CN107339136B - 电加热式催化转换器及其制造方法 - Google Patents

电加热式催化转换器及其制造方法 Download PDF

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Publication number
CN107339136B
CN107339136B CN201710292494.9A CN201710292494A CN107339136B CN 107339136 B CN107339136 B CN 107339136B CN 201710292494 A CN201710292494 A CN 201710292494A CN 107339136 B CN107339136 B CN 107339136B
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Prior art keywords
electrical heating
heating type
protective film
type catalyst
sio
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CN107339136A (zh
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森连太郎
笠井义幸
大宫好雅
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NGK Insulators Ltd
Toyota Motor Corp
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NGK Insulators Ltd
Toyota Motor Corp
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    • 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
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
    • F01N3/2013—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating using electric or magnetic heating means
    • F01N3/2026—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating using electric or magnetic heating means directly electrifying the catalyst substrate, i.e. heating the electrically conductive catalyst substrate by joule effect
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
    • F01N3/2013—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating using electric or magnetic heating means
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    • B01D53/34—Chemical or biological purification of waste gases
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Abstract

一种电加热式催化转换器，其至少具备具有催化剂涂层的导电性基材和固定于基材上的电极部件，在电极部件的至少一部分的表面形成有保护膜，保护膜由Al2O3、SiO2、Al2O3与SiO2的复合材料、或以它们为主成分的复合氧化物形成，并且，具有非晶结构或者结晶化率为30体积％以下的部分结晶化玻璃结构，并且，膜厚在100nm～2μm的范围。

Description

电加热式催化转换器及其制造方法
技术领域
本发明涉及在废气的排气***中配置的电加热式催化转换器和其制造方法。
背景技术
在各种产业界，针对减轻环境影响负荷的各种努力正在全球范围内进行，其中，在汽车产业中，燃油经济性能优异的汽油发动机车辆自不必说，面向混合动力车、电动车等所谓的环保车的普及及其进一步的性能提高的开发每天都在推进着。
但是，在将车辆发动机和消音器连接的废气的排气***中，有时搭载电加热式催化转换器(EHC:Electrically Heated Converter)，所述电加热式催化转换器除了将通常运转时的废气进行净化以外，还在寒冷时通过电加热进行升温来使催化剂尽可能快地活化从而净化废气。
该电加热式催化转换器，是在配置于废气的排气***中的蜂窝催化剂上安装例如一对电极，并由具有电源的外部电路将这一对电极连接的结构，是通过对电极进行通电来加热蜂窝催化剂，提高蜂窝催化剂的活性，从而将通过该催化剂的废气无害化的。
但是，作为电加热式催化转换器的一例，可列举出如下形态：如日本特开2014-105694所记载的那样，由担载有催化剂的陶瓷制的基材(载体)、在基材的外周面上彼此相对并且在基材的轴方向上延伸的一对表面电极膜、从外部向表面电极膜供电的梳齿状的配线、和将配线固定到表面电极上的多个配线固定层构成，且经由表面电极膜将基材进行通电加热。再者，可将表面电极膜和梳齿状的配线以及配线固定层统称为电极部件。
在上述的电极部件的表面，为了在使用环境下在氧化性气氛下对电极部件进行保护而形成有Cr2O3等的保护膜，但该种保护膜的耐氧化温度低于1000℃。
另一方面，对于构成电加热式催化转换器的电极部件的保护膜，已开始要求1000℃以上的耐氧化温度，开发新的保护膜来代替由Cr2O3等构成的保护膜是迫切的课题。再者，在日本特开2014-105694中也公开了具有由Cr2O3构成的保护膜的电加热式催化转换器(在此，为通电加热式催化装置)。
在此，虽然代替Cr2O3等的Al2O3、SiO2等非导体材料的耐氧化温度为1000℃以上，但是由于引起这些原料金属Al、Si的氧化反应的气氛温度为1200℃以上这样的极高的温度，因此与在使用环境下所形成的由Cr2O3构成的保护膜相比，需要在高温气氛下的成膜加工。
因此，需要开发能够在尽可能低的气氛温度下形成由耐氧化温度高的Al2O3、SiO2等构成的保护膜的技术。
发明内容
本发明提供形成有在1000℃以上的高温下的耐氧化性优异的保护膜的电加热式催化转换器、和能够在尽可能低的气氛温度下形成耐氧化温度为1000℃以上的保护膜的电加热式催化转换器的制造方法。
本发明涉及一种电加热式催化转换器，该电加热式催化转换器至少具备具有催化剂涂层的导电性基材和固定于该基材上的电极部件，且在该电极部件的至少一部分的表面形成有保护膜。所述保护膜，由Al2O3、SiO2、Al2O3与SiO2的复合材料、或以它们为主成分的复合氧化物构成，并且，所述保护膜整体由非晶结构构成、或者具有结晶化率相对于所述保护膜整体为30体积％以下的部分结晶化玻璃结构，并且，膜厚在100nm～2μm的范围。
本发明的电加热式催化转换器，在电极部件的表面形成的保护膜，由Al2O3、SiO2、Al2O3与SiO2的复合材料、或以它们为主成分的复合氧化物形成，并且，上述保护膜整体由非晶结构构成、或者具有结晶化率相对于上述保护膜整体为30体积％以下的部分结晶化玻璃结构，由此耐氧化温度为1000℃以上。另外，保护膜除了具有非晶结构或者部分结晶化玻璃结构以外，其膜厚在100nm～2μm的范围，由此难以产生热应力，成为难以开裂的保护膜。膜厚也可以为100nm～1μm。
在此，所谓“电极部件”，是包括在基材表面上在基材的轴方向上延伸的表面电极膜、从外部向该表面电极膜供电的配线、将配线固定到表面电极上的多个配线固定层的意思，通常在基材表面配置一对电极部件来使用。
由于保护膜整体由非晶结构构成、或者具有结晶化率相对于保护膜整体为30体积％以下的部分结晶化玻璃结构，即，不具有晶体结构或者晶体结构少，因此能够将保护膜的杨氏模量、热膨胀系数抑制为较低，其结果，能够形成难以开裂的保护膜。
再者，在晶体结构的保护膜的情况下，有时在相转变温度附近产生体积变化(SiO2结晶的相转变温度在280℃附近，SiO2-Al2O3结晶(莫来石结晶)的相转变温度在970℃附近)，通过该体积变化而会产生裂纹。
另外，当保护膜的膜厚超过2μm时保护膜变得过硬，有可能由于其与基材、梳齿状的配线的热膨胀差而开裂，当膜厚小于100nm时气体阻隔性变低，因此将保护膜的膜厚规定在100nm～2μm的范围。
在此，导电性基材具有通电性和发热性，可以为例如SiC等的导电性陶瓷。另外，为具有三角形、四角形、六角形等的多个孔的多孔质基材，一般称为蜂窝结构体。而且，在基材的多个孔室的表面形成有催化剂涂层，所述催化剂涂层是在氧化铝等氧化物载体上担载有铂、钯等贵金属催化剂的涂层。
电加热式催化转换器的构成要素，有基材和例如一对电极部件、由将一对电极部件之间连接的电缆和介于电缆的途中的电源构成的外部电路等。
作为基材和构成电极部件的表面电极膜以及配线固定层的形成用的材料，可应用与上述的特开2014-105694所记载的NiCr基的热喷涂材料相比热膨胀性低的陶瓷材料，可举出SiC、SiC与Si的复合材料、SiC与MoSi2的复合材料、MoSi2与Si的复合材料、SiC等与导电性陶瓷材料的复合材料(硼化物、硅化物等)等。
本发明人实证到：构成本发明的电加热式催化转换器的保护膜的耐氧化温度为1000℃以上，更详细地讲，为1000℃～1100℃。另外，电极部件可以为金属部件或陶瓷部件、或者金属和陶瓷的复合部件，构成电极部件的表面电极和配线固定层可以是多孔质的，且气孔率为5％以上。根据这样的构成，电极部件和基材的热膨胀率为大致相同的程度，能够提高在实际发动机中使用时的耐热冲击性。再者，所谓热膨胀率为大致相同的程度，只要是接近于实际在发动机中使用时不会由起因于热膨胀率差的热冲击导致催化转换器破损的程度的热膨胀率值即可。
另外，本发明还涉及一种电加热式催化转换器的制造方法，该制造方法是制造下述电加热式催化转换器的方法，所述电加热式催化转换器至少具备具有催化剂涂层的导电性基材和固定于该基材上的电极部件，在该电极部件的至少一部分的表面上形成有保护膜，该制造方法包括以下步骤：第1步骤：制备溶胶凝胶溶液，所述溶胶凝胶溶液是在溶剂中含有Al2O3的纳米材料、SiO2的纳米材料、Al2O3与SiO2的复合材料的纳米材料、或者以Al2O3、SiO2、Al2O3与SiO2的复合材料为主成分的复合氧化物的纳米材料中的任一种而成的；第2步骤：在所述电极部件的至少一部分的表面涂布所述溶胶凝胶溶液，进行干燥，在500℃以下的温度下进行烧成从而形成保护膜，来制造电加热式催化转换器。
通过使用在溶剂中含有Al2O3的纳米材料、SiO2的纳米材料、Al2O3与SiO2的复合材料的纳米材料、或者以Al2O3、SiO2、Al2O3与SiO2的复合材料为主成分的复合氧化物的纳米材料中的任一种而成的溶胶凝胶溶液，能够实现形成保护膜时的烧成温度为500℃以下。在此，“纳米材料”包括纳米粒子、纳米纤维、无机高分子。
本发明人发现，当烧成温度为700℃左右时，保护膜的成膜速度变快，在所形成的保护膜内产生残余应力，因而不优选。
在本发明的制造方法中，将形成保护膜时的烧成温度规定在500℃以下，其中，可以将烧成温度设为比较低温的100～200℃的范围，并以缓慢的加热速度进行烧成。
通过在100～200℃的范围进行缓慢烧成，能够形成尽可能一样且均质的保护膜。
这样，以Al2O3的纳米材料、SiO2的纳米材料等为原料，通过使用了溶胶凝胶溶液的水解反应来形成保护膜，由此能够形成对于氧气(O2气体)等的气体阻隔性优异的致密的保护膜。
如通过以上说明能够理解的那样，根据本发明的电加热式催化转换器及其制造方法，在电极部件的表面形成的保护膜，由Al2O3、SiO2、Al2O3与SiO2的复合材料、或以它们为主成分的复合氧化物形成，并且，保护膜整体由非晶结构构成、或者具有结晶化率相对于保护膜整体为30体积％以下的部分结晶化玻璃结构，并且，膜厚在100nm～2μm的范围，由此，能够提供能在500℃以下的烧成温度下形成保护膜，具有耐氧化温度为1000℃以上、难以产生热应力、难以开裂的保护膜的电加热式催化转换器。
附图说明
以下参照附图来说明本发明的典型的实施方式的特征、优点以及技术和工业意义，附图中的标记代表部件。
图1是说明本发明的电加热式催化转换器(EHC)的实施方式的示意图。
图2是试验体的示意图。
图3A是图2的IIIa部的SEM照片图，
图3B是将图3A的b部放大了的SEM照片图。
图4是表示氧化劣化试验的结果的图。
图5A是表示Al2O3膜的XRD图谱的图，
图5B是表示SiO2膜的XRD图谱的图。
具体实施方式
以下，参照附图，说明本发明的电加热式催化转换器及其制造方法的实施方式。
(电加热式催化转换器及其制造方法的实施方式)
图1是说明本发明的电加热式催化转换器(EHC)的实施方式的示意图。图示的电加热式催化转换器10，被装在废气的排气***内，更具体而言，被装在将未图示的发动机、电加热式催化转换器10(EHC)、未图示的三元催化转换器以及未图示的副消音器和主消音器按顺序配置、且相互用***管连接的排气***内。在起动了发动机时，将构成电加热式催化转换器10的贵金属催化剂尽可能快地加热升温至规定温度，用该贵金属催化剂将从发动机流通出来的废气净化，没有被电加热式催化转换器10彻底净化的废气由位于其下游的三元催化净化装置进行净化。
电加热式催化转换器10，其整体大体上由以下部分构成：未图示的金属制的外管(金属壳体)；蜂窝结构的基材1，其通过未图示的垫(保持材料)固定在外管的中空部中，且在孔室壁1a的表面具备未图示的催化剂涂层；外部电路，其由将配置于基材1的表面的一对电极部件5之间连接的未图示的电缆和介于电缆的途中的未图示的电源构成。一对电极部件5的一方为正极，另一方为负极，通过电极部件5向基材1供给电流，来进行通电加热。
电极部件5由以下部分构成：在基材1的表面配置的表面电极膜2；在表面电极膜2的表面配置的梳齿状的配线3；和将构成梳齿状的配线3且在基材1的周向上延伸的多条第一配线3a固定的配线固定层4。
梳齿状的配线3由在基材1的长度方向上延伸的第二配线3b、和从第二配线3b分支出来且在基材1的周向上延伸的多条第一配线3a构成，第一配线3a和第二配线3b都与表面电极膜2电连接。
在发动机起动时将电源控制为接通(ON)时，就会对位于基材1的中央的一对电极部件5通电，形成在基材1的截面内的直径路径中流动的通路、和经由表面电极膜2在基材1的截面内直线性地流动的通路，这样，通过构成电极部件5的表面电极膜2具有的电流的扩散功能，能谋求基材1整体中的尽可能均等的通电，能谋求等量电流的扩散和整流。
在基材1中形成有由多个孔室壁1a构成的蜂窝结构的排气流路，在孔室壁1a上形成有未图示的催化剂涂层。该催化剂涂层，是使氧化铝(Al2O3)等氧化物担载钯(Pd)、铑(Rh)、铂(Pt)等铂族元素和/或铂族元素化合物，或者使氧化铝、氧化铈-氧化锆(CeO2-ZrO2)系复合氧化物担载其以外的贵金属和/或贵金属化合物，并将之与氧化铝溶胶和/或水一起调制形成浆液，将该浆液应用浸渗法、离子交换法、溶胶凝胶法、洗涂(wash coating)法等形成于基材骨架上而形成的。
从废气的排气***的上游侧流下来的(X方向)废气，在由多个孔室壁1a构成的排气流路中流通的过程中利用贵金属催化剂的活性而被净化，被净化了的废气从电加热式催化转换器10向排气***的下游侧流通下去。
首先，基材1和构成电极部件5的表面电极膜2以及配线固定层4都可由金属材料或者陶瓷材料构成，基材1可由SiC、SiC与Si的复合材料、SiC与MoSi2的复合材料等形成，构成电极部件5的表面电极膜2和配线固定层4可由Ni-Cr、CrB-Si、MoSi2-Si、TiB2-Si的热喷涂材料等形成。
在电极部件5的表面形成有保护膜6。形成保护膜6的电极部件5的表面，包含与电极部件5与基材1接触的部分对应的表面的范围。该保护膜6由Al2O3、SiO2、Al2O3与SiO2的复合材料、或以它们为主成分的复合氧化物形成，保护膜整体由非晶结构构成、或者具有结晶化率相对于保护膜整体为30体积％以下的部分结晶化玻璃结构，膜厚在100nm～2μm的范围。
保护膜6由非晶结构构成、或者具有结晶化率相对于保护膜整体为30体积％以下的部分结晶化玻璃结构，即，不具有晶体结构或者晶体结构少，因此能够将保护膜6的杨氏模量、热膨胀系数抑制为较低，其结果，保护膜6具有难以开裂的性能。
进而，通过使保护膜6的膜厚在100nm～2μm的范围，难以产生热应力，由此保护膜6也变得难以开裂。为了防止保护膜6开裂，优选将保护膜6的膜厚设为1μm以下。
接着，以保护膜6的成膜方法为中心来说明电加热式催化转换器10的制造方法。
首先，使由水和醇组成的溶剂中含有Al2O3的纳米材料、SiO2的纳米材料、Al2O3与SiO2的复合材料的纳米材料、或者以Al2O3、SiO2、Al2O3与SiO2的复合材料为主成分的复合氧化物的纳米材料中的任一种，来制备溶胶凝胶溶液(第1步骤)。
接着，在电极部件5的表面涂布溶胶凝胶溶液，进行干燥，经过水解、缩聚等化学反应后，在500℃以下的温度进行烧成，由此除去残留在内部的溶剂，并促进致密化，从而形成保护膜6，来制造电加热式催化转换器10(第2步骤)。
这样，通过使用使溶剂中含有Al2O3的纳米材料、SiO2的纳米材料、Al2O3与SiO2的复合材料的纳米材料、或者以Al2O3、SiO2、Al2O3与SiO2的复合材料为主成分的复合氧化物的纳米材料的任一种而成的溶胶凝胶溶液，能够实现形成保护膜6时的烧成温度为500℃以下。
关于该烧成温度为500℃以下，其中，通过设为更低温的100～200℃的范围，并以缓慢的加热速度进行烧成，能够形成尽可能一样且均质的保护膜6，因而优选。
根据该制造方法，能够在尽可能低的500℃以下的气氛温度下制造具有耐氧化温度为1000℃以上的保护膜6的电加热式催化转换器10。
(氧化劣化试验及其结果)
本发明人进行了验证保护膜的有无与氧化劣化的关系的实验。具体而言，如图2所示，在由SiC/Si制的多孔体构成的基材K的表面形成由Ni-Cr热喷涂材料构成的电极端子D(厚度为50μm以下)来制作出试验体TP。该试验体TP的配线固定层的气孔率，通过图像解析试验体TP的截面照片而求出的结果为14％。进而，在电极端子D的表面形成了以下两种保护膜。
在实施例1中，为SiO2(非晶二氧化硅)制的保护膜。其形成方法是将作为无机高分子的前驱体的全氢聚硅氮烷(PHPS)在减压气氛下采用浸渍的方法涂布于电极端子的表面，在400℃下进行1小时的大气干燥后，在500℃下、在N2气气氛下进行了1小时的烧成。再者，膜厚可利用PHPS的稀释浓度、烧成条件来控制。
另一方面，在实施例2中，为Al2O3(非晶氧化铝)制的保护膜。其形成方法是将Al2O3溶胶在减压气氛下采用浸渍的方法涂布于电极端子的表面，在200℃下、大气气氛下进行了2小时的烧成。再者，其膜厚也可利用Al2O3溶胶的稀释浓度、烧成条件来控制。相对于实施例1、2，作为比较例，准备了没有保护膜的试验体。
试验方法是在1000℃下进行24小时的大气处置(老化处理)从而使其氧化劣化后，测定了各试验体的体积电阻率。
首先，在图2所示的试验体TP的IIIa部被覆了实施例2的Al2O3(非晶氧化铝)制的保护膜，并将其SEM照片图示于图3A。将图3A的b部放大了的SEM照片图示于图3B。由图3B可知Al2O3膜被覆了一次粒子的表面。
另外，图4示出氧化劣化试验的结果。由该图可知，比较例与初期的状态相比，由于氧化劣化而导致体积电阻率大大地增加了。
另一方面可知，实施例1、2，与初期的状态相比，由氧化劣化引起的体积电阻率的增加都极少。
由本实验可知，通过在电极端子的表面形成非晶Al2O3制或非晶SiO2制的保护膜，能抑制体积电阻率的变化，耐氧化性提高。
另外，图5A示出Al2O3膜的XRD图谱，图5B示出SiO2膜的XRD图谱。
在图5A、5B中，未检测出起因于结晶性的峰，可确认出是以非晶结构成膜的。
以上，使用附图详细描述了本发明的实施方式，但具体的构成并不被该实施方式限定，即使有不脱离本发明的要旨的范围内的设计变更等，它们也都包含在本发明中。

Claims (8)

1.一种电加热式催化转换器，其至少具备具有催化剂涂层的导电性基材和固定于该基材上的电极部件，且在该电极部件的至少一部分的表面形成有保护膜，其特征在于，
所述保护膜，由Al2O3、SiO2、Al2O3与SiO2的复合材料、或以它们为主成分的复合氧化物形成，并且，所述保护膜整体由非晶结构构成、或者具有结晶化率相对于所述保护膜整体为30体积％以下的部分结晶化玻璃结构，并且，膜厚在100nm～2μm的范围。
2.根据权利要求1所述的电加热式催化转换器,其特征在于，所述导电性基材是以SiC为主成分的导电性陶瓷。
3.根据权利要求1或2所述的电加热式催化转换器,其特征在于，所述电极部件为金属部件或陶瓷部件、或金属和陶瓷的复合部件，该电极部件由表面电极和配线固定层构成，所述表面电极和所述配线固定层是多孔质的，且气孔率均为5％以上。
4.一种电加热式催化转换器的制造方法，所述电加热式催化转换器至少具备具有催化剂涂层的导电性基材和固定于该基材上的电极部件，且在该电极部件的至少一部分的表面形成有保护膜，所述制造方法的特征在于，包括以下步骤：
第1步骤：制备溶胶凝胶溶液，所述溶胶凝胶溶液是在溶剂中含有Al2O3的纳米材料、SiO2的纳米材料、Al2O3与SiO2的复合材料的纳米材料、或者以Al2O3、SiO2、Al2O3与SiO2的复合材料为主成分的复合氧化物的纳米材料中的任一种而成的，
第2步骤：在所述电极部件的至少一部分的表面涂布所述溶胶凝胶溶液，进行干燥，在500℃以下的温度下进行烧成从而形成保护膜，来制造电加热式催化转换器。
5.根据权利要求4所述的电加热式催化转换器制造方法,其特征在于，所述导电性基材是以SiC为主成分的导电性陶瓷。
6.根据权利要求4或5所述的电加热式催化转换器的制造方法，其特征在于，所述电极部件为金属部件或陶瓷部件、或金属和陶瓷的复合部件，构成该电极部件的表面电极和配线固定层是多孔质的，且气孔率均为5％以上。
7.根据权利要求4或5所述的电加热式催化转换器的制造方法,其特征在于，在所述第2步骤中，烧成温度设为100～200℃的范围。
8.根据权利要求6所述的电加热式催化转换器的制造方法,其特征在于，在所述第2步骤中，烧成温度设为100～200℃的范围。
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