CN113464245B - 柱状蜂窝结构体及其制造方法 - Google Patents
柱状蜂窝结构体及其制造方法 Download PDFInfo
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- CN113464245B CN113464245B CN202110188659.4A CN202110188659A CN113464245B CN 113464245 B CN113464245 B CN 113464245B CN 202110188659 A CN202110188659 A CN 202110188659A CN 113464245 B CN113464245 B CN 113464245B
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- China
- Prior art keywords
- honeycomb structure
- hole sealing
- mass
- columnar honeycomb
- peripheral side
- Prior art date
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
-
- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
- B01D46/244—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the plugs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2068—Other inorganic materials, e.g. ceramics
- B01D39/2072—Other inorganic materials, e.g. ceramics the material being particulate or granular
- B01D39/2079—Other inorganic materials, e.g. ceramics the material being particulate or granular otherwise bonded, e.g. by resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
- B01D46/24491—Porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
- B01D46/24492—Pore diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2476—Monolithic structures
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Abstract
本发明提供一种柱状蜂窝结构体及其制造方法。该柱状蜂窝结构体能够抑制装罐时封孔剥落等不良,并且,能够有效地预防侵蚀。一种柱状蜂窝结构体,其具备:外周侧壁;多个第一隔室,该多个第一隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,第一底面呈开口而在第二底面具有平均空隙率为4%以下的封孔部;以及多个第二隔室,该多个第二隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,在第一底面具有平均空隙率为4%以下的封孔部且第二底面呈开口,多个第一隔室和多个第二隔室夹着隔壁而交替地相邻配置。
Description
技术领域
本发明涉及柱状蜂窝结构体及其制造方法。
背景技术
在从柴油发动机等内燃机排出的废气中包含有大量引起环境污染的以碳为主成分的颗粒(粒子状物质)。因此,通常在柴油发动机等的排气系统搭载有用于捕集颗粒的过滤器(Diesel Particulate Filter:DPF)。另外,近年来,从汽油发动机排出的颗粒也被视为问题,在汽油发动机也搭载过滤器(Gasoline Particulate Filter:GPF)。
作为过滤器,已知壁流式的柱状蜂窝结构体,其是将外周侧壁、多个第一隔室以及多个第二隔室夹着隔壁交替地相邻配置而得到的,其中,多个第一隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,第一底面呈开口而在第二底面具有封孔部,多个第二隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,在第一底面具有封孔部而第二底面呈开口。
将具有封孔部的柱状蜂窝结构体作为过滤器使用的情况下,通常柱状蜂窝结构体隔着缓冲材料而收纳于金属外壳内(装罐)。该收纳工序(装罐工序)中,有时对柱状蜂窝结构体的外周侧壁施加较强的压力(应力)。结果,在封孔部与隔壁之间的分界面产生剪切应力。此时,该剪切应力从封孔蜂窝结构体的中心部趋向外周侧壁而逐渐增强,如果该应力超过隔壁的剪切强度,则在封孔部与隔壁之间的分界面从外周趋向内侧而发生开裂,在柱状蜂窝结构体的外周侧壁附近产生封孔剥落等不良。因此,为了防止装罐时封孔剥落等不良,已知有使封孔部的气孔率升高的方法(专利文献1:日本特开2018-126869号公报)。
另外,在具备具有封孔部的柱状蜂窝结构体的过滤器中,封孔部发挥出防止所捕捉的粒子状物质从过滤器漏出(侵蚀)的作用。因此,在规定的位置以规定的深度形成有封孔部对于确保过滤器性能非常重要。以往,封孔部中存在:外侧端面凹陷的部分、在封孔部的内部不规则地具有较大气泡的部分、封孔部的封孔深度不均匀的部分等,使过滤器升降温时,热应力集中于一部分,有时蜂窝过滤器发生破损等。
因此,专利文献2(国际公开第2011/040145号)中,提出一种柱状蜂窝结构体,其特征在于,封孔部的外侧端面平坦,封孔部不存在直径0.3mm以上的气泡,此外,封孔部的封孔深度的标准偏差除以封孔部的平均封孔深度得到的值为0.15以下。根据该文献,通过该特征,能够使各封孔部的热容量、热膨胀(率)、杨氏模量等的偏差变得极少,在发生了温度变化等时,能够抑制产生应力集中的部分,从而能够抑制在发生了温度变化等时蜂窝结构体发生龟裂、变形等。
现有技术文献
专利文献
专利文献1:日本特开2018-126869号公报
专利文献2:国际公开第2011/040145号
发明内容
专利文献1中,提出了为了防止装罐时封孔剥落等不良而使封孔部的气孔率提高的方案。另外,在专利文献1中还提出了防止由封孔部的气孔率提高所导致的副作用、即产生粗大的凝聚物的方案。然而,对粒子状物质从封孔部漏出的侵蚀未进行充分的研究。
专利文献2中,虽然作为课题列举了抑制在发生温度变化等时蜂窝结构体发生龟裂、变形等,但是,对侵蚀的问题未充分进行讨论。另外,与装罐时封孔剥落等不良相关的考察也不足。
本发明是鉴于上述情况而实施的,在一个实施方式中,其课题在于,提供能够有助于抑制装罐时封孔部剥落等不良、且对预防侵蚀也有效的柱状蜂窝结构体。另外,本发明在另一实施方式中,其课题在于,提供上述柱状蜂窝结构体的制造方法。
本发明的发明人为了解决上述课题而进行了潜心研究,结果发现,对比气孔率宏观的规定封孔部的内部结构的空隙率进行控制在解决上述课题方面非常重要。本发明是基于该见解而完成的,以下进行例示。
[1]一种柱状蜂窝结构体,其具备:外周侧壁;多个第一隔室,该多个第一隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,第一底面呈开口而在第二底面具有平均空隙率为4%以下的封孔部;以及多个第二隔室,该多个第二隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,在第一底面具有平均空隙率为4%以下的封孔部且第二底面呈开口,多个第一隔室和多个第二隔室夹着隔壁而交替地相邻配置。
[2]根据[1]所述的柱状蜂窝结构体,其中,第一底面及第二底面的封孔部的平均气孔率均为65%~75%。
[3]一种柱状蜂窝结构体的制造方法,该柱状蜂窝结构体具备:外周侧壁;多个第一隔室,该多个第一隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,第一底面呈开口而在第二底面具有封孔部;以及多个第二隔室,该多个第二隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,在第一底面具有封孔部且第二底面呈开口,多个第一隔室和多个第二隔室夹着隔壁而交替地相邻配置,
所述柱状蜂窝结构体的制造方法包括以如下方法形成各封孔部的工序,该方法为:向第一隔室及第二隔室的待形成封孔部的开口部填充封孔部形成用浆料,然后,将所填充的该浆料干燥并烧成,由此形成各封孔部,
该封孔部形成用浆料相对于陶瓷原料100质量份含有增粘剂0.1~0.5质量份、粘合剂0.2~1.0质量份、造孔材料7~15质量份、水30~50质量份。
[4]根据[3]所述的柱状蜂窝结构体的制造方法,其中,所述封孔部形成用浆料相对于陶瓷原料100质量份含有增粘剂0.2~0.4质量份、粘合剂0.2~0.5质量份、造孔材料7~15质量份、水35~40质量份。
[5]根据[3]或[4]所述的柱状蜂窝结构体的制造方法,其中,所述封孔部形成用浆料的采用布鲁克菲尔德型单旋转式B型粘度计利用JIS R1652:2003的粘度测定方法以25℃、1.04sec-1的剪切速度所测定的粘度为250~350dPa·秒。
[6]根据[3]~[5]中的任一项所述的柱状蜂窝结构体的制造方法,其中,造孔材料为发泡树脂。
[7]根据[3]~[6]中的任一项所述的柱状蜂窝结构体的制造方法,其中,造孔材料为利用激光衍射散射法求出的体积基准的累积粒度分布中的D80超过55μm、D90超过70μm的粉末。
发明效果
根据本发明的一个实施方式,可以提供能够有助于抑制装罐时封孔剥落等不良、且对侵蚀的预防也有效的柱状蜂窝结构体。
附图说明
图1是示意性地表示壁流型的柱状蜂窝结构体的立体图。
图2是从与隔室延伸的方向平行的截面观察壁流型的柱状蜂窝结构体时的示意性的截面图。
图3是示意性地表示利用刮浆方式形成封孔部的形成方法的一例的说明图。
符号说明
100…柱状蜂窝结构体、102…外周侧壁、104…第一底面、106…第二底面、108…第一隔室、109…封孔部、110…第二隔室、112…隔壁、120…卡盘、121…薄膜、122…刮板、124…封孔部形成用浆料、125…隔室、126…孔。
具体实施方式
接下来,参照附图,对本发明的实施方式详细地进行说明。本发明并不限定于以下的实施方式,应当理解:可以在不脱离本发明的主旨的范围内基于本领域技术人员的通常知识适当加以设计的变更、改良等。
(1.柱状蜂窝结构体)
图1及图2中分别例示了壁流型的能够用作汽车用废气过滤器和/或催化剂载体的柱状蜂窝结构体(100)的示意性的立体图及截面图。该柱状蜂窝结构体(100)具备:外周侧壁(102);多个第一隔室(108),它们配置于外周侧壁(102)的内周侧,从第一底面(104)延伸至第二底面(106),且第一底面(104)呈开口而在第二底面(106)具有封孔部(109);以及多个第二隔室(110),它们配置于外周侧壁(102)的内周侧,从第一底面(104)延伸至第二底面(106),且在第一底面(104)具有封孔部(109)而第二底面(106)呈开口。该柱状蜂窝结构体(100)中,第一隔室(108)及第二隔室(110)夹着隔壁(112)而交替地相邻配置。
当向柱状蜂窝结构体(100)的上游侧的第一底面(104)供给包含烟灰等粒子状物质的废气时,废气被导入第一隔室(108)并在第一隔室(108)内向下游前进。由于第一隔室(108)的下游侧的第二底面(106)被封孔,所以废气从区划形成第一隔室(108)和第二隔室(110)的多孔质的隔壁(112)透过而向第二隔室(110)流入。粒子状物质无法通过隔壁(112),因此,在第一隔室(108)内被捕集并堆积。粒子状物质被除去后,流入至第二隔室(110)的清洁废气在第二隔室(110)内向下游前进,从下游侧的第二底面(106)流出。
在一个实施方式中,第一底面及第二底面的封孔部的平均空隙率均为4%以下,优选为3%以下,更优选为2%以下,例如为2~4%。通过使平均空隙率为4%以下,能够抑制装罐时封孔剥落等不良,并且,能够预防侵蚀。
本说明书中,利用以下步骤测定封孔部的平均空隙率。首先,将待测定空隙率的封孔部以与柱状蜂窝结构体的高度方向(隔室延伸的方向)平行的剖切面切成两半,切出封孔部的截面。利用激光显微镜(例:Keyence公司制形状解析激光显微镜VK X250/260)对得到的一处封孔部的一个截面整体进行拍摄,生成封孔部的截面图像。从得到的截面图像中仅选择封孔部,利用激光显微镜所附带的图像处理软件进行解析,以该截面为水平的基准面,求出空隙在深度230μm处所占据的面积A。使深度为230μm是为了不将微细的气孔识别为空隙。另外,利用封孔部的截面积B=隔室间距×封孔部的深度计算出封孔部的截面积B。隔室间距是指:在该截面图像中,区划出形成有作为空隙率的测定对象的封孔部的隔室的一对隔壁间的距离。封孔部的深度是指:在该截面图像中,作为空隙率的测定对象的封孔部在隔室延伸的方向上的长度。具体是指:从形成有作为空隙率的测定对象的封孔部的隔室的端部至封孔部所存在的最深的位置为止的在隔室延伸的方向上的长度。该封孔部的空隙率利用空隙率(%)=A/B×100(%)来表示。针对各底面的任意10处测定封孔部中的空隙率,将其平均值作为各底面中的平均空隙率。
在一个实施方式中,第一底面及第二底面的封孔部的平均深度均为3~7mm。通过封孔部的平均深度为3mm以上,能够确保封孔部的强度。封孔部的平均深度优选为4.2mm以上。另外,通过封孔部的平均深度为7mm以下,能够防止隔室内捕集粒子状物质的隔壁的面积减小。封孔部的平均深度优选为6mm以下。针对各底面的任意20处测定封孔部的深度,将其平均值作为各底面中的封孔部的平均深度。
在一个实施方式中,第一底面及第二底面的封孔部的平均气孔率均为65%~75%。使封孔部的平均气孔率为65%以上对抑制装罐时封孔剥落等不良是有利的。封孔部的平均气孔率优选为70%以上。另外,使封孔部的平均气孔率为75%以下在防止侵蚀方面是有利的。因此,通过与上述的封孔部的平均空隙率结合并将封孔部的气孔率控制在规定的范围内,使得抑制装罐时的不良的效果及抑制侵蚀的效果更加优异。
仅获取封孔部而直接测定封孔部的气孔率是非常困难的,因此,可以利用JIS1655:2003中规定的压汞法按以下步骤来测定封孔部的气孔率。
·获取未形成封孔部的隔壁部的试验片,测定该试验片的气孔率P1(隔壁部的气孔率)。
·获取包含封孔部的隔壁部的试验片,测定该试验片的气孔率P(隔壁部+封孔部的气孔率)。
·在包含封孔部的隔壁部的试验片中,测定隔壁部的包含气孔在内的体积V1。
·在包含封孔部的隔壁部的试验片中,测定封孔部的包含气孔在内的体积V2。
当将封孔部的气孔率设为P2时,P、P1、P2、V1以及V2满足式(1)的关系。
P=P1×V1/(V1+V2)+P2×V2/(V1+V2)…(1)
因此,可以利用式(2)求出P2。
P2=P×(V1+V2)/V2-P1×V1/V2…(2)
针对各底面的任意20处测定封孔部中的气孔率P2,将其平均值作为各底面中的封孔部的平均气孔率。
应予说明,在包含封孔部的隔壁部的试验片中,将隔壁部的包含气孔在内的体积V1的体积比例设为v1,将封孔部的包含气孔在内的体积V2的体积比例设为v2时,可以利用式(3)求出P2。
P2=P×(v1+v2)/v2-P1×v1/v2…(3)
构成封孔部的材料没有特别限制,从强度、耐热性的观点考虑,优选为陶瓷。作为陶瓷,优选含有选自由堇青石、多铝红柱石、锆石、钛酸铝、碳化硅、硅-碳化硅复合材料、氮化硅、氧化锆、尖晶石、印度石、假蓝宝石、刚玉、以及二氧化钛构成的组中的至少1种的陶瓷。这些陶瓷可以单独含有1种,也可以同时含有2种以上。封孔部优选由包含合计50质量%以上的上述陶瓷的材料形成,更优选由包含合计80质量%以上的上述陶瓷的材料形成。由于能够使烧成时的膨胀率相同并实现耐久性提高,所以封孔部更优选采用与隔壁相同的材料组成。
柱状蜂窝结构体的底面形状没有限制,例如可以采用圆形、椭圆形、跑道形、长圆形、三角形、四边形等多边形以及不规则形状。图示的柱状蜂窝结构体(100)的底面形状为圆形,整体为圆柱状。
与隔室延伸的方向垂直的截面中的隔室的形状没有限制,优选为四边形、六边形、八边形或这些形状的组合。其中,优选为正方形及六边形。通过使隔室形状为上述形状,能够使流体流经柱状蜂窝结构体时的压力损失减小,净化性能优异。
隔室密度(每单位截面积的隔室的数量)没有特别限制,例如可以为6~2000隔室/平方英寸(0.9~311隔室/cm2),更优选为50~1000隔室/平方英寸(7.8~155隔室/cm2),特别优选为100~600隔室/平方英寸(15.5~92.0隔室/cm2)。此处,通过隔室的总数(包括被封孔的隔室在内。)除以柱状蜂窝结构体的除了外周侧壁以外的一个底面积来计算出隔室密度。
隔壁可以为多孔质。隔壁的平均气孔率根据用途适当调整即可,从将流体的压力损失抑制在较低水平的观点考虑,优选为40%以上,更优选为50%以上,进一步优选为60%以上。另外,从确保柱状蜂窝结构体的强度的观点考虑,隔壁的平均气孔率优选为80%以下,更优选为75%以下,进一步优选为70%以下。依据JIS R1655:2003,利用压汞法来测定隔壁的气孔率。以包括柱状蜂窝结构体的中心部及外周部在内的方式均匀地获取20个隔壁试验片,测定各自的气孔率,将其平均值作为平均气孔率。
隔壁的平均细孔径优选根据用途而设定为适当的范围。例如,作为过滤器用途使用柱状蜂窝结构体的情况下,隔壁的平均细孔径优选为24μm以下,更优选为22μm以下,进一步优选为20μm以下。通过隔壁的平均细孔径为上述范围,使得粒子状物质的捕集效率明显提高。另外,隔壁的平均细孔径优选为5μm以上,更优选为10μm以上,进一步优选为15μm以上。通过隔壁的平均细孔径为上述范围,能够抑制压力损失降低。依据JIS R1655:2003,利用压汞法来测定隔壁的平均细孔径。以包括柱状蜂窝结构体的中心部及外周部在内的方式均匀地获取20个隔壁试验片,测定各自的平均细孔径,将其平均值作为整个柱状蜂窝结构体的平均细孔径。
从提高柱状蜂窝结构体的强度及过滤器用途时的捕集效率的观点考虑,隔壁的厚度优选为150μm以上,更优选为170μm以上,进一步优选为190μm以上。另外,从抑制压力损失的观点考虑,隔壁的厚度优选为260μm以下,更优选为240μm以下,进一步优选为220μm以下。
柱状蜂窝结构体的高度(从第一底面至第二底面的长度)也没有特别限制,例如可以为40mm~300mm。
构成隔壁及外周侧壁的材料没有特别限制,从强度、耐热性的观点考虑,优选为陶瓷。作为陶瓷,例如优选为含有选自由堇青石、多铝红柱石、锆石、钛酸铝、碳化硅、硅-碳化硅复合材料、氮化硅、氧化锆、尖晶石、印度石、假蓝宝石、刚玉、二氧化钛构成的组中的至少1种的陶瓷。并且,这些陶瓷可以单独含有1种,也可以同时含有2种以上。隔壁及外周侧壁优选由包含合计50质量%以上的上述陶瓷的材料形成,更优选由包含合计80质量%以上的上述陶瓷的材料形成。
将柱状蜂窝结构体作为催化剂载体使用的情况下,可以在隔壁的表面涂敷与目的相对应的催化剂。作为催化剂,没有限定,可以举出:用于使烃(HC)及一氧化碳(CO)氧化燃烧而提高废气温度的氧化催化剂(DOC)、对烟灰等PM的燃烧进行辅助的PM燃烧催化剂、用于除去氮氧化物(NOx)的SCR催化剂及NSR催化剂、以及能够同时除去烃(HC)、一氧化碳(CO)以及氮氧化物(NOx)的三元催化剂。催化剂可以适当含有例如贵金属(Pt、Pd、Rh等)、碱金属(Li、Na、K、Cs等)、碱土金属(Mg、Ca、Ba、Sr等)、稀土金属(Ce、Sm、Gd、Nd、Y、La、Pr等)、过渡金属(Mn、Fe、Co、Ni、Cu、Zn、Sc、Ti、Zr、V、Cr等)等。
(2.制造方法)
对于具有封孔部的柱状蜂窝结构体,除了封孔部的形成方法以外,可以利用公知的制造方法来制造,以下例示性地进行说明。首先,将含有陶瓷原料、分散介质、造孔材料以及粘合剂的原料组合物混炼,形成坯土后,将坯土挤出成型,由此成型为所期望的柱状蜂窝结构体。原料组合物中可以根据需要而配合分散剂等添加剂。挤出成型时,可以采用具有所期望的整体形状、隔室形状、隔壁厚度、隔室密度等的口模。
陶瓷原料为在金属氧化物及金属等烧成后残留下来而以陶瓷的形式构成蜂窝烧成体的骨架的部分的原料。陶瓷原料可以以例如粉末的形态提供。作为陶瓷原料,可以举出用于得到堇青石、多铝红柱石、锆石、钛酸铝、碳化硅、硅-碳化硅复合材料、氮化硅、氧化锆、尖晶石、印度石、假蓝宝石、刚玉、二氧化钛等陶瓷的原料。具体而言,没有限定,可以举出:二氧化硅、滑石、氧化铝、高岭土、蛇纹石、叶蜡石、水镁石、勃姆石、多铝红柱石、菱镁矿、氢氧化铝等。陶瓷原料可以单独使用1种,也可以组合使用2种以上。
在DPF及GPF等过滤器用途的情况下,作为陶瓷可以优选使用堇青石。这种情况下,作为陶瓷原料,可以使用堇青石化原料。堇青石化原料为经烧成而成为堇青石的原料。堇青石化原料优选化学组成为氧化铝(Al2O3)(包含转化为氧化铝的氢氧化铝成分):30~45质量%、氧化镁(MgO):11~17质量%以及二氧化硅(SiO2):42~57质量%。
作为造孔材料,烧成后成为气孔即可,没有特别限定,例如可以举出:小麦粉、淀粉、发泡树脂、吸水性树脂、硅胶、碳(例:石墨)、陶瓷漂珠、聚乙烯、聚苯乙烯、聚丙烯、尼龙、聚酯、丙烯酸树脂、酚醛类等。造孔材料可以单独使用1种,也可以组合使用2种以上。从提高烧成后的柱状蜂窝结构体的气孔率的观点考虑,造孔材料的含量相对于陶瓷原料100质量份而言,优选为0.5质量份以上,更优选为2质量份以上,进一步优选为3质量份以上。从确保烧成后的柱状蜂窝结构体的强度的观点考虑,造孔材料的含量相对于陶瓷原料100质量份而言,优选为10质量份以下,更优选为7质量份以下,进一步优选为4质量份以下。
作为粘合剂,可以例示:甲基纤维素、羟丙氧基甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素、羧甲基纤维素、聚乙烯醇等有机粘合剂。另外,从提高烧成前的柱状蜂窝结构体的强度的观点考虑,粘合剂的含量相对于原料100质量份而言,优选为4质量份以上,更优选为5质量份以上,进一步优选为6质量份以上。从抑制烧成工序中因异常发热而发生开裂的观点考虑,粘合剂的含量相对于陶瓷原料100质量份而言,优选为9质量份以下,更优选为8质量份以下,进一步优选为7质量份以下。粘合剂可以单独使用1种,也可以组合使用2种以上。
分散剂可以使用乙二醇、糊精、脂肪酸皂、聚醚多元醇等。分散剂可以单独使用1种,也可以组合使用2种以上。分散剂的含量相对于陶瓷原料100质量份而言,优选为0~2质量份。
作为分散介质,可以举出水或水与醇等有机溶剂的混合溶剂等,不过,可以特别优选使用水。
实施干燥工序之前的柱状蜂窝结构体的水的含量相对于陶瓷原料100质量份而言,优选为20~90质量份,更优选为60~85质量份,进一步优选为70~80质量份。通过柱状蜂窝结构的水的含量相对于陶瓷原料100质量份而言为20质量份以上,容易得到柱状蜂窝结构的品质易稳定的优点。通过柱状蜂窝结构体的水的含量相对于陶瓷原料100质量份而言为90质量份以下,干燥时的收缩量减小,能够抑制变形。本说明书中,柱状蜂窝结构体的水的含量是指利用干燥减量法测定的值。
柱状蜂窝结构体的干燥可以采用例如热风干燥、微波干燥、介电干燥、减压干燥、真空干燥、冷冻干燥等以往公知的干燥方法。其中,就能够将柱状蜂窝结构体整体迅速且均匀地干燥这一点而言,优选为将热风干燥和微波干燥或介电干燥组合的干燥方法。
将柱状蜂窝结构体干燥后,在柱状蜂窝结构体的两底面形成封孔部。各封孔部可以利用如下方法来形成,即,向第一隔室及第二隔室的待形成封孔部的开口部填充封孔部形成用浆料,然后,将所填充的该浆料干燥并烧成,由此形成各封孔部。在一个实施方式中,封孔部形成用浆料相对于陶瓷原料100质量份而言,含有增粘剂0.1~0.5质量份、粘合剂0.2~1.0质量份、造孔材料7~15质量份、水30~50质量份。
具有该组成的封孔部形成用浆料与以往相比,造孔材料的配合比例较少。通过减少造孔材料的配合比例,能够抑制封孔部的气孔率。不过,只是减少造孔材料的配合比例,容易在封孔部产生较大的空隙,不太能够期待防止侵蚀的效果。进一步地使增粘剂的配合比例也比以往少,由此得到的封孔部的空隙率较小而理想。结果,可抑制装罐时发生不良,还得到防止侵蚀的效果。因此,封孔部形成用浆料中的增粘剂相对于陶瓷原料100质量份而言,优选为0.5质量份以下,更优选为0.4质量份以下。不过,如果增粘剂的含量过少,则封孔部形成用浆料的流动性降低,从而向第一隔室及第二隔室的待形成封孔部的开口部填充封孔部形成用浆料变得困难。因此,封孔部形成用浆料中的增粘剂相对于陶瓷原料100质量份而言,优选为0.1质量份以上,更优选为0.2质量份以上。
因此,在优选的实施方式中,封孔部形成用浆料相对于陶瓷原料100质量份而言,含有增粘剂0.2~0.4质量份、粘合剂0.2~0.5质量份、造孔材料7~15质量份、水35~40质量份。由具有该组成的封孔部形成用浆料得到的封孔部的空隙率更理想,能够更有效地抑制装罐时发生不良及侵蚀。
在一个实施方式中,封孔部形成用浆料的采用布鲁克菲尔德型单旋转式B型粘度计并利用JIS R1652:2003的粘度测定方法以25℃、1.04sec-1的剪切速度测定得到的粘度为250~350dPa·秒,优选为270~320dPa·秒。通过将封孔部形成用浆料的粘度设定为该范围,容易将封孔部形成用浆料以所期望的深度填充到所述隔室的开口部中。
作为封孔部形成用浆料中使用的陶瓷原料,例如可以举出用于得到堇青石、多铝红柱石、锆石、钛酸铝、碳化硅、硅-碳化硅复合材料、氮化硅、氧化锆、尖晶石、印度石、假蓝宝石、刚玉、二氧化钛等陶瓷的原料。具体而言,没有限定,可以举出:二氧化硅、滑石、氧化铝、高岭土、蛇纹石、叶蜡石、水镁石、勃姆石、多铝红柱石、菱镁矿、氢氧化铝等。陶瓷原料可以单独使用1种,也可以组合使用2种以上。
作为封孔部形成用浆料中使用的增粘剂,可以举出:果胶、瓜尔胶、黄原胶、丙二醇、聚环氧乙烷。其中,优选为溶液即使低浓度也显示出高粘度、具有流动性改质效果的聚环氧乙烷。增粘剂可以单独使用1种,也可以组合使用2种以上。
作为粘合剂,可以例示:甲基纤维素、羟丙氧基甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素、羟乙基甲基纤维素、羧甲基纤维素、聚乙烯醇等有机粘合剂。粘合剂可以单独使用1种,也可以组合使用2种以上。
作为造孔材料,在烧成后成为气孔即可,没有特别限定,例如可以举出:小麦粉、淀粉、发泡树脂、吸水性树脂、硅胶、碳(例:石墨)、陶瓷漂珠、聚乙烯、聚苯乙烯、聚丙烯、尼龙、聚酯、丙烯酸树脂、酚醛类等。造孔材料可以单独使用1种,也可以组合使用2种以上。
封孔部形成用浆料可以适当含有分散剂。分散剂相对于陶瓷原料100质量份而言,例如可以含有5~15质量份,优选含有8~12质量份。作为分散剂,可以例举:乙二醇、糊精、脂肪酸皂、以及多元醇等。分散剂可以单独使用1种,也可以组合使用2种以上。
水可以使用通常的精制水或离子交换水等。
可以利用例如以下的“刮浆方式”来实施封孔部形成用浆料在隔室的开口部的填充。如图3所示,在采用卡盘(120)固定的干燥后的柱状蜂窝结构体(100)的上侧的底面(此处为图中的第二底面(106))粘贴薄膜(121),向该薄膜(121)的与封孔部的配设条件(例如“棋盘格状”等)相对应的位置照射激光,在薄膜(121)贯穿设置多个孔(126)。
然后,将封孔部形成用浆料(124)载放于薄膜(121)之上,进行使刮板(122)沿着薄膜(121)在图3中的箭头方向上移动的操作。由此,向在与薄膜(121)的孔(126)相对应的位置呈开口的隔室(125)填充一定量的封孔部形成用浆料(124)。
可以通过刮板(122)的移动操作的次数、刮板(122)与薄膜(121)之间的接触角度、刮板(122)相对于薄膜(121)的按压力、以及封孔部形成用浆料(124)的粘度等来使封孔部的深度发生变化。
在封孔部形成用浆料(124)填充后,将薄膜(121)剥下,对柱状蜂窝结构体(100)整体进行干燥。由此,填充至隔室(125)的封孔部形成用浆料(124)干燥,形成烧成前的封孔部。例如,可以于100~230℃的干燥温度以60~100秒左右的条件实施干燥。干燥后,封孔部以与薄膜的厚度相应的量从柱状蜂窝结构体的底面突出,因此,可以根据需要刮掉。
薄膜的材料没有特别限制,由于用于形成孔的热加工容易,所以优选为聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚酰亚胺、或特氟龙(注册商标)。另外,薄膜优选具备粘结层,粘结层的材料优选为丙烯酸系树脂、橡胶系(例如以天然橡胶或合成橡胶为主成分的橡胶)或硅系树脂。薄膜可以优选使用例如厚度为20~50μm的粘结薄膜。
除了上述“刮浆方式”以外,作为封孔部形成用浆料向隔室的开口部填充的方法,可以举出“压入方式”。“压入方式”为如下方法,即,将粘贴薄膜并穿有孔的柱状蜂窝结构体的底面部浸渍于贮存有封孔部形成用浆料的液槽,向隔室填充封孔部形成用浆料。在这种情况下,可以通过将柱状蜂窝结构体浸渍于封孔部形成用浆料中的深度来使封孔部的深度发生变化。
柱状蜂窝结构体通常在之后实施脱脂及烧成而以烧成体的形式进行提供。粘合剂的燃烧温度为200℃左右,造孔材料的燃烧温度为300~1000℃左右。因此,将蜂窝成型体加热到200~1000℃左右的范围来实施脱脂工序即可。加热时间没有特别限定,通常为10~100小时左右。经过脱脂工序后的蜂窝成型体称为预烧体。烧成工序还取决于柱状蜂窝结构体的材料组成,例如,可以将预烧体加热到1350~1600℃并保持3~10小时来进行烧成工序。
实施例
以下,例示用于更好地理解本发明及其优点的实施例,不过,本发明并不限定于实施例。
(1)柱状蜂窝结构体的制造
在堇青石化原料100质量份中添加造孔材料3.5质量份、分散介质65质量份、有机粘合剂6质量份、分散剂1.0质量份,进行混合、混炼,制备坯土。作为堇青石化原料,使用氧化铝、氢氧化铝、高岭土、滑石、以及二氧化硅。作为分散介质,使用水,作为造孔材料,例如可以举出石墨等碳、小麦粉、淀粉、酚醛树脂、聚甲基丙烯酸甲酯等丙烯酸树脂、聚乙烯、或聚对苯二甲酸乙二醇酯等有机造孔材料。作为有机粘合剂,例如可以使用羟丙基甲基纤维素、甲基纤维素、羟乙基纤维素、羧甲基纤维素、聚乙烯醇等,作为分散剂,例如可以优选使用乙二醇、糊精、脂肪酸皂、多元醇、月桂酸钾皂等。
将该坯土放入挤出成型机中,借助规定形状的口模而进行挤出成型,由此得到圆柱状的柱状蜂窝结构体。对得到的柱状蜂窝结构体进行介电干燥及热风干燥后,按规定的尺寸将两底面切断,以120℃×1小时的条件进行干燥。
干燥后的柱状蜂窝结构体的规格如下。
整体形状:直径117mm×高度122mm的圆柱状
与隔室的流路方向垂直的截面中的隔室形状:正方形
隔室密度(每单位截面积的隔室的数量):300隔室/平方英寸
隔壁厚度:203μm(基于口模的规格得到的标称值)
(2)封孔部形成用浆料的制备
制备具有表1中记载的组成的实施例及比较例的各封孔部形成用浆料。作为粘合剂,使用甲基纤维素、羟乙基甲基纤维素。作为增粘剂,使用聚环氧乙烷。作为分散剂,使用多元醇。作为造孔材料,使用丙烯酸树脂。
针对各封孔部形成用浆料,采用布鲁克菲尔德型单旋转式B型粘度计(Rion公司制、型号VT-06),利用JIS R1652:2003的粘度测定方法,以25℃、1.04sec-1的剪切速度测定粘度。将结果示于表1。
(3)封孔部的形成
采用前述的“刮浆方式”,按第一隔室及第二隔室交替地相邻配置的方式将封孔部形成用浆料向两底面填充。然后,在大气气氛下,以100~230℃×100秒以下的条件进行干燥。接下来,在大气气氛下于约200℃进行加热脱脂,此外,在大气气氛下,于1410~1450℃的温度进行3~10小时烧成,由此得到具有封孔部的柱状蜂窝结构体。
(4)封孔部的特性
针对烧成后的各柱状蜂窝结构体,采用Keyence公司制形状解析激光显微镜VKX250/260,以前述的步骤测定封孔部的平均深度及平均空隙率。另外,针对烧成后的各柱状蜂窝结构体,采用孔度计(Micromeritics公司制、型号Auto PoreIV),利用前述的方法测定封孔部的平均气孔率。将结果示于表1。
(5)侵蚀特性
按以下步骤评价侵蚀特性。将得到的烧成后的各柱状蜂窝结构体装罐(收纳)于罐体,将所装罐的柱状蜂窝结构体配置于气体燃烧器试验机。接下来,利用气体燃烧器试验机,使SiC制的磨粒冲撞柱状蜂窝结构体的一个底面。使磨粒冲撞的条件如下。
投入磨粒量:30g
向柱状蜂窝结构体流入的气体的温度:700℃
向柱状蜂窝结构体流入的气体的流量:10Nm3/分钟
试验时间:30分钟,期间一点一点地放入磨粒。
关于侵蚀量,采用产业用CT,测定被磨粒冲撞的底面中的全部隔室的封孔侵蚀深度,将平均值作为侵蚀量。关于各隔室的封孔侵蚀深度,根据CT观测截面图,将实际上封孔部因磨粒而被刮掉的最大深度(自底面起算的隔室延伸的方向上的距离)作为测定值。将结果示于表1。比较例1中,侵蚀量为2.5mm,与此相对,比较例2中,观察到封孔部分完全贯通。另一方面,比较例3中,侵蚀量为2.5mm。实施例1、实施例2、实施例3中,能够确认到侵蚀量被抑制在1.0mm。
(6)装罐特性
利用卷绕试验,实施装罐模拟试验。在各柱状蜂窝结构体的外周侧壁卷绕垫片,在该垫片上卷绕厚度1mm左右的金属板(SUS304)。以该状态,将柱状蜂窝结构体设置于卷绕试验机,在金属板的外周卷绕金属丝,一边提高压力,一边将金属丝逐渐地收紧,确认封孔部有无剥落。比较例1、比较例2、比较例3、实施例1、实施例2、实施例3均确认到在1.1MPa以下的压力下没有发生封孔部剥落。
(7)考察
由上述的试验结果可知,比较例1的侵蚀防止效果不充分。相对于比较例1,比较例2通过减少封孔部形成用浆料中的造孔材料的含量而使得封孔部的平均气孔率降低。然而,平均空隙率反而增大,针对侵蚀的特性没有提高。如果对比较例1的封孔部进行截面观察,则在内部观察到许多空隙。
另一方面,比较例3相对于比较例2进一步减少了封孔部形成用浆料中的增粘剂的含量。由此,封孔部中的平均空隙率明显降低,针对侵蚀的防止效果提高。另外,没有发现装罐时存在封孔部剥落等不良。但是,比较例3中,在封孔部的内侧端部确认到缩孔。
实施例1、2、3相对于比较例3进一步减少了封孔部形成用浆料中的增粘剂的含量。由此,封孔部中的平均空隙率进一步降低,也没有发现缩孔。因此,针对侵蚀的防止效果进一步提高。另外,没有观察到装罐时存在封孔部剥落等不良。
表1
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Claims (7)
1.一种柱状蜂窝结构体,其特征在于,具备:
外周侧壁;
多个第一隔室,该多个第一隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,第一底面呈开口而在第二底面具有平均空隙率为2%~4%的封孔部;以及
多个第二隔室,该多个第二隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,在第一底面具有平均空隙率为2%~4%的封孔部且第二底面呈开口,
多个第一隔室和多个第二隔室夹着隔壁而交替地相邻配置。
2.根据权利要求1所述的柱状蜂窝结构体,其特征在于,
第一底面及第二底面的封孔部的平均气孔率均为65%~75%。
3.一种柱状蜂窝结构体的制造方法,是权利要求1或2所述的柱状蜂窝结构体的制造方法,该柱状蜂窝结构体具备:外周侧壁;多个第一隔室,该多个第一隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,第一底面呈开口而在第二底面具有封孔部;以及多个第二隔室,该多个第二隔室配置于外周侧壁的内周侧,从第一底面延伸至第二底面,在第一底面具有封孔部且第二底面呈开口,多个第一隔室和多个第二隔室夹着隔壁而交替地相邻配置,
所述柱状蜂窝结构体的制造方法的特征在于,包括以如下方法形成各封孔部的工序,该方法为:向第一隔室及第二隔室的待形成封孔部的开口部填充封孔部形成用浆料,然后,将所填充的该浆料干燥并烧成,由此形成各封孔部,
该封孔部形成用浆料相对于陶瓷原料100质量份含有增粘剂0.1~0.5质量份、粘合剂0.2~1.0质量份、造孔材料7~15质量份、水30~50质量份。
4.根据权利要求3所述的柱状蜂窝结构体的制造方法,其特征在于,
所述封孔部形成用浆料相对于陶瓷原料100质量份含有增粘剂0.2~0.4质量份、粘合剂0.2~0.5质量份、造孔材料7~15质量份、水35~40质量份。
5.根据权利要求3或4所述的柱状蜂窝结构体的制造方法,其特征在于,
所述封孔部形成用浆料的采用布鲁克菲尔德型单旋转式B型粘度计利用JIS R1652:2003的粘度测定方法以25℃、1.04sec-1的剪切速度所测定的粘度为250~350dPa·秒。
6.根据权利要求3或4所述的柱状蜂窝结构体的制造方法,其特征在于,
造孔材料为发泡树脂。
7.根据权利要求3或4所述的柱状蜂窝结构体的制造方法,其特征在于,
造孔材料为利用激光衍射散射法求出的体积基准的累积粒度分布中的D80超过55μm、D90超过70μm的粉末。
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