JP2007197267A - Ultra-rapid-hardening/high-flow cement composition and mortar or concrete using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide ultra-quick-hardening/high-flow mortar or concrete which is excellent in flow property, can suppress the occurrence of settling (material separation), ensures a sufficient pot life and is favorable in terms of strength development at a low temperature. <P>SOLUTION: An ultra-quick-hardening/high-flow cement composition comprises portland cement, calcium aluminate having a molar ratio of CaO to Al<SB>2</SB>O<SB>3</SB>of 0.75-1.5, anhydrous gypsum, calcium hydroxide, an alkali metal aluminate, an alkali metal carbonate other than lithium carbonate, an organic acid, a plasticizer and a gas foaming substance. Preferably, anhydrous gypsum is acidic anhydrous gypsum, and the gas foaming substance is a percarbonate. The mortar comprises the ultra-quick-hardening/high-flow cement composition and fine aggregate preferably having roundness of 0.8 or larger. The concrete is obtained by compounding coarse aggregate with the mortar, wherein the coarse aggregate preferably has roundness of 0.8 or larger. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention mainly relates to a super-fast-hardening / high-fluidity cement composition used in the civil engineering and construction industry, and mortar or concrete using the same.

  When aiming for streamlined construction, high-fluidity mortar with super-hardness and self-filling and self-leveling properties is often required, and super-fast-hardening and high-fluidity mortars that exhibit practical strength in 3 hours have been proposed (patents) Literature 1 to Patent Literature 3). In addition, in order to meet the demands for further rationalization construction and new needs, there is a strong demand for the development of ultra-fast hardening and high-flow mortar that can produce practical strength in a shorter time.

However, the pot life is also an important performance requirement for ultra-fast hardening and high-flow mortar. Considering the construction time and the cleaning time of equipment used, the pot life is at least 10 minutes, preferably 15 minutes or more. It is desirable to secure time, but securing a long pot life will delay the curing time and it will be difficult to meet the required strength at an age of 1 hour. While ensuring, there was no material satisfying 20 N / mm ² or more at an age of 1 hour.

  Conventional super-hardening / high-flowing mortar has a large temperature dependence, and the strength development in a low temperature environment has been an issue. That is, although the required strength is satisfied at a predetermined age at 20 ° C. or higher, it is difficult to satisfy the required strength at a predetermined age at low temperatures in autumn and winter.

  On the other hand, in order to give rapid hardening, adding calcium aluminate and gypsum to Portland cement has been studied for a long time (Patent Document 4). However, these cement compositions are highly temperature dependent.

  Therefore, in order to improve the temperature dependence, super-hard cement (patent document 5) in which calcium carbonate is blended with calcium aluminate and gypsum, and mortar in which calcium aluminate, anhydrous gypsum, lithium carbonate and slaked lime are blended with Portland cement. It has been proposed (Patent Document 6).

Japanese Patent Laid-Open No. 03-12350 Japanese Patent Laid-Open No. 01-230455 Japanese Patent Laid-Open No. 11-139859 U.S. Pat. No. 903019 JP-A-01-290543 JP-A-2005-75712

  INDUSTRIAL APPLICABILITY The present invention is a super-fast-hardening / high-fluidity cement composition that has excellent fluidity, can suppress the occurrence of subsidence (material separation), has an effect such as good strength development at low temperatures while ensuring sufficient pot life And a mortar or concrete using the same.

The present invention includes (1) Portland cement, calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of 0.75 to 1.5, anhydrous gypsum, calcium hydroxide, alkali metal aluminate, carbonic acid Super fast hardening / high flow cement composition comprising alkali metal carbonate other than lithium, organic acid, fluidizing agent and gas foaming material, (2) Portland cement, calcium aluminate, anhydrous gypsum and water (1) Super-hardening in which Portland cement is 35 to 55 parts, calcium aluminate is 20 to 40 parts, anhydrous gypsum is 10 to 25 parts, and calcium hydroxide is 1 to 10 parts in a total of 100 parts of calcium oxide. High flow cement composition, (3) Portland cement, calcium aluminate, anhydrous gypsum and calcium hydroxide total 10 Parts, alkali metal aluminate 0.03-0.5 part, alkali metal carbonate 0.1-1 part other than lithium carbonate, organic acid 0.1-0.5 part, fluidizing agent 0. 1 to 1.5 parts (1) or (2) super-fast-hardening / high-fluidity cement composition, (4) anhydrous gypsum is acid-free anhydrous gypsum (1) to (3) High-fluidity cement composition, (5) Super fast-hardening / high-fluidity cement composition according to any one of (1) to (4), wherein the gas foaming substance is percarbonate, (6) containing fiber substance (5) any one of the super-fast-hardening / high-fluidity cement composition, (7) mortar containing any one of the super-fast-hardening / high-fluidity cement composition and (1) to (6), (8) Mortar of (7) whose roundness of fine aggregate is 0.8 or more, (9) Portland cement, calcium (7) or (8) mortar comprising 100-200 parts of fine aggregates for a total of 100 parts of luminescent, anhydrous gypsum and calcium hydroxide, (10) 30/43% water / binder ratio is prepared by adding water so that, J ₁₄ funnel flow value is 9 ± 4 seconds (7) to one of (9) mortar, (11) 10 ° C. low temperature in wood age 1 hour of The mortar according to any one of (7) to (10), wherein the compressive strength is 20 N / mm ² or more,
(12) Concrete obtained by blending coarse aggregate in any one of (7) to (11), (13) Concrete according to (12), wherein roundness is 0.8 or more, It is.

  The super-hard-hardening / high-fluidity cement composition of the present invention and the mortar or concrete using the cement composition are excellent in fluidity, can suppress the occurrence of subsidence (material separation), secure sufficient pot life, There are effects such as good strength development.

  In the present invention, “parts” and “%” are based on mass unless otherwise specified.

  The Portland cement of the present invention is usually various Portland cements such as early strength, very early strength, low heat, and moderate heat, various mixed cements obtained by mixing blast furnace slag, fly ash, or silica with these Portland cements, Examples include filler cement mixed with limestone powder and blast furnace slow-cooled slag fine powder, environmentally friendly cement manufactured using various industrial wastes as main raw materials, so-called eco-cement, etc., one or two of these That's it.

The calcium aluminate of the present invention is a general term for compounds mainly composed of CaO and Al ₂ O ₃ . In the present invention, calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of 0.75 to 1.5 is used. Calcium Examples of aluminate, for _{example, CaO · 2Al 2 O 3,} CaO · Al 2 O 3, 12CaO · 7Al 2 O 3, 11CaO · 7Al 2 O 3 · CaF 2, 3CaO · 3Al 2 O 3 · CaSO Examples thereof include crystalline calcium aluminates represented as _{4 and the} like, and amorphous compounds mainly composed of CaO and Al ₂ O ₃ components. If the CaO / Al ₂ O ₃ molar ratio is less than 0.75, sufficient strength development cannot be obtained. Conversely, if the CaO / Al ₂ O ₃ molar ratio exceeds 1.5, sufficient fluidity and pot life cannot be obtained.

Examples of a method for obtaining calcium aluminate include a method in which a CaO raw material and an Al ₂ O ₃ raw material are heat-treated with a rotary kiln or an electric furnace. Examples of the CaO raw material for producing calcium aluminate include calcium carbonate such as limestone and shells, calcium hydroxide such as slaked lime, and calcium oxide such as quick lime. As the Al ₂ O ₃ raw material, for example, other industrial products, called bauxite, aluminum residual ash, include aluminum powder and the like.

When calcium aluminate is obtained industrially, impurities may be contained. Specific examples _{thereof, SiO 2, Fe 2 O 3} , MgO, TiO 2, MnO, Na 2 O, K 2 O, Li 2 O, S, like P 2 _{O 5,} and F or the like. The presence of these impurities is not particularly problematic as long as the object of the present invention is not substantially impaired. Specifically, there is no particular problem if the total of these impurities is in the range of 10% or less.

The _{compound, 4CaO · Al 2 O 3 ·} Fe 2 O 3, 6CaO · 2Al 2 O 3 · Fe 2 O 3, calcium such as _{6CaO · Al 2 O 3 · 2Fe} 2 O 3 alumino ferrite, 2CaO · Fe ₂ O ₃ and CaO · _Fe 2 _{O 3} calcium such as ferrite, gehlenite _{2CaO · Al 2 O 3 · SiO} 2, calcium aluminosilicate, such as anorthite _{CaO · Al 2 O 3 · 2SiO} 2, Merubinaito 3CaO · MgO · 2SiO ₂ , Akerumanaito 2CaO · MgO · 2SiO _2, Monch celite CaO · MgO · SiO ₂ such as calcium magnesium silicate, tri-calcium silicate 3CaO · SiO _2, dicalcium silicate 2CaO · SiO _2, rankinite night 3CaO · 2SiO _2, straw It may contain calcium silicates such as strite CaO · SiO ₂ , calcium titanate CaO · TiO ₂ , free lime, leucite (K ₂ O, Na ₂ O) · Al ₂ O ₃ · SiO _{2, and the} like. In the present invention, these crystalline or amorphous materials may be mixed.

The particle size of the calcium aluminate of the present invention is not particularly limited, but is usually in the range of 3000 to 9000 cm ² / g in terms of Blaine specific surface area, and more preferably about 4000 to 80000 cm ² / g. If it is less than 3000 cm ² / g, strength development may not be sufficient, and if it exceeds 9000 cm ² / g, it may be difficult to ensure fluidity and pot life.

The anhydrous gypsum of the present invention is not particularly limited, but it is preferable to use type II anhydrous gypsum, among which it is possible to use acidic anhydrous gypsum having a pH of 4.5 or less. This is preferable because it is easy to ensure the strength and the subsequent strength enhancement is good. Here, the pH of anhydrous gypsum means the pH of the supernatant when 1 g of anhydrous gypsum is added to 100 cc of pure water and stirred. The particle size of the anhydrous gypsum is preferably 3000~9000cm ² / g in Blaine specific surface area, 4000~8000cm ² / g is more preferable.

The calcium hydroxide of the present invention is not particularly limited. This is a general term for compounds represented by Ca (OH) ₂ . The impurities are not particularly limited as long as they do not contain harmful substances for the environment. The Ca (OH) ₂ content is preferably 80% or more, more preferably 90% or more. Impurities may include calcium carbonate and calcium oxide.

Although the specific surface area of calcium hydroxide is not particularly limited, is preferably from ^{20 m} 2 / g in BET specific surface area, ^{15 m} 2 / g or less is more preferable. When the BET specific surface area of calcium hydroxide exceeds 20 m ² / g, the fluidity tends to deteriorate or it becomes difficult to ensure the pot life.

The alkali metal aluminate of the present invention is a general term for compounds of R ₂ O and Al ₂ O ₃ and is represented by the general formula mR ₂ O.Al ₂ O ₃ .nH ₂ O. Here, R means sodium or potassium. Moreover, m in a formula exists in the range of 0.5-2. And n exists in the range of 0-10.

In the present invention, the alkali metal aluminate has the effect of conspicuously exhibiting the initial strength at low temperatures. In particular, the use of an anhydrous salt is preferable from the viewpoint of ensuring fluidity. The R ₂ O / Al ₂ O ₃ molar ratio is preferably in the range of 0.8 to 1.2. When the R ₂ O / Al ₂ O ₃ molar ratio is less than 0.8, the effect of improving the initial strength development at low temperatures is small, whereas when it exceeds 1.2, it is difficult to ensure fluidity There is.

  Alkali metal carbonates other than lithium carbonate of the present invention play an important role in fluidization and securing the pot life. The alkali metal carbonate is not particularly limited, and specific examples thereof include sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and the like.

  The organic acid of the present invention plays an important role in securing fluidization and pot life together with carbonates and fluidizing agents. The organic acid is not particularly limited, but specific examples thereof include, for example, citric acid, tartaric acid, malic acid, gluconic acid, succinic acid and other oxycarboxylic acids and their sodium, potassium, calcium, magnesium, ammonium And salts such as aluminum. Of these, citric acid and its salts are preferred. In the present invention, one or more of these can be used in combination.

  The fluidizing agent of the present invention facilitates kneading of materials, helps to disperse each material, and plays a role of imparting fluidity to the kneaded material. The fluidizing agent is not particularly limited, but specific examples thereof include, for example, naphthalene-based products, a product name “Leobuild SP-9 series” manufactured by NMB, a product name “Mighty 2000 series” manufactured by Kao Corporation, And Nippon Paper Industries' product name “Sunflow HS-100”. Moreover, as a melamine type | system | group, Nippon Seika Co., Ltd. brand name "Sea Kament 1000 series", Nippon Paper Industries Co., Ltd. brand name "Sunflow HS-40", etc. are mentioned. Furthermore, as an aminosulfonic acid type | system | group, the product name "FP-200 series" by Floric etc. are mentioned. Examples of polycarboxylic acid-based products include the product name “Leobuild SP-8 Series” manufactured by NMB, the product name “Darlex Super 100PHX” manufactured by Grace Chemicals, and the product names “Tupol HP-8 Series” manufactured by Takemoto Yushi Co., Ltd. And “Tupole HP-11 series”. In the present invention, one or more of these fluidizing agents can be used.

  Some of the above fluidizing agents are in powder form. Specifically, as a polyalkylallyl sulfonate condensate, the product name “Cellflow 110P” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., the product name “IPC” manufactured by Idemitsu Petrochemical Co., Ltd., and naphthalene sulfonate Condensates include Kao's trade name “Mighty 100” and Sanyo Kasei Kogyo's trade name “Sanyo Reberon P”, etc., and melamine-based products such as “Seacament FF” made by Sika, Examples of carboxylic acid-based products include trade name “Quinflow 750” manufactured by Mitsubishi Chemical Corporation and trade name “Mighty 21P” manufactured by Kao Corporation.

The blending ratio of the fluidizing agent is not particularly limited, but usually it is preferably in the range of 0.1 to 1.5 parts in terms of solid content with respect to 100 parts of the binder. If it is less than 0.1 part, fluidity | liquidity is not enough, and when it exceeds 1.5 parts, material separation may occur.
Here, the binder is composed of Portland cement, calcium aluminate, anhydrous gypsum and calcium hydroxide.

The fine aggregate of the present invention is not particularly limited, but a spheroidized fine aggregate having a roundness of 0.8 or more improves fluidity, reduces heat generation and dimensional changes, and ensures durability. From the viewpoint of
The spheroidization referred to in the present invention means that the angle of the particle surface is removed and the degree of sphericity of the particle shape is increased. The degree of spheroidization can be expressed by roundness.
The roundness is expressed by (projected area of particles) / (area of a circle having the same peripheral length as the projected peripheral length of the particles). The method for measuring the roundness is not particularly limited, but can be obtained, for example, by measuring the projected area (A) of the particle and the projected peripheral length (PM) of the particle from a micrograph (Japanese Patent Laid-Open 11-60298 etc.). When the area of a perfect circle having the same circumference as the projected circumference of the particle is (B), the roundness is roundness = A / B = 4πA / (PM) ² (however, the roundness is 0 to 1). ). In addition, it is preferable to analyze an image taken with a scanning electron microscope, a stereomicroscope, or the like with an image analysis apparatus such as an image analysis apparatus manufactured by Nippon Avionics, image analysis software, or the like. The roundness of the spheroidized fine aggregate of the present invention is preferably 0.8 or more, and more preferably 0.9 or more.
As specific examples, the fine aggregates are classified into, for example, a silica sand system, a limestone system, a slag system, and a recycled aggregate system. In the present invention, it is preferable to select a silica sand system or a slag system from the viewpoint of high roundness and good fluidity.

The blending ratio of each material in the mortar using the super fast hardening / high fluidity cement composition of the present invention is as follows: Portland cement, calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of 0.75 to 1.5, and anhydrous gypsum And in a total of 100 parts of calcium hydroxide, 35 to 55 parts of Portland cement, 20 to 40 parts of calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of 0.75 to 1.5, and 10 to 25 of anhydrous gypsum Parts and calcium hydroxide are preferably 1 to 10 parts.

If the Portland cement is less than 35 parts, it may be difficult to ensure the pot life or long-term durability may be difficult to obtain. On the other hand, if it exceeds 55 parts, there may be cases where excellent initial strength developability cannot be obtained. If the calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of 0.75 to 1.5 is less than 20 parts, excellent initial strength development may not be obtained. It may be difficult to secure time or long-term durability may be difficult to obtain. If the amount of anhydrous gypsum is less than 10 parts, it may be difficult to ensure the pot life, and if it exceeds 25 parts, excellent initial strength development may not be obtained or overexpansion may occur. If calcium hydroxide is less than 1 part, sufficient initial strength developability may not be obtained, or material separation resistance may not be obtained. If it exceeds 10 parts, initial strength and long-term strength develop poorly. In addition, there is a tendency to increase the amount of kneading water and a tendency to require a large amount of fluidizing agent, and as a result, it may be difficult to ensure the stability of quality.

If the blending ratio of the alkali metal aluminate is less than 0.01 part with respect to 100 parts of the binder, the initial strength development at low temperature may not be sufficient. That is, there is a case where a compressive strength of 20 N / mm ² or more cannot be expressed at an age of 1 hour. On the contrary, even if it exceeds 0.5 parts, further enhancement of the effect cannot be expected. Not only that, the fluidity may deteriorate. The preferred range is 0.03 to 0.3 part. More preferably, it is 0.05-0.10 part.

If the blending ratio of the alkali metal carbonate other than lithium carbonate is less than 0.1 part with respect to 100 parts of the binder, it is difficult to ensure fluidity and sufficient pot life, and if it exceeds 1 part, the setting delay is strong. Therefore, there may be a case where a compressive strength of 20 N / mm ² or more cannot be expressed at an age of 1 hour.

If the blending ratio of the organic acid is less than 0.1 part with respect to 100 parts of the binder, it is difficult to ensure fluidity and sufficient pot life, and if it exceeds 0.5 part, the setting delay becomes strong, and the age of the material There are cases where a compressive strength of 20 N / mm ² or more cannot be expressed in one hour.

  When the blending ratio of the fine aggregate is less than 150 parts with respect to 100 parts of the binder, the calorific value is large, the shrinkage of the hardened body is large, and cracks are likely to occur. Moreover, if it exceeds 200 parts, fluidity may not be obtained.

The blending ratio of water is not particularly limited because it varies depending on the purpose and application of use and the blending ratio of each material. Usually, in mortar, the water / binder ratio is preferably in the range of 30 to 43%, 33-40% is more preferable. Liquidity is preferably J ₁₄ funnel flow value is 9 ± 4 seconds. If the water / binder ratio is less than 30%, it is difficult to obtain such fluidity, and it is difficult to blend 150 parts or more of fine aggregate, resulting in a very large amount of heat generation. Conversely, if it exceeds 43%, the strength development tends to be reduced.

  The gas foam material of the present invention, when using the super fast hardening / high flow mortar of the present invention as a grout material, the super fast hardening / high flow mortar in a state where it has not yet solidified sinks or shrinks in order to integrate the structure. It plays the role of deterring Specific examples of the gas foaming material include aluminum powder and carbon material, as well as peroxidation materials such as percarbonate, persulfate, perborate and permanganate. In the present invention, it is preferable to use a carbon substance or a peroxide substance such as a percarbonate, a persulfate, a perborate, and a permanganate because the effect of suppressing settlement is great. Of these, the use of percarbonate is most preferable.

  The blending ratio of the gas foaming substance is not particularly limited, but usually, aluminum powder or a peroxide substance can be used in the range of 0.0001 to 0.1 part with respect to 100 parts of the binder, A range of 0.001 to 0.01 part is more preferable. If the amount is less than 0.0001 part, a sufficient initial expansion effect may not be imparted. If the amount exceeds 0.1 part, excessive expansion may occur and strength development may be deteriorated. Moreover, if a gas foaming substance is a carbonaceous substance, it can be used in 1-15 parts with respect to 100 parts of binders, and the range of 3-10 parts is more preferable. If it is less than 1 part, a sufficient initial expansion effect may not be imparted, and if it is used in excess of 15 parts, it may be over-expanded and strength development may be deteriorated.

  In the present invention, a fiber material can be used in combination. The fiber material plays a role in improving crack resistance. The fiber material is not particularly limited, and specific examples thereof include steel fiber, vinylon fiber, carbon fiber, wollastonite fiber, and the like. The mixing ratio of the fiber substance can be used in the range of 0.1 to 3 parts, more preferably 0.5 to 2 parts, with respect to 100 parts of the binder. If it is less than 0.1 part, the crack reduction effect may not be sufficient. Conversely, even if it exceeds 3 parts, further enhancement of the effect cannot be expected.

In the present invention, further, a coarse aggregate can be blended with the mortar using the super fast hardening / high fluidity cement composition of the present invention to obtain concrete. By using concrete, it can be applied to structures with large construction thickness.
The coarse aggregate is not particularly limited, but a spherical one is preferable. If it is not a spheroidized coarse aggregate, fluidity may be impaired. The spheroidized coarse aggregate means that the corner of the particle surface can be taken and the degree of the spherical shape of the particle shape increases. The degree of spheroidization can be expressed by roundness as with the spheroidized fine aggregate. It is preferable to use a coarse aggregate having a roundness of 0.8 or more. The maximum diameter of the spheroidized coarse aggregate is not particularly limited, but is usually preferably 20 mm or less, and more preferably 15 mm or less. When the maximum particle size of the spheroidized coarse aggregate exceeds 20 mm, material separation may occur or strength development may be deteriorated. The blending ratio of the spheroidized coarse aggregate is not particularly limited, but it can be generally blended within a range of 1000 kg or less per 1 m ^{3 of the} concrete composition composed of the super fast hard / high fluid mortar and the spheroidized coarse aggregate. When the blending ratio of the spheroidized coarse aggregate exceeds 1000 kg / m ³ , fluidity may be impaired.

  In the present invention, limestone fine powder, blast furnace slow-cooled slag fine powder, sewage sludge incineration ash and its molten slag, admixture materials such as municipal waste incineration ash and its molten slag, pulp sludge incineration ash, water reducing agent, AE water reducing agent, high Performance water-reducing agent, high-performance AE water-reducing agent, antifoaming agent, thickening agent, rust preventive agent, anti-freezing agent, shrinkage reducing agent, polymer, setting modifier, clay minerals such as bentonite, and anion exchange such as hydrotalcite One or more of the body and the like can be used within a range that does not substantially impair the object of the present invention.

  In the present invention, the mixing method of each material is not particularly limited, and each material may be mixed at the time of construction, or a part or all of them may be mixed in advance.

  Any existing device can be used as the mixing device, and for example, a tilting mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used.

  Using various calcium aluminates as shown in Table 1, a binder consisting of 45 parts of cement, 30 parts of calcium aluminate, 20 parts of anhydrous gypsum and 5 parts of calcium hydroxide was prepared. 0.05 parts of alkali metal aluminate A, 0.3 parts of alkali metal carbonate (1) other than lithium carbonate, 0.2 part of organic acid α, 0.5 part of fluidizing agent A, 0.02 part of gas foaming substance a, Mortar was prepared by blending 150 parts of fine aggregate. At this time, 37 parts of the kneading water was used for a total of 100 parts of the binder. The fluidity, pot life, initial expansion rate, compressive strength, and rate of change in length of the prepared mortar were measured under an environment of 10 ° C. The results are also shown in Table 1.

<Materials used>
Cement: Commercial ordinary Portland cement calcium aluminate A: CaO / Al ₂ O ₃ molar ratio 0.75, crystalline, CaO · Al ₂ O ₃ and CaO · 2Al ₂ O ₃ as main components, Blaine specific surface area 5000 cm ² / g
Calcium aluminate B: CaO / Al ₂ O ₃ molar ratio 1.00, crystalline, CaO · Al ₂ O ₃ is the main component, Blaine specific surface area 5000 cm ² / g
Calcium aluminate C: CaO / Al ₂ O ₃ molar ratio 1.50, crystalline, CaO · Al ₂ O ₃ and 12CaO · 7Al ₂ O ₃ as main components, Blaine specific surface area 5000 cm ² / g
Calcium aluminate D: CaO / Al ₂ O ₃ molar ratio 1.00, amorphous, 5% of reagent grade silica added to calcium aluminate B, melted at 1650 ° C., and then rapidly cooled to synthesize, Blaine specific surface area of 5000cm ² / g
Calcium aluminate E: CaO / Al ₂ O ₃ molar ratio 1.50, amorphous, calcium aluminate C 3% of reagent grade silica was added, melted at 1650 ° C., and then rapidly cooled to synthesize, Blaine specific surface area 5000 cm ² / g
Calcium aluminate F: CaO / Al ₂ O ₃ molar ratio 0.60, crystalline, CaO · Al ₂ O ₃ and CaO · 2Al ₂ O ₃ as main components, Blaine specific surface area 5000 cm ² / g
Calcium aluminate G: CaO / Al ₂ O ₃ molar ratio 1.60, crystalline, CaO · Al ₂ O ₃ , 12CaO · 7Al ₂ O ₃ as main components, Blaine specific surface area 5000 cm ² / g
Anhydrous gypsum: type II anhydrous gypsum, pH 3.0, Blaine specific surface area 5000 cm ² / g
Calcium hydroxide: commercial product, BET specific surface area of 10 m ² / g
Alkali metal aluminate A: Commercially available sodium aluminate, anhydride, Na ₂ O / Al ₂ O ₃ molar ratio 1.0
Alkali metal carbonates other than lithium carbonate (1): Reagent primary potassium carbonate Organic acid α: Reagent primary citric acid fluidizer A: Commercially available naphthalene-based gas foaming material a: Reagent sodium percarbonate water: Tap water fine aggregate B: Equal volume mixture of spheroidized No. 6 silica sand and No. 7 silica sand, roundness 0.8

<Measurement method>
Liquidity and pot life: in accordance with JSCE, it was evaluated by measuring the J ₁₄ funnel flow value. In addition, the pot life was the time when the J ₁₄ funnel flow value is greater than 20 seconds, sufficient cast is no longer possible.
Initial expansion rate: Japan Society of Civil Engineers "Expanded concrete design and construction guidelines (draft)" Appendix 2. Measured according to the appendix “Construction Procedures for Filling Mortar Using Expandable Material (Draft)”. However,-in a table | surface shows a contraction side and + shows an expansion | swelling side.
Length change rate: Measured according to JIS A 6202 (B) (measuring material age 7 days).
Compressive strength: A molded body of 4 cm × 4 cm × 16 cm was prepared by filling a mortar into a mold, and the compressive strength at the age of 28 days was measured according to JIS R 5201.

  From Table 1, the mortar using the super fast hardening / high fluidity cement composition of the present invention has excellent fluidity, no subsidence, and sufficient pot life, and strength under low temperature (10 ° C.). It can be seen that the expression is good.

  The same procedure as in Example 1 was conducted except that calcium aluminate B was used and the blending ratio of cement, calcium aluminate, anhydrous gypsum and calcium hydroxide was changed as shown in Table 2. The results are also shown in Table 2.

  From Table 2, the mortar using the ultra-fast hardening / high fluidity cement composition of the present invention has excellent fluidity, no subsidence, and sufficient pot life, and strength under low temperature (10 ° C.). It can be seen that the expression is good.

  In Experiment No. 1-2 of Example 1, with respect to 100 parts of the binder, the types and blending ratios of alkali metal aluminate, alkali metal carbonate other than lithium carbonate, and organic acid were changed as shown in Table 3. Except that, the same procedure as in Example 1 was performed. The results are also shown in Table 3.

<Materials used>
Alkali metal carbonates other than lithium carbonate (2): Reagent primary sodium carbonate Alkali metal carbonates other than lithium carbonate (3): Reagent primary sodium hydrogen carbonate alkali metal aluminate B: Sodium aluminate (prototype), Anhydride, Na ₂ O / Al ₂ O ₃ molar ratio 0.8
Alkali metal aluminate C: sodium aluminate (prototype), anhydride, Na ₂ O / Al ₂ O ₃ molar ratio 1.2
Alkali metal aluminate D: Reagent primary sodium aluminate, pentahydrate, Na ₂ O / Al ₂ O ₃ molar ratio 1.5
Alkali metal aluminate E: Reagent primary potassium aluminate, tetrahydrate, K ₂ O / Al ₂ O ₃ molar ratio 1.3
Organic acid β: Reagent primary tartaric acid Organic acid γ: Reagent primary sodium gluconate

  From Table 3, the mortar using the ultrafast hardening / high fluidity cement composition of the present invention is excellent in fluidity, does not cause settlement, and has a sufficient pot life and strength at a low temperature (10 ° C.). It can be seen that the expression is good.

  In Experiment No. 1-2 of Example 1, it carried out like Example 1 except having changed the compounding ratio of the fine aggregate with respect to 100 parts of binders, and water / binder ratio as shown in Table 4. A temperature rise experiment was also conducted. The results are also shown in Table 4.

<Measurement method>
Temperature rise: 200 cc of mortar was put in a polystyrene cup, only the upper surface was opened and covered with a heat insulator, and a thermocouple was provided to measure the maximum temperature reached.

  Table 4 shows that the mortar using the super-hard setting / high-fluidity cement composition of the present invention has excellent fluidity, no subsidence, and has a sufficient pot life and strength at a low temperature (10 ° C.). It can be seen that the expression is good and the temperature rise of the mortar is small.

  In Experiment No. 1-2 of Example 1, it carried out like Example 1 except having changed the kind and compounding ratio of a gas foaming material with respect to 100 parts of binders as shown in Table 5.

<Materials used>
Gas foaming material b: Commercial coke gas foaming material c: Reagent primary sodium perborate gas foaming material d: Commercial aluminum powder

  From Table 5, the mortar using the ultrafast hardening / high fluidity cement composition of the present invention is excellent in fluidity, does not cause settlement, and has a sufficient pot life and strength at a low temperature (10 ° C.). It can be seen that the expression is good.

  In Experiment No. 1-2 of Example 1, it carried out like Example 1 except having changed the kind and mixture ratio of the fiber substance as shown in Table 6 with respect to 100 parts of binders. In addition, crack resistance was confirmed. The results are also shown in Table 6.

<Materials used>
Fiber material A: Commercially available vinylon fiber, length 6 mm, diameter 200 μm
Fiber material B: Commercial steel fiber, length 30 mm, diameter 600 μm
Fiber material C: commercially available wollastonite fiber, length 600 μm, diameter 40 μm

<Measurement method>
Crack resistance: A mortar was applied on a 50 cm × 50 cm concrete plate at a thickness of 1 cm and dried in an environment with a relative humidity of 60% and a temperature of 20 ° C. The state of cracks generated in the applied mortar was observed. ◎ No cracks at all, ○ No more than 2 cracks, 3 to 5 cracks, and more than 5 cracks.

  Table 6 shows that the mortar using the super-hard setting / high-fluidity cement composition of the present invention has excellent fluidity, no subsidence, and has a sufficient pot life and strength at low temperatures (10 ° C.). It can be seen that the development is good and the crack resistance is excellent.

  In Experiment No. 1-2 of Example 1, it carried out like Example 1 except having prepared mortar with the kind of fine aggregate shown in Table 7. The results are also shown in Table 7.

<Materials used>
Fine Aggregate B: Equivalent mixture of No. 6 silica sand and No. 7 silica sand, roundness 0.65
Fine aggregate C: Lime sand 0.6mm below and lime sand 1.2-0.6mm equal mixture, roundness 0.55

  From Table 7, the mortar using the super-fast hardening / high-fluidity cement composition of the present invention has excellent fluidity, no subsidence, strength at a low temperature (10 ° C.) while ensuring sufficient pot life. It can be seen that the expression is good.

  Concrete is prepared by blending coarse aggregates in the ratio shown in Table 8 with the mortar of Experiment No. 1-2 in Example 1, and the fluidity of the concrete, pot life, initial expansion coefficient, calorific value (temperature rise) The compressive strength and the rate of change in length were measured in an environment of 10 ° C. The results are also shown in Table 8.

<Materials used>
Coarse aggregate i: Commercially available gravel, silica-based, Gmax 15 mm, roundness 0.8, density 2.65
Coarse aggregate B: Commercially available crushed stone, quartzite, Gmax 15 mm, roundness 0.65, density 2.65

<Measurement method>
Concrete fluidity: Slump flow was measured and evaluated according to JIS A 1150.
Pot life: The concrete temperature was measured with a thermocouple, and the temperature was increased by 2 ° C. from the kneading temperature.
Initial expansion rate: Japan Society of Civil Engineers "Expanded concrete design and construction guidelines (draft)" Appendix 2. Measured according to the appendix “Construction Procedures for Filling Mortar Using Expandable Material (Draft)”. However,-in a table | surface shows a contraction side and + shows an expansion | swelling side.
Heat value of concrete: Concrete was filled in a cylindrical frame of φ10 cm × height 20 cm, the temperature of the center of the specimen was measured with a thermocouple, and the maximum temperature reached was observed.
Compressive strength: measured according to JIS A 1108.
Length change rate: Measured according to JIS A 6202 (B) (measuring material age 7 days).

  From Table 8, the concrete using the super-fast-hardening / high-fluidity cement composition of the present invention is excellent in fluidity, does not cause subsidence, and has a sufficient pot life and strength at a low temperature (10 ° C.). It can be seen that the expression is good and the temperature rise of the concrete is small.

  The super fast hardening / high fluidity cement mortar of the present invention can ensure excellent fluidity and sufficient pot life, and has excellent strength development in a short time at low temperature, so it can be widely used in civil engineering and construction applications. . For example, it is suitable for gap filling, self-leveling flooring, lining material and the like. Furthermore, the concrete in which the coarse aggregate is blended with the ultrafast hardening / high flow mortar of the present invention has a small calorific value, and therefore is suitable for applications having a large thickness, for example, a machine foundation or under-track filling concrete.

Claims (13)

Portland cement, calcium aluminate with a CaO / Al ₂ O ₃ molar ratio of 0.75 to 1.5, anhydrous gypsum, calcium hydroxide, alkali metal aluminate, and alkali metal carbonates other than lithium carbonate And a super-fast-hardening / high-fluidity cement composition comprising an organic acid, a fluidizing agent, and a gas foaming substance. Of the total 100 parts of Portland cement, calcium aluminate, anhydrous gypsum and calcium hydroxide, 35 to 55 parts of Portland cement, 20 to 40 parts of calcium aluminate, 10 to 25 parts of anhydrous gypsum, 1 to 1 of calcium hydroxide The super-fast-hardening / high-fluidity cement composition according to claim 1, which is 10 parts. For a total of 100 parts of Portland cement, calcium aluminate, anhydrous gypsum and calcium hydroxide, 0.03 to 0.5 part of alkali metal aluminate, 0.1 to 1 part of alkali metal carbonate other than lithium carbonate, The super fast hardening / high fluidity cement composition according to claim 1 or 2, wherein the organic acid is 0.1 to 0.5 part and the fluidizing agent is 0.1 to 1.5 part. The super-fast-hardening / high-fluidity cement composition according to any one of claims 1 to 3, wherein the anhydrous gypsum is acidic anhydrous gypsum. The super-fast-hardening / high-fluidity cement composition according to any one of claims 1 to 4, wherein the gas foaming substance is percarbonate. The super-fast-hardening / high-fluidity cement composition according to any one of claims 1 to 5, comprising a fiber substance. A mortar comprising the super-fast-hardening / high-fluidity cement composition according to any one of claims 1 to 6 and a fine aggregate. The mortar according to claim 7, wherein the roundness of the fine aggregate is 0.8 or more. The mortar according to claim 7 or 8, comprising 150 to 200 parts of fine aggregate with respect to 100 parts in total of Portland cement, calcium aluminate, anhydrous gypsum and calcium hydroxide. Water / binder ratio is prepared by adding water so that 30 to 43%, according to any one of claims 7-9, wherein J ₁₄ funnel flow value is 9 ± 4 seconds Mortar. The mortar according to any one of claims 7 to 10, wherein a compressive strength at an age of 1 hour at a low temperature of 10 ° C is 20 N / mm ² or more. The concrete formed by mix | blending a coarse aggregate with the mortar of any one of Claims 7-11. The concrete according to claim 12, wherein the roundness of the coarse aggregate is 0.8 or more.