EP0221434B1 - Amélioration de la conductibilité de matières plastiques contenant des matières de charge métalliques - Google Patents

Amélioration de la conductibilité de matières plastiques contenant des matières de charge métalliques Download PDF

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Publication number
EP0221434B1
EP0221434B1 EP86114549A EP86114549A EP0221434B1 EP 0221434 B1 EP0221434 B1 EP 0221434B1 EP 86114549 A EP86114549 A EP 86114549A EP 86114549 A EP86114549 A EP 86114549A EP 0221434 B1 EP0221434 B1 EP 0221434B1
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EP
European Patent Office
Prior art keywords
composite
insulating material
group
thermoplastic
ionization potential
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Expired - Lifetime
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EP86114549A
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German (de)
English (en)
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EP0221434A1 (fr
Inventor
Stefan Jacek Rzad
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General Electric Co
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General Electric Co
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Classifications

    • 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
    • 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

Definitions

  • the present invention relates to electrically conductive plastic composite materials and particularly to methods for making such materials. More particularly, this invention relates to a method for increasing the electrical conductivity of such composite materials and to the products of such a method. While the invention relates primarily to solid or foamed resinous composites, it is believed that the principles of the invention may be applicable to materials other than resinous materials including various other high resistivity composite materials such as ceramics, wood composites, and concrete, for example.
  • the improved electrical conductivity of these materials is based on the fact that the metal fibers or filaments, which are of relatively short length are either in direct contact with each other at enumerable points throughout the volume of the plastic or are so closely adjacent each other that despite the small separation by the plastic, improved conductivity nevertheless results.
  • thermoplastics the short lengths of metal coated fibers or conductive filaments are combined with fluid polymerizable material.
  • the many individual lengths of conductive filaments develop a thin film of the insulating plastic thereon.
  • This thin insulating film may increase the distance between adjacent conductive fibers in the finished material to the extent that the desired electrical conductivity is not achieved.
  • the metallic or conductive fibers are interspersed throughout the volume of the plastic in a three dimensional random network, the overall conductivity of the plastic is the cumulative effect of the conductivity of the many various individual current paths between adjacent metallic elements.
  • One obvious way to increase conductivity in such composites is to increase the ratio of metallized particles or fibers carried in the material.
  • EP-A-0144127 describes an insulating polymer film containing a metallic element, the electrical conductivity of which is realized by treating the film in an electrochemical polymerization solution of acetonitrile-tetrahydrofuran- chlorobenzene containing pyrrole and tetraethyl ammonium perchlorate.
  • a yet further object of the invention is to produce a conductive plastic composite having a given electrical conductivity with a lower weight percentage of conductive material therein.
  • the product of the above-noted process is highly useful for various applications such as enclosures for electronic equipment where conductivity, shielding, and grounding are important including, for example, cabinetry for electronic equipment such as communications equipment, instruments and computers.
  • the intended improvement in the electrostatic shielding capability of plastic composite materials may be sufficiently great to allow their use as a low cost alternative to metallic enclosures.
  • a method of forming a composite having increased electrical conductivity comprising an electrically insulating material having a gas phase ionization potential ranging between 8.3 and 9.3 eV and having disposed therein metallic elements, characterized in that it comprises incorporating into said composite 0.1 to 10% by weight of said insulating material of an adder material having a gas phase ionization potential 15 to 30% less than the insulating material.
  • the method of the present invention relates primarily to a wide variety of conductive resinous composite materials, such as conductive plastic composite materials where the plastics include both thermoplastics and thermosets.
  • suitable thermoplastics include, but are not limited to polycarbonates, polyesters, oxide polymers, polyurethanes, polyamides, acrylics, polyvinylchlorides and hydrocarbon polymers.
  • suitable thermosets include, but are not limited to polyesters, epoxies, ureas and silicones.
  • Suitable conductive materials useful for incorporation into the plastic composites include various types of metal fibers and ribbons and metal particles of various shapes, metallized glass, metallized graphite or other conductive or nonconductive fibers, and carbon fiber and carbon particles of various shapes.
  • the choice metal is wide; however, for practical reasons the choice is usually narrowed to inexpensive metals that have good conductivity and are easily formed.
  • Aluminum is the most preferred as fitting the above criteria. However, the processes are equally applicable to composites having other metals such as stainless steel, silver, copper, zinc, iron, nickel, carbon steel, etc. and mixtures thereof.
  • metallized glass fibers are preferably coated with aluminum due to the above criteria and due to its low melting point, which facilitates its manufacture.
  • test samples were cut from molded plaques of the designated matrix of base material.
  • the samples were typically 6 cm long, 0.5 cm wide and 0.33 cm thick.
  • the small sides of each sample 0.5x0.331 were painted with Dupont conducting paint 4817 and the resistance between them measured before and after treatment, using a Beckman RMS3030 multimeter. From the measured resistance the resistivity was then calculated and is reported in the Tables.
  • a plurality of samples cut from molded plaques of a polymer that is sold under the trademark Noryl ® and which. are designated as SE90-960 and containing 6% by weight stainless steel fibers were exposed in a bell jar at atmospheric pressure to a vapor of N,N' dimethylaniline (DMA).
  • DMA N,N' dimethylaniline
  • the table below relates the resistivity of each sample before exposure to the DMA with the resistivity after absorption of the listed % by weight of DMA.
  • Noryl O resin designated as SE90-GH100, also containing 6% by weight of stainless steel fibers were tested as in Example 1 above and Table 11 reflects the results of such tests.
  • Example 3 Same as Example 3 except that the test samples were exposed to vapors of tetrathia fulvalene (TTF) under a vacuum at 130°C. Measurements were taken as in the previous examples with Table IV below reflecting the values measured.
  • TTF tetrathia fulvalene
  • Example 4 Same as Example 4 except that the test samples were exposed to vapors of N,N,N',N' tetramethyl p-phenylene diamine (TMPD) under vacuum at 60°C. Measurements were taken as in the previous examples and are reflected in Table V below.
  • TMPD N,N,N',N' tetramethyl p-phenylene diamine
  • Example 5 Again a procedure similar to Example 5 was performed with the exception that Lexan ® polycarbonate samples were exposed to vapors of 2-methyl naphthalene (2MN) in air at atmospheric pressure at 50°C. Table Vl shows the values of resistivity measured before and after addition of 2MN to the test samples at stated concentrations of 2MN.
  • 2MN 2-methyl naphthalene
  • Example 5 Again a procedure similar to Example 5 was performed with the exception that the Lexan @ polycarbonate contained 26% by weight aluminum flakes and was exposed to DMA in air in a bell jar at atmospheric pressure. Table VII shows the values of resistivity measured before and after the treatment.
  • the low ionization materials used in the examples above are but a few of those which could be used to achieve a similar result.
  • the ionization potential of a material refers to the energy required to remove an electron from the highest filled orbital (most loosely bound electron) of a neutral molecule of such material in its ground state.
  • a low ionization potential material is, therefore, generally characterized by the fact that, when added to the base plastic/ metallic composites, it operates to supply electrons upon the application of a relatively small electrical potential, and thereby increases the overall conductivity of the composite.
  • These materials must, of course, be selected in part, based on their compatability with the matrix or base plastic material employed.
  • the gas phase ionization potentials for the materials used in the examples discussed above are as follows: N,N' DMA, 7.14 eV; 2MN, 7.96 eV; TMPO 6.33 eV and TTF, 7.0 eV.
  • the base or matrix polymer materials have gas phase ionization potentials which range between 8.3 eV and 9.3 eV.
  • materials having an ionization potential in the range between 15%-30% lower than the matrix plastic material have been shown to produce significant reductions in resistivity. It is believed that a broader range of matrix/low ionization potential materials may be utilized to produce similar effects.
  • the effective percentages by weight of low ionization potential materials needed in order to produce a measurable reduction in resistivity may vary considerably based on the specific makeup of the composite. Generally, however, a mini-mum value of approximately 0.1% by weight appears plausible based on the above examples.
  • the maximum amount of low ionization material will likely be governed in large measure by the impact such larger amounts of the low ionization potential material will have on the overall chemical and physical properties of the composite. In general, an upper limit of approximately 10% by weight is predicted.
  • Some low ionization materials may exhibit instability when combined with specific base plastics, however, it is believed that suitable stable compositions may be selected or, alternatively, known stabilizing techniques employed to improve the characteristics of the final composite.
  • the low ionization potential materials were added to a previously prepared base composite plastic/metal filler material
  • the thermoplastic composition may be heated within an extruder to a temperature sufficiently high to provide a viscosity that allows the thermoplastic polymer to flow and be blended with other constituents.
  • temperatures will, of course, depend on the thermoplastic selected.
  • the low ionization potential adder material and metallic filler are injected into the extruder at a point where the thermoplastic composition is molten.
  • conventional techniques are utilized to obtain a uniform dispersion of the constituents within the composite material.
  • the resulting blended composition may then be passed through a die at the end of the extruder and pelletized. These pellets may be subsequently utilized in extrusion processes, injection molding processes, etc. to obtain finished products, suitable for a particular high conductivity application.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (16)

1. Procédé pour former un composite ayant une conductibilité électrique accrue, ledit composite comprenant une matière électriquement isolante ayant un potentiel d'ionisation en phase gazeuse compris dans la gamme de 1,33 à 1,49 aJ (8,3 à 9,3 eV) dans laquelle des éléments métalliques sont dispersés, caractérisé en ce qu'il comprend l'incorporation audit composite de 0,1 à 10%, relativement au poids de ladite matière isolante, d'un additif ayant un potentiel d'ionisation en phase gazeuse inférieur de 15 à 30% à celui de la matière isolante.
2. Procédé selon la revendication 1, dans lequel lesdits éléments métalliques sont choisis dans le groupe constitué par l'aluminium, l'acier inoxydable, l'argent, le cuivre, le zinc, le fer, le nickel, l'acier au carbone et leurs mélanges.
3. Procédé selon la revendication 1, dans lequel ladite matière isolante est choisie dans le groupe constitué par les matières thermoplastiques et thermodurcissables.
4. Procédé selon la revendication 3, dans lequel ladite matière isolante est une matière thermoplastique.
5. Procédé selon la revendication 4, dans lequel ladite matière thermoplastique est choisie dans le groupe constitué par les polycarbonates, les polyamides, les polyesters, les polymères d'oxydes, les polyuréthannes, les acryliques, les chlorures de polyvinyle et les polymères d'hydrocarbures.
6. Procédé selon la revendication 1, dans lequel la matière isolante est une matière résineuse.
7. Procédé selon la revendication 1, dans lequel lesdits éléments métalliques sont choisis dans le groupe constitué par les fibres de verre revêtues de métal, les fibres de graphite revêtues de métal et les bandelettes d'aluminium.
8. Procédé selon la revendication 1, caractérisé en ce que ledit additif est choisi dans le groupe constitué de la N,N'-diméthylaniline, la N,N,N',N'- tétraméthyl-p-phénylènediamine, le 2-méthyl- naphtalène et le tétrathiafulvalène.
9. Composite conducteur perfectionné comprenant une matière électriquement isolante ayant un potentiel d'ionisation en phase gazeuse compris entre 1,33 et 1,40 aJ (8,3 et 9,3 eV) et des éléments de matières de charge métalliques dispersés, caractérisé en ce qu'on lui a incorporé 0,1 à 10%, relativement au poids de ladite matière isolante, d'un additif ayant un potentiel d'ionisation en phase gazeuse inférieur de 15 à 30% à celui de la matière isolante.
10. Composite selon la revendication 9, dans lequel lesdits éléments métalliques sont choisis dans le groupe constitué par l'aluminium, l'acier inoxydable, l'argent, le cuivre, le zinc, le fer, le nickel, l'acier au carbone et leurs mélanges.
11. Composite selon la revendication 9, dans lequel ladite matière isolante est choisie dans le groupe constitué par les matières thermoplastiques et thermodurcissables.
12. Composite selon la revendication 11, dans lequel ladite matière isolante est une matière thermoplastique.
13. Composite selon la revendication 12, dans lequel ladite matière thermoplastique est choisie dans le groupe constitué par les polycarbonates, les polyamides, les polyesters, les polymères d'oxydes, les polyuréthannes, les acryliques, les chlorures de polyvinyle et les polymères d'hydrocarbures.
14. Composite selon la revendication 9, dans lequel la matière isolante est une matière résineuse.
15. Composite selon la revendication 9, dans lequel les éléments métalliques sont choisis dans le groupe constitué par les fibres de verre revêtues de métal, les fibres de graphite revêtues de métal et les bandelettes d'aluminium.
16. Composite selon la revendication 9, caractérisé en ce que ledit additif est choisi dans le groupe constitué de la N,N'-diméthylaniline, la N,N,N',N,'-tétraméthyl-p-phénylènediamine, le 2-méthylnaphtalène et le tétrathiafulvalène.
EP86114549A 1985-11-04 1986-10-21 Amélioration de la conductibilité de matières plastiques contenant des matières de charge métalliques Expired - Lifetime EP0221434B1 (fr)

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US79499585A 1985-11-04 1985-11-04
US794995 1985-11-04

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EP0221434A1 EP0221434A1 (fr) 1987-05-13
EP0221434B1 true EP0221434B1 (fr) 1990-03-14

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JP (1) JPS62135564A (fr)
DE (1) DE3669611D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4997674A (en) * 1987-06-30 1991-03-05 Akzo America Inc. Conductive metallization of substrates via developing agents
US4961879A (en) * 1988-06-08 1990-10-09 Akzo America Inc. Conductive metal-filled substrates via developing agents
US5252255A (en) * 1988-06-08 1993-10-12 Akzo America Inc. Conductive metal-filled substrates via developing agents
US6524721B2 (en) * 2000-08-31 2003-02-25 Matsushita Electric Industrial Co., Ltd. Conductive adhesive and packaging structure using the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0663237A (ja) * 1992-08-25 1994-03-08 Osamu Ishitobi パチンコ台及びパチンコ台配置構造

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0131067B2 (fr) * 1983-07-11 1995-08-16 Toshiba Chemical Corporation Matériau conducteur moulable en résine synthétique
JPS6063237A (ja) * 1983-09-14 1985-04-11 Nissin Electric Co Ltd 電界緩和用高分子組成物
US4559112A (en) * 1983-10-07 1985-12-17 Nippon Telegraph & Telephone Electrically conducting polymer film and method of manufacturing the same
GB2156361B (en) * 1984-03-07 1987-07-15 Mitsui Toatsu Chemicals Iodine-containing conductive resin composition
DE3431132A1 (de) * 1984-08-24 1986-03-06 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von verbundstoffen aus nichtleitenden und intrinsisch leitfaehigen polymeren

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0663237A (ja) * 1992-08-25 1994-03-08 Osamu Ishitobi パチンコ台及びパチンコ台配置構造

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JPS62135564A (ja) 1987-06-18
EP0221434A1 (fr) 1987-05-13
DE3669611D1 (de) 1990-04-19

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