WO2023171770A1 - Cement composition - Google Patents

Cement composition Download PDF

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WO2023171770A1
WO2023171770A1 PCT/JP2023/009168 JP2023009168W WO2023171770A1 WO 2023171770 A1 WO2023171770 A1 WO 2023171770A1 JP 2023009168 W JP2023009168 W JP 2023009168W WO 2023171770 A1 WO2023171770 A1 WO 2023171770A1
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Prior art keywords
cement
mass
cement composition
parts
gypsum
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PCT/JP2023/009168
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French (fr)
Japanese (ja)
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聖一 寺崎
泰一郎 森
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デンカ株式会社
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Priority to JP2023531695A priority Critical patent/JPWO2023171770A1/ja
Publication of WO2023171770A1 publication Critical patent/WO2023171770A1/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
    • 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
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
    • 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 a cement composition.
  • Patent Document 1 is a blend of Portland cement with calcium aluminate, anhydrous gypsum, and lithium carbonate.
  • Patent Document 1 does not discuss the amount of tricalcium aluminate in cement, and therefore, it was necessary to further add lithium carbonate to ordinary Portland cement in order to promote the reaction of calcium aluminate.
  • An object of the present invention is to provide a cement composition that can exhibit high initial strength by examining the amount of tricalcium aluminate in cement.
  • the present invention is as follows.
  • the cement composition according to the present embodiment includes cement, amorphous calcium aluminate, and gypsum, and contains 5 to 10.5 of tricalcium aluminate (hereinafter sometimes referred to as "C 3 A") in the cement. Including mass%. It is inferred that by including these, it is possible to improve the rapid hardening property, especially the initial strength shown in the compressive strength after 3 hours. Further, it is presumed that the tricalcium aluminate present in a predetermined amount in the cement efficiently exhibits good rapid hardening properties.
  • amorphous calcium aluminate (Amorphous calcium aluminate)
  • the amorphous calcium aluminate (hereinafter sometimes referred to as "amorphous CA") used in this embodiment is made by mixing raw materials containing calcia and raw materials containing alumina, heating and melting the mixture, and then rapidly cooling the mixture. It is a general term for amorphous substances with hydration activity, which are mainly composed of CaO and Al 2 O 3 and have a vitrification rate of 70% or more.
  • the vitrification rate of the amorphous calcium aluminate is preferably 70% or more, more preferably 80% or more.
  • Amorphous calcium aluminate can be obtained, for example, by bringing a clinker of calcium aluminate melted in an electric furnace into contact with compressed air or water and rapidly cooling it.
  • raw materials containing calcia include calcium carbonate such as limestone and shells, calcium hydroxide such as slaked lime, and calcium oxide such as quicklime.
  • examples of raw materials containing alumina include bauxite and industrial byproducts called aluminum residual ash.
  • the molar ratio of CaO to Al 2 O 3 in the amorphous calcium aluminate should be 1.65 to 1.85 from the viewpoint of hydration activity and strength development. is preferable, and 1.7 to 1.8 is more preferable.
  • the target material is annealed at 1000°C for 2 hours, and then slowly cooled at a cooling rate of 5°C per minute to crystallize it. Then, the crystallized material is measured by powder X-ray diffraction to determine the area S of the main peak of the crystalline mineral. Next, the main peak area S 0 of the crystal of the substance before annealing is determined, and the vitrification rate X is determined using the following formula.
  • X (%) 100 x (1-S 0 /S)
  • the fineness of the amorphous calcium aluminate is preferably 3000 to 9000 cm 2 /g, more preferably 4000 to 8000 cm 2 /g in terms of Blaine specific surface area (hereinafter sometimes referred to as "Blaine value"). preferable.
  • Blaine value Blaine specific surface area
  • the Blaine value is 3000 cm 2 /g or more, the rapid hardening, initial strength development, etc. of the cement composition are likely to be improved.
  • the Blaine value is 9000 cm 2 /g or less, a decrease in workability can be prevented while maintaining good effects.
  • the amorphous calcium aluminate preferably has a loss on ignition of 0.2 to 1.5%, more preferably 0.5 to 1%.
  • the loss on ignition is 0.2 to 1.5%, it becomes easier to ensure fluidity and pot life, and it becomes easier to obtain good strength development.
  • the method for achieving an ignition loss of 0.2 to 1.5% is not particularly limited, but examples include a method of supplying moisture or moisture, a method of supplying carbon dioxide gas, and the like.
  • the loss on ignition can be determined by the method specified in JIS R 5202 (Method of Chemical Analysis of Cement), Method for Quantifying Loss on Ignition.
  • Gypsum is used from the viewpoint of setting properties and strength development properties.
  • Gypsum is a general term for anhydrous, hemihydrous, and dihydric, and is not particularly limited, but from the viewpoint of initial strength development, it is preferable to use anhydrous gypsum or semihydrous gypsum, and it is more preferable to use anhydrous gypsum.
  • the particle size of the gypsum is preferably a Blaine value of 3000 cm 2 /g or more, more preferably 3000 to 9000 cm 2 /g, and 4000 to 8000 cm 2 /g, considering the initial strength development of the cement composition. It is more preferable that
  • the content of gypsum is preferably 100 to 200 parts by mass, more preferably 150 to 200 parts by mass, based on 100 parts by mass of amorphous calcium aluminate.
  • amount of gypsum is 100 parts by mass or more, it is easy to promote long-term strength development of the cement composition, while when it is 200 parts by mass or less, delay in initial setting is prevented and the initial strength development is improved. Can be done.
  • the rapid hardening component consisting of amorphous calcium aluminate and gypsum is preferably 10 to 35 parts by mass, more preferably 15 to 25 parts by mass out of the total 100 parts by mass of the cement composition.
  • the amount is 10 parts by mass or more, it is possible to improve initial strength development, and when it is 35 parts by mass or less, good workability and long-term strength can be easily obtained.
  • the cement according to this embodiment contains 5 to 10.5% by mass of tricalcium aluminate. If the C 3 A content is less than 5% by mass, the time from the start of setting to hardening becomes longer, resulting in lower initial strength development. If it exceeds 10.5% by mass, the time from the start of setting to hardening will be shortened, but the initial strength development will be low.
  • the amount of tricalcium aluminate is preferably 6 to 10.5% by mass, more preferably 7 to 10.5% by mass.
  • the above cement can be prepared by using various cements alone or in combination so that the content of tricalcium aluminate is 5 to 10.5% by mass.
  • the types of cement used for preparation include ordinary, early strength, ultra early strength, moderate heat, low heat, and sulfate-resistant Portland cement; these Portland cements are mixed with blast furnace slag, fly ash, or fine limestone powder. Examples include various mixed cements.
  • the cement composition of this embodiment preferably further contains a setting modifier from the viewpoint of ensuring sufficient working time and satisfying initial strength development.
  • the above-mentioned setting modifier is not particularly limited. Specific examples thereof include oxycarboxylic acids or salts thereof such as citric acid, tartaric acid, malic acid, gluconic acid, and succinic acid or their salts such as sodium, potassium, calcium, magnesium, ammonium, and aluminum; , alkali metal carbonates of sodium carbonate, potassium carbonate, and lithium carbonate (hereinafter referred to as alkali carbonates), ammonium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, and carbonates such as ammonium bicarbonate. , one or more of these can be used.
  • oxycarboxylic acids or a salt thereof such as citric acid, tartaric acid, malic acid, gluconic acid, and succinic acid or their salts such as sodium, potassium, calcium, magnesium, ammonium, and aluminum
  • the amount of setting modifier used is determined based on 100 parts by mass of the cement composition consisting of cement, amorphous calcium aluminate, and gypsum according to this embodiment, from the viewpoint of ensuring sufficient working time and satisfying initial strength development.
  • the amount is preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight.
  • the total of each component of cement, amorphous calcium aluminate, and gypsum is 100% by mass or less, and from the viewpoint of fully exhibiting these effects, 90% by mass It is preferably at least 95% by mass, more preferably at least 98% by mass, even more preferably at least 99.9% by mass.
  • each material when producing a cement composition is not particularly limited, and each material may be mixed at the time of construction, or some or all of the materials may be mixed in advance. There is no harm in leaving it as is.
  • the mixing device any existing device can be used, such as a tilting mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer.
  • a cement composition was prepared by mixing each of the prepared trial cements, calcium aluminate (CA-1 or crystalline CA), and various types of gypsum in the proportions shown in Table 2, and a setting modifier was added to 100 parts of the cement composition. One part was mixed.
  • a mortar was prepared by adding 200 parts of fine aggregate to 100 parts of the cement composition, adding 40 parts of water to 100 parts of the cement composition, and kneading the mixture. The compressive strength of the mortar was measured. The compressive strength was measured in accordance with JIS R 5201 by preparing a 4 x 4 x 16 cm test piece and measuring it after 3 hours, 1 day, and 28 days. The results are shown in Table 1.
  • Calcium aluminate CA-1 (amorphous): CaO/Al 2 O 3 molar ratio 1.78, vitrification rate 91%, Blaine value 5900 cm 2 /g, loss on ignition: 0.9% Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.7 to 1.8, melted at 1650° C., then rapidly cooled and pulverized.
  • ⁇ Crystalline CA (crystalline): CaO/Al 2 O 3 molar ratio 1.77, vitrification rate 0%, Blaine value 6000 cm 2 /g Limestone was used as a calcia source and bauxite was used as an alumina source. After firing at 1450° C., it was slowly cooled and pulverized.
  • Gypsum/anhydrous gypsum Commercially available product, Blaine value 5600 cm 2 /g ⁇ Hemihydrate gypsum: Commercial product, Blaine value 5700cm 2 /g ⁇ Dihydrate gypsum: Commercial product, Blaine value 5500cm 2 /g (3) A mixture of 25 parts by mass of citric acid, a first-grade reagent, and 75 parts by mass of potassium carbonate, a first-grade reagent (4) Fine aggregate, silica sand: Commercially available product, No. 3: 30 parts by mass, No. 5 : 40 parts by mass, No. 6: 30 parts by mass mixture
  • Example 2 Experiment No. of Experimental Example 1.
  • a cement composition was prepared in the same manner as in Experimental Example 1, except that each of the following CA-2 to CA-5 was used instead of CA-1, and mortar was prepared to increase the compressive strength. It was measured. The results are shown in Table 3.
  • ⁇ CA-3 (amorphous): CaO/Al 2 O 3 molar ratio 1.67, vitrification rate 92%, Blaine value 5800 cm 2 /g, loss on ignition: 0.9% Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.6 to 1.7, melted at 1650° C., then rapidly cooled and pulverized.
  • ⁇ CA-4 (amorphous): CaO/Al 2 O 3 molar ratio 1.83, vitrification rate 90%, Blaine value 6070 cm 2 /g, loss on ignition: 0.9% Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.8 to 1.9, melted at 1650° C., then rapidly cooled and pulverized.
  • ⁇ CA-5 (amorphous): CaO/Al 2 O 3 molar ratio 1.96, vitrification rate 91%, Blaine value 6240 cm 2 /g, loss on ignition: 0.9% Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.9 to 2.0, melted at 1650° C., then rapidly cooled and pulverized.
  • the present invention can be widely used in the civil engineering and construction fields, etc., in situations where early use is required.

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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)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

A cement composition comprising cement, amorphous calcium aluminate, and gypsum, the cement containing 5-10.5 mass% of tricalcium aluminate (C3A).

Description

セメント組成物cement composition
　本発明は、セメント組成物に関する。 The present invention relates to a cement composition.
　世界各地で急速にインフラ整備が進められており、用いられるセメントの生産量が増加している。インフラ整備が急がれる国においては、使用する材料として早期に供用可能とする材料が求められている。 Infrastructure development is progressing rapidly around the world, and the production volume of cement used is increasing. In countries where infrastructure development is urgent, there is a need for materials that can be put into use quickly.
　そこで、最近では、急硬性セメント組成物の改良が検討され、ポルトランドセメントに、カルシウムアルミネート、無水セッコウ、及び炭酸リチウムを配合した超速硬セメント（特許文献１参照）が提案されている。 Therefore, recently, improvements in rapidly hardening cement compositions have been studied, and an ultra-fast hardening cement (see Patent Document 1) has been proposed, which is a blend of Portland cement with calcium aluminate, anhydrous gypsum, and lithium carbonate.
特開平０１－２９０５４３号公報Japanese Patent Application Publication No. 01-290543
　しかし、特許文献１にはセメント中のアルミン酸三カルシウムの量についての検討は無く、そのため、カルシウムアルミネートの反応を促進するために、通常のポルトランドセメントにさらに炭酸リチウムを添加する必要があった。
　本発明は、セメント中のアルミン酸三カルシウムの量を検討することで、高い初期強度を発現できるセメント組成物を提供することを目的とする。 However, Patent Document 1 does not discuss the amount of tricalcium aluminate in cement, and therefore, it was necessary to further add lithium carbonate to ordinary Portland cement in order to promote the reaction of calcium aluminate. .
An object of the present invention is to provide a cement composition that can exhibit high initial strength by examining the amount of tricalcium aluminate in cement.
　上記課題に鑑み鋭意検討した結果、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 in view of 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］　セメント、非晶質カルシウムアルミネート、及びセッコウを含み、前記セメント中にアルミン酸三カルシウムを５～１０．５質量％含むセメント組成物。
［２］　前記非晶質カルシウムアルミネートのＣａＯとＡｌ２Ｏ３とのモル比（ＣａＯ／Ａｌ２Ｏ３）が１．６５～１．８５である［１］に記載のセメント組成物。
［３］　前記非晶質カルシウムアルミネート１００質量部に対して前記セッコウが１００～２００質量部である［１］又は［２］に記載のセメント組成物。
［４］　さらに、凝結調整剤を含む［１］～［３］のいずれかに記載のセメント組成物。 [1] A cement composition containing cement, amorphous calcium aluminate, and gypsum, and containing 5 to 10.5% by mass of tricalcium aluminate in the cement.
[2] The cement composition according to [1], wherein the amorphous calcium aluminate has a molar ratio of CaO to Al 2 O 3 (CaO/Al 2 O 3 ) of 1.65 to 1.85.
[3] The cement composition according to [1] or [2], wherein the gypsum is contained in an amount of 100 to 200 parts by mass based on 100 parts by mass of the amorphous calcium aluminate.
[4] The cement composition according to any one of [1] to [3], further comprising a setting modifier.
　本発明によれば、高い初期強度を発現できるセメント組成物を提供することができる。 According to the present invention, it is possible to provide a cement composition that can exhibit high initial strength.
　以下、本発明の一実施形態（本実施形態）を詳細に説明する。なお、本明細書における部や％は、特に規定しない限り質量基準で示す。 Hereinafter, one embodiment of the present invention (this embodiment) will be described in detail. Note that parts and percentages in this specification are expressed on a mass basis unless otherwise specified.
　本実施形態に係るセメント組成物は、セメント、非晶質カルシウムアルミネート、及びセッコウを含み、セメント中にアルミン酸三カルシウム（以下、「Ｃ３Ａ」ということがある）を５～１０．５質量％含む。これらを含むことで、良好な急硬性、特に３時間後圧縮強度に示される初期強度を高くすることができると推察される。また、セメント中に所定量存在するアルミン酸三カルシウムにより、効率よく良好な急硬性が発現されると推察される。 The cement composition according to the present embodiment includes cement, amorphous calcium aluminate, and gypsum, and contains 5 to 10.5 of tricalcium aluminate (hereinafter sometimes referred to as "C 3 A") in the cement. Including mass%. It is inferred that by including these, it is possible to improve the rapid hardening property, especially the initial strength shown in the compressive strength after 3 hours. Further, it is presumed that the tricalcium aluminate present in a predetermined amount in the cement efficiently exhibits good rapid hardening properties.
（非晶質カルシウムアルミネート）
　本実施形態で使用する非晶質カルシウムアルミネート（以下、「非晶質ＣＡ」ということがある）は、カルシアを含む原料とアルミナを含む原料などを混合して、加熱溶融し、これを急冷することによって得られるＣａＯとＡｌ２Ｏ３とを主成分とする水和活性を有する非晶質物質の総称で、ガラス化率が７０％以上である。
　非晶質カルシウムアルミネートのガラス化率は７０％以上が好ましく、８０％以上がより好ましい。 (Amorphous calcium aluminate)
The amorphous calcium aluminate (hereinafter sometimes referred to as "amorphous CA") used in this embodiment is made by mixing raw materials containing calcia and raw materials containing alumina, heating and melting the mixture, and then rapidly cooling the mixture. It is a general term for amorphous substances with hydration activity, which are mainly composed of CaO and Al 2 O 3 and have a vitrification rate of 70% or more.
The vitrification rate of the amorphous calcium aluminate is preferably 70% or more, more preferably 80% or more.
　非晶質カルシウムアルミネートは、例えば、電気炉で溶融したカルシウムアルミネートのクリンカーを圧縮空気や水に接触させ、急冷することで得られる。
　なお、カルシアを含む原料としては、石灰石や貝殻等の炭酸カルシウム、消石灰等の水酸化カルシウム、生石灰等の酸化カルシウム等が挙げられる。またアルミナを含む原料としては、ボーキサイト、アルミ残灰と呼ばれる産業副産物等が挙げられる。 Amorphous calcium aluminate can be obtained, for example, by bringing a clinker of calcium aluminate melted in an electric furnace into contact with compressed air or water and rapidly cooling it.
In addition, examples of raw materials containing calcia include calcium carbonate such as limestone and shells, calcium hydroxide such as slaked lime, and calcium oxide such as quicklime. Further, examples of raw materials containing alumina include bauxite and industrial byproducts called aluminum residual ash.
　非晶質カルシウムアルミネートのＣａＯとＡｌ２Ｏ３との含有モル比（ＣａＯ／Ａｌ２Ｏ３モル比）は、水和活性や強度発現の観点から、１.６５～１．８５であることが好ましく、１．７～１．８であることがより好ましい。 The molar ratio of CaO to Al 2 O 3 in the amorphous calcium aluminate (CaO/Al 2 O 3 molar ratio) should be 1.65 to 1.85 from the viewpoint of hydration activity and strength development. is preferable, and 1.7 to 1.8 is more preferable.
　非晶質カルシウムアルミネートのガラス化率は、まず、対象物質を１０００℃で２時間焼きなました後、毎分５℃の冷却速度で徐冷して結晶化させる。そして、結晶化させたものを粉末Ｘ線回折法により測定し、結晶鉱物のメインピークの面積Ｓを求める。次いで、焼きなます前の物質の結晶のメインピーク面積Ｓ０を求め、以下の式によりガラス化率Ｘを求める。
Ｘ（％）＝１００×（１－Ｓ０／Ｓ） To determine the vitrification rate of amorphous calcium aluminate, first, the target material is annealed at 1000°C for 2 hours, and then slowly cooled at a cooling rate of 5°C per minute to crystallize it. Then, the crystallized material is measured by powder X-ray diffraction to determine the area S of the main peak of the crystalline mineral. Next, the main peak area S 0 of the crystal of the substance before annealing is determined, and the vitrification rate X is determined using the following formula.
X (%) = 100 x (1-S 0 /S)
　非晶質カルシウムアルミネートの粉末度は、ブレーン比表面積（以下、「ブレーン値」ということがある）で３０００～９０００ｃｍ２／ｇであることが好ましく、４０００～８０００ｃｍ２／ｇであることがより好ましい。ブレーン値で３０００ｃｍ２／ｇ以上であることで、セメント組成物の急硬性や初期強度発現性等が向上しやすくなる。一方、ブレーン値が９０００ｃｍ２／ｇ以下であれば、良好な効果を維持しながら、作業性の低下を防ぐことができる。 The fineness of the amorphous calcium aluminate is preferably 3000 to 9000 cm 2 /g, more preferably 4000 to 8000 cm 2 /g in terms of Blaine specific surface area (hereinafter sometimes referred to as "Blaine value"). preferable. When the Blaine value is 3000 cm 2 /g or more, the rapid hardening, initial strength development, etc. of the cement composition are likely to be improved. On the other hand, if the Blaine value is 9000 cm 2 /g or less, a decrease in workability can be prevented while maintaining good effects.
　非晶質カルシウムアルミネートは、強熱減量が０．２～１．５％のものを使用することが好ましく、０．５～１％がより好ましい。強熱減量が０．２～１．５％であることで、流動性や可使時間が確保しやすくなり、良好な強度発現性が得られやすくなる。強熱減量を０．２～１．５％とする方法は特に限定されるものではないが、水分や湿分を供給する方法や炭酸ガスを供給する方法等が挙げられる。
　なお、強熱減量は、ＪＩＳ　Ｒ　５２０２（セメントの化学分析方法）強熱減量の定量方法に規定される方法で求めることができる。 The amorphous calcium aluminate preferably has a loss on ignition of 0.2 to 1.5%, more preferably 0.5 to 1%. When the loss on ignition is 0.2 to 1.5%, it becomes easier to ensure fluidity and pot life, and it becomes easier to obtain good strength development. The method for achieving an ignition loss of 0.2 to 1.5% is not particularly limited, but examples include a method of supplying moisture or moisture, a method of supplying carbon dioxide gas, and the like.
Incidentally, the loss on ignition can be determined by the method specified in JIS R 5202 (Method of Chemical Analysis of Cement), Method for Quantifying Loss on Ignition.
（セッコウ）
　本実施形態では、凝結性や強度発現性の観点からセッコウを使用する。セッコウは無水、半水、二水の総称であり、特に限定されるものではないが、初期強度発現性の観点から無水セッコウ又は半水セッコウの使用が好ましく、無水セッコウの使用がより好ましい。 (Gypsum)
In this embodiment, gypsum is used from the viewpoint of setting properties and strength development properties. Gypsum is a general term for anhydrous, hemihydrous, and dihydric, and is not particularly limited, but from the viewpoint of initial strength development, it is preferable to use anhydrous gypsum or semihydrous gypsum, and it is more preferable to use anhydrous gypsum.
　セッコウの粒度は、セメント組成物の初期強度発現性を考慮して、ブレーン値３０００ｃｍ２／ｇ以上であることが好ましく、３０００～９０００ｃｍ２／ｇであることがより好ましく、４０００～８０００ｃｍ２／ｇであることがさらに好ましい。 The particle size of the gypsum is preferably a Blaine value of 3000 cm 2 /g or more, more preferably 3000 to 9000 cm 2 /g, and 4000 to 8000 cm 2 /g, considering the initial strength development of the cement composition. It is more preferable that
　セッコウの含有量は、非晶質カルシウムアルミネート１００質量部に対して、１００～２００質量部であることが好ましく、１５０～２００質量部であることがより好ましい。セッコウが１００質量部以上であると、セメント組成物の長期強度発現性を促進しやすくなり、一方、２００質量部以下であると、初期凝結の遅れを防ぎ、初期強度発現性を良好にすることができる。 The content of gypsum is preferably 100 to 200 parts by mass, more preferably 150 to 200 parts by mass, based on 100 parts by mass of amorphous calcium aluminate. When the amount of gypsum is 100 parts by mass or more, it is easy to promote long-term strength development of the cement composition, while when it is 200 parts by mass or less, delay in initial setting is prevented and the initial strength development is improved. Can be done.
　非晶質カルシウムアルミネートとセッコウからなる急硬成分は、セメント組成物の合計１００質量部中、１０～３５質量部が好ましく、１５～２５質量部がより好ましい。１０質量部以上であることで初期強度発現性を良好にすることが可能で、３５質量部以下であることで良好な作業性や長期強度が得やすくなる。 The rapid hardening component consisting of amorphous calcium aluminate and gypsum is preferably 10 to 35 parts by mass, more preferably 15 to 25 parts by mass out of the total 100 parts by mass of the cement composition. When the amount is 10 parts by mass or more, it is possible to improve initial strength development, and when it is 35 parts by mass or less, good workability and long-term strength can be easily obtained.
（セメント）
　本実施形態に係るセメントは、当該セメント中にアルミン酸三カルシウムを５～１０．５質量％含む。Ｃ３Ａが５質量％未満では、凝結開始から硬化までの時間が長くなることで初期強度発現性は小さくなってしまう。また１０．５質量％を超えると、凝結開始から硬化までの時間は短くなるものの初期強度発現性は小さくなる。アルミン酸三カルシウムは、６～１０．５質量％であることが好ましく、７～１０．５質量％であることがより好ましい。 (cement)
The cement according to this embodiment contains 5 to 10.5% by mass of tricalcium aluminate. If the C 3 A content is less than 5% by mass, the time from the start of setting to hardening becomes longer, resulting in lower initial strength development. If it exceeds 10.5% by mass, the time from the start of setting to hardening will be shortened, but the initial strength development will be low. The amount of tricalcium aluminate is preferably 6 to 10.5% by mass, more preferably 7 to 10.5% by mass.
　上記のようなセメントは、アルミン酸三カルシウムを５～１０．５質量％となるように、各種セメントを単独あるいは組み合わせて調製することができる。調製に使用するセメントの種類としては、普通、早強、超早強、中庸熱、低熱及び耐硫酸塩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、フライアッシュ、又は、石灰石微粉末を混合した各種混合セメント等が挙げられる。 The above cement can be prepared by using various cements alone or in combination so that the content of tricalcium aluminate is 5 to 10.5% by mass. The types of cement used for preparation include ordinary, early strength, ultra early strength, moderate heat, low heat, and sulfate-resistant Portland cement; these Portland cements are mixed with blast furnace slag, fly ash, or fine limestone powder. Examples include various mixed cements.
（凝結調整剤）
　本実施形態のセメント組成物は、充分な作業時間の確保と初期強度発現性を満足する観点から、さらに、凝結調整剤を含むことが好ましい。
　上記凝結調整剤は特に限定されるものではない。その具体例としては、例えば、クエン酸、酒石酸、リンゴ酸、グルコン酸、及びコハク酸又はそれらのナトリウム、カリウム、カルシウム、マグネシウム、アンモニウム、及びアルミニウムなどの塩のオキシカルボン酸又はそれらの塩、さらに、炭酸ナトリウム、炭酸カリウム、及び炭酸リチウムのアルカリ金属炭酸塩（以下、炭酸アルカリという）、炭酸アンモニウム、重炭酸ナトリウム、重炭酸カリウム、重炭酸リチウム、並びに、重炭酸アンモニウムなどの炭酸塩類が挙げられ、これらの一種又は二種以上が使用可能である。
　本実施形態では、充分な可使時間と初期強度発現性の双方を良好に満足する観点から、オキシカルボン酸又はその塩と炭酸アルカリの併用が好ましい。 (setting regulator)
The cement composition of this embodiment preferably further contains a setting modifier from the viewpoint of ensuring sufficient working time and satisfying initial strength development.
The above-mentioned setting modifier is not particularly limited. Specific examples thereof include oxycarboxylic acids or salts thereof such as citric acid, tartaric acid, malic acid, gluconic acid, and succinic acid or their salts such as sodium, potassium, calcium, magnesium, ammonium, and aluminum; , alkali metal carbonates of sodium carbonate, potassium carbonate, and lithium carbonate (hereinafter referred to as alkali carbonates), ammonium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, and carbonates such as ammonium bicarbonate. , one or more of these can be used.
In this embodiment, from the viewpoint of satisfactorily satisfying both sufficient pot life and early strength development, it is preferable to use oxycarboxylic acid or a salt thereof in combination with an alkali carbonate.
　凝結調整剤の使用量は、充分な作業時間の確保と初期強度発現性を満足する観点から、本実施形態に係るセメント、非晶質カルシウムアルミネート、セッコウからなるセメント組成物１００質量部に対して、０．１～２質量部であることが好ましく、０．５～１．５質量部であることがより好ましい。 The amount of setting modifier used is determined based on 100 parts by mass of the cement composition consisting of cement, amorphous calcium aluminate, and gypsum according to this embodiment, from the viewpoint of ensuring sufficient working time and satisfying initial strength development. The amount is preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight.
　ここで、本実施形態のセメント組成物において、セメント、非晶質カルシウムアルミネート、及びセッコウの各成分の合計は１００質量％以下であり、これらの効果を充分に発揮させる観点から、９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることがより好ましく、９９．９質量％以上であることがよりさらに好ましい。 Here, in the cement composition of this embodiment, the total of each component of cement, amorphous calcium aluminate, and gypsum is 100% by mass or less, and from the viewpoint of fully exhibiting these effects, 90% by mass It is preferably at least 95% by mass, more preferably at least 98% by mass, even more preferably at least 99.9% by mass.
　本実施形態において、セメント組成物を作製する際の各材料の混合方法は特に限定されるものではなく、それぞれの材料を施工時に混合しても良いし、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。混合装置としては、既存のいかなる装置、例えば、傾胴ミキサ、オムニミキサ、ヘンシェルミキサ、Ｖ型ミキサ、及びナウタミキサなどの使用が可能である。 In this embodiment, the method of mixing each material when producing a cement composition is not particularly limited, and each material may be mixed at the time of construction, or some or all of the materials may be mixed in advance. There is no harm in leaving it as is. As the mixing device, any existing device can be used, such as a tilting mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer.
［実験例１］
　市販品である、普通セメント、早強セメント、高Ｃ３Ａセメント、及び中庸熱セメントの少なくともいずれかを用いて、セメント組成中のＣ３Ｓを一定としＣ３Ａを変化させて、表１に示す鉱物組成の試製セメント１～６を作製した。 [Experiment example 1]
Using at least one of commercially available ordinary cement, early strength cement, high C 3 A cement, and moderate heat cement, C 3 S in the cement composition was kept constant and C 3 A was varied. Table 1 Trial cements 1 to 6 with the mineral compositions shown below were prepared.
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000001
 
　作製した各試製セメント、カルシウムアルミネート（ＣＡ－１若しくは結晶ＣＡ）、各種セッコウを表２に示す配合で混合してセメント組成物を作製し、さらに凝結調整剤をセメント組成物１００部に対して１部混合した。セメント組成物１００部に対して細骨材を２００部とし、セメント組成物１００部に対しに水４０部を加え練り混ぜてモルタルを作製し、その圧縮強度を測定した。圧縮強度はＪＩＳ　Ｒ　５２０１に準じて４×４×１６ｃｍの試験体を作製し、３時間後、１日後、及び２８日後のそれぞれを測定した。結果を表１に示す。 A cement composition was prepared by mixing each of the prepared trial cements, calcium aluminate (CA-1 or crystalline CA), and various types of gypsum in the proportions shown in Table 2, and a setting modifier was added to 100 parts of the cement composition. One part was mixed. A mortar was prepared by adding 200 parts of fine aggregate to 100 parts of the cement composition, adding 40 parts of water to 100 parts of the cement composition, and kneading the mixture.The compressive strength of the mortar was measured. The compressive strength was measured in accordance with JIS R 5201 by preparing a 4 x 4 x 16 cm test piece and measuring it after 3 hours, 1 day, and 28 days. The results are shown in Table 1.
＜使用材料＞
（１）カルシウムアルミネート
・ＣＡ－１（非晶質）：ＣａＯ／Ａｌ２Ｏ３モル比１．７８、ガラス化率９１％、ブレーン値５９００ｃｍ２／ｇ、強熱減量：０．９％
　ＣａＯ／Ａｌ２Ｏ３モル比１．７～１．８の範囲となるようにカルシア源として石灰石とアルミナ源としてのボーキサイトを使用し、１６５０℃で溶融後に急冷し、粉砕して作製した。
・結晶ＣＡ（結晶質）：ＣａＯ／Ａｌ２Ｏ３モル比１．７７、ガラス化率０％、ブレーン値６０００ｃｍ２／ｇ
　カルシア源として石灰石とアルミナ源としてボーキサイトを使用し、１４５０℃で焼成後に徐冷し、粉砕して作製した。
（２）セッコウ
・無水セッコウ：市販品、ブレーン値５６００ｃｍ２／ｇ
・半水セッコウ：市販品、ブレーン値５７００ｃｍ２／ｇ
・二水セッコウ：市販品、ブレーン値５５００ｃｍ２／ｇ
（３）凝結調整剤
・試薬１級のクエン酸２５質量部と試薬１級の炭酸カリウム７５質量部の混合品
（４）細骨材
・珪砂：市販品、３号：３０質量部、５号：４０質量部、６号：３０質量部の混合品 <Materials used>
(1) Calcium aluminate CA-1 (amorphous): CaO/Al 2 O 3 molar ratio 1.78, vitrification rate 91%, Blaine value 5900 cm 2 /g, loss on ignition: 0.9%
Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.7 to 1.8, melted at 1650° C., then rapidly cooled and pulverized.
・Crystalline CA (crystalline): CaO/Al 2 O 3 molar ratio 1.77, vitrification rate 0%, Blaine value 6000 cm 2 /g
Limestone was used as a calcia source and bauxite was used as an alumina source. After firing at 1450° C., it was slowly cooled and pulverized.
(2) Gypsum/anhydrous gypsum: Commercially available product, Blaine value 5600 cm 2 /g
・Hemihydrate gypsum: Commercial product, Blaine value 5700cm 2 /g
・Dihydrate gypsum: Commercial product, Blaine value 5500cm 2 /g
(3) A mixture of 25 parts by mass of citric acid, a first-grade reagent, and 75 parts by mass of potassium carbonate, a first-grade reagent (4) Fine aggregate, silica sand: Commercially available product, No. 3: 30 parts by mass, No. 5 : 40 parts by mass, No. 6: 30 parts by mass mixture
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［実験例２］
　実験例１の実験Ｎｏ．４において、ＣＡ－１の代わりに、下記のＣＡ－２～ＣＡ－５をそれぞれ用いた以外は、実験例１と同様にして、セメント組成物を作製し、さらにモルタルを作製して圧縮強度を測定した。結果を表３に示す。 [Experiment example 2]
Experiment No. of Experimental Example 1. In Example 4, a cement composition was prepared in the same manner as in Experimental Example 1, except that each of the following CA-2 to CA-5 was used instead of CA-1, and mortar was prepared to increase the compressive strength. It was measured. The results are shown in Table 3.
＜使用材料＞
・ＣＡ－２（非晶質）：ＣａＯ／Ａｌ２Ｏ３モル比１．５５、ガラス化率９０％、ブレーン値６３１０ｃｍ２／ｇ、強熱減量：０．９％
　ＣａＯ／Ａｌ２Ｏ３モル比１．５～１．６の範囲となるようにカルシア源として石灰石とアルミナ源としてのボーキサイトを使用し、１６５０℃で溶融後に急冷し、粉砕して作製した。
・ＣＡ－３（非晶質）：ＣａＯ／Ａｌ２Ｏ３モル比１．６７、ガラス化率９２％、ブレーン値５８００ｃｍ２／ｇ、強熱減量：０．９％
　ＣａＯ／Ａｌ２Ｏ３モル比１．６～１．７の範囲となるようにカルシア源として石灰石とアルミナ源としてのボーキサイトを使用し、１６５０℃で溶融後に急冷し、粉砕して作製した。
・ＣＡ－４（非晶質）：ＣａＯ／Ａｌ２Ｏ３モル比１．８３、ガラス化率９０％、ブレーン値６０７０ｃｍ２／ｇ、強熱減量：０．９％
　ＣａＯ／Ａｌ２Ｏ３モル比１．８～１．９の範囲となるようにカルシア源として石灰石とアルミナ源としてのボーキサイトを使用し、１６５０℃で溶融後に急冷し、粉砕して作製した。
・ＣＡ－５（非晶質）：ＣａＯ／Ａｌ２Ｏ３モル比１．９６、ガラス化率９１％、ブレーン値６２４０ｃｍ２／ｇ、強熱減量：０．９％
　ＣａＯ／Ａｌ２Ｏ３モル比１．９～２．０の範囲となるようにカルシア源として石灰石とアルミナ源としてのボーキサイトを使用し、１６５０℃で溶融後に急冷し、粉砕して作製した。 <Materials used>
・CA-2 (amorphous): CaO/Al 2 O 3 molar ratio 1.55, vitrification rate 90%, Blaine value 6310 cm 2 /g, loss on ignition: 0.9%
Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.5 to 1.6, melted at 1650° C., then rapidly cooled and pulverized.
・CA-3 (amorphous): CaO/Al 2 O 3 molar ratio 1.67, vitrification rate 92%, Blaine value 5800 cm 2 /g, loss on ignition: 0.9%
Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.6 to 1.7, melted at 1650° C., then rapidly cooled and pulverized.
・CA-4 (amorphous): CaO/Al 2 O 3 molar ratio 1.83, vitrification rate 90%, Blaine value 6070 cm 2 /g, loss on ignition: 0.9%
Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.8 to 1.9, melted at 1650° C., then rapidly cooled and pulverized.
・CA-5 (amorphous): CaO/Al 2 O 3 molar ratio 1.96, vitrification rate 91%, Blaine value 6240 cm 2 /g, loss on ignition: 0.9%
Limestone was used as a calcia source and bauxite was used as an alumina source so that the CaO/Al 2 O 3 molar ratio was in the range of 1.9 to 2.0, melted at 1650° C., then rapidly cooled and pulverized.
Figure JPOXMLDOC01-appb-T000003
 
Figure JPOXMLDOC01-appb-T000003
 
［実験例３］
　実験例１の実験Ｎｏ．４において、無水セッコウの量を表４のように変更した以外は、実験例１と同様にして、セメント組成物を作製し、さらにモルタルを作製して圧縮強度を測定した（実験Ｎｏ．１４～１７）。結果を表４に示す。 [Experiment example 3]
Experiment No. of Experimental Example 1. In Experiment No. 4, a cement composition was prepared in the same manner as in Experimental Example 1, except that the amount of anhydrous gypsum was changed as shown in Table 4, and mortar was further prepared and the compressive strength was measured (Experiment No. 14 to 17). The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
 
Figure JPOXMLDOC01-appb-T000004
 
　本発明は、土木・建築分野等で、早期に供用が必要な状況下で幅広く使用することができる。 The present invention can be widely used in the civil engineering and construction fields, etc., in situations where early use is required.

Claims (4)

  1. 　セメント、非晶質カルシウムアルミネート、及びセッコウを含み、前記セメント中にアルミン酸三カルシウムを５～１０．５質量％含むセメント組成物。 A cement composition containing cement, amorphous calcium aluminate, and gypsum, and containing 5 to 10.5% by mass of tricalcium aluminate in the cement.
  2. 　前記非晶質カルシウムアルミネートのＣａＯとＡｌ２Ｏ３とのモル比（ＣａＯ／Ａｌ２Ｏ３）が１．６５～１．８５である請求項１に記載のセメント組成物。 The cement composition according to claim 1, wherein the amorphous calcium aluminate has a molar ratio of CaO to Al 2 O 3 (CaO/Al 2 O 3 ) of 1.65 to 1.85.
  3. 　前記非晶質カルシウムアルミネート１００質量部に対して前記セッコウが１００～２００質量部である請求項１又は２に記載のセメント組成物。 The cement composition according to claim 1 or 2, wherein the gypsum is present in an amount of 100 to 200 parts by mass based on 100 parts by mass of the amorphous calcium aluminate.
  4. 　さらに、凝結調整剤を含む請求項１～３のいずれか１項に記載のセメント組成物。
     

          The cement composition according to any one of claims 1 to 3, further comprising a setting modifier.
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