EP1115122A1 - Electrically conductive inorganic polymer - Google Patents

Electrically conductive inorganic polymer Download PDF

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Publication number
EP1115122A1
EP1115122A1 EP00126467A EP00126467A EP1115122A1 EP 1115122 A1 EP1115122 A1 EP 1115122A1 EP 00126467 A EP00126467 A EP 00126467A EP 00126467 A EP00126467 A EP 00126467A EP 1115122 A1 EP1115122 A1 EP 1115122A1
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Prior art keywords
metal
polymer
main stage
copper
stage
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EP00126467A
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German (de)
French (fr)
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EP1115122B1 (en
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Walter Dr. Schmid
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    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of 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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides

Definitions

  • the invention relates to an electrically conductive inorganic polymer containing at least one metal a) which is selected from the group consisting of copper, an alkali metal and an alkaline earth metal, and at least one metal b) which is selected from the group consisting of a metal of the 1st, 2nd, 4th, 5th, 6th, 7th and 8th subgroup as well as the 3rd, 4th and 5th, Main group of the periodic table from atom number 31, a polymer intermediate and a process for producing the inorganic Polymer.
  • JP 62084091 A is an electrically conductive inorganic polymer known that contains a metal of the 5th group. To make this polymer is a metal dithiolate complex with a metal of the 5th group thermal decomposes.
  • the object of the present invention is to provide an electrically conductive To provide inorganic polymer that not only has a high has electrical conductivity, but also good mechanical properties owns and can be easily processed.
  • the electrically conductive inorganic polymer according to the invention is hereinafter only called polymer and is based on three main stages comprehensive procedures available. Is it the inventive Metal a) around copper, then a preliminary stage must be carried out in which Copper carbonate with an oxide of at least one metal b) with the addition of Water is mixed to a pulp. This turns the water into heat evaporates.
  • the material obtained can be pulverized, for example become.
  • copper carbonate includes pure copper carbonate, hydrated copper carbonate and hydroxy carbonates of copper.
  • the polymer of the invention is a carbonate of at least one metal a) with the exception of copper and / or that obtained according to the preliminary stage, copper-containing material with at least one oxide of a metal b) merged.
  • a metal in which it is used as metal b) for this metal oxide a metal from the 1st and 2nd as well as the 4th to 8th subgroup and the III. to V. Main group of the periodic table from atom number 31.
  • the oxide can become a Metal b) also copper oxide or an oxide of another metal b) act.
  • an alkali and / or alkaline earth carbonate is used, it means that a single alkali carbonate, a only alkaline earth carbonate, a mixture of several alkali carbonates, one Mixture of several alkaline earth carbonates or a mixture of one or more alkali carbonate (s) and one or more Alkaline earth carbonate (s) can be used.
  • a single alkali carbonate, a only alkaline earth carbonate, a mixture of several alkali carbonates, one Mixture of several alkaline earth carbonates or a mixture of one or more alkali carbonate (s) and one or more Alkaline earth carbonate (s) can be used.
  • the metal oxide applies the like.
  • the alkali and / or alkaline earth carbonate and / or that in the pre-main stage can be coated with an oxide of one, two, three, etc. Metals b) are fused.
  • the weight ratio of carbonate or the material of the precursor to the oxide is in the 1st main stage preferably 25:75 to 60:40. With this range, all of them encompassed narrower, at least integer range, and thus disclosed, for example 30:70; 35:65; 38:72; 45:55; 50:50; 53:47 and 58:42.
  • the melt obtained in the first main stage expediently becomes slow cooled and then ground if necessary.
  • the material obtained in the first main stage is marked with a fused another oxide of a metal b). It can therefore be an oxide trade one, two, three or more of the metals b).
  • metal b) according to the invention one from the 1st, 2nd, 4th, 5th, 6th, 7th and 8th Subgroup and the 3rd, 4th and 5th main group of the periodic table from Atom number 31 used.
  • the specification "from atomic number 31" relates only on the metals of the main groups.
  • the material obtained in the 1st main stage becomes in the 2nd main stage preferably used in excess.
  • the weight ratio of that in the 1st main stage material obtained to the oxide is in 2nd main stage preferably 60:40 to 70:30.
  • the first main stage is heated to a temperature which is lower than the temperature in the 2nd main stage.
  • The is preferably Temperature in the 1st main stage 300 to 850 ° C and in the 2nd main stage 700 to 1200 ° C.
  • the product obtained after the 2nd main stage is used in the present Documentation referred to as an intermediate polymer product, that too valuable End products can be processed, which is discussed below becomes.
  • the 1st and 2nd Main stage used the same metal oxide or the same metal oxides.
  • Titanium, vanadium, nickel preferably serve as metal b) for the metal oxide, Gallium, germanium, molybdenum, rhodium, indium, antimony, tellurium, tungsten, Rhenium, iridium, thallium, bismuth, copper, gold, silver and zinc.
  • the melt obtained in the 2nd main stage can be allowed to cool, expediently slow.
  • the resulting polymer intermediate can then be pulverized, for example ground, and already has an electrical conductivity.
  • This intermediate polymer product can then be processed further.
  • To it is preferably in a 3rd main stage in an aqueous solvent solved, for example with the help of acids or alkalis, and then galvanically, with reduction in an electrolytic cell on a particularly conductive Deposited substrate which is poled as a cathode.
  • a direct current source such as a battery, or a regulated power supply unit can serve as the current source for the operation of this electrolytic cell.
  • the voltage is expediently in the range from about 1 to 25 V.
  • a voltage in the range from 2 to 12 V has proven to be particularly expedient.
  • the current density is usually in the range from 1 to 100 mA / cm 2 , further preferably in the range from 1.0 to 35 mA / cm 2 .
  • the electrolyte solution should not exceed the temperature of + 80 ° C. in the generally has a reaction temperature in the range of + 40 ° C to + 70 ° C proved to be very advantageous.
  • the coating deposited on a substrate in this way is the final electrically conductive inorganic polymer.
  • the powdered polymer intermediate as described above can according to a further preferred embodiment in the 3rd main stage again melted and then reduced. Both for this melting as well as for the melting processes in the 1st and 2nd main stage expediently a suitable crucible in which the melting substances and materials can be entered.
  • the melt from the polymer intermediate can not be otherwise can only be obtained by - as described above - after the second
  • the intermediate polymer obtained in the main stage melts again.
  • Man can also use the melt obtained in the 2nd main stage directly without to cool this melt beforehand.
  • the melt from the polymer intermediate is then preferred electrolytically, using a real gas or using a reducing agent reduced with a reduction potential of -0.100 to -0.900 E ° inV. At this Reduction polymer crystals separate from the melt.
  • the melt from the intermediate polymer this is melted in a crucible at 650 to 900 ° C.
  • the electrolysis is carried out with direct current, a current density of 10 to 35 mA / cm 2 being preferred.
  • the voltage depends on the melt composition and should be 0.8 to 3.5 V. Those made of graphite or precious metal have proven themselves as electrodes.
  • the polymer according to the invention is deposited in the form of crystals on these electrodes, more precisely the cathode. These are then removed and expediently washed and dried.
  • this reduction can also be carried out by simply: a reducing agent is immersed in the melt. You can do this, for example Use an iron rod on which the crystals from the Form polymer according to the invention.
  • crystals with a perovskite-like structure and a tetragonal symmetry are obtained.
  • the density of the crystals is in particular 4 to 20 g / cm 3 .
  • the polymer according to the invention is very well conductive and has advantageous mechanical properties. It can act as a leader in the Electrical industry, medical technology, electroplating and auto industry used become.
  • the polymer according to the invention can be easily processed and deposit on substrates in the form of a coating. It also has a good acid and alkali resistance.
  • the conductivity of the polymer according to the invention on a Excess of electrons is based and these are freely movable and over the crystals are distributed.
  • the crystals can be viewed as doped metal oxides, where the conductivity of the content of alkali metal and / or alkaline earth metal and / or copper depends. Salts of alkali metals can thus be used as doping agents and / or alkaline earth metals and / or copper.
  • the electrical conductivity thus seems to be based on a mechanism that is different from an alloy or an intermetallic Connection.
  • oxides of metals b) in the 1st and 2nd main stage of a process for All oxides can also be used to prepare the polymers according to the invention of the metals used.
  • the invention also relates to a method for producing a electrically conductive inorganic polymer or polymer intermediate and use as a leader in the electrical industry, Medical technology, electroplating and auto industry.
  • the ranges specified within the scope of the present documents indicate all values between the range limits, at least whole numbers, and are thus disclosed. This applies regardless of the unit of measurement for the specified ranges, be it ° C, V, mA / cm 2 and weight ratios.
  • the range specification also includes all smaller / narrower range specifications contained therein.
  • the invention is preferred below with reference to the following Examples describing embodiments are explained in more detail.
  • the parts information refer to parts by weight.
  • a mixture of 6 parts of sodium carbonate (Na 2 CO 3 ) and 4 parts of titanium oxide (Ti 2 O 3 ) is produced. This mixture is heated in a crucible with melting to a temperature of 400 ° C.
  • the melt thus obtained is cooled and ground to a powder.
  • a second main stage 2 parts of the material obtained in the first main stage are mixed with 1 part of titanium oxide (Ti 2 O 3 ). This mixture is heated in a melting pot to approx. 1000 ° C; the melt obtained is kept at this temperature for about 4 h and then cooled at room temperature. The polymer intermediate product thus obtained is processed into a powder.
  • Ti 2 O 3 titanium oxide
  • This intermediate polymer product can be used for electroplating become.
  • Example 2 The procedure is as in Example 1, but the sodium carbonate is replaced by potassium carbonate (K 2 CO 3 ) and the titanium oxide by vanadium oxide (V 2 O 5 ).
  • the melt is not cooled in the second main stage. Rather it will in the absence of air into the melt obtained in the 2nd main stage Reducing agents introduced, e.g. an iron rod around which crystals of the Form polymer.
  • the melt is kept in the calm flow for 2 hours so that the crystals form and can grow; then allowed to cool at room temperature.
  • the crystalline polymer is then washed and dried and is ready for further processing.
  • Example 2 The procedure is as in Example 1. However, the second level obtained melt was not cooled. Rather, graphite electrodes introduced and electrolysis using a DC voltage source carried out.
  • Example 1 The procedure is as in Example 1.
  • the following starting substances are melted at the specified melting temperature: example Main level Parts Parts Melt ° C 4th 1 70 Ga 2 O 3 30 Na 2 CO 3 420 2 65.2 Material from main level 1 34.8 Ga 2 O 3 850 5 1 50 Mo 2 O 3 50 Na 2 CO 3 470 2 68 Material from main level 1 32 Mo 2 O 3 780 6 1 50 WO 3 25 Li 2 CO 3 25 Na 2 CO 3 410 2 64 Material from main level 1 36 WO 3 815
  • a second main stage two parts of the material obtained in the first main stage are mixed with one part of molybdenum trioxide (MoO 3 ).
  • MoO 3 molybdenum trioxide
  • This mixture is heated in a melting pot to approx. 1,000 ° C; the melt obtained is obtained at this temperature for about 4 h and then cooled at room temperature.
  • the polymer intermediate product thus obtained is processed into a powder.
  • Example 7 The procedure is as in Example 7. However, the second level obtained melt was not cooled. Rather, graphite electrodes introduced and electrolysis using a DC voltage source carried out.
  • Crystals form from the polymer on the cathode and become removed and then washed and dried.

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Abstract

An electrically conductive inorganic polymer contains at least one metal (a) selected from copper, an alkali metal and an alkaline earth metal, and at least one metal (b) selected from metal of the 1st, 2nd, 4th, 5th, 6th, 7th and 8th subgroup and the 3rd, 4th and 5th main group of the periodic system, starting with atom number 31. An electrically conductive inorganic polymer, is obtained by: (A) mixing, if metal (a) is copper, in a preliminary stage, copper carbonate with an oxide of at least one metal (b) to form a slurry with the addition of water and evaporating the water contained in the slurry by heating; (B) by fusing under heat, in a first main stage, a carbonate of at least one metal (a) except copper, or the copper-containing material obtained in the first step, with an oxide of at least one metal (b) and allowing the resulting melt to cool down; (C) by fusing under heat, in a second main stage, the material obtained in the first main stage with at least one further oxide of at least one metal (b); and by (D) educing, in a third main stage, the intermediate polymer obtained in the second main stage.

Description

Die Erfindung betrifft ein elektrisch leitendes anorganisches Polymerisat enthaltend mindestens ein Metall a), das ausgewählt ist aus der Gruppe bestehend aus Kupfer, einem Alkalimetall und einem Erdalkalimetall, und mindestens ein Metall b), das ausgewählt ist aus der Gruppe bestehend aus einem Metall der 1., 2., 4., 5., 6., 7. und 8. Nebengruppe sowie der 3., 4. und 5., Hauptgruppe des Periodensystems ab der Atomzahl 31, ein Polymerisat-Zwischenprodukt und ein Verfahren zur Herstellung des anorganischen Polymerisats.The invention relates to an electrically conductive inorganic polymer containing at least one metal a) which is selected from the group consisting of copper, an alkali metal and an alkaline earth metal, and at least one metal b) which is selected from the group consisting of a metal of the 1st, 2nd, 4th, 5th, 6th, 7th and 8th subgroup as well as the 3rd, 4th and 5th, Main group of the periodic table from atom number 31, a polymer intermediate and a process for producing the inorganic Polymer.

Es sind schon die verschiedensten Metall-Legierungen und auch intermetallische Verbindungen bekannt. Diese lassen sich jedoch häufig nur schwer weiterverarbeiten oder herstellen.There are various metal alloys and also intermetallic compounds known. However, this can often only be done difficult to process or manufacture.

So ist aus der JP 62084091 A ein elektrisch leitendes anorganisches Polymer bekannt, das ein Metall der 5. Gruppe enthält. Zur Herstellung dieses Polymers wird ein Metalldithiolatkomplex mit einem Metall der 5. Gruppe thermisch zersetzt.JP 62084091 A is an electrically conductive inorganic polymer known that contains a metal of the 5th group. To make this polymer is a metal dithiolate complex with a metal of the 5th group thermal decomposes.

Aufgabe der vorliegenden Erfindung ist es, ein elektrisch leitendes anorganisches Polymerisat bereitzustellen, das nicht nur über eine hohe elektrische Leitfähigkeit verfügt, sondern auch gute mechanische Eigenschaften besitzt und leicht weiter verarbeitet werden kann.The object of the present invention is to provide an electrically conductive To provide inorganic polymer that not only has a high has electrical conductivity, but also good mechanical properties owns and can be easily processed.

Gelöst wird diese Aufgabe durch ein elektrisch leitendes anorganisches Polymerisat gemäß der Lehre der Ansprüche.This task is solved by an electrically conductive inorganic Polymer according to the teaching of the claims.

Das erfindungsgemäße elektrisch leitende anorganische Polymerisat wird nachstehend nur noch Polymerisat genannt und ist nach einem drei Hauptstufen umfassenden Verfahren erhältlich. Handelt es sich bei dem erfindungsgemäßen Metall a) um Kupfer, dann ist eine Vorstufe durchzuführen, in der Kupfercarbonat mit einem Oxid mindestens eines Metalls b) unter Zugabe von Wasser zu einem Brei vermengt wird. Daraus wird das Wasser durch Erhitzen verdampft. Das dabei erhaltene Material kann beispielsweise pulverisiert werden.The electrically conductive inorganic polymer according to the invention is hereinafter only called polymer and is based on three main stages comprehensive procedures available. Is it the inventive Metal a) around copper, then a preliminary stage must be carried out in which Copper carbonate with an oxide of at least one metal b) with the addition of Water is mixed to a pulp. This turns the water into heat evaporates. The material obtained can be pulverized, for example become.

Der Ausdruck "Kupfercarbonat" umfasst dabei reines Kupfercarbonat, hydratwasserhaltiges Kupfercarbonat und Hydroxycarbonate von Kupfer.The term "copper carbonate" includes pure copper carbonate, hydrated copper carbonate and hydroxy carbonates of copper.

In der ersten Hauptstufe des Verfahrens zur Herstellung des erfindungsgemäßen Polyermisats wird ein Carbonat mindestens eines Metalls a) mit Ausnahme von Kupfer und/oder das gemäß der Vorstufe erhaltene, kupferhaltige Material mit mindestens einem Oxid eines Metalls b) verschmolzen.In the first main stage of the process for producing the The polymer of the invention is a carbonate of at least one metal a) with the exception of copper and / or that obtained according to the preliminary stage, copper-containing material with at least one oxide of a metal b) merged.

Als Metall b) für dieses Metalloxid wird dabei ein Metall eingesetzt, bei dem es sich um ein Metall aus der 1. und 2. sowie der 4. bis 8. Nebengruppe und der III. bis V. Hauptgruppe des Periodensystems ab der Atomzahl 31 handelt.A metal in which it is used as metal b) for this metal oxide a metal from the 1st and 2nd as well as the 4th to 8th subgroup and the III. to V. Main group of the periodic table from atom number 31.

Wird Kupfer als Metall a) eingesetzt, dann kann es sich bei dem Oxid eines Metalls b) auch um Kupferoxid oder um ein Oxid eines anderen Metalls b) handeln.If copper is used as metal a), then the oxide can become a Metal b) also copper oxide or an oxide of another metal b) act.

Wenn erfindungsgemäß davon die Rede ist, dass zur Herstellung des erfindungsgemäßen Polymerisats ein Alkali- und/oder Erdalkalicarbonat eingesetzt wird, dann bedeutet dies, dass ein einziges Alkalicarbonat, ein einziges Erdalkalicarbonat, eine Mischung aus mehreren Alkalicarbonaten, eine Mischung aus mehreren Erdalkalicarbonaten oder eine Mischung aus einem oder mehreren Alkalicarbonat(en) und einem oder mehreren Erdalkalicarbonat(en) eingesetzt werden kann. Bezüglich des Metalloxides gilt ähnliches.If, according to the invention, there is talk of producing the Polymer according to the invention an alkali and / or alkaline earth carbonate is used, it means that a single alkali carbonate, a only alkaline earth carbonate, a mixture of several alkali carbonates, one Mixture of several alkaline earth carbonates or a mixture of one or more alkali carbonate (s) and one or more Alkaline earth carbonate (s) can be used. Regarding the metal oxide applies the like.

Das Alkali- und/oder Erdalkalicarbonat und/oder das in der VorHauptstufe erhaltene, kupferhaltige Material kann mit einem Oxid aus einem, zwei, drei usw. Metallen b) verschmolzen werden. Das Gewichtsverhältnis von Carbonat bzw. dem Material der Vorstufe zu dem Oxid beträgt in der 1. Hauptstufe dabei vorzugsweise 25:75 bis 60:40. Mit dieser Bereichsangabe werden alle davon umfassten engeren, zumindest ganzzahligen Bereich bezeichnet und somit offenbart, beispielsweise 30:70; 35:65; 38:72; 45:55; 50:50; 53:47 und 58:42.The alkali and / or alkaline earth carbonate and / or that in the pre-main stage The copper-containing material obtained can be coated with an oxide of one, two, three, etc. Metals b) are fused. The weight ratio of carbonate or the material of the precursor to the oxide is in the 1st main stage preferably 25:75 to 60:40. With this range, all of them encompassed narrower, at least integer range, and thus disclosed, for example 30:70; 35:65; 38:72; 45:55; 50:50; 53:47 and 58:42.

Die in der 1. Hauptstufe erhaltene Schmelze wird zweckmäßigerweise langsam abgekühlt und dann ggf. gemahlen.The melt obtained in the first main stage expediently becomes slow cooled and then ground if necessary.

In einer 2. Hauptstufe wird das in der 1. Hauptstufe erhaltene Material mit einem weiteren Oxid eines Metalls b) verschmolzen. Es kann sich somit um ein Oxid mit einem, zwei, drei oder mehreren der Metalle b) handeln. Als Metall b) wird dabei erfindungsgemäß ein solches aus der 1., 2., 4. 5., 6., 7. und 8. Nebengruppe sowie der 3., 4. und 5. Hauptgruppe des Periodensystems ab der Atomzahl 31 eingesetzt. Die Angabe "ab der Atomzahl 31" bezieht sich dabei nur auf die Metalle der Hauptgruppen.In a second main stage, the material obtained in the first main stage is marked with a fused another oxide of a metal b). It can therefore be an oxide trade one, two, three or more of the metals b). As metal b) according to the invention one from the 1st, 2nd, 4th, 5th, 6th, 7th and 8th Subgroup and the 3rd, 4th and 5th main group of the periodic table from Atom number 31 used. The specification "from atomic number 31" relates only on the metals of the main groups.

Das in der 1. Hauptstufe erhaltene Material wird in der 2. Hauptstufe vorzugsweise im Überschuß eingesetzt. Das Gewichtsverhältnis von dem in der 1. Hauptstufe erhaltenen Material zu dem Oxid beträgt in der 2. Hauptstufe vorzugsweise 60:40 bis 70:30.The material obtained in the 1st main stage becomes in the 2nd main stage preferably used in excess. The weight ratio of that in the 1st main stage material obtained to the oxide is in 2nd main stage preferably 60:40 to 70:30.

Zweckmäßigerweise erhitzt man in der 1. Hauptstufe auf eine Temperatur, die niedriger liegt als die Temperatur in der 2. Hauptstufe. Vorzugsweise beträgt die Temperatur in der 1. Hauptstufe 300 bis 850 °C und in der 2. Hauptstufe 700 bis 1200 °C.Advantageously, the first main stage is heated to a temperature which is lower than the temperature in the 2nd main stage. The is preferably Temperature in the 1st main stage 300 to 850 ° C and in the 2nd main stage 700 to 1200 ° C.

Das nach der 2. Hauptstufe erhaltene Produkt wird im Rahmen der vorliegenden Unterlagen als Polymerisat-Zwischenprodukt bezeichnet, das zu wertvollen Endprodukten weiterverarbeitet werden kann, worauf nachstehend eingegangen wird.The product obtained after the 2nd main stage is used in the present Documentation referred to as an intermediate polymer product, that too valuable End products can be processed, which is discussed below becomes.

Nach einer bevorzugten Ausführungsform werden in der 1. und der 2. Hauptstufe dasselbe Metalloxid bzw. dieselben Metalloxide eingesetzt.According to a preferred embodiment, in the 1st and 2nd Main stage used the same metal oxide or the same metal oxides.

Als Metall b) für das Metalloxid dienen vorzugsweise Titan, Vanadium, Nickel, Gallium, Germanium, Molybdän, Rhodium, Indium, Antimon, Tellur, Wolfram, Rhenium, Iridium, Thallium, Wismut, Kupfer, Gold, Silber und Zink. Titanium, vanadium, nickel, preferably serve as metal b) for the metal oxide, Gallium, germanium, molybdenum, rhodium, indium, antimony, tellurium, tungsten, Rhenium, iridium, thallium, bismuth, copper, gold, silver and zinc.

Die in der 2. Hauptstufe erhaltene Schmelze kann man abkühlen lassen, zweckmäßigerweise langsam. Das dabei erhaltene Polymerisat-Zwischenprodukt kann dann pulverisiert, beispielsweise gemahlen, werden und besitzt bereits eine elektrische Leitfähigkeit.The melt obtained in the 2nd main stage can be allowed to cool, expediently slow. The resulting polymer intermediate can then be pulverized, for example ground, and already has an electrical conductivity.

Dieses Polymerisat-Zwischenprodukt kann dann weiterverarbeitet werden. Dazu wird es vorzugsweise in einer 3. Hauptstufe in einem wässrigen Lösungsmittel gelöst, beispielsweise mit Hilfe von Säuren oder Laugen, und dann galvanisch, unter Reduktion in einer elektrolytischen Zelle auf einem insbesondere leitenden Substrat abgeschieden, das als Kathode gepolt ist.This intermediate polymer product can then be processed further. To it is preferably in a 3rd main stage in an aqueous solvent solved, for example with the help of acids or alkalis, and then galvanically, with reduction in an electrolytic cell on a particularly conductive Deposited substrate which is poled as a cathode.

Als Stromquelle für den Betrieb dieser elektrolytischen Zelle kann eine Gleichstromquelle, wie eine Batterie, oder ein geregeltes Netzteil dienen. Zweckmäßigerweise liegt die Spannung dabei im Bereich von etwa 1 bis 25 V. Als besonders zweckmäßig hat sich eine Spannung im Bereich von 2 bis 12 V erwiesen. Die Stromdichte liegt üblicherweise im Bereich von 1 bis 100 mA/cm2, weiterhin bevorzugt im Bereich von 1,0 bis 35 mA/cm2.A direct current source, such as a battery, or a regulated power supply unit can serve as the current source for the operation of this electrolytic cell. The voltage is expediently in the range from about 1 to 25 V. A voltage in the range from 2 to 12 V has proven to be particularly expedient. The current density is usually in the range from 1 to 100 mA / cm 2 , further preferably in the range from 1.0 to 35 mA / cm 2 .

Die Elektrolytlösung sollte die Temperatur von +80°C nicht überschreiten. Im allgemeinen hat sich eine Reaktionstemperatur im Bereich von +40°C bis +70°C als sehr vorteilhaft erwiesen.The electrolyte solution should not exceed the temperature of + 80 ° C. in the generally has a reaction temperature in the range of + 40 ° C to + 70 ° C proved to be very advantageous.

Bei dem auf diese Weise auf eine Substrat abgeschiedenen Überzug handelt es sich um das endgültige elektrisch leitende anorganische Polymerisat.The coating deposited on a substrate in this way is the final electrically conductive inorganic polymer.

Das wie oben beschriebene, pulverisierte Polymerisat-Zwischenprodukt kann nach einer weiterhin bevorzugten Ausführungsform in der 3. Hauptstufe erneut aufgeschmolzen und dann reduziert werden. Sowohl für dieses Aufschmelzen als auch für die Schmelzvorgänge in der 1. und 2. Hauptstufe bedient man sich zweckmäßigerweise eines geeigneten Schmelztiegels, in den die zu schmelzenden Substanzen und Materialien eingegeben werden.The powdered polymer intermediate as described above can according to a further preferred embodiment in the 3rd main stage again melted and then reduced. Both for this melting as well as for the melting processes in the 1st and 2nd main stage expediently a suitable crucible in which the melting substances and materials can be entered.

Die Schmelze aus dem Polymerisat-Zwischenprodukt kann man im übrigen nicht nur dadurch erhalten, daß man - wie oben beschrieben - das nach der 2. Hauptstufe erhaltene Polymerisat-Zwischenprodukt erneut aufschmilzt. Man kann auch die in der 2. Hauptstufe erhaltene Schmelze direkt verwenden, ohne diese Schmelze vorher abzukühlen.The melt from the polymer intermediate can not be otherwise can only be obtained by - as described above - after the second The intermediate polymer obtained in the main stage melts again. Man can also use the melt obtained in the 2nd main stage directly without to cool this melt beforehand.

Die Schmelze aus dem Polymerisat-Zwischenprodukt wird dann vorzugsweise elektrolytisch, mittels eines realen Gases oder mittels eines Reduktionsmittels mit einem Reduktionspotential von -0,100 bis -0,900 E°inV reduziert. Bei dieser Reduktion scheiden sich Polymerisat-Kristalle aus der Schmelze ab.The melt from the polymer intermediate is then preferred electrolytically, using a real gas or using a reducing agent reduced with a reduction potential of -0.100 to -0.900 E ° inV. At this Reduction polymer crystals separate from the melt.

Zur Durchführung der Elektrolyse der Schmelze aus dem Polymerisat-Zwischenprodukt wird dieses in einem Tiegel bei 650 bis 900 °C aufgeschmolzen. Die Elektrolyse wird mit Gleichstrom durchgeführt, wobei eine Stromdichte von 10 bis 35 mA/cm2 bevorzugt ist. Die Spannung ist abhängig von der Schmelzzusammensetzung und sollte 0,8 bis 3,5 V betragen. Als Elektroden haben sich solche aus Graphit oder Edelmetall bewährt. An diesen Elektroden, genauer der Kathode, scheidet sich das erfindungsgemäße Polymerisat in Form von Kristallen ab. Diese werden dann entnommen und zweckmäßigerweise gewaschen und getrocknet.To carry out the electrolysis of the melt from the intermediate polymer, this is melted in a crucible at 650 to 900 ° C. The electrolysis is carried out with direct current, a current density of 10 to 35 mA / cm 2 being preferred. The voltage depends on the melt composition and should be 0.8 to 3.5 V. Those made of graphite or precious metal have proven themselves as electrodes. The polymer according to the invention is deposited in the form of crystals on these electrodes, more precisely the cathode. These are then removed and expediently washed and dried.

Diese Reduktion kann man jedoch auch dadurch durchführen, daß man lediglich ein Reduktionsmittel in die Schmelze eintaucht. Dazu kann man beispielsweise einen Eisenstab verwenden, an dem sich dann die Kristalle aus dem erfindungsgemäßen Polymerisat bilden.However, this reduction can also be carried out by simply: a reducing agent is immersed in the melt. You can do this, for example Use an iron rod on which the crystals from the Form polymer according to the invention.

Bei der geschilderten Reduktion werden Kristalle mit einer perowskitartigen Struktur und einer tetragonalen Symmetrie erhalten. Die Dichte der Kristalle beträgt insbesondere 4 bis 20 g/cm3.In the described reduction, crystals with a perovskite-like structure and a tetragonal symmetry are obtained. The density of the crystals is in particular 4 to 20 g / cm 3 .

Das erfindungsgemäße Polymerisat ist sehr gut leitfähig und verfügt über vorteilhafte mechanische Eigenschaften. Es kann als Leiter in der Elektroindustrie, Medizintechnik, Galvanotechnik und Autoindustrie eingesetzt werden. Das erfindungsgemäße Polymerisat läßt sich gut weiterverarbeiten und in Form eines Überzuges auf Substrate abscheiden. Es verfügt zudem über eine gute Säure- und Laugenbeständigkeit. The polymer according to the invention is very well conductive and has advantageous mechanical properties. It can act as a leader in the Electrical industry, medical technology, electroplating and auto industry used become. The polymer according to the invention can be easily processed and deposit on substrates in the form of a coating. It also has a good acid and alkali resistance.

Es wird im übrigen angenommen, ohne an diese Erklärung gebunden zu sein, daß die Leitfähigkeit des erfindungsgemäßen Polymerisats auf einem Überschuß von Elektronen beruht und diese frei beweglich und über die Kristalle verteilt sind. Die Kristalle können als gedopte Metalloxide angesehen werden, wobei die Leitfähigkeit vom Gehalt an Alkalimetall und/oder Erdalkalimetall und/oder Kupfer abhängt. Als Dopingmittel können somit Salze der Alkalimetalle und/oder Erdalkalimetalle und/oder von Kupfer angesehen werden. Die elektrische Leitfähigkeit scheint somit auf einem Mechanismus zu beruhen, der ein anderer ist als bei einer Legierung oder bei einer intermetallischen Verbindung.Otherwise it is assumed, without being bound by this declaration, that that the conductivity of the polymer according to the invention on a Excess of electrons is based and these are freely movable and over the crystals are distributed. The crystals can be viewed as doped metal oxides, where the conductivity of the content of alkali metal and / or alkaline earth metal and / or copper depends. Salts of alkali metals can thus be used as doping agents and / or alkaline earth metals and / or copper. The electrical conductivity thus seems to be based on a mechanism that is different from an alloy or an intermetallic Connection.

Als Oxide der Metalle b) in der 1. und 2. Hauptstufe eines Verfahrens zur Herstellung der erfindungsgemäßen Polymerisate können im übrigen alle Oxide der eingesetzten Metalle verwendet werden.As oxides of metals b) in the 1st and 2nd main stage of a process for All oxides can also be used to prepare the polymers according to the invention of the metals used.

Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung eines elektrisch-leitenden anorganischen Polymerisates oder Polymerisat-Zwischproduktes und die Verwendung als Leiter in der Elektroindustrie, Medizintechnik, Galvanotechnik und Autoindustrie.The invention also relates to a method for producing a electrically conductive inorganic polymer or polymer intermediate and use as a leader in the electrical industry, Medical technology, electroplating and auto industry.

Ganz allgemein darf noch einmal darauf hingewiesen werden, dass mit den im Rahmen der vorliegenden Unterlagen angegebenen Bereichen alle zwischen den Bereichsgrenzen liegenden, zumindest ganzzahligen Werte bezeichnet werden und somit offenbart sind. Dies gilt unabhängig von der Maßeinheit für die angegebenen Bereiche, seien es nun °C, V, mA/cm2 und Gewichtsverhältnisse. Zudem umfassen die Bereichsangabe auch alle darin liegenden kleineren/engeren Bereichsangaben.In general, it should be pointed out once again that the ranges specified within the scope of the present documents indicate all values between the range limits, at least whole numbers, and are thus disclosed. This applies regardless of the unit of measurement for the specified ranges, be it ° C, V, mA / cm 2 and weight ratios. In addition, the range specification also includes all smaller / narrower range specifications contained therein.

Die Erfindung wird im folgenden anhand der nachstehenden, bevorzugte Ausführungsformen beschreibenden Beispiele näher erläutert. Die Teileangaben beziehen sich dabei auf Gewichtsteile. The invention is preferred below with reference to the following Examples describing embodiments are explained in more detail. The parts information refer to parts by weight.

Beispiel 1:Example 1:

In einer 1. Hauptsstufe wird eine Mischung aus 6 Teilen Natriumcarbonat (Na2CO3) und 4 Teilen Titaniumoxid (Ti2O3) hergestellt. Diese Mischung wird in einem Schmelztiegel unter Schmelzen auf eine Temperatur von 400 °C erhitzt.In a first main stage, a mixture of 6 parts of sodium carbonate (Na 2 CO 3 ) and 4 parts of titanium oxide (Ti 2 O 3 ) is produced. This mixture is heated in a crucible with melting to a temperature of 400 ° C.

Die so erhaltene Schmelze wird abgekühlt und zu einem Pulver vermahlen.The melt thus obtained is cooled and ground to a powder.

In einer 2. Hauptstufe werden 2 Teile des in der 1. Hauptstufe erhaltenen Materials mit 1 Teil Titaniumoxid (Ti2O3) vermischt. Diese Mischung wird in einem Schmelztiegel auf ca. 1000 °C erhitzt; die dabei erhaltene Schmelze wird ca. 4 h bei dieser Temperatur gehalten und anschließend bei Raumtemperatur abgekühlt. Das so erhaltene Polymerisat-Zwischenprodukt wird zu einem Pulver verarbeitet.In a second main stage, 2 parts of the material obtained in the first main stage are mixed with 1 part of titanium oxide (Ti 2 O 3 ). This mixture is heated in a melting pot to approx. 1000 ° C; the melt obtained is kept at this temperature for about 4 h and then cooled at room temperature. The polymer intermediate product thus obtained is processed into a powder.

Dieses Polymerisat-Zwischenprodukt kann für die Galvanotechnik eingesetzt werden.This intermediate polymer product can be used for electroplating become.

Beispiel 2:Example 2:

Es wird wie im Beispiel 1 gearbeitet, jedoch wird das Natriumcarbonat durch Kaliumcarbonat (K2CO3) und das Titaniumoxid durch Vanadiumoxid (V2O5) ersetzt.The procedure is as in Example 1, but the sodium carbonate is replaced by potassium carbonate (K 2 CO 3 ) and the titanium oxide by vanadium oxide (V 2 O 5 ).

Zudem wird die Schmelze in der 2. Hauptstufe nicht abgekühlt. Vielmehr wird unter Luftabschluß in die in der 2. Hauptstufe erhaltenen Schmelze ein Reduktionsmittel eingebracht, z.B. ein Eisenstab, um den sich dann Kristalle des Polymerisats bilden.In addition, the melt is not cooled in the second main stage. Rather it will in the absence of air into the melt obtained in the 2nd main stage Reducing agents introduced, e.g. an iron rod around which crystals of the Form polymer.

Die Schmelze wird 2 h im ruhigen Fluß gehalten, damit sich die Kristalle bilden und wachsen können; danach wird bei Raumtemperatur abkühlen gelassen.The melt is kept in the calm flow for 2 hours so that the crystals form and can grow; then allowed to cool at room temperature.

Das kristallförmige Polymerisat wird anschließend gewaschen und getrocknet und steht zur Weiterverarbeitung bereit. The crystalline polymer is then washed and dried and is ready for further processing.

Beispiel 3:Example 3:

Es wird wie im Beispiel 1 gearbeitet. Allerdings wird die in der 2. Hauptstufe erhaltene Schmelze nicht abgekühlt. Vielmehr werden Graphitelektroden eingebracht und eine Elektrolyse mit Hilfe einer Gleichspannungsquelle durchgeführt.The procedure is as in Example 1. However, the second level obtained melt was not cooled. Rather, graphite electrodes introduced and electrolysis using a DC voltage source carried out.

An der Kathode bilden sich Kristalle aus dem Polymerisat; diese werden entnommen und anschließend gewaschen und getrocknet.Crystals form from the polymer on the cathode; these will removed and then washed and dried.

Beispiele 4 bis 6:Examples 4 to 6

Es wird wie im Beispiel 1 verfahren. Dabei werden folgende Ausgangssubstanzen bei der angegebenen Schmelztemperatur verschmolzen: Beispiel Hauptstufe Teile Teile Schmelze °C 4 1 70 Ga2O3 30 Na2CO3 420 2 65,2 Material aus Hauptstufe 1 34,8 Ga2O3 850 5 1 50 Mo2O3 50 Na2CO3 470 2 68 Material aus Hauptstufe 1 32 Mo2O3 780 6 1 50 WO3 25 Li2CO3
25 Na2CO3 410 2 64 Material aus Hauptstufe 1 36 WO3 815 The procedure is as in Example 1. The following starting substances are melted at the specified melting temperature: example Main level Parts Parts Melt ° C 4th 1 70 Ga 2 O 3 30 Na 2 CO 3 420 2 65.2 Material from main level 1 34.8 Ga 2 O 3 850 5 1 50 Mo 2 O 3 50 Na 2 CO 3 470 2 68 Material from main level 1 32 Mo 2 O 3 780 6 1 50 WO 3 25 Li 2 CO 3
25 Na 2 CO 3 410 2 64 Material from main level 1 36 WO 3 815

Beispiel 7:Example 7:

In einer Vorstufe wird eine Mischung aus 2 Teilen Kupfercarbonat (CUCO3 . (OH)2) und 1 Teil Molybdäntrioxid (MoO3) hergestellt. Diese Mischung wird zu einem dünnen Brei mit dest. Wasser verrührt. Die Mischung wird bei ca. 70°-80° für 2 - 3 Stunden auf Temperatur gehalten, anschließend auf 130° erhitzt, so dass das Wasser verdampft. Das erhaltene Pulver wird anschliessend gemahlen. In a preliminary stage, a mixture of 2 parts of copper carbonate (CUCO 3. (OH) 2 ) and 1 part of molybdenum trioxide (MoO 3 ) is produced. This mixture becomes a thin paste with dist. Water stirred. The mixture is kept at a temperature of about 70 ° -80 ° for 2-3 hours, then heated to 130 °, so that the water evaporates. The powder obtained is then ground.

In der 1. Hauptstufe werden zwei Teile des in der Vorstufe erhaltenen Materials mit einem Teil Molybdäntrioxid vermischt. Diese Mischung wird in einem Schmelztiegel auf 800 °C erhitzt. Die dabei erhaltene Schmelze wird ca. 4 h bei dieser Temperatur gehalten und anschliessend bei Raumtemperatur abgekühlt. Das so erhaltene Produkt wird zu einem Pulver verarbeitet.In the 1st main stage there are two parts of the material obtained in the preliminary stage mixed with a part of molybdenum trioxide. This mixture is in one Crucible heated to 800 ° C. The melt obtained is about 4 hours maintained at this temperature and then cooled at room temperature. The product thus obtained is processed into a powder.

In einer 2. Hauptstufe werden zwei Teile des in der 1. Hauptstufe erhaltenen Materials mit einem Teil Molybdäntrioxid (MoO3) vermischt. Diese Mischung wird in einem Schmelztiegel auf ca. 1.000 °C erhitzt; die dabei erhaltene Schmelze wird ca. 4 h bei dieser Temperatur erhalten und anschließend bei Raumtemperatur abgekühlt. Das so erhaltene Polymerisat-Zwischenprodukt wird zu einem Pulver verarbeitet.In a second main stage, two parts of the material obtained in the first main stage are mixed with one part of molybdenum trioxide (MoO 3 ). This mixture is heated in a melting pot to approx. 1,000 ° C; the melt obtained is obtained at this temperature for about 4 h and then cooled at room temperature. The polymer intermediate product thus obtained is processed into a powder.

Beispiel 8:Example 8:

Es wird wie im Beispiel 7 gearbeitet. Allerdings wird die in der 2. Hauptstufe erhaltene Schmelze nicht abgekühlt. Vielmehr werden Graphitelektroden eingebracht und eine Elektrolyse mit Hilfe einer Gleichspannungsquelle durchgeführt.The procedure is as in Example 7. However, the second level obtained melt was not cooled. Rather, graphite electrodes introduced and electrolysis using a DC voltage source carried out.

An der Kathode bilden sich Kristalle aus dem Polymerisat, diese werden entnommen und anschliessend gewaschen und getrocknet.Crystals form from the polymer on the cathode and become removed and then washed and dried.

Claims (11)

Elektrisch leitendes anorganisches Polymerisat enthaltend mindestens ein Metall a), das ausgewählt ist aus der Gruppe bestehend aus Kupfer, einem Alkalimetall und einem Erdalkalimetall, und mindestens ein Metall b), das ausgewählt aus der Gruppe bestehend aus einem Metall der 1., 2., 4., 5., 6., 7. und 8. Nebengruppe sowie der 3., 4. und 5. Hauptgruppe des Periodensystems ab der Atomzahl 31,
dadurch erhältlich, dass,
sofern es sich bei dem Metall a) um Kupfer handelt, in einer Vorstufe Kupfercarbonat mit einem Oxid mindestens eines Metalls b) unter Zugabe von Wasser zu einem Brei vermengt wird und das Wasser daraus durch Erhitzen verdampft wird, in einer 1. Hauptstufe ein Carbonat mindestens eines Metalls a) mit Ausnahme von Kupfer oder das gemäß der Vorstufe erhaltene kupferhaltige Material mit einem Oxid mindestens eines Metalls b) unter Erhitzen verschmolzen wird und die erhaltene Schmelze abkühlen gelassen wird in einer 2. Hauptstufe das in der 1. Stufe erhaltene Material mit mindestens einem weiteren Oxid mindestens eines Metalls b) unter Erhitzen verschmolzen wird und in einer 3. Hauptstufe das in der 2. Hauptstufe erhaltene Polymerisat-Zwischenprodukt reduziert wird. Electrically conductive inorganic polymer containing at least one metal a) which is selected from the group consisting of copper, an alkali metal and an alkaline earth metal, and at least one metal b) which is selected from the group consisting of a metal of the 1st, 2nd, 4th, 5th, 6th, 7th and 8th subgroup as well as the 3rd, 4th and 5th main group of the periodic table from atomic number 31,
obtainable by
if the metal a) is copper, copper carbonate is mixed in a preliminary stage with an oxide of at least one metal b) with the addition of water to give a paste and the water is evaporated from it by heating, in a first main stage, a carbonate of at least one metal a) with the exception of copper or the copper-containing material obtained according to the preliminary stage is fused with an oxide of at least one metal b) with heating and the melt obtained is allowed to cool in a second main stage, the material obtained in the first stage is fused with at least one further oxide of at least one metal b) with heating and in a third main stage, the polymer intermediate product obtained in the second main stage is reduced. Polymerisat nach Anspruch 1,
dadurch erhältlich, dass
in der 1. und 2. Hauptstufe ein Oxid desselben Metalls b) eingesetzt wird.Polymer according to claim 1,
obtainable in that
an oxide of the same metal b) is used in the 1st and 2nd main stages. Polymerisat nach Anspruch 1 oder 2,
dadurch erhältlich, dass
das Metall b) ausgewählt ist aus der Gruppe bestehend aus Titan, Vanadium, Nickel, Gallium, Germanium, Molybdän, Rhodium, Indium, Antimon, Tellur, Wolfram, Rhenium, Iridium, Thallium, Wismut, Kupfer, Gold, Silber und Zink.Polymer according to claim 1 or 2,
obtainable in that
the metal b) is selected from the group consisting of titanium, vanadium, nickel, gallium, germanium, molybdenum, rhodium, indium, antimony, tellurium, tungsten, rhenium, iridium, thallium, bismuth, copper, gold, silver and zinc. Polymerisat nach einem der vorhergehenden Ansprüche,
dadurch erhältlich, dass
in der 1. Hauptstufe auf eine Temperatur erhitzt wird, die niedriger ist als die Temperatur, auf die in der 2. Hauptstufe erhitzt wird, wobei die Temperatur in der 1. Hauptstufe insbesondere 300 bis 850 °C und die Temperatur in der 2. Hauptstufe insbesondere 700 bis 1200 °C beträgt.Polymer according to one of the preceding claims,
obtainable in that
in the first main stage is heated to a temperature which is lower than the temperature to which it is heated in the second main stage, the temperature in the first main stage in particular 300 to 850 ° C. and the temperature in the second main stage is in particular 700 to 1200 ° C. Polymerisat nach einem der vorhergehenden Ansprüche,
dadurch erhältlich, dass
die Schmelze der 2. Hauptstufe abkühlen gelassen und gegebenenfalls pulverisiert wird.Polymer according to one of the preceding claims,
obtainable in that
the melt of the 2nd main stage is allowed to cool and is optionally pulverized. Polymerisat nach Anspruch 5,
dadurch erhältlich, dass
das Polymerisat-Zwischenprodukt in der 3. Hauptstufe in einem wäßrigen Lösungsmittel gelöst und elektrolytisch bzw. galvanisch unter Reduktion auf einem Substrat abgeschieden wird.Polymer according to claim 5,
obtainable in that
the intermediate polymer in the third main stage is dissolved in an aqueous solvent and electrolytically or galvanically deposited on a substrate with reduction. Polymerisat nach Anspruch 5,
dadurch erhältlich, dass
das Polymerisat-Zwischenprodukt in der 3. Hauptstufe erneut aufgeschmolzen wird und dann reduziert wird.Polymer according to claim 5,
obtainable in that
the intermediate polymer product is melted again in the 3rd main stage and then reduced. Polymerisat nach einem der Ansprüche 1 bis 4 oder 7,
dadurch erhältlich, dass
die Schmelze aus dem Polymerisat-Zwischenprodukt elektrolytisch, mittels eines realen Gases oder mittels eines Reduktionsmittels mit einem Reduktionspotential von -0,100 bis -0,900 E°inV, insbesondere durch einen Eisenstab und unter Luftausschluß, reduziert wird. Polymer according to one of claims 1 to 4 or 7,
obtainable in that
the melt from the intermediate polymer product is reduced electrolytically, by means of a real gas or by means of a reducing agent with a reduction potential of -0.100 to -0.900 E ° inV, in particular by means of an iron rod and with the exclusion of air. Polymerisat nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die erhaltenen Kristalle über eine perowskitartige Struktur verfügen.Polymer according to one of the preceding claims,
characterized in that
the crystals obtained have a perovskite-like structure. Polymerisat-Zwischenprodukt erhältlich nach den in vorhergehenden Ansprüchen für die Vorstufe und für die 1. und 2. Hauptstufe beschriebenen Verfahrensschritten.Intermediate polymer available according to the previous Requirements for the preliminary stage and for the 1st and 2nd main level described process steps. Verfahren zur Herstellung eines elektrisch leitenden anorganischen Polymerisats oder Polymerisat-Zwischenproduktes nach einem der Ansprüche 1 bis 9,
dadurch gekennzeichnet,
dass die in den Ansprüchen 1 bis 8 beschriebenen Verfahrensschritte durchgeführt werden.Process for producing an electrically conductive inorganic polymer or polymer intermediate according to one of Claims 1 to 9,
characterized,
that the method steps described in claims 1 to 8 are carried out.
EP20000126467 1999-12-07 2000-12-07 Electrically conductive inorganic polymer Expired - Lifetime EP1115122B1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6284091A (en) * 1985-10-08 1987-04-17 Idemitsu Petrochem Co Ltd Production of electrically conductive inorganic high polymer containing group v metal

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6284091A (en) * 1985-10-08 1987-04-17 Idemitsu Petrochem Co Ltd Production of electrically conductive inorganic high polymer containing group v metal

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 290 (C - 447) 18 September 1987 (1987-09-18) *

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