DE102004045814A1 - Process for the preparation of a precursor ceramic - Google Patents
Process for the preparation of a precursor ceramic Download PDFInfo
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- DE102004045814A1 DE102004045814A1 DE200410045814 DE102004045814A DE102004045814A1 DE 102004045814 A1 DE102004045814 A1 DE 102004045814A1 DE 200410045814 DE200410045814 DE 200410045814 DE 102004045814 A DE102004045814 A DE 102004045814A DE 102004045814 A1 DE102004045814 A1 DE 102004045814A1
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Abstract
Es wird ein Verfahren zur Herstellung einer Precursor-Keramik durch Pyrolyse von sauerstoffhaltigen elementorganischen Precursor-Polymer-Formteilen vorgestellt, wobei die Precursor-Polymer-Formteile Kontaktdrähte aufweisen, bei denen ein Ende frei aus dem Formteil herausragt. Das frei aus dem Formteil herausragende Ende der Kontaktdrähte wird vor der Pyrolyse mit einer Flüssigkeit beschichtet, die einen Precursor enthält, der sich während der Pyrolyse in eine Keramik umwandelt.The invention relates to a method for producing a precursor ceramic by pyrolysis of oxygen-containing element-organic precursor polymer molded parts, wherein the precursor polymer molded parts have contact wires in which one end protrudes freely from the molded part. The free protruding from the molding end of the contact wires is coated prior to pyrolysis with a liquid containing a precursor, which converts into a ceramic during pyrolysis.
Description
Verfahren zur Herstellung einer Precursorkeramikmethod for producing a precursor ceramic
Die Erfindung betrifft allgemein ein Verfahren zur Herstellung einer Precursor-Keramik nach dem Oberbegriff des unabhängigen Anspruchs. Speziell betrifft die Erfindung die Herstellung solcher Precursor-Keramiken, die Kontaktdrähte aufweisen. Die Erfindung betrifft außerdem eine mit Hilfe des Verfahrens hergestellte Precursor-Keramik.The The invention relates generally to a process for the preparation of a Precursor ceramic according to the preamble of the independent claim. specially the invention relates to the preparation of such precursor ceramics, the contact wires exhibit. The invention also relates to a method using the method prepared precursor ceramic.
Bei der Herstellung von keramischen Glühstiftkerzen aus Keramik-Verbundwerkstoffen werden durch die Pyrolyse von elementorganischen Precursoren amorphe SiOC – Keramiken gewonnen. Vorteile des Precursor-Thermolyse-Verfahrens gegenüber den konventionellen Herstellungsverfahren für Keramiken (Sintern) sind die wesentlich niedrigeren Prozesstemperaturen und die einfache Verarbeitbarkeit und Formbarkeit von Polysiloxanharzen.at the production of ceramic glow plugs from ceramic composites become amorphous by the pyrolysis of elemental organic precursors SiOC ceramics won. Advantages of the precursor thermolysis process over the conventional manufacturing method for ceramics (sintering) are the much lower process temperatures and the simple Processability and moldability of polysiloxane resins.
Die Herstellung von Formkörpern ist aber nur bei Einsatz von zusätzlichen Füllstoffen möglich, da sonst Schwindungsrisse und Poren während der Pyrolyse auftreten. Mittels geeigneter Füllstoffe lassen sich auf diese Weise die Eigenschaften (Wärmeausdehnungskoeffizient, Wärmeleitfähigkeit, spezifischer elektrischer Widerstand) des Komposits genau einstellen. Hierbei ist es möglich, wie in der EP-B-0 412 428 offenbart, reaktive Füller einzusetzen, um eine bessere Anbindung der Füllstoffe an die Matrix zu erreichen oder auch inerte Füllstoffe zu verwenden.The Production of moldings but only with the use of additional fillers possible, otherwise shrinkage cracks and pores during pyrolysis occur. By means of suitable fillers In this way, the properties (thermal expansion coefficient, thermal conductivity, specific electrical resistance) of the composite. Here it is possible as disclosed in EP-B-0 412 428, to use reactive fillers for a better Connection of fillers to reach the matrix or to use inert fillers.
Die Entwicklung der keramischen Glühstiftkerze zielt auf eine weitere Reduktion des Durchmessers der keramischen Glühstiftkerze sowie der Integration weiterer Funktionen (z.B. Druckmessung im Brennraum). Durch die Reduktion des Durchmessers der Glühstiftkerze wird die elektrische Kontaktierung auf der Oberfläche des keramischen Glühstifts erheblich aufwändiger. Eine kostengünstige Variante der Kontaktierung ist es, Kontaktdrähte bei der kunststofftechnischen Formgebung des Glühstift-Precursors zu umspritzen, so dass es ein Teil des Kontaktdrahtes im Glühstift sitzt und der andere Teil als freies Ende herausragt. Auch die Integration eines Drucksensors in den keramischen Glühstift erfordert zwei Kontaktdrähte, durch die das Messsignal vom Drucksensor abgegriffen werden kann.The Development of the ceramic glow plug aims to further reduce the diameter of the ceramic glow plug and the integration of additional functions (e.g. Combustion chamber). By reducing the diameter of the glow plug is the electrical contact on the surface of the ceramic glow plug considerably more complex. An inexpensive Variant of contacting is to contact wires in the plastic technical Shaping the glow plug precursor to overmold, so that it sits a part of the contact wire in the glow plug and the other part stands out as a free end. Also the integration a pressure sensor in the ceramic glow plug requires two contact wires, through the measuring signal can be tapped by the pressure sensor.
Ein schwerwiegender Nachteil der direkten Kontaktierung mit Umspritzen der Kontaktdrähte bei der Formgebung ist, dass auf Grund der für die Herstellung des keramischen Glühstifts notwendigen Pyrolyse in reduzierender Atmosphäre und der anschließenden Wärmebehandlung in oxidierender Atmosphäre (beide Prozesse laufen bei Temperaturen oberhalb von 1200°C ab) die Anforderung an die chemische Beständigkeit der Kontaktdrähte extrem hoch sind. Geeignete Drähte sind daher unverhältnismäßig teuer.One serious disadvantage of direct contact with encapsulation the contact wires in the shaping is that due to the for the production of the ceramic glow plug necessary pyrolysis in a reducing atmosphere and the subsequent heat treatment in an oxidizing atmosphere (Both processes occur at temperatures above 1200 ° C) the Requirement on the chemical resistance of the contact wires extremely are high. Suitable wires are therefore disproportionately expensive.
Ziel der vorliegenden Erfindung ist es daher, die Nachteile des Standes der Technik zu vermeiden und die Kontaktdrähte auf einfache Weise gegen Oxidation zu schützen. Dabei ist anzumerken, dass die vorliegende Erfindung nicht nur auf keramische Glühstiftkerzen anwendbar ist, vielmehr können mit Hilfe des erfindungsgemäßen Verfahrens beliebige Heizer hergestellt werden.aim It is therefore the object of the present invention to overcome the disadvantages of the prior art avoid the technique and the contact wires in a simple way against To protect oxidation. It should be noted that the present invention is not limited to ceramic glow plugs is applicable, rather can with the aid of the method according to the invention any heaters are made.
Vorteile der ErfindungAdvantages of invention
Das erfindungsgemäße Verfahren zur Herstellung von Precursor-Keramiken durch Pyrolyse von sauerstoffhaltigen elementorganischen Precursor-Polymer-Formteilen hat gegenüber dem Stand der Technik den Vorteil, dass sich damit auf einfache Art und Weise die Kontaktdrähte an einem Formteil aus Precursorkeramik vor einer Oxidation während der Wärmebehandlung schützen lassen.The inventive method for the production of precursor ceramics by pyrolysis of oxygen-containing has organometallic precursor polymer moldings over the State of the art has the advantage that so that in a simple way and way the contact wires on a molded part of precursor ceramic before oxidation during the heat treatment protect to let.
Weiterhin ist vorteilhaft, dass das Verfahren relativ kostengünstig ist.Farther is advantageous that the method is relatively inexpensive.
Ein weiterer Vorteil liegt darin, dass preisgünstige, nicht oxidationsstabile metallische Drähte verwendet werden können.One Another advantage is that inexpensive, not oxidation-stable metallic wires can be used.
Vorteilhafte Weiterbildungen der Erfindung ergeben sich aus den in den Unteransprüchen genannten Maßnahmen.advantageous Further developments of the invention will become apparent from the measures mentioned in the dependent claims.
Ausführungsbeispieleembodiments
Kern der Erfindung ist die Verwendung von Zubereitungen aus Precursoren, wie z.B. siliziumorganischen Precursoren wie Polysilsesquioxanen, Polysiloxanen, Polycarbosilanen und Polysilanen oder die Verwendung von aluminiumorganischen Precursoren wie Aluminoxanen als Tauchlack für die Beschichtung der freien Enden von Kontaktdrähten. Die Zubereitungen können die Precursoren in flüssiger, gelöster oder geschmolzener Form enthalten.core the invention is the use of preparations of precursors, such as. organosilicon precursors such as polysilsesquioxanes, Polysiloxanes, polycarbosilanes and polysilanes or the use of organoaluminum precursors such as aluminoxanes as dip for the Coating the free ends of contact wires. The preparations can the Precursors in liquid, dissolved or molten form.
Die Zubereitung kann insbesondere für die siliziumorganischen Precursoren weiterhin Additive enthalten, wie z.B. Bor, Cer, Wismut, Natrium, etc., für die Einstellung bestimmter Eigenschaften wie z.B. Viskosität, Schichtdicke, Wärmeausdehnungskoeffizient, Benetzung des Kontaktdrahtes durch die Oxidationsschutzschicht, der aus dem Precursor entstehenden Keramik. So lässt sich bspw. durch Zugabe von pyrogener Kieselsäure die Einstellung der rheologischen Eigenschaften (z.B. Thixotropierung) der Zubereitung variieren. Durch Verwendung von pyrogener Kieselsäure und/oder siliziumorganischer Precursoren in Kombination mit aluminiumorganischen Precursoren (Aluminoxane) kann ein Film erzeugt werden, der nach der Wärmebehandlung Mullit enthält.The Preparation can be especially for the organosilicon precursors further contain additives, such as. Boron, cerium, bismuth, sodium, etc., for the setting of certain Properties such as e.g. Viscosity, layer thickness, Thermal expansion coefficient, Wetting of the contact wire by the oxidation protection layer, the resulting from the precursor ceramic. Thus, for example, by adding of fumed silica the adjustment of rheological properties (e.g., thixotroping) vary the preparation. By using fumed silica and / or organosilicon precursors in combination with organoaluminum Precursors (aluminoxanes), a film can be produced after the heat treatment Mullite contains.
Mit Hilfe der vorliegenden Erfindung lassen sich auf einfache Art und Weise freie Enden von Kontaktdrähten, die aus einem Formteil aus Precursorkeramik hervorstehen, vor der Oxidation während der Wärmebehandlung in sauerstoffhaltiger Atmosphäre schützen. Dazu werden die freien Enden der Kontaktdrähte vor der Pyrolyse des Formteils in ein Bad aus einer Zubereitung eines Precursors getaucht. Der anhaftende Film der Zubereitung wandelt sich während der Pyrolyse in eine Keramik um. Dieser keramische Film wird während der nachfolgenden Wärmebehandlung in sauerstoffhaltiger Atmosphäre an seiner Oberfläche oxidiert, im Falle der siliziumorganischen Precursoren zu SiO2, im Falle der aluminiumorganischen Precursoren zu Al2O3. SiO2 und Al2O3 sind starke Diffusionsbarrieren für Sauerstoff, so dass diese SiO2- bzw. Al2O3-Schicht auf dem freien Ende des Kontaktdrahtes diesen während der Wärmebehandlung vor der Oxidation durch Sauerstoff schützt. Durch Anschleifen nur einer Kontaktstelle bleibt der Draht auch weiterhin vor Korrosion geschützt.With the aid of the present invention, it is possible in a simple manner to protect free ends of contact wires, which protrude from a precursor ceramic molding, from oxidation during the heat treatment in an oxygen-containing atmosphere. For this purpose, the free ends of the contact wires are dipped before the pyrolysis of the molding in a bath of a preparation of a precursor. The adhering film of the preparation transforms into a ceramic during pyrolysis. This ceramic film is oxidized on its surface during the subsequent heat treatment in an oxygen-containing atmosphere, in the case of the organosilicon precursors to SiO 2 , in the case of the organoaluminum precursors to Al 2 O 3 . SiO 2 and Al 2 O 3 are strong diffusion barriers for oxygen, so that this SiO 2 or Al 2 O 3 layer on the free end of the contact wire protects it during the heat treatment from oxidation by oxygen. By grinding only one contact point, the wire continues to be protected against corrosion.
Als Precursoren kommen folgende Polymere in Frage: Polysiloxane, Polysilsesquioxane, Polycarbosilane, Polysilane und Aluminoxane.When Precursors are the following polymers in question: polysiloxanes, polysilsesquioxanes, Polycarbosilanes, polysilanes and aluminoxanes.
Als Zusatzstoffe zur Einstellung der Schmelzviskosität des Films bei siliziumorganischen Precursoren (nach der Keramisierung durch die Wärmebehandlung) können u.a. folgende Elemente sowie deren organische und anorganische Verbindungen verwendet werden: Bor, Wismut, Barium, Natrium.
- Wirkung: + erniedrigend o neutral – erhöhend
- Effect: + degrading o neutral - increasing
Diese Zusatzstoffe werden bevorzugt als Nanopulver des Elements oder des Oxids oder in flüssiger elementorganischer Form (auch in gelöster elementorganischer Form) der Zubereitung zugegeben.These Additives are preferred as nanopowders of the element or the Oxides or in liquid organoelement Form (also in dissolved organometallic form) is added to the preparation.
Beispiele für flüssige elementorganische Formen sind:
- Smp. = Schmelzpunkt
- M.p. = melting point
Beispielexample
Einwiegen
von:
100g dieser Mischung wird in einem Mischgefäß eingewogen und 10 min lang mit einem Rührer (z.B., Ultraturax (Hersteller: IKA-Werke)) gerührt.100 g This mixture is weighed into a mixing vessel and left for 10 minutes with a stirrer (e.g., Ultraturax (manufacturer: IKA-Werke)).
Anschließend werden die freien Enden der Kontaktdrähte, d.h., der Teil der Kontaktdrähte, der aus dem Formteil herausragt, das aus dem Precursor des keramischen Glühstifts durch kunststofftechnische Formgebung hergestellt wurde, in die Flüssigkeit eingetaucht.Then be the free ends of the contact wires, that is, the part of the contact wires, which protrudes from the molding, which consists of the precursor of the ceramic glow plug was produced by plastic molding in the liquid immersed.
Die
anschließende
Pyrolyse wird unter folgenden Bedingungen durchgeführt:
Aufheizen
mit 200 K/min, bis 1300°C
erreicht sind;
2h Halten bei 1300°C;
Abkühlen mit 300 K/min, bis Raumtemperatur
erreicht ist.The subsequent pyrolysis is carried out under the following conditions:
Heating at 200 K / min until 1300 ° C are reached;
2h hold at 1300 ° C;
Cool at 300 K / min until room temperature is reached.
Die
anschließende
Wärmebehandlung
in Luft findet unter folgenden Bedingungen statt:
Aufheizen
mit 200 K/min, bis 1300°C
erreicht sind;
2 h Halten bei 1300°C;
Abkühlen mit 300 K/min, bis Raumtemperatur
erreicht ist.The subsequent heat treatment in air takes place under the following conditions:
Heating at 200 K / min until 1300 ° C are reached;
2 h hold at 1300 ° C;
Cool at 300 K / min until room temperature is reached.
An Stelle von Bor können Wismut und/oder Barium und/oder Natrium bzw. deren Verbindungen in ähnlichen Mengen zugegeben werden.At Place of boron can Bismuth and / or barium and / or sodium or their compounds in similar Quantities are added.
Bevor die elektrische Kontaktierung durchgeführt wird, muss die elektrisch isolierende Oxidationsschutzschicht vom Kontaktdrahtende entfernt werden. Dies kann mit zwei verschiedenen Verfahren durchgeführt werden:
- – Die Drahtenden werden mittels einer Walze oder Presse flachgepresst. Durch die Deformation des Kontaktdrahtes platzt die Oxidationsschutzschicht im deformierten Bereich von dem Draht ab.
- – Die Oxidationsschutzschicht wird mechanisch durch Schaben oder Schleifen entfernt.
- - The wire ends are pressed flat by means of a roller or press. Due to the deformation of the contact wire, the oxidation protection layer bursts in the deformed region of the wire.
- - The oxidation protection layer is mechanically removed by scraping or grinding.
Die Dicke des SiOC-SiO2-Films liegt je nach Auftragsmenge des Precursors zwischen 1 und 10 μm. Ein ungeschützter Molybdändraht ist nach der Wärmebehandlung bei 1300°C in Luft vollständig zu flüchtigen Oxiden oxidiert. Ein mit dem erfindungsgemäßen Verfahren behandelter Molybdändraht ist nach der gleichen Wärmebehandlung noch intakt.Depending on the application quantity of the precursor, the thickness of the SiOC-SiO 2 film is between 1 and 10 μm. An unprotected molybdenum wire is completely oxidized to volatile oxides after heat treatment at 1300 ° C in air. A molybdenum wire treated with the method according to the invention is still intact after the same heat treatment.
Claims (8)
Priority Applications (2)
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DE200410045814 DE102004045814A1 (en) | 2004-09-22 | 2004-09-22 | Process for the preparation of a precursor ceramic |
PCT/EP2005/053570 WO2006032559A1 (en) | 2004-09-22 | 2005-07-22 | Method for producing a ceramic precursor |
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DE200410045814 DE102004045814A1 (en) | 2004-09-22 | 2004-09-22 | Process for the preparation of a precursor ceramic |
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US7795538B2 (en) | 2007-11-06 | 2010-09-14 | Honeywell International Inc. | Flexible insulated wires for use in high temperatures and methods of manufacturing |
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DE3926077A1 (en) * | 1989-08-07 | 1991-02-14 | Peter Prof Dr Greil | CERAMIC COMPOSITES AND METHOD FOR THEIR PRODUCTION |
JPH10169982A (en) * | 1996-12-11 | 1998-06-26 | Isuzu Ceramics Kenkyusho:Kk | Ceramic heater and its manufacture |
US20030085214A1 (en) * | 2001-11-07 | 2003-05-08 | University Of Colorado At Boulder | Micro-glow plug and method of making same field of the invention |
US20050153825A1 (en) * | 2002-01-30 | 2005-07-14 | Ralf Riedel | Ceramic composite material, method for the production thereof, and pencil-type glow plug containing such a composite material |
DE10326567A1 (en) * | 2003-06-12 | 2004-12-30 | Robert Bosch Gmbh | Process for the production of a ceramic composite material and ceramic composite material |
DE10326565A1 (en) * | 2003-06-12 | 2004-12-30 | Robert Bosch Gmbh | Process for producing an insulating ceramic composite material and insulating ceramic composite material |
-
2004
- 2004-09-22 DE DE200410045814 patent/DE102004045814A1/en not_active Withdrawn
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