EP1274102A1 - Polymer compound with non linear current-voltage characteristic and method of making a polymer compound - Google Patents
Polymer compound with non linear current-voltage characteristic and method of making a polymer compound Download PDFInfo
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- EP1274102A1 EP1274102A1 EP01810645A EP01810645A EP1274102A1 EP 1274102 A1 EP1274102 A1 EP 1274102A1 EP 01810645 A EP01810645 A EP 01810645A EP 01810645 A EP01810645 A EP 01810645A EP 1274102 A1 EP1274102 A1 EP 1274102A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/105—Varistor cores
- H01C7/108—Metal oxide
- H01C7/112—ZnO type
Definitions
- the invention is based on a polymer compound after the The preamble of claim 1 and of a method for producing a Polymer compounds according to the preamble of claim 14.
- the Polymer compound contains a polymer matrix in which as a filler electrically conductive Particles, such as conductivity black and / or metal powder and / or electrically semiconducting particles such as SiC or ZnO are embedded.
- This Polymer compound has a non-linear current-voltage characteristic, which is influenced by the filler content and the dispersion of the filler.
- the one by the Current-voltage characteristic specific resistance and others electrical properties can vary depending on the strength of an am Polymer compound applied electric field in general only over the Filler content and the degree of dispersion can be influenced.
- the polymer compound can be used as a base material in advantage voltage limiting resistors (varistors) are used or as Field-controlling material in power engineering plants and apparatus, such as especially in cable terminations or in cable connection sleeves.
- a polymer compound of the type mentioned in the introduction and a method of the type mentioned in the introduction are described in an article by R. Strümpler et al. "Smart Varistor Composites” Proc.of the 8 th CIMTEC Ceramic Congress. June 1994 and in EP 875 087 B1 and WO 99/56290 A1.
- As filler doped and sintered particles of zinc oxide are provided in this polymer compound.
- Typical dopants are metals such as those used in the production of metal oxide varistors and typically include Bi, Cr, Co, Mn and Sb.
- Doped ZnO powder is sintered at 800 to 1300 ° C. By suitable Rated sintering temperatures and times become desirable electrical Properties of the filler achieved. After sintering, each particle has one electrical conductivity, which is dependent on an applied electric field changes nonlinearly. Each particle therefore acts as a small varistor. Due to the appropriately sized sintering conditions, the non-linear Behavior of the filler can be adjusted within certain limits. The nonlinear electrical properties of the polymer compound can therefore during the manufacture of the compound not only about the filler content and the degree of dispersion but also on the sintering conditions of the filler be set.
- the object is based on creating a polymer compound of the type mentioned, its non-linear electrical properties during the manufacturing process in can be adjusted easily and a method of producing a specify such polymer compounds, with the economically Polymer compounds with predetermined nonlinear electrical properties can be made.
- the filler contains at least two Filler components with divergent non-linear current-voltage characteristics.
- these Filler components can thus be a polymer compound with either of these two Characteristics deviating non-linear current-voltage characteristic reached become.
- the polymer compound according to the invention is therefore characterized that, despite well-defined nonlinear electrical properties, it can be used with low cost can be produced. From a small base set Filler components each with a defined non-linear current-voltage characteristic can polymer compounds with almost arbitrarily designed current-voltage characteristics be made.
- the combination of the two filler components allows the Polymer compound not only given predetermined electrical properties Because of this, its thermal conductivity can also be decisive to be influenced.
- polymer compounds as Field control material such as in cable sets, this is particularly important because of Dielectric losses in the polymer compound and electrical losses in the metallic conductor the cable set is strongly heated.
- the generally low thermal conductivity of the polymer is canceled by suitable selected filler components, which in addition to the good electrical Behavior of the polymer compound also sufficiently good thermal conductivity give.
- the two Filler components each of a doped, sintered metal oxide with Grain boundary-containing particles are formed and differ from each other by deviating stoichiometry of the dopants and / or by each other different, caused by different sintering conditions Grain boundary structures with different grain sizes.
- the metal oxide is in general zinc oxide, but may also be tin dioxide or titanium dioxide with advantage.
- the divergent current-voltage characteristics can be achieved are different weight percent of the dopants, i. by different recipes of the two filler components or through different conditions when sintering the filler components.
- the Sintering conditions mainly include the sintering temperature, the residence time, the Gas composition of the sintering atmosphere and the heating and cooling rates.
- the sintering temperature by increasing the sintering temperature, the conductivity of a plurality of metals doped powdered zinc oxide at a given electric field strength can be increased.
- the polymer compound can electrically conductive or electrically semiconducting material, such as Conductivity soot or metal powder, included. By this material will be present but all in all a better contacting of the individual particles of the nonlinear achieved electrical behavior exhibiting filler components.
- the Energy absorption of the polymer compound is significantly increased.
- One Surge arrester containing polymer compound according to the invention is characterized by a high pulse strength. To get a sufficient To achieve effect, the proportion of additional component should be 0.01 to 15 Percent by volume of the polymer compound.
- the Additional component particles with a large length-to-diameter ratio contains, in particular Nanotubes.
- the polymer matrix in the production the polymer compound as by injection molding in a preferred direction Aligned so can because of the large length-to-diameter ratio
- These particles oriented in the preferred direction and so in a simple Way reaches a polymer compound with anisotropic electrical properties become.
- Such a material can advantageously for the solution of field control tasks used in cable connection sleeves or in cable terminations.
- the polymer compound has a high dielectric constant.
- the polymer compound according to the invention can then easily control an electric field.
- Such a field control can relate, for example, to the homogenization of the distribution of electrical fields of energy-technical installations or apparatuses in normal operation.
- the field-controlling function of the polymer according to the invention can be improved in that the filler has an additional component of a material with a high dielectric constant.
- additional components are, for example, BaTiO 3 or TiO 2 .
- the polymer matrix typically contains a single polymer or mixture of polymers.
- the dielectric behavior of the polymer compound can thereby be further improved if the single polymer or at least one of Polymers of the mixture contains polar groups and / or an intrinsic electrical is conductive polymer.
- a typical polymer with polar groups is, for example a polyamide.
- the proportion of polar group-containing polymer and / or intrinsically electrically conductive polymer is advantageously from 0.01 to 50 Volume percent of the polymer matrix.
- the polymer compound may additionally be provided an additive which at least one stabilizer, a flame retardant and / or a Contains processing aids.
- the proportion of this additive can be between 0.01 to 5 Percent by volume of the polymer compound.
- a flame-retardant polymer compound can then be particularly economical be manufactured when it acts as a flame retardant aluminum and / or Contains magnesium hydroxide. Because of the flame retardant the Polymer matrix in many cases a predetermined LOI (Limited Oxygen Index) value the smaller the LOI value, the easier it can be Burning Polymer Compound) can be obtained by using the inexpensive Hydroxides of the LOI value can be increased in a very cost-effective manner.
- LOI Lited Oxygen Index
- the polymer compound has good mechanical strength when in addition, an adhesion promoter which increases the adhesion between polymer and filler is provided.
- the proportion of adhesion promoter should be between 0.01 to 5 Percent by volume of the polymer compound.
- the bonding agent which is preferably formed as a silane, the polymer matrix couples firmly to the Filler on. Cracking in the polymer compound due to lack of adhesion of the Polymer matrix on the filler and thereby initiated material breakage is so with great security avoided. At the same time the bonding agent improves the electrical properties of the inventive polymer compound entirely essential.
- the filler is a base set of at least two filler components with divergent non-linear current-voltage characteristics mixed.
- the mixing ratio of the components becomes so selected that the polymer compound has the predetermined characteristic.
- the Polymer compound can now be easier without extensive preliminary investigations and be manufactured economically.
- the mixing ratio is selected from a predetermined characteristic field of polymer compounds, two of which, respectively contain at most one of the at least two filler components and at least one more, the at least two with a predetermined ratio mixed filler components.
- varistor powders R1, R2, S1 and S2 were prepared.
- the Powders contained sintered as the main ingredient (more than 90 mole percent) Zinc oxide, which with additives, mainly Sb, Bi, Co, Mn and Cr, (total less than 10 mole percent).
- the varistor powder R1 had a smaller one Bismuth content as the varistor powder R2.
- the powders R1 and R2 were under produced sintering conditions at about 1100 ° C in a ceramic tube of a rotary kiln.
- the powders S1 and S2 had the same Composition, but were at different sintering conditions produced.
- the powder S1 was prepared by a continuous sintering process in a rotary kiln at a maximum sintering temperature of about 1070 ° C. prepared, the powder S2 in a batch oven at maximum sintering temperature from about 1200 ° C and a residence time of the batches in the oven of about 18 hours. Sieving, preceded by grinding, if necessary, made the particle sizes The powder is restricted to values typically between 32 and 125 microns lay.
- Oil was used as the matrix material, since in a particularly simple manner Test specimens could be manufactured. But instead of oil can also Duromer, an elastomer, a thermoplastic, a copolymer, a thermoplastic Elastomer or a gel or a mixture of at least two of these substances be used.
- a variable DC voltage source was applied to the two electrodes.
- the electric field E [V / mm] acting in the associated specimen was adjusted and the current flowing in the specimen was measured.
- the current density J [A / cm 2 ] determined therefrom the DC current-voltage characteristics shown in FIGS. 1 and 2 were obtained.
- the mixing ratio can be determined. By Mixing the filler components according to this mixing ratio is the Made filler and the desired polymer compound by mixing the Filler made with polymer, such as silicone.
- polymer compounds with fillers which by Mixing the filler components R1 or R2 and S1 or S2 or by mixing of three or four of these filler components can be achieved.
- the filler components do not necessarily have to be ZnO powder be. You can also use another powdered material with non-linear current-voltage characteristics, such as doped silicon carbide, tin dioxide or Titanium dioxide, included.
- electrically conductive or electrically semiconducting Material such as Si
- the electrical conductivity of the Polymer compounds in the range of small electric field strengths by several Magnitudes are increased, and so a polymer with a flat-running DC current-voltage characteristic can be achieved.
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- Thermistors And Varistors (AREA)
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Abstract
Description
Bei der Erfindung wird ausgegangen von einem Polymercompound nach dem
Oberbegriff von Patentanspruch 1 sowie von einem Verfahren zur Herstellung eines
Polymercompounds nach dem Oberbegriff von Patentanspruch 14. Der
Polymercompound enthält eine Polymermatrix, in die als Füllstoff elektrisch leitende
Teilchen, wie Leitfähigkeitsruss und/oder Metallpulver und/oder elektrisch
halbleitende Teilchen, wie etwa SiC oder ZnO, eingebettet sind. Dieser
Polymercompound weist eine nichtlineare Strom-Spannungs-Kennlinie auf, welche
vom Füllstoffgehalt und der Dispersion des Füllstoffs beeinflusst wird. Der durch die
Strom-Spannungs-Kennlinie bestimmte spezifische Widerstand und andere
elektrische Eigenschaften können in Abhängigkeit von der Stärke eines am
Polymercompound anliegenden elektrischen Feldes im allgemeinen nur über den
Füllstoffgehalt und den Dispersionsgrad beeinflusst werden.The invention is based on a polymer compound after the
The preamble of
Der Polymercompound kann mit Vorteil als Basismaterial in spannungsbegrenzenden Widerständen (Varistoren) eingesetzt werden oder als feldsteuerndes Material in energietechnischen Anlagen und Apparaten, wie insbesondere in Kabelendverschlüssen oder in Kabelverbindungsmuffen.The polymer compound can be used as a base material in advantage voltage limiting resistors (varistors) are used or as Field-controlling material in power engineering plants and apparatus, such as especially in cable terminations or in cable connection sleeves.
Ein Polymercompound der eingangs genannten Art und ein Verfahren der eingangs genannten Art sind in einem Aufsatz von R. Strümpler et al. "Smart Varistor Composites" Proc.of the 8th CIMTEC Ceramic Congress. June 1994 sowie in EP 875 087 B1 und WO 99/56290 A1 beschrieben. Als Füllstoff sind in diesem Polymercompound dotierte und gesinterte Teilchen von Zinkoxid vorgesehen. A polymer compound of the type mentioned in the introduction and a method of the type mentioned in the introduction are described in an article by R. Strümpler et al. "Smart Varistor Composites" Proc.of the 8 th CIMTEC Ceramic Congress. June 1994 and in EP 875 087 B1 and WO 99/56290 A1. As filler doped and sintered particles of zinc oxide are provided in this polymer compound.
Typische Dotierstoffe sind Metalle, wie sie bei der Herstellung von Metalloxid-Varistoren verwendet werden und typischerweise Bi, Cr, Co, Mn und Sb umfassen. Dotiertes ZnO-Pulver wird bei 800 bis 1300°C gesintert. Durch geeignet bemessene Sintertemperaturen und -zeiten werden erwünschte elektrische Eigenschaften des Füllstoffs erreicht. Nach dem Sintern weist jedes Teilchen eine elektrische Leitfähigkeit auf, welche sich in Abgängigkeit von einem angelegten elektrischen Feld nichtlinear ändert. Jedes Teilchen wirkt daher als kleiner Varistor. Durch die geeignet bemessenen Sinterbedingungen kann das nichtlineare Verhalten des Füllstoffs innerhalb bestimmter Grenzen eingestellt werden. Die nichtlinearen elektrischen Eigenschaften des Polymercompounds können daher während der Herstellung des Compounds nicht nur über den Füllstoffgehalt und den Dispersionsgrad sondern auch über die Sinterbedingungen des Füllstoffs eingestellt werden.Typical dopants are metals such as those used in the production of metal oxide varistors and typically include Bi, Cr, Co, Mn and Sb. Doped ZnO powder is sintered at 800 to 1300 ° C. By suitable Rated sintering temperatures and times become desirable electrical Properties of the filler achieved. After sintering, each particle has one electrical conductivity, which is dependent on an applied electric field changes nonlinearly. Each particle therefore acts as a small varistor. Due to the appropriately sized sintering conditions, the non-linear Behavior of the filler can be adjusted within certain limits. The nonlinear electrical properties of the polymer compound can therefore during the manufacture of the compound not only about the filler content and the degree of dispersion but also on the sintering conditions of the filler be set.
Der Erfindung, wie sie in den Patentansprüchen angegeben ist, liegt die Aufgabe zugrunde, einen Polymercompound der eingangs genannten Art zu schaffen, dessen nichtlinearen elektrischen Eigenschaften während des Herstellprozesses in einfacher Weise eingestellt werden können und ein Verfahren zur Herstellung eines solchen Polymercompounds anzugeben, mit dem in wirtschaftlicher Weise Polymercompounds mit vorgegebenen nichtlinearen elektrischen Eigenschaften gefertigt werden können.The invention, as indicated in the claims, the object is based on creating a polymer compound of the type mentioned, its non-linear electrical properties during the manufacturing process in can be adjusted easily and a method of producing a specify such polymer compounds, with the economically Polymer compounds with predetermined nonlinear electrical properties can be made.
Beim erfindungsgemässen Polymercompound enthält der Füllstoff mindestens zwei Füllstoffkomponenten mit voneinander abweichenden nichtlinearen Strom-Spannungs-Kennlinien. Durch Auswahl geeignet bemessener Mengen dieser Füllstoffkomponenten kann so ein Polymercompound mit einer von diesen beiden Kennlinien abweichenden nichtlinearen Strom-Spannungs-Kennlinie erreicht werden. Der erfindungsgemässe Polymercompound zeichnet sich daher dadurch aus, dass er trotz genau definierter nichtlinearer elektrischer Eigenschaften mit geringem Aufwand hergestellt werden kann. Aus einem kleinen Basissatz an Füllstoffkomponenten jeweils mit definierter nichtlinearer Strom-Spannungs-Kennlinie können Polymercompounds mit nahezu beliebig ausgebildeten Strom-Spannungs-Kennlinien gefertigt werden. In the novel polymer compound, the filler contains at least two Filler components with divergent non-linear current-voltage characteristics. By selecting appropriately sized quantities of these Filler components can thus be a polymer compound with either of these two Characteristics deviating non-linear current-voltage characteristic reached become. The polymer compound according to the invention is therefore characterized that, despite well-defined nonlinear electrical properties, it can be used with low cost can be produced. From a small base set Filler components each with a defined non-linear current-voltage characteristic can polymer compounds with almost arbitrarily designed current-voltage characteristics be made.
Durch die Kombination der beiden Füllstoffkomponenten können dem Polymercompound nicht nur vorbestimmte elektrische Eigenschaften verliehen werden, es kann dadurch auch dessen Wärmeleitfähigkeit ganz entscheidend beeinflusst werden. Bei der Verwendung von Polymercompounds als Feldsteuermaterial etwa in Kabelgarnituren ist dies besonders wichtig, da wegen dielektrischer Verluste im Polymercompound und wegen elektrischer Verluste im metallischen Leiter die Kabelgarnitur stark erwärmt wird. Die im allgemeinen geringe Wärmeleitfähigkeit des Polymers wird aufgehoben durch geeignet ausgewählte Füllstoffkomponenten, welche neben dem guten elektrischen Verhalten dem Polymercompound auch ausreichend gute Wärmeleitfähigkeit geben.The combination of the two filler components allows the Polymer compound not only given predetermined electrical properties Because of this, its thermal conductivity can also be decisive to be influenced. When using polymer compounds as Field control material such as in cable sets, this is particularly important because of Dielectric losses in the polymer compound and electrical losses in the metallic conductor the cable set is strongly heated. The generally low thermal conductivity of the polymer is canceled by suitable selected filler components, which in addition to the good electrical Behavior of the polymer compound also sufficiently good thermal conductivity give.
Bei Anwendungen des Polymercompounds, bei denen wie bei Überspannungsableitern oder Feldsteuermaterial nichtlineares elektrisches Verhalten im Vordergrund steht, ist es besonders vorteilhaft, wenn die beiden Füllstoffkomponenten jeweils von einem dotierten, gesinterten Metalloxid mit Korngrenzen enthaltenden Teilchen gebildet sind und sich voneinder unterscheiden durch abweichende Stöchiometrie der Dotierstoffe und/oder durch voneinander abweichende, durch unterschiedliche Sinterbedingungen hervorgerufene Korngrenzenstrukturen mit unterschiedlichen Korngrössen. Das Metalloxid ist im allgemeinen Zinkoxid, kann mit Vorteil aber auch Zinndioxid oder Titandioxid sein. Die voneinander abweichenden Strom-Spannungs-Kennlinien können erreicht werden durch unterschiedliche Gewichtsanteile der Dotierstoffe, d.h. durch unterschiedliche Rezepturen der beiden Füllstoffkomponenten oder durch unterschiedlich Bedingungen beim Sintern der Füllstoffkomponenten. Die Sinterbedingungen umfassen vor allem die Sintertemperatur, die Verweildauer, die Gaszusammensetzung der Sinteratmosphäre sowie die Aufheiz- und Abkühlraten. Im allgemeinen kann durch Erhöhen der Sintertemperatur die Leitfähigkeit von mit mehreren Metallen dotiertem pulverförmigem Zinkoxid bei einer vorgegebenen elektrischen Feldstärke erhöht werden.For applications of the polymer compound in which as in Surge arresters or field control material non-linear electrical Behavior is paramount, it is particularly beneficial if the two Filler components each of a doped, sintered metal oxide with Grain boundary-containing particles are formed and differ from each other by deviating stoichiometry of the dopants and / or by each other different, caused by different sintering conditions Grain boundary structures with different grain sizes. The metal oxide is in general zinc oxide, but may also be tin dioxide or titanium dioxide with advantage. The divergent current-voltage characteristics can be achieved are different weight percent of the dopants, i. by different recipes of the two filler components or through different conditions when sintering the filler components. The Sintering conditions mainly include the sintering temperature, the residence time, the Gas composition of the sintering atmosphere and the heating and cooling rates. In general, by increasing the sintering temperature, the conductivity of a plurality of metals doped powdered zinc oxide at a given electric field strength can be increased.
Um die Strom-Spannungs-Kennlinie zu verändern, kann der Polymercompound elektrisch leitendes oder elektrisch halbleitendes Material, wie etwa Leitfähigkeitsruss oder Metallpulver, enthalten. Durch dieses Material wird vor allem aber eine bessere Kontaktierung der einzelnen Teilchen der nichtlineares elektrisches Verhalten aufweisenden Füllstoffkomponenten erreicht. Die Energieaufnahme des Polymercompounds wird so wesentlich erhöht. Ein einen erfindungsgemässen Polymercompound enthaltender Überspannungsableiter zeichnet sich dann durch eine hohe Impulsfestigkeit aus. Um eine ausreichende Wirkung zu erreichen, sollte der Anteil an Zusatzkomponente 0,01 bis 15 Volumenprozent des Polymercompounds betragen.In order to change the current-voltage characteristic, the polymer compound can electrically conductive or electrically semiconducting material, such as Conductivity soot or metal powder, included. By this material will be present but all in all a better contacting of the individual particles of the nonlinear achieved electrical behavior exhibiting filler components. The Energy absorption of the polymer compound is significantly increased. One Surge arrester containing polymer compound according to the invention is characterized by a high pulse strength. To get a sufficient To achieve effect, the proportion of additional component should be 0.01 to 15 Percent by volume of the polymer compound.
Zur Lösung feldsteuernder Aufgaben ist es von besonderem Vorteil, wenn die Zusatzkomponente Teilchen mit einem grossen Länge-zu-Durchmesser-Verhältnis enthält, wie insbesondere Nanotubes. Wird die Polymermatrix bei der Herstellung des Polymercompounds etwa durch Spritzgiessen in einer Vorzugsrichtung ausgerichtet, so könnnen wegen des grossen Länge-zu-Durchmesser-Verhältnisses diese Teilchen in Vorzugsrichtung orientiert und so in einfacher Weise ein Polymercompound mit anisotropen elektrische Eigenschaften erreicht werden. Ein solches Material kann mit Vorteil zur Lösung von Feldsteueraufgaben in Kabelverbindungsmuffen oder in Kabelendverschlüssen eingesetzt werden.To solve field-controlling tasks, it is of particular advantage if the Additional component particles with a large length-to-diameter ratio contains, in particular Nanotubes. Will the polymer matrix in the production the polymer compound as by injection molding in a preferred direction Aligned, so can because of the large length-to-diameter ratio These particles oriented in the preferred direction and so in a simple Way reaches a polymer compound with anisotropic electrical properties become. Such a material can advantageously for the solution of field control tasks used in cable connection sleeves or in cable terminations.
Wird als Füllstoff dotiertes Metalloxid, wie etwa dotiertes Zinkoxid eingesetzt, so weist der Polymercompound eine hohe Dielektrizitätszahl auf. Der erfindungsgemässe Polymercompound kann dann in einfacher Weise ein elektrisches Feld steuern. Ein solche Feldsteuerung kann beispielsweise die Homogenisierung der Verteilung elektrischer Felder energietechnischer Anlagen oder Apparate im Normalbetrieb betreffen. Die feldsteuernde Funktion des erfindungsgemässen Polymers kann dadurch verbessert werden, dass der Füllstoff eine Zusatzkomponente aufweist aus einem Material mit einer hohen Dielektrizitätszahl. Solche Zusatzkomponenten sind beispielsweise BaTiO3 oder TiO2.If doped metal oxide, such as doped zinc oxide, is used as filler, the polymer compound has a high dielectric constant. The polymer compound according to the invention can then easily control an electric field. Such a field control can relate, for example, to the homogenization of the distribution of electrical fields of energy-technical installations or apparatuses in normal operation. The field-controlling function of the polymer according to the invention can be improved in that the filler has an additional component of a material with a high dielectric constant. Such additional components are, for example, BaTiO 3 or TiO 2 .
Die Polymermatrix enthält typischerweise ein einzelnes Polymer oder ein Gemisch von Polymeren. Das dielektrische Verhalten des Polymercompounds kann dadurch weiter verbessert werden, wenn das einzelne Polymer oder mindestens eines der Polymere des Gemischs polare Gruppen enthält und/oder ein intrinsisch elektrisch leitfähiges Polymer ist. Ein typisches Polymer mit polaren Gruppen ist zum Beispiel ein Polyamid. Der Anteil an polare Gruppen enthaltendem Polymer und/oder intrinsisch elektrisch leitfähigem Polymer beträgt mit Vorteil 0,01 bis 50 Volumenprozent der Polymermatrix. The polymer matrix typically contains a single polymer or mixture of polymers. The dielectric behavior of the polymer compound can thereby be further improved if the single polymer or at least one of Polymers of the mixture contains polar groups and / or an intrinsic electrical is conductive polymer. A typical polymer with polar groups is, for example a polyamide. The proportion of polar group-containing polymer and / or intrinsically electrically conductive polymer is advantageously from 0.01 to 50 Volume percent of the polymer matrix.
Im Polymercompound kann zusätzlich ein Additiv vorgesehen sein, welches mindestens einen Stabilisator, ein Flammschutzmittel und/oder ein Verarbeitungshilfsmittel enthält. Der Anteil dieses Additivs kann zwischen 0,01 bis 5 Volumenprozent des Polymercompounds betragen.In the polymer compound may additionally be provided an additive which at least one stabilizer, a flame retardant and / or a Contains processing aids. The proportion of this additive can be between 0.01 to 5 Percent by volume of the polymer compound.
Ein flammgeschützter Polymercompound kann dann besonders wirtschaftlich gefertigt werden, wenn er als Flammschutzmittel wirkendes Aluminium- und/oder Magnesiumhydroxid enthält. Da aus Gründen des Flammschutzes die Polymermatrix in vielen Fällen einen vorgegebenen LOI (Limited Oxygen Index)-Wert nicht unterschreiten darf (je kleiner der LOI-Wert, umso leichter kann der Polymercompound brennen), kann durch den Einsatz der preiswert erhältlichen Hydroxide der LOI-Wert in äusserst kostengünstiger Weise erhöht werden.A flame-retardant polymer compound can then be particularly economical be manufactured when it acts as a flame retardant aluminum and / or Contains magnesium hydroxide. Because of the flame retardant the Polymer matrix in many cases a predetermined LOI (Limited Oxygen Index) value the smaller the LOI value, the easier it can be Burning Polymer Compound) can be obtained by using the inexpensive Hydroxides of the LOI value can be increased in a very cost-effective manner.
Eine gute mechanische Festigkeit weist der Polymercompound dann auf, wenn zusätzlich ein die Haftung zwischen Polymer und Füllstoff erhöhender Haftvermittler vorgesehen ist. Der Anteil an Haftvermittler sollte zwischen 0,01 bis 5 Volumenprozent des Polymercompounds betragen. Der Haftvermittler, welcher vorzugsweise als Silan ausgebildet ist, koppelt die Polymermatrix fest an den Füllstoff an. Rissbildung im Polymercompound aufgrund mangelnder Haftung der Polymermatrix am Füllstoff und dadurch eingeleiteter Materialbruch wird so mit grosser Sicherheit vermieden. Zugleich verbessert der Haftvermittler die elektrischen Eigenschaften des erfindungsgemässen Polymercompounds ganz wesentlich. Dies vor allem deswegen, da durch die verbesserte Haftung die Bildung kleiner Hohlräume im Polymercompound vermieden und so das Risiko des Auftretens unerwünschten Teilentladungen bei der Einwirkung eines starken elektrischen Feldes ganz wesentlich reduziert wird. Diese Wirkung ist besonders vorteilhaft bei einem Polymercompound auf der Basis eines elastomeren Polymers, so wie er etwa als Feldsteuerelement für Kabelendverschlüsse oder Kabelverbindungsmuffen eingesetzt wird, da dann der Compound stark verformt werden kann, ohne dass unerwünschte Hohlraum- oder Rissbildung auftritt.The polymer compound has good mechanical strength when in addition, an adhesion promoter which increases the adhesion between polymer and filler is provided. The proportion of adhesion promoter should be between 0.01 to 5 Percent by volume of the polymer compound. The bonding agent, which is preferably formed as a silane, the polymer matrix couples firmly to the Filler on. Cracking in the polymer compound due to lack of adhesion of the Polymer matrix on the filler and thereby initiated material breakage is so with great security avoided. At the same time the bonding agent improves the electrical properties of the inventive polymer compound entirely essential. This is mainly because of the improved adhesion formation small cavities in the polymer compound avoided and so the risk of Occurrence of unwanted partial discharges when exposed to a strong electric field is significantly reduced. This effect is special advantageous in a polymer compound based on an elastomeric polymer, as he used as a field control for cable terminations or Cable connection sleeves is used, since then the compound deformed greatly can be without unwanted cavitation or cracking occurs.
Beim erfindungsgemässen Verfahren zur Herstellung eines Polymercompounds wird der Füllstoff aus einem Basissatz von mindestens zwei Füllstoffkomponenten mit voneinander abweichenden nichtlinearen Strom-Spannungs-Kennlinien gemischt. Hierbei wird das Mischungsverhältnis der Komponenten derart ausgewählt, dass das Polymercompound die vorbestimmte Kennlinie aufweist. Der Polymercompound kann nun ohne umfangreiche Voruntersuchungen in einfacher und wirtschaftlicher Weise gefertigt werden. Für eine besonders einfache Fertigung empfiehlt es sich, dass das Mischungsverhältnis ausgewählt wird aus einem vorbestimmten Kennlinienfeld von Polymercompounds, von denen zwei jeweils höchstens eine der mindestens zwei Füllstoffkomponenten enthalten und mindestens ein weiterer die mindestens zwei mit einem vorgegebenen Verhältnis gemischten Füllstoffkomponenten.In the inventive method for producing a polymer compound For example, the filler is a base set of at least two filler components with divergent non-linear current-voltage characteristics mixed. Here, the mixing ratio of the components becomes so selected that the polymer compound has the predetermined characteristic. Of the Polymer compound can now be easier without extensive preliminary investigations and be manufactured economically. For a particularly simple production It is recommended that the mixing ratio is selected from a predetermined characteristic field of polymer compounds, two of which, respectively contain at most one of the at least two filler components and at least one more, the at least two with a predetermined ratio mixed filler components.
Anhand von Zeichnungen werden Ausführungsbeispiele der Erfindung erläutert. Hierbei zeigen alle Figuren DC-Strom-Spannungs-Kennlinien von Polymercompounds nach dem Stand der Technik und nach der Erfindung (Kennlinienfelder).With reference to drawings, embodiments of the invention will be explained. All figures show DC current-voltage characteristics of Polymer compounds according to the prior art and the invention (Characteristic curves).
Nach bekannten, beispielsweise im einleitend genannten Stand der Technik beschriebenen Verfahren wurden Varistorpulver R1, R2, S1 und S2 hergestellt. Die Pulver enthielten als Hauptbestandteil (mehr als 90 Molprozent) gesintertes Zinkoxid, welches mit Zusatzstoffen, vorwiegend Sb, Bi, Co, Mn und Cr, (insgesamt weniger als 10 Molprozent) dotiert war. Das Varistorpulver R1 wies einen kleineren Bismutanteil auf als das Varistorpulver R2. Die Pulver R1 und R2 wurden unter gleichen Sinterbedingungen hergestellt, nämlich durch Sintern bei ca. 1100°C in einem Keramikrohr eines Drehrohrofens. Die Pulver S1 und S2 hatten die gleiche Zusammensetzung, wurden aber bei unterschiedlichen Sinterbedingungen hergestellt. Das Pulver S1 wurde durch einen kontinuierlichen Sinterprozess in einem Drehrohrofen bei einer maximalen Sintertemperatur von ca. 1070 °C hergestellt, das Pulver S2 in einem Chargen-Ofen bei maximalen Sintertemperatur von ca 1200 °C und einer Verweilzeit der Chargen im Ofen von ca. 18 Stunden. Durch Sieben, dem gegebenenfalls Mahlen voranging, wurden die Teilchengrössen der Pulver auf Werte eingeschränkt, die typischerweise zwischen 32 und 125 µm lagen. According to known, for example, in the introductory mentioned prior art varistor powders R1, R2, S1 and S2 were prepared. The Powders contained sintered as the main ingredient (more than 90 mole percent) Zinc oxide, which with additives, mainly Sb, Bi, Co, Mn and Cr, (total less than 10 mole percent). The varistor powder R1 had a smaller one Bismuth content as the varistor powder R2. The powders R1 and R2 were under produced sintering conditions at about 1100 ° C in a ceramic tube of a rotary kiln. The powders S1 and S2 had the same Composition, but were at different sintering conditions produced. The powder S1 was prepared by a continuous sintering process in a rotary kiln at a maximum sintering temperature of about 1070 ° C. prepared, the powder S2 in a batch oven at maximum sintering temperature from about 1200 ° C and a residence time of the batches in the oven of about 18 hours. Sieving, preceded by grinding, if necessary, made the particle sizes The powder is restricted to values typically between 32 and 125 microns lay.
Aus den Varistorpulvern wurden Mischungen hergestellt, deren
Zusammensetzungen aus der nachfolgenden Tabelle ersichtlich sind:
In eine als elektrisch isolierendes Rohr ausgebildete Form aus Kunststoff mit einem Innendurchmesser von 1 bis 2 Zentimetern wurde auf einer Höhe von 2 bis 5 Millimeter Füllstoff eingefüllt. Um eine Vergleichsbasis zu haben, wurden stets die gleichen Füllstoffmengen, beispielsweise 50 Vol% des herzustellenden Compounds, eingefüllt. Der Füllstoff wurde unter Vakuum mit Öl, beispielsweise einem Silikon- oder Esteröl, getränkt und so einem Polymercompound vergleichbare Probekörper gebildet. Diese Probekörper wurden oben und unten im vertikal gehaltenen Rohr mit Elektroden kontaktiert und flüssigkeitsdicht abgeschlossen.In a designed as an electrically insulating tube plastic mold with a Inner diameter of 1 to 2 centimeters was at a height of 2 to 5 Millimeter filler filled. In order to have a basis for comparison, always the same amounts of filler, for example 50 vol% of the produced Compounds, filled. The filler was vacuumed with oil, for example a silicone or ester oil, soaked and so a polymer compound formed comparable specimens. These specimens were top and bottom in the vertically held tube contacted with electrodes and liquid-tight completed.
Als Matrixmaterial wurde Öl eingesetzt, da so in besonders einfacher Weise Probekörper gefertigt werden konnten. Anstelle von Öl kann aber auch ein Duromer, ein Elastomer, ein Thermoplast, ein Copolymer, ein thermoplastisches Elastomer oder ein Gel oder eine Mischung mindestens zweier dieser Stoffe verwendet werden.Oil was used as the matrix material, since in a particularly simple manner Test specimens could be manufactured. But instead of oil can also Duromer, an elastomer, a thermoplastic, a copolymer, a thermoplastic Elastomer or a gel or a mixture of at least two of these substances be used.
An die beiden Elektroden wurde eine variable Gleichspannungsquelle angelegt. Durch Verändern der Höhe der Gleichspannung wurde das im zugeordneten Probekörper wirkende elektrische Feld E [V/mm] eingestellt und der im Probekörper fliessende Strom gemessen. Über die hieraus ermittelte Stromdichte J [A/cm2] wurden so die aus den Figuren 1 und 2 ersichtlichen DC-Strom-Spannungs-Kennlinien gewonnen.A variable DC voltage source was applied to the two electrodes. By changing the level of the DC voltage, the electric field E [V / mm] acting in the associated specimen was adjusted and the current flowing in the specimen was measured. As a result of the current density J [A / cm 2 ] determined therefrom, the DC current-voltage characteristics shown in FIGS. 1 and 2 were obtained.
Aus Fig.1 ist ersichtlich, dass die durch Mischen der zwei unterschiedliche Stöchiometrie aufweisenden Füllstoffkomponenten R1 und R2 gebildeten Füllstoffe R82, R55 und R28 zu Probekörpern führen, deren DC-Strom-Spannungs-Kennlinien einem Kennlinienfeld angehören, welches von den beiden Kennlinien der mit R1 und R2 gefüllten Probekörper begrenzt ist. Durch Veränderung des Mischungsverhältnisses der beiden Füllstoffkomponenten wurden so in einfacher Weise Probekörper mit Kennlinien erreicht, die zwischen den beiden Grenz-Kennlinien liegen.From Fig.1 it can be seen that by mixing the two different Stoichiometric having filler components R1 and R2 formed fillers R82, R55 and R28 lead to test specimens whose DC current-voltage characteristics belong to a characteristic field, which of the two characteristics the specimen filled with R1 and R2 is limited. By changing the Mixing ratio of the two filler components were so in a simple Way test specimens with characteristics achieved between the two limit characteristics lie.
Entsprechend ist aus Fig.3 ersichtlich, dass die durch Mischen der zwei bei unterschiedlichen Sinterbedingungen erzeugten Füllstoffkomponenten S1 und S2 gebildeten Füllstoffe S73 und S37 zu Probekörpern führen, deren DC-Strom-Spannungs-Kennlinien einem Kennlinienfeld angehören, welches von den beiden Kennlinien der mit S1 und S2 gefüllten Probekörpern begrenzt ist. Durch Veränderung des Mischungsverhältnisses der beiden Füllstoffkomponenten wurden auch mit diesen Füllstoffen in einfacher Weise Probekörper mit Kennlinien erreicht, die zwischen den beiden Grenz-Kennlinien liegen.Accordingly, it can be seen from Figure 3, that by mixing the two at different sintering conditions produced filler components S1 and S2 formed fillers S73 and S37 lead to test specimens whose DC current-voltage characteristics belong to a characteristic field, which of the two Characteristics of the filled with S1 and S2 specimens is limited. By Change in the mixing ratio of the two filler components were Even with these fillers in a simple manner test specimen with characteristics achieved which lie between the two limit characteristics.
Soll nun ein Polymercompound mit einer vorgegebenen Kennlinie hergestellt werden, so kann aus einem in entsprechender Weise für Polymercompounds ermittelten Kennlinienfeld das Mischungsverhältnis bestimmt werden. Durch Mischen der Füllstoffkomponenten gemäss diesem Mischungsverhältnis wird der Füllstoff erstellt und der gewünschte Polymercompound durch Mischen des Füllstoffs mit Polymer, beispielsweise Silikon, gefertigt.If now a polymer compound is produced with a predetermined characteristic may be from a corresponding manner for polymer compounds determined characteristic field, the mixing ratio can be determined. By Mixing the filler components according to this mixing ratio is the Made filler and the desired polymer compound by mixing the Filler made with polymer, such as silicone.
Entsprechendes gilt auch für Polymercompounds mit Füllstoffen, welche durch Mischen der Füllstoffkomponenten R1 oder R2 und S1 oder S2 oder durch Mischen von drei oder vier dieser Füllstoffkomponenten erreicht werden.The same applies to polymer compounds with fillers, which by Mixing the filler components R1 or R2 and S1 or S2 or by mixing of three or four of these filler components can be achieved.
Die Füllstoffkomponenten müssen nicht notwendigerweise von ZnO-Pulver gebildet sein. Sie können auch ein anderes pulverförmiges Material mit nichtlinearer Strom-Spannungs-Kennlinie, wie etwa dotiertes Siliciumcarbid, Zinndioxid oder Titandioxid, enthalten.The filler components do not necessarily have to be ZnO powder be. You can also use another powdered material with non-linear current-voltage characteristics, such as doped silicon carbide, tin dioxide or Titanium dioxide, included.
Durch geeignete Zugabe von elektrisch leitendem oder elektrisch halbleitendem Material, beispielsweise Si, kann die elektrische Leitfähigkeit des Polymercompounds im Bereich kleiner elektrischer Feldstärken um mehrere Grössenordnungen erhöht werden, und so ein Polymer mit einer flach verlaufenden DC-Strom-Spannungs-Kennlinie erreicht werden.By suitable addition of electrically conductive or electrically semiconducting Material, such as Si, the electrical conductivity of the Polymer compounds in the range of small electric field strengths by several Magnitudes are increased, and so a polymer with a flat-running DC current-voltage characteristic can be achieved.
Claims (15)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
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| EP01810645A EP1274102B1 (en) | 2001-07-02 | 2001-07-02 | Polymer compound with non linear current-voltage characteristic and method of making a polymer compound |
| DE50115800T DE50115800D1 (en) | 2001-07-02 | 2001-07-02 | Polymer compound with non-linear current-voltage characteristic and method for producing a polymer compound |
| AT01810645T ATE499691T1 (en) | 2001-07-02 | 2001-07-02 | POLYMER COMPOUND WITH NON-LINEAR CURRENT-VOLTAGE CHARACTERISTICS AND METHOD FOR PRODUCING A POLYMER COMPOUND |
| AU50684/02A AU5068402A (en) | 2001-07-02 | 2002-06-27 | Polymer compound with nonlinear current-voltage characteristic and process for producing a polymer compound |
| US10/180,078 US7320762B2 (en) | 2001-07-02 | 2002-06-27 | Polymer compound with nonlinear current-voltage characteristic and process for producing a polymer compound |
| CA002390195A CA2390195A1 (en) | 2001-07-02 | 2002-06-28 | Polymer compound with nonlinear current-voltage characteristic and process for producing a polymer compound |
| RU2002117582/04A RU2282263C2 (en) | 2001-07-02 | 2002-07-01 | Polymer compound with nonlinear volt-ampere characteristics and method for producing the same |
| JP2002192413A JP2003049084A (en) | 2001-07-02 | 2002-07-01 | Polymer blend having non-linear current-voltage- characteristic curve and method for producing the same blend |
| PL354829A PL206222B1 (en) | 2001-07-02 | 2002-07-02 | Polymer composite featuring non-linear current-voltage chracteristic and method of manufacture of polymer composite featuring pre-set non-linear current-voltage characteristic |
| CN02140255.8A CN1277888C (en) | 2001-07-02 | 2002-07-02 | Polymer having nonlinear current-voltage characteristics and method for producing the polymer |
| US11/892,148 US7618550B2 (en) | 2001-07-02 | 2007-08-20 | Polymer compound with nonlinear current-voltage characteristic and process for producing a polymer compound |
Applications Claiming Priority (1)
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|---|---|---|---|
| EP01810645A EP1274102B1 (en) | 2001-07-02 | 2001-07-02 | Polymer compound with non linear current-voltage characteristic and method of making a polymer compound |
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| EP1274102A1 true EP1274102A1 (en) | 2003-01-08 |
| EP1274102B1 EP1274102B1 (en) | 2011-02-23 |
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| EP01810645A Expired - Lifetime EP1274102B1 (en) | 2001-07-02 | 2001-07-02 | Polymer compound with non linear current-voltage characteristic and method of making a polymer compound |
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| US (2) | US7320762B2 (en) |
| EP (1) | EP1274102B1 (en) |
| JP (1) | JP2003049084A (en) |
| CN (1) | CN1277888C (en) |
| AT (1) | ATE499691T1 (en) |
| AU (1) | AU5068402A (en) |
| CA (1) | CA2390195A1 (en) |
| DE (1) | DE50115800D1 (en) |
| PL (1) | PL206222B1 (en) |
| RU (1) | RU2282263C2 (en) |
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- 2001-07-02 DE DE50115800T patent/DE50115800D1/en not_active Expired - Lifetime
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- 2002-06-27 US US10/180,078 patent/US7320762B2/en not_active Expired - Lifetime
- 2002-06-27 AU AU50684/02A patent/AU5068402A/en not_active Abandoned
- 2002-06-28 CA CA002390195A patent/CA2390195A1/en not_active Abandoned
- 2002-07-01 RU RU2002117582/04A patent/RU2282263C2/en not_active IP Right Cessation
- 2002-07-01 JP JP2002192413A patent/JP2003049084A/en active Pending
- 2002-07-02 PL PL354829A patent/PL206222B1/en unknown
- 2002-07-02 CN CN02140255.8A patent/CN1277888C/en not_active Expired - Lifetime
-
2007
- 2007-08-20 US US11/892,148 patent/US7618550B2/en not_active Expired - Lifetime
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| DE2363172A1 (en) | 1973-12-14 | 1975-06-19 | Siemens Ag | Varistor with components of different conductivity type - and value and different particle size, giving increased performance |
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| US4981624A (en) * | 1987-09-11 | 1991-01-01 | Fuji Electric Co., Ltd. | Method of producing a voltage-nonlinear resistor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654457A (en) * | 1984-08-10 | 1987-03-31 | Sumitomo Chemical Company, Limited | Method for selective dealkylation of 1,4-dialkylbenzene |
| US7651636B2 (en) | 2004-04-06 | 2010-01-26 | Abb Research Ltd | Nonlinear electrical material for high and medium voltage applications |
| EP1603140A1 (en) * | 2004-06-04 | 2005-12-07 | ABB Technology AG | Active component for an encapsulated surge arrester |
Also Published As
| Publication number | Publication date |
|---|---|
| PL354829A1 (en) | 2003-01-13 |
| US7320762B2 (en) | 2008-01-22 |
| CN1394914A (en) | 2003-02-05 |
| CN1277888C (en) | 2006-10-04 |
| US20030010960A1 (en) | 2003-01-16 |
| US7618550B2 (en) | 2009-11-17 |
| AU5068402A (en) | 2003-01-09 |
| CA2390195A1 (en) | 2003-01-02 |
| RU2282263C2 (en) | 2006-08-20 |
| US20080023678A1 (en) | 2008-01-31 |
| EP1274102B1 (en) | 2011-02-23 |
| PL206222B1 (en) | 2010-07-30 |
| JP2003049084A (en) | 2003-02-21 |
| ATE499691T1 (en) | 2011-03-15 |
| DE50115800D1 (en) | 2011-04-07 |
| RU2002117582A (en) | 2004-01-20 |
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