EP2812184A1 - Matériau composite plan - Google Patents

Matériau composite plan

Info

Publication number
EP2812184A1
EP2812184A1 EP13707292.2A EP13707292A EP2812184A1 EP 2812184 A1 EP2812184 A1 EP 2812184A1 EP 13707292 A EP13707292 A EP 13707292A EP 2812184 A1 EP2812184 A1 EP 2812184A1
Authority
EP
European Patent Office
Prior art keywords
composite material
material according
layers
layer
fibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13707292.2A
Other languages
German (de)
English (en)
Inventor
Burak Baser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Quadrant Plastic Composites AG
Original Assignee
Quadrant Plastic Composites AG
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 Quadrant Plastic Composites AG filed Critical Quadrant Plastic Composites AG
Priority to EP13707292.2A priority Critical patent/EP2812184A1/fr
Publication of EP2812184A1 publication Critical patent/EP2812184A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered 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
    • B32B5/22—Layered 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
    • B32B5/24—Layered 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
    • B32B5/26—Layered 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
    • 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
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
    • B29C39/20—Making multilayered or multicoloured articles
    • B29C39/203—Making multilayered articles
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/30—Making multilayered or multicoloured articles
    • B29C43/305—Making multilayered articles
    • 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
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
    • B29C51/145—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets having at least one layer of textile or fibrous material combined with at least one plastics layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/24—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least three directions forming a three dimensional structure
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    • 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]
    • B29C70/504—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] using rollers or pressure bands
    • B29C70/506—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] using rollers or pressure bands and impregnating by melting a solid material, e.g. sheet, powder, fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00—Layered 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
    • B32B5/02—Layered 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
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    • B32B5/00—Layered 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
    • B32B5/02—Layered 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
    • B32B5/06—Layered 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/02—Layered 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
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    • B32B5/02—Layered 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
    • B32B5/10—Layered 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 reinforced with filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/02—Layered 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
    • B32B5/12—Layered 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
    • 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
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    • 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
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • Y10T428/24058—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
    • Y10T428/24074—Strand or strand-portions
    • Y10T428/24091—Strand or strand-portions with additional layer[s]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24132—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in different layers or components parallel

Definitions

  • the invention relates to a sheet-like composite material according to the preamble of claim 1 and a method for its production and a use thereof.
  • Thermoplastics are used because of their low weight increasingly for the production of moldings, in particular of components for motor vehicles. To give them sufficient strength and rigidity, they are usually bonded with reinforcing fibers.
  • flat semi-finished products made of glass mat-reinforced thermoplastics are produced by combining endless glass fiber mats with random fibers and thermoplastic melt webs and consolidating on a double belt press. From the flat semi-finished product obtained can be produced by hot pressing in a mold components.
  • the fiber reinforcement is undirected, that is, it acts uniformly in all directions without preferential direction, so that the strength of such composites is limited. In many cases, however, you need components that are reinforced in preferred directions.
  • WO 2006/1 1 1037 a planar composite material is described which contains a nonwoven layer of thermoplastic fibers and a fabric or scrim layer of parallel reinforcing fiber bundles.
  • the individual layers can either be stitched together, sewn together or thermally bonded together.
  • This composite material can be processed by hot pressing into components with targeted reinforcement.
  • the fiber bundles When needling, the fiber bundles are opened and the fibers are partially broken. In the process, however, the individual fibers are displaced slightly relative to one another, so that the orientation is partially canceled and the reinforcing effect is reduced.
  • the fiber bundles When sewing the individual fiber bundles through Binding threads connected to each other and to the fibers of the nonwoven layer. In this case, however, the fiber bundles are not opened, so that the thermoplastic melt can impregnate the fabric or scrim layer only incompletely, which leads to lower carrying capacity of components produced therefrom.
  • the invention therefore an object of the invention to provide fiber reinforced reinforced composite materials that do not have the respective disadvantages mentioned. Another object was to provide sheet composites that have multi-directional reinforcement from which components with bidirectional reinforcement can be made.
  • EP 0 203 803 A1 relates to a reinforced resin composition which contains layers of parallel reinforcing fibers and buffer layers of aramid fibers.
  • the fiber structure is embedded in a hardened resin.
  • Aramid fibers are high-performance reinforcing fibers made of an aromatic polyamide, which, in contrast to aliphatic polyamides, are not meltable and therefore can not be processed thermoplastically.
  • US 3,761,345 A describes a fibrous structure which can absorb a resin. This can be made by curing the resin glass fiber reinforced resin article.
  • the fiber structure consists of a plurality of layers. In these, the fibers may be either unidirectional or in the form of loops; furthermore, the middle layer can also consist of tangled bundles of short cut fibers.
  • Non-woven fabric layers in which the fibers at least partially consist of a thermoplastic are not disclosed in US Pat. No. 3,761,345 A, moreover the production of components or semi-finished products by thermoplastic hot-pressing of the composite
  • the invention thus relates to a planar composite material, comprising at least one layer A of a nonwoven fabric consisting of 40 to 100 wt .-% thermoplastic fibers and 60 to 0 wt .-% reinforcing fibers, or a thermoplastic film, and
  • the layers are sewn together as well as needled.
  • thermoplastic is to be understood to mean that the respective materials are meltable and thermoplastically deformable under conventional processing conditions.
  • the nonwoven fabric of the layer A contains up to 50 wt .-% reinforcing fibers. According to another advantageous embodiment, the nonwoven fabric of the layer A contains no reinforcing fibers and is accordingly formed solely from thermoplastic fibers. According to a further advantageous embodiment, the layer A is formed from a thermoplastic film. "Bidirectional" in the context of two fiber webs B and B 'means that the longitudinal axis of the fiber web B is not parallel to the longitudinal axis of the fiber web B'. Another object of the invention are methods for producing such composite materials. There are two variants:
  • the nonwoven layer (s) A are produced according to the carding, Airlay or spunbonding method or else according to the so-called papermaking method, then the bidirectionally aligned scrim layers B and B 'are produced with the or the layer (s) A continuously merged. The layers are then sewn together and then needled.
  • Preferred layer arrangements are B - A - B 'and B - A - B' - A - B. Further arrangements with several, up to 20 layers are possible. It is preferred that always a nonwoven or thermoplastic film layer A is disposed between two scrim layers B and B '. For special applications, an arrangement in which a layer A is outside is possible.
  • the fiber orientation of the layers B and B ' is bidirectional, preferred orientations are 0 90 °, 30 -30 °, 457-45 ° and 607-60 ° with respect to a reference direction in the layer arrangement such as the longitudinal axis L. Accordingly, the acute inter-angle is between the respective fiber directions preferably 60 ° or 90 °.
  • the layer layers are preferably to be arranged symmetrically. FIG.
  • the basis weights of the individual layers are preferably between 20 and 1 ⁇ 00 g / m 2 , in particular 30 to 1 ⁇ 00 g / m 2 , especially between 150 and 300 g / m 2 .
  • the individual scrim layers can also have different basis weights.
  • the basis weights are to be selected so that the proportion of the total reinforcing fibers in the composite material is preferably 20 to 80 wt .-%, in particular 30 to 70 wt .-% and particularly preferably about 60 wt .-%.
  • Preferred reinforcing fibers are glass fibers and carbon fibers, besides aramid fibers, basalt fibers, natural fibers, and fibers of higher melting polymers and hybrid fibers, such as glass fibers and polypropylene fibers are suitable.
  • the types of fibers in each layer are the same.
  • the reinforcing fibers of the fabric are preferably present as fiber bundles with a titer between 300 and 4,800 tex.
  • Preferred thermoplastics in the nonwoven fabric or in the thermoplastic film are polypropylene and fusible polyamides, in particular aliphatic polyamides; In addition, other thermoplastics such as polyesters, polyethersulfone, polyether ketones and polyetherimide are suitable.
  • Polyether ketones are characterized in particular by a good temperature resistance.
  • Composites with particularly good flowability are obtained when the thermoplastic polypropylene with a melt flow index (MFI) (230 ° C, 2.16 kg) between 10 and 400, in particular at about 120 g / 10 min.
  • MFI melt flow index
  • the thermoplastics for making the nonwoven fabric layer A can be provided in very different dimensions and geometries. The individual layers of the composite material are sewn together as well as needled.
  • Suitable sewing threads can be formed from glass, polypropylene, polyamide, as well as from PET or polyether ketones. Acetate and viscose threads can also be used.
  • the sewing threads are formed of the same thermoplastic as the thermoplastic fibers or the thermoplastic film of the layer A, preferably therefore of polypropylene or polyamide.
  • FIG. 2 shows the layer arrangement B-A-B 'of FIG. 1 in a cross-section along the fiber orientation of the layer B after sewing.
  • the sewing thread N connects the fiber bundles of the layers B 'and B. As a result, this layer arrangement is still needled.
  • Needling can be done on standard needle chairs with felt nails.
  • the number of pinholes may be between 5 and 100 per cm 2 , in particular between 20 and 40 punctures per cm 2 .
  • thermoplastic melt from the nonwoven fabric or the thermoplastic film can penetrate during the subsequent hot pressing in the Gelege- layers and this can soak evenly.
  • sewing thread consists of the same thermoplastic, it also melts when hot-pressing; he is no longer required after that anyway.
  • the sheetlike composite materials according to the invention can be pressed directly into three-dimensional components at temperatures above the softening range of the thermoplastic in molds, or they can be pressed by hot pressing, e.g. in a double belt press, to flat semi-finished products, preferably with a thickness of 0.5 to 5 mm, be consolidated.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Laminated Bodies (AREA)
  • Nonwoven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un matériau composite plan, comprenant au moins une couche A dans un non-tissé thermoplastique ou une feuille thermoplastique et au moins deux couches de canevas de fibres unidirectionnelles B et B', les couches B et B' présentant une orientation des fibres bidirectionnelle. Les couches sont aussi bien cousues ensemble que aiguilletées.
EP13707292.2A 2012-02-08 2013-02-08 Matériau composite plan Withdrawn EP2812184A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13707292.2A EP2812184A1 (fr) 2012-02-08 2013-02-08 Matériau composite plan

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12154516.4A EP2626200A1 (fr) 2012-02-08 2012-02-08 Matière première composite plate
EP13707292.2A EP2812184A1 (fr) 2012-02-08 2013-02-08 Matériau composite plan
PCT/EP2013/052616 WO2013117743A1 (fr) 2012-02-08 2013-02-08 Matériau composite plan

Publications (1)

Publication Number Publication Date
EP2812184A1 true EP2812184A1 (fr) 2014-12-17

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EP12154516.4A Ceased EP2626200A1 (fr) 2012-02-08 2012-02-08 Matière première composite plate
EP13707292.2A Withdrawn EP2812184A1 (fr) 2012-02-08 2013-02-08 Matériau composite plan

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US (3) US20150030804A1 (fr)
EP (2) EP2626200A1 (fr)
CN (1) CN104169077B (fr)
WO (1) WO2013117743A1 (fr)

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CN104859155A (zh) * 2015-05-11 2015-08-26 华东理工大学 一种具有三维结构的连续纤维增强热塑性板材的制备方法
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CN106677129B (zh) * 2016-12-28 2018-11-02 上海蓝坤环境科技有限公司 一种点状针刺复合表层热熔抗冲刷的网络结构的加工方法
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US20150030804A1 (en) 2015-01-29
CN104169077A (zh) 2014-11-26
US20200238659A1 (en) 2020-07-30
WO2013117743A1 (fr) 2013-08-15
US20180001594A1 (en) 2018-01-04
EP2626200A1 (fr) 2013-08-14
CN104169077B (zh) 2017-02-22

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