JP2007217261A - Quick-hardening hydraulic composition - Google Patents

Quick-hardening hydraulic composition Download PDF

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JP2007217261A
JP2007217261A JP2006043188A JP2006043188A JP2007217261A JP 2007217261 A JP2007217261 A JP 2007217261A JP 2006043188 A JP2006043188 A JP 2006043188A JP 2006043188 A JP2006043188 A JP 2006043188A JP 2007217261 A JP2007217261 A JP 2007217261A
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portland cement
hydraulic composition
hardening
rapid
calcium aluminate
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Yutaka Nakajima
裕 中島
Kazuhiko Nakahara
和彦 中原
Yasuhide Hojo
泰秀 北条
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Taiheiyo Materials Corp
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    • 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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • 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

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  • 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)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a quick-hardening hydraulic composition containing portland cement as a main hydraulic component which has a stable quick-hardening property, where, even when a variation of quality and property of portland cement used occurs within a range of standard allowed as portland cement, the variation hardly influences the hydration reactivity and curability of the hydraulic composition. <P>SOLUTION: The quick-hardening hydraulic composition contains portland cement, slag powder, and calcium aluminate particles having a hydration layer on their surfaces. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、ポルトランドセメントを主硬化成分とする急硬性の水硬組成物に関する。   The present invention relates to a quick-setting hydraulic composition containing Portland cement as a main curing component.

セメント系ペースト、モルタル又はコンクリート等の水和による硬化時間を短縮するため、カルシウムアルミネートを加えることが広く行われている。（例えば、特許文献１参照。）一方で、カルシウムアルミネートは非常に水和反応活性が高いため、主硬化成分にポルトランドセメントを用いた水硬組成物では、製造時の原燃料の多様化傾向や製造ロットの違いに起因するポルトランドセメントの僅かな品質性状の変動によって、凝結の始発時間や終結時間等の凝結性及び硬化時間や強度発現性等の硬化性状などに大きな差異が現れ易い。カルシウムアルミネートの配合量を少なくすればポルトランドセメントの品質変化による凝結性や硬化性状への影響が現れ難くなるが、急硬性が低下する。一方、ポルトランドセメントの使用量を減らせば、その品質変動の影響を低減できる可能性がある。この場合、ポルトランドセメント使用量低減により結合相形成成分が不足し、強度発現性の低下をまねくが、結合相形成成分の不足を潜在水硬物質であるスラグ粉末を用いて補えば、強度を始めとする硬化性状の低下を回避できることも知られている。（例えば、特許文献２〜３参照。）
特開昭６０−１０８３５２号公報 特開昭６１−２８１０５７号公報 特開２００５−２７２２６０号公報 In order to shorten the hardening time by hydration of cement paste, mortar, concrete, etc., adding calcium aluminate is widely performed. (For example, refer to Patent Document 1) On the other hand, calcium aluminate has a very high hydration reaction activity, and therefore hydraulic compositions using Portland cement as the main curing component tend to diversify raw fuel during production. Due to slight variations in quality properties of Portland cement caused by differences in production lots, large differences are likely to appear in setting properties such as setting time and setting time of setting, and setting properties such as setting time and strength. If the amount of calcium aluminate is reduced, the effect of the quality change of Portland cement on the setting property and hardenability becomes difficult to appear, but the rapid hardening property decreases. On the other hand, if the amount of Portland cement used is reduced, there is a possibility that the influence of quality fluctuations can be reduced. In this case, a decrease in the amount of Portland cement used results in a shortage of binder phase forming components, leading to a decrease in strength development. However, if the shortage of binder phase forming components is compensated for by using slag powder, which is a latent hydraulic substance, strength will increase. It is also known that it is possible to avoid a decrease in curable properties. (For example, refer to Patent Documents 2 to 3.)
JP 60-108352 A JP 61-281577 A1 JP 2005-272260 A

しかし、急硬性を十分付与できる量のカルシウムアルミネートを用いた急硬性の水硬組成物では、硬化成分中のポルトランドセメントをスラグ粉末に置換してポルトランドセメントの使用量を少なくすると、ポトランドセメントに対してはカルシウムアルミネートが過剰となり、ポルトランドセメントに対する活性促進作用が強くなり過ぎて、やはりポルトランドセメントの品質差が急硬性の水硬組成物の諸性状に顕著に反映され易くなる。本発明は、急硬性の水硬組成物であって、使用するポルトランドセメントにポルトランドセメントとして許容される規格範囲内での品質性状の変動差があっても、その影響が水硬組成物の水和反応活性や硬化性状に現れ難く、安定した急硬性を有する水硬組成物の提供を課題とする。   However, in the case of a quick-setting hydraulic composition using calcium aluminate in an amount sufficient to provide rapid hardening, if Portland cement in the hardening component is replaced with slag powder and the amount of Portland cement used is reduced, Potland cement On the other hand, calcium aluminate becomes excessive, and the activity promoting action for Portland cement becomes too strong, and the quality difference of Portland cement is also easily reflected in the properties of the rapid hardening hydraulic composition. The present invention is a rapid-hardening hydraulic composition, and even if the Portland cement used has a variation in quality properties within a standard range acceptable as Portland cement, the effect is affected by the water content of the hydraulic composition. It is an object of the present invention to provide a hydraulic composition that is less likely to appear in the sum reaction activity and curability and has a stable rapid hardening property.

本発明者等は、課題解決のため鋭意検討を重ねた結果、硬化成分としてポルトランドセメントの一部をスラグ粉末で置換し、また急硬性付与作用があるカルシウムアルミネート粒の表面を水和物層で覆った粒を併用すると、セメント凝結初期に於ける反応活性が抑制され、ポルトランドセメントの品質変動が及ぼす凝結性や硬化性への影響を著しく低減できることに加えて、十分な急硬性が発現できたことから本発明を完成するに至った。   As a result of intensive studies for solving the problems, the present inventors have replaced part of Portland cement as a hardening component with slag powder, and the surface of calcium aluminate grains having an effect of imparting rapid hardening is a hydrate layer. When used together with grains covered with, the reaction activity in the early stage of cement setting is suppressed, and in addition to significantly reducing the influence of Portland cement quality change on setting and hardenability, sufficient rapid hardening can be achieved. Thus, the present invention has been completed.

即ち、本発明は、ポルトランドセメント、スラグ粉末及び表面に水和物層を有するカルシウムアルミネート粒を含有してなる急硬性水硬組成物である。   That is, the present invention is a rapid hardening hydraulic composition comprising Portland cement, slag powder and calcium aluminate grains having a hydrate layer on the surface.

また、本発明は、さらに石膏を含有してなる前記の急硬性水硬組成物である。   Moreover, this invention is said rapid hardening hydraulic composition formed by containing gypsum further.

本発明によれば、使用するポルトランドセメントの品質性状に変動があっても、それに影響されることなく安定した急硬性や強度発現性等の硬化性状を呈するセメント系ペースト、モルタル又はコンクリートを得ることができる。   According to the present invention, a cement-based paste, mortar, or concrete that exhibits stable curing properties such as rapid hardening and strength development without being affected by variations in the quality properties of the Portland cement used is obtained. Can do.

本発明の急硬性水硬組成物に使用するポルトランドセメントは、普通、早強、超早強、中庸熱、低熱等の何れのポルトランドセメントであっても良い。また、例えば日本工業規格（ＪＩＳ Ｒ ５２１０「ポルトランドセメント」）で定められている範囲であれば、如何なる品質性状のポルトランドセメントであっても良い。使用するポルトランドセメントの粒度も特には制限されないが、好ましくは急硬性や早期強度発現性が得られ易いことから粉末度としてブレーン比表面積が２５００〜５０００ｃｍ2／ｇのものが良い。 The Portland cement used in the rapid-hardening hydraulic composition of the present invention may be any Portland cement such as normal, early strength, ultra-early strength, moderate heat, and low heat. For example, any quality Portland cement may be used as long as it is within the range defined by Japanese Industrial Standards (JIS R 5210 “Portland Cement”). The particle size of the Portland cement to be used is not particularly limited, but preferably has a Blaine specific surface area of 2500 to 5000 cm 2 / g because it is easy to obtain rapid hardening and early strength development.

また、本発明の急硬性水硬組成物に使用するスラグ粉末は、特に限定されるものでなく、例えば高炉スラグ等の製鋼時の鉱滓や他の金属精錬時の鉱滓、下水汚泥溶融スラグ、都市ゴミ焼却灰溶融スラグ等の粉末を挙げることができる。この中でも、安定した性状のものが入手し易いことから高炉スラグの粉末が好ましい。スラグ粉末の粉末度は急硬性を発現する上で、ブレーン比表面積が３０００〜１００００ｃｍ2／ｇが好ましい。ブレーン比表面積が３０００ｃｍ2／ｇ未満のスラグ粉末では急硬性が低下することがあり、また、ブレーン比表面積が１００００ｃｍ2／ｇを超えるスラグ粉末は製造コストが高くなり過ぎる。スラグ粉末の使用量は、ポルトランドセメントとスラグ粉末の合計使用量１００質量部に対し、３５〜５０質量部であることが好ましい。スラグ粉末が３５質量部未満では、セメントの品質変動の差が急硬性水硬組成物の水和反応活性や硬化性状にも強く現れることがあり、また、スラグ粉末が５０質量部を超えると、急硬性や早期強度発現性が低下することがある。スラグ粉末をポルトランドセメントと併用することで凝結性や硬化性に支障を及ぼすことなくポルトランドセメントの使用量を低減できることからポルトランドセメントに因る系中の活性が下がり、その結果、ポルトランドセメントの品質変動差が急硬性水硬組成物の諸性状に現れ難くなる。 Further, the slag powder used in the rapid-hardening hydraulic composition of the present invention is not particularly limited, for example, slag during steelmaking such as blast furnace slag, slag during other metal refining, sewage sludge molten slag, urban A powder such as garbage incineration ash molten slag can be mentioned. Among these, blast furnace slag powder is preferable because stable properties are easily available. The fineness of the slag powder is preferably 3000 to 10,000 cm 2 / g in terms of brane specific surface area in order to exhibit rapid hardening. In the case of slag powder having a specific surface area of less than 3000 cm 2 / g, the rapid hardening may be deteriorated, and in the case of slag powder having a specific surface area of more than 10,000 cm 2 / g, the production cost becomes too high. It is preferable that the usage-amount of slag powder is 35-50 mass parts with respect to 100 mass parts of total usage-amounts of Portland cement and slag powder. If the slag powder is less than 35 parts by mass, the difference in the quality variation of the cement may appear strongly in the hydration reaction activity and curability of the rapid-hardening hydraulic composition, and when the slag powder exceeds 50 parts by mass, Rapid hardening and early strength development may be reduced. By using slag powder in combination with Portland cement, the amount of Portland cement used can be reduced without affecting the setting and hardening properties, resulting in lower activity in the system due to Portland cement, resulting in fluctuations in the quality of Portland cement. Differences are less likely to appear in the properties of the rapid-hardening hydraulic composition.

また、本発明の急硬性水硬組成物に使用する表面に水和物層を有するカルシウムアルミネート粒は、カルシウムアルミネートの表面の少なくとも一部、望ましくは全表面が、水和物で覆われた粒状のものである。カルシウムアルミネートは、ＣａＯとＡｌ2Ｏ3を主要化学成分とする化合物、固溶体、ガラス質若しくはこれらの何れかが混合した物の総称であって、多少とも水和活性を有するものなら限定されず、例えば、化学成分としての鉱物組成が１２ＣａＯ・７Ａｌ2Ｏ3、ＣａＯ・Ａｌ2Ｏ3、３ＣａＯ・Ａｌ2Ｏ3、１１ＣａＯ・７Ａｌ2Ｏ3・ＣａＦ2、４ＣａＯ・３Ａｌ2Ｏ3・ＳＯ3などのものを挙げることができ、これらの２種以上が共存するものでも良く、またアルミナセメントでも良い。 In addition, the calcium aluminate grains having a hydrate layer on the surface used for the rapid-hydraulic hydraulic composition of the present invention are such that at least a part of the surface of the calcium aluminate, preferably the entire surface, is covered with the hydrate. It is grainy. Calcium aluminate is a general term for compounds containing CaO and Al 2 O 3 as main chemical components, solid solution, glassy material or a mixture of any of these, and is not limited as long as it has a hydration activity. , for example, mineral composition as a chemical component 12CaO · 7Al 2 O 3, CaO · Al 2 O 3, 3CaO · Al 2 O 3, 11CaO · 7Al 2 O 3 · CaF 2, 4CaO · 3Al 2 O 3 · SO 3 2 or more of these may coexist, and alumina cement may be used.

カルシウムアルミネートの表面を覆う水和物は、例えばＣａＯ・Ａｌ2Ｏ3・１０Ｈ2Ｏ、２ＣａＯ・Ａｌ2Ｏ3・８Ｈ2Ｏ、３ＣａＯ・Ａｌ2Ｏ3・６Ｈ2Ｏ、３ＣａＯ・Ａｌ2Ｏ3・８Ｈ2Ｏ、４ＣａＯ・Ａｌ2Ｏ3・１３Ｈ2Ｏ、４ＣａＯ・Ａｌ2Ｏ3・１９Ｈ2Ｏ、Ａｌ2Ｏ3・３Ｈ2Ｏ等の水和物を好適に挙げることができるが、これらに限定されるものではなく水和物なら何れのものでも良い。カルシウムアルミネート粒の表面を覆う水和物の量は、カルシウムアルミネートと水和物の合計質量の０．３〜５％であることが好ましく、０．３〜４％がより好ましい。０．３％未満ではカルシウムアルミネートの反応活性が高まりすぎて、ポルトランドセメントとの反応作用が強くなり、ポルトランドセメントの僅かな品質性状差も急硬性水硬組成物の諸性状に反映され易くなることがある他、使用量によっては瞬結化を起こすことがあるので適当ではない。また５％を超えると反応活性が低過ぎて所望の急硬性が得られ難くなることがある。カルシウムアルミネート表面を水和物で覆う方法は何等限定されない。比較的簡易な一例を示すと、分散させたカルシウムアルミネート粒の表面に、これを例えば振動機等を用いて転動させながら、常温又はそれ以下の温度でカルシウムアルミネート質量の概ね０．２〜３．５％に相当する質量の水を市販の噴霧装置で噴霧することで、容易に表面に水和物層を生成させることが可能である。また、表面に水和物層を有するカルシウムアルミネート粒の粉末度は、ブレーン比表面積でおよそ３０００ｃｍ2／ｇ以上が好ましく、４０００〜１００００ｃｍ2／ｇがより好ましい。ブレーン比表面積がおよそ３０００ｃｍ2／ｇ未満では反応活性が低くなり過ぎて十分な急硬性が得られないことがある。 Hydrate covering the surface of the calcium aluminate may, for example CaO · Al 2 O 3 · 10H 2 O, 2CaO · Al 2 O 3 · 8H 2 O, 3CaO · Al 2 O 3 · 6H 2 O, 3CaO · Al 2 O 3 · 8H 2 O, 4CaO · Al 2 O 3 · 13H 2 O, 4CaO · Al 2 O 3 · 19H 2 O, may be mentioned Al 2 O 3 · 3H 2 hydrate O such suitably However, it is not limited to these, and any hydrate may be used. The amount of hydrate covering the surface of the calcium aluminate grains is preferably 0.3 to 5% of the total mass of calcium aluminate and hydrate, and more preferably 0.3 to 4%. If it is less than 0.3%, the reaction activity of calcium aluminate is excessively increased, and the reaction action with Portland cement becomes strong, and slight quality property differences of Portland cement are easily reflected in various properties of the rapid hardening hydraulic composition. In addition, depending on the amount of use, it may cause instantaneous linking, which is not appropriate. On the other hand, if it exceeds 5%, the reaction activity is too low, and it may be difficult to obtain the desired rapidity. The method for covering the calcium aluminate surface with hydrate is not limited. As a relatively simple example, the surface of dispersed calcium aluminate grains is rolled using, for example, a vibrator or the like, and the mass of calcium aluminate is approximately 0.2 at room temperature or lower. It is possible to easily form a hydrate layer on the surface by spraying water with a mass corresponding to ˜3.5% with a commercially available spray device. Calcium aluminate particle fineness having a hydrate layer on the surface is approximately 3000 cm 2 / g or more preferably at Blaine specific surface area, 4000~10000cm 2 / g is more preferable. When the specific surface area of the brane is less than about 3000 cm 2 / g, the reaction activity becomes too low and sufficient rapid hardening may not be obtained.

本発明の急硬性水硬組成物に使用する表面に水和物層を有するカルシウムアルミネート粒の量は、ポルトランドセメントとスラグ粉末の合計使用量１００質量部に対し、５〜１００質量部とするのが好ましい。５質量部未満では急硬性や早期強度発現性が低迷し易く、また１００質量部を超える使用量では硬化性状が不安定となり、十分な急硬性が得られなくなることがあるので適当ではない。   The amount of calcium aluminate grains having a hydrate layer on the surface used in the rapid-hardening hydraulic composition of the present invention is 5 to 100 parts by mass with respect to 100 parts by mass of the total usage of Portland cement and slag powder. Is preferred. If the amount is less than 5 parts by mass, the rapid hardening property and early strength development are likely to be sluggish, and if the amount exceeds 100 parts by mass, the curing property becomes unstable and sufficient rapid hardening property may not be obtained.

本発明の急硬性水硬組成物には、さらに石膏が配合されることが好ましい。石膏を配合することでカルシウムアルミネートの水和が促進され、より確実にポルトランドセメントの品質変動差を急硬発見性に影響を及ぼし難くすることができる。石膏は無水、半水、二水の何れの石膏でも使用することができるが、反応性が高く、またコスト的にも有利な点から無水石膏が好ましい。使用する石膏の粉末度は、ブレーン比表面積で３０００〜２００００ｃｍ2／ｇのものが好ましい。ブレーン比表面積が３０００ｃｍ2／ｇ未満では反応性が低くなることがあり、また、ブレーン比表面積が２００００ｃｍ2／ｇを超えると、調整コストが高騰するため適当ではない。本発明の急硬性水硬組成物の石膏使用量は、表面に水和物層を有するカルシウムアルミネート粒の使用量１００質量部に対し、３０〜１５０質量部が好ましく、５０〜１００質量部がより好ましい。３０質量部未満の使用では石膏配合による効果が得られ難くなり、また、１５０質量部を超えると過度の膨張を引き起こし易くなる。 It is preferable that gypsum is further blended in the rapid-hardening hydraulic composition of the present invention. By blending gypsum, the hydration of calcium aluminate is promoted, and the difference in quality variation of Portland cement can be made more difficult to affect the rapid hardenability. Gypsum can be used in any form of anhydrous, semi-water, or dihydrate, but anhydrous gypsum is preferred because of its high reactivity and advantageous cost. The fineness of the gypsum used is preferably 3000-20000 cm 2 / g in terms of Blaine specific surface area. When the specific surface area of the brane is less than 3000 cm 2 / g, the reactivity may be low, and when the specific surface area of the brane exceeds 20000 cm 2 / g, the adjustment cost increases, which is not appropriate. The amount of gypsum used in the rapid-hardening hydraulic composition of the present invention is preferably 30 to 150 parts by mass, and 50 to 100 parts by mass with respect to 100 parts by mass of calcium aluminate grains having a hydrate layer on the surface. More preferred. When the amount is less than 30 parts by mass, it is difficult to obtain the effect of the gypsum compounding. When the amount exceeds 150 parts by mass, excessive expansion tends to occur.

また、本発明の急硬性水硬組成物は、本発明の効果を喪失させるものでない限り、前記のポルトランドセメント、表面に水和物層を有するカルシウムアルミネート粒及び石膏以外の成分も含むことができる。このような成分として、例えば、アルカリ金属の硫酸塩や水酸化物、アルカリ土類金属の水酸化物、硫酸アルミニウム又はアルミン酸アルカリ等の凝結促進剤、フライアッシュやシリカフューム等のポゾラン反応物質、膨張材、収縮低減剤、減水剤、高性能減水剤、ＡＥ減水剤、高性能ＡＥ減水剤、分散剤、空気連行剤、消泡剤、撥水剤、白華防止剤、増粘剤、発泡剤、顔料、抗菌剤等を挙げることができる。特に、急硬性を維持しつつ可使時間をより長く確保したい場合は、クエン酸、酒石酸、グルコン酸、ヘプトン酸等のオキシカルボン酸又はその塩、リン酸塩、硼酸又はその塩、さらには以上の化合物の何れか１種以上とアルカリ金属炭酸塩の混合物等の、モルタルやコンクリートに使用できる凝結遅延剤を、ポルトランドセメント、スラグ粉末及びカルシウムアルミネートの合計使用量１００質量部に対し、０．０５〜５質量部配合されるのが好ましい。   Further, the rapid-hardening hydraulic composition of the present invention may contain components other than the Portland cement, calcium aluminate grains having a hydrate layer on the surface, and gypsum unless the effects of the present invention are lost. it can. Such components include, for example, alkali metal sulfates and hydroxides, alkaline earth metal hydroxides, setting accelerators such as aluminum sulfate or alkali aluminate, pozzolanic reactants such as fly ash and silica fume, and swelling. Material, shrinkage reducing agent, water reducing agent, high performance water reducing agent, AE water reducing agent, high performance AE water reducing agent, dispersing agent, air entraining agent, antifoaming agent, water repellent, white flower inhibitor, thickener, foaming agent , Pigments, antibacterial agents and the like. In particular, when it is desired to ensure a longer pot life while maintaining rapid hardening, oxycarboxylic acids such as citric acid, tartaric acid, gluconic acid and heptonic acid or salts thereof, phosphates, boric acid or salts thereof, or more A setting retarder that can be used in mortar or concrete, such as a mixture of any one or more of the above compounds and an alkali metal carbonate, is added in an amount of 0. 0 to 100 parts by mass of the total amount of Portland cement, slag powder, and calcium aluminate used. It is preferable that 0.5-5 mass parts is mix | blended.

また、本発明の急硬性水硬組成物は、従来の急硬性や速硬性セメントと概ね同様に扱うことができ、例えば骨材や水を加えて適宜混練することで施工使用することができる。推奨される水の配合量は、本発明の急硬性水硬組成物１００質量部に対し、２０〜７０質量部とするのが、所望の強度発現性を得る上で、また材料分離防止や混合性の点から良い。   The rapid-hardening hydraulic composition of the present invention can be handled in the same manner as conventional rapid-hardening and fast-setting cements, and can be used by, for example, adding aggregate and water and kneading appropriately. The recommended blending amount of water is 20 to 70 parts by mass with respect to 100 parts by mass of the rapid-hardening hydraulic composition of the present invention. Good in terms of sex.

以下、実施例により本発明を具体的に詳しく説明する。   Hereinafter, the present invention will be described in detail by way of examples.

［表面を水和物で被覆したカルシウムアルミネート粒の作製］ カルシウムアルミネート粒としてブレーン比表面積５０００ｃｍ2／ｇの市販のアルミナセメントを用い、該アルミナセメント５０Ｋｇを内容量１３０リットルのレーディゲミキサに入れ、回転させながら５００ｇの水を市販噴霧器を用いて約１分かけて全量噴霧した。噴霧終了後１０分間ミキサを回転し続けた後、ミキサから噴霧済みの粒子を取り出して３０日間放置した。以上の作業及び放置は温度２０℃、湿度約７０％に管理された屋内で行った。このようにして得た粒子はエックス線回折により定性分析を行い、３ＣａＯ・Ａｌ2Ｏ3・６Ｈ2Ｏが生成していることが確認された。また、走査型電子顕微鏡及びエックス線マイクロアナライザーを用いて粒子中の水和物の生成位置を確認した結果、粒子表面全体に水和物生成層を確認した。更に熱分析装置を用いて粒子中の化合水量を測定し、その値から３ＣａＯ・Ａｌ2Ｏ3・６Ｈ2Ｏの生成量を算出した結果、粒子全体の質量中約３．５％を占めるものであった。 [Preparation of Calcium Aluminate Particles with Surface Covered with Hydrate] Commercially available alumina cement having a Blaine specific surface area of 5000 cm 2 / g was used as calcium aluminate particles, and 50 kg of the alumina cement was put into a Laedige mixer having an internal volume of 130 liters. While rotating, 500 g of water was sprayed over the course of about 1 minute using a commercial sprayer. After the spraying was finished, the mixer was kept rotating for 10 minutes, and then the sprayed particles were taken out of the mixer and left for 30 days. The above work and leaving were performed indoors controlled at a temperature of 20 ° C. and a humidity of about 70%. The thus obtained particles perform qualitative analysis by X-ray diffraction, it was confirmed that 3CaO · Al 2 O 3 · 6H 2 O are generated. Moreover, as a result of confirming the production | generation position of the hydrate in particle | grains using the scanning electron microscope and the X-ray microanalyzer, the hydrate production | generation layer was confirmed on the whole particle | grain surface. Even more measured compound water in the particles using a thermal analysis apparatus, which occupies its value 3CaO · Al 2 O 3 · 6H 2 O result of calculating the production amount of from about 3.5% in the total particle mass Met.

［水硬組成物の作製］ 前記作製の水和物被覆されたアルミナセメント、水和物で被覆していないアルミナセメント、表１に表す粒径、主要化学成分及び水和発熱量を有する５種類の普通ポルトランドセメント（Ａ〜Ｅ）、ブレーン比表面積４０００ｃｍ2／ｇの高炉スラグ粉末及びブレーン比表面積７１００ｃｍ2／ｇのＩＩ型無水石膏（市販試薬）から選定された材料を表２に表す配合量となるようレーディゲミキサに入れ、５分間混合して水硬組成物を得た。尚、表１の普通ポルトランドセメントの水和発熱量は、温度２０℃、湿度５０％の室内に設置した微小熱量計（株式会社東京理工製マルチマイクロカロリーメーター）を用い、測定試料ホルダー内に普通ポルトランドセメント６．５ｇを入れ、次いでこれに蒸留水１３．０ｇを加え、蒸留水を加えた時点から２０分間の総水和発熱量を測定した値である。 [Preparation of hydraulic composition] Alumina cement coated with hydrate, alumina cement not coated with hydrate, 5 types having particle sizes, main chemical components and hydration calorific values shown in Table 1 ordinary Portland cement (a-E), the amount represented in Table 2. a material selected from the Blaine specific surface area of 4000 cm 2 / g of blast furnace slag powder and Blaine specific surface area of 7100cm 2 / g of type II anhydrous gypsum (commercially available reagent) The mixture was placed in a Laedige mixer so as to obtain a hydraulic composition by mixing for 5 minutes. In addition, the hydration calorific value of normal Portland cement in Table 1 is usually measured in a measurement sample holder using a microcalorimeter (multi-micro calorimeter manufactured by Tokyo Riko Co., Ltd.) installed in a room with a temperature of 20 ° C. and a humidity of 50%. This is a value obtained by adding 6.5 g of Portland cement, then adding 13.0 g of distilled water, and measuring the total hydration calorific value for 20 minutes from the time when distilled water was added.

Figure 2007217261
Figure 2007217261

Figure 2007217261
Figure 2007217261

［水硬組成物の活性度の把握］ 得られた各水硬組成物の活性を、温度２０℃、湿度５０％の室内に設置した前記と同じ微小熱量計を用い、測定試料ホルダー内に、前記の如く作製した水硬組成物６．５ｇを入れ、これに蒸留水１３．０ｇを加え、蒸留水を加えた時点から２０分間の総水和発熱量を測定することにより把握した。測定された総水和発熱量の値は表２に表す。   [Understanding the Activity of Hydraulic Composition] The activity of each obtained hydraulic composition was measured in the measurement sample holder using the same microcalorimeter installed in a room at a temperature of 20 ° C. and a humidity of 50%. It was grasped by adding 6.5 g of the hydraulic composition prepared as described above, adding 13.0 g of distilled water thereto, and measuring the total hydration calorific value for 20 minutes from the time when the distilled water was added. The measured total hydration exotherm values are shown in Table 2.

［モルタル供試体での性状評価］ 表２の配合の水硬組成物１８００ｇに、砕砂（表乾密度２．６３Ｋｇ／リットル、最大粒径５ｍｍ）２７００ｇ、ポリカルボン酸系高性能減水剤（太平洋マテリアル株式会社製「ＮＦ−１００」）１．８ｇ、クエン酸ナトリウム７ｇ、炭酸リチウム１８ｇ及び水５４０ｇを加え、ホバートミキサで約３分２０℃の温度下で混合した。得られた混合物は直ちに４×４×１６ｃｍの型枠に流し込み、そのまま２０℃の大気中で６時間養生した後脱型することでモルタル供試体を作製した。モルタル供試体は脱型後直ぐに、ＪＩＳ Ｒ ５２０１に準じた方法で圧縮強度を測定した。その結果を表３に表す。   [Property Evaluation with Mortar Specimen] 1800 g of hydraulic composition having the composition shown in Table 2 was added to 2700 g of crushed sand (surface dry density 2.63 kg / liter, maximum particle size 5 mm), polycarboxylic acid-based high-performance water reducing agent (Pacific Material) 1.8 g of “NF-100” (trade name), 7 g of sodium citrate, 18 g of lithium carbonate, and 540 g of water were added, and the mixture was mixed for about 3 minutes at a temperature of 20 ° C. with a Hobart mixer. The obtained mixture was immediately poured into a 4 × 4 × 16 cm mold, cured as it was in the atmosphere at 20 ° C. for 6 hours, and then demolded to prepare a mortar specimen. Immediately after demolding, the mortar specimen was measured for compressive strength by a method according to JIS R 5201. The results are shown in Table 3.

Figure 2007217261
Figure 2007217261

表１及び２より、品質的に水和反応活性（総水和発熱量）の異なる普通ポルトランドセメントを使用しても、本発明による組成物にすれば、水和反応活性の差が組成物では大幅に縮小されることがわかり、また表３より、本発明の水硬組成物を用いたモルタルでは短時間強度の発現性が普通ポルトランドセメントの品質性状差に拘わらず、ほぼ一定となることがわかる。   From Tables 1 and 2, even if ordinary Portland cement having different hydration reaction activity (total hydration calorific value) is used in terms of quality, if the composition according to the present invention is used, the difference in hydration reaction activity is From Table 3, it can be seen that the mortar using the hydraulic composition of the present invention shows that the short-time strength development is almost constant regardless of the quality property difference of ordinary Portland cement. Recognize.

Claims (2)

ポルトランドセメント、スラグ粉末及び表面に水和物層を有するカルシウムアルミネート粒を含有してなる急硬性水硬組成物。 A rapid-hardening hydraulic composition comprising portland cement, slag powder, and calcium aluminate grains having a hydrate layer on the surface. さらに、石膏を含有する請求項１記載の急硬性水硬組成物。 Furthermore, the rapid-hardening hydraulic composition of Claim 1 containing gypsum.
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