WO2012016234A1 - Article extrudé par étirage et son procédé de fabrication - Google Patents

Article extrudé par étirage et son procédé de fabrication Download PDF

Info

Publication number
WO2012016234A1
WO2012016234A1 PCT/US2011/046097 US2011046097W WO2012016234A1 WO 2012016234 A1 WO2012016234 A1 WO 2012016234A1 US 2011046097 W US2011046097 W US 2011046097W WO 2012016234 A1 WO2012016234 A1 WO 2012016234A1
Authority
WO
WIPO (PCT)
Prior art keywords
impregnated
reinforcement
functional filler
continuous
continuous reinforcement
Prior art date
Application number
PCT/US2011/046097
Other languages
English (en)
Inventor
Kevin J. Spoo
Keith M. Konieczka
Original Assignee
Ocv Intellectual Capital, Llc
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 Ocv Intellectual Capital, Llc filed Critical Ocv Intellectual Capital, Llc
Publication of WO2012016234A1 publication Critical patent/WO2012016234A1/fr

Links

Classifications

    • 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
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
    • B29C70/025—Combinations of fibrous reinforcement and non-fibrous material with particular filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/523—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement in the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/525—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • B29C70/545—Perforating, cutting or machining during or after moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0005—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0007—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0016—Non-flammable or resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0058—Inert to chemical degradation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • B29K2995/0064—Non-uniform density

Definitions

  • the general inventive concepts relate generally to a pultrusion process, and more particularly, to a pultrusion process that utilizes an injection die to add functional fillers selectively to the exterior surface of a pultruded article.
  • Glass fibers are useful in a variety of technologies, and may be used in the form of continuous or chopped filaments, strands, rovings, woven fabrics, nonwoven mats, meshes, and scrims to reinforce polymers.
  • Reinforced polymeric composites can be formed from a polymeric matrix material, reinforcing material, or any other desired components in a variety of ways.
  • Such composites are formed using glass fiber reinforcements which provide dimensional stability and excellent mechanical properties to the resulting composites. For example, glass fibers provide dimensional stability as they do not shrink or stretch in response to changes in atmospheric conditions. Further, glass fibers have high tensile strength, heat resistance, moisture resistance, and high thermal conductivity.
  • Continuous glass fibers and/or glass mats are commonly used as reinforcements in pultrusion processes to form pultruded parts.
  • pultrusion involves impregnating continuous fibers and/or continuous fibers/mat combinations with a suitable resin material and passing the impregnated fibers and/or mat through a heated die.
  • the continuous fibers are impregnated with a liquid resin material, such as by passing the fibers through a resin bath, to wet or coat the individual fibers within the roving.
  • the coated fibers and/or mat are then consolidated and passed through a pultrusion die where the fibers and mat are formed into a desired shape, heated, and the resin is cured to hold the fibers and mat together.
  • the composite part exiting the heated die is then cut to a desired length.
  • the continuous fibers are impregnated with a polymer resin, and the resin and fibers are shaped into the form of the composite.
  • the continuous nature of the pultrusion process advantageously enables composites of any desired length to be produced.
  • the pultruded part may have inner and outer portions with different properties (e.g., strength vs. flexibility), due to the portions being formed from two different resin materials.
  • fillers are added mainly to reduce costs, but may also provide other benefits. For example, clays or pigments may be added to improve the finish of the pultruded parts. Other fillers may impart particular properties, such as corrosion resistance, to the pultruded parts.
  • fillers can interfere with the formation of strong composite articles by interfering with the ability of the resin to completely impregnate the reinforcement (whether roving or mat) and sufficiently cover or encase the fibrous materials. This typically weakens the reinforcement and, ultimately, the pultruded article. Additionally, when modifications are made to the process to ensure complete impregnation of the reinforcement, the increased volume of the filler displaces some of the glass fiber which reduces the structural capability of the pultruded shape.
  • the general inventive concepts provide a process for forming a pultruded article having a desired functionality in an outer layer.
  • the process includes: (1) impregnating at least one first continuous reinforcement material with a first resin material to form an impregnated inner layer; (2) contacting the impregnated inner layer with at least one second continuous reinforcement material to form a reinforcement pack; (3) impregnating the reinforcement pack with at least one second resin material containing one or more functional filler materials to form an impregnated reinforcement pack; and (4) curing the impregnated reinforcement pack to form a pultruded article having an outer layer.
  • the functional filler material becomes impregnated throughout the second continuous reinforcement material to impart a desired functionality to the outer layer of the pultruded article substantially without becoming impregnated in the first continuous reinforcement material.
  • the continuous reinforcement material forming the inner layer is formed of continuous glass fiber rovings and the continuous reinforcement material forming the outer layer is a glass mat, such as a continuous filament mat, a non-woven mat, or a chopped strand mat.
  • the functional filler material desirably has a particle size that is at least half the size of the diameter of the filaments of the rovings forming the interior layer adjacent to the exterior mat.
  • the functional filler material is positioned in the exterior surface of the pultruded article to the exclusion of the placement of the functional filler material in the inner core or layer forming the interior portion of the pultruded article.
  • the functional filler material in the second resin system fills the spaces within the architecture of the exterior glass mat without displacing any structural reinforcement.
  • the structural integrity of the exterior layers of the pultruded product is maintained and a superior and stronger end product is formed.
  • the exterior of the pultruded article may have imparted thereto a desired functionality through a selection of desired functional filler materials.
  • a process for forming a pultruded article including the step of impregnating at least one first continuous reinforcement material with a first resin material, further comprises impregnating at least two continuous reinforcement materials ⁇ a primary and a secondary — with resin materials that may be the same or different and consolidating them into a combined impregnated inner layer prior to contacting the impregnated inner layer with the second continuous reinforcement material.
  • a pultruded article comprising: a first continuous reinforcement material impregnated with a first resin material to form an impregnated inner layer; and a second continuous reinforcement material adjacent the impregnated inner layer and impregnated with a second resin material containing at least one functional filler material to form an impregnated reinforcement pack, the impregnated reinforcement pack being shaped and cured by a die to form the pultruded article.
  • the first and second resins are allowed to intermix at an interface where the second continuous reinforcement material lies adjacent said impregnated inner layer, and wherein the at least one functional filler material is incorporated into the second continuous reinforcement material but not the first continuous reinforcement material.
  • the functional filler material when the exterior layers are formed of an exterior mat, has a particle size that is at least half the size of the diameter of the rovings forming the interior layer adjacent to the exterior mat.
  • An exemplary advantage attributable to the general inventive concepts is that the filled resin material permits the inclusion of desired properties to the exterior surface of the pultruded article, without any substantial decrease in the structural capability of the external layer of the final pultruded article as a result of the inclusion of one or more filler materials into the continuous exterior layers.
  • Another exemplary advantage attributable to the general inventive concepts is that the first reinforcement material, e.g., rovings, acts to filter the functional filler material to keep it in the outer layer or at the exterior surface of the pultruded article, while the functional filler material fills the spaces within the architecture of the exterior mats forming the continuous exterior layers without displacing any of the structural reinforcement.
  • Another exemplary advantage attributable to the general inventive concepts is that less functional filler material is required to achieve the desired property compared to conventional pultrusion processes in which the filler material is distributed throughout the pultruded article.
  • the desired functional filler materials are intentionally placed in the exterior surface of the pultruded article to the exclusion of placement of the functional filler material in the inner layers.
  • FIG. 1 is a schematic illustration of a pultrusion process utilizing an injection die to impregnate functional fillers into the exterior of the pultruded article, according to one exemplary embodiment
  • FIG. 2 is a schematic illustration of a pultrusion process utilizing an injection die to impregnate functional fillers into the exterior of the pultruded article, according to another exemplary embodiment.
  • FIG. 3 is a schematic cross-sectional illustration of a pultruded article, according to one exemplary embodiment.
  • Continuous fibers as used herein means that the material is or contains unidirectional fibers that may extend for the complete length of a pultruded article. Continuous fibers are produced in reels or packages typically extending from at least 100 feet up to or exceeding tens of thousands of feet in length. Such materials are generally wound onto creels, spools, cakes, bobbins or the like, and stored until used. "Continuous” may refer to individual or grouped unidirectional fibers, as in filaments, strands or rovings, such as Type 30® Single End rovings, available from Owens Corning, Toledo, OH; or to 2-dimensional or 3 -dimensional matrices of such continuous fibers with other discontinuous fibers, such as veils and mats.
  • the general inventive concepts encompass a pultrusion process that incorporates one or more functional filler materials that impart a desired functionality to the exterior of the pultruded article.
  • a first resin is used to wet the reinforcements with the exception of the exterior layers.
  • the exterior of the pultruded article has imparted thereto a desired functionality through the selection of the filler materials.
  • the pultrusion process is useful for manufacturing a wide variety of pultruded articles, including but not limited to window and door frames, automobile, truck and bus parts, ladders, grating, utility poles, and building panels. It is particularly well suited for manufacturing pultruded articles where a certain functionality is desired but where the loss of strength caused by the use of most fillers would not be satisfactory.
  • a resin-injected pultrusion process is depicted generally in Fig. 1.
  • two separate resin systems are utilized to form the final pultruded article.
  • spools 12a, 12b provide continuous reinforcement materials 14, 22, respectively, which are utilized to form a pultruded part 100.
  • spools 12a supply continuous reinforcement material 22 that form the inner layers 23 in the reinforcement pack 36
  • spools 12b supply continuous reinforcement material 14 that form the outer layers in the reinforcement pack 36. It is to be appreciated that although ten total spools are illustrated, more or fewer spools may be utilized to form the pultruded article 100.
  • the continuous reinforcement materials 14, 22 may take many shapes and forms. They may have individual fibers or fibers grouped into bundles (or some of both); they may be in the form of 2-dimensional, essentially mono-layer matrices or 3- dimensional, lofted matrices (or some of both); their fibers may be unidirectional or multidirectional (or some of both); and they may include continuous or discontinuous fibers (or some of both). However, for pultrusion, at least some of the reinforcement material fibers must be continuous and unidirectional in order to be "pulled" through the processing equipment as is characteristic of pultrusion.
  • Continuous, unidirectional reinforcements include fibers, rovings, bundles of fibers, and yarns; and multi-directional reinforcements include mats, polymer cloths, veils, fabrics, or combinations thereof
  • a continuous reinforcement may have multiple types and orientations of fibers, e.g., rovings embedded in a fibrous mat.
  • the fibers may be any type of continuous glass fiber, such as A-type glass fibers, C-type glass fibers, E-type glass fibers, R-type glass fibers, S-type glass fibers, E-CR-type glass fibers (e.g., Advantex® glass fibers commercially available from Owens Corning).
  • the diameter of filaments making up glass rovings are typically within the range of 11 to 32 microns, but may range from about 8 to 40 microns or even fall outside this range.
  • the continuous fibers may also include or be mineral fibers, carbon fibers, ceramic fibers, natural fibers, and/or synthetic fibers.
  • natural fiber as used in conjunction with the general inventive concepts refers to plant fibers extracted from any part of a plant, including, but not limited to, the stem, seeds, leaves, roots, or bast.
  • natural fibers suitable for use as the reinforcing fiber material include basalt, cotton, jute, bamboo, ramie, bagasse, hemp, coir, linen, kenaf, sisal, flax, henequen, and combinations thereof.
  • synthetic fibers as used herein is meant to indicate any man-made fiber having suitable reinforcing characteristics, such as, for example, polyester, polyethylene, polyethylene terephthalate, polypropylene, polyamide, aramid, and/or polyaramid fibers.
  • the outer continuous reinforcement material 14 is a fibrous mat structure formed from glass fibers (e.g., a continuous filament mat into which the functional filler materials can penetrate) and the continuous reinforcement material 22 that forms the interior layers 23 is a plurality of continuous glass fiber rovings.
  • the continuous reinforcement material 22 forming the inner layers 23 passes through the impregnation die 16 where the reinforcement material 22 is impregnated with at least one first resin material 29 (not shown in Fig 1).
  • the impregnation die 16 generally contains a passageway 26 for passing the continuous reinforcement material 22 forming the inner layers 23 therethrough.
  • a resin supply system 28 in fluid communication with the impregnation die 16 supplies a first resin material 29 to the die 16.
  • Additional resin supply systems may also be coupled to the impregnation die 16 to supply additional resin materials as desired.
  • the resin material is supplied to the impregnation die 16 at a constant or substantially constant pressure.
  • the impregnated interior layers may then be fed through a shaping die 38, where excess resin is removed and the layers are shaped into a consolidated structure 27.
  • the consolidated structure 27 is combined with the outer layers 24 to form a reinforcement pack 36.
  • the reinforcement pack 36 then enters into an injection die 18, which generally includes an entry portion 40, an internal passageway 42, and an exit portion 44. In operation, the reinforcement pack 36 enters the injection die 18 through the entry portion 40 and moves into the internal passageway 42. As the reinforcement pack 36 passes through the injection die 18, the pack 36 is compressed and impregnated with a second resin material.
  • the injection die 18 is sealingly coupled or integrally formed with the curing die 20. Therefore, as the impregnated reinforcement pack 36 exits the injection die 18, it immediately enters the curing die 20. As a result, the impregnated reinforcement pack is not exposed to the atmosphere or the surrounding environment, which could expose the reinforcement pack to unwanted contaminants. In addition, the impregnated reinforcement pack 36 is maintained under constant pressure, thereby minimizing any unwanted expansion.
  • the injection die 18 is separate from and not coupled to the curing die 20 or any other die. Such an independent injection die 18 acts to provide the same function, namely to inject at least one second resin material into the impregnated reinforcement pack 36.
  • the second resin material is supplied to the injection die 18 by one or more second resin supply systems 46. Similar to the first resin supply system 28, the second resin supply system 46 is in fluid communication with the injection die 18 and the resin is fed to the injection die 18 under constant or substantially constant pressure.
  • One or more resin systems may be utilized to inject multiple resins into the injection die 18.
  • the second resin material 47 saturates and impregnates the outer layers 24 and contacts the inner layers 23 of the impregnated reinforcement pack 36.
  • a functional filler material 74 within the second resin material 47 is unable to enter or pass through the inner layers 23.
  • the first and second resin materials 29, 47 may be the same or different. When the resin materials 29, 47 are different, different properties can be imparted to the inner and outer layers 23, 24.
  • the first and second resin materials have the ability to combine or mix at the adjacent interior and exterior layers 23, 24 as shown, for example, at A and A 1 in Fig. 3.
  • a portion of the first resin material 29 may migrate into one or more of the exterior layers 24 while a portion of the second resin material 47 (exclusive of the filler material 74) migrates into one or more of the interior layers 23.
  • This migration and intermixing of resin materials reduces the likelihood of voids or zones of little or no resin material at the interface between the interior and exterior layers 23, 24.
  • Resins useful for pultruded articles are well known to those skilled in the art. Generally, such resins are selected from among polyesters, polyvinyl esters, polyurethanes, epoxy resins and phenolic resins. Suitable thermoplastic resins include, for example, unsaturated polyester resins based on maleic-5 anhydride, isophthalic acid, terephthalic acid, orthophthalic acid, dicyclopentadiene, and vinyl ester chemistries. Other suitable resins include polyamides, copolyamides polyolefms and polyetherketoneketone (PEKK). The resin in the inner layer 23 may be the same or different from the resin in the outer layer 24.
  • the second resin material 47 contains one or more functionalized filler materials 74.
  • Filler materials may conveniently be categorized into groups according to the purpose for which they are included in a pultruded article. By way of example, fillers may be divided into three broad groups, although such categorizations are generalizations and overlaps are likely to occur: (1) fillers that are primarily cost-reducers and essentially impart no other intended or desired property; (2) fillers that are selected to impart a particular aesthetic finish to the pultruded article, such as pigments and smoothing fillers; and (3) fillers that are selected to impart desired physical or mechanical properties.
  • a “functionalized filler material,” as used herein, is a compound or material, or combinations of compounds or materials, that fall into the third category, and are selected for their ability to impart a particular or desired mechanical or physical feature or property to the pultruded article or to at least its outer layer. While color and smoothness might be considered a “desired” physical property, they are nonetheless excluded from the definition of “functionalized fillers” for purposes of this application, unless such filler also has a desired functional property and could also be classified in the third category.
  • fillers of the first type include calcium carbonate, wood flour, fly ash and recycled plastic grinds.
  • fillers of the second type include clays like kaolin or talc; and pigments like carbon black, titanium dioxide, as well as all other pigments.
  • Functionalized filler materials 74 of the third type may be further divided and categorized based on the property or feature they impart; and further still on the mechanism by which they achieve that purpose. Thus, functionalized fillers may be fire or flame retardants, electrical conductors or insulators, corrosion resistors, density increasors or decreasors, and the like.
  • Flame retardant fillers may function by releasing water, free radical scavenging, char formation catalysts or insulators, or smoke suppressants.
  • Density increasors generally act by adding highly dense filler materials, and density decreasors work by adding lower density material, generally by entrapping air or other gas within the filler.
  • Density decreasors may be organic or inorganic. Typically, density decreasors afford lighter weight pultruded articles without loss of strength.
  • Some specific examples of density decreasor functionalized fillers are given in Table 1.
  • Some specific examples of flame retardant functionalized fillers are given in Table 2.
  • scavengers containing organic based on halogen DE83R (Chemtura) compounds e.g., Decabromo- content. Hetron 1540 diphenyl ether; Decabromo- (Ashland) diphenyl oxide;
  • the functional filler material 74 is impregnated into and remains in the exterior layers 24 only.
  • the functionalized fillers can impart their intended properties to the outer layer 24 without significantly impacting the strength of the pultraded part 100, as in the case of conventional pultrusion processes, and do not require having to cure the first resin layer before applying the second resin. This is important to allow the two resin layers to intermix and bond together more strongly as previously discussed. Without intending to be bound by any particular theory, it is believed this occurs as a result of two factors.
  • the continuous reinforcement material 14 is a mat, such as a continuous filament mat or chopped strand mat.
  • the functional filler material 74 has a particle size that is at least half the size of the diameter of the filaments of the continuous, unidirectional reinforcement materials 22 (e.g., rovings) forming the interior layers 23 adjacent to the exterior mat 14. Utilizing a particle size that is greater than or equal to half the size of the diameter of the reinforcement materials 22 restricts the flow or entry of the functional filler material 74 into the reinforcement materials 22, thereby leaving the functional filler material 74 in the exterior surface of the pultruded article.
  • the rovings act to filter the resin material such that the resin itself can pass into the inner layers or cores but the functional filler material 74 is forced to remain in the outer layers.
  • the functional filler material 74 in the second resin system 47 fills the spaces within the architecture of the exterior mat 14 without substantially displacing any structural reinforcement therein.
  • the term “substantially displacing” or “substantial displacement” is meant to denote that there is no displacement of the structural reinforcement or almost no displacement of the structural reinforcement so as not to reduce the structural performance of the pultruded article.
  • the structural mtegrity of the exterior layers of the pultruded product is maintained and a superior and stronger end product is formed, particularly when compared to conventional pultruded articles where the filler materials displace fibers and reduce the structural capability of the final pultruded article.
  • the functional filler material 74 is not integrated into the roving 22, the pultruded article retains its structural integrity and strength.
  • the functional filler material 74 may have a median particle size from about 2 microns to about 1000 microns, and in some exemplary embodiments, from about 8 microns to about 300 microns. By contrast, sizes of the reinforcement matrix (e.g., about 11-32 microns) are often significantly smaller than this.
  • the functional filler material 74 may be present in the second resin material in an amount from about 2 to about 60% by weight, and in some exemplary embodiments in an amount from about 5 to about 35% by weight, of the second resin material 47.
  • the impregnated pack leaves the impregnation die 18, it enters the curing die 20 where the impregnated pack is shaped and cured into its final intended shape to form the final pultruded article 100.
  • the curing die 20 may contain an entry 54, a central passage 56, and an exit 58. Additionally, in some exemplary embodiments, the pultruded article 100 may be cut by a cutting apparatus 60 located externally and downstream from the curing die 20.
  • Conventional pulling means are provided downstream from the curing die 20 for pulling the reinforcement materials 14, 22 from the spools 12a, 12b sequentially through the impregnation die 16, the shaping die 38, the impregnation die 18, and the curing die 20.
  • spools 13a and 13b provide primary and secondary first reinforcement materials 62, 64 that are utilized to form a pultruded part 110.
  • the primary first continuous reinforcement materials 62 pass through a first impregnation die 66 and the secondary first continuous reinforcement materials 64 pass through a second impregnation die 68.
  • the first and second impregnation dies 66, 68 perform a similar function to the impregnation die 16 described herein.
  • the primary and secondary first reinforcement materials 62, 64 may be any of the reinforcement materials described herein.
  • the first reinforcement materials 62, 64 are continuous glass fiber rovings.
  • the impregnation die 66 impregnates the primary first reinforcement materials 62 with a resin material and the impregnation die 68 impregnates the secondary first reinforcement materials 64 with a resin material to form inner layers 67, 69, respectively, which are then combined.
  • the resin material injected into the first impregnation die 66 is desirably different from the resin material injected into the second injection die 68 so as to provide differing properties to the two inner layers 67, 69.
  • the resins could be the same or provide the same property.
  • the interior layers may be further divided into sub-layers (not illustrated).
  • impregnation dies When these sub-layers are present and each of the sublayers is to be separately impregnated, an equivalent number of impregnation dies may be utilized.
  • the multiple impregnation dies may be provided in series, such as, for example, the first interior layer may be impregnated in a first impregnation die with a first resin material and then impregnated with a second resin material in a second impregnation die that is located downstream from the first impregnation die.
  • the impregnated inner layers 67, 69 are combined and fed into a shaping die 38 where the excess resin is removed and the layers are shaped into a consolidated structure 71.
  • the second reinforcement materials 14 forming the outer layers 24 are unwound from spools 13 and are combined with the consolidated structure 71 to form a reinforcement pack 70.
  • the reinforcement pack 70 is then passed through an injection die 18, which, as discussed herein, provides a second resin material (third in discussion sequence) that includes at least one filler material to impart a desired functionality to the surface of the pultruded part 110.
  • the impregnated reinforcement pack is then passed through a curing die 20 where the impregnated pack is shaped and cured into its final intended shape and form the final pultruded article 110.
  • the pultruded article 110 may be cut into segmented pieces with a cutting apparatus 60.
  • the filled resin material (e.g., functional filler material in the exterior layers) provides for the inclusion of desired properties to the exterior surface or outer layer of the pultruded article.
  • the general inventive concepts provide a process for the inclusion of a desired functional filler material in the exterior surface of the pultruded article to the exclusion of the placement of the filler material in the inner layers.
  • the filler materials are intentionally placed in the exterior layers as a result of the process.
  • An exemplary advantage provided by the general inventive concepts is that the functional fillers added to the external layers do not displace any structural reinforcement, and as a result, there is no substantial decrease in the structural capability of the external layer, and consequently, the pultruded part, hi addition, the filler material on the exterior surface of the pultruded article eliminates the need for a post-finish (such as by painting).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

L'invention porte sur un procédé d'extrusion par étirage qui comprend un ou plusieurs matériaux de remplissage pour communiquer la fonctionnalité voulue à l'extérieur d'un article extrudé par étirage (100). Dans le procédé, au moins une couche intérieure ou centrale (23) est imprégnée d'un premier matériau résineux (29). La couche intérieure imprégnée (23) peut ensuite être combinée à au moins une couche extérieure (24) pour former un bloc de renforcement (36). Une filière d'injection (18) injecte un matériau résineux, contenant un matériau de remplissage fonctionnel (74), dans les couches extérieures (24) du bloc de renforcement (36), à l'exclusion de l'introduction d'un matériau de remplissage fonctionnel (74) dans les couches intérieures. Avantageusement, le matériau de remplissage fonctionnel (74) ajouté aux couches extérieures (24) ne déplace pas les fibres du matériau de renforcement continu qui forme les couches extérieures. Par conséquent, l'intégrité structurale des couches extérieures (24) de l'article extrudé par étirage (100) est conservée et un produit final de qualité supérieure et plus résistant est formé.
PCT/US2011/046097 2010-07-30 2011-08-01 Article extrudé par étirage et son procédé de fabrication WO2012016234A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US36940810P 2010-07-30 2010-07-30
US61/369,408 2010-07-30

Publications (1)

Publication Number Publication Date
WO2012016234A1 true WO2012016234A1 (fr) 2012-02-02

Family

ID=44504242

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/046097 WO2012016234A1 (fr) 2010-07-30 2011-08-01 Article extrudé par étirage et son procédé de fabrication

Country Status (1)

Country Link
WO (1) WO2012016234A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103286963A (zh) * 2012-03-02 2013-09-11 深圳光启创新技术有限公司 玻璃钢的制备方法、玻璃钢天线罩及其制备方法
CN106393739A (zh) * 2016-08-03 2017-02-15 内蒙古文德茵莱节能门窗有限公司 一种玻璃钢型材的加工生产线
CN109070494A (zh) * 2016-04-20 2018-12-21 Fp创新研究所 通过拉挤成型来生产连续复合夹层结构的方法
CN110588023A (zh) * 2019-09-11 2019-12-20 常州市新创智能科技有限公司 一种曲面拉挤件成型方法
WO2020126771A1 (fr) * 2018-12-19 2020-06-25 Structil S.A. Procédé de fabrication d'un produit par pultrusion et appareil pour exécuter un tel procédé
CN113696577A (zh) * 2021-08-09 2021-11-26 安徽森泰木塑集团股份有限公司 一种连续性纤维增强板材、制备方法及模具

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5262212A (en) * 1992-05-08 1993-11-16 Fibercast Company Highly filled polyester compositions, articles, and methods of production
US5783013A (en) 1995-06-07 1998-07-21 Owens-Corning Fiberglas Technology Inc. Method for performing resin injected pultrusion employing multiple resins
US6221295B1 (en) * 1996-10-07 2001-04-24 Marshall Industries Composites, Inc. Reinforced composite product and apparatus and method for producing same
US20090023870A1 (en) * 2006-02-07 2009-01-22 Resin Systems, Inc Method of Pultrusion Employing Multiple Resins

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5262212A (en) * 1992-05-08 1993-11-16 Fibercast Company Highly filled polyester compositions, articles, and methods of production
US5783013A (en) 1995-06-07 1998-07-21 Owens-Corning Fiberglas Technology Inc. Method for performing resin injected pultrusion employing multiple resins
US6221295B1 (en) * 1996-10-07 2001-04-24 Marshall Industries Composites, Inc. Reinforced composite product and apparatus and method for producing same
US20090023870A1 (en) * 2006-02-07 2009-01-22 Resin Systems, Inc Method of Pultrusion Employing Multiple Resins

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Advances in ATH benefit composite products", REINFORCED PLASTICS, ELSEVIER ADVANCED TECHNOLOGY, NEW YORK, NY, US, vol. 47, no. 8, 1 September 2003 (2003-09-01), pages 44 - 46, XP004456309, ISSN: 0034-3617 *
J.M. HUBER CORPORATION: "MoldX Alumina Trihydrate", 31 December 2008 (2008-12-31), Online, pages 1 - 6, XP055009925, Retrieved from the Internet <URL:http://web.archive.org/web/20100308021024/http://hubermaterials.com/saleslit/moldxbrochurehubermaterials.pdf> [retrieved on 20111019] *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103286963A (zh) * 2012-03-02 2013-09-11 深圳光启创新技术有限公司 玻璃钢的制备方法、玻璃钢天线罩及其制备方法
CN109070494A (zh) * 2016-04-20 2018-12-21 Fp创新研究所 通过拉挤成型来生产连续复合夹层结构的方法
EP3445572A4 (fr) * 2016-04-20 2019-11-20 FPInnovations Procédés de production de structures continues composites en sandwich par pultrusion
CN106393739A (zh) * 2016-08-03 2017-02-15 内蒙古文德茵莱节能门窗有限公司 一种玻璃钢型材的加工生产线
WO2020126771A1 (fr) * 2018-12-19 2020-06-25 Structil S.A. Procédé de fabrication d'un produit par pultrusion et appareil pour exécuter un tel procédé
CN110588023A (zh) * 2019-09-11 2019-12-20 常州市新创智能科技有限公司 一种曲面拉挤件成型方法
CN110588023B (zh) * 2019-09-11 2020-11-20 常州市新创智能科技有限公司 一种曲面拉挤件成型方法
CN113696577A (zh) * 2021-08-09 2021-11-26 安徽森泰木塑集团股份有限公司 一种连续性纤维增强板材、制备方法及模具

Similar Documents

Publication Publication Date Title
US7144625B2 (en) Wire reinforced thermoplastic coating
EP3408077B1 (fr) Produit composite; procédé continu de pultrusion pour sa fabrication
US11135788B2 (en) System of continuous pultrusion method for manufacturing of bio-composite products; process and products thereof
US5727357A (en) Composite reinforcement
WO2012016234A1 (fr) Article extrudé par étirage et son procédé de fabrication
US4812343A (en) Pultruded fiber reinforced plastic marking devices
US20160273161A1 (en) Pre-impregnated composite material
KR101771287B1 (ko) 연속섬유 보강 수지 복합재 및 그 성형품
EP2618977A1 (fr) Fibres de renfort en carbone et matériau les contenant
JP5670230B2 (ja) 紐状強化繊維複合体
EP3070116A1 (fr) Matériau composite pré-imprégné
WO2011116923A2 (fr) Pâte renforcée fibres, dispositif et méthode pour sa fabrication, dispositif et méthode de fabrication de laminés et autres pièces finies à partir de la pâte, et laminé fabriqué à partir de la pâte
JP3530956B2 (ja) 複合強化原糸を用いた複合材料及びその製造法並びに構造体
KR100791109B1 (ko) 섬유 강화 플라스틱 및 그 제조 방법
US20170159212A1 (en) Fiber-reinforced composite material and method for producing the same
WO2017012802A1 (fr) Matériau pourvu d&#39;au moins une enveloppe bicouche
CN105934316B (zh) 纤维复合材料及其生产方法
KR20180079729A (ko) 준등방성 특성을 가지는 섬유 강화 플라스틱 성형품 및 이의 제조방법
KR100997447B1 (ko) 섬유 강화 플라스틱 및 그 제조 방법
CN115464905A (zh) 一种提高frp筋抗剪强度的编织方法
EP1361949B1 (fr) Composites
JPS62288633A (ja) 連続炭素繊維とポリオレフイン樹脂との複合材料
JP4692870B2 (ja) 複合強化原糸を用いた板状の複合材料
JP6620255B1 (ja) プリプレグおよびその製造方法
CN2921516Y (zh) 高环刚度阻燃抗静电塑料管

Legal Events

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

Ref document number: 11746711

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11746711

Country of ref document: EP

Kind code of ref document: A1