JPS6316353B2 - - Google Patents
Info
- Publication number
- JPS6316353B2 JPS6316353B2 JP53095521A JP9552178A JPS6316353B2 JP S6316353 B2 JPS6316353 B2 JP S6316353B2 JP 53095521 A JP53095521 A JP 53095521A JP 9552178 A JP9552178 A JP 9552178A JP S6316353 B2 JPS6316353 B2 JP S6316353B2
- Authority
- JP
- Japan
- Prior art keywords
- binder
- sheet
- sheet material
- inorganic
- ceramic
- 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.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 44
- 239000011230 binding agent Substances 0.000 claims description 28
- 239000010455 vermiculite Substances 0.000 claims description 9
- 229910052902 vermiculite Inorganic materials 0.000 claims description 9
- 235000019354 vermiculite Nutrition 0.000 claims description 9
- 239000002657 fibrous material Substances 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 239000012784 inorganic fiber Substances 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 description 11
- 239000000835 fiber Substances 0.000 description 8
- 239000000123 paper Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010425 asbestos Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052895 riebeckite Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229940037003 alum Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
- D21H5/18—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of inorganic fibres with or without cellulose fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/001—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing unburned clay
-
- 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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/38—Inorganic fibres or flakes siliceous
- D21H13/44—Flakes, e.g. mica, vermiculite
Description
【発明の詳細な説明】
本発明は耐熱性があり、膨張後弾性があり、か
つ良好な引張強さを保持する可撓性膨張性シート
物質に関連する。
触媒反応装置は空気汚染を抑制するため自動車
排気中の(1)一酸化炭素と炭化水素の酸化、及び(2)
窒素酸化物の還元に必要であることが認められて
いる。これらの触媒反応過程で発生する比較的高
温度のため通常触媒支持体としてセラミツク材料
が選択される。特に有用な支持体の例は米国再発
行特許第27747号明細書に記述されるようなセラ
ミツク製蜂の巣構造体である。
セラミツク支持体は脆弱で、又金属容器の熱膨
張率と著しく異なる熱膨張率を有するものが多
い。従つてこのセラミツク体の容器内への装着に
は衝突と振動による機械的衝撃及び循環的熱変化
による熱衝撃に対する抵抗性が必要である。これ
らの熱衝撃及び機械的衝撃はセラミツク支持体を
劣化する恐れがあり、一度劣化が起こると急速に
進んで最終的には使用不能になる。米国特許第
3916057号明細書には上記目的に対する有用な充
填物質が示され、この充填物質は本質的に30〜80
％（以下すべて重量％）の膨張性物質、０〜60％
の無機繊維物質、10〜70％の無機結合剤、及び無
機結合剤に対して任意の少量、例えば約0.4又は
それ以下の比率の有機結合剤で構成される。しか
し、前記米国特許の充填物質は、シート材料の成
形時に排水時間が長い欠点がある。他の有用な物
質には30〜75％の膨張性物質、20〜65％の無機繊
維物質、及び５〜20％の有機エラストマー結合剤
（1974年11月４日提出の特許出願第520675号及び
1976年６月25日提出の特許出願第699787号に記述
されている）からなる組成物である。上記の両種
物質で、無機結合剤を使用すると得られるシート
物質が幾分堅くなつて小さい直径の輸送用ロール
に巻くことが困難になり、又有機結合剤を使用す
ると加熱後の所望引張強さが得られない欠点があ
ることが判明した。
本発明の目的は、厚さが少くとも約2.5mmの場
合でもき裂を生ずることなく半径５cm又はそれ以
下のロール状に巻くことができ、排水時間を短縮
できると共に、膨張後良好な引張強さを保持する
可撓性膨張性シート物質、を製作することにあ
る。他の目的は下記説明から明らかになろう。
本発明により、約40〜75％の未膨張ひる石、約
15〜35％の無機繊維物質、及び0.5〜1.5の比率の
有機結合剤と無機結合剤との組合せ結合剤、約10
〜25％で可撓性膨張性シート物質を作ることがで
きることが発見された。このシート物質は製紙技
術によつて約0.5〜６mmの任意の厚さに製作する
ことができる。
有機結合剤は種々の重合体と、ラテツクス型エ
ラストマー、例えば天然ゴムラテツクス、スチレ
ン―ブタジエンラテツクス、ブタジエン―アクリ
ロニトリルラテツクス、アクリル酸エステル、メ
タクリル酸エステル重合体及び共重合体等のラテ
ツクスを包含する。
無機結合剤はベントナイトである。
上記の可撓性膨張性物質は現位置（in situ）
の膨張によつて装着用材料として自動車排気用触
媒反応変換器に利用される。この膨張シートは変
換容器即ちカニスター内の所定位置にセラミツク
コア即ち触媒支持体を保持する。膨張後の膨張性
シートの熱安定性と弾性は、金属カニスターとセ
ラミツク基質の熱膨張の差異、脆弱なセラミツク
装置に伝達される振動、及び金属表面又はセラミ
ツク表面の凹凸を補償する。
上記のシート物質は手抄き又は機械抄きの何れ
かの標準的製紙技術によつて作られるが、摩砕物
質の集合体であるウエブには粒子が均一に分散す
るように適当な注意を払わなければならない。こ
のシート物質は所望によつて選択されるクラフト
紙、プラスチツクフイルム、合成繊維不織布等の
裏張りシートと一時的に積層する。粒径が約0.1
〜６mm、好適には約２mm以下の選鉱した未膨張ひ
る石鉱石フレーク約40〜75％を大量の水の中で、
約15〜35％の無機繊維物質、例えばクリソタイル
アスベスト又はアンフイボールアスベスト；チヨ
ツプド・イー・ガラスの商品名の軟質ガラス繊
維、ジルコニア―シリカ繊維、結晶アルミナウイ
スカー（ひげ結晶）繊維及びアルミノケイ酸塩繊
維（フアイバーフラツクス（Fiberfrax）、セラフ
アイバー（Cerafiber）及びカオウール
（Kaowool）の商品名で市販されている）の固形
物と、上記のように0.5〜1.5の比率の有機エラス
トマー結合剤と無機結合剤からなる結合剤約10〜
25％とを混合する。又少量の界面活性剤、泡立て
剤及び凝集剤をシート形成前に添加してもよい。
凝集は電解質、例えばミヨウバン、バリウム
塩、非イオン性アリールアミド高分子電解質（商
品名セパラン（Separan）NP―10のダウケミカ
ル社製）を使用して良好に行われる。ひる石、無
機繊維物質及び結合剤は重量で５〜100倍程度の
大量の水の中で混合し、次に凝集剤又は他の添加
剤を添加する。又少量の界面活性剤又は泡立て剤
を本発明の範囲内でひる石分散を良好にするため
使用できる。上記のシート物質を作る際に、健康
障害の恐れがあるアスベストの使用を避けるため
に、ガラス繊維物質又は耐火性（結晶性又は非結
晶性）繊維又はウイスカー繊維を使用してもシー
ト物質の特性を低下することはない。一般に、ア
スベスト繊維は他の繊維より廉価である。
上記のシート物質は手抄き用器具又は長網式抄
紙機スクリーンを使用する標準的製紙技術で作る
ことができる。0.5〜1.5の比率の有機結合剤と無
機結合剤との組合せ結合剤を使用すると、シート
物質形成の際に無機結合剤を単独で使用するより
も排水が良好に行われる。得られた未乾燥シート
物質を圧縮して約90℃に乾燥すると約0.5ｇ/ml又
はそれ以上の乾燥重量密度が得られ、手で取り扱
うことができ、又容易に曲げられる弾性を有する
膨張性シート物質になる。幅約2.5cm、厚さが1.5
〜3.0mmのシート物質のストリツプは約0.5〜2.0Kg
又はそれ以上の荷重を支持する性能があり、き裂
を生ずることなく約4.5〜６cmの半径に曲げるこ
とができる。本発明の膨張性シート物質は500〜
800℃の温度の焼成で膨張する。勿論、ある有用
な組成物、即ちシート物質は大きい半径に曲げる
ことができ、これが厚ければ小さい半径に曲げる
ことができないが、厚さが薄ければ小さい半径に
曲げることができる。
本発明の膨張性シート物質は膨張性能のため有
用である。従つてこのシート物質形成時の未乾燥
状態の厚さと加熱乾燥後の厚さとを測定すること
により膨張性が示され、この膨張性は使用したひ
る石の濃度によつて変わるが約165〜300％のオー
ダーである。本発明のシート物質に得られる加熱
乾燥後の良好な引張強きは、特に充分に膨張した
場合の振動及び機械的衝撃に対する優れた抵抗性
を示すものと考えられる。
膨張性充填物質をセラミツク構造体に使用する
場合には、膨張性シートの膨張間に剛性容器に作
用する力がセラミツク基質を圧滑する程度に充分
大きいことに注意すべきである。従つて上記の膨
張性シート物質を設計しかつ使用する際にはシー
ト物質の厚さ、膨張性及びセラミツク基質と容器
間の隙間を考慮しなければならない。
上記に本発明を概説したが、下記に本発明の実
施例を説明する。この例は本発明を実施する最良
態様を示すものである。
例 １
本発明のシート物質の一般的な製作方法は次の
通りである：
35℃の水（2500ml）を大型ワーリングブレンダ
ーの混合室内に入れ、低速度で撹拌し、これに所
望量の有機結合剤と所要量のベントナイト（テキ
サス州のドレツサー・インダストリーズ社製のイ
エローストーンベントナイトクレー）に対して40
％の量の57―ブタジエン―10―スチレン―33―ア
クリロニトリルラテツクス（グツドイヤ・ケミカ
ル・デイビジヨン社製、商標：ケミガム
（Chemigam）3077）を添加する。数秒間撹拌後、
所望量の無機繊維物質（例えばカーボランダム社
製フアイバーフラツクス）を添加し、１分間高速
度で撹拌後、未膨張ひる石鉱石（ダブリユー・ア
ール・グレース社製の直径0.4〜1.7mmの第４級ひ
る石：商品名ゾノライト（Zonolite））を徐々に
添加し、更に約15秒間撹拌を継続する。この懸濁
液に、30mlの10％ミヨウバン溶液と10mlの１％セ
バランNP―10溶液を添加して凝集させ、約10秒
間混合する。得られた懸濁液を手抄き用器で約19
×20cm即ち総面積約380cm2の手抄シートに成形し、
このシートを吸取紙の間に入れて約10ｇ/cm2の圧
力で圧縮して水を除去し、次にこれを普通の写真
印画紙用乾燥器で乾燥する。
上記のような一連のランを、ひる石、無機繊維
物質（フアイバーフラツクス）、及び有機結合剤
と無機結合剤の配合比率を変えて行う。又比較の
ために有機結合剤又は無機結合剤を配合しないラ
ンも行う。これら２種のランをそれぞれＡとＢの
文字で示し、他のランを数字で示す。重量部、即
ち使用物質のグラム数、有機結合剤対無機結合剤
の比率、更に排水時間（秒）、半径約4.5cmの湾曲
（＋記号は可撓性を、又−記号はき裂発生を示
す）、幅2.5cmのストリツプのKgで表わした引張強
さ、650℃、15分間の焼成前後のシート物質の厚
さ（mm）及び測定した膨張率を下記第１表に示
す。数字と文字“ａ”で示されるランは、配合を
半量にしてシート物質の厚さを約半分にしたラン
を示す。そのために排水時間、引張強さ及び厚さ
は“ａ”のないランの約1/2である。
第１表から、ランＡは非常に長い排水時間のた
め、又ランＢは焼成後の低い引張強さのため、ラ
ンＡ及びＢは所望特性範囲外にあることがわか
る。同様にラン14も引張強さが非常に低いため本
発明の範囲外にある。ラン５、６及び７は所望の
可撓性を有しないから本発明の範囲外にある。ラ
ン４、８及び９は有機結合剤対無機結合剤の比率
の下限を示し、これらすべてのランは厚さが大き
い（約３mm）場合には半径4.5cmに曲げることが
困難であるが、シート物質は薄く（厚さ約1.5mm）
なれば充分な可撓性が得られる。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to flexible expandable sheet materials that are heat resistant, resilient after expansion, and retain good tensile strength. Catalytic reactors are used to reduce air pollution by (1) oxidizing carbon monoxide and hydrocarbons in automobile exhaust, and (2)
It has been recognized that it is necessary for the reduction of nitrogen oxides. Because of the relatively high temperatures that occur during these catalytic reaction processes, ceramic materials are commonly selected as catalyst supports. An example of a particularly useful support is a ceramic honeycomb structure, such as that described in US Patent Reissue No. 27,747. Ceramic supports are fragile and often have coefficients of thermal expansion that are significantly different from those of metal containers. Therefore, the ceramic body must be resistant to mechanical shocks due to collisions and vibrations and thermal shocks due to cyclic thermal changes when installed in a container. These thermal and mechanical shocks can degrade the ceramic support, and once degradation occurs, it progresses rapidly and eventually becomes unusable. US Patent No.
No. 3,916,057 discloses a filler material useful for the above purpose, which filler material consists essentially of 30 to 80
% (all percentages by weight) of expansive substances, 0-60%
of inorganic fibrous material, 10-70% inorganic binder, and any minor amount of organic binder to inorganic binder, such as about 0.4 or less. However, the filling material of the above-mentioned US patent has the disadvantage of a long drainage time when forming a sheet material. Other useful materials include 30-75% intumescent material, 20-65% inorganic fibrous material, and 5-20% organic elastomer binder (see Patent Application No. 520,675 filed Nov. 4, 1974).
No. 699,787 filed June 25, 1976). For both of the above materials, the use of inorganic binders makes the resulting sheet material somewhat stiffer and difficult to roll onto small diameter transport rolls, and the use of organic binders increases the desired tensile strength after heating. It turns out that there are some drawbacks that cannot be obtained. The object of the present invention is to be able to roll into rolls with a radius of 5 cm or less without cracking even when the thickness is at least about 2.5 mm, to shorten drainage time, and to have good tensile strength after expansion. The purpose of the present invention is to fabricate a flexible, expandable sheet material that retains its strength. Other purposes will become apparent from the description below. According to the present invention, about 40-75% unexpanded vermiculite, about
15-35% inorganic fiber material and a combination binder of organic binder and inorganic binder in the ratio of 0.5-1.5, about 10
It has been discovered that flexible expandable sheet materials can be made with ~25%. This sheet material can be made to any thickness from about 0.5 to 6 mm by papermaking techniques. Organic binders include various polymers and latexes such as latex-type elastomers such as natural rubber latex, styrene-butadiene latex, butadiene-acrylonitrile latex, acrylic ester, methacrylic ester polymers and copolymers. The inorganic binder is bentonite. The above flexible expandable material is in situ.
When expanded, it is used as a mounting material in catalytic reaction converters for automobile exhaust. The expanded sheet holds the ceramic core or catalyst support in place within the conversion vessel or canister. The thermal stability and elasticity of the expandable sheet after expansion compensates for differences in thermal expansion between the metal canister and the ceramic substrate, vibrations transmitted to the fragile ceramic device, and irregularities in the metal or ceramic surface. The sheet materials described above are made by standard papermaking techniques, either hand or machine, but appropriate care is taken to ensure a uniform distribution of particles in the web, which is a collection of ground material. have to pay. This sheet material is temporarily laminated with a backing sheet of kraft paper, plastic film, synthetic nonwoven fabric, etc., as desired. Particle size is approximately 0.1
About 40-75% beneficent unexpanded vermiculite flakes of ~6 mm, preferably less than about 2 mm, are mixed in a large volume of water.
Approximately 15 to 35% of inorganic fibrous materials such as chrysotile asbestos or amphibol asbestos; soft glass fibers under the trade name Chopped E.Glass, zirconia-silica fibers, crystalline alumina whisker fibers and aluminosilicate fibers. (commercially available under the trade names Fiberfrax, Cerafiber and Kaowool) with an organic elastomer binder and an inorganic binder in a ratio of 0.5 to 1.5 as described above. A binder consisting of about 10~
Mix with 25%. Small amounts of surfactants, foaming agents and flocculants may also be added before sheet formation. Coagulation is successfully carried out using electrolytes such as alum, barium salts, non-ionic arylamide polyelectrolytes (manufactured by Dow Chemical under the trade name Separan NP-10). The vermiculite, inorganic fiber material and binder are mixed in a large volume of water, on the order of 5 to 100 times by weight, and then the flocculant or other additives are added. Small amounts of surfactants or foaming agents can also be used within the scope of the present invention to improve vermiculite dispersion. When making the above-mentioned sheet materials, in order to avoid the use of asbestos, which may pose a health hazard, glass fiber materials or refractory (crystalline or amorphous) fibers or whisker fibers may be used, but the characteristics of the sheet materials will not decrease. Generally, asbestos fibers are less expensive than other fibers. The sheet materials described above can be made using standard paper making techniques using hand paper machines or Fourdrinier paper machine screens. The use of a combination binder of organic binder and inorganic binder in a ratio of 0.5 to 1.5 provides better drainage than the use of inorganic binder alone during sheet material formation. The resulting wet sheet material is compressed and dried to about 90°C to give a dry weight density of about 0.5 g/ml or more, and is expandable with elasticity that allows for manual handling and easy bending. Becomes a sheet material. Approximately 2.5cm wide and 1.5cm thick
~3.0mm sheet material strip approximately 0.5~2.0Kg
or more, and can be bent to a radius of approximately 4.5 to 6 cm without cracking. The expandable sheet material of the present invention has a
It expands when fired at a temperature of 800℃. Of course, some useful compositions, ie, sheet materials, can be bent to large radii; if they are thick, they cannot be bent to small radii, but if they are thin, they can be bent to small radii. The expandable sheet materials of the present invention are useful for their expansion performance. Therefore, by measuring the thickness of this sheet material in an undried state and the thickness after heating and drying, the expansibility can be shown, and this expansibility varies depending on the concentration of vermiculite used, but is about 165 to 300. It is on the order of %. The good tensile strength after heat drying obtained in the sheet material of the present invention is believed to be indicative of its excellent resistance to vibration and mechanical shock, especially when fully expanded. When using expandable filler materials in ceramic structures, care should be taken that the forces acting on the rigid container during expansion of the expandable sheet are sufficiently large to compress the ceramic substrate. Therefore, when designing and using the above-described expandable sheet materials, consideration must be given to the thickness of the sheet material, its expandability, and the gap between the ceramic substrate and the container. Having outlined the invention above, examples of the invention are described below. This example illustrates the best mode of carrying out the invention. EXAMPLE 1 A general method for making the sheet material of the present invention is as follows: Water (2500 ml) at 35° C. is placed in the mixing chamber of a large Waring blender, stirred at low speed, and added with the desired amount of organic bonds. 40 for the agent and the required amount of bentonite (Yellowstone Bentonite Clay, manufactured by Dretsser Industries, Texas).
% of 57-butadiene-10-styrene-33-acrylonitrile latex (manufactured by Gudoiya Chemical Division, trademark: Chemigam 3077) is added. After stirring for a few seconds,
After adding the desired amount of inorganic fibrous material (e.g. Fiberflux manufactured by Carborundum) and stirring at high speed for 1 minute, unexpanded vermiculite ore (manufactured by W. R. Grace, with a diameter of 0.4-1.7 mm) is added. Gradually add vermiculite (trade name: Zonolite) and continue stirring for an additional 15 seconds. To this suspension, add 30 ml of 10% alum solution and 10 ml of 1% Sebaran NP-10 solution to aggregate and mix for about 10 seconds. The resulting suspension was heated in a handmade vessel for approximately 19 minutes.
x 20cm, or a total area of about 380cm2 , formed into a handmade sheet.
The sheet is placed between blotter papers and compressed at a pressure of about 10 g/cm 2 to remove water, and then dried in a conventional photographic paper dryer. A series of runs as described above are performed by changing the blending ratio of vermiculite, inorganic fiber material (fiber flux), and organic binder to inorganic binder. For comparison, a run was also conducted in which no organic binder or inorganic binder was added. These two types of runs are designated by the letters A and B, respectively, and the other runs are designated by numbers. Parts by weight, i.e. grams of material used, ratio of organic to inorganic binder, drainage time (in seconds), and curvature of approximately 4.5 cm radius (+ sign indicates flexibility, - sign indicates crack initiation). The tensile strength in Kg of a 2.5 cm wide strip, the thickness (mm) of the sheet material before and after firing at 650 DEG C. for 15 minutes and the measured expansion coefficient are shown in Table 1 below. Runs designated by a number and the letter "a" indicate runs where the formulation was halved and the thickness of the sheet material was approximately halved. Therefore, the drainage time, tensile strength and thickness are about 1/2 of the run without "a". From Table 1, it can be seen that runs A and B are outside the desired property range due to run A's very long drainage time and run B's low tensile strength after firing. Similarly, run 14 also has a very low tensile strength and is therefore outside the scope of the present invention. Runs 5, 6 and 7 do not have the desired flexibility and are therefore outside the scope of the present invention. Runs 4, 8 and 9 show the lower limit of the ratio of organic binder to inorganic binder, and all these runs are difficult to bend to a radius of 4.5 cm when the thickness is large (approximately 3 mm), but the sheet The material is thin (about 1.5mm thick)
This will provide sufficient flexibility. 【table】
Claims (1)
〜35重量％の無機繊維物質、及び10〜25重量％の
結合剤からなり、該結合剤は、0.5〜1.5の比率の
有機エラストマー結合剤とベントナイトとの組合
せであり、６cm又はそれ以下の半径を有するロー
ル状に巻くことのできる可撓性膨張性シート物
質。 ２ 上記無機繊維物質は、アルミノケイ酸塩であ
る特許請求の範囲第１項記載の可撓性膨張性シー
ト物質。[Claims] 1. Essentially 40-75% by weight of unexpanded vermiculite, 15
~35% by weight inorganic fibrous material and 10-25% by weight binder, which is a combination of organic elastomer binder and bentonite in a ratio of 0.5-1.5, with a radius of 6 cm or less A flexible expandable sheet material that can be rolled into a roll. 2. The flexible expandable sheet material according to claim 1, wherein the inorganic fiber material is an aluminosilicate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82251877A | 1977-08-08 | 1977-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5430218A JPS5430218A (en) | 1979-03-06 |
| JPS6316353B2 true JPS6316353B2 (en) | 1988-04-08 |
Family
ID=25236251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9552178A Granted JPS5430218A (en) | 1977-08-08 | 1978-08-07 | Flexible and expandable sheet material |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5430218A (en) |
| DE (1) | DE2834548A1 (en) |
| GB (1) | GB1604908A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06124291A (en) * | 1992-10-14 | 1994-05-06 | Hitachi Ltd | Handwritten character inputting method for plant operation monitor ytem and plant operation monitor system |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5846557U (en) * | 1981-09-22 | 1983-03-29 | ブラザー工業株式会社 | vacuum cleaner |
| JPS59230737A (en) * | 1983-06-15 | 1984-12-25 | Ibiden Co Ltd | Elastic heat resisting sheet-shaped article |
| JPS609729A (en) * | 1983-06-29 | 1985-01-18 | Chuo Spring Co Ltd | Manufacture of thermal expansion seal |
| JPS60192740U (en) * | 1984-05-29 | 1985-12-21 | シャープ株式会社 | vacuum cleaner |
| JPS6177654A (en) * | 1984-09-20 | 1986-04-21 | トヨタ自動車株式会社 | Heat-resistant high expansion sheet matter for catalyst carrier support and manufacture |
| DE3579823D1 (en) * | 1985-10-31 | 1990-10-25 | Asturienne Mines Comp Royale | HEATING DEVICE, WITH A LAYER OF VERMICULIT. |
| CA1333822C (en) * | 1986-11-07 | 1995-01-03 | Robert S. Beyersdorf | Latex compositions useful as binders in composite board having dimensional stability and strength |
| US4775586A (en) * | 1987-02-17 | 1988-10-04 | Armstrong World Industries, Inc. | Paper, paper products, films composites and other silicate-polymer, construction materials |
| DE3837746C1 (en) * | 1988-11-07 | 1990-03-29 | Manfred Zeuner | |
| US5139615A (en) * | 1988-12-28 | 1992-08-18 | Hercules Incorporated | Composite sheet made from mechanically delaminated vermiculite |
| DE8902212U1 (en) * | 1989-02-24 | 1989-05-03 | Fa. J. Eberspaecher, 7300 Esslingen, De | |
| EP0441996B1 (en) * | 1990-02-12 | 1994-04-13 | Hercules Incorporated | Composite sheet made from mechanically delaminated vermiculite |
| GB2250996A (en) * | 1990-12-19 | 1992-06-24 | Lycab Limited | Composite material |
| WO1993005118A1 (en) * | 1991-09-09 | 1993-03-18 | Chemische Fabrik Budenheim Rudolf A. Oetker | Composition with integral intumescence properties |
| GB9215184D0 (en) * | 1992-07-17 | 1992-09-02 | Alcan Int Ltd | Intumescent systems |
| GB9220949D0 (en) * | 1992-10-06 | 1992-11-18 | T & N Technology Ltd | Intumescent material |
| CA2224325C (en) * | 1995-06-30 | 2007-07-31 | Minnesota Mining And Manufacturing Company | Intumescent sheet material |
| US5686039A (en) * | 1995-06-30 | 1997-11-11 | Minnesota Mining And Manufacturing Company | Methods of making a catalytic converter or diesel particulate filter |
| US5523059A (en) * | 1995-06-30 | 1996-06-04 | Minnesota Mining And Manufacturing Company | Intumescent sheet material with glass fibers |
| US5853675A (en) * | 1995-06-30 | 1998-12-29 | Minnesota Mining And Manufacturing Company | Composite mounting system |
| US5736109A (en) * | 1995-06-30 | 1998-04-07 | Minnesota Mining And Manufacturing Company | Intumescent sheet material and paste with organic binder |
| US5962603A (en) * | 1996-07-23 | 1999-10-05 | Georgia-Pacific Resins, Inc. | Intumescent composition and method |
| JP4922861B2 (en) * | 2007-08-10 | 2012-04-25 | ニチアス株式会社 | Retaining material for catalytic converter |
| KR101900849B1 (en) * | 2018-07-17 | 2018-09-20 | 전일랑 | Building panel and method of manufacturing building panel |
| CN115893984B (en) * | 2022-10-27 | 2023-06-27 | 湖南驰鑫特种隔热材料有限公司 | Ceramic vermiculite heat insulation board and preparation process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50109213A (en) * | 1974-02-05 | 1975-08-28 | ||
| US3916057A (en) * | 1973-08-31 | 1975-10-28 | Minnesota Mining & Mfg | Intumescent sheet material |
| JPS5169507A (en) * | 1974-11-04 | 1976-06-16 | Minnesota Mining & Mfg | Kato bochoseishiitozairyo |
-
1978
- 1978-05-31 GB GB2536378A patent/GB1604908A/en not_active Expired
- 1978-08-07 DE DE19782834548 patent/DE2834548A1/en active Granted
- 1978-08-07 JP JP9552178A patent/JPS5430218A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3916057A (en) * | 1973-08-31 | 1975-10-28 | Minnesota Mining & Mfg | Intumescent sheet material |
| JPS50109213A (en) * | 1974-02-05 | 1975-08-28 | ||
| JPS5169507A (en) * | 1974-11-04 | 1976-06-16 | Minnesota Mining & Mfg | Kato bochoseishiitozairyo |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06124291A (en) * | 1992-10-14 | 1994-05-06 | Hitachi Ltd | Handwritten character inputting method for plant operation monitor ytem and plant operation monitor system |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2834548C2 (en) | 1987-08-20 |
| DE2834548A1 (en) | 1979-02-22 |
| GB1604908A (en) | 1981-12-16 |
| JPS5430218A (en) | 1979-03-06 |
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