WO2005112048A1 - Keramischer widerstand - Google Patents
Keramischer widerstand Download PDFInfo
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- WO2005112048A1 WO2005112048A1 PCT/EP2005/051240 EP2005051240W WO2005112048A1 WO 2005112048 A1 WO2005112048 A1 WO 2005112048A1 EP 2005051240 W EP2005051240 W EP 2005051240W WO 2005112048 A1 WO2005112048 A1 WO 2005112048A1
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- WIPO (PCT)
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- ceramic
- aluminum
- molybdenum
- filler
- resistor according
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
- H01C17/0656—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of silicides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/58085—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicides
- C04B35/58092—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicides based on refractory metal silicides
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
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- H01C17/20—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by pyrolytic processes
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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Definitions
- the invention relates to a ceramic resistor and a method for its production and its use according to the preamble of the independent
- Molybdenum disilicide can be adjusted.
- the filled polymer is cured at 200 ° C and then pyrolyzed at temperatures between 800 and 1400 ° C.
- the resulting ceramic resistance is resistant to high temperatures;
- its long-term stability is limited because molybdenum disilicide tends to oxidize at elevated temperatures and the molybdenum oxides that form in the process lead to structural disruption (so-called molybdenum disulicide plague).
- Oxidation at higher temperatures is like pure molybdenum disilicide.
- the object of the present invention is to provide a ceramic resistor that is largely inert to oxidation processes even in the context of applications at higher temperatures in a corrosive gas atmosphere.
- the object on which the invention is based is advantageously achieved in that a ceramic electrical resistance is proposed which can be produced by pyrolysis of an organosilicon polymer and at least one filler, the filler containing mobybdenum disilicide.
- the ceramic resistor also contains elemental aluminum, which leads to a significant improvement in the long-term stability of the ceramic resistor.
- Molybdenum disilicide content in the material of the ceramic resistor Covering the filler parcel with aluminum also favors the sintering activity of the ceramic, which additionally ensures sufficient stability of the ceramic resistance.
- the filler content in the material of the ceramic resistor advantageously being a total of 35 to 65% by volume.
- the ceramic resistor is first produced in a first step
- Molybdenum disilicide powder is mechanically alloyed with elemental aluminum powder in a grinding process, so that fine aluminum particles are practically forged onto the comparatively coarser molybdenum particles, and in a second step the aluminum-provided molybdenum disilicide is mixed with an organosilicon polymer and possibly other fillers and hardened. This leads to a particularly intimate mixing of the elemental aluminum with the molybdenum disilicide to be protected. It is particularly advantageous if the mechanical alloying of the molybdenum disilicide powder with aluminum powder takes place by means of grinding balls, the main component of which is aluminum oxide, and preferably in an unglazed grinding vessel made of aluminum oxide, since in this way no further undesirable chemical elements are introduced.
- platelet-shaped aluminum powder as the aluminum powder, which is used on an industrial scale for metallic paints.
- FIG. 1 and 2 show two exemplary embodiments of glow plugs in longitudinal section, which contain the ceramic resistor according to the invention.
- FIG. 1 shows a longitudinal section through a first embodiment of a glow plug containing the ceramic resistor according to the invention.
- the glow plug 10 here comprises a cylindrical metal tube 11.
- the cylindrical metal tube 11 represents the housing of the glow plug and is used for screwing into an engine block by means of a thread 12 applied on the outside.
- the cylindrical metal tube 11 also serves as a holder for the glow plug, which protrudes into the combustion chamber and here heats a self-igniting fuel mixture, for example a diesel mixture.
- the glow plug is designed as a ceramic heating device 13, the head end of the combustion chamber serving as a heating element.
- the metal tube 11 is positioned in an engine block (not shown) of an internal combustion engine in such a way that one end of the ceramic heating device 13 projects in a unsupported state into a combustion chamber (not shown) of the internal combustion engine.
- the ceramic heater 13 consists of an electrically conductive ceramic, which has the shape of a sleeve closed on one side.
- the end of the cylindrical metal tube 11 facing away from the combustion channel comprises a connecting bolt 14, which is electrically insulated from the cylindrical metal tube 11 by means of an insulation layer 15.
- the connecting pin 14 is contacted via a contact 16 with the ceramic heating device 13 in such a way that the contact 16 is electrically conductively connected to the closed end of the ceramic heating device 13 on the combustion chamber side.
- the ceramic heating device 13 is electrically contacted on its circumferential surface held by the cylindrical metal ear 11 with the cylindrical metal ear 11, so that the end of the ceramic heating device 13 on the combustion chamber side, on the one hand, with the supply voltage, which is supplied, for example, by a battery of a motor vehicle, not shown, via the contact 16 is connected and on the other hand is in contact with the ground via the cylindrical metal ear 11
- the wall thickness of the ceramic heating device 13 is preferably not over the entire ceramic one
- Heater 13 of the same size. Rather, the wall thickness at the cantilevered end of the ceramic heating device 13 is smaller than at the edge of the sleeve-shaped ceramic. This increases the resistance on the combustion chamber side of the ceramic heating device 13, so that the ceramic heating device heats up particularly strongly at this point.
- the ceramic heating device it is not absolutely necessary for the ceramic heating device to have a sleeve shape.
- a U-shaped ceramic heating device is also conceivable, the wall thickness of the end of the ceramic heating device on the combustion chamber also being tapered here compared to the end of the ceramic heating device fastened in the cylindrical metal ear.
- FIG. 2 shows the longitudinal section of a second embodiment of a glow plug containing the ceramic resistor according to the invention.
- the same reference numerals designate the same component components.
- the wall of the ceramic heater 13 has recesses 17, the number, diameter and position of the recesses 17 being used to precisely define and set the location of the smallest material cross section and thus the hottest location of the ceramic heater 13 can be.
- the inner cavity of the ceramic heating device 13 is filled with a heat-resistant, electrically insulating, for example ceramic material.
- the heating device 13 is made of an electrically conductive ceramic with a high electrical resistance. This is preferably a ceramic based on a polysiloxane or polysilazane provided with fillers.
- a condensation-crosslinking polysiloxane or an addition-crosslinking polysiloxane such as, for example, a methylphenyl vinyl hydrogen polysiloxane (Wacker Sihcon impregnating resin H62 C), is used as the polysiloxane.
- a suitable solvent such as acetone or tetrahydrofuran and mixed with suitable fillers.
- the electrical resistance of the resulting ceramic can be set in a targeted manner by selecting and adding one or more suitable fillers.
- a suitable filler is, for example, molybdenum disicide alone or in a mixture with silicon carbide, aluminum oxide or silicon powder.
- the filler preferably has an average grain size of 0.01 to 100 ⁇ m, in particular of 3.5 to 5 ⁇ m.
- the organosilicon polymer mixed with the filler (s) is first dried and then cured preferably at an elevated pressure of approximately 10 MPa and at a temperature of approximately 200 ° C. in a period of 15 to 45 minutes.
- pyrolysis takes place under protective gas, for example in an argon atmosphere, at a temperature of up to 1200 ° C.
- protective gas for example in an argon atmosphere, at a temperature of up to 1200 ° C.
- a ceramic material is formed from the organosilicon polymer.
- the invention it is proposed to improve the oxidation resistance of molybdenum disuicide by adding elemental aluminum.
- This can be done, for example, by using pre-alloyed filler particles of the formula Mop + X ) (Al x Si) 2 .
- aluminum in the form of a suitable powder can first be brought into contact with the molybdenum disulicide provided as the filler or with the molybdenum disulicide already pre-alloyed with aluminum before the molybdenum sulcide thus coated with aluminum is supplied to the organic silicon precursor material.
- the aluminum as fine as possible on the surface of the
- aluminum powder and molybdenum disulfide powder are preferably subjected to a moderate grinding process, for example in a ball mill or a RoUeribock mill. It is particularly advantageous if both the grinding vessel and the grinding balls used for grinding are made of aluminum oxide or at least largely consist of aluminum oxide.
- the grinding vessel is unglazed.
- the intended ceramic material contains molybdenum disulicide in a mixture with other fillers, there is the possibility of subjecting the corresponding filler mixture to a grinding process with aluminum powder or according to a preferred one
- Embodiment to subject each filler separately to such a grinding process with aluminum powder. This prevents particularly hard filler particles such as silicon carbide particles from causing the filler particles to be crushed during the grinding process.
- the molybdenum disulicide particles alloyed superficially with aluminum in this way are then, as already described, mixed with the organic silicon precursor material, hardened and pyrohsieri.
- the ceramic material obtained in this way shows a significantly improved stability compared to oxidation processes at high temperatures.
- Precursor material in addition to the aluminum alloyed alloys, further aluminum powder added. In this way, both the homogeneous distribution of aluminum in the molybdenum disulfide powder and a preheatful aluminum enrichment on the surface of the molybdenum disulfide particles are ensured.
- the ceramic resistor according to the invention is not only suitable as a heating element for glow plugs, but also for heating devices of flame candles or ceramic gas sensors.
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP05728231A EP1747562A1 (de) | 2004-05-11 | 2005-03-17 | Keramischer widerstand |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102004023064.1 | 2004-05-11 | ||
DE200410023064 DE102004023064A1 (de) | 2004-05-11 | 2004-05-11 | Keramischer Widerstand |
Publications (1)
Publication Number | Publication Date |
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WO2005112048A1 true WO2005112048A1 (de) | 2005-11-24 |
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ID=34962317
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2005/051240 WO2005112048A1 (de) | 2004-05-11 | 2005-03-17 | Keramischer widerstand |
Country Status (3)
Country | Link |
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EP (1) | EP1747562A1 (de) |
DE (1) | DE102004023064A1 (de) |
WO (1) | WO2005112048A1 (de) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19538695A1 (de) * | 1994-10-19 | 1996-04-25 | Bosch Gmbh Robert | Keramischer elektrischer Widerstand und dessen Verwendung |
DE19910446A1 (de) * | 1999-03-10 | 2000-10-12 | Bosch Gmbh Robert | Keramischer elektrischer Widerstand |
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2004
- 2004-05-11 DE DE200410023064 patent/DE102004023064A1/de not_active Withdrawn
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2005
- 2005-03-17 EP EP05728231A patent/EP1747562A1/de not_active Withdrawn
- 2005-03-17 WO PCT/EP2005/051240 patent/WO2005112048A1/de active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19538695A1 (de) * | 1994-10-19 | 1996-04-25 | Bosch Gmbh Robert | Keramischer elektrischer Widerstand und dessen Verwendung |
DE19910446A1 (de) * | 1999-03-10 | 2000-10-12 | Bosch Gmbh Robert | Keramischer elektrischer Widerstand |
Non-Patent Citations (4)
Title |
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DATABASE INSPEC [online] THE INSTITUTION OF ELECTRICAL ENGINEERS, STEVENAGE, GB; April 2000 (2000-04-01), RAMBERG C E ET AL: "Fabrication and high-temperature phase stability of Mo(Al,Si)2-MoSi2 intermetallics", XP002329057, Database accession no. 6594258 * |
DATABASE INSPEC [online] THE INSTITUTION OF ELECTRICAL ENGINEERS, STEVENAGE, GB; February 2002 (2002-02-01), RAMBERG C E ET AL: "Oxidation kinetics and composite scale formation in the system Mo(Al,Si)2", XP002329056, Database accession no. 7242146 * |
JOURNAL OF THE AMERICAN CERAMIC SOCIETY AMERICAN CERAMIC SOC USA, vol. 83, no. 4, April 2000 (2000-04-01), pages 946 - 948, ISSN: 0002-7820 * |
JOURNAL OF THE AMERICAN CERAMIC SOCIETY AMERICAN CERAMIC SOC USA, vol. 85, no. 2, February 2002 (2002-02-01), pages 444 - 452, ISSN: 0002-7820 * |
Also Published As
Publication number | Publication date |
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EP1747562A1 (de) | 2007-01-31 |
DE102004023064A1 (de) | 2005-12-01 |
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