WO2007050467A1 - Processus thermoplastique à fibres longues pour composites conducteurs et composites ainsi obtenus - Google Patents

Processus thermoplastique à fibres longues pour composites conducteurs et composites ainsi obtenus Download PDF

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Publication number
WO2007050467A1
WO2007050467A1 PCT/US2006/041120 US2006041120W WO2007050467A1 WO 2007050467 A1 WO2007050467 A1 WO 2007050467A1 US 2006041120 W US2006041120 W US 2006041120W WO 2007050467 A1 WO2007050467 A1 WO 2007050467A1
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WO
WIPO (PCT)
Prior art keywords
fibers
fiber
thermoplastic
shielding
article
Prior art date
Application number
PCT/US2006/041120
Other languages
English (en)
Inventor
Thomas P. Hager
Original Assignee
Ocv Intellectual Capital, Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ocv Intellectual Capital, Llc filed Critical Ocv Intellectual Capital, Llc
Priority to JP2008537816A priority Critical patent/JP2009512774A/ja
Publication of WO2007050467A1 publication Critical patent/WO2007050467A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/46—Means for plasticising or homogenising the moulding material or forcing it into the mould
    • B29C2045/466—Means for plasticising or homogenising the moulding material or forcing it into the mould supplying the injection unit directly by a compounder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity

Definitions

  • the present invention relates to a polymer article that includes electrically conductive fibers to provide electrical electromagnetic interference (EMI) shielding and their method of manufacture. More particularly, the invention relates to a method for forming shielding materials by impregnating conductive fibers in a polymer material via direct injection of the conductive fibers into the extrusion process.
  • EMI shielded polymers of the present invention may be formed into a wide variety of products such as radio- frequency and electromagnetic shielded plastic articles.
  • a number of electrically conductive materials have been developed to fabricate composite articles, such as plastic articles, for electromagnetic shielding, electrostatic dissipation, and other electrically enhanced characteristics.
  • Plastic articles formed from electrically conductive materials are particularly convenient as compared to traditional metal materials because they are lightweight, easily produced using injection molding techniques, and low cost.
  • these electrically conductive materials are composites of plastics and conductive powders and chopped fibers.
  • FIG. 1 illustrates a traditional thermoplastic extrusion compounding technique, which has been commonly employed.
  • a thermoplastic resin 112 is fed into the compounder 110.
  • the resin 112 is heated to a molten temperature and then fibers or powders (collectively indicated as 114) are fed into the compounder 110 to mix in the conductive powders or chopped fibers.
  • the resin/broken fiber mixture is extruded 118, cooled in a water bath 120, then chopped by a Strand Cutter 122 into pellets 124.
  • Pellets 124 are then typically fed into the melting section of an injection molding machine (not shown).
  • the pellets of the process shown in FIG.l include fibers that are broken due to the cutting action by the screw 116 and by the shear force applied to melt the resin.
  • the fibers are broken during the compounding process so that the resulting composite article contains only relatively short broken fibers.
  • the shortened fibers impart reduced electromagnetic shielding properties to the composite due to their reduced ability to form a conductive fiber network and conduct electricity through the composite article.
  • conductive powders when mixing conductive powders with the molten thermoplastic it is typically necessary to employ a very large amount of the conductive powder. Such large amounts of powder can result in a poor dispersion of the powder or reduced mechanical strength of the final product. Accordingly, composite articles formed with broken fibers and powders require higher loadings or filler concentrations which leads to decreased mechanical strength of the composite article formed and higher material costs.
  • thermoplastic polymer Heating of the thermoplastic polymer during the wire coating process and again during the injection molding process degrades the performance of the polymer. Severe degradation can break down the polymer and form gasses that result in voids and a subsequent loss of shielding and mechanical properties. Additionally, to achieve good mold filling, the polymer must be at a melt flow sufficient to fill ribs or other small features of a part. Melt flow is achieved by the selection of the thermoplastic material, the temperature, dwell time and shear from the screw. High shear from the screw provides for sufficiently high melt flow but breaks the conductive fibers into smaller and smaller lengths and diminishes the ability of the fibers to form a continuous network of fibers.
  • Shielding effectiveness may be determined by ASTM-D4935, which measures far field shielding effectiveness, or by ASTM ES7-83, which measures near field effectiveness.
  • US 2002/0108699 produces a electromagnetic shielded article with a shielding effectiveness of 80-90 dB (far field) and less than 8OdB (near field) at a frequency of 30- 1500 MHz and a 15 wt. % fiber loading.
  • An alternative dry blend method of forming shielded articles requires that chopped conductive fibers are mixed with the resin directly at the injection molding operation.
  • FIG. 1 shows the in-line process according to US 2002/0108699 in which a fiber tow 103 is unwound from a package or spool 105 and drawn through an aqueous silane bath 106 to apply a conductive coating to the tow 103. The tow 103 is then drawn through an aqueous silane bath 104 and through an oven 108.
  • the tow 103 then passes though a nonaqueous sizing bath 107.
  • the tow 103 is then wound onto a package (or spool) 113.
  • the coated fibers are subsequently pelletized and place into the extruder of an injection- molding machine.
  • EMI shielding resins are used in goods such as mobile phones and lap top computers which are expected to resist the impact from a fall of up to a meter or more without breakage.
  • a thermoplastic resin filled to 10-20 wt. % fibers becomes brittle and susceptible to breakage.
  • U.S. Patent No. 6,676,864 entitled "Resin and Fiber Compounding Process for Molding Operations" (herein incorporated in its entirety by reference) describes an apparatus and process for preparing fiber reinforced resin and molding that resin.
  • the '864 Patent shows an injection molding apparatus including a two stage extruder the first to impart shear forces to melt a polymer and the second to feed molten thermoplastic into a mold. Reinforcing fibers, such as glass fibers, carbon-graphite fiber or Kevlar fibers, are supplied between the two stages of the extruder.
  • the molding device of U.S. Patent No. 6,676,864 does not contemplate electromagnetic shielding.
  • the invention answers the problems connected with previous methods of forming EMI shielded polymer.
  • Long fiber thermoplastic technology allows the conductive fibers, to maintain a length sufficient to provide EMI shielding at lower fiber loading.
  • the long fiber thermoplastic process for forming EMI shielding composite articles also provides increased impact resistance, enhanced surface aesthetics and improved extrusion and injection molding processing at a lower material cost and with decreased waste and scrap.
  • FIG. 1 is a schematic representation of a prior art wire coating process for compounding an EMI shielding thermoplastic extrusion material.
  • FIG. 2 is a plan view, partially in cross section, of one extruder useful in practicing the present invention.
  • Thermoplastic resin preferably in the form of pellets, is provided to resin primary extruder 12 from a resin supply 14.
  • the resin may be any of a variety of acceptable thermoplastic resins for the product purpose intended, such as polypropylene, nylon, polyurethane, and polyesters.
  • a melting screw 16 is rotates within melting barrel 18 of extruder 10. While the shear force of melting screw 16 may provide sufficient heating to melt and condition the polymer, the melting barrel 18 may be provided with an additional heat source as is known in the art.
  • a flow control plate 20 may be used at the downstream end of barrel 40 to control the flow of resin 15 out of the extruder barrel 18 and into coating die 22. The plate 20 typically restricts the flow of resin 15 by a reduction in the diameter or by otherwise constricting the flow within the barrel 18.
  • the coating die 22 and any apparatus in contact with the resin 15 may include suitable heat elements to maintain the desired temperature of the resin.
  • the pressure within the coating die may be monitored by a pressure transducer which provides a control signal to the drive motor
  • Fiber spool 24 provides a direct feed of a tow of shielding fibers 26.
  • the shielding fibers may be of any suitable composition for example nickel, copper or and conductive material coated on carbon, aramid, glass or other suitable substrate, alternatively stainless steel, copper or similar metallic fibers may be used.
  • the fibers are pulled though injection nozzle 28 into the coating chamber 32 of coating die 22.
  • the shielding fibers 26 are then intimately blended and coated with the molten polymer material 15.
  • the coated shielding fibers 26 then exit the coating die 22 through die orifice 36 of interchangeable insert 30.
  • the diameter of the die orifice 36 can adjusted by changing insert 30 to control the ratio of shielding fibers 26 to resin 15.
  • the resin 15, fiber 26 mixture exits coating die 22 and the shielding fibers 26 may be cut by blade 52 in cutting chamber 50 in housing 54, 56.
  • the mixture of resin 15 and fibers 26 exit chamber 50 via orifice 58 into extruder 60.
  • the extruder 60 typically includes a barrel 62 that feeds the mixture of resin 15 and fibers 26 into extrusion die 64.
  • a feed screw 66 rotates with barrel 62 and may optionally reciprocate along axis 72 to feed a charge of molding material through orifice 63 into the molding cavity 68 of die 64.
  • the feed screw 66 is driven by a power unit 70.
  • the temperature within the barrel 18, coating chamber 32, cutting chamber 50 and extruder 60 may be controlled by one or more heating elements and temperature probes controlled a microprocessor (not shown).
  • Suitable polymers include thermoplastic polymers such as acrylonitrile-butadiene-styrene (ABS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene (PA) and other thermoplastic materials have suitable mechanical, thermal and melt flow properties.
  • ABS acrylonitrile-butadiene-styrene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PA polyethylene
  • the article molded within molding cavity 68 includes a number of individual shielding fibers 26 where each fiber is of a predetermined length, as established by the action of blade 52.
  • the molded article includes fibers which are roughly 3 times the length of wire-coated and pelletized method shown in FIG. 1. Average lengths from wire coating, pelletizing and injection molding the pellets was about 0.5 mm. Expected average lengths of the Ni-C fiber would be 1.5 mm or more.
  • the shielding properties of the molded material are defined by the number of fibers in contact to create a conductive network.
  • the long fiber thermoplastic should be able to reduce the number of fibers needed to achieve the same connectivity to 1/4 to 1/3 the original amount.
  • LFTP could reduce the fiber needed to as low as 4-5% by weight of composite.
  • Example 1 acrylonitrile-butadiene-styrene (ABS) polymer is melted and 10 % by weight Nickel coated carbon (NCC) fibers are added to the ABS. The fibers are cut to length and the ABS/f ⁇ ber melt is extruded to form a composite part.
  • ABS acrylonitrile-butadiene-styrene
  • NCC Nickel coated carbon
  • Example 2 ABS polymer is melted and 7.5% by weight NCC fibers are added to the ABS. The fibers are cut to length and the ABS/fiber melt is extruded to form a composite part.
  • Example 3 ABS polymer is melted and 5.0% by weight NCC fibers are added to the ABS. The fibers are cut to length and the ABS/f ⁇ ber melt is extruded to form a composite part.
  • the properties of the examples are estimated below.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Reinforced Plastic Materials (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

La présente invention concerne un objet polymère qui comprend des fibres conductrices d’électricité servant à produire un écran contre les interférences électromagnétiques électriques (EMI) et leur procédé de fabrication. L’invention concerne un procédé de fabrication de matériaux écrans en imprégnant des fibres conductrices dans un matériau polymère au moyen de l'injection directe des fibres conductrices dans le processus d'extrusion. L'invention concerne également des polymères écrans aux EMI et des produits qui sont protégés contre les fréquences radio et les radiations électromagnétiques par des éléments constitués du polymère écran.
PCT/US2006/041120 2005-10-24 2006-10-20 Processus thermoplastique à fibres longues pour composites conducteurs et composites ainsi obtenus WO2007050467A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008537816A JP2009512774A (ja) 2005-10-24 2006-10-20 導電複合材料のための長繊維熱可塑性樹脂の製法及びそれにより形成される複合材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US72969505P 2005-10-24 2005-10-24
US60/729,695 2005-10-24

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WO2007050467A1 true WO2007050467A1 (fr) 2007-05-03

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JP (1) JP2009512774A (fr)
CN (1) CN101309959A (fr)
WO (1) WO2007050467A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9469743B2 (en) 2011-12-09 2016-10-18 Industrial Technology Research Institute Composite material with conductive and ferromagnetic properties and hybrid slurry

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GB0917257D0 (en) * 2009-10-02 2009-11-18 Technical Fibre Products Ltd Magnetic material
CN101838470B (zh) * 2009-12-02 2012-06-27 上海科斗电子科技有限公司 电磁屏蔽塑料
CN103238382A (zh) * 2010-10-06 2013-08-07 因特瓦产品有限责任公司 用于提供具有电磁干扰屏蔽的增强复合材料的方法和设备
JP6777710B2 (ja) * 2013-05-30 2020-10-28 ダイセルポリマー株式会社 レーダの送受信アンテナの保護部材
US11917802B2 (en) * 2018-10-16 2024-02-27 Avient Corporation Conductive long fiber thermoplastic compounds for electromagnetic shielding
CN110450488B (zh) * 2019-07-31 2020-07-28 山东大学 一种具有高电磁屏蔽性能的不同堆叠层碳纤维布/tpu复合材料的制备方法

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US5089326A (en) * 1987-05-29 1992-02-18 Phillips Petroleum Company EMI shielded composites and process of making same
US5904980A (en) * 1996-05-13 1999-05-18 Rivas; Victor A. Electromagnetic interference (EMI) shielding and electrostatic discharge degradable polymers and monomers
US6182486B1 (en) * 1997-12-30 2001-02-06 National Science Council Superplastic alloy-containing conductive plastic article for shielding electromagnetic interference and process for manufacturing the same
WO2002002686A2 (fr) * 2000-06-30 2002-01-10 Parker Hannifin Corporation Composites renfermant des fibres dispersees dans une matrice polymere presentant un blindage ameliore au moyen de faibles quantites de fibres conductrices
US20020108699A1 (en) * 1996-08-12 2002-08-15 Cofer Cameron G. Method for forming electrically conductive impregnated fibers and fiber pellets
EP1336645A1 (fr) * 2000-10-26 2003-08-20 NIPPON A&L INC. Composition de resine thermoplastique attenuant les interferences electromagnetiques et ignifugeante

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US4566990A (en) * 1982-11-05 1986-01-28 General Electric Company Synergistic effect of metal flake and metal or metal coated fiber on EMI shielding effectiveness of thermoplastics
US5089326A (en) * 1987-05-29 1992-02-18 Phillips Petroleum Company EMI shielded composites and process of making same
US5904980A (en) * 1996-05-13 1999-05-18 Rivas; Victor A. Electromagnetic interference (EMI) shielding and electrostatic discharge degradable polymers and monomers
US20020108699A1 (en) * 1996-08-12 2002-08-15 Cofer Cameron G. Method for forming electrically conductive impregnated fibers and fiber pellets
US6182486B1 (en) * 1997-12-30 2001-02-06 National Science Council Superplastic alloy-containing conductive plastic article for shielding electromagnetic interference and process for manufacturing the same
WO2002002686A2 (fr) * 2000-06-30 2002-01-10 Parker Hannifin Corporation Composites renfermant des fibres dispersees dans une matrice polymere presentant un blindage ameliore au moyen de faibles quantites de fibres conductrices
EP1336645A1 (fr) * 2000-10-26 2003-08-20 NIPPON A&L INC. Composition de resine thermoplastique attenuant les interferences electromagnetiques et ignifugeante

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9469743B2 (en) 2011-12-09 2016-10-18 Industrial Technology Research Institute Composite material with conductive and ferromagnetic properties and hybrid slurry

Also Published As

Publication number Publication date
CN101309959A (zh) 2008-11-19
US20070134482A1 (en) 2007-06-14
JP2009512774A (ja) 2009-03-26

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