CN101808956A - 蜂窝结构体及使用其的净化装置 - Google Patents
蜂窝结构体及使用其的净化装置 Download PDFInfo
- Publication number
- CN101808956A CN101808956A CN200880108592A CN200880108592A CN101808956A CN 101808956 A CN101808956 A CN 101808956A CN 200880108592 A CN200880108592 A CN 200880108592A CN 200880108592 A CN200880108592 A CN 200880108592A CN 101808956 A CN101808956 A CN 101808956A
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- China
- Prior art keywords
- honeycomb structure
- partition wall
- flow holes
- tio
- partition walls
- 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.)
- Granted
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- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000012530 fluid Substances 0.000 claims abstract description 8
- 238000005192 partition Methods 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 32
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 31
- 238000007789 sealing Methods 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910014455 Ca-Cb Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011222 crystalline ceramic Substances 0.000 claims description 2
- 229910002106 crystalline ceramic Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000035939 shock Effects 0.000 abstract description 15
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000395 magnesium oxide Substances 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 14
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
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- 238000000034 method Methods 0.000 description 10
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- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 8
- 229910003079 TiO5 Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
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- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
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- 238000010304 firing Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
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- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- 238000002485 combustion reaction Methods 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
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- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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Abstract
期望耐热性及耐热冲击性等优越,难以热分解,即使进行热处理,机械特性也稳定的蜂窝结构体及使用其的净化装置。本发明的蜂窝结构体的特征在于,以具有MgTi2O5-Al2TiO5的结晶的陶瓷体为蜂窝结构。另外,本发明的净化装置,其特征在于,具备蜂窝结构体,以及收容蜂窝结构体且具有流入口及流出口的壳体,从壳体的流入口进入的流体经过蜂窝结构体并从壳体的流出口流出。
Description
技术领域
本发明涉及包括陶瓷的蜂窝结构体。另外,用于捕集在内燃机或锅炉等中产生的排气等流体中包含的微粒的蜂窝结构体及使用其的净化装置。
背景技术
以往,出于捕集在内燃机等中产生的排气中包含的以碳为主成分的微粒(尤其柴油发动机的排气中的微粒(柴油微粒))的目的,使用了包括陶瓷的蜂窝结构体。
该蜂窝结构体具备:利用包括多孔性的陶瓷的格子状隔壁隔开的多个流通孔。另外,各流通孔的一端、和另一端的任一方被交替地密封。由此,排气从过滤器的入口流入从出口流出时排气中的微粒被隔壁捕集。
当前,期望耐热性及耐热冲击性等优越,难以热分解,即使进行热处理,机械特性也稳定的蜂窝结构体及使用其的净化装置。
【专利文献1】国际公开第2005/005019号手册
发明内容
本发明的一方式的蜂窝结构体,其特征在于,以具有MgTi2O5-Al2TiO5的结晶的陶瓷体为蜂窝结构。
另外,本发明的一方式的蜂窝结构体,其特征在于,其具备多个被含有陶瓷的隔壁隔开且从一端到达另一端的流通孔,具有交替地密封了这些多个流通孔的一端和另一端的任一方的密封部,所述隔壁具有MgTi2O5-Al2TiO5的结晶。
另外,本发明的一方式的蜂窝结构体,其特征在于,其具备多个被在单轴方向上延伸的含有陶瓷的隔壁隔开且从一端到达另一端的流通孔,具有交替地密封了这些多个流通孔的一端和另一端的任一方的密封部,所述隔壁具有MgTi2O5-Al2TiO5的结晶,将所述隔壁在1200℃温度下维持2小时的热处理前后,由下述式(1)表示的变化率CR为20以下,
CR=(|Ca-Cb|/Ca)×100···(1)
其中,
Ca:所述热处理前的所述单轴方向上的压缩破坏强度(MPa)
Cb:所述热处理后的所述单轴方向上的压缩破坏强度(MPa)。
另外,本发明的一方式的蜂窝结构体,其特征在于,其具备多个被含有陶瓷的隔壁隔开且从一端到达另一端的流通孔,具有交替地密封了这些多个流通孔的一端和另一端的任一方的密封部,所述隔壁具有MgTi2O5-Al2TiO5的结晶,将所述密封部的气孔率设为Ps,将所述隔壁的气孔率设为Pw时,由下述式(2)表示的比率PR为84以下,
PR=(|Pw-Ps|/Pw)×100···(2)。
本发明的一方式的净化装置,其特征在于,具备所述蜂窝结构体,以及收容所述蜂窝结构体且具有流入口及流出口的壳体,从所述壳体的流入口进入的流体经过所述蜂窝结构体并从所述壳体的流出口流出。
根据所述蜂窝结构体及净化装置可知,耐热性及耐热冲击性等优越。另外,钛酸镁(MgTi2O5)抑制钛酸铝(Al2TiO5)的高温下的分解。进而,MgTi2O5-Al2TiO5为化学计量组成,因此,与非化学计量组成的结晶相比,难以出现在结晶中发生的力学变形。由此,即使进行热处理,在热处理前后,机械特性的变化也少。
附图说明
图1是说明本发明的一方式的蜂窝结构体的立体图。
图2是图1中的B-B线剖面图。
图3是说明本发明的一方式的蜂窝结构体的图,是表示入口端面的一部分的俯视图。
图4是说明本发明的一方式的蜂窝结构体的图,是表示出口端面的一部分的俯视图。
图5是说明本发明的一方式的蜂窝结构体的图,是表示入口端面的一部分的俯视图。
图6是说明本发明的一方式的蜂窝结构体的图,是表示出口端面的一部分的俯视图。
图7是说明本发明的一方式的蜂窝结构体的图,是表示入口端面的一部分的俯视图。
图8是说明本发明的一方式的蜂窝结构体的图,是表示出口端面的一部分的俯视图。
图9是说明本发明的一方式的净化装置的概略剖面图。
符号说明:
1-蜂窝结构体;
2-流通孔;
3-密封部;
4-隔壁;
5-排气流入口;
6-排气流出口;
7-壳体;
8-绝热材料层;
9-排气管;
10-净化装置。
具体实施方式
如图1、图2所示,本实施方式的蜂窝结构体1具备:多个从包括多孔性的陶瓷的隔壁4的一端4a到达另一端4b的流通孔2。即,这些流通孔2例如通过在单轴方向(图示的箭头A方向)上为长格状的隔壁4隔开而构成。进而,蜂窝结构体1具有:用于密封各流通孔2的一端和另一端的任一方的密封部3。
另外,在俯视蜂窝结构体1的一端(图3)及另一端(图4)的情况下,邻接的流通孔2的任一方被密封部3(3a、3b)密封。如图3、4所示,密封部3a、3b例如配置为方格花纹状。另外,各流通孔2的平面形状可以形成为圆形状、多种方形状、角部为圆弧状的四边形状、或组合了四边形状和八边形状等的各种形状。另外,在一个蜂窝结构体1中混合不同的平面形状的流通孔2也可。例如,图5所示的蜂窝结构体1包含:平面形状为四边形状的流通孔2、和平面形状为八边形状的流通孔2。另外,多个流通孔2只要具有交替地被密封的部分即可,不限定于方格花纹状。
蜂窝结构体1如图1、2所示,整体例如为圆柱状,其外径为100~200mm,单轴方向的长度L为100~250mm。在相对于单轴方向(A)垂直的剖面中,流通孔2的个数例如在每一平方英寸为50~800个。该剖面中的各流通孔2的剖面积例如为1~10mm2。隔开各流通孔2的隔壁4的厚度(相对于单轴方向垂直的方向的厚度)例如为0.05~1.0mm。
隔壁4为具有化学计量组成的镁铝钛酸盐(MgTi2O5-Al2TiO5)的结晶而成。在此,镁铝钛酸盐为固溶体,在X射线衍射图中,在2θ=25.5°~26.5°具有主峰。
隔壁4为化学计量组成的镁铝钛酸盐的固溶体,因此,钛酸镁(MgTi2O5)抑制钛酸铝(Al2TiO5)的高温下的分解。钛酸镁及钛酸铝均由化学计量组成(恒定比)而成,因此,与非化学计量组成的结晶相比,抑制在结晶中产生的力学变形。因此,在热处理前后,隔壁4的机械特性也稳定,在热处理后,机械强度不会显著降低。
在隔壁4中,作为微量成分,也可含有氧化钛(TiO2)、氧化钾(K2O)、氧化钠(Na2O)、氧化镁(MgO)、氧化铝(Al2O3)等氧化物。在这些微量成分中,为了成为适当的多孔性的蜂窝结构体,氧化钾(K2O)为0.2质量%以下,氧化钠(Na2O)为0.9质量%以下即可。另外,氧化钾(K2O)及氧化钠(Na2O)的各含量可以通过荧光X射线分析法或ICP(Inductivity Coupled Plasma)发光分析法来求出。具体来说,关于氧化钾(K2O)及氧化钠(Na2O),分别测定金属元素的K、Na的含量,换算为氧化物即可。
化学计量组成的镁铝钛酸盐(MgTi2O5-Al2TiO5)的结晶及上述微量成分的组成可以通过X射线衍射法来鉴定。另外,隔壁4中的各成分的比率可以通过荧光X射线分析法或ICP(Inductivity Coupled Plasma)发光分析法来求出。
尤其,相对于构成隔壁4的成分100质量%,适合的是,钛酸铝(Al2TiO5)为60~70质量%,钛酸镁(MgTi2O5)为16~26质量%,余量为氧化铁(Fe2O3)。
通常,钛酸铝(Al2TiO5)在850~1280℃的范围下热分解。因此,隔壁4为包含钛酸铝(Al2TiO5)的陶瓷的情况下,要求即使发生该化合物的热分解,也难以破坏的耐热冲击性。本实施方式的蜂窝结构体1包含钛酸镁,因此,抑制热分解,其结果,能够实现下述式(1)的值小的压缩破坏强度的变化率。即,在温度1200℃下维持2小时的热处理前后,由下述式(1)表示的变化率CR为20以下。
CR=(|Ca-Cb|/Ca)×100···(1)
其中,
Ca:所述热处理前的单轴方向(图1、2中的A方向)上的压缩破坏强度(MPa)
Cb:所述热处理后的所述单轴方向上的压缩破坏强度(MPa)
压缩破坏强度Ca、Cb是例如依据JASO M 505-87测定的,通过式(1)来求出变化率CR即可。作为测定用试料,使用从蜂窝结构体1切下一边的长度为10mm的立方体后的蜂窝结构体即可。
若变化率CR为20以下,则钛酸铝(Al2TiO5)难以在高温下分解,因此,即使重复使用,也能够以高的状态维持耐热冲击性。由此,即使反复进行蜂窝结构体1的再生(通过使隔壁4所捕集的微粒烧却或反洗等来将其除去,形成可以再使用的状态),也不容易破坏。
另外,本实施方式的蜂窝结构体1在将密封部3的气孔率设为Ps,将隔壁4的气孔率设为Pw的情况下,由下述式(2)规定的气孔率的比率PR为84以下。由此,在为了再生而进行的热处理中,在隔壁4和密封部3的边界发生的裂纹及溶损难以发生。
PR=(|Ps-Pw|/Pw)×100···(2)
若由式(2)表示的气孔率的比率PR为84以下,则烧结工序中的隔壁4及密封部3的收缩率之差变小。其结果,隔壁4和密封部3的边界的应力集中减小,因此,蜂窝结构体1的耐热冲击性提高。由此,能够减少再生中的隔壁4和密封部3的边界发生的裂纹及溶损。另外,进行调节以使烧成工序中的密封部3的收缩率与隔壁4的收缩率预先大致相等,这样,即使一体地烧成密封部3和隔壁4,也抑制在烧成后于密封部3和隔壁4之间发生龟裂的情况。
尤其,隔壁4的气孔率(Pw)为30%以上且60%以下,密封部3的气孔率(Ps)为9.6%以上且60%以下即可,这些气孔率(Pw)、(Ps)可以使用水银压入法来测定。
如图5所示,将俯视了隔壁4的入口端面的情况下的流通孔2的开放部分的形状形成为比密封部分的面积宽的例如八边形状,如图6所示,将出口端面的开放部分的形状形成为比密封部分窄的例如四边形状也可。另一方面,流通孔2的密封部分的形状也可与上述开放部分的形状相反,将隔壁4的入口端面侧形成为四边形状,将出口端面侧形成为八边形状。
另外,如图7所示,将俯视隔壁4的入口端面时的流通孔2的开放部分的形状形成为比密封部分的面积宽的角部为圆弧状的例如四边形状,也可以如图8所示,将出口端面的开放部分的形状形成为比密封部分窄的例如四边形状。另一方面,也可以使流通孔2的密封部分的形状与开放部分的形状相反,将隔壁4的入口端面侧形成为四边形状,将出口端面侧形成为角部为圆弧状的例如四边形状。
通过这样构成,如图3、4所示,与流通孔2的形状仅为四边形状的情况相比,能够增大捕集微粒的隔壁4的表面积,因此,能够增大微粒的捕集量。另外,通过进一步扩大流通孔2的开口面积,能够适当地捕集微粒。
尤其,在图7中,适合的是,角部为圆弧状的四边形状的流通孔2的水力直径相对于面积比其小的流通孔2的水力直径为1.55倍以上且1.95倍以下。这样,通过将水力直径之比设为1.55倍以上,能够增大微粒的捕集量。在此,流通孔2的水力直径是指俯视隔壁4的一端面的情况时与隔壁4接触的内切圆的直径,可以使用光学显微镜来测定。
其次,说明蜂窝结构体1的制造方法。
首先,准备调合原料。为了得到隔壁4具有化学计量组成的镁铝钛酸盐(MgTi2O5-Al2TiO5)的结晶的蜂窝结构体,需要控制作为原料的氧化钛(TiO2)、氧化铝(Al2O3)及氧化镁(MgO)的各平均粒径。
准备平均粒径为1~10μm的氧化钛(TiO2)和平均粒径为1~10μm的氧化铝(Al2O3)。再将氧化钛(TiO2)及氧化铝(Al2O3)按摩尔比设为TiO2∶Al2O3=40~60∶60~40,在包括氧化钛(TiO2)及氧化铝(Al2O3)的成分100质量份中调合平均粒径为1~10μm的氧化镁(MgO)1~10质量份、和二氧化硅(SiO2)1~10质量份,得到调合原料。
在此,代替氧化镁(MgO),可以为包含Mg的尖晶石型结构的氧化物或通过烧成来转化为MgO的含Mg化合物的任一个。
蜂窝结构体中的压缩破坏强度的变化率(CR)受到二氧化硅(SiO2)的含量的影响。即,二氧化硅(SiO2)的含量越高,变化率(CR)越低,二氧化硅(SiO2)的含量越低,变化率(CR)越高。从这样的观点来说,为了得到变化率(CR)为20以下的蜂窝结构体,将调合原料中的二氧化硅(SiO2)设为3~10质量份即可。
向如上所述地得到的调合原料中添加石墨、淀粉或树脂粉末等造孔剂的规定量之后,进而加入增塑剂、增粘剂、润滑剂及水等,使用万能搅拌机、旋转磨机或V型搅拌机等,形成为混合物。再使用三根辊磨机或混炼机等,将该混合物混炼,得到增塑化的瓷器粘土(日文:杯土)。
其次,使用模具,使用挤出成形机来成形。确定成形体的外径的内径例如为100~250mm,使用具有用于形成蜂窝结构体1的隔壁4的狭缝的模具。向装配了该模具的挤出成形机中投入所述瓷器粘土,施加压力,成形为蜂窝状。然后,干燥成形体,切断加工为规定长度。
密封成形体的流通孔2的一端和另一端的任一方。对多个流通孔2中的一部分有选择地实施掩蔽。此时,例如,选择掩蔽的流通孔2以使密封的流通孔2配置为方格花纹。将实施了掩蔽的出口端面(图2的符号OF)浸渍于浆料中。另外,对于具有未实施掩蔽的出口端面(OF)的流通孔2,预先从入口端面(图2的符号IF)涂敷疏水性的树脂,将前端面的形状平坦的销从入口端面(IF)插入流通孔2,在常温下干燥。由此,形成成形体的出口侧的密封部3b。再拔出所述销,在入口端面(IF)侧也进行与上述作业相同的作业,形成成形体的入口侧的密封部3a。
其次,烧成得到的成形体。通过使用电炉或气炉等烧成炉,在温度1250~1700℃下将成形体保持0.5小时~5小时而烧成。
这样制作的蜂窝结构体1由于钛酸镁(MgTi2O5)及钛酸铝(Al2TiO5)为化学计量组成(恒定比),因此,能够抑制在结晶相发生的力学变形,能够降低隔壁4的热处理前后中的机械特性的变化。
另外,这样制作的蜂窝结构体1可以长期效率良好地捕集流体中的微粒。
说明将本实施方式的蜂窝结构体1用作捕集柴油发动机(未图示)的排气中的柴油微粒的过滤器的情况。如图9所示,本实施方式的净化装置10具备:蜂窝结构体1、将其收容的壳体7。壳体7例如为不锈钢等金属制,其中央部形成为圆筒状,两端部形成为圆锥台状。在壳体7的中央部收容蜂窝结构体1,在壳体7的两端部分别形成有排气(EG)的流入口及流出口6。另外,在壳体7的中央部内表面形成有包围蜂窝结构体1的侧面的例如包括陶瓷纤维、玻璃纤维、碳纤维及陶瓷晶须的至少任一种的绝热材料层8。在壳体7的流入口5连结有排气管9。排气(EG)从排气管9流入壳体7内。
若柴油发动机(未图示)运行,排气(EG)从排气管9流入壳体7,则排气(EG)从蜂窝结构体1的入口端面(IF)导入未被密封部3a密封的流通孔2中。导入排气(EG)的流通孔2由于出口端面(OF)侧的端部被密封部3b密封,因此,排气(EG)的流出被隔断。被隔断流出的排气(EG)通过多孔性的隔壁4,从出口端面(OF)侧未被密封部3b密封的邻接的流通孔2排出。在隔壁4中,在其内部的气孔内,捕集排气(EG)中的柴油微粒。即,被净化的空气流入邻接的流通孔2中。而且,邻接的流通孔2的入口端面(IF)侧的端部被密封部3a密封,因此,排气(EG)不会混入被净化的空气中。这样,导入净化装置10的蜂窝结构体1的排气(EG)被净化为不包含柴油微粒的状态,从出口端面(OF)向外部排出。
在这样的净化装置10中,可以将本实施方式的蜂窝结构体1作为过滤器适当地使用,能够长期效率良好地捕集柴油微粒。
还有,在本实施方式中,说明作为流体,使用了排气的例子,但作为流体,也可以使用液体。例如,作为流体,可以使用自来水或污水,也可以将本实施方式的净化装置作为液体的过滤用来适用。
【实施例1】
首先,调合表1所示的氧化钛X∶氧化钛Y∶氧化铝的比率按摩尔比为20∶20∶60的成分100质量份、氧化镁(MgO)5质量份、和二氧化硅(SiO2)5质量份,得到了调合原料。
在该调合原料中,作为造孔剂,添加了规定量的石墨。然后,进而加入增塑剂、增粘剂、润滑剂及水,使用旋转磨机,形成为浆料。再使用混炼机,混合了通过旋转磨机得到的浆料,得到了增塑化的瓷器粘土。
其次,确定成形体的外径的内径为250mm,向装配了具有用于形成蜂窝结构体1的隔壁4的狭缝的模具的挤出成形机中投入所述瓷器粘土。向所述瓷器粘土施加压力,成形为蜂窝状。然后,干燥成形体,切断加工为规定长度。
其次,以成为方格花纹状的方式对一部分的流通孔2实施掩蔽后,将出口端面(OF)浸渍于浆料中。将涂敷了疏水性的树脂的前端部的形状为平坦的销从入口端面(IF)插入流通孔2中,在常温下干燥。由此,形成了成形体的出口侧的密封部3b。再拔出销,在入口端面(IF)侧也进行与上述作业相同的作业,形成了成形体的入口侧的密封部3a。另外,密封部3a、3b均使用与形成隔壁4所使用的调合原料相同种类的调合原料。
再使用电炉,将成形体在1500℃下烧成4小时,得到了蜂窝结构体。
关于构成得到的蜂窝结构体的隔壁4的陶瓷的组成,使用X射线衍射法来鉴定。将其组成式示于表1。
另外,由蜂窝结构体1分别制作了20个切成一边的长度为10mm的立方状的试料(不包含密封部3a、3b)。然后,测定各试料的单轴方向A的压缩破坏强度,算出了测定值的平均值及标准偏差。另外,单轴方向A上的压缩破坏强度是依据JASO M 505-87来测定。其结果示出在表1中。
【表1】
从表1可知,构成隔壁4的组成中钛酸镁及钛酸铝的至少任一个为非化学计量组成(不定比)的试料No.2~4的压缩破坏强度的平均值均为3.82MPa以下,标准偏差为0.6MPa以上。
另一方面,钛酸镁及钛酸铝以化学计量组成(恒定比)固溶的试料No.1的压缩破坏强度的平均值为4.32MPa,比试料No.2~4高。进而,试料No.1的标准偏差为0.4MPa,比试料No.2~4小。从这些结果可知,如试料No.1一样,包含化学计量组成的钛酸镁及钛酸铝的蜂窝结构体1为隔壁4的机械特性高,其标准偏差小的蜂窝结构体。
【实施例2】
其次,调合表2所示的、平均粒径均为5μm的氧化钛X∶氧化钛Y∶氧化铝的比率按摩尔比为20∶20∶60的成分100质量份、平均粒径为5μm的氧化镁(MgO)5质量份、和二氧化硅(SiO2)5质量份,得到了调合原料。
然后,通过与实施例1所示的方法相同的方法,制作了蜂窝结构体。
关于构成得到的蜂窝结构体的密封部3的陶瓷的组成,使用X射线衍射法来测定。其组成式示出在表2中。
另外,为了观察密封部3和隔壁4的接合状态,使用纤维镜,从A轴方向照射光。若在密封部3和隔壁4之间没有间隙,则光不从端面透过,若在密封部3和隔壁4之间有间隙,则光从端面透过。将即使从端面部分地确认到光的透过的蜂窝结构体设为“确认”,将未确认到的蜂窝结构体设为“未确认”。其结果示出在表2中。
【表2】
从表2可知,对于构成密封部3的钛酸镁及钛酸铝均为非化学计量组成(不定比)的试料No.6~8确认到间隙。另一方面,对于构成密封部3的组成为钛酸镁及钛酸铝均为化学计量组成(恒定比)的试料No.5未确认有间隙。从这些结果可知,如试料No.5一样,包含化学计量组成的钛酸镁及钛酸铝的蜂窝结构体1为捕集效率高的蜂窝结构体。
【实施例3】
首先,在氧化钛及氧化铝的比率按摩尔比为TiO2∶Al2O3=40∶60的成分100质量份中,调合氧化镁(MgO)5质量份、和表3所示的含量的二氧化硅(SiO2),得到了调合原料。
其次,利用与实施例1所示的方法相同的方法,由得到的调合原料制作了蜂窝结构体。再测定了从得到的各蜂窝结构体切下为一边的长度为10mm的立方状的试料的A轴方向上的压缩破坏强度。该测定值作为Ca示出在表3中。
另外,在温度1200℃下对蜂窝结构体热处理2小时。然后,测定了切成一边长度为10mm的立方状的试料在A轴方向上的压缩破坏强度。该测定值作为Cb示出在表3中。由单轴方向(A轴方向)上的压缩破坏强度Ca、Cb算出了压缩破坏强度的变化率(CR)。
另外,将利用相同方法得到的其他蜂窝结构体放入电炉中,在一定温度下保持了1小时。然后,取出到室温(24℃)中。将该蜂窝结构体确认到裂纹时的所述一定温度与室温(24℃)之间的温差作为耐热冲击温度示出在表3中。
【表3】
从表3可知,相对于压缩破坏强度的变化率(CR)超过20的试料No.12(能够再生的次数738次),压缩破坏强度的变化率(CR)为20以下的试料No.9~11的耐热冲击温度高,能够再生的次数也多达755次。从该结果可知,如试料No.12一样,压缩破坏强度的变化率CR为20以下的蜂窝结构体1为耐热冲击性高的蜂窝结构体。
【实施例4】
准备了平均粒径为5μm的TiO2和平均粒径为5μm的Al2O3。在摩尔比为TiO2∶Al2O3=40∶60的成分100质量份中,调合平均粒径为5μm的氧化镁(MgO)5质量份和二氧化硅(SiO2)5质量份,得到了调合原料。
然后,利用与实施例1所示的方法相同的方法,制作了蜂窝结构体。另外,根据作为造孔剂的石墨的体积比率来调节密封部3a、3b的气孔率。该石墨的体积比率示出在表4中。
将得到的蜂窝结构体放入电炉中,在一定温度下保持了1小时。然后,取出到室温(24℃)中。将该蜂窝结构体确认到裂纹时的所述一定温度与室温(24℃)之间的温差作为耐热冲击温度示出在表4中。
另外,利用水银压入法,测定密封部3及隔壁4的各自的气孔率(Ps)、(Pw),将其测定值及由该测定值算出的比率(PR)示出在表4中。
【表4】
从表4可知,相对于比率(PR)超过84的试料No.13(耐热冲击温度720℃),比率(PR)为84以下的试料No.14~17的耐热冲击温度高达760℃以上。从该结果可知,如试料No.14~17一样,气孔率的比率PR为84以下的蜂窝结构体1为耐热冲击性高的蜂窝结构体。
Claims (8)
1.一种蜂窝结构体,其特征在于,
以具有MgTi2O5-Al2TiO5的结晶的陶瓷体为蜂窝结构。
2.根据权利要求1所述的蜂窝结构体,其特征在于,
所述陶瓷体为多孔性。
3.一种蜂窝结构体,其特征在于,
具备多个被含有陶瓷的隔壁隔开且从一端到达另一端的流通孔,
具有交替地密封了这些多个流通孔的一端和另一端的任一方的密封部,
所述隔壁具有MgTi2O5-Al2TiO5的结晶。
4.一种蜂窝结构体,其特征在于,
具备多个被在单轴方向上延伸的含有陶瓷的隔壁隔开且从一端到达另一端的流通孔,
具有交替地密封了这些多个流通孔的一端和另一端的任一方的密封部,
所述隔壁具有MgTi2O5-Al2TiO5的结晶,将所述隔壁在1200℃温度维持2小时的热处理前后,由下述式(1)表示的变化率CR为20以下,
CR=(|Ca-Cb|/Ca)×100···(1)
式中,
Ca:所述热处理前的所述单轴方向上的压缩破坏强度,单位为MPa,
Cb:所述热处理后的所述单轴方向上的压缩破坏强度,单位为MPa。
5.一种蜂窝结构体,其特征在于,
具备多个被含有陶瓷的隔壁隔开且从一端到达另一端的流通孔,
具有交替地密封了这些多个流通孔的一端和另一端的任一方的密封部,
所述隔壁具有MgTi2O5-Al2TiO5的结晶,将所述密封部的气孔率设为Ps、所述隔壁的气孔率设为Pw时,由下述式(2)表示的比率PR为84以下,
PR=(|Pw-Ps|/Pw)×100···(2)。
6.根据权利要求3~5中任一项所述的蜂窝结构体,其特征在于,
俯视所述隔壁的一端面时,所述流通孔是角部为圆弧状的四边形状。
7.根据权利要求3~5中任一项所述的蜂窝结构体,其特征在于,
俯视所述隔壁的一端面时,所述流通孔有四边形状的流通孔和八边形状的流通孔。
8.一种净化装置,其特征在于,
具备:权利要求3~7中任一项所述的蜂窝结构体,以及收容所述蜂窝结构体且具有流入口及流出口的壳体,
从所述壳体的流入口进入的流体经过所述蜂窝结构体并从所述壳体的流出口流出。
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FR2948657B1 (fr) * | 2009-07-28 | 2013-01-04 | Saint Gobain Ct Recherches | Grains fondus d'oxydes comprenant al, ti et produits ceramiques comportant de tels grains |
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JP4439236B2 (ja) * | 2003-10-23 | 2010-03-24 | イビデン株式会社 | ハニカム構造体 |
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