ZA200409614B - Fabrication of low thermal expansion calcium aluminate articles. - Google Patents
Fabrication of low thermal expansion calcium aluminate articles. Download PDFInfo
- Publication number
- ZA200409614B ZA200409614B ZA200409614A ZA200409614A ZA200409614B ZA 200409614 B ZA200409614 B ZA 200409614B ZA 200409614 A ZA200409614 A ZA 200409614A ZA 200409614 A ZA200409614 A ZA 200409614A ZA 200409614 B ZA200409614 B ZA 200409614B
- Authority
- ZA
- South Africa
- Prior art keywords
- article
- thermal expansion
- less
- temperature range
- calcium aluminate
- Prior art date
Links
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 17
- 239000000919 ceramic Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 description 18
- 239000000758 substrate Substances 0.000 description 14
- 230000035939 shock Effects 0.000 description 13
- 239000000292 calcium oxide Substances 0.000 description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 241000264877 Hippospongia communis Species 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229910052878 cordierite Inorganic materials 0.000 description 7
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 2
- 206010017076 Fracture Diseases 0.000 description 2
- 208000013201 Stress fracture Diseases 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 229960002900 methylcellulose Drugs 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- -1 calcium aluminate compound Chemical class 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 210000003371 toe Anatomy 0.000 description 1
Landscapes
- Catalysts (AREA)
Description
L ’
FABRICATION OF LOW THERMAL EXPANSION
CALCIUM ALUMINATE ARTICLES
[0001] This invention relates to calciumaluminate compositions, articles made from these compositions and methods of making such articles. More particularly, the invention relates to low thermal expansion calcium aluminate compositions and articles and methods of making low expansion articles.
[0002] Low thermal expansion ceramic bodies are desirable in a wide variety of applications. For example, low expansion bodies have been used as filters for fluids, in particular, as diesel particulate filters and as substrates for catalytic converters, an example of which is known in the art as a honeycomb substrate. Additionally, low thermal expansion bodies are desirable in applications where the thermal shock resistance and the ultimate use temperature are high.
Substrates used under conditions of high thermal gradients are examples of this application. For example, structures such as honeycomb and cellular substrates are subjected to harsh environments, which require high thermal shock resistance, low thermal expansion, and high mechanical shock properties.
Maintaining these properties for extended periods of time in their intended environments eliminates many potentially useful refractory materials.
[0003] Cordierite substrates, typically in the form of a honeycomb body, have long been preferred for use as substrates to support catalytically active components for catalytic converters on automobiles, in part due to high thermal shock i WO 03/093192 PCT/USO3/13241 resistance of cordierite ceramics. The thermal shock resistance is inversely proportional to the coefficient of thermal expansion. That is, honeycombs with a low thermal expansion have a good thermal shock resistance and can survive the wide temperature fluctuations that are encountered in the application. Manufacturers work continuously to optimize the characteristics of cordierite substrates to enhance their utility as catalyst carriers. Specifically, manufacturers continually strive to optimize the thermal shock resistance and other properties of the cordierite substrates.
[0004] Another property of certain types of catalysts is the ability to purify exhaust gases and the ability to convert carbon monoxide, hydrocarbons and nitrogen oxides (NO) produced during engine operation into less environmentally harmful gases. Some catalyst systems utilize alkali metals contained on the catalyst support store nitrogen oxides, and such catalysts are referred to in the art as NOx adsorbers. A disadvantage of presently available catalyst and purification
Systems is that most of the alkali metals contained on the catalyst support for storing NOy readily react with cordierite within the temperature range of interest for NO. adsorber use.
For example, potassium, a widely used alkali adsorber material, appears to readily react with cordierite, which draws the potassium out of the high surface area washcoat and prevents it from performing its adsorber function.
Furthermore, the potassium reacts with cordierite to form relatively high coefficient of thermal expansion (CTE) phases that make the substrate and the catalyst system much less thermal shock resistant.
[0005] There is a need to provide alternative low CTE materials that are useful in high temperature applications.
It would be desirable to provide materials that have a low CTE and excellent thermal shock resistance.
¢ v
[0006] One embodiment of the invention relates to a ceramic article comprised of calcium aluminate including a main phase of Caal,0; and minor phase of CaAl.04, and which exhibits a thermal expansion of less than about 25 X 1077/°C over the temperature range of about 25°C to 800°C. Other embodiments relate to a calcium aluminate article having a thermal expansion less than about 20 X 1077/°C over the temperature range 25°C to 800°C. Still other embodiments relate to a calcium aluminate article having a thermal expansion less than
X 1077/°C over the temperature range 25°C to 800°C. Other embodiments relate to calcium aluminate articles having a thermal expansion less than about 10 X 1077/°C over the temperature range 25°C to 800°C, and alternative embodiments relate to calcium aluminate articles having thermal expansions less than about 5 X 1077/°C over the temperature range 25°C to 800°C. In certain embodiments, the articles contain a network of microcracks and include grains having a median grain size of between about 10 microns and 100 microns. The articles of the present invention can be used in a wide variety of applications, including but not limited to manufacturing honeycomb substrates for high temperature applications and honeycomb substrates for NOx adsorption applications.
[0007] Other embodiments of the invention relate to methods of manufacturing a calcium aluminate article which exhibits low thermal expansion. In one embodiment, the method includes mixing CaO and Al,0; source powders, forming a shaped article from the powders and heating the article to a temperature exceeding about 1500°C to form an article containing between 21.6% and 30% by weight CaO. In some embodiments, the article is fired to a temperature such that a network of microcracks and grains sized between 10 microns and 100 microns are present in the article after firing.
[0008] It is to be understood that both the foregoing general description and the following detailed description are exemplary and are intended to provide further explanation of the invention as claimed.
[0009] Fig. 1 is a phase diagram of Ca0-2a1,0;.
[0010] Before describing several exemplary embodiments of the invention, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description. The invention is capable of other embodiments and of being practiced or carried out in various ways.
[0011] The various embodiments of the present invention provide materials, methods and articles having low coefficients of thermal expansion. It has been discovered that to achieve this low thermal expansion, varying the combination of raw materials and the firing schedule can be utilized to achieve the desired properties. By controlling the final stoichiometry of the fired article proper combinations of raw material types and the firing schedules utilized in the production of the ceramic articles, the thermal expansion of articles can be lowered.
[0012] The general method of producing the articles of the present invention includes mixing the appropriate batch materials, preferably materials having an average particle diameter of less than about 150 microns. In certain embodiments, the average particle diameter of the starting powders is less than about 50 microns, and in alternative bd - embodiments, the average particle diameter is less than about microns. The mixed powders are then blended and then formed by extrusion or other appropriate forming methods into a green article, for example, a honeycomb body. The article is then subsequently sintered to a hard porous structure.
Various lubricants and organic binders such as methylcellulose are added to the batch during the mixing step to provide viscosity control and strength prior to firing and to provide porosity to the structure after firing. Porosity is also governed by the raw materials and the firing temperature.
Higher firing temperatures result in lower porosity structures. In certain embodiments, the firing temperature is greater than about 1450°C, and in other embodiments, greater than about 1500°C. In other embodiments, the articles are fired to temperatures greater than about 1550°C, and in some embodiments, the articles are fired to at least about 1600°cC.
As will become evident in the examples below, the actual firing temperature will depend on the stoichiometry of the ceramic body.
[0013] Another embodiment of the present invention relates to calcium aluminate materials that have low thermal expansions which can be used in the manufacture of catalyst system supports. Calcium aluminate is a relatively inert refractory material that typically exhibits coefficients of thermal expansion in the range of about 40 to 60 X 1077/°C over the temperature range of 25°C to 800°C. Although in some applications, this range of thermal expansion is considered to be acceptable, this range is prohibitive in several applications because the thermal shock conditions and thermal stresses are too severe for articles in monolithic form.
[0014] Thus, a lower CTE is desirable to make monolithic articles more resistant to failure under certain thermal shock conditions. Applicants have surprisingly discovered that
. . calcium aluminate articles can be manufactured that have much lower CTE values than typically exhibited by articles made from this material. Variation of the ratio of calcium oxide to aluminum oxide ratio and the firing temperature of the articles provides a calcium aluminate compound having surprisingly low CTE values. The new compounds were formed by mixing between about 21.6%-30% by weight source powders of Cao and the remainder aluminum oxide source powder formed into articles and fired to temperatures exceeding about 1500°C, and in certain embodiments, to temperatures preferably about 1600°C. However, the actual firing temperature will depend on the composition of the body. Examples of CaO source powders include calcium carbonate, calcium oxalate, calcium fluoride and calcium dihydroxide powders. Although calcium oxide can be used in its pure state, one skilled in the art will recognize that pure calcium oxide is highly reactive with water, and it is thus difficult to handle and store. Tf calcium carbonate is used as the source powder for calcium oxide, the weight of the powder used to obtain the Proper weight percent of CaO must be adjusted upward by a factor of 1.785 to reflect the desired weight equivalent of Cao.
According to certain embodiments of the invention, articles were produced that had CTEs as low as about -1 X 1077/°C over the temperature range of about 25°C to 800°C.
[0015] According to one specific embodiment of the invention, substrates for catalysts systems for the purification of exhaust gases are provided, particularly for improved NO, adsorption efficiency. In certain embodiments, the substrates are resistant to alkali migration below 1000°cC and have a coefficient of thermal expansion less than about
X 1077/°C over the temperature range of about 25°C to 800°C.
In some embodiments, the coefficient of thermal expansion is less than about 20 X 107'/°C over the temperature range of
LJ » -7 = about 25°C to 800°C, and in certain embodiments, the CTE of the articles are less than about 15 Xx 1077/°C over the temperature range of about 25°C to 800°C. In other embodiments, the CTE is less than about 10 X 1077/°C over the temperature range of about 25°C to 800°C.
[0016] Without intending to limit the invention in any manner, the present invention will be more fully described by the following examples.
[6017] Inorganic powder batch mixes suitable for the formation of calcium aluminate ceramic bodies are shown in
Table I and listed by weight percent. The inorganic compositions were formed by dry mixing calcium carbonate and alumina source powders having an average particle size between about 0.5 and 20 microns together with a cellulose ether binder, being either a methyl - cellulose or another cellulose ether derivative, in the range of 2 - 6 % by weight of the inorganic components. Water is then added to the resulting batch in the range of 15 - 25% by weight of the inorganic components and the resulting batch is further mixed to form a plasticized ceramic batch mixture. All of the thus prepared batches were then extruded through a honeycomb die using a ram extruder to form a ceramic honeycomb structure. The formed honeycomb bodies were dried overnight and fired to temperatures ranging from about 1320°C to 1600°C to sinter the parts and form calcium aluminate honeycomb structures in the desired stoichiometry. The compositions fired to 1320°C were held at the top temperature for about 24 hours, while all the other samples were held for about 8-24 hours. The compositions reported below are based on weight Percent CaO s WO 03/093192 PCT/US03/13241 and Al,0;, but using calcium carbonate as the source material for cao.
[0018] Compositions containing about 50% and 40% Cal were not fired to temperatures higher than about 1320°C because firing these compositions to higher temperatures would result in melting of the bodies. Compositions containing greater than about 21.6% Cal were not fired to temperatures higher than about 1600°C because firing to higher temperatures would result in melting of the bodies.
Table I
Cao 21,0, Caal,o, (wt %) | (wt %) (wt %) 1320°C | 1400°C_ 1450°C 1500°C 1550°C 1575°c | 1600°C so [oso Jo fy pe a0 |e [oo fe 32 | ee | mle ea 20.2 | vos | AS ee ns
L278 J ea | SS Sea seg p26. Toes | 65 sass are 20.0 Vrs. |S es ase
L2a.0 [osz | 7 ey ss ies 230 Pres [8 TT To aa se ae
SEF EN i A I NYY SA WR WY Se Ny EE 2t ged [T00 [ m —— we |e ey]
BET TJ EE - I
Ls [es | 0
[0019] Applicants determined that varying the particle size of the starting raw materials has a negligible impact on the final CTEs of the formed bodies for the compositions and firing temperatures tested. The results in the table indicate that calcium aluminate bodies having surprisingly low CTEs less than about 25 X 1077/°C can be obtained with bodies containing between about 27.8 and 21.6 weight percent Cao.
Bodies containing higher amounts of CaO required firing to higher temperatures to achieved low CTEs. The compositions in this range exhibited surprisingly low CTEsS compared to the
7% 96 other examples and relative to typical CTEs published in the literature for calcium aluminate, which are typically 40 X 1077/°C and higher over the temperature range of about 25°C to 800°C. Accordingly, compositions having starting CaO contents of between about 20% and 30% by weight and between about 70% and 80% aluminum oxide content by weight and fired in excess of 1500°C will exhibit low CTEs, that 1s, CTEs less than about
X 1077/°C over the temperature range of about 25°C to 800°C.
These low CTE materials are of use in applications where thermal shock conditions may be encountered because lower CTE values result in improved thermal shock resistance for the material. These materials will be particularly suitable in the manufacture of catalyst substrates used in automotive applications.
[00201] While the present invention should not be limited by any particular theory, it is believed that a network of microcracks is formed on cooling after firing the novel calcium aluminate bodies described herein. The bodies having low CTEs are comprised of a major phase of CaAl,0; (Grossite or calcium dialuminate or CA;) and minor phase of CaAl;0, (calcium monoaluminate or CA). The microcracks are thought to form as a result of thermal expansion anisotropy in the Caal,0; unit cell. This thermal expansion anisotropy creates areas of local mismatch stresses between grains of differing orientations, which if high enough, is able to create microfractures within the ceramic microstructure. The higher firing temperature presumably allows the grains to grow greater than the critical average size required for microcrack formation. It is believed that the network of microcracks is effective in decreasing the macroscopic thermal expansion coefficient, because on heating, the microcracks are healed.
This healing of the microcracks is accomplished by accommodating positive thermal expansion of surrounding grains. Since the positive thermal expansion is used to heal the microcrack, the effect is to lower the overall thermal expansion of the polycrystalline sample. This reduction in observed thermal expansion coefficient continues until the cracks are sufficiently healed, whereupon the obsérved CTE returns to the average of the linear expansion in the three axes of the unit cell. On cooling, the process is reversed, and the cracks re-open again due to the fracture energy generated by locally misaligned neighboring grains.
[0021] Viewing the CaO - Al,0; phase diagram (shown in
Figure 1), it can be seen that compositions falling within the
CA + CA; phase field (containing about 64.5-78.4% Al,0;) result in the formation of some liquid when fired to temperatures approaching 1600°C (or somewhat lower depending on levels of impurities). In the inventive compositions which fall within this range of alumina content, it is likely that liquid formation at high temperatures in firing results in some liquid-phase sintering. This liquid probably also supports the tremendous grain growth which is necessary to form the network of microcracks.
[0022] When compositions in the CA + CA, phase field are fired to high enough temperatures, a liquid phase is formed, and the stable phases are CA; + liquid. The amount of liquid formed at a given temperature increases as the level of alumina in the base composition decreases as defined by the lever rule. Therefore, compositions falling in this phase field increase in alumina content up to almost 78.4%, the amount of liquid present above the solidus temperature decreases. It is believed that the smallest amount of liquid required to get sufficient grain growth would be preferred from a processing standpoint. This is because large volumes of liquid phase can result in significant distortion of the part and sticking to the setter on which the ceramic article is fired.
[0023] Therefore, to achieve a low coefficient of thermal expansion in compositions rich in CA;, a body should contain a network of fine microcracks, which act to moderate bulk expansion as the cracks are healed during heating.
Conversely, upon cooling, the cracks reversibly open again, resulting in a reduced thermal expansion as the opening of cracks serves to reduce the thermal expansion coefficient compared to a body where no cracks open upon cooling. It has also been observed in SEM micrographs of samples that a certain grain size of the CA, phase is required to generate enough fracture energy to create the microfractures in neighboring misaligned grains. This grain size is believed to be between about 10 and 100um.
[0024] It will be apparent to those skilled in the art that various modifications and variations can be made to the bresent invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
Claims (1)
- L.-J - What is claimed is:1. A ceramic article comprised of calcium aluminate including a main phase of CaAlys0; and minor phase of CalAl,Qq, and which exhibits a thermal expansion of less than X 1077/°C over the temperature range 25°C to 800°C.2. The article of claim 1, wherein the article exhibits a thermal expansion of less than 15 X 1077/°C over the temperature range of about 25°C to 80Q°cC.3. The article of claim 1, wherein the article exhibits a thermal expansion of less than 10 X 1077/°C over the temperature range of about 25°C to 800°C.4. The ceramic article of claim 1, wherein the article exhibits a thermal expansion of less than 5 X 1077/°C over the temperature range of about 25°C to 800°C.5. The ceramic article of claim 1, wherein the article contains a network of microcracks.6. The ceramic article of claim 5, wherein the article includes grains having an average grain size between 10 microns and 100 microns.7. The ceramic article of claim 6, wherein the article is a catalyst for purification of exhaust gases.8. A method of manufacturing a calcium aluminate article which exhibits a thermal expansion of less than 20 X 1077 /0c over the temperature range of about 25°C to 800°C comprising mixing CaO and Al,0; source Powders, the mixture containing-13-~ source powders to produce a final phase containing between21.6% and 30% by weight CaO and the balance Al;0;, forming a shaped article from the powders, and heating the article to a temperature exceeding about 1450°C.9. The method of claim 8, wherein the mixture contains source powders to produce a final phase containing between21.6% and 22% by weight CaO and the balance Al,03 source powder and the article is fired to a temperature exceeding about 1550°cC.10. The method of claim 8, wherein the mixture contains source powders to produce a final phase containing between22.3% and 25% by weight CaO and the balance Al,03 and the article is fired to a temperature between about 1450°C and 1600°cC.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US37746602P | 2002-05-01 | 2002-05-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
ZA200409614B true ZA200409614B (en) | 2005-07-18 |
Family
ID=35266069
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200409614A ZA200409614B (en) | 2002-05-01 | 2004-11-29 | Fabrication of low thermal expansion calcium aluminate articles. |
Country Status (1)
Country | Link |
---|---|
ZA (1) | ZA200409614B (en) |
-
2004
- 2004-11-29 ZA ZA200409614A patent/ZA200409614B/en unknown
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6809051B2 (en) | Fabrication of low thermal expansion calcium aluminate articles | |
US7011803B2 (en) | Honeycomb structure and method for its manufacture | |
EP1133457B1 (en) | Fabrication of low thermal expansion, high strength porous cordierite structures | |
US6391813B1 (en) | Low sintering temperature cordierite batch and cordierite ceramic produced therefrom | |
EP1364928B1 (en) | Honeycomb structure | |
EP1493724B1 (en) | Porous material and method for production thereof | |
JP2007507667A (en) | Highly porous honeycomb and manufacturing method thereof | |
US7575794B2 (en) | High strength substantially non-microcracked cordierite honeycomb body and manufacturing method | |
EP1680206A1 (en) | Ceramic body based on aluminum titanate | |
ZA200208006B (en) | Honeycomb structure and method for preparation thereof. | |
CA2533387A1 (en) | Honeycomb carrier for exhaust gas-cleaning catalyst and process for its production | |
ZA200206263B (en) | Honeycomb structure and method for manufacture thereof. | |
MX2011002888A (en) | Method for making porous mullite-containing composites. | |
JP3311650B2 (en) | Method for manufacturing cordierite-based ceramic honeycomb structure | |
JPH10174885A (en) | Cordierite honeycomb structural body and its production | |
JPWO2009041369A1 (en) | Ceramic honeycomb structure and manufacturing method thereof | |
US6689707B1 (en) | Low thermal expansion calcium aluminate articles | |
KR20050065607A (en) | Silicon carbide-based catalytic material and process for producing the same | |
JP5128989B2 (en) | Cordierite ceramics manufacturing method | |
ZA200409614B (en) | Fabrication of low thermal expansion calcium aluminate articles. | |
US6686305B1 (en) | Methods of making low thermal expansion calcium aluminate articles | |
JP2007244993A (en) | Ceramic carrier, ceramic catalytic body and methods for manufacturing them | |
JPH1192215A (en) | Cordierite-based ceramic sintered product, composition therefor and production |