WO2017116349A1 - Thermoplastic prepreg production method - Google Patents

Thermoplastic prepreg production method Download PDF

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Publication number
WO2017116349A1
WO2017116349A1 PCT/TR2016/050341 TR2016050341W WO2017116349A1 WO 2017116349 A1 WO2017116349 A1 WO 2017116349A1 TR 2016050341 W TR2016050341 W TR 2016050341W WO 2017116349 A1 WO2017116349 A1 WO 2017116349A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic
production method
yarn
yarns
thermoplastic prepreg
Prior art date
Application number
PCT/TR2016/050341
Other languages
French (fr)
Inventor
Deniz KORKMAZ
Elcin CAKAL SARAC
Egemen BILGE
Original Assignee
Kordsa Teknik Tekstil Anonim Sirketi
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 Kordsa Teknik Tekstil Anonim Sirketi filed Critical Kordsa Teknik Tekstil Anonim Sirketi
Priority to TR2018/09192A priority Critical patent/TR201809192T1/en
Publication of WO2017116349A1 publication Critical patent/WO2017116349A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10Coating or impregnating independently of the moulding or shaping step
    • B29B15/12Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/504Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
    • B29C70/506Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands and impregnating by melting a solid material, e.g. sheet, powder, fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024Woven fabric
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/06Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
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    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
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    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/12Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2101/00Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12Thermoplastic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B2250/00Layers arrangement
    • B32B2250/20All layers being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • B32B2260/023Two or more layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02Synthetic macromolecular fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02Synthetic macromolecular fibres
    • B32B2262/0223Vinyl resin fibres
    • B32B2262/023Aromatic vinyl resin, e.g. styrenic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2262/14Mixture of at least two fibres made of different materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514Oriented
    • B32B2307/516Oriented mono-axially
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
    • D04H3/115Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by applying or inserting filamentary binding elements
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/14Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding

Definitions

  • the present invention relates to a thermoplastic prepreg production method which is developed in order to be used as structural and visual material in all industrial fields, mainly aviation, defense industry and automotive, and which enables the thermoplastic resin to be impregnated into the stitched fabric formed with a yarn that is manufactured from reinforcing fibers.
  • thermoset and thermoplastic are divided into two main categories, namely thermoset and thermoplastic.
  • the thermoplastic prepreg is a structure comprised of thermoplastic resin impregnated yarns manufactured from reinforcing fibers.
  • the thermoplastic prepregs are very popular today due to their lightweight, recycling potential, and resistance against corrosion properties.
  • thermoplastic prepreg production Today, the resin used in thermoplastic prepreg production is applied as powder, film or granule.
  • the thermoplastic prepregs that are obtained are then transformed into composite material which is the final product with production methods such as, thermoforming, compression molding via heat and pressure or overmolding.
  • thermoplastic prepreg production materials such as polyamides (PA) (polyamide 6 (PA6), polyamide 6,6 (PA66), polyphthalamide (PPA)), polyphenylene sulfide (PPS), polysulfone (PSU) polyarylenethersulfone, polyolefines (polyethylene (PE), polypropylene (PP) etc.), polyimide (PI), polyesters, preferably such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether ether ketone (PEEK) can be used.
  • Manual or automatic methods are preferred in feeding the resin in powder, film and granule form to the system.
  • thermoplastic prepreg production is performed with discontinuous or continuous methods.
  • both discontinuous and continuous methods even in case of feeding the resin in powder form is automatic, the thermoplastic resin/reinforcing fiber ratio cannot be applied in the desired accuracy. Variations occur in the powder amounts used in unit area.
  • resin particles sizes are too big, accumulations occur since homogenous melting cannot be provided on the thermoplastic prepreg.
  • the impregnation of the resin in the fiber structure is not easy due to same reason. In other words, the resin cannot penetrate into the structure comprised of yarn manufactured from reinforcing fiber homogenously.
  • the wall thickness of the thermoplastic prepregs of the present invention can be produced in range of 0.3 and 6.0 mm.
  • the said invention can function in a limited field since it is not for thermoplastic prepregs with bigger wall thickness.
  • the objective of the present invention is to provide a thermoplastic prepreg production method which enables the resin used in prepreg application to penetrate more into the stitched fabric relative to the conventional applications, in other words which enables the wettability of the fabric formed with a yarn that is manufactured from reinforcing fiber.
  • Another objective of the present invention is to provide a thermoplastic prepreg production method which enables to apply more accurate amount of resin to the stitched fabrics comprising reinforcing yarn and thermoplastic yarn and also to provide more easily processing of them.
  • Figure 1 is the view of the stitched fabric used for unidirectional thermoplastic prepreg manufactured with the inventive thermoplastic prepreg application method.
  • Figure 2 is the view of the stitched fabric used for triaxial thermoplastic prepreg manufactured with the inventive thermoplastic prepreg application method.
  • Figure 3 is the view of the stitched fabric used for biaxial thermoplastic prepreg manufactured with the inventive thermoplastic prepreg application method.
  • FIG 4 is the view of the stitching yarn (C) used in the inventive thermoplastic prepreg application method.
  • the components shown in the figures are each given reference numbers as follows:
  • Unidirectional thermoplastic prepreg is obtained in a way disclosed in the invention, for example, after stitching the fabrics with stitching yarn in order to hold the unidirectional fabrics manufactured from thermoplastic yarn used in first and last layer of the stitched fabric and the fabric manufactured from unidirectional reinforcing yarn used in middle layer of the same stitched fabric shown in figure 1.
  • the stitching types used in production of stitched fabric may be pillar, tricot and the like.
  • the inventive uni-directional, biaxial, triaxial or multiaxial thermoplastic prepreg production method which enables the resin to penetrate into the fabric homogenously and deeply in resin impregnation process realized in order to reinforce the stitched fabric which is manufactured, and comprises the steps of
  • thermoplastic yarns and reinforcing yarns determined in thermoplastic prepreg design during fabric production phase
  • thermoplastic resin in yarn form to penetrate between the fibers of the reinforcing yarn inside the fabric by melting
  • T g glass transition temperature
  • thermoplastic yarns used in forming the stitched fabric is used in form of a thermoplastic yarn (B) selected from a group comprising polyamides (such as polyamide 6 (PA6), polyamide 6,6 (PA66), polyphthalamide (PPA) ), polyphenylene sulfide (PPS), polysulfone (PSU) (such as polyethersulfone (PES), polyarylenethersulfone), polyarylenesulfide, fluoropolymer, polyacetal, polycarbonate, styrenic polymer, polyolefins (such as polyethylene (PE), polypropylene (PP)), polyimide (PI), polyetherimide, polyesters preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether ether ketone (PEEK), polyether ketone (PEK), or combinations thereof.
  • polyamides such as polyamide 6 (PA6), polyamide 6,6 (PA66), polyphthalamide (PPA
  • reinforcing yarn (A) used in forming the stitched fabric a yarn produced from a material selected from the group comprising glass fiber, carbon fiber, aramid fiber, natural fiber, or a combination thereof is used.
  • stitched fabric used in the invention is defined as a system comprised of one or more than one unidirectional fiber layers, and formed by holding these layers together by stitching with a nonstructural stitching yarn, preferably a stitching yarn manufactured from thermoplastic polymer.
  • a nonstructural stitching yarn preferably a stitching yarn manufactured from thermoplastic polymer.
  • the fabrics can be unidirectional, biaxial, triaxial or multiaxial.
  • dtex used in the invention is the weight in grams per 10000 meters yarn.
  • tex used in the invention is the weight in grams per 1000 meters yarn.
  • the resin being in form of yarn manufactured from thermoplastic fiber enables the amount of resin/reinforcing fiber ratio in the thermoplastic prepreg to be adjusted easily.
  • the wall thickness of the thermoplastic prepregs which are the final products formed by penetrating the resin into the stitched yarn is adjusted to be in range of 0.25 and 8 mm.
  • the wall thickness of the thermoplastic prepregs comprising single layer reinforcing fiber depends on the type of the used reinforcing yarn, areal weight of fabric and the pressure which is applied.
  • the wall thickness of the thermoplastic prepregs manufactured from stitched fabric obtained by holding the system comprising at least "single layer reinforcing yarn” and produced as at least two layers together with a nonstructural stitching yarn depends on the number of the used unidirectional fiber layers, type of the reinforcing yarn, areal weight of the stitched fabric and the pressure.
  • the present invention comprises application of 0-100 bars, preferably in range of 1-40, of pressure on the resin in step of heating of the resin.
  • the cooling of the resin penetrating into the reinforcing yarns of the stitched fabric is carried out under 0-100 bars of pressure, preferably in range of 1-40 bars of pressure.
  • the weight of the thermoplastic resin is in range of 10% to 90%, preferably 30% to 70% of the weight of the yarn manufactured from reinforcing fibers.
  • unidirectional (UD) thermoplastic prepreg production unidirectional and single layered reinforcing yarns (A) and layers comprising thermoplastic yarn (B) on lower and/or upper surface of the said layer are used.
  • the stitched fabric is obtained by stitching at least two woven fabrics, which are obtained by weaving thermoplastic yarn and reinforcing yarn together, with a stitching yarn together.
  • thermoplastic prepregs can be used as structural and visual material in all industrial fields, mainly aviation, defense industry and automotive.
  • the final product that is obtained is the semi-product called as the thermoplastic prepreg or organosheet.
  • thermoplastic prepreg production discontinuous or continuous methods can be used.
  • the main principle used in both methods is to apply pressure (0-100 bars) at a temperature above softening or melting point of the thermoplastic resin, and to enable the resin to be impregnated into the reinforcing fibers in this way.
  • Cooling process is applied after temperature and pressure is applied for a determined time between 2 minutes and 120 minutes. Cooling process can be applied without pressure or under pressure (0-100 bar) depending on the structure of the polymer.
  • the cooling temperature is below the glass transition temperature (T g ) of the resin.
  • T g glass transition temperature
  • the machine in which the inventive thermoplastics are produced can be heated up to 450°C depending on the structure of the plastic.
  • the temperature range that can be used in cooling process is between 25°C and 200°C.
  • the wall thickness of the inventive thermoplastic prepregs is in range of 0.25 mm to 8mm.
  • the applications known in the state of the art cannot provide the resin to be homogenously impregnated into the fibers.
  • the resin/reinforcing fiber ratio can be accurately adjusted.
  • resin homogenization in amount is provided before starting the process.
  • the different dtex, different filament diameter and number of yarn produced from thermoplastic fibers can be used.
  • thermoplastic resins used in the stitched fabric application are applied in form of yarn on different layers of the fabric.
  • the yarns manufactured from reinforcing fibers (glass, carbon, aramid, natural fiber, etc.) are applied in single layer or different layers of the fabric in the same way, and the obtained hybrid structure is enabled to be appropriate for thermoplastic prepreg production.
  • Two or more kinds of reinforcing yarns (A) can be used in hybrid fabrics.
  • carbon, glass and thermoplastic yarn (B) can be used in the same stitched fabric.
  • raw material of the thermoplastic prepreg is obtained from the fabric comprising reinforcing yarn (A) and thermoplastic yarn (B) from the multiaxial textiles production machine which is being currently used. Therefore, there is no extra process step required as conventional thermoplastic prepreg production during powder, film or granule coating application, and thus the production is carried out faster.
  • thermoplastic prepregs stitched fabrics comprising reinforcing yarn (A) and thermoplastic yarn (B) can be processed in more accurate resin amounts, and they can be processed more easily.
  • the thermoplastic composite structure which is the end product can easily reach the required strength values with the design of stitched fabric layers.
  • thermoplastic prepregs with different mechanical properties can be obtained.
  • the composite structure can be varied compatible with the field of use of the end user.
  • the stitched fabric application is suitable for being used in wide range of application fields since it allows placing the reinforcing yarn in different axes.

Abstract

The present invention relates to a thermoplastic prepreg production method which is developed in order to be used as structural and visual material in all industrial fields, mainly aviation, defense industry and automotive, and which enables the thermoplastic resin to be impregnated into the stitched fabric formed with a reinforcing yarn (A). The objective of the present invention is to provide a thermoplastic prepreg production method which enables to apply more accurate resin amount to the stitched fabrics comprising reinforcing yarn (A) and thermoplastic yarn (B), and to be processed more easily.

Description

THERMOPLASTIC PREPREG PRODUCTION METHOD
Field of the Invention
The present invention relates to a thermoplastic prepreg production method which is developed in order to be used as structural and visual material in all industrial fields, mainly aviation, defense industry and automotive, and which enables the thermoplastic resin to be impregnated into the stitched fabric formed with a yarn that is manufactured from reinforcing fibers.
Background of the Invention
The prepregs are divided into two main categories, namely thermoset and thermoplastic. The thermoplastic prepreg is a structure comprised of thermoplastic resin impregnated yarns manufactured from reinforcing fibers. The thermoplastic prepregs are very popular today due to their lightweight, recycling potential, and resistance against corrosion properties.
Today, the resin used in thermoplastic prepreg production is applied as powder, film or granule. The thermoplastic prepregs that are obtained are then transformed into composite material which is the final product with production methods such as, thermoforming, compression molding via heat and pressure or overmolding.
In thermoplastic prepreg production, materials such as polyamides (PA) (polyamide 6 (PA6), polyamide 6,6 (PA66), polyphthalamide (PPA)), polyphenylene sulfide (PPS), polysulfone (PSU) polyarylenethersulfone, polyolefines (polyethylene (PE), polypropylene (PP) etc.), polyimide (PI), polyesters, preferably such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether ether ketone (PEEK) can be used. Manual or automatic methods are preferred in feeding the resin in powder, film and granule form to the system. Especially powder and granule applications used in thermoplastic prepreg production cause homogenization problem in distributing resin, difficulty in using optimum raw material, and high amount of waste occurring during production. Thermoplastic prepreg production is performed with discontinuous or continuous methods. In both discontinuous and continuous methods, even in case of feeding the resin in powder form is automatic, the thermoplastic resin/reinforcing fiber ratio cannot be applied in the desired accuracy. Variations occur in the powder amounts used in unit area. In case it is supplied in granule form, since resin particles sizes are too big, accumulations occur since homogenous melting cannot be provided on the thermoplastic prepreg. The impregnation of the resin in the fiber structure is not easy due to same reason. In other words, the resin cannot penetrate into the structure comprised of yarn manufactured from reinforcing fiber homogenously.
United States Patent Document no US5445701, an application known in the state of the art, discloses a thermoplastic resin method in form of film. However, this method is expensive, as well as difficulties in supplying the film compatible for the desired thermoplastic material can be experienced.
In United States Patent Document no US20140030582, an application known in the state of the art, the wall thickness of the thermoplastic prepregs of the present invention can be produced in range of 0.3 and 6.0 mm. The said invention can function in a limited field since it is not for thermoplastic prepregs with bigger wall thickness.
United States Patent Document no US5464684, an application known in the state of the art, discloses a production method of the polyamide based hybrid yarn. In this method, thermoplastic yarn and reinforcing yarn are produced by mixing with each other by air application. Depending on the complexity of the yarn mixing process and application of twisting process on carbon fiber which is very brittle, causes decrease of the linear strength of the carbon fiber.
Summary of the Invention
The objective of the present invention is to provide a thermoplastic prepreg production method which enables the resin used in prepreg application to penetrate more into the stitched fabric relative to the conventional applications, in other words which enables the wettability of the fabric formed with a yarn that is manufactured from reinforcing fiber.
Another objective of the present invention is to provide a thermoplastic prepreg production method which enables to apply more accurate amount of resin to the stitched fabrics comprising reinforcing yarn and thermoplastic yarn and also to provide more easily processing of them.
Detailed Description of the Invention
The "Thermoplastic prepreg application method" developed to fulfill the objectives of the present invention is illustrated in the accompanying figures, in which:
Figure 1 is the view of the stitched fabric used for unidirectional thermoplastic prepreg manufactured with the inventive thermoplastic prepreg application method.
Figure 2 is the view of the stitched fabric used for triaxial thermoplastic prepreg manufactured with the inventive thermoplastic prepreg application method.
Figure 3 is the view of the stitched fabric used for biaxial thermoplastic prepreg manufactured with the inventive thermoplastic prepreg application method.
Figure 4 is the view of the stitching yarn (C) used in the inventive thermoplastic prepreg application method. The components shown in the figures are each given reference numbers as follows:
A. Reinforcing yarn
B. Thermoplastic yarn
C: Stitching yarn
Unidirectional thermoplastic prepreg is obtained in a way disclosed in the invention, for example, after stitching the fabrics with stitching yarn in order to hold the unidirectional fabrics manufactured from thermoplastic yarn used in first and last layer of the stitched fabric and the fabric manufactured from unidirectional reinforcing yarn used in middle layer of the same stitched fabric shown in figure 1.
The stitching types used in production of stitched fabric may be pillar, tricot and the like.
The inventive uni-directional, biaxial, triaxial or multiaxial thermoplastic prepreg production method, which enables the resin to penetrate into the fabric homogenously and deeply in resin impregnation process realized in order to reinforce the stitched fabric which is manufactured, and comprises the steps of
- Stitching with the stitching yarn in order to combine the thermoplastic yarns and reinforcing yarns determined in thermoplastic prepreg design during fabric production phase,
- Placing each one of the unidirectional layers manufactured with reinforcing yarn comprising thermoplastic yarn on its lower and/or upper surface,
- Being comprised of at least two layers such that at least one of the layers will comprise a layer including "unidirectional reinforcing fiber",
- Increasing the temperature of the stitched fabric above the softening point or melting point of the thermoplastic yarn, - Applying pressure (0-100 bar) on the stitched fabric at this temperature,
- Applying pre-tensioning (0-5 g/tex) on the stitched fabric at this temperature,
- Enabling the thermoplastic resin in yarn form to penetrate between the fibers of the reinforcing yarn inside the fabric by melting,
- Applying temperature and pressure for a time in range of 2-120 minutes,
- Obtaining the ready to use final product by cooling until it reaches a temperature below glass transition temperature (Tg) of the resin without pressure or under pressure.
In the said invention, the thermoplastic yarns used in forming the stitched fabric is used in form of a thermoplastic yarn (B) selected from a group comprising polyamides (such as polyamide 6 (PA6), polyamide 6,6 (PA66), polyphthalamide (PPA) ), polyphenylene sulfide (PPS), polysulfone (PSU) (such as polyethersulfone (PES), polyarylenethersulfone), polyarylenesulfide, fluoropolymer, polyacetal, polycarbonate, styrenic polymer, polyolefins (such as polyethylene (PE), polypropylene (PP)), polyimide (PI), polyetherimide, polyesters preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether ether ketone (PEEK), polyether ketone (PEK), or combinations thereof.
In the said invention, as reinforcing yarn (A) used in forming the stitched fabric, a yarn produced from a material selected from the group comprising glass fiber, carbon fiber, aramid fiber, natural fiber, or a combination thereof is used.
The term "stitched fabric" used in the invention is defined as a system comprised of one or more than one unidirectional fiber layers, and formed by holding these layers together by stitching with a nonstructural stitching yarn, preferably a stitching yarn manufactured from thermoplastic polymer. When the angles of the unidirectional layers forming the stitched fabrics, the fabrics can be unidirectional, biaxial, triaxial or multiaxial. The term "dtex" used in the invention is the weight in grams per 10000 meters yarn. The term "tex" used in the invention is the weight in grams per 1000 meters yarn.
In the inventive thermoplastic prepreg production method, the resin being in form of yarn manufactured from thermoplastic fiber enables the amount of resin/reinforcing fiber ratio in the thermoplastic prepreg to be adjusted easily. In the present invention, the wall thickness of the thermoplastic prepregs which are the final products formed by penetrating the resin into the stitched yarn is adjusted to be in range of 0.25 and 8 mm. The wall thickness of the thermoplastic prepregs comprising single layer reinforcing fiber depends on the type of the used reinforcing yarn, areal weight of fabric and the pressure which is applied. The wall thickness of the thermoplastic prepregs manufactured from stitched fabric obtained by holding the system comprising at least "single layer reinforcing yarn" and produced as at least two layers together with a nonstructural stitching yarn depends on the number of the used unidirectional fiber layers, type of the reinforcing yarn, areal weight of the stitched fabric and the pressure.
The present invention comprises application of 0-100 bars, preferably in range of 1-40, of pressure on the resin in step of heating of the resin.
In the present invention, the cooling of the resin penetrating into the reinforcing yarns of the stitched fabric is carried out under 0-100 bars of pressure, preferably in range of 1-40 bars of pressure.
In the present invention, the weight of the thermoplastic resin is in range of 10% to 90%, preferably 30% to 70% of the weight of the yarn manufactured from reinforcing fibers. In a preferred embodiment of the invention, in order to enable unidirectional (UD) thermoplastic prepreg production, unidirectional and single layered reinforcing yarns (A) and layers comprising thermoplastic yarn (B) on lower and/or upper surface of the said layer are used.
In a preferred embodiment of the invention, in order to enable biaxial thermoplastic prepreg production, biaxial and two layered reinforcing yarns (A) and layers comprising thermoplastic yarn (B) on lower and/or upper surfaces of the said layers are used. In a preferred embodiment of the invention, in order to enable triaxial thermoplastic prepreg production, triaxial and three layered reinforcing yarns (A) and layers comprising thermoplastic yarn (B) on lower and/or upper surfaces of the said layers are used. In a preferred embodiment of the invention, in order to enable multiaxial thermoplastic prepreg production, minimum quadraxial and four layered reinforcing yarns (A) and layers comprising thermoplastic yarn (B) on lower and/or upper surfaces of the said layers are used. In a preferred embodiment of the invention, the stitched fabric is obtained by stitching at least two woven fabrics, which are obtained by weaving thermoplastic yarn and reinforcing yarn together, with a stitching yarn together.
The inventive thermoplastic prepregs can be used as structural and visual material in all industrial fields, mainly aviation, defense industry and automotive. The final product that is obtained is the semi-product called as the thermoplastic prepreg or organosheet.
In thermoplastic prepreg production, discontinuous or continuous methods can be used. The main principle used in both methods is to apply pressure (0-100 bars) at a temperature above softening or melting point of the thermoplastic resin, and to enable the resin to be impregnated into the reinforcing fibers in this way. Cooling process is applied after temperature and pressure is applied for a determined time between 2 minutes and 120 minutes. Cooling process can be applied without pressure or under pressure (0-100 bar) depending on the structure of the polymer. The cooling temperature is below the glass transition temperature (Tg) of the resin. The machine in which the inventive thermoplastics are produced can be heated up to 450°C depending on the structure of the plastic. The temperature range that can be used in cooling process is between 25°C and 200°C. The wall thickness of the inventive thermoplastic prepregs is in range of 0.25 mm to 8mm. The applications known in the state of the art cannot provide the resin to be homogenously impregnated into the fibers. On the other hand, in the inventive method, since the resin is used in yarn form, the resin/reinforcing fiber ratio can be accurately adjusted. In summary, with the newly developed method, resin homogenization in amount is provided before starting the process. In order to provide the resin/reinforcing fiber ratio homogenously in a desired ratio in everywhere, the different dtex, different filament diameter and number of yarn produced from thermoplastic fibers can be used. With the thermoplastic yarn application, increasing in plastic surface area and regular material orientation enable the resin to be melt more easily relative to especially the powder and granule applications. Therefore, product with higher quality can be obtained in a machine which has lower accuracy. At the same time, the defects related to areal weight of resin that can occur during application are prevented.
The thermoplastic resins used in the stitched fabric application are applied in form of yarn on different layers of the fabric. The yarns manufactured from reinforcing fibers (glass, carbon, aramid, natural fiber, etc.) are applied in single layer or different layers of the fabric in the same way, and the obtained hybrid structure is enabled to be appropriate for thermoplastic prepreg production. Two or more kinds of reinforcing yarns (A) can be used in hybrid fabrics. For example, carbon, glass and thermoplastic yarn (B) can be used in the same stitched fabric. Within the scope of the inventive method, raw material of the thermoplastic prepreg is obtained from the fabric comprising reinforcing yarn (A) and thermoplastic yarn (B) from the multiaxial textiles production machine which is being currently used. Therefore, there is no extra process step required as conventional thermoplastic prepreg production during powder, film or granule coating application, and thus the production is carried out faster.
In production of thermoplastic prepregs, stitched fabrics comprising reinforcing yarn (A) and thermoplastic yarn (B) can be processed in more accurate resin amounts, and they can be processed more easily. The thermoplastic composite structure which is the end product can easily reach the required strength values with the design of stitched fabric layers. By means of the stitched fabric types that are designed differently, thermoplastic prepregs with different mechanical properties can be obtained. By this means the composite structure can be varied compatible with the field of use of the end user.
The stitched fabric application is suitable for being used in wide range of application fields since it allows placing the reinforcing yarn in different axes.

Claims

1. A thermoplastic prepreg material production method characterized by the steps of
a) obtaining a fabric by at least two layers comprising reinforcing yarns and thermoplastic yarns being stitching together with stitching yarns, b) impregnating the said thermoplastic yarns into the said stitched fabric by melting of softening,
c) cooling the said impregnated stitched fabric to a temperature below the glass transition temperature of the said thermoplastic yarns.
2. A thermoplastic prepreg production method according to claim 1, characterized in that it comprises the step of applying pressure on the said stitched fabric during melting and softening process of the said thermoplastic yarn.
A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that it comprises the step of applying pressure in range of 0-100 bars on the said stitched fabric during melting and softening process of the said thermoplastic yarn.
A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that it comprises the step of applying pressure on the said stitched fabric during the cooling process of the said thermoplastic prepreg material.
A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that it comprises the step of applying pressure in range of 0-100 bars on the said stitched fabric during the cooling process of the said thermoplastic prepreg material.
6. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the said thermoplastic yarns are comprised of polyamide, polyolefin, polyether ketone, polyether ether ketone, polyimide, polyetherimide, polyaryleneketone, polyarylene sulfone, polyarylene ether sulfone, polyarylene sulfide, fluoropolymer, polyacetal, polycarbonate, styrenic polymer, polyester or combinations thereof.
7. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the said reinforcing yarns
(A) used in forming the said fabric is manufactured from a material selected from the group including glass, carbon, aramid or natural fiber, or a combination thereof.
8. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the said stitching yarns are thermoplastic.
9. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the said stitched fabric is formed by stitching the said reinforcing yarn layer(s) and the said thermoplastic yarn layer(s) with stitching yarns.
10. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the said stitched fabric comprises reinforcing yarn layer(s) formed by stitching with stitching yarns and thermoplastic yarn layer(s) formed by stitching with stitching yarns.
11. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the said reinforcing yarn layer(s) and the said thermoplastic yarn layer(s) are unidirectional.
12. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the said unidirectional layers comprised by the said stitched fabric is obtained as unidirectional, biaxial, triaxial or multiaxial by stitching them with different angles to each other.
13. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the layers of the said fabric comprising the said unidirectional reinforcing yarns is formed of same kind or hybrid yarns.
14. A thermoplastic prepreg production method according to claims 1-8, characterized in that the said stitched fabric comprises weave fabrics obtained by weaving by using thermoplastic yarn and reinforcing yarn.
15. A thermoplastic prepreg production method according to any one of the preceding claims, characterized in that the ratio of the weight of the said thermoplastic yarn to the weight of the said reinforcing yarn is at least 10%.
PCT/TR2016/050341 2015-12-31 2016-09-08 Thermoplastic prepreg production method WO2017116349A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445701A (en) 1987-05-08 1995-08-29 Research Association For New Technology Development Of High Performance Polymer Apparatus of manufacturing a sheet-prepreg reinforced with fibers
US5464684A (en) 1991-11-14 1995-11-07 Cytec Technology Corp. Hybrid yarn comprising a core of intermixed polyamide filaments and reinforcing rilaments wherein the core is wrapped by a polyamide fiber
WO2012152242A1 (en) * 2011-05-12 2012-11-15 Skl Schwergewebekonfektion Lichtenstein Gmbh Textile multiple-layer reinforcing structure having an integrated thermoplastic matrix for producing fibre-composite semi-finished structures which can be shaped
DE102011102342A1 (en) * 2011-05-24 2012-11-29 C. Cramer, Weberei, Heek-Nienborg, Gmbh & Co. Kg Textile fabric, its use and method for producing composites
US20140030582A1 (en) 2010-09-01 2014-01-30 Lanxess Deutschland Gmbh Emf-shielded plastic prepreg hybrid structural component

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445701A (en) 1987-05-08 1995-08-29 Research Association For New Technology Development Of High Performance Polymer Apparatus of manufacturing a sheet-prepreg reinforced with fibers
US5464684A (en) 1991-11-14 1995-11-07 Cytec Technology Corp. Hybrid yarn comprising a core of intermixed polyamide filaments and reinforcing rilaments wherein the core is wrapped by a polyamide fiber
US20140030582A1 (en) 2010-09-01 2014-01-30 Lanxess Deutschland Gmbh Emf-shielded plastic prepreg hybrid structural component
WO2012152242A1 (en) * 2011-05-12 2012-11-15 Skl Schwergewebekonfektion Lichtenstein Gmbh Textile multiple-layer reinforcing structure having an integrated thermoplastic matrix for producing fibre-composite semi-finished structures which can be shaped
DE102011102342A1 (en) * 2011-05-24 2012-11-29 C. Cramer, Weberei, Heek-Nienborg, Gmbh & Co. Kg Textile fabric, its use and method for producing composites

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