JP2014058749A - 無機繊維及びそれを用いた成形体 - Google Patents
無機繊維及びそれを用いた成形体 Download PDFInfo
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- JP2014058749A JP2014058749A JP2012203414A JP2012203414A JP2014058749A JP 2014058749 A JP2014058749 A JP 2014058749A JP 2012203414 A JP2012203414 A JP 2012203414A JP 2012203414 A JP2012203414 A JP 2012203414A JP 2014058749 A JP2014058749 A JP 2014058749A
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- inorganic fiber
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- inorganic
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
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- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
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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
- F01N3/24—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 constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
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- F16L59/028—Composition or method of fixing a thermally insulating material
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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
- F01N3/24—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 constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2839—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
- F01N3/2853—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration using mats or gaskets between catalyst body and housing
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Abstract
【解決手段】Al2O3:43.2〜53.0モル%、SiO2:12.8〜25.2モル%、CaO:26.0〜40.0モル%含み、これら成分の合計が98モル%以上である無機繊維。より好ましくは、Al2O3:43.2〜51.2モル%、SiO2:12.8〜20.8モル%、CaO:32.0〜40.0モル%の組成を有する無機繊維。さらに好ましくは、Al2O3:44.2〜50.2モル%、SiO2:13.8〜19.8モル%、CaO:33.0〜39.0モル%の組成を有する無機繊維。
【選択図】なし
Description
1.以下の組成を有する無機繊維。
Al2O3 43.2〜53.0モル%
SiO2 12.8〜25.2モル%
CaO 26.0〜40.0モル%
上記成分の合計は98モル%以上である。
2.以下の組成を有する1記載の無機繊維。
Al2O3 43.2〜51.2モル%
SiO2 12.8〜20.8モル%
CaO 32.0〜40.0モル%
3.以下の組成を有する1又は2記載の無機繊維。
Al2O3 44.2〜50.2モル%
SiO2 13.8〜19.8モル%
CaO 33.0〜39.0モル%
4.ヨシオカイト構造を有する1〜3のいずれか記載の無機繊維。
5.1〜4のいずれか記載の無機繊維を含む成形体。
6.クッション材又は保持材である5記載の成形体。
7.触媒担体と、触媒担体を収容するケーシングとの間隙に介装される保持材である6記載の成形体。
8.0.3g/cm3の充填密度及び12.5%の開放率における1,000サイクル試験後に1.2N/cm2以上である開放面圧(i)、又は、
0.3g/cm3の充填密度及び8%の開放率における1,000サイクル試験後に2.0N/cm2以上である開放面圧(ii)を、有する5〜7のいずれか記載の成形体。
9.前記開放面圧(i)と前記開放面圧(ii)を共に有する8記載の成形体。
Al2O3 43.2〜53.0モル%
SiO2 12.8〜25.2モル%
CaO 26.0〜40.0モル%
上記成分の合計は98モル%以上である。
Al2O3 43.2〜51.2モル%
SiO2 12.8〜20.8モル%
CaO 32.0〜40.0モル%
上記成分の合計は98モル%以上である。
Al2O3 44.2〜50.2モル%
SiO2 13.8〜19.8モル%
CaO 33.0〜39.0モル%
上記成分の合計は98モル%以上である。
Al2O3 57.4〜65.4質量%
SiO2 8.9〜16.9質量%
CaO 21.7〜29.7質量%
上記成分の合計は98質量%以上である。
より好ましくは、
Al2O3 58.4〜64.4質量%
SiO2 9.9〜15.9質量%
CaO 22.7〜28.7質量%
上記成分の合計は98質量%以上である。
上記の無機繊維は、好ましくは、CaOを25モル%超えて含む。
上記の無機繊維は、Al2O3を50質量%未満とすることができる。
上記の無機繊維は、Al2O3、SiO2、CaOの合計を、99モル%以上又は100モル%(不可避不純物を含む)とすることができる。
ヨシオカイト構造を有することは、X線回折測定により観測することができる。
また、好ましくは、0.3g/cm3の充填密度における圧縮面圧(冷却時の面圧に相当)が13.0N/cm2以上である。圧縮面圧が高ければ開放面圧も高い傾向があるため、圧縮面圧は高ければ高い方が好ましい。
開放面圧及び圧縮面圧は実施例に記載の方法で測定する。
面圧残存率は実施例に記載の方法で測定できる。
面圧残存率は、繊維脆さの指標である。残存率が低いと繊維が脆く、耐久にて面圧低下する可能性がある。
耐熱性は実施例に記載の方法で測定できる。
溶解速度定数は実施例に記載の方法で測定できる。
水性媒体としては、水が好ましく、溶液の安定性を向上させたり、紡糸の安定性を向上させるために、水を主成分として水に可溶な他の媒体、例えばアルコール類、ケトン類、アミン類、アミド類、カルボン酸類等を添加したものであってもよい。また、これらの媒体に対して塩化アンモニウム等の有機塩を添加したものであってもよい。
焼成温度は、800℃以上液相生成温度未満が好ましく、900℃以上液相生成温度未満がより好ましく、1000℃以上液相生成温度未満がさらに好ましい。焼成時間は、所望する無機繊維が得られれば特に制限はなく、適宜設定されればよい。
尚、得られる無機繊維にはO(酸素)単独として現われるバランス成分が含まれる場合があるが、この場合はバランス成分を除いた金属酸化物の合計値が100モル%(100質量%)となるように、補正計算を行うものとする。
尚、本出願書類において、無機繊維の平均繊維径は、走査型電子顕微鏡(日本電子製 JSM‐5800LV)により撮影した写真(倍率500〜2000倍)から無作為に100〜400本選定して繊維の幅を計測し、これ等の幅から算出した平均値を意味する。
具体的には、ゴム類の例としては、n−ブチルアクリレートとアクリロニトリルの共重合体、エチルアクリレートとアクリロニトリルの共重合体、ブタジエンとアクリロニトリルの共重合体、ブタジエンゴム等が挙げられる。水溶性有機高分子化合物の例としては、カルボキシメチルセルロース、ポリビニルアルコール等が挙げられる。熱可塑性樹脂の例としては、アクリル酸、アクリル酸エステル、アクリルアミド、アクリロニトリル、メタクリル酸、メタクリル酸エステル等の単独重合体及び共重合体、アクリロニトリル・スチレン共重合体、アクリロニトリル・ブタジエン・スチレン共重合体等が挙げられる。熱硬化性樹脂としては、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂等が挙げられる。有機バインダーの使用量は、通常、無機繊維100質量部に対して0.1〜10質量部である。
開放面圧(i)と開放面圧(ii)は実施例記載の方法で測定できる。
具体的には、無機繊維と少量の有機バインダーとを湿式成形した後、圧縮した状態で乾燥した圧縮マットを製造する方法、無機繊維を集綿したものをニードル加工したブランケットからマットを製造する方法等幾つかの異なる方法が挙げられる。
この場合の、保持材の製法は、無機繊維とバインダーと膨張材としてバーミキュライトとを任意の比率にて配合した水性スラリーを、湿式成形した後、乾燥すればよい。
触媒担体12が保持材13によって保持された状態の斜視図を図2に示す。
保持材の形状の一例(平面図)を図3(A)に示す。平板状の本体部41において、その一端に凸部42が形成され、他端に凸部42と嵌合可能な形状の凹部43が形成されている。尚、凸部42及び凹部43の形状は、図示される矩形の他に、三角形や半円形状であってもよい。また、凸部42及び凹部43の個数も1個には限定されず、2個以上であってもよい。
図3(B)に示すように、触媒担体12の外周面に本体41を巻き付け、凸部42と凹部43とを係合させることで本体41を触媒担体12に巻装する。
保持材の厚さには特に制限はないが、例えば6〜12mmである。
得られる無機繊維が表1,2の組成となるように、アルミニウム源として塩基性塩化アルミニウム(多木化学(株)製タキバイン)、カルシウム源として硝酸カルシウム(和光純薬工業(株)製)、ケイ素源としてアニオン性コロイダルシリカ(日産化学工業(株)製スノーテックスO)、紡糸助剤として部分けん化ポリビニルアルコール((株)クラレ製PVA217)を用い、液体媒体として水を用いて紡糸原料溶液を調製した。
尚、固形分換算したときに、上記塩基性塩化アルミニウム、硝酸カルシウム及びアニオン性コロイダルシリカの合計含有量100質量部に対し、紡糸助剤を10質量部加えた。
無機繊維を、初期高さから30%圧縮したときに、もとの位置に復元するものを○とし、復元はするが繊維破壊により粉落ちが発生するものを△とした。さらに、圧縮したときにもとの位置に復元しなかったものを×とした。
結晶構造は、RIGAKU(株)製X線回折装置 RINT-UltimaIIIにて、多目的試料高温装置を用いて、1100℃に加熱保持しながら測定した。
耐熱性は、SEIKO電子工業(株)製TMA320にて、空のPtパンの中に得られた無機繊維を20mg〜30mg充填し、所定の負荷荷重を加えた状態で1200℃まで加熱し、熱膨張率が急激に低下する前後2点の変曲点から算出した。
面圧を万能試験機で測定した。具体的には、0.094gの無機繊維を、圧縮盤上に静置した直径10.2mmの容器中に詰めた状態で、上部から圧縮棒により徐々に圧縮し、無機繊維の充填密度が0.30g/cm3に達した荷重(圧縮力)を圧縮面圧として得た。その状態から、上記圧縮棒による荷重(圧縮力)を徐々に低減し、圧縮盤と圧縮棒とのGap(距離)をX(mm)としたときに、圧縮盤と圧縮棒との距離がX+0.125X(mm)になったとき(圧縮盤と圧縮棒とのGap開放率が12.5%(充填密度0.267g/cm3)になるまで)の荷重(圧縮力)を開放面圧として得た。
上記の方法で得た圧縮面圧と開放面圧から、下記式により算出した。
面圧残存率(%)={(距離X+0.125Xにおける面圧(Pa))/(距離Xにおける面圧(Pa))×100
繊維を、メンブレンフィルター上に置き、繊維上にマイクロポンプによりpH4.5及びpH7.4の生理食塩水を滴下させ、繊維、フィルターを通った濾液を容器内に貯めた。貯めた濾液を24時間経過後に取り出し、溶出成分をICP発光分析装置により定量し、溶解度及び溶解速度定数を算出した。測定元素はAl、Si、Caの3元素である。尚、繊維径を測定して単位表面積・単位時間当たりの溶出量である溶解速度定数(単位:ng/cm2・h)に換算した。
実施例2及び比較例6の無機繊維を用いて保持材を製造した。無機繊維100質量部に対し、有機バインダーとしてフィブリル化したパルプを0.8質量部、水を4000質量部含む水性スラリーを作製し、これを脱水成形して湿式マットを得た。この湿式マットを圧縮しながら170℃で乾燥することにより、マット(保持材)(密度0.12g/cm3)を得た。得られたマットを700℃で加熱し、脱バインダー処理した。これらマットの耐熱性、溶解性は、無機繊維と対応するものであった。
特に自動車は、冷却−膨張を繰返し使用されるため、繰返し圧縮試験における開放率12.5%での面圧値が重要となる。
11 ケーシング
12 触媒担体
13 保持材
16 導入管
17 排出管
41 本体部
42 凸部
43 凹部
Claims (9)
- 以下の組成を有する無機繊維。
Al2O3 43.2〜53.0モル%
SiO2 12.8〜25.2モル%
CaO 26.0〜40.0モル%
上記成分の合計は98モル%以上である。 - 以下の組成を有する請求項1記載の無機繊維。
Al2O3 43.2〜51.2モル%
SiO2 12.8〜20.8モル%
CaO 32.0〜40.0モル% - 以下の組成を有する請求項1又は2記載の無機繊維。
Al2O3 44.2〜50.2モル%
SiO2 13.8〜19.8モル%
CaO 33.0〜39.0モル% - ヨシオカイト構造を有する請求項1〜3のいずれか記載の無機繊維。
- 請求項1〜4のいずれか記載の無機繊維を含む成形体。
- クッション材又は保持材である請求項5記載の成形体。
- 触媒担体と、触媒担体を収容するケーシングとの間隙に介装される保持材である請求項6記載の成形体。
- 0.3g/cm3の充填密度及び12.5%の開放率における1,000サイクル試験後に1.2N/cm2以上である開放面圧(i)、又は、
0.3g/cm3の充填密度及び8%の開放率における1,000サイクル試験後に2.0N/cm2以上である開放面圧(ii)を、有する請求項5〜7のいずれか記載の成形体。 - 前記開放面圧(i)と前記開放面圧(ii)を共に有する請求項8記載の成形体。
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MX2008000323A (es) * | 2005-06-30 | 2008-04-07 | Unifrax I Llc | Fibras inorganicas revestidas de fosfato y metodos de preparacion y uso. |
ATE476396T1 (de) * | 2005-11-10 | 2010-08-15 | Morgan Crucible Co | Hochtemperaturfeste fasern |
GB0522980D0 (en) * | 2005-11-10 | 2005-12-21 | Morgan Crucible Co | High temperature resistant fibres |
JP4922861B2 (ja) * | 2007-08-10 | 2012-04-25 | ニチアス株式会社 | 触媒コンバーター用保持材 |
EP2188505B1 (en) * | 2007-08-31 | 2019-05-15 | Unifrax I LLC | Mounting mat for exhaust gas treatment device and exhaust gas treatment device |
GB0809462D0 (en) * | 2008-05-23 | 2008-07-02 | Morgan Crucible Co | Inorganic fibre compositions |
WO2010092668A1 (ja) * | 2009-02-10 | 2010-08-19 | イビデン株式会社 | ハニカム構造体用シール材、ハニカム構造体、及び、ハニカム構造体の製造方法 |
JP5883227B2 (ja) | 2010-02-25 | 2016-03-09 | ニチアス株式会社 | 無機繊維 |
WO2012114565A1 (ja) * | 2011-02-24 | 2012-08-30 | ニチアス株式会社 | 無機繊維 |
US9302947B2 (en) * | 2012-01-31 | 2016-04-05 | Nichias Corporation | Inorganic fiber and process for manufacturing same |
-
2012
- 2012-09-14 JP JP2012203414A patent/JP5272103B1/ja active Active
-
2013
- 2013-08-27 CN CN201380047801.7A patent/CN104769169B/zh active Active
- 2013-08-27 US US14/427,494 patent/US20150210598A1/en not_active Abandoned
- 2013-08-27 WO PCT/JP2013/005041 patent/WO2014041753A1/ja active Application Filing
- 2013-08-27 EP EP13836398.1A patent/EP2896727B1/en active Active
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016136258A1 (ja) * | 2015-02-25 | 2016-09-01 | ニチアス株式会社 | 保持材、その製造方法及びそれを用いた気体処理装置 |
CN107250500A (zh) * | 2015-02-25 | 2017-10-13 | 霓佳斯株式会社 | 保持材料、其制造方法以及使用其的气体处理装置 |
JPWO2016136258A1 (ja) * | 2015-02-25 | 2017-12-07 | ニチアス株式会社 | 保持材、その製造方法及びそれを用いた気体処理装置 |
US10422060B2 (en) | 2015-02-25 | 2019-09-24 | Nichias Corporation | Retainer material, manufacturing method thereof, and gas treatment device using the same |
KR101724233B1 (ko) * | 2016-05-27 | 2017-04-11 | 주식회사 나노 | 성형성이 우수한 시트형 카트리지 및 이를 포함하는 대기오염 저감용 촉매 담체 |
Also Published As
Publication number | Publication date |
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EP2896727B1 (en) | 2017-11-08 |
EP2896727A4 (en) | 2016-04-27 |
US20150210598A1 (en) | 2015-07-30 |
EP2896727A1 (en) | 2015-07-22 |
CN104769169A (zh) | 2015-07-08 |
CN104769169B (zh) | 2016-10-19 |
JP5272103B1 (ja) | 2013-08-28 |
WO2014041753A1 (ja) | 2014-03-20 |
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