JP2019119611A - Rapidly hardening cement composition for use in high temperature installation - Google Patents
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本発明は、高温打設に適した凍害抵抗性の高い速硬性のセメント組成物に関する。 The present invention relates to a frost-resistant high-speed setting cement composition suitable for high-temperature casting.
セメントペースト、モルタル又はコンクリート等のセメント組成物の凍害は、セメント組成物の硬化体の気孔中の残存水分が厳寒期に凍結し、凍結過程で膨張を伴うため、硬化体に膨張圧が加わって亀裂を生じるもので、強度や耐久性の低下をもたらす。セメント組成物に空気連行剤（ＡＥ剤）を配合し、多数の微細気泡を導入すると、硬化後の水分凍結による膨張圧の緩和を行うことができ、凍害を抑止できる。しかし、セメント組成物が速硬化や急硬化のための代表的成分であるカルシウムアルミネートを含むと、従来のＡＥ剤配合では空気連行性が低下し、微細気泡をセメント組成物硬化体に十分導入できないことがあった。 The freezing damage of the cement composition such as cement paste, mortar or concrete is caused by the expansion pressure being applied to the hardened body, since the remaining moisture in the pores of the hardened body of the cement composition freezes in the extremely cold period and is accompanied by expansion in the freezing process. It causes cracking, resulting in reduced strength and durability. When the air entraining agent (AE agent) is blended in the cement composition and a large number of fine air bubbles are introduced, the expansion pressure due to water freezing after hardening can be alleviated and the frost damage can be suppressed. However, when the cement composition contains calcium aluminate, which is a typical component for quick curing and rapid curing, air entrainment decreases in the conventional AE agent formulation, and micro bubbles are sufficiently introduced into the cement composition cured body. There was something I could not do.
その改善策としてアビエチン酸塩を含むＡＥ剤を使用すると、カルシウムアルミネートを含む高温打設用の速硬セメント組成物の空気連行性の低下を抑止できることが提案されている。（例えば、特許文献１参照。）一方で、例えばセメント組成物の夏場の打設などでは、セメント組成物は高温に曝される。カルシウムアルミネートを含むセメント組成物を例えば３０℃以上の高温環境下で製造・打設しようとすると、アビエチン酸塩を用いたＡＥ剤を配合しても、高温での粘性低下により一旦取り込まれた気泡は抜け易くなり、セメント組成物内に必要な微細気泡量を安定して確保できない。セメント組成物に増粘剤を多く配合するほど、粘性の増大によりＡＥ剤で取り込まれた微細気泡を抜け難くできるものの、凍害防止に有効な微細気泡量を確保するために必要な量の増粘剤の使用は、同時に凍害抑止効果の無い粗大気孔も取り込み易くなり、比較的大きな空隙が硬化後も残存するため強度低下に繋がる。 As an improvement measure, it has been proposed that the use of an AE agent containing abietic acid salt can suppress the decrease in air entrainment of a rapid-hardening cement composition for high-temperature casting containing calcium aluminate. (See, for example, Patent Document 1). On the other hand, for example, in summer placement of a cement composition, the cement composition is exposed to high temperatures. When a cement composition containing calcium aluminate is to be produced and placed in a high temperature environment of, for example, 30 ° C. or more, even if it is compounded with an AE agent using abietic acid salt, it is once taken in due to viscosity reduction at high temperature Air bubbles are likely to be released, and the amount of fine air bubbles required in the cement composition can not be stably secured. The more the thickener added to the cement composition, the more the fine bubbles taken up by the AE agent can be made more difficult to escape due to the increase in viscosity, but the thickening of the amount necessary to secure the amount of fine bubbles effective for frost damage prevention At the same time, the use of the agent also makes it easy to take in rough air holes that do not have the effect of suppressing frost damage, and relatively large voids remain even after curing, leading to a decrease in strength.
このような支障をきたすほどの量の増粘剤の使用を避け、取り込んだ微細気泡を安定に保持し、耐凍害性を増進させる手段として特定量のポリアクリル酸又はその塩を有効成分とする気泡安定化剤を併用することが、本出願人により提案されている。（例えば、特許文献２参照。）しかしながら、施工時に高温になるほど、硬化性低下や材料分離を起こさない範囲でポリアクリル酸又はその塩を有効成分とする気泡安定化剤を使用した場合、スランプロスやフローロスの進行が速くなり、例えば比較的容積の大きい型枠や複雑な形状の型枠への打設などでは、打設中の打設物の時間的な性状差が生じ易く、施工上の問題となることがあった。 Avoid using such thickeners in an amount that causes such problems, keep the incorporated microbubbles stable, and use a specific amount of polyacrylic acid or its salt as an active ingredient as a means to enhance the resistance to frost damage. It has been proposed by the applicant that a foam stabilizer be used in combination. (See, for example, Patent Document 2.) However, when a foam stabilizer containing polyacrylic acid or a salt thereof as an active ingredient is used within a range that does not cause curability deterioration or material separation as the temperature rises during construction, slump loss And flow loss accelerates, and for example, when placing on a relatively large mold frame or a mold frame with a complicated shape, it is likely to cause a time-related difference in the properties of the casting during casting, It could have been a problem.
本発明は、カルシウムアルミネートを含む速硬性のセメント組成物の凍害を強度低下を起こさせずに防止することに加え、例えば３０℃以上の高温で施工する必要があった場合でも、硬化性状に支障を及ぼすことなく、施工に適した性状が維持される可使時間の調整を容易に行うことのできる速硬セメント組成物の提供を課題とする。 The present invention, in addition to preventing freezing damage of a cement composition containing a calcium aluminate quick-hardening without causing a reduction in strength, for example, even when it is necessary to apply at a high temperature of 30 ° C or more, It is an object of the present invention to provide a quick-hardening cement composition which can be easily adjusted in pot life in which properties suitable for construction are maintained without any hindrance.
本発明者等は、前記課題解決のため検討した結果、カルシウムアルミネートを含有する速硬セメント組成物に、特定量のアビエチン酸類を含む空気連行剤と、特定量のポリアクリル酸又はポリアクリル酸塩を有効成分とする気泡安定化剤の配合により、適量の空気量の気泡を取り込み、増粘剤を用いずに、取り込んだ気泡の温度上昇による脱離を抑え、硬化時まで安定に留められたことで、優れた耐凍害性を付与でき、さらに使用するセメントを、化学成分としてのＫ2Ｏ及びＳＯ3を、通常市販されているようなポルトランドセメントに含まれる量とは幾分異なる特定量を含有させたものにすることで、高温環境下でも、硬化性状に支障を及ぼさずに、施工に適した流動性を打設作業完了までの間維持調整することが容易にできたことから本発明を完成させた。 As a result of investigations for solving the above problems, the present inventors have found that a calcium aluminate-containing quick-hardening cement composition, an air entrainer containing a specified amount of abietic acids, a specified amount of polyacrylic acid or polyacrylic acid The incorporation of a foam stabilizer containing a salt as an active ingredient incorporates bubbles of an appropriate amount of air, suppresses detachment due to the temperature rise of the taken-in bubbles without using a thickener, and remains stable until curing. As a result, it is possible to impart excellent freeze resistance, and further to specify the cement to be used, the amount of K 2 O and SO 3 as chemical components is somewhat different from the amount contained in portland cement which is usually marketed. By containing the amount, it was possible to easily maintain and adjust the flowability suitable for the construction until the completion of the placing operation without affecting the hardening property even in a high temperature environment without affecting the hardening property. Invention was allowed to complete.
即ち、本発明は、次の（１）〜（４）で表わす高温打設用の速硬セメント組成物である。（１）化学成分としてのＫ2Ｏを０．４０〜０．６０質量％および化学成分としてのＳＯ3を２．５〜３．０質量％含有するポルトランドセメント１００質量部、カルシウムアルミネート３〜８質量部、アビエチン酸類を有効成分とする空気連行剤３〜１０質量部およびポリアクリル酸又はその塩を有効成分とする気泡安定化剤１５〜３５質量部を含有する高温打設用の速硬セメント組成物。（２）骨材を含まない速硬セメント組成物のスラリーの粘度が、３０℃で２〜６Ｐａ・ｓであることを特徴とする前記（１）の高温打設用の速硬セメント組成物。（３）混練水（Ｗ）とポルトランドセメント（Ｃ）の含有質量比（Ｗ／Ｃ）が、３６〜４４％であることを特徴とする前記（１）又は（２）の高温打設用のセメント組成物。（４）成形型に打設されるものであることを特徴とする前記（１）〜（３）何れかの高温打設用の速硬セメント組成物。 That is, this invention is the rapid-hardening cement composition for high temperature placement shown by following (1)-(4). (1) 100 parts by mass of Portland cement containing 0.40 to 0.60% by mass of K 2 O as a chemical component and 2.5 to 3.0% by mass of SO 3 as a chemical component, calcium aluminate 3 to 3 8 parts by mass, 3 to 10 parts by mass of air entraining agent containing abietic acid as an active ingredient, and 15 to 35 parts by mass of a foam stabilizer containing polyacrylic acid or a salt thereof as an active ingredient Cement composition. (2) The quick-hardening cement composition for high-temperature casting according to the above (1), wherein the viscosity of the slurry of the quick-hardening cement composition containing no aggregate is 2 to 6 Pa · s at 30 ° C. (3) The high-temperature casting according to the above (1) or (2), wherein the content weight ratio (W / C) of the kneading water (W) and the portland cement (C) is 36 to 44%. Cement composition. (4) The rapid curing cement composition for high temperature placement according to any one of the above (1) to (3), which is to be placed in a mold.
本発明により、製造時や打設の際の温度にかかわらず、強度等の性状に支障を及ぼすことなくカルシウムアルミネートを含む速硬性セメントの凍害を十分防止できるので、従来困難であった寒冷地向けの速硬性セメントの夏場等の高温時の打設も、優れた施工作業性により、平易に行うことができる。 According to the present invention, regardless of the temperature at the time of production or placement, the frost damage of the quick-hardening cement containing calcium aluminate can be sufficiently prevented without affecting the properties such as strength, so that the cold region has hitherto been difficult The casting at high temperatures such as summer in the fast-hardening cement for the purpose can also be easily performed by the excellent construction workability.
本発明の高温打設用の速硬セメント組成物は、結合成分として特定のセメントを必須使用する。使用するセメントは水硬性のポルトランドセメントであって、化学成分としてのＫ2Ｏを０．４０〜０．６０質量％および化学成分としてのＳＯ3を２．５〜３．０質量％含有するポルトランドセメントとする。好ましい化学成分としてのＫ2Ｏの含有量は０．４６〜０．５４質量％であり、また、好ましい化学成分としてのＳＯ3の含有量は２．６〜２．８質量％である。このような成分含有量のポルトランドセメントであれば、何れのものでも良く、例えば普通、早強、超早強、中庸熱、低発熱等の各種ポルトランドセメントや、このようなポルトランドセメントを使用した高炉セメントやフライアッシュセメント等の各種混合セメントでも良い。また、このうち２種以上を併用しても良い。本発明では、化学成分としてのＫ2Ｏを０．４０〜０．６０質量％および化学成分としてのＳＯ3を２．５〜３．０質量％含有するポルトランドセメントの使用によって、例えば３０℃以上の高温で打設しても、速硬性や硬化体物性等に支障を及ぼすことなく、打設作業に要するような時間中、打設に適した性状をセメントスラリーに安定して付与することができる。 The high temperature placing quick-hardening cement composition of the present invention essentially uses a specific cement as a bonding component. The cement used is hydraulic Portland cement containing 0.40 to 0.60% by mass of K 2 O as a chemical component and 2.5 to 3.0% by mass of SO 3 as a chemical component. It is assumed that The content of K 2 O as a preferred chemical component is 0.46 to 0.54% by mass, and the content of SO 3 as a preferred chemical component is 2.6 to 2.8% by mass. Any Portland cement having such a component content may be used, for example, various Portland cements such as normal, early strong, ultra early strong, moderate heat, low heat generation, and blast furnaces using such Portland cement. Various mixed cements such as cement and fly ash cement may be used. In addition, two or more of these may be used in combination. In the present invention, for example, by using Portland cement containing 0.40 to 0.60 mass% of K 2 O as a chemical component and 2.5 to 3.0 mass% of SO 3 as a chemical component, for example, 30 ° C. or higher Even if it is casted at high temperature, the cement slurry can be stably imparted with a property suitable for casting during the time required for the casting operation without affecting the rapid curing property and the physical properties of the cured body, etc. it can.
ポルトランドセメント中の化学成分としてのＫ2Ｏ含有量は、ポルトランドセメント中に例えば化合物や非晶質体の状態で存在するカリウムを、酸化物換算した質量に基づくものであり、特記無い限りは、ポルトランドセメント中の含有率（質量％）で示される。化学成分としてのＫ2Ｏの含有量は、前記の通り０．４０〜０．６０質量％とするが、化学成分としてのＫ2Ｏの含有量が０．４０質量％未満のポルトランドセメントでは、硬化が早まらないため好ましくない。また、化学成分としてのＫ2Ｏの含有量が０．６０質量％を超えるポルトランドセメントでは、しまりが早く、打設に適した流動性状が確保し難くなるため好ましくない。 The K 2 O content as a chemical component in portland cement is based on, for example, the oxide equivalent weight of potassium present in the form of a compound or an amorphous substance in portland cement, and unless otherwise specified, It shows by the content rate (mass%) in portland cement. The K 2 O content of the chemical component is a 0.40 to 0.60 mass% as described above, in the Portland cement K 2 O content of the chemical components is less than 0.40 wt%, It is not preferable because curing does not accelerate. Further, in the Portland cement K 2 O content of the chemical components is more than 0.60 mass%, interference is fast, is not preferable because the flow properties suitable for pouring is difficult to secure.
ポルトランドセメント中の化学成分としてのＳＯ3含有量は、ポルトランドセメント中に存在する例えば無水石膏を初めとする石膏類などを構成する硫黄を、酸化物換算した質量に基づくものであり、特記無い限りは、ポルトランドセメント中の含有率（質量％）で示される。化学成分としてのＳＯ3の含有量は、前記の通り２．５〜３．０質量％とするが、化学成分としてのＳＯ3の含有量が２．５質量％未満のポルトランドセメントでは、強度発現性が低下するため好ましくない。また、化学成分としてのＳＯ3の含有量が３．０質量％を超えるポルトランドセメントでは、良好な流動性や得難くなるので好ましくない。 The SO 3 content as a chemical component in portland cement is based on the oxide-equivalent mass of sulfur contained in portland cement, for example, gypsum including anhydrite and the like, unless otherwise specified. Is indicated by the content (% by mass) in portland cement. Although the content of SO 3 as a chemical component is 2.5 to 3.0% by mass as described above, the strength development occurs in portland cement in which the content of SO 3 as a chemical component is less than 2.5% by mass. It is not preferable because the property is reduced. Moreover, in the Portland cement where the content of SO 3 as a chemical component exceeds 3.0% by mass, it is not preferable because it becomes difficult to obtain good fluidity and to be obtained.
本発明の高温打設用の速硬セメント組成物はカルシウムアルミネートを含有するものである。使用するカルシウムアルミネートは、化学成分としてＣａＯとＡｌ2Ｏ3からなる結晶質やガラス化が進んだ構造の水和活性物質であれば何れのものでも良く、若しくは、ＣａＯとＡｌ2Ｏ3に加えて他の化学成分が加わった化合物、固溶体、ガラス質物質又はこれらの混合物等でも本発明の効果を実質喪失させないものであれば、何れのものでも良い。前者は、例えば１２ＣａＯ・７Ａｌ2Ｏ3、ＣａＯ・Ａｌ2Ｏ3、３ＣａＯ・Ａｌ2Ｏ3、ＣａＯ・２Ａｌ2Ｏ3、ＣａＯ・６Ａｌ2Ｏ3等が挙げられ、後者は、例えば４ＣａＯ・３Ａｌ2Ｏ3・ＳＯ3、１１ＣａＯ・７Ａｌ2Ｏ3・ＣａＦ2、Ｎａ2Ｏ・８ＣａＯ・３Ａｌ2Ｏ3、ＣａＯ・２ＮａＯ・５Ａｌ2Ｏ3等が挙げられる。好ましくは、低温での強度発現性に優れることから、非晶質の１２ＣａＯ・７Ａｌ2Ｏ3、ＣａＯ・Ａｌ2Ｏ3又は／及び３ＣａＯ・Ａｌ2Ｏ3を少なくとも一部含むものが良い。このようなカルシウムアルミネートの調整方法は、例えば、所定配合比にしたＣａＯ源とＡｌ2Ｏ3源の原料混合物を加熱溶融し、溶融させた温度から急冷すれば得られる。急冷は水中急冷以外の方法が望ましく、最高加熱温度付近から炉外に取り出し、炉外で自然放冷するか、窒素やアルゴン等の不活性ガスを加熱物表面に吹き付ける方法が例示できる。また、カルシウムアルミネートとして前述のアルミナセメントを使用することもでき、その場合は本発明ではアルミナセメントを総てカルシウムアルミネートと見なして使用する。カルシウムアルミネートはセメント組成物に速硬・急硬作用を発現させるために用いられる。本発明の高温打設用の速硬セメント組成物でのカルシウムアルミネートの含有量は、安定した急硬・速硬性を具備する上で、含有するポルトランドセメント１００質量部に対し、３〜８質量部である。好ましい含有量は。ポルトランドセメント１００質量部に対し、４〜６質量部である。 The high temperature placing quick-hardening cement composition of the present invention contains calcium aluminate. The calcium aluminate used may be any crystalline or vitrified hydrated active substance composed of CaO and Al 2 O 3 as chemical components, or CaO and Al 2 O 3 In addition, any compound to which other chemical components are added, a solid solution, a vitreous substance or a mixture thereof may be used as long as the effect of the present invention is not substantially lost. The former, for example, 12CaO · 7Al 2 O 3, CaO · Al 2 O 3, 3CaO · Al 2 O 3, CaO · 2Al 2 O 3, CaO · 6Al 2 O 3 and the like, the latter, for example, 4CaO · 3Al etc. 2 O 3 · SO 3, 11CaO · 7Al 2 O 3 · CaF 2, Na 2 O · 8CaO · 3Al 2 O 3, CaO · 2NaO · 5Al 2 O 3 and the like. Preferably, at least a part of amorphous 12CaO · 7Al 2 O 3 , CaO · Al 2 O 3 and / or 3CaO · Al 2 O 3 is preferably contained because of excellent strength development at low temperatures. Such a method for adjusting calcium aluminate can be obtained, for example, by heating and melting a raw material mixture of a CaO source and an Al 2 O 3 source at a predetermined compounding ratio, and rapidly cooling from the melted temperature. A method other than quenching in water is desirable for quenching, and it can be taken out of the furnace from around the maximum heating temperature and naturally cooled outside the furnace, or a method of spraying inert gas such as nitrogen or argon onto the surface of the heating material can be exemplified. Moreover, the above-mentioned alumina cement can also be used as a calcium aluminate, In this case, in the present invention, all alumina cements are used as calcium aluminate. Calcium aluminate is used to make a cement composition express a rapid hardening and rapid hardening action. The content of calcium aluminate in the rapid hardening cement composition for high temperature placing according to the present invention is 3 to 8 mass with respect to 100 parts by mass of portland cement contained, in order to provide stable rapid hardening and rapid hardening. It is a department. The preferred content is It is 4 to 6 parts by mass with respect to 100 parts by mass of portland cement.
本発明の高温打設用の速硬セメント組成物は、アビエチン酸類を有効成分とする空気連行剤を含有する。アビエチン酸類はモルタルやコンクリートに使用できるものなら何れのものでも良く、例えば、アビエチン酸、アビエチン酸のアルカリ金属塩等を挙げることができる。アビエチン酸類を有効成分とする空気連行剤の使用によってカルシウムアルミネートを含むセメント組成物でも、通常の混練操作で、微細な気泡を所望の空気量だけ容易に導入することが可能となる。このような作用を具備させるには、アビエチン酸類を有効成分とする空気連行剤を、本発明の高温打設用の速硬セメント組成物中のポルトランドセメント含有量１００質量部に対し、３〜１０質量部となるよう含有させる。アビエチン酸類を有効成分とする空気連行剤の含有量が３質量部未満では、微細な気泡を所望の空気量だけ導入することが困難になるので好ましくない。また、１０質量部を超える含有量では、導入される気泡が過剰空気量になり易く、強度や耐久性の低下を起こす虞があるので好ましくない。 The rapid-hardening cement composition for high-temperature casting according to the present invention contains an air entrainer containing abietic acid as an active ingredient. The abietic acids may be any of those which can be used for mortar and concrete, and examples thereof include abietic acid and alkali metal salts of abietic acid. By using an air entraining agent containing abietic acid as an active ingredient, it becomes possible to easily introduce a fine air bubble by a desired amount of air even in a cement composition containing calcium aluminate in a usual kneading operation. In order to have such an effect, the air entraining agent containing abietic acid as an active ingredient is contained in an amount of 3 to 10 based on 100 parts by mass of the portland cement content in the rapid curing cement composition for high-temperature casting of the present invention. It is contained to be part by mass. If the content of the air entraining agent containing abietic acid as an active ingredient is less than 3 parts by mass, it is not preferable because it becomes difficult to introduce a fine air bubble by a desired amount of air. On the other hand, if the content is more than 10 parts by mass, it is not preferable because air bubbles to be introduced are likely to become an excess air amount and a decrease in strength and durability may occur.
また、本発明の高温打設用の速硬セメント組成物はポリアクリル酸又はポリアクリル酸塩を含有する。本発明で使用するポリアクリル酸又はポリアクリル酸塩は少なくとも増粘作用を実質的に有さないものが好ましい。実質的に増粘作用を具備しないものとは、ポルトランドセメントの１０〜３５℃の水性スラリーに含有するポルトランドセメント１００質量部に対し最大３５質量部のポリアクリル酸又はポリアクリル酸塩を添加したときに、同じ温度の無添加時の水性スラリーからの粘度上昇が概ね１０％以下（粘度減少するものも含む。）となるものを云う。このような実質的に増粘作用を具備しないポリアクリル酸又はポリアクリル酸塩であれば、何れのものでも用いることができる。また、ポリアクリル酸とポリアクリル酸塩は何れか１種の含有で次に説示するような効果が得られるが、併用を妨げるものではない。本発明では、ポリアクリル酸又はポリアクリル酸塩は、空気連行剤で取り込まれた微細空気泡の気泡膜を強化し、微細な空気泡をセメント組成物内に安定して留めておくのに寄与する。特に、微細気泡の凝集によって隣接する気泡境界が消失して凍害防止に寄与しない粗大気泡が形成されるのを抑制できる他、混練水添加後のセメント組成物スラリーが高温環境下で粘性低下を起こし、上昇し易くなった気泡がセメント組成物表面で破泡するのを防ぐことができる。ポリアクリル酸又はポリアクリル酸塩の含有量は、セメント組成物中に含有するポルトランドセメント１００質量部に対し、１５〜３５質量部とする。ポリアクリル酸又はポリアクリル酸塩の含有量が１５質量部未満では取り込んだ微細気泡を所望量保持し続けるのが困難なので好ましくなく、また３５質量部を越えるとセメント組成物が凝結遅延を起こし、速硬性に支障が生じる為、好ましくない。また、増粘性付与作用を具備したポリアクリル酸又はポリアクリル酸塩を使用すると、凍害防止効果のない粗大気孔も取り込まれ易くなり、一方で微細気泡は取り込まれ難くなって凍害防止が向上し難くなるので好ましくない。 Further, the high temperature placing quick-hardening cement composition of the present invention contains polyacrylic acid or polyacrylate. It is preferable that the polyacrylic acid or polyacrylate used in the present invention has at least substantially no thickening effect. When substantially 35 parts by mass of polyacrylic acid or polyacrylate is added to 100 parts by mass of portland cement contained in a 10 to 35 ° C. aqueous slurry of portland cement, those substantially having no thickening effect In addition, the viscosity rise from the aqueous slurry without addition at the same temperature is about 10% or less (including a viscosity decrease). Any polyacrylic acid or polyacrylate having substantially no thickening effect can be used. In addition, although polyacrylic acid and polyacrylate contain any one of them, the following effects can be obtained, but they do not prevent the combined use. In the present invention, the polyacrylic acid or polyacrylate strengthens the bubble film of the fine air bubbles taken up by the air entrainer and contributes to the stable retention of the fine air bubbles in the cement composition. Do. In particular, it is possible to suppress the formation of coarse cells which do not contribute to the prevention of frost damage due to the disappearance of adjacent cell boundaries due to the aggregation of fine cells, and the cement composition slurry after addition of kneading water causes viscosity drop under high temperature environment. It is possible to prevent bubbles that have become easy to rise from bursting on the cement composition surface. The content of polyacrylic acid or polyacrylate is 15 to 35 parts by mass with respect to 100 parts by mass of portland cement contained in the cement composition. If the content of polyacrylic acid or polyacrylate is less than 15 parts by mass, it is difficult to maintain the desired amount of microbubbles incorporated, which is not preferable. If it exceeds 35 parts by mass, the cement composition causes setting delay. Unfavorable because problems occur in rapid hardening. Moreover, when polyacrylic acid or polyacrylate having a thickening property imparting action is used, it becomes easy to take in the coarse air holes having no freeze damage preventing effect, while it becomes difficult to take in fine air bubbles and it is difficult to improve the freeze damage prevention. It is not preferable because
また、本発明の高温打設用の速硬セメント組成物は凝結調整剤を含有するのが好ましい。凝結調整剤は大別すると、主に凝結促進作用の付与するものと主に凝結遅延作用を付与するものがあり、本発明では何れのものでも使用でき、両方を併用しても良い。より具体的には、主に凝結促進作用を付与する凝結調整剤は、例えば、硫酸アルミニウム、何れもアルカリ金属やアルカリ土類金属の、炭酸塩、硫酸塩、硝酸塩、アルミン酸塩、水酸塩、蟻酸塩等を挙げることができる。好ましくは、アルカリ金属炭酸塩や石膏類を挙げることができる。ここで石膏類とは硫酸カルシウム、無水石膏、半水石膏、二水石膏の何れか又は二種以上を云う。また、主に凝結遅延作用を付与する凝結調整剤は、例えば、ヒドロキシ酸等の有機酸、珪フッ化物、燐酸塩、硼酸塩等を挙げることができる。好ましくは、ヒドロキシ酸、より好ましくはクエン酸や酒石酸を挙げることができる。このうち、凝結促進作用を付与する凝結調整剤は、カルシウムアルミネートによる速硬性や急硬性を向上させ、初期の硬化強度発現性を向上させる作用を呈する。また、凝結遅延作用を付与する凝結調整剤は、カルシウムアルミネートを含有する速硬セメント組成物の可使時間の確保に有用である。凝結調整剤の含有量は、所望の作用をセメント組成物に付与する上で、カルシウムアルミネート含有量１００質量部に対し、５０〜２００質量部が好ましく、主に凝結促進作用を付与する凝結調整剤は、５〜５０質量部が好ましい。 In addition, it is preferable that the rapid-hardening cement composition for high-temperature casting according to the present invention contains a setting regulator. The coagulation modifiers are roughly classified into those to which the coagulation promoting action is mainly imparted and those to which the coagulation delaying action is mainly imparted, and any of them may be used in the present invention, and both may be used in combination. More specifically, the modifier for mainly imparting a setting promoting action is, for example, aluminum sulfate, carbonates, sulfates, nitrates, aluminates, hydroxides of any of alkali metals and alkaline earth metals. And formate. Preferably, alkali metal carbonates and gypsums can be mentioned. Here, gypsum refers to calcium sulfate, anhydrous gypsum, hemihydrate gypsum, gypsum dihydrate or two or more of them. Further, as a setting regulator mainly imparting a setting delaying action, for example, organic acids such as hydroxy acid, silicofluoride, phosphate, borate and the like can be mentioned. Preferably, hydroxy acids can be mentioned, more preferably citric acid and tartaric acid. Among them, a setting modifier which imparts a setting promoting action has an action to improve rapid hardening and rapid hardening by calcium aluminate, and to improve initial hardening strength development. In addition, a setting adjusting agent which imparts a setting delaying action is useful for securing a working life of a quick-hardening cement composition containing calcium aluminate. The content of the setting adjusting agent is preferably 50 to 200 parts by mass with respect to 100 parts by mass of the calcium aluminate content to impart the desired action to the cement composition, and the setting adjustment mainly imparts the setting promoting action The agent is preferably 5 to 50 parts by mass.
また、本発明の高温打設用の速硬セメント組成物は、セメントペースト、モルタル又はコンクリートの何れの態様であっても良く、モルタルの場合は細骨材のみを含み、コンクリートの場合は少なくとも粗骨材を含有する。細骨材や粗骨材は、水と反応せず溶解も実質しない材質のものであれば、限定されない。使用可能な細骨材を例示すると、山砂、川砂、海砂、砕砂、珪砂、石灰石砂、天然又は人工の軽量細骨材等を挙げることができる。使用可能な粗骨材を例示すると、川砂利、砕石、石灰石破砕物、スラグ骨材、天然又は人工の軽量粗骨材等を挙げることができる。また、その含有量も特に制限されるものではない。好ましくは、セメント含有量１００質量部に対し、モルタルでは５０〜５００質量部、コンクリートでは１００〜１０００質量部の含有とする。 In addition, the rapid hardening cement composition for high-temperature casting according to the present invention may be any form of cement paste, mortar or concrete, and in the case of mortar comprises only fine aggregate, and in the case of concrete at least coarse. Contains aggregate. The fine aggregate and the coarse aggregate are not limited as long as they are materials that do not react with water and do not substantially dissolve. Examples of fine aggregates that can be used include mountain sand, river sand, sea sand, crushed sand, silica sand, limestone sand, natural or artificial lightweight fine aggregate, and the like. Examples of usable coarse aggregate include river gravel, crushed stone, crushed limestone, slag aggregate, and natural or artificial lightweight coarse aggregate. Also, the content thereof is not particularly limited. Preferably, 50 to 500 parts by mass of mortar and 100 to 1000 parts by mass of concrete are contained with respect to 100 parts by mass of cement content.
前記以外の成分であっても本発明の効果を実質的に喪失させるものでない限り、その含有は許容される。含有可能な成分として、例えば、モルタルやコンクリートに使用することができるポゾラン反応性物質、スラグ微粉、石灰石微粉、収縮低減剤、減水剤（分散剤、高性能減水剤を含む。）、流動化剤、粘土鉱物粉、防凍剤、繊維、高分子エマルション等を挙げることができる。 Even if it is a component other than the above, the content is acceptable unless it substantially loses the effect of the present invention. As components which can be contained, for example, pozzolanic reactive substances which can be used for mortar and concrete, slag fine powder, limestone fine powder, shrinkage reducing agent, water reducing agent (including dispersant, high performance water reducing agent), fluidizing agent Clay mineral powder, antifreeze agent, fiber, polymer emulsion and the like.
本発明の高温打設用の速硬セメント組成物に対する混練水の量は、特に制限されない。好ましくは、骨材を除いた高温打設用の速硬セメント組成物のスラリーのＪＩＳ Ｚ ２８８０３で規定する単一円筒型回転粘度計によって計測した温度３０℃（±１℃）での粘度が、２〜６Ｐａ・ｓになるような混練水の質量にすることが推奨される。骨材を除いた高温打設用の速硬セメント組成物の３０℃のスラリー粘度が２Ｐａ・ｓ未満では、凍害抑止に寄与するだけの微細気泡を十分得るのが容易でないことがあり、また６Ｐａ・ｓを超える粘度では強度が向上し難くなることがあるので、２〜６Ｐａ・ｓの粘性にすることが推奨される。この粘性範囲に適うような具体的な混練水量（３０℃）の目安を例示すると、ポルトランドセメント含有量１００質量部に対し、概ね３５〜４５質量部である。 The amount of kneading water to the high-temperature setting rapid-hardening cement composition of the present invention is not particularly limited. Preferably, the viscosity at a temperature of 30 ° C. (± 1 ° C.) measured by a single cylindrical rotational viscometer defined by JIS Z 28803 of a slurry of a rapid-hardening cement composition for high temperature casting excluding aggregates is It is recommended to set the mass of the mixing water to be 2 to 6 Pa · s. If the slurry viscosity at 30 ° C of the quick-hardening cement composition for high-temperature casting excluding aggregates is less than 2 Pa · s, it may not be easy to obtain enough fine air bubbles to contribute to the suppression of frost damage. If the viscosity exceeds s, the strength may be difficult to improve, so it is recommended to make the viscosity 2 to 6 Pa · s. A concrete standard of the amount of kneading water (30 ° C.) suitable for this viscosity range is, for example, approximately 35 to 45 parts by mass with respect to 100 parts by mass of the portland cement content.
本発明の高温打設用の速硬セメント組成物は、３０℃以上の施工環境下での打設、製造工程が主として３０℃以上の環境下で行われるもの等の比較的高温の環境を経るものに好適である。しかし、２０℃付近の常温でも、また例えば１０℃以下の低温でも、硬化性状に支障なく打設することが可能である。本発明の高温打設用の速硬セメント組成物は、前記のような良好な流動性状を、打設作業に必要とされるような適度な時間、高温でも概ね安定して維持できるので、例えば大型成形型や形状が複雑な成形型等を含め、特に成形型への打設に好適に用いることができる。 The rapid-hardening cement composition for high-temperature casting according to the present invention undergoes a relatively high-temperature environment such as casting in a construction environment of 30 ° C. or higher, and a production process mainly performed in an environment of 30 ° C. or higher. It is suitable for things. However, even at a normal temperature around 20 ° C., or even at a low temperature of, for example, 10 ° C. or less, it is possible to cast without any problem in the curing properties. The rapid-hardening cement composition for high-temperature casting according to the present invention can maintain, for example, the above-mentioned good flow properties almost stably even at high temperatures for a suitable time required for casting work. It can be suitably used particularly for casting to a mold including a large mold and a mold having a complicated shape and the like.
以下、本発明を実施例によって具体的に説明するが、本発明は記載実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the described examples.
次の、Ａ１〜Ａ２、Ｂ１〜Ｂ９（表１で表わす。）、Ｅ１〜Ｅ３及びＦから選定される非液体状の材料を用い、表２に表す配合量となるよう、レーディゲミキサを使用し、３分間混合して非液体状混合物を作製した。尚、カルシウムアルミネート（Ａ１〜Ａ２）は、バン土頁岩及び炭酸カルシウム（何れも市販品）を原料とし、化学成分としてのＣａＯとＡｌ2Ｏ3が所望の含有モル比となるように配合した混合物を、バッチ式電気炉で約１６００℃で２時間加熱した後、炉内で自然放冷したクリンカを粉砕分級した粉末（ブレーン比表面積約３０００ｃｍ2／ｇ）である。カルシウムアルミネートのガラス化率は、粉末エックス線回折装置を用い、質量がＭ１のアルミン酸カルシウムに含まれる各鉱物の質量を内部標準法等で定量し、定量できた含有鉱物相の総和質量；Ｍ２を算出し、残部が純ガラス相と見なし、次式でガラス化率を算出した。
ガラス化率（％）＝（１−Ｍ２／Ｍ１）×１００
Using a non-liquid material selected from the following A1 to A2, B1 to B9 (represented in Table 1), E1 to E3 and F, using a Lagege mixer to achieve the blending amounts shown in Table 2, The mixture was mixed for 3 minutes to make a non-liquid mixture. Calcium aluminate (A1 to A2) was prepared using van earth shale and calcium carbonate (both commercially available products) as raw materials, and CaO and Al 2 O 3 as chemical components to be in the desired molar ratio The mixture is heated in a batch electric furnace at about 1600 ° C. for 2 hours, and then the clinker which is naturally cooled in the furnace is a pulverized powder (class specific surface area of about 3000 cm 2 / g). The vitrification ratio of calcium aluminate is determined by measuring the mass of each mineral contained in calcium aluminate having a mass of M1 using an X-ray powder diffractometer by the internal standard method and the like, and the total mass of the contained mineral phase determined; M2 The remainder was regarded as a pure glass phase, and the vitrification ratio was calculated by the following equation.
Vitrification rate (%) = (1-M2 / M1) x 100
また、表１で表す化学成分含有量の普通ポルトランド（Ｂ１〜Ｂ９）は試供品であり、調整は所望の化学成分含有量になるように配合した原料（天然石灰石及び市販試薬）混合物を、電気炉により最高温度１４１０±１０℃で加熱し、得られたクリンカを粉砕し、これにＩＩ型無水石膏（市販試薬）粉末を所定量加え、乾式混合した。その化学成分含有量（質量％）は、前記乾式混合した物を化学分析し、酸化物換算した各成分の含有質量に基づくものである。 In addition, ordinary portland (B1 to B9) having a chemical component content shown in Table 1 is a sample, and a mixture of raw materials (natural limestone and commercially available reagent) formulated so as to have a desired chemical component content is The resulting clinker was crushed by heating with an electric furnace at a maximum temperature of 1410 ± 10 ° C., and a predetermined amount of type II anhydrous gypsum (commercially available reagent) powder was added to this and dry mixed. The chemical component content (% by mass) is based on the content mass of each component after chemical analysis of the dry-mixed material and conversion to oxide.
Ａ１；カルシウムアルミネート（ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）；１．３、ガラス化率；３０％）
Ａ２；カルシウムアルミネート（ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）；１．５、ガラス化率；５０％）
Ｃ１；アルキルオキシエチレン系スルホン酸ナトリウム塩を有効成分とする空気連行剤（商品名；マスターエア１０１、ＢＡＳＦジャパン社製）
Ｃ２；アルキルオキシエチレン系スルホン酸ナトリウム塩を有効成分とする空気連行剤（商品名；マスターエア３０３Ａ、ＢＡＳＦジャパン社製）
Ｃ３；アルキルオキシエチレン系スルホン酸ナトリウム塩を有効成分とする空気連行剤（商品名；ＣＡＥ−２０、ＢＡＳＦジャパン社製）
Ｃ４；アビエチン酸ナトリウムを有効成分とする空気連行剤（商品名；ヴィンソル、花王社製）
Ｄ１；ポリアクリル酸ナトリウム（商品名；アクアリック、日本触媒社製）
Ｄ２；ポリアクリル酸ナトリウムとポリアクリル酸の混合物（商品名；ソカラン、ＢＡＳＦジャパン社製）
Ｄ３；ポリアクリル酸（市販試薬）
Ｅ１；ＩＩ型無水石膏（市販試薬）
Ｅ２；炭酸ナトリウム（市販試薬）と炭酸リチウム（市販試薬）の等質量混合剤
Ｅ３；クエン酸（試薬）
Ｆ；セルロース誘導体を有効成分とする増粘剤（商品名；メトローズ、信越化学工業社製）
A1: Calcium aluminate (Molar content ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ): 1.3, vitrification ratio: 30%)
A2: Calcium aluminate (Molar content ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ); 1.5, vitrification ratio: 50%)
C1: Air entraining agent containing alkyloxyethylene-based sulfonic acid sodium salt as an active ingredient (trade name: Master Air 101, manufactured by BASF Japan Ltd.)
C2: Air entraining agent containing alkyloxyethylene sodium sulfonate sodium salt as an active ingredient (trade name: Master Air 303A, manufactured by BASF Japan Ltd.)
C3: Air entraining agent containing alkyloxyethylene sulfonic acid sodium salt as an active ingredient (trade name: CAE-20, manufactured by BASF Japan Ltd.)
C4: Air entraining agent containing sodium abietic acid as an active ingredient (trade name: Vinsol, manufactured by Kao Corporation)
D1: Sodium polyacrylate (trade name: Aquaric, manufactured by Nippon Shokubai Co., Ltd.)
D2: Mixture of sodium polyacrylate and polyacrylic acid (trade name: Sokaran, manufactured by BASF Japan Ltd.)
D3: Polyacrylic acid (commercially available reagent)
E1; Type II anhydrous gypsum (commercially available reagent)
E2: Equal mass mixture of sodium carbonate (commercially available reagent) and lithium carbonate (commercially available reagent) E3; Citric acid (reagent)
F: Thickener containing cellulose derivative as an active ingredient (trade name: Metrose, Shin-Etsu Chemical Co., Ltd.)
次いで、前記普通ポルトランドセメント１００質量部に対し、表３で表す量の混練水と、表２で表す配合量の上記Ｃ１〜Ｃ４及びＤ１〜Ｄ３から選定される液状材料を、ほぼ同時に前記非液体状混合物に加え、恒温設定保持可能な容器中でハンドミキサーで１分間混練し、３０℃と３５℃でのセメント組成物のスラリーを作製した。 Then, with respect to 100 parts by mass of the ordinary portland cement, the non-liquid of the kneading water of the amount shown in Table 3 and the liquid material selected from the C1 to C4 and D1 to D3 of the compounding amount shown in Table 2 almost simultaneously The mixture was added to the mixture and kneaded for 1 minute with a hand mixer in a container capable of maintaining a constant temperature setting, to prepare a slurry of the cement composition at 30.degree. C. and 35.degree.
３０℃及び３５℃のセメント組成物のスラリーは、作製後概ね１分以内と作製から１５分経過後に、ＪＩＳ Ｚ ２８８０３で規定する単一円筒型回転粘度計でそれぞれの粘度を測定した。また、３０℃及び３５℃の温度で作製直後のセメント組成物のスラリーに巻き込まれた空気量と、更に３０秒間追加混練したスラリーの空気量を、ＪＩＳ Ａ １１１６で規定の「フレッシュコンクリートの単位容積質量試験方法及び空気量の質量による試験方法」に準じて測定した。また、前記セメント組成物のスラリー作製後から３０℃及び３５℃の環境下で１時間放置した後のセメント組成物のプロクター貫入抵抗値を、ＪＩＳ Ａ １１４７「コンクリートの凝結時間試験方法」に準じて測定し、速硬性の評価とした。また、各温度で作製したセメント組成物のスラリーを内径５ｃｍで高さ１０ｃｍの円筒状の成形用サミットモールドに充填し、これをスラリー作製温度と同じ温度の恒温室内に静置して１日後に脱型した。脱型物を２０℃の恒温度室内でビニール袋に密封して保管し、材齢７日の供試体として、ＪＩＳ Ａ １１０８で規定の「コンクリートの圧縮強度試験方法」に準じて一軸圧縮強度を測定した。さらに、強度試験後の破断面を拡大鏡で目視観察し、粗大気孔（およそ１ｍｍ以上）の存在有無を確認した。以上の結果は表４に表す。 The slurries of the cement compositions at 30 ° C. and 35 ° C. were measured for their respective viscosities with a single cylindrical rotational viscometer defined in JIS Z 28803, generally within 1 minute after preparation and 15 minutes after preparation. In addition, the unit volume of fresh concrete specified in JIS A 1116 is the amount of air caught in the slurry of the cement composition immediately after preparation at a temperature of 30 ° C. and 35 ° C., and the amount of air of the slurry additionally kneaded for 30 seconds. It measured according to "the mass test method and the test method by mass of air content". In addition, the proctor penetration resistance value of the cement composition after leaving for 1 hour in an environment of 30 ° C. and 35 ° C. after preparing the slurry of the cement composition is measured according to JIS A 1147 “Test method for setting time of concrete”. It measured and set it as evaluation of quick hardening. In addition, the slurry of the cement composition prepared at each temperature is filled in a cylindrical summit mold for molding having an inner diameter of 5 cm and a height of 10 cm, and this is allowed to stand in the thermostatic chamber at the same temperature as the slurry preparation temperature. I was demolded. The demolded product is sealed and stored in a plastic bag in a constant temperature room at 20 ° C., and as a 7-day-old specimen, uniaxial compressive strength is applied according to “Concrete compressive strength test method” specified in JIS A 1108. It was measured. Furthermore, the fractured surface after the strength test was visually observed with a magnifying glass to confirm the presence or absence of coarse air holes (approximately 1 mm or more). The above results are shown in Table 4.
表４の結果から、本発明のセメント組成物は、速硬性を具備しつつ高温（３０℃及び３５℃）でも十分な空気量が導入保持されており、しかも打設作業のために確保が必要な適度な可使時間も具備できることがわかる。さらに、破断面観察からは、粗大気泡の存在は見られず、圧縮強度の低下も見られなかった。これに対し、従来の空気連行剤を使用したものは、高温（３０℃及び３５℃）では、取り込まれる気泡量が著しく少ないか、粗大気泡が抜けきらずに硬化後も存在し、圧縮強度が低下した。また、本発明品で使用するポルトランドセメントよりもＫ2ＯとＳＯ3含有量が少ないポルトランドセメントを使用したものでは、高温打設時の可使時間が著しく短いか、強度発現性が低迷していることがわかる。 From the results in Table 4, it is found that the cement composition of the present invention has a rapid curing property and that a sufficient amount of air is introduced and maintained even at high temperatures (30 ° C. and 35 ° C.). It can be seen that a reasonable pot life can also be provided. Furthermore, from the fracture surface observation, the presence of coarse bubbles was not observed, and no decrease in compressive strength was also observed. On the other hand, those using the conventional air entraining agent have very small amount of air bubbles taken in at high temperature (30 ° C and 35 ° C), or coarse air bubbles do not come off and exist even after curing, and the compressive strength decreases did. In addition, in the case of using Portland cement having a K 2 O and SO 3 content lower than that of Portland cement used in the product of the present invention, the usable life at the time of high temperature placing may be extremely short or the strength developing property may be deteriorated. I understand that
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| JPS5669257A (en) * | 1979-10-31 | 1981-06-10 | Seitetsu Kagaku Co Ltd | Cement composition |
| JPH0421551A (en) * | 1990-05-15 | 1992-01-24 | Denki Kagaku Kogyo Kk | Quick hardenable ae concrete composition |
| JPH10509780A (en) * | 1996-02-16 | 1998-09-22 | ベー・ハンス・ペーター | Semi-finished products for coating surfaces-building materials |
| JP2015101519A (en) * | 2013-11-26 | 2015-06-04 | 太平洋マテリアル株式会社 | Quick-hardening cement composition with frost damage resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5669257A (en) * | 1979-10-31 | 1981-06-10 | Seitetsu Kagaku Co Ltd | Cement composition |
| JPH0421551A (en) * | 1990-05-15 | 1992-01-24 | Denki Kagaku Kogyo Kk | Quick hardenable ae concrete composition |
| JPH10509780A (en) * | 1996-02-16 | 1998-09-22 | ベー・ハンス・ペーター | Semi-finished products for coating surfaces-building materials |
| JP2015101519A (en) * | 2013-11-26 | 2015-06-04 | 太平洋マテリアル株式会社 | Quick-hardening cement composition with frost damage resistance |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10790891B2 (en) | 2015-07-02 | 2020-09-29 | Huawei Technologies Co., Ltd. | Method, access point, and station for transmitting channel state information |
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