WO2018142660A1 - コンクリート組成物及びコンクリート組成物の製造方法 - Google Patents
コンクリート組成物及びコンクリート組成物の製造方法 Download PDFInfo
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- WO2018142660A1 WO2018142660A1 PCT/JP2017/033786 JP2017033786W WO2018142660A1 WO 2018142660 A1 WO2018142660 A1 WO 2018142660A1 JP 2017033786 W JP2017033786 W JP 2017033786W WO 2018142660 A1 WO2018142660 A1 WO 2018142660A1
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- concrete composition
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Classifications
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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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/26—Carbonates
- C04B14/28—Carbonates of calcium
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
-
- 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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/38—Polysaccharides or derivatives 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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a concrete composition and a method for producing the concrete composition.
- the performance required for concrete is largely classified into workability, strength and durability.
- the index indicating the performance of concrete is representative and general of slump or slump flow belonging to workability and compressive strength belonging to strength.
- the compressive strength of concrete greatly depends on the water-cement ratio, if this compressive strength is set appropriately, the durability that also largely depends on the water-cement ratio is secured.
- the type of cement may be selected according to the required performance. Since the slump or the slump flow has become too typical and general as an index indicating workability, there are cases where the workability is judged only by the numerical value. In practice, material separation resistance and / or impact deformation resistance belonging to workability are also important indicators of concrete performance.
- the material separation resistance and / or impact deformation resistance are greatly related to the viscosity of concrete, but if the fluidity is increased too much in order to improve the workability, the material separation resistance and / or the impact deformation resistance. Decreases. When material separation occurs, which is a phenomenon in which the coarse aggregate is separated from the mortar portion, strength and durability are lowered. In addition, when the degree of deformation of the concrete composition with respect to impact increases, the material separation resistance decreases. That is, material separation resistance and / or impact deformation resistance are not only related to workability, but also related to improvement in strength and durability.
- JP 2014-114176 A Japanese Patent Laid-Open No. 2005-281888
- the present invention aims to provide a concrete composition which is excellent in cost effectiveness and environmental load reduction, ensures a high level of material separation resistance and / or impact deformation resistance, and has excellent workability. To do.
- the present inventor considers cost-effectiveness and environmental load reduction, and blends pulverized fly ash obtained by pulverizing fly ash raw powder so as to have specific physical properties.
- the present inventors have found that a material composition resistance and / or impact deformation resistance at a high level can be secured and a concrete composition excellent in workability can be provided, and the present invention has been conceived. That is, the present invention is as follows.
- a concrete composition in which the water powder mass ratio of the mixture is 23 to 27%.
- a method for producing a concrete composition containing cement and pulverized fly ash obtained by pulverizing fly ash raw powder A step of pulverizing the fly ash raw powder into the pulverized fly ash so that the specific gravity only after pulverization is increased by 1.5% or more and 3.0% or less with respect to the specific gravity before pulverization;
- the manufacturing method of the concrete composition including the process of mix
- the concrete composition according to the embodiment of the present invention contains cement and pulverized fly ash obtained by pulverizing fly ash raw powder, and the pulverized fly ash contains 50 parts by mass of water with respect to 100 parts by mass of pulverized fly ash.
- the fly ash paste contained has a JA funnel flow time in the range of 17 to 27 seconds.
- the JA funnel flow-down time refers to a flow-down time measured using a grouting flow cone of MIC-363-0-03 in accordance with “PC Grout fluidity test method” of JSCE-F531.
- the JA funnel flowing time of fly ash paste containing 50 parts by mass of water with respect to 100 parts by mass of fly ash may be described as “JA funnel flowing time” or “JA funnel flowing time of fly ash paste”. is there.
- pulverized fly ash refers to a pulverized fly ash powder.
- the pulverized fly ash may satisfy JIS regulations.
- the pulverized fly ash is not necessarily required to be obtained by pulverizing all the individual particles contained in the fly ash raw powder. Even if the particles are included without being crushed even after being pulverized, when the fly ash raw powder is pulverized, it is referred to as pulverized fly ash.
- a pulverizing apparatus for performing the pulverization process a ball mill, a vibration mill (vibrating the container and transmitting the vibration to the medium (ball and rod) inside the container to make the powder finer), and the like can be used.
- the pulverized fly ash obtained has a JA funnel flow time of 17 to 27 seconds in a fly ash paste containing 50 parts by mass of water with respect to 100 parts by mass of the pulverized fly ash. .
- the concrete composition containing the pulverized fly ash is excellent in fluidity and suitable. It has viscosity and can improve the workability.
- the pulverized fly ash contained in the concrete composition has a JA funnel flow time of the fly ash paste in the range of 17 to 27 seconds, high material separation resistance can be secured due to appropriate fluidity.
- the material separation resistance can be indirectly evaluated by the rebound reduction effect, and the impact deformation resistance of the concrete composition can also be evaluated by the rebound reduction effect.
- the rebound reduction effect can be evaluated as the rebound reduction effect is larger and the material separation resistance and / or impact deformation resistance is better as the number of spreads measured by the test method described in the examples is larger. If pulverized fly ash has a JA funnel flow time of fly ash paste of less than 17 seconds, the fluidity of the concrete composition containing pulverized fly ash increases, the viscosity decreases too much, and conversely, the workability is improved. May decrease. On the other hand, if the pulverized fly ash has a JA funnel flow time of fly ash paste longer than 27 seconds, the fluidity may be lowered and the workability may not be improved.
- the pulverized fly ash in which the JA funnel flow time of fly ash paste containing 50 parts by mass of water with respect to 100 parts by mass of pulverized fly ash is in the range of 17 to 27 seconds can improve workability and ensure high material separation resistance
- the pulverized fly ash stirs the mixture of the pulverized fly ash and water with “9.2.3 Mechanical kneader” of JIS R5201
- the current flowing to the mechanical kneader It is preferable that the water powder mass ratio of the mixture is 23 to 27% when the maximum is.
- pulverized fly ash with a JA funnel flowing time of fly ash paste containing 50 parts by mass of water to 100 parts by mass of pulverized fly ash in the range of 17 to 27 seconds has improved workability and high material separation resistance.
- the specific gravity only after grinding is increased by 1.5% or more and 3.0% or less with respect to the specific gravity before grinding.
- a concrete composition according to an embodiment of the present invention includes cement and pulverized fly ash obtained by pulverizing fly ash raw powder, and the pulverized fly ash is a mixture of the pulverized fly ash and water according to JIS R5201.
- the mixture is stirred by “9.2.3 Mechanical kneader”
- the water powder mass ratio of the mixture when the current flowing through the mechanical kneader is maximized is 23 to 27%. is there.
- the water powder mass ratio at the maximum current value is a numerical value specific to the target powder.
- the water powder mass ratio at the maximum current value can also be defined as the constrained water ratio, and is recognized as a numerical value specific to powder.
- the restrained water ratio represents the mass of water restrained by the powder.
- the mechanical kneader When the pulverized fly ash is kneaded and stirred with the pulverized fly ash and water using JIS R5201 “9.2.3 mechanical kneader”, the mechanical kneader is energized.
- the water powder mass ratio with the maximum current value is 23 to 27%
- the pulverized fly ash adsorbs water appropriately, and the concrete composition containing this pulverized fly ash has excellent fluidity and moderate It is possible to improve workability by having a good viscosity.
- the pulverized fly ash When the pulverized fly ash kneads and stirs the fly ash and water, the pulverized fly ash having a water powder mass ratio of 23 to 27% that maximizes the stirring torque adsorbs water appropriately.
- the concrete composition containing this fly ash can ensure high material separation resistance and / or impact deformation resistance.
- the mass ratio of the water powder that maximizes the current value supplied to the mechanical kneader is 23. If it is less than%, the amount of water restrained by the pulverized fly ash is small, and when shot concrete is taken as an example, rebound increases, and the rebound reduction effect tends to decrease.
- the mass ratio of water powder that maximizes the current value supplied to the kneader for mechanical kneading is 27. If the amount exceeds 50%, the amount of water restrained by the pulverized fly ash increases, and in addition to the decrease in fluidity in the fresh state at the beginning of kneading, the viscosity increases while absorbing too much water and rebounds. As a result, the impact deformation resistance required for rebound reduction is reduced.
- the water powder that maximizes the current applied to the mechanical kneader is a fly ash paste having a JA funnel flow time of 17 to 27% from the viewpoint of improving workability and ensuring high material separation resistance and / or impact deformation resistance. A range of 27 seconds is preferable.
- the mass ratio of the water powder that maximizes the current applied to the mechanical kneader is 23 to 27%.
- Some pulverized fly ash has a specific gravity of 1.5% or more only after pulverization with respect to the specific gravity before pulverization from the viewpoint of improving workability and ensuring high material separation resistance and / or impact deformation resistance. It is preferably increased by 0.0% or less.
- the concrete composition according to the embodiment of the present invention contains cement and pulverized fly ash obtained by pulverizing fly ash raw powder, and the pulverized fly ash has a specific gravity of 1 only after pulverization relative to the specific gravity before pulverization. Increased by 5% or more and 3.0% or less.
- the rate of increase in the specific gravity only after pulverization relative to the specific gravity before pulverization of fly ash may be referred to as “increase rate in specific gravity of tsutsuka”.
- the pulverized fly ash preferably has a specific gravity increased only by 1.6% or more and 2.9% or less after pulverization with respect to the specific gravity before pulverization, and is preferably 1.7% or more and 2.8%. % Is more preferable, and more preferably 1.8% or more and 2.7% or less.
- MiTsukasa gravity JIS R 5201 after filling the powder (fly ash) to be measured in an iron vessel volume 400 cm 3 or more 410Cm 3 below: by flow table defined in 2015 It represents the apparent density of the powder when the dropping motion is applied 70 times.
- the crushed fly ash which has an increased specific gravity of 1.5% or more and 3.0% or less after pulverization compared to the specific gravity before pulverization, has improved workability, high material separation resistance and / or impact deformation. From the viewpoint of securing resistance, it is preferable that the JA funnel flow time of the fly ash paste is in the range of 17 to 27 seconds.
- the crushed fly ash which has an increased specific gravity of 1.5% or more and 3.0% or less after pulverization relative to the specific gravity before pulverization, has improved workability and high material separation resistance and / or impact deformation resistance.
- the mechanical kneader is energized. It is preferable that the water powder mass ratio that maximizes the current value is 23 to 27%.
- the pulverized fly ash preferably has a grazing specific gravity of 1.12 to 1.13 g / cm 3 .
- the specific gravity of the crushed fly ash is 1.12 to 1.13 g / cm 3
- the concrete composition containing the pulverized fly ash has excellent fluidity and moderate viscosity, thereby improving workability.
- the ignition loss of pulverized fly ash is preferably 3% by mass or more and 10% by mass or less from the viewpoint of ensuring sufficient workability.
- the ignition loss of pulverized fly ash is more preferably 3% by mass or more and 9% by mass or less, and further preferably 3% by mass or more and 8% by mass or less.
- the ignition loss can be measured by the method described in Examples described later.
- the mechanism by which the loss on ignition of pulverized fly ash contributes to workability is not clear, but if the loss on ignition of pulverized fly ash is 3% by mass or more and 10% by mass or less, this pulverized fly ash and concrete containing cement Appropriate viscosity is imparted to the composition, and sufficient workability is obtained.
- the type of cement contained in the concrete composition is not particularly limited, and is preferably at least one selected from the group consisting of ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, and low heat Portland cement.
- the blending amount of cement in the concrete composition is preferably 300 kg or more and 420 kg or less, more preferably 320 kg or more and 400 kg or less, and further preferably 340 kg or more and 380 kg or less per 1 m 3 of the volume of the concrete composition. .
- the concrete composition can further contain, for example, water, fine aggregate, coarse aggregate, admixture and the like as a constituent material.
- the fine aggregate has a particle size of 5 mm or less.
- known aggregates such as river sand, mountain sand, land sand, crushed sand, sea sand, and quartz sand can be used.
- the coarse aggregate has a particle size of more than 5 mm.
- known aggregates such as gravel and sandstone crushed stone can be used.
- the blending amount of fine aggregate in the concrete composition is preferably 850 kg or more and 1050 kg or less, more preferably 875 kg or more and 1025 kg or less, and 900 kg or more and 1000 kg or less per 1 m 3 of the volume of the concrete composition. Further preferred.
- the blending amount of the coarse aggregate in the concrete composition is preferably 600 kg or more and 900 kg or less, more preferably 650 kg or more and 850 kg or less, and more preferably 700 kg or more and 800 kg or less per 1 m 3 of the volume of the concrete composition. Further preferred.
- the concrete composition preferably further contains at least one selected from admixtures and special admixtures. It is preferable to contain the admixture and the special admixture in a range suitable for cost effectiveness and environmental load reduction.
- the admixture include blast furnace slag fine powder, limestone fine powder and silica fume.
- Special admixtures include thickeners and non-separable admixtures in water.
- the thickener include cellulose thickeners such as methylcellulose; biopolymer thickeners such as water-soluble polysaccharides; and acrylic thickeners such as acrylic polymers.
- the water inseparable admixture include a cellulose admixture mainly composed of a cellulose-based water-soluble polymer; and an acrylic admixture mainly composed of a polyacrylamide-based water-soluble polymer.
- the blending amount of the pulverized fly ash in the concrete composition is 20 kg or more and 150 kg or less per 1 m 3 of the volume of the concrete composition from the viewpoint of ensuring high material separation resistance and / or impact deformation resistance and sufficient workability.
- the content of pulverized fly ash is more preferably 30 kg or more and 140 kg or less, and further preferably 40 kg or more and 130 kg or less.
- the ignition loss of the fly ash raw powder is preferably 3% by mass or more and 10% by mass or less from the viewpoint of ensuring sufficient workability.
- the ignition loss of the fly ash raw powder is more preferably 3% by mass or more and 9% by mass or less, and further preferably 3% by mass or more and 8% by mass or less.
- the ignition loss can be measured by the method described in Examples described later.
- the mechanism by which the loss on ignition of pulverized fly ash contributes to workability is not clear, but if the loss on ignition of pulverized fly ash is 3% by mass or more and 10% by mass or less, this pulverized fly ash and concrete containing cement Appropriate viscosity is imparted to the composition, and sufficient workability is obtained.
- the fly ash raw powder whose ignition loss is in the above range is, for example, ash discharged from a thermal power plant, and is produced by pulverized coal combustion.
- fly ash raw powder the fly ash dropped from the combustion gas of the combustion boiler when passing through the air regenerator or the economizer, the fly ash collected by the electric dust collector, and dropped to the furnace bottom of the combustion boiler Including ash.
- the concrete composition according to the embodiment of the present invention is preferably used for shotcrete.
- the shotcrete refers to concrete used for a method of compressing concrete containing a concrete composition and water, and spraying the compressed composition from a nozzle tip to a predetermined location using a compressed air.
- the aggregate is rebounded by the impact of the sprayed concrete, and the planned amount of concrete is not sprayed, causing a loss in the amount of concrete called rebound.
- the rebound reduction effect means an effect that the sprayed concrete can withstand the impact, the aggregate does not rebound, the concrete close to the planned amount can be sprayed, and the loss of the concrete is small.
- a concrete composition having a rebound reducing effect has little separation between aggregates and components other than aggregates (cement, fly ash, etc.), that is, high material separation resistance. Moreover, the concrete composition which has a rebound reduction effect does not bounce off the aggregate, and has high impact deformation resistance. By confirming the superiority or inferiority of the rebound reduction effect of shotcrete, the superiority or inferiority of material separation resistance or impact deformation resistance can be indirectly evaluated.
- a method for producing a concrete composition according to an embodiment of the present invention is a method for producing a concrete composition containing cement and pulverized fly ash obtained by pulverizing fly ash raw powder, and only for the specific gravity before pulverization.
- pulverization apparatus for producing pulverized fly ash, a ball mill, a vibration mill (vibrating the container and transmitting vibration to the medium (ball and rod) inside the container to make the powder finer), etc. it can.
- the rotation speed of the mill is preferably 45 rpm or more and 75 rpm or less, more preferably 50 rpm or more and 70 rpm or less, and further preferably 55 rpm or more and 65 rpm or less.
- the pulverization time when using a ball mill is preferably 3 minutes or longer and 15 minutes or shorter, more preferably 3 minutes or longer and 12 minutes or shorter, and further preferably 3 minutes or longer and 10 minutes or shorter.
- a concrete composition can be prepared by blending cement, pulverized fly ash and other constituent materials in a required mixing ratio and mixing them with a mixer or the like.
- the concrete composition according to the embodiment of the present invention produces a concrete kneaded material by kneading the solid material and water contained in the concrete composition, but preparing a solid material contained in the concrete composition in advance.
- This may be mixed with water to form a concrete kneaded material, and is not particularly limited as long as it can be uniformly kneaded even if all the solid materials and water contained in the concrete composition are mixed at once.
- the amount of water used for kneading can be changed depending on the type and blending of the materials used, so it is not uniquely determined, but the water cement ratio is 50% by mass or more and 70% by mass or less. It is more preferable that it is 55 mass% or more and 65 mass% or less.
- kneading conditions there is no limitation in kneading conditions, the kind of kneader, etc., it is possible to use a conventional kneader.
- the obtained concrete kneaded material can be subjected to curing such as steam curing and underwater curing to obtain concrete.
- the concrete composition of the present invention a high level of material separation resistance can be ensured by blending pulverized fly ash obtained by pulverizing fly ash raw powder so as to have specific physical properties. And since the material composition resistance of the concrete composition is high, the workability of the concrete composition is excellent, and the work efficiency can be improved.
- the ignition loss of the fly ash raw powder and the pulverized fly ash was determined according to JIS A 6201: 2015 : fly ash for concrete (975 ° C., 15 minutes ignited).
- the pulverization of fly ash raw powder uses a tilting ball mill having a drum with a capacity of 100 liters.
- the balls to be thrown are chrome steel balls (about 3.5 kg / piece) with a diameter of 10 mm.
- a ball is thrown into the fly ash raw powder in the drum (weight ratio, maximum is 100 kg for 10 kg of fly ash raw powder).
- the mill was placed in a horizontal position, the rotation speed of the mill was set to 60 rpm, and the tilting ball mill was operated for the predetermined time to perform pulverization.
- a mixture containing pulverized fly ash having different mass ratios of water powder and water is prepared.
- JIS R5201 “9.2.3 Mechanical kneader” stirs and kneads a plurality of mixtures having different water-powder ratios, and measures the current flowing through the mechanical kneader.
- the current flowing through the mechanical kneader is measured by using one of the two single-phase power cables of the mechanical kneader as a current measuring device (product name: Memory HiCorder MR8870, Hioki).
- the mechanical kneader can be energized with a maximum current of 500 amperes (A).
- Table 1 shows the measured values of the electric current supplied to the mechanical kneader after each of the mixtures with the amount of water added was stirred with the mechanical kneader.
- Table 1 shows the water powder mass ratio at the maximum value of the current passed through the mechanical kneader when measured in the same manner as the fly ash (1) II seed ash.
- slump About each concrete composition manufactured with the mixing
- the concrete compositions of Examples 1 to 6 have a JA flow time of fly ash paste of 17 to 27 seconds, have excellent fluidity, have an appropriate viscosity, and improve workability.
- the number of times of spreading increased as compared with the concrete compositions of Comparative Examples 1 to 9.
- the concrete compositions of Examples 1 to 6 were kneaded and stirred with the fly ash and water by “9.2.3 Mechanical kneader” of JIS R5201
- the mass ratio of the water powder that maximizes the current applied to the kneader for mechanical kneading is 23 to 27%, and the pulverized fly ash in the concrete composition adsorbs water appropriately.
- the contained concrete composition was excellent in fluidity and had an appropriate viscosity, and the number of spreading was increased as compared with the concrete compositions of Comparative Examples 1 to 9. From Table 4, the rate of increase in specific gravity of crushed fly ash ground for 4 minutes and 5 minutes was 2.7%, and the rate of increase in specific gravity of ground fly ash ground for 3 minutes and 10 minutes was 1.8%.
- the concrete compositions of Examples using this pulverized fly ash increased in the number of times of spreading compared with the concrete compositions of Comparative Examples 1 to 9.
- the concrete compositions of Examples 1 to 6 were considered to have increased rebound reduction effect as shotcrete because the number of times of expansion increased compared to the concrete compositions of Comparative Examples 1 to 9, and material separation resistance and / Or was excellent in impact deformation resistance.
- the concrete compositions of Comparative Examples 6 and 7 including the pulverized fly ash having a water powder mass ratio at the maximum current value exceeding 27% are large in the amount of water restrained by the pulverized fly ash.
- the flow rate in the fresh state at the beginning of kneading of the concrete composition and water decreases and the viscosity increases, while water is absorbed too much and rebound increases, and the number of times of spreading increases by about 1 to 6.
- the impact deformation resistance required for rebound reduction was reduced.
- the concrete compositions of Comparative Examples 8 and 9 including the pulverized fly ash having a small water powder mass ratio of less than 23% at the maximum current value have a small amount of water restrained by the pulverized fly ash.
- the rebound increased, the number of spreads did not increase as much as in Examples 1 to 6, the rebound reduction effect decreased, and the material separation resistance and / or impact deformation resistance decreased.
- pulverized fly ash obtained by pulverizing fly ash raw powder so as to have specific physical properties, high material separation resistance and / or impact deformation resistance can be ensured, and workability is improved. It is possible to provide an excellent concrete composition.
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Abstract
Description
スランプ又はスランプフローが施工性を示す指標として代表的かつ一般的になり過ぎたため、その数値のみで施工性を判断してしまうケースが生じている。実際には、施工性に属する材料分離抵抗性及び/又は衝撃変形抵抗性もコンクリートの性能を示す重要な指標である。材料分離抵抗性及び/又は衝撃変形抵抗性は、コンクリートの粘性と大きく関係しているが、施工性を向上させるために流動性を高くしすぎると、材料分離抵抗性及び/又は衝撃変形抵抗性が低下する。粗骨材がモルタル部分から離れる現象である、材料分離を生じると、強度及び耐久性が低下する。また、衝撃に対するコンクリート組成物の変形の程度が大きくなると、材料分離抵抗性が低下する。つまり、材料分離抵抗性及び/又は衝撃変形抵抗性は、施工性に関連するばかりでなく、強度及び耐久性の向上にも関連する。
しかし、粉体又は微粒分には、使用量の限度があり、材料分離抵抗性及び/又は衝撃変形抵抗性を確保する上で必要な量を使用できない場合もある。そこで、材料分離抵抗性及び/又は衝撃変形抵抗性を確保する上で粉体及び微粒分では補いきれない場合、高炉スラグ微粉末、石灰石微粉末、フライアッシュ及びシリカフューム等の混和材を使用する場合がある。
このように、コンクリートの材料分離抵抗性を高めるために、粉体、微粒分及び混和材を含む材料をコンクリート材料としてバランスよく配合することが提案されている(例えば、特許文献1参照)。一方、増粘剤及び水中不分離性混和剤等の特殊混和剤によって化学的に粘性を付与させ、材料分離抵抗性を高める技術も提案されている(例えば、特許文献2参照)。
そこで、シリカフューム等の混和材、並びに、増粘剤及び水中不分離性混和剤等の特殊混和剤を含ませることが得策とされている。しかし、これらの混和材及び特殊混和剤は非常に高価な材料であり、材料分離抵抗性及び/又は衝撃変形抵抗性の確保のためだけに含ませるのであれば対費用効果に見合わないといった問題がある。
前記粉砕フライアッシュが、粉砕フライアッシュ100質量部に対して水50質量部を含むフライアッシュペーストのJAロート流下時間が17~27秒の範囲のものである、コンクリート組成物。
[2]セメントと、フライアッシュ原粉を粉砕した粉砕フライアッシュとを含有し、
前記粉砕フライアッシュが、前記粉砕フライアッシュと水との混合物をJIS R5201の「9.2.3 機械練り用練混ぜ機」により撹拌した際に前記機械練り用練混ぜ機に流れる電流が最大となるときの前記混合物の水粉体質量比が23~27%のものである、コンクリート組成物。
[3]セメントとフライアッシュ原粉を粉砕した粉砕フライアッシュをと含有し、前記粉砕フライアッシュは、粉砕前のみつかさ比重に対して粉砕後のみつかさ比重が1.5%以上3.0%以下増加したものである、コンクリート組成物。
[4]前記粉砕フライアッシュの強熱減量が、3質量%以上10質量%以下である、前記[1]~[3]のいずれかに記載のコンクリート組成物。
[5]前記粉砕フライアッシュの含有量が、コンクリート組成物の容積1m3当り、20kg以上150kg以下である、前記[1]~[4]のいずれかに記載のコンクリート組成物。
[6]混和材及び特殊混和剤から選ばれる少なくとも1種をさらに含有する、前記[1]~[5]のいずれかに記載のコンクリート組成物。
[7]前記セメントが、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント及び低熱ポルトランドセメントからなる群より選ばれる少なくとも1種である、前記[1]~[6]のいずれかに記載のコンクリート組成物。
[8]セメントとフライアッシュ原粉を粉砕した粉砕フライアッシュとを含有するコンクリート組成物の製造方法であって、
粉砕前のみつかさ比重に対して粉砕後のみつかさ比重が1.5%以上3.0%以下増加したものとなるように、前記フライアッシュ原粉を粉砕して前記粉砕フライアッシュとする工程と、
前記セメントと前記粉砕フライアッシュとを配合する工程とを含むコンクリート組成物の製造方法。
[9]前記フライアッシュ原粉の強熱減量が、3質量%以上10質量%以下である、前記[8]に記載のコンクリート組成物の製造方法。
本明細書において、JAロート流下時間は、JSCE-F531の「PCグラウトの流動性試験方法」に準拠して、MIC-363-0-03のグラウトフローコーンを用いて測定した流下時間をいう。
本明細書において、フライアッシュ100質量部に対して水50質量部を含むフライアッシュペーストのJAロート流下時間を「JAロート流下時間」又は「フライアッシュペーストのJAロート流下時間」と記載する場合がある。
粉砕加工を施す粉砕装置としては、ボールミル、振動ミル(容器に振動を与えて、容器内部の媒体(ボール及びロッド)に振動を伝えて粉体を細粒化させる)等を用いることができる。フライアッシュ原粉の粉砕は、得られた粉砕フライアッシュが、粉砕フライアッシュ100質量部に対して水50質量部を含むフライアッシュペーストのJAロート流下時間が17~27秒の範囲のものである。
また、粉砕フライアッシュ100質量部に対して水50質量部を含むフライアッシュペーストのJAロート流下時間が17~27秒の範囲である粉砕フライアッシュは、施工性の向上と高い材料分離抵抗性の確保の観点から、粉砕前のみつかさ比重に対して粉砕後のみつかさ比重が1.5%以上3.0%以下増加したものであることが好ましい。
粉砕フライアッシュと水とを前記機械練り用練混ぜ機を用いて混練撹拌した際に、前記機械練り用練混ぜ機に通電される電流が最大となる水粉体質量比が23~27%である粉砕フライアッシュは、施工性の向上と、高い材料分離抵抗性及び/又は衝撃変形抵抗性の確保の観点から、粉砕前のみつかさ比重に対して粉砕後のみつかさ比重が1.5%以上3.0%以下増加したものであることが好ましい。
本明細書において、「みつかさ比重」とは、容積400cm3以上410cm3以下の鉄製容器に測定対象となる粉体(フライアッシュ)を充填した後にJIS R 5201:2015で規定されたフローテーブルによる落下運動を70回加えた際の粉体の見かけの密度を表す。
粉砕前のみつかさ比重に対して粉砕後のみつかさ比重が1.5%以上3.0%以下増加したものである粉砕フライアッシュは、施工性の向上と高い材料分離抵抗性及び/又は衝撃変形抵抗性の確保の観点から、前記粉砕フライアッシュと水とをJIS R5201の「9.2.3 機械練り用練混ぜ機」を用いて混練撹拌した際に、前記機械練り用練混ぜ機に通電される電流値が最大となる水粉体質量比が23~27%のものであることが好ましい。
コンクリート組成物におけるセメントの配合量は、コンクリート組成物の容積1m3当り、300kg以上420kg以下であることが好ましく、320kg以上400kg以下であることがより好ましく、340kg以上380kg以下であることがさらに好ましい。
コンクリート組成物における細骨材の配合量は、コンクリート組成物の容積1m3当り、850kg以上1050kg以下であることが好ましく、875kg以上1025kg以下であることがより好ましく、900kg以上1000kg以下であることがさらに好ましい。
コンクリート組成物における粗骨材の配合量は、コンクリート組成物の容積1m3当り、600kg以上900kg以下であることが好ましく、650kg以上850kg以下であることがより好ましく、700kg以上800kg以下であることがさらに好ましい。
混和材としては、高炉スラグ微粉末、石灰石微粉末及びシリカフュームが挙げられる。
特殊混和剤としては、増粘剤及び水中不分離性混和剤が挙げられる。
増粘剤としては、例えば、メチルセルロース等のセルロース系増粘剤;水溶性ポリサッカライド等のバイオポリマー系増粘剤;アクリル系ポリマー等のアクリル系増粘剤が挙げられる。
水中不分離性混和剤としては、例えば、セルロース系水溶性高分子を主成分としたセルロース系混和剤;ポリアクリルアミド系水溶性高分子を主成分としたアクリル系混和剤が挙げられる。
粉砕フライアッシュを作製する粉砕装置としては、ボールミル、振動ミル(容器に振動を与えて、容器内部の媒体(ボール及びロッド)に振動を伝えて粉体を細粒化させる)等を用いることができる。
粉砕装置として、ボールミルを用いた場合のミルの回転数は、45rpm以上75rpm以下であることが好ましく、50rpm以上70rpm以下であることがより好ましく、55rpm以上65rpm以下であることがさらに好ましい。また、ボールミルを用いた場合の粉砕時間は、3分以上15分以下であることが好ましく、3分以上12分以下であることがより好ましく、3分以上10分以下であることがさらに好ましい。
混練に使用する水の量は、使用する材料の種類及び配合により変化させることができるため、一義的に決定されるものではないが、水セメント比が50質量%以上70質量%以下であることが好ましく、55質量%以上65質量%以下であることがより好ましい。
また、混練条件、混練機の種類等に限定はなく慣用の混練機を使用することが可能である。
得られたコンクリート混練物は、例えば、蒸気養生、水中養生等の養生をして、コンクリートを得ることができる。
・セメント:普通ポルトランドセメント(住友大阪セメント社製)
・水:上水道水
・細骨材:山砂
・粗骨材:砂岩砕石
・フライアッシュ(FA):以下に示す(1)~(10)
(1)II種灰(JIS A 6201:2015 コンクリート用フライアッシュ II種適合品(分級品)、強熱減量2.75質量%)
(2)原粉(フライアッシュ原粉、国内火力発電所産、強熱減量6.21質量%)
(3)1分粉砕FA(粉砕フライアッシュ、国内火力発電所産、強熱減量6.21質量%)
(4)2分粉砕FA(粉砕フライアッシュ、国内火力発電所産、強熱減量6.21質量%)
(5)3分粉砕FA(粉砕フライアッシュ、国内火力発電所産、強熱減量6.21質量%)
(6)4分粉砕FA(粉砕フライアッシュ、国内火力発電所産、強熱減量6.21質量%)
(7)5分粉砕FA(粉砕フライアッシュ、国内火力発電所産、強熱減量6.21質量%)
(8)10分粉砕FA(粉砕フライアッシュ、国内火力発電所産、強熱減量6.21質量%)
(9)20分粉砕FA(粉砕フライアッシュ、国内火力発電所産、強熱減量6.21質量%)
(10)30分粉砕FA(粉砕フライアッシュ、国内火力発電所産、強熱減量6.21質量%)
フライアッシュ原粉の粉砕は、容量100リットルのドラムを持つ可傾式ボールミルを使用する。投入するボールはφ10mmのクローム鋼球(約3.5kg/個)である。ドラム中のフライアッシュ原粉に対してボールを投入する(重量比とし、最大でフライアッシュ原粉10kgに対してボール100kg)。ボール投入後にミルを水平位置とし、ミルの回転数を60rpmとし、上記所定の時間可傾式ボールミルを運転して粉砕を行った。
容積400cm3以上410cm3以下の鉄製容器に測定対象となるフライアッシュを充填し、JIS R5201:2015「セメントの物理試験方法」の「12.2 フロー値の測定」に規定されたフローテーブルを用い、このフローテーブルによる落下運動を70回加えた後のフライアッシュのみかけ密度(かさ密度)をみつかさ比重として、測定した。
粉砕前のフライアッシュ原粉のみつかさ比重をd1とし、粉砕後の粉砕フライアッシュのみつかさ比重をd2とし、下記式(1)により、フライアッシュ原粉に対する粉砕フライアッシュのみつかさ比重の増加率を測定した。
粉砕フライアッシュのみつかさ比重の増加率(%)=(d2-d1)/d1×100 (1)
測定対象となるフライアッシュを1500gと、水750g(フライアッシュ100質量部に対して水50質量部)とを混練、撹拌し、フライアッシュペーストを作製した。フライアッシュと水との混練は、JIS R5201:2015「セメントの物理試験方法」の「9.4.1 セメントペーストの練混ぜ」に準拠して行なった。得られたフライアッシュペーストについて、JSCE-F531の「PCグラウトの流動性試験方法」に準拠して、MIC-363-0-03のグラウトフローコーンを用いて流下時間を測定した。
複数種の水粉体質量比の異なる粉砕フライアッシュと水とを含む混合物を準備する。
JIS R5201の「9.2.3 機械練り用練混ぜ機」により、水粉体比の異なる複数種の混合物を撹拌混練し、前記機械練り用練混ぜ機に流れる電流を測定する。前記機械練り用練混ぜ機に流れる電流の測定は、前記機械練り用練混ぜ機の単相2本の電源ケーブルのうち、いずれか1本を電流測定装置(製品名:メモリハイコーダMR8870、日置電機株式会社)のクランプで挟み込み、前記混合物を撹拌した際に前記機械練り用練混ぜ機に流れる電流を測定し、複数種の水粉体質量比の異なる混合物のうち、前記機械練り用練混ぜ機に流れる電流が最大となるときの水粉体質量比を最大電流値における水粉体質量比として測定した。前記機械練り用練混ぜ機には、最大で500アンペア(A)の電流を通電することができる。
最大電流値における水粉体質量比の測定の一例として、前記フライアッシュ(1)II種灰(JIS A 6201:2015 コンクリート用フライアッシュ II種適合品(分級品))1000gに対して、表1に示す量の水を添加した各混合物を前記機械練り用練混ぜ機で撹拌し、前記機械練り用練混ぜ機に通電された電流の測定値を表1に示す。各フフライアッシュについて、前記フライアッシュ(1)II種灰と同様に測定した際に、前記機械練り用練混ぜ機に通電される電流の最大値における水粉体質量比を表1に示す。
(実施例1~6及び比較例1~9)
各フライアッシュを用いて、表3に示す配合で、実施例及び比較例のコンクリート組成物を製造した。
表3に示す配合で製造した各コンクリート組成物について、JIS A1101:2014「コンクリートのスランプ試験方法」に準拠して、スランプ(cm)を測定した。
表3に示す配合で製造したコンクリート組成物につき、材料分離抵抗性の評価試験として、ドイツ工業規格であるDIN1048に準拠した試験を行った。この試験は、吹付コンクリートに要求される高いレベルでの材料分離抵抗性を評価するものであり、この試験値によって吹付コンクリートのリバウンド低減を間接的に評価できる。また、この試験によってリバウンド低減に必要とされる衝撃変形抵抗性も評価できる。
この試験方法について概説すると、JIS A 1101:2014 コンクリートのスランプ試験方法によるスランプ(cm)を測定した後、スランプ板の片側を4cm持ち上げて落下させる操作を繰り返す。この落下操作の繰り返しにより、コンクリートのフローが60cmに到達した際の回数(拡がり回数)を測定した。この拡がり回数が多いほど、吹付コンクリートとしての材料分離抵抗性及び/又は衝撃変形抵抗性に優れ、リバウンド低減に効果があるという評価となる。
また、表4に示す結果により、実施例1~6のコンクリート組成物は、前記フライアッシュと水とをJIS R5201の「9.2.3 機械練り用練混ぜ機」により混練撹拌した際に、前記機械練り用練混ぜ機に通電される電流が最大となる水粉体質量比が23~27%であり、コンクリート組成物中の粉砕フライアッシュが適度に水を吸着し、この粉砕フライアッシュを含むコンクリート組成物が、流動性に優れるとともに適度な粘性を有し、比較例1~9のコンクリート組成物に比べて拡がり回数が増加した。
表4より、4分及び5分粉砕した粉砕フライアッシュのみつかさ比重の増加率は2.7%であり、3分及び10分粉砕した粉砕フライアッシュのみつかさ比重の増加率は1.8%であり、この粉砕フライアッシュを使用した実施例のコンクリート組成物は、比較例1~9のコンクリート組成物に比べて拡がり回数が増加した。
実施例1~6のコンクリート組成物は、比較例1~9のコンクリート組成物に比べて拡がり回数が増加したことから、吹付コンクリートとしてのリバウンド低減効果が大きくなったと考えられ、材料分離抵抗性及び/又は衝撃変形抵抗性に優れていた。
表4に示すように、JAロート流下時間が27秒を超えて大きい粉砕フライアッシュを含む比較例6及び7のコンクリート組成物は、流動性が低下した。比較例6及び7で使用した粉砕フライアッシュは、フライアッシュ原粉の物性と大差なく、粉砕による品質改善効果が得られなかったと考えられる。
表4に示すように、JAロート流下時間が17秒未満の粉砕フライアッシュを含む比較例8及び9のコンクリート組成物は、流動性が低下した。一方、比較例8及び9で使用した粉砕フライアッシュは、JAロート流下時間が17秒未満と短く、粘性が不十分であったと考えられる。
表4に示すように、最大電流値における水粉体質量比が23%未満と小さい粉砕フライアッシュを含む比較例8及び9のコンクリート組成物は、粉砕フライアッシュに拘束される水の量が少なく、リバウンドが多くなり、拡がり回数が実施例1~6ほど増加せず、リバウンド低減効果が低下し、材料分離抵抗性及び/又は衝撃変形抵抗性が低下した。
Claims (9)
- セメントと、フライアッシュ原粉を粉砕した粉砕フライアッシュとを含有し、
前記粉砕フライアッシュが、粉砕フライアッシュ100質量部に対して水50質量部を含むフライアッシュペーストのJAロート流下時間が17~27秒の範囲のものである、コンクリート組成物。 - セメントと、フライアッシュ原粉を粉砕した粉砕フライアッシュとを含有し、
前記粉砕フライアッシュが、前記粉砕フライアッシュと水との混合物をJIS R5201の「9.2.3 機械練り用練混ぜ機」により撹拌した際に前記機械練り用練混ぜ機に流れる電流が最大となるときの前記混合物の水粉体質量比が23~27%のものである、コンクリート組成物。 - セメントとフライアッシュ原粉を粉砕した粉砕フライアッシュとを含有し、
前記粉砕フライアッシュは、粉砕前のみつかさ比重に対して粉砕後のみつかさ比重が1.5%以上3.0%以下増加したものである、コンクリート組成物。 - 前記粉砕フライアッシュの強熱減量が、3質量%以上10質量%以下である、請求項1~3のいずれか1項に記載のコンクリート組成物。
- 前記粉砕フライアッシュの配合量が、コンクリート組成物の容積1m3当り、20kg以上150kg以下である、請求項1~4のいずれか1項に記載のコンクリート組成物。
- 混和材及び特殊混和剤から選ばれる少なくとも1種をさらに含有する、請求項1~5のいずれか1項に記載のコンクリート組成物。
- 前記セメントが、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント及び低熱ポルトランドセメントからなる群より選ばれる少なくとも1種である、請求項1~6のいずれか1項に記載のコンクリート組成物。
- セメントとフライアッシュ原粉を粉砕した粉砕フライアッシュとを含有するコンクリート組成物の製造方法であって、
粉砕前のみつかさ比重に対して粉砕後のみつかさ比重が1.5%以上3.0%以下増加したものとなるように、前記フライアッシュ原粉を粉砕して前記粉砕フライアッシュとする工程と、
前記セメントと前記粉砕フライアッシュとを配合する工程とを含むコンクリート組成物の製造方法。 - 前記フライアッシュ原粉の強熱減量が、3質量%以上10質量%以下である、請求項8に記載のコンクリート組成物の製造方法。
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CN101372403A (zh) * | 2008-10-15 | 2009-02-25 | 登电集团水泥有限公司 | 一种粉煤灰水泥的制备方法 |
CN101580348B (zh) * | 2009-06-22 | 2012-11-07 | 准格尔旗粉煤灰煤矸石研发中心 | 大掺量粉煤灰水泥及其制备方法 |
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CN101870565B (zh) * | 2010-07-14 | 2012-01-11 | 岳阳华泰资源开发利用有限责任公司 | 一种混凝土复合矿物掺和料及其制备方法 |
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JPH0354139A (ja) * | 1989-07-24 | 1991-03-08 | Mitsubishi Heavy Ind Ltd | コンクリート混和材の製造方法 |
JPH0570194A (ja) * | 1991-09-10 | 1993-03-23 | Ask:Kk | セメント成形体 |
JPH0664955A (ja) * | 1992-08-19 | 1994-03-08 | Mitsubishi Materials Corp | 低分離性フライアッシュの製造方法及び低分離性コンクリートの製造方法 |
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PH12018501225A1 (en) | 2019-01-28 |
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