EP1472197A1 - Keramischer verbundwerkstoff, verfahren zu dessen herstellung und glühstiftkerze mit einem solchen verbundwerkstoff - Google Patents
Keramischer verbundwerkstoff, verfahren zu dessen herstellung und glühstiftkerze mit einem solchen verbundwerkstoffInfo
- Publication number
- EP1472197A1 EP1472197A1 EP02794999A EP02794999A EP1472197A1 EP 1472197 A1 EP1472197 A1 EP 1472197A1 EP 02794999 A EP02794999 A EP 02794999A EP 02794999 A EP02794999 A EP 02794999A EP 1472197 A1 EP1472197 A1 EP 1472197A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- boron
- composite material
- ceramic composite
- ceramic
- starting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
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- 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
- C04B35/5603—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 with a well-defined oxygen content, e.g. oxycarbides
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Definitions
- Ceramic composite Process for its manufacture and glow pencil candle with such a composite material
- the invention relates to a ceramic composite material, a method for its production and a glow pencil candle with such a composite material according to the preamble of the independent claims.
- ceramic composites in particular amorphous Si-0-C ceramics, are used which, in particular due to the partial pyrolysis of organic elements Precursors are won.
- Sintering lies in the much lower process temperature and the easy processability and formability of polysiloxane resins. This procedure is described in detail in DE 195 38 695 AI.
- the production of moldings from these ceramic composites is only possible using additional fillers, otherwise shrinkage cracks and pores will occur during pyrolysis.
- EP 0412 428 B1 it has already been proposed in EP 0412 428 B1 to precisely set the properties of the ceramic composite material obtained, such as its coefficient of thermal expansion, thermal conductivity or specific electrical resistance, using selected fillers in an initial composite.
- reactive fillers to achieve a better connection of the fillers to the matrix, but also to use inert fillers.
- the object of the present invention was to provide a ceramic composite material which can be used in a glow plug, with a particularly increased specific electrical resistance, which should be as independent as possible of fillers additionally used in the composite material, and improved durability.
- the ceramic composite material should have no or as little aging as possible of the functional properties when used in a glow pencil candle, in particular with regard to the heating-up time and glow temperature.
- improved glazing in the ceramic composite material is achieved, which is at least partially attributable to the formation of boron-containing glasses or corresponding glass-like areas in the composite material with a lower glass transition temperature, and which increases the durability, in particular glow plugs produced therewith.
- a dense glass layer is now often formed in and or on the surface of the composite material, and there is no oxidation in the interior of the material used, even after longer aging times, for example 100 h, ie no M0O 3 is formed there , M ⁇ 5 Si 3 or crystalline Si0 2 , which facilitates self-healing processes in the material when cracks form and increases its strength overall.
- the onset of crystallization of a ceramic matrix based on Si-OC formation with the formation of cristobalite is suppressed by the addition of comparatively small amounts of boron at 1300 ° C for 100 h or at 1350 ° C for 8 h, which the durability and thermal shock resistance of the material are also increased.
- aging of the specific electrical resistance in the ceramic composite material is suppressed by the boron used and an improvement in its functional properties and thus also in a glow pencil candle produced therewith, especially with regard to the heating-up time and glow temperature, is achieved.
- the manufacturing composite is used in a glow plug, it is also advantageous that this increases the specific electrical resistance of the insulation layer of the glow plug, suppresses undesired aging of the resistance of the insulation layer and / or the conductive layer of the glow plug, and narrows the resistance distribution in the Control layer is achieved, which among other things leads to a reduced effort in production, quality control and resistance classification.
- FIG. 1 shows the difference in the percentage pyrolysis shrinkage of a boron-containing ceramic composite compared to a boron-free one as a function of the pyrolysis temperature
- FIG. 2 shows a Raman spectrum of the boron-containing and the boron-free composite material according to FIG. 1 at a temperature of 1325 ° C.
- FIG. 3 shows the specific electrical resistance of a boron-containing composite material as a function of the exposure time in air at 1300 ° C exposure temperature
- FIG. 4 dilatometer measurements to determine the thermal expansion coefficient of a boron-containing composite material compared to a boron-free one as a function of the exposure time in air at 1300 ° C exposure temperature.
- a ceramic composite material made of precursor ceramic is used in the "Rapitherm" ceramic glow pencil candle developed by Robert Bosch GmbH, as is known from DE 100 20 329 AI and in particular also from DE 195 38 695 AI a particular partial pyrolysis, for example at 600 ° C. to 1400 ° C., in particular 1200 ° C. to 1300 ° C.
- the starting material is a polysiloxane, ie a polymer made of Si, C, O and H, which is filled with fillers such as MoSi 2 , SiC, A1 2 0 3 , TiC, B 4 C, BN, TiN, mullite or Fe is mixed.
- the electrical and physical property profile of the ceramic composite material of the glow pencil candle resulting after pyrolysis can be tailored to the respective requirements professional 1.
- an oxygen-containing polysiloxane precursor as the starting material also enables particularly simple processing in air and thus the production of inexpensive products.
- a pyrolysis product or ceramic composite made from a filled polysiloxane has very good properties
- thermolysis process according to DE 195 38 695 AI compared to conventional manufacturing processes for ceramic composite materials such as sintering is that a much larger spectrum of possible fillers is available, since the pyrolysis used compared to conventional sintering Temperatures of typically more than 1600 ° C (especially in the case of Si 3 N 4 ) occur at much lower temperatures. In this respect, liquid or volatile fillers can still be used in the precursor pyrolysis process used even at conventional, comparatively high sintering temperatures, and phase reactions which otherwise occur are avoided even at higher temperatures.
- polysiloxane resins as meltable thermosetting polymers and precursors that are soluble in organic solvents, allow simple and very homogeneous incorporation of fillers, for example by kneading or dissolving.
- the influence of the matrix on the respective property should initially be as small as possible.
- the matrix forms a coherent network in ceramic composite materials, such as those used for ceramic glow plugs, for example in the case of an insulating intermediate layer to be produced in a glow plug, the problem often arises from this material that the matrix unites after the layer has been manufactured has too low specific electrical resistance, or that the matrix or the entire composite material due to phase transformations,
- the modification of the polymer or precursor material by boron for example in the form of boric acid esters and / or the addition of boron, for example as an additive in the form of one or more boron-containing fillers such as elemental boron, B 2 0 3 , BN or B 4 C, initially leads to an improved high-temperature resistance of the material with regard to phase separation and crystallization behavior. Furthermore, the durability of the material obtained is improved and the aging of the specific electrical resistance is reduced.
- the use of boron has the effect that the resistance of the insulation layer of the glow plug can be stabilized in a range above 10,000 ohm cm, without any significant change in the mass composition of the insulation layer being necessary.
- such an insulation layer resistance is a prerequisite for the manufacture of a glow pencil with a reduced shaft diameter.
- Boron-containing ceramic composites are preferably produced, either by adding boron-containing fillers to a polysiloxane or by modifying the corresponding polymeric precursor with boron and subsequent pyrolysis in a gas atmosphere adapted to the application in the temperature range between 600 ° C. and 1400 ° C., in particular 1100 ° C to 1300 ° C have been obtained.
- insulation materials and conductive compounds for glow plugs known from DE 195 38 695 A1 were incorporated during the preparation of boron-containing additives such as B 2 0 3 , and the pyrolysis was then carried out in the usual manner.
- Si0 2 / B 2 ⁇ 3 mixture contains 80% by weight Si0 2 and 20% by weight boron or B 2 0 3 .
- the masses were prepared by grinding in the corresponding starting powders, then sieving with a mesh size of 150 ⁇ m and then crosslinking and shaping using hot pressing. The samples were then pyrolyzed to compact samples at a heating rate of 25 K / h to a final temperature of 1300 ° C.
- FIG. 1 shows a comparison of the shrinkage profile of the Si0 2 -containing sample and the Si0 2 / B 2 0 3 -containing sample, it being clearly recognizable that the addition of boron leads to a shrinkage which starts at comparatively low temperatures, which by formation of a borosilicate-like glass, which lowers the glass transition temperature, and / or by the action of boron as a sintering aid.
- boron-containing insulation materials for a ceramic glow pencil candle are produced, the preparation of which, starting from appropriate ceramic starting mixtures, The next step is to use a conventional mixing and kneading process and then shape it using transfer molding.
- composition of the various ceramic starting mixtures produced is in each case within the ranges 50 to 80 vol polysiloxane (with a
- the boron-containing samples had a comparatively high length shrinkage ⁇ l / 1 of approx. -9.8%, a mass loss ⁇ m / m of approx. -4.7% and a specific electrical resistance of more than 10 6 ⁇ cm after pyrolysis and aging, while the boron-free reference samples showed only a shrinkage ⁇ l / 1 of approx. - 8.9%, a mass loss ⁇ m / m of approx. -4.5% and a specific electrical resistance of 10 4 ⁇ cm after pyrolysis and Showed outsourcing.
- FIG. 3 shows the temperature-dependent specific electrical resistance of one of the insulation compositions explained above with an addition or proportion of 3% by weight boron in the form of elemental boron after 8 hours, 20 hours and 100 hours of exposure to air at 1300 ° C.
- FIG. 4 shows a dilatometric measurement of the coefficient of thermal expansion as a function of the temperature for a sample with boron addition corresponding to FIG. 3, ie with 3% by weight boron, which was previously exposed to air at 1300 ° C., and corresponding measurements on samples without boron -Additive that was previously stored in air at 0 h, 12 h, 50 h or 150 h at 1300 ° C.
- the measurements according to FIG. 4 were carried out at a heating rate of 5 K / min in an argon atmosphere.
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- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10203714 | 2002-01-30 | ||
DE10203714 | 2002-01-30 | ||
DE10243017 | 2002-09-17 | ||
DE10243017A DE10243017B4 (de) | 2002-01-30 | 2002-09-17 | Keramischer Verbundwerkstoff und Glühstiftkerze mit einem solchen Verbundwerkstoff |
PCT/DE2002/004584 WO2003064346A1 (de) | 2002-01-30 | 2002-12-16 | Keramischer verbundwerkstoff, verfahren zu dessen herstellung und glühstiftkerze mit einem solchen verbundwerkstoff |
Publications (1)
Publication Number | Publication Date |
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EP1472197A1 true EP1472197A1 (de) | 2004-11-03 |
Family
ID=27664550
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP02794999A Withdrawn EP1472197A1 (de) | 2002-01-30 | 2002-12-16 | Keramischer verbundwerkstoff, verfahren zu dessen herstellung und glühstiftkerze mit einem solchen verbundwerkstoff |
Country Status (4)
Country | Link |
---|---|
US (1) | US20050153825A1 (de) |
EP (1) | EP1472197A1 (de) |
JP (1) | JP2005515956A (de) |
WO (1) | WO2003064346A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004045814A1 (de) * | 2004-09-22 | 2006-03-23 | Robert Bosch Gmbh | Verfahren zur Herstellung einer Precursorkeramik |
US20090184101A1 (en) * | 2007-12-17 | 2009-07-23 | John Hoffman | Sheathed glow plug |
CN109824364A (zh) * | 2019-03-26 | 2019-05-31 | 华南理工大学 | 一种SiAlZrOC陶瓷的合成方法 |
CN112441824B (zh) * | 2020-12-11 | 2021-06-29 | 湖南兴诚电瓷电器有限公司 | 一种耐低温高压输电用瓷绝缘子及其制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US4033776A (en) * | 1975-08-18 | 1977-07-05 | Saxonburg Ceramics, Inc. | Composition of ceramic material |
DE3926077A1 (de) * | 1989-08-07 | 1991-02-14 | Peter Prof Dr Greil | Keramische verbundkoerper und verfahren zu ihrer herstellung |
US5527872A (en) * | 1990-09-14 | 1996-06-18 | At&T Global Information Solutions Company | Electronic device with a spin-on glass dielectric layer |
JPH10169982A (ja) * | 1996-12-11 | 1998-06-26 | Isuzu Ceramics Kenkyusho:Kk | セラミックヒータ及びその製造方法 |
DE10020328A1 (de) * | 1999-08-27 | 2001-03-01 | Bosch Gmbh Robert | Keramische Glühstiftkerze |
-
2002
- 2002-12-16 EP EP02794999A patent/EP1472197A1/de not_active Withdrawn
- 2002-12-16 JP JP2003563974A patent/JP2005515956A/ja active Pending
- 2002-12-16 US US10/503,314 patent/US20050153825A1/en not_active Abandoned
- 2002-12-16 WO PCT/DE2002/004584 patent/WO2003064346A1/de active Application Filing
Non-Patent Citations (1)
Title |
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See references of WO03064346A1 * |
Also Published As
Publication number | Publication date |
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JP2005515956A (ja) | 2005-06-02 |
WO2003064346A1 (de) | 2003-08-07 |
US20050153825A1 (en) | 2005-07-14 |
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