EP2925921A1 - Tissu unidirectionnel infusible - Google Patents

Tissu unidirectionnel infusible

Info

Publication number
EP2925921A1
EP2925921A1 EP13812254.4A EP13812254A EP2925921A1 EP 2925921 A1 EP2925921 A1 EP 2925921A1 EP 13812254 A EP13812254 A EP 13812254A EP 2925921 A1 EP2925921 A1 EP 2925921A1
Authority
EP
European Patent Office
Prior art keywords
unidirectional
fibers
fabric
bridges
infusible
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Withdrawn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
EP13812254.4A
Other languages
German (de)
English (en)
Inventor
Xin Li
Ryan W. Johnson
Joseph E. Rumler
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.)
Rumler Joseph E
Milliken and Co
Original Assignee
Rumler Joseph E
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
Application filed by Rumler Joseph E, Milliken and Co filed Critical Rumler Joseph E
Publication of EP2925921A1 publication Critical patent/EP2925921A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D06M15/51—Unsaturated polymerisable polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/20—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/22—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
    • B29C70/226—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure the structure comprising mainly parallel filaments interconnected by a small number of cross threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/002—Inorganic yarns or filaments
    • D04H3/004—Glass yarns or filaments
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/282—Selecting composite materials, e.g. blades with reinforcing filaments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24132—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in different layers or components parallel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component

Definitions

  • the present invention generally relates to infusible, unidirectional fabrics.
  • An infusible, unidirectional fabric containing a plurality of unidirectional fibers spaced uniformly in the unidirectional fabric, a plurality of bridges, and a plurality of void spaces between the unidirectional fibers.
  • Each bridge is connected to at least 2 unidirectional fibers and at least 70% by number of fibers have at least one bridge connected thereto forming a bridged network of unidirectional fibers.
  • the void spaces are interconnected and the fabric has a volume fraction of voids of between about 8 and 70%, a volume fraction of fibers of between about 35 and 85%, and at least 50% by number of the bridges have a bridge width minimum less than about 2 millimeters.
  • Figure 1 is a cross-sectional illustrative view of one embodiment of an infusible, unidirectional fabric.
  • Figure 2 is a cross-sectional illustrative view of one embodiment of an infused, unidirectional composite.
  • Figure 3 is a photographic, cross-sectional image of one embodiment of an infusible, unidirectional fabric.
  • Figure 4 is a photographic, cross-sectional image of one embodiment of an infused, unidirectional composite.
  • Figure 5A is a micrograph of one embodiment of the
  • Figure 5B is an illustration of Figure 5A.
  • Figure 6 illustrates the method for determining uniformly spaced fibers.
  • Figure 7 is an illustrative view of a wind turbine.
  • Figures 8-12 are illustrative views of a turbine blade.
  • FIG. 1 is an illustration of one embodiment of an infusible, unidirectional fabric 1 0.
  • the infusible, unidirectional fabric 10 contains a bridged network of unidirectional fibers 100 which contain a plurality of fibers 1 10 and a plurality of bridges 200.
  • the infusible, unidirectional fabric 10 also contains void spaces 120 surrounding the fibers 1 10.
  • the bridged network of unidirectional fibers 1 00 has an upper inner surface 10a and a lower inner surface 1 0b. The upper and lower inner surfaces are defined as the
  • FIG. 3 is a micrograph image of one embodiment of the infusible, unidirectional fabric.
  • the unidirectional fabric may be any suitable width and in any suitable shape. In some embodiments where the width of the fabric is smaller, typically between about 2 and 300 mm, the fabric may be referred to as a unidirectional tape or fabric band.
  • an infused, unidirectional composite 400 illustrated in Figure 2 is formed.
  • the resin 300 coats and at least partially infuses into the bridged network of unidirectional fibers 100 and cures at least partially filling the void space 120 in the bridged network of unidirectional fibers 1 00.
  • Figure 4 is a micrograph image of one embodiment of an infused, unidirectional composite.
  • a fabric with the above described structure will be infusible in vacuum assisted resin transfer molding (also called vacuum assisted resin infusion) process.
  • the word "infusible”, in this invention, refers to fabrics having the following characteristics:
  • the fabrics can be used to make fiber reinforced polymer composites having a thickness greater than 2 mm by using a standard vacuum assisted resin transfer molding (also called vacuum assisted resin infusion) method and low viscosity infusion grade thermoset resin.
  • the infusion process has a typical processing time scale ranging from minutes to hours.
  • the finished composite with the infusible fabric typically has a void content as measured by a standard test such as ASTM D2734 of less than 5%, more preferably less than 2%.
  • a simple method to predict whether a fabric is infusible or not can be described as follows.
  • Several water droplets with 0.01 % water soluble color dye for example, Acid Blue 9
  • the time duration required for the droplets to completely infuse into the fabric is used as an indication of infusibility.
  • "completely infuse into the fabric” means that more than 99% by mass of the water from the original droplet has been absorbed between the upper inner surface and lower inner surface of the fabric.
  • a fabric is considered “infusible” in this invention if the average water droplet infusion time is less than 1 minute.
  • This method is a method to indicate that the fabric is "infusible", if the average water droplet infusion time is longer than 1 minute, it is not necessary to mean that the fabric is not resin infusible due to the hydrophobic nature of most thermoset resin. This test method may not be accurate if there is coating strong hydrophobic tendencies on the fabric.
  • the infusible, unidirectional fabric 10 is self-supporting.
  • Self-supporting in this invention, means that the fabric is dimensionally stable, and the fibers in the fabric will not fall apart due to their own weight under gravity.
  • the fabric has a well-defined width and thickness. Additional components may be attached to the fabric but are not required.
  • additional stabilizing means such as stitching, scrims, films, and the like are not needed to handle and convey the infusible, unidirectional fabric 10.
  • the void spaces are interconnected and the fabric has a void fraction of preferably between about 8 and 70%, more preferably between about 1 0 and 70%.
  • the infusible, unidirectional self-supporting fabric preferably has a fiber volume fraction between 35% and 85%, preferably between 45% and 80%, more preferably between 50% and 80%.
  • a fiber volume fraction less than about 30% may make the fiber reinforcement less practical as a composite reinforcement.
  • a fiber volume fraction greater than 85% could have negative consequences as it may slow down the resin infusion process, reduce the mechanical properties perpendicular to the fiber direction, or reduce the fatigue durability of the composite. If the void spaces are not interconnected, there may be to too few channels for resin infusion. If there is not enough void content in the fabric, resin infusion may be very slow and difficult.
  • the sample (piece of fabric) is placed in an oven, heated at 700 °C for 4 hours to burn off all organic content in the fabric, and the mass of inorganic component is measured (mass (m f )) after this burn off step.
  • V f % (m f /pf)/V 0 , where p f is the density of the material which made the fiber, p can be measure by any suitable density measurement methods, or obtained from technical data sheet of the fiber material. The method works only when there is no or very small amount (less than 1 %) other inorganic component such (for example, silica nanoparticles) in the fabric.
  • Another method to measure the void content in the fabric can be described as the following: use the infusible unidirectional fabric to make a fiber reinforced composite material by using vacuum assisted resin infusion method (detail description of this method is described in the Example section below) and do a SEM or optical imaging to a typical cross section of the composite, where the cross section is perpendicular to the fiber direction.
  • the void content can be calculated by measuring the total cross section area of infused resin, divided by the total cross section area of the composite. To help identifying the infused resin area, about 0.01 % to 0.1 % by weight of color dye or fluorescent dye can be added into the resin before resin infusion.
  • the infusible, unidirectional self-supporting fabric also comprises polymer bridges, where the volume ratio of polymer bridges to fibers is between 1 :370 and 1 :2, more preferably between 1 : 40 and 1 : 4, more preferably between 1 : 12 and 1 : 4.
  • the polymer bridges are a main source of support to the fabric structure and help prevent fibers fall apart due to gravity.
  • the overall polymer bridge structure will not be strong enough to support the fabric structure if there are too few polymer bridges in the fabric. If there is too much polymer in the fabric, there may not be enough void space for resin infusion.
  • the infusible, unidirectional fabric 10 contains a bridging polymer which forms bridges 200 between and connected to at least a portion of the fibers 1 10. This is shown in both Figures 1 and 2.
  • each bridge is connected to at least 2 unidirectional fibers forming bridged fibers.
  • at least 70% by number, at least 80% by number, or at least essentially all of the fibers 1 10 are bridged to at least one other fiber 1 10 somewhere along the length of the fiber. "Essentially all", this this context means that enough of the fibers are attached such that there are no loose fibers, therefore the fabric acts as a unit not like a yarn.
  • at least about 90% by number of the fibers 1 1 0 are bridged to at least one other fiber 1 10 somewhere along the length of the fiber. As the % connected by number of fibers is anywhere along the length of the fiber, in a typical single cross-section, fewer connections will be seen.
  • between about 10 and 100% by number of fibers contain bridges to one or more fibers within the bridged network of unidirectional fibers 100 (composite 400).
  • between about 15 and 100% by number of fibers in a given cross- section contain bridges to one or more fibers, more preferably between about 50 and 100%, more preferably between about 60 and 100%more preferably between about 75 and 100% by number of fibers in a given cross-section.
  • bridged network of unidirectional fibers 100 there are a plurality of bridges 200 between and connected to at least a portion of fibers 1 1 0.
  • the bridging between fibers 1 10 helps control the position of the fibers 1 1 0 relative to other fibers and the fabric.
  • the bridging attaches the fibers together and creates a stable fabric form.
  • These bridges are connected and adhered to the surface of the fibers 1 1 0.
  • a bridging polymer that extends between at least two fibers 1 10 but is not attached to at least two fibers 1 10 is not a bridge as defined in this application.
  • the bridging increases the interaction between fibers 1 10 while still allowing resin to flow between and around the fibers 1 10.
  • the bridging polymer preferably has an elasticity which is characterized as elongation at break at least about 50%, more preferably higher than 100%, and more preferably higher than 300%.
  • the elasticity of the bridges helps the fabric remain flexible (able to conform to curved mold shapes) and helps the bridges survive bending or folding of the fabric.
  • the bridging polymer may be physically or chemically bonded
  • a thin layer between anchoring surface and fiber surface for example, a coating layer or sizing
  • interactions including but not limited to hydrogen bonding, van der Waals interactions, ionic interactions, electrostatic
  • the anchoring surface may be physically or chemically bonded to a coating or sizing that was previously applied to the fiber, through interactions including hydrogen bonding, van der Waals interactions, ionic interactions, electrostatic interactions, or a portion of the anchoring surface may chemically react with the coating or sizing on the surface of the fiber to form covalent bonds between the coating or sizing on the fiber surface and the anchoring surface.
  • the anchoring surface may interpenetrate with the fiber surface on a nanometer or micrometer length scale. It is important that the bridging polymer has good adhesion to fiber surface, because all the fibers in the unidirectional fabric structure are held together by the bridges.
  • At least a number of the bridges contain a width gradient, where the width of the bridge is greatest at the anchoring surface and decreases in a gradient away from the anchoring surface.
  • the greater width at the anchoring surface helps increase the strength of the adhesion between the bridge and the fiber, and a narrower width away from the anchoring surface leaves more void space in the fabric 10 for resin infusion.
  • An optimized system is preferred which has sufficient strength for maintaining fabric integrity during handling while minimizing the time required to infuse the structure with resin.
  • the bridges preferably at least 50% of the bridges have a bridge width minimum narrower than 2 mm, more preferably narrower than 0.5 mm, more preferably narrower than 0.2 mm.
  • the bridge width minimum is defined as the minimum width of the bridge (in the direction of fiber length) from surface of the first fiber to the surface of the second connected fiber.
  • the bridges typically have approximately the same width along the fiber direction from the surface of one fiber to the connected fiber. In this case, the bridge width is approximately constant in the bridge. In another
  • the bridge is wider where the bridge attaches to the fibers and is the narrowest (and has the minimum width) between the two fibers.
  • the width of the bridges in fiber direction can be measured by optical microscopic image or SEM image. In this measurement, dry fabric (before resin infusion) is preferred to be used to take images. The images are taken from the cross section which is parallel to fiber direction.
  • Figures 5A and 5B show some typical bridges in the unidirectional fabric and composites.
  • Figure 5A is a micrograph image and Figure 5B is an illustration of the photograph of Figure 5A.
  • Figures 5A and 5B show some typical bridges. If the width of the bridges in the fiber direction is too wide (and therefore the bridge width minimum is too large), the resin is less able to infuse through the fabric in the thickness direction.
  • the bridges 200 preferably form between about 0.1 and 60% of the effective cross-sectional area of the infusible, unidirectional fabric 1 0 (and infused, unidirectional composite 400). In another embodiment, the bridges 200 form between about 0.1 and 30% of the effective cross-sectional area of the fabric and composite, more preferably between about 0.3% and 10%, more preferably between about 0.5% and 5%. "Effective cross-sectional area", in this application, is measured by taking a cross- sectional image of the fabric and calculating the area of bridge. If the cross- sectional area of bridges is less than about 0.1 %, there may not be enough bridges to enhance the mechanical properties of the composite. If the cross- sectional area of bridges is larger than 30%, there may not be enough porosity in the fabric for resin infusion leading to lower performance due to dry spots or voids in the composite systems.
  • bridging occurs in the fabric 10 depends on a number of factors including but not limited to the type of bridging polymer, solvent, film forming preventing agent, surface chemistry of fiber, separation distance between fibers, coating process conditions, drying conditions, post mechanical treatment during and after drying.
  • the time required for bridging to occur also depends on concentration of bridging polymer, concentration of co-stabilizer, concentration of surfactant, surface chemistry of fiber, initial size of dispersed phase in the emulsion, temperature, solidification time of the bridging polymer, separation distance between adjacent fibers, and coating process conditions, [0034]
  • the bridging polymer forms between about 1 % and 20% by weight of the infusible, unidirectional fabric.
  • the cross sectional area of the fibers is between 30% and 80% of the total cross sectional area of the fabric, and the ratio by cross sectional area of polymer: void is between 1 : 0.5 and 1 : 93.
  • the anchoring surfaces of bridges cover less than 100% of the fiber surfaces (this includes all of the surface area of the fiber).
  • the uncovered fiber surfaces can bond to the resin directly in composites and increase the interaction between fibers and infused resin in composite.
  • the anchoring surfaces of bridges cover about 10% to 99% of the fiber surface.
  • the anchoring surfaces of bridges cover about 30% to 90% of the fiber surface.
  • the bridges in the infusible, unidirectional fabric are formed from a bridging polymer including but not limited to thermoset resin, thermoplastic resin, ionomer, dendrimer, and mixtures thereof.
  • Thermoset resins such as epoxy, polyurethane, acrylic resin, rubbers, and phenolic, are liquid resins which harden by a process of chemical curing, or cross-linking, which takes place during the coating process.
  • Thermoplastic resins such as polyethylene, polypropylene, polyolefin copolymer elastomer, thermoplastic polyurethane, polyvinyl alcohol (PVA), PET and PEEK, are liquefied by the application of heat prior to coating and re-harden as they cool within the fabric.
  • the bridging polymer has good adhesion on fiber surface.
  • the bridging polymer (or the polymer in organic solvent solution, or the chemicals that form polymer during process) can be uniformly dispersed in water before coating.
  • the bridging polymer is ethylene vinyl acetate (EVA) copolymer, styrene butadiene rubber (SBR), water borne polyurethane, polyolefin elastomer (POE), or a mixture thereof.
  • EVA ethylene vinyl acetate
  • SBR styrene butadiene rubber
  • POE polyolefin elastomer
  • SBR and polyurethane are preferred due to its moderate cost, good mechanical properties, and good adhesion to fibers.
  • the polymer bridges are formed beginning with a polymer in water dispersion or polymer water solution.
  • SBR latex or water borne polyurethane are preferred due to its moderate cost, good mechanical properties, good adhesion to fibers.
  • Film-forming preventing agents are preferred to be added in to the polymer water dispersion or polymer water solution, because the film-forming preventing agents can create void space and channels between fibers by preventing the polymer forming continuous film.
  • the film-forming preventing agent is solid or liquid particles which can be dispersed or dissolved in the polymer in water dispersion or polymer water solution. This type of film forming preventing agent will be removed from the fabric after the polymer solidified. Silica particles are one of the examples.
  • the film-forming preventing agent is water soluble material, which can phase separate from the polymer and form continuous phase during water evaporation. One requirement of the water soluble materials is that they don't make the polymer in water dispersion or polymer water solution unstable. In one embodiment, sugar or other water soluble non-ionic materials are preferred.
  • glycerin or propylene carbonate is used as a film forming preventing agent to create the void space. After water evaporation and polymer solidified, the film forming preventing agent rich phase will be removed from the fabric, leaving voids and channels in the fabric.
  • the film-forming preventing agents are a combination of blowing agents, and frothing agents or foaming agents.
  • the blowing agent can be any suitable material that can create bubbles during coating process.
  • the blowing agent is water. Water can quickly evaporate under heat and creates bubbles.
  • the blowing agent is carbon dioxide that has dissolved in water.
  • the blowing agent is low boiling point organic liquid.
  • the blowing agent can chemically decompose and release gas under heat. This type of blowing agent includes but not limit to NaHCO 3 , azodicarbonamide, and p-p ' -oxbis (benzensulfonyl hydrazide).
  • the frothing agents or foaming agents include but not limited to ionic surfactant such as sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (NaDDBS), or non-ionic block copolymer such as ethylene oxide and propylene oxide copolymer.
  • SDS sodium dodecyl sulfate
  • NaDDBS sodium dodecylbenzenesulfonate
  • non-ionic block copolymer such as ethylene oxide and propylene oxide copolymer.
  • Pluronic ® Pluronic ® from BASF.
  • a gelling agent is also preferred to be added to stabilize the polymer foam.
  • the gelling agent includes but not limited to acacia, alginic acid, bentonite, carbomers, carboxymethylcellulose. ethylcellulose, gelatin,
  • a gelling agent with lower critical solution temperature (LCST) is preferred because it is soluble in cold water and gels in hot water.
  • LCST critical solution temperature
  • Pluronics® F-127 One example of the gelling agent with LCST characteristic is Pluronics® F-127.
  • sugar is used as the film-forming preventing agent.
  • the polymer solid content is between about 1 % and 60% of the polymer in water dispersion or polymer in water solution. More preferably the polymer solid content is between about 3% and 20%.
  • the sugar to polymer solid content ratio by weight is between about 0.5:1 and 10:1 , more preferably between 1 :1 and 5:1 . Too little sugar cannot prevent polymer forming films and cannot create enough void space and channels in the fabric; Too much sugar makes the polymer bridges weak.
  • glycerin is used as the film-forming preventing agent.
  • the polymer solid content is between about 1 % and 60% of the polymer in water dispersion or polymer in water solution. More preferably the polymer solid content is between about 3% and 20%.
  • the glycerin to polymer solid content ratio by weight is between about 0.5:1 and 20:1 , more preferably between 1 :1 and 10:1 . Too little glycerin cannot prevent polymer forming films and cannot create enough void space and channels in the fabric; too much glycerin makes polymer dispersion unstable and the polymer bridges are weak.
  • foaming agents and gelling agents are used as the film-forming preventing agent.
  • the polymer solid content is between about 1 % and 60% of the polymer in water dispersion or polymer in water solution. More preferably the polymer solid content is between about 3% and 20%.
  • the frothing agent is between about 0.1 % and 20% of the total weight, more preferably between about 1 % and 10% of the total weight.
  • the gelling agent is between about 0.1 % and 40% of the total weight, more preferably between 1 % and 10% of the total weight.
  • Pluronics® F-127 is used as a foaming agent and also a gelling agent, preferably between 1 % and 15% by weight in the coating mixture, more preferably between 3% and 10% by weight in the coating mixture.
  • the bridging polymer and the resin 300 have different chemical compositions. Having a different chemical composition, in this application, means that materials having a different molecular composition or having the same chemicals at different ratios or concentrations. Having different chemical compositions may be able to help redistribute stress in composites. In another embodiment, the bridging polymer and the resin 300 have the same chemical compositions. Having the same compositions may make the infusing resin wet the fabric more easily.
  • the bridged network of unidirectional fibers 100 may be any suitable fibers for the end product.
  • "Unidirectional fibers", in this application means that the majority of fibers aligned in one direction with the axis along the length of the fibers being generally parallel.
  • the composite 400 may contain a plurality of fibers in a bundle (the bundles may be part of 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 bridged network of unidirectional fibers 1 00 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 bridged network of unidirectional fibers 100 contains an average of at least about 2 fibers, more preferably at least about 20 fibers.
  • the fibers 1 10 within the fabric 10 generally are aligned and parallel, meaning that the axes along the lengths of the fibers 1 10 are generally aligned and parallel.
  • Each fiber has a fiber surface defined to be the outer surface of the fiber and a fiber diameter.
  • the infusible, unidirectional fabric 10 contains unidirectional fibers 1 10 that are spaced uniformly in the unidirectional fabric 10.
  • Spaced uniformly or “uniformly spaced”, in this application, means that in a typical fabric cross section, within the bridged network of unidirectional fibers, there is no clear boundary of any fiber bundle, yarn, roving, or tow.
  • fiber distribution uniformity can be measured by the following method.
  • a typical cross section image of the unidirectional fabric or composite made thereof is prepared by standard microscopy mounting and imaging techniques.
  • Unidirectional fabrics are typically encapsulated in a polymer such as mounting epoxy and cut with a diamond wafer saw orthogonal to the fiber direction through the sample.
  • Composites can often be sectioned without requiring mounting because the fibers are already stabilized by the composite matrix polymer.
  • the surface of the cross section to be viewed is ground and polished to enable unobstructed viewing of the sample through optical or electron microscopy.
  • the polishing process is repeated until the contrast between fiber and matrix in the images at the target resolution is sufficient to compute the fiber area fraction within the cross section.
  • the perimeter of each fiber should be clearly distinguishable.
  • the image must be of a sufficient size scale to encompass the entire thickness of at least one layer of the fabric.
  • An example image of a composite reinforced with two layers of unidirectional fabric, 501 and 501 , comprising glass fibers is shown in Figure 6.
  • 501 Within the layer to be analyzed, 501 , the upper inner surface, 10a, and lower inner surface, 10b, are located. The distance between the upper inner surface and the lower inner surface is defined as the bulk thickness, t b .
  • a grid of squares is overlaid onto the image, 510.
  • the grid contains a square pattern of non- overlapping connected squares which share edges and corners, 520.
  • Each square in the grid has sides of length t b /2.
  • the image must be of sufficient size to contain at least four such squares.
  • the number of grid squares should be the maximum possible within the cross section area of the fabric where each sub-region remains fully within the fabric cross section.
  • Each area of the image within the borders of each square, 521 is defined as a sub-region.
  • the fiber area fraction is computed.
  • the fiber area fraction for a sub-region is the ratio of the area within the sub-region that is occupied by fiber divided by the total area of the sub-region. This calculation is readily done by standard image processing algorithms based on the image contrast or color difference between the fiber and the matrix region.
  • the overall average fiber area ratio can be computed.
  • a uniform distribution is defined as one in which at least 85% of the sub-regions have a fiber area ratio value that falls within the range defined by ⁇ 15% of the overall average fiber area ratio. More preferably the distribution is characterized by at least 95% of the sub-regions having a fiber area ratio value within the range defined by ⁇ 15% of the overall average fiber area ratio. Most preferably, the distribution is characterized by at least 98% of the sub-regions having a fiber area ratio value within the range defined by ⁇ 15% of the overall average fiber area ratio.
  • a composite contains more than one fabric or a group of fabrics.
  • the same definition of "uniform distribution" can be applied across cross section images containing regions of more than one unidirectional fabric.
  • a grid as described above is created within one layer of the reinforcement, and then extended to encompass the entire unidirectional region of the composite less any residual area that does not fit within a full square defined by the grid.
  • Fiber area ratios are computed within each sub- region. After all sub-regions of the typical cross section image have been analyzed, the overall average fiber area ratio can be computed.
  • a uniform distribution is defined as one in which at least 85% of the sub-regions have a fiber area ratio value that falls within the range defined by ⁇ 15% of the overall average fiber area ratio.
  • the distribution is characterized by at least 95% of the sub-regions having a fiber area ratio value within the range defined by ⁇ 15% of the overall average fiber area ratio. Most preferably, the distribution is characterized by at least 98% of the sub-regions having a fiber area ratio value within the range defined by ⁇ 15% of the overall average fiber area ratio.
  • a composite comprising multiple layers of conventional unidirectional fabrics may not be considered to have a uniform fiber distribution if the gaps created between the unidirectional yarns or rovings or tows within the fabric or the gaps created between the layers of fabric are large enough to prohibit satisfying the criteria requiring at least 85% of the sub-regions have a fiber area ratio value that falls within the range defined by ⁇ 15% of the overall average fiber area ratio.
  • a fabric having yarns or threads woven into the unidirectional fibers in the direction perpendicular to the unidirectional fibers would fall under the definition of spaced uniformly as typically the gap between rovings or bundles are about 4 times of the fiber diameter. If a typical bundle of rovings is used, then the unidirectional fibers are grouped into bundles where the fibers in those bundles are held closer together and there is typically a space between bundles where little to no fibers reside. Preferably, there are no additional fibers or yarns holding the unidirectional fibers together.
  • the strength and free-standing nature of the bridged network of unidirectional fibers 1 00 is due mostly to the bridges 200.
  • the bridged fibers (containing no additional reinforcements besides the bridges) have enough tensile strength to be handled in a manufacturing process without any additional reinforcement fabrics or layers.
  • the bridged fibers have a tensile strength of at least 200Pa in the direction perpendicular to the length direction of the unidirectional fibers.
  • the bridged fibers have a tensile strength of at least 700 Pa, more preferably higher than 10 kPa in the direction perpendicular to the length direction of the unidirectional fibers.
  • the tensile strength of the fabric is measured by gripping two ends of a rectangular piece fabric in a tensile strength test machine (for example, Instron), while the tensile test direction is perpendicular to the unidirectional fiber direction.
  • the fabric is then stretched under a constant speed (typically about 1 -10 cm / minute).
  • the tensile strength is calculate by measuring the maximum tensile force before fabric is broken, divided by the area of cross section of the fabric.
  • the fabric does not suffer significant structural damage under a peel strength of 0.25 Ibf/inch (0.44 N/cm) in a peel strength test between the fabric and an adhesive tape.
  • the fabric contains no additional stitching fibers, reinforcement layers, or reinforcement fabrics such as stitching yarns or scrims.
  • the infusible unidirectional fabric has enough strength to be used as a stand-alone fabric, for example allowing the fabric to be placed in the mold before infusion with resin. Because additional stitching fibers, reinforcement layers, or reinforcement fabrics usually creates gap or space with very few fibers, as a result, the fibers may not be spaced uniformly.
  • the fibers 1 10 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 have a circular cross-section which due to packing limitations intrinsically provides the void space needed to host the bridges.
  • the fibers 1 10 can 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. Preferably, the fibers are continuous. The fiber lengths can be sampled from a normal distribution or from a bi-, tri- or multi-modal distribution
  • 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 facilitate processing of the glass fibers into textile layers and enhances fiber - polymer matrix interaction.
  • the fibers 1 1 0 being glass fibers do not contain a sizing.
  • the non-sizing surface may help to simplify the coating process and give better control of polymer - fiber interaction.
  • Fiberglass fibers typically have diameters in the range of between about 1 0 - 35 microns and more typically 17 - 19 microns.
  • Carbon fibers typically have diameters in the range of between about 5 - 1 0 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 1 0 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.
  • composite preforms can be further processed to create composite preforms.
  • One example would be to wrap the fabric 10 around foam strips or other shapes to create three dimensional structures.
  • These intermediate structures can then be formed into composite structures 400 by the addition of resin in at least a portion of the void space 1 20 in the fabric 10.
  • the infusible, unidirectional fabric 10 can be further processed into an infused, unidirectional composite 400 as illustrated in Figure 2 with the addition of resin in at least a portion of the void space 120 in the fabric 10, preferably filling up approximately all of the void space within the fabric 10.
  • the infusible, unidirectional fabric 10 is impregnated or infused with a resin 300 which flows, preferably under differential pressure, through the fabric 1 0 at least partially filling the void space creating the infused,
  • the infused, unidirectional composite 400 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 infusible, unidirectional fabric 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 polyurethane resin, a bismaleimide resin, a phenol resin, a melamine resin, a silicone resin, or thermoplastic PBT or Nylon or mixtures thereof.
  • Unsaturated polyester and epoxy are preferred due to their 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 uniformly spaced fibers in the fabric 10 may increase the performance of a composite 400 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.
  • 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 fabric may be further pre-impregnated (pre-pregged) with partially cured thermoset resins, thermoplastic resins, or intermingled with thermoplastic fibers which are subsequently cured (or melted and solidified) by the application of heat.
  • the infused, unidirectional 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.
  • 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.
  • fatigue life is an important consideration.
  • the infused, unidirectional composite 400 may improve the fatigue performance of these structural parts.
  • Composites incorporating a bridged network of unidirectional fibers 1 00 can realize higher fiber volume fractions compared to those made with conventional reinforcements. Higher fiber volume fractions increase the modulus and strength of the composites, particularly in the direction of the fiber axis. The uniformity of fiber distribution and lack of fiber crimp due to stitching or off-axis fibers enables higher compression strength and enhanced fatigue durability. Composites with these characteristics are also resistant to determination and therefore provide significant damage tolerance. These benefits can allow for longer, lighter, more durable and/or lower cost structures in numerous applications including wind turbine blades.
  • Wind turbine blades are an example of a large composite structure that can benefit from use of infusible, unidirectional fabrics 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 sufficiently resistant to buckling to avoid collapsing when flexed under the combined stress induced by the blade itself and the wind loads.
  • Figure 7 is a schematic of a wind turbine 1 700 which contains a tower 1 702, a nacelle 1704 connected to the top of the tower, and a rotor 1706 attached to the nacelle.
  • the rotor contains a rotating hub 1708 protruding from one side of the nacelle, and wind turbine blades 1710 attached to the rotating hub.
  • Figure 8 is a schematic of a wind turbine blade 1710.
  • the blade represents a type of airfoil for converting wind into mechanical motion.
  • the airfoil 1 800 extends from a root section 1 802 at one end along a longitudinal axis to the tip section 1804 at the opposing end.
  • Sectional view A-A in Figure 9 from Figure 8 shows a typical blade cross section and identifies four functional regions around the perimeter of the wind turbine blade air foil.
  • the leading edge 1806 and trailing edge 1808 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 1 810 and a pressure side shell 1812.
  • the blade shells are connected via a shear web 1814 which helps stabilize the cross section of the blade during service.
  • the blade shells generally consist of one or more reinforcing layers 1816 and may include core materials 1818 between the reinforcing layers for increased stiffness.
  • Figure 9 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 10 and 1 1 .
  • Figure 10 represents a plan view of a blade as viewed from either the pressure side or suction side of the blade while Figure 10 is the sectional view B-B as illustrated in Figure 8.
  • Figure 9 also identifies a leading edge spar 1822 structural element within the leading edge region, and an additional trailing edge spar 1824 structural element within the trailing edge region.
  • Figure 12 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 infusible, unidirectional fabric 10 may be formed by any suitable manufacturing method.
  • unidirectional fabric begins with forming the fabric, or fiber tows.
  • the fabric contains a plurality of fibers and void space between the fibers.
  • the fabric then goes through one or multiple fiber tow spreading devices, which spread a fiber bundle into a fabric sometimes in the form of a fiber tape or fiber band. This step can break the binder which has already existed in the fiber bundle and re-distribute fiber space more uniformly.
  • the tow spreading device can be any suitable design.
  • the tow spreading device(s) comprising several football-shaped rolls, and the fabric is spread when it is pushed against the football shaped rolls.
  • the fabric is spread by blowing air to the bundle.
  • the fabric is spread by immersing into water and nipped under pressure.
  • the fabric is then combined with other spread bundles of fibers in the fiber direction to form a heavier or wider unidirectional fiber tape, fiber sheet, fiber band, or fabric.
  • two 9600 Tex (Tex is a unit of measure for the linear mass density of fibers and is defined as the mass in grams per 1000 meters) bundles of fibers are spread independently and then combined together to form a 25.4 mm wide fabric or tape.
  • eight 9600 Tex bundles of fibers are combined together to form an approximately 500 gsm, 150mm wide fabric.
  • multiple 9600 Tex bundles of fibers are combined together to form an approximately 1000 gsm, 400 mm wide fabric.
  • multiple 4800 Tex bundles of fibers are combined together to form the unidirectional fabric.
  • the fabric in the form of a fiber tape, fiber band or fabric
  • a coating liquid that contains the bridge polymer or the chemicals that can react and make the bridge polymer.
  • the polymer bridges are formed beginning with a polymer in water dispersion or polymer water solution.
  • the polymer in water dispersion is an emulsion.
  • the emulsion contains both a continuous solvent phase and a discontinuous dispersed liquid phase. The two phases are chosen so that the discontinuous dispersed phase is sufficiently stable that it does not agglomerate or solidify on the time scale required for emulsion preparation and coating at typical emulsion preparation and coating temperatures. This typically requires the resin to be stable for a period of at least several minutes.
  • the average size of the particles in the dispersed phase (called dispersed particles or micelles or referred to as the discontinuous phase) in the emulsion is less than 50 ⁇ , preferably less than 1 0 ⁇ . These dispersed particles make up at least about 0.5% by weight of the emulsion, more preferably at least about 1 % by weight, more preferably at least about 3% by weight. In another embodiment, the emulsion contains between about 3 and 10% by weight of dispersed particles.
  • the continuous phase of the emulsion can contain an aqueous, a non-aqueous liquid, or a mixture of both.
  • the solvent is aqueous or polar because of the cost and environmental concerns, wettability of the fiber, flammability issues and ability to create an emulsion with the dispersed phase.
  • the solvent may also contain a surfactant, which may improve the stability of the dispersed phase after emulsification or may make emulsification a more reliable and efficient process.
  • film-forming preventing agents in to the polymer water dispersion or polymer water solution, because the film-forming preventing agents are able to create void space and channels between fibers by preventing the polymer forming a continuous film.
  • the film-forming preventing agent is a water soluble material, which can phase separate from the polymer and form solid or liquid phase during water evaporation.
  • the water soluble materials do not make the polymer in water dispersion or polymer water solution unstable.
  • Sugar (solid or in liquid form) or other water soluble non- ionic materials are preferred.
  • sugar is used as the film-forming preventing agent.
  • the polymer solid content is between about 1 % and 60% of the polymer in water dispersion or polymer in water solution. More preferably the polymer solid content is between about 3% and 20%.
  • the sugar to polymer solid content ratio by weight is between about 0.5:1 and 10:1 , more preferably between 1 :1 and 5:1 . Too little sugar may not prevent the polymer from forming films and may not create enough void space and channels in the fabric; too much sugar may make the polymer bridges weak.
  • glycerin is used as the film-forming preventing agent.
  • the polymer solid content is between about 1 % and 60% of the polymer in water dispersion or polymer in water solution. More preferably the polymer solid content is between about 3% and 20%.
  • the glycerin to polymer solid content ratio by weight is between about 0.5:1 and 20:1 , more preferably between 1 :1 and 10:1 . Too little glycerin may not prevent the polymer from forming films and may not create enough void space and channels in the fabric; too much may make the polymer bridges weak.
  • the polymer in water dispersion or polymer in water solution may be applied to the fiber bundles by any suitable coating method that results in the coating liquid filling the void spaces between the fibers and wetting the surface of the fibers.
  • the fiber tape, fiber band or fabric is then treated to cause solidification of the bridge polymer and forming phase separation between bridge polymer and this type of film forming preventing agent.
  • the bridge polymer chemical(s) can solidify by undergoing chemical reaction, cooling below its(their) melt point, precipitating, crystallizing, or evaporation of a portion of the mixture. In one preferred embodiment, this phase change occurs because of evaporation of water.
  • this phase change occurs because of a chemical reaction, such as polymerization or crosslinking of mixture that may contain monomers, oligomers, cross-linkers, and initiators; these are commonly available as thermosetting resins that are paired with either a hardener or initiator.
  • the liquid may also contain catalysts which may affect the rate of solidification of the polymer. It may also contain other solvents that affect the stability of emulsion, the rate of solidification.
  • the film-forming preventing agents are a combination of blowing agents and frothing agents (or foaming agents).
  • a gelling agent is also added to stabilize the polymer foam.
  • the blowing agents may be any suitable materials that can generate small air bubbles when exposed to a stimulus after coating the polymer in water dispersion or polymer in water solution onto the fabric. Frothing agents or foaming agent in the coating liquid help stabilize the air bubbles, making the bubbles stable for longer periods of time and also allowing them to grow bigger (with the help from the blowing agents).
  • bridge polymer chemical(s) start to solidify by undergoing chemical reaction, cooling below its melt point, precipitating, crystallizing, or evaporation of a portion of the mixture.
  • this phase change occurs because of evaporation of water.
  • this phase change occurs because of a chemical reaction, such as polymerization or crosslinking of mixture that may contain monomers, oligomers, cross-linkers, and initiators; these are commonly available as thermosetting resins that are paired with either a hardener or initiator.
  • the liquid may also contain catalysts which may affect the rate of solidification of the polymer.
  • the gelling agent can increase the viscosity of the liquid, transfer the solvent from liquid state to a gel state. It can help to further stabilize the bubbles and polymer foam, and locks the phase structure of the coating material during the polymer solidify step.
  • the blowing agent is water. Water can quickly evaporate under heat and creates bubbles. In another embodiment, the blowing agent is carbon dioxide that has dissolved in water. In another embodiment, the blowing agent is low boiling point organic liquid.
  • the frothing agents or foaming agents include but not limited to ionic surfactant such as sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (NaDDBS), or non-ionic block copolymer such as ethylene oxide and propylene oxide copolymer. One example of the block copolymer is Pluronic ® from BASF.
  • a gelling agent is also preferred to be added to stabilize the polymer foam.
  • the gelling agent includes but not limited to acacia, alginic acid, bentonite, carbomers, carboxymethylcellulose. ethylcellulose, gelatin,
  • a gelling agent with lower critical solution temperature is preferred because it is soluble in cold water and gels in hot water.
  • One example of the gelling agent with LCST characteristic is
  • Pluronics® F-127 foaming agents and gelling agents are used as the film-forming preventing agent.
  • the polymer solid content is between about 1 % and 60% of the polymer in water dispersion or polymer in water solution. More preferably the polymer solid content is between about 3% and 20%.
  • the frothing agent is between about 0.1 % and 20% of the total weight, more preferably between about 1 % and 10% of the total weight.
  • the gelling agent is between about 0.1 % and 40% of the total weight, more preferably between 1 % and 10% of the total weight.
  • Pluronics® F-127 is used as a foaming agent and also a gelling agent, preferably between 1 % and 15% by weight in the coating mixture, more preferably between 3% and 10% by weight in the coating mixture.
  • the coating mixture with the blowing agent, frothing agent (or foaming agent) and gelling agent can be applied to the fiber tape, fiber band or fabric through many coating methods that are typically used to apply coating mixture to fiber bundles or fabrics.
  • the emulsion can be applied using dip, nip, roll, kiss transfer, spray, slot, slide, die, curtain, or knife coating processes among others.
  • the coating should be applied so that it fills the void spaces within the fiber bundles and so that it does not destabilize the coating mixture during the coating process.
  • Mechanical action such as passing over a series of rollers, passing over a roller with a patterned surface, pumping the emulsion through the fiber bundles, repeated saturation of the bundles with the emulsion, sonication or oscillating the fiber bundle tension may aid in homogeneously filling the void spaces between fibers within the fiber bundle.
  • the amount of applied coating mixture can be metered using routinely practiced metering methods available for the aforementioned coating methods.
  • the blowing agent is activated by exposing to a stimulus to generate bubbles.
  • water is used as the blowing agent.
  • the coated fiber tape, fiber band or fabric is exposed to heat, resulting rapid vaporization of water and bubble formation in water.
  • the wet fibers are directly contact on a hot surface.
  • the temperature of the hot surface is at least 100 °C, more preferably the temperature of the hot surface is at least 120 °C, more preferably the temperature of the hot surface is at least 150 °C.
  • the bubbles that are generated by the blowing agent are stabilized by the frothing agent or foaming agent, and are further stabilized by the gelling agent.
  • Pluronics® F-127 is used as a foaming agent and also a gelling agent, preferably between 1 % and 1 5% by weight in the coating mixture, more preferably between 3% and 10% by weight in the coating mixture.
  • a gelling agent preferably between 1 % and 1 5% by weight in the coating mixture, more preferably between 3% and 10% by weight in the coating mixture.
  • the size of the void space or channel in the fiber tape, fiber band or fabric is controlled by the concentration of the polymer in the coating mixture, the concentration of the film-forming preventing agents, and the method to dry the fibers.
  • the foaming agent and gelling agent is critical to prevent the polymer forming a film. If the blowing agent is not functioning well before the polymer has solidified, the polymer will want to form a continuous film on and between fibers. If the foam structure is not stable enough and breaks before the polymer has solidified, the polymer will also want to form a continuous film on and between fibers. [0092] Likewise, if the water is removed from the system before the polymer has solidified, the polymer will want to spread out onto the
  • the coated fabric may be dried to remove the residual solvent.
  • the drying process has been shown to impact the performance of the infusible, unidirectional fabric in composite.
  • the coated fabric 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 fabric 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 fabric 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 fabric is preferably less than 1 % by weight, more preferably less than about 0.1 % by weight.
  • 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 fabric around a roller under tension, moving the fabric normal to its uniaxial or machine 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. It has been found that the addition of mechanical action during production of the infusible,
  • unidirectional fabric may temporarily increase or decrease the space between fibers either once or multiple times, provide a pressure gradient to increase flow of the emulsion or suspension into, throughout and out of the bundle, and homogenize the distribution of dispersed polymer phase within the bundle.
  • the coated fabric is subjected to mechanical action after the coating step.
  • the coated fabric is subjected to mechanical action during the drying step.
  • the coated fabric 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 large polymer bridges into smaller pieces.
  • the infusible, unidirectional fabric may be further processed into a bridged composite using the infusing the infusible,
  • 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 (less than 35 5 C for room temperature testing). This means that lower stress level testing can be done at higher frequencies than higher stress level tests.
  • 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 800 N/mm of specimen gage section width was applied with an R value of 0.1 (tension-tension fatigue) 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 same loading levels of 800 N/mm were also applied to a control composite samples made from traditional reinforcing fabrics.
  • 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. 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 O90 layer of unidirectional fabric that was aligned and placed with the unidirectional side down.
  • the next 9oO layer of unidirectional fabric was placed with the unidirectional tows up and a final O90 layer was placed with the unidirectional tows facing down.
  • 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.
  • An unsaturated polyester control sample was made using the sample layup procedure using the OQO fabric and the ⁇ 45 fabric.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of less than 50 mbar with unsaturated polyester resin (Aropol Q67700 available from Ashland) and 1 .5 parts per hundred resin (phr) methyl ethyl ketone peroxide (MEKP).
  • the resin flow direction was along the 0° direction of the O90 fabric.
  • Example 2 to Example 7 showed how the film forming preventing agents affect the infusibility of the fiber fabric.
  • the fiberglass fabrics used in Examples 2-6, and 8 were in small widths so will be referred to herein as fiberglass tapes.
  • a fiberglass tape was made in the following manner. First, a 9600 Tex fiberglass tow from PPG (HYBON® 2026) was spread into a 20 mm wide tape by a fiber tow spreading device. Next, four of the 20 mm wide tapes were combined and aligned in the same direction to form a 40 mm wide tape with twice the original tape thickness. A SBR latex (GENCAL® 7555 from OMNOVA) was mixed with water at a SBR latex to deionized water ratio of 1 : 4. The fiber tape was then dipped in the coating mixture and dried in an oven at 150 °C for 30 minutes. Next, the fiber tape was washed using deionized water and dried in oven at 150 °C for 15 minutes.
  • a 40 mm wide, fiberglass tape was made using the same fiberglass materials and process as Example 2.
  • a SBR latex (GENCAL® 7555 from OMNOVA) was mixed with water and glycerin at a SBR latex to deionized water to glycerin ratio of 1 : 2 : 2.
  • the fiber tape was dipped in the coating mixture and dried in an oven at 1 50 °C for 30 minutes. Next, the fiber tape was washed by deionized water and dried in oven at 150 °C for 15 minutes.
  • a 40 mm wide, fiberglass tape was made using the same fiberglass materials and process as Example 2.
  • a SBR latex (GENCAL® 7555 from OMNOVA) was mixed with glycerin at a SBR latex to glycerin ratio of 1 : 4.
  • the fiber tape was dipped in the coating mixture and dried in an oven at 1 50 °C for 30 minutes. Next, the fiber tape was washed by deionized water and dried in oven at 150 °C for 15 minutes.
  • a 40 mm wide, fiberglass tape was made using the same fiberglass materials and process as Example 2.
  • a SBR latex (GENCAL® 7555 from OMNOVA) was mixed with water and glycerin at a SBR latex to water to glycerin ratio of 1 : 1 : 8.
  • the fiber tape was then dipped in the coating mixture and dried in an oven at 150 °C for 30 minutes. Next, the fiber tape was washed by deionized water and dried in oven at 150 °C for 15 minutes.
  • a 40 mm wide, fiberglass tape was made using the same fiberglass materials and process as Example 2.
  • a waterborne polyurethane (SYNTEGRA® YM 2000 from Dow Chemical) was mixed with water at a YM 2000 to deionized water ratio of 1 : 6.
  • the fiber tape was then dipped in the coating mixture and dried in an oven at 80 °C for 4 hours. Next, the fiber tape was washed by deionized water and dried in oven at 80 °C for 1 2 hours.
  • a fiberglass tape was made in the following manner. First, a 4800
  • Tex fiberglass tow from PPG was wrapped on a piece of plastic to form a roughly 1 000 gsm fabric.
  • Example 2 For the fiber tape in Example 2, the droplets stayed on the surface of the tape and cannot infuse into the tape. For the tape in Example 3, the droplets took about several seconds to infuse into the tape. For the tape in Example 4 and 5, the droplets immediately infused into the tape. The differences between these three examples showed how the film forming preventing agent (glycerin in Example 2, 3 and 4) affected the infusibility of the final article.
  • a fiberglass tape was made in the following manner.
  • FIG. 3 shows an SEM image of the cross section of the fabric. One can see the polymer bridges connecting fibers.
  • a fiberglass fabric was made in the following manner. 7.6 g waterborne polyurethane (BONDTHANE J-884-A from Bond Polymers
  • a stack of textiles was formed in order: Two (2) layers of the infusible fabric of Example 9, the fibers in the two layers were parallel. The side having SPUNFAB web was on the outer side.
  • the stacked textiles were infused in a standard vacuum infusion apparatus at a vacuum of -25 in. Hg (about 169 mbar) with 98.77%wt unsaturated polyester resin (Aropol G300 available from Ashland) and 1 .33%wt methyl ethyl ketone peroxide (MEKP 925H available from Norox).
  • the resin flow direction was along the fibers.
  • the panel was cured at room temperature more than 8 hours and further post cured at 80 °C for more than 4 hours forming the composite.
  • Figure 4 shows a cross section view of the composite.
  • the tensile modulus of the composite is 5% higher than Example 1 which comprises traditional stitched unidirectional fabric.
  • the peak stress and peak strain in static tensile test of the composite is about 20% higher than Example 1 .
  • a fiberglass fabric was made in the following manner. 8 g waterborne polyurethane (SYNTEGRA YM 2000 from Dow Chemical), 0.5 g crosslinking agent (Milliken MRX), 1 3.5 g sugar and 150 g water was mixed to made the coating solution. A total mass of about 260 g fiber rovings (HYBON® 2002 ) from PPG were uniformly fixed on an 14" by 24" plate by holing ends of rovings under tension. A piece of SPUNFAB lightweight adhesive web was put on top of the rovings. Another total mass of about 260 g fiber rovings
  • Example 1 1 The fabric in Example 1 1 was infused in a standard vacuum infusion apparatus at a vacuum of 25 in. Hg (about 169 mbar) with 98.77%wt unsaturated polyester resin (Aropol G300 available from Ashland) and 1 .33%wt methyl ethyl ketone peroxide (MEKP 925H available from Norox).
  • the resin flow direction was along the fibers.
  • the panel was cured at room temperature more than 8 hours and further post cured at 80 °C for more than 4 hours. This formed the composite.
  • the tensile modulus of the composite is 5% higher than Example 1 which comprises traditional stitched unidirectional fabric.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Woven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un tissu unidirectionnel infusible contenant une pluralité de fibres undirectionnelles espacées de manière uniforme dans le tissu unidirectionnel, une pluralité de ponts, et une pluralité d'espaces vides entre les fibres unidirectionnelles. Chaque pont est raccordé à au moins 2 fibres unidirectionnelles et au moins 70 % par nombre de fibres ont au moins un pont connecté à celles-ci à des fins de formation d'un réseau à ponts de fibres unidirectionnelles. Les espaces vides sont interconnectés et le tissu a une fraction volumique de fibres entre environ 8 et 70 %, une fraction volumique de fibres entre environ 35 et 85 %, et au moins 50 % par nombre de ponts ont une largeur de pont minimum inférieure à environ 2 millimètres.
EP13812254.4A 2012-11-28 2013-11-26 Tissu unidirectionnel infusible Withdrawn EP2925921A1 (fr)

Applications Claiming Priority (3)

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US201261730677P 2012-11-28 2012-11-28
US14/085,095 US20140147620A1 (en) 2012-11-28 2013-11-20 Infusible unidirectional fabric
PCT/US2013/071918 WO2014085409A1 (fr) 2012-11-28 2013-11-26 Tissu unidirectionnel infusible

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EP2925921A1 true EP2925921A1 (fr) 2015-10-07

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JP6990562B2 (ja) 2017-11-10 2022-01-12 パナソニック株式会社 複合樹脂射出成形体
WO2020041107A1 (fr) 2018-08-21 2020-02-27 Ocv Intellectual Capital, Llc Tissu de renforcement multiaxial avec un fil de couture pour infusion de tissu améliorée
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US20140147620A1 (en) 2014-05-29

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