CN103339087A - 碳化硅材料、蜂窝结构体及电热式催化剂载体 - Google Patents
碳化硅材料、蜂窝结构体及电热式催化剂载体 Download PDFInfo
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- CN103339087A CN103339087A CN201280007375XA CN201280007375A CN103339087A CN 103339087 A CN103339087 A CN 103339087A CN 201280007375X A CN201280007375X A CN 201280007375XA CN 201280007375 A CN201280007375 A CN 201280007375A CN 103339087 A CN103339087 A CN 103339087A
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- tunicle
- matrix
- silicon carbide
- carbofrax material
- silicon
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 42
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims description 19
- 238000005485 electric heating Methods 0.000 title abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims description 77
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 18
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 15
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011800 void material Substances 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 238000007669 thermal treatment Methods 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 238000005245 sintering Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910017488 Cu K Inorganic materials 0.000 description 3
- 229910017541 Cu-K Inorganic materials 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
- 229910000174 eucryptite Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- -1 triphane Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
本发明的碳化硅材料，具备以碳化硅为主成分或以碳化硅和金属硅为主成分的基体、覆盖该基体表面的至少一部分的被膜，该被膜以至少含有锂（Li）、铝（Al）、硅（Si）、氧（O）4元素的相为主成分。作为此种碳化硅材料，可举出例如，具备：具有碳化硅粒子通过金属硅而结合的结构的基体、和覆盖该碳化硅粒子表面的一部分的锂铝硅酸盐被膜的材料。此种碳化硅材料可用于DPF和电热式的催化转换器等。
Description
技术领域
本发明关于碳化硅材料、蜂窝结构体及电热式催化剂载体。
背景技术
由于柴油发动机排出的尾气中含有PM（颗粒物质），因此通过设置在排气路径中的DPF（柴油机颗粒过滤器）捕捉收集PM后放出至大气中。此外，由于汽油发动机排出的尾气中含有烃（HC）、一氧化碳（CO）和氮氧化物（NOx），因此通过设置在排气路径中的催化转换器进行氧化·还原反应而转变为水、二氧化碳和氮后放出至大气中。此种DPF和催化转换器中，有时会使用以碳化硅（SiC）为主成分的蜂窝过滤器。例如，专利文献1中公开了含有碳化硅粒子和金属硅、覆盖它们表面的被膜中存在由氧化硅构成的相的蜂窝过滤器。此外，专利文献2中公开了含有碳化硅粒子和金属硅、覆盖它们表面的被膜中存在莫来石结晶相的蜂窝过滤器。此外，专利文献3中公开了碳化硅发热体中具有含钾铝硅酸盐被膜之物。
现有技术文献
专利文献
【专利文献1】日本专利特开2002-154882号公报
【专利文献2】WO2005/014171
【专利文献3】日本专利特开平2-186598号公报
发明内容
但是，将专利文献1～3中公开的材料使用于上述的DPF和催化转换器时，在耐热冲击性方面会产生问题。即，专利文献1的材料中，由于被膜氧化硅的热膨胀系数较高，因此与之伴随着的是，材料的热膨胀系数也变高，存在耐热冲击性低的问题。专利文献2的材料中，由于被膜所含的莫来石的热膨胀系数并不很低，因此耐热冲击性称不上充分。专利文献3的材料中，由于钾铝硅酸盐的热膨胀系数高，因此存在耐热冲击性也低的问题。此种问题在催化转换器中，特别是在通过电加热而使催化剂尽早活化的方式中较为显著。
本发明是为了解决此种问题，主要目的是提供耐热冲击性好于以往的碳化硅材料。
本发明者们对于覆盖含碳化硅的基体表面的至少一部分的被膜材料进行了各种研究后发现，较之于方英石、莫来石、石英、钾铝硅酸盐，以锂辉石为代表的锂铝硅酸盐的耐热冲击性更为优异，从而完成了本发明。
即，本发明第1发明是一种碳化硅材料，具备以碳化硅为主成分或以碳化硅和金属硅为主成分的基体、和覆盖该基体表面的至少一部分的被膜，所述被膜以至少含有锂（Li）、铝（Al）、硅（Si）、氧（O）4元素的相为主成分。在这里，“基体表面”指的是，除了基体的外表面以外，当基体为多孔质时也包含气孔内表面。此外，“被膜”只要含有Li、Al、Si及O这4种元素即可，不限定于是化合物、混合物或复合物，也不限定于结晶质相或非晶质相。
本发明的第2及第3发明各自是由本发明的第1发明的碳化硅材料构成的蜂窝结构体及电热式催化剂。
本发明的第1发明的碳化硅材料，耐热冲击性较以往良好。其原因可认为是，较之于基体的热膨胀率，被膜的热膨胀率较低，因此被膜可以抑制基体的热膨胀。本发明的第2发明的蜂窝结构体和本发明的第3发明的电热式催化剂载体均使用了本发明的第1发明的碳化硅材料，因此耐热冲击性良好。
附图说明
【图1】实施例1的基体的SEM照片（背散射电子图像）。
【图2】实施例1的样品的SEM照片（背散射电子图像）。
具体实施方式
本发明的第1发明的碳化硅材料，具备以碳化硅为主成分或以碳化硅和金属硅为主成分的基体、和覆盖该基体表面的至少一部分的被膜，所述被膜以至少含有锂（Li）、铝（Al）、硅（Si）、氧（O）4元素的相为主成分。
在这里，基体只要是以碳化硅为主成分或以碳化硅和金属硅为主成分的，则并无特别限定，特别优选具有碳化硅粒子通过金属硅而结合的结构的基体。基体中，作为烧结助剂，可含有硼、碳、或金属氧化物，特别优选含有B4C、碱土类或稀土类金属的氧化物。此外，作为基体，也可使用气孔率为20～70%的多孔体。其中，将碳化硅材料用于DPF时，为了在维持基体强度的同时不增加压力损失，气孔率优选为40～70%，更优选45～60%。此外，将碳化硅材料用于电热式催化剂载体时，为了在容易负载催化剂的同时容易进行电加热，气孔率优选为20～50%，更优选30～45%。气孔率可通过造孔剂的量、Si/SiC比、烧结助剂量、烧结气氛等调整。作为基体的形状，可举出例如，板状、管状、藕状、蜂窝状等。蜂窝状的情况下，例如可以是，隔壁的厚度为50～500μm、孔格密度为10～100孔格/cm2。另外，以碳化硅为主成分的基体指的是，碳化硅在50wt%以上的，也可含有硅的氧化物或氮化物等。
被膜优选实质上不含钾。这是由于钾元素存在腐蚀碳化硅的担忧。在这里，实质上不含指的是，除了含量为0的情况外，也包括作为杂质微量含有（例如检测限以下的量）的情况。此外，被膜优选含有锂铝硅酸盐。作为锂铝硅酸盐，可举出有，锂辉石、锂霞石、石英固溶体等，其中优选锂辉石。这是由于锂辉石在锂铝硅酸盐中熔点高，是热稳定的结晶相。
此种被膜的最大膜厚优选2～102μm。这是由于，在此范围内的话，可得到充分的耐热冲击性。膜厚越厚，就必须提高附着原料的浓度，因此会产生膜厚难以均匀化、难以附着在气孔内、附着物的干燥时间变长等不佳状况。因此，最大膜厚更优选为2～50μm，进一步优选2～20μm。此外，被膜的膜重量比例优选为4.1～58.3wt%以下。这是由于，在此范围内的话，可以得到充分的耐热冲击性。膜重量比例越低，可以减少原料的附着量、降低原料成本。因此，膜重量比例优选为4.1～50wt%，进一步优选4.1～30wt%。另外，膜重量比例指的是，被膜形成后的碳化硅烧结体的重量与被膜形成前的碳化硅烧结体重量的差除以前者的重量，以百分率表示比例。另外，被膜优选由氧化锂（Li2O）：1～37wt%、氧化铝（Al2O3）：3～49wt%、氧化硅（SiO2）：48～96wt%的组成构成。这是由于，在此范围内的话，可以得到充分的耐热冲击性。此外，为了通过增加锂铝硅酸盐而变为更加热稳定的物质，被膜优选由Li2O：20～37wt%、Al2O3：3～49wt%、SiO2：48～96wt%的组成构成，进一步优选由Li2O：20～37wt%、Al2O3：3～45wt%、SiO2：48～96wt%的组成构成。
作为本发明的第1发明的碳化硅材料的制造方法，可举出例如，包括下述工序的方法：（a）在含有碳化硅的基体表面附着氧化铝或通过热处理可变为氧化铝的氧化铝前驱体和氧化锂或通过热处理可变为氧化锂的氧化锂前驱体的工序、（b）通过将所述工序（a）得到的基体在含氧气氛下以900～1300℃热处理、使所述基体表面的至少一部分生成含锂铝硅酸盐的被膜的工序。工序（a）中，另外，也可附着氧化硅或通过热处理可变为氧化硅的氧化硅前驱体。
在这里，基体如上所述。作为氧化铝前驱体，并无特别限定，可举出有，氧化铝溶胶、碱性氯化铝、碱性乳酸铝、氯化铝、硝酸铝、硫酸铝等。其中，由于氧化铝溶胶及碱性乳酸氧化铝溶胶容易控制附着量、反应性高、容易生成锂铝硅酸盐，因此优选。作为氧化锂前驱体，并无特别限定，可举出有，氧化锂溶胶、氢氧化锂、醋酸锂、柠檬酸锂、碳酸锂等。其中，由于氢氧化锂的反应性高、容易生成锂铝硅酸盐，因此优选。作为氧化硅前驱体，并无特别限定，可举出有，胶态二氧化硅、硅酸乙酯等。其中，胶态二氧化硅容易控制附着量、反应性高、容易生成锂铝硅酸盐，因此优选。含锂铝硅酸盐的被膜的膜厚和膜重量比例可通过例如，调整氧化锂或其前驱体、氧化铝原料或其前驱体、氧化硅或其前驱体的使用量而任意变化。
工序（a）中，优选在基体表面附着氧化铝或氧化铝前驱体时使用含有氧化铝或氧化铝前驱体的水溶液或水性悬浮液，在附着氧化锂或氧化锂前驱体时使用含有氧化锂或氧化锂前驱体的水溶液或水性悬浮液。此外，工序（a）中，进一步附着氧化硅或氧化硅前驱体时，优选使用含有氧化硅或氧化硅前驱体的水溶液或水性悬浮液。这样，工序（b）中生成的主要是水蒸气，无需有害挥发成分的净化设备，因此可简化制造工序。
工序（a）中，在基体表面附着氧化铝或氧化铝前驱体、附着氧化锂或氧化锂前驱体、附着氧化硅或氧化硅前驱体时，可通过浸渍、涂布、或喷涂等进行。
工序（b）中，被膜所含的锂铝硅酸盐的二氧化硅中，也可含有基体内的硅成分经热处理而氧化而成之物。这样，基体上附着氧化硅时，可以减少该氧化硅的量。或者锂铝硅酸盐的二氧化硅也可以全部是基体内的硅成分经热处理而氧化而成之物。这样，可以省略在基体上附着氧化硅的工序。
工序（b）中，含氧气氛中也可含有水蒸气。在这里，可以使水蒸气从外部混入气氛中。此外，热处理在900～1300℃下进行。在此范围内的话，锂铝硅酸盐的生成率高，可以得到耐热冲击性优异的含硅材料。
本发明的第1发明的碳化硅材料可利用于蜂窝结构体。在这里，蜂窝结构体通过例如负载贵金属催化剂可用作DPF和催化转换器。即，蜂窝结构体的一个应用方式是催化剂载体。此外，催化转换器中通过电加热使催化剂尽早活化的方式中，由于要求较高的耐热冲击性，因此特别优选利用本发明的第1发明的碳化硅材料。
【实施例】
[实施例1]
准备由碳化硅粒子和金属硅构成的、气孔率为40%的多孔性基体。该基体如下制作。作为陶瓷原料，将碳化硅（SiC）粉末和金属硅（Si）粉末以重量比80：20的比例混合，向其中添加作为粘合剂的羟丙基甲基纤维素、水，制为成形原料，将成形原料混炼，通过真空捏合机制作圆柱状的坯土。粘合剂的含量为，相对于碳化硅（SiC）粉末和金属硅（Si）粉末的合计为7质量%，水的含量可适当调整，以使坯土硬度适宜挤出成形，相对于碳化硅（SiC）粉末和金属硅（Si）粉末的合计为约23质量%。碳化硅粉末的平均粒径为33μm，金属硅粉末的平均粒径为6μm。碳化硅、金属硅及造孔剂的平均粒径是通过激光衍射法测定的值。
将得到的坯土使用挤出成形机成形，得到蜂窝成形体。将得到的蜂窝成形体以高频电介质加热干燥后，使用热风干燥机以120℃干燥2小时，将该蜂窝成形体在大气气氛下进行550℃、3小时的脱脂，然后，在Ar惰性气氛下进行约1450℃、2小时烧结，使SiC结晶粒子通过Si结合，得到多孔性的基体。另外，气孔率通过压汞仪测定。图1是该基体的SEM照片。
将该多孔性的基体浸渍于氧化铝粒径10nm～100nm、浓度10wt%、醋酸稳定型的氧化铝溶胶中，从而在基体表面附着氧化铝，在大气中以110℃干燥。接着，将该基体浸渍于2wt%的氢氧化锂水溶液中，从而在基体表面附着氢氧化锂，在大气中以110℃干燥。接着，将该基体在大气下进行1100℃、3.5小时热处理。由此，得到由含硅材料所构成的实施例1的样品，所述含硅材料具备：含碳化硅和金属硅的基体、以及覆盖该基体表面的至少一部分的被膜。该样品的被膜含有由氧化锂、氧化铝、二氧化硅反应生成的锂铝硅酸盐，但实质上不含钾元素。在这里，实质上不含指的是，除了含量为0的情况以外，也包括作为杂质微量含有（例如检测限以下的量）的情况。通过X射线衍射（X射线源Cu-Kα）中2θ=25.0°～26.3°出现峰，确认了被膜为锂铝硅酸盐。锂铝硅酸盐中的锂辉石、锂霞石及石英固溶体均在此位置出现峰值。此外，通过X射线衍射（X射线源Cu-Kα）中2θ=22.0°～23.0°出现峰，确认了含有锂辉石的结晶相。锂辉石在此位置出现峰，但锂霞石和石英固溶体在此位置不出现峰。
对于得到的实施例1的样品，求得膜重量比例（wt%）、被膜的组成比（重量比）、被膜的最大膜厚（μm）、样品的热膨胀变化率（%）及强度变化率（%），其结果汇总于表1。另外，测定各参数。
·膜重量比例（wt%）
根据下式求得。
膜重量比例=（样品的重量-基体的重量）/样品的重量×100
另外，样品指的是基体上形成了被膜的碳化硅材料，基体指的是未形成被膜的碳化硅材料。
·被膜的组成比（重量比）
依据JIS R1616实施样品和基体的化学分析，从样品的定量值减去基体的定量值，从而求得被膜中存在的3成分（Li2O，Al2O3，SiO2）的重量，根据各重量算出3成分的组成比。
·被膜的最大膜厚（μm）
通过倍率1000倍的样品截面SEM图像实测膜厚，以其中的最大值为最大膜厚。图2显示的是实施例1的样品的SEM图像。深灰色的部分为碳化硅粒子，浅灰色的部分为金属硅。图2中，确认了碳化硅粒子及金属硅的表面形成的锂铝硅酸盐被膜的最大膜厚为5μm。另外，膜厚于95×120μm的视野内（视野×5处）实测。
·热膨胀变化率（%）
依据JIS R1618测定室温～800℃的平均线热膨胀系数，以此值为热膨胀率。以（样品的值-基体的值）/基体的值×100（%）为热膨胀变化率。
·锂辉石结晶相
依据JIS K0131测定粉末X射线衍射（X射线源Cu-Kα），由此进行物质鉴定。通过2θ=22.0°～23.0°出现峰，确认了含有锂辉石的结晶相。
[实施例2～14]
依据实施例1，通过调整Si/SiC比、烧结助剂量、烧结气氛、造孔剂量等，制作表1所示的气孔率的基体，对该基体调整附着量、附着铝源及锂源后，通过在900～1300℃下进行热处理，得到基体表面的至少一部分上具有被膜的样品。对于得到的样品，与实施例1同样地测定各参数。其结果一并显示于表1。
[实施例15]
准备碳化硅粒子构成的致密基体。该基体如下制作。添加平均粒径0.6μm的碳化硅粉末100质量份、平均粒径1.5μm的B4C粉末2.0质量份、平均粒径0.02μm的碳粉末1.5质量份。将该添加物投入介质搅拌式粉碎机内，进行20小时混合·粉碎，得到悬浮液。然后，将该悬浮液用喷雾干燥器干燥，制造平均粒径50μm的造粒粉末。将该造粒粉末填充至橡胶模具内，以压力2.5ton/cm2静水压加压成形。将该成形体在1个大气压的氩气氛中进行2100℃、1小时烧结，得到致密的SiC烧结体。另外，气孔率依据JIS R1634测定。在该基体上附着铝源及锂源后，通过进行1100℃的热处理，得到基体表面的至少一部分上具有被膜的样品。对于得到的样品，与实施例1同样地测定各参数。其结果一并显示于表1。
[实施例16]
混合平均粒径100μm的粗粒碳化硅粉末45质量份、平均粒径2μm的微粒碳化硅粉末55质量份，添加20质量份的水和2质量份的粘合剂，得到悬浮液。将该悬浮液流入石膏模具而制作。将得到的成形体在压力1atm的氩气中进行2200℃、2小时烧结，从而得到多孔质的重结晶碳化硅烧结体。另外，气孔率通过压汞仪测定。令该基体附着铝源及锂源后，通过进行1100℃的热处理，得到基体表面的至少一部分上具有被膜的样品。对于得到的样品，与实施例1同样地测定各参数。其结果一并显示于表1。
[比较例1]
将实施例1制作的多孔性的基体在大气下进行1100℃、3.5小时热处理，从而得到基体表面的至少一部上具有二氧化硅被膜的样品。对于得到的样品，与实施例1同样地测定各参数。其结果一并显示于表1。确认了碳化硅粒子表面形成的二氧化硅被膜的最大膜厚为2μm。
[比较例2]
将实施例1制作的多孔性的基体浸渍于实施例1使用的氧化铝溶胶中，从而在基体表面附着氧化铝后，在大气中进行110℃的干燥。然后，通过在大气下进行1300℃、3.5小时热处理，得到基体表面的至少一部分上具有含铝硅酸盐的被膜的样品。对于得到的样品，与实施例1同样地测定各参数。其结果一并显示于表1。
[比较例3]
将实施例1制作的多孔性的基体浸渍于实施例1使用的氢氧化锂水溶液中，从而在基体表面附着氢氧化锂后，在大气中进行110℃的干燥。然后，通过在大气下进行1100℃、3.5小时热处理，得到基体表面的至少一部分具有含锂硅酸盐的被膜的样品。对于得到的样品，与实施例1同样地测定各参数。其结果一并显示于表1。
[比较例4]
通过将实施例12制作的多孔性的基体在大气下进行1300℃、3.5小时热处理，得到基体表面的极小一部分上具有二氧化硅被膜的样品。对于得到的样品，与实施例1同样地测定各参数。其结果一并显示于表1。
[比较例5]
将实施例1制作的多孔性基体浸渍于实施例1使用的氧化铝溶胶中，从而在基体的表面附着氧化铝后，在大气中进行110℃的干燥。接着，通过将该基体浸渍于2wt%的氯化钾水溶液中，在基体表面附着氯化钾，在大气中进行110℃的干燥。接着，将该基体在大气下进行1300℃、3.5小时热处理。由此，得到基体表面的至少一部上具有含钾铝硅酸盐的被膜的样品。对于得到的样品，与实施例1同样地测定各参数。其结果一并显示于表1。
实施例、比较例的样品中，使用实施例1、7、10、14、比较例1、2、3、5的样品实施电炉剥落试验（急速冷却试验），实施例的样品均未产生裂纹，比较例的样品均产生了裂纹。另外，电炉剥落试验具体指的是，将样品在电炉中进行550℃×2h加热，使温度均匀后，取出至室温下，通过样品有无产生裂纹而评价耐热冲击性的试验。
如表1所示，实施例1～16的热膨胀变化率为负值，与此相对，比较例1～5的热膨胀变化率为正值。在这里，热膨胀变化率为负值意味着被膜的热膨胀率低于基体。实施例1～16中，较之于比较例1～5，样品加热时的基体的热膨胀可通过热膨胀率低的被膜抑制，其结果是耐热冲击性提升。此外，热膨胀变化率的负值的绝对值越大，耐热冲击性越高。即，热膨胀变化率是评价耐热冲击性的指标。实施例1～16的热膨胀变化率为负值，可认为是由于被膜以热膨胀率低的相、具体是含有锂（Li）、铝（Al）、硅（Si）、氧（O）4元素的相（特别是含有锂铝硅酸盐的相）为主成分。
此外，比较实施例4和实施例9，实施例9的热膨胀变化率的负值的绝对值较大。因此，实施例9的基体热膨胀抑制效果较大，耐热冲击性进一步提升。其原因推测为，构成实施例9的被膜的锂铝硅酸盐为热膨胀率低的锂辉石，与此相对，构成实施例4的被膜的锂铝硅酸盐是热膨胀率不像锂辉石那么低的结晶相。
【表1】
从表1可明确，实施例1～16的样品较比较例1～4的样品的热膨胀率下降，因此耐热冲击性良好。
本申请以2011年2月4日提交的日本国专利申请第2011-022498号为优先权主张基础，通过引用，其全部内容包含于本说明书。
工业可利用性
本发明的第1发明的碳化硅材料可用于蜂窝结构体。在这里，蜂窝结构体通过例如负载贵金属催化剂而用作DPF或催化转换器。即，蜂窝结构体的一个应用方式是催化剂载体。特别是催化转换器中通过电加热使催化剂尽早活化的方式中，由于要求较高的耐热冲击性，因此特别优选利用本发明的第1发明碳化硅材料。
Claims (11)
1.一种碳化硅材料，具备：
以碳化硅为主成分或以碳化硅和金属硅为主成分的基体、
覆盖该基体表面的至少一部分的被膜，
所述被膜以至少含有锂（Li）、铝（Al）、硅（Si）、氧（O）4元素的相为主成分。
2.根据权利要求1所述的碳化硅材料，其中，所述被膜不含钾。
3.根据权利要求1或2所述的碳化硅材料，其中，所述被膜含有锂铝硅酸盐。
4.根据权利要求3所述的碳化硅材料，其中，所述锂铝硅酸盐为锂辉石。
5.根据权利要求1～4任意一项所述的碳化硅材料，其中，所述基体具有碳化硅粒子通过金属硅而结合的结构。
6.根据权利要求1～5任意一项所述的碳化硅材料，其中，所述基体的气孔率为20～70%。
7.根据权利要求1～6任意一项所述的碳化硅材料，其中，所述被膜的最大膜厚为2～102μm。
8.根据权利要求1～7任意一项所述的碳化硅材料，其中，所述被膜的膜重量比例为4.1～58.3wt%以下。
9.根据权利要求1～8任意一项所述的碳化硅材料，其中，所述被膜由氧化锂（Li2O）：1～37wt%、氧化铝（Al2O3）：3～49wt%、氧化硅（SiO2）：48～96wt%的组成构成。
10.一种蜂窝结构体，由权利要求1～9任意一项所述的碳化硅材料构成。
11.一种电热式催化剂载体，利用了权利要求1～9任意一项所述的碳化硅材料。
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- 2012-01-30 JP JP2012555851A patent/JPWO2012105478A1/ja active Pending
- 2012-01-30 WO PCT/JP2012/051940 patent/WO2012105478A1/ja active Application Filing
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2013
- 2013-07-31 US US13/955,247 patent/US20130316129A1/en not_active Abandoned
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108025984A (zh) * | 2015-08-25 | 2018-05-11 | 赛丹思科大学 | 制备含多孔α碳化硅的本体的方法和由该方法制备的本体 |
| CN108025984B (zh) * | 2015-08-25 | 2020-11-13 | 赛丹思科大学 | 制备含多孔α碳化硅的本体的方法和由该方法制备的本体 |
| JPWO2021065355A1 (ja) * | 2019-10-02 | 2021-10-21 | 日本碍子株式会社 | 耐火物 |
| CN114430733A (zh) * | 2019-10-02 | 2022-05-03 | 日本碍子株式会社 | 耐火物 |
| JP7225376B2 (ja) | 2019-10-02 | 2023-02-20 | 日本碍子株式会社 | 耐火物 |
| CN110833978A (zh) * | 2019-11-15 | 2020-02-25 | 一汽解放汽车有限公司 | 一种使用乙烯基苯甲酸钾辅助的涂覆壁流式催化器催化层的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012105478A1 (ja) | 2012-08-09 |
| EP2671857A1 (en) | 2013-12-11 |
| EP2671857A4 (en) | 2015-09-23 |
| JPWO2012105478A1 (ja) | 2014-07-03 |
| CN103339087B (zh) | 2015-10-21 |
| US20130316129A1 (en) | 2013-11-28 |
| EP2671857B1 (en) | 2021-10-13 |
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