WO2023022172A1 - セメント混和材、セメント混和材の製造方法及びセメント組成物 - Google Patents

セメント混和材、セメント混和材の製造方法及びセメント組成物 Download PDF

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Publication number
WO2023022172A1
WO2023022172A1 PCT/JP2022/031072 JP2022031072W WO2023022172A1 WO 2023022172 A1 WO2023022172 A1 WO 2023022172A1 JP 2022031072 W JP2022031072 W JP 2022031072W WO 2023022172 A1 WO2023022172 A1 WO 2023022172A1
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WO
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Prior art keywords
cement
cement admixture
sio
raw material
2cao
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PCT/JP2022/031072
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English (en)
French (fr)
Japanese (ja)
Inventor
大樹 島崎
泰一郎 森
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デンカ株式会社
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Priority to CN202280045966.XA priority Critical patent/CN117580812A/zh
Publication of WO2023022172A1 publication Critical patent/WO2023022172A1/ja

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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
    • C04B22/08—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
    • 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
    • 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 cement admixture used in the fields of civil engineering, construction, etc., a method for producing the cement admixture, and a cement composition.
  • cement In order to reduce the total amount of CO2 emitted when manufacturing concrete products, cement can be used by blending large amounts of special admixtures and industrial by-products (granulated blast furnace slag, fly ash, etc.) as substitutes for cement. It is effective to reduce the amount, and various studies are underway.
  • ⁇ -C 2 S one or two kinds of steelmaking slag powder, and Portland cement are contained as powder components, and ⁇ -C 2 S and steelmaking slag powder account for the above total content. is 25 to 95% by mass and the water-cement ratio W/C is 80 to 250% by mass.
  • W/C water-cement ratio
  • Patent Document 1 and Patent Document 2 do not disclose any initial strength.
  • An object of the present invention is to provide a cement admixture that can impart expressiveness.
  • the cement admixture contains a specific non-hydraulic compound and illimite, and the content of illimite is set within a predetermined range.
  • the present invention is as follows.
  • the cement admixture according to the present embodiment includes at least one non-hydraulic compound selected from the group consisting of ⁇ -2CaO ⁇ SiO 2 , 3CaO ⁇ 2SiO 2 , ⁇ -CaO ⁇ SiO 2 , and calcium magnesium silicate; including.
  • ⁇ -2CaO ⁇ SiO 2 , 3CaO ⁇ 2SiO 2 , ⁇ -CaO ⁇ SiO 2 , and calcium magnesium silicate including.
  • the non-hydraulic compound and illimite and the content of illimite is 0.1 to 10%, good initial strength can be maintained.
  • the said non-hydraulic compound may be used individually by 1 type, and may be used in combination of 2 or more type. Each component and the like will be described below.
  • the cement admixture of the present invention contains at least one non-hydraulic compound selected from the group consisting of ⁇ -2CaO ⁇ SiO 2 , 3CaO ⁇ 2SiO 2 , ⁇ -CaO ⁇ SiO 2 and calcium magnesium silicate.
  • ⁇ -2CaO-SiO 2 is a compound represented by 2CaO.SiO 2 and is known as a low temperature phase . It is completely different from ⁇ -2CaO ⁇ SiO 2 . All of these are represented by 2CaO.SiO 2 , but have different crystal structures and densities.
  • ⁇ -2CaO SiO 2 is a non-hydraulic compound, and by forcibly carbonating (salting) concrete mixed with this as an admixture, it absorbs CO 2 and densifies the surface layer for durability.
  • ⁇ -2CaO SiO 2 reacts with CO 2 to form a gel rich in CaCO 3 and SiO 2 , fills voids in the cement matrix, and dramatically improves the durability of the surface layer of concrete products.
  • the carbonation (salt) curing reduces the total CO2 emissions in obtaining concrete products by the amount of CO2 absorbed by the concrete, making it a suitable compound from the point of view of environmental protection. .
  • 3CaO.2SiO2 3CaO.2SiO 2 is a mineral containing CaO in pseudowollastonite and is called rankinite. It is a chemically stable mineral with no hydration activity, but has a large densification effect due to carbonation (salting).
  • ⁇ -CaO.SiO 2 ⁇ -CaO ⁇ SiO 2 ( ⁇ -type wollastonite) is a compound represented by CaO ⁇ SiO 2 and is known as a high-temperature phase.
  • ⁇ -CaO ⁇ SiO 2 is a low-temperature phase. They are completely different. All of these are represented by CaO.SiO 2 , but have different crystal structures and densities.
  • Naturally occurring wollastonite is the low temperature phase ⁇ -CaO.SiO 2 .
  • ⁇ -CaO SiO 2 has needle- like crystals and is used as an inorganic fibrous material such as wollastonite fiber. The densification effect by salinization is small.
  • Calcium magnesium silicate is a general term for CaO--MgO-- SiO.sub.2 -based compounds, and in the present embodiment, it is Merwinite represented by 3CaO.MgO.2SiO.sub.2 ( C.sub.3MS.sub.2 ) . is preferred.
  • melvinite Densification is achieved by a large promotion of carbonation (salt).
  • the above non-hydraulic compounds may be used alone or in combination of two or more, preferably at least 60%, more preferably at least 80%, in the cement admixture. When it is 60% or more, a sufficient densification effect can be obtained by carbonation (salting) curing. Although the upper limit is not particularly limited, it is preferably 95% or less from the viewpoint of storage stability. When two or more non-hydraulic compounds are used, the above content refers to the total amount of the two or more non-hydraulic compounds.
  • the proportion of ⁇ -2CaO ⁇ SiO 2 in the non-hydraulic compound is preferably 50% or more, more preferably 70% or more. There is no particular upper limit, and ⁇ -2CaO ⁇ SiO 2 may be 100% in the non-hydraulic compound.
  • Ilimite is a mineral represented by 3CaO.3Al2O3.CaSO4 , which is hydrated in the presence of gypsum or the like to form ettringite ( 3CaO.Al2O3.3CaSO4.32H2 O) and contributes to the improvement of the initial strength.
  • the content of illimite be in the range of 0.1 to 10% by mass. If the content of illimite is less than 0.1% by mass, sufficient initial strength cannot be obtained, and if it exceeds 10% by mass, the strength developability is lowered when carbonate (modified) curing is performed.
  • the content of illimite is preferably in the range of 0.3 to 10% by mass, more preferably in the range of 1 to 9% by mass, and particularly preferably in the range of 2 to 7% by mass. By containing illimite in such an amount, it is possible to increase the initial strength and improve the strength development property when carbonate (modified) curing is performed.
  • the cement admixture according to the present embodiment may contain a hydraulic compound other than illimite in addition to the non-hydraulic compound and illimite.
  • the hydraulic compound is not particularly limited as long as it is commonly used in cement compositions, and includes calcium silicate represented by 3CaO.SiO 2 , 2CaO.SiO 2 and 4CaO.Al 2 O 3 .Fe 2 O 3 . and calcium aluminoferrite represented by 6CaO.2Al 2 O 3 .Fe 2 O 3 , 6CaO.Al 2 O 3 .Fe 2 O 3 , and calcium ferrites such as 2CaO.Fe 2 O 3 .
  • These hydraulic compounds may be used singly or in combination of two or more.
  • CaO raw material, Al 2 O 3 raw material, SiO 2 raw material, MgO raw material, and SO 3 raw material are prepared, appropriately blended at a predetermined molar ratio, and pulverized and mixed. to obtain a mixture and heat-treating the mixture.
  • CaO raw materials include, for example, calcium carbonate such as limestone, calcium hydroxide such as slaked lime, acetylene by-product slaked lime, fine powder generated from waste concrete blocks, and the like.
  • Examples of SiO 2 raw materials include silica stone, clay, and various siliceous dusts generated as industrial by-products such as silica fume and fly ash.
  • MgO raw materials examples include magnesium hydroxide, basic magnesium carbonate, and dolomite.
  • Al 2 O 3 raw materials include bauxite and aluminum residue ash
  • CaSO 4 raw materials SO 3 raw materials
  • the CaO raw material is selected from industrial by-products containing CaO, such as acetylene by-product slaked lime, fine powder generated from waste concrete mass, etc. It is preferable to use two or more kinds.
  • the heat treatment method is not particularly limited, but it can be performed, for example, by using a rotary kiln or an electric furnace.
  • the heat treatment temperature is not uniquely determined, it is usually performed in the range of about 1,000 to 1,800.degree. C., and often in the range of about 1,200 to 1,600.degree.
  • This embodiment can also use industrial by-products containing the aforementioned non-hydraulic compounds. At this time, impurities coexist.
  • industrial by-products include steelmaking slag and the like.
  • the CaO raw material, SiO2 raw material, MgO raw material, Al2O3 raw material, and SO3 raw material may contain impurities, they pose no particular problem as long as they do not impair the effects of the present invention.
  • impurities include Fe2O3 , TiO2 , MnO, Na2O , K2O , P2O5 , B2O3 , fluorine, and chlorine.
  • Coexisting compounds include free calcium oxide, calcium hydroxide, calcium aluminate, calcium aluminosilicate, calcium ferrite, calcium aluminoferrite, calcium phosphate, calcium borate, magnesium silicate, leucite (K 2 O, Na 2 O).Al 2 O 3 .SiO 2 , spinel MgO.Al 2 O 3 , magnetite Fe 3 O 4 and the like.
  • Hydraulic 2CaO ⁇ SiO 2 may be mixed in the cement admixture in addition to the non-hydraulic compounds described above, and can be mixed up to a maximum of 35%.
  • each crystal phase is calculated from chemical analysis values, Rietveld method by powder X-ray diffraction, etc.
  • a method of identifying each crystal phase by powder X-ray diffractometry and then calculating each crystal phase from chemical analysis values was used.
  • the cement admixture according to the present embodiment preferably contains particles in which a non-hydraulic compound and illimite are present in the same particles.
  • the particles can be obtained by selecting an appropriate raw material composition and heat treatment conditions in the above-described production method. Whether or not the non-hydraulic compound and illimite are present in the same particles can be confirmed by an electron microscope or the like. Specifically, the cement admixture is embedded in resin, surface treated with an argon ion beam, and the structure of the cross section of the particle is observed. You can check if it exists in
  • the Blaine specific surface area of the cement admixture is not particularly limited, it is preferably 1,500 cm 2 /g or more, and the upper limit is preferably 8,000 cm 2 /g or less. Among them, 2,000 to 6,000 cm 2 /g is more preferable, and 3,000 to 6,000 cm 2 /g is most preferable.
  • the Blaine specific surface area is 1,500 cm 2 /g or more, good material separation resistance is obtained, and the carbonation (salt) promotion effect is sufficient.
  • it is 8,000 cm 2 /g or less, the power required for pulverization is not large, which is economical, and weathering is suppressed, so that deterioration of quality over time can be suppressed.
  • the cement composition according to this embodiment contains the cement admixture of the present invention.
  • the amount of the cement admixture used is not particularly limited, it is usually preferably 5 to 80 parts, more preferably 5 to 60 parts, and even more preferably 10 to 50 parts out of 100 parts in total of the cement and the present admixture. . When it is 5 parts or more, the heat of hydration can be lowered, and when it is 80 parts or less (especially 50 parts or less), the initial strength development property becomes good.
  • the amount of water used for the cement composition of this embodiment is not particularly limited, and may be within a normal usage range. Specifically, the amount of water is preferably 25 to 60 parts per 100 parts in total of the cement and the present admixture. When it is 25 parts or more, sufficient workability can be obtained, and when it is 60 parts or less, sufficient strength development and carbonation (salt) promotion effect can be obtained.
  • the cement used in the cement composition of the present embodiment is not particularly limited, but preferably contains Portland cement, for example, various Portland cements such as normal, early strength, ultra early strength, low heat, and moderate heat. be done.
  • various mixed cements in which blast furnace slag, fly ash, or silica is mixed with these Portland cements waste-use cement manufactured using as raw materials such as municipal waste incineration ash and sewage sludge incineration ash, so-called ecocement (R), and filler cement mixed with limestone powder and the like.
  • ecocement ecocement
  • geopolymer cement sulfoaluminate cement
  • limestone calcined clay cement LC3
  • the cement composition of the present embodiment has a low water-binder ratio, it is beneficial for blast-furnace cement and eco-cement, which are strongly required to suppress neutralization, and it is most preferable that the cement composition contains blast-furnace cement.
  • the particle size of the cement composition of the present embodiment is not particularly limited because it depends on the purpose and application of use. 000 to 6,000 cm 2 /g is more preferred. When it is 2,500 cm 2 /g or more, sufficient strength development can be obtained, and when it is 8,000 cm 2 /g or less, workability can be improved.
  • aggregates such as sand and gravel, ground granulated blast furnace slag, air-cooled blast furnace slag powder, fine limestone powder, fly ash, silica fume, volcanic ash
  • Admixtures such as natural pozzolans, expansive agents, hardening agents, water reducing agents, AE water reducing agents, high performance water reducing agents, high performance AE water reducing agents, antifoaming agents, thickeners, rust inhibitors, antifreeze agents, shrinkage reduction
  • additives and admixtures used in ordinary cement materials such as additives such as agents, polymers, setting modifiers, clay minerals such as bentonite, and anion exchangers such as hydrotalcite.
  • the present invention can be used within a range that does not substantially hinder the object of the present invention.
  • the cement composition of this embodiment may be prepared by mixing each material during construction, or may be partially or wholly mixed in advance. Also, the method of mixing each material and water is not particularly limited, and the rest of the material may be mixed after part of the material is mixed with water.
  • any existing device can be used, for example, a tilting mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used.
  • Example 1 (1-1 to 1-9) CaO raw material, SiO 2 raw material, MgO raw material, Al 2 O 3 raw material, and SO 3 raw material were blended so as to have the mineral ratio shown in Table 1, mixed and pulverized, and then fired at the temperature shown in Table 1 for 2 hours.
  • a clinker was synthesized using a ball mill, and pulverized to a Blaine specific surface area of 3,000 cm 2 /g to prepare a cement admixture.
  • the mineral composition was determined by a method of identifying each crystal phase by powder X-ray diffractometry and then calculating each crystal phase from chemical analysis values.
  • the cement admixture contained ⁇ -2CaO ⁇ SiO 2 as a hydraulic compound in addition to the non-hydraulic compound, Ilimite.
  • a scanning fluorescent X-ray analyzer "ZSX Primus IV” manufactured by Rigaku Co., Ltd.
  • the powder X-ray diffractometer a fully automatic multi-purpose X-ray diffractometer "SmartLab” manufactured by Rigaku Co., Ltd. is used. board.
  • cement admixture 50 parts by mass of cement admixture (admixture addition rate of 50% by mass) is used in 100 parts by mass of a cement composition consisting of cement and cement admixture, and 100 parts by mass of cement composition
  • a mortar containing 50 parts by mass of water (water/cement composition ratio of 50% by mass) and a cement composition/sand ratio of 1/3 (mass ratio) was prepared in a room at 20°C. After demolding at 1 day of material age in the formwork, accelerated carbonation curing was performed until 28 days of material age in an environment of temperature 20° C., relative humidity 60%, and CO 2 concentration 5%, and compressive strength was measured.
  • CaO raw material calcium carbonate (reagent grade 1)
  • SiO2 raw material silicon dioxide (reagent grade 1)
  • MgO raw material Magnesium oxide (reagent grade 1)
  • Al 2 O 3 raw material ⁇ -alumina (reagent grade 1)
  • SO3 raw material calcium sulfate dihydrate (reagent grade 1)
  • Sand JIS standard sand Cement: Ordinary Portland cement, manufactured by Denka Co., Ltd., specific gravity 3.15, Blaine specific surface area 3,300 cm 2 /g Water: tap water
  • Example 3 (3-1) The CaO raw material and the SiO 2 raw material were blended at a molar ratio of 2:1, mixed and pulverized, fired at 1400 ° C. for 2 hours, pulverized using a ball mill to a Blaine specific surface area of 3,000 cm 2 /g, and ⁇ -2CaO. - SiO2 was obtained. Further, ⁇ -2CaO.SiO 2 was calcined at 1100° C. for 1 hour, allowed to stand at room temperature, pulverized, and the same heat treatment was repeated until no peak of ⁇ -2CaO.SiO 2 was confirmed by XRD.
  • the cement composition using the cement admixture of the present invention can ensure initial strength and can be carbonated (salt) cured at an early stage. It is also found that the use of ⁇ -2CaO ⁇ SiO 2 as the non-hydraulic compound increases the compressive strength. Furthermore, it can be seen that when the content of illimite is within an appropriate range, the compressive strength is further increased. From the results in Table 2, when the content of the non-hydraulic compound in the cement admixture is 50% by mass or more, the compressive strength is increased, and when it is 60% by mass or more, the compressive strength is further increased. .
  • the cement admixture of the present invention is particularly useful as a cement admixture used in the fields of civil engineering and construction, and can be suitably used as a cement composition.
PCT/JP2022/031072 2021-08-19 2022-08-17 セメント混和材、セメント混和材の製造方法及びセメント組成物 WO2023022172A1 (ja)

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JP2021134146A JP7181355B1 (ja) 2021-08-19 2021-08-19 セメント混和材、セメント混和材の製造方法及びセメント組成物

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006182583A (ja) * 2004-12-27 2006-07-13 Kajima Corp 表層緻密化モルタルまたはコンクリートおよびその製造法
WO2015170685A1 (ja) * 2014-05-07 2015-11-12 電気化学工業株式会社 セメンティング組成物、セメンティング方法及び坑井掘削方法
JP2019058091A (ja) * 2017-09-26 2019-04-18 デンカ株式会社 防草材及びそれの使用方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006182583A (ja) * 2004-12-27 2006-07-13 Kajima Corp 表層緻密化モルタルまたはコンクリートおよびその製造法
WO2015170685A1 (ja) * 2014-05-07 2015-11-12 電気化学工業株式会社 セメンティング組成物、セメンティング方法及び坑井掘削方法
JP2019058091A (ja) * 2017-09-26 2019-04-18 デンカ株式会社 防草材及びそれの使用方法

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Title
HIGUCHI, TAKAYUKI ET AL.: "Effect of high-temperature carbonation condition on the expansion properties of expansive additive", PROCEEDINGS OF THE JAPAN CONCRETE INSTITUTE, NIHON KONKURITO KOGAKU KYOKAI, JP, vol. 38, no. 1, 1 January 2016 (2016-01-01), JP , pages 639 - 644, XP009543582, ISSN: 1347-7560 *
ZEA-GARCIA JESUS D.; SANTACRUZ ISABEL; ARANDA MIGUEL A.G.; DE LA TORRE ANGELES G.: "Alite-belite-ye'elimite cements: Effect of dopants on the clinker phase composition and properties", CEMENT AND CONCRETE RESEARCH., PERGAMON PRESS, ELMSFORD, NY., US, vol. 115, 29 October 2018 (2018-10-29), US , pages 192 - 202, XP085534365, ISSN: 0008-8846, DOI: 10.1016/j.cemconres.2018.10.019 *

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JP7181355B1 (ja) 2022-11-30

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