WO2023190108A1 - Cement admixture, and cement composition - Google Patents

Cement admixture, and cement composition Download PDF

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Publication number
WO2023190108A1
WO2023190108A1 PCT/JP2023/011711 JP2023011711W WO2023190108A1 WO 2023190108 A1 WO2023190108 A1 WO 2023190108A1 JP 2023011711 W JP2023011711 W JP 2023011711W WO 2023190108 A1 WO2023190108 A1 WO 2023190108A1
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water
cement
mass
cement admixture
parts
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PCT/JP2023/011711
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French (fr)
Japanese (ja)
Inventor
一也 本間
慎 庄司
偉沢 王
泰之 二階堂
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デンカ株式会社
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Publication of WO2023190108A1 publication Critical patent/WO2023190108A1/en

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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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • 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
    • C04B22/10—Acids or salts thereof containing carbon in the anion
    • 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
    • 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

Definitions

  • the present invention relates to cement admixtures and cement compositions.
  • the strength of cement and concrete largely depends on the water/cement ratio, and it is now common to use water reducers and high-performance water reducers to reduce the water/cement ratio as much as possible. .
  • the fluidity of mortar or concrete containing polycarboxylate-based water reducing agents may change markedly, or the reaction rate may be reduced due to insufficient dispersion of particles. This may cause the strength to decrease.
  • the present invention makes it possible to develop good fluidity while maintaining strength development even when the water/cement ratio is small, without using a large amount of water reducing agent or high performance water reducing agent.
  • the purpose is to provide cement admixtures.
  • the present invention is as follows.
  • a cement admixture comprising pozzolanic fine powder, gypsum, and one or more water-soluble calcium salts of inorganic or organic acids other than gypsum.
  • the cement admixture according to [3], wherein the calcium acetate has an average particle size of 5 to 100 ⁇ m.
  • the cement can exhibit good fluidity while maintaining strength without using a large amount of water reducing agent or high performance water reducing agent. Admixtures can be provided.
  • the cement admixture according to the present embodiment contains one or more types of pozzolanic fine powder, gypsum, and water-soluble calcium salts of inorganic or organic acids other than gypsum (hereinafter sometimes referred to as “water-soluble calcium salts"). It will be done.
  • the pozzolanic fine powder and gypsum provide strength, and the presence of the water-soluble calcium salt provides good fluidity. In the present invention, both strength development and fluidity were achieved through these combinations.
  • Pozzolanic fine powders include silica fume generated during the production of silicon alloys and metal silicon in electric furnaces, silica fume derived from zirconia, classified fly ash obtained by classifying fly ash produced by pulverized coal-fired power plants, and gasified coal. Coal gasification fly ash, fused silica fine powder, and synthesized aerosil, which are by-produced from thermal power plants that are burned, can be used, and one or more of them can be used.
  • silica fume is the most preferable because it improves both fluidity and strength.
  • Classified fly ash, coal gasified fly ash, fused silica fine powder, etc. can be expected to improve fluidity, but they cannot be expected to have the same strength effects as silica fume.
  • the combined use of a small amount of silica fume and a fine spherical pozzolanic powder such as classified fly ash or fused silica is particularly preferred because it not only further promotes fluidity but also synergistically increases strength.
  • the mass mixing ratio of silica fume and at least one non-silica fume pozzolanic fine powder of classified fly ash, coal gasified fly ash, and fused silica fine powder is 1/1 to 5. /1 is preferable, and 2/1 to 4/1 is more preferable. When the ratio is 1/1 to 5/1, fluidity and strength can be improved.
  • the particle size of gypsum is preferably 3,000 cm 2 /g or more in Blaine value, more preferably 4,000 to 8,000 cm 2 /g.
  • Water-soluble calcium salts of inorganic or organic acids excluding gypsum Water-soluble calcium salts of inorganic or organic acids other than gypsum may be water-soluble as long as they dissolve in water to produce calcium ions, such as acetic acid, nitric acid, nitrous acid, thiocyanic acid, and cyanic acid. , formic acid and other calcium salts. Specific examples include calcium acetate, calcium formate, and calcium nitrate, but calcium acetate is preferred from the viewpoint of solubility in water and maintenance of fluidity of mortar and concrete.
  • the average particle diameter (median diameter) of the water-soluble calcium salt is preferably 5 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, from the viewpoint of solubility and ease of handling.
  • the average particle size can be measured using a laser diffraction particle size distribution analyzer.
  • the amount of pozzolanic fine powder is preferably 50 to 90 parts by mass from the viewpoint of strength development and fluidity.
  • the amount of gypsum is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass.
  • the water-soluble calcium salt is preferably 1 to 10 parts by mass, more preferably 3 to 7 parts by mass.
  • the total amount of pozzolanic fine powder, gypsum, and water-soluble calcium salt in 100 parts by mass of the cement admixture is preferably 90 parts by mass or more, and 95 parts by mass or more. More preferably, it is 99.4 parts by mass or more.
  • water-soluble sodium salt of inorganic or organic acid Water-soluble sodium salt of inorganic or organic acid
  • a water-soluble sodium salt of an inorganic or organic acid hereinafter sometimes referred to as “water-soluble sodium salt” may be contained.
  • the water-soluble sodium salt may be any salt having water solubility such that it dissolves in water to generate sodium ions, such as sodium carbonate, sodium sulfate, sodium chloride, sodium bicarbonate, sodium nitrate, sodium nitrite, etc.
  • Inorganic acid sodium salts, organic acid sodium salts such as sodium tartrate (monosodium tartrate, disodium tartrate), sodium malate, sodium citrate, sodium gluconate, etc. are used for dehydration during centrifugal molding of concrete. From the viewpoint of properties and compaction properties, sodium sulfate and/or sodium gluconate are preferred.
  • the total amount of water-soluble sodium salt is preferably 0.6 parts by mass or less, and 0.1 to 0.4 parts by mass, from the viewpoint of the total alkali content of concrete and the influence on setting. It is more preferable that
  • cement composition contains the cement admixture of this embodiment in cement.
  • Portland cement there are various types of Portland cement such as normal, early strength, and super early strength, various mixed cements made by mixing blast furnace slag, fly ash, etc. with these Portland cements, moderate heat Portland cement, and B-Lite cement. Can be mentioned.
  • the cement admixture of this embodiment is preferably 1 to 30 parts by mass, more preferably 4 to 20 parts by mass, from the viewpoint of strength development. .
  • aggregates such as sand and gravel, setting accelerators, AE agents, thickeners, cement rapid hardening materials, cement expansion materials, rust preventives, antifreeze agents, polymers, etc.
  • the object of the present invention is to use one or more of emulsions, clay minerals such as bentonite and montmorillonite, ion exchangers such as zeolite, hydrotalcite, and hydrocalumite, inorganic phosphates, and boric acid. may be contained within a range that does not substantially inhibit.
  • a water reducing agent such as a water reducing agent, an AE water reducing agent, a high performance water reducing agent, a high performance AE water reducing agent, etc. may be contained, but the content thereof is 6 parts by mass in 100 parts by mass of the cement composition of this embodiment. It is preferably at most 3 parts by mass, more preferably at most 3 parts by mass. Since the cement composition of this embodiment includes the cement admixture of this embodiment, the amount of water reducing agent used can be reduced.
  • any existing stirring device can be used, such as a tilting mixer, an omni mixer, a V-type mixer, a Henschel mixer, etc. , Nauta mixer, etc. can be used.
  • each material may be mixed at the time of construction, or some or all of the materials may be mixed in advance.
  • the water/cement ratio is preferably 30% by mass or less, more preferably 15 to 25% by mass. Since it contains the cement admixture of this embodiment, it can be used at a low water/cement ratio as described above.
  • a cement admixture was prepared by mixing pozzolanic fine powder, gypsum, water-soluble calcium salt, and water-soluble sodium salt in the mass proportions shown in Table 1.
  • ⁇ Measurement method> The following measurements were performed. The results are shown in Table 1.
  • the cement admixture of the present invention can be suitably used in the fields of civil engineering and construction, especially when it is desired to reduce the water/cement ratio.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Provided is a cement admixture containing: a pozzolanic fine powder; gypsum; and one or more kinds of water-soluble calcium salts of an inorganic acid or an organic acid, excluding gypsum.

Description

セメント混和材、セメント組成物Cement admixtures, cement compositions
　本発明は、セメント混和材、セメント組成物に関する。 The present invention relates to cement admixtures and cement compositions.
　セメントやコンクリートの強度は、水／セメント比に依存するところが大きく、水／セメント比をできる限り小さくするために、減水剤や高性能減水剤を使用することが現在では一般的に普及している。 The strength of cement and concrete largely depends on the water/cement ratio, and it is now common to use water reducers and high-performance water reducers to reduce the water/cement ratio as much as possible. .
　そのような中、近年のポリカルボン酸塩系減水剤の減水率は飛躍的に向上している。その結果、電気炉によるシリコン合金や金属シリコン製造時に発生するシリカフューム、微粉炭焚き火力発電所から副生するフライアッシュ、２０μｍ又は１０μｍ以下に分級した分級フライアッシュ、ガス化した石炭を燃焼させる火力発電所から副生する石炭ガス化フライアッシュ、及びその他の球形のポゾラン質微粉末を適量併用することにより、水結合材比を極限まで下げることが可能となり、設計基準強度１００～１５０Ｎ／ｍｍ２の、高流動コンクリートによる建築柱や梁等が容易に製造、施工されるようになっている。さらに、高強度コンクリート製品であるパイルも、従来の設計基準強度８０～８５Ｎ／ｍｍ２に対して、１０５～１２３Ｎ／ｍｍ２の遠心力成形供試体が開発され、日本建築センターの認可が得られるようになっている（例えば、特許文献１、２参照）。 Under these circumstances, the water reduction rate of polycarboxylate water reducing agents has improved dramatically in recent years. As a result, silica fume generated during the production of silicon alloys and metal silicon using electric furnaces, fly ash as a by-product from pulverized coal-fired power plants, classified fly ash classified to 20 μm or less than 10 μm, and thermal power generation that burns gasified coal. By using an appropriate amount of coal gasified fly ash, which is a by-product from coal gasification, and other spherical pozzolanic fine powder, it is possible to reduce the water-binder ratio to the maximum, achieving a design standard strength of 100 to 150 N/ mm2. , architectural columns and beams made of high-flow concrete can now be easily manufactured and constructed. Furthermore, for piles, which are high-strength concrete products, a centrifugally formed specimen with a strength of 105 to 123 N/mm 2 was developed, compared to the conventional design standard strength of 80 to 85 N/mm 2 , and was approved by the Japan Building Center. (For example, see Patent Documents 1 and 2).
特開昭６３－００８２４８号公報Japanese Patent Application Laid-open No. 63-008248 特開２００１－１９５２７号公報Japanese Patent Application Publication No. 2001-19527
　しかしながら、セメントや、セメントにポゾラン質微粉末を含んだ結合材により、ポリカルボン酸塩系減水剤を添加したモルタル又はコンクリートの流動性が顕著に変わったり、粒子の分散が不充分で反応率が低下して強度が低下したりすることがあった。 However, due to cement or a binder containing pozzolanic fine powder in cement, the fluidity of mortar or concrete containing polycarboxylate-based water reducing agents may change markedly, or the reaction rate may be reduced due to insufficient dispersion of particles. This may cause the strength to decrease.
　同様にコンクリートを高強度化または早強化を図る場合、一般的に水／セメント比を低減する方法があるが、この場合、粘性が増し、作業性が悪くなる。そのため減水剤や高性能減水剤を用いる場合があるが、多量に使用した場合、セメントの水和が阻害され強度発現性に乏しくなる。また、ギ酸カルシウムや塩化カルシウムなどの塩類を用いてセメントの水和反応を促進する方法もあるが、スランプロスが大きく、作業時間の確保が難しい。 Similarly, when trying to strengthen or quickly strengthen concrete, there is generally a method of reducing the water/cement ratio, but in this case, viscosity increases and workability deteriorates. For this reason, water reducing agents and high-performance water reducing agents are sometimes used, but if used in large quantities, hydration of the cement is inhibited and strength development becomes poor. Another method is to use salts such as calcium formate and calcium chloride to promote the hydration reaction of cement, but this method results in large slump losses and makes it difficult to secure enough working time.
　以上から、本発明は、水／セメント比が小さい場合でも、減水剤又は高性能減水剤を多量に使用することなく、強度発現性を保持しつつ、良好な流動性を発現させることが可能なセメント混和材を提供することを目的とする。 From the above, the present invention makes it possible to develop good fluidity while maintaining strength development even when the water/cement ratio is small, without using a large amount of water reducing agent or high performance water reducing agent. The purpose is to provide cement admixtures.
　上記課題を解決すべく鋭意検討した結果、本発明者らは下記本発明に想到し当該課題を解決できることを見出した。すなわち本発明は下記のとおりである。 As a result of intensive studies to solve the above problems, the present inventors came up with the following invention and found that the problems could be solved. That is, the present invention is as follows.
［１］　ポゾラン質微粉末、石膏、および石膏を除く無機酸または有機酸の水溶性のカルシウム塩を一種以上含有してなるセメント混和材。
［２］　更に無機酸または有機酸の水溶性ナトリウム塩を一種以上含有してなる［１］記載のセメント混和材。
［３］　前記無機酸または有機酸の水溶性のカルシウム塩が、酢酸カルシウムである［１］又は［２］記載のセメント混和材。
［４］　前記酢酸カルシウムの平均粒径が５～１００μｍである［３］記載のセメント混和材。
［５］　前記無機酸または有機酸の水溶性ナトリウム塩が硫酸ナトリウムおよび／またはグルコン酸ナトリウムである［２］～［４］のいずれかに記載のセメント混和材。
［６］　セメント混和材１００質量部中、前記酢酸カルシウムが１～１０質量部である［３］～［５］のいずれかに記載のセメント混和材。
［７］　セメント混和材１００質量部中、水溶性ナトリウム塩の総量が０．６質量部以下である［２］～［６］のいずれかに記載のセメント混和材。
［８］　［１］～［７］のいずれかに記載のセメント混和材をセメントに含有してなるセメント組成物。 [1] A cement admixture comprising pozzolanic fine powder, gypsum, and one or more water-soluble calcium salts of inorganic or organic acids other than gypsum.
[2] The cement admixture according to [1], further comprising one or more water-soluble sodium salts of inorganic or organic acids.
[3] The cement admixture according to [1] or [2], wherein the water-soluble calcium salt of an inorganic or organic acid is calcium acetate.
[4] The cement admixture according to [3], wherein the calcium acetate has an average particle size of 5 to 100 μm.
[5] The cement admixture according to any one of [2] to [4], wherein the water-soluble sodium salt of the inorganic or organic acid is sodium sulfate and/or sodium gluconate.
[6] The cement admixture according to any one of [3] to [5], wherein the calcium acetate is 1 to 10 parts by mass in 100 parts by mass of the cement admixture.
[7] The cement admixture according to any one of [2] to [6], wherein the total amount of water-soluble sodium salt is 0.6 parts by mass or less in 100 parts by mass of the cement admixture.
[8] A cement composition comprising the cement admixture according to any one of [1] to [7].
　本発明によれば、水／セメント比が小さい場合でも、減水剤又は高性能減水剤を多量に使用することなく、強度発現性を保持しつつ、良好な流動性を発現させることが可能なセメント混和材を提供することができる。 According to the present invention, even when the water/cement ratio is small, the cement can exhibit good fluidity while maintaining strength without using a large amount of water reducing agent or high performance water reducing agent. Admixtures can be provided.
　以下、本発明に係る一実施形態（以下、「本実施形態」ということがある）について、説明する。
［セメント混和材］
　本実施形態に係るセメント混和材は、ポゾラン質微粉末、石膏、および石膏を除く無機酸または有機酸の水溶性のカルシウム塩（以下、「水溶性カルシウム塩」ということがある）を一種以上含有してなる。ポゾラン質微粉末及び石膏により強度発現性が発現し、さらに、水溶性カルシウム塩が存在することで良好な流動性が発現する。本発明においては、強度発現と流動性との両立をこれらの配合により達成した。 Hereinafter, one embodiment (hereinafter sometimes referred to as "this embodiment") according to the present invention will be described.
[Cement admixture]
The cement admixture according to the present embodiment contains one or more types of pozzolanic fine powder, gypsum, and water-soluble calcium salts of inorganic or organic acids other than gypsum (hereinafter sometimes referred to as "water-soluble calcium salts"). It will be done. The pozzolanic fine powder and gypsum provide strength, and the presence of the water-soluble calcium salt provides good fluidity. In the present invention, both strength development and fluidity were achieved through these combinations.
（ポゾラン質微粉末）
　ポゾラン質微粉末としては、電気炉によるシリコン合金や金属シリコン製造時に発生するシリカフューム、ジルコニア起源のシリカフューム、微粉炭焚き火力発電所から副生するフライアッシュを分級した分級フライアッシュ、ガス化した石炭を燃焼させる火力発電所から副生する石炭ガス化フライアッシュ、溶融シリカ微粉末、及び、合成したエアロジル等が挙げられ、そのうちの１種又は２種以上が使用可能である。 (Pozzolanic fine powder)
Pozzolanic fine powders include silica fume generated during the production of silicon alloys and metal silicon in electric furnaces, silica fume derived from zirconia, classified fly ash obtained by classifying fly ash produced by pulverized coal-fired power plants, and gasified coal. Coal gasification fly ash, fused silica fine powder, and synthesized aerosil, which are by-produced from thermal power plants that are burned, can be used, and one or more of them can be used.
　その他に、粘土鉱物を熱処理した白土、メタカオリン等の微粉末、非晶質ＳｉＯ２が主成分のケイ化木の焼却灰、ケイソウ土、及びオパール質シリカ粉末等のポゾラン質微粉末を、強度を高めるために適宜使用できる。なお、ポゾラン物質のなかでもシリカフュームは流動性の向上と強度の両方を改善するので最も好ましいものである。 In addition, we use white clay heat-treated clay minerals, fine powders such as metakaolin, incinerated ash of silicified wood whose main component is amorphous SiO2 , diatomaceous earth, and pozzolanic fine powders such as opalescent silica powder to improve strength. Can be used as appropriate to enhance Incidentally, among the pozzolan substances, silica fume is the most preferable because it improves both fluidity and strength.
　分級フライアッシュ、石炭ガス化フライアッシュ、及び溶融シリカ微粉末等は流動性の向上等は期待できるが、シリカフュームのような強度的効果は期待できない。しかしながら、シリカフュームと、分級フライアッシュや溶融シリカなどの球形ポゾラン物微粉末との少量の併用は、より流動性を助長するだけでなく、相乗的に強度も高めるので特に好ましい。 Classified fly ash, coal gasified fly ash, fused silica fine powder, etc. can be expected to improve fluidity, but they cannot be expected to have the same strength effects as silica fume. However, the combined use of a small amount of silica fume and a fine spherical pozzolanic powder such as classified fly ash or fused silica is particularly preferred because it not only further promotes fluidity but also synergistically increases strength.
　シリカフュームと分級フライアッシュ、石炭ガス化フライアッシュ、及び溶融シリカ微粉末の少なくともいずれかの非シリカフュームポゾラン質微粉末との質量混合比（シリカフューム／非シリカフュームポゾラン質微粉末）は、１／１～５／１であることが好ましく、２／１～４／１であることがより好ましい。１／１～５／１であることで、流動性と強度を良好にすることができる。 The mass mixing ratio of silica fume and at least one non-silica fume pozzolanic fine powder of classified fly ash, coal gasified fly ash, and fused silica fine powder (silica fume/non-silica fume pozzolanic fine powder) is 1/1 to 5. /1 is preferable, and 2/1 to 4/1 is more preferable. When the ratio is 1/1 to 5/1, fluidity and strength can be improved.
（石膏）
　石膏としては、無水石膏、二水石膏、半水石膏のいずれも使用できるが、高い強度を得る観点から、無水石膏が好ましい。石膏の粒度は良好な強度を得る観点から、ブレ－ン値で３，０００ｃｍ２／ｇ以上が好ましく、４，０００～８，０００ｃｍ２／ｇがより好ましい。 (plaster)
As the gypsum, any of anhydrite, dihydrate, and hemihydrate can be used, but anhydrite is preferable from the viewpoint of obtaining high strength. From the viewpoint of obtaining good strength, the particle size of gypsum is preferably 3,000 cm 2 /g or more in Blaine value, more preferably 4,000 to 8,000 cm 2 /g.
（石膏を除く無機酸または有機酸の水溶性のカルシウム塩）
　石膏を除く無機酸または有機酸の水溶性のカルシウム塩としては、水に溶解してカルシウムイオンを生じるような水溶性を有するものであればよく、酢酸、硝酸、亜硝酸、チオシアン酸、シアン酸、蟻酸等のカルシウム塩が挙げられる。具体的には、酢酸カルシウム、蟻酸カルシウム、及び硝酸カルシウム等が挙げられるが、水に対する溶解性、モルタル、コンクリートの流動性保持の観点から、酢酸カルシウムが好ましい。 (Water-soluble calcium salts of inorganic or organic acids excluding gypsum)
Water-soluble calcium salts of inorganic or organic acids other than gypsum may be water-soluble as long as they dissolve in water to produce calcium ions, such as acetic acid, nitric acid, nitrous acid, thiocyanic acid, and cyanic acid. , formic acid and other calcium salts. Specific examples include calcium acetate, calcium formate, and calcium nitrate, but calcium acetate is preferred from the viewpoint of solubility in water and maintenance of fluidity of mortar and concrete.
　水溶性カルシウム塩の平均粒径（メジアン径）は、溶解性、取り扱いのしやすさの観点から、５～１００μｍであることが好ましく、１０～８０μｍであることがより好ましい。当該平均粒径はレーザー回折式粒度分布測定装置により測定することができる。 The average particle diameter (median diameter) of the water-soluble calcium salt is preferably 5 to 100 μm, more preferably 10 to 80 μm, from the viewpoint of solubility and ease of handling. The average particle size can be measured using a laser diffraction particle size distribution analyzer.
　セメント混和材１００質量部中、ポゾラン質微粉末は、強度発現性および流動性の観点から、５０～９０質量部であることがより好ましい。
　石膏は、強度発現性の観点から、１～３０質量部であることが好ましく、５～２５質量部であることがより好ましい。
　水溶性カルシウム塩は、流動性付与の観点から、１～１０質量部であることが好ましく、３～７質量部であることがより好ましい。
　上記３成分の複合効果を充分に発揮させる観点から、セメント混和材１００質量部中、ポゾラン質微粉末、石膏、及び水溶性カルシウム塩の合計は、９０質量部以上が好ましく、９５質量部以上がより好ましく、９９．４質量部以上がさらに好ましい。 In 100 parts by mass of the cement admixture, the amount of pozzolanic fine powder is preferably 50 to 90 parts by mass from the viewpoint of strength development and fluidity.
From the viewpoint of strength development, the amount of gypsum is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass.
From the viewpoint of imparting fluidity, the water-soluble calcium salt is preferably 1 to 10 parts by mass, more preferably 3 to 7 parts by mass.
From the viewpoint of fully exhibiting the combined effect of the above three components, the total amount of pozzolanic fine powder, gypsum, and water-soluble calcium salt in 100 parts by mass of the cement admixture is preferably 90 parts by mass or more, and 95 parts by mass or more. More preferably, it is 99.4 parts by mass or more.
（無機酸または有機酸の水溶性ナトリウム塩）
　本実施形態においては、遠心成型における成型性の観点から、無機酸または有機酸の水溶性ナトリウム塩（以下、「水溶性ナトリウム塩」ということがある）を含有してもよい。 (Water-soluble sodium salt of inorganic or organic acid)
In this embodiment, from the viewpoint of moldability in centrifugal molding, a water-soluble sodium salt of an inorganic or organic acid (hereinafter sometimes referred to as "water-soluble sodium salt") may be contained.
　水溶性ナトリウム塩は、水に溶解してナトリウムイオンを生じるような水溶性を有するものであればよく、例えば、炭酸ナトリウム、硫酸ナトリウム、塩化ナトリウム、炭酸水素ナトリウム、硝酸ナトリウム、亜硝酸ナトリウム等の無機酸ナトリウム塩や、酒石酸ナトリウム類（酒石酸一ナトリウム、酒石酸二ナトリウム）、リンゴ酸ナトリウム、クエン酸ナトリウム類、グルコン酸ナトリウム等の有機酸ナトリウム塩等が挙げられ、コンクリートの遠心成形時における、脱水性、締固め性の観点から、硫酸ナトリウムおよび／またはグルコン酸ナトリウムであることが好ましい。 The water-soluble sodium salt may be any salt having water solubility such that it dissolves in water to generate sodium ions, such as sodium carbonate, sodium sulfate, sodium chloride, sodium bicarbonate, sodium nitrate, sodium nitrite, etc. Inorganic acid sodium salts, organic acid sodium salts such as sodium tartrate (monosodium tartrate, disodium tartrate), sodium malate, sodium citrate, sodium gluconate, etc. are used for dehydration during centrifugal molding of concrete. From the viewpoint of properties and compaction properties, sodium sulfate and/or sodium gluconate are preferred.
　セメント混和材１００質量部中、水溶性ナトリウム塩の総量はコンクリートのアルカリ総量、および凝結への影響の観点から、０．６質量部以下であることが好ましく、０．１～０．４質量部であることがより好ましい。 In 100 parts by mass of cement admixture, the total amount of water-soluble sodium salt is preferably 0.6 parts by mass or less, and 0.1 to 0.4 parts by mass, from the viewpoint of the total alkali content of concrete and the influence on setting. It is more preferable that
［セメント組成物］
　本実施形態のセメント組成物は、本実施形態のセメント混和材をセメントに含有してなる。 [Cement composition]
The cement composition of this embodiment contains the cement admixture of this embodiment in cement.
　セメントとしては、普通、早強、及び超早強等の各種ポルトランドセメント、これらポルトランドセメントに、高炉スラグやフライアッシュ等を混合した各種混合セメント、中庸熱ポルトランドセメント、並びに、ビ－ライトセメント等が挙げられる。 As cement, there are various types of Portland cement such as normal, early strength, and super early strength, various mixed cements made by mixing blast furnace slag, fly ash, etc. with these Portland cements, moderate heat Portland cement, and B-Lite cement. Can be mentioned.
　本実施形態のセメント組成物１００質量部中、本実施形態のセメント混和材は、強度発現性の観点から、１～３０質量部であることが好ましく、４～２０質量部であることがより好ましい。 In 100 parts by mass of the cement composition of this embodiment, the cement admixture of this embodiment is preferably 1 to 30 parts by mass, more preferably 4 to 20 parts by mass, from the viewpoint of strength development. .
　本実施形態のセメント組成物においては、その他に、砂、砂利等の骨材、凝結促進材、ＡＥ剤、増粘剤、セメント急硬材、セメント膨張材、防錆剤、防凍剤、高分子エマルジョン、ベントナイトやモンモリロナイト等の粘土鉱物、ゼオライト、ハイドロタルサイト、及びハイドロカルマイト等のイオン交換体、無機リン酸塩、並びに、ホウ酸等のうちの１種又は２種以上を本発明の目的を実質的に阻害しない範囲で含有してもよい。 In the cement composition of this embodiment, in addition, aggregates such as sand and gravel, setting accelerators, AE agents, thickeners, cement rapid hardening materials, cement expansion materials, rust preventives, antifreeze agents, polymers, etc. The object of the present invention is to use one or more of emulsions, clay minerals such as bentonite and montmorillonite, ion exchangers such as zeolite, hydrotalcite, and hydrocalumite, inorganic phosphates, and boric acid. may be contained within a range that does not substantially inhibit.
　なお、減水剤、ＡＥ減水剤、高性能減水剤、高性能ＡＥ減水剤等の減水剤を含有してもよいが、その含有量は、本実施形態のセメント組成物１００質量部中、６質量部以下であることが好ましく、３質量部以下であることがより好ましい。本実施形態のセメント組成物は、本実施形態のセメント混和材を含むため、減水剤の使用量を低減することができる。 Note that a water reducing agent such as a water reducing agent, an AE water reducing agent, a high performance water reducing agent, a high performance AE water reducing agent, etc. may be contained, but the content thereof is 6 parts by mass in 100 parts by mass of the cement composition of this embodiment. It is preferably at most 3 parts by mass, more preferably at most 3 parts by mass. Since the cement composition of this embodiment includes the cement admixture of this embodiment, the amount of water reducing agent used can be reduced.
　本実施形態のセメント混和材及びセメント組成物を製造する際の混合装置としては、既存のいかなる撹拌装置も使用可能であり、例えば、傾胴ミキサ－、オムニミキサ－、Ｖ型ミキサ－、ヘンシェルミキサ－、及びナウタ－ミキサ－等が使用可能である。また、混合は、それぞれの材料を施工時に混合してもよいし、あらかじめ一部を、あるいは全部を混合しておいても差し支えない。 As a mixing device for producing the cement admixture and cement composition of this embodiment, any existing stirring device can be used, such as a tilting mixer, an omni mixer, a V-type mixer, a Henschel mixer, etc. , Nauta mixer, etc. can be used. In addition, each material may be mixed at the time of construction, or some or all of the materials may be mixed in advance.
　本実施形態のセメント組成物が、モルタルやコンクリート場合の水／セメント比は３０質量％以下とすることが好ましく、１５～２５質量％とすることがより好ましい。本実施形態のセメント混和材を含有するため、上記のような低い水／セメント比で使用に供することができる。 When the cement composition of this embodiment is mortar or concrete, the water/cement ratio is preferably 30% by mass or less, more preferably 15 to 25% by mass. Since it contains the cement admixture of this embodiment, it can be used at a low water/cement ratio as described above.
　ポゾラン質微粉末、石膏、水溶性カルシウム塩、水溶性ナトリウム塩を表１に示す質量割合となるように混合してセメント混和材を作製した。作製したセメント混和材１３質量部、セメント８７質量部、減水剤１．０質量部、及び細骨材１５０質量部を混合してセメント組成物を作製し、水／セメント＝３０質量％となるように水を添加して、各種の測定を行った。 A cement admixture was prepared by mixing pozzolanic fine powder, gypsum, water-soluble calcium salt, and water-soluble sodium salt in the mass proportions shown in Table 1. A cement composition was prepared by mixing 13 parts by mass of the prepared cement admixture, 87 parts by mass of cement, 1.0 parts by mass of water reducing agent, and 150 parts by mass of fine aggregate, so that water/cement = 30% by mass. Water was added to the solution and various measurements were made.
＜使用材料＞
・ポゾラン質微粉末：シリカフューム（エルケム社製、顆粒状、密度２．４４ｇ／ｃｍ３）および分級フライアッシュ（２０μｍ以下に分級したもの、密度２．４４ｇ／ｃｍ３）を質量比で３：１とした混合品
・石膏：無水石膏、ブレーン５，０００ｃｍ２／ｇ、天然石膏
・水溶性カルシウム塩
　水溶性カルシウム塩Ａ：酢酸カルシウム一水和物（試薬）　メジアン径：５０μｍ
　水溶性カルシウム塩Ｂ：酢酸カルシウム一水和物（試薬）　メジアン径：３μｍ
　水溶性カルシウム塩Ｃ：酢酸カルシウム一水和物（試薬）　メジアン径：１０μｍ
　水溶性カルシウム塩Ｄ：酢酸カルシウム一水和物（試薬）　メジアン径：９０μｍ
　水溶性カルシウム塩Ｅ：酢酸カルシウム一水和物（試薬）　メジアン径：１１０μｍ
　水溶性カルシウム塩Ｆ：ギ酸カルシウム（試薬）
　水溶性カルシウム塩Ｇ：塩化カルシウム（試薬）
・水溶性ナトリウム塩
　水溶性ナトリウム塩Ａ：硫酸ナトリウム（試薬）
　水溶性ナトリウム塩Ｂ：グルコン酸ナトリウム（試薬）
　水溶性ナトリウム塩Ｃ：塩化ナトリウム（試薬）
・セメント：普通ポルトランドセメント（市販品）
・減水剤：ポリカルボン酸系減水剤
・細骨材：川砂
・水：水道水 <Materials used>
- Pozzolanic fine powder: 3:1 mass ratio of silica fume (manufactured by Elkem, granular, density 2.44 g/cm 3 ) and classified fly ash (classified to 20 μm or less, density 2.44 g/cm 3 ) Mixed product/Gypsum: Anhydrite, Blaine 5,000cm 2 /g, Natural gypsum/Water-soluble calcium salt Water-soluble calcium salt A: Calcium acetate monohydrate (reagent) Median diameter: 50 μm
Water-soluble calcium salt B: Calcium acetate monohydrate (reagent) Median diameter: 3 μm
Water-soluble calcium salt C: calcium acetate monohydrate (reagent) Median diameter: 10 μm
Water-soluble calcium salt D: Calcium acetate monohydrate (reagent) Median diameter: 90 μm
Water-soluble calcium salt E: Calcium acetate monohydrate (reagent) Median diameter: 110 μm
Water-soluble calcium salt F: Calcium formate (reagent)
Water-soluble calcium salt G: Calcium chloride (reagent)
・Water-soluble sodium salt Water-soluble sodium salt A: Sodium sulfate (reagent)
Water-soluble sodium salt B: Sodium gluconate (reagent)
Water-soluble sodium salt C: Sodium chloride (reagent)
・Cement: Ordinary Portland cement (commercially available)
・Water reducer: Polycarboxylic acid water reducer ・Fine aggregate: River sand ・Water: Tap water
＜測定方法＞
　下記測定を行った。結果を表１に示す。
・モルタルフロー：ＪＩＳ　Ｒ５２０１に準じ、抜き上げたときのフロー値を測定した。ただし、フローテーブルの上に５０×５０×２ｃｍのアクリルガラス板を乗せてその上で落下振動を与えずに行った。測定のタイミングはフローコーンを抜いてから３分後とした。
・圧縮強度：ＪＳＣＥ－Ｇ５０５に準じた。供試体寸法は、φ５×１０ｃｍとし、蒸気養生を８５℃で５時間かけたのち、材齢１日の圧縮強度を測定した。 <Measurement method>
The following measurements were performed. The results are shown in Table 1.
- Mortar flow: The flow value when the mortar was pulled up was measured according to JIS R5201. However, an acrylic glass plate of 50 x 50 x 2 cm was placed on the flow table, and the test was carried out without applying any drop vibration. The measurement timing was 3 minutes after the flow cone was removed.
・Compressive strength: According to JSCE-G505. The specimen size was φ5×10 cm, and after steam curing at 85° C. for 5 hours, the compressive strength of the material at 1 day old was measured.
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000001
 
　本発明のセメント混和材は、土木、建築分野で、特に水／セメント比を小ささくしたい場合でも好適に使用できる。 The cement admixture of the present invention can be suitably used in the fields of civil engineering and construction, especially when it is desired to reduce the water/cement ratio.

Claims (8)

  1. 　ポゾラン質微粉末、石膏、および石膏を除く無機酸または有機酸の水溶性のカルシウム塩を一種以上含有してなるセメント混和材。 A cement admixture containing pozzolanic fine powder, gypsum, and one or more water-soluble calcium salts of inorganic or organic acids other than gypsum.
  2. 　更に無機酸または有機酸の水溶性ナトリウム塩を一種以上含有してなる請求項１記載のセメント混和材。 The cement admixture according to claim 1, further comprising one or more water-soluble sodium salts of inorganic or organic acids.
  3. 　前記無機酸または有機酸の水溶性のカルシウム塩が、酢酸カルシウムである請求項１記載のセメント混和材。 The cement admixture according to claim 1, wherein the water-soluble calcium salt of an inorganic or organic acid is calcium acetate.
  4. 　前記酢酸カルシウムの平均粒径が５～１００μｍである請求項３記載のセメント混和材。 The cement admixture according to claim 3, wherein the calcium acetate has an average particle size of 5 to 100 μm.
  5. 　前記無機酸または有機酸の水溶性ナトリウム塩が硫酸ナトリウムおよび／またはグルコン酸ナトリウムである請求項２に記載のセメント混和材。 The cement admixture according to claim 2, wherein the water-soluble sodium salt of the inorganic or organic acid is sodium sulfate and/or sodium gluconate.
  6. 　セメント混和材１００質量部中、前記酢酸カルシウムが１～１０質量部である請求項３に記載のセメント混和材。 The cement admixture according to claim 3, wherein the calcium acetate is 1 to 10 parts by mass in 100 parts by mass of the cement admixture.
  7. 　セメント混和材１００質量部中、水溶性ナトリウム塩の総量が０．６質量部以下である請求項２に記載のセメント混和材。 The cement admixture according to claim 2, wherein the total amount of water-soluble sodium salts is 0.6 parts by mass or less in 100 parts by mass of the cement admixture.
  8. 　請求項１～７のいずれか１項に記載のセメント混和材をセメントに含有してなるセメント組成物。 A cement composition comprising the cement admixture according to any one of claims 1 to 7 in cement.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08301642A (en) * 1995-05-09 1996-11-19 Denki Kagaku Kogyo Kk Cement admixture and cement composition
JP2000281412A (en) * 1999-03-30 2000-10-10 Denki Kagaku Kogyo Kk Cement admixture and cement composition
JP2001039758A (en) * 1999-07-28 2001-02-13 Denki Kagaku Kogyo Kk Low environmental load type ultra high early strength concrete
JP2012201532A (en) * 2011-03-24 2012-10-22 Ube Industries Ltd High fluidity mortar composition
JP2014015356A (en) * 2012-07-10 2014-01-30 Denki Kagaku Kogyo Kk Cement admixture, cement composition, and cement mortar using them
JP2015127284A (en) * 2013-12-28 2015-07-09 太平洋マテリアル株式会社 Splay mortar
JP2015127283A (en) * 2013-12-28 2015-07-09 太平洋マテリアル株式会社 Polymer cement grout mortar
JP2020152634A (en) * 2019-03-15 2020-09-24 大成建設株式会社 Hydraulic composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08301642A (en) * 1995-05-09 1996-11-19 Denki Kagaku Kogyo Kk Cement admixture and cement composition
JP2000281412A (en) * 1999-03-30 2000-10-10 Denki Kagaku Kogyo Kk Cement admixture and cement composition
JP2001039758A (en) * 1999-07-28 2001-02-13 Denki Kagaku Kogyo Kk Low environmental load type ultra high early strength concrete
JP2012201532A (en) * 2011-03-24 2012-10-22 Ube Industries Ltd High fluidity mortar composition
JP2014015356A (en) * 2012-07-10 2014-01-30 Denki Kagaku Kogyo Kk Cement admixture, cement composition, and cement mortar using them
JP2015127284A (en) * 2013-12-28 2015-07-09 太平洋マテリアル株式会社 Splay mortar
JP2015127283A (en) * 2013-12-28 2015-07-09 太平洋マテリアル株式会社 Polymer cement grout mortar
JP2020152634A (en) * 2019-03-15 2020-09-24 大成建設株式会社 Hydraulic composition

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