WO2021024853A1 - Additif pour ciment et composition hydraulique - Google Patents

Additif pour ciment et composition hydraulique Download PDF

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Publication number
WO2021024853A1
WO2021024853A1 PCT/JP2020/028848 JP2020028848W WO2021024853A1 WO 2021024853 A1 WO2021024853 A1 WO 2021024853A1 JP 2020028848 W JP2020028848 W JP 2020028848W WO 2021024853 A1 WO2021024853 A1 WO 2021024853A1
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Prior art keywords
parts
cement
aluminum sulfate
cement admixture
admixture
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PCT/JP2020/028848
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English (en)
Japanese (ja)
Inventor
貴光 室川
博貴 水野
孝記 榊原
岩崎　昌浩
三島　俊一
Original Assignee
デンカ株式会社
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Priority claimed from JP2019142847A external-priority patent/JP6675033B1/ja
Priority claimed from JP2020047902A external-priority patent/JP6972214B2/ja
Priority claimed from JP2020047886A external-priority patent/JP6902643B1/ja
Priority claimed from JP2020047915A external-priority patent/JP6902644B1/ja
Priority claimed from JP2020047873A external-priority patent/JP6972213B2/ja
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Publication of WO2021024853A1 publication Critical patent/WO2021024853A1/fr

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Classifications

    • 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
    • C04B22/06—Oxides, Hydroxides
    • 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
    • C04B22/10—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
    • 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
    • C04B28/04—Portland cements

Definitions

  • the present invention relates to a cement admixture and a hydraulic composition used in the fields of civil engineering, construction, etc.
  • simplification of construction is a very important factor in considering the safety of workers.
  • simplification of construction means, for example, comprehensive rationalization such as improvement of construction speed, unification of materials, and improvement of handleability.
  • Various hydraulic compositions having the above have been proposed (for example, Patent Documents 1 to 3).
  • the performance required for hydraulic compositions has been increasing more and more with further improvement in simplification of construction and support for new applications.
  • a cement admixture is blended in the hydraulic composition for the purpose of improving various properties such as curing speed.
  • an alkaline admixture has been used as the cement admixture, but from the viewpoint of safety, it is desired to use an acidic admixture.
  • a hydraulic substance such as cement is strongly alkaline, it is difficult to combine it with an acidic cement admixture, and there is a problem that a hydraulic composition having desired properties cannot be obtained.
  • a conventional acidic cement admixture suitable for improving the curing rate and premixing is added to the hydraulic composition, the storage stability of the hydraulic composition, the strength of the cured product, and the like are lowered. In addition, good cohesiveness and high strength from the very beginning may not be obtained.
  • a first object of the present invention is to provide a cement admixture capable of providing a hydraulic composition capable of obtaining a cured product having high strength. Further, according to the present invention, even if the hydraulic composition is preliminarily blended with an alkaline admixture, the storage stability is unlikely to decrease, and the hydraulic composition exhibits good cohesiveness and high strength can be obtained from the very beginning.
  • a second object is to provide a cement admixture capable of giving a substance.
  • the present inventors have conducted the above-mentioned problems, particularly the above-mentioned problems, in spite of the fact that the cement admixture containing aluminum sulfate having specific properties is acidic.
  • the object of 1 can be solved, and have completed the first invention of the present invention. That is, the first invention is as follows.
  • the aluminum sulfate is amorphous.
  • the solid aluminum sulfate 27 In the spectrum obtained by Al-NMR, the chemical shift has a peak at -0.20 to -20.00 ppm, and the half width of the peak is 10.00 to 35.00 ppm. ..
  • the pH of the aluminum sulfate is 1 to 6.
  • Particles having a particle size of 100 ⁇ m or more are 70% by mass or less, and particles having a particle size of 10 ⁇ m or less are less than 30% by mass.
  • the present inventors have found that a cement admixture containing calcium aluminate and aluminum sulfate having specific properties is a problem, particularly the second problem.
  • the object can be solved, and have completed the second invention of the present invention. That is, the second invention is as follows.
  • the aluminum sulfate is amorphous.
  • the solid aluminum sulfate 27 In the spectrum obtained by Al-NMR, the chemical shift has a peak at -0.20 to -20.00 ppm, and the half width of the peak is 10.00 to 35.00 ppm. .. (3) Particles having a particle size of 100 ⁇ m or more are 70% by mass or less, and particles having a particle size of 10 ⁇ m or less are less than 30% by mass.
  • the present inventors have solved the above problems, particularly the second purpose, with a cement admixture containing sodium silicate and aluminum sulfate having specific properties. He found out that he could do it, and completed the third invention, which is the present invention. That is, the third invention is as follows.
  • the aluminum sulfate is amorphous.
  • the solid aluminum sulfate 27 In the spectrum obtained by Al-NMR, the chemical shift has a peak at -0.20 to -20.00 ppm, and the half width of the peak is 10.00 to 35.00 ppm. .. (3) Particles having a particle size of 100 ⁇ m or more are 70% by mass or less, and particles having a particle size of 10 ⁇ m or less are less than 30% by mass.
  • the present inventors have solved the above problems, particularly the second object, with a cement admixture containing calcium sulfate and aluminum sulfate having specific properties. He found out that he could do it, and completed the fourth invention, which is the present invention. That is, the fourth invention is as follows.
  • the aluminum sulfate is amorphous.
  • the solid aluminum sulfate 27 In the spectrum obtained by Al-NMR, the chemical shift has a peak at -0.20 to -20.00 ppm, and the half width of the peak is 10.00 to 35.00 ppm. .. (3) Particles having a particle size of 100 ⁇ m or more are 70% by mass or less, and particles having a particle size of 10 ⁇ m or less are less than 30% by mass.
  • the present inventors have made a cement admixture containing by-product slaked lime and aluminum sulfate having specific properties the above-mentioned problems, particularly the second purpose.
  • the fifth invention is as follows.
  • the aluminum sulfate is amorphous.
  • the solid aluminum sulfate 27 In the spectrum obtained by Al-NMR, the chemical shift has a peak at -0.20 to -20.00 ppm, and the half width of the peak is 10.00 to 35.00 ppm. .. (3) Particles having a particle size of 100 ⁇ m or more are 70% by mass or less, and particles having a particle size of 10 ⁇ m or less are less than 30% by mass.
  • the storage stability is unlikely to decrease, and a hydraulically hardened body having ultrafast hardness and high strength can be obtained.
  • a cement admixture that can provide the composition can be provided.
  • the second invention even if the hydraulic composition is premixed with an alkaline admixture, the storage stability does not easily decrease, and the cement exhibits good cohesiveness and can obtain high strength from the very beginning. An admixture can be provided.
  • the hydraulic composition containing the cement admixture does not easily deteriorate in storage stability, and has high cohesive properties and high strength from the very beginning in a low temperature (5 ° C or lower) or high temperature (30 ° C or higher) environment. Since it can be obtained, in underground construction such as tunnels, stable rebound and adhesion can be achieved even in a spring water environment to some extent.
  • the third invention even if the hydraulic composition is premixed with an alkaline admixture, the storage stability does not easily decrease, and the cement exhibits good cohesiveness and can obtain high strength from the very beginning.
  • An admixture can be provided.
  • the hydraulic composition containing the cement admixture can have the above-mentioned effect and self-healing performance independent of the environmental temperature caused by sodium silicate.
  • the fourth invention it is possible to provide a cement admixture that exhibits good cohesiveness and can obtain high strength from the very beginning. In particular, it is possible to obtain a constant long-term strength without much dependence on the long-term strength in a high-temperature environment and the water-cement ratio of cement paste, cement mortar, and cement concrete.
  • the fifth invention even if the hydraulic composition is premixed with an alkaline admixture, the storage stability does not easily decrease, and the cement exhibits good cohesiveness and can obtain high strength from the very beginning.
  • An admixture can be provided. In particular, condensation and initial strength development in a low temperature environment can be stably obtained, and it is possible to prevent the physical properties from being affected by the timing of addition to cement.
  • the cement admixture of the first invention contains aluminum sulfate that satisfies the following (1) to (4).
  • Aluminum sulfate is amorphous. When aluminum sulfate is not amorphous, it is difficult to premix it with a hydraulic substance showing strong alkalinity such as cement, and even if it can be premixed, the storage stability of the hydraulic composition is lowered.
  • whether or not aluminum sulfate is amorphous can be determined by X-ray diffraction analysis.
  • the X-ray diffraction spectrum of aluminum sulfate is broad, it can be determined to be amorphous.
  • the half width of the peak is preferably 10 to 35 ppm, more preferably 25 to 32 ppm.
  • the solid 27 Al-NMR measurement of aluminum sulfate can be carried out under the following conditions using a commercially available measuring device, for example, a superconducting nuclear magnetic resonance device “ECX-400” manufactured by JEOL Ltd. .. Observation nucleus: 27 Al Sample tube rotation speed: 10 KHz Measurement temperature: Room temperature Pulse width: 3.3 ⁇ sec (90 ° pulse) Waiting time: 5 seconds External standard: Aluminum nitrate
  • the heating temperature when heating a mixture of various raw materials may be adjusted.
  • the pH of aluminum sulfate is 1 to 6. If the pH of aluminum sulfate is out of the above range, the curing rate of the hydraulic composition will decrease.
  • the pH is preferably 2 to 5, more preferably 2 to 4. Further, in order to set the pH of aluminum sulfate to 1 to 6, the above heating temperature may be adjusted. In the present specification, the pH can be measured by adding 10 g to 100 ml of water at 20 ⁇ 2 ° C. and stirring at 500 rpm using a pH meter.
  • 70% or less of the particles have a particle size of 100 ⁇ m or more, and less than 30% of the particles have a particle size of 10 ⁇ m or less. If the particle size of 100 ⁇ m or more exceeds 70%, the curing rate of the hydraulic substance cannot be sufficiently obtained, and if the particles having a particle size of 10 ⁇ m or less are 30% or more, an alkaline admixture having a pH of 8 or more. By coexisting with, storage deterioration becomes remarkable.
  • the particles having a particle size of 100 ⁇ m or more are preferably 50% or less, more preferably 30% or less. Further, the particles having a particle size of 10 ⁇ m or less are preferably 40% or more, more preferably 50% or more.
  • the particle size can be adjusted by, for example, a sieve. It should be noted that the admixture using aluminum sulfate in the range of (4) does not mean that a sufficient curing rate can be obtained from low temperature to high temperature, and it is expected that the curing rate will increase particularly at high temperature. Since it is thought that the curing rate can be controlled by the coexistence of alkaline substances with pH 8 or higher, it can be used in a wide temperature range from low temperature (10 ° C) to high temperature (30 ° C), so it can be applied stably in both summer and winter. is there.
  • Aluminum sulfate satisfying the above-mentioned (1) to (4) is prepared by mixing raw materials such as Al 2 O 3 source and SO 3 source using an Al 2 O 3 source and an SO 3 source to prepare a mixture.
  • a method of heating treatment a method of directly chemically reacting Al 2 O 3 source and SO 3 source, a method is a chemical reaction after mixing was charged with Al 2 O 3 source and SO 3 source in a solvent such as pure water or the like Can be used.
  • a solvent such as pure water or the like
  • the Al 2 O 3 source is not particularly limited, but aluminum sulfate, aluminate, and other inorganic aluminum compounds, organoaluminum compounds, and aluminum complexes can be used.
  • the sulfate of aluminum is not particularly limited, and examples thereof include ammonium alum, aluminum hydroxysulfate, and aluminum sulfate.
  • the alumate is not particularly limited, and examples thereof include lithium aluminate, sodium aluminate, potassium aluminate, calcium aluminate, and magnesium aluminate.
  • Other inorganic aluminum compounds are not particularly limited, but are, for example, bokisite, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum phosphate, aluminum nitrate, aluminum fluoride, polyaluminum chloride, aluminum carbonate, synthetic hydrotal. Sight, aluminum metasilicate and the like.
  • the organoaluminum compound is not particularly limited, and examples thereof include aluminum stearate, aluminum oxalate, aluminum isopropoxide, and aluminum formate.
  • the aluminum complex is not particularly limited, and examples thereof include tris (8-hydroxyquinolinato) aluminum.
  • Al 2 O 3 source a single species can be used, but two or more species may be used in combination.
  • aluminum sulfate is preferable because it has high solubility in water, low production cost, and excellent cohesiveness, but aluminum hydroxide is also preferable.
  • the SO 3 source but are not limited to, in addition to elemental sulfur, such as sulfur and sulfur oxide, sulfide, sulfate, sulfate, sulfite, sulfite, thiosulfate, sulfate, and organic sulfur compounds such as Can be used.
  • the sulfide is not particularly limited, and examples thereof include magnesium sulfide, calcium sulfide, iron sulfide, and phosphorus pentasulfide.
  • the sulfate is not particularly limited, and examples thereof include aniline sulfate, aluminum sulfate, ammonium sulfate, magnesium sulfate, manganese sulfate, barium sulfate, calcium sulfate, sodium sulphate, potassium sulphate, ammonium sulphate, and hydroxylamine sulfate.
  • the sulfite salt is not particularly limited, and examples thereof include ammonium hydrogen sulfite and calcium sulfite.
  • the thiosulfate is not particularly limited, and examples thereof include ammonium thiosulfate and barium thiosulfate.
  • the organic sulfur compound is not particularly limited, and examples thereof include resins such as a sulfonic acid derivative, a salt of a sulfonic acid derivative, mercaptan, thiophene, a thiophene derivative, polysulfone, polyether sulfone, and polyphenylene sulfide.
  • the SO 3 source can be used single type may be used in combination of two or more. Among the various SO 3 source of the high solubility in water, from the viewpoint of excellent cheap and caking manufacturing cost, preferably sulfuric acid or sulfates, and most preferably sulfuric acid or ammonium alum.
  • the obtained aluminum sulfate is pulverized by, for example, a known mill or the like so as to satisfy the requirement (4) by sieving or the like.
  • the first invention it is preferable to contain any one of calcium aluminate, powdered sodium silicate, calcium sulfate, and by-product slaked lime.
  • the second invention described later when calcium aluminate is contained the third invention described later when containing powdered sodium silicate, the fourth invention described later when calcium sulfate is contained, and the fourth invention described later when containing by-product slaked lime will be described later.
  • the fourth invention is incorporated by reference.
  • the cement admixture according to the present embodiment contains calcium aluminate and specific acidic aluminum sulfate.
  • CA Calcium aluminumate Calcium aluminate
  • CaO and Al 2 O 3 as main components and having hydration activity
  • Ca O and / or Al 2 O 3 alkali metal oxidation.
  • amorphous calcium aluminate is preferable.
  • the vitrification rate is preferably 80% or more.
  • the calcium aluminate used in the present embodiment is mixed with a trace amount of alkali metal and / or alkaline earth metal from the industrial raw material, and some CAs containing the alkali metal and / or alkaline earth metal are generated. It is possible, but not limited by the presence of these few alkali metals and / or alkaline earth metals.
  • Calcium aluminate is preferably alkaline, and more preferably has a pH of 10-14. Being alkaline (particularly pH 10 to 14) makes it easier to exert the characteristics of calcium aluminate.
  • the CaO / Al 2 O 3 molar ratio of calcium aluminate is not particularly limited, but the molar ratio is preferably 2.0 to 3.0 in consideration of the strength development in the very early stage. When the molar ratio is 2.0 or more, the cohesive property at the very early stage can be improved, and when it is 3.0 or less, good long-term strength development can be easily obtained.
  • the specific surface area of the brain of calcium aluminate (hereinafter, may be simply referred to as "brain") is preferably 4000 to 8000 cm 2 / g, and more preferably 5000 to 7000 cm 2 / g. When it is 4000 to 8000 cm 2 / g, the initial strength development can be easily obtained, and the handleability of the mortar and / or concrete at the time of spraying can be improved.
  • the brain specific surface area is measured based on the specific surface area test described in JIS R 5201 “Physical test method for cement”.
  • the average particle size of calcium aluminate is preferably 1 to 250 ⁇ m, and more preferably 1 to 150 ⁇ m, from the viewpoint of mixing with specific aluminum sulfate described later and exhibiting a good effect by mixing.
  • the average particle size can be measured and obtained by the laser diffraction / diffusion method.
  • the aluminum sulfate according to the present embodiment is acidic aluminum sulfate that satisfies the following (1) to (3).
  • Aluminum sulfate is amorphous. The above (1) is the same as (1) according to the first invention.
  • Particles having a particle size of 100 ⁇ m or more are 70% by mass or less, and particles having a particle size of 10 ⁇ m or less are less than 30% by mass.
  • the above (3) is the same as (2) according to the first invention.
  • the pH of aluminum sulfate is preferably 1 to 6.
  • the pH is preferably 2 to 5, more preferably 2 to 4.
  • the heating temperature described above may be adjusted.
  • the pH can be measured by adding 10 g to 100 ml of water at 20 ⁇ 2 ° C. and stirring at 500 rpm using a pH meter.
  • Acidic aluminum sulfate satisfying the above-mentioned (1) to (3) is mixed with raw materials such as Al 2 O 3 source and SO 3 source using Al 2 O 3 source and SO 3 source to form a mixture.
  • raw materials such as Al 2 O 3 source and SO 3 source using Al 2 O 3 source and SO 3 source
  • a method of directly chemically reacting Al 2 O 3 source and SO 3 source, react chemically after mixing was charged with Al 2 O 3 source and SO 3 source in a solvent such as pure water A method or the like can be used.
  • Al 2 O 3 source and SO 3 source in a solvent such as pure water
  • the Al 2 O 3 source and the SO 3 source are the same as those according to the first invention.
  • the obtained acidic aluminum sulfate is pulverized by, for example, a known mill or the like so as to satisfy the requirement (3) by sieving or the like.
  • the mixing ratio of calcium aluminate and acidic aluminum sulfate (calcium aluminate / acidic aluminum sulfate: mass ratio) according to the present embodiment may be 1 to 40 from the viewpoint of fully exerting mutual effects. It is preferably 2 to 30, and more preferably 2 to 30.
  • cement admixture contains sodium silicate and specific acidic aluminum sulfate.
  • Soda silicate a powdered quick-setting admixture
  • cement mortar cement mortar for spraying mortar
  • cement concrete cement concrete for spraying cement
  • the sodium silicate is preferably in the form of powder.
  • the molar ratio of SiO 2 to Na 2 O (SiO 2 / Na 2 O) in sodium silicate is preferably 0.5 to 5, as a powdered quick-setting admixture, for example, for promoting the loss of fluidity in the very early stage.
  • 0.5 to 1.5 is more preferable, and 0.9 to 1.3 is even more preferable.
  • the molar ratio is 0.5 or more, the powder is easy to handle, and when it is 1.5 or less, the fluidity disappears and the initial strength develops significantly immediately after the addition to cement mortar and cement concrete. It will be easier to obtain.
  • sodium silicate examples include sodium orthosilicate, sodium metasilicate, and sodium sesquisilicate, and sodium metasilicate is preferable.
  • the sodium silicate is not particularly limited whether it is a hydrate or an anhydride, but the number of hydrated water is preferably 9 or less, more preferably 5 or less, and further preferably the use of anhydrous.
  • Blaine specific surface area of the sodium silicate is preferably 300 ⁇ 1000cm 2 / g, more preferably 500 ⁇ 800cm 2 / g. When it is 300 to 1000 cm 2 / g, the initial strength development can be easily obtained, and the handleability of the mortar and / or concrete at the time of spraying can be improved.
  • the brain specific surface area is measured based on the specific surface area test described in JIS R 5201 “Physical test method for cement”.
  • the average particle size of sodium silicate is preferably 1 to 300 ⁇ m, and more preferably 1 to 250 ⁇ m, from the viewpoint of mixing with specific aluminum sulfate described later and exhibiting a good effect by mixing.
  • the average particle size can be determined by using, for example, a laser diffraction / scattering type particle size distribution measuring device manufactured by HORIBA.
  • the content of sodium silicate in the powdered quick-setting admixture of the present embodiment is preferably 0.5 to 20 parts, more preferably 1 to 10 parts out of 100 parts of the powdered quick-setting admixture. With 0.5 to 20 parts, the self-repairing function against cracks can be improved.
  • the aluminum sulfate according to the present embodiment is the same as that of the "specific acidic aluminum sulfate" in the second invention.
  • the mixing ratio of sodium silicate and acidic aluminum sulfate (soda silicate / acidic aluminum sulfate: mass ratio) according to the present embodiment is 5/5 to 5/40 from the viewpoint of fully exerting mutual effects. Is preferable, and 5/5 to 5/20 is more preferable.
  • the cement admixture according to the present embodiment contains calcium sulfate and specific acidic aluminum sulfate.
  • Calcium sulfate imparts an effect of increasing the compressive strength to cement mortar and cement concrete mainly for a short period of time to a long period of time (for example, 28 days of age).
  • Calcium sulfate includes anhydrous, semi-aqueous, and binary depending on the presence or absence of water of crystallization, but both can be used.
  • the brain specific surface area of calcium sulfate is preferably 1000 cm 2 / g or more, more preferably 2000 cm 2 / g or more, and further preferably 3000 cm 2 / g or more. When it is 1000 cm 2 / g or more, it is easy to obtain strength development from a short time to a long period of time, and it is possible to improve the handleability of mortar and / or concrete at the time of spraying.
  • Blaine specific surface area is preferably at 6000 cm 2 / g or less, and more preferably less 5000 cm 2 / g.
  • the brain specific surface area is measured based on the specific surface area test described in JIS R 5201 “Physical test method for cement”.
  • Calcium sulfate is preferably contained in 10 to 60 parts, more preferably 15 to 60 parts, further preferably 15 to 50 parts, and particularly 20 to 50 parts in 100 parts of the powdered quick-setting admixture. Is more preferable. By including 10 to 60, the effect of increasing the long-term strength is more likely to be imparted.
  • the average particle size of calcium sulfate is preferably 1 to 150 ⁇ m, more preferably 10 to 100 ⁇ m, from the viewpoint of mixing with specific aluminum sulfate described later and exhibiting a good effect by mixing.
  • the average particle size can be measured and obtained by a laser diffraction / diffusion method.
  • the aluminum sulfate according to the present embodiment is the same as that of the "specific acidic aluminum sulfate" in the second invention.
  • the mixing ratio of calcium sulfate and acidic aluminum sulfate (calcium sulfate / acidic aluminum sulfate: mass ratio) according to the present embodiment is preferably 1 to 40 from the viewpoint of sufficiently exerting mutual effects. More preferably, it is 2 to 20.
  • the cement admixture according to the present embodiment contains by-product slaked lime and specific acidic aluminum sulfate.
  • By-product slaked lime is an effective material for ensuring the decrease in fluidity at the very beginning and the long-term strength development.
  • By-product slaked lime refers to the carbide slag produced when the carbide is hydrated.
  • Commercially available calcium hydroxide can be used in combination as appropriate.
  • the content of by-product slaked lime is preferably 5 to 30 parts, more preferably 10 to 25 parts, out of 100 parts of the powdered quick-setting admixture. By having 5 or more parts, it is possible to ensure the quick-setting property and the long-term strength development. When the number of parts is 20 or less, good initial strength development can be easily obtained.
  • Blaine specific surface area of the by-product calcium hydroxide is preferably 1000 ⁇ 3000cm 2 / g, and more preferably 1500 ⁇ 2500cm 2 / g. When it is 1000 to 3000 cm 2 / g, it is possible to secure the quick-setting property and the long-term strength development, and it is possible to easily obtain a good initial strength development.
  • the brain specific surface area is measured based on the specific surface area test described in JIS R 5201 “Physical test method for cement”.
  • the average particle size of the by-product slaked lime is preferably 1 to 300 ⁇ m, more preferably 1 to 250 ⁇ m, from the viewpoint of mixing with specific aluminum sulfate described later and exhibiting a good effect by mixing.
  • the average particle size can be determined by using, for example, a laser diffraction / scattering type particle size distribution measuring device manufactured by HORIBA.
  • the aluminum sulfate according to the present embodiment is the same as that of the "specific acidic aluminum sulfate" in the second invention.
  • the mixing ratio of by-product slaked lime and acidic aluminum sulfate (by-product slaked lime / acidic aluminum sulfate: mass ratio) according to the present embodiment is 10/30 to 30/10 from the viewpoint of fully exerting mutual effects. It is preferably 10/30 to 20/10, and more preferably.
  • the cement admixture according to the first to fifth inventions is mixed with an alkaline admixture having a pH of 8 or more.
  • alkaline admixture examples include alkali metal aluminate, alkaline earth metal aluminate, alkaline earth metal carbonate, alkali metal hydroxide, alkali metal carbonate, alkaline earth metal hydroxide and the like. Of these, alkali metal carbonates and alkaline earth metal hydroxides are preferably contained.
  • Alkali metal carbonate can impart further cohesiveness and rapid hardness to cement.
  • the alkali metal carbonate include sodium carbonate, sodium hydrogencarbonate, calcium carbonate, potassium carbonate, lithium carbonate, lithium hydrogencarbonate, beryllium carbonate, magnesium carbonate, etc. Among them, sodium carbonate, sodium hydrogencarbonate, calcium carbonate, and carbonate. Potassium is preferred.
  • the content of the alkali metal carbonate in the alkaline admixture is preferably 50% or more, more preferably 80% or more.
  • Alkaline earth metal hydroxide can impart further cohesiveness, rapid hardness, and long-term strength development to cement.
  • Examples of the alkaline earth metal hydroxide include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, beryllium hydroxide and the like, among which calcium hydroxide, magnesium hydroxide and hydroxide are used. Sodium and potassium hydroxide are preferable.
  • the content of the alkaline earth metal hydroxide in the alkaline admixture is preferably 50% or more, more preferably 80% or more.
  • the alkaline admixture used in the cement admixture according to the first to fifth inventions preferably contains a combination of an alkali metal carbonate and an alkaline earth metal hydroxide. This combination makes it possible to impart significant cement coagulation, rapid hardening, and strength development.
  • the combination of the alkali metal carbonate and the alkaline earth metal hydroxide in the alkaline admixture is preferably 50% or more, and more preferably 80% or more.
  • the mass ratio of alkali metal carbonate to alkaline earth metal hydroxide in the combination is preferably 30/70 to 70/30 for alkali metal carbonate / alkaline earth metal hydroxide. , 40/60 to 60/40, more preferably.
  • the cement admixture and the alkaline admixture according to the first to fifth inventions are preferably mixed when added to a hydraulic substance, but the cement admixture according to the present invention has excellent storage stability with respect to alkali. , Preferably mixed 2-3 weeks before addition to the hydraulic material.
  • the hydraulic composition according to the present invention contains the cement admixture and the hydraulic substance according to the first to fifth inventions, and preferably further contains the above-mentioned alkaline admixture.
  • the cement admixture according to the first to fifth inventions can be used together with various hydraulic substances to prepare a hydraulic composition.
  • the cement admixtures according to the first to fifth inventions can be used together with an alkaline hydraulic substance even though they are acidic.
  • the storage stability tends to decrease, but the cement admixture according to the present invention is an alkaline hydraulic substance.
  • the hydraulic composition prepared by using the cement admixture according to the present invention can be stored for a long period of time without any special storage method, construction method or handling method. Further, this hydraulic composition has ultrafast hardness and can form a cured product having high strength. Therefore, by using this hydraulic composition, it is possible to simplify the construction.
  • the water-hardening substance used in the water-hardening composition is not particularly limited, but for example, various Portland cements such as ordinary, fast-strength, moderate heat, low heat, and white; manufactured from city waste incineration ash and sewage sludge incineration ash as raw materials.
  • Eco-cement to be used examples include mixed cement containing blast furnace slag, silica fume, limestone, fly ash, gypsum and the like.
  • the pH of the hydraulic substance is not particularly limited, but is preferably more than 7, more preferably 8 or more, and further preferably 10 or more.
  • the hydraulic composition can contain known additives that can be generally blended as long as the effects of the present invention are not impaired.
  • Additives are not particularly limited, but are rust preventives, colorants, polymers, fibers, fluidizers, neutralization inhibitors, waterproofing agents, thickeners, waterproofing agents, retarding agents, fast-strengthening agents, and accelerators. , Water reducing agent, high performance (AE) water reducing agent, foaming agent, foaming agent, AE agent, drying shrinkage reducing agent, quick-setting agent, leavening agent, cold resistance accelerator, efflorescence inhibitor, alkaline aggregate reaction inhibitor, Examples include black unevenness reducing agents and environmental purification admixtures. These additives can be used alone or in combination of two or more.
  • the cement admixture according to the first to fifth inventions in the hydraulic composition is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, respectively.
  • the amount of the alkaline admixture is preferably 2 to 30 parts with respect to 100 parts of each cement admixture according to the first to fifth inventions, and 2 to 20 parts. Is more preferable.
  • Aluminum sulfates A to E were prepared by mixing an Al 2 O 3 source, an SO 3 source, and a solvent at a molar ratio of 2: 3:10, and heating and reacting the mixture at each temperature shown in Table 1. .. Then, it was pulverized using a ball mill, and pulverized by a sieve so that particles having a particle size of 100 ⁇ m or more were 30% and particles having a particle size of 10 ⁇ m or less were 20%. The aluminum sulfate prepared above was subjected to X-ray diffraction, solid 27 Al-NMR, and pH evaluation.
  • Alkaline admixture a Sodium carbonate, reagent, pH11 Alkaline admixture a: Sodium hydrogen carbonate, reagent, pH 8.3 Alkaline admixture c: Calcium carbonate, reagent, pH10 Alkaline admixture d: Potassium carbonate, reagent, pH12 Alkaline admixture e: Calcium hydroxide, reagent, pH11 Alkaline admixture F: Magnesium hydroxide, reagent, pH 10.5 Alkaline admixture: sodium hydroxide, reagent, pH14 Alkaline admixture: potassium hydroxide, reagent, pH13
  • the setting time changed with the number of storage days. This is considered to be due to storage deterioration of the compound and the admixture.
  • the aluminum sulfates B to E did not show any storage deterioration, and that the aluminum sulfates B to D were particularly likely to have a promoting effect.
  • the admixture using aluminum sulfate in the range of the first invention can be used in a wide temperature range from low temperature (10 ° C.) to high temperature (30 ° C.), and is stable in both summer and winter. Is applicable.
  • the hydraulic composition which has ultra-fast hardness and high strength of the cured product, as well as the storage stability is unlikely to decrease even if it is blended in the hydraulic composition in advance.
  • a cement admixture capable of feeding can be provided.
  • alkaline admixtures a, b, c, d, o, mosquito, ki, and ku in this example are the same as those used in the example according to the first invention.
  • the admixture using aluminum sulfate within the range of the present invention can be used in a wide temperature range from low temperature (5 ° C) to high temperature (30 ° C), and therefore can be stably applied in both summer and winter. It is possible.
  • Calcium aluminate B Raw materials (CaCO 3 and Al 2 O 3 ) are pulverized and mixed so as to have a CaO / Al 2 O 3 molar ratio of 2.5, melted in an electric furnace, rapidly cooled, and vitrified by 90%.
  • Brain 5500 cm 2 / g, pH 12, and calcium aluminate having an average particle size of 0.4 ⁇ m were prepared.
  • Calcium aluminate C Raw materials (CaCO 3 and Al 2 O 3 ) are pulverized and mixed so as to have a CaO / Al 2 O 3 molar ratio of 2.5, melted in an electric furnace, rapidly cooled, and vitrified by 90%.
  • Calcium aluminate D Raw materials (CaCO 3 and Al 2 O 3 ) are pulverized and mixed so as to have a CaO / Al 2 O 3 molar ratio of 2.5, melted in an electric furnace, rapidly cooled, and vitrified by 90%.
  • Calcium aluminate E Raw materials (CaCO 3 and Al 2 O 3 ) are pulverized and mixed so as to have a CaO / Al 2 O 3 molar ratio of 2.5, melted in an electric furnace, rapidly cooled, and vitrified by 90%. , Brain 5500 cm 2 / g, pH 11, and calcium aluminate having an average particle size of 300 ⁇ m were prepared.
  • the hydraulic composition which has ultra-fast hardness and high strength of the cured product, as well as the storage stability is unlikely to decrease even if it is blended in the hydraulic composition in advance.
  • a cement admixture capable of feeding can be provided.
  • alkaline admixtures a, b, c, d, o, mosquito, ki, and ku in this example are the same as those used in the example according to the first invention.
  • the setting time changed with the number of storage days. This is considered to be due to storage deterioration of the compound and the admixture.
  • the aluminum sulfates B to E did not show any storage deterioration, and that the aluminum sulfates B to D were particularly likely to have a promoting effect.
  • the admixture using aluminum sulfate within the range of the present invention can be used in a wide temperature range from low temperature (5 ° C) to high temperature (30 ° C), and therefore can be stably applied in both summer and winter. It is possible.
  • Example 2 As shown in Table 22, all tests were carried out in the same manner as in Experimental Example 1 except that sodium silicates having different SiO 2 / Na 2 O molar ratios were used.
  • the composition of the powdered quick-setting admixture was described in Experiment No. It was prepared to have a composition of 1-5.
  • the fluidity decrease time, the setting time, and the compressive strength from the time when 80 g of the powdered quick-setting agent was added to the mortar to prepare the quick-setting mortar were measured. The results are also shown in Table 22 below.
  • Example 3 The test was carried out in the same manner as in Experimental Example 1 except that the hydrates of sodium silicates shown in Table 23 were used.
  • the composition of the powdered quick-setting admixture was described in Experiment No. It was prepared to have a composition of 1-5.
  • the fluidity decrease time, the setting time, and the compressive strength from the time when 80 g of the powdered quick-setting agent was added to the mortar to prepare the quick-setting mortar were measured. The results are also shown in Table 23.
  • Example 4 Concrete (sprayed concrete) of 360 kg of cement, 216 kg of water, 1049 kg of fine aggregate, and 716 kg of coarse aggregate (Himekawa water system No. 6 crushed stone, Niigata prefecture, density 2.67 g / cm 3 ) was prepared.
  • a concrete pump manufactured by MAYCO (Suprema) pumped concrete at a setting of 5 m 3 / h, and mixed and merged with compressed air from another system on the way to carry air. Further, at 3 m before discharge, the powdered quick-setting admixture shown in Table 24 below is applied by the transport device Werner Mader (WM-14 FU) so that the amount of the powdered quick-setting admixture is 10 parts per 100 parts of cement.
  • Test method Initial strength: The initial strength was measured by spraying on a mold according to JSCE-G561 and converting the pull-out strength at the age of 10 minutes, 3 hours, and 1 day into compression strength.
  • Rebound rate amount of dropped concrete sprayed (kg) / amount of concrete sprayed used for spraying (kg) x 100 (%).
  • the rebound rate is preferably 20% or less.
  • a test piece was prepared by spraying sprayed concrete onto each of two 10 cm ⁇ 10 cm ⁇ 40 cm molds. Immediately after production, the 40 cm surfaces of the two specimens were placed in parallel and fixed so that the gap was 0.1 mm, and underwater curing was carried out at 20 ° C. for 6 months, observed with a microscope, and 0.1 mm width. The repair rate for the gap was calculated.
  • the crack repair rate is preferably 50% or more.
  • the hydraulic composition which has ultra-fast hardness and high strength of the cured product, as well as the storage stability is unlikely to decrease even if it is blended in the hydraulic composition in advance.
  • a cement admixture capable of feeding can be provided.
  • alkaline admixtures a, b, c, d, o, mosquito, ki, and ku in this example are the same as those used in the example according to the first invention.
  • the setting time changed with the number of storage days. This is considered to be due to storage deterioration of the compound and the admixture.
  • the aluminum sulfates B to E did not show any storage deterioration, and that the aluminum sulfates B to D were particularly likely to have a promoting effect.
  • the admixture using aluminum sulfate within the range of the present invention can be used in a wide temperature range from low temperature (5 ° C) to high temperature (30 ° C), and therefore can be stably applied in both summer and winter. It is possible.
  • the temperature (test temperature) for obtaining the hydraulic composition was set to 20 ° C. to 10 ° C. by using calcium sulfates B to E having the average particle diameter shown in Table 31 below instead of calcium sulfate A.
  • a hydraulic composition composed of 100 parts of ordinary Portland cement (pH 14, industrial product) and 10 parts of a cement admixture was obtained in the same manner except that the temperature was set to 30 ° C.
  • 40 parts by mass of water (tap water) was further mixed with this hydraulic composition and mixed, and a coagulation test was conducted.
  • the setting test was carried out in accordance with JIS R5201 “Physical test method for cement”.
  • the condensation test measured the onset time of condensation. The results of each of the above evaluations are shown in Table 31.
  • the fourth invention it is possible to provide a cement admixture capable of providing a hydraulic composition having ultrafast hardness and high strength of a cured product. Further, according to the fourth invention, it is possible to provide a hydraulic composition having ultrafast hardness and high strength of a cured product.
  • alkaline admixtures a, b, c, d, o, mosquito, ki, and ku in this example are the same as those used in the example according to the first invention.
  • a cement admixture is prepared by mixing and mixing with parts, and after storing at the number of days shown in Table 33, temperature 20 ° C., and humidity 60%, 100 parts of ordinary Portland cement (pH 14, industrial product), cement admixture 10 A hydraulic composition consisting of parts was obtained. Then, 40 parts by mass of water (tap water) was further mixed with this hydraulic composition, and a coagulation test and a measurement of compressive strength were performed. The setting test and the measurement of the compressive strength were carried out in accordance with JIS R5201 “Physical test method for cement”. The condensation test measured the onset time of condensation. The results of each of the above evaluations are shown in Table 33.
  • a cement admixture is prepared by blending and mixing with parts, and after storing at the number of days shown in Table 34, temperature 20 ° C., and humidity 60%, 100 parts of ordinary Portland cement (pH 14, industrial product), cement admixture A hydraulic composition consisting of 10 parts was obtained. Then, 40 parts by mass of water (tap water) was further mixed with this hydraulic composition, and a coagulation test and a measurement of compressive strength were performed. The setting test and the measurement of the compressive strength were carried out in accordance with JIS R5201 “Physical test method for cement”. The condensation test measured the onset time of condensation. The results of each of the above evaluations are shown in Table 34.
  • the admixture using aluminum sulfate within the range of the present invention can be used in a wide temperature range from low temperature (5 ° C) to high temperature (30 ° C), and therefore can be stably applied in both summer and winter. It is possible.
  • the temperature (test temperature) at the time of obtaining the hydraulic composition by using the following by-product slaked limes B to E having different particle sizes instead of the by-product slaked lime A is set to 20 ° C. to 5 ° C. or 30 ° C.
  • a hydraulic composition composed of 100 parts of ordinary Portland cement (pH 14, industrial product) and 10 parts of cement admixture was obtained in the same manner except that the temperature was set to ° C.
  • 40 parts by mass of water (tap water) was further mixed with this hydraulic composition and mixed, and a coagulation test was conducted.
  • the setting test was carried out in accordance with JIS R5201 “Physical test method for cement”.
  • the condensation test measured the onset time of condensation. The results of each of the above evaluations are shown in Table 38.
  • the hydraulic composition which has ultra-fast hardness and high strength of the cured product, as well as the storage stability is unlikely to decrease even if it is blended in the hydraulic composition in advance.
  • a cement admixture capable of feeding can be provided.
  • the present invention can be suitably applied to cement admixtures used in the fields of civil engineering, construction and the like.

Abstract

La présente invention concerne un mélange de ciment comprenant du sulfate d'aluminium qui satisfait les conditions suivantes : (1) le sulfate d'aluminium est amorphe ; (2) dans un spectre obtenu par RMN 27Al solide du sulfate d'aluminium, un pic est à un décalage chimique de -0,20 ppm à -20,0 ppm, et la largeur de demi-valeur du pic est de 10,00 ppm à 35,00 ppm ; (3) le sulfate d'aluminium a un pH de 1 à 6 ; et (4) le mélange de ciment a au plus 70 % en masse de particules ayant un diamètre de particule de 100 µm ou plus, et moins de 30 % en masse de particules ayant un diamètre de particule de 10 µm ou moins.
PCT/JP2020/028848 2019-08-02 2020-07-28 Additif pour ciment et composition hydraulique WO2021024853A1 (fr)

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JP2019-142847 2019-08-02
JP2020047902A JP6972214B2 (ja) 2020-03-18 2020-03-18 セメント混和剤及び水硬性組成物
JP2020-047873 2020-03-18
JP2020-047915 2020-03-18
JP2020-047902 2020-03-18
JP2020-047886 2020-03-18
JP2020047886A JP6902643B1 (ja) 2020-03-18 2020-03-18 セメント混和剤及び水硬性組成物
JP2020047915A JP6902644B1 (ja) 2020-03-18 2020-03-18 セメント混和剤及び水硬性組成物
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CN113773012A (zh) * 2021-08-18 2021-12-10 辽宁壹立方砂业有限责任公司 用于3d打印的外加剂组合物、砂浆材料及其制备方法

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JP2015522516A (ja) * 2012-07-18 2015-08-06 マペイ ソシエタ ペル アチオニＭＡＰＥＩ Ｓ．ｐ．Ａ． 吹付コンクリート用の粉体形状の凝結硬化促進剤
JP2019043805A (ja) * 2017-08-31 2019-03-22 デンカ株式会社 セメント混和剤及び水硬性組成物
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JPH10101389A (ja) * 1996-10-02 1998-04-21 Chichibu Onoda Cement Corp セメント用硬化促進材
JPH10265248A (ja) * 1997-03-24 1998-10-06 Denki Kagaku Kogyo Kk セメント混和材及びそれを用いたセメント組成物
KR100518682B1 (ko) * 2003-02-04 2005-10-05 주식회사 실크로드시앤티 분사 콘크리트용 급결 혼화제 조성물
JP2011037688A (ja) * 2009-08-18 2011-02-24 Denki Kagaku Kogyo Kk 急結性吹付けセメントコンクリートの吹付け工法
JP2012017235A (ja) * 2010-07-09 2012-01-26 Denki Kagaku Kogyo Kk 発泡状急結剤、吹付け材料及びそれを用いた吹付け工法
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Publication number Priority date Publication date Assignee Title
CN113773012A (zh) * 2021-08-18 2021-12-10 辽宁壹立方砂业有限责任公司 用于3d打印的外加剂组合物、砂浆材料及其制备方法

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