JP2002326881A - Manufacturing method of porous ceramic - Google Patents
Manufacturing method of porous ceramicInfo
- Publication number
- JP2002326881A JP2002326881A JP2001131835A JP2001131835A JP2002326881A JP 2002326881 A JP2002326881 A JP 2002326881A JP 2001131835 A JP2001131835 A JP 2001131835A JP 2001131835 A JP2001131835 A JP 2001131835A JP 2002326881 A JP2002326881 A JP 2002326881A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- honeycomb structure
- ceramic
- hollow
- microspheres
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000004005 microsphere Substances 0.000 claims abstract description 57
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 22
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 abstract description 30
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 6
- 241000264877 Hippospongia communis Species 0.000 abstract 2
- 239000000126 substance Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005192 partition Methods 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 6
- 235000013312 flour Nutrition 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002276 dielectric drying Methods 0.000 description 1
- 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 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 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 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Filtering Materials (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、多孔質セラミック
ハニカム構造体の製造方法に関するものである。なかで
も、ディーゼル機関から排出される微粒子を捕集するた
めのフィルタに使用される多孔質セラミックハニカム構
造体の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a porous ceramic honeycomb structure. In particular, the present invention relates to a method for manufacturing a porous ceramic honeycomb structure used for a filter for collecting fine particles discharged from a diesel engine.
【０００２】[0002]
【従来の技術】ディーゼル機関から排出される微粒子を
除去するため、セラミックハニカム構造体の隔壁を多孔
質構造とし、その隔壁に微粒子を含んだ排気ガスを通過
せしめる構造の微粒子捕集用フィルタ（ディーゼルパテ
ィキュレートフィルタ）が使用されている。図１に、こ
のフィルタの概略形状を示す。このフィルタの特性に関
しては、微粒子の捕集効率、圧力損失（圧損）、微粒子
の捕集時間（捕集開始から一定圧損に達するまでの時
間）の３つが重要とされている。中でも、捕集効率と圧
損は相反する関係にあり、捕集効率を高くしようとする
と、圧損が増大し、捕集時間が短くなり、また圧損を低
くすると、捕集時間は長くできるが、捕集効率が悪くな
る。これらの相反するフィルタの特性を満足するよう
に、セラミックハニカム構造体に対しては、その気孔
率、気孔分布を制御し、最適化する技術が従来から検討
されており、一般に気孔率は４０％以上のものが使用さ
れている。また、セラミック材質には、その低熱膨張特
性からコージェライトを主成分とするものを使用するの
が一般的であるが、その他に、炭化珪素、窒化珪素等の
耐熱性セラミック材料も使用されている。2. Description of the Related Art In order to remove fine particles discharged from a diesel engine, a partition wall of a ceramic honeycomb structure has a porous structure, and a fine particle trapping filter (diesel) having a structure in which exhaust gas containing fine particles passes through the partition walls. Particulate filter) is used. FIG. 1 shows a schematic shape of this filter. Regarding the characteristics of this filter, three are important: the collection efficiency of the fine particles, the pressure loss (pressure loss), and the collection time of the fine particles (the time from the start of collection to the time when a certain pressure loss is reached). Above all, the collection efficiency and the pressure loss are in a contradictory relationship. To increase the collection efficiency, the pressure loss increases, the collection time becomes shorter, and if the pressure loss is made lower, the collection time can be made longer. The collection efficiency becomes worse. Techniques for controlling and optimizing the porosity and porosity of ceramic honeycomb structures so as to satisfy the characteristics of these contradictory filters have been conventionally studied. Generally, the porosity is 40%. The above are used. Further, as the ceramic material, it is common to use a material containing cordierite as a main component because of its low thermal expansion characteristic, but in addition, heat-resistant ceramic materials such as silicon carbide and silicon nitride are also used. .
【０００３】従来、上記のような気孔率の大きなセラミ
ックハニカム構造体を製造する際には、セラミックス原
料に造孔剤等を加えて、混練し、押出成形後、乾燥、焼
成するのが一般的である。造孔剤には可燃性物質が使用
され、焼成温度に達する前の昇温過程で燃焼して消失
し、造孔剤の形跡が気孔としてセラミックス中に残留す
る。その一例として、特公昭６３−２７３０３号公報で
は、澱粉粉を使用したコージェライトハニカム構造体の
製造法が開示され、澱粉粉の造孔効果が示されている。
また特公昭６０−３１８００号公報では、黒鉛粉末すな
わちグラファイト粉末を使用した高寸法精度を有する多
孔質セラミックスハニカム構造体の製造法が開示され、
その中でグラファイト粉末の造孔効果を示している。更
には特許第２５６２１８６号公報では、造孔剤として、
大気雰囲気中６５０℃、１時間保持の熱処理において、
重量減少率が５０％以上である易燃焼性のカーボン粉を
使用する多孔質セラミックハニカム構造体の製造法が開
示され、易燃焼性カーボン粉が短い焼成時間で造孔効果
の得られることを開示している。また、特開平９−７７
５７３号公報では、セラミック原料に対して１００℃以
下で発泡する有機発泡材、又は焼成温度よりも低い温度
で燃焼する可燃性物質を５〜５０重量％加えて使用する
ハニカム構造体の製造方法が開示され、有機発泡剤及び
可燃性物質の造孔効果が示されている。更に特開平５−
３３０９４３号公報では、グラファイト、水に不溶なセ
ルロースを添加してディーゼル用フィルターとして使用
するのに好適な多孔質セラミック製品の製造方法が開示
され、グラファイトと水に不溶なセルロースの組合せに
より造孔効果を損なわずに、完全な誘電乾燥を行えるこ
とが示されている。Conventionally, when a ceramic honeycomb structure having a large porosity as described above is manufactured, it is general to add a pore-forming agent or the like to a ceramic raw material, knead, extrude, dry, and fire. It is. A flammable substance is used as the pore-forming agent, which burns and disappears during the heating process before reaching the firing temperature, and traces of the pore-forming agent remain in the ceramics as pores. As one example, JP-B-63-27303 discloses a method for producing a cordierite honeycomb structure using starch powder, and shows a pore-forming effect of the starch powder.
JP-B-60-31800 discloses a method for manufacturing a porous ceramic honeycomb structure having high dimensional accuracy using graphite powder, that is, graphite powder,
It shows the pore-forming effect of graphite powder. Furthermore, in Japanese Patent No. 2562186, as a pore-forming agent,
In the heat treatment of holding at 650 ° C. for one hour in the air atmosphere,
A method for manufacturing a porous ceramic honeycomb structure using a combustible carbon powder having a weight reduction rate of 50% or more is disclosed, and discloses that a combustible carbon powder can obtain a pore-forming effect in a short firing time. are doing. Also, JP-A-9-77
No. 573 discloses a method for manufacturing a honeycomb structure using an organic foaming material which foams at a temperature of 100 ° C. or lower with respect to a ceramic raw material or a combustible substance which burns at a temperature lower than a firing temperature by adding 5 to 50% by weight. Disclosed are the pore-forming effects of organic blowing agents and flammable materials. Further, Japanese Patent Laid-Open No. 5-
No. 330943 discloses a method for producing a porous ceramic product suitable for use as a diesel filter by adding graphite and water-insoluble cellulose, and discloses a pore-forming effect by a combination of graphite and water-insoluble cellulose. It has been shown that complete dielectric drying can be achieved without compromising.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、従来技
術の可燃性物質を造孔剤として使用し、焼成温度より低
い温度で可燃性物質を燃焼させてセラミック中に細孔を
形成して多孔質セラミックスを製造する場合、以下のよ
うな問題があった。上記可燃性物質は、ハニカム構造体
の外部からの加熱では加熱されにくく、また一旦燃焼す
ると急激に燃焼、発熱（しかもそれぞれの可燃性物質に
よって燃焼する温度が異なる）するという性質がある。
このため、ハニカム構造体の内部と外壁部との間に大き
な温度差が発生し、この温度差によりハニカム構造体の
内部及び端面にクラックが発生したり、内部が溶損する
という問題があった。さらには上記可燃性物質の燃焼
は、それぞれの物質に対してある固有の温度領域で急激
に発生することから、燃焼ガスが発生する際の体積膨張
によりハニカム構造体の内部及び端面にクラックが発生
したり、或いは発生した燃焼ガスのセラミック系外への
排出がスムーズに行われず、ハニカム構造体の内部及び
端面にクラックの発生することもあった。例えば、前述
の小麦粉の場合２５０〜３５０℃、グラファイトの場合
７５０〜８５０℃で急激に燃焼が発生する。特に、この
クラックの現象は、外径１４０ｍｍ以上、長さ１５０ｍ
ｍ以上の寸法の大きなハニカム構造体では顕著に現れ、
実質的にこれ以上の大きさで、且つ４０％以上の気孔率
を有するハニカム構造体を得るのは困難であった。この
ため従来は、クラックの発生、及び内部の溶損を防ぐた
め、昇温速度を遅くし、内部の急激な発熱を抑えるよう
にしていたが、昇温速度を遅くすると焼成時間が長くな
り、製造効率を極端に悪くするという問題点があった。However, using a flammable substance of the prior art as a pore-forming agent and burning the flammable substance at a temperature lower than the firing temperature to form pores in the ceramic to form a porous ceramic The following problems have been encountered in the production of The combustible material has a property that it is difficult to be heated by heating the honeycomb structure from the outside, and that once combusted, the combustible material rapidly burns and generates heat (and the combustion temperature differs depending on each combustible material).
For this reason, a large temperature difference is generated between the inside and the outer wall of the honeycomb structure, and there is a problem that the temperature difference causes cracks in the inside and end faces of the honeycomb structure and melts the inside. Furthermore, since the combustion of the above combustible substances occurs rapidly in a specific temperature range for each substance, cracks are generated inside and at the end face of the honeycomb structure due to volume expansion when the combustion gas is generated. In some cases, the generated combustion gas was not smoothly discharged to the outside of the ceramic system, and cracks were sometimes generated inside and at the end face of the honeycomb structure. For example, combustion occurs rapidly at 250 to 350 ° C. in the case of the above-mentioned flour and 750 to 850 ° C. in the case of graphite. In particular, this crack phenomenon is caused by an outer diameter of 140 mm or more and a length of 150 m.
remarkable in large honeycomb structures with dimensions of at least m
It has been difficult to obtain a honeycomb structure having a size substantially larger than this and having a porosity of 40% or more. For this reason, in the past, in order to prevent the occurrence of cracks and internal melting, the heating rate was slowed down to suppress rapid internal heat generation, but if the heating rate was slowed down, the firing time would increase, There is a problem that manufacturing efficiency is extremely deteriorated.
【０００５】本発明の目的は、多孔質セラミックハニカ
ム構造体を製造する際に、上述した課題を解消して、焼
成時間の短縮が可能で生産性を向上させることのできる
多孔質セラミックハニカム構造体の製造方法を提供しよ
うとするものである。An object of the present invention is to solve the above-mentioned problems when manufacturing a porous ceramic honeycomb structure, to reduce the firing time, and to improve the productivity. It is intended to provide a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するた
め、本発明者は鋭意検討を行った結果、不燃性の中空セ
ラミックス微小球を使用することにより、焼成の昇温過
程で発生するクラックや溶損を防止でき、かつ気孔率の
大きい多孔質セラミックスが容易に得られることを見出
した。すなわち、本発明の多孔質セラミックハニカム構
造体の製造方法は、平均粒径３００μｍ以下の中空セラ
ミックス微小球を５０質量％以下含有するセラミックス
原料粉末を使用することを特徴とするものである。ここ
で、中空セラミックス微小球の含有量は２質量％以上４
０質量％以下がより好ましい。また、多孔質セラミック
ハニカム構造体の気孔率が４０％以上であることを特徴
とするものである。また、本発明の多孔質セラミックハ
ニカム構造体の製造方法は、中空セラミックスを含有す
るセラミクス原料粉末がコージェライト化原料であるこ
とが良く、中空セラミックス微小球の主成分がＳｉ
Ｏ２、Ａｌ２Ｏ３であり、且つ中空セラミックス微小球
のＦｅ２Ｏ３が１．５質量％以下、ＣａＯが１．０質量
％以下、ＴｉＯ２が２．５質量％以下であることが好ま
しい。Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies. As a result, by using non-combustible hollow ceramic microspheres, cracks generated during the temperature rise process of firing are reduced. It has been found that porous ceramics which can prevent erosion and have high porosity can be easily obtained. That is, the method for producing a porous ceramic honeycomb structure of the present invention uses a ceramic raw material powder containing 50% by mass or less of hollow ceramic microspheres having an average particle size of 300 μm or less. Here, the content of the hollow ceramic microspheres is 2% by mass or more and 4% by mass or more.
0 mass% or less is more preferable. Further, the porosity of the porous ceramic honeycomb structure is 40% or more. In the method for producing a porous ceramic honeycomb structure of the present invention, the ceramic raw material powder containing hollow ceramics is preferably a cordierite-forming raw material, and the main component of the hollow ceramic microspheres is Si.
O 2 and Al 2 O 3 , and the hollow ceramic microspheres may have Fe 2 O 3 of 1.5% by mass or less, CaO of 1.0% by mass or less, and TiO 2 of 2.5% by mass or less. preferable.
【０００７】[0007]
【作用】次に、本発明における作用効果につき説明す
る。本発明の多孔質セラミックハニカム構造体の製造方
法は、平均粒径３００μｍ以下の中空セラミックス微小
球を５０質量％以下含有するセラミックス原料粉末を使
用することから、従来多孔質セラミックハニカム構造体
を製造する際に、造孔剤として可燃性物質を使用した場
合に発生していた焼成時の昇温過程でのクラックや溶損
等の問題を起こすことがない。すなわち中空セラミック
ス微小球は、不燃性であることから、昇温過程で燃焼す
ることがなく、燃焼に伴う、クラックや溶損の問題は発
生せず、急昇温が可能になるため、焼成時間の短縮が可
能になるからである。更には、中空微小球であることか
ら、中空部分が焼成後に気孔としてセラミックス中に残
留するため、急昇温時のクラックや溶損の心配無しに気
孔率を大きくすることが容易となるのである。ここで、
中空セラミックス微小球の平均粒径を３００μｍ以下と
しているのは、平均粒径が３００μｍを越えると、特に
ディーゼルパティキュレートフィルターとして、一般的
に使用されている隔壁厚４３０μｍのハニカム構造体を
公知の押出成形法により成形する際に、口金スリット内
に中空セラミックス微小球が詰まったり、ひっかかった
りして、隔壁が形成されない不良が発生し易くなるから
である。好ましくは１５０μｍ以下である。また、中空
セラミックス微小球の添加量を５０質量％以下とするの
は、５０質量％を越えると中空セラミックス微小球同士
の接触が起こることから、原料の流動性が悪くなり、ハ
ニカム構造体の成形が困難になるからである。また、中
空セラミックス微小球のより好ましい含有量を２質量％
以上４０質量％以下としているのは、２質量％以上であ
ると、いわゆる造孔効果が大きく現れるからであり、４
０質量％を越えると、中空セラミックス微小球同士の接
触が起こる場合もあり、成形の条件によっては、押出成
形の際、隔壁が形成されない不良が発生することもある
からである。Next, the function and effect of the present invention will be described. The method for producing a porous ceramic honeycomb structure of the present invention uses a ceramic raw material powder containing 50% by mass or less of hollow ceramic microspheres having an average particle size of 300 μm or less, and thus conventionally produces a porous ceramic honeycomb structure. At this time, there is no problem such as cracking or melting during the heating process during firing, which occurred when a combustible substance was used as the pore-forming agent. That is, since the hollow ceramic microspheres are non-flammable, they do not burn during the heating process, and do not cause cracks or melting damage due to the burning, and can rapidly rise in temperature. This is because it becomes possible to shorten the time. Further, since the hollow microspheres, the hollow portion remains in the ceramics as pores after firing, so that it becomes easy to increase the porosity without fear of cracking or melting during rapid temperature rise. . here,
The reason why the average particle diameter of the hollow ceramic microspheres is 300 μm or less is that when the average particle diameter exceeds 300 μm, a honeycomb structure having a partition wall thickness of 430 μm, which is generally used as a diesel particulate filter, is known in the art. This is because when molding by the molding method, the hollow ceramic microspheres are clogged or caught in the die slit, so that a defect that a partition wall is not formed easily occurs. Preferably it is 150 μm or less. Further, the addition amount of the hollow ceramic microspheres is set to 50% by mass or less. When the amount exceeds 50% by mass, the hollow ceramic microspheres come into contact with each other, so that the flowability of the raw material deteriorates, and the honeycomb structure is formed. Is difficult. Further, the more preferable content of the hollow ceramic microspheres is 2% by mass.
The reason why the content is set to not less than 40% by mass is that when the content is not less than 2% by mass, a so-called pore-forming effect is greatly exhibited.
If the content exceeds 0% by mass, the hollow ceramic microspheres may come into contact with each other, and depending on the molding conditions, there may be a defect that partition walls are not formed during extrusion molding.
【０００８】また、本発明の多孔質セラミックスの製造
方法において多孔質セラミックハニカム構造体の気孔率
を４０％以上が好ましい範囲としているのは、特に気孔
率が４０％を越えるような多孔質セラミックハニカム構
造体の場合に、造孔剤として可燃性物質を使用すると、
焼成時の昇温過程でのクラックや溶損の問題が起こりや
すくなることから、中空セラミックス微小球を使用した
効果が絶大となるからである。即ち、中空セラミックス
微小球が有する中空部分が焼成後に気孔として残留する
ことから、昇温過程でのクラックや溶損の問題を発生さ
せずに、気孔率４０％以上の多孔質セラミックスが得ら
れる。また、本発明の多孔質セラミックスの製造方法に
おいて、中空セラミックスを含有するセラミクス原料粉
末がコージェライト化原料であることを好ましいとして
いるのは、元来コージェライトが有する低熱膨張特性に
加えて、焼成時の昇温過程でのクラックや溶損の問題を
発生させず、気孔率を大きくできることから、熱衝撃に
強く、低圧損のハニカムフィルターが得られるからであ
る。そして、好適な中空セラミックス微小球の主成分を
ＳｉＯ２、Ａｌ２Ｏ３としたのは、コージェライトを主
成分とする多孔質セラミックハニカム構造体を製造する
際に、コージェライト組成がＳｉＯ２４２〜５６質量
％、Ａｌ２Ｏ３３０〜４５質量％、ＭｇＯ１２〜１６質
量％であることから、中空セラミックス微小球の主成分
がＳｉＯ２、Ａｌ２Ｏ３であれば、その他のコージェラ
イト化原料粉末のカオリン、タルク、アルミナ、水酸化
アルミニウム、シリカ等のＳｉＯ２、Ａｌ ２Ｏ３源原料
の添加量の調整により、コージェライト組成を得ること
が容易となるからである。また、中空セラミックス微小
球のＦｅ２Ｏ３が１．５質量％以下、ＣａＯが１．０質
量％以下、ＴｉＯ２が２．５質量％以下としたのは、結
晶相の主成分をコージェライト相とし、不純物から生成
する高膨張のガラス相を少なくするためである。そのほ
か該微小球は不可避的に混入する成分、Ｎａ２Ｏ、Ｋ２
Ｏ、Ｐ２Ｏ ５、ＰｂＯ等を全体として２質量％以下含ん
でも良い。Further, the production of the porous ceramic of the present invention
Porosity of Porous Ceramic Honeycomb Structure in Method
Is preferably in the range of 40% or more,
Porous ceramic honeycomb structure whose percentage exceeds 40%
When using flammable substances as pore-forming agents in the case of structures,
Cracks and melting problems during the heating process during firing
Uses hollow ceramic microspheres
This is because the effect is enormous. That is, hollow ceramics
Hollow portion of microspheres remains as pores after firing
As a result, problems such as cracks and melting
Without obtaining a porous ceramic with a porosity of 40% or more
It is. Further, in the method for producing a porous ceramic of the present invention,
Ceramic raw material powder containing hollow ceramics
Preferably, the powder is a cordierite-forming raw material.
Is due to the low thermal expansion characteristic of cordierite
In addition, cracking and melting problems during the heating process during firing
Because it can increase the porosity without generating,
A strong, low-pressure-drop honeycomb filter can be obtained.
You. Then, the main component of a suitable hollow ceramic microsphere is
SiO2, Al2O3It is mainly cordierite
Manufacture porous ceramic honeycomb structure as a component
When the cordierite composition is SiO242-56 mass
%, Al2O330-45 mass%, MgO12-16 quality
%, The main component of hollow ceramic microspheres
Is SiO2, Al2O3If so, other cojella
Kaolin, talc, alumina, hydroxide of raw material powder
SiO such as aluminum and silica2, Al 2O3Source material
Of cordierite composition by adjusting the amount of
This becomes easy. Also, hollow ceramic micro
Sphere Fe2O3Is 1.5 mass% or less, and CaO is 1.0 quality
% Or less, TiO2Is 2.5% by mass or less
The main component of the crystalline phase is the cordierite phase, generated from impurities
This is for reducing the high expansion glass phase. That
Or the microspheres are unavoidably mixed components, Na2O, K2
O, P2O 5, PbO etc. as a whole in an amount of 2% by mass or less
But it is good.
【０００９】上記に説明したような中空セラミックス微
小球は、例えば以下のようにして得ることが出来る。コ
ージェライト化原料粉末を調合し、これに水を加えてコ
ージェライトスラリーを作製した後、スプレー乾燥機に
より、水分を蒸発せしめ、球状のコージェライト化顆粒
を得る。このとき、スラリーの水分量、粘度、やスプレ
ー乾燥機の運転条件を制御することによって、顆粒内が
中空部分を有する閉鎖型の中空体が得られる。この中空
体を１３００℃以上の温度で焼成することにより、コー
ジェライト組成を有する中空セラミックス微小球が得ら
れる。或いは、火力発電所から発生するフライアッシュ
の一部は、閉鎖型中空体で、高強度のものが得られるこ
とから、これを使用することも可能である。図２に中空
セラミックス微小球の４２０倍の拡大写真を、図３には
中空セラミックス微小球の４２０倍の断面写真を示す。
尚、図中の右下の線は１０μｍを示すことから、図に示
す中空セラミックス微小球の直径は概ね８５〜９０μｍ
となる。以上の中空セラミックス微小球は概ね球状であ
ることから、コージェライトセラミックス中に形成され
る気孔も略球状となるため、気孔での応力集中を低減で
き、機械的強度にも優れたディーゼルパティキュレート
フィルタを得ることも可能となる。[0009] The hollow ceramic microspheres described above can be obtained, for example, as follows. A cordierite-forming raw material powder is prepared, and water is added thereto to prepare a cordierite slurry. Then, water is evaporated by a spray dryer to obtain spherical cordierite-formed granules. At this time, by controlling the water content and viscosity of the slurry and the operating conditions of the spray dryer, a closed hollow body having a hollow portion inside the granule can be obtained. By firing this hollow body at a temperature of 1300 ° C. or more, hollow ceramic microspheres having a cordierite composition can be obtained. Alternatively, a part of fly ash generated from a thermal power plant is a closed hollow body, and a high-strength one can be used. FIG. 2 shows a 420 times enlarged photograph of the hollow ceramic microsphere, and FIG. 3 shows a 420 times cross-sectional photograph of the hollow ceramic microsphere.
In addition, since the lower right line in the figure shows 10 μm, the diameter of the hollow ceramic microspheres shown in the figure is approximately 85 to 90 μm.
Becomes Since the above hollow ceramic microspheres are generally spherical, the pores formed in cordierite ceramics are also substantially spherical, so that the concentration of stress in the pores can be reduced and the diesel particulate filter has excellent mechanical strength. It is also possible to obtain.
【００１０】以上のように、本発明をコージェライトセ
ラミックスを例にあげて説明したが、本発明はこれに限
定されるものでなく、ムライト、アルミナ、窒化珪素、
炭化珪素、窒化アルミ、リチウムアルミニウムシリケー
ト、チタン酸アルミニウム、ジルコニア、等の種々の耐
熱性セラミック材料に適用できる。As described above, the present invention has been described by taking cordierite ceramics as an example, but the present invention is not limited to this, and mullite, alumina, silicon nitride,
The present invention can be applied to various heat-resistant ceramic materials such as silicon carbide, aluminum nitride, lithium aluminum silicate, aluminum titanate, and zirconia.
【００１１】[0011]
【発明の実施の形態】以下、本発明の実施例を説明す
る。 （実施例）ＳｉＯ２が４２〜５６質量％、Ａｌ２Ｏ３が
３０〜４５質量％、ＭｇＯが１２〜１６質量％となるよ
うに、表１に特性を示す中空セラミックス微小球及びそ
の他のコージェライト化原料粉末を調合し、このコージ
ェライト化原料１００質量部に対して、必要に応じて表
２に特性を示す可燃性物質の造孔剤を、表３に示す割合
で添加し、さらにメチルセルロース４質量部及び水を加
えて、混練し、押出成形可能な坏土とした。中空セラミ
ックス微小球Ａはコージェライト、中空セラミックス微
小球Ｂ〜Ｆは、ＳｉＯ２、Ａｌ２Ｏ３を主成分とするも
のである。Embodiments of the present invention will be described below. (Example) SiO 2 is 42 to 56 wt%, Al 2 O 3 is 30 to 45 wt%, so that MgO is 12 to 16 wt%, microspheres and other hollow ceramics show the characteristics in Table 1 Koje A raw material powder was prepared, and a pore-forming agent of a flammable substance having characteristics shown in Table 2 was added to 100 parts by mass of the cordierite raw material, if necessary, in a ratio shown in Table 3, and methylcellulose was further added. 4 parts by mass and water were added and kneaded to obtain an extrudable clay. The hollow ceramic microspheres A are mainly composed of cordierite, and the hollow ceramic microspheres BF are mainly composed of SiO 2 and Al 2 O 3 .
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【表２】 [Table 2]
【００１４】[0014]
【表３】 [Table 3]
【００１５】次いで、それぞれのバッチの坏土を公知の
押出成形法により隔壁厚４３０μｍ、１平方センチ当た
りのセル数１６個を有する直径２６７ｍｍ、長さ３０４
ｍｍの円筒形ハニカム構造体を成形した。このとき成形
が問題なく行えたバッチを（◎）、セル欠陥は発生した
がその発生率が５％未満であったバッチを（○）、セル
欠陥が連続的に発生しハニカム構造体の成形が困難であ
ったバッチを（×）として成形性を評価した結果を表４
に示す。次いでそれぞれのバッチによるハニカム構造体
は、乾燥後図４に示す焼成条件で焼成し、材料特性とし
て気孔率、及び４０〜８００℃間の熱膨張係数の評価、
焼成体の特性としてクラックの発生、ハニカム構造体中
心部の溶損発生の観察を実施した。気孔率の測定は水銀
ポロシメーターを使用して行った。これらの結果を表４
に示す。Next, the kneaded clay of each batch is extruded by a known extrusion molding method to have a partition wall thickness of 430 μm, 16 cells per square centimeter, a diameter of 267 mm and a length of 304.
mm was formed into a cylindrical honeycomb structure. At this time, a batch that could be formed without any problem (◎), a batch in which cell defects were generated but the occurrence rate was less than 5% (○), and cell defects were continuously generated and the honeycomb structure was formed. Table 4 shows the results of evaluation of the moldability with the batches that were difficult as (x).
Shown in Then, the honeycomb structure of each batch was dried and fired under the firing conditions shown in FIG. 4 to evaluate the porosity and the coefficient of thermal expansion between 40 and 800 ° C. as material properties.
As characteristics of the fired body, the occurrence of cracks and the occurrence of erosion at the center of the honeycomb structure were observed. The porosity was measured using a mercury porosimeter. Table 4 shows these results.
Shown in
【００１６】[0016]
【表４】 [Table 4]
【００１７】試験Ｎｏ．１は比較例で、触媒担体に使用
されるコージェライトセラミックスであるため気孔率は
３５．６％である。試験Ｎｏ．２〜７は、本発明の実施
例で、試験Ｎｏ．１に対してコージェライト組成の中空
セラミックス微小球Ａを５〜４８質量％添加しているこ
とから、焼成体の組成はコージェライト組成ＳｉＯ２：
４２〜５６質量％、Ａｌ２Ｏ３：３０〜４５質量％、Ｍ
ｇＯ：１２〜１６質量％となる。また、いずれも成形性
は良好の（◎）〜（○）で、中空セラミックス微小球の
添加量を増やすことにより、気孔率が大きくなってい
る。このため試験Ｎｏ．２〜７の焼成体では、４０％以
上の高気孔率、５〜７×１０-7／℃の低熱膨張係数が得
られるにも係わらず、可燃性物質の造孔剤を添加してい
ないことから、焼成条件ａ〜ｃのいずれの条件でも焼成
によるクラックや溶損もなく、品質の安定したものが得
られている。一方、試験Ｎｏ．８は、本発明の比較例
で、試験Ｎｏ．１対してコージェライト組成の中空セラ
ミックス微小球Ａを５５質量％添加していることから、
成形性評価は（×）であり、ハニカム構造体の成形が困
難であった。このため焼成が行えず、材料特性、焼成体
特性の評価は実施できなかった。Test No. Reference numeral 1 is a comparative example, which has a porosity of 35.6% because it is cordierite ceramic used for a catalyst carrier. Test No. Test Nos. 2 to 7 are examples of the present invention. 1 to 5 to 48% by mass of the hollow ceramic microspheres A having a cordierite composition, the composition of the fired body has a cordierite composition SiO 2 :
42 to 56 wt%, Al 2 O 3: 30~45 wt%, M
gO: 12 to 16% by mass. In all cases, the moldability was good (◎) to (○), and the porosity was increased by increasing the amount of the hollow ceramic microspheres added. Therefore, Test No. In the fired bodies 2 to 7, a high porosity of 40% or more and a low coefficient of thermal expansion of 5 to 7 × 10 −7 / ° C. are obtained, but a flammable substance pore-forming agent is not added. Thus, under any of the firing conditions a to c, there was no crack or melting damage due to firing, and a product having stable quality was obtained. On the other hand, Test No. Test No. 8 is a comparative example of the present invention. On the other hand, since 55% by mass of the hollow ceramic microspheres A having a cordierite composition was added,
The evaluation of formability was (x), and it was difficult to form the honeycomb structure. For this reason, sintering could not be performed, and evaluation of material characteristics and sintering characteristics could not be performed.
【００１８】試験Ｎｏ．９〜１３は、本発明の実施例
で、ＳｉＯ２、Ａｌ２Ｏ３を主成分とする中空セラミッ
クス微小球Ｂを使用したものである。その他のコージェ
ライト化原料の添加量を調整し、コージェライト組成の
ＳｉＯ２：４２〜５６質量％、Ａｌ２Ｏ３：３０〜４５
質量％、ＭｇＯ：１２〜１６質量％が得られるように調
整した。また試験Ｎｏ．２〜８と同様に、いずれも成形
性は良好の（◎）で、中空セラミックス微小球の添加量
を増やすことにより、気孔率が大きくなっている。この
ため試験Ｎｏ．９〜１３の焼成体では、４０％以上の高
気孔率、４〜９×１０-7／℃の低熱膨張係数が得られる
にも係わらず、可燃性物質の造孔剤を添加していないこ
とから、焼成条件ａ〜ｃのいずれの条件でも焼成による
クラックや溶損もなく、品質の安定したものが得られて
いる。試験Ｎｏ．１４〜１６は、本発明の実施例で、試
験Ｎｏ．９〜１３と同様ＳｉＯ２、Ａｌ２Ｏ３を主成分
とする中空セラミックス微小球Ｃ及びＤを使用したもの
で、いずれも成形性は良好の（◎）で、中空セラミック
スで平均粒径が異なる微小球の添加量を増やすことによ
り、気孔率が大きくなっている。このため試験Ｎｏ．１
４〜１６の焼成体では、４０％以上の高気孔率、５〜７
×１０-7／℃の低熱膨張係数が得られるにも係わらず、
可燃性物質の造孔剤を添加していないことから、焼成条
件ａ〜ｃのいずれの条件でも焼成によるクラックもな
く、品質の安定したものが得られている。Test No. 9-13, in the embodiment of the present invention is obtained by using hollow ceramic microspheres B composed mainly of SiO 2, Al 2 O 3. The amount of the other cordierite-forming raw materials was adjusted, and the cordierite composition of SiO 2 : 42 to 56% by mass and Al 2 O 3 : 30 to 45
% By mass, and MgO: 12 to 16% by mass. Test No. As in the cases of Nos. 2 to 8, the moldability was good (い ず れ), and the porosity was increased by increasing the amount of the hollow ceramic microspheres added. Therefore, Test No. In the fired bodies of Nos. 9 to 13, a high porosity of 40% or more and a low coefficient of thermal expansion of 4 to 9 × 10 -7 / ° C are obtained, but no flammable substance pore-forming agent is added. Thus, under any of the firing conditions a to c, there was no crack or melting damage due to firing, and a product having stable quality was obtained. Test No. Test Nos. 14 to 16 are examples of the present invention. As in 9 to 13, hollow ceramic microspheres C and D containing SiO 2 and Al 2 O 3 as main components were used, all of which have good moldability (◎) and different average particle diameters of hollow ceramics. The porosity is increased by increasing the amount of the added microspheres. Therefore, Test No. 1
In the fired bodies of 4 to 16, high porosity of 40% or more, 5 to 7
Despite obtaining a low coefficient of thermal expansion of × 10 -7 / ° C,
Since no flammable substance pore-forming agent was added, there was no crack due to firing under any of the firing conditions a to c, and a product of stable quality was obtained.
【００１９】試験Ｎｏ．１７は、本発明の比較例で、主
成分はＳｉＯ２、Ａｌ２Ｏ３の中空セラミックス微小球
を使用しているが、平均粒径が３２１μｍの粒径の大き
い中空セラミック微小球Ｅを使用していることから、押
出成形時に金型スリットに微小球が詰まってしまい、セ
ル欠陥のないハニカム構造体を得ることが困難で、評価
は実施できなかった。一方、試験Ｎｏ．１８では、試験
Ｎｏ．９〜１６と同様ＳｉＯ２、Ａｌ２Ｏ３を主成分と
する中空セラミックス微小球Ｆを使用しており、成形性
は良好の（◎）であった。中空セラミック微小球Ｆは、
微小球Ａ〜Ｅに比べてＣａＯ量が高く１．３質量％含有
していることから、得られたコージェライト焼成体のＣ
ａＯ濃度も高くなったため、熱膨張係数が１１．３×１
０-7／℃とやや高めとはなっているが、可燃性物質の造
孔剤を添加していないことから、焼成条件ａ〜ｃのいず
れの条件でも焼成によるクラックや溶損もなく、品質の
安定したものが得られている。試験Ｎｏ．１９〜２３は
比較例で、可燃性物質の造孔剤を使用した例である。こ
れらは、いずれも成形性は良好であった。試験Ｎｏ．１
９、２０の小麦粉を造孔剤として使用した場合、試験Ｎ
ｏ．２０では、小麦粉を１０質量％加えたことから、焼
成条件ａ、ｂ、ｃのいずれの条件でも焼成体にクラック
が発生した。一方、試験Ｎｏ．１９では小麦粉の添加量
が５質量％になっていることから、焼成条件ａではクラ
ック発生しているものの、焼成条件ｂ、ｃではクラック
は発生しなくなっているが、気孔率が３８．２％でディ
ーゼルパティキュレートフィルタとして使用するには、
気孔率が不足している。また試験Ｎｏ．２１のグラファ
イトを使用した場合、焼成条件ａ、ｂ、ｃのいずれの条
件でも焼成体にクラックが発生すると共に、溶損不良が
発生した。試験Ｎｏ．２２、２３の有機発泡剤を造孔剤
として使用した場合、試験Ｎｏ．２３では、有機発泡剤
を５質量％加えたことから、焼成条件ａ、ｂ、ｃのいず
れの条件でも焼成体にクラックが発生した。一方、試験
Ｎｏ．２２では有機発泡剤の添加量が２．５質量％にな
っていることから、焼成条件ａではクラック発生してい
るものの、焼成条件ｂ、ｃではクラックは発生しなくな
っているが、気孔率が３９．６％でディーゼルパティキ
ュレートフィルタとして使用するには、気孔率が不足し
ている。試験Ｎｏ．２４、２５は本発明の実施例で、中
空セラミックス微小球と、可燃性物質の造孔剤を組合せ
使用した例である。試験Ｎｏ．２４では、ＳｉＯ２、Ａ
ｌ２Ｏ３を主成分とする中空セラミックス微小球Ｂ、そ
の他のコージェライト化原料及び小麦粉５質量％を使用
している。小麦粉を単独で使用した試験Ｎｏ．１９に比
べて、中空セラミックス微小球を使用していることか
ら、４９．３％の高気孔率が得られ、ディーゼルパティ
キュレートフィルタとして使用しうる特性が得られるよ
うになった。また試験Ｎｏ．２５では、ＳｉＯ２、Ａｌ
２Ｏ３を主成分とする中空セラミックス微小球Ｂ、その
他のコージェライト化原料及び有機発泡剤２．５質量％
を使用している。有機発泡剤を単独で使用した試験Ｎ
ｏ．２２に比べて、中空セラミックス微小球を使用して
いることから、５１．２％の高気孔率が得られ、ディー
ゼルパティキュレートフィルタとして使用しうる特性が
得られるようになった。以上試験Ｎｏ．２４、２５で示
したように、焼成過程でのクラック発生に影響を与えな
い範囲での可燃性物質造孔剤と中空セラミックス微小球
の併用も可能である。Test No. Reference numeral 17 denotes a comparative example of the present invention, in which hollow ceramic microspheres having SiO 2 and Al 2 O 3 as main components are used, and hollow ceramic microspheres E having a large average particle diameter of 321 μm are used. Therefore, microspheres were clogged in the mold slit during extrusion molding, and it was difficult to obtain a honeycomb structure having no cell defects, and the evaluation could not be performed. On the other hand, Test No. In Test No. 18, Test No. As in 9 to 16, the hollow ceramic microspheres F mainly composed of SiO 2 and Al 2 O 3 were used, and the moldability was good (◎). Hollow ceramic microspheres F
Since the CaO content is higher than that of the microspheres A to E and contains 1.3% by mass, the obtained cordierite fired body C
Since the aO concentration also increased, the thermal expansion coefficient was 11.3 × 1
Although it is slightly higher than 0 -7 / ° C, no cracking or melting damage due to sintering was observed under any of the sintering conditions a to c because no pore-forming agent of a flammable substance was added. Are stable. Test No. 19 to 23 are comparative examples, in which a combustible substance pore former was used. All of these had good moldability. Test No. 1
When the flours 9 and 20 were used as pore-forming agents, the test N
o. In No. 20, cracks occurred in the fired body under any of the firing conditions a, b, and c because the flour was added at 10% by mass. On the other hand, Test No. In 19, since the amount of added flour was 5% by mass, cracks were not generated under firing conditions a, but cracks were not generated under firing conditions b and c, but the porosity was 38.2%. To use as a diesel particulate filter in
Poor porosity. Test No. In the case of using graphite No. 21, cracks occurred in the fired body under any of the firing conditions a, b, and c, and defective erosion occurred. Test No. When the organic foaming agents of Nos. 22 and 23 were used as pore-forming agents, Test Nos. In No. 23, since the organic foaming agent was added at 5% by mass, cracks occurred in the fired body under any of the firing conditions a, b, and c. On the other hand, Test No. In No. 22, since the addition amount of the organic foaming agent was 2.5% by mass, cracks occurred under the firing conditions a, but no cracks occurred under the firing conditions b and c. Porosity is insufficient for use as a diesel particulate filter at 39.6%. Test No. Reference numerals 24 and 25 show embodiments of the present invention, in which hollow ceramic microspheres are used in combination with a combustible material pore former. Test No. 24, SiO 2 , A
hollow ceramic microspheres composed mainly of l 2 O 3 B, using other 5 mass% of the cordierite-forming raw material, and wheat flour. Test No. 1 using flour alone. Since the hollow ceramic microspheres were used as compared with No. 19, a high porosity of 49.3% was obtained, and characteristics that could be used as a diesel particulate filter were obtained. Test No. 25, SiO 2 , Al
Hollow ceramic microspheres B mainly composed of 2 O 3 , other cordierite-forming raw materials, and 2.5% by mass of an organic foaming agent
You are using Test N using organic foaming agent alone
o. Compared to No. 22, the use of hollow ceramic microspheres resulted in a high porosity of 51.2%, and characteristics that could be used as a diesel particulate filter were obtained. Test No. As shown by 24 and 25, a combustible substance pore former and hollow ceramic microspheres can be used together within a range that does not affect the generation of cracks during the firing process.
【００２０】[0020]
【発明の効果】以上の説明から明らかなように、本発明
によれば、気孔率の大きい多孔質コージェライトハニカ
ム構造体を得る際に、原料粉末に中空セラミックス微小
球を使用していることから、昇温過程での可燃性物質造
孔剤によるクラックや溶損発生もなく、ディーゼルパテ
ィキュレートフィルタとして好適な多孔質セラミックハ
ニカム構造体を得ることができる。As is apparent from the above description, according to the present invention, when a porous cordierite honeycomb structure having a high porosity is obtained, hollow ceramic microspheres are used as a raw material powder. In addition, a porous ceramic honeycomb structure suitable as a diesel particulate filter can be obtained without cracks or melting damage caused by the combustible material pore former during the temperature raising process.
【図１】（ａ）及び（ｂ）はそれぞれハニカム構造体を
使用したフィルターの一例を示す正面図及び側面図であ
る。FIGS. 1A and 1B are a front view and a side view showing an example of a filter using a honeycomb structure.
【図２】本発明に係わる中空セラミックス微小球の顕微
鏡写真である。FIG. 2 is a micrograph of a hollow ceramic microsphere according to the present invention.
【図３】本発明に係わる中空セラミックス微小球の断面
顕微鏡写真である。FIG. 3 is a cross-sectional micrograph of a hollow ceramic microsphere according to the present invention.
【図４】は実施例で使用した焼成条件を示す図である。FIG. 4 is a diagram showing firing conditions used in Examples.
１ セラミックハニカム構造体、 ２ 隔壁、 ３ 貫
通孔、４ セラミックハニカムフィルタ、５ 封じ材Reference Signs List 1 ceramic honeycomb structure, 2 partition wall, 3 through hole, 4 ceramic honeycomb filter, 5 sealing material
フロントページの続き Ｆターム(参考） 3G090 AA02 4D019 AA01 BA05 BB06 BD01 CA01 CB06 4G019 LB01 LC11 Continued on the front page F term (reference) 3G090 AA02 4D019 AA01 BA05 BB06 BD01 CA01 CB06 4G019 LB01 LC11
Claims (5)
クス微小球を５０質量％以下含有するセラミックス原料
粉末を使用することを特徴とする多孔質セラミックハニ
カム構造体の製造方法。1. A method for producing a porous ceramic honeycomb structure, comprising using a ceramic raw material powder containing 50% by mass or less of hollow ceramic microspheres having an average particle size of 300 μm or less.
クス微小球の含有量が２質量％以上４０質量％以下であ
ることを特徴とする請求項１記載の多孔質セラミックハ
ニカム構造体の製造方法。2. The method for producing a porous ceramic honeycomb structure according to claim 1, wherein the content of the hollow ceramic microspheres in the ceramic raw material powder is 2% by mass or more and 40% by mass or less.
率が４０％以上であることを特徴とする請求項１乃至２
記載の多孔質セラミックハニカム構造体の製造方法。3. The porous ceramic honeycomb structure according to claim 1, wherein the porosity is 40% or more.
A method for producing the porous ceramic honeycomb structure according to the above.
ミックス原料粉末がコージェライト化原料であることを
特徴とする請求項１乃至３記載の多孔質セラミックハニ
カム構造体の製造方法。4. The method for producing a porous ceramic honeycomb structure according to claim 1, wherein the ceramic raw material powder containing hollow ceramic microspheres is a cordierite forming raw material.
Ｏ２、Ａｌ２Ｏ３であり、且つ中空セラミックス微小球
のＦｅ２Ｏ３が１．５質量％以下、ＣａＯが１．０質量
％以下、ＴｉＯ２が２．５質量％以下であることを特徴
とする請求項１乃至４記載の多孔質セラミックハニカム
構造体の製造方法。5. The main component of the hollow ceramic microspheres is Si.
O 2 and Al 2 O 3 , and Fe 2 O 3 of the hollow ceramic microspheres is 1.5% by mass or less, CaO is 1.0% by mass or less, and TiO 2 is 2.5% by mass or less. The method for manufacturing a porous ceramic honeycomb structure according to any one of claims 1 to 4, wherein
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| JP2001131835A JP2002326881A (en) | 2001-04-27 | 2001-04-27 | Manufacturing method of porous ceramic |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001131835A JP2002326881A (en) | 2001-04-27 | 2001-04-27 | Manufacturing method of porous ceramic |
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| JP2002326881A true JP2002326881A (en) | 2002-11-12 |
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ID=18979947
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|---|---|---|---|
| JP2001131835A Pending JP2002326881A (en) | 2001-04-27 | 2001-04-27 | Manufacturing method of porous ceramic |
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| JP (1) | JP2002326881A (en) |
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| WO2004060830A1 (en) * | 2003-01-07 | 2004-07-22 | Ngk Insulators, Ltd. | Method of baking ceramic honeycomb structure |
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| JP2009502469A (en) * | 2005-07-29 | 2009-01-29 | サン−ゴバン サントル ドゥ ルシェルシェ エ デトゥードゥ ユーロペン | Method for producing porous structure using silica-based pore forming agent |
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