JP2017178758A - Quick setting substance and quick setting material for cement composition - Google Patents
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Abstract
【課題】 急結助剤類の増量併用を行わなくても、高い急結性を十分発現させることのできる、コストパフォーマンスと急結性に格段に優れたカルシウムアルミネート系の急結性物質とこれを用いたセメント組成物用急結材を提供する。【解決手段】 化学成分としてのＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．０〜２．６であって、前記ＣａＯとＡｌ2Ｏ3を合計で９０ 〜９４質量％含み、かつ珪素とカリウムを酸化物換算した含有質量比（ＳｉＯ2／Ｋ2Ｏ）が２４．３〜３４．３であって、前記酸化物換算したＳｉＯ2とＫ2Ｏを合計で４〜５質量％含むＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体からなる急結性物質。【選択図】 なしPROBLEM TO BE SOLVED: To provide a calcium aluminate-based rapid-setting substance having remarkably excellent cost performance and quick-setting property, which can sufficiently develop high quick-setting property without increasing the amount of quick-setting aids. Provided is a quick-setting material for a cement composition using this. SOLUTION: The molar ratio (CaO / Al2O3) of CaO and Al2O3 as chemical components is 2.0 to 2.6, the total amount of CaO and Al2O3 is 90 to 94% by mass, and silicon and potassium. CaO-Al2O3-SiO2-K2O system in which the oxide-converted content mass ratio (SiO2 / K2O) is 24.3 to 34.3 and the oxide-converted SiO2 and K2O are contained in a total of 4 to 5% by mass. A quick-setting substance consisting of an amorphous substance. [Selection diagram] None
Description
本発明は、モルタル、コンクリート等のセメント組成物に対し、急結性を付与するための急結性物質およびセメント組成物用急結材に関する。 The present invention relates to a quick setting substance for imparting quick setting property to a cement composition such as mortar and concrete, and a quick setting material for cement composition.
例えば、山岳や地下トンネルの掘削、地中構造物や法面等の建設工事に対し、地山や構築物補強のために、壁面、天井面又は傾斜面にセメントスラリー、スラリー状のセメントモルタル又はコンクリートを吹付けることが行われている。 For example, for excavation of mountains and underground tunnels, construction work such as underground structures and slopes, cement slurry, slurry-like cement mortar or concrete on the wall surface, ceiling surface or inclined surface to reinforce ground mountains and structures Has been done.
吹付工法として汎用されている湿式吹付施工では、セメントに骨材と水、必要により混和剤（材）を配合したベースモルタルやベースコンクリートに、吹付直前に急結剤（材）を添加してモルタルやコンクリート等の吹付材とし、短時間にセメントの凝結を完了させることで付着性を得ている。吹付材は良好な付着性を具備することが不可欠である。 In wet spraying, which is widely used as a spraying method, mortar is prepared by adding a quick setting agent (material) just before spraying to base mortar or base concrete containing cement and aggregate, water, and if necessary, admixture (material). Adhesion is obtained by using a spraying material such as or concrete and completing the setting of cement in a short time. It is essential that the spray material has good adhesion.
また、トンネル、地下空間、法面等の建設工事では、しばしば壁面、天井面又は斜面等から漏水や湧水を伴うことがあり、吹付施工によるモルタルまたはコンクリート吹付材で、漏水や湧水箇所周辺を止水補強することも行われている。通常の吹付施工では、吹付けられたモルタルやコンクリートが自重による垂れや剥落を起こさない程度の強度を具備することが要求されるが、漏水防止目的に用いる吹付材では、これに加えて、吹付直後から溢れ出る漏水に耐えて付着がなされなければならない。そのため、施工作業に大きな支障を及ぼさない範囲で一刻も早く凝結が終結するように、特に高い急結性が必要とされる。このような要求性能を得易い粉末状の急結剤として、カリウムをＫ2Ｏ換算で１重量％以上含むカルシウムアルミネートと、アルミン酸ナトリウムおよびアルカリ金属炭酸塩等の無機塩とを含有する急結剤を使用した吹付材（例えば、特許文献１参照。）が知られている。この急結材に用いるカリウム含有カルシウムアルミネートは急結性に優れる反面、十分高い急結性を発現するにはカルシウムアルミネート中にカリウムを酸化物換算で５〜１２重量％は必要とされており、高価なＫ2Ｏ源原料を相当量使用せねばならずコスト的に高騰する。Ｋ2Ｏ源原料の使用を減らす為、含有するＫ2Ｏの一部をＮａ2Ｏで置換させたカルシウムアルミネートを使用することも知られている。（例えば、特許文献２参照。）しかし、Ｎａ2Ｏへの置換量を増やすに連れて、製造コストは低減するものの、可溶性のナトリウム量が増えるため、アルカリ骨材反応による吹付けた施工物の耐久性劣化が避けられない。 Also, in construction work such as tunnels, underground spaces, slopes, etc., water leakage or spring water often comes from the wall surface, ceiling surface or slope, etc., and mortar or concrete spraying material by spraying construction, around the leakage and spring water location The water is also reinforced with water. In normal spraying construction, it is required that the mortar and concrete sprayed have sufficient strength not to cause dripping or peeling due to their own weight, but in addition to spray materials used for the purpose of preventing water leakage, It must be able to withstand the leaking water that immediately overflows. Therefore, a particularly high quick setting property is required so that the setting can be completed as soon as possible within a range that does not cause a major hindrance to the construction work. As a powdery accelerating agent that easily obtains the required performance, a rapid containing a calcium aluminate containing 1 wt% or more of potassium in terms of K 2 O and an inorganic salt such as sodium aluminate and alkali metal carbonate. A spraying material using a binder (see, for example, Patent Document 1) is known. The potassium-containing calcium aluminate used for this quick setting material is excellent in quick setting, but 5 to 12% by weight of potassium in terms of oxide is required in calcium aluminate to express sufficiently high setting speed. Therefore, a considerable amount of expensive K 2 O source material must be used, which increases the cost. In order to reduce the use of the K 2 O source material, it is also known to use calcium aluminate in which a part of the K 2 O contained is substituted with Na 2 O. (For example, refer to Patent Document 2) However, as the amount of substitution with Na 2 O increases, the manufacturing cost decreases, but the amount of soluble sodium increases. Durability deterioration is inevitable.
前述のようにカリウムを含有させたカルシウムアルミネートを使用した急結剤は非常に高い急結性を発現できる可能性がある。本発明では、カリウムの含有により最も高い急結性が発現できたときのカリウム含有量よりも、カリウム含有量を大幅に減らしても、急結助剤類の増量併用を行わなくても、カリウムの含有により最も高い急結性が発現できたときと概ね同等の急結性を、他の性状を阻害することなく発現させることができる、コストパフォーマンスと急結性に格段に優れたカルシウムアルミネート系の急結性物質とこれを用いたセメント組成物用急結材の提供を課題とする。 As described above, there is a possibility that a rapid setting agent using calcium aluminate containing potassium can exhibit a very high quick setting property. In the present invention, even if the potassium content is greatly reduced from the potassium content when the highest rapid setting property can be expressed by the inclusion of potassium, the potassium content can be reduced without performing the combined use of the quick setting aids. Calcium aluminate with excellent cost performance and quick setting, which can express the quick setting almost the same as when the highest quick setting can be achieved by the inclusion of N It is an object of the present invention to provide a rapid setting material of a system and a quick setting material for cement composition using the same.
本発明者は、前記課題の解決のため検討を重ねた結果、特定の含有モル比でＣａＯとＡｌ2Ｏ3を主成分として含有し、残部に特定の酸化物換算含有量の関係で珪素とカリウムを含有するＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体が、非常に高い急結性を得るに適した物質であることがわかり、これと特定の急結助剤等を組み合わせたセメント組成物用急結材が、非常に高い急結性と高い初期強度発現性を具備し、しかも、これをモルタルやコンクリート等のセメント系組成物に混和しても、性状が阻害され難いことから、本発明を完成するに至った。 As a result of repeated investigations to solve the above problems, the present inventor contains CaO and Al 2 O 3 as main components at a specific content molar ratio, and the balance with silicon in relation to a specific oxide equivalent content. It has been found that a CaO—Al 2 O 3 —SiO 2 —K 2 O-based amorphous material containing potassium is a substance suitable for obtaining very high quick setting properties, and a specific quick setting aid. The quick setting material for cement composition combined with the above has an extremely high quick setting property and high initial strength, and even if it is mixed with a cement-based composition such as mortar or concrete, the properties thereof Since it is difficult to be inhibited, the present invention has been completed.
即ち、本発明は、次の（１）で表す急結性物質、及び（２）〜（５）で表すセメント組成物用急結材である。（１）化学成分としてのＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．０〜２．６であって、前記ＣａＯとＡｌ2Ｏ3を合計で９０ 〜９４質量％含み、かつ珪素とカリウムを酸化物換算した含有質量比（ＳｉＯ2／Ｋ2Ｏ）が２４．３〜３４．３であって、前記酸化物換算したＳｉＯ2とＫ2Ｏを合計で４〜５質量％含むＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体からなる急結性物質。（２）前記（１）の急結性物質、アルミン酸ナトリウムおよびアルカリ金属炭酸塩を含有するセメント組成物用急結材。（３）さらに石膏を含有する前記（２）のセメント組成物用急結材。（４）前記（１）の急結性物質１００質量部、アルミン酸ナトリウム３〜１１質量部およびアルカリ金属炭酸塩８〜１３質量部を含有するセメント組成物用急結材。 That is, this invention is the quick setting material represented by following (1), and the quick setting material for cement compositions represented by (2)-(5). (1) The content molar ratio (CaO / Al 2 O 3 ) of CaO and Al 2 O 3 as a chemical component is 2.0 to 2.6, and the total amount of CaO and Al 2 O 3 is 90 to 94. The content ratio (SiO 2 / K 2 O) of silicon and potassium converted to oxide is 24.3 to 34.3, and the oxide converted SiO 2 and K 2 O in total quick-substance consisting of CaO-Al 2 O 3 -SiO 2 -K 2 O based amorphous material containing 4-5 wt%. (2) A quick setting material for a cement composition comprising the quick setting substance of (1), sodium aluminate and alkali metal carbonate. (3) The quick setting material for a cement composition according to (2), further containing gypsum. (4) A quick setting material for a cement composition comprising 100 parts by mass of the quick setting substance of (1), 3 to 11 parts by mass of sodium aluminate, and 8 to 13 parts by mass of alkali metal carbonate.
本発明によれば、高価な原料を多く使用せずとも非常に高い急結性を具備した急結性物質が得られるため、前記急結性物質を有効成分とするセメント組成物用急結材は、併用する急結助剤類の使用量を従来より大幅に減らしても、高い急結性と初期強度発現性をセメント組成物に付与することができる。この面からもコスト的に優れたセメント組成物用急結材を得ることができる。しかも、前記セメント組成物用急結材は、耐久性を初めとするセメント組成物の性状を阻害し難いものであるため、吹付材を始め、特に高い急結性や急硬性を必要とする広範囲な用途に使用することができる。 According to the present invention, a quick setting material having a very high quick setting property can be obtained without using many expensive raw materials. Therefore, the quick setting material for a cement composition containing the quick setting material as an active ingredient. Even if the usage-amount of the rapid setting aid used together is reduced significantly conventionally, high rapid setting property and initial stage strength development property can be provided to a cement composition. From this aspect, it is possible to obtain a quick setting material for cement composition which is excellent in cost. In addition, the rapid setting material for cement composition is difficult to inhibit the properties of the cement composition including durability, and therefore includes a wide range of materials that require particularly high quick setting properties and rapid hardening properties, including spraying materials. Can be used for various purposes.
本発明の急結性物質であるＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体は、化学成分としてのＣａＯとＡｌ2Ｏ3を、含有モル比（ＣａＯ／Ａｌ2Ｏ3）で２．０〜２．６、好ましくは２．２〜２．５、前記ＣａＯとＡｌ2Ｏ3を合計で９０〜９４質量％含み、かつ珪素とカリウムを酸化物換算した含有質量比（ＳｉＯ2／Ｋ2Ｏ）が２４．３〜３４．３、好ましくは２８．０〜３２．５、前記酸化物換算したＳｉＯ2とＫ2Ｏを合計で４〜５質量％含むものである。化学成分としてのＣａＯとＡｌ2Ｏ3を前記のように含むことで、瞬結化に近い高い急結性を付与できる。化学成分としてのＣａＯとＡｌ2Ｏ3の合計含有量が、９０質量％未満では、水に対する反応活性が低過ぎて、所望の急結性や速硬性が得られ難くなるため好ましくない。また、９４質量％を超えると瞬結性が強まり過ぎて、例えば吹付コンクリートに使用すると対象面に到達前に凝結が終結して付着できない虞があるので好ましくない。また、化学成分としてのＣａＯとＡｌ2Ｏ3は含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．０未満だと急結性が低下するため好ましくなく、前記含有モル比（ＣａＯ／Ａｌ2Ｏ3）が２．６を超えると瞬結性が強まり過ぎるため好ましくない。さらに、珪素とカリウムを酸化物換算による質量比（ＳｉＯ2／Ｋ2Ｏ）で２４．３〜３４．３となるよう含むことで、より高い急結性の発現が達成できる。前記含有質量比（ＳｉＯ2／Ｋ2Ｏ）が３４．３を超えると、高い急結性が発現され難くなるので好ましくなく、２４．３未満では原料コストの高騰に繋がる虞がある他、強度発現性が低下することがあるので好ましくない。また、前記酸化物換算としてのＳｉＯ2とＫ2Ｏの含有量は、前記の質量比であることに加え、高い初期強度発現性がより得易くなることから、酸化物換算によるＳｉＯ2とＫ2Ｏの合計量で前記本非晶質体中に４．０〜５．０質量％含むものとする。好ましくは、４．１〜４．８質量％含むものとする。酸化物換算したＳｉＯ2とＫ2Ｏの含有量が、４質量％未満では、高い急結性が得られ難くなるため好ましくない。また、５質量％を超えると瞬結性が強まり過ぎて、例えばコンクリート吹付材に使用すると対象面に到達前に凝結が終結して付着できない虞があるので好ましくない。前記ＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体中でケイ素とカリウムは、化学成分的には実質的に、ＳｉＯ2、Ｋ2Ｏとして含まれる。また、前記ＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体は、前記以外の成分を含むことは、本発明の効果を阻害しない限り、制限はされない。 The CaO—Al 2 O 3 —SiO 2 —K 2 O-based amorphous material, which is the rapid setting substance of the present invention, contains CaO and Al 2 O 3 as chemical components in a molar ratio (CaO / Al 2 O 3 ) 2.0 to 2.6, preferably 2.2 to 2.5, containing 90 to 94% by mass of CaO and Al 2 O 3 in total, and containing mass ratio in terms of oxides of silicon and potassium (SiO 2 / K 2 O) is 24.3 to 34.3, preferably 28.0 to 32.5, and contains 4 to 5% by mass in total of SiO 2 and K 2 O in terms of the oxide. By containing CaO and Al 2 O 3 as chemical components as described above, it is possible to impart high quick setting properties close to instantaneous setting. If the total content of CaO and Al 2 O 3 as chemical components is less than 90% by mass, the reaction activity with respect to water is too low, and it becomes difficult to obtain desired quick setting properties and fast curing properties. On the other hand, if it exceeds 94% by mass, the instantaneous setting property becomes too strong. For example, if it is used for shotcrete, it is not preferable because the condensation may end before reaching the target surface and cannot adhere. Also, CaO and Al 2 O 3 as a chemical component molar ratio (CaO / Al 2 O 3) is not preferable because the rapid setting is lowered as less than 2.0, the molar ratio (CaO / Al 2 If O 3 ) exceeds 2.6, it is not preferable because the instantaneous setting is too strong. Furthermore, by including silicon and potassium in a mass ratio (SiO 2 / K 2 O) in terms of oxides of 24.3 to 34.3, higher rapidity can be achieved. If the content mass ratio (SiO 2 / K 2 O) exceeds 34.3, it is not preferable because high rapidity is difficult to be expressed, and if it is less than 24.3, the raw material cost may increase, This is not preferable because the expression may be lowered. Moreover, since the content of SiO 2 and K 2 O in terms of oxide is not only the above-described mass ratio, but also high initial strength development is more easily obtained, SiO 2 and K in terms of oxide are more easily obtained. The total amount of 2 O is 4.0 to 5.0% by mass in the amorphous body. Preferably, the content is 4.1 to 4.8% by mass. If the content of SiO 2 and K 2 O in terms of oxide is less than 4% by mass, it is difficult to obtain high rapid setting properties, which is not preferable. On the other hand, if it exceeds 5% by mass, the instantaneous setting property is too strong. For example, if it is used for a concrete spraying material, the condensation may be terminated before reaching the target surface. In the CaO—Al 2 O 3 —SiO 2 —K 2 O-based amorphous material, silicon and potassium are substantially contained as SiO 2 and K 2 O in terms of chemical components. Further, the CaO—Al 2 O 3 —SiO 2 —K 2 O-based amorphous material is not limited as long as it does not inhibit the effects of the present invention.
また、前記ＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体は、例えば水和反応の如く常温で水と反応を起こすものであることを要す。また、前記ＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体は、完全に非晶質である必要はなく、概ねガラス化率７５％以上、好ましくはガラス化率９０％以上であれば良い。ガラス化が進んだ構造であることによって高い反応活性が得られ、急結性の向上に寄与する。ここで、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ＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｆｅ2Ｏ3系非晶質水和活性物質に含まれる各鉱物の質量を内部標準法等で定量し、定量できた含有鉱物相の総和質量；Ｍ２を算出し、残部が純ガラス相と見なし、次式でガラス化率を算出した。
ガラス化率（％）＝（１−Ｍ２／Ｍ１）×１００
Further, the CaO—Al 2 O 3 —SiO 2 —K 2 O-based amorphous material needs to react with water at room temperature such as a hydration reaction. Further, the CaO—Al 2 O 3 —SiO 2 —K 2 O-based amorphous body does not have to be completely amorphous, and generally has a vitrification rate of 75% or more, preferably a vitrification rate of 90% or more. If it is good. High reaction activity is obtained by virtue of the vitrified structure, which contributes to the improvement of rapid setting. Here, the vitrification rate uses the powder X-ray diffractometer and the mass of each mineral contained in the CaO—Al 2 O 3 —SiO 2 —Fe 2 O 3 -based amorphous hydration active substance having a mass of M1 The total mass of the contained mineral phases quantified by a standard method or the like; M2 was calculated, the remainder was regarded as a pure glass phase, and the vitrification rate was calculated by the following formula.
Vitrification rate (%) = (1-M2 / M1) × 100
本発明の急結性物質は、前記ＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体からなるものである。本発明の急結性物質は粉体で使用するのが望ましいが、その粉末度は特に制限されない。好ましくは、所定の反応活性を確保する上で、ブレーン比表面積が４０００〜１００００ｃｍ2／ｇに調整したものが良い。 The rapid setting substance of the present invention is composed of the CaO—Al 2 O 3 —SiO 2 —K 2 O-based amorphous material. Although the rapid setting substance of the present invention is desirably used in powder form, the fineness thereof is not particularly limited. Preferably, the brane specific surface area is adjusted to 4000 to 10,000 cm 2 / g in order to ensure a predetermined reaction activity.
また、前記ＣａＯ−Ａｌ2Ｏ3−ＳｉＯ2−Ｋ2Ｏ系非晶質体を製造する方法は、特に限定されるものではない。一例を示すと、ＣａＯ源、Ａｌ2Ｏ3源、ＳｉＯ2源、Ｋ2Ｏ源となる天然鉱物や市販工業用薬品等の各原料（複数の化学成分を含む原料でも良い。）を所定の配合で混合し、原料混合物を作製する。この混合物を加熱装置で概ね１２００〜１４００℃で溶融するまで加熱し、加熱温度から溶融物を水中急冷以外の手段で急冷することで得ることができる。 The method for producing the CaO—Al 2 O 3 —SiO 2 —K 2 O-based amorphous material is not particularly limited. For example, each raw material (a raw material containing a plurality of chemical components may be used) such as a natural mineral or a commercial industrial chemical as a CaO source, an Al 2 O 3 source, a SiO 2 source, and a K 2 O source. Mix by blending to make a raw material mixture. This mixture can be heated by a heating device until it is melted at approximately 1200 to 1400 ° C., and the melt can be rapidly cooled from the heating temperature by means other than quenching in water.
また、本発明のセメント組成物用急結材は、前記急結性物質、アルミン酸ナトリウム及びアルカリ金属炭酸塩を含むものである。使用するアルミン酸ナトリウム（二酸化ナトリウムアルミニウム）は粉体状のものであれば限定されない。例えば市販の工業用薬品や理化学用試薬等の何れも使用できる。但し、潮解性があるため、できるだけ変質の進んでいないものを使用することが望ましい。アルミン酸ナトリウムを含むことで凝結始発時間をより確実に早めることができる。本発明のセメント組成物用急結材中に含まれるアルミン酸ナトリウムの量は、含有効果が過不足無く発現させる上で、前記急結性物質の含有量１００質量部に対し、３〜１１質量部、好ましくは４〜９質量部とする。また、使用するアルミン酸ナトリウムの粉末度は特に制限されるものではないが、適度な反応活性を確保し、且つ経済性も考慮すると、ブレーン比表面積で概ね４０００〜９００００ｃｍ2／ｇのものが好ましい。 Moreover, the quick setting material for a cement composition of the present invention contains the quick setting substance, sodium aluminate and alkali metal carbonate. The sodium aluminate to be used (sodium aluminum dioxide) is not limited as long as it is powdery. For example, any commercially available industrial chemicals or physicochemical reagents can be used. However, since it has deliquescence, it is desirable to use one that has not deteriorated as much as possible. By including sodium aluminate, the initial setting time can be shortened more reliably. The amount of sodium aluminate contained in the rapid setting material for a cement composition of the present invention is 3 to 11 parts by mass with respect to 100 parts by mass of the quick setting substance in order to express the content effect without excess or deficiency. Parts, preferably 4 to 9 parts by mass. Further, the fineness of sodium aluminate used is not particularly limited, but when the appropriate reaction activity is ensured and the economic efficiency is taken into consideration, a brane specific surface area of approximately 4000 to 90000 cm 2 / g is preferable. .
また、本発明のセメント組成物用急結材に含有使用するアルカリ金属炭酸塩は、具体的には炭酸ナトリウム、炭酸カリウム、炭酸リチウムを挙げることができ、その何れでも良く、またこのうち任意の２種以上を使用しても良い。アルカリ金属炭酸塩を含むことで凝結反応が促進され、その結果凝結の終結時間がより早まる。本発明のセメント組成物用急結材中のアルカリ金属炭酸塩の含有量は、かような作用を確実に発現させる上で、前記急結性物質の含有量１００質量部に対し、８〜１３質量部、好ましくは、９〜１２質量部とする。 In addition, the alkali metal carbonate contained and used in the rapid setting material for cement composition of the present invention can specifically include sodium carbonate, potassium carbonate, and lithium carbonate, and any of them can be used. Two or more kinds may be used. Inclusion of the alkali metal carbonate accelerates the setting reaction, resulting in a faster setting end time. The content of the alkali metal carbonate in the rapid setting material for a cement composition of the present invention is 8 to 13 with respect to 100 parts by weight of the quick setting substance in order to ensure such an effect. Part by mass, preferably 9 to 12 parts by mass.
また、本発明のセメント組成物用急結材は、好ましくは、さらに石膏を含有するものとする。石膏は、無水石膏、半水石膏、二水石膏又は硫酸カルシウムの何れでも良く、このうち二種以上を併用しても良い。より好ましくは、無水石膏を使用する。石膏の含有により、セメント水和後におけるエトリンガイトの生成が促進され、良好な強度発現性が得られる。また、中長期に亘り安定した強度値が維持される。セメント組成物用急結材に石膏を含有させる場合の含有量は、前記含有作用を十分発現させ、また含有による急結性低下や過膨張を避ける上で、好ましくは、前記急結性物質の含有量１００質量部に対し、１１．０〜１７．５質量部、より好ましくは１２．５〜１６質量部とする。また、使用する石膏の粉末度は特に制限されないが、適度な反応活性を確保し、且つ経済性も考慮すると、ブレーン比表面積で概ね６０００〜１００００ｃｍ2／ｇのものが好ましい。尚、本発明のセメント組成物用急結材は、ポルトランドセメント等を含むセメント組成物に混和使用されるが、セメント組成物中のポルトランドセメントに由来する石膏分は、本発明のセメント組成物用急結材に含有される石膏量の一部として見なさないものとする。 The rapid setting material for a cement composition of the present invention preferably further contains gypsum. The gypsum may be any of anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum, or calcium sulfate, and two or more of these may be used in combination. More preferably, anhydrous gypsum is used. The inclusion of gypsum promotes the formation of ettringite after cement hydration, and good strength development is obtained. In addition, a stable strength value is maintained over the medium to long term. When gypsum is included in the rapid setting material for cement composition, the content is sufficiently expressed, and in order to avoid rapid deterioration due to inclusion and excessive expansion, preferably, It is 11.0-17.5 mass parts with respect to 100 mass parts of content, More preferably, you may be 12.5-16 mass parts. The fineness of gypsum to be used is not particularly limited. However, when appropriate reaction activity is ensured and economic efficiency is taken into consideration, a brane specific surface area of approximately 6000 to 10,000 cm 2 / g is preferable. The quick setting material for a cement composition of the present invention is used in a cement composition containing Portland cement or the like, but the gypsum component derived from Portland cement in the cement composition is used for the cement composition of the present invention. It shall not be considered as part of the amount of gypsum contained in the quick setting material.
また、本発明のセメント組成物用急結材は、前記以外の成分も本発明の効果を阻害しない範囲で含有することができる。含有可能な成分は、例えばモルタルやコンクリート用の凝結遅延剤、アルカリ金属又はアルカリ土類金属の重炭酸塩、亜硝酸塩又は硝酸塩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。 Moreover, the quick setting material for cement compositions of the present invention can contain components other than those described above as long as the effects of the present invention are not impaired. Examples of components that can be included include a setting retarder for mortar and concrete, bicarbonates, nitrites, and nitrates of alkali metals or alkaline earth metals, but are not limited to the examples described.
また、本発明のセメント組成物用急結材のセメント組成物に対する使用量は、特に制限されるものではなく、目的、用途、セメント組成物の配合内容及び施工環境等に応じて適宜定めれば良い。ここで、セメント組成物としては、セメントペースト、モルタル、コンクリートの何れでも良く、その配合も何等制限されない。具体的な一例として、湿式吹付工法で施工する吹付コンクリートへの急結材に使用する場合の添加量は、吹付コンクリート中のポルトランドセメント含有量１００質量部に対し、４〜１０質量部が好ましく、より好ましくは６〜９質量部とする。 In addition, the amount of the quick setting material for cement composition of the present invention used for the cement composition is not particularly limited, and may be appropriately determined according to the purpose, application, blending content of the cement composition, construction environment, and the like. good. Here, the cement composition may be any of cement paste, mortar, and concrete, and the blending thereof is not limited at all. As a specific example, the addition amount in the case of using for the quick setting material to the shotcrete constructed by the wet spraying method is preferably 4 to 10 parts by mass with respect to 100 parts by mass of the Portland cement content in the shotcrete, More preferably 6 to 9 parts by mass.
本発明のセメント組成物用急結材は、好適には、地山や地下構造物等の補強用としての吹付コンクリートや吹付モルタルに混和使用でき、漏水や湧水等の止水材にも混和使用できる他、高い急硬性や初期強度発現性を具備するため、このような性状を必要とするものなら吹付用以外のセメント組成物にも使用できる。 The quick setting material for cement composition according to the present invention can be suitably used in spray concrete and spray mortar for reinforcing natural ground, underground structures, etc., and also in water-stopping materials such as water leakage and spring water. In addition to being able to be used, since it has a high rapid hardening property and an initial strength development property, if it requires such properties, it can be used for cement compositions other than those for spraying.
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。また、施工試験や各種特性測定は常温（２０±１℃）環境下で行った。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the described examples. Moreover, the construction test and various characteristic measurements were performed in a normal temperature (20 ± 1 ° C.) environment.
［急結性物質の作製］
何れも市販薬品の炭酸カルシウム、酸化珪素、酸化アルミニウム及び炭酸カリウムを用い、所望の化学組成の急結性物質が得られるよう秤量し、ヘンシェル型ミキサで乾式混合した。乾式混合した混合物を電気炉を使用し、温度約１５００℃（±５０℃）で６０分間加熱し、加熱時間経過後は直ちに被加熱物を炉外に取出した。取出した被加熱物表面に冷却用の窒素ガスを流速約３０ｍｌ／秒で吹付けて急冷し、主な含有成分の酸化物換算による含有割合（質量％）が表１に表す急結性物質を得た。また、表１には得られた急結性物質のガラス化率も記した。尚、一部の被加熱物については炉外への取出しまでは前記に準じるものの、その後の冷却用の窒素ガスは流速や吹付け時間を減らして吹付け、ガラス化率を調製した。得られた急結性物質は粉砕・分級操作により整粒し、ブレーン比表面積約５０００ｃｍ2／ｇの粉末にした。
[Production of quick-set substances]
In each case, commercially available chemicals such as calcium carbonate, silicon oxide, aluminum oxide and potassium carbonate were weighed so as to obtain a quick setting substance having a desired chemical composition, and dry-mixed with a Henschel mixer. The dry-mixed mixture was heated for 60 minutes at a temperature of about 1500 ° C. (± 50 ° C.) using an electric furnace, and immediately after the heating time, the heated object was taken out of the furnace. Nitrogen for cooling is blown to the surface of the object to be heated at a flow rate of about 30 ml / second to quench the substance. Obtained. Table 1 also shows the vitrification rate of the quick setting substance obtained. Although some of the objects to be heated conform to the above until taking out to the outside of the furnace, the nitrogen gas for subsequent cooling was sprayed at a reduced flow rate and spraying time to adjust the vitrification rate. The obtained quick setting substance was sized by pulverization / classification operation to obtain a powder having a Blaine specific surface area of about 5000 cm 2 / g.
［セメント組成物用急結材の作製］
前記作製の急結性物質粉末、何れも市販薬品のアルミン酸ナトリウム、炭酸ナトリウム、硫酸ナトリウムおよびＩＩ型無水石膏から選定される材料を、前記非晶質粉末１００質量部あたりの配合量で表した表２の配合となるようヘンシェルミキサに一括投入した。このミキサで約２分間混合することで、セメント組成物用急結材を作製した。
[Preparation of rapid setting material for cement composition]
The prepared quick setting substance powders, all of which are selected from commercially available sodium aluminate, sodium carbonate, sodium sulfate, and type II anhydrous gypsum, are expressed in a blending amount per 100 parts by mass of the amorphous powder. The Henschel mixer was added all at once so as to have the composition shown in Table 2. By mixing with this mixer for about 2 minutes, a quick setting material for cement composition was produced.
［ベースモルタル（セメント組成物）の作製］
普通ポルトランドセメント（市販品、比重３．１６）４９３ｇ、混練水２９５ｇ、及び細骨材（掛川産陸砂（Ｆ．Ｍ．＝２．７、表乾密度；２．５８））１４２２ｇを混合機に一括投入し、約９０秒間混練し、ベースモルタルを得た。混合機は市販の卓上モルタルミキサを使用した。
[Preparation of base mortar (cement composition)]
543 g of ordinary Portland cement (commercial product, specific gravity 3.16), 295 g of kneaded water, and 1422 g of fine aggregate (land sand from Kakegawa (FM = 2.7, surface dry density; 2.58)) Was added all at once and kneaded for about 90 seconds to obtain a base mortar. A commercially available tabletop mortar mixer was used as the mixer.
［急結性の評価］
前記ベースモルタルを、底付の円筒容器に入れ、ハンドミキサで１分間混合した後、屋内に３０分静置した。この静置後、ハンドミキサで１分間再混合し、前記セメント組成物用急結材をベースモルタル中のポルトランドセメント含有量１００質量部あたり表３に記載した量で加え、さらに５秒間攪拌して急結性評価用のモルタルを作製した。前記セメント組成物用急結材の添加３０秒経過時点、６０秒経過時点、１２０秒経過時点及び１８０秒経過時点のモルタルに対し、プロクター貫入抵抗値を測定することで急結性の評価を行った。プロクター貫入抵抗値の測定方法は、土木学会コンクリート標準指方書「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た。この貫入抵抗値の測定結果を表４に表す。
[Evaluation of quick setting]
The base mortar was put into a bottomed cylindrical container, mixed for 1 minute with a hand mixer, and then allowed to stand indoors for 30 minutes. After this standing, remix for 1 minute with a hand mixer, add the quick setting material for cement composition in the amount described in Table 3 per 100 parts by mass of Portland cement content in the base mortar, and further stir for 5 seconds. A mortar for quick setting evaluation was prepared. The quick setting property is evaluated by measuring the penetration resistance of the proctor with respect to the mortar at 30 seconds, 60 seconds, 120 seconds and 180 seconds after the addition of the cement composition rapid setting material. It was. Proctor penetration resistance value is measured in accordance with the Japan Society of Civil Engineers Concrete Standard Specification "Quality Standards for Sprayed Concrete" Annex "Method for Measuring Instantaneous Mortation Time of Mortar Using Penetration Resistance", with a cross-sectional area of 0.125 cm 2 Procter needles were used. Table 4 shows the measurement results of the penetration resistance value.
［モルタル吹付材の作製］
また、前記のベースモルタルを湿式吹付装置（市販品）に圧送し、湿式吹付装置内で輸送中のベースモルタルに前記セメント組成物用急結材を連続的に添加した。前記添加により実質的な混合がなされ、各ベースモルタルと前記セメント組成物用急結材からなるモルタル吹付材を得た。ベースモルタルへ添加するセメント組成物用急結材の種類と添加量は、表３に表した前記の急結性評価用のモルタルと同一とした。
[Production of mortar spray material]
Moreover, the said base mortar was pumped to the wet spraying apparatus (commercial item), and the said quick setting material for cement compositions was continuously added to the base mortar currently transported within the wet spraying apparatus. Substantially mixed by the addition, a mortar spraying material composed of each base mortar and the quick setting material for cement composition was obtained. The kind and addition amount of the cement composition quick setting material added to the base mortar were the same as the mortar for quick setting evaluation shown in Table 3.
［吹付特性の評価］
前記のように作製したモルタル吹付材を、前記湿式吹付装置の噴射用ノズルから約１００ｃｍ離れた地点に垂直に設置された３ｍ四方のコンクリート製平滑壁面に向かって、前記噴射用ノズルから１６０ｍｌ／分の流量で吹付けた。吹付性の評価は、何れも目視観察で、前記壁面からの吹付材の跳ね返り（リバウンド）を調べ、跳ね返りが見られなかったものをリバウンド「無」と判断し、跳ね返りが見られたものをリバウンド「有」と判断した。また、壁面に吹付けた吹付物に垂れが見られたり剥落が起こったりすることなく、付着し続けたものを付着性が「良好」と判断し、それ以外の状態になったものは全て付着性が「不良」と判断した。また、このような吹付けを３分間連続して行った直後に、湿式吹付装置のノズル孔に固結物による閉塞が部分的にでも塞ぐような状況となったものを閉塞発生「有」と判断し、このような閉塞が全く見られなかったもののみを閉塞発生「無」と判断した。この結果を表５に表す。
[Evaluation of spray characteristics]
160 ml / min of the mortar spray material produced as described above from the spray nozzle toward a 3 m square concrete smooth wall surface installed vertically at a point about 100 cm away from the spray nozzle of the wet spray device. Sprayed at a flow rate of. In the evaluation of sprayability, the rebound (rebound) of the spray material from the wall surface was checked by visual observation, and those that did not rebound were judged as “no rebound”, and those that rebounded were rebounded. Judged “Yes”. In addition, the sprayed material sprayed on the wall surface is not dripping or peeling off. The sex was judged as “bad”. Immediately after performing such spraying for 3 minutes, the nozzle hole of the wet spraying device is blocked by a solidified substance even if it is partially blocked. Judgment was made, and only those in which such occlusion was not found at all were judged as “no”. The results are shown in Table 5.
［強度発現性の評価］
また、前記急結性評価用に作製したモルタルを、セメント組成物用急結材の添加から概ね１分以内に、内寸４０×４０×１６０ｍｍの成形用型枠に流し込み、これを屋内の空気中に１２０分間静置し、静置後に脱型して所定時間２０℃の湿空養生し、材齢３時間、１日及び２８日の供試体を得た。この供試体の圧縮強度をＪＩＳ Ｒ ５２０１に準じた方法でアムスラー式強度試験機で測定した。この強度測定結果も表５に表す。
[Evaluation of strength development]
Also, the mortar prepared for evaluating the quick setting property is poured into a molding mold having an inner size of 40 × 40 × 160 mm within about 1 minute from the addition of the quick setting material for cement composition, and this is put into indoor air. The sample was allowed to stand for 120 minutes, removed from the mold, and then cured at a temperature of 20 ° C. for a predetermined time to obtain specimens having a material age of 3 hours, 1 day, and 28 days. The compressive strength of this specimen was measured with an Amsler type strength tester by a method according to JIS R 5201. This strength measurement result is also shown in Table 5.
表４の結果から、本発明のセメント組成物用急結材を用いたモルタルは、接水から１５秒経過した時点で既に貫入抵抗値の急上昇が見られ１２０秒以内に概ね終結しており、しかも高い抵抗値を示したことから、強固な凝結体が早々と得られ、非常に高い急結作用を具備することがわかる。また、表５の結果から、本発明のセメント組成物用急結材を用いたモルタルは、良好な吹付性状を具備し、また、材齢２８日の長期強度発現性も高い値であったことから、耐久性の劣化も起き難いことがわかる。 From the results in Table 4, the mortar using the rapid setting material for the cement composition of the present invention has already seen a sudden increase in penetration resistance value at the time when 15 seconds have passed since the contact with water, and is generally terminated within 120 seconds. Moreover, since a high resistance value was exhibited, it can be seen that a strong aggregate is obtained quickly and has a very high rapid setting action. Moreover, from the result of Table 5, the mortar using the quick setting material for cement composition of the present invention had a good spraying property and had a high value of long-term strength development at 28 days of age. Therefore, it can be seen that the durability is hardly deteriorated.
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|---|---|---|---|---|
| JP2022142307A (en) * | 2021-03-16 | 2022-09-30 | 太平洋マテリアル株式会社 | Calcium aluminate, quick-setting agent and quick-hardening concrete using the same |
| JP2022163971A (en) * | 2021-04-15 | 2022-10-27 | デンカ株式会社 | Foaming quick-setting agent and spraying method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826797A (en) * | 1994-07-12 | 1996-01-30 | Denki Kagaku Kogyo Kk | Cement quick-setting material and cement composition |
| JPH08104556A (en) * | 1994-08-11 | 1996-04-23 | Denki Kagaku Kogyo Kk | Cement quick-setting material and cement composition |
| JPH08119698A (en) * | 1994-10-26 | 1996-05-14 | Denki Kagaku Kogyo Kk | Cement quick-setting material and cement composition |
| JPH09169557A (en) * | 1995-10-17 | 1997-06-30 | Denki Kagaku Kogyo Kk | Spraying material and spraying method using the same |
| JP2013014495A (en) * | 2011-07-05 | 2013-01-24 | Union Corp | Cement mineral based quick setting agent using amorphous calcium aluminate mineral produced by water cooling method, and its production method |
| JP2014218405A (en) * | 2013-05-09 | 2014-11-20 | 電気化学工業株式会社 | Spray material and spray method |
-
2016
- 2016-03-31 JP JP2016073221A patent/JP6660229B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826797A (en) * | 1994-07-12 | 1996-01-30 | Denki Kagaku Kogyo Kk | Cement quick-setting material and cement composition |
| JPH08104556A (en) * | 1994-08-11 | 1996-04-23 | Denki Kagaku Kogyo Kk | Cement quick-setting material and cement composition |
| JPH08119698A (en) * | 1994-10-26 | 1996-05-14 | Denki Kagaku Kogyo Kk | Cement quick-setting material and cement composition |
| JPH09169557A (en) * | 1995-10-17 | 1997-06-30 | Denki Kagaku Kogyo Kk | Spraying material and spraying method using the same |
| JP2013014495A (en) * | 2011-07-05 | 2013-01-24 | Union Corp | Cement mineral based quick setting agent using amorphous calcium aluminate mineral produced by water cooling method, and its production method |
| JP2014218405A (en) * | 2013-05-09 | 2014-11-20 | 電気化学工業株式会社 | Spray material and spray method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022142307A (en) * | 2021-03-16 | 2022-09-30 | 太平洋マテリアル株式会社 | Calcium aluminate, quick-setting agent and quick-hardening concrete using the same |
| JP7612301B2 (en) | 2021-03-16 | 2025-01-14 | 太平洋マテリアル株式会社 | Accelerator and fast-hardening concrete |
| JP2022163971A (en) * | 2021-04-15 | 2022-10-27 | デンカ株式会社 | Foaming quick-setting agent and spraying method |
| JP7697809B2 (en) | 2021-04-15 | 2025-06-24 | デンカ株式会社 | Foaming quick-setting agent and spraying method |
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| JP6660229B2 (en) | 2020-03-11 |
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