JP6586417B2 - Quick setting admixture - Google Patents
Quick setting admixtureInfo
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- JP6586417B2 JP6586417B2 JP2016523169A JP2016523169A JP6586417B2 JP 6586417 B2 JP6586417 B2 JP 6586417B2 JP 2016523169 A JP2016523169 A JP 2016523169A JP 2016523169 A JP2016523169 A JP 2016523169A JP 6586417 B2 JP6586417 B2 JP 6586417B2
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
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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
Description
本発明は、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を急速凝結するための混和材に関する。 The present invention relates to an admixture for rapidly setting a cement composition such as cement paste, mortar or concrete.
トンネル、地下空間、急斜面等の掘削・造成工事においては、モルタルやコンクリート等を地山や壁面に吹付けて補強している。通常、吹付に用いるモルタルやコンクリートは急結剤が加えられ、セメント凝結を極短時間で終えることで、吹付物の付着・固定化を行っている。急結剤は、例えば粉末状のカルシウムアルミネートや液状の硫酸アルミニウムなどが使用されるが、これらを併用すると、中長期強度の向上と硬化状態の長期安定化に寄与することが知られている（例えば、特許文献１参照）。しかし、両者を併用しただけでは高い初期強度が得難くなり、特に、例えば１０℃未満の低温で施工すると初期強度発現性が大きく低下する。この低温下での初期強度発現性低下の改善には、カルシウムアルミネートと硫酸アルミニウムを併用した急結剤にアルカリ金属の硫酸塩を加えると効果があることが知られている（例えば、特許文献２，３参照）。 In excavation and construction work for tunnels, underground spaces, steep slopes, etc., mortar and concrete are reinforced by spraying them on natural ground and walls. Usually, a mortar or concrete used for spraying is added with a quick setting agent, and cementation is completed in an extremely short time, thereby adhering and fixing the sprayed material. For example, powdery calcium aluminate or liquid aluminum sulfate is used as the quick setting agent, and it is known that when these are used in combination, it contributes to improvement of medium-long-term strength and long-term stabilization of the cured state. (For example, refer to Patent Document 1). However, it is difficult to obtain a high initial strength only by using both in combination. In particular, when the construction is performed at a low temperature of, for example, less than 10 ° C., the initial strength development is greatly reduced. It is known that an improvement in the initial strength development at low temperatures is effective when an alkali metal sulfate is added to a rapid setting agent using calcium aluminate and aluminum sulfate in combination (for example, Patent Documents). 2 and 3).
しかしながら、この改善方法では低温になるに連れて瞬結性が失われる傾向があることが判明した。特に、温度の低い施工環境下で吹付けると、吹付けたモルタルやコンクリートが吹付面に十分固定できず、垂れたり剥落する虞があった。 However, it has been found that this improvement method tends to lose the instantaneous setting properties as the temperature is lowered. In particular, when sprayed in a low-temperature construction environment, the sprayed mortar and concrete could not be sufficiently fixed to the sprayed surface, and there was a risk of dripping or peeling off.
本発明は、セメント系組成物に、急結性を始めとし、中長期強度の向上と硬化状態の長期安定性という特性を付与させることに加え、例えば１０℃未満のような低温環境下で施工しても、初期強度発現性が低下せず、かつ瞬結性の低下を従来のものよりも著しく少なくし、低温での実用に適う瞬結性を十分付与できる急結用混和材の提供を課題とする。 The present invention is applied to a cementitious composition in a low temperature environment such as less than 10 ° C., in addition to imparting properties such as rapid setting, improvement of medium to long-term strength and long-term stability of a cured state. However, it is possible to provide a quick-setting admixture that does not decrease the initial strength, significantly reduces the decrease in quick setting than conventional ones, and provides sufficient quick setting suitable for practical use at low temperatures. Let it be an issue.
本発明者は、前記課題を解決するため検討した結果、特定の配合比のカルシウムアルミネートと硫酸アルミニウムとアルカリ金属及び／又はアルカリ土類金属の硫酸塩とから構成される、セメント組成物を急速凝結するための混和材において、硫酸アルミニウムとして特定の異成分を含む硫酸アルミニウムを使用することで、前記課題を総じて解決できることを見出し、本発明を完成させた。 As a result of studying to solve the above problems, the present inventor has rapidly developed a cement composition composed of calcium aluminate, aluminum sulfate, and alkali metal and / or alkaline earth metal sulfate having a specific mixing ratio. The present inventors have found that the above problems can be solved as a whole by using aluminum sulfate containing specific different components as the aluminum sulfate in the admixture for condensing, thereby completing the present invention.
すなわち、本発明は、次の〔１〕〜〔９〕を提供するものである。 That is, the present invention provides the following [1] to [9].
〔１〕（Ａ）カルシウムアルミネート１００質量部と、（Ｂ）硫酸アルミニウム１０〜４０質量部と、（Ｃ）アルカリ金属硫酸塩及びアルカリ土類金属硫酸塩から選ばれる１種以上７．５〜７５質量部を含有する混和材であって、前記成分（Ｂ）硫酸アルミニウムがアルカリ金属含有物質をアルカリ金属酸化物換算で０．０３〜３．５質量％含有することを特徴とする急結用混和材。
〔２〕成分（Ｂ）の含有量が、１５〜３５質量部である〔１〕記載の急結用混和材。
〔３〕成分（Ｃ）の含有量が、７．５〜５５質量部である〔１〕又は〔２〕記載の急結用混和材。
〔４〕成分（Ａ）が、ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）１．８以上でガラス化率８０％以上のカルシウムアルミネートである〔１〕〜〔３〕のいずれかに記載の急結用混和材。
〔５〕〔１〕〜〔４〕のいずれかに記載の急結用混和材を含有するセメント組成物。
〔６〕前記急結用混和材の含有量が、セメント１００質量部に対し７〜２０質量部である〔５〕記載のセメント組成物。
〔７〕〔１〕〜〔４〕のいずれかに記載の急結用混和材を含有する吹付けコンクリート組成物。
〔８〕前記急結用混和材の含有量が、セメント１００質量部に対し７〜２０質量部である〔７〕記載の吹付けコンクリート組成物。
〔９〕前記急結用混和材の含有量が、セメント１００質量部に対し１１〜１５質量部である〔７〕記載の吹付けコンクリート組成物。[1] (A) 100 parts by mass of calcium aluminate, (B) 10 to 40 parts by mass of aluminum sulfate, and (C) one or more selected from alkali metal sulfate and alkaline earth metal sulfate 7.5 to An admixture containing 75 parts by mass, wherein the component (B) aluminum sulfate contains an alkali metal-containing substance in an amount of 0.03 to 3.5% by mass in terms of an alkali metal oxide. Admixture.
[2] The quick setting admixture according to [1], wherein the content of the component (B) is 15 to 35 parts by mass.
[3] The rapid setting admixture according to [1] or [2], wherein the content of the component (C) is 7.5 to 55 parts by mass.
[4] The component (A) is a calcium aluminate having a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 1.8 or more and a vitrification rate of 80% or more [1] to [3 ] The quick-setting admixture according to any one of the above.
[5] A cement composition containing the quick setting admixture according to any one of [1] to [4].
[6] The cement composition according to [5], wherein the content of the quick setting admixture is 7 to 20 parts by mass with respect to 100 parts by mass of cement.
[7] A shotcrete composition containing the rapid setting admixture according to any one of [1] to [4].
[8] The shotcrete composition according to [7], wherein the content of the quick setting admixture is 7 to 20 parts by mass with respect to 100 parts by mass of cement.
[9] The shotcrete composition according to [7], wherein the content of the quick setting admixture is 11 to 15 parts by mass with respect to 100 parts by mass of cement.
本発明によれば、セメントペースト、モルタルやコンクリート等のセメント組成物を吹付施工する場合、例えば１０℃未満の低温環境下でも瞬結性の落ち込みが著しく改善されることから、吹付面への付着固定を確実に行うことができる。また、高い初期強度を発現できる他、中長期の強度発現性も低下せずに良好な硬化状態を保ち続けるため、長期に亘って安定した硬化状態を呈することができる。 According to the present invention, when spraying a cement composition such as cement paste, mortar or concrete, for example, the drop in instantaneous setting is remarkably improved even in a low temperature environment of less than 10 ° C. Fixing can be performed reliably. In addition to being able to develop a high initial strength, it can maintain a good cured state without decreasing the medium-to-long-term strength development property, and thus can exhibit a stable cured state over a long period of time.
本発明の急結用混和材は、（Ａ）カルシウムアルミネート１００質量部と、（Ｂ）硫酸アルミニウム１０〜４０質量部と、（Ｃ）アルカリ金属硫酸塩及びアルカリ土類金属硫酸塩から選ばれる１種以上７．５〜７５質量部を含有する混和材であって、前記（Ｂ）硫酸アルミニウムがアルカリ金属含有物質をアルカリ金属酸化物換算で０．０３〜３．５質量％含有することを特徴とする。 The quick setting admixture of the present invention is selected from (A) 100 parts by weight of calcium aluminate, (B) 10 to 40 parts by weight of aluminum sulfate, and (C) alkali metal sulfate and alkaline earth metal sulfate. It is an admixture containing 7.5 to 75 parts by mass of one or more kinds, wherein the (B) aluminum sulfate contains an alkali metal-containing substance in an amount of 0.03 to 3.5% by mass in terms of an alkali metal oxide. Features.
本発明の急結用混和材に使用する（Ａ）カルシウムアルミネート（成分（Ａ））は、化学成分としてＣａＯとＡｌ2Ｏ3からなる結晶質又は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、また、本発明の効果を実質喪失させるものでない限り、含有化学成分としてＣａＯとＡｌ2Ｏ3に加えて、他の化学成分が含まれてなる化合物、固溶体若しくはガラス質物質又はこれらの混合物等の何れであっても良い。前者は、例えば１２ＣａＯ・７Ａｌ2Ｏ3、ＣａＯ・Ａｌ2Ｏ3、３ＣａＯ・Ａｌ2Ｏ3、ＣａＯ・２Ａｌ2Ｏ3等が挙げられる。また、後者は、例えば４ＣａＯ・３Ａｌ2Ｏ3・ＳＯ3、１１ＣａＯ・７Ａｌ2Ｏ3・ＣａＦ2、Ｎａ2Ｏ・８ＣａＯ・３Ａｌ2Ｏ3等が挙げられる。何れも記載例に限定されるものではない。好ましくは、水和活性が高く、より高い急結性が得られる可能性があることから、ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．８以上のカルシウムアルミネートが良い。より好ましくは、ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．０以上のカルシウムアルミネートである。またＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．３以下のカルシウムアルミネートが好ましい。さらに具体的には、ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．８〜２．３のものが好ましく、２．０〜２．３のものがさらに好ましい。
カルシウムアルミネートはセメント組成物の注水後の早い段階で凝結を起こさせる急結性付与成分として寄与する。また、カルシウムアルミネートはガラス化率が高いものほど高い急結性を付与し易くなることから、８０％以上のガラス化率のものが好ましいが、ガラス化率を制限するものではない。より好ましくは非晶質（ガラス化率が実質１００％）のカルシウムアルミネートを使用する。尚、ガラス化率は、粉末エックス線回折装置を用い、質量がＭ１のカルシウムアルミネート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、残部を純ガラス相と見なすと、次式でガラス化率が得られる。
ガラス化率（％）＝（１−Ｍ２／Ｍ１）×１００
好ましいカルシウムアルミネートは、ＣａＯ／Ａｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．８以上、より好ましくは２．０以上、さらに好ましくは１．８〜２．３、さらに好ましくは２．０〜２．３であり、ガラス化率が８０％以上、より好ましくは８０〜１００％のものである。(A) Calcium aluminate (component (A)) used in the rapid setting admixture of the present invention is a hydrated active substance having a crystallized or vitrified structure consisting of CaO and Al 2 O 3 as chemical components As long as the effect of the present invention is not substantially lost, a compound, a solid solution, or a compound containing other chemical components in addition to CaO and Al 2 O 3 as contained chemical components Any of a vitreous substance or a mixture thereof may be used. The former, for example, 12CaO · 7Al 2 O 3, CaO · Al 2 O 3, 3CaO · Al 2 O 3, CaO · 2Al 2 O 3 and the like. The latter is, for example, 4CaO · 3Al 2 O 3 · SO 3, 11CaO · 7Al 2 O 3 · CaF 2, Na 2 O · 8CaO · 3Al 2 O 3 and the like. None of them are limited to the description examples. Preferably, calcium aluminum having a high molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 1.8 or more because hydration activity is high and there is a possibility that higher quick setting properties can be obtained. Nate is good. More preferably, calcium aluminate having a molar ratio of CaO to Al 2 O 3 (CaO / Al 2 O 3 ) of 2.0 or more. The molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3) is 2.3 or less of calcium aluminate are preferred. More specifically, the molar ratio of CaO to Al 2 O 3 (CaO / Al 2 O 3 ) is preferably 1.8 to 2.3, more preferably 2.0 to 2.3.
Calcium aluminate contributes as a quick setting component that causes agglomeration at an early stage after water injection of the cement composition. Further, calcium aluminate having a higher vitrification rate is more likely to impart high quick setting properties, and therefore, a vitrification rate of 80% or more is preferable, but the vitrification rate is not limited. More preferably, an amorphous calcium aluminate (substantially 100% vitrification) is used. The vitrification rate is determined by using a powder X-ray diffractometer, quantifying the mass of each mineral contained in the calcium aluminate having a mass of M1 by an internal standard method or the like, and calculating the total mass (M2) of the contained mineral phases. When the calculation is made and the remainder is regarded as a pure glass phase, the vitrification rate is obtained by the following formula.
Vitrification rate (%) = (1-M2 / M1) × 100
A preferred calcium aluminate has a CaO / Al 2 O 3 content molar ratio (CaO / Al 2 O 3 ) of 1.8 or more, more preferably 2.0 or more, more preferably 1.8 to 2.3, Preferably, it is 2.0 to 2.3, and the vitrification rate is 80% or more, more preferably 80 to 100%.
ガラス化が進んだカルシウムアルミネートの製造方法は特に限定されない。一例を示すと、ＣａＯとＡｌ2Ｏ3を所定の含有モル比となるようにＣａＯ又はＣａＯ源となる原料とＡｌ2Ｏ3又はＡｌ2Ｏ3源となる原料を配合した混合物を、これが溶融するまで加熱し、次いで望ましくは水中急冷及び散水急冷以外の任意の方法で急冷することで所望のガラス化率のカルシウムアルミネートを製造することができる。急冷したカルシウムアルミネートは所望の反応活性を得るため、ブレーン比表面積で概ね４０００ｃｍ2／ｇ以上、粉砕コストを考慮すれば概ね４０００〜７０００ｃｍ2／ｇに粉砕分級処理すると良い。The method for producing calcium aluminate which has been vitrified is not particularly limited. As an example, a mixture obtained by blending the raw material as a raw material and the Al 2 O 3 or Al 2 O 3 source to be CaO or CaO source to the CaO and Al 2 O 3 becomes a predetermined molar ratio, which is melted And then quenching by any method other than underwater quenching and sprinkling quenching can produce calcium aluminate with the desired vitrification rate. In order to obtain the desired reaction activity, the rapidly cooled calcium aluminate is preferably subjected to a pulverization classification treatment with a Blaine specific surface area of approximately 4000 cm 2 / g or more, and considering the pulverization cost, approximately 4000 to 7000 cm 2 / g.
本発明の急結用混和材に使用する（Ｂ）硫酸アルミニウム（成分（Ｂ））は、アルカリ金属含有物質を含有し、その含有量が、アルカリ金属酸化物換算で０．０３〜３．５質量％であることを特徴とする。硫酸アルミニウムは、セメント等の水硬性物質の初期凝結の促進に寄与し、特にアルカリ金属含有物質を含有したものは、常温近傍で瞬結性が得られることは勿論、例えば約１０℃未満の低温環境下でも十分な瞬結性を付与できると共に、このような低温での初期強度の顕著な低下を防止することも可能になる。硫酸アルミニウム中のアルカリ金属含有物質の含有量が酸化物換算で０．０３質量％未満では低温環境下で瞬結性を発現し難く、また初期強度発現性の低下が大きくなることがあるので好ましくない。また、アルカリ金属含有物質の含有量が酸化物換算で３．５質量％を超える場合は、初期凝結の促進作用が低下し、温度環境に拘わらず瞬結性が発現し難くなることがあるので好ましくない。所定量のアルカリ金属含有物質を含有する硫酸アルミニウムを使用することによって前記作用が発現できるのであって、アルカリ金属含有物質を含有しない硫酸アルミニウムに加えて、例えば市販試薬の酸化カリウムや酸化リチウム等のアルカリ金属酸化物を後から添加混合しても前記のような作用は十分得られない。
好ましい硫酸アルミニウム中のアルカリ金属含有物質の含有量は、酸化物換算で０．１〜１．２質量％であり、より好ましくは０．２〜１．０質量％である。
ここで、アルカリ金属含有物質とは、少なくともＮａ、Ｋ、Ｌｉの何れか１種以上を構成成分とする物質であれば特に限定されず、アルカリ金属単体、アルカリ金属化合物、アルカリ金属含有固溶体、アルカリ金属含有非晶質体等の何れであっても良く、またこれらの何れかが共存した物質でも良い。具体的には、例えば、アルカリ金属、アルカリ金属酸化物（Ｎａ2Ｏ、Ｋ2Ｏ、ＬｉＯ2など）、アルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ金属酸化物としての硫酸アルミニウム中への固溶体などが挙げられる。好ましくは、アルカリ金属硫酸塩は含まない。
(B) Aluminum sulfate (component (B)) used for the rapid setting admixture of the present invention contains an alkali metal-containing substance, and its content is 0.03 to 3.5 in terms of alkali metal oxide. It is characterized by mass % . Aluminum sulfate contributes to the promotion of the initial setting of hydraulic materials such as cement, and particularly those containing an alkali metal-containing material can provide quick setting near room temperature, for example, at a low temperature of less than about 10 ° C. Sufficient instantaneous setting can be imparted even under the environment, and it is possible to prevent such a significant decrease in initial strength at low temperatures. If the content of the alkali metal-containing substance in aluminum sulfate is less than 0.03% by mass in terms of oxide, it is difficult to express instantaneous setting in a low-temperature environment and the initial strength development may be greatly reduced, which is preferable. Absent. In addition, when the content of the alkali metal-containing substance exceeds 3.5% by mass in terms of oxide, the initial setting acceleration action is reduced, and it may be difficult to express instantaneous setting regardless of the temperature environment. It is not preferable. By using aluminum sulfate containing a predetermined amount of an alkali metal-containing substance, the above action can be achieved. In addition to aluminum sulfate containing no alkali metal-containing substance, for example, commercially available reagents such as potassium oxide and lithium oxide Even if an alkali metal oxide is added and mixed later, the above-mentioned effects cannot be obtained sufficiently.
The preferred content of alkali metal-containing material of sulphate in aluminum is 0.1 to 1.2 mass% in oxides terms, more preferably from 0.2 to 1.0 wt%.
Here, the alkali metal-containing substance is not particularly limited as long as it is a substance having at least one of Na, K, and Li as a constituent component. Alkali metal alone, alkali metal compound, alkali metal-containing solid solution, alkali Any of a metal-containing amorphous body, etc., or a substance in which any of these may coexist may be used. Specifically, for example, alkali metal, alkali metal oxide (Na 2 O, K 2 O, LiO 2 etc.), alkali metal hydroxide, alkali metal carbonate, aluminum sulfate as alkali metal oxide into aluminum sulfate Examples include solid solutions. Preferably, no alkali metal sulfate is contained.
また、硫酸アルミニウムは結晶水を有するものや無水物のどちらも使用できる。好ましくは結晶水を有すものが良く、これを吹付用のセメント組成物に使用すると、吹付時のリバウンドを防止し易くなる。
本使用に適したアルカリ金属含有物質を含有する硫酸アルミニウムは、その製造原料に由来し、例えば、何れもアルカリ金属化合物を不純物として含むボーキサイト、アルミニウムスラッジ又はギブス石等を原料とし、蒸留水で希釈した硫酸処理することで得られるが、記載例に限定されるものではない。As the aluminum sulfate, either one having crystal water or an anhydride can be used. Those having crystal water are preferable, and when this is used for a cement composition for spraying, it becomes easy to prevent rebound during spraying.
Aluminum sulfate containing an alkali metal-containing substance suitable for this use is derived from the raw material of its production, for example, bauxite, aluminum sludge or gibbstone containing alkali metal compounds as impurities, and diluted with distilled water. However, the present invention is not limited to the examples described.
本発明の急結用混和材における（Ｂ）硫酸アルミニウム（成分（Ｂ））の含有量は、所定量のアルカリ金属含有物質を含有する硫酸アルミニウムを、前記カルシウムアルミネート１００質量部に対し、１０〜４０質量部であり、１５〜３５質量部がより好ましく、１５〜３０質量部がさらに好ましい。（Ｂ）硫酸アルミニウムの含有量が１０質量部未満では十分な初期凝結性が得られず、４０質量部を超えると、相対的にカルシウムアルミネートの量が不足し、初期凝結性が低下することとなり、好ましくない。 The content of (B) aluminum sulfate (component (B)) in the quick-setting admixture of the present invention is 10 to 100 parts by mass of aluminum sulfate containing a predetermined amount of alkali metal-containing substance. It is -40 mass parts, 15-35 mass parts is more preferable, and 15-30 mass parts is further more preferable. (B) When the content of aluminum sulfate is less than 10 parts by mass, sufficient initial coagulation cannot be obtained, and when it exceeds 40 parts by mass, the amount of calcium aluminate is relatively insufficient and the initial coagulation is reduced. This is not preferable.
本発明の急結用混和材は、（Ｃ）アルカリ金属硫酸塩及びアルカリ土類金属硫酸塩から選ばれる１種以上を含有する。少なくともアルカリ金属硫酸塩又はアルカリ土類金属硫酸塩の何れか１種を含有すれば良いが、任意の２種以上を含有することもできる。好ましくは、アルカリ土類金属硫酸塩、又はアルカリ土類金属硫酸塩とアルカリ金属硫酸塩の含有とする。硫酸塩を形成するアルカリ金属としては、リチウム、ナトリウム、カリウムを挙げることができ、アルカリ土類金属としては、カルシウム、マグネシウム、ストロンチウム、バリウムを挙げることができる。
好適には、アルカリ金属硫酸塩として例えば硫酸リチウム、アルカリ土類金属硫酸塩として例えば無水石膏を用い、その何れか一方の使用又は両者の併用が挙げられる。併用する場合の両者の配合質量比は制限されない。成分（Ｃ）の含有により、中長期の強度発現性を向上でき、安定した硬化状態を長期間保つことができる。The rapid setting admixture of the present invention contains (C) one or more selected from alkali metal sulfates and alkaline earth metal sulfates. At least one of alkali metal sulfates and alkaline earth metal sulfates may be contained, but any two or more of them may be contained. Preferably, alkaline earth metal sulfate, or alkaline earth metal sulfate and alkali metal sulfate are contained. Examples of the alkali metal that forms the sulfate include lithium, sodium, and potassium, and examples of the alkaline earth metal include calcium, magnesium, strontium, and barium.
Preferably, for example, lithium sulfate is used as the alkali metal sulfate, and anhydrous gypsum is used as the alkaline earth metal sulfate, and either one of them or a combination of both is used. The combined mass ratio of the two when used in combination is not limited. By containing the component (C), the medium-to-long-term strength development can be improved, and a stable cured state can be maintained for a long period.
本発明急結用混和材中の成分（Ｃ）の含有量は、前記カルシウムアルミネートの含有量１００質量部に対し、合計含有量で７．５〜７５質量部であり、より好ましくは７．５〜５５質量部であり、さらに好ましくは３０〜５０質量部である。
また、成分（Ｃ）がアルカリ金属の硫酸塩（Ｃ１）とアルカリ土類金属の硫酸塩（Ｃ２）を同時に含む場合は、両者の含有割合は制限されるものではないが、より好ましくは、両者の含有割合は質量比（Ｃ１／Ｃ２）で１／４〜７／３にする。成分（Ｃ）の含有量が７．５質量部未満では中長期の強度発現性が不足し、また７５質量部を超えると相対的にカルシウムアルミネートや硫酸アルミニウムの量が不足し、初期凝結性が低下することとなるため、好ましくない。The content of the component (C) in the admixture for rapid setting of the present invention is 7.5 to 75 parts by mass in total with respect to 100 parts by mass of the calcium aluminate, and more preferably 7. It is 5-55 mass parts, More preferably, it is 30-50 mass parts.
In the case where the component (C) contains the alkali metal sulfate (C1) and the alkaline earth metal sulfate (C2) at the same time, the content ratio of both is not limited, but more preferably both The content ratio is made 1/4 to 7/3 in terms of mass ratio (C1 / C2). If the content of component (C) is less than 7.5 parts by mass, the medium to long-term strength development will be insufficient, and if it exceeds 75 parts by mass, the amount of calcium aluminate and aluminum sulfate will be relatively insufficient, and the initial setting property will be insufficient. Is unfavorable because it decreases.
本発明の急結用混和材は、本発明の効果を喪失させない限り、前記以外の成分を含有するものであっても良い。かかる成分として例えば、硫酸アルミニウム中に含有されずに存在するアルカリ金属の炭酸塩、アルカリ金属のアルミン酸塩、セメントに使用できる各種凝結調整剤等を挙げることができるが、これらに限定されるものではない。前記アルカリ金属の炭酸塩やアルミン酸塩を含有する場合の好ましい含有量は、カルシウムアルミネートの含有量１００質量部に対し、５〜１００質量部であり、この含有量にすることで接水直後の極初期の急結性やこれを吹付けコンクリート組成物に使用したときの極初期の付着性がより向上し易くなる。 The rapid setting admixture of the present invention may contain components other than those described above as long as the effects of the present invention are not lost. Examples of such components include, but are not limited to, alkali metal carbonates that are not contained in aluminum sulfate, alkali metal aluminates, and various setting modifiers that can be used for cement. is not. The preferable content in the case of containing the alkali metal carbonate or aluminate is 5 to 100 parts by mass with respect to 100 parts by mass of calcium aluminate. The initial quick setting property and the very early adhesion when this is used in a shotcrete composition are more likely to be improved.
本発明の急結用混和材を用いれば、初期凝結性、初期強度発現性及び施工性が良好なセメント組成物、例えば吹付けコンクリート組成物を調製することができる。吹付けコンクリート組成物等のセメント組成物を調製するには、本発明の急結用混和材を、初期凝結性、初期強度発現性及び施工性が良好なセメント系組成物を得易くする上で、セメント１００質量部に対し、好ましくは７〜２０質量部、より好ましくは９〜１５質量部、さらに好ましくは１１〜１５質量部、配合使用することが推奨される。また、特に、低温環境下での吹付け施工に適した吹付コンクリート組成物を調整するには、セメント１００質量部に対し、好ましくは９〜１５質量部、より好ましくは１１〜１５質量部、配合使用することが推奨される。また、本発明の急結用混和材を配合使用するセメント組成物には、使用目的に応じてモルタル・コンクリートに使用できる他の混和材や骨材を併用することができる。併用する混和材は特に制限されるものではないが、例えば、粉塵発生防止用に増粘剤、吹付用のモルタル・コンクリートの流動性を改善するための減水剤類、特に高性能減水剤などを挙げることができる。 If the rapid setting admixture of the present invention is used, a cement composition having good initial setting property, initial strength development property and workability, for example, shotcrete composition can be prepared. In order to prepare a cement composition such as shotcrete composition, the rapid setting admixture of the present invention is used to make it easy to obtain a cement-based composition having good initial setting, initial strength development and workability. It is recommended to use 7 to 20 parts by weight, more preferably 9 to 15 parts by weight, and still more preferably 11 to 15 parts by weight, based on 100 parts by weight of cement. In particular, in order to prepare a sprayed concrete composition suitable for spraying under a low temperature environment, it is preferably 9 to 15 parts by mass, more preferably 11 to 15 parts by mass, with respect to 100 parts by mass of cement. Recommended to use. In addition, the cement composition containing the rapid setting admixture of the present invention can be used in combination with other admixtures and aggregates that can be used for mortar and concrete depending on the purpose of use. The admixture used in combination is not particularly limited, but for example, a thickener for preventing dust generation, a water reducing agent for improving the fluidity of mortar and concrete for spraying, especially a high performance water reducing agent, etc. Can be mentioned.
ここで用いられるセメントとしては、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、超早強ポルトランドセメント等のポルトランドセメント、及びこれらのポルトランドセメントにフライアッシュや高炉スラグ等の成分を配合した各種混合セメントが挙げられる。このうち、普通ポルトランドセメント、早強ポルトランドセメントがより好ましい。 The cement used here includes ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, Portland cement such as ultra-early strength Portland cement, and various Portland cements containing components such as fly ash and blast furnace slag. A mixed cement is mentioned. Of these, ordinary Portland cement and early-strength Portland cement are more preferable.
また、骨材としては、細骨材、粗骨材のいずれも用いることができる。細骨材としては川砂、山砂、石灰砂、珪砂等が挙げられ、粗骨材としては川砂利、山砂利、石灰砂利等が挙げられる。 As the aggregate, either fine aggregate or coarse aggregate can be used. Examples of the fine aggregate include river sand, mountain sand, lime sand, and quartz sand, and examples of the coarse aggregate include river gravel, mountain gravel, and lime gravel.
吹付けコンクリート組成物を用いた吹付け工法としては、例えば粉末状又はスラリー状の急結用混和材とセメントコンクリートとを、別々に圧送して合流混合させて急結性コンクリートとして吹付ける方法が挙げられる。 As a spraying method using the shotcrete composition, for example, a powdery or slurry rapid setting admixture and cement concrete are separately fed, mixed and mixed to spray as quick setting concrete. Can be mentioned.
次に本発明の好ましい態様を挙げる。
＜１＞（Ａ）カルシウムアルミネート１００質量部と、（Ｂ）硫酸アルミニウム１０〜４０質量部と、（Ｃ）アルカリ金属硫酸塩及びアルカリ土類金属硫酸塩から選ばれる１種以上７．５〜７５質量部を含有する混和材であって、前記（Ｂ）硫酸アルミニウムがアルカリ金属含有物質をアルカリ金属酸化物換算で０．０３〜３．５質量％含有することを特徴とする急結用混和材。Next, preferred embodiments of the present invention are listed.
<1> (A) 100 parts by mass of calcium aluminate, (B) 10 to 40 parts by mass of aluminum sulfate, and (C) one or more selected from alkali metal sulfates and alkaline earth metal sulfates 7.5 to 7.5 An admixture containing 75 parts by mass, wherein the aluminum sulfate (B) contains an alkali metal-containing substance in an amount of 0.03 to 3.5% by mass in terms of an alkali metal oxide. Wood.
＜２＞成分（Ａ）が、化学成分としてＣａＯとＡｌ2Ｏ3からなる結晶質又はガラス化が進んだ構造の水和活性物質であり、好ましくは１２ＣａＯ・７Ａｌ2Ｏ3、ＣａＯ・Ａｌ2Ｏ3、３ＣａＯ・Ａｌ2Ｏ3、ＣａＯ・２Ａｌ2Ｏ3、４ＣａＯ・３Ａｌ2Ｏ3・ＳＯ3、１１ＣａＯ・７Ａｌ2Ｏ3・ＣａＦ2、及びＮａ2Ｏ・８ＣａＯ・３Ａｌ2Ｏ3から選ばれる１種又は２種以上である＜１＞記載の急結用混和材。
＜３＞成分（Ａ）が、好ましくはＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．８以上のカルシウムアルミネート、より好ましくは、ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．０以上のカルシウムアルミネート、さらに好ましくはＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．３以下のカルシウムアルミネートであり、さらに好ましくはＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．８〜２．３のカルシウムアルミネート、さらに好ましくはＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．０〜２．３のカルシウムアルミネートである＜１＞又は＜２＞記載の急結用混和材。
＜４＞成分（Ａ）が、好ましくはガラス化率８０％以上、より好ましくはガラス化率８０〜１００％である＜１＞〜＜３＞のいずれかに記載の急結用混和材。
＜５＞成分（Ａ）が、ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）１．８以上、好ましくは１．８〜２．３で、ガラス化率８０％以上、好ましくは８０〜１００％のカルシウムアルミネートである＜１＞〜＜４＞のいずれかに記載の急結用混和材。
＜６＞成分（Ａ）が、ブレーン比表面積４０００ｃｍ2／ｇ以上、好ましくは４０００〜７０００ｃｍ2／ｇのカルシウムアルミネートである＜１＞〜＜５＞のいずれかに記載の急結用混和材。<2> The component (A) is a hydrated active substance having a crystallized structure or advanced vitrification composed of CaO and Al 2 O 3 as chemical components, preferably 12CaO · 7Al 2 O 3 , CaO · Al 2 O 3, selected from 3CaO · Al 2 O 3, CaO · 2Al 2 O 3, 4CaO · 3Al 2 O 3 · SO 3, 11CaO · 7Al 2 O 3 · CaF 2, and Na 2 O · 8CaO · 3Al 2 O 3 The quick setting admixture according to <1>, wherein the admixture is one type or two or more types.
<3> Component (A) is preferably a calcium aluminate having a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 1.8 or more, more preferably CaO and Al 2 O 3 Calcium aluminate having a molar ratio (CaO / Al 2 O 3 ) of 2.0 or more, more preferably a calcium aluminum having a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 2.3 or less A calcium aluminate having a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 1.8 to 2.3, more preferably a molar ratio of CaO and Al 2 O 3 . The rapid setting admixture according to <1> or <2>, which is a calcium aluminate having a ratio (CaO / Al 2 O 3 ) of 2.0 to 2.3.
<4> The rapid setting admixture according to any one of <1> to <3>, wherein the component (A) is preferably a vitrification rate of 80% or more, more preferably a vitrification rate of 80 to 100%.
<5> Component (A) is a CaO and Al 2 O 3 content molar ratio (CaO / Al 2 O 3 ) of 1.8 or more, preferably 1.8 to 2.3, and a vitrification rate of 80% or more, The admixture for quick setting according to any one of <1> to <4>, which is preferably 80 to 100% calcium aluminate.
<6> The rapid setting admixture according to any one of <1> to <5>, wherein the component (A) is a calcium aluminate having a brain surface area of 4000 cm 2 / g or more, preferably 4000 to 7000 cm 2 / g. .
＜７＞成分（Ｂ）の含有量が、成分（Ａ）１００質量部に対して、１５〜３５質量部、好ましくは１５〜３０質量部である＜１＞〜＜６＞のいずれかに記載の急結用混和材。
＜８＞成分（Ｂ）が、アルカリ金属含有物質をアルカリ金属酸化物換算で０．１〜１．２質量％、好ましくは０．２〜１．０質量％含有する硫酸アルミニウムである＜１＞〜＜７＞のいずれかに記載の急結用混和材。
＜９＞（Ｂ）硫酸アルミニウム中に含まれるアルカリ金属含有物質が、少なくともＮａ、Ｋ、Ｌｉの何れか１種以上を構成成分とする物質であり、好ましくはアルカリ金属単体、アルカリ金属化合物、アルカリ金属含有固溶体及びアルカリ金属含有共晶体から選ばれる１種以上、より好ましくはアルカリ金属、アルカリ金属酸化物（Ｎａ2Ｏ、Ｋ2Ｏ、ＬｉＯ2など）、アルカリ金属水酸化物、アルカリ金属炭酸塩、及びアルカリ金属酸化物としての硫酸アルミニウム中への固溶体から選ばれる１種又は２種以上である＜１＞〜＜８＞のいずれかに記載の急結用混和材。
＜10＞成分（Ｃ）の含有量が、成分（Ａ）１００質量部に対して、７．５〜５５質量部、好ましくは３０〜５０質量部である＜１＞〜＜９＞のいずれかに記載の急結用混和材。
＜11＞＜１＞〜＜１０＞のいずれかに記載の急結用混和材を含有するセメント組成物。
＜12＞前記急結用混和材の含有量が、セメント１００質量部に対し７〜２０質量部、好ましくは９〜１５質量部、さらに好ましくは１１〜１５質量部である＜１１＞記載のセメント組成物。
＜13＞＜１＞〜＜１０＞のいずれかに記載の急結用混和材を含有する吹付けコンクリート組成物。
＜14＞前記急結用混和材の含有量が、セメント１００質量部に対し７〜２０質量部、好ましくは９〜１５質量部、さらに好ましくは１１〜１５質量部である＜１３＞記載の吹付けコンクリート組成物。<7> The content of the component (B) is 15 to 35 parts by mass, preferably 15 to 30 parts by mass with respect to 100 parts by mass of the component (A). Admixture for quick setting.
<8> Component (B) is aluminum sulfate containing an alkali metal-containing substance in terms of alkali metal oxide in an amount of 0.1 to 1.2% by mass, preferably 0.2 to 1.0% by mass. <1> The quick-setting admixture according to any one of to <7>.
<9> (B) The alkali metal-containing substance contained in aluminum sulfate is a substance containing at least one of Na, K, and Li as a constituent component, preferably an alkali metal simple substance, an alkali metal compound, an alkali One or more selected from metal-containing solid solutions and alkali metal-containing eutectics, more preferably alkali metals, alkali metal oxides (Na 2 O, K 2 O, LiO 2 etc.), alkali metal hydroxides, alkali metal carbonates And the rapid setting admixture according to any one of <1> to <8>, which is one or more selected from solid solutions in aluminum sulfate as an alkali metal oxide.
<10> Any of <1> to <9>, wherein the content of component (C) is 7.5 to 55 parts by mass, preferably 30 to 50 parts by mass, relative to 100 parts by mass of component (A). The quick-setting admixture described in 1.
<11> A cement composition containing the quick setting admixture according to any one of <1> to <10>.
<12> The cement according to <11>, wherein the content of the quick setting admixture is 7 to 20 parts by mass, preferably 9 to 15 parts by mass, and more preferably 11 to 15 parts by mass with respect to 100 parts by mass of the cement. Composition.
<13> A shotcrete composition containing the rapid setting admixture according to any one of <1> to <10>.
<14> The blowing according to <13>, wherein the content of the quick setting admixture is 7 to 20 parts by mass, preferably 9 to 15 parts by mass, and more preferably 11 to 15 parts by mass with respect to 100 parts by mass of cement. Attached concrete composition.
以下、本発明を実施例によって具体的に説明するが、本発明は記載した実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the described examples.
以下の略号で示す材料を用い、表１の配合割合となるようにヘンシェル型ミキサに投入し、約１０分間乾式混合し、急結用混和材を作製した。作製後の急結用混和材は使用に供すまで乾燥容器中で保管した。尚、硫酸アルミニウム中に含まれる各種アルカリ金属含有物質（酸化物換算）と他の成分（不純物を含む。）は、硫酸アルミニウムを無水物換算したときの化学分析による含有量が０．０１質量％未満のものについては実質無含有と見なし、０．０１質量％以上の含有成分のみ明示した。また、硫酸アルミニウム中のアルカリ金属酸化物の結晶相の存在は粉末エックス線回折でも確認した（ＡＳ７）。 Using the materials indicated by the following abbreviations, the mixture was put into a Henschel mixer so as to have the blending ratio shown in Table 1, and dry-mixed for about 10 minutes to prepare an admixture for quick setting. The quick setting admixture after preparation was stored in a dry container until it was used. In addition, various alkali metal-containing substances (oxide conversion) and other components (including impurities) contained in aluminum sulfate have a content by chemical analysis of 0.01 mass% when aluminum sulfate is converted to anhydride. Those less than that were regarded as substantially free, and only the content of 0.01% by mass or more was clearly indicated. The presence of an alkali metal oxide crystal phase in aluminum sulfate was also confirmed by powder X-ray diffraction (AS7) .
ＣＡ１；ＣａＯ及びＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．２の非晶質カルシウムアルミネート（ブレーン比表面積５１００ｃｍ2／ｇ）
ＣＡ２；ＣａＯ及びＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．８の非晶質カルシウムアルミネート（ブレーン比表面積５９００ｃｍ2／ｇ）
ＣＡ３；ＣａＯ及びＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．２でガラス化率８０％のカルシウムアルミネート（ブレーン比表面積５１００ｃｍ2／ｇ）
ＣＡ４；ＣａＯ及びＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．７の非晶質カルシウムアルミネート（ブレーン比表面積５９００ｃｍ2／ｇ）
ＡＳ１；Ｋ2Ｏを０．９８質量％含有する硫酸アルミニウム（１６水和物）※１
ＡＳ２；Ｋ2Ｏを３．０２質量％含有する硫酸アルミニウム（１６水和物）※１
ＡＳ３；Ｋ2Ｏを０．０５質量％含有する硫酸アルミニウム（１６水和物）※１
ＡＳ４；Ｎａ2Ｏを１．０２質量％含有する硫酸アルミニウム（１６水和物）※２
ＡＳ５；Ｎａ2Ｏを０．５０質量％含有する無水硫酸アルミニウム※２
ＡＳ６；硫酸アルミニウム水和物以外の成分含有総量が０．０１質量％未満の硫酸アルミニウム（１６水和物）
ＡＳ７；Ｋ2Ｏを６．４１質量％含有する無水硫酸アルミニウム※１
ＡＳ８；Ｋ2Ｏを０．０３質量％含有する無水硫酸アルミニウム※１
ＣＳ；無水石膏
ＮＳ；無水硫酸ナトリウム
ＫＯ；酸化カリウム粉末（最大粒径約５５μｍ、平均粒径約２０μｍ）
但し、
※１・・・Ｋ2Ｏ以外のアルカリ金属含有物質の総含有量は０．０１質量％未満
※２・・・Ｎａ2Ｏ以外のアルカリ金属含有物質の総含有量は０．０１質量％未満CA1; amorphous calcium aluminate with a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 2.2 (Brain specific surface area of 5100 cm 2 / g)
CA2; amorphous calcium aluminate having a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 1.8 (Brain specific surface area of 5900 cm 2 / g)
CA3; calcium aluminate with a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 2.2 and a vitrification rate of 80% (Brain specific surface area of 5100 cm 2 / g)
CA4; amorphous calcium aluminate having a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) of 1.7 (Brain specific surface area of 5900 cm 2 / g)
AS1; aluminum sulfate (16 hydrate) containing 0.98% by mass of K 2 O * 1
AS2; Aluminum sulfate containing 16% by mass of K 2 O (16 hydrate) * 1
AS3: Aluminum sulfate containing 16% by mass of K 2 O (16 hydrate) * 1
AS4; Aluminum sulfate containing 16% by mass of Na 2 O (16 hydrate) * 2
AS5: anhydrous aluminum sulfate containing 0.50% by mass of Na 2 O * 2
AS6: Aluminum sulfate (16 hydrate) whose total content other than aluminum sulfate hydrate is less than 0.01% by mass
AS7; anhydrous aluminum sulfate containing 6.41% by mass of K 2 O * 1
AS8; anhydrous aluminum sulfate containing 0.03% by mass of K 2 O * 1
CS; anhydrous gypsum NS; anhydrous sodium sulfate KO; potassium oxide powder (maximum particle size of about 55 μm, average particle size of about 20 μm)
However,
* 1 ... The total content of alkali metal-containing substances other than K 2 O is less than 0.01% by mass. * 2 ... The total content of alkali metal-containing substances other than Na 2 O is less than 0.01% by mass.
普通ポルトランドセメント４００ｇと水２００ｇを内容量５００ｃｃの底付円筒容器に入れ、ハンドミキサで約１分間混合した後、温度８℃（±０．５℃、以下特記無い限り温度に関する誤差範囲は同じ。）に保った屋内に約３０分間静置した。この静置後ハンドミキサで約１分間混練し、この混練物に、前記急結用混和材（ＱＭ１〜２２）４８ｇを添加し５秒間攪拌してセメント組成物ペースト（Ｐ１〜Ｐ２２）、前記急結用混和材（ＱＭ１）４４ｇを添加し５秒間攪拌することでセメント組成物ペースト（Ｐ２３）又は前記急結用混和材（ＱＭ１）６０ｇを添加し５秒間攪拌することでセメント組成物ペースト（Ｐ２４）を作製した。次いで、急結用混和材添加３０秒後の前記セメント組成物ペーストに対し、８℃でのプロクター貫入抵抗値を計測することで前記急結用混和材の瞬結特性を評価した。また、同様に得たセメント組成物ペーストに対し、前記急結用混和材添加６０秒後及び５分経過後の８℃でのプロクター貫入抵抗値も計測した。また、併せて前記急結用混和材を添加しないセメント組成物ペースト（Ｐ２５）も同様に作製し、混練終了から３０秒、６０秒及び５分経過後の８℃でのプロクター貫入抵抗値を測定した。プロクター貫入抵抗値の計測方法は、土木学会コンクリート標準示方書「吹付コンクリート用急結剤品質規格」付属書「貫入抵抗によるモルタルの瞬結時間測定方法」に準拠し、断面積０．１２５ｃｍ2のプロクター針を使用して行った。以上の計測結果を表２に表す。After putting 400 g of ordinary Portland cement and 200 g of water into a cylindrical container with a bottom of 500 cc and mixing for about 1 minute with a hand mixer, the temperature range is 8 ° C. (± 0.5 ° C., unless otherwise specified). ) Was kept indoors for about 30 minutes. After this standing, the mixture is kneaded with a hand mixer for about 1 minute. To this kneaded product, 48 g of the quick setting admixture (QM1-22) is added and stirred for 5 seconds to obtain the cement composition paste (P1 to P22), 44 g of the admixture for ligation (QM1) was added and stirred for 5 seconds to add cement composition paste (P23) or 60 g of the admixture for quick setting (QM1) and stirred for 5 s to obtain the cement composition paste (P24 ) Was produced. Next, the instantaneous setting characteristics of the rapid setting admixture were evaluated by measuring the Procter penetration resistance value at 8 ° C. for the cement composition paste 30 seconds after the rapid setting admixture was added. In addition, with respect to the cement composition paste obtained in the same manner, the Procter penetration resistance value at 8 ° C. was measured 60 seconds after the addition of the rapid setting admixture and 5 minutes later. In addition, a cement composition paste (P25) to which the admixture for rapid setting is not added is prepared in the same manner, and the proctor penetration resistance value at 8 ° C. is measured after 30 seconds, 60 seconds and 5 minutes from the end of kneading. did. Proctor penetration resistance value measurement method conforms to the Japan Society of Civil Engineers concrete standard specification "Quality standards for sprayed concrete quality" appendix "Method for measuring instantaneous setting time of mortar by penetration resistance", with a cross-sectional area of 0.125 cm 2 Performed using a proctor needle. The above measurement results are shown in Table 2.
また、温度条件の比較のため、普通ポルトランドセメント４００ｇと水２００ｇを内容量５００ｃｃの底付円筒容器に入れ、ハンドミキサで約１分間混合した後、温度２０℃に保った屋内に約３０分間静置した。この静置後ハンドミキサで約１分間混練し、この混練物に、前記急結用混和材（ＱＭ１、ＱＭ１６又はＱＭ１８）２８ｇを添加し５秒間攪拌してセメント組成物ペースト（Ｐ３０〜Ｐ３２）、前記急結用混和材（ＱＭ１、ＱＭ５、又はＱＭ７）４８ｇを添加し５秒間攪拌してセメント組成物ペースト（Ｐ３３〜Ｐ３５）又は前記急結用混和材（ＱＭ１）８０ｇを添加し５秒間攪拌してセメント組成物ペースト（Ｐ３６）を作製した。作製したセメント組成物ペーストは、温度のみ２０℃とした以外は前記と同じ方法で、急結性混和材添加から３０秒、６０秒及び５分経過時点で２０℃でのプロクター貫入抵抗値を計測した。この結果を表３に示す。 For comparison of temperature conditions, 400 g of ordinary Portland cement and 200 g of water are placed in a bottomed cylindrical container having an internal capacity of 500 cc, mixed for about 1 minute with a hand mixer, and then kept indoors at a temperature of 20 ° C. for about 30 minutes. I put it. After this standing, kneading with a hand mixer for about 1 minute, to this kneaded product, 28 g of the quick-setting admixture (QM1, QM16 or QM18) was added and stirred for 5 seconds to obtain a cement composition paste (P30 to P32). 48 g of the quick setting admixture (QM1, QM5, or QM7) was added and stirred for 5 seconds, and then 80 g of cement composition paste (P33 to P35) or the quick setting admixture (QM1) was added and stirred for 5 seconds. Thus, a cement composition paste (P36) was prepared. The produced cement composition paste was measured in the same manner as described above except that only the temperature was 20 ° C., and the Procter penetration resistance value at 20 ° C. was measured at 30 seconds, 60 seconds and 5 minutes after the rapid setting admixture was added. did. The results are shown in Table 3.
さらに、普通ポルトランドセメント４００ｇと水２００ｇを内容量５００ｃｃの底付円筒容器に入れ、ハンドミキサで約１分間混合した後、温度３０℃に保った屋内に約３０分間静置した。この静置後ハンドミキサで約１分間混練し、これに、急結用混和材にＱＭ１前記急結用混和材４８ｇを添加し、５秒間攪拌してセメント組成物ペースト（Ｐ４０）を作製した。このセメント組成物ペースト（Ｐ４０）の急結性混和材添加から３０秒、６０秒及び５分経過時点で３０℃でのプロクター貫入抵抗値を前記と同様の方法で計測した。計測結果は、急結性混和材添加から３０秒経過時で６．３Ｎ／ｍｍ２、６０秒経過時で１５．２Ｎ／ｍｍ２秒及び５分経過時で２９．３Ｎ／ｍｍ２であった。Further, 400 g of ordinary Portland cement and 200 g of water were placed in a bottomed cylindrical container having an internal volume of 500 cc, mixed for about 1 minute with a hand mixer, and then allowed to stand indoors at a temperature of 30 ° C. for about 30 minutes. After this standing, the mixture was kneaded with a hand mixer for about 1 minute. To this, 48 g of QM1 quick setting admixture was added and stirred for 5 seconds to prepare a cement composition paste (P40). After 30 seconds, 60 seconds and 5 minutes had elapsed from the addition of the rapid setting admixture of the cement composition paste (P40), the Procter penetration resistance value at 30 ° C. was measured by the same method as described above. Measurement results, in a time lapse of 30 seconds from the addition quick-setting property admixture with at elapsed 6.3N / mm 2, 60 seconds after the elapse 15.2N / mm 2 seconds and 5 minutes was 29.3N / mm 2 .
また、前記のセメント組成物ペースト（Ｐ１〜Ｐ２５）を、作製後直ちに吹付装置（市販のモルタルガン）に移し、８℃の温度環境下で、吹付装置から１５０ｃｍ離れた場所の地面に垂直に設置した２ｍ四方のコンクリート製平滑壁面に向かって吹付けた。吹付け終了から約３分経過後目視観察することで、付着性を評価した。即ち、壁面に吹付けたセメント組成物ペーストが垂れや剥落・剥離が見られずに付着し続けたものを付着性が「良好」と判定した。また、それ以外の状態になったものは全て付着性が「不良」と判定した。さらに、前記付着性が「良好」と判定されたセメント組成物ペーストを吹付けた平滑壁面については、放置期間中の平均気温が２０℃であった外気と通じた屋内に６０日間放置し、吹付けた壁面を再度目視観察した。壁面に吹付けたセメント組成物ペーストが剥落や剥離もなく硬化し、また表面に亀裂も見られなかったものを硬化安定性「良好」と判断し、それ以外の状況になったものを硬化安定性「不良」と判断した。この結果も表２に示す。 Moreover, immediately after preparation, the cement composition paste (P1 to P25) is transferred to a spraying device (commercially available mortar gun), and installed vertically on the ground at a location 150 cm away from the spraying device under a temperature environment of 8 ° C. It sprayed toward the 2 m square concrete smooth wall surface. Adhesiveness was evaluated by visual observation after about 3 minutes from the end of spraying. That is, when the cement composition paste sprayed on the wall surface continued to adhere without dripping, peeling, or peeling, the adhesion was determined as “good”. In addition, all of the other conditions were judged to have “adhesiveness”. Further, the smooth wall surface sprayed with the cement composition paste determined to have “adhesiveness” was left in an indoor room where the average temperature during the standing period was 20 ° C. for 60 days, and was blown. The attached wall was visually observed again. The cement composition paste sprayed on the wall hardened without peeling off or peeling, and the one with no cracks on the surface was judged as “good”, and the other ones were cured. It was judged that the sex was “bad”. The results are also shown in Table 2.
また、一部の前記セメント組成物ペースト（Ｐ３０〜Ｐ３６）は、作製後直ちに前記と同じ吹付装置に移し、２０℃の温度環境下で、前記と同様に設置された２ｍ四方のコンクリート製平滑壁面に向かって吹付けた。該壁面に吹付けられたセメント組成物ペーストの付着性及び硬化安定性を前記と同様の方法で評価した。この結果も表３に示す。 In addition, a part of the cement composition paste (P30 to P36) was transferred to the same spraying device as described above immediately after production, and was installed in the same manner as above in a 2 m square concrete smooth wall surface at a temperature environment of 20 ° C. I sprayed towards. The adhesion and curing stability of the cement composition paste sprayed on the wall surface were evaluated by the same method as described above. The results are also shown in Table 3.
さらに、前記Ｐ４０のセメント組成物ペーストについては、このセメント組成物ペーストを、作製後前記と同じ吹付装置に移し、３０℃の温度環境下で、前記と同様に設置された２ｍ四方のコンクリート製平滑壁面に向かって吹付けた。該壁面に吹付けられたセメント組成物ペーストの付着性及び硬化安定性を前記と同様の方法で評価したが、何れも「良好」であった。 Further, regarding the cement composition paste of P40, the cement composition paste was transferred to the same spraying device as described above after being produced, and the concrete smoothing made of 2 m square was installed in the same manner as described above in a temperature environment of 30 ° C. Sprayed toward the wall. The adhesion and curing stability of the cement composition paste sprayed onto the wall surface were evaluated by the same method as described above, but both were “good”.
また、普通ポルトランドセメント４５０ｇ、ＪＩＳ標準砂（最大粒径２ｍｍで粒径０．０８ｍｍ未満の含有率が２％未満である珪砂）１３５０ｇと水２２５ｇを内容量約４．７リットルのホバートミキサに一括投入し、１分間混合後、２０℃に温度調節した屋内に３０分間静置した。静置時間経過後、約１分間ホバートミキサで再混合し、これに前記急結用混和材（ＱＭ１〜ＱＭ２２）４０ｇを添加し、さらに１０秒間混合し、セメントモルタルを作製した。前記セメントモルタルは作製後、直ちに、内寸が４０×４０×１６０ｍｍの直方体状の成形用型枠に充填し、このまま２０℃に調整した屋内に放置した。充填物は所定材齢到達時点で脱型し、供試体とした。材齢１日、７日及び２８日の供試体の２０℃での一軸圧縮強度をアムスラー式圧縮強度試験機で測定し、常温での強度発現性を評価した。尚、比較のため急結用混和材を添加しなかった以外は前記と同様の方法で作製したセメントモルタル（Ｍ２５）についても前記と同様の方法で２０℃での一軸圧縮強度を測定した。これらの測定結果を表４に示す。 Also, 450 g of normal Portland cement, 1350 g of JIS standard sand (silica sand with a maximum particle size of 2 mm and a particle size of less than 0.08 mm and less than 2%) and 225 g of water are put together in a Hobart mixer with an internal capacity of about 4.7 liters. Then, after mixing for 1 minute, it was allowed to stand for 30 minutes in a room whose temperature was adjusted to 20 ° C. After the standing time, the mixture was remixed with a Hobart mixer for about 1 minute, 40 g of the quick-setting admixture (QM1 to QM22) was added thereto, and the mixture was further mixed for 10 seconds to prepare a cement mortar. Immediately after preparation, the cement mortar was filled into a rectangular parallelepiped molding mold having an inner size of 40 × 40 × 160 mm, and left as it was in a room adjusted to 20 ° C. as it was. The filler was demolded when a predetermined age was reached and used as a specimen. The uniaxial compressive strength at 20 ° C. of specimens having a material age of 1 day, 7 days and 28 days was measured with an Amsler type compressive strength tester, and the strength development property at normal temperature was evaluated. For comparison, the uniaxial compressive strength at 20 ° C. was also measured for cement mortar (M25) produced by the same method as described above except that the quick setting admixture was not added. These measurement results are shown in Table 4.
また、前記と同様の配合及び手順で作製したセメントモルタルについて、作製後直ちに内寸が４０×４０×１６０ｍｍの直方体状の成形用型枠に充填し、このまま温度８℃に調整された屋内に放置した。充填物は所定材齢期間到達時点で脱型し、供試体とした。材齢１日、７日及び２８日の供試体の８℃での一軸圧縮強度をアムスラー式圧縮強度試験機で測定し、低温での強度発現性を評価した。尚、比較のため急結用混和材を添加しなかった以外は前記と同様の方法で作製したセメントモルタルについても前記と同様の方法で８℃での一軸圧縮強度を測定した。これらの測定結果も表４に示す。 In addition, the cement mortar produced by the same composition and procedure as described above was filled in a rectangular parallelepiped molding mold with an inner dimension of 40 × 40 × 160 mm immediately after production, and left as it was indoors at a temperature adjusted to 8 ° C. did. The filler was demolded when the predetermined age period was reached and used as a specimen. The uniaxial compressive strength at 8 ° C. of specimens having a material age of 1 day, 7 days and 28 days was measured with an Amsler type compressive strength tester to evaluate the strength development at low temperature. For comparison, the uniaxial compressive strength at 8 ° C. was also measured for the cement mortar produced by the same method as described above except that the quick setting admixture was not added. These measurement results are also shown in Table 4.
表２から、従来の急結材（ＱＭ１６）は低温になるとプロクター貫入抵抗値は著しく低下し瞬結性が付与し難くなるが、本発明の急結性混和材は低温（８℃）でも従来品に比べてプロクター貫入抵抗値がかなり大きく、低温での瞬結性の低下が著しく改善されていることがわかる。このことは低温下での付着性についても該当し、表２及び表３から、本発明の急結性混和材を使用したセメント組成物ペーストは何れも常温（２０℃）での付着性に劣ることなく良好な付着性を具備することがわかる。また、表４から、本発明の急結性混和材を添加したセメントモルタルは、低温での圧縮強度、特に材齢初期の圧縮強度の低下が、本発明外の急結性混和材を添加したセメントモルタルと比べ、著しく少なくなっていることがわかる。
From Table 2, the conventional quick setting material (QM16) has a significantly reduced Procter penetration resistance value and it is difficult to impart quick setting properties at low temperatures. However, the quick setting admixture of the present invention is conventional even at low temperatures (8 ° C). It can be seen that the resistance to penetration of the proctor is considerably larger than that of the product, and the reduction in instantaneous setting at low temperatures is remarkably improved. This also applies to adhesion at low temperatures. From Tables 2 and 3, the cement composition paste using the quick setting admixture of the present invention is inferior in adhesion at room temperature (20 ° C.). It turns out that it has favorable adhesiveness without. Also, from Table 4, the cement mortar to which the quick-setting admixture of the present invention was added had a decrease in compressive strength at low temperatures, particularly the compressive strength at the early age of the age, but the quick-setting admixture outside the present invention was added. It can be seen that it is significantly less than cement mortar.
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| WO2022059372A1 (en) * | 2020-09-17 | 2022-03-24 | デンカ株式会社 | Low-dust sprayed concrete and low-dust spraying method using same |
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| JP7077146B2 (en) * | 2018-05-31 | 2022-05-30 | 太平洋マテリアル株式会社 | Quickly miscible material |
| JP7403918B2 (en) | 2019-11-29 | 2023-12-25 | 太平洋マテリアル株式会社 | Rapid setting admixtures and shotcrete |
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| JP4657428B2 (en) * | 2000-08-10 | 2011-03-23 | 電気化学工業株式会社 | Quick setting agent, spraying material and spraying method using the same |
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| WO2022059372A1 (en) * | 2020-09-17 | 2022-03-24 | デンカ株式会社 | Low-dust sprayed concrete and low-dust spraying method using same |
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