JPS63100079A - Extrusion formed product and manufacture - Google Patents
Extrusion formed product and manufactureInfo
- Publication number
- JPS63100079A JPS63100079A JP24435486A JP24435486A JPS63100079A JP S63100079 A JPS63100079 A JP S63100079A JP 24435486 A JP24435486 A JP 24435486A JP 24435486 A JP24435486 A JP 24435486A JP S63100079 A JPS63100079 A JP S63100079A
- Authority
- JP
- Japan
- Prior art keywords
- molded product
- raw material
- synthetic resin
- curing
- cementitious
- 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.)
- Granted
Links
- 238000001125 extrusion Methods 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002994 raw material Substances 0.000 claims description 93
- 239000000057 synthetic resin Substances 0.000 claims description 50
- 229920003002 synthetic resin Polymers 0.000 claims description 50
- 238000001723 curing Methods 0.000 claims description 47
- 239000011324 bead Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 31
- 239000000378 calcium silicate Substances 0.000 claims description 30
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 20
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 12
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000013007 heat curing Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 235000012438 extruded product Nutrition 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000012783 reinforcing fiber Substances 0.000 claims description 4
- 239000002075 main ingredient Substances 0.000 claims 3
- 239000002585 base Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000004568 cement Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- -1 calcium silicate hydrates Chemical class 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000012615 aggregate Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は建物の外ｒｉ笠に用いられる成形品に関し、特
に内部に独立気泡孔を有し保温性に優れた珪酸カルシウ
ム系の軽量押出し成形品、及びその製造方法に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a molded product used for the outside of a building, particularly a lightweight extrusion molded product made of calcium silicate, which has closed cell pores inside and has excellent heat retention properties. related to products and their manufacturing methods.
〈従来技術〉
珪酸質原料と石灰質原料と少量の有機質又はアスベスト
の如き無ａ質の補強用１１！維質原料と成形用助剤とを
加えて乾式分散混合してから注水混練した後押出機によ
り押出し成形して成形体となし、トバモライト（Ｔｏｂ
ｅｒｍｏｒｉｔｅ −５Ｃａ０・６Ｓｉ０２ ・５Ｈ，
０）又はゾノトライト（Ｘｏｎｏｔ Ｉ ｉｔｅ −６
Ｃａ０ ・６Ｓ ｉｏｚ ・ＨｚＯ）系組成物の成形体
を生成せしめる蒸気中で加熱硬化させ、後乾燥させるこ
とにより珪酸カルシウム成形品を製造する方法が知られ
ている（特開昭５１−１１２８３２号）。<Prior art> Silicic raw material, calcareous raw material, and a small amount of organic material or non-aluminous material such as asbestos for reinforcement 11! A fibrous raw material and a molding aid are added, dry dispersed mixed, water poured and kneaded, and then extruded using an extruder to form a molded product.
ermorite-5Ca0・6Si02・5H,
0) or Xonotlite (Xonot I ite-6
There is a known method for producing a calcium silicate molded article by heating and curing a molded body of a Ca0 .6S ioz .HzO) composition in steam and then drying it (Japanese Patent Laid-Open No. 112832/1983). .
〈発明が解決しようとする問題点〉
一般に珪酸カルシウム系板体は、トバモライト及び／又
はゾノトライトの結晶が箔状或いは繊維状乃至針状の微
細な結晶で構成されているので、低密度の軽量成形体で
はあるが強度が低いものであった。<Problems to be Solved by the Invention> In general, calcium silicate-based plates are composed of tobermorite and/or xonotlite crystals that are foil-like, fibrous, or needle-like, so they cannot be formed into low-density lightweight moldings. Although it was a physical body, its strength was low.
また、上記したような押出し成形によって珪酸カルシウ
ム系成形品を得る場合には強度上昇を図ることができる
ものの、押出成形機を用いて一般に１５０〜３５０Ａｙ
／ｃｍ”のような高圧で押出し成形されるため、高比重
のものとならざるを得す、軽量化の要請に反することと
なっていた。In addition, although it is possible to increase the strength when obtaining calcium silicate molded products by extrusion molding as described above, generally 150 to 350 Ay is obtained using an extrusion molding machine.
Since it is extruded under a high pressure such as "/cm", it has to have a high specific gravity, which goes against the demand for weight reduction.
く問題点を解決するための手段〉
従って本発明は、高強度且つ低比重の珪酸カルシウム系
成形品を提供することを目的とする。Means for Solving the Problems> Accordingly, an object of the present invention is to provide a calcium silicate molded product having high strength and low specific gravity.
本発明の別の目的は、押出し成形における押出圧力によ
っても破壊或いは変形されることのない、珪酸カルシウ
ム系成形品を提供することにある。Another object of the present invention is to provide a calcium silicate molded article that is not destroyed or deformed by extrusion pressure during extrusion molding.
本発明の更に別の目的は、珪酸質原料と石灰質原料とセ
メント質原料とを主成分とし、珪酸カルシウム水和物の
結晶体とセメント硬化体とが複合して基材を構成してい
る新規な押出し成形品を提供することにある。Still another object of the present invention is to provide a new material which has a silicate raw material, a calcareous raw material, and a cementitious raw material as its main components, and whose base material is composed of a composite of calcium silicate hydrate crystals and a hardened cement material. Our objective is to provide extruded products with excellent quality.
これら目的を達成し、上記従来技術の問題点を解決すべ
く創案された本発明は、珪酸質原料と石灰質原料とセメ
ント質原料とを主成分とした混練物を押出し成形して得
られる押出し成形品であって、その成形品基材の内部に
多数の独立気泡孔を有すると共に該独立気泡孔の内面に
その一部が該基材に含浸された合成樹脂被膜が形成され
ていることを特徴とする押出し成形品である。The present invention, which was created to achieve these objects and solve the problems of the prior art described above, is an extrusion molding product obtained by extruding a kneaded material mainly composed of a silicic raw material, a calcareous raw material, and a cementitious raw material. A product characterized by having a large number of closed cell pores inside the molded product base material, and a synthetic resin coating partially impregnated with the base material is formed on the inner surface of the closed cell pores. It is an extrusion molded product.
本発明はまた、このような押出し成形品の製造方法をも
提供するものであって、珪酸質原料と石灰質原料とセメ
ント質原料と補強繊維と合成樹脂ビーズとＩ！ｉ量の水
とを原材料とし、これらを適宜混合して得な混練物を押
出し成形機により押出し成形し、得られた成形物を加熱
養生してセメント質原料を硬化又は半硬化せしめると共
に、これと同時に或いはその後に混入した合成樹脂ビー
ズの溶融温度以上の温度条件でオートクレーブ養生又は
加熱養生することによって養生硬化させることを特徴と
する押出し成形品の製造方法である。この方法において
は、珪酸質原料と石灰質原料とを含む混合物を珪酸カル
シウム水和物であるトバモライト又はゾノトライトを生
成せしめる温度以上の温度条件に加熱せしめることが必
須であるが、この工程は押出し成形機による押出し成形
の工程に先立って行ってもよく、また該押出し成形工程
の後に、セメント質原料の硬化又は半硬化のための加熱
養生と同時に或いはその後であって、合成樹脂ビーズの
溶融温度以上の温度条件で行うオートクレーブ養生又は
加熱養生の前又は同時に行うようにしてもよい。The present invention also provides a method for manufacturing such an extrusion molded product, which includes a silicic raw material, a calcareous raw material, a cementitious raw material, reinforcing fibers, synthetic resin beads, and I! i amount of water as raw materials, mix them appropriately, extrude the obtained kneaded product using an extrusion molding machine, heat cure the obtained molded product to harden or semi-harden the cementitious raw material, and This is a method for producing an extrusion molded product, which is characterized by curing and curing by curing in an autoclave or heating at a temperature higher than the melting temperature of synthetic resin beads mixed at the same time or after. In this method, it is essential to heat the mixture containing the silicic raw material and the calcareous raw material to a temperature higher than the temperature that produces tobermorite or xonotlite, which are calcium silicate hydrates, but this step is carried out using an extrusion molding machine. It may be carried out prior to the extrusion molding step, or after the extrusion molding step, at the same time as or after heat curing for hardening or semi-hardening of the cementitious raw material, heating at a temperature higher than the melting temperature of the synthetic resin beads may be carried out. It may be performed before or simultaneously with autoclave curing or heat curing under temperature conditions.
く作用〉
珪酸質原料と石灰質原料とセメント質原料とを主成分と
した混練物を押出し成形して得られる押出し成形品にお
いて、合成樹脂ビーズが添加混入されているため、これ
を養生して得られる該成形品内部には独立気泡孔が多数
形成される。Effect> Synthetic resin beads are added to the extruded product obtained by extruding a kneaded material mainly composed of silicic raw materials, calcareous raw materials, and cementitious raw materials. A large number of closed cell pores are formed inside the molded product.
該成形品は、添加混入された合成樹脂ビーズの溶融温度
以上の温度条件でオートクレーブ養生されて養生硬化さ
れるため、該養生過程において該合成樹脂ビーズが溶融
してその一部が基材に含浸され、また独立気泡孔の内面
が合成樹脂被膜によって被覆形成される。The molded product is cured and cured in an autoclave at a temperature higher than the melting temperature of the added synthetic resin beads, so during the curing process, the synthetic resin beads melt and some of them impregnate the base material. In addition, the inner surfaces of the closed cell pores are coated with a synthetic resin film.
該成形品の製造工程においては、合成樹脂ビーズの溶融
温度以上の温度条件での養生に先立って又は同時に、珪
酸カルシウム水和物であるトバモライト又はゾノトライ
トを生成せしめ、珪酸カルシウム系の軽重押出し成形体
が得られる。In the manufacturing process of the molded product, tobermorite or xonotrite, which is a calcium silicate hydrate, is produced before or at the same time as curing at a temperature higher than the melting temperature of the synthetic resin beads, and a light and heavy extruded body of calcium silicate is produced. is obtained.
く構成の異体的な説明〉
本発明による押出し成形品は、成形品基材の内部に多数
の独立気泡孔を有すると共に該独立気泡孔の内面に一部
基材に含浸された合成樹脂被膜が形成された押出し成形
品であって、その−例は第１図に略図的に示す通りであ
る。即ち、本発明による押出し成形品１には多数の独立
気泡孔２が形成されている。この独立気泡孔の−につい
て拡大して示したのが第２図であり、該独立気泡孔２の
周面は混入合成樹脂ビーズの溶融によって形成された合
成樹脂被膜４によって被覆形成されていると共に、その
一部が基材３ （第１図）に浸透含浸されて樹脂含浸部
５を形成している。これら図面により、本発明の押出し
成形品においては、独立気泡孔２と基材３とが合成樹脂
被膜４を介して密着形成されていることが理解されるで
あろう。Different explanation of structure> The extrusion molded product according to the present invention has a large number of closed cell pores inside the molded product base material, and a synthetic resin coating partially impregnated in the base material on the inner surface of the closed cell pores. An example of an extruded article formed is shown schematically in FIG. That is, a large number of closed cell pores 2 are formed in the extrusion molded product 1 according to the present invention. FIG. 2 shows an enlarged view of the closed cell pore 2, and the peripheral surface of the closed cell pore 2 is covered with a synthetic resin coating 4 formed by melting mixed synthetic resin beads. , a part of which is penetrated and impregnated into the base material 3 (FIG. 1) to form a resin-impregnated portion 5. From these drawings, it will be understood that in the extrusion molded product of the present invention, the closed cell pores 2 and the base material 3 are formed in close contact with each other via the synthetic resin coating 4.
このような本発明の押出し成形品を製造するに当たって
必要とされる原料は、珪酸質原料、石灰質原料、セメン
ト質原料、ｍａ質原料、合成樹脂ビーズ、適量の水、及
び必要に応じて添加配合される骨材、メチルセルロース
、保水剤等の助剤等である。The raw materials required for manufacturing the extrusion molded product of the present invention include silicic raw materials, calcareous raw materials, cementitious raw materials, ma materials, synthetic resin beads, an appropriate amount of water, and addition and blending as necessary. auxiliaries such as aggregate, methyl cellulose, and water retention agents.
珪酸質原料としては、珪砂、珪藻土、クレー、シリカゲ
ル、ホワイトカーボン、シリカダスト、フェロシリコン
ダスト等の珪酸質物質を用いることができる。As the siliceous raw material, siliceous substances such as silica sand, diatomaceous earth, clay, silica gel, white carbon, silica dust, and ferrosilicon dust can be used.
石灰質原料は、生石灰、消石灰、カーバイド残渣等であ
る。Calcareous raw materials include quicklime, slaked lime, and carbide residue.
セメント質原料は、ポルトランドセメント、高炉セメン
ト、フライアッシュセメント、シリカセメント、アルミ
ナセメント、急硬性セメント、熱硬化性セメント等であ
る。Cementitious raw materials include Portland cement, blast furnace cement, fly ash cement, silica cement, alumina cement, rapid hardening cement, and thermosetting cement.
繊維質原料としては、アスベスト、炭素側り合成＆！維
、木ａ繊維、麻１１！！、耐アルカリ性ガラス繊維等を
用いることができる。As fibrous raw materials, asbestos, carbon side synthesis &! fiber, wood a fiber, hemp 11! ! , alkali-resistant glass fiber, etc. can be used.
また、合成樹脂ビーズは、ポリエチレン、ポリスチレン
、ポリプロピレン、アクリル、ビニル系等のものを適宜
選択して用いることができる。Furthermore, the synthetic resin beads can be appropriately selected from polyethylene, polystyrene, polypropylene, acrylic, vinyl, and the like.
また、上記した各々の原料においては、それらを単独で
或いは適宜複数種を併用して用いることができる。In addition, each of the above-mentioned raw materials can be used alone or in combination as appropriate.
これら原料を用いて本発明の押出し成形品を製造する方
法は、大別して次の３つの加熱工程を含んでいる。The method of manufacturing the extrusion molded product of the present invention using these raw materials includes the following three heating steps.
第一の加熱工程は、珪酸質原料と石灰質原料とを水熱反
応させて、珪酸カルシウム水和物であるトバモライト又
はゾノトライトに結晶化させるために行なわれる。この
工程は、押出し成形の工程の前に行なわれる場合は、珪
酸質原料と石灰質原料とに適量の水を加えて混練して得
られた混練物をオートクレーブ中で撹拌し、これら原料
を水熱反応させてトバモライト又はゾノトライトの結晶
スラリーとし、残余の原料を混合し、場合によっては適
当な水分量となるまで脱水した後、該混合物を押出し成
形する。また、全ての原料を配合して得た混練物を押出
し成形した後に、得られた成形物をトバモライト又はゾ
ノトライトを生成せしめる温度以上でオートクレーブ養
生してこの工程を行ってもよい、また、前者において、
水熱反応が一部行なわれた段階でオートクレーブを中断
し、トバモライト又はゾノトライトの半結晶スラリーと
し、残部の結晶ｆヒを押出し成形後オートクレーブ養生
によって行うようにしてもよい。The first heating step is performed to cause a hydrothermal reaction between the siliceous raw material and the calcareous raw material, and to crystallize the calcium silicate hydrate tobermorite or xonotlite. When this step is performed before the extrusion molding step, the silicic raw material and calcareous raw material are mixed with an appropriate amount of water, the resulting kneaded product is stirred in an autoclave, and these raw materials are heated by hydrothermal heating. The mixture is reacted to form a tobermorite or xonotrite crystal slurry, mixed with the remaining raw materials, and optionally dehydrated to an appropriate moisture content, and then extruded. Alternatively, this step may be carried out by extrusion molding a kneaded product obtained by blending all the raw materials, and then curing the obtained molded product in an autoclave at a temperature higher than that at which tobermorite or xonotlite is produced. ,
The autoclave may be interrupted when a portion of the hydrothermal reaction has been carried out to form a semi-crystalline slurry of tobermorite or xonotlite, and the remaining crystals may be extruded and then cured in an autoclave.
第二の加熱工程は、セメント質原料を硬化させるために
行なわれる。この加熱硬化のための工程は押出し成形の
後に得られた成形物に対して行なわれるが、場合によっ
てはこの工程を２段階に分けて行い、−次養生によって
セメント質原料を半硬化させてハンドリング性を向上さ
せた後に次工程に搬送し、二次養生によって更に硬化さ
せるようにしてもよい、この第二の加熱工程は、第一の
加熱工程が押出し成形の前に行なわれる場合にはそれよ
りも後に行なわれることとなるが、第一の加熱工程を押
出し成形の後に行う場合には、押出し成形により得られ
た成形物をまずこの第二の加熱工程に付してセメント質
原料を養生硬化せしめ、その後に第一の加熱工程を行っ
て珪酸カルシウム水和物を生成せしめるようにすること
が望ましい。A second heating step is performed to harden the cementitious raw material. This process for heat curing is carried out on the molded product obtained after extrusion molding, but in some cases this process is divided into two stages, and the cementitious raw material is semi-hardened by curing and then handled. After improving the properties, it may be transported to the next step and further hardened by secondary curing. This second heating step is similar to the first heating step when it is performed before extrusion molding. If the first heating step is performed after extrusion molding, the molded product obtained by extrusion molding is first subjected to this second heating step to cure the cementitious raw material. It is desirable to harden and then perform a first heating step to form calcium silicate hydrate.
このようにすれば、セメント硬化体の空隙中に珪酸カル
シウム水和物であるトバモライト又はゾノトライトの結
晶が入り込むようにして結晶化するので、密な基材を形
成させることができる。In this way, the crystals of tobermorite or xonotlite, which are calcium silicate hydrates, are crystallized so as to enter the voids of the hardened cement body, so that a dense base material can be formed.
第三の加熱工程は、合成樹脂ビーズを溶融させて基材中
に独立気泡孔を多数形成させるために行なわれる。従っ
て、この加熱工程は該合成樹脂ビーズの溶融温度以上の
温度条件でオートクレーブ養生又は加熱養生することに
よって行なわれる。The third heating step is performed to melt the synthetic resin beads and form a large number of closed cell pores in the base material. Therefore, this heating step is carried out by autoclaving or heat curing at a temperature higher than the melting temperature of the synthetic resin beads.
また、この工程が基材の形成よりも前に行なわれると、
合成樹脂ビーズの溶融によっても十分な独立気泡孔が基
材内部に形成されなくなるので、第−及び／又は第二の
加熱工程によって成形物がある程度養生硬化されて基材
が形成された後に行なわれなければならない。Also, if this step is performed before the formation of the base material,
Even by melting the synthetic resin beads, sufficient closed cell pores cannot be formed inside the base material, so this step is carried out after the molded product has been cured to some extent and the base material has been formed by the first and/or second heating process. There must be.
以上説明した第一乃至第三の加熱工程を含む本発明方法
を実施する具体的手法には何通りもの態様が考えられる
が、大別すると、次のＡ、〜Ｄ。Although there are many possible ways to carry out the method of the present invention including the first to third heating steps described above, they can be roughly divided into the following A and D.
に示す通りである。なお、以下の説明においては、本発
明方法の実施において適宜配合添加されるメチルセルロ
ース、骨材、助剤等については、便宜上省略されている
。また、いずれの場合においても、押出し成形は、その
押出し方向に連続した貫通孔を有する中空押出しとして
行うこともできる。As shown. In the following description, methyl cellulose, aggregate, auxiliary agents, etc. that are appropriately added in the implementation of the method of the present invention are omitted for convenience. Moreover, in any case, extrusion molding can also be performed as hollow extrusion having continuous through holes in the extrusion direction.
Ａ、珪酸質原料、石灰質原料、セメント質原料、繊維質
原料及び合成樹脂ビーズを混合し、空練りした後、適量
の水を加えて混練し、得られた混練物を押出し成形機に
投入して押出し成形し、任意長さに切断した後、成形物
をパレットに受は取り、この成形物に対して第一乃至第
三の加熱工程を施す方法。A. Mix silicic raw materials, calcareous raw materials, cementitious raw materials, fibrous raw materials, and synthetic resin beads, dry knead them, then add an appropriate amount of water and knead them, and put the resulting kneaded product into an extrusion molding machine. A method in which the molded product is extruded and cut into desired lengths, then the molded product is placed on a pallet, and the molded product is subjected to the first to third heating processes.
第一乃至第三の加熱工程の順序については、（１）−次
養生にてセメント質原料を加熱硬化せしめ（第二の加熱
工程）、二次養生において珪酸カルシウム水和物を生成
せしめ（第一の加熱工程）、三次養生にて合成樹脂ビー
ズを溶融せしめる（第三の加熱工程）方法、〈２）−次
養生にてセメント質原料を硬化せしめ（第二の加熱工程
）、二次養生にて珪酸カルシウム水和物の生成と合成樹
脂ビーズの溶融とを一工程で行わしめる（第−及び第二
の加熱工程）方法、（３）−次養生にてセメント質原料
を半硬化させてハンドリング性を持たせた後、二次双生
にて該セメント質原料を硬化せしめ、三次養生にて珪酸
カルシウム水和物の生成、四次養生にて合成樹脂ビーズ
の溶融を行う方法、（４）−次養生にてセメント質原料
を半硬化させてハンドリング性を持たせた後、二次養生
にて該セメント質原料の硬化と珪酸カルシウム水和物の
生成とを一工程で行い、三次養生にて合成樹脂ビーズを
溶融せしめる方法、（５）−次養生にてセメント質原料
を半硬化させてハンドリング性を持たせた後、二次養生
にて該セメント質原料の硬化、珪酸カルシウム水和物の
生成及び合成樹脂ビーズの溶融を全て一工程で行わしめ
る方法、のいずれがを採用することができる。Regarding the order of the first to third heating steps, (1) the cementitious raw material is heated and hardened in the second curing (second heating step), and the calcium silicate hydrate is produced in the second curing (the second heating step). 1 heating step), a method of melting synthetic resin beads in the tertiary curing (third heating step), <2) - hardening the cementitious raw material in the next curing (second heating step), and a second curing A method in which the production of calcium silicate hydrate and the melting of synthetic resin beads are performed in one step (first and second heating steps), (3) semi-hardening of the cementitious raw material in the next curing. After imparting handleability, the cementitious raw material is hardened in a secondary twinning, a calcium silicate hydrate is produced in a tertiary curing, and synthetic resin beads are melted in a fourth curing, (4) - In the second curing, the cementitious raw material is semi-hardened to give it handling properties, and then in the second curing, the cementitious raw material is hardened and calcium silicate hydrate is produced in one step, and then in the tertiary curing. (5) - In the next curing, the cementitious raw material is semi-hardened to give it handling properties, and then in the second curing, the cementitious raw material is hardened and calcium silicate hydrate is melted. Any method can be adopted in which the production of the synthetic resin beads and the melting of the synthetic resin beads are all carried out in one step.
Ｂ、珪酸質原料と石灰質原料とに適量加水して混練し、
得られた混練物をオートクレーブ中で撹拌し水熱反応に
より珪酸カルシウム水和物の結晶スラリーを生成せしめ
（第一の加熱工程）、これにセメント質原料、繊維質原
料及び合成樹脂ビーズを混合して得た混合物を、場合に
よっては適当な水分量となるまで脱水してから、押出し
成形宍に投入して押出し成形し、任意長さに切断した後
、得られた成形物をパレットに受は取り、この成形物に
対して第二及び第三の加熱工程を施す方法。B. Add appropriate amount of water to silicate raw material and calcareous raw material and knead;
The obtained kneaded material is stirred in an autoclave to generate a crystal slurry of calcium silicate hydrate through a hydrothermal reaction (first heating step), and a cementitious raw material, a fibrous raw material, and a synthetic resin bead are mixed with this. Depending on the case, the resulting mixture is dehydrated to an appropriate moisture content, then put into an extrusion molding machine for extrusion molding, cut into arbitrary lengths, and the resulting molded products are placed on a pallet. A method in which the molded product is then subjected to second and third heating steps.
押出し成形後の具体的順序としては、（１）−次養生に
てセメント質原料の硬化と合成樹脂ビーズの溶融とを一
工程で行う方法、（２）−次養生にてセメント質原料を
硬化せしめ、二次養生にて合成樹脂ビーズを溶融せしめ
る方法、（３）−次賛生にてセメント質原料を半硬化せ
しめ、二次養生にて該セメント質原料を硬化せしめると
共に合成樹脂ビーズ溶融を行う方法、（４）−次養生に
てセメント質原料を半硬化せしめ、二次養生にて該セメ
ント原料を硬化せしめた俺、三次養生にて合成樹脂ビー
ズを溶融せしめる方法、のいずれかを採用することがで
きる。The specific order after extrusion molding is as follows: (1) Hardening the cementitious raw material and melting the synthetic resin beads in the next curing in one step, (2) Hardening the cementitious raw material in the next curing A method of melting the synthetic resin beads in the second curing, (3) semi-hardening the cementitious raw material in the second curing, hardening the cementitious raw material in the second curing, and melting the synthetic resin beads. (4) - Semi-hardening the cementitious raw material in the second curing, curing the cement raw material in the second curing, or melting the synthetic resin beads in the third curing. can do.
Ｃ１珪酸質原料と石灰質原料とに適量加水し混練して得
られた混練物をオートクレーブ中で撹拌し、その一部が
水熱反応により珪酸カルシウム水和物のトバモライト又
はゾノトライトに結晶化した時にオートクレーブを中断
してこれらの半結晶スラリーを生成せしめ、これにセメ
ント質原料、１ａ維質原料及び合成樹脂ビーズを混合し
て得た混合物を、そのまま或いは適当な水分量となるま
で脱水した後、押出し成形機に投入して押出し成形し、
任意長さに切断した後、得られた成形物をパレットに受
は取り、この成形物に対して残余の第一の加熱工程及び
第二及び第三の加熱工程を施す方法。The kneaded product obtained by adding an appropriate amount of water to C1 silicic raw material and calcareous raw material and kneading is stirred in an autoclave, and when a part of it is crystallized into tobermorite or xonotrite, which is a calcium silicate hydrate, by a hydrothermal reaction, the autoclave is removed. The process is interrupted to produce a semi-crystalline slurry, and the mixture obtained by mixing the cementitious raw material, the fibrous raw material 1a, and the synthetic resin beads is extruded as it is or after dehydration to an appropriate moisture content. Put it in a molding machine and extrude it,
After cutting to a desired length, the resulting molded product is placed on a pallet, and the remaining molded product is subjected to the remaining first heating step and second and third heating steps.
押出し成形後の具体的順序としては、（１）−次養生に
てセメント質原料の硬化を行い、二次養生にて残余の珪
酸カルシウム水和物の生成とき成樹脂ビーズの溶融とを
一工程で行う方法、（２）−次養生にてセメント質原料
を硬化せしめ、二次養生にて残余の珪酸カルシウム水和
物の生成を行い、三次養生にて合成樹脂ビーズを溶融せ
しめる方法、（３）−次養生にてセメント質原料を半硬
化せしめてハンドリング性を持たせた後、二次養生にて
該セメント質原料を硬化せしめ、三次養生にて残余の珪
酸力ルシウーム水和物の生成と共に合成樹脂ビーズの溶
融を行わしめる方法、（４）−次養生にてセメント質原
料を半硬化せしめ、二次養生にて該セメント質原料を硬
化せしめ、三次養生にて残余の珪酸カルシウム水和物を
生成させた後、四次養生にて合成樹脂ビーズ溶融を行う
方法、のいずれがを採用することができる。The specific sequence after extrusion molding is as follows: (1) The cementitious raw material is hardened in the second curing, and the remaining calcium silicate hydrate is produced in the second curing and the synthetic resin beads are melted in one step. (2) A method of hardening the cementitious raw material in the second curing, producing residual calcium silicate hydrate in the second curing, and melting the synthetic resin beads in the third curing, (3) ) - After semi-hardening the cementitious raw material in the next curing to give it handling properties, the cementitious raw material is hardened in the second curing, and the remaining silicic acid lucium hydrate is produced in the third curing. A method of melting synthetic resin beads, (4) - Semi-hardening the cementitious raw material in the second curing, hardening the cementitious raw material in the second curing, and curing the remaining calcium silicate hydrate in the third curing. After producing the synthetic resin beads, the synthetic resin beads are melted in the fourth curing.
Ｄ、珪酸質原料、石灰質原料及びセメント質原料に３ｉ
！量の水を加えて混練し、得られた混練物をオートクレ
ーブ中で撹拌し水熱反応により珪酸カルシウム水和物の
結晶スラリー又は半結晶スラリーを得、このスラリー中
に繊維質原料と合成樹脂ビーズとを加えて得た混合物を
、そのまま或いは適当な水分量となるまで脱水してから
、押出し成形機に投入して押出し成形し、任意長さに切
断した後、成形物をパレットに受は取る。D, 3i for silicic raw materials, calcareous raw materials and cementitious raw materials
! The resulting kneaded product is stirred in an autoclave to obtain a crystalline slurry or semi-crystalline slurry of calcium silicate hydrate through a hydrothermal reaction, and the fibrous raw material and synthetic resin beads are added to this slurry. The mixture obtained by adding the above is either as it is or dehydrated to an appropriate moisture content, then put into an extrusion molding machine for extrusion molding, cut into desired lengths, and then the molded product is placed on a pallet. .
この成形物に対する工程は、上記したＢ、又はＣ９の各
態様と同じである。The steps for this molded product are the same as those for embodiments B and C9 described above.
なお、このり、の方法による場合は、押出し成形の前に
セメント質原料が硬化するのを防ぐために、予め硬化遅
延剤を混入しておく必要がある。In addition, when using this method, it is necessary to mix a hardening retarder in advance in order to prevent the cementitious raw material from hardening before extrusion molding.
このようにして、いずれにしても、珪酸カルシウム水和
物であるトバモライト又はゾノトライトの結晶構造及び
セメント硬化体より成る成形物基材中で合成樹脂ビーズ
が溶融状態になされ、その一部が基材中に浸透含浸され
、内面が３成樹脂被膜で被覆形成されている独立気泡孔
が多数含有された第１図図示の如き押出し成形品が得ら
れる。In this way, in any case, the synthetic resin beads are brought into a molten state in the molded product base material consisting of the crystal structure of tobermorite or xonotlite, which is a calcium silicate hydrate, and a cement hardened product, and a part of the synthetic resin beads are melted in the base material. An extrusion molded product as shown in FIG. 1 is obtained, which contains a large number of closed cell pores whose inner surfaces are coated with a three-component resin film.
〈発明の効果〉
本発明においては珪酸カルシウム系押出し成形品におい
て強度的に優れた合成樹脂ビーズを添加混入しているた
め、高強度且つ軽量の珪酸カルシウム系押出し成形品が
得ら゛れる。<Effects of the Invention> In the present invention, since synthetic resin beads having excellent strength are added and mixed into a calcium silicate extrusion molded product, a high strength and lightweight calcium silicate extrusion molded product can be obtained.
また、得られた成形品を混入合成樹脂ビーズの溶融温度
以上の温度条件でオートクレーブ養生することから、成
形品内部に多数形成される独立気泡孔の内面が合成樹脂
被膜によって被覆形成され且つ該被膜の一部が基材に浸
透含浸されるため、成形品の強度が著しく向上する。更
に、該独立気泡孔が多数存在することから、成形品の軽
量化と共に保温性の向上をもたらす、独立気泡孔は合成
樹脂被膜によって被覆されているので、雨水等の水分の
浸透が防止され、保温性を低下させることがない。Furthermore, since the obtained molded product is cured in an autoclave at a temperature higher than the melting temperature of the mixed synthetic resin beads, the inner surfaces of the many closed cell pores formed inside the molded product are covered with a synthetic resin coating, and the coating Because a portion of the material penetrates and impregnates the base material, the strength of the molded product is significantly improved. Furthermore, the presence of a large number of closed cell pores reduces the weight of the molded product and improves its heat retention.Since the closed cell pores are covered with a synthetic resin coating, penetration of moisture such as rainwater is prevented. Does not reduce heat retention.
また、本発明による押出し成形品は珪酸カルシウム水和
物の結晶構造とセメント硬化体との複合組織より成る基
材を有しており、特にセメント硬化体の空隙中に珪酸カ
ルシウム水和物の結晶が入り込んで密な基材を構成して
いる。Furthermore, the extrusion molded product according to the present invention has a base material consisting of a composite structure of a crystal structure of calcium silicate hydrate and a cement hardened body, and in particular, calcium silicate hydrate crystals are present in the voids of the cement hardened body. penetrates and forms a dense base material.
更に、本発明方法は従来の押出し成形製造設備をそのま
ま使用して実施することができるので、経済性に優れて
いる。Furthermore, the method of the present invention can be carried out using conventional extrusion manufacturing equipment as is, and is therefore highly economical.
第１図は本発明の押出し成形品の一例についてその構造
を略解的に示す破断面図、第２図は第１図図示のものの
一部を拡大して示す拡大図である。
符号の説明
１・・・押出し成形品 ２・・・独立気泡孔３・・基
材 ４・・・合成樹脂被膜５・・・樹脂含浸
部FIG. 1 is a broken cross-sectional view schematically showing the structure of an example of the extrusion molded product of the present invention, and FIG. 2 is an enlarged view showing a part of the product shown in FIG. 1. Explanation of symbols 1... Extruded product 2... Closed cell pores 3... Base material 4... Synthetic resin coating 5... Resin impregnated part
Claims (4)
成分とした混練物を押出し成形して得られる押出し成形
品であって、その成形品基材の内部に多数の独立気泡孔
を有すると共に該独立気泡孔の内面にその一部が該基材
に含浸された合成樹脂被膜が形成されていることを特徴
とする押出し成形品。(1) An extrusion molded product obtained by extrusion molding a kneaded material mainly composed of a siliceous raw material, a calcareous raw material, and a cementitious raw material, which has a large number of closed cell pores inside the molded product base material. An extrusion molded product characterized in that a synthetic resin coating, a part of which is impregnated with the base material, is formed on the inner surface of the closed cell pores.
成分とし、これに補強繊維と合成樹脂ピースと適量の水
とを加えて混練し、 得られた混練物を押出し成形機により押出し成形し、 得られた成形物を加熱養生して該セメント質原料を硬化
ないし半硬化せしめ、 その後、該成形物を珪酸カルシウム水和物であるトバモ
ライト又はゾノトライトを生成せしめる温度以上の温度
条件でオートクレーブ養生し、 該トバモライト又はゾノトライトの生成と同時に或いは
その後、該成形物を該合成樹脂ビーズの溶融温度以上の
温度条件でオートクレーブ養生又は加熱養生することを
特徴とする、押出し成形品の製造方法。(2) The main ingredients are silicic raw materials, calcareous raw materials, and cementitious raw materials, and reinforcing fibers, synthetic resin pieces, and an appropriate amount of water are added and kneaded, and the resulting kneaded product is extruded using an extrusion molding machine. The obtained molded product is heated and cured to harden or semi-harden the cementitious raw material, and then the molded product is autoclaved at a temperature higher than that at which tobermorite or xonotlite, which is calcium silicate hydrate, is produced. A method for producing an extrusion molded product, which comprises curing the molded product in an autoclave or heating it at a temperature higher than the melting temperature of the synthetic resin beads, simultaneously with or after the production of the tobermorite or xonotlite.
適量の水を加えて混練し、 得られた混練物をオートクレーブ中で攪拌し、その全部
又は一部を水熱反応させてトバモライト又はゾノトライ
トの結晶スラリー又は半結晶スラリーを得、 該スラリーにセメント質原料と補強繊維と合成樹脂ビー
ズとを混合し、 得られた混合物を押出し成形機により押出し成形し、 得られた成形物を加熱養生して該セメント質原料を硬化
ないし半硬化せしめ、 該加熱養生と同時に或いはその後、該成形物を該合成樹
脂ビーズの溶融温度以上の温度条件でオートクレーブ養
生し或いは加熱養生することを特徴とする、押出し成形
品の製造方法。(3) The main ingredients are silicic raw materials and calcareous raw materials, and an appropriate amount of water is added and kneaded. The resulting kneaded material is stirred in an autoclave, and all or part of it is subjected to a hydrothermal reaction to produce tobermorite. Alternatively, obtain a crystalline or semi-crystalline slurry of xonotlite, mix cementitious raw materials, reinforcing fibers, and synthetic resin beads with the slurry, extrude the obtained mixture using an extrusion molding machine, and heat the obtained molded product. The cementitious raw material is cured to harden or semi-harden, and simultaneously with or after the heat curing, the molded product is autoclaved or heated at a temperature higher than the melting temperature of the synthetic resin beads. , a method for producing extruded products.
成分とし、これに該セメント質原料の硬化遅延剤と適量
の水とを加えて混練し、 得られた混練物をオートクレーブ中で撹拌し、その全部
又は一部を水熱反応させてトバモライト又はゾノトライ
トの結晶スラリー又は半結晶スラリーを得、 該スラリーに補強繊維と合成樹脂ビーズとを混合し、 得られた混合物を押出し成形機により押出し成形し、 得られた成形物を加熱養生して該セメント質原料を硬化
ないし半硬化せしめ、 該加熱養生と同時に或いはその後、該成形物を該合成樹
脂ビーズの溶融温度以上の温度条件でオートクレーブ養
生し或いは加熱養生することを特徴とする、押出し成形
品の製造方法。(4) The main ingredients are a silicic raw material, a calcareous raw material, and a cementitious raw material, and a hardening retarder for the cementitious raw material and an appropriate amount of water are added and kneaded, and the obtained kneaded product is stirred in an autoclave. Then, all or part of it is subjected to a hydrothermal reaction to obtain a crystal slurry or semi-crystalline slurry of tobermorite or xonotrite, and reinforcing fibers and synthetic resin beads are mixed with the slurry, and the resulting mixture is extruded using an extrusion molding machine. molding, heat curing the obtained molded product to harden or semi-harden the cementitious raw material, and simultaneously or after the heat curing, autoclave the molded product at a temperature equal to or higher than the melting temperature of the synthetic resin beads. 1. A method for producing an extrusion molded product, characterized by curing or heat curing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61244354A JPH0631172B2 (en) | 1986-10-15 | 1986-10-15 | Extruded product and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61244354A JPH0631172B2 (en) | 1986-10-15 | 1986-10-15 | Extruded product and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63100079A true JPS63100079A (en) | 1988-05-02 |
| JPH0631172B2 JPH0631172B2 (en) | 1994-04-27 |
Family
ID=17117451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61244354A Expired - Lifetime JPH0631172B2 (en) | 1986-10-15 | 1986-10-15 | Extruded product and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0631172B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0316975A (en) * | 1989-06-15 | 1991-01-24 | Kubota Corp | Production of lightweight cement product |
| WO2011015751A1 (en) * | 2009-08-05 | 2011-02-10 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Porous ceramic material having a macroporosity controlled by layering pore-forming agents |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4963729A (en) * | 1972-10-23 | 1974-06-20 | ||
| JPS56134549A (en) * | 1980-03-21 | 1981-10-21 | Sumitomo Metal Mining Co | Manufacture of waterproofing vapor-cured lightweght foamed concrete |
| JPS5717458A (en) * | 1980-07-02 | 1982-01-29 | Sumitomo Metal Mining Co | Good impact-resistance steam-cured lightweight foamed concrete |
| JPS57170886A (en) * | 1981-04-13 | 1982-10-21 | Toyo Pairu Hiyuumukan Seisakus | Inorganic heat-insulating board manufacture and heat-insulating board |
-
1986
- 1986-10-15 JP JP61244354A patent/JPH0631172B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4963729A (en) * | 1972-10-23 | 1974-06-20 | ||
| JPS56134549A (en) * | 1980-03-21 | 1981-10-21 | Sumitomo Metal Mining Co | Manufacture of waterproofing vapor-cured lightweght foamed concrete |
| JPS5717458A (en) * | 1980-07-02 | 1982-01-29 | Sumitomo Metal Mining Co | Good impact-resistance steam-cured lightweight foamed concrete |
| JPS57170886A (en) * | 1981-04-13 | 1982-10-21 | Toyo Pairu Hiyuumukan Seisakus | Inorganic heat-insulating board manufacture and heat-insulating board |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0316975A (en) * | 1989-06-15 | 1991-01-24 | Kubota Corp | Production of lightweight cement product |
| WO2011015751A1 (en) * | 2009-08-05 | 2011-02-10 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Porous ceramic material having a macroporosity controlled by layering pore-forming agents |
| FR2948884A1 (en) * | 2009-08-05 | 2011-02-11 | Air Liquide | POROUS CERAMIC MATERIAL HAVING POROGENIC STACK CONTROLLED MACROPOROSITY |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0631172B2 (en) | 1994-04-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |