CN112805264A - 多孔质陶瓷层叠体以及其制造方法 - Google Patents
多孔质陶瓷层叠体以及其制造方法 Download PDFInfo
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- CN112805264A CN112805264A CN201980066601.3A CN201980066601A CN112805264A CN 112805264 A CN112805264 A CN 112805264A CN 201980066601 A CN201980066601 A CN 201980066601A CN 112805264 A CN112805264 A CN 112805264A
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- Prior art keywords
- porous layer
- porous
- metal oxide
- ceramic laminate
- pore diameter
- 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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Abstract
本发明提供能够减少流体的压力损失的多孔质陶瓷层叠体。本发明涉及一种多孔质陶瓷层叠体,其具有第一多孔质层和第二多孔质层,上述第二多孔质层接触地或隔着空气层叠于上述第一多孔质层之上,其中,上述第二多孔质层的一部分接触地层叠于上述第一多孔质层之上,上述第一多孔质层和上述第二多孔质层均包含金属氧化物,上述第一多孔质层的平均细孔径Da与上述第二多孔质层的平均细孔径Db之比Da/Db为10以上,上述第一多孔质层与上述第二多孔质层的距离小于1μm的部分之比例为70%以下。
Description
技术领域
本发明涉及多孔质陶瓷层叠体以及其制造方法。
背景技术
就多孔质陶瓷来说,其以微滤膜、超滤膜、纳滤膜、反渗透膜、离子交换膜、气体分离膜之类的具有对气体、液体等流体进行分离、浓缩、过滤等的功能的膜的形式被用于各种领域。
例如,专利文献1公开了一种陶瓷多孔体,其是由无机质支撑体和包覆上述支撑体的一层以上的无机质包覆层形成的陶瓷多孔质非对称膜,其包含薄层状的无机多孔质体作为包覆上述支撑体的一层以上的无机质包覆层之中的至少一层。就专利文献1来说,在平均细孔径为11.0或14.2μm的多孔质支撑体上对包含平均粒径为3或5μm的氧化铝的浆料膜进行制膜并进行烧成,由此在上述多孔质支撑体上形成有多孔质层。另外,专利文献2公开了一种非对称膜,其由支撑层和多孔质层形成,上述多孔质层形成于上述支撑层的内表面或外表面。就专利文献2来说,使用平均粒径为5μm的氧化铝颗粒、其他无机物质的颗粒来作成连通气孔径为1~2μm的支撑层,使用分散有平均粒径为0.5μm的氧化铝微粉末的液体在上述支撑层的表面形成了多孔质层。
现有技术文献
专利文献
专利文献1:日本特开平11-292653号公报
专利文献2:日本特开昭62-186908号公报
发明内容
发明所要解决的问题
在使用多孔质陶瓷对流体进行分离等的情况下,重要的是充分发挥分离等功能并且使流体容易在上述陶瓷多孔体中流动即流体的压力损失小,但可知通过上述专利文献1和2是难以减少流体的压力损失的。
因此,本发明的目的在于:提供能够减少流体的压力损失的多孔质陶瓷层叠体。
用于解决问题的手段
达成了上述问题的本发明如下所述。
[1]一种多孔质陶瓷层叠体,其具有第一多孔质层和第二多孔质层,上述第二多孔质层接触地或隔着空气层叠于上述第一多孔质层之上,
其中,上述第二多孔质层的一部分接触地层叠于上述第一多孔质层之上,
上述第一多孔质层和上述第二多孔质层均包含金属氧化物,
上述第一多孔质层的平均细孔径Da与上述第二多孔质层的平均细孔径Db之比Da/Db为10以上,
上述第一多孔质层与上述第二多孔质层的距离小于1μm的部分之比例为70%以下。
[2]根据[1]所述的多孔质陶瓷层叠体,其中,上述Da/Db为30以上。
[3]根据[1]或[2]所述的多孔质陶瓷层叠体,其中,上述第一多孔质层与上述第二多孔质层的距离小于1μm的部分之比例为50%以下。
[4]根据[1]~[3]中任一项所述的多孔质陶瓷层叠体,其中,上述第一多孔质层包含金属氧化物A和金属氧化物B作为上述金属氧化物,上述金属氧化物B具有比上述金属氧化物A的熔点高的熔点,
上述第二多孔质层包含金属氧化物C作为上述金属氧化物,上述金属氧化物C具有比上述金属氧化物A的熔点高的熔点,
其包括与上述第一多孔质层和上述第二多孔质层这两者接触并且包含上述金属氧化物A和上述金属氧化物C的区域。
[5]一种方法,其是[1]~[4]中任一项所述的多孔质陶瓷层叠体的制造方法,其包括下述工序:
向上述第一多孔质层的至少一个表面涂布拒水剂或拒油剂;
向涂布了上述拒水剂或上述拒油剂的上述第一多孔质层的表面涂布包含上述第二多孔质层中所含的上述金属氧化物、溶剂和增稠剂的浆料;以及
对涂布了上述浆料的上述第一多孔质层进行热处理。
发明效果
本发明的多孔质陶瓷层叠体能够减少气体、液体等流体的压力损失。
附图说明
图1是表示本发明的优选实施方式中的多孔质陶瓷层叠体的截面的示意图。
图2是表示实施例1的截面SEM观察图像的附图替代照片。
图3是表示比较例1的截面SEM观察图像的附图替代照片。
图4是表示实施例2中的Lc和Ld的分析要点的附图替代照片。
图5是表示捕获了实施例2中的与第一多孔质层和第二多孔质层这两者接触并且包含金属氧化物A和金属氧化物C的区域的截面SEM观察图像的附图替代照片。
具体实施方式
本发明者们进行了研究,结果发现了下述多孔质陶瓷层叠体能够减少流体的压力损失,该多孔质陶瓷层叠体具有第一多孔质层和第二多孔质层,上述第二多孔质层接触地或隔着空气层叠于上述第一多孔质层之上,其中,上述第二多孔质层的一部分接触地层叠于上述第一多孔质层之上,上述第一多孔质层和上述第二多孔质层均包含金属氧化物,上述第一多孔质层的平均细孔径Da与上述第二多孔质层的平均细孔径Db之比Da/Db为10以上,优选为30以上,上述第一多孔质层与上述第二多孔质层的距离小于1μm的部分之比例为70%以下,优选为50%以下。
本发明的多孔质陶瓷层叠体具有上述第一多孔质层和第二多孔质层,上述第二多孔质层接触地或隔着空气层叠于上述第一多孔质层之上。上述第二多孔质层的一部分接触地层叠于上述第一多孔质层之上。即,上述第二多孔质层的一部分接触地层叠于上述第一多孔质层之上,上述第二多孔质层的其他部分隔着空气层叠于上述第一多孔质层之上。
就本发明的多孔质陶瓷层叠体来说,上述第一多孔质层的平均细孔径Da与上述第二多孔质层的平均细孔径Db之比Da/Db为10以上。如此,使Da与Db之差增大对于减少从本发明的多孔质陶瓷层叠体透过的流体的压力损失是重要的。上述比Da/Db优选为30~60,更优选为33~60,进一步优选为35~60,更进一步优选为40~60。此外,就上述专利文献1来说,其是使用包含平均粒径为3或5μm的氧化铝的浆料在上述多孔质支撑体上形成了上述多孔质层,从上述氧化铝的粒径考虑可知上述多孔质层的平均细孔径为1μm左右,而上述多孔质支撑体的平均细孔径如上所述为11.0或14.2μm。因此,可知上述专利文献1中的上述支撑体的平均细孔径与上述多孔质层的平均细孔径之比最大也就是14左右。另外,就专利文献2来说,上述支撑层的连通气孔径为1~2μm,上述多孔质层的气孔径为0.2μm,因此上述支撑层的连通气孔径与上述多孔质层的气孔径之比最大也就是10。
只要上述比Da/Db为上述范围,Da和Db各自的值就没有限定,Da例如为1.5μm~600μm,优选为5μm~300μm,更优选为9μm~60μm,Db例如为0.01μm~10μm,优选为0.05μm~5μm,更优选为0.15μm~1μm,进一步优选为0.25μm~1μm。
就本发明的多孔质陶瓷层叠体来说,上述第一多孔质层与上述第二多孔质层的距离小于1μm的部分(以下也称为接近部位)之比例为70%以下,优选为50%以下。使上述接近部位之比例为规定以下对于减少流体的压力损失也是重要的。上述接近部位之比例的算出方法如下所述。首先,以与上述第一多孔质层和上述第二多孔质层的层叠方向平行的截面对本发明的多孔质陶瓷层叠体进行观察。在上述截面中,对上述第一多孔质层与上述第二多孔质层的距离小于1μm的部分之比例进行测定。上述距离是上述第一多孔质层的表面至距上述第一多孔质层的表面最近的第二多孔质层的表面的距离。即,在上述截面中,将与上述第一多孔质层的距离小于1μm的上述第二多孔质层的表面的总计长度设定成Lc,将与上述第一多孔质层的距离为1μm以上的上述第二多孔质层的表面的总计长度设定成Ld,并分别进行测定,求出Lc与Lc和Ld的总计之比例。图1示出本发明的优选实施方式中的上述截面的示意图。图1中,1表示上述第一多孔质层,2表示上述第二多孔质层,3表示空气,4表示上述第二多孔质层2的层叠方向,5表示上述第一多孔质层1与上述第二多孔质层2的距离,5的长度为1μm,6表示上述第一多孔质层1与上述第二多孔质层2的距离小于1μm的范围,7表示上述第一多孔质层1与上述第二多孔质层2的距离为1μm以上的范围,8表示与上述第一多孔质层和上述第二多孔质层这两者接触并且包含上述金属氧化物A和上述金属氧化物C的区域。以下,将与上述第一多孔质层和上述第二多孔质层这两者接触并且包含上述金属氧化物A和上述金属氧化物C的区域称为“第三区域”。在上述第一多孔质层1与上述第二多孔质层2的距离小于1μm的范围6,由粗实线表示的上述第二多孔质层2的表面的长度的总计相当于Lc;在上述第一多孔质层1与上述第二多孔质层2的距离为1μm以上的范围7,由常规实线表示的上述第二多孔质层2的表面的长度的总计相当于Ld。在本发明的多孔质陶瓷层叠体包含第三区域的情况下,和上述第三区域接触的上述第一多孔质层与上述第二多孔质层的距离视为0。就本发明的多孔质陶瓷层叠体来说,上述接近部位之比例即Lc与Lc和Ld的总计之比例为70%以下,优选为50%以下,更优选为45%以下,进一步优选为40%以下,更进一步优选为30%以下,特别优选为15%以下。从上述第一多孔质层与上述第二多孔质层的粘接强度的观点考虑,Lc与Lc和Ld的总计之比例优选为5%以上,更优选为8%以上,进一步优选为10%以上。
在上述截面中,上述第二多孔质层的表面的总计长度只要通过以成为上述第一多孔质层的平均细孔径的100倍以上的方式取得图像并对Lc与Lc和Ld的总计之比例进行测定就行。
上述第一多孔质层的厚度例如为500μm~3000μm,优选为1400μm~2800μm。上述第二多孔质层的厚度例如为3μm~30μm,优选为3μm~15μm,更优选为3μm~10μm。上述第二多孔质层只要层叠于上述第一多孔质层的至少单侧面就行,优选仅层叠于上述第一多孔质层的单侧面。本发明的多孔质陶瓷层叠体的形状没有特别限定,可以为平面状、圆筒状或蜂窝状,优选为圆筒状。在本发明的多孔质陶瓷层叠体为圆筒状的情况下,上述第二多孔质层也可以层叠于上述第一多孔质层的外周面或内周面中的任意面,优选仅层叠于上述第一多孔质层的外周面或仅层叠于内周面,更优选上述第二多孔质层仅层叠于上述第一多孔质层的外周面。
上述第一多孔质层和上述第二多孔质层均包含金属氧化物。此外,本发明中,金属是以包含Si、Ge等半金属的意义来使用的。上述第一多孔质层优选包含金属氧化物A和金属氧化物B作为上述金属氧化物,上述金属氧化物B具有比上述金属氧化物A的熔点高的熔点,上述第二多孔质层优选包含金属氧化物C作为上述金属氧化物,上述金属氧化物C具有比上述金属氧化物A的熔点高的熔点。上述金属氧化物B和上述金属氧化物C可以相同也可以不同。
上述第一多孔质层包含上述金属氧化物A和上述金属氧化物B作为上述金属氧化物、上述第二多孔质层包含上述金属氧化物C作为上述金属氧化物的本发明的多孔质陶瓷层叠体优选包含第三区域。通过上述第三区域,上述第一多孔质层与上述第二多孔质层的粘接强度提高。由后述的实施例的方法测得的第三区域的个数为2个~40个,优选为2个~20个,更优选为5个~20个,进一步优选为7个~12个。
上述第三区域的孔隙率通常比上述第一多孔质层的孔隙率小,并且上述第三区域的平均细孔径通常比上述第一多孔质层的平均细孔径小。另外,上述第三区域的孔隙率通常比上述第二多孔质层的孔隙率小,并且上述第三区域的平均细孔径通常比上述第二多孔质层的平均细孔径小。
上述金属氧化物A优选熔点为95℃~1600℃。作为上述金属氧化物A,具体可以列举出B2O3、SiO2、GeO2、Al2O3、V2O5、As2O5、Sb2O5、ZrO2,TiO2、ZnO、PbO、ThO2、BeO、CdO、Ta2O5、Nb2O5、WO3、ScO2、La2O3、Y2O3、SnO2、Ga2O3、In2O3、PbO2、MgO、Li2O、BaO、CaO、SrO、Na2O、K2O、Rb2O、HgO、Cs2O、Ag2O、TeO2、Tl2O等,优选可以列举出SiO2。即,上述金属氧化物A可以列举出以上述的氧化物中的至少一种为构成成分的那些,优选特别是以上述的氧化物中的至少一个为构成成分的玻璃,特别优选为石英玻璃、硼硅酸盐玻璃、铝硅酸盐玻璃之类的包含硅的氧化物(特别是SiO2)的玻璃。上述金属氧化物B和上述金属氧化物C可以相同也可以不同,熔点均优选为2000℃~2800℃。作为上述金属氧化物B和上述金属氧化物C,具体可以列举出Al2O3、ZrO2、MgO、Cr2O3、Y2O3等,优选可以列举出Al2O3。
本发明的多孔质陶瓷层叠体中的上述第二多孔质层表面的表面粗糙度Ra根据上述第一多孔质层的表面粗糙度、构成上述第二多孔质层的金属氧化物的粒径等而变化,例如为0.5μm~7μm,优选为1μm~5μm。此外,层叠上述第二多孔质层之前的上述第一多孔质层的表面粗糙度Ra例如为5μm~15μm,优选为7μm~10μm。本发明的多孔质陶瓷层叠体中的上述第二多孔质层表面的表面粗糙度可以比层叠上述第二多孔质层之前的上述第一多孔质层的表面粗糙度小。
本发明的多孔质陶瓷层叠体能够减少流体的压力损失。本发明的多孔质陶瓷层叠体能够实现实用上足够的渗透率,即,不仅能够使在后述的实施例中进行评价的渗透率为3.0×10-6m3/(m2·sec·Pa),更能够使之优选为7.0×10-6m3/(m2·sec·Pa)以上。上述渗透率优选为0.8×10-5m3/(m2·sec·Pa)以上,更优选为1.0×10-5m3/(m2·sec·Pa)以上,例如为5.0×10-5m3/(m2·sec·Pa)以下。
如上所述,就本发明的多孔质陶瓷层叠体来说,上述第一多孔质层的平均细孔径Da与上述第二多孔质层的平均细孔径Db之比Da/Db为10以上,优选为30以上。通常,在要使具有这样大的平均细孔径之差的两层层叠的情况下,第二多孔质层的构成成分掺入具有大的平均细孔径的第一多孔质层的细孔内,因此难以使第二多孔质层在第一多孔质层之上形成平滑的层状。
本发明的多孔质陶瓷层叠体的制造方法包括下述工序:向上述第一多孔质层的至少一个表面涂布拒水剂或拒油剂;向涂布了上述拒水剂或上述拒油剂的上述第一多孔质层的表面涂布包含上述第二多孔质层中所含的上述金属氧化物、溶剂和增稠剂的浆料;以及对涂布了上述浆料的上述第一多孔质层进行热处理。根据本发明的方法,上述浆料不会掺入上述第一多孔质层的细孔内,因此可以在具有大的平均细孔径的第一多孔质层之上层叠具有小的平均细孔径的第二多孔质层。
上述拒水剂或上述拒油剂只要具有拒水和拒油中的至少一个功能就行,也可以是具有拒水和拒油这两个功能的拒水拒油剂。作为上述拒水剂或上述拒油剂,可以列举出:链烷烃系拒水拒油剂、氟系拒水拒油剂、聚硅氧烷系拒水拒油剂等。向上述第一多孔质层的至少一个表面涂布上述拒水剂或上述拒油剂的方法没有特别限定,可以列举出喷涂、浸涂、棒涂、吸涂、超声波喷雾、刷涂、刮刀涂布、擦拭涂布等。
作为上述溶剂,可以列举出水、有机系溶剂等。上述第二多孔质层中所含的金属氧化物优选包含上述金属氧化物C。上述金属氧化物的浆料中的浓度例如为2质量%~15质量%,优选为4质量%~13质量%。在上述第二多孔质层包含多种金属氧化物的情况下,上述浓度是指多种金属氧化物的总计浓度。上述第二多孔质层中所含的金属氧化物的平均粒径例如为0.1μm~50μm。
作为上述增稠剂,可以列举出甲基纤维素、羟乙基甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、聚环氧烷、聚乙烯醇、聚丙烯酸钠、聚乙烯基吡咯烷酮、聚丙烯酰胺、聚甲基丙烯酸二甲基氨基乙酯等。上述增稠剂在浆料中的浓度例如为0.5质量%~5质量%,优选为1质量%~3质量%。
向涂布了上述拒水剂或上述拒油剂的上述第一多孔质层的表面涂布上述浆料的方法没有特别限定,可以列举出浸涂、喷涂、辊涂、棒涂、旋涂、狭缝涂布、刷涂等。
上述热处理的温度例如为95℃以上,优选为265℃以上,更优选为500℃以上,进一步优选为1000℃以上。上述热处理的温度例如为1600℃以下,优选为1400℃以下。上述热处理的温度优选为上述金属氧化物A的软化温度以上,具体来说,上述热处理的温度为1000℃以上,优选为1500℃以下,更优选为1100℃~1400℃。通过使上述热处理的温度为上述金属氧化物A的软化温度以上,在上述热处理中可能会发生包含上述金属氧化物A的熔融物从上述第一多孔质层局部地流入上述第二多孔质层的现象。其结果是,在上述热处理后所得到的本发明的多孔质陶瓷层叠体中局部地形成第三区域。上述热处理的温度下的保持时间例如为30分钟~10小时,优选为1小时~8小时,更优选为3小时~7小时。
本发明的多孔质陶瓷层叠体可用作微滤膜。通过在本发明的多孔质陶瓷层叠体中的上述第二多孔质层之上进一步层叠功能膜,层叠了上述功能膜的本发明的多孔质陶瓷层叠体可用作超滤膜、纳滤膜、反渗透膜、离子交换膜、气体分离膜等膜的基材。
本申请基于2018年10月15日申请的日本专利申请第2018-194512号主张优先权利益。2018年10月15日申请的日本专利申请第2018-194512号的说明书的全部内容援引至本申请以用于参考。
实施例
以下,列举实施例对本发明进行更具体说明。本发明不因下述实施例而受限,当然还可以在能够满足上述、下述主旨的范围施以适当变更来实施,这些均包含在本发明的技术范围中。
由下述实施例和下述比较例得到的陶瓷层叠体通过下述方法进行了评价。
(1)渗透率的测定
由圆筒形的多孔质陶瓷层叠体试样的外侧使空气以1.0m3/小时的固定流速流动,使空气从上述试样的内侧透过。对上述试样的透过前后的压力差进行了测定。使用所测得的结果,由下述式算出了渗透率。
(2)Lc和Ld的测定和第三区域的确认
以与轴向垂直的截面切断圆筒形的多孔质陶瓷层叠体,按照可以观察切断面的方式埋入树脂,进行研磨,并且以扫描型电子显微镜(SEM,Scanning Electron Microscope)进行了观察。以使上述第二多孔质层的上述第一多孔质层侧表面的总计长度在周向上成为2mm以上的方式取得图像,对上述第二多孔质层的上述第一多孔质层侧表面之中与上述第一多孔质层的距离小于1μm的范围的总计长度Lc和与上述第一多孔质层的距离为1μm以上的范围的总计长度Ld分别进行测定,算出了Lc与Lc和Ld的总计之比例。另外,对上述SEM的观察图像的上述2mm的范围存在多少处第三区域进行了计数。
(3)细孔径的测定
以120℃对多孔质陶瓷层叠体试样进行了4小时干燥,然后使用AutoPore IV9520(micromeritics公司制造),通过压汞法进行了测定。在对层叠第二多孔质层之前的第一多孔质层和下述实施例的多孔质陶瓷层叠体试样进行测定的情况下,就以横轴为细孔径的log微分细孔容积分布来说,层叠第二多孔质层之前的第一多孔质层观测到了一个峰,下述实施例的多孔质陶瓷层叠体观测到了两个峰。以层叠第二多孔质层之前的第一多孔质层所观测到的峰位置为Da。下述实施例的多孔质陶瓷层叠体所观测到的两个峰之中,以低细孔径侧的峰位置为Db。
(4)表面粗糙度的测定方法
使用基恩士公司制激光显微镜VK-9510以十倍物镜按照Z方向0.5μm间距对多孔质陶瓷层叠体试样的235μm×220μm的外周面进行测定,对算数平均表面粗糙度Ra进行了测定。此外,下述实施例中的层叠第二多孔质层之前的第一多孔质层表面的表面粗糙度Ra为9.3μm。
(5)膜强度的评价
在多孔质陶瓷层叠体试样的外周面贴附并剥离尺寸为5mm×5mm的3M公司制透明修补胶带(scotch mending tape)时,以未观察到明显剥离的为○,以观察到明显剥离的为×。
(6)第二多孔质层的膜厚的测定
以与轴向垂直的截面切断圆筒形的多孔质陶瓷层叠体,按照可以观察切断面的方式埋入树脂,进行研磨,并且以扫描型电子显微镜(SEM,Scanning Electron Microscope)进行了观察。以使上述第二多孔质层的上述第一多孔质层的与上述第一多孔质层侧表面相当的线在周向上成为250μm以上的方式取得图像,求出第二多孔质层的面积,并且除以周向的长度,由此算出了膜厚。
实施例1~4
作为第一多孔质层,使用了包含氧化铝和SiO2的蔌玻璃(Hagi Glass)公司制氧化铝基材A-12。上述基材A-12的形状是内径为8.6mm、外径为11.5mm、长度为5cm的圆筒形。将株式会社哥伦布斯制的拒水拒油喷剂“AMEDAS”喷涂在上述基材A-12的外周面,使之干燥。上述拒水拒油喷剂包含含氟树脂和石油系烃。接着,以表1所述的浓度将住友化学株式会社制的氧化铝粉末AKP-3000和作为增稠剂的信越化学工业株式会社制的羟丙基甲基纤维素65SH-30000与水混合而准备了浆料。此外,上述氧化铝粉末AKP-3000的平均粒径为0.7μm。为了使上述浆料不进入上述基材A-12的内周面,对上述基材A-12的上端和下端进行密封,并以上述浆料对上述基材A-12进行了浸涂。之后,以1200℃对向上述外周面涂布了上述浆料的上述基材A-12进行了3小时热处理。
比较例1
除了不涂布拒水拒油喷剂而直接以与上述实施例1相同的浆料对上述基材A-12进行了浸涂并且使热处理温度为1100℃以外,与实施例1同样地进行。
实施例5
除了使用了细孔径为4.8μm的基材作为第一多孔质层并且使浆料的增稠剂浓度为1.5重量%以外,与实施例1同样地进行。
比较例2
除了不涂布拒水拒油喷剂以外,与实施例5同样地进行。
比较例3
除了使用了细孔径为1.8μm的基材作为第一多孔质层以外,与实施例5同样地进行。
将结果示于表1。此外,图2示出实施例1的截面SEM观察图像,图3示出比较例1的截面SEM观察图像,图4示出实施例2中的Lc和Ld的分析要点,图5示出捕获了实施例2中的第三区域的截面SEM观察图像。
如图2所示,就向作为第一多孔质层的上述基材A-12涂布拒水拒油喷剂之后以上述浆料进行了浸涂的实施例1来说,在上述第一多孔质层之上形成了由氧化铝构成的第二多孔质层。另一方面,就没有使用拒水拒油喷剂的比较例1来说,如图3所示,氧化铝掺入上述第一多孔质层的细孔的里面,未在上述第一多孔质层之上形成第二多孔质层。另外,图4示出实施例2中的与第一多孔质层和第二多孔质层的层叠方向平行的截面,上述第二多孔质层的上述第一多孔质层侧表面之中与上述第一多孔质层的距离小于1μm的范围以黑色实线来表示,与上述第一多孔质层的距离为1μm以上范围以白色实线来表示。由上述黑色实线表示的范围与图1中示作6的范围相当,由上述白色实线表示的范围与图1中示作7的范围相当。由以图4所示的要点测得的Lc和Ld求出的Lc/(Lc+Ld)之比例在实施例1~5中为70%以下,使空气在多孔质陶瓷层叠体流动时的渗透率为3.0×10-6m3/(m2·sec·Pa)以上,优选为7.0×10-6m3/(m2·sec·Pa)以上。另外,如图5所示,就实施例2来说,上述第一多孔质层中的玻璃成分在被白色实线包围的部位熔融并渗出至上述第二多孔质层中而固化,对形成了第三区域的情况进行观察,上述第二多孔质层与上述第一多孔质层良好地粘接,这也与表1所示的膜强度的结果相一致。另外,比较例2的Lc/(Lc+Ld)之比例超过70%,比较例3的Da/Db的值小于10并且Lc/(Lc+Ld)之比例超过了70%,因此渗透率的值均下降。
符号说明
1 第一多孔质层
2 第二多孔质层
3 空气
4 第二多孔质层的层叠方向
5 第一多孔质层1与第二多孔质层2的距离
6 第一多孔质层1与第二多孔质层2的距离小于1μm的范围
7 第一多孔质层1与第二多孔质层2的距离为1μm以上的范围
8 第三区域
Claims (5)
1.一种多孔质陶瓷层叠体,其具有第一多孔质层和第二多孔质层,所述第二多孔质层接触地或隔着空气层叠于所述第一多孔质层之上,
其中,所述第二多孔质层的一部分接触地层叠于所述第一多孔质层之上,
所述第一多孔质层和所述第二多孔质层均包含金属氧化物,
所述第一多孔质层的平均细孔径Da与所述第二多孔质层的平均细孔径Db之比Da/Db为10以上,
所述第一多孔质层与所述第二多孔质层的距离小于1μm的部分之比例为70%以下。
2.根据权利要求1所述的多孔质陶瓷层叠体,其中,所述Da/Db为30以上。
3.根据权利要求1所述的多孔质陶瓷层叠体,其中,所述第一多孔质层与所述第二多孔质层的距离小于1μm的部分之比例为50%以下。
4.根据权利要求1~3中任一项所述的多孔质陶瓷层叠体,其中,所述第一多孔质层包含金属氧化物A和金属氧化物B作为所述金属氧化物,所述金属氧化物B具有比所述金属氧化物A的熔点高的熔点,
所述第二多孔质层包含金属氧化物C作为所述金属氧化物,所述金属氧化物C具有比所述金属氧化物A的熔点高的熔点,
其包括与所述第一多孔质层和所述第二多孔质层这两者接触并且包含所述金属氧化物A和所述金属氧化物C的区域。
5.一种方法,其是权利要求1~4中任一项所述的多孔质陶瓷层叠体的制造方法,其包括下述工序:
向所述第一多孔质层的至少一个表面涂布拒水剂或拒油剂;
向涂布了所述拒水剂或所述拒油剂的所述第一多孔质层的表面涂布包含所述第二多孔质层中所含的所述金属氧化物、溶剂和增稠剂的浆料;以及
对涂布了所述浆料的所述第一多孔质层进行热处理。
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CN1419469A (zh) * | 2000-11-24 | 2003-05-21 | 日本碍子株式会社 | 多孔质蜂窝状过滤器及其制造方法 |
JP2007045691A (ja) * | 2005-08-12 | 2007-02-22 | Research Institute Of Innovative Technology For The Earth | メソポーラス複合体およびその製造方法 |
JP2009235487A (ja) * | 2008-03-27 | 2009-10-15 | Toshiba Corp | 多孔質材料、及び多孔質材料の製造方法 |
WO2012111792A1 (ja) * | 2011-02-17 | 2012-08-23 | 京セラ株式会社 | 炭素膜付き複合体およびその製造方法 |
WO2017014130A1 (ja) * | 2015-07-23 | 2017-01-26 | 昭和電工株式会社 | 多孔質膜、水処理膜及び多孔質膜の製造方法 |
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JPH11292653A (ja) * | 1998-04-02 | 1999-10-26 | Noritake Co Ltd | セラミック多孔体及びその製造方法 |
JP4673497B2 (ja) * | 2001-04-12 | 2011-04-20 | 株式会社ソフト99コーポレーション | 皮革用撥水艶出しクロス |
JP2018194512A (ja) | 2017-05-22 | 2018-12-06 | 日立オートモティブシステムズ株式会社 | 電子制御装置の検査方法 |
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CN1419469A (zh) * | 2000-11-24 | 2003-05-21 | 日本碍子株式会社 | 多孔质蜂窝状过滤器及其制造方法 |
JP2007045691A (ja) * | 2005-08-12 | 2007-02-22 | Research Institute Of Innovative Technology For The Earth | メソポーラス複合体およびその製造方法 |
JP2009235487A (ja) * | 2008-03-27 | 2009-10-15 | Toshiba Corp | 多孔質材料、及び多孔質材料の製造方法 |
WO2012111792A1 (ja) * | 2011-02-17 | 2012-08-23 | 京セラ株式会社 | 炭素膜付き複合体およびその製造方法 |
WO2017014130A1 (ja) * | 2015-07-23 | 2017-01-26 | 昭和電工株式会社 | 多孔質膜、水処理膜及び多孔質膜の製造方法 |
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EP3868733A4 (en) | 2022-07-06 |
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