistance of the curable resin absent the surface modified nanoparticles when cured.
  • the present disclosure provides methods of improving the erosion resistance of a composite article.
  • the method comprises infusing a fibrous layer with any of the impregnating resin systems described herein and curing the curable resin to form a cured composite article.
  • the present disclosure relates to the use of surface-modified nanoparticles in an impregnating resin system to improve the erosion resistance of a composite article.
  • FIG. 1 illustrates an exemplary composite article according some embodiments of the present disclosure.
  • FIG. 2 illustrates a cross-section of a surface-modified nanoparticle according to some embodiments of the present disclosure.
  • FIG. 3 illustrates a Rain Erosion Resistance apparatus.
  • FIG. 4 illustrates the feed portion of the Rain Erosion Resistance apparatus of FIG. 3.
  • FIG. 5 is an image of the surface of the composite article of Comparative Example 2.
  • FIG. 6 is an image of the surface of the composite article of Example 2.
  • Composite materials comprising a resin-impregnated fibrous matrix are used in a wide variety of applications.
  • applications e.g., aerospace, wind blade, architectural, sporting goods, marine and other transportation (i.e. rail cars) the composites suffer from limited erosion resistance in use environments.
  • Helicopter blades for example, see substantial deterioration of their composite structure upon flying in rainstorms.
  • Bike frames on traditional road and off-road bikes experience considerable pitting and scratching through normal use that may lead to shortened product life due to composite fatigue.
  • Composites used in wind towers see considerable rain exposure and will see increasing exposure to rough climates as more off-shore turbines are built and exposed to sea-air environments (e.g., salt).
  • the use of protective coatings or films to impart erosion resistance has several deficiencies.
  • the coating or film can be expensive to apply and may require multiple additional steps.
  • the coatings or films add weight to the structure, particularly when adhesives, primers, or adhesion promoters are used to bond the coatings or films to the surface of the composite.
  • the coatings or films can interfere with desirable aesthetic features of the underlying composite, e.g., the visually striking and distinctive carbon weave pattern observed with in applications using carbon fiber based composites, e.g., sporting goods.
  • coatings and films can craze and/or delaminate leading to failure or costly repairs.
  • the present inventors have discovered that the erosion resistance of a composite can be significantly enhanced through the use of nanoparticle-containing impregnating resin systems.
  • One method of assessing erosion resistance is described herein as the "Rain Erosion Resistance” test.
  • upon curing the erosion resistance, as determined by the Rain Erosion Resistance test of the nanoparticle-containing impregnating resin systems is at least 2 times greater, in some embodiments, at least 5 times greater, and in some embodiments, at least 10 times greater than the erosion resistance of the same cured resin system absent the surface modified nanoparticles.
  • the erosion resistance (as determined by the Rain Erosion Resistance test) of the cured composite article is at least 2 times greater, in some embodiments, at least 5 times greater, and in some embodiments, at least 10 times greater than the erosion resistance of the same cured composite article absent the surface-modified nanoparticles.
  • these resin systems can be used in current composite infusion processes and with current fibrous matrices offering great design flexibility without drastically affecting cure kinetics or resin viscosity.
  • the use of resin systems of the present disclosure may result in lower weight composites while providing improved erosion resistance.
  • the increase in mechanical properties obtained by using some resin systems of the present disclosure may enable a reduction in the number of fibrous plies while maintaining or enhancing the mechanical properties relative to part produced using traditional resin systems, i.e., resin systems lacking surface-modified nanoparticles.
  • Composite part 100 comprises fibrous layer 110 impregnated with an impregnating resin system.
  • the impregnating resin system comprises resin 120, and surface-modified nanoparticles 130.
  • fibrous layer 110 includes multiple fibrous plies.
  • the fibrous layer comprises inorganic fibers, e.g., glass fibers.
  • the fibrous layer comprises organic fibers, including, e.g., natural fibers.
  • the fibrous layer comprises carbon fibers. In some embodiments, combinations of these and other fibers may be used.
  • the present disclosure relates to any composite part including e.g., those used in aerospace applications, architectural applications, marine and other transportation applications, and sporting goods.
  • surface 101 of the composite parts of the present disclosure exhibit improved erosion resistance relative to composite parts made with the same resin system absent the surface modified nanoparticles.
  • the erosion resistance is at least 2 times greater, in some embodiments, at least 5 times greater, and in some embodiments, at least 10 times greater
  • resin 120 is a curable resin, e.g., a thermosetting resin. Any curable resin may be used. Exemplary curable resins include epoxies, vinyl esters, polyesters, acrylics and the like.
  • the resin system may include a reactive diluent, e.g., styrene, in addition to the curable resin. Generally, reactive diluents co-react with the curable resin and/or with other components of the resin system.
  • nanoparticles 130 comprise core 131, having an inorganic surface 132.
  • the core comprises an inorganic material and the surface is integral to the core.
  • inorganic surface 132 may comprise a separate layer surrounding core 131. In such embodiments, the core may comprise organic and/or inorganic materials.
  • surface 132 comprises a metal oxide. Any known metal oxide may be used. Exemplary metal oxides include silica, titania, alumina, zirconia, vanadia, chromia, antimony oxide, tin oxide, zinc oxide, ceria, and mixtures thereof.
  • the nanoparticle comprises an oxide of one metal (e.g., a surface layer) deposited on an oxide of another metal (e.g., a core). In some embodiments, the nanoparticle comprises a metal oxide surface deposited on a non-metal oxide core.
  • the nanoparticles have a primary particle size of between about 5 nanometers to about 500 nanometers, and in some embodiments from about 5 nanometers to about 250 nanometers, and even in some embodiments from about 50 nanometers to about 200 nanometers.
  • the cores have an average diameter of at least about 5 nanometers, in some embodiments, at least about 10 nanometers, at least about 25 nanometers, at least about 50 nanometers, and in some embodiments, at least about 75 nanometers. In some embodiments the cores have an average diameter of no greater than about 500 nanometers, no greater than about 250 nanometers, and in some embodiments no greater than about 150 nanometers.
  • primary particle size refers to the maximum cross-section dimension of a particle.
  • the primary particle size would correspond to the diameter of the spherical particle.
  • the primary particle size would correspond to the major axis of the particle. Particle size measurements can be based on, e.g., transmission electron microscopy.
  • Exemplary zirconias are available from Nalco Chemical Co. under the trade designation “Nalco 00SS008” and from Buhler AG Uzwil, Switzerland under the trade designation “Buhler zirconia Z-WO sol”.
  • Zirconia nanoparticle can also be prepared using known techniques such as described in U.S. Patent Application serial No. 11/027426 filed Dec. 30, 2004 and U.S. Patent No. 6,376,590.
  • Exemplary mixed metal oxides for use in materials of the invention are commercially available from Catalysts & Chemical Industries Corp., Kawasaki, Japan, under the trade designation "Optolake 3.
  • Commercially available silicas include those available from Nalco Chemical Company, Naperville, Illinois (for example, NALCO 1040, 1042, 1050, 1060, 2327 and 2329) and Nissan Chemical America Company, Houston, Texas.
  • the core is substantially spherical. In some embodiments, the cores are relatively uniform in primary particle size. In some embodiments, the cores have a narrow particle size distribution. In some embodiments, the core is substantially fully condensed. In some embodiments, the core is amorphous. In some embodiments, the core is isotropic. In some embodiments, the core is at least partially crystalline. In some embodiments, the core is substantially crystalline. In some embodiments, the particles are substantially non-agglomerated. In some embodiments, the particles are substantially non-aggregated in contrast to, for example, fumed or pyrogenic silica.
  • nanoparticles 130 are surface-modified, i.e., surface treatment agent 134 is attached to inorganic surface 132.
  • a surface treatment agent is an organic species having a first functional group capable of attaching (e.g., chemically (e.g., covalently or ionically) attaching, or physically (e.g., strong physisorptively) attaching) to the surface of a nanoparticle, wherein the attached surface treatment agent alters one or more properties of the nanoparticle.
  • surface treatment agents have no more than three functional groups for attaching to the core.
  • the surface treatment agents have a low molecular weight, e.g., a weight average molecular weight less than 1000.
  • the surface-modified nanoparticles may be reactive; i.e., at least one of the surface treatment agents used to surface modify the nanoparticles of the present disclosure includes a functional group capable of reacting with one or more components of the impregnating resin system, e.g., the curable resin(s) and/or the optional reactive diluent(s).
  • the surface treatment agent further includes one or more additional functional groups providing one or more additional desired properties.
  • an additional functional group may be selected to provide a desired degree of compatibility between the reactive, surface modified nanoparticles and one or more of the additional constituents of the resin system, e.g., one or more of the crosslinkable resins and/or reactive diluents.
  • an additional functional group may be selected to modify the rheology of the resin system, e.g., to increase or decrease the viscosity, or to provide non-Newtonian rheological behavior, e.g., thixotropy (shear-thinning).
  • each surface treatment agent may provide a different property, e.g., one surface treatment agent may react with a component of the resin system, and one surface treatment agent may provide compatibility with the resin system.
  • two or more surface treatment agents will be selected to achieve a desired value for a particular property, e.g., a combination of polar and non-polar surface treatment agents may be selected to achieve the desired compatibility with the resin system.
  • Nanoparticle resin systems according to the present disclosure having a wide range of rheological behavior can be obtained by different combinations of particle surface treatment agents, curable resins and reactive diluents.
  • Surface treatment agents that make the particles more compatible with the resins and/or reactive diluents tend to provide fluid, relatively low viscosity, substantially Newtonian compositions.
  • Surface treatment agents that make the particles only marginally compatible with the curable resins and/or reactive diluents tend to provide compositions that exhibit one or more of thixotropy, shear thinning, and/or reversible gel formation, preferably in combination with low elasticity.
  • Examples of surface treatment agents include alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, silanes and titanates.
  • the selection of a particular treatment agent is determined, in part, by the chemical nature of the metal oxide surface.
  • silanes may be used for silica and other for siliceous fillers.
  • silanes and carboxylic acids may be used for metal oxides such as zirconia.
  • the surface modification can be done either prior to mixing with one or more of the other components of the resin system or after mixing. In some embodiments, it may be useful to react the silanes with the particle or nanoparticle surface before incorporation into the other components of the resin system.
  • the required amount of surface treatment agent is dependant upon several factors such particle size, particle type, particle surface area, surface treatment agent molecular weight, and surface treatment agent type. In some embodiments, approximately a monolayer of surface treatment agent is attached to the surface of the particle. The attachment procedure or reaction conditions required also depend on the surface treatment agent used. In some embodiments, e.g., with silanes, it may be useful to surface treat at elevated temperatures under acidic or basic conditions for from 1-24 hours. Surface treatment agents such as carboxylic acids may not require elevated temperatures or extended time.
  • Representative types of surface treatment agents suitable for the compositions of the present disclosure include compounds such as, for example, [2-(3-cyclohexenyl) ethyl] trimethoxysilane, trimethoxy(7-octen-l-yl) silane, isooctyl trimethoxy-silane, N-(3- triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate, N-(3- triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate, 3- (methacryloyloxy)propyltrimethoxysilane, allyl trimethoxysilane, 3- acryloxypropy ltrimethoxy silane ,
  • the surface modification of the particles in the colloidal dispersion can be accomplished in a variety of ways.
  • the process involves mixing an inorganic dispersion with surface treatment agents.
  • a co-solvent may be added, e.g., l-methoxy-2-propanol, ethanol, isopropanol, ethylene glycol, N,N-dimethylacetamide, ethyl acetate, and/or l-methyl-2-pyrrolidinone.
  • the co-solvent can enhance the solubility of the surface treatment agents as well as the surface modified particles.
  • the mixture comprising the inorganic sol and surface treatment agents is subsequently reacted at room or an elevated temperature, with or without mixing.
  • the mixture can be reacted at about 80 0 C for about 16 hours, resulting in the surface modified sol.
  • the surface treatment of the metal oxide may involve the adsorption of acidic molecules to the particle surface.
  • the surface modification of the heavy metal oxide may take place at room temperature.
  • the surface modification of zirconia with silanes can be accomplished under acidic conditions or basic conditions.
  • silanes are heated under acid conditions for a suitable period of time, at which time the dispersion is combined with aqueous ammonia (or other base). This method allows removal of the acid counter ion from the zirconia surface as well as reaction with the silane.
  • the particles are precipitated from the dispersion and separated from the liquid phase.
  • the surface modified particles can then be combined with the other components of the resin system (e.g., the curable resin and/or the reactive diluent) using any of a variety of methods.
  • a solvent exchange procedure is used whereby the curable resin and/or the reactive diluent is added to the surface modified sol, followed by removal of the water and co-solvent (if used) via evaporation, thus leaving the particles dispersed in the curable resin and/or the reactive diluent.
  • the evaporation step can be accomplished for example, via distillation, rotary evaporation or oven drying.
  • the surface modified particles can be extracted into a water immiscible solvent followed by solvent exchange, if so desired.
  • another method for incorporating the surface modified nanoparticles in one or more of the other components of the resin system involves the drying of the modified particles into a powder, followed by the dispersion of this powder into one or more of the reactive diluent, curable resin and a solvent.
  • the solvent can be acetone or ethanol.
  • the drying step in this method can be accomplished by conventional means suitable for the system, such as, for example, oven drying, gap drying or spray drying.
  • composite parts may be assembled by a variety of infusion techniques which include vacuum assisted resin transfer molding (VARTM) and resin transfer molding (RTM).
  • VARTM vacuum assisted resin transfer molding
  • RTM resin transfer molding
  • a composite part made by the VARTM process are created with the fibrous layer placed in a suitable open mold, vacuum bag containing a fibrous layer, with peel ply and flow aids in place to easily infuse the resin system containing surface modified nanoparticles.
  • VARTM vacuum assisted resin transfer molding
  • RTM resin transfer molding
  • a composite part made by the VARTM process are created with the fibrous layer placed in a suitable open mold, vacuum bag containing a fibrous layer, with peel ply and flow aids in place to easily infuse the resin system containing surface modified nanoparticles.
  • a detailed description of an exemplary VARTM process is outlined in the Examples Section.
  • RTM employs a closed mold geometry typically made of 316 stainless steel, wherein composite parts are made by using a combination of vacuum and pressure to in
  • FIGS. 3 and 4 A schematic of the apparatus used to test for Rain Erosion Resistance Test is shown in FIGS. 3 and 4. This apparatus is described in detail in pending U.S. Patent Application No. 11/680,784, filed June 26, 2007 ("METHOD OF TESTING LIQUID DROP IMPACT AND APPARATUS" Daniels, et. al).
  • pellets 31 were fed to gun 10 via hopper 30 that allows for continuous feeding for the pellets.
  • the hopper consisted of a 50.8 cm long by 5.7 cm wide by 3.8 cm deep container with a V-shaped bottom ending in channel 32 for dispensing pellets to the gun.
  • the width of the channel has an opening smaller than the diameter of the pellet (e.g. 3.2 mm).
  • the channel When the channel is open, the channel has an opening slightly larger than the diameter of a single pellet (e.g. 4.8 mm) yet narrower than the diameter of two pellets to allow a single row of pellets to enter the channel.
  • the channel was designed such that when closed, the pellets within the channel were pushed with finger 33 freely, single file, toward the gun while preventing other pellets from entering the channel.
  • the row of pellets was advanced forward toward the front of the hopper by attaching finger 33 to cable 34 that was tensioned with hanging weight 35.
  • the 0.9 kg (2 pound) weight was used to advance the pellets up feeding tube 36 into magazine 12, which fed gun 10. This weight provided sufficient force to advance the pellets up the tube, but not excessive force such that the pellets bypassed the propulsion site.
  • the apparatus included stainless steel barrel 11. Pellets fired from gun 10 travel along barrel 11, ultimately exiting the barrel inside chamber 50. After the pellets leave the barrel of the gun, they travel less than about 5 centimeters (2 inches) before impacting the test sample.
  • test samples 55 were mounted within 10.2 cm long by 13.3 cm wide by 17.8 cm tall chamber 50 that contained the muzzle of the gun. A single test sample was mounted within the chamber for each test. The test sample is stationary during impact, and was mounted at an angle of about 85 degrees relative to the path of the pellets. This ensured that the pellets would not be deflected back into the path of a subsequent pellet and allowed the pellet to fall into a collection receptacle.
  • the test sample was fixed in a substantially vertical position.
  • Re-circulating pump 60 ((Part No. 23609-170, VWR, West Chester, Pennsylvania) was used to deliver a continuous film of water to the surface of the test sample at a rate of 600 milliliters per minute.
  • Polyethylene tube 65 having a diameter of 6.4 mm (1/4 inch), extended from the pump to the surface of the test sample. The end of the tube that delivered water to the test specimen was cut at an angle such that when the tube was pressed against the test specimen, a sheet or film of water covered the test sample.
  • the Rain Erosion Resistance Apparatus was assembled using 0.177 caliber air gun 10 ("Drozd Air Gun", European American Armory Corporation, Cocoa, Florida,) and 6.4 mm (1/4 inch) diameter stainless steel hose as barrel 11 (Swagelok Company, Solon, Ohio). 4.5 mm Grade II acetate pellets 31 (Engineering Laboratories, Inc, Oakland, New Jersey) were propelled through use of pellet gun 10 which was connected to a tank of compressed nitrogen (Oxygen Service Company, St. Paul, Minnesota) (not shown) via tube 20. The pressure was set at 620 kPA (90 psi).
  • the force of the impacting pellets in combination with the liquid layer on the surface of the test sample is believed to create a pressure that is at least as high as water hammer pressure.
  • power washing produces about 1/10 of the pressure created by the impacting pellets.
  • Fiberglass fibers of various plies and configurations were stacked on a flat glass plate which has been treated with a release coating such as (Safelease #30, Airtech International, Inc., Huntington Beach, California.).
  • the plate was heated from the underside by use of a heating pad (Stock Composite Curing Heaters, Watlow, Anaheim, California.) which was temperature controlled (Digi-Sense Temperature Controller, Chicago Illinois) and equipped with a type J thermocouple which was taped to the glass panel.
  • the fibers and flow media were then bagged by positioning double-sided sealant tape (AT-200Y, Airtech International, Inc.) around the perimeter of the stack, installing ports for a vacuum source and resin infusion and applying the plastic vacuum bag (Econolon, Airtech International, Inc.) securely around the taped area.
  • a vacuum pump (DD- 100 model, Precision Scientific, Chicago, Illinois) equipped with a pressure pot (Lagrange Products, Freemont Illinois) was attached at this point and the bagged area was checked for leakage by closing off the vacuum to the bagged area and reestablishing vacuum at 5 minutes and 30 minutes and monitoring vacuum levels (ca. 30 mm Hg).
  • resin was infused into the multi-ply glass fiber stack, typically over 60 minutes. The resin entrance and vacuum ports were then sealed and the resin was allowed to cure for 18 hours.
  • Comparative Example 1 Test specimens were generated by mixing 230 g of Hexion 135i with 69 g of Hexion Epikote MGS® RIMH 137 and pouring approximately 17 g of the resultant solution between two 10 cm by 10 cm glass sheets with rubber gasket spacers to generate a plaque of thermoset material. After 18 hours the panel was demolded and post cured at 60 0 C for 15 hours. The plaque was cut to yield test specimens with dimensions of 7.6 cm (length) by 7.6 cm (width) by 0.15 cm (thick) specimens. The sample was subjected to the test outlined in the General Procedure for Rain Erosion testing and was ablated to break after 61 rounds of pellets.
  • Example 1 Test specimens were generated by mixing 275 g of Silica Nanoparticles in Epoxy with 47.5 g of Hexion Epikote MGS® RIMH 137 and pouring approximately 17 g of the resultant solution between two 10 cm by 10 cm glass sheets with rubber gasket spacers to generate a plaque of thermoset material. The plaque was cut to yield test specimens with dimensions of 7.6 cm (length) by 7.6 cm (width) by 0.15 cm specimens. The sample was subjected to the test outlined in the General procedure for Rain Erosion testing and was ablated to break after 950 rounds of pellets.
  • Comparative Example 2 A blend of 165 g of HYDREX® IOOHF and 2.5 g Superox® 46727 (1.5 wt % vs. resin portion) was mixed using a DAC 600 FVZ SpeedmixerTM (Flacktek, Inc., Landrum, South Carolina) at 2000 rpm for 2 minutes at room temperature. This solution was then infused according to the Procedure for Fiber Infusion Process into a 17.8 cm by 30.5 cm, 4 ply (+/-45, 0,0 -/+45) fiberglass-containing vacuum mold. Vacuum was maintained for approximately one hour at which time the resin inlet and vacuum outlets were closed and the panel was allowed to cure over a period of 18 hours.
  • DAC 600 FVZ SpeedmixerTM Flacktek, Inc., Landrum, South Carolina
  • Example 2 A solution of 235 g of Silica Nanoparticles in Vinyl Ester and 2.1 g of Superox® 46727 (1.5 wt % vs. resin portion of nanocomposite) was mixed using a DAC mixer at 2000 rpm for 2 minutes at room temperature.
  • the particle loading may be selected based in part on the desired erosion resistance. For example, comparing FIGS. 5 and 6, Generally, performance enhancements of at least 1000% (10X) were seen when standard composites were infused with formulations containing engineered nanoparticles at loadings of about 30-40 wt% (based on resin usage). In fact, FIGS. 5 and 6 illustrate a substantially greater degree of erosion resistance associated with the composites of the present disclosure, as the sample of FIG. 6 indicates a far lower degree of erosion even though it was subject to impact by ten times as many particles as the comparative example of FIG. 5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur des systèmes de résine d'imprégnation présentant une résistance à l'érosion améliorée lors d'un durcissement. Les systèmes de résine d'imprégnation comprennent une résine durcissable et des nanoparticules à surface modifiée. Les nanoparticules à surface modifiée comprennent un noyau, une surface et un agent de modification de surface attaché à la surface. Les articles composites comprennent une couche fibreuse imprégnée par de tels systèmes de résine d'imprégnation. L'invention porte également sur des procédés d'amélioration de la résistance à l'érosion d'articles composites.
PCT/US2008/075101 2007-09-18 2008-09-03 Systèmes et composites de résine d'imprégnation résistants à l'érosion Ceased WO2009038971A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US97320507P 2007-09-18 2007-09-18
US60/973,205 2007-09-18

Publications (1)

Publication Number Publication Date
WO2009038971A1 true WO2009038971A1 (fr) 2009-03-26

Family

ID=39876873

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/075101 Ceased WO2009038971A1 (fr) 2007-09-18 2008-09-03 Systèmes et composites de résine d'imprégnation résistants à l'érosion

Country Status (1)

Country Link
WO (1) WO2009038971A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120040106A1 (en) * 2010-08-16 2012-02-16 Stefan Simmerer Apparatus for impregnating a fiber material with a resin and methods for forming a fiber-reinforced plastic part
WO2014099702A1 (fr) 2012-12-21 2014-06-26 3M Innovative Properties Company Composition comprenant un additif particulaire d'aide à l'écoulement
CN103899571A (zh) * 2014-03-17 2014-07-02 安徽华瑞塑业有限公司 独立式轴流泵叶片
CN115179609A (zh) * 2022-05-25 2022-10-14 航天材料及工艺研究所 一种轻质疏导防隔热复合材料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3416662A1 (de) * 1983-11-05 1985-05-15 Hoechst Ag, 6230 Frankfurt Schwerentflammbare strangpresskoerper, insbesondere strangpressplatten, sowie schwerentflammbare furnierte oder beschichtete strangpressplatten, ein verfahren zu ihrer herstellung und ihre verwendung
EP0672707A2 (fr) * 1994-03-15 1995-09-20 Toray Industries, Inc. Agent de durcissement encapsulé pour compositions de résine thermodurcissable
WO1995030632A1 (fr) * 1994-05-10 1995-11-16 Sri International Matieres ceramiques fabriquees a partir de precurseurs ceramiques a base d'hydridosiloxane et de poudres ceramiques et/ou metalliques
EP0938925A1 (fr) * 1998-02-25 1999-09-01 Rengo Co., Ltd. Composition contenant un materiau composite fabriqué à partir de cristaux inorganiques poreux et de macromolecules hydrophiles et produit obtenu à partir de celle-ci
WO2000000988A1 (fr) * 1998-06-30 2000-01-06 3M Innovative Properties Company Particules enrobees electroconductrices, legerement teintees, et composites obtenus
WO2003042315A1 (fr) * 2001-11-13 2003-05-22 Degussa Ag Assemblages colles durcissables et dissociables
US20040225079A1 (en) * 2003-05-05 2004-11-11 Analytical Services And Materials Inc. Erosion-resistant silicone coatings
US20050019589A1 (en) * 2003-07-25 2005-01-27 Analytical Services And Materials, Inc.. Erosion-resistant silicone coatings for protection of fluid-handling parts

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3416662A1 (de) * 1983-11-05 1985-05-15 Hoechst Ag, 6230 Frankfurt Schwerentflammbare strangpresskoerper, insbesondere strangpressplatten, sowie schwerentflammbare furnierte oder beschichtete strangpressplatten, ein verfahren zu ihrer herstellung und ihre verwendung
EP0672707A2 (fr) * 1994-03-15 1995-09-20 Toray Industries, Inc. Agent de durcissement encapsulé pour compositions de résine thermodurcissable
WO1995030632A1 (fr) * 1994-05-10 1995-11-16 Sri International Matieres ceramiques fabriquees a partir de precurseurs ceramiques a base d'hydridosiloxane et de poudres ceramiques et/ou metalliques
EP0938925A1 (fr) * 1998-02-25 1999-09-01 Rengo Co., Ltd. Composition contenant un materiau composite fabriqué à partir de cristaux inorganiques poreux et de macromolecules hydrophiles et produit obtenu à partir de celle-ci
WO2000000988A1 (fr) * 1998-06-30 2000-01-06 3M Innovative Properties Company Particules enrobees electroconductrices, legerement teintees, et composites obtenus
WO2003042315A1 (fr) * 2001-11-13 2003-05-22 Degussa Ag Assemblages colles durcissables et dissociables
US20040225079A1 (en) * 2003-05-05 2004-11-11 Analytical Services And Materials Inc. Erosion-resistant silicone coatings
US20050019589A1 (en) * 2003-07-25 2005-01-27 Analytical Services And Materials, Inc.. Erosion-resistant silicone coatings for protection of fluid-handling parts

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120040106A1 (en) * 2010-08-16 2012-02-16 Stefan Simmerer Apparatus for impregnating a fiber material with a resin and methods for forming a fiber-reinforced plastic part
WO2014099702A1 (fr) 2012-12-21 2014-06-26 3M Innovative Properties Company Composition comprenant un additif particulaire d'aide à l'écoulement
CN104870543A (zh) * 2012-12-21 2015-08-26 3M创新有限公司 包含粒子流动助剂的组合物
EP2935445A4 (fr) * 2012-12-21 2016-07-27 3M Innovative Properties Co Composition comprenant un additif particulaire d'aide à l'écoulement
CN103899571A (zh) * 2014-03-17 2014-07-02 安徽华瑞塑业有限公司 独立式轴流泵叶片
CN115179609A (zh) * 2022-05-25 2022-10-14 航天材料及工艺研究所 一种轻质疏导防隔热复合材料及其制备方法
CN115179609B (zh) * 2022-05-25 2024-03-15 航天材料及工艺研究所 一种轻质疏导防隔热复合材料及其制备方法

Similar Documents

Publication Publication Date Title
Zhao et al. Robust, transparent, superhydrophobic coatings using novel hydrophobic/hydrophilic dual-sized silica particles
US11725110B2 (en) Superhydrophobic coating containing silica nanoparticles
Zhang et al. A durable and photothermal superhydrophobic coating with entwinned CNTs-SiO2 hybrids for anti-icing applications
EP3924166B1 (fr) Impression 3d de pièces par co-réactifs
US20210403755A1 (en) Curable coating compostions comprising nanoparticle-polymer compositions and superamphiphobic nanoparticles having anti-corrosion and superamphiphobicity properties
US9017797B2 (en) Metal coating
US8063119B2 (en) Barrier coating of a non-elastomeric polymer and a dispersed layered filler in a liquid carrier and coated articles
EP2534199B1 (fr) Système de résine comprenant des nanoparticules multimodales dispersées modifiées en surface
WO2008027979A2 (fr) Systèmes de résine comprenant des nanoparticules réactive modifiées en surface
EP2283081A2 (fr) Procede de modification de surface de particules
KR20070044002A (ko) 차단성 있는 결합제 및 나노입자
CN102002319B (zh) 一种耐高温的超疏水表面及其制备方法
US9630209B2 (en) Methods of making large-area carbon coatings
WO2009038971A1 (fr) Systèmes et composites de résine d'imprégnation résistants à l'érosion
KR20180101599A (ko) 배리어 복합재
CN105705598A (zh) 包含氮丙啶化合物的含氟聚合物涂料
TW201335250A (zh) 複合材料
US11260592B2 (en) 3-D printing surface
JP2007510052A (ja) 帯電防止被覆された成形体の製造方法
Esposito Corcione et al. Analysis of the structure and mass transport properties of nanocomposite polyurethane
CN114269815A (zh) 阻气性包装材料
CN101955693A (zh) 一种用硼酸酯与环氧基硅烷复合改性微晶白云母粉的方法
JP6816568B2 (ja) ガスバリア積層体、及びガスバリア積層体の製造方法
Yong et al. Monodisperse SiC/vinyl ester nanocomposites: Dispersant formulation, synthesis, and characterization
EP4159819A1 (fr) Revêtement composite multifonctions

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08799108

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08799108

Country of ref document: EP

Kind code of ref document: A1