US20130210298A1 - Method for producing a flat semi-finished product from a fiber composite material and flat semi-finished product - Google Patents

Method for producing a flat semi-finished product from a fiber composite material and flat semi-finished product Download PDF

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Publication number
US20130210298A1
US20130210298A1 US13/588,135 US201213588135A US2013210298A1 US 20130210298 A1 US20130210298 A1 US 20130210298A1 US 201213588135 A US201213588135 A US 201213588135A US 2013210298 A1 US2013210298 A1 US 2013210298A1
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Prior art keywords
fibers
carbon
fiber
carbon fibers
mixture
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US13/588,135
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Inventor
Gerald Ortlepp
Renate Luetzkendorf
Thomas Reussmann
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SGL Automotive Carbon Fibers GmbH and Co KG
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SGL Automotive Carbon Fibers GmbH and Co KG
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Application filed by SGL Automotive Carbon Fibers GmbH and Co KG filed Critical SGL Automotive Carbon Fibers GmbH and Co KG
Assigned to SGL AUTOMOTIVE CARBON FIBERS GMBH & CO. KG reassignment SGL AUTOMOTIVE CARBON FIBERS GMBH & CO. KG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LUETZKENDORF, RENATE, ORTLEPP, GERALD, REUSSMANN, THOMAS
Publication of US20130210298A1 publication Critical patent/US20130210298A1/en
Priority to US14/467,693 priority Critical patent/US9896784B2/en
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    • 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
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01G—PRELIMINARY TREATMENT OF FIBRES, e.g. FOR SPINNING
    • D01G15/00—Carding machines or accessories; Card clothing; Burr-crushing or removing arrangements associated with carding or other preliminary-treatment machines
    • 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
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
    • 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
    • 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
    • D04H3/015—Natural 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
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of 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
    • 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
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12—Thermoplastic materials
    • 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
    • B29K2707/00—Use of elements other than metals for preformed parts, e.g. for inserts
    • B29K2707/04—Carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3707—Woven fabric including a nonwoven fabric layer other than paper
    • Y10T442/3715—Nonwoven fabric layer comprises parallel arrays of strand material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/643—Including parallel strand or fiber material within the nonwoven fabric
    • Y10T442/644—Parallel strand or fiber material is glass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/643—Including parallel strand or fiber material within the nonwoven fabric
    • Y10T442/645—Parallel strand or fiber material is inorganic [e.g., rock wool, mineral wool, etc.]

Definitions

  • the present invention relates to a method for producing a flat semifinished product from a fiber composite material containing fibers and at least one thermoplastic matrix material, wherein fibers are isolated from wastes or used parts containing fibers, then the fibers are blended with thermoplastic fibers and laid out in a sheet in a carding operation, thus producing a fiber web, which is pressed under the influence of heat to form a sheet material in at least one subsequent step.
  • Carbon fibers are used as the fiber reinforcement for fiber composite materials (FRP) bonded with a thermoplastic or thermoset plastic material. To achieve the maximum reinforcement effect, this has previously been done primarily in the form of continuous carbon fiber materials such as filament yarns, multifilament yarns or so-called rovings. However, carbon fibers used as cut fibers having finite fiber lengths in the range of 20 mm to 80 mm, for example, such as those known from the field of classical textile processing, are not available on the market, although they could be processed with fewer problems.
  • FRP fiber composite materials
  • Carbon fiber materials have been used as high-performance fiber reinforcement to an increasing extent for several years now.
  • the main applications are in aviation, shipbuilding, automotive engineering and wind power plants, for example.
  • Due to the broader and broader mass application the quantity of production waste containing carbon fibers has increased along with the volume of worn-out used parts.
  • carbon fibers are very expensive. Prices vary between approximately 15 /kg and approximately 300 /kg for special grades. It is therefore desirable for scientific reasons as well as for reasons pertaining to environmental policy to create possibilities for processing waste and used materials and to send the carbon fiber content contained in such waste for new applications in which it may at least partially replace expensive primary carbon fibers.
  • primary carbon fibers are usually produced either from suitable organic precursor fibers, such as polyacrylonitrile (PAN) or viscose fibers by controlled pyrolysis, or from pitch, whereby in this case a pitch fiber is first produced by melt spinning and then is oxidized and carbonized.
  • PAN polyacrylonitrile
  • a corresponding method is known from published, European patent application EP1 696 057 A1, corresponding to U.S. Pat. No. 7,634,840, for example, where the primary fibers produced from pitch are processed to staple fiber mats in which the fibers have an orientation in a preferred direction.
  • the known method contains, among other things, a combing process for aligning the fibers in parallel. However, ultimately a yarn is produced from a carbon fiber web and thus a linear product.
  • German patent DE 198 45 863 corresponding to U.S. Pat. No. 6,355,337, describes a structural element containing unidirectional rovings of carbon-fiber-reinforced plastic, each embedded in sheathing. A great unidirectional stiffness is to be achieved with these structural elements which are provided for aviation. However, rovings with continuous fibers are used here. This document does not contain any reference to the use of fibers from recycling of fiber-based waste products or used parts.
  • thermoplastic material namely fiber waste from carpet production
  • a waste material from production of automotive roof liners and then carded on a carding machine.
  • the thermoplastic fibers may consist of polypropylene, polyethylene, nylon or PET. These fibers are shredded into strips up to approximately 50 mm long before further processing.
  • the waste material from the production of roof liners is shredded by rollers having needle-like elevations and divided into strips.
  • the object of the present invention is to make available a method for producing a flat semi-finished product of fiber-reinforced composite material of the type defined in the introduction in which carbon fibers that are available inexpensively can be used as the reinforcing fibers and a flat semi-finished product having an arrangement of reinforcing fibers that is suitable for loads can be implemented.
  • a flat semi-finished product should be suitable in particular for the production of structural parts for high mechanical loads.
  • finite carbon fibers, carbon fiber bundles or mixtures thereof are isolated from wastes or used parts that contain fibers, then these finite fibers are mixed with thermoplastic non-carbon fibers laid out to form a flat web in a carding operation, thus producing a fibrous web having a targeted orientation of the fibers (in the longitudinal direction) which is then pressed under the influence of heat in at least one following step to form a sheet material.
  • Inexpensive high-performance carbon fibers are obtained from recycling processes and then are deposited in a mat-type semi-finished product together with thermoplastic non-carbon fibers in a preferential direction in a targeted manner so as to yield a reinforcing fiber configuration that is adequate for loads.
  • Carbon fibers are difficult to process by traditional carding techniques and in particular are difficult to align in a certain preferential direction in a card web because they are smooth and do not have any crimp. It has surprisingly been possible now by admixture of textile non-carbon fibers such as polypropylene to increase the degree of fiber orientation of the carbon fibers as well significantly and in a defined manner.
  • the degree of longitudinal orientation of the carbon fibers in the card web depends on the geometry of the added non-carbon fibers, in particular the fiber length and the amount added, among other things. Small amounts of non-carbon fibers, for example, approximately 10% and short non-carbon fibers, for example, on the order of 35-40 mm yield lower degrees of fiber orientation. Long non-carbon fibers more than 60 mm in length, for example, and amounts of more than 30% for example yield a high-fiber orientation of the carbon fibers.
  • the carbon fibers can be extracted and separated from used parts or wastes, for example, of the product categories of woven fabrics, non-crimp fabrics, braidings or materials in the form of preforms and/or from waste materials or used products from the product category of fiber-reinforced composite materials in a cardable fiber and/or fiber bundle form in an unorganized arrangement and with average fiber lengths and fiber bundle lengths, preferably in the range of 20 mm to 150 mm, more preferably approximately 40 mm to approximately 70 mm.
  • One example of a suitable device for separating textile fiber bundles into individual fibers is described in published, non-prosecuted German patent application DE 10 2009 023641 A1, the content of which is herewith referenced.
  • tearing and reprocessing of hard carbon-fiber-reinforced composite plastics (CFRP) by pyrolysis or solvent treatment are also known as separating processes.
  • CFRP hard carbon-fiber-reinforced composite plastics
  • the most homogeneous possible mixture of thermoplastic bonding fibers and finite carbon fibers, carbon fiber bundles or mixtures thereof is preferably processed by a carding operation to form a fiber mat.
  • the carbon fibers are more or less oriented in a targeted manner, and portions of the thermoplastic fibers are converted by heat to a tacky state, then compacted and pressed to form a flat material, which is then cooled.
  • the method according to the invention makes it possible to use carbon fibers, carbon fiber bundles or mixtures thereof, such as those obtained by separation from textile production waste, bonded or cured production waste, reprocessed used CFRP components or the like from reinforcing fibers, a less expensive starting material is thus available and the carbon fibers contained in the aforementioned used materials can be recycled appropriately.
  • the method according to the invention is thus advantageously not limited to chopped woven fabric residues as the starting material.
  • Other forms of waste that are generated in much larger quantities such as non crimp fabrics, braids, stacks, bonded multilayer semi-finished products or even fully cured CFRP residues and used parts may serve as a source for recycled carbon fibers isolated therefrom and can also be used in this method.
  • the carbon fibers are first freed of the interfering matrix substances.
  • pyrolysis techniques have been used for this or the wastes are treated with supercritical solvents. These separation processes yield finite carbon fibers, carbon fiber bundles or mixtures thereof as a web.
  • a preferred feature of the method according to the present invention is that the starting material contains at least a certain amount of carbon fibers derived from reprocessing of textile-type carbon waste and/or from sorted recycling of CFRP components plus optionally a portion of chopped primary fibers (new material).
  • At least one layer of finite carbon fibers is produced by laying out finite carbon fibers in a flat-sheet in a carding operation.
  • a card sliver is not produced first but instead a fiber layer being fed into the carding system is processed directly to form a thin fibrous web having a uniform weight per unit of area.
  • thermoplastic fibers and random finite carbon fibers and/or tangled carbon fiber bundles is aligned by a carding operation and processed to form a fiber mat, at least some portions of the thermoplastic fibers are converted to a tacky state by applying heat and then pressed to form a sheet material and then cooled.
  • the carbon fibers and/or carbon fiber bundles that are used according to the invention preferably have an average fiber length of 10 mm to 150 mm, preferably from 25 mm to 150 mm.
  • the cardability is determined by a necessary amount of longer backing fibers. The rule here is that the shorter the carbon fibers, the greater the amount of longer backing fibers that should additionally be fed to the carding machine. These may be longer carbon fibers as well as longer non-carbon-based fibers.
  • thermoplastic matrix material there are various preferred options for mixing the carbon fibers and/or the carbon fiber bundles with the thermoplastic matrix material.
  • carbon fibers and thermoplastic fibers may each be sent as a separate layer to the input of a carding system and then blended in this carding machine.
  • thermoplastic component in the form of finite fibers may be mixed thoroughly and homogeneously with the carbon fibers before or during the formation of a layer.
  • individual fiber components namely carbon fibers, thermoplastic matrix fibers and optionally additional fibers of different compositions, but each being pure on its own, may be deposited in various flat layers as fibrous webs or as nonwoven sheeting, one above the other, and then measures may be taken to achieve adequate penetration of all layers by the thermoplastic matrix component and compact bonding of the layers to one another after thermal solidification.
  • thermoplastic bonding fibers it is preferable to produce a mixture of random carbon fibers, random carbon fiber bundles or mixtures thereof and thermoplastic bonding fibers by an independent fiber blending operation prior to production of the fiber mat or by a fiber blending ration during the formation of the mat.
  • a semi-finished product according to the invention may also contain a certain amount of carbon fibers in the form of finite primary material (new material) in addition to carbon fibers from waste or used parts containing carbon fibers.
  • This flat semi-finished product may also contain, for example, additional fiber components in finite form having a reinforcing effect, in particular para-aramid, glass fibers, natural fibers, non-melting manmade fibers and/or fibers having a higher melting point than the matrix fibers may also be used in addition to carbon fibers.
  • Carbon fiber starting materials for this method include, for example:
  • shredded primary fibers shredded and/or frayed non crimp fabric, woven fabric or braiding residues, shredded and/or frayed fiber wastes, roving residues, edge cuttings from production of non crimp fabrics or residual bobbin material, shredded and/or frayed and/or thermally pretreated prepreg wastes or solvent-pretreated prepreg waste or shredded and/or frayed and thermally treated resin-containing wastes or solvent-treated waste, hard CFRP parts and used parts.
  • Fibrous admixed components such as thermoplastic fibers which will subsequently have a bonding effect may be mixed homogeneously with the carbon fibers in the carding machine, for example, in an independent step before formation of the layers, e.g., via a textile fiber mixing line, or directly during the formation of the layers, e.g., in a carding machine.
  • the carbon fibers in an intimate and homogeneous mixture are processed to form a flat fibrous web with a uniform weight per unit of area for example by a textile carding machine which has been adapted to the processing of carbon fibers with respect to its roll fittings and which is sealed with respect to the outside to prevent the escape of electrically conductive carbon fiber dust.
  • the fibrous web having a uniform weight per unit of area preferably approximately 15 to 60 g/m 2 is lined, for example, in a downstream lining operation until achieving the desired final weight per unit of area of the thermally bonded semi-finished product with longitudinal or transverse liners, or this is achieved by moving a number of n webs of n carding machines operating in series and passing them over one another.
  • the weight per unit of area of the web coating can be adjusted in a defined manner based on the parameters of the weight per unit of area of the web discharged from the carding machine, and the lining process. Different fiber length orientations in the card web can be achieved through the choice of the carding parameters, in particular the ratio of the fiber intake speed and the fiber discharge speed.
  • This adjustment in the carding machine and/or an additional following nonwoven drawing of a card web that has previously been lined or doubled repeatedly allow a degree of fiber orientation to develop, such that in an FRCP sheet produced therefrom with a thermoplastic matrix, for example, a polypropylene matrix, anisotropies of the composite strengths and/or composite stiffnesses can be adjusted in the range of 1:1.5 to 1:10, preferably 1:2 to 1:7 in particular.
  • the desired fiber orientation anisotropy
  • Such an FRCP sheet is produced according to the following specifications, for example:
  • the PP film is preferably additionally punched out with approximately the same length and width;
  • the carbon card webs are laid one above the other, wherein the webs are laid one above the other in the same direction of travel. If the carbon content in the card web exceeds approximately 40%, then the PP films additionally punched out, starting at the top side and bottom side, are preferably inserted between the card web layers, also in alternation, if necessary;
  • the sandwich thereby formed is pressed in a sheet press at temperatures of approximately 200° C., for example, and at a pressure of approximately 400 N/cm 2 , for example, which is set on the press;
  • sample bodies are cut from the CF/PP composite, cutting once longitudinally and once at a 90° angle to the fiber orientation, so that then the tensile stresses can be determined in MPa and the tensile E-modulus can be determined in GPa, for example;
  • this loose, flat fiber nonwoven of a uniform mixture and weight consisting of finite aligned carbon fibers and textile thermoplastic fibers may be heated to such an extent that the thermoplastic fibers soften or melt and can then be compacted by pressing pressure, and are solidified while cooling under pressure or without any additional external mechanical pressure.
  • the sheet products produced in this way can then be rolled up, for example, cut to form sheets or punched to form irregular flat shapes.
  • the amount of the thermoplastic component preferably determines the compactness of the product that can be achieved.
  • the thermoplastic fiber content in the carbon fibers There are no technological limits on the thermoplastic fiber content in the carbon fibers. From a product standpoint, use will vary in the range of 5% to 95% carbon fiber content, preferably in the range of 30% to 80% carbon fibers.
  • finite fiber materials such as natural fibers, para-aramid fibers, glass fibers, ceramic fibers or polyacrylonitrile fibers may also be used in this process. These fibers are blended intimately and homogeneously with one another before being carded or during the carding by analogy with the thermoplastic fibers.
  • the thoroughly homogeneous blending on the carding machine is preferably accomplished by the fact that a fiber coating of an accurate weight per unit of area and a constant weight per unit of area is supplied to the carding machine; the different fiber substances to be blended in the carding machine are supplied as fiber layers arranged one above the other with the most accurate possible weight per unit of area and a constant weight per unit of area of the fiber layers.
  • Such layers that are accurate per unit of area and are constant per unit of area and can be produced by running loose fibers from series-connected conventional carding machine feeds such as filling chutes, fiber spreaders or by only slightly solidified separate nonwoven layers.
  • the fibrous composition of the individual layers may vary, and individual layers may already consist of a defined mixture of different fiber materials.
  • the fiber webs that can be produced by such a carding operation having oriented carbon fibers may additionally be combined with known reinforcing structures of continuous fiber materials such as threads, rovings, non crimp fabrics, wovens, meshes, braidings and knits that are bonded to the fiber web layers of the carding machine in the thermal solidification process to form a semi-finished product for fiber-reinforced composite materials with a thermoplastic matrix.
  • the carbon fiber lengths can be introduced directly into the process of forming the layer or may be further shredded to improve processability and/or may be finished and/or blended with a sizing, adhesion-promoting substances or other additional agents that would have effects in the plastic products such as flame retardants, dyes, unmolding aids or tribology aids. It is also possible to add functional non-carbon fiber materials in addition to the carbon fiber materials for impact modification, for example, or for mechanical reinforcement such as para-aramid, glass fibers, natural fibers or non-melting manmade fibers and/or fibers having a melting point higher than that of the matrix fibers.
  • Fibrous additive components such as thermoplastic fibers which later have a bonding effect may be blended as thoroughly and homogeneously as possible with the remaining fiber components in an independent process step before forming the layer, e.g., in a textile fiber mixing line or directly during the formation of the layer, e.g., in a carding machine. If the possibilities of a system mixing are utilized, the individual fiber components in pure form are deposited over one another, for example, in different layers as the fiber web or nonwoven webs. It is important here that the thermoplastic bonding component penetrates through all the layers to ensure a compact bonding of all the layers to one another after thermal solidification.
  • thermoplastic and reinforcing component This can be achieved by homogeneously mixing all the components together, for example, with an alternating structure of thin layers with thermoplastic and reinforcing component or by extensive needling of thermoplastic bonding fibers by the carbon fiber layer, for example, using a needling operation.
  • a sandwich structure in which the non-melting components are arranged as a core layer is sufficient.
  • thermoplastic bonding component As a rule, a wide variety of thermoplastic matrices known from the prior art may be considered for use as the thermoplastic bonding component here. This ranges from low-melting polyethylene to polypropylene, polyamides to the high-melting thermoplastics PEEK or PEI.
  • the thermal solidification parameters such as temperature, dwell time, pressure and possible use of an inert gas atmosphere must be adapted to the particular details of these polymers.
  • the forms of the thermoplastic bonding components that can be used range from small particles such as powders to short fibers, long textile fibers, nonwoven layers or fibrous layers, spun-bonded nonwovens, films and polymer melts.
  • thermoplastic binders After combining the finite carbon fibers with the thermoplastic binders in a flat layer arrangement with the most constant possible weight ratio of carbon fiber to thermoplastic, this coating is heated so that the thermoplastic component softens or melts. When using a polymer melt, however, this step would not be necessary.
  • the thermoplastic material may be applied through flat-sheet dies to the carbon fiber layer—then compacted by applying pressure and solidified while cooling under pressure without any additional external mechanical pressure.
  • the amount of the thermoplastic component determines the achievable compactness of the sheet material.
  • the lower limit of the thermoplastic component is preferably approximately 5%, wherein carbon fibers and the thermoplastic component should be mixed together as homogeneously and thoroughly as possible in order to achieve a detectable solidification effect. In sandwich methods, a minimum binder content of approximately 15% to 25% is advantageous.
  • the hardness of the flat semi-finished product sheeting can be varied in a wide range by varying the amount of the thermoplastic component. This ranges from a compact pore-free state to an increasing porosity and then to a thermally solidified fiber nonwoven condition of a low density.
  • additional fiber substances in a finite form may also be used. These may be added before or during the formation of the layer or as separate system components in the layering of the material by analogy with the carbon fiber components through fiber mixing processes.
  • the subject matter of the present invention is also a flat semi-finished product of a fiber-reinforced composite plastic which was produced in a method of the aforementioned type and in which the amount of thermoplastic matrix material in the semi-finished product is in a range between approximately 5% and approximately 95%, preferably approximately 30% to approximately 70%.
  • the carbon fibers, carbon fiber bundles or mixture thereof prefferably have finite lengths and/or to have a length distribution and for the carbon fibers and/or carbon fiber bundles to be present in the semi-finished material in such a way that portions thereof do not permeate throughout the entire semi-finished product without interruption.
  • this flat semi-finished product is preferable for this flat semi-finished product to be produced from finite carbon fibers, carbon fiber bundles or mixtures thereof and additional finite-reinforcing fibers, in particular selected from natural fibers, para-aramid fibers and glass fibers.
  • a flat semi-finished product can also be combined with continuous reinforcing fibers such as continuous carbon rovings, para-aramid yarns and/or glass filament yarns in the form of threads, non crimp fabrics, woven fabrics or meshes.
  • a homogeneous fiber blend of 70% polypropylene of the fineness 7 dtex and a nominal fiber length of 60 mm and 30% waste carbon fibers from non-crimp fabric production with an average fiber length of 65 mm were processed on a carding machine equipped with three worker/turner pairs to form a fiber web with a weight per unit of area of 25 g/m 2 .
  • the carding operation created such a longitudinal orientation of the fiber in the fiber web that a fiber-reinforced composite plastic was obtained by processing 10 layers of this web by placing them one above the other in the same direction of the material and then pressing them in a plate press at 200° C.
  • this fiber-reinforced composite plastic product had a tensile E-modulus value that was higher by a factor of 5 in the running direction of the carded web in fiber-reinforced composite plastic in comparison with the modulus at an angle of 90° thereto.
  • recycled carbon fibers with an average fiber length of 40 mm and a commercial textile PA6 staple fiber of 3.3 dtex, 60 mm were used as the starting materials for the production of flat carbon-fiber-based semi-finished materials.
  • the two materials were blended together thoroughly in a weight ratio of 30% PA6 and 70% recycled carbon fibers (RCF) via a mixing bed of a type conventional in the textile industry and then using a mixed opening technique as so-called flock mixture. This fiber mixture was then placed in a carding system.
  • RCF recycled carbon fibers
  • the fiber orientation produced in the fiber web due to the carding operation was such that when processing 10 layers of this web by stacking them one above the other in the same direction of the material with intermediate insertion of PA6 films to a final carbon fiber content of 35% and pressing this in a plate press at 240° C., this would yield a fiber-reinforced composite plastic having a tensile E-modulus in the running direction of the carded web in the fiber-reinforced composite plastic that was higher by a factor of 3 than the modulus measured at a 90° angle thereto.
  • nonwoven webs were produced with a weight per unit of area of 180 g/m 2 comprised of 100% commercial textile PA6 fiber of 3.3 dtex, 60 mm. The two nonwoven webs were needled lightly only once from above at 12 stitches/cm 2 .
  • recycled carbon fibers obtained 100% from fabric wastes having an average fiber length of 40 mm were processed by a carding technique modified technically to work specifically in processing carbon fibers to form a flat card web with a uniform weight per unit of area of 30 g/m 2 of card web, and this web which was drawn off continuously from the carding machine with a transverse liner was deposited on a deposit sheet running continuously at a 90° angle to the former in a transverse and overlapping arrangement so as to yield a weight per unit of area of 780 g/m 2 .
  • One of the needled nonwoven webs finished previously was laid out between the deposit sheet and the carbon fiber web layer system to be lined so that the carbon fiber layering was arranged on the PA6 needled nonwoven.
  • the second PA6 needled nonwoven having 180 g/m 2 was rolled up as the cover layer so that this formed a sandwich construction of 180 g/m 2 PA6 needled nonwoven—780 g/m 2 RCF web layering—180 g/m 2 PA6 needled nonwoven.
  • the sandwich was needled and solidified from above and below with 25 stitches/cm 2 .
  • Portions of the PA6 nonwoven cover layers were needled through the RCF layer by this needling operation, which had a positive effect on the stability of the degree of thermal solidification to be achieved subsequently.
  • the needled nonwovens produced in this way with a PA6 outer layer and RCF in the core area were stacked one above the other as pieces measuring 30 cm ⁇ 30 cm and were pressed using a multiplaten press for 100 s at 240° C. and 50 bar and then cooled. Soft, as yet unsolidified edges were removed from the resulting sheets using guillotine shears.
  • FIGURE of the drawing is a simplified schematic diagram showing the principle operation of a carding system, which is suitable, for example, for producing a fiber web containing carbon fibers by a method according to the present invention.
  • At least one fiber layer 14 (at the left in the drawing) being fed into the carding system, passing initially over feed rollers 1 , 2 onto a licker-in 3 rotating in the opposite direction from the intake rollers.
  • a transfer roller 4 rotating in a direction opposite that of the licker-in 3 and the main drum 5 is arranged between the licker-in 3 and the main drum 5 (tambour) rotating in the same direction of rotation as the licker-in 3 .
  • Various workers 6 and turners 7 are arranged on the circumference of the main drum 5 in various circumferential positions. The object of these devices is to shred the incoming fiber layer 14 in the carding system down to individual fibers and then shape them back into a thin fiber web having a uniform weight and a defined weight per unit of area.
  • a longitudinal fiber orientation is preferably the goal here.
  • a takeoff drum 10 rotating in the opposite direction is arranged downstream from a wheel 8 with a wheel cleaner 9 , a hacker 11 being situated on the downstream end of the drum.
  • a fiber web 12 in the form of a continuous surface with a weight per unit of area up to max. approximately 80 g/m 2 , preferably approximately 15-30 g/m 2 is discharged from this takeoff drum 10 , wherein the carbon fibers which are present in the web in a proportional amount have a preferred longitudinal orientation of the fibers, which is set in a defined manner.

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  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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CA2789837A1 (en) 2011-08-25
PL2536546T3 (pl) 2018-06-29
WO2011101094A1 (de) 2011-08-25
ES2653952T3 (es) 2018-02-09
EP2536546A1 (de) 2012-12-26
US9896784B2 (en) 2018-02-20
CN102869485A (zh) 2013-01-09
WO2011101094A4 (de) 2012-05-03
DE102010008370A1 (de) 2011-08-18
EP2536546B1 (de) 2017-10-25
JP5901540B2 (ja) 2016-04-13
PT2536546T (pt) 2018-01-04
US20160362817A1 (en) 2016-12-15
KR101434077B1 (ko) 2014-08-25
JP2013519546A (ja) 2013-05-30
KR20120123705A (ko) 2012-11-09
MX2012009461A (es) 2012-11-30

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ORTLEPP, GERALD;LUETZKENDORF, RENATE;REUSSMANN, THOMAS;REEL/FRAME:029210/0551

Effective date: 20120907

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION