JP2015124140A - Fast curing accelerator - Google Patents
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本発明は、速硬性や急硬性を付与するためにセメントや水硬性組成物に配合使用されるカルシウムアルミネート系の速硬化促進材に関する。 The present invention relates to a calcium aluminate-based rapid curing accelerator used in a cement or a hydraulic composition in order to impart rapid curing or rapid curing.
非常に速い硬化特性を具備するカルシウムアルミネートは、水和後の強度の大幅低下の回避のため、例えばポルトランドセメントや混合セメント等の水硬性物質や該水硬性物質を結合相形成成分として含む水硬性組成物に配合使用されることが多い。一方で、カルシウムアルミネートのセメントや水硬性組成物等への配合は、セメントに対して急速な凝結作用を及ぼすため、施工作業等を行う上で必要な可使時間を如何に確保するかが問題になる。この問題の対策として、従来よりオキシカルボン酸又はその塩を有効成分とする凝結遅延剤の併用が行われてきた。このような凝結遅延剤の使用は、例えば２０℃付近の常温や５〜１０℃付近の低温では、他の性状に支障をきたすことなく、所望の可使時間の確保が比較的行い易い。カルシウムアルミネートによるセメントや水硬性組成物の接水後の急速な凝結を、オキシカルボン酸又はその塩によって遅延化するには、カルシウムアルミネートの水和反応時にオキシカルボン酸又はその塩が溶解している必要があるが、例えば３０℃前後の高温では温度上昇に連れ溶解度の伸びが鈍化し、高温で高活性となったカルシウムアルミネートの急速な凝結時間を減退するのが困難になる。そのため高温環境下で所望の可使時間を確保しようとすると、大量の凝結遅延剤を予め配合する必要があったが、大量配合は強度発現性の低下など硬化性状に支障を及ぼす虞があった。この対策として、適量のオキシカルボン酸又はその塩と共に炭酸ナトリウムを併用すると、３０℃前後の高温でも可使時間が確保し易くなることが知られている。（例えば、特許文献１参照。） Calcium aluminate, which has very fast curing properties, is a water-containing material that contains a hydraulic substance such as Portland cement or mixed cement, or such a hydraulic substance as a binder phase forming component in order to avoid a significant decrease in strength after hydration. It is often used in a hard composition. On the other hand, the combination of calcium aluminate with cement or hydraulic composition has a rapid setting action on cement, so how to ensure the pot life required for construction work etc. It becomes a problem. As a countermeasure against this problem, a coagulation retarder containing oxycarboxylic acid or a salt thereof as an active ingredient has been used conventionally. The use of such a setting retarder is relatively easy to ensure a desired pot life, for example, at a room temperature around 20 ° C. or at a low temperature around 5-10 ° C. without affecting other properties. To delay the rapid setting of cement and hydraulic compositions after contact with calcium aluminate with oxycarboxylic acid or its salt, the oxycarboxylic acid or its salt dissolves during the hydration reaction of calcium aluminate. However, at a high temperature of about 30 ° C., for example, the solubility increase slows with increasing temperature, and it becomes difficult to reduce the rapid setting time of calcium aluminate that has become highly active at high temperature. Therefore, in order to secure the desired pot life in a high-temperature environment, it was necessary to blend a large amount of setting retarder in advance, but there was a possibility that the large amount of blending may affect the curing properties such as a decrease in strength development. . As a countermeasure, it is known that when sodium carbonate is used in combination with an appropriate amount of oxycarboxylic acid or a salt thereof, the pot life can be easily secured even at a high temperature of about 30 ° C. (For example, refer to Patent Document 1.)
炭酸ナトリウムは高温になるほど大幅に溶解度が高くなる傾向があり、カルシウムアルミネートの水和反応時に十分な量が溶解し、溶解した炭酸ナトリウムは接水直後から水和反応最初期においては強い凝結遅延作用を奏す。それ故、過大量のオキシカルボン酸又はその塩を配合せずとも凝結終結までの時間を遅延でき、可使時間を確保し易くなる。しかし、より高温下で比較的長い可使時間を確保しようとすると、限られた量の炭酸ナトリウムの併用では限界があり、やはりオキシカルボン酸又はその塩の配合量そのものを増やす必要があった。炭酸ナトリウムの併用量を増やせば、オキシカルボン酸又はその塩の過度の添加を避けられ、高温でも凝結終結までの時間を遅延できる可能性が高まるが、炭酸ナトリウムの増量は中〜長期強度の発現性を低下させる。 Sodium carbonate tends to be much more soluble at higher temperatures. A sufficient amount of calcium carbonate dissolves during the hydration reaction of calcium aluminate. Has an effect. Therefore, it is possible to delay the time until the end of the setting without blending an excessive amount of oxycarboxylic acid or a salt thereof, and it is easy to secure the pot life. However, in order to ensure a relatively long pot life at higher temperatures, there is a limit to the combined use of a limited amount of sodium carbonate, and it is necessary to increase the blending amount of oxycarboxylic acid or its salt. Increasing the combined amount of sodium carbonate avoids excessive addition of oxycarboxylic acid or its salt, and increases the possibility of delaying the time to completion of condensation even at high temperatures, but increasing the amount of sodium carbonate exhibits medium to long-term strength. Reduce sex.
本発明は、速硬・急硬化成分としてカルシウムアルミネートを配合使用するセメントや水硬性組成物の可使時間を、温度に拘わらず、例えば３０℃を超える高温でも、所望の時間確保するのに適し、しかも強度発現性等の硬化性状に支障を及ぼすことのないカルシウムアルミネート系の速硬化促進材の提供を課題とする。 The present invention secures a usable time of a cement or a hydraulic composition containing calcium aluminate as a fast-curing / quick-curing component, regardless of the temperature, for example, even at a high temperature exceeding 30 ° C. It is an object of the present invention to provide a calcium aluminate-based rapid curing accelerator that is suitable and does not affect the curing properties such as strength development.
本発明者は、前記課題解決のため検討を行った過程で、オキシカルボン酸又はその塩と併用する炭酸ナトリウムを、より活性な炭酸ナトリウムとすることで炭酸ナトリウムの併用量を増加させずに、過剰量でなく適量のオキシカルボン酸又はその塩を配合使用したときに、高温での可使時間の確保・延長が行い易くなるという知見から、実用性のある高活性な炭酸ナトリウムについてさらに探求を進めた結果、微粉化した炭酸カルシウムは極めて高い活性が得られ、大量使用しなくても所望の作用が得られることを確認した。しかし、潮解性が強まって性状劣化に繋がることから、耐風化抵抗があり、接水すると高活性化するライト灰に着目し、これを炭酸ナトリウム源として適量のオキシカルボン酸又はその塩と共にカルシウムアルミネートに配合使用したところ、前記課題を総じて解決でき、本発明を完成させるに至った。 The present inventor, in the process of studying to solve the problem, without increasing the combined amount of sodium carbonate by making sodium carbonate used in combination with oxycarboxylic acid or a salt thereof more active sodium carbonate, Further exploration of practical and highly active sodium carbonate from the knowledge that it becomes easy to secure and extend the pot life at high temperatures when an appropriate amount of oxycarboxylic acid or its salt is added and used in an excess amount. As a result, it was confirmed that finely divided calcium carbonate has a very high activity and that a desired action can be obtained without using a large amount. However, since deliquescence increases and leads to deterioration of properties, we focus on light ash that has weathering resistance and is highly activated when in contact with water. Using this as a sodium carbonate source, calcium aluminum together with an appropriate amount of oxycarboxylic acid or its salt When blended and used in an ate, the above problems could be solved as a whole, and the present invention was completed.
即ち、本発明は、次の（１）〜（２）で表す速硬化促進材である。（１）カルシウムアルミネート１００質量部、炭酸リチウム０．２〜１０質量部、オキシカルボン酸又はその塩０．２〜５質量部及びライト灰０．１〜１０質量部を含有する速硬化促進材。（２）セメント１００質量部に対し、３０〜１００質量部配合することを特徴とする前記（１）の速硬化促進材。 That is, the present invention is a rapid curing accelerator represented by the following (1) to (2). (1) Fast curing accelerator containing 100 parts by weight of calcium aluminate, 0.2 to 10 parts by weight of lithium carbonate, 0.2 to 5 parts by weight of oxycarboxylic acid or a salt thereof, and 0.1 to 10 parts by weight of light ash . (2) The rapid curing accelerator according to (1), wherein 30 to 100 parts by mass is blended with 100 parts by mass of cement.
本発明によれば、強度発現性等の硬化性状に支障を及ぼすことなく、例えば３０℃以上の高温でも可使時間の確保が容易な速硬性のセメント又は水硬性組成物が得られる。 According to the present invention, a fast-setting cement or hydraulic composition in which it is easy to ensure the pot life even at a high temperature of, for example, 30 ° C. or more without affecting the curable properties such as strength development.
本発明の速硬化促進材に含まれ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、また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るものでない限り何れのものでも許容される。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等を挙げられる。また、化学成分としてのＣａＯとＡｌ2Ｏ3の含有モル比（化学組成比）は制限されないが、高温で可使時間を確保し易くなることから含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．０〜１．６のものが好ましい。また、カルシウムアルミネートの粉末度は制限されない。所定の速硬性を発現でき、高温で過度の反応活性の発現を避ける上で、好ましくはブレーン比表面積が３０００〜８０００ｃｍ2／ｇものが好ましい。 Calcium aluminate contained in the rapid curing accelerator of the present invention may be any hydration active substance having a crystallized structure or advanced vitrification composed of CaO and Al 2 O 3 as chemical components. Any compound, solid solution, vitreous substance, or mixture thereof in which other chemical components are added in addition to CaO and Al 2 O 3 are acceptable as long as the effects of the present invention are 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 2 O 3 · SO 3 , 11CaO · 7Al 2 O 3 · CaF 2, like the Na 2 O · 8CaO · 3Al 2 O 3 or the like. Moreover, although the content molar ratio (chemical composition ratio) of CaO and Al 2 O 3 as a chemical component is not limited, the content molar ratio (CaO / Al 2 O 3 ) is easy to ensure the pot life at high temperatures. The thing of 1.0-1.6 is preferable. Moreover, the fineness of calcium aluminate is not limited. A brane specific surface area of preferably 3000 to 8000 cm 2 / g is preferable in order to exhibit a predetermined rapid hardening property and to avoid an excessive reaction activity at a high temperature.
また、本発明の硬化促進材は炭酸リチウムを含む。炭酸リチウムは、カルシウムアルミネートと併用することにより強度発現性を向上させる作用を具備する。炭酸リチウムは何れのものでも使用できる。本発明の速硬化促進材中の炭酸リチウムの含有量は、カルシウムアルミネートの含有量１００質量部に対し、０．２〜１０質量部とする。炭酸リチウムの含有量が０．２質量部未満では強度発現性が低迷し実用に値しないことがあるので好ましくなく、炭酸リチウムの含有量が１０質量部を超えると長期強度発現性の低下をまねくことがあるので好ましくない。 The curing accelerator of the present invention contains lithium carbonate. Lithium carbonate has the effect of improving strength development by being used in combination with calcium aluminate. Any lithium carbonate can be used. The content of lithium carbonate in the rapid curing accelerator of the present invention is 0.2 to 10 parts by mass with respect to 100 parts by mass of calcium aluminate. If the lithium carbonate content is less than 0.2 parts by mass, the strength development will be sluggish and may not be practical, and if the lithium carbonate content exceeds 10 parts by mass, the long-term strength development will decrease. This is not preferable.
また、本発明の速硬化促進材はオキシカルボン酸又はその塩を含む。オキシカルボン酸又はその塩は可使時間の確保に有用であり、何れか１種の含有で含有効果が奏されるが、２種以上の併用を阻むものではない。含有可能なオキシカルボン酸は、特に限定されない。具体的には、例えば、クエン酸、酒石酸、グルコン酸、ヘプトン酸等を挙げることができるが、記載例に限定されない。また、速硬化促進材に含むことができるオキシカルボン酸塩も、特に限定されない。具体的には、例えば、クエン酸ナトリウム、クエン酸カリウム、ロッシェル塩、グルコン酸ナトリウム、ヘプトン酸ナトリウム等を挙げることができるが、記載例に限定されない。オキシカルボン酸又はその塩の含有量は、カルシウムアルミネートの含有量１００質量部に対し、０．２〜５質量部とする。オキシカルボン酸又はその塩の含有量が０．２質量部未満では可使時間が確保できないことがあるので好ましくなく、オキシカルボン酸又はその塩の含有量が５質量部を超えると短時間強度発現性が低下するので好ましくない。 The rapid curing accelerator of the present invention contains oxycarboxylic acid or a salt thereof. Oxycarboxylic acid or a salt thereof is useful for securing the pot life, and the inclusion effect can be obtained by containing any one of them, but it does not prevent the combined use of two or more. The oxycarboxylic acid that can be contained is not particularly limited. Specific examples include citric acid, tartaric acid, gluconic acid, heptonic acid and the like, but are not limited to the description examples. Moreover, the oxycarboxylate which can be included in the rapid curing accelerator is not particularly limited. Specifically, for example, sodium citrate, potassium citrate, Rochelle salt, sodium gluconate, sodium heptonate and the like can be mentioned, but are not limited to the description examples. Content of oxycarboxylic acid or its salt shall be 0.2-5 mass parts with respect to 100 mass parts of calcium aluminate content. If the content of oxycarboxylic acid or a salt thereof is less than 0.2 parts by mass, the pot life may not be secured, which is not preferable. If the content of oxycarboxylic acid or a salt thereof exceeds 5 parts by mass, the strength will be expressed in a short time. This is not preferable because the properties are lowered.
また、本発明の硬化促進材はライト灰を含む。ライト灰は特に限定されず、例えば市販の工業用化学薬品や試薬などを使用することができる。ライト灰を含有することによって、ライト灰及び前記オキシカルボン酸又はその塩を、何れも強度発現性などの硬化性状に支障を及ぼすほど大量に配合しなくとも、温度に拘わらず可使時間を比較的長く確保することが可能になる。本発明の速硬化促進材はライト灰以外の炭酸ナトリウム源の混在使用を拒むものではないが、好ましくは炭酸ナトリウム源としてライト灰以外の、例えばデンス灰も含むことができるが、その場合、含有するライト灰との合計量の２０質量％以下の含有量にするのが好ましい。２０質量％を超える割合で含有すると、高温での長時間の可使時間の確保が行い難くなることがある。より好ましくは、不可避不純物として微量混入する場合を除き、ライト灰以外の炭酸ナトリウムの混在は極力無いものとする。また、本発明の速硬化促進材中のライト灰の含有量は、カルシウムアルミネートの含有量１００質量部に対し、０．１〜１０質量部とする。０．１質量部未満では配合効果が実質得られないので好ましくない。また、１０質量部を超えると中〜長期の強度発現性が低下することがあるので好ましくない。 Moreover, the hardening accelerator of the present invention contains light ash. Light ash is not particularly limited, and for example, commercially available industrial chemicals and reagents can be used. By containing light ash, even if the light ash and the oxycarboxylic acid or salt thereof are not added in such a large amount as to impair the curing properties such as strength development, the pot life is compared regardless of the temperature. It is possible to secure for a long time. The rapid curing accelerator of the present invention does not refuse the mixed use of a sodium carbonate source other than light ash, but preferably can also contain, for example, dense ash other than light ash as the sodium carbonate source, It is preferable to set the content to 20% by mass or less of the total amount with the light ash. If the content exceeds 20% by mass, it may be difficult to ensure a long pot life at high temperatures. More preferably, the mixture of sodium carbonate other than light ash is minimized as long as it is mixed in a small amount as an inevitable impurity. Moreover, content of the light ash in the rapid hardening accelerator of this invention shall be 0.1-10 mass parts with respect to 100 mass parts of calcium aluminate content. If the amount is less than 0.1 parts by mass, the blending effect cannot be obtained. On the other hand, if it exceeds 10 parts by mass, the medium-to-long-term strength development may decrease, which is not preferable.
また、本発明の速硬化促進材は、前記カルシウムアルミネート、オキシカルボン酸又はその塩、炭酸リチウムおよびライト灰以外の成分も、本発明の効果を喪失させない限り含有することができる。このような成分として、例えば、何れもモルタルやコンクリートに使用する、ポゾラン反応性物質、スラグ微粉、凝結調整剤（オキシカルボン酸又はその塩、炭酸リチウム及び炭酸ナトリウム類を除く）等を挙げることができる。好ましくは、石膏類を含有するのが良い。石膏類は中〜長期強度発現性を向上させる作用がある。使用する石膏類は、例えば、無水石膏、半水石膏、二水石膏、硫酸カルシウムを挙げることができ、その何れでも良く、また二種以上の併用でも良い。より好ましくは、無水石膏を含有する。含有する石膏類の粉末度は特に制限されるものではないが、所望の作用を十分発現するに適した活性が得る上で、ブレーン比表面積で３０００〜１００００ｃｍ2／ｇであることが推奨される。石膏類を含有する場合、速硬化促進材中の含有量は、前記作用が良好に発現される可能性が高いことから、カルシウムアルミネートの含有量１００質量部に対し、２０〜２５０質量部とする。 Moreover, the rapid hardening accelerator of this invention can contain components other than the said calcium aluminate, oxycarboxylic acid or its salt, lithium carbonate, and light ash, as long as the effect of this invention is not lost. Examples of such components include, for example, pozzolanic reactive substances, slag fine powders, and setting modifiers (excluding oxycarboxylic acids or salts thereof, lithium carbonate and sodium carbonates) used in mortar and concrete. it can. Preferably, gypsum is contained. Gypsum has the effect of improving medium to long-term strength development. Examples of the gypsum used include anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum, and calcium sulfate, any of which may be used, or two or more types may be used in combination. More preferably, it contains anhydrous gypsum. The fineness of gypsum to be contained is not particularly limited, but it is recommended that the specific surface area of Blaine is 3000 to 10,000 cm 2 / g in order to obtain an activity suitable for fully expressing the desired effect. . When gypsum is contained, the content in the fast-curing accelerator is highly likely to be exhibited well, so that the content of calcium aluminate is 20 to 250 parts by mass with respect to 100 parts by mass of calcium aluminate. To do.
また、本発明の速硬化促進材は、セメント１００質量部に対し、好ましくは３０〜１００質量部配合される。ここで、配合対象のセメントは、何れのセメントでも良い。具体的には、例えば、普通、早強、超早強、中庸熱、低熱等の各種ポルトランドセメント、高炉セメント、フライアッシュセメント又はシリカセメント等の混合セメント、白色セメントやエコセメント等の特殊セメントを挙げることができる。また、これらのうち２種以上を併用しても良い。尚、アルミナセメントはカルシウムアルミネートを有効成分とするため、配合対象のセメントとする際は、他のポルトランドセメントと併用されるのが望ましく、より望ましくは、本発明ではカルシウムアルミネートとして扱うのが適当である。速硬化促進材のセメント１００質量部に対する配合量が３０質量部未満ではセメント又は該セメントを含む水硬性組成物を十分速硬化できないことがあり、また１００質量部を超える配合量では、長期強度発現性が低迷することがある。 Further, the rapid curing accelerator of the present invention is preferably blended in an amount of 30 to 100 parts by mass with respect to 100 parts by mass of cement. Here, the cement to be blended may be any cement. Specifically, for example, various portland cements such as normal, early strength, super early strength, moderate heat, low heat, mixed cement such as blast furnace cement, fly ash cement or silica cement, special cement such as white cement and eco-cement. Can be mentioned. Two or more of these may be used in combination. In addition, since alumina cement contains calcium aluminate as an active ingredient, when it is used as a cement to be blended, it is preferably used in combination with other Portland cement, and more preferably, it is treated as calcium aluminate in the present invention. Is appropriate. If the blending amount of the fast curing accelerator with respect to 100 parts by mass of cement is less than 30 parts by mass, the cement or the hydraulic composition containing the cement may not be sufficiently cured, and if it exceeds 100 parts by mass, long-term strength is exhibited. Sexuality may be sluggish.
また、本発明の速硬化促進材は、セメント又は水硬性組成物に好適に配合使用される。本発明の速硬化促進材の使用に際しては、他の材料との併用は特に制限されない。併用材料としては、何れもモルタルやコンクリートに配合できる混和剤・材や骨材などが挙げられる。具体的には、例えば、減水剤類、膨張材、乾燥収縮低減剤、保水剤、増粘剤、セメント用ポリマー、繊維、空気連行剤、白華防止剤、消泡剤、アルミ粉等を挙げることができるが、記載例に限定されるものではない。また、速硬化促進材を配合したセメントや水硬性組成物の用途も特に制限されない。 Further, the rapid curing accelerator of the present invention is suitably used in cement or hydraulic composition. When using the rapid curing accelerator of the present invention, combined use with other materials is not particularly limited. Examples of the combined materials include admixtures / materials and aggregates that can be blended with mortar and concrete. Specifically, for example, water reducing agents, expansion agents, drying shrinkage reducing agents, water retention agents, thickeners, cement polymers, fibers, air entraining agents, anti-whitening agents, antifoaming agents, aluminum powder, etc. However, the present invention is not limited to the description examples. Moreover, the use of cement or a hydraulic composition containing a fast curing accelerator is not particularly limited.
以下、本発明を実施例によって具体的に詳しく説明する。本発明は記載された実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples. The invention is not limited to the embodiments described.
［カルシウムアルミネートの作製］
使用原料は石灰石（ＣａＯ含有率５６質量％、Ａｌ2Ｏ3及びＳｉＯ2含有率は何れも０．５質量％未満か無含有）とバン土頁岩（Ａｌ2Ｏ3含有率８７質量％、Ｆｅ2Ｏ3含有率２質量％、ＳｉＯ2含有率５質量％、ＣａＯ含有率は０．１質量％未満）を用い、表１に表す配合量となるよう調合した。調合した混合物は、電気炉で最高温度１５５０（±５０℃）で２時間焼成した。また、焼成物の冷却は、加熱時間終了時点で最高温度から炉外に取出し、これを常温大気中に放置して自然放冷させた。放冷した冷却物は、粉砕機を用い、粉砕時間を調整することでブレーン比表面積約５０００ｃｍ2／ｇに整粒し、粉末状のカルシウムアルミネートを得た。尚、カルシウムアルミネートのガラス化率は、先ず、冷却物中の結晶質の全鉱物の含有量を粉末エックス線回折による内部標準法により測定し、次いで冷却物中の残部をガラス相と見なし、その含有質量割合を算出することで求めた。作製したカルシウムアルミネートのＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）を原料の配合量から算出し、前記ガラス化率と共に表１に表す。
[Preparation of calcium aluminate]
Using raw materials limestone (CaO content 56 mass%, Al 2 O 3 and both less than one-free 0.5% by weight SiO 2 content) and alum shale (Al 2 O 3 content of 87 wt%, Fe 2 O 3 content 2% by mass, SiO 2 content 5% by mass, and CaO content less than 0.1% by mass) were prepared so as to have the compounding amounts shown in Table 1. The prepared mixture was baked in an electric furnace at a maximum temperature of 1550 (± 50 ° C.) for 2 hours. In addition, the fired product was cooled by taking it out of the furnace from the maximum temperature at the end of the heating time, and allowing it to stand in a normal temperature atmosphere to cool naturally. The cooled product was allowed to cool, and the particle size was adjusted to a Blaine specific surface area of about 5000 cm 2 / g by adjusting the pulverization time using a pulverizer to obtain a powdery calcium aluminate. The vitrification rate of calcium aluminate is determined by first measuring the content of all crystalline minerals in the cooled product by an internal standard method by powder X-ray diffraction, and then considering the remainder in the cooled product as the glass phase. It calculated | required by calculating a content-mass ratio. The CaO and Al 2 O 3 content molar ratio (CaO / Al 2 O 3 ) of the prepared calcium aluminate is calculated from the blending amount of the raw materials and is shown in Table 1 together with the vitrification rate.
［速硬化促進材の作製］
表１で表すカルシウムアルミネートと次に表すＢ１〜Ｂ３、Ｃ、Ｄ１〜Ｄ２及びＥから選定される材料を使用し、表２に表す配合量になるようヘンシェル型混合機で約３分間乾式混合し、速硬化促進材を作製した。
Ｂ１；ライト灰（トクヤマ社製）
Ｂ２；デンス灰（トクヤマ社製）
Ｂ３；炭酸ナトリウム（市販試薬、最大粒径約１５０μｍ）
Ｃ；ＩＩ型無水石膏（ブレーン比表面積；５０００ｃｍ2／ｇ）
Ｄ１；クエン酸（市販試薬）
Ｄ２；クエン酸ナトリウム（市販試薬）
Ｅ；炭酸リチウム（市販試薬）
[Production of fast curing accelerator]
Using calcium aluminate shown in Table 1 and materials selected from B1 to B3, C, D1 to D2 and E shown below, dry mixing with a Henschel type mixer for about 3 minutes so as to have the compounding amount shown in Table 2 Thus, a fast curing accelerator was produced.
B1: Light ash (manufactured by Tokuyama)
B2: Dense ash (manufactured by Tokuyama)
B3: Sodium carbonate (commercially available reagent, maximum particle size of about 150 μm)
C: Type II anhydrous gypsum (Blaine specific surface area: 5000 cm 2 / g)
D1; citric acid (commercially available reagent)
D2; sodium citrate (commercially available reagent)
E: Lithium carbonate (commercially available reagent)
［速硬化促進材の評価］
前記作製した速硬化促進材、普通ポルトランドセメント（市販品）と水を表３に表す配合量となるよう混合用容器に投入し、ハンドミキサで２分間混練してセメントペーストを作製した。
[Evaluation of fast curing accelerator]
The prepared fast-curing accelerator, ordinary Portland cement (commercially available product) and water were put into a mixing container so as to have a blending amount shown in Table 3, and kneaded for 2 minutes with a hand mixer to prepare a cement paste.
次いで、作製したセメントペーストに対し、日本薬液注入会（薬液注入協会）で規定された「カップ倒立法」に準じて、３０℃と３５℃の温度にせしめたセメントペーストのゲルタイムを測定し、可使時間の評価とした。また、作製したセメントペーストに対し、速硬性の評価として、ＪＩＳ Ａ １２１６「土の一軸圧縮試験方法」に準じた方法で３０℃と３５℃での材齢３時間の一軸圧縮強度を測定した。また、前記作製したセメントペーストを用い、型枠充填によって直径５０ｍｍ、高さ１００ｍｍの硬化性円柱状成形物を得た。ここで、型枠充填から脱型までの時間は１２時間とし、脱型までの間は約２０℃の大気中で静置させた。該硬化成形物を３０℃と３５℃に保ったそれぞれ湿度８０％の恒温恒湿器中に２８日間放置し、放置期間終了時に成形物を恒温恒湿器から取り出し、直ちに一軸圧縮強度を測定し、高温での長期強度発現性の評価とした。強度測定に際しては、ＪＩＳ Ｒ ５２０１に規定する測定方法に準拠した。以上の評価結果を表３に纏めて表す。尚、該当温度での凝結が早過ぎて、前記各方法でのゲルタイムの測定及び一軸圧縮強度測定が困難であったセメントペーストに関しては測定不能とした。 Next, the gel time of the cement paste that was allowed to reach 30 ° C and 35 ° C was measured according to the “Cup Inversion Method” prescribed by the Japan Chemical Injection Association (Chemical Injection Association). It was set as the evaluation of working time. In addition, for the cement paste thus prepared, uniaxial compressive strength at 30 ° C. and 35 ° C. for 3 hours was measured by a method in accordance with JIS A 1216 “Soil Uniaxial Compression Test Method” as an evaluation of fast hardening. Further, a curable columnar molded product having a diameter of 50 mm and a height of 100 mm was obtained by filling the mold using the produced cement paste. Here, the time from mold filling to demolding was 12 hours, and the mold was allowed to stand in the atmosphere at about 20 ° C. until demolding. The cured molded product was left in a constant temperature and humidity chamber of 80% humidity maintained at 30 ° C. and 35 ° C. for 28 days. At the end of the standing period, the molded product was taken out of the constant temperature and humidity chamber and immediately measured for uniaxial compressive strength. Evaluation of long-term strength development at high temperatures was made. In measuring the strength, the measurement method specified in JIS R 5201 was used. The above evaluation results are summarized in Table 3. It should be noted that the cement paste, which was difficult to measure the gel time and the uniaxial compressive strength by the above-mentioned methods because the setting at the corresponding temperature was too early, could not be measured.
表３の結果から、本発明品を使用したセメントペーストは何れも３０℃と３５℃のゲルタイム（分）の差は概ね１５分以内となり、３５℃以上の高温でも炭酸ナトリウムやオキシカルボン酸の配合量を増加させなくとも、例えば施工作業上必要な程度の可使時間は確保できることがわかる。これに対し、従来技術に基づく又は本発明から外れる参考品は、３０℃と３５℃のゲルタイム（分）の差がかなり大きく高温ほどゲルタイムが短くなったか、或いは３０℃と３５℃のゲルタイム（分）の差を小さくしたものでは、３５℃での短時間強度の激しい低下が見られることがわかる。特に、ゲルタイムが殆ど測定されないほどの急結化作用を付与するもの（参考品２２〜２５）については、実用には適し難いものであった。 From the results in Table 3, the cement paste using the product of the present invention has a difference in gel time (min) of 30 ° C and 35 ° C within about 15 minutes, and it contains sodium carbonate and oxycarboxylic acid even at high temperature of 35 ° C or higher. It can be seen that, for example, the pot life required for the construction work can be secured without increasing the amount. On the other hand, in the reference products based on the prior art or outside the present invention, the difference in the gel time (minute) between 30 ° C. and 35 ° C. is considerably large, and the gel time is shortened as the temperature is higher, or It can be seen that when the difference in) is made small, a sharp decrease in strength at 35 ° C. is observed for a short time. In particular, those that give a quick-setting effect such that the gel time is hardly measured (reference products 22 to 25) are difficult to be practically used.
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| JP2019099444A (en) * | 2017-12-08 | 2019-06-24 | 太平洋セメント株式会社 | Construction method of mortar or concrete using ultra rapid hardening cement |
| CN115849404A (en) * | 2022-12-02 | 2023-03-28 | 贵州大学 | Method for removing sodium and fixing sodium by utilizing crystal form conversion process of phosphogypsum in solution under normal pressure |
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| JP2008201605A (en) * | 2007-02-19 | 2008-09-04 | Taiheiyo Material Kk | Rapid-hardening material for highly flowable hydraulic composition and highly flowable hydraulic composition |
| JP2010053023A (en) * | 2008-07-29 | 2010-03-11 | Tachibana Material Co Ltd | Grouting material |
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| JP2006062888A (en) * | 2004-08-24 | 2006-03-09 | Taiheiyo Material Kk | Quick-hardening admixture and quick-hardening cement composition |
| JP2008201605A (en) * | 2007-02-19 | 2008-09-04 | Taiheiyo Material Kk | Rapid-hardening material for highly flowable hydraulic composition and highly flowable hydraulic composition |
| JP2010053023A (en) * | 2008-07-29 | 2010-03-11 | Tachibana Material Co Ltd | Grouting material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019099444A (en) * | 2017-12-08 | 2019-06-24 | 太平洋セメント株式会社 | Construction method of mortar or concrete using ultra rapid hardening cement |
| CN115849404A (en) * | 2022-12-02 | 2023-03-28 | 贵州大学 | Method for removing sodium and fixing sodium by utilizing crystal form conversion process of phosphogypsum in solution under normal pressure |
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