EP2874961A2 - Faisceau de fibres revêtues d'un nuage de particules agglomérées en réseau - Google Patents

Faisceau de fibres revêtues d'un nuage de particules agglomérées en réseau

Info

Publication number
EP2874961A2
EP2874961A2 EP13730738.5A EP13730738A EP2874961A2 EP 2874961 A2 EP2874961 A2 EP 2874961A2 EP 13730738 A EP13730738 A EP 13730738A EP 2874961 A2 EP2874961 A2 EP 2874961A2
Authority
EP
European Patent Office
Prior art keywords
fibers
cloud network
agglomerated
particle cloud
bundle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13730738.5A
Other languages
German (de)
English (en)
Inventor
Ryan W. JOHNSON
Xin Li
Paul J. WESSON
Padmakumar PUTHILLATH
Philip T. Wilson
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.)
Milliken and Co
Original Assignee
Milliken and 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
Priority claimed from US13/555,257 external-priority patent/US20140023513A1/en
Priority claimed from US13/555,277 external-priority patent/US20140023862A1/en
Application filed by Milliken and Co filed Critical Milliken and Co
Publication of EP2874961A2 publication Critical patent/EP2874961A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/465—Coatings containing composite materials
    • C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Definitions

  • the present invention generally relates to fiber bundles coated with an agglomerated particle cloud network and agglomerated particle cloud network composites.
  • Wind turbines have gained increased attention as the quest for renewable energy sources continues.
  • Composites are used extensively in the blades of wind turbines.
  • the quest to generate more energy from wind power has prompted technology advances which allow for increased sizes of wind turbines and new designs of wind turbine components.
  • Fatigue performance of candidate materials has an important role in the design and materials selection process.
  • Material technologies that can enhance the fatigue performance of glass reinforced polymer composites could enable a transition from use of epoxy resin to use of vinyl ester (VE) or unsaturated polyester (UP) resins for high performance utility scale wind turbine blades.
  • the transition from epoxy to VE or UP resins would reduce the resin cost to the wind blade manufacturer, allow use of lower cost molds and enable a significant reduction in mold cycle time through the elimination of complex post- curing processes.
  • the use of textile-based manufacturing processes to build novel microstructural features within the composite may produce this benefit.
  • An agglomerated particle cloud network coated fiber bundle contains a bundle of fibers and an agglomerated particle cloud network.
  • the bundle of fibers contains a plurality of fibers and void space between the fibers.
  • the agglomerated particle cloud network contains a plurality of agglomerated nanoparticles located in at least a portion of the void space in the bundle of fibers.
  • the agglomerated nanoparticles form bridges between adjacent fibers. Between 10 and 100% by number of fibers contain bridges to one or more adjacent fibers within the agglomerated particle cloud network coated fiber bundle.
  • the agglomerated nanoparticles form between about 1 and 60% of the effective cross-sectional area of the agglomerated particle cloud network coated fiber bundle.
  • Figure 1 is cross-sectional illustrative view of one embodiment of an agglomerated particle cloud network coated fiber bundle.
  • Figure 2 is a side view SEM of one embodiment of an
  • Figure 3 is cross-sectional illustrative view of one embodiment of an agglomerated particle cloud network composite.
  • Figure 4A is a cross-sectional view SEM of one embodiment of an agglomerated particle cloud network composite.
  • Figure 4B is an illustrative version of the SEM of Figure 4A.
  • Figure 5 is cross-sectional view SEM of one embodiment of an agglomerated particle cloud network coated fiber bundle.
  • Figures 6 and 7 are diagrams showing adjacent fibers.
  • Figure 8 is an illustrative cross-sectional view illustrating bridging between adjacent fibers.
  • Figure 9 is an SEM showing in detail the area between the fibers in the fiber bundle.
  • Figure 10 is a illustrative version of the SEM of Figure 9.
  • Figure 1 1 is an illustrative view of a wind turbine.
  • Figures 12-16 are illustrative views of a turbine blade.
  • Figure 17 is a schematic of guide bars for Example 1 .
  • Figure 18 is a chart showing peak stress to cycles to failure for the some select examples.
  • Figure 19 is an SEM of Example 3.
  • Figure 20 is an SEM of Example 5.
  • Figure 21 is an SEM of Example 7.
  • Figure 22 is an SEM of Example 8.
  • Figure 23 is an SEM of Example 14.
  • Figure 24 is an SEM of Example 15.
  • Figure 25 is an SEM of Example 28.
  • Figure 26 is an SEM of Example 30.
  • Figure 27 is a chart showing average cycles to failure for some examples.
  • Figure 1 illustrates one embodiment of an agglomerated particle cloud network coated fiber bundle.
  • the agglomerated particle cloud network coated fiber bundle 10 contains a bundle of fibers 100 and an agglomerated particle cloud network 200.
  • the bundle of fibers contains fibers 1 10 and void spaces 120.
  • Figure 2 is a scanning electron microscope (SEM) image taken at 5,000x along the length of the fibers in an agglomerated particle cloud network coated fiber bundle.
  • SEM scanning electron microscope
  • an agglomerated particle cloud network composite 400 shown in Figure 3, is formed.
  • the resin 300 coats and infuses into the bundle of fibers 100 and cures at least partially filling the void spaces 120 in the bundle of fibers 100.
  • Figure 4A is an SEM image of the agglomerated particle cloud network composite (the same agglomerated particle cloud network coated fiber bundle as Figure 2 after resin infusion) but at a cross-sectional view at 1 0OOx magnification in back-scattered electrons mode.
  • Figure 4B is an illustration of the SEM image of Figure 4A for ease of viewing and labeling. Figure 4B shows the
  • agglomerated particle cloud network composite 400 containing a bundle of fibers 100, an agglomerated particle cloud network 200, and resin 300.
  • the bundle of fibers 1 00 contains fibers 1 10 and resin 300 filling the void spaces.
  • the agglomerated particle cloud network 200 contains agglomerated nanoparticles 21 0.
  • the "agglomerated particle cloud network” in this application, is a collection of nanoparticle agglomerates of varying bulk size and density which are said to form a network due to their interconnected nature.
  • the cloud network is porous meaning that it fills only a portion of the void space between the fibers in the fiber bundles thus allowing composite resin to flow within, among, and around the agglomerates.
  • the agglomerated particle cloud network coated fiber bundle is a combination of fibers, agglomerated particles, and void space.
  • the cloud network will also typically contain some non-agglomerated, or primary, nanoparticles.
  • the agglomerated cloud network structure is unique from most common coating morphologies.
  • the agglomerated cloud network structure is a three dimensional heterogeneous non-uniform structure hosted within the fiber bundles of the substrate and serves to directly interact with a significantly higher volume fraction of the composite system than traditional unstructured coatings or individual fiber coatings would allow.
  • the fiber sizing is applied during fiber manufacture and is intended to remain in place through fabric forming and molding operations.
  • the fiber sizing has several well defined functions including protecting the filaments from self-abrasion, lubricating the yarn for further processing, maintaining fiber bundle integrity, promoting fiber separation and wet-out when in contact with the resin, and bonding the fiber surface to the resin.
  • thermoplastics are generally considered tougher than thermosets.
  • high cycle fatigue
  • thermoset systems typically outperform thermoplastic systems due to the differences in crack initiation, crack growth, and crack interaction behavior.
  • thermosetting polymers remain the dominant choice in long fiber reinforced composites due to their cost and processing benefits, particularly in large structures.
  • thermosetting polymers Due to their use as structural materials in critical applications such as high performance aircraft, numerous material technologies for improving the toughness of thermosetting polymers have been developed. The most ubiquitous approach is to utilize a naturally tough material such as elastomers and combine the tough material with the thermosetting polymer to achieve improved toughness. Improvements on elastomer based concepts employ thermoplastics as the toughening agents which can achieve similar
  • nanomaterial enhanced resins must be prepared such that the nanomaterials are very well dispersed and remain stable with minimum agglomeration.
  • these systems tend to exhibit a characteristic increase in resin viscosity due to the presence of the nanomaterials.
  • the nanoparticles were added directly into the resin instead of being coated onto the fabric, the resin became very viscous with a paste-like consistency which was unable to be used to impregnate the fabric.
  • the nanomaterials can be filtered by the fibers as the resin fills the reinforcement. This filtering action results in non-uniform distribution of the additive which imparts a non-uniform distribution of composite properties throughout the system.
  • Nanomaterials are assembled into structured coatings within the fiber reinforcement forming a network which helps resist the micro-scale damage initiation and growth mechanisms underlying fatigue failure of composites. This approach builds upon standard reinforcement fabrics and allows the use of standard thermoset resins in standard composite processes.
  • This system differs from others in that it provides architectures uniquely suited to enhancing the fatigue durability of fiber reinforced polymer composites.
  • the assembly of highly porous nanoparticle agglomerates is an efficient way to influence a large volume of the composite material without a significant mass addition.
  • Deliberate use of nanoparticle agglomerates to form bridges among fibers helps strengthen the fiber-fiber interaction and provides a means of more efficient load sharing.
  • One implication of these alternative load sharing paths is to reduce the critical fiber length enabling a fiber to carry more load over shorter lengths and allowing the system to tolerate a higher number of local failure instances thus increasing the fatigue life.
  • the assembly of highly porous nanoparticle agglomerates is an efficient way to influence a large volume of the composite material without a significant mass addition.
  • Deliberate use of nanoparticle agglomerates to form bridges among fibers helps strengthen the fiber-fiber interaction and provides a means of more efficient load sharing.
  • One implication of these alternative load sharing paths is to reduce the critical fiber length
  • the agglomerated nanoparticles form bridges.
  • Figure 5 shows a SEM image of a cross-section of agglomerated particle cloud network bundle of fibers. One can see the bridges between adjacent fibers. Preferably, between about 10 and 100% by number of fibers contain bridges to one or more adjacent fibers within the agglomerated particle cloud network coated fiber bundle.
  • between about 50 and 100% by number of fibers contain bridges to one or more adjacent fibers within the agglomerated particle cloud network coated fiber bundle, more preferably between about 60 and 100%, more preferably between about 75 and 100% by number.
  • the percentage of bridging may be calculated by taking a typical cross-section of the coated bundle of fibers, determining the number of fibers that are connected to at least one of their adjacent fibers by agglomerated particles divided by the total number of fibers. This bridging is formed by the agglomerated nanoparticles, which extend between two adjacent fibers.
  • the adjacent fibers are defined using the following method. Starting from the center of a specific fiber, all fibers whose centers are within 10 average fiber diameters with a significant line of sight from the center of the specified fiber are considered adjacent. A significant line of sight means that at least half of the possibly adjacent fiber is visible from the center of the specified fiber and is not covered by parts of other fibers that are closer to the specified fiber than the possibly adjacent fiber. Examples of this are shown in Figure 6 where fiber 150 is the specified fiber.
  • solid tangent lines from the center of fiber 150 are drawn to fibers 151 , 153, 154, and 156 and represent areas that those fibers block the view of additional fibers from the center of fiber 150, while dashed tangent lines are drawn to fibers 152, 155, and 157 to represent the full size of fibers that have a partially blocked view of fiber 150.
  • fibers 1 51 , 153, 1 54, and 1 56 are visible, so they are considered adjacent to fiber 150.
  • Fiber 152 is also adjacent to fiber 150 as more than half of its surface is visible from the center of fiber 150, even though part of it is blocked by fiber 151 .
  • Fiber 155 is not adjacent to fiber 150, as more than half of its view is blocked by fibers 153 and 154.
  • fiber 1 57 is not adjacent to fiber 150 as more than half of its view is blocked by fiber 156.
  • the determination of a significant line of sight can be done either by making a geometric measurement from a cross sectional image of a fiber bundle or by doing a calculation.
  • the geometric measurement can be done on fibers 1 53 and 1 54 by first drawing lines from the center of fiber 1 50 that are tangent to both sides of each fiber.
  • the angle formed by the lines that are tangent to fiber 155 defines its size (which is 2 8155), while the visible portion is determined by the angle a 155 between the tangent lines on fibers 153 and 154. Since 0:155 ⁇ 6155, fiber 155 is not adjacent to fiber 1 50.
  • tangent lines can be drawn to fibers 151 and 152.
  • the amount of fiber 152 that is visible is then given by the angle a 152 between the tangent line A to fiber 152 and tangent line B to fiber 151 . Since 0:152 > 6152, fiber 152 is adjacent to fiber 1 50.
  • each fiber with a diameter of d that may be adjacent to the specified fiber can be defined by a distance c, between the center of the specified fiber and the center of fiber i and an angle ⁇ , between the line connecting the center of the specified fiber and the center of fiber i and a reference line passing through the center of the specified fiber (see Figure 7).
  • each fiber may block a new region around the specified fiber that covers some angle ⁇ ,.
  • the region may be disconnected (fibers 156 and 157), and its size measured as a sum of the angles defining the size of the individual parts.
  • an agglomerate that extends between the two adjacent fibers 1 1 0 but is not attached two both fibers 1 10 still forms a bridge as defined in this application.
  • the bridges between two (or more than 2) adjacent fibers 1 10 are adhered to at least one of the fibers 1 10, more preferably adhered to both (or all) of the fibers 1 10.
  • the bridging increases the interaction between fibers, prevents compression of the space between fibers, and still allows resin to flow between and around the agglomerated particle and fibers.
  • Inter-fiber bridging also changes the way cracks initiate, propagate, and interact within the composites. Bridging may be seen in the schematic drawing of Figure 4B.
  • agglomerated nanoparticle bridging occurs in the bundle of fibers 1 00 depends on a number of factors including but not limited to the type of nanoparticle, solvent, surface chemistry of fiber, separation distance between adjacent fibers, coating process conditions, drying conditions, post mechanical treatment during and after drying.
  • One factor is the separation distance "d" between adjacent fibers. It has been shown that there is a greater tendency towards bridging to occur when the separation distance "d" between two adjacent fibers is less than about the average diameter of the fibers 1 10.
  • There are some important factors that control the bridge forming dynamics including capillary forces, nanoparticle- nanoparticle interactions, nanoparticle-fiber interactions, nanoparticle-solvent interactions and solvent-fiber interactions.
  • the coating process conditions can affect the space between fibers, the distribution of nanoparticles in the bundle of fibers, and the wet pickup during coating.
  • the drying conditions affect the solvent evaporation speed and the amount of solvent that can be removed from the bundle of fibers. An appropriate drying rate must be employed to form agglomerated particle bridging among fibers instead of strictly forming a fiber surface coating.
  • Post mechanical treatment may affect the space between fibers, the quantity of bridging in the bundle of fibers, and the agglomerated particle size.
  • the agglomerated nanoparticles form between about 1 and 60% of the effective cross-sectional area of the agglomerated particle cloud network coated fiber bundle. In another embodiment, the agglomerated nanoparticles form between about 5 and 50% of the effective cross-sectional area of the agglomerated particle cloud network coated fiber bundle, more preferably between about 10% and 45%, more preferably between about 15% and 40%. "Effective cross-sectional area", in this application, is measured by taking a cross-sectional image of the fiber bundle and calculating the apparent area of the agglomerated nanoparticles.
  • the effective area of the agglomerated particles is large compared to the amount (summed weight or summed volume) of nanoparticles in the cloud network coated fiber bundles. If the effective cross-sectional area of agglomerated particle is less than about 1 %, there may not be enough agglomerated particles to form the bridging structure required for the cloud network in the fiber bundle. If the effective cross-sectional area of agglomerated particle is larger than about 60%, there may not be enough porosity in the cloud network for resin infusion leading to lower performance due to dry spots or voids in the composite system.
  • One method to measure the effective cross-sectional area of the agglomerates is by utilizing an SEM image of a typical cross section in the agglomerated particle cloud network composite. From a highly magnified image of a typical cross section, one can see that the agglomerate is a porous structure containing many agglomerated nanoparticles. Because of this porosity, the area covered by individual nanoparticles is not a good measure for the effective area of the agglomerate. Instead, the area of the agglomerated particles includes not only the area of the nanoparticles forming the agglomerate but also the area of the pores or resin that is enclosed within the outer boundary of the agglomerate.
  • One method of identifying the outer surface of the agglomerate is using scanning electron microscopy at a magnification between 200X- 5000X in the back-scattered electrons (BSE) mode, where the fibers will have a consistent shade intensity, the resin another, and the agglomerates may have a third shade intensity and may have a distinct pattern.
  • the external edge of the effective area is then defined by a change in the image intensity from either agglomerate to fiber or agglomerate to resin. In the case that this edge is a gradual transition, threshold shade intensity can be used to consistently define a line for each image.
  • the area of the agglomerate can then be obtained by measuring the area enclosed by the outer boundary.
  • the agglomerate has large holes or cracks within the external boundary, the cracks or holes can be traced around and their area subtracted from the area enclosed by the external border. The total area for all agglomerates is then divided by the area of the fibers in the image to give a percentage.
  • imaging methods could be used to identify these surfaces including: light microscopy, transmission electron microscopy, atomic force microscopy, magnetic resonance imaging or computed tomography scanning.
  • the SEM in figure 9 of a agglomerated particle cloud network composite has been redrawn in Figure 10 to highlight the external edges between agglomerated nanoparticle and resin or fibers.
  • the agglomerated nanoparticles 210 have edges defined by the fibers 1 10 and resin 300.
  • the agglomerated nanoparticles 210 contain individual nanoparticles 220 (sized not to scale).
  • the resin 300 fills an area of a crack in the nanoparticle agglomerate 210.
  • the total area of nanoparticles 21 0 can then be divided by the total area of the Figure to obtain the effective cross sectional area of the agglomerates relative to a small sample of the bundle. In a typical measurement, 100 or more fibers and their interstitial spaces should be included in the SEM to produce a more representative measurement relative to the bulk average.
  • Figure 4B is converted from Figure 4A by using this method.
  • the percentage of effective area of agglomerated particles to the fiber bundle can be calculated by using image analysis software such as Adobe Photoshop, MATLAB Image Processing Toolbox, or Image-Pro to count the number of pixels in the agglomerated particle area divided by total number of pixels in the image.
  • the percentage of effective area of agglomerated particles to the fibers can be calculated by using image analysis software such as Adobe Photoshop, MATLAB Image Processing Toolbox, or Image-Pro to count the number of pixels in the agglomerated particle area divided by total number of pixels in the fiber region. Based on this method, the effective area of
  • agglomerated particles to the whole fiber bundle is 15.7%.
  • the effective area of agglomerated particles to the fibers is 24.2%.
  • measurements of the bundle of fibers are taken after infusion because cutting a bundle of fibers may produce a large amount of debris which can make identifying the bridges difficult. Moreover, during SEM, the fibers and bridges may develop an electrostatic potential, possibly causing them to move and making imaging significantly more difficult. Finally, it is difficult to obtain a straight and perpendicular cut through the fiber bundle in order to have a flat cross section to measure. It believed that the cloud structure in the agglomerated particle cloud network coated fiber bundle is substantially the same as the cloud structure in the agglomerated particle cloud network composite.
  • Agglomerated particle cloud network coated fiber bundles may be measured before infusion if they are held in place, for instance by pulling out a single tow from a fabric then wrapping it in heat shrink tubing and shrinking the tubing before cleaving it to image a cross section.
  • Figure 5 shows an SEM image taken by this method. One can see the bridging structure between adjacent fibers before resin infusion. While this provides a better image, it does not yield a flat surface that can be used for quantification.
  • the agglomerated particle cloud network 200 may cover between about 3 and 100% of the surface area of the fibers 1 1 0, the
  • agglomerated nanoparticles are discontinuous on the surface. This means that while the fibers may have a thin coating of non-agglomerated nanoparticles, binders, and other coating additives, the agglomerated nanoparticles do not cover the surface of the fibers completely.
  • the fibers may have a thin coating of non-agglomerated nanoparticles, binders, and other coating additives, the agglomerated nanoparticles do not cover the surface of the fibers completely.
  • agglomerated nanoparticles cover between about 3% and 99% of the
  • the bundle of fibers 100 may be any suitable bundle of fibers for the end product.
  • the composite may contain a single bundle of fibers or the bundle of fibers may be in a textile layer including but not limited to a woven textile, non-woven textile (such as a chopped strand mat), bonded textile, knit textile, a unidirectional textile, and a sheet of strands.
  • the bundle of fibers 100 are formed into unidirectional strands such as rovings and may be held together by bonding, knitting a securing yarn across the rovings, or weaving a securing yarn across the rovings.
  • the textile can have fibers that are disposed in a multi- (bi- or tri- or quadri-) axial direction.
  • the bundle of fibers contains an average of at least about 2 fibers, more preferably at least about 20 fibers.
  • the fibers 1 10 within the bundles of fibers 1 00 generally are aligned and parallel, meaning that the axes along the lengths of the fibers 1 10 are generally aligned and parallel.
  • the textile is a woven textile, for example, plain, satin, twill, basket-weave, poplin, jacquard, and crepe weave textiles.
  • a plain weave textile has been shown to have good abrasion and wear
  • a twill weave has been shown to have good properties for compound curves.
  • the textile is a knit textile, for example a circular knit, reverse plaited circular knit, double knit, single jersey knit, two-end fleece knit, three-end fleece knit, terry knit or double loop knit, weft inserted warp knit, warp knit, and warp knit with or without a micro-denier face.
  • the textile is a multi-axial textile, such as a tri-axial textile (knit, woven, or non-woven).
  • the textile is a non-woven textile.
  • the term non-woven refers to structures incorporating a mass of fibers that are entangled and/or heat fused so as to provide a structure with a degree of internal coherency.
  • Non-woven textiles may be formed from many processes such as for example, meltspun processes, hydroentangeling processes, mechanically entangled processes, stitch-bonded, wet-laid, and the like.
  • the textile is a unidirectional textile and may have overlapping fiber bundles or may have gaps between the fiber bundles.
  • the bundles of fibers 100 are in a multi-axial knit textile.
  • a multi-axial knit has high modulus, non-crimp fibers that can be oriented to suit a combination of property requirements and may create three dimensional structures.
  • the bundles of fibers 100 are in a single roving as in filament winding.
  • the bundles of fibers 100 contain fibers 1 10 which may be any suitable fiber for the end use.
  • Fiber used herein is defined as an elongated body and includes yarns, tape elements, and the like.
  • the fiber may have any suitable cross-section such as circular, multi-lobal, square or rectangular (tape), and oval.
  • the fibers may be monofilament or multifilament, staple or continuous, or a mixture thereof.
  • the fibers Preferably, the fibers have a circular cross-section which due to packing limitations intrinsically provides the void space needed to host the agglomerated particle cloud network.
  • a circular cross-section can provide enough void space for the agglomerated particle cloud network.
  • the fibers 1 10 have an average length of at least about 3 millimeters. In another embodiment, the fiber length is at least about 100 times the fiber diameter. In another embodiment, the average fiber length is at least about 10 centimeters. In another embodiment, the average fiber length is at least about 1 meter.
  • the fiber lengths can be sampled from a normal distribution or from a bi-, tri- or multimodal distribution depending on how the fiber bundles and fabrics are
  • the average lengths of fibers in each mode of the distribution can be selected from any of the fiber length ranges given in the above embodiments.
  • the fibers 1 10 can be formed from any type of fiberizable material known to those skilled in the art including fiberizable inorganic materials, fiberizable organic materials and mixtures of any of the foregoing.
  • the inorganic and organic materials can be either man-made or naturally occurring materials.
  • the fiberizable inorganic and organic materials can also be polymeric materials.
  • polymeric material means a material formed from macromolecules composed of long chains of atoms that are linked together and that can become entangled in solution or in the solid state.
  • fiberizable means a material capable of being formed into a generally continuous or staple filament, fiber, strand or yarn.
  • the fibers 1 10 are selected from the group consisting of carbon, glass, aramid, boron, polyalkylene, quartz, polybenzimidazole, polyetheretherketone, basalt, polyphenylene sulfide, poly p- phenylene benzobisoaxazole, silicon carbide, phenolformaldehyde, phthalate and napthenoate, polyethylene.
  • the fibers are metal fibers such as steel, aluminum, or copper.
  • the fibers 1 10 are formed from an inorganic, fiberizable glass material.
  • Fiberizable glass materials useful in the present invention include but are not limited to those prepared from fiberizable glass compositions such as S glass, S2 glass, E glass, R glass, H glass, A glass, AR glass, C glass, D glass, ECR glass, glass filament, staple glass, T glass and zirconium oxide glass, and E-glass derivatives.
  • E-glass derivatives means glass compositions that include minor amounts of fluorine and/or boron and most preferably are fluorine-free and/or boron-free.
  • minor amounts of fluorine means less than 0.5 weight percent fluorine, preferably less than 0.1 weight percent fluorine
  • minor amounts of boron means less than 5 weight percent boron, preferably less than 2 weight percent boron.
  • Basalt and mineral wool are examples of other fiberizable glass materials useful in the present invention.
  • Preferred glass fibers are formed from E-glass or E-glass derivatives.
  • the glass fibers of the present invention can be formed in any suitable method known in the art, for forming glass fibers.
  • glass fibers can be formed in a direct-melt fiber forming operation or in an indirect, or marble-melt, fiber forming operation.
  • a direct-melt fiber forming operation raw materials are combined, melted and homogenized in a glass melting furnace. The molten glass moves from the furnace to a forehearth and into fiber forming apparatuses where the molten glass is attenuated into continuous glass fibers.
  • pieces or marbles of glass having the final desired glass composition are preformed and fed into a bushing where they are melted and attenuated into continuous glass fibers.
  • the marbles are fed first into the pre-melter, melted, and then the melted glass is fed into a fiber forming apparatus where the glass is attenuated to form continuous fibers.
  • the glass fibers are preferably formed by the direct-melt fiber forming operation.
  • the fibers 1 10 when the fibers 1 10 are glass fibers, the fibers contain a sizing. This sizing may help processability of the glass fibers into textile layers and also helps to enhance fiber - polymer matrix interaction. In another embodiment, the fibers 1 10 being glass fibers do not contain a sizing. The non-sizing surface may help to simplify the coating process and give better control of particle - fiber interaction and particle agglomeration.
  • Fiberglass fibers typically have diameters in the range of between about 10 - 35 microns and more typically 17 - 19 microns. Carbon fibers typically have diameters in the range of between about 5 - 10 microns and typically 7 microns, the fibers (fiberglass and carbon) are not limited to these ranges.
  • Non-limiting examples of suitable non-glass fiberizable inorganic materials include ceramic materials such as silicon carbide, carbon, graphite, mullite, basalt, aluminum oxide and piezoelectric ceramic materials.
  • suitable fiberizable organic materials include cotton, cellulose, natural rubber, flax, ramie, hemp, sisal and wool.
  • suitable fiberizable organic polymeric materials include those formed from polyamides (such as nylon and aramids), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), acrylics (such as polyacrylonitriles), polyolefins, polyurethanes and vinyl polymers (such as polyvinyl alcohol).
  • the fibers 1 10 preferably have a high strength to weight ratio.
  • the fibers 1 10 have strength to weight ratio of at least 0.7 GPa/g/cm 3 as measured by standard fiber properties at 23°C and a modulus of at least 69 GPa.
  • the separation distance between the fibers 1 10 within the bundle of fibers 1 00 is represented by "d" on Figure 4B.
  • separation distances d may be little to none, less than the average diameter of the fibers, greater than the average diameter of the fibers to 4 times the diameter of the fibers, or greater than 4 times the average diameter of the fibers.
  • This separation distance d along with the properties of the agglomerated particle cloud network affects the performance of the final product.
  • the agglomerated nanoparticles particle cloud network 200 contains agglomerated nanoparticles 210. These agglomerated nanoparticles 210 contain nanoparticles 220 which each may be any suitable composition and formation for the desired end product and are shown in Figure 10.
  • Agglomerated nanoparticles in this application, means a plurality of
  • the agglomerated nanoparticles 210 typically comprise at least 10 nanoparticles adhered together. In one embodiment, the agglomerated nanoparticles 210 have at least one dimension between about 1 to 100 microns. In another embodiment, the agglomerated nanoparticles 210 preferably have at least one dimension of between 0.25 and 4 times the average fiber diameter.
  • the nanoparticles 220 may be any suitable nanoparticle including but not limited to silica, fumed silica, alumina, carbon nanotubes, polymeric material, and mixtures thereof.
  • Nanoparticle in this application is defined to mean particles having at least one dimension less than one micron.
  • the nanoparticles 220 may have a median particle diameter less than one micron. Preferably, the nanoparticles 220 have a median particle diameter less than 0.2 micron. The smaller particle diameter helps the particles to penetrate into fiber bundles.
  • the nanoparticle may have any suitable shape including but not limited to sphere, needle, disc, or amorphous shape. In one embodiment, the nanoparticles may contain a surface treatment.
  • nanoparticle may have surface treatment, including but not limited to a coupling agent, grafted oligomers or polymers, or surface charge modifiers.
  • the surface treatments can be chosen so as to help the nanoparticles disperse in a solvent, remain dispersed in a solvent, build a desirable agglomerated nanoparticle network structure during drying, or provide better adhesion between the particles and the resin or the fibers.
  • the nanoparticles 220 comprise fumed silica.
  • the shape of individual fumed silica nanoparticles is typically spherical with a median diameter less than 0.2 micron.
  • the fumed silica comprises a surface treatment.
  • the surface treatment helps fumed silica to disperse in water and to form agglomerated structures during drying. The surface treatment may also help to build a stronger interface between particles and resin in the composite.
  • the surface treatment on the fumed silica is a cationic surface treatment. This cationic fumed silica has been observed to yield a consistent coating on glass fibers.
  • the agglomerated nanoparticles 21 0 are found both in the void space 120 and on the surface of the fibers 1 1 0 of the bundle of fibers 100.
  • the average size of the agglomerated nanoparticles 210 is between about 0.25 and 4 times the average separation distance of adjacent fibers 1 10. This is calculated by measuring the fiber diameters and
  • agglomerated nanoparticles within a defined area imaged by SEM.
  • the average size of the agglomerated nanoparticles is the average size of the agglomerate, not of the individual nanoparticles making up the agglomerate.
  • Textiles or other assemblies of the agglomerated particle cloud network coated fiber bundle can be further processed to create composite preforms.
  • One example would be to wrap the fiber bundles around foam strips or other shapes to create three dimensional structures.
  • These intermediate structures can then be formed into composite structures by the addition of resin in at least a portion of the void space in the fiber bundle.
  • the agglomerated particle cloud network coated fiber bundle can be further processed into an agglomerated particle cloud network composite as shown in Figure 3 with the addition of resin in at least a portion of the void space in the fiber bundle.
  • the agglomerated particle cloud network coated fiber bundle 1 0 is impregnated or infused with a resin 300 which flows, preferably under differential pressure, through the coated fiber bundle 10 at least partially filling the void space creating the agglomerated particle cloud network composite 400.
  • the agglomerated particle cloud network composite could also be created by other wetting or composite laminating processes including but not limited to hand lay- up, filament winding, and pultrusion.
  • the resin flows throughout the coated bundle of fibers 10 (and all of the other reinforcing materials such as reinforcing sheets, skins, optional stabilizing layers, and strips) and cures to form a rigid, composite 400.
  • Thermoset resins such as unsaturated polyester, vinyl ester, epoxy, polyurethane, acrylic resin, and phenolic, are liquid resins which harden by a process of chemical curing, or cross-linking, which takes place during the molding process.
  • Thermoplastic resins such as polyethylene, polypropylene, PET and PEEK, are liquefied by the application of heat prior to infusing the reinforcements and re-harden as they cool within the panel.
  • the resin 300 is an unsaturated polyester, a vinylester, an epoxy resin, a bismaleimide resin, a phenol resin, a melamine resin, a silicone resin, or thermoplastic PBT or Nylon or mixtures thereof.
  • Unsaturated polyester is preferred due to its moderate cost, good mechanical properties, good working time, and cure characteristics.
  • the epoxy based resins have higher performance (fatigue, tensile strength and strain at failure) than polyester based resins, but also have a higher cost.
  • the addition of the cloud network to the bundle of fibers increases the performance of a composite using an unsaturated polyester resin to levels similar to the performance levels of the epoxy resin composite, but with a lower cost than the epoxy resin system.
  • Having the resin 300 flow throughout the coated fiber bundle 10 under differential pressure may be accomplished by processes such as vacuum bag molding, resin transfer molding or vacuum assisted resin transfer molding
  • VARTM VARTM molding
  • the components of the composite are sealed in an airtight mold commonly having one flexible mold face, and air is evacuated from the mold, which applies atmospheric pressure through the flexible face to conform the composite 400 to the mold.
  • Catalyzed resin is drawn by the vacuum into the mold, generally through a resin distribution medium or network of channels provided on the surface of the panel, and is allowed to cure. Additional fibers or layers such as surface flow media can also be added to the composite to help facilitate the infusion of resin.
  • a series of thick yarns such as heavy ravings or monofilaments can be spaced equally apart in one or more axis of the reinforcement to tune the resin infusion rate of the composite.
  • the coated bundle of fibers 10 may be further pre-impregnated
  • thermoset resins thermoplastic resins
  • thermoplastic fibers which are subsequently cured by the application of heat.
  • the agglomerated particle cloud network composite 400 may be used as a structure or the composite 400 have additional processes performed to it or have additional elements added to form it into a structure. It may also be bonded to other materials to create a structure including incorporation into a sandwich panel. In one embodiment, skin sheet materials such as steel, aluminum, plywood or fiberglass reinforced polymer may be added to a surface of the composite 400. This may be achieved by adding the additional reinforcement layers while the resin cures or by adhesives.
  • Examples of structures the composite may be (or be part of) include but are not limited to wind turbine blades, boat hulls and decks, rail cars, bridge decks, pipe, tanks, reinforced truck floors, pilings, fenders, docks, reinforced beams, retrofitted concrete structures, aircraft structures, reinforced extrusions or injection moldings or other like structural parts.
  • the agglomerated particle cloud network composite 400 as compared to a composite without the agglomerated particle cloud network, typically has increased local stiffness, increased local toughness, longer crack path length, and more uniform fiber distribution with the bundles.
  • composites having the agglomerated particle cloud network also may have enhanced fatigue, enhanced resistance to delamination, enhanced impact damage tolerance. These benefits may allow for longer, lighter, more durable and/or lower cost structures in numerous applications including wind turbine blades.
  • One benefit of fiber bundles enhanced with agglomerated particle cloud networks is the opportunity to utilize the enhanced fiber bundles in specific subsections of the structure where the demonstrated performance benefit is most applicable.
  • Wind turbine blades are an example of a large composite structure that can benefit from use of an agglomerated particle cloud network in specific areas.
  • the loading patterns on wind turbine blades are complex, and the structure is designed to satisfy a range of load requirements.
  • wind turbine blades are designed using at least four different design criteria. The blade must be stiff enough to not strike the turbine tower, strong enough to withstand the maximum expected wind gust loads, durable enough to tolerate hundreds of millions of cycles due to the rotation of the generator, and
  • Figure 1 1 is a schematic of a wind turbine 700 which contains a tower 702, a nacelle 704 connected to the top of the tower, and a rotor 706 attached to the nacelle.
  • the rotor contains a rotating hub 708 protruding from one side of the nacelle, and wind turbine blades 71 0 attached to the rotating hub.
  • Figure 12 is a schematic of a wind turbine blade 710.
  • the blade represents a type of airfoil for converting wind into mechanical motion.
  • the airfoil 800 extends from a root section 802 at one end along a longitudinal axis to the tip section 804 at the opposing end.
  • Sectional view A-A in Figure 13 from Figure 12 shows a typical blade cross section and identifies four functional regions around the perimeter of the wind turbine blade air foil.
  • the leading edge 806 and trailing edge 808 are the regions at the ends of the line extending along the maximum chord width W.
  • the leading and trailing edge regions are connected by two portions of a blade shell, a suction side shell 81 0 and a pressure side shell 812.
  • the blade shells are connected via a shear web 814 which helps stabilize the cross section of the blade during service.
  • the blade shells generally consist of one or more reinforcing layers 816 and may include core materials 81 8 between the reinforcing layers for increased stiffness.
  • Figure 13 also identifies two primary structural elements or spar caps 820 located within both the pressure side and suction side shell regions which both extend along the longitudinal axis of the blade as shown in Figures 14 and 15.
  • Figure 14 represents a plan view of a blade as viewed from either the pressure side or suction side of the blade while Figure 15 is the sectional view B-B as illustrated in Figure 12.
  • Figure 13 also identifies a leading edge spar 822 structural element within the leading edge region, and an additional trailing edge spar 824 structural element within the trailing edge region.
  • Figure 16 is a view along the length of the blade showing a piece of the blade shell with various layers.
  • the size of the spar caps can be based on the stiffness requirements to avoid hitting the turbine tower or the fatigue requirements over which the spar cap can be expected to remain intact over hundreds of millions of load cycles.
  • the nature of the design process and the requirements imposed on the various sections of the blade can benefit from materials which offer the opportunity to be deployed locally within that section.
  • a spar cap reinforcement material with improved fatigue resistance could allow more optimized wind turbine blades when fatigue performance dictates the size and weight of the spar caps.
  • the agglomerated particle cloud network coated fiber bundle may be formed by any suitable manufacturing method.
  • One method to form the agglomerated particle cloud network coated fiber bundle begins with forming the bundle of fibers.
  • the bundle of fibers contains a plurality of fibers and void space between the fibers. Each fiber contains a surface and the distance between adjacent fibers is defined as the separation distance.
  • the bundle of fibers is coated with a nanoparticle solution, where the nanoparticle solution contains a solvent and a plurality of well dispersed nanoparticles. Typically the nanoparticle dispersion is stable longer than the processing time scale.
  • the dispersion is stable for at least several days.
  • the solvent may be an aqueous or non-aqueous solvent.
  • the solvent is aqueous because of the cost and environmental concerns, possible wettability of the fiber, ability to create a stable dispersion of particles, and flammability issues.
  • the nanoparticle solution may also contain a film-former or binder. Having a film-former or binder in the nanoparticle solution may be advantageous because the film-former or binder may help to maintain the coating structure during handling, transportation, and storage.
  • the nanoparticle solution may also contain surfactants, stabilizing agents, wetting agents, foaming agents, defoamers, and other processing aids. Surfactants in the nanoparticle solution may be advantageous because the nanoparticles can be dispersed easier and are more stable in the presence of surfactants than in dispersions without surfactants.
  • the nanoparticle solution contains at least about 0.5% by weight nanoparticles, more preferably at least about 1 % by weight, more preferably at least about 3% by weight. In another embodiment, the nanoparticle solution contains between about 3 and 10% by weight nanoparticles. In another embodiment, the add-on weight of nanoparticles after solvent removal is between 0.7% and 5% by weight of the bundle of fibers. After coating the bundle of fibers (but before drying), the bundle of fibers may be optionally passed through a nip roller. The nip roller may push the nanoparticle solution further into the bundles, while also squeezing the excess liquid out.
  • the nip may optionally be padded with rubber, wool or other material with a Shore hardness less than that of glass to reduce breakage of the glass fibers.
  • the pressure in the nip is controlled to remove excess fluid from the fiber bundles without significantly reducing the tensile strength of the fabric.
  • the coated bundle of fibers is dried at a temperature above room temperature forming an agglomerated particle cloud network coated fiber bundle.
  • the drying process has been shown to impact the formation of the agglomerated particle cloud network structure.
  • Drying parameters including drying temperature, drying time, air flow rate, fiber bundle tension, and contact pressure during drying may all affect the resulting structure. How the coated fibers are dried (in addition to other processing and material considerations) affects how much the nanoparticles agglomerate and if an agglomerated nanoparticle cloud network or alternative structure is formed. In addition to the agglomerated cloud network formed after drying, the nanoparticles may also form a surface coating on the fiber.
  • the coated bundle of fibers is dried at a temperature between about 80 and 150°C for a time of between about 3 and 60 minutes. In one particular embodiment, the coated bundle of fibers is dried at temperature of 150°C for 3 minutes. In another embodiment, the surface temperature of fiber bundles immediately after drying is at least 1 10°C. The energy imparted to the bundle of fibers is sufficient to remove at least 90% of the solvent by weight, preferably at least 99.7% by weight. After drying in one embodiment, the solvent content in the bundle of fibers is preferably less than 1 % by weight, more preferably less than about 0.1 % by weight. [0096] Mechanical action may also be used during various steps of production.
  • Mechanical action may be used only once in the process, or many times during different steps of the process.
  • Mechanical action may be in the form of sonication, wrapping the bundle of fibers around a roller under tension, moving fabric normal to uniaxial direction in the coating bath, compressing / relaxing fabric, increasing or reducing the tension of the fabric, passing it through a nip, pumping the coating liquor through the fabric, using rollers in the process with surface patterns.
  • These surface patterns can have similar characteristic dimensions to the diameter of the fiber, the outside diameter of the fiber bundle, or the width of the fabric.
  • the addition of mechanical action during production of the agglomerated particle cloud network coated fiber bundle may temporarily increase or decrease the space between fibers either once or multiple times, provide a pressure gradient to increase flow of the nanoparticle dispersions into and out of the bundle, and homogenize the distribution of nanoparticles within the bundle.
  • the bundle of fibers is subjected to mechanical action during the coating step.
  • the coated bundle of fibers is subjected to mechanical action after the coating step.
  • the coated bundle of fibers is subjected to mechanical action during the drying step.
  • the coated bundle of fibers is subjected to mechanical action after the drying step.
  • the mechanical action may help to soften the fabric and create additional discontinuity in the coating by breaking big agglomerated particle into smaller pieces.
  • any other alternate coating method may be used including but not limited to powder coating, electrostatic deposition, spray coating, foam coating and the like.
  • powder coating method the particles are free -flowing, dry powder. The particles are sprayed to the bundle of fiber. The particles may be further moved into the bundle with the help of vacuum or other mechanical processes.
  • electrostatic deposition the dry powder of particles or small droplets of particle solution are charged and then accelerated toward the bundle of fibers by an electric field. The bundle of fiber may be further treated such as heat treatment to fix the coating structure.
  • the agglomerated particle cloud network coated fiber bundle After the agglomerated particle cloud network coated fiber bundle is formed, it may be further processed into an agglomerated particle cloud composite using the infusing the agglomerated particle cloud network coated fiber bundle with resin as described previously.
  • composite tabs were adhesively bonded to the grip areas of the specimen.
  • strain gages were bonded to the surface of the gage section of the specimen to measure strain levels.
  • the specimens were environmentally conditioned for 40 hours at 23 °C +/- 3°C and 50% +/- 10% relative humidity.
  • Typical schemes employ testing at a given R value with peak stress values chosen for the different tests of 80%, 60%, 40%, and 20% of the quasi-static strength. Test frequency is chosen to accelerate testing while ensuring the specimen temperature does not increase significantly. This means that lower stress level testing can be done at higher frequencies than higher stress level tests.
  • S-N curve The output of a typical fatigue testing regimen at a given R value is known as an S-N curve which relates the number of cycles a material can survive to specified loading conditions. S-N curves provide the most common comparison tool for basic fatigue performance evaluation. S-N curves for well-defined conditions are frequently used to compare the fatigue
  • Wind blades are generally designed to withstand over 10 8 loading and unloading cycles, however testing materials to such extremes is an impractical exercise. Comparisons are often made among materials at intermediate points such as the one million or 10 6 cycle performance.
  • a specific peak loading level of 1450 N/mm of specimen gage section width was applied and the number of cycles to failure was measured for each sample. This loading was chosen to balance the amount of time required to perform an experiment with the reliability of the data for predicting fatigue performance at more typical levels of strain.
  • the loading level of 1450N/mm was also chosen such that the epoxy control sample would withstand about 10 5 cycles.
  • ⁇ 45/ ⁇ 45/9oO/09o where the ⁇ 45 refers to a ply of ⁇ 45° bi-axial E-glass fabric (Devoid AMT DB 810-E05) .
  • the 90O refers to a ply of predominantly 0° unidirectional E-glass fabric with a small quantity of 90° oriented fibers and chopped fibers stitched to one side (Devoid AMT L1200/G50-E07), which was used as received for control samples and coated for other examples.
  • the orientation of the fabric is defined by the order of the terms in the laminate specification. Overall the laminate was symmetric and contained 8 plies of fabric.
  • the layup procedure was to stack the layers on top of a flat glass tool prepared with a mold release and covered with one layer of release fabric (peel ply).
  • a laser crosshair was used to provide a fixed reference for alignment of the fibers in each layer.
  • two layers of ⁇ 45 fabric were placed on the tool and aligned so that the fibers ran at a 45° angle to the crosshair. Both pieces of fabric were placed so that the fibers on the top surfaces ran in the same direction.
  • a 90O layer of the unidirectional fabric was aligned with the crosshair and placed with the unidirectional tows up. This was followed with a 090 layer of unidirectional fabric that was aligned and placed with the
  • the vacuum infusion molding process was used to impregnate the laminates with resin.
  • a layer of flow media was used to facilitate resin flowing into the reinforcement plies.
  • the entire laminate was covered with a vacuum bagging film which was sealed around the perimeter of the glass mold. Vacuum was applied to the laminate and air was evacuated from the system. Resin was then prepared and pulled into the reinforcement stack under vacuum until complete impregnation occurred. After the resin was cured, the composite panel was removed from the mold and placed in an oven for post-curing.
  • the 090 and 90O fabric in the examples refers to Devoid AMT L1 200/G50-E07 obtained from PPG.
  • This fabric has a basis weight of 1250 gsm with unidirectional glass fiber bundles about 1 1 50 gsm in the 0 ° direction (machine direction), 50 gsm fibers in a second direction (cross-machine direction), and 50 gsm chopped fibers stitch bonded to the face containing the fibers in a second direction.
  • the face of this fabric is the exposed unidirectional glass fiber bundles and the back of this fabric is the side containing the chopped fibers.
  • the ⁇ 45 fabric in the following examples refers to as received Devoid AMT DB 81 0-E05 obtained from PPG.
  • the cationic fumed silica refers to CAB-O-SPERSE PG-022 from Cabot Corporation. It is an aqueous dispersion of cationic fumed silica particles with a mean particle diameter of less than 0.2 ⁇ as specified by Cabot Corporation. As received it contains about 20% by weight of dispersed fumed silica nanoparticles. When diluted with water and stored at room temperature, the dispersions are stable for more than 1 day.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the O90 fabric with a dispersion of cationic fumed silica diluted to a 5% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and subjected to sonication and wrapping and travelling around 9 guide bars as shown in Figure 17. The fabric bending angle after each guide bar was 21 .95° to the face, 68.05° to the face, 176, 15° to the face, 184,75° to the back, 184.70° to the face, 183.56° to the back, 183.56° to the face, 183.56° to the back, 97.07° to the face. After the guide bars, the textile travelled through a nip roller at a pressure of about 20,000 N/m and was dried at 150 ° C for 3 minutes. This formed the agglomerated particle cloud network coated fiber bundle.
  • FIG. 2 An SEM of the agglomerated particle cloud network coated fiber bundle is shown in Figure 2 shows the presence of the agglomerated particle cloud network on the bundle of fibers.
  • SEM image One can see from the SEM image the agglomerates of nanoparticles, the bridging between adjacent fibers, and the discontinuous nature of the aggregates on the surface of the fibers.
  • FIG. 4A An SEM of the agglomerated particle cloud network composite is shown in Figure 4A and shows the presence of the agglomerated particle cloud network on the bundle of fibers.
  • SEM image One can see from the SEM image the agglomerates of nanoparticles, the bridging between adjacent fibers, and the discontinuous nature of the aggregates on the around the cross-section of the fibers.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the OQO fabric with a dispersion of cationic fumed silica diluted to a 5% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and subjected to sonication and wrapping and travelling around 3 guide bars. The fabric bending angle after each guide bar was 21 .95° to the face, 68.05° to the face, 90° to the face. After the guide bars, the textile travelled through a nip roller at a pressure of about 20,000 N/m and was dried at 150°C for 3 minutes. This formed the agglomerated particle cloud network coated fiber bundle.
  • FIG. 19 An SEM of the agglomerated particle cloud network coated fiber bundle is shown in Figure 19 and shows the presence of the agglomerated particle cloud network on the bundle of fibers.
  • SEM image One can see from the SEM image the agglomerates of nanoparticles, the bridging between adjacent fibers, and the discontinuous nature of the aggregates on the surface of the fibers.
  • An unsaturated polyester control test sample was made using the sample layup procedure using the coated OQO fabric from example 3 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the OQO fabric.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the OQO fabric with a dispersion of cationic fumed silica diluted to a 5% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and wrapping and travelling around 9 guide bars according the setup mentioned in Example 1 without any sonication treatment. After the guide bars, the textile travelled through a nip roller at a pressure of about 20,000 N/m and was dried at 150°C for 3 minutes. This formed the agglomerated particle cloud network coated fiber bundle.
  • FIG. 20 An SEM of the agglomerated particle cloud network coated fiber bundle is shown in Figure 20 and shows the presence of the agglomerated particle cloud network on the bundle of fibers.
  • SEM image One can see from the SEM image the agglomerates of nanoparticles, the bridging between adjacent fibers, and the discontinuous nature of the aggregates on the surface of the fibers.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated OQO fabric from example 5 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the OQO fabric with a dispersion of cationic fumed diluted to a 5% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and travelling around 3 guide bars according the setup mentioned in example 3 without any sonication treatment. After the guide bars, the textile travelled through a nip roller at 20,000 N/m and was dried at 1 50 °C for 3 minutes. This formed the agglomerated particle cloud network coated fiber bundle.
  • FIG. 21 An SEM of the agglomerated particle cloud network coated fiber bundle is shown in Figure 21 and shows the presence of the agglomerated particle cloud network on the bundle of fibers.
  • SEM image One can see from the SEM image the agglomerates of nanoparticles, the bridging between adjacent fibers, and the discontinuous nature of the aggregates on the surface of the fibers.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated OQO fabric from example 7 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • the panel was cured at room temperature for more than 8 hours and further post cured at 80 °C for more than 4 hours.
  • Examples 1 -8 illustrated how the coating processing conditions may affect the coating structure and mechanical performance. More mechanical action (guide bars and sonication treatment) may open up the fiber spacing "d" locally and help facilitate the penetration of the coating solution into the voids in the fiber bundle more effectively.
  • a silica coated fiber bundle was formed by coating the OQO fabric with a dispersion of cationic fumed silica diluted to a 0.2% by weight
  • the coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 150°C for 10 minutes.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated OQO fabric from example 9 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • a silica coated fiber bundle was formed by coating the OQO fabric with a dispersion of cationic fumed silica diluted to a 0.5% by weight
  • the coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 150°C for 10 minutes.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated OQO fabric from example 1 1 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • a silica particle coated fiber bundle was formed by coating the O90 fabric with a dispersion of cationic fumed silica diluted to a 1 % by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and subjected to sonication and wrapping and travelling around 9 guide bars according the setup mentioned in example 1 . After the guide bars, the textile travelled through a nip roller at 20,000 N/m and was dried at 1 50 ⁇ for 3 minutes. This formed the silica particle coated fiber bundle.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated OQO fabric from example 1 3 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • the panel was cured at room temperature for more than 8 hours and further post cured at 80 °C for more than 4 hours.
  • a silica coated fiber bundle was formed by coating the O90 fabric with a dispersion of cationic fumed silica that was diluted to a 1 % by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and travelling around 3 guide bars according the setup mentioned in example 3 without any sonication treatment. After the guide bars, the textile travelled through a nip roller at 20,000 N/m and was dried at 150°C for 3 minutes.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated OQO fabric from example 1 5 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the O90 fabric with a dispersion of cationic fumed silica that was diluted to a 3% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 1 50 °C for 10 minutes. This formed the agglomerated particle cloud network coated fiber bundle.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated O90 fabric from example 1 7 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the OQO fabric with a dispersion of cationic fumed silica that was diluted to a 5% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 1 50 °C for 10 minutes. This formed the agglomerated particle cloud network coated fiber bundle.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated OQO fabric from example 1 9 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the O90 fabric with a dispersion of cationic fumed silica that was diluted to a 10% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 1 50 °C for 10 minutes. This formed the agglomerated particle cloud network coated fiber bundle.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated OQO fabric from example 21 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the O90 fabric with a dispersion of as received cationic fumed silica. The coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 1 50 ⁇ for 10 minutes. This formed the
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated O90 fabric from example 23 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • the panel was cured at room temperature for more than 8 hours and further post cured at 80 °C for more than 4 hours.
  • Example 9-16 showed that when the silica particle concentration in the coating solution was lower than 3%wt, there were little to no bridging between adjacent fibers resulting in a tensile fatigue improvement was less than 4 times of that Control Example 1 .
  • Example 17-22 showed that when the silica particle in the coating solution was between 3% and 10%, the agglomerated silica particles formed around 3% ⁇ 36% by volume of the bundle of fibers. In this range the agglomerated particles formed an agglomerated particle cloud network having bridges between adjacent fibers. As a result, the tensile fatigue improvement was more than 10 times of that Control Example 1 .
  • Example 23-24 showed that for a silica particle concentration of 20%wt, the large amount of agglomerated particles may have formed a less porous structure within the fabric. Thus as a result, the resin could not infuse as well into the fabric and the tensile fatigue improvement was lower than that of Examples 17-22.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the O90 fabric with a dispersion of cationic fumed silica that was diluted to a 5% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 80°C for 8 hours. This formed the agglomerated particle cloud network coated fiber bundle.
  • An epoxy test sample was made using the sample layup procedure using the coated OQO fabric from example 25 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 150 mbar with 76.92%wt epoxy resin (EPIKOTETM Resin MGS ® RIMR 135 available from Momentive), 18.46% curing agent (EPIKURETM Curing Agent MGS® RIMH 137 available from Momentive) and 4.62%wt curing agent
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the O90 fabric with a dispersion of cationic fumed silica that was diluted to a 5% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 80°C for 8 hours. This formed the agglomerated particle cloud network coated fiber bundle.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated O90 fabric from example 27 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • the panel was cured at room temperature for more than 8 hours and further post cured at 80 °C for more than 4 hours.
  • Figure 25 shows the presence of the agglomerated particle cloud network on the bundle of fibers.
  • a silica coated fiber bundle was formed by coating the O90 fabric with a dispersion of as Aerosil 200 from Evonik Industries dispersed to a 5% by weight concentration in water.
  • the silica was stated by the manufacturer to have a specific surface area of 200 m 2 /g measured by BET method.
  • the nanoparticles were well dispersed and the dispersion was stable for more than one day.
  • the coating was conducted at room temperature and the textile was under tension in the machine direction and travelled through a nip roller at 20,000 N/m and was dried at 80 °C for 8 hours.
  • An unsaturated polyester test sample was made using the sample layup procedure using the coated O90 fabric from example 29 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • the panel was cured at room temperature for more than 8 hours and further post cured at 80 °C for more than 4 hours.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the O90 fabric with a dispersion of cationic fumed silica diluted to a 3% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and subjected to sonication and wrapping and travelling around 9 guide bars. The fabric bending angle after each guide bar was 180° and alternated on each bar from the face to the back of the fabric (total of five bends to the face and four to the back). After the guide bars, the textile travelled through a nip roller at a pressure of about 50,000 N/m and was dried in contact with steam cans at 130 ° C for about 2.3 minutes.
  • An agglomerated particle cloud network coated fiber bundle was formed by coating the OQO fabric with a dispersion of cationic fumed silica diluted to a 3% by weight concentration in water. The coating was conducted at room temperature and the textile was under tension in the machine direction and wrapping and travelling around 9 guide bars. The fabric bending angle after each guide bar was 180° and alternated on each bar from the face to the back of the fabric (total of five bends to the face and four to the back). After the guide bars, the textile travelled through a nip roller at a pressure of about 50,000 N/m and was dried in contact with steam cans at 1 30 ° C for about 2.3 minutes. This formed the agglomerated particle cloud network coated fiber bundle.
  • An unsaturated polyester control test sample was made using the sample layup procedure using the coated OQO fabric from example 33 and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with 98.52%wt unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .48%wt methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.

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Abstract

L'invention porte sur un faisceau de fibres revêtues d'un nuage de particules agglomérées en réseau contenant un faisceau de fibres et un nuage de particules agglomérées en réseau. Le faisceau de fibres contient une pluralité de fibres et un espace vide entre les fibres. Le nuage de particules agglomérées en réseau contient une pluralité de nanoparticules agglomérées placées dans au moins une partie de l'espace vide dans le faisceau de fibres. Les nanoparticules agglomérées forment des ponts entre des fibres adjacentes. Entre 10 et 100 % en nombre de fibres contiennent des ponts vers une ou plusieurs fibres adjacentes dans le faisceau de fibres revêtues d'un nuage de particules agglomérées en réseau. Les nanoparticules agglomérées forment entre 1 et 60 % de l'aire de section transversale effective du faisceau de fibres revêtues d'un nuage de particules agglomérées en réseau.
EP13730738.5A 2012-07-23 2013-06-05 Faisceau de fibres revêtues d'un nuage de particules agglomérées en réseau Withdrawn EP2874961A2 (fr)

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US13/555,257 US20140023513A1 (en) 2012-07-23 2012-07-23 Agglomerated particle cloud network coated fiber bundle
US13/555,277 US20140023862A1 (en) 2012-07-23 2012-07-23 Process for forming an agglomerated particle cloud network coated fiber bundle
PCT/US2013/044239 WO2014018164A2 (fr) 2012-07-23 2013-06-05 Faisceau de fibres revêtues d'un nuage de particules agglomérées en réseau

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