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WO2008125271A2 - Spinning material for the production of oxide ceramic fibers - Google Patents

Spinning material for the production of oxide ceramic fibers Download PDF

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Publication number
WO2008125271A2
WO2008125271A2 PCT/EP2008/002833 EP2008002833W WO2008125271A2 WO 2008125271 A2 WO2008125271 A2 WO 2008125271A2 EP 2008002833 W EP2008002833 W EP 2008002833W WO 2008125271 A2 WO2008125271 A2 WO 2008125271A2
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WIPO (PCT)
Prior art keywords
metal oxide
fibers
oxide particles
spinning
dope
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PCT/EP2008/002833
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German (de)
French (fr)
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WO2008125271A3 (en
Inventor
Norbert Roesch
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Clariant Finance (Bvi) Limited
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Publication of WO2008125271A2 publication Critical patent/WO2008125271A2/en
Publication of WO2008125271A3 publication Critical patent/WO2008125271A3/en

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Definitions

  • alumina fibers and mullite fibers are used as starting materials corresponding precursors of metal oxides.
  • Silica is often used to stabilize the crystal phases and to suppress crystal growth (EP 0 318 203 and EP 0 206 634). Further additives for influencing the crystal structure and the crystal growth in the fibers, such. As MgO and iron oxide, are described in EP 0 294 208th
  • Aluminum salts such as aluminum chlorohydrate (EP 0 318 203) or aluminum formate acetate mixed salts (EP 0 294 208) are used as precursors for the production of aluminum oxide and mullite fibers.
  • Aluminum salts such as aluminum chlorohydrate (EP 0 318 203) or aluminum formate acetate mixed salts (EP 0 294 208) are used as precursors for the production of aluminum oxide and mullite fibers.
  • Impurities and temperature fluctuations can now cause the desired crystal phases to form only insufficient.
  • Amorphous portions or portions of foreign phases can adversely affect the mechanical properties of the fibers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Fibers (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

A spinning material for producing oxide ceramic fibers is claimed. Said spinning material contains a colloidal suspension of metal oxide particles. Said suspensions are used as seed crystals and bring about a reduction in the temperature required for forming the desired crystal phase.

Description

Beschreibung description
Spinnmasse zur Herstellung von oxidischen KeramikfasemSpinning mass for the production of oxidic ceramic fibers
Die vorliegende Erfindung betrifft die Herstellung von kolloidalenThe present invention relates to the preparation of colloidal
Metalloxidsuspensionen und die Verwendung dieser Suspensionen bei der Herstellung von oxidischen Keramikfasern als Kristallisationskeime.Metal oxide suspensions and the use of these suspensions in the production of oxide ceramic fibers as crystallization nuclei.
Keramische Fasern werden seit vielen Jahren hergestellt und in unterschiedlichen Bereichen eingesetzt. Sie zeichnen sich durch die hoheCeramic fibers have been produced for many years and used in various fields. They are characterized by the high
Chemikalienbeständigkeit, hohe thermische Stabilität und bemerkenswerte mechanische Eigenschaften aus. Während Kurzfasern eine enorme Bedeutung in Hochtemperatur-Isoliermaterial als Ersatz für Asbest erlangt haben, stellen die erhältlichen Filamentfasem Nischenprodukte dar, die aufgrund des hohen Preises nur in begrenztem Umfang für Spezialanwendungen eingesetzt werden.Chemical resistance, high thermal stability and remarkable mechanical properties. While short fibers have gained tremendous importance in high temperature insulation as a substitute for asbestos, the available filament fibers are niche products which, due to the high price, are only used to a limited extent for special applications.
Als Isoliermaterial finden die keramischen Fasern auf Basis Aluminiumoxid und Aluminiumoxid / Siliciumdioxid (Mullit) Anwendung im Ofenbau, in der Luft- und Raumfahrt und im Automobilbereich.As insulating material, the ceramic fibers based on alumina and alumina / silica (mullite) are used in furnace construction, in the aerospace and automotive industries.
Bei der Herstellung dieser Aluminiumoxidfasern und Mullitfasern dienen als Ausgangsmaterialien entsprechende Vorstufen der Metalloxide. Zur Stabilisierung der Kristallphasen und zur Unterdrückung von Kristallwachstum wird häufig Siliciumdioxid verwendet (EP 0 318 203 und EP 0 206 634). Weitere Zusätze zur Beeinflussung der Kristallstruktur und des Kristallwachstums in den Fasern, wie z. B. MgO und Eisenoxid, sind beschrieben in EP 0 294 208.In the preparation of these alumina fibers and mullite fibers are used as starting materials corresponding precursors of metal oxides. Silica is often used to stabilize the crystal phases and to suppress crystal growth (EP 0 318 203 and EP 0 206 634). Further additives for influencing the crystal structure and the crystal growth in the fibers, such. As MgO and iron oxide, are described in EP 0 294 208th
Als Vorstufen für die Herstellung von Aluminiumoxid- und Mullitfasern kommen Aluminiumsalze wie Aluminiumchlorohydrat (EP 0 318 203) oder Aluminiumformiat-acetat-Mischsalze (EP 0 294 208) zum Einsatz. InAluminum salts such as aluminum chlorohydrate (EP 0 318 203) or aluminum formate acetate mixed salts (EP 0 294 208) are used as precursors for the production of aluminum oxide and mullite fibers. In
US 3 808 015 wird hingegen von Mischungen aus Aluminiumoxidpartikeln (13 - 80 %-Anteil) und entsprechenden Bindern, wie z. B. Aluminiumchlorohydrat ausgegangen. Die gemäß US 3 808 015 benutzten Aluminiumoxidpartikel sollen eine Korundgrößenverteilung von 99,5 % kleiner 5 μm, 98 % kleiner 3 μm und 50 % größer 0,2 μm sind.US Pat. No. 3,808,015, by contrast, is based on mixtures of aluminum oxide particles (13-80% proportion) and corresponding binders, such as, for example, B. aluminum chlorohydrate. The aluminum oxide particles used according to US Pat. No. 3,808,015 are intended a Korundgrößenverteilung of 99.5% less than 5 microns, 98% less than 3 microns and 50% greater than 0.2 microns.
Zur Verbesserung der Rheologie und Spinnbarkeit der Massen werden häufig wasserlösliche Polymere wie z. B. Polyethylenoxid oder Polyvinylalkohol zugesetzt. Nach Herstellung der Fasern durch entsprechende Spinnprozesse müssen diese in die keramische Faser überführt werden. Dies geschieht durch thermische Behandlung in geeigneten Öfen. Dabei wird meist mit Temperaturgradienten gearbeitet, wobei im unteren Temperaturbereich je nach Vorstufe meist Wasser und die entsprechenden Zersetzungsprodukte der Vorstufen freigesetzt werden. Bei höheren Temperaturen erfolgen dann die Phasenumwandlungen unter Bildung der gewünschten Kristallstruktur.To improve the rheology and spinnability of the masses are often water-soluble polymers such. As polyethylene oxide or polyvinyl alcohol added. After production of the fibers by appropriate spinning processes, these must be converted into the ceramic fiber. This is done by thermal treatment in suitable ovens. It is usually worked with temperature gradients, wherein in the lower temperature range, depending on the precursor usually water and the corresponding decomposition products of the precursors are released. At higher temperatures, the phase transformations take place to form the desired crystal structure.
Verunreinigungen und Temperaturschwankungen können nun bewirken, dass sich die gewünschten Kristallphasen nur unzureichend ausbilden. Amorphe Anteile oder Anteile von Fremdphasen können die mechanischen Eigenschaften der Fasern negativ beeinflussen.Impurities and temperature fluctuations can now cause the desired crystal phases to form only insufficient. Amorphous portions or portions of foreign phases can adversely affect the mechanical properties of the fibers.
Gegenstand der Erfindung ist eine Spinnmasse zur Herstellung von oxidischen Keramikfasern enthaltend eine kolloidale Suspension von Metalloxidpartikeln.The invention relates to a spinning composition for the production of oxide ceramic fibers containing a colloidal suspension of metal oxide particles.
Dabei wird von solchen Metalloxiden ausgegangen, die in ihrer Kristallphase identisch sind mit dem Metalloxid der fertigen Keramikfaser. Diese Metalloxidpartikel dienen als Kristallisationskeime und sollen die jeweiligen Kristallphasen in den keramischen Fasern stabilisieren und die Temperatur für die Phasenumwandlung bei deren Herstellung senken. Sie dienen nicht als Rohstoff zur Herstellung der Keramikfasern, sondern werden zusätzlich zu den für die Bildung der Keramikfasern benötigten Rohstoffen eingesetzt. Da diese Metalloxide als Kristallisationskeime dienen, müssen sie in ihren chemischen und physikalischen Eigenschaften mit den fertigen Keramikfasern übereinstimmen. Dies bedeutet beispielsweise, dass die Metalloxidpartikel aus Mullit bestehen müssen, wenn die fertige Keramikfaser aus Mullit besteht, oder die Metalloxidpartikel müssen im Fall der Herstellung einer Korundfaser ebenfalls aus Korund bestehen.It is assumed that such metal oxides, which are identical in their crystal phase with the metal oxide of the finished ceramic fiber. These metal oxide particles serve as crystallization nuclei and are intended to stabilize the respective crystal phases in the ceramic fibers and lower the temperature for the phase transformation during their production. They do not serve as a raw material for the production of ceramic fibers, but are used in addition to the raw materials needed for the formation of ceramic fibers. Since these metal oxides serve as crystallization seeds, they must match in their chemical and physical properties with the finished ceramic fibers. This means, for example, that the metal oxide particles must consist of mullite, if the finished ceramic fiber consists of mullite, or the Metal oxide particles must also consist of corundum in the case of the production of a corundum fiber.
Als Metalloxide kommen beispielsweise in Frage alle Kristallmodifikationen von Aluminiumoxid, beispielsweise Korund, die Tonerdemodifikationen, Mischungen dieser Kristallmodifikationen, Mischoxide zwischen Siliciumdioxid und Aluminiumoxid, beispielsweise Mullit, Zirkoniumoxid, Mischoxide zwischen Aluminium und Zirkoniumoxid, Metallaluminate und Yttriumaluminiumgranat. Es kann mit Pulver oder auch mit keramischen Fasern gestartet werden. Im Fall von keramischen Fasern können diese in einer Mühle zerkleinert werden. DieSuitable metal oxides are, for example, all crystal modifications of alumina, for example corundum, the clay demodifications, mixtures of these crystal modifications, mixed oxides between silica and alumina, for example mullite, zirconium oxide, mixed oxides between aluminum and zirconium oxide, metal aluminates and yttrium aluminum garnet. It can be started with powder or with ceramic fibers. In the case of ceramic fibers, they can be comminuted in a mill. The
Herstellung der kolloidalen Suspension kann dann mit einem Dispergator, einer Perlmühle oder mit Ultraschall erfolgen. Es kann auch von entsprechenden Nanooxiden, die leicht dispergierbar sind, ausgegangen werden. Die kolloidale Suspension wird vorzugsweise mit entsprechenden Stabilisatoren versetzt um die dispergierten Partikel zu stabilisieren. Als Stabilisatoren kommen Tenside, Polymere (z. B. Acrylate, Polyethylenglykole, Polyvinylalkohole, Polykationen, Polyanionen), organische Säuren, anorganische Säuren und Beschichtungsmittel wie Silane oder Siloxane in Frage. Als Dispergiermittel kommen Wasser, Alkohole, Ether, Ester, Toluol, XyIoI und geeignete Mischungen der genannten Dispergiermittel in Frage. Bevorzugt kommt Wasser zum Einsatz, da die Spinnlösungen meist auf wässriger Basis beruhen.Production of the colloidal suspension can then take place with a dispersing agent, a bead mill or with ultrasound. It can also be assumed that corresponding nanooxides, which are easily dispersible. The colloidal suspension is preferably treated with appropriate stabilizers to stabilize the dispersed particles. Suitable stabilizers are surfactants, polymers (for example acrylates, polyethylene glycols, polyvinyl alcohols, polycations, polyanions), organic acids, inorganic acids and coating agents such as silanes or siloxanes. Suitable dispersants are water, alcohols, ethers, esters, toluene, xylene and suitable mixtures of the dispersants mentioned. Water is preferably used since the spinning solutions are usually based on water.
Die Partikel der hergestellten Kolloide sollten möglichst fein vorliegen um eine effektive Keimung zu ermöglichen. Bevorzugt werden Partikel < 0,5 μm verwendet, besonders bevorzugt < 0,2 μm. Der Feststoffgehalt der kolloidalen Suspensionen kann bis zu 50 Gew.-% betragen.The particles of the prepared colloids should be as fine as possible to allow effective germination. Preference is given to using particles <0.5 μm, more preferably <0.2 μm. The solids content of the colloidal suspensions may be up to 50% by weight.
Die kolloidalen Suspensionen von Partikeln mit der gewünschten Kristallphase werden mit den Spinnmassen gemischt, wobei der Gehalt an kolloidal suspendierten Metalloxidpartikeln (Kristallisationskeimen) zwischenThe colloidal suspensions of particles with the desired crystal phase are mixed with the spinning masses, wherein the content of colloidally suspended metal oxide particles (crystallization nuclei) between
0,1 - 20 Gew.-% bezogen auf den rechnerischen Gehalt an Metalloxid in der Spinnmasse. Besonders bevorzugt werden Gehalte an Kristallisationskeimen von 0,5 - 5 Gew.-%. Die kolloidale Suspension von Metalloxidpartikeln (Kristallisationskeimen) sollte möglicht homogen mit den Spinnmassen gemischt werden. Dies geschieht unter Zuhilfenahme von Rührern, Dispergatoren, Ultraschall oder sonstigen Mischeinrichtungen die eine homogene Einmischung der Kristallisationskeime erlauben.0.1 - 20 wt .-% based on the calculated content of metal oxide in the dope. Particular preference is given to contents of crystallization seeds of from 0.5 to 5% by weight. The colloidal suspension of metal oxide particles (Crystallization germs) should be mixed as homogeneously as possible with the spinning masses. This is done with the aid of stirrers, dispersants, ultrasound or other mixing devices which allow a homogeneous mixing of the nuclei.
Die Spinnmassen sind qualitativ und quantitativ so zusammengesetzt, wie bei derartigen Spinnmassen zur Herstellung von oxidischen Fasern bekannt. Als Spinnmassen kommen Gemische von Salzen oder Metallorganische Verbindungen in Frage die bei der Kalzinierung Mullitphasen (3 AI2O3 * 2 SiO2), Tonerdephasen, Korund, Zirkoniumoxidphasen, Metallaluminatphasen und Granatphasen (z. B. Yttriumaluminiumgranat) ergeben. Polymere werden ebenfalls zugegeben, um die Rheologie für die Spinnbarkeit der Masse einzustellen. Besonders bevorzugt werden wasserlösliche Polymere, wie Polyvinylalkohole, Polyethylenoxide, Polyvinylpyrrolidone, wobei der Gehalt an Polymer im Bereich 0,5 - 40 Gew.-% (bezogen auf den Oxidgehalt der Mischung) liegen kann. Zur Erhöhung des Feststoffgehalts kann es noch vorteilhaft sein, der Spinnmasse Lösungsmittel (Wasser) zu entziehen. Dies kann unter Erwärmung bei Normaldruck oder im Vakuum erfolgen.The spinning masses are qualitatively and quantitatively composed as known in such spinning masses for the production of oxide fibers. As dopes mixtures of salts or organometallic compounds in question, in the calcination mullite phases (3 Al 2 O 3 * 2 SiO 2), alumina phases, corundum, Zirkoniumoxidphasen, Metallaluminatphasen and garnet phases (z. B. yttrium aluminum garnet) yield. Polymers are also added to adjust the rheology for bulk spinnability. Particularly preferred are water-soluble polymers, such as polyvinyl alcohols, polyethylene oxides, polyvinylpyrrolidones, wherein the content of polymer in the range 0.5 to 40 wt .-% (based on the oxide content of the mixture) may be. To increase the solids content, it may also be advantageous to extract solvent (water) from the dope. This can be done under normal pressure or under vacuum.
Die erfindungsgemäße Spinnmasse wird durch Düsen geblasen oder ausgedrückt, wobei die entstehenden Grünfasern als Kurzfaser gesammelt werden. Es ist auch möglich, mit der erfindungsgemäßen Spinnmasse Langfasern herzustellen, wobei in diesem Fall der Faden aufgenommen und auf Spulen gewickelt wird. Die so erhaltene Grünfaser wird in einem anschließenden Kalzinierungsschritt in die gewünschte Keramikfaser überführt. Dies geschieht bei der für die Ausbildung der gewünschten Kristallphase charakteristischen Temperatur.The spinning dope according to the invention is blown or expressed through nozzles, wherein the resulting green fibers are collected as short fiber. It is also possible to produce long fibers with the spinning composition according to the invention, in which case the thread is taken up and wound on bobbins. The green fiber thus obtained is converted into the desired ceramic fiber in a subsequent calcination step. This happens at the characteristic for the formation of the desired crystal phase temperature.
Durch den Einsatz der kolloidalen Suspension der Metalloxidpartikel (Kristallisationskeime) ist diese charakteristische Temperatur zu niedrigeren Temperaturen hin verschoben im Vergleich zu den Spinnmassen ohne Kristallisationskeime. Außerdem zeigt sich, dass die Fasern weniger amorphe Anteile oder Fremdphasen enthalten und der Prozess dadurch stabiler zu gestalten ist. Außerdem zeigen die Fasern in der Regel geringere Kristallitgrößen, dichtere Gefüge und weniger Defekte im Kristallgitter. Makroskopisch wirkt sich dies in höheren Zugfestigkeiten und verbessertem Bruchverhalten aus.Through the use of the colloidal suspension of the metal oxide particles (crystallization nuclei), this characteristic temperature is shifted towards lower temperatures in comparison to the spinning masses without nuclei. It also shows that the fibers contain less amorphous or foreign phases, making the process more stable shape is. In addition, the fibers usually show smaller crystallite sizes, denser microstructures and fewer defects in the crystal lattice. Macroscopically, this results in higher tensile strengths and improved fracture behavior.
Die erfindungsgemäßen Langfasern eigenen sich insbesondere zur Herstellung von Keramikfaser-Geweben und als Ausgangsmaterial für die Herstellung von Keramikmatrix- und Metallmatrix-Verbundwerkstoffen.The long fibers according to the invention are particularly suitable for the production of ceramic fiber fabrics and as starting material for the production of ceramic matrix and metal matrix composite materials.
Beispiel 1example 1
Eine 50 %ig wässrige Lösung von Aluminiumchlorohydrat wurde mit soviel Kieselsol (Klebosol) versetzt, dass nach der Kalzinierung das Verhältnis von Aluminiumoxid zu Siliziumdioxid 97 : 3 Gew.-% beträgt. Außerdem wurden der Lösung 2 Gew.-% Kristaliisationskeime (bezogen auf den Oxidgehalt) in Form einer Suspension aus gamma/eta-Aluminiumoxid zugesetzt.To a 50% aqueous solution of aluminum chlorohydrate was added so much silica sol (Klebosol) that after calcination the ratio of alumina to silica 97: 3 wt .-% is. In addition, 2% by weight of crystallization nuclei (based on the oxide content) in the form of a suspension of gamma / eta-alumina were added to the solution.
Diese kolloidalen Suspensionen der Kristallisationskeime wurden zuvor aus am Markt erhältlichen keramischen Aluminiumoxidfasern hergestellt, indem die Fasern trocken in einer Mühle pulverisiert wurden. Das Pulver wurde dann in einer Perlmühle in Wasser dispergiert. Als Stabilisator kam 1 Gew.-% Trioxadecansäure zum Einsatz. Der Feststoffgehalt (Aluminiumoxid) in Wasser betrug 10 Gew.-%.These colloidal suspensions of nuclei were previously prepared from commercially available ceramic alumina fibers by dry pulverizing the fibers in a mill. The powder was then dispersed in water in a bead mill. The stabilizer used was 1% by weight of trioxadecanoic acid. The solid content (alumina) in water was 10% by weight.
Nachdem die Lösung durch Rühren homogenisiert wurde, erfolgte die Zugabe einer wässrigen Lösung von Polyethylenglykol-Polymer mit einemAfter the solution was homogenized by stirring, the addition of an aqueous solution of polyethylene glycol polymer with a
Molekulargewicht von 1 Mio. Nach der Aufkonzentrierung durch Abdampfen von Wasser im Vakuum wurde die Spinnmasse in einem Trockenspinnverfahren durch eine Einlochdüse versponnen. Die erhaltenen Grünfasern wurden in einer DTA (Differentialthermoanalyse) langsam bis auf 1.300 0C erhitzt. Der Vergleich mit der Faser, die ohne Kristallisationskeime hergestellt wurde zeigte eine Absenkung der Bildungstemperaturen für Tonerde von ca. 100 0C. Molecular weight of 1 million. After concentration by evaporation of water in vacuo, the dope was spun in a dry spinning process through a single hole die. The obtained green fibers were slowly heated in a DTA (differential thermal analysis) up to 1300 0 C. The comparison with the fiber, which was produced without crystallization nuclei showed a lowering of the formation temperatures for alumina of about 100 0 C.

Claims

Patentansprüche: claims:
1. Spinnmasse zur Herstellung von oxidischen Keramikfasern enthaltend eine kolloidale Suspension von Metalloxidpartikeln.1. A spinning composition for the production of oxide ceramic fibers containing a colloidal suspension of metal oxide particles.
2. Spinnmasse nach Anspruch 1 , dadurch gekennzeichnet, dass die Metalloxidpartikel in ihrer Kristallphase identisch sind mit dem Metalloxid der fertigen Keramikfaser.2. spinning mass according to claim 1, characterized in that the metal oxide particles are identical in their crystal phase with the metal oxide of the finished ceramic fiber.
3. Spinnmasse nach Anspruch 1 wobei die kolloidale Suspensionen aus Metalloxidpartikel ausgehend von Metalloxidfasern hergestellt wird, indem die Fasern pulverisiert werden, vorzugsweise durch trockene Vermahlung und Dispergierung der Metalloxidpartikel in Perlmühlen, Dissolvem oder durch Ultraschall unter Verwendung von Dispergiermitteln und Stabilisatoren.The dope of Claim 1 wherein the colloidal suspensions are prepared from metal oxide particles from metal oxide fibers by pulverizing the fibers, preferably by dry milling and dispersing the metal oxide particles in bead mills, dissolvers or ultrasonically using dispersants and stabilizers.
4. Spinnmasse nach Anspruch 2, dadurch gekennzeichnet, dass als Dispergiermittel Wasser verwendet wird.4. dope according to claim 2, characterized in that water is used as the dispersant.
5. Spinnmasse nach Anspruch 2, dadurch gekennzeichnet, dass als Stabilisatoren Tenside, Polymere, organische Säuren, anorganische Säuren und Beschichtungsmittel wie Silane oder Siloxane zum Einsatz kommen.5. spinning mass according to claim 2, characterized in that as stabilizers surfactants, polymers, organic acids, inorganic acids and coating agents such as silanes or siloxanes are used.
6. Spinnmasse nach Anspruch 1 , dadurch gekennzeichnet, dass die kolloidale Suspensionen aus Metalloxidpartikeln ausgehend von Metalloxidpulver hergestellt wird, indem das Pulver in Perlmühlen, Dissolvem oder durch Ultraschall unter Verwendung von Dispergiermitteln und Stabilisatoren dispergiert wird.6. A dope according to claim 1, characterized in that the colloidal suspensions of metal oxide particles is prepared starting from metal oxide powder by the powder is dispersed in bead mills, dissolvers or by ultrasound using dispersants and stabilizers.
7. Spinnmasse nach Anspruch 1 , dadurch gekennzeichnet, dass die Spinnmassen die kolloidal suspendierten Metalloxidpartikel im Bereich 0,1 - 20 Gew.-%, bevorzugt im Bereich 0,5 - 5 Gew.-% bezogen auf den rechnerischen Gehalt an Metalloxid in der Spinnmasse als Kristallisationshilfe enthalten. 7. spinning mass according to claim 1, characterized in that the spinning masses, the colloidally suspended metal oxide particles in the range 0.1 to 20 wt .-%, preferably in the range 0.5 to 5 wt .-% based on the calculated content of metal oxide in the Containing dope as a crystallization aid.
PCT/EP2008/002833 2007-04-16 2008-04-10 Spinning material for the production of oxide ceramic fibers WO2008125271A2 (en)

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EP0206634A2 (en) * 1985-06-21 1986-12-30 Imperial Chemical Industries Plc Inorganic oxide fibres and their production
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