JPH06239655A - Inorganic composition - Google Patents

Inorganic composition

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Publication number
JPH06239655A
JPH06239655A JP2522393A JP2522393A JPH06239655A JP H06239655 A JPH06239655 A JP H06239655A JP 2522393 A JP2522393 A JP 2522393A JP 2522393 A JP2522393 A JP 2522393A JP H06239655 A JPH06239655 A JP H06239655A
Authority
JP
Japan
Prior art keywords
aqueous solution
fly ash
weight
inorganic
alkali metal
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
Application number
JP2522393A
Other languages
Japanese (ja)
Other versions
JP3253395B2 (en
Inventor
Katsuzo Nitta
勝三 新田
Masatake Kamiya
昌岳 神谷
Tatsutoshi Nakano
龍俊 中野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to JP2522393A priority Critical patent/JP3253395B2/en
Publication of JPH06239655A publication Critical patent/JPH06239655A/en
Application granted granted Critical
Publication of JP3253395B2 publication Critical patent/JP3253395B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • 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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glanulating (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

PURPOSE:To obtain the inorganic composition improved in strength and durability by compounding fly ash, an alkali metal hydroxide aqueous solution or alkali metal silicate salt aqueous solution, and quartz sand in a specific ratio. CONSTITUTION:Fly ash containing 40-80wt.% of SiO2 and 10-40wt.% of Al2O3 is classified to obtain the powder of the fly ash containing particles having an average particle diameter of >=10mum in an amount of 180wt.% 100 pts.wt. of the fly ash is mixed with 10-300 pts.wt. of the >=10wt.% aqueous solution of an alkali metal hydroxide of the formula: MOH (M is Li, K, Na or their mixture) or the >=10wt.% aqueous solution of an alkali metal silicate salt of the formula: M2O.SiO2, (M is Li, K, Na or their mixture) and quartz sand having particle diameters of 40-200mum. 100 pts.wt. of the inorganic mixture powder is, if necessary, mixed with <=200 pts.wt. of a foaming agent having a specific gravity of 0.01-1 and <=10 pts.wt. of reinforcing fibers having a fiber diameter of 1-500mum and a fiber length of 1-15mm to obtain an inorganic composition. The inorganic composition is molded and subsequently thermally cured to obtain an inorganic molded product excellent in durability.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、住宅やビルディング等
の内外壁、床材、瓦等の建築用部材として有用な、不燃
性、強度及び耐久性に優れた無機質成形体を成形する原
料として好適に使用される、無機質組成物に関するもの
である。FIELD OF THE INVENTION The present invention is used as a raw material for molding an inorganic molded article having excellent nonflammability, strength and durability, which is useful as a building member such as inner and outer walls of houses and buildings, flooring materials, roof tiles and the like. The present invention relates to an inorganic composition that is preferably used.

【０００２】[0002]

【従来の技術】アルカリの存在下で熱により硬化する無
機質組成物について幾つかの提案がされている。例え
ば、特開平４─５９６４８号公報に記載の如く、アルカ
リ金属珪酸塩水溶液とメタカオリン、コランダムあるい
はムライトの製造時に発生する集塵装置の灰、フライア
ッシュ等の無機固体成分、及び、充填材や有機ベントナ
イト等の混和材を混入することにより建築資材に有用な
無機成形体を製造することが提案され、特開平４─６１
３８号公報に記載されているように、フライアッシュを
アルカリ金属珪酸塩水溶液と混合し加熱硬化させること
により無機成形体とすることが提案されている。2. Description of the Related Art Several proposals have been made for an inorganic composition which is cured by heat in the presence of an alkali. For example, as described in JP-A-4-59648, ash of a dust collector generated during the production of an alkali metal silicate aqueous solution and metakaolin, corundum or mullite, an inorganic solid component such as fly ash, and a filler or an organic material. It has been proposed to produce an inorganic molded body useful for building materials by mixing an admixture such as bentonite.
As described in Japanese Patent Publication No. 38-38, it has been proposed that an inorganic molded body is obtained by mixing fly ash with an alkali metal silicate aqueous solution and heating and curing.

【０００３】[0003]

【発明が解決しようとする課題】しかし、この種の無機
質組成物を硬化させて無機質成形体を成形した場合、成
形過程における反応は、フライアッシュ等と金属珪酸塩
水溶液を主とする脱水縮合反応であるため体積収縮が生
じる。このため得られた無機質成形体にクラックが発生
し易く強度が低く、又、クラックが発生しない場合でも
無機質成形体内に残存応力があるため、耐熱水性等が低
く、耐久性が劣るという問題点がある。However, when an inorganic molded body is molded by curing this type of inorganic composition, the reaction in the molding process is a dehydration condensation reaction mainly composed of fly ash and an aqueous metal silicate solution. Therefore, volume contraction occurs. Therefore, the strength of the resulting inorganic molded body is apt to crack, and the strength is low, and even if the crack does not occur, there is residual stress in the inorganic molded body, so that the hot water resistance is low and the durability is poor. is there.

【０００４】本発明は、上記の如き従来の問題点を解消
し、特定のフライアッシュを用いることによりアルカリ
金属水酸化物溶液もしくはアルカリ金属珪酸塩水溶液と
の反応性を高め、又、反応硬化時の体積収縮を防止する
ことにより、又、特定の粉砕フライアッシュを用いるこ
とにより更にアルカリ金属水酸化物溶液もしくはアルカ
リ金属珪酸塩水溶液との反応性を高めることにより、不
燃性、強度、耐久性に優れた無機質硬化体を得ることが
できる無機質組成物を提供することを目的としてなされ
たものである。The present invention solves the above-mentioned conventional problems and enhances the reactivity with an alkali metal hydroxide solution or an alkali metal silicate aqueous solution by using a specific fly ash, and at the time of reaction curing. To prevent non-flammability, strength, and durability by increasing the reactivity with alkali metal hydroxide solution or alkali metal silicate aqueous solution by preventing specific volumetric shrinkage and by using specific pulverized fly ash. The purpose of the present invention is to provide an inorganic composition capable of obtaining an excellent inorganic cured product.

【０００５】[0005]

【課題を解決するための手段】本発明１は、粒径１０μ
ｍ以下の粉体を８０重量％以上含有するフライアッシュ
１００重量部と、アルカリ金属水酸化物溶液もしくはア
ルカリ金属珪酸塩水溶液１０〜３００重量部と、４０〜
２００μｍの粒径を有する珪砂１００〜３００μｍから
なる無機質組成物である。The present invention 1 has a particle size of 10 μm.
100 parts by weight of fly ash containing 80% by weight or more of powder of m or less, 10 to 300 parts by weight of alkali metal hydroxide solution or aqueous solution of alkali metal silicate, and 40 to 40 parts by weight.
It is an inorganic composition composed of silica sand having a particle size of 200 μm and having a particle size of 100 to 300 μm.

【０００６】一般に、フライアッシュとは、石炭火力発
電所のボイラーから排出される石炭灰のうち集塵機で捕
集した微細な灰からなり、ＪＩＳ Ａ ６２０１に合格
するものをいい、化学的組成として、ＳｉＯ2 とＡｌ2
Ｏ3 を主成分として含有し、Ｆｅ2 Ｏ3 、ＭｇＯ、Ｃａ
Ｏ等を副成分として含有する結晶質物質と非晶質物質の
混合物であり、その粒度分布は、粒径数〜数百μｍの広
い分布を有している。[0006] In general, fly ash means fine ash collected from a dust collector of coal ash discharged from a boiler of a coal-fired power plant, and has a chemical composition of JIS A 6201. SiO 2 and Al 2
Fe containing O 3 as a main component, Fe 2 O 3 , MgO, Ca
It is a mixture of a crystalline substance and an amorphous substance containing O and the like as an accessory component, and its particle size distribution has a wide distribution of several to several hundred μm.

【０００７】このようなフライアッシュを、そのままア
ルカリ金属水酸化物溶液もしくはアルカリ金属珪酸塩水
溶液と反応させても、強度、耐久性に優れた無機質硬化
体は得られない。そこで、フライアッシュの反応性を高
める方法について検討した結果、フライアッシュは各粒
度により粒子形、組成、構造等が異なる特異な特性を有
しており、その中で粒径１０μｍ以下のフライアッシュ
がアルカリ金属水酸化物溶液もしくはアルカリ金属珪酸
塩水溶液と驚異的な反応性を示すことを見出した。Even if such a fly ash is directly reacted with an alkali metal hydroxide solution or an alkali metal silicate aqueous solution, an inorganic cured product excellent in strength and durability cannot be obtained. Therefore, as a result of investigating a method for increasing the reactivity of fly ash, the fly ash has peculiar characteristics that the particle shape, composition, structure, etc. differ depending on each particle size. Among them, the fly ash having a particle size of 10 μm or less is It has been found that it shows a surprising reactivity with an alkali metal hydroxide solution or an alkali metal silicate aqueous solution.

【０００８】本発明１においては、粒径１０μｍ以下の
粉体を８０重量％以上含有するフライアッシュを用い
る。上記範囲を外れるフライアッシュを用いた場合は、
アルカリ金属水酸化物溶液もしくはアルカリ金属珪酸塩
水溶液との反応性が低く、強度、耐久性に優れた無機質
硬化体は得られない。In the present invention 1, fly ash containing 80% by weight or more of powder having a particle size of 10 μm or less is used. When using fly ash outside the above range,
The reactivity with an alkali metal hydroxide solution or an alkali metal silicate aqueous solution is low, and an inorganic cured product excellent in strength and durability cannot be obtained.

【０００９】更に、本発明１において使用されるフライ
アッシュの化学成分は、ＳｉＯ2 ４０〜８０重量％、Ａ
ｌ2 Ｏ3 １０〜４０重量％のものが好適である。又、粒
径１０μｍ以下のフライアッシュを作製する方法として
は、例えば、湿式沈降分級、風力分級、比重による分離
等通常行われている分級技術を使用することが可能であ
る。Further, the chemical composition of the fly ash used in the present invention 1 is 40 to 80% by weight of SiO 2 , A
Those having 10 to 40% by weight of l 2 O 3 are preferable. Further, as a method for producing fly ash having a particle size of 10 μm or less, it is possible to use a commonly used classification technique such as wet sedimentation classification, air classification, separation by specific gravity.

【００１０】本発明１において、アルカリ金属水酸化物
水溶液としては、一般式ＭＯＨ（ＭはＬｉ，Ｋ，Ｎａ又
はこれらの混合物を示す）で表されるものが使用でき、
その濃度は１０％以上である必要があり、１０〜５０％
の範囲が好適である。In the present invention 1, as the alkali metal hydroxide aqueous solution, one represented by the general formula MOH (M represents Li, K, Na or a mixture thereof) can be used,
The concentration must be 10% or more, 10-50%
Is preferred.

【００１１】本発明１において、アルカリ金属珪酸塩水
溶液としては、一般式Ｍ2 Ｏ・ｎＳｉＯ2 （ＭはＬｉ，
Ｋ，Ｎａ又はこれらの混合物を示し、ｎは８以下を示
す）で表されるものが使用できる。その水溶液濃度は１
０％以上である必要があり、１０〜５０％の範囲が好適
である。ｎが８を超えた場合、アルカリ金属珪酸塩水溶
液がゲル化をおこし易く粘度が急激に上昇するため、粉
体との混合が困難になる。In the present invention 1, the aqueous alkali metal silicate solution has the general formula M 2 O.nSiO 2 (M is Li,
K, Na or a mixture thereof and n is 8 or less) can be used. The concentration of the aqueous solution is 1
It is necessary to be 0% or more, and a range of 10 to 50% is preferable. When n exceeds 8, the alkali metal silicate aqueous solution is apt to gel and the viscosity rapidly increases, so that it becomes difficult to mix it with the powder.

【００１２】本発明１において、アルカリ金属水酸化物
水溶液もしくはアルカリ金属珪酸塩水溶液の添加量は、
上記のフライアッシュ１００重量部に対して、１０〜３
００重量部である必要があり、４０〜２５０重量部の範
囲が好ましい。添加量が１０重量部未満の場合には、粉
体と混練するのが難しくなり、逆に、３００重量部を超
える場合には、得られる無機質成形体の機械的強度が低
下する。In the present invention 1, the addition amount of the alkali metal hydroxide aqueous solution or the alkali metal silicate aqueous solution is
10 to 3 with respect to 100 parts by weight of the above fly ash
It should be 100 parts by weight, preferably in the range of 40 to 250 parts by weight. When the addition amount is less than 10 parts by weight, it is difficult to knead with the powder, and conversely, when the addition amount is more than 300 parts by weight, the mechanical strength of the obtained inorganic molded body decreases.

【００１３】本発明１においては、上記フライアッシュ
１００重量部に対して、粒径４０〜２００μｍ、好まし
くは粒径４０〜１５０μｍを有する珪砂１００〜３００
重量部が添加される。粒径が４０μｍ未満の場合、又は
粒径４０〜２００μｍのものの添加量が１００重量部未
満の場合には、フライアッシュとアルカリ金属水酸化物
水溶液もしくはアルカリ金属珪酸塩水溶液との脱水縮合
反応による体積収縮を十分防止できず、得られた無機質
成形体の耐水性試験による強度低下が大きくなり、逆
に、２００μｍを超えるか、粒径４０〜２００μｍのも
のの添加量が３００重量部を超える場合には、混練が困
難となり、更に得られる無機質成形体の機械的強度が低
下し、耐水試験による強度低下を大きくなる。In the present invention 1, 100 to 300 of silica sand having a particle size of 40 to 200 μm, preferably 40 to 150 μm, relative to 100 parts by weight of the fly ash.
Parts by weight are added. When the particle size is less than 40 μm, or when the amount of particles having a particle size of 40 to 200 μm is less than 100 parts by weight, the volume due to the dehydration condensation reaction between fly ash and the aqueous solution of alkali metal hydroxide or aqueous solution of alkali metal silicate. When the resulting inorganic molded article cannot be sufficiently prevented from shrinking, the strength of the resulting inorganic molded article is greatly reduced by the water resistance test. However, the kneading becomes difficult, the mechanical strength of the obtained inorganic molded article is reduced, and the strength reduction due to the water resistance test becomes large.

【００１４】本発明１のには、必要に応じて材料の軽量
化を目的として、有機質発泡体や無機質発泡体等の発泡
体が添加されてもよい。有機質発泡体としては、例え
ば、ポリ塩化ビニル、フェノール樹脂、ユリア樹脂、ポ
リスチレン、ポリウレタン、ポリエチレン等の合成樹脂
の粒状発泡体等が挙げられる。If desired, a foam such as an organic foam or an inorganic foam may be added to the first invention for the purpose of reducing the weight of the material. Examples of the organic foam include granular foam of synthetic resin such as polyvinyl chloride, phenol resin, urea resin, polystyrene, polyurethane and polyethylene.

【００１５】無機質発泡体としては、例えば、ガラスバ
ルーン、シラスバルーン、フライアッシュバルーン、シ
リカバルーン、パーライト、ヒル石、粒状発泡シリカ等
の粒状発泡体等が挙げられる。これらの発泡体は単独で
使用されてもよいし、又、併用されてもよい。Examples of the inorganic foams include granular foams such as glass balloons, shirasu balloons, fly ash balloons, silica balloons, perlite, leucite, and granular expanded silica. These foams may be used alone or in combination.

【００１６】これらの発泡体の比重は、０．０１〜１が
好適であり、０．０３〜０．７が更に好ましい。比重が
０．０１未満の場合には、得られる無機質成形体の機械
的強度が低下する傾向があり、逆に、１を超える場合に
は、得られる無機質成形体の軽量化の効果が得られない
傾向がある。The specific gravity of these foams is preferably 0.01 to 1, and more preferably 0.03 to 0.7. When the specific gravity is less than 0.01, the mechanical strength of the obtained inorganic molded body tends to decrease, and conversely, when the specific gravity exceeds 1, an effect of reducing the weight of the obtained inorganic molded body is obtained. Tend not to.

【００１７】これらの発泡体の添加量は、無機質粉体１
００重量部に対して、２００重量部以下が好ましい。添
加量が２００重量部を超える場合には、得られる無機質
成形体の機械的強度が低下する傾向がある。The amount of addition of these foams is 1
It is preferably 200 parts by weight or less with respect to 00 parts by weight. If the amount added exceeds 200 parts by weight, the mechanical strength of the resulting inorganic molded article tends to decrease.

【００１８】本発明１には、必要に応じて補強繊維が添
加されてもよい。補強繊維は、得られる無機質成形体に
付与したい性能に応じて任意のものが使用でき、例え
ば、ビニロン、ポリアミド、ポリエステル、ポリプロピ
レン、カーボン、アラミド、アクリル、レーヨン等の材
料からなる合成繊維、ガラス繊維、チタン酸カリウム、
鋼等の材料からなる無機繊維等が使用できる。In the present invention 1, reinforcing fibers may be added if necessary. As the reinforcing fiber, any one can be used according to the performance to be imparted to the obtained inorganic molded body, for example, vinylon, polyamide, polyester, polypropylene, carbon, aramid, acryl, synthetic fiber made of a material such as rayon, glass fiber. , Potassium titanate,
Inorganic fibers made of materials such as steel can be used.

【００１９】補強繊維は、繊維径１〜５００μｍ、繊維
長１〜１５ｍｍのものが好ましい。補強繊維の太さは、
細すぎると混合時に再凝集し、交絡によりファイバーボ
ールが形成され易く、得られる無機質成形体の強度はそ
れ以上改善されない傾向があり、太過ぎるか短か過ぎる
と引張り強度向上等の補強効果が小さい傾向があり、長
過ぎると補強繊維の分散性及び配向性が低下する傾向が
ある。The reinforcing fiber preferably has a fiber diameter of 1 to 500 μm and a fiber length of 1 to 15 mm. The thickness of the reinforcing fiber is
If it is too thin, it reaggregates during mixing, fiber balls are easily formed by entanglement, and the strength of the resulting inorganic molded article tends not to be improved further.If it is too thick or too short, the reinforcing effect such as improvement in tensile strength is small. If the length is too long, the dispersibility and orientation of the reinforcing fibers tend to deteriorate.

【００２０】補強繊維の添加量は、無機質粉体１００重
量部に対して、１０重量部以下が好ましい。添加量が１
０重量部を超える場合には、補強繊維の分散性が低下す
る傾向がある。The amount of the reinforcing fiber added is preferably 10 parts by weight or less with respect to 100 parts by weight of the inorganic powder. Addition amount is 1
If the amount exceeds 0 parts by weight, the dispersibility of the reinforcing fibers tends to decrease.

【００２１】本発明１の無機質組成物から無機質成形体
を成形する方法としては、本発明の無機質組成物と、ア
ルカリ金属水酸化物水溶液もしくはアルカリ金属珪酸塩
水溶液と、必要に応じて、無機質充填材、有機質発泡体
もしくは無機質発泡体、補強繊維とを混練して得られた
混合物を原料として、注型法、プレス法、押出成形法等
の従来公知の方法により、成形する方法が採用できる。
無機質成形体は常温で硬化させてもよいが、５０〜２０
０℃の温度で加熱硬化させるのが好ましい。As a method for molding an inorganic molded body from the inorganic composition of the present invention 1, the inorganic composition of the present invention and an aqueous solution of an alkali metal hydroxide or an aqueous solution of an alkali metal silicate, and if necessary, an inorganic filling A molding method can be adopted by a conventionally known method such as a casting method, a pressing method or an extrusion molding method using a mixture obtained by kneading a material, an organic foam or an inorganic foam and a reinforcing fiber as a raw material.
Although the inorganic molded body may be cured at room temperature, it may be 50 to 20.
It is preferable to heat-cure at a temperature of 0 ° C.

【００２２】本発明２は、本発明１の無機質組成物と、
粒径０．０１〜３０μｍのシリカ粉１〜６００重量部か
らなる無機質組成物である。The present invention 2 is the inorganic composition of the present invention 1,
An inorganic composition comprising 1 to 600 parts by weight of silica powder having a particle size of 0.01 to 30 μm.

【００２３】シリカ粉の粒径が０．０１未満の場合、又
は粒径０．０１〜３０μｍのものの添加量が１重量部未
満の場合には、シリカ粉の比表面積が大きく、混練に必
要なアルカリ金属水酸化物水溶液もしくはアルカリ金属
珪酸塩水溶液の添加量が多くなるため、得られる無機質
成形体の機械的強度及び耐久性が低下し、逆に、３０μ
ｍを超える場合、又は粒径０．０１〜３０μｍのものの
添加量が６００重量部を超えるには、珪砂との細密充填
効果が得られず、得られる無機質成形体の機械的強度及
び耐久性が低下する。When the particle size of silica powder is less than 0.01, or when the addition amount of particles having a particle size of 0.01 to 30 μm is less than 1 part by weight, the specific surface area of silica powder is large and necessary for kneading. Since the addition amount of the alkali metal hydroxide aqueous solution or the alkali metal silicate aqueous solution is large, the mechanical strength and durability of the obtained inorganic molded body are deteriorated, and conversely, 30 μm
If it exceeds m, or if the addition amount of particles having a particle size of 0.01 to 30 μm exceeds 600 parts by weight, the effect of finely packing with silica sand cannot be obtained, and the mechanical strength and durability of the obtained inorganic molded article are descend.

【００２４】又、本発明２の無機質組成物から無機質成
形体を成形する方法としては、本発明１と同様の方法が
採用できる。As a method for molding an inorganic molded body from the inorganic composition of the present invention 2, the same method as in the present invention 1 can be adopted.

【００２５】更に、１０μｍよりも大きい粒径のフライ
アッシュの形態、構造を詳細に検討した結果、粒径１０
〜２００μｍのフライアッシュは、シリカクォーツ、カ
ルシウム、鉄を主成分とする結晶粒子や、珪素やアルニ
ウムの中空状粒子並びに多孔性粒子の他に、１０μｍ以
下の小球状の粉体を内包する中空状粒子があることを見
出した。Furthermore, as a result of detailed examination of the morphology and structure of fly ash having a particle size of more than 10 μm, a particle size of 10
~ 200μm fly ash is a hollow particle containing silica particles, calcium and iron as the main components, hollow particles of silicon and alnium, and porous particles, as well as small spherical particles of 10μm or less. We found that there were particles.

【００２６】そこで、粒径１０〜２００μｍのフライア
ッシュであって、１０μｍ以下の小球状の粉体を内包す
る中空状粒子を含むものを破壊して、強度的欠陥をなく
すと共に、反応活性な内部小球を抽出することにより本
粒径の粒子を有効に使用できると考え、フライアッシュ
の粉砕法について検討を行った。Therefore, fly ash having a particle size of 10 to 200 μm, which contains hollow particles enclosing a small spherical powder having a particle size of 10 μm or less, is destroyed to eliminate a strength defect and to have a reaction-active internal structure. We considered that particles of this size could be effectively used by extracting small spheres, and examined the method of crushing fly ash.

【００２７】その結果、粒径１０〜２００μｍの粒子の
存在量が１０重量％以上であって、且つ、その領域中の
粒子内に形状が小球状の粉体を内包しているフライアッ
シュを、１０μ以下の粒径の存在量が８０重量％以上に
なるまで粉砕分級した粉砕フライアッシュとすることに
より、著しいアルカリ反応性と、無機質硬化体に強度を
発揮させることができることに成功した。As a result, the fly ash in which the abundance of particles having a particle size of 10 to 200 μm is 10% by weight or more, and the particles in the region contain a small spherical powder, By using a crushed fly ash that has been crushed and classified until the amount of particles having a particle size of 10 μm or less reaches 80% by weight or more, it has succeeded in exerting remarkable alkali reactivity and strength of an inorganic cured body.

【００２８】本発明３は、小球状の粉体を内包した粒径
１０〜２００μｍの粒子が１０重量％以上存在している
フライアッシュを、粒径１０μｍ以下の粉体を８０重量
％以上含有するまで粉砕したフライアッシュ１００重量
部と、水溶液濃度が１０％以上のアルカリ金属水酸化物
水溶液もしくはアルカリ金属珪酸塩水溶液１０〜３００
重量部からなる無機質組成物である。The present invention 3 contains fly ash containing 10% by weight or more of particles having a particle size of 10 to 200 μm, which contains a small spherical powder, and 80% by weight or more of powder having a particle size of 10 μm or less. 100 parts by weight of fly ash crushed up to 10% and an aqueous solution of alkali metal hydroxide or alkali metal silicate having a concentration of 10% or more
It is an inorganic composition consisting of parts by weight.

【００２９】ここで、フライアッシュ原粉を１０μｍ以
下の粒径の存在量が８０重量％以上になるまで粉砕して
本発明３において使用するフライアッシュとなす方法と
しては、ジェット粉砕機、ボール媒体ミル、ロール転動
型粉砕機等の微粉砕機を使用することにより可能であ
る。更に、風力、ふるい、動力等を利用する乾式分級機
が粉砕機内の備わった内部分級方式の粉砕分級システム
もしくは上記粉砕機と分級機を連続化した閉回路粉砕方
式の粉砕分級システムを使用することにより粉砕処理効
率が向上するため有効である。中でもジェット粉砕機と
風力粉砕機が組み合わさった粉砕分級システムが、処理
効率、処理量的に好ましい。Here, as a method of crushing the fly ash raw powder until the existing amount of particles having a particle size of 10 μm or less reaches 80% by weight or more to obtain the fly ash used in the present invention 3, a jet crusher and a ball medium are used. It is possible by using a fine pulverizer such as a mill or a roll rolling type pulverizer. Furthermore, use an internal partial classification type pulverization classification system in which a dry type classification machine utilizing wind power, a sieve, power, etc. is used in the pulverizer, or a closed circuit pulverization classification system in which the above pulverizer and classifier are continuous. This is effective because the efficiency of crushing treatment is improved. Above all, a pulverizing / classifying system in which a jet pulverizer and a wind pulverizer are combined is preferable in terms of treatment efficiency and treatment amount.

【００３０】本発明３においては、フライアッシュとし
ては、上記のフライアッシュ原粉を、粒径１０μｍ以下
の粉体を８０重量％以上含有するまで粉砕したものを用
いることが重要であり、この範囲を外れる場合には、反
応性が顕著に高く、顕著に強度、耐久性の面で、優れた
無機質成形体を成形することができない。In the present invention 3, as the fly ash, it is important to use the above-mentioned fly ash raw powder pulverized to a content of 80% by weight or more of powder having a particle size of 10 μm or less. If it is out of the range, the reactivity is remarkably high, and it is not possible to mold an excellent inorganic molded body in terms of strength and durability.

【００３１】本発明３において、アルカリ金属水酸化物
水溶液もしくはアルカリ金属珪酸塩水溶液としては、本
発明１と同様のものが同様の添加量使用される。本発明
３においては、必要に応じて、本発明１と同様の発泡
体、補強繊維が添加されてもよい。In the present invention 3, the same alkali metal hydroxide aqueous solution or alkali metal silicate aqueous solution as in the first invention is used in the same addition amount. In the present invention 3, the same foam and reinforcing fiber as in the present invention 1 may be added, if necessary.

【００３２】又、本発明３においては、必要に応じて、
無機質充填材が添加されてもよい。無機質充填材として
は、例えば、タルク、ベントナイト、珪砂、ジルコンサ
ンド、フライアッシュ、シリカヒューム、スラグ、炭酸
カルシウム、マイカ、粘土、ばん土頁岩、ウォラストナ
イト、火山灰、ポーキサイト、セメント、石灰、石膏、
アルミナ、フピオゥライト等の一般にセメント等の無機
硬化材料に使用されている材料が使用できる。In the present invention 3, if necessary,
Inorganic fillers may be added. Examples of the inorganic filler include talc, bentonite, silica sand, zircon sand, fly ash, silica fume, slag, calcium carbonate, mica, clay, shale shale, wollastonite, volcanic ash, poxite, cement, lime, gypsum,
Materials generally used for inorganic hardened materials such as cement such as alumina and fupiolite can be used.

【００３３】これらの無機質充填材は、得られる無機質
成形体の用途に応じて適宜選択され、単独で使用しても
よいし、混合して使用してもよい。無機質充填材の添加
量は、フライアッシュ１００重量部に対して、５００重
量部以下が好ましい。添加量が５００重量部を超える場
合には、得られる無機質成形体の機械的強度が低下する
傾向がある。These inorganic fillers are appropriately selected according to the intended use of the obtained inorganic molded body, and may be used alone or in combination. The addition amount of the inorganic filler is preferably 500 parts by weight or less with respect to 100 parts by weight of fly ash. If the amount added exceeds 500 parts by weight, the mechanical strength of the obtained inorganic molded body tends to decrease.

【作用】本発明１の無機質組成物は、粒径１０μｍ以下
の粉体を８０重量％以上含有するフライアッシュ１００
重量部と、水溶液の濃度が１０％以上のアルカリ金属水
酸化物溶液もしくはアルカリ金属珪酸塩水溶液１０〜３
００重量部と、粒径４０〜２００μｍの珪砂１００〜３
００重量部からなることにより、フライアッシュとアル
カリ金属水酸化物溶液もしくはアルカリ金属珪酸塩水溶
液との反応性が高く、且つ、フライアッシュとアルカリ
金属水酸化物水溶液もしくはアルカリ金属珪酸塩水溶液
との脱水縮合反応による体積収縮を、珪砂が十分吸収す
るので、不燃性、強度及び耐久性に優れた無機質硬化体
を得ることができる。The inorganic composition of the present invention 1 is a fly ash 100 containing 80% by weight or more of powder having a particle size of 10 μm or less.
10 parts by weight of an alkali metal hydroxide solution or an alkali metal silicate solution having a concentration of 10% or more by weight.
00 parts by weight and 100 to 3 of silica sand having a particle size of 40 to 200 μm
By comprising 100 parts by weight, the reactivity of fly ash with the alkali metal hydroxide solution or the alkali metal silicate aqueous solution is high, and the dehydration between the fly ash and the alkali metal hydroxide aqueous solution or the alkali metal silicate aqueous solution is carried out. Since the silica sand sufficiently absorbs the volume shrinkage due to the condensation reaction, it is possible to obtain an inorganic cured product having excellent nonflammability, strength and durability.

【００３４】本発明２の無機質組成物は、本発明１の無
機質組成物と、粒径０．０１〜３０μｍのシリカ粉１〜
６００重量部からなることにより、フライアッシュとア
ルカリ金属水酸化物水溶液もしくはアルカリ金属珪酸塩
水溶液との脱水縮合反応による体積収縮を、珪砂とシリ
カ粉とが細密充填状態で十分吸収するので、更に、不燃
性、強度及び耐久性に優れた無機質硬化体を得ることが
できる。The inorganic composition of the present invention 2 comprises the inorganic composition of the present invention 1 and silica powder 1 to 1 having a particle diameter of 0.01 to 30 μm.
By comprising 600 parts by weight, the volumetric shrinkage due to the dehydration condensation reaction between the fly ash and the alkali metal hydroxide aqueous solution or the alkali metal silicate aqueous solution is sufficiently absorbed by the silica sand and the silica powder in a closely packed state. It is possible to obtain an inorganic cured product having excellent nonflammability, strength and durability.

【００３５】本発明３の無機質組成物は、小球状の粉体
を内包した粒径１０〜２００μｍの粒子が１０重量％以
上存在しているフライアッシュを、粒径１０μｍ以下の
粉体を８０重量％以上含有するまで粉砕したフライアッ
シュ１００重量部と、水溶液濃度が１０％以上のアルカ
リ金属水酸化物水溶液もしくはアルカリ金属珪酸塩水溶
液１０〜３００重量部からなることにより、フライアッ
シュとアルカリ金属水酸化物溶液もしくはアルカリ金属
珪酸塩水溶液との反応性が高いので、不燃性、強度及び
耐久性に優れた無機質硬化体を得ることができる。The inorganic composition of the present invention 3 comprises a fly ash containing 10% by weight or more of particles having a particle size of 10 to 200 μm containing a small spherical powder, and 80% by weight of a powder having a particle size of 10 μm or less. % Of fly ash pulverized to a content of 10% or more and 10 to 300 parts by weight of an aqueous alkali metal hydroxide solution or an aqueous alkali metal silicate solution having an aqueous solution concentration of 10% or more. Since it has high reactivity with the material solution or the aqueous solution of alkali metal silicate, it is possible to obtain an inorganic cured product having excellent noncombustibility, strength and durability.

【００３６】[0036]

【実施例】１０μｍ以下のフライアッシュの調整方法 フライアッシュ（関電化工社製、平均粒径２０μｍ、比
重面積１．８ｍ2 ／ｇ、ＪＩＳ Ａ ６２０１相等品）
を分級機（日清エンジニアリング社製、商品名「ＴＣ─
１５」）を用いて、粒径１０μｍ以下のフライアッシュ
を作製した。その粉体を粒度分布測定装置（レーザー回
折式粒度分布計、セイシン企業社製、商品名「ＰＲＯ─
７０００Ｓ」）を用いて、粒度分布を測定した結果、全
て粒径１０μｍ以下であった。[Example] Method for adjusting fly ash of 10 μm or less Fly ash (manufactured by KANDENKA CORPORATION, average particle size 20 μm, specific gravity area 1.8 m 2 / g, JIS A 6201 phase equivalent product)
Classifier (manufactured by Nisshin Engineering Co., Ltd., trade name "TC-
15 ") was used to prepare fly ash having a particle size of 10 μm or less. Particle size distribution measuring device (laser diffraction type particle size distribution meter, manufactured by Seishin Enterprise Co., Ltd., trade name "PRO-
7000S ") was used to measure the particle size distribution. As a result, all the particle sizes were 10 μm or less.

【００３７】珪砂の分級方法 珪砂をＪＩＳ規格の分級ふるいを用いて、粒径４０〜１
４９μｍ、２１０〜５９０μｍ、４２０〜８４０μｍに
それぞれ分級した。 Method for classifying silica sand Particle size of silica sand is 40 to 1 using a JIS standard classification sieve.
The particles were classified into 49 μm, 210 to 590 μm, and 420 to 840 μm, respectively.

【００３８】実施例１〜８、比較例１〜８ 表１及び表２に示した所定量の粒径１０μｍ以下のフラ
イアッシュ、各粒度に分級した珪砂、珪石粉（住友セメ
ント社製、粒径１〜２０μｍ）、ビニロン繊維（太さ
１．８デニール、長さ６ｍｍ）、所定量のアルカリ金属
珪酸塩水溶液を、オムニミキサーに供給し、５分間混合
した。得られた混合物を大きさ１５０×５０ｍｍ、高さ
１０ｍｍの型枠内に注入し、オーブン内で表１及び表２
に記載した温度、時間で硬化させて、無機質硬化体を得
た。得られた無機質硬化体について、以下の項目につい
て評価した。その結果を表１及び表２に示した。 Examples 1 to 8 and Comparative Examples 1 to 8 Fly ash having a predetermined particle size of 10 μm or less shown in Table 1 and Table 2, silica sand classified to each particle size, silica stone powder (manufactured by Sumitomo Cement Co., particle size 1 to 20 μm), vinylon fibers (thickness 1.8 denier, length 6 mm), and a predetermined amount of an alkali metal silicate aqueous solution were supplied to an omni mixer and mixed for 5 minutes. The obtained mixture was poured into a mold having a size of 150 × 50 mm and a height of 10 mm, and the mixture was placed in an oven as shown in Table 1 and Table 2.
It was cured at the temperature and time described in 1. to obtain an inorganic cured product. The following items were evaluated for the obtained inorganic cured product. The results are shown in Tables 1 and 2.

【００３９】硬化状態 目視により外観を評価した。曲げ強度 得られた無機質硬化体の曲げ強度を、ＪＩＳ Ａ １４
０８の方法に準じて測定した。ブランクの硬化体につい
ては、５時間硬化させた後、５０℃のオーブン内に５時
間乾燥後、気乾状態に達した無機質硬化体について曲げ
強度を測定した。The appearance was evaluated by visual inspection of the cured state . Bending strength The bending strength of the obtained inorganic cured product was measured according to JIS A 14
It measured according to the method of 08. The blank cured product was cured for 5 hours, dried in an oven at 50 ° C. for 5 hours, and then the flexural strength of the air-dried inorganic cured product was measured.

【００４０】熱水試験 ９８℃以上の熱水中に無機質硬化体を８時間放置し、割
れ、クラックを確認し、上記の測定方法により曲げ強
度を測定し、ブランクに対する強度維持率を測定した。Hot Water Test The cured inorganic material was allowed to stand in hot water at 98 ° C. or higher for 8 hours, cracks and cracks were confirmed, the bending strength was measured by the above measuring method, and the strength retention ratio to the blank was measured.

【００４１】実施例９、１０ 表１及び表２に示した所定量の粒径１０μｍ以下のフラ
イアッシュ、各粒度に分級した珪砂、珪石粉（住友セメ
ント社製、粒度分布１〜２０μｍ）、ビニロン繊維（太
さ１．８デニール、長さ６ｍｍ）、所定濃度のアルカリ
金属珪酸塩水溶液をオムニミキサーに供給し、５分間混
合した。得られた混合物を大きさ１５０×１５０ｍｍ、
高さ１０ｍｍの型枠内ち注入し、オーブン内で表１及び
表２に記載した温度時間にて硬化させた。得られた無機
質硬化体について、実施例１〜８と同様の評価を行っ
た。その結果を表１及び表２に示した。 Example 9, 10 Fly ash having a particle size of 10 μm or less in a predetermined amount shown in Table 1 and Table 2, silica sand classified to each particle size, silica stone powder (manufactured by Sumitomo Cement Co., particle size distribution 1 to 20 μm), vinylon Fiber (thickness 1.8 denier, length 6 mm) and an alkali metal silicate aqueous solution having a predetermined concentration were supplied to an omni mixer and mixed for 5 minutes. The resulting mixture is sized 150 × 150 mm,
It was poured into a mold having a height of 10 mm and cured in the oven at the temperature and time shown in Table 1 and Table 2. The obtained inorganic cured product was evaluated in the same manner as in Examples 1-8. The results are shown in Tables 1 and 2.

【００４２】[0042]

【表１】 [Table 1]

【００４３】[0043]

【表２】 [Table 2]

【００４４】表１及び表２からも明らかな如く、実施例
１〜１０の場合には、いずれも得られた無機質成形体の
曲げ強度及び熱水試験後の強度維持率が高い。これに対
して、比較例１、２の如く、粒径４０〜２００μｍの珪
砂の添加量が少な過ぎる場合には、得られた無機質成形
体の熱水試験後の強度維持率が低く、比較例３の如く、
粒径４０〜２００μｍの珪砂の添加量が多い過ぎたり、
比較例４、５の如く珪砂の粒径が２００μｍを超える場
合には、得られた無機質成形体の曲げ強度及び熱水試験
後の強度維持率が低くなるか、混練できなくなってしま
う。As is clear from Tables 1 and 2, in each of Examples 1 to 10, the bending strength of the obtained inorganic molded articles and the strength retention rate after the hot water test are high. On the other hand, as in Comparative Examples 1 and 2, when the addition amount of silica sand having a particle size of 40 to 200 μm is too small, the strength retention rate of the obtained inorganic molded body after the hot water test is low, and Comparative Example Like 3
Too much added silica sand with a particle size of 40-200 μm,
When the particle diameter of the silica sand exceeds 200 μm as in Comparative Examples 4 and 5, the bending strength of the obtained inorganic molded body and the strength retention rate after the hot water test become low, or the kneading becomes impossible.

【００４５】又、比較例６の如く、シリカ粉の添加量が
多過ぎる場合には、得られた無機質成形体の熱水試験後
の強度維持率が低くなってしまう。又、比較例７の如
く、アルカリ金属珪酸塩水溶液の添加量が多過ぎる場合
には、得られた無機質成形品にクラックが発生し、比較
例８の如く、アルカリ金属珪酸塩水溶液の添加量が少過
ぎる場合には、混練できなくてってしまう。When the amount of silica powder added is too large as in Comparative Example 6, the strength retention of the obtained inorganic molded article after the hot water test becomes low. Further, as in Comparative Example 7, when the amount of the alkali metal silicate aqueous solution added was too large, cracks occurred in the obtained inorganic molded product, and as in Comparative Example 8, the amount of the alkali metal silicate aqueous solution added was If it is too small, it will not be possible to knead.

【００４６】フライッシュの粉砕分級方法 表３に示した及びの小球状粉体包含フライアッシュ
を、それぞれ、粉砕分級システム（マキノ社製、ＦＰ型
ジェットミル）を用いて、圧力３．５ｋｇｆ／ｃｍ2 、
粉砕風量２．７Ｎｍ3 ／ｍｉｎで粉砕した。 Method for crushing and classifying flysh Each of the fly ash containing the small spherical powders of and shown in Table 3 was subjected to a pressure of 3.5 kgf / cm using a crushing and classification system (FP type jet mill manufactured by Makino Co., Ltd.). 2 ,
The powder was crushed with a crushing air volume of 2.7 Nm 3 / min.

【００４７】次に、その粉体を粒度分析装置（レーザー
回折式粒度分析計 セイシン企業社製、商品名「ＰＲＯ
−７０００Ｓ」）を用いて、粒度分布を測定した結果、
粒径１０μｍ以下の粉砕フライアッシュが、では９５
％（以下、粉砕フライアッシュＡという）、では９７
％（以下、粉砕フライアッシュＢという）であった。Next, the powder was analyzed by a particle size analyzer (laser diffraction type particle size analyzer manufactured by Seishin Enterprise Co., Ltd. under the trade name "PRO").
-7000S ") was used to measure the particle size distribution,
Milled fly ash with a particle size of 10 μm or less
% (Hereinafter referred to as crushed fly ash A), 97
% (Hereinafter referred to as crushed fly ash B).

【００４８】表３に示した及びの小球状粉体包含フ
ライアッシュを、それぞれ、振動ミル（三英製作所製、
商品名「ＭＢ−１」）で２４時間粉砕した。次に、その
粉体を上記と同様の粒度分析装置を用いて、粒度分布を
測定した結果、粒径１０μｍ以下の粉砕フライアッシュ
が、では８１％（以下、粉砕フライアッシュＣとい
う）、では８６％（以下、粉砕フライアッシュＤとい
う）であった。The fly ash containing small spherical powders of and shown in Table 3 were respectively subjected to a vibration mill (manufactured by Sanei Seisakusho,
The product was crushed for 24 hours under the trade name "MB-1"). Next, the particle size distribution of the powder was measured using the same particle size analyzer as described above. As a result, 81% of the pulverized fly ash having a particle size of 10 μm or less (hereinafter referred to as pulverized fly ash C) and 86 were obtained. % (Hereinafter referred to as crushed fly ash D).

【００４９】尚、表３に示した及びの小球状粉体包
含フライアッシュを破壊したもの、顕微鏡にて観察した
ところ、中空状粒子内に小球状粉体を内包しているのが
観察された。When the fly ash containing the small spherical powders shown in and of Table 3 was destroyed and observed under a microscope, it was observed that the small spherical powders were included in the hollow particles. .

【００５０】[0050]

【表３】 [Table 3]

【００５１】実施例１１〜１４ 表４に示した粉砕フライアッシュの所定量、８号珪砂２
００重量部、ビニロン繊維（クラレ社製、商品名「ＲＭ
１８２」）２重量部を、オムニミキサーで５分間混合
後、表４に示したＫ2 Ｏ１モル当りＳｉＯ2 が１．５モ
ルを含有する水溶液濃度５０％のアルカリ珪酸塩水溶液
の所定量を添加し、更に５分間混合し、その混合物を大
きさ４０×１５０ｍｍ、厚さ１５ｍｍの型枠中に流し込
み、これを９０℃のオーブン中で硬化した脱型し、５０
℃のオーブン中で４時間乾燥させて、無機質成形体を得
た。得られた無機質成形体について、実施例１〜８と同
様の評価を行った。その結果を表４に示す。 Examples 11 to 14 Predetermined amount of crushed fly ash shown in Table 4, No. 8 silica sand 2
00 parts by weight, vinylon fiber (Kuraray Co., Ltd., trade name "RM
182 ") 2 parts by weight with an omni mixer for 5 minutes, and then added with a predetermined amount of an aqueous solution of an alkali silicate having an aqueous solution concentration of 50% containing 1.5 mol of SiO 2 per mol of K 2 O shown in Table 4. And mix for an additional 5 minutes, pour the mixture into a mold 40 × 150 mm in size and 15 mm thick, which was cured in an oven at 90 ° C.
It was dried in an oven at ℃ for 4 hours to obtain an inorganic molded body. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 4.

【００５２】実施例１５、１６ Ｋ2 Ｏ１モル当りＳｉＯ2 が１．５モルを含有する水溶
液濃度５０％アルカリ珪酸塩水溶液９７重量部の代わり
に、表４に示した水溶液濃度５０％ＫＯＨ水溶液の所定
量を使用したこと以外は実施例１１〜１４と同様にし
て、無機質成形体を得た。得られた無機質成形体につい
て、実施例１〜８と同様の評価を行った。その結果を表
４に示した。 Examples 15 and 16 In place of 97 parts by weight of a 50% aqueous solution of an alkali silicate solution containing 1.5 moles of SiO 2 per 1 mole of K 2 O, an aqueous solution of KOH having a concentration of 50% shown in Table 4 was used. Inorganic moldings were obtained in the same manner as in Examples 11 to 14 except that a predetermined amount was used. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 4.

【００５３】実施例１７ Ｋ2 Ｏ１モル当りＳｉＯ2 が１．５モルを含有する水溶
液濃度５０％アルカリ珪酸塩水溶液９７重量部の代わり
に、Ｎａ2 Ｏ１モル当りＳｉＯ2 が１．５モルを含有す
る水溶液濃度５０％アルカリ珪酸塩水溶液９９重量部を
使用したこと以外は実施例１１〜１４と同様にして、無
機質成形体を得た。得られた無機質成形体について、実
施例１〜８と同様の評価を行った。その結果を表４に示
した。 Example 17 : 1.5 mol of SiO 2 per mol of K 2 O Concentration of aqueous solution of 97% by weight of 50% alkali silicate aqueous solution, 1.5 mol of SiO 2 per mol of Na 2 O An inorganic molded body was obtained in the same manner as in Examples 11 to 14 except that 99 parts by weight of an aqueous solution of alkali silicate having a concentration of 50% was used. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 4.

【００５４】実施例１８ 粉砕フライアッシュＢ１００重量部、８号珪砂２００重
量部、ビニロン繊維（クラレ社製、商品名「ＲＭ１８
２」）２重量部をオムニミキサーで５分間混合後、Ｋ2
Ｏ１モル当りＳｉＯ2 が１．５モル含有する水溶液濃度
５０％のアルカリ珪酸塩水溶液５０重量部を添加し、更
に５分間混合し、その混合物を大きさ４０×１５０ｍ
ｍ、厚み１５ｍｍの型枠中に充填後、温度１１０℃、圧
力６０ｋｇｆ／ｃｍ2 でプレスし、脱型後５０℃のオー
ブン中で４時間乾燥して無機質を得た。得られた無機質
成形体について、実施例１〜８と同様の評価を行った。
その結果を表４に示した。 Example 18 Pulverized fly ash B 100 parts by weight, No. 8 silica sand 200 parts by weight, vinylon fiber (Kuraray Co., Ltd., trade name "RM18"
2 ") 2 parts by weight are mixed in an omni mixer for 5 minutes and then K 2
50 parts by weight of an aqueous solution of alkali silicate having a concentration of 50% aqueous solution containing 1.5 mol of SiO 2 per 1 mol of O is added and mixed for 5 minutes, and the mixture is 40 × 150 m in size.
After filling in a mold having a thickness of m and a thickness of 15 mm, the mold was pressed at a temperature of 110 ° C. and a pressure of 60 kgf / cm 2 , and after demolding, dried in an oven at 50 ° C. for 4 hours to obtain an inorganic substance. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body.
The results are shown in Table 4.

【００５５】実施例１９ 粉砕フライアッシュＢ１００重量部、８号珪砂２００重
量部、ビニロン繊維（クラレ社製、商品名「ＲＭ１８
２」）２重量部をオムニミキサーで５分間混合後、Ｋ2
Ｏ１モル当りＳｉＯ2 が１．５モル含有する水溶液濃度
５０％のアルカリ珪酸塩水溶液５０重量部を添加し、更
に５分間混合した。その混合物を、振動プレス成形機
（アサヒエンジニアリング社製、商品名「ＳＡ−５
０」）上に設置された大きさ４０×１５０ｍｍ、厚み１
５ｍｍの型枠中に充填後、温度１１０℃、圧力６０ｋｇ
ｆ／ｃｍ2 、振動数１０００Ｈｚ、振幅１０μｍでプレ
スし、脱型後５０℃のオーブン中で４時間乾燥して無機
質を得た。得られた無機質成形体について、実施例１〜
８と同様の評価を行った。その結果を表４に示した。 Example 19 100 parts by weight of crushed fly ash B, 200 parts by weight of No. 8 silica sand, vinylon fiber (trade name "RM18 manufactured by Kuraray Co., Ltd."
2 ") 2 parts by weight are mixed in an omni mixer for 5 minutes and then K 2
50 parts by weight of an aqueous solution of alkali silicate having a concentration of 50% aqueous solution containing 1.5 mol of SiO 2 per 1 mol of O was added, and the mixture was further mixed for 5 minutes. A vibration press molding machine (manufactured by Asahi Engineering Co., Ltd., trade name "SA-5"
0 ") size 40 x 150 mm installed on top, thickness 1
After filling into a 5 mm mold, temperature 110 ° C, pressure 60 kg
It was pressed at f / cm 2 , frequency of 1000 Hz, and amplitude of 10 μm, and after demolding, dried in an oven at 50 ° C. for 4 hours to obtain an inorganic substance. About the obtained inorganic molded body, Example 1
The same evaluation as in 8 was performed. The results are shown in Table 4.

【００５６】比較例９ 粉砕フライアッシュＡの代わり、表１中ののフライア
ッシュ原粉を用いたこと、Ｋ2 Ｏ１モル当りＳｉＯ2 が
１．５モルを含有する水溶液濃度５０％アルカリ珪酸塩
水溶液９７重量部の代わりに、水溶液濃度５０％ＫＯＨ
水溶液１０５重量部を使用したこと以外は実施例１１と
同様にして、無機質成形体を得た。得られた無機質成形
体について、実施例１〜８と同様の評価を行った。その
結果を表５に示した。 Comparative Example 9 Instead of the pulverized fly ash A, the fly ash raw powder shown in Table 1 was used, and an aqueous solution containing 50% of an aqueous solution containing 1.5 mol of SiO 2 per 1 mol of K 2 O was used. Instead of 97 parts by weight, aqueous solution concentration 50% KOH
An inorganic molded body was obtained in the same manner as in Example 11 except that 105 parts by weight of the aqueous solution was used. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 5.

【００５７】比較例１０ 粉砕フライアッシュＡの代わり、表１中ののフライア
ッシュ原粉を用いたこと、Ｋ2 Ｏ１モル当りＳｉＯ2 が
１．５モルを含有する水溶液濃度５０％アルカリ珪酸塩
水溶液の添加量を１０３重量部としたこと以外は、実施
例１１と同様にして、無機質成形体を得た。得られた無
機質成形体について、実施例１〜８と同様の評価を行っ
た。その結果を表５に示した。 Comparative Example 10 The fly ash raw powder shown in Table 1 was used in place of the pulverized fly ash A, and an aqueous solution containing 50 mol of an aqueous solution containing 1.5 mol of SiO 2 per mol of K 2 O was used. An inorganic molded body was obtained in the same manner as in Example 11 except that the addition amount of 10 was 103 parts by weight. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 5.

【００５８】比較例１１ 粉砕フライアッシュＡの代わり、表１中ののフライア
ッシュ原粉を振動ミルで３０分間粉砕した粉砕フライア
ッシュ（粒径１０μｍ以下の粉砕フライアッシュ６０
％）を用いたこと、Ｋ2 Ｏ１モル当りＳｉＯ2 が１．５
モルを含有する水溶液濃度５０％アルカリ珪酸塩水溶液
の添加量を１０２重量部としたこと以外は、実施例１１
と同様にして、無機質成形体を得た。得られた無機質成
形体について、実施例１〜８と同様の評価を行った。そ
の結果を表５に示した。 Comparative Example 11 Instead of the crushed fly ash A, the crushed fly ash in Table 1 was crushed for 30 minutes by a vibration mill (crushed fly ash having a particle size of 10 μm or less 60
%), SiO 2 is 1.5 per mol of K 2 O.
Example 11 except that the addition amount of a 50% aqueous solution of an alkali silicate containing a mole was 102 parts by weight.
An inorganic molded body was obtained in the same manner as in. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 5.

【００５９】比較例１２ 粉砕フライアッシュＡの代わり、表１中ののフライア
ッシュ原粉を振動ミルで３０分間粉砕した粉砕フライア
ッシュ（粒径１０μｍ以下の粉砕フライアッシュ６０
％）を用いたこと、Ｋ2 Ｏ１モル当りＳｉＯ2 が１．５
モルを含有する水溶液濃度５０％アルカリ珪酸塩水溶液
の添加量を１０２重量部としたこと以外は、実施例１１
と同様にして、無機質成形体を得た。得られた無機質成
形体について、実施例１〜８と同様の評価を行った。そ
の結果を表５に示した。 Comparative Example 12 Instead of the crushed fly ash A, the crushed fly ash shown in Table 1 was crushed for 30 minutes by a vibration mill (crushed fly ash having a particle size of 10 μm or less 60
%), SiO 2 is 1.5 per mol of K 2 O.
Example 11 except that the addition amount of a 50% aqueous solution of an alkali silicate containing a mole was 102 parts by weight.
An inorganic molded body was obtained in the same manner as in. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 5.

【００６０】比較例１３ Ｋ2 Ｏ１モル当りＳｉＯ2 が１．５モルを含有する水溶
液濃度５０％のアルカリ珪酸塩水溶液の添加量を３５０
重量部としたこと以外は、実施例１２と同様にして、無
機質成形体を得た。得られた無機質成形体について、実
施例１〜８と同様の評価を行った。その結果を表５に示
した。 Comparative Example 13 The addition amount of an aqueous solution of alkali silicate having a concentration of 50% and containing 1.5 mol of SiO 2 per mol of K 2 O was 350.
An inorganic molded body was obtained in the same manner as in Example 12 except that the weight part was used. The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 5.

【００６１】比較例１４ Ｋ2 Ｏ１モル当りＳｉＯ2 が１．５モルを含有する水溶
液濃度５０％のアルカリ珪酸塩水溶液８重量部を用いた
こと以外は、実施例１２と同様にして、無機質成形体を
得た。得られた無機質成形体について、実施例１〜８と
同様の評価を行った。その結果を表５に示した。 Comparative Example 14 Inorganic molding was carried out in the same manner as in Example 12 except that 8 parts by weight of an aqueous solution of an alkali silicate having a concentration of 50% aqueous solution containing 1.5 mol of SiO 2 per 1 mol of K 2 O was used. Got the body The same evaluation as in Examples 1 to 8 was performed on the obtained inorganic molded body. The results are shown in Table 5.

【００６２】比較例１５ Ｋ2 Ｏ１モル当りＳｉＯ2 が１．５モルを含有する水溶
液濃度５０％アルカリ珪酸塩水溶液９７重量部の代わり
に、Ｋ2 Ｏ１モル当りＳｉＯ2 が１．５モルを含有する
水溶液濃度５％のアルカリ珪酸塩水溶液１０２重量部を
用いたこと以外は、実施例１１と同様にして、無機質成
形体を得た。得られた無機質成形体について、実施例１
〜８と同様の評価を行った。その結果を表５に示した。[0062] contains instead, K 2 O1 moles per SiO 2 1.5 moles of Comparative Example 15 K 2 O1 moles per SiO 2 aqueous solution concentration of 50% alkaline silicate solution 97 parts by weight containing 1.5 mol An inorganic molded body was obtained in the same manner as in Example 11 except that 102 parts by weight of an aqueous solution of an alkali silicate having a concentration of 5% of the aqueous solution was used. Regarding the obtained inorganic molded body, Example 1
The same evaluations as ~ 8 were performed. The results are shown in Table 5.

【００６３】[0063]

【表４】 [Table 4]

【００６４】[0064]

【表５】 [Table 5]

【００６５】表４及び表５からも明らかな如く、実施例
１１〜１９の場合には、いずれも得られた無機質成形体
の、外観が良好であり、曲げ強度及び熱水試験後強度維
持率が高い。これに対して、比較例９〜１２の如く、粉
砕フライアッシュの粒径１０μｍ以下の割合が少過ぎる
場合には、いずれも、硬化が遅く、得られた無機質成形
体が熱水試験後に破壊してしまう。又、比較例１３〜１
５の如く、アルカリ金属珪酸塩水溶液の添加量が多過ぎ
たり、少な過ぎたり、濃度が低い場合には、硬化しない
か、成形することができない。As is clear from Tables 4 and 5, in each of Examples 11 to 19, the obtained inorganic molded articles had a good appearance, and the bending strength and the strength retention rate after the hot water test were high. Is high. On the other hand, as in Comparative Examples 9 to 12, when the proportion of the pulverized fly ash having a particle size of 10 μm or less is too small, the curing is slow and the obtained inorganic molded articles are destroyed after the hot water test. Will end up. In addition, Comparative Examples 13 to 1
As described in 5, when the amount of the alkali metal silicate aqueous solution added is too large or too small or the concentration is low, the resin does not cure or cannot be molded.

【００６６】[0066]

【発明の効果】本発明１の無機質組成物は、上記の如き
構成であるので、不燃性、強度及び耐久性に優れた無機
質硬化体を得ることができる。EFFECT OF THE INVENTION Since the inorganic composition of the present invention 1 has the constitution as described above, it is possible to obtain an inorganic cured product having excellent nonflammability, strength and durability.

【００６７】本発明２の無機質組成物は、上記の如き構
成であるので、更に、不燃性及び強度、耐久性に優れた
無機質硬化体を得ることができる。Since the inorganic composition of the present invention 2 has the constitution as described above, it is possible to obtain an inorganic cured product which is further excellent in noncombustibility, strength and durability.

【００６８】本発明３の無機質組成物は、上記の如き構
成であるので、不燃性、強度及び耐久性に優れた無機質
硬化体を得ることができる。Since the inorganic composition of the present invention 3 has the above-mentioned constitution, it is possible to obtain an inorganic cured product having excellent nonflammability, strength and durability.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 粒径１０μｍ以下の粉体を８０重量％以
上含有するフライアッシュ１００重量部と、水溶液の濃
度が１０％以上のアルカリ金属水酸化物溶液もしくはア
ルカリ金属珪酸塩水溶液１０〜３００重量部と、粒径４
０〜２００μｍの珪砂１００〜３００重量部からなるこ
とを特徴とする無機質組成物。1. 100 parts by weight of fly ash containing 80% by weight or more of a powder having a particle size of 10 μm or less, and 10 to 300 parts by weight of an alkali metal hydroxide solution or an alkali metal silicate aqueous solution having an aqueous solution concentration of 10% or more. Part and particle size 4
An inorganic composition comprising 100 to 300 parts by weight of silica sand of 0 to 200 μm. 【請求項２】 請求項１の無機質組成物と、粒径０．０
１〜３０μｍのシリカ粉１〜６００重量部からなること
を特徴とする無機質組成物。2. The inorganic composition according to claim 1, and a particle size of 0.0.
An inorganic composition comprising 1 to 600 parts by weight of silica powder of 1 to 30 μm. 【請求項３】 小球状の粉体を内包した粒径１０〜２０
０μｍの粒子が１０重量％以上存在しているフライアッ
シュを、粒径１０μｍ以下の粉体を８０重量％以上含有
するまで粉砕したフライアッシュ１００重量部と、水溶
液濃度が１０％以上のアルカリ金属水酸化物水溶液もし
くはアルカリ金属珪酸塩水溶液１０〜３００重量部から
なることを特徴とする無機質組成物。3. A particle size of 10 to 20 containing a small spherical powder.
100 parts by weight of fly ash obtained by crushing fly ash in which 0 μm particles are present in an amount of 10% by weight or more until 80% by weight or more of a powder having a particle size of 10 μm or less and alkali metal water having an aqueous solution concentration of 10% or more An inorganic composition comprising 10 to 300 parts by weight of an oxide aqueous solution or an alkali metal silicate aqueous solution.
JP2522393A 1993-02-15 1993-02-15 Inorganic composition Expired - Fee Related JP3253395B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2522393A JP3253395B2 (en) 1993-02-15 1993-02-15 Inorganic composition

Applications Claiming Priority (1)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003045869A1 (en) * 2001-11-30 2003-06-05 The University Of Western Australia Particulate additive for dispersing admixtures in hydraulic cements
US10214453B2 (en) * 2016-10-05 2019-02-26 Council Of Scientific & Industrial Research Advanced cement free composition for concrete and panels and method of preparation thereof
CN117960173A (en) * 2024-03-28 2024-05-03 山东龙安泰环保科技有限公司 Preparation method of load-blending type ozone catalyst

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003045869A1 (en) * 2001-11-30 2003-06-05 The University Of Western Australia Particulate additive for dispersing admixtures in hydraulic cements
US10214453B2 (en) * 2016-10-05 2019-02-26 Council Of Scientific & Industrial Research Advanced cement free composition for concrete and panels and method of preparation thereof
CN117960173A (en) * 2024-03-28 2024-05-03 山东龙安泰环保科技有限公司 Preparation method of load-blending type ozone catalyst
CN117960173B (en) * 2024-03-28 2024-06-11 山东龙安泰环保科技有限公司 Preparation method of load-blending type ozone catalyst

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