(19)
(11)EP 2 617 756 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
25.03.2020 Bulletin 2020/13

(21)Application number: 13151746.8

(22)Date of filing:  17.01.2013
(51)International Patent Classification (IPC): 
C08G 77/58(2006.01)
C08G 77/50(2006.01)
C08G 77/38(2006.01)
C08G 77/56(2006.01)
C08G 77/60(2006.01)
C04B 35/571(2006.01)

(54)

METHOD OF FORMING A PRECERAMIC MATERIAL

VERFAHREN ZUR FORMUNG EINES VORKERAMIKMATERIALS

PROCÉDÉ DE FORMATION DE MATÉRIAUX PRÉCÉRAMIQUES


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 18.01.2012 US 201213352584

(43)Date of publication of application:
24.07.2013 Bulletin 2013/30

(73)Proprietor: United Technologies Corporation
Farmington, CT 06032 (US)

(72)Inventor:
  • Schmidt, Wayde R.
    Pomfret Center, CT Connecticut 06259 (US)

(74)Representative: Dehns 
St. Bride's House 10 Salisbury Square
London EC4Y 8JD
London EC4Y 8JD (GB)


(56)References cited: : 
US-A- 4 347 347
US-A1- 2003 114 540
US-A- 4 359 559
US-B1- 6 395 826
  
  • DATABASE WPI Week 200851 Thomson Scientific, London, GB; AN 2008-J04920 -& WO 2008/066060 A1 (JSR CORP) 5 June 2008 (2008-06-05)
  • DATABASE WPI Week 201131 Thomson Scientific, London, GB; AN 2011-E18903 -& JP 2011 081268 A (JSR CORP) 21 April 2011 (2011-04-21)
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

BACKGROUND



[0001] This disclosure relates to processing of preceramic materials and, more particularly, to treating a preceramic polymer material.

[0002] Machine components, such as components of gas turbine engines, are subjected to high temperatures, corrosive and oxidative conditions and elevated stress levels. In order to improve the thermal and oxidative stability of such components, the components may include a thermally resistant ceramic material. There are different ceramic processing techniques for forming ceramic material, including thermal conversion of a preceramic polymer. For instance US 4 359 559 A discloses a polycarbosilane comprising a metal (titanium or zirconium) linked through an oxygen atom to a silicon atom, further used to prepare a ceramic material.

SUMMARY



[0003] A disclosed example method of forming a preceramic material includes modifying a moiety Si-O-R of polycarbosilane or polycarbosiloxane material with at least one metal (M), where M is according to claim 1, and where Si is silicon, O is oxygen and R includes an alkyl or aryl moiety, by reaction to substitute R with M to produce a preceramic polycarbosilane or polycarbosiloxane material that includes a moiety Si-O-M.

[0004] In a further embodiment of the foregoing method, the reaction includes at least one of a hydrolysis and a condensation reaction.

[0005] In a further embodiment of the foregoing method, the polycarbosilane or polycarbosiloxane material is alkoxy-modified polycarbosilane or polycarbosiloxane.

[0006] A further embodiment of the foregoing method includes providing the at least one metal (M) in a metal alkoxy or aryloxy compound and reacting the metal alkoxy or aryloxy compound with the moiety Si-O-R to substitute R with M.

[0007] A further embodiment of the foregoing method includes providing the at least one metal (M) in a metal alkoxy or aryloxy compound and dissolving the metal alkoxy or aryloxy compound and the polycarbosilane or polycarbosiloxane material in a solvent.

[0008] In a further embodiment of the foregoing method, the solvent is selected from a group consisting of methanol, hexane, tetrahydrofuran, 2-methyl-1-propanol and combinations thereof.

[0009] In a further embodiment of the foregoing method, the solvent is 2-methyl-1-propanol.

[0010] A further embodiment of the foregoing method includes providing the at least one metal (M) in a metal alkoxy or aryloxy compound, dissolving the metal alkoxy or aryloxy compound and the polycarbosilane or polycarbosiloxane material in a solvent to form a solution and catalyzing the reaction or reactions in the solution using an acid.

[0011] A further embodiment of the foregoing method includes, after the reaction or reactions, removing the solvent to produce a substantially dry solid reaction product comprising the preceramic polycarbosilane or polycarbosiloxane material that includes the moiety Si-O-M.

[0012] The method as recited in claim 1, including thermally converting the preceramic polycarbosilane or polycarbosiloxane material that includes the moiety Si-O-M into a ceramic material.

[0013] A further embodiment of the foregoing method includes mixing the preceramic polycarbosilane or polycarbosiloxane material that includes the moiety Si-O-M with a different preceramic polymer material.

[0014] According to the invention, the at least one metal (M) is selected from a group consisting of aluminum, boron, alkaline earth metals, transition metals, refractory metals, rare earth metals and combinations thereof.

[0015] In a further embodiment of the foregoing method, the at least one metal is selected from a group consisting of aluminum, boron and combinations thereof.

[0016] In a further embodiment of the foregoing method, the at least one metal is a transition metal selected from a group consisting of hafnium, vanadium, chromium and combinations thereof.

[0017] In a further embodiment of the foregoing method, the at least one metal is a refractory metal selected from a group consisting of niobium, tantalum, molybdenum, tungsten, rhenium and combinations thereof.

[0018] In a further embodiment of the foregoing method, the at least one metal is a rare earth metal selected from a group consisting of scandium, ytterbium, gadolinium, yttrium, lanthanum, neodymium, dysprosium, lutetium and combinations thereof.

[0019] In a further embodiment of the foregoing method, the at least one metal is an alkaline earth metal selected from a group consisting of barium, strontium, calcium, magnesium, and combinations thereof.

[0020] In another aspect, a method of forming a preceramic material further comprises providing a preceramic polycarbosilane or polycarbosiloxane material that includes a moiety Si-O-M and thermally converting the preceramic polycarbosilane or polycarbosiloxane material that includes the moiety Si-O-M into a ceramic material.

[0021] A further embodiment of the foregoing method includes thermally converting the preceramic polycarbosilane or polycarbosiloxane material produces a ceramic material having a composition SiOxMzCy, wherein x < 2, y > 0 and z < 1 and x and z are non-zero.

[0022] The various features and advantages of the disclosed examples will become apparent to those skilled in the art from the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT



[0023] As will be described, disclosed is a method of forming a preceramic material. The method includes modifying a moiety Si-O-R of a polycarbosilane or polycarbosiloxane material with at least one metal (M), where M is according to claim 1, and where Si is silicon, O is oxygen and R includes an alkyl or aryl moiety, by reaction to substitute R with M to produce a preceramic polycarbosilane or polycarbosiloxane material that includes a moiety Si-O-M (hereafter "preceramic polycarbosilane" or "preceramic polycarbosiloxane" material, respectively).

[0024] Upon eventual thermal conversion of the preceramic polycarbosilane or polycarbosiloxane material into a ceramic material, the metal forms a thermally stable glass or crystalline ceramic compound or both in the microstructure. For example, the microstructure of the resulting ceramic material includes regions of glass or crystalline ceramic that include the metal. The glass or crystalline ceramic regions are dispersed within regions of Si-O-C ceramic material. The glass can be a low melting point glass relative to the surrounding Si-O-C ceramic material, which serves to seal microcracks and getter oxygen within the microstructure and thus improves the properties, durability and densification of the ceramic material in oxidizing environments.

[0025] In examples based upon boron or aluminum, the glass is borosilicate or aluminosilicate glass, respectively, or both if boron and aluminum are used as the metal. The glass can have a local melting temperature that is lower than the surrounding Si-O-C regions. The low melting point glass regions thereby soften or melt upon exposure to elevated temperatures and are thus able to move into microcracks to seal those areas. Additionally, the presence of the metal also serves to getter oxygen in-situ and thus intercepts oxygen that might otherwise react to form unfavorable or undesired phases.

[0026] The selected metal or metals preserve the glass-forming capability and the crystallization behavior of the ceramic material that forms from the preceramic polycarbosilane or polycarbosiloxane material. In this sense, and herein, a glass is defined as an amorphous, generally non-crystalline, oxygen-containing solid with minimal long range structural order. The metal-containing glass of this example may also readily and further oxidize upon exposure to environmental oxidizing conditions, such as the environmental operating conditions within a gas turbine engine, further forming a glassy or crystalline oxide product. Thus, it is to be understood that the composition can change upon oxidation.

[0027] As a comparison, Si-O-C alone, without the glass and metal, is subject to detrimental reactions with elements from the operating environmental, such as oxygen, under relatively high environmental temperatures in the presence of moisture. The disclosed method yields a preceramic polycarbosilane or polycarbosiloxane material that can ultimately be thermally converted into a ceramic material having enhanced durability.

[0028] In the disclosed method, the moiety Si-O-R of the polycarbosilane or polycarbosiloxane material is reactive such that the metal can be substituted for the alkyl or aryl moiety R to produce the preceramic polycarbosilane or polycarbosiloxane material. Thus, the metal becomes covalently incorporated into the polymeric structure prior to thermal conversion of the material to produce a ceramic material.

[0029] In one embodiment, the reaction sequence to substitute the alkyl or aryl moiety R with the metal M includes at least one of a hydrolysis and a condensation reaction.

[0030] In one example reaction sequence that includes both a hydrolysis reaction and a condensation reaction, the polycarbosilane or polycarbosiloxane material having the moiety Si-O-R is alkoxy-modified polycarbosilane or polycarbosiloxane and is reacted with a metal alkoxy or aryloxy compound. In the reaction, the metal of the metal alkoxy or aryloxy compound supplants the alkyl or aryl moiety R to produce the moiety Si-O-M in the preceramic polycarbosilane or polycarbosiloxane material.

[0031] In embodiments, the alkoxy-modified polycarbosilane material is selected from dimethoxypolycarbosilane, diethoxypolycarbosilane, methoxyethoxypolycarbosilane, isopropoxycarbosilane, butoxycarbosilane or other alkoxy-modified polycarbosilane (available from Starfire® Systems).

[0032] In embodiments, the metal alkoxy compound is metal alkoxide. In one example based on aluminum as the metal, the metal alkoxide compound is aluminum isopropoxide. In another example based on boron as the metal, the metal alkoxide compound is boron methoxide. Likewise, for other target metals, the metal or metals are provided in alkoxy or aryloxy compounds to carry out the reaction.

[0033] The metal or metals are according to claim 1 and selected from aluminum, boron, alkaline earth metals, transition metals, refractory metals, rare earth metals and combinations thereof. These metals are glass-forming metals in that they can be incorporated, for example, through covalent bonding, into oxide-based glasses. As an example, the selected metal or metals are glass-forming metals that can readily and further oxidize upon exposure to environmental oxidizing conditions, such as the environmental operating conditions within a gas turbine engine.

[0034] In another example, the metal or metals are alkaline earth metals selected from barium, strontium, calcium or magnesium.

[0035] In a further example, the metal or metals are transition metals selected from, hafnium, vanadium, chromium and combinations thereof.

[0036] In another embodiment, the metal or metals are refractory metals selected from niobium, tantalum, molybdenum, tungsten, rhenium and combinations thereof.

[0037] In another embodiment, the metal or metals are rare earth metals, such as scandium, ytterbium, gadolinium, yttrium, lanthanum, neodymium, dysprosium, lutetium and combinations thereof.

[0038] In further examples, the preceramic polycarbosilane or polycarbosiloxane material may additionally include impurities that do not affect the properties of the material or elements that are unmeasured or undetectable in the material. In other examples, the preceramic polycarbosilane or polycarbosiloxane material includes any one of the example metals, to the exclusion of any other metals that are present in more than trace amounts as inadvertent impurities. In other examples, the preceramic polycarbosilane or polycarbosiloxane material includes a plurality of the example metals, in any combination, to the exclusion of any other metals that are present in more than trace amounts as inadvertent impurities.

[0039] In one embodiment, the reaction to substitute the metal or metals for the alkyl or aryl moiety R in the polycarbosilane or polycarbosiloxane material is conducted within a solvent solution. For example, the starting polycarbosilane or polycarbosiloxane material and a metal organic material of the selected metal or metals are dissolved within a solvent. The selected solvent is compatible with the selected starting polycarbosilane or polycarbosiloxane material and selected metal organic material or materials. That is, the solvent is suitable for dissolving the starting polycarbosilane or polycarbosiloxane material and the metal organic material or materials. For example, the solvent is selected from methanol, hexane, tetrahydrofuran, 2-methyl-1-propanol and combinations thereof. In a further example, the solvent is 2-methyl-1-propanol and is able to readily dissolve the polycarbosilane or polycarbosiloxane material, the metal organic material or materials and water that may be added to the solution to control reaction rate.

[0040] In one embodiment, the reaction between the starting polycarbosilane or polycarbosiloxane material and selected metal organic material or materials proceeds without the aid of a catalyst. For example, the metal organic material is aluminum isopropoxide.

[0041] In another embodiment, the metal or metals are initially provided as a solid in the solvent. In one example based on aluminum, discrete nano-particles of aluminum are provided in the solvent. The nano-particles may not be soluble in the solvent, but with the addition of isopropyl alcohol to the solution, the aluminum reacts with the isopropyl alcohol to form aluminum isopropoxide. Similarly, other target metals can be provided in solid form with reactive solvents to form metal organic compounds that then react with the starting polycarbosilane or polycarbosiloxane material.

[0042] In another embodiment that uses a catalyzed reaction, the starting polycarbosilane or polycarbosiloxane material and the metal organic material or materials that are dissolved within the solvent are provided with a catalyst, such as an acid catalyst, to promote the reaction. As an example, the acid is or includes hydrochloric acid. Optionally, the reaction rate is controlled by controlling the amount of acid added to the solution and an amount of water added in the solution. However, if no acid catalyst is used, the rate of the reaction can alternatively be controlled by controlling the amount of metal organic material or materials that are added in the solution.

[0043] In a further embodiment, the reaction rate is controlled by providing atmospheric humidity as the source of water rather than adding water to the solution. In the above examples, all the reactions may be carried out at ambient temperature conditions of 65°-75°F (18°-24°C). However, it is to be understood that different temperatures can alternatively be used to further control the rate of reaction.

[0044] In a further embodiment, the starting polycarbosilane or polycarbosiloxane material is initially a liquid material that is added to the solvent to form the solution. Upon the reaction or reactions to substitute the metal or metals for the alkyl or aryl moiety R of the polycarbosilane or polycarbosiloxane material, a solid or semi-solid precipitant results. Upon completion or substantial completion of the reaction or reactions, the solvent can then be removed, leaving the solid or semi-solid reaction product. The reaction product is the preceramic polycarbosilane or polycarbosiloxane material that includes the moiety Si-O-M. In one embodiment, the resulting solid or semi-solid is further dried under the vacuum and/or at elevated temperatures to remove or substantially remove all of the solvent.

[0045] In a further embodiment, the preceramic polycarbosilane or polycarbosiloxane material is then further processed to produce a ceramic material. As an example, the preceramic polycarbosilane or polycarbosiloxane material is thermally converted into a ceramic material having a composition SiOxMzCy, where Si is silicon, O is oxygen, M is the metal or metals as claimed and C is carbon and wherein x < 2, y > 0 and z < 1 and x and z are non-zero. It is to be understood that the metal composition includes the combined composition of all covalently bonded metals M.

[0046] In one example of thermally converting the preceramic polycarbosilane or polycarbosiloxane material, the resulting solid or semi-solid from the above-described reaction or reactions is heated to approximately 1000°C in air, argon or nitrogen and held for approximately 2 hours to produce a ceramic material. It is to be understood that different thermal conversion conditions can be used. However, a combination of heating and atmospheric exposures can be used if desired. In this example, the choice of atmosphere type, exposure time and exposure temperature is used to control the resulting ceramic phase(s). In one example, the ceramic yield is in a range of approximately 60-65 wt.% with regard to the starting mass of the preceramic polycarbosilane or polycarbosiloxane material. In a further example, the metal constitutes approximately 0.5-20 at.% of the resulting ceramic material, and in a further example constitutes approximately 1-10 at.% in the ceramic material.

[0047] In another example, the preceramic polycarbosilane or polycarbosiloxane material that results from the above-described reaction or reactions is thermally converted in an argon environment at a temperature of 1000°C or greater for approximately two hours. The resulting ceramic material is then crushed into a particulate material and further thermally treated for approximately eight hours at a temperature of 1500°C in either generally inert or oxidizing environments, such as argon or air, respectively.

[0048] In another embodiment, the thermal treatment is applied to a mixture of the preceramic polycarbosilane or polycarbosiloxane material that results from the above-described reaction or reactions and another, different preceramic polymer. Alternatively, the ceramic powder that results after the thermal treatment at 1000°C is mixed with another ceramic powder, such as Si-O-C ceramic material and then further thermally treated at the 1500°C temperature in either generally inert or oxidizing environments, such as argon or air, respectively.

[0049] In a further embodiment, prior to thermal conversion of the preceramic polycarbosilane or polycarbosiloxane material, the material is mixed with other, different preceramic polymers and/or additives. The selected preceramic polymer and/or additives will depend upon the desired resultant ceramic material. In general, the additives can include metallic materials and/or ceramic materials. In one example, the preceramic polycarbosilane or polycarbosiloxane material is mixed with a ceramic material and/or glass or glass ceramic material that includes carbides, oxides, nitrides, borides, silicides, oxycarbides, oxynitrides, carbonitrides, aluminides, silicates, titanates, phosphates, phosphides or combinations thereof. The glass and glass-ceramic materials may include silica, borosilicates, barium aluminosilicates, lanthanum aluminosilicates, strontium magnesium silicates, barium magnesium aluminosilicates, calcium magnesium aluminosilicates and lithium-containing glasses. The metal may include a superalloy material, for example.

[0050] In a further embodiment, the preceramic polycarbosilane or polycarbosiloxane material, or mixture with another, different preceramic polymer and/or additive, is then further processed to produce a ceramic material. The ceramic material may be a coating or a layer that is applied onto a component, a filler that is incorporated into a matrix of another material, a matrix that is filled with another, different material, or as a standalone, self-supporting body. In some examples, the ceramic material that is produced from the preceramic polycarbosilane or polycarbosiloxane material may be a combustion chamber, a turbine vane, compressor blade or vane, blade outer air seal, other component within a gas turbine engine or a portion thereof, for example.

[0051] Although a combination of features is shown in the illustrated examples, not all of them need to be combined to realize the benefits of various embodiments of this disclosure. Moreover, selected features of one example embodiment may be combined with selected features of other example embodiments.

[0052] The preceding description is exemplary rather than limiting in nature. Variations and modifications to the disclosed examples may become apparent to those skilled in the art that do not necessarily depart from the essence of this disclosure. The scope of legal protection given to this disclosure can only be determined by studying the following claims.


Claims

1. A method of forming a preceramic material, the method comprising:

modifying a moiety Si-O-R of a polycarbosilane or polycarbosiloxane material with at least one metal (M), where Si is silicon, O is oxygen and R includes an alkyl or aryl moiety, by reaction to substitute R with M to produce a preceramic polycarbosilane or polycarbosiloxane material that includes a moiety Si-O-M, wherein the at least one metal (M) is selected from a group consisting of aluminum, boron, alkaline earth metals, transition metals, refractory metals, rare earth metals and combinations thereof; and

wherein the transition metal is selected from a group consisting of hafnium, vanadium, chromium and combinations thereof; and

wherein the refractory metal is selected from a group consisting of niobium, tantalum, molybdenum, tungsten, rhenium and combinations thereof; and

wherein rare earth metal is selected from a group consisting of scandium, ytterbium, gadolinium, yttrium, lanthanum, neodymium, dysprosium, lutetium and combinations thereof; and

wherein alkaline earth metal is selected from a group consisting of barium, strontium, calcium, magnesium, and combinations thereof.


 
2. The method as recited in claim 1, wherein the method includes at least one of a hydrolysis and a condensation reaction.
 
3. The method as recited in claim 1 or claim 2, wherein the polycarbosilane or polycarbosiloxane material is alkoxy-modified polycarbosilane or polycarbosiloxane.
 
4. The method as recited in any of claims 1 to 3, including providing the at least one metal (M) in a metal alkoxy or aryloxy compound and reacting the metal alkoxy or aryloxy compound with the moiety Si-O-R to substitute R with M.
 
5. The method as recited in any of claims 1 to 4, including providing the at least one metal (M) in a metal alkoxy or aryloxy compound and dissolving the metal alkoxy or aryloxy compound and the polycarbosilane or polycarbosiloxane material in a solvent.
 
6. The method as recited in any of claims 1 to 5, including providing the at least one metal (M) in a metal alkoxy or aryloxy compound, dissolving the metal alkoxy or aryloxy compound and the polycarbosilane or polycarbosiloxane material in a solvent to form a solution and catalyzing the reaction or reactions in the solution using an acid.
 
7. The method as recited in any of claims 1 to 6, further comprising mixing the preceramic polycarbosilane or polycarbosiloxane material that includes the moiety Si-O-M with a different preceramic polymer material.
 
8. The method as recited in any of claims 1 to 7, wherein the at least one metal is selected from a group consisting of aluminum, boron and combinations thereof.
 


Ansprüche

1. Verfahren zur Formung eines Vorkeramikmaterials, wobei das Verfahren Folgendes umfasst:

Modifizieren einer Einheit Si-O-R eines Polycarbosilan- oder eines Polycarbosiloxanmaterials mit mindestens einem Metall (M), wobei Si Silikon ist, O Sauerstoff ist und R eine Alkyl- oder eine Aryleinheit durch Reaktion zum Ersetzen von R mit M beinhaltet, um ein vorkeramisches Polycarbosilan- oder Polycarbosiloxanmaterial herzustellen, das eine Einheit Si-O-M beinhaltet, wobei das mindestens eine Metall (M) aus einer Gruppe bestehend aus Aluminium, Bor, Erdalkalimetallen, Übergangsmetallen, hochschmelzenden Metallen, Seltenerdmetallen und Kombinationen daraus ausgewählt ist; und

wobei das Übergangsmetall aus einer Gruppe bestehend aus Hafnium, Vanadium, Chrom und Kombinationen daraus ausgewählt ist; und

wobei das hochschmelzende Metall aus einer Gruppe bestehend aus Niob, Tantal, Molybdän, Wolfram, Rhenium und Kombinationen daraus ausgewählt ist; und

wobei das Seltenerdmetall aus einer Gruppe bestehend aus Scandium, Ytterbium, Gadolinium, Yttrium, Lanthan, Neodym, Dysprosium, Lutetium und Kombinationen daraus ausgewählt ist; und

wobei das Erdalkalimetall aus einer Gruppe bestehend aus Barium, Strontium, Kalzium, Magnesium und Kombinationen daraus ausgewählt ist.


 
2. Verfahren nach Anspruch 1, wobei das Verfahren mindestens eins von einer Hydrolyse und einer Kondensationsreaktion beinhaltet.
 
3. Verfahren nach Anspruch 1 oder 2, wobei das Polycarbosilan- oder Polycarbosiloxanmaterial ein Alkoxymodifiziertes Polycarbosilan oder Polycarbosiloxan ist.
 
4. Verfahren nach einem der Ansprüche 1 bis 3, wobei das Verfahren das Bereitstellen des mindestens einen Metalls (M) in einer Metallalkoxy- oder Aryloxyverbindung und das Reagieren der Metallakoxy- oder Aryloxyverbindung mit der Einheit Si-O-R beinhaltet, um R mit M zu ersetzen.
 
5. Verfahren nach einem der Ansprüche 1 bis 4, wobei das Verfahren das Bereitstellen des mindestens einen Metalls (M) in einer Metallalkoxy- oder Aryloxyverbindung und das Auflösen der Metallalkoxy- oder Aryloxyverbindung und des Polycarbosilan- oder Polycarbosiloxanmaterials in einem Lösungsmittel beinhaltet.
 
6. Verfahren nach einem der Ansprüche 1 bis 5, wobei das Verfahren das Bereitstellen des mindestens einen Metalls (M) in einer Metallalkoxy- oder Aryloxyverbindung beinhaltet, wobei die Metallalkoxy- oder Aryloxyverbindung und das Polycarbosilan- oder Polycarbosiloxanmaterial in einem Lösungsmittel aufgelöst werden, um eine Lösung zu bilden und die Reaktion oder die Reaktionen in der Lösung unter Anwendung einer Säure zu katalysieren.
 
7. Verfahren nach einem der Ansprüche 1 bis 6, ferner umfassend das Mischen des vorkeramischen Polycarbosilan- oder Polycarbosiloxanmaterials, das die Einheit Si-O-M beinhaltet, mit einem anderen vorkeramischen Polymermaterial.
 
8. Verfahren nach einem der Ansprüche 1 bis 7, wobei das mindestens eine Metall (M) aus einer Gruppe bestehend aus Aluminium, Bor, und Kombinationen daraus ausgewählt ist.
 


Revendications

1. Procédé de formation d'un matériau précéramique, le procédé comprenant :

la modification d'une fraction Si-O-R d'un matériau en polycarbosilane ou polycarbosiloxane avec au moins un métal (M), où Si est le silicium, O est l'oxygène et R comporte une fraction alkyle ou aryle, par réaction pour remplacer R par M afin de produire un matériau en polycarbosilane ou polycarbosiloxane précéramique qui comporte une fraction Si-O-M, dans lequel l'au moins un métal (M) est choisi dans un groupe constitué de l'aluminium, du bore, de métaux alcalinoterreux, de métaux de transition, de métaux réfractaires, de métaux de terres rares, et de combinaisons de ceux-ci ; et

dans lequel le métal de transition est choisi dans un groupe constitué de l'hafnium, du vanadium, du chrome et de combinaisons de ceux-ci ; et

dans lequel le métal réfractaire est choisi dans un groupe constitué du niobium, du tantale, du molybdène, du tungstène, du rhénium et de combinaisons de ceux-ci ; et

dans lequel un métal de terres rares est choisi dans un groupe constitué du scandium, de l'ytterbium, du gadolinium, de l'yttrium, du lanthane, du néodyme, du dysprosium, du lutétium et de combinaisons de ceux-ci ; et

dans lequel le métal alcalinoterreux est choisi dans un groupe constitué du baryum, du strontium, du calcium, du magnésium, et de combinaisons de ceux-ci.


 
2. Procédé selon la revendication 1, dans lequel le procédé comporte au moins l'une d'une hydrolyse et d'une réaction de condensation.
 
3. Procédé selon la revendication 1 ou la revendication 2, dans lequel le matériau en polycarbosilane ou polycarbosiloxane est un polycarbosilane ou polycarbosiloxane modifié par alcoxy.
 
4. Procédé selon l'une quelconque des revendications 1 à 3, comportant la fourniture de l'au moins un métal (M) dans un composé alcoxy ou aryloxy métallique et la mise en réaction du composé alcoxy ou aryloxy métallique avec la fraction Si-O-R pour remplacer R par M.
 
5. Procédé selon l'une quelconque des revendications 1 à 4, comportant la fourniture de l'au moins un métal (M) dans un composé alcoxy ou aryloxy métallique et la dissolution du composé alcoxy ou aryloxy métallique et du matériau en polycarbosilane ou polycarbosiloxane dans un solvant.
 
6. Procédé selon l'une quelconque des revendications 1 à 5, comportant la fourniture de l'au moins un métal (M) dans un composé alcoxy ou aryloxy métallique, la dissolution du composé alcoxy ou aryloxy métallique et du matériau en polycarbosilane ou polycarbosiloxane dans un solvant pour former une solution et la catalyse de la ou des réactions dans la solution à l'aide d'un acide.
 
7. Procédé selon l'une quelconque des revendications 1 à 6, comprenant en outre le mélange du matériau en polycarbosilane ou polycarbosiloxane précéramique qui comporte la fraction Si-O-M avec un matériau polymère précéramique différent.
 
8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel l'au moins un métal est choisi dans un groupe constitué de l'aluminium, du bore et de combinaisons de ceux-ci.
 






Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description