WO2021193367A1 - Cement clinker, cement composition, and cement clinker production method - Google Patents

Cement clinker, cement composition, and cement clinker production method Download PDF

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Publication number
WO2021193367A1
WO2021193367A1 PCT/JP2021/011168 JP2021011168W WO2021193367A1 WO 2021193367 A1 WO2021193367 A1 WO 2021193367A1 JP 2021011168 W JP2021011168 W JP 2021011168W WO 2021193367 A1 WO2021193367 A1 WO 2021193367A1
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mass
cement
cement clinker
content
3cao
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PCT/JP2021/011168
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French (fr)
Japanese (ja)
Inventor
清水　準
曜 山田
亨介 山縣
友樹 佐藤
英由希 那須
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住友大阪セメント株式会社
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Application filed by 住友大阪セメント株式会社 filed Critical 住友大阪セメント株式会社
Priority to NZ782785A priority Critical patent/NZ782785A/en
Priority to SG11202113195YA priority patent/SG11202113195YA/en
Priority to AU2021242720A priority patent/AU2021242720B2/en
Priority to CN202180004145.7A priority patent/CN114007995B/en
Priority to KR1020217033530A priority patent/KR102338232B1/en
Publication of WO2021193367A1 publication Critical patent/WO2021193367A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/02—Portland cement
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/02—Portland cement
    • C04B7/04—Portland cement using raw materials containing gypsum, i.e. processes of the Mueller-Kuehne type
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/02—Portland cement
    • C04B7/06—Portland cement using alkaline raw materials
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/44—Burning; Melting

Definitions

  • the present invention relates to cement clinker and cement composition, and particularly to ordinary Portland cement.
  • Non-Patent Document 1 As a method for reducing the heat of hydration of the cement composition, as moderate heat Portland cement and low heat Portland cement, and techniques C 3 S and C 3 A is controlled to a low mineral composition, a method of mixing with blast furnace slag It is known (for example, Non-Patent Document 1 and Non-Patent Document 2).
  • Non-Patent Document 3 reports the effects of TiO 2 and MgO, which are trace components in cement clinker, on the mineral composition and the physical characteristics of cement.
  • Non-Patent Document 3 as the MgO content increases, decreases aluminate phase (C 3 A) are, tend to heat of hydration is reduced further, often the total content of MgO and TiO 2 It is disclosed that the heat of hydration tends to be smaller.
  • Non-Patent Document 3 it is also possible to reduce the heat of hydration by the content of MgO and TiO 2 in the clinker.
  • various trace components are introduced into the clinker actually produced, which is derived from industrial waste and by-products.
  • no consideration is given to the influence of other trace components on physical properties such as heat of hydration.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a cement clinker capable of reducing heat of hydration and a cement composition containing the cement clinker cement composition.
  • the present invention provides the following ⁇ 1> to ⁇ 5>.
  • the total ratio of 3CaO ⁇ Al 2 O 3 and 4 CaO ⁇ Al 2 O 3 ⁇ Fe 2 O 3 is 15 to 22% by mass, and contains MgO, TiO 2 , MnO and ZnO, and satisfies the following formula (1). , Cement clinker.
  • C Mg-C3A represents the content rate (mass%) of MgO in 3CaO ⁇ Al 2 O 3 and represents.
  • C Ti-C3A represents the content rate (mass%) of TiO 2 in 3CaO ⁇ Al 2 O 3 and represents.
  • C Mn-C3A represents the content rate (mass%) of MnO in 3CaO ⁇ Al 2 O 3 and represents.
  • C Zn—C3A represents the content rate (mass%) of ZnO in 3CaO ⁇ Al 2 O 3.
  • ⁇ 2> The cement clinker according to ⁇ 1>, wherein the content of Fe 2 O 3 in the 3 CaO ⁇ Al 2 O 3 is less than 6.32% by mass.
  • ⁇ 3> The cement clinker according to ⁇ 1> or ⁇ 2>, wherein the content of TiO 2 is less than 0.24% by mass.
  • ⁇ 4> A cement composition containing the cement clinker according to any one of ⁇ 1> to ⁇ 3> and gypsum.
  • ⁇ 5> A method for producing cement clinker, which includes a step of blending raw materials and a step of firing the blended raw materials, wherein the cement clinker after firing is 3CaO ⁇ SiO 2 calculated by the Borg formula.
  • C Ti-C3A represents the content rate (mass%) of TiO 2 in 3CaO ⁇ Al 2 O 3 and represents.
  • C Mn-C3A represents the content rate (mass%) of MnO in 3CaO ⁇ Al 2 O 3 and represents.
  • C Zn—C3A represents the content rate (mass%) of ZnO in 3CaO ⁇ Al 2 O 3.
  • the present invention it is possible to obtain a cement clinker capable of reducing the heat of hydration.
  • a cement composition having a low heat of hydration can be obtained.
  • Cement clinker of the present invention is 50 to 75 mass% ratio of the calculated 3CaO ⁇ SiO 2 is in the Borg type, the fraction of 2CaO ⁇ SiO 2 calculated in Borg formulas 5 to 25 mass%, Borg
  • the total ratio of 3CaO ⁇ Al 2 O 3 and 4 CaO ⁇ Al 2 O 3 ⁇ Fe 2 O 3 calculated by the formula is 15 to 22% by mass, and includes MgO, TiO 2 , MnO and ZnO, and the following formula ( Cement clinker that satisfies 1).
  • C Mg-C3A represents the content rate (mass%) of MgO in 3CaO ⁇ Al 2 O 3 and represents.
  • C Ti-C3A represents the content rate (mass%) of TiO 2 in 3CaO ⁇ Al 2 O 3 and represents.
  • C Mn-C3A represents the content rate (mass%) of MnO in 3CaO ⁇ Al 2 O 3 and represents.
  • C Zn—C3A represents the content rate (mass%) of ZnO in 3CaO ⁇ Al 2 O 3.
  • the cement clinker of the present invention is preferably commonly used for Portland cement.
  • the cement clinker of the present invention is a main composition constituting a cement composition, and is a limestone (CaO component), clay (Al 2 O 3 component, SiO 2 component), silica stone (SiO 2 component) and an iron oxide raw material (SiO 2 component). Fe 2 O 3 component) and the like are mixed and fired to produce.
  • the cement cleaner of the present invention may contain industrial waste such as coal ash, construction soil, blast furnace slag, converter slag, by-product plaster, and municipal waste incineration ash as raw materials.
  • Cement clinker of the present invention 3CaO ⁇ SiO 2 (abbreviation: C 3 S), 2CaO ⁇ SiO 2 ( abbreviation: C 2 S), 3CaO ⁇ Al 2 O 3 ( abbreviation: C 3 A), and 4CaO ⁇ Al 2 Includes O 3 and FeO 3 (abbreviation: C 4 AF).
  • Cement clinker is composed of the main minerals of alite (C 3 S) and belite (C 2 S) and the aluminate phase (C 3 A) and ferrite phase (C 4 AF) existing between the crystals of the main minerals. It is composed of interstitial phases and the like.
  • the ratios of C 3 S, C 2 S, C 3 A and C 4 AF in cement clinker are CaO, SiO 2 , Al 2 O in cement clinker measured by JIS R 5204: 2019 “Method of fluorescent X-ray analysis of cement”. From the ratio of 3 and Fe 2 O 3 , it can be obtained by a calculation formula called the Borg formula in the field of cement chemistry (for example, "Cement Science” edited by Masaki Daimon, Uchida Otsuruho (1989), p.11. reference).
  • the ratio of 3CaO ⁇ SiO 2 calculated by the Borg formula in the cement clinker of the present invention is 50 to 75% by mass. If the ratio of 3CaO ⁇ SiO 2 calculated by the Borg formula is less than 50% by mass, the strength of concrete or mortar expressed by cement clinker may decrease. If the ratio of 3CaO ⁇ SiO 2 calculated by the Borg formula is larger than 75% by mass, the heat of hydration of the cement composition may become too high.
  • the ratio of 3CaO ⁇ SiO 2 calculated by the Borg formula is preferably 50 to 70% by mass, more preferably 55 to 70% by mass, and even more preferably 55 to 67% by mass.
  • the ratio of 2CaO ⁇ SiO 2 calculated by the Borg formula in the cement clinker of the present invention is 5 to 25% by mass.
  • the ratio of 2CaO ⁇ SiO 2 calculated in Borg formula is less than 5 mass%, resulting in, the higher the proportion of 3CaO ⁇ SiO 2, which may heat of hydration of the cement composition becomes too high.
  • the ratio of 2CaO ⁇ SiO 2 calculated by the Borg formula becomes larger than 25% by mass, the short-term strength of concrete or mortar expressed by the cement composition may become too low.
  • the ratio of 2CaO ⁇ SiO 2 calculated by the Borg formula is preferably 10 to 25% by mass, more preferably 11 to 23% by mass, and even more preferably 12 to 22% by mass.
  • the total percentage of 3CaO ⁇ Al 2 O 3 and 4CaO ⁇ Al 2 O 3 ⁇ FeO 3 calculated by the Borg type in the cement clinker of the present invention is 15-22% by weight. If the total ratio of 3CaO / Al 2 O 3 and 4 CaO / Al 2 O 3 / FeO 3 calculated by the Borg equation is less than 15% by mass, the amount of the liquid phase generated during the firing of the cement clinker is small.
  • the solid-phase-liquid phase reaction due to the intervention of the liquid phase does not proceed rapidly, and the calcination of the cement clinker becomes insufficient.
  • dust is scattered during the cement kiln and radiant heat from the burner is blocked, so that the cement clinker may not be fired efficiently.
  • the total ratio of 3CaO / Al 2 O 3 and 4 CaO / Al 2 O 3 / FeO 3 calculated by the Borg formula is larger than 22% by mass, calcium is likely to cause poor operation and at the same time contribute to strength. Since the production of silicate minerals is reduced, the strength of the cement composition using the cement clinker of the present invention may be reduced. In addition, the heat of hydration of the cement composition may become too high.
  • the total ratio of 3CaO / Al 2 O 3 and 4 CaO / Al 2 O 3 / FeO 3 calculated by the Borg equation is preferably 17 to 22% by mass, more preferably 18 to 22% by mass. , 18 to 20% by mass, more preferably.
  • Proportion of 3CaO ⁇ Al 2 O 3 calculated by the Borg type in the cement clinker of the present invention is preferably 5.5 to 12.5 wt%, more preferably 7-12 wt%, more preferably It is 8 to 11% by mass. If the proportion of 3CaO ⁇ Al 2 O 3 calculated by the Borg type is in the above range, to suppress the decrease in viscosity of the liquid phase produced during sintering of the cement clinker, suitably allowed to proceed granulation of the cement clinker, cement By reducing the particle size of the clinker, it is possible to prevent the layer pressure in the clinker cooler from becoming constant and to reduce the heat of hydration. If the layer pressure in the clinker cooler is not constant, it may interfere with the rapid cooling of the cement clinker.
  • Proportion of 4CaO ⁇ Al 2 O 3 ⁇ FeO 3 (C 4 AF)> Proportion of 4CaO ⁇ Al 2 O 3 ⁇ FeO 3 calculated by the Borg type in the cement clinker of the present invention is preferably 8.5 to 12.5 wt%, more preferably 9.0 to 11.5 mass %, More preferably 9.5 to 11.0% by mass.
  • the ratio of 4CaO, Al 2 O 3, and FeO 3 calculated by the Borg formula is in the above range, the strength developed by the cement composition can be further increased, and the heat of hydration can be further reduced. ..
  • the cement clinker of the present invention contains MgO, TiO 2 , MnO and ZnO as trace components.
  • the contents of MgO, TiO 2 , and MnO are measured in accordance with JIS R 5204: 2019 "Fluorescent X-ray Analysis Method for Cement”.
  • the ZnO content is measured in accordance with JCAS I-53: 2018 “Method for quantifying trace components in cement”.
  • MgO is introduced into the cement clinker, for example, by using slag containing a large amount of MgO as a raw material for the cement clinker.
  • TiO 2 is introduced into cement clinker by using, for example, titanium gypsum or fly ash as a raw material for cement clinker.
  • MnO is introduced into cement clinker by using, for example, blast furnace slag and converter slag as raw materials for cement clinker.
  • ZnO is introduced into cement clinker, for example, by using municipal waste incineration ash as a raw material for cement clinker.
  • the content of MgO in the cement clinker is preferably 0.50 to 2.00% by mass, more preferably 0.80 to 1.80% by mass, and further preferably 0.95 to 1.60% by mass. %.
  • the cement clinker can be fired well and hydration expansion during hardening of concrete or mortar can be suppressed.
  • the content (mass%) of MgO, TiO 2 , MnO and ZnO in 3CaO ⁇ Al 2 O 3 satisfies the following formula (1).
  • C Mg-C3A Content of MgO in 3CaO ⁇ Al 2 O 3 (mass%)
  • C Ti-C3A Content of TiO 2 in 3CaO ⁇ Al 2 O 3 (mass%)
  • C Mn-C3A Content of MnO in 3CaO ⁇ Al 2 O 3 (mass%)
  • C Zn-C3A ZnO content (mass%) in 3CaO ⁇ Al 2 O 3
  • C Mg-C3A , C Ti-C3A, C Mn-C3A, C Zn-C3A represent the content ratio of each component contained in C 3 A in the actual cement clinker. Equation (1) can be obtained by multiple regression analysis.
  • C Mg-C3A , C Ti-C3A , C Mn-C3A , and C Zn-C3A can be obtained by the following steps.
  • EPMA electron probe microanalyzer
  • each mineral is specified based on the following characteristics.
  • C 3 S polygonal particles, light gray, size of several tens [mu] m.
  • C 2 S Elliptical particles, dark gray, tens of ⁇ m in size.
  • C 3 A Atypical structure found between C 3 S and C 2 S and the identified particles, dark gray, a few ⁇ m to a dozen ⁇ m in size.
  • C 4 AF Amorphous structure found between C 3 S and C 2 S and the identified particles, white, several ⁇ m to ten and several ⁇ m in size. Characteristic X-ray analysis of C 3 A specified by the above index is performed by an electron probe microanalyzer (EPMA) to determine the content (mass%) of MgO, TiO 2 , MnO and ZnO in C 3 A.
  • EPMA electron probe microanalyzer
  • characteristic X-ray analysis is performed on a plurality of points in the region specified as C 3 A in the composition image, and 1.35 ⁇ (CaO content) / (Al 2 O 3 content + Fe 2 O). 3 Content rate)
  • the points within the range of ⁇ 2.2 are adopted as analysis points.
  • the average of the measured values of each component at the 20 analysis points is defined as C Mg-C3A , C Ti-C3A , C Mn-C3A , and C Zn-C3A , respectively.
  • Equation (1) MgO in C 3 A, indicates that the content of TiO 2, MnO and ZnO is small.
  • minor component in C 3 A is small, decreases the activity of C 3 A, the result is presumed that the heat of hydration is reduced.
  • the left side of the formula (1) is preferably 0.0008 or less.
  • the left side of the equation (1) is preferably 0.0001 or more.
  • the minor component satisfies the formula (1) is in the C 3 A, becomes relatively other phase Mg, Ti, Mn, that Zn is more solid solution.
  • Mg, Ti, Mn, and Zn are dissolved in C 4 AF, Al is easily incorporated into C 4 AF, and the precipitation of C 3 A is relatively reduced, so that the heat of hydration is reduced.
  • MnO and ZnO although in a typical Portland cement clinker is a very small amount of components, the effect in relation to the crystal structure in the C 3 A relative amount of precipitation of reduced or C 3 A in respect of hydration heat It is not considered to be negligible.
  • C Fe— C 3A the content of Fe 2 O 3 in 3 CaO ⁇ Al 2 O 3 (C 3 A) (hereinafter, may be referred to as “C Fe— C 3A”) is less than 6.32% by mass. Is preferable.
  • C Fe-C3A like C Mg-C3A and the like, is obtained from analysis with an electron probe microanalyzer (EPMA). Specifically, the foregoing steps, carried out characteristic X-ray analysis by electron probe microanalyzer (EPMA) for the identified C 3 A, obtains the content of Fe 2 O 3 in C 3 A (mass%). Then, the average of the measured values of each component at the 20 analysis points is defined as C Fe-C3A .
  • Fe 2 O 3 and Al 2 O 3 in the cement clinker are easily consumed for the precipitation of C 4 AF, which leads to a relative reduction in the proportion of C 3 A in the cement clinker.
  • the content of Fe 2 O 3 in C 3 A is more preferably 6.00% by mass or less, further preferably 5.90% by mass or less, and preferably 5.80% by mass or less. Especially preferable.
  • C Ti-C3A (the content of C 3 TiO 2 in A) above C Ti-C3A is preferably less than 0.24 wt%.
  • C Ti-C3A is within the above range, it is possible to suppress the deposition of C 3 A, reduce the heat of hydration.
  • the chemical composition in the actual minerals of cement clinker can be adjusted by the chemical composition of cement clinker, the firing conditions (heat history) at the time of manufacturing cement clinker, and the like.
  • Equation (2) the content of C Al2 O3 is Al 2 O 3 (wt%), C Fe2 O3 content of the Fe 2 O 3 (wt%), C MgO is MgO content (mass%), C TiO2 Is the content of TiO 2 (mass%), C MnO is the content of MnO (% by mass), and C ZnO is the content of ZnO (% by mass).
  • C Al2O3, C Fe2O3, C MgO, C TIO2, C MnO were measured in accordance with JIS R 5204: 2019 "X-ray fluorescence analysis method of cement", and C ZnO was JCAS I-53: 2018 "in cement". It is measured according to "Method for quantifying trace components". Equation (2) can be obtained by multiple regression analysis.
  • the coefficient of each term on the left side of the formula (2) corresponds to the contribution of the component to the heat of hydration.
  • the formula (2) means that the mineral composition of the interstitial phase changes due to the combined action of the trace components MgO, TiO 2, MnO and ZnO.
  • MnO and ZnO since the coefficients of MnO and ZnO, which are very trace components, are high in general Portland cement clinker, it can be said that MnO and ZnO also affect the composition ratio of minerals in the interstitial phase.
  • the formula (1) when the chemical composition of the cement clinker satisfies the formula (2), the formula (1) can be easily satisfied.
  • the firing conditions include the firing atmosphere, firing temperature, cooling rate, and the like.
  • the firing atmosphere when the firing atmosphere is in a reduced state, the firing temperature is high, and the cooling rate is rapid cooling, the equation (1) can be easily satisfied.
  • the clinker of the present invention can be produced, for example, as follows.
  • the clinker raw material in addition to Ca, Si, Al and Fe, those containing at least Mg, Ti, Mn and Zn are used.
  • it can be used in any form such as elemental substances, oxides, carbon oxides, etc., and mixtures thereof can be used.
  • natural raw materials include limestone, clay, silica stone, and iron oxide raw materials
  • industrial raw materials include waste raw materials containing the above elements, blast furnace slag, fly ash, and the like.
  • the composition of the components corresponds to the target Borg formula value, and the raw material composition is determined as in the formula (1) in the cement clinker after firing.
  • the raw materials are blended so that the chemical composition of the cement clinker satisfies the formula (2).
  • the clinker raw material mixed with a composition that can obtain the desired clinker is fired under predetermined firing conditions and cooled. Firing is usually performed using an electric furnace, a rotary kiln, or the like.
  • a firing method for example, a first firing step in which a clinker raw material is heated and fired at a predetermined first firing temperature and a first firing time, and after the first firing step, a predetermined first firing temperature is used. 2
  • the temperature and time of each step can be set with the cement clinker after firing satisfying the formula (1) as a guide.
  • the clinker raw material is heated at a firing temperature of 950 to 1100 ° C. (first firing temperature) for 30 to 60 minutes (first firing time) to perform firing (first firing step), and then 1420 to 1480 ° C. (1st firing step). After raising the temperature to the second firing temperature) over 30 to 60 minutes (heating time) (heating step), and further heating at 1420 to 1480 ° C. for 15 to 45 minutes (second firing time) to perform firing. (Second firing step) The clinker can be produced by quenching the fired product.
  • the cement composition of the present invention contains the above-mentioned cement clinker and gypsum.
  • a Blaine specific surface area of the mixture of cement clinker and gypsum is preferably from 3000 cm 2 / g or more 3400 cm 2 / g, and more preferably less 3100 cm 2 / g or more 3300cm 2 / g.
  • the proportion of gypsum in the cement compositions of the present invention are preferably converted to SO 3 content from 0.5 to 2.5 mass%, more preferably 1.0-1.8% by weight.
  • the ratio of SO 3 in gypsum can be measured according to JIS R 5202: 2010 “Chemical analysis method of Portland cement”. Ratio of the mass in terms of SO 3 gypsum cement composition can be determined from the ratio of SO 3 contained in the amount and gypsum plaster.
  • the gypsum any of anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum can be used.
  • Fly ash, blast furnace slag, silica fume and the like can be further added to the cement composition of the present invention for adjusting the fluidity, hydration rate or strength development.
  • an AE water reducing agent, a high-performance water reducing agent or a high-performance AE water reducing agent, particularly a polycarboxylic acid-based high-performance AE water reducing agent can be added to the cement composition of the present invention.
  • cement milk can be prepared by mixing the cement composition of the present invention with water.
  • a mortar can be prepared by mixing the cement composition of the present invention with water and sand. Concrete can be produced by mixing the cement composition of the present invention with water, sand and gravel. Further, when producing mortar or concrete from the above cement composition, blast furnace slag, fly ash or the like can be added.
  • MgO content in C 3 A (mass%), TiO 2 content (wt%), MnO content (wt%) , ZnO content (mass%) and Fe 2 O 3 content (mass%) were determined.
  • ⁇ EPMA tissue image observation conditions > ⁇ Acceleration voltage: 15kV ⁇ Irradiation current: 3.0 ⁇ 10-8 A ⁇ Beam diameter: Approximately 1 ⁇ m -Correction calculation method: Oxide-ZAF method The above analysis was performed on multiple cement clinker particles in the sample, the content rate (mass%) of each component at a total of 20 analysis points was obtained, and the average value was C 3 It was designated as C Mg-C3A , C Ti-C3A , C Mn-C3A , C Zn-C3A , and C Fe-C3A in A. Further, the value on the left side of the formula (1) was calculated from the content of each component obtained. The results are shown in Table 2.
  • C 4 AF performs a characteristic X-ray analysis under the same conditions as described above, was determined the content of Fe 2 O 3 in C 4 AF (mass%).
  • 20 analysis points are set as analysis points in the range of 0.8 ⁇ (CaO content) / (Al 2 O 3 content + Fe 2 O 3 content) ⁇ 1.35.
  • the average value in (C Fe-C4AF) was defined as C Fe-C4AF.
  • Table 2 The results are shown in Table 2.
  • a powder X-ray diffractometer X'Part Powerer manufactured by PANalytical Co., Ltd.
  • cement clinker minerals were used using software for crystal structure analysis (manufactured by PANalytical, X'Part High Score Plus version 2.1b) provided in the powder X-ray diffractometer.
  • the cement clinker minerals to be analyzed are C 3 S-M1 (M1 phase), C 3 S-M3 (M3 phase), C 2 S- ⁇ 'H ( ⁇ 'H phase), C 2 S- ⁇ ( ⁇ phase). ), C 3 A-cubic (cubic crystal), C 3 A-ortho (orthorhombic crystal), and C 4 AF.
  • the raw materials mixed with different amounts were put into an electric furnace and fired at 1000 ° C for 30 minutes. Then, the temperature was raised from 1000 ° C. to 1450 ° C. over 45 minutes, and further calcined at 1450 ° C. for 30 minutes. Then, the fired product was rapidly cooled by taking it out into the atmosphere to prepare cement clinker of Examples 1 to 9 and Comparative Examples 1 and 2.
  • mortar was prepared according to JIS R 5201: 2015 “Physical test method for cement”. The obtained mortar was cast into three metal molds having a size of 40 mm ⁇ 40 mm ⁇ 160 mm, and after 24 hours, the mortar was demolded to prepare three specimens each. Then, the mortar specimens of each Example and Comparative Example were obtained by curing in water at 20 ° C. up to 3 days of age.

Abstract

Provided are a cement clinker and a cement composition which can be reduced in heat of hydration and are excellent in short term strength development. A cement clinker in which the proportion of C3S determined by Bogue calculation is 50-75% by mass, the proportion of C2S determined by Bogue calculation is 5-25% by mass, and the total proportion of C3A and C4AF determined by Bogue calculation is 15-22% by mass, and which contains MgO, TiO2, MnO and ZnO, and satisfies the following formula (1).　(1): CMg-C3A×CTi-C3A×CMn-C3A×CZn-C3A≤0.0010 (in the formula (1), CMg-C3A represents the MgO content (% by mass) in C3A, CTi-C3A represents the TiO2 content (% by mass) in C3A, CMn-C3A represents the MnO content (% by mass) in C3A, and CZn-C3A represents the ZnO content (% by mass) in C3A).

Description

セメントクリンカ及びセメント組成物、並びにセメントクリンカの製造方法Cement clinker and cement composition, and method for manufacturing cement clinker
　本発明は、セメントクリンカ及びセメント組成物に関し、特に普通ポルトランドセメントに関する。 The present invention relates to cement clinker and cement composition, and particularly to ordinary Portland cement.
　コンクリートのひび割れ抑制の観点から、水和熱の低いセメント組成物が求められている。例えば、「土木工事共通仕様書（平成３１年４月改定）」（国土交通省関東地方整備局）、第２編「材料編」、第６節「セメント及び混和材料」、２－２－６－２「セメント」、表２－２－１８「普通ポルトランドセメントの品質」によると、セメントの水和熱に関し、７日材齢で３５０Ｊ／ｇ以下、２８日材齢で４００Ｊ／ｇ以下の管理目標値が示されている。 From the viewpoint of suppressing cracks in concrete, a cement composition with low heat of hydration is required. For example, "Common Specifications for Civil Engineering Work (Revised in April 2019)" (Ministry of Land, Infrastructure, Transport and Tourism, Kanto Regional Development Bureau), Volume 2, "Materials", Section 6, "Cement and Admixtures", 2-2-6 -2 According to "Cement" and Table 2-2-18 "Quality of ordinary Portland cement", the heat of hydration of cement is controlled to 350 J / g or less at 7-day age and 400 J / g or less at 28-day age. The target value is shown.
　近年、セメント原料として、石炭灰や建設発生土といった、Ａｌを多量に含有する各種廃棄物及び副産物が用いられてきている。しかしながら、これらの廃棄物及び副産物を用いると、セメントクリンカの鉱物組成中のＣ３Ａ量が増加し、水和熱が高くなってしまう。セメントクリンカの原料として上記廃棄物及び副産物を使用する場合には、その使用量は制限されてしまうのが現状である。 In recent years, various wastes and by-products containing a large amount of Al, such as coal ash and construction-generated soil, have been used as cement raw materials. However, the use of these wastes and by-products, an increase in C 3 A content of the mineral in the composition of the cement clinker, heat of hydration is increased. When the above wastes and by-products are used as raw materials for cement clinker, the amount used is currently limited.
　セメント組成物の水和熱を低減する方法としては、中庸熱ポルトランドセメントや低熱ポルトランドセメントのように、Ｃ３Ｓ及びＣ３Ａが低い鉱物組成に制御する手法や、高炉スラグと混合する方法が知られている（例えば、非特許文献１及び非特許文献２）。 As a method for reducing the heat of hydration of the cement composition, as moderate heat Portland cement and low heat Portland cement, and techniques C 3 S and C 3 A is controlled to a low mineral composition, a method of mixing with blast furnace slag It is known (for example, Non-Patent Document 1 and Non-Patent Document 2).
　非特許文献３には、セメントクリンカ中の微量成分であるＴｉＯ２及びＭｇＯが鉱物組成及びセメントの物性に与える影響が報告されている。非特許文献３には、ＭｇＯ含有量が増加するに伴い、アルミネート相（Ｃ３Ａ）が減少して、水和熱が低下する傾向があり更に、ＭｇＯ及びＴｉＯ２の合計含有量が多い程、水和熱が小さくなる傾向があることが開示されている。 Non-Patent Document 3 reports the effects of TiO 2 and MgO, which are trace components in cement clinker, on the mineral composition and the physical characteristics of cement. Non-Patent Document 3, as the MgO content increases, decreases aluminate phase (C 3 A) are, tend to heat of hydration is reduced further, often the total content of MgO and TiO 2 It is disclosed that the heat of hydration tends to be smaller.
　非特許文献３のように、クリンカ中のＭｇＯ及びＴｉＯ２の含有量によって、水和熱を低減させることも可能である。しかしながら、現実に製造されるクリンカには、産業廃棄物や副産物などに由来して、種々の微量成分が導入される。非特許文献３では、他の微量成分が水和熱などの物性に与える影響について何ら考慮されていない。 As in Non-Patent Document 3, it is also possible to reduce the heat of hydration by the content of MgO and TiO 2 in the clinker. However, various trace components are introduced into the clinker actually produced, which is derived from industrial waste and by-products. In Non-Patent Document 3, no consideration is given to the influence of other trace components on physical properties such as heat of hydration.
　本発明は、上記課題に鑑みなされたものであり、水和熱を低減させることができるセメントクリンカ、及び、該セメントクリンカセメント組成物を含むセメント組成物を提供することを目的とする。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a cement clinker capable of reducing heat of hydration and a cement composition containing the cement clinker cement composition.
　現実のセメントクリンカ製造及びセメント製造では、鉱物組成やセメントの物性は、ＭｇＯ及びＴｉＯ２以外の種々の微量成分や、製造条件などの影響を受ける。本発明者らは、微量成分の配合量などの製造条件が異なるクリンカと、水和熱との関連性について調査し、クリンカを鉱物組成中の化学成分に着目した結果、特にアルミネート相（Ｃ３Ａ）中の微量成分の含有量が水和熱に大きく影響することを見出し、本願発明を完成させた。 In actual cement clinker production and cement production, the mineral composition and physical properties of cement are affected by various trace components other than MgO and TiO 2 and production conditions. The present inventors investigated the relationship between clinker, which has different production conditions such as the amount of trace components, and heat of hydration, and focused on the chemical components in the mineral composition of clinker. 3 a) content of the trace components in the heading that greatly affects the heat of hydration, and completed the present invention.
　すなわち、上記課題を解決するために、本発明は、以下の＜１＞～＜５＞を提供する。
＜１＞ボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合が５０～７５質量％であり、ボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合が５～２５質量％であり、ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３の合計の割合が１５～２２質量％であり、ＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯを含み、下記式（１）を満たす、セメントクリンカ。
　　ＣＭｇ－Ｃ３Ａ×ＣＴｉ－Ｃ３Ａ×ＣＭｎ－Ｃ３Ａ×ＣＺｎ－Ｃ３Ａ≦０．００１０　・・・（１）
　式（１）中、
　ＣＭｇ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｇＯの含有率（質量％）を表し、
　ＣＴｉ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＴｉＯ２の含有率（質量％）を表し、
　ＣＭｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｎＯの含有率（質量％）を表し、
　ＣＺｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＺｎＯの含有率（質量％）を表す。
＜２＞前記３ＣａＯ・Ａｌ２Ｏ３中のＦｅ２Ｏ３の含有率が、６．３２質量％未満である、＜１＞に記載のセメントクリンカ。
＜３＞前記ＴｉＯ２の含有率が、０．２４質量％未満である、＜１＞または＜２＞に記載のセメントクリンカ。
＜４＞＜１＞～＜３＞のいずれかに記載のセメントクリンカと、石膏とを含むセメント組成物。
＜５＞原料を配合する工程と、配合された前記原料を焼成する工程と、を含むセメントクリンカの製造方法であって、焼成後のセメントクリンカが、ボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合が５０～７５質量％であり、ボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合が５～２５質量％であり、ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３の合計の割合が１５～２２質量％であり、ＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯを含み、下記式（１）を満たす、製造方法。
　　ＣＭｇ－Ｃ３Ａ×ＣＴｉ－Ｃ３Ａ×ＣＭｎ－Ｃ３Ａ×ＣＺｎ－Ｃ３Ａ≦０．００１０　・・・（１）
　式（１）中、
　ＣＭｇ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｇＯの含有率（質量％）を表し、
　ＣＴｉ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＴｉＯ２の含有率（質量％）を表し、
　ＣＭｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｎＯの含有率（質量％）を表し、
　ＣＺｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＺｎＯの含有率（質量％）を表す。 That is, in order to solve the above problems, the present invention provides the following <1> to <5>.
<1> ratio of 3CaO · SiO 2 calculated in Borg formula of 50-75 wt%, 5-25 wt% ratio of 2CaO · SiO 2, which is calculated by the Borg type is calculated by Borg formula The total ratio of 3CaO · Al 2 O 3 and 4 CaO · Al 2 O 3 · Fe 2 O 3 is 15 to 22% by mass, and contains MgO, TiO 2 , MnO and ZnO, and satisfies the following formula (1). , Cement clinker.
C Mg-C3A x C Ti-C3A x C Mn-C3A x C Zn-C3A ≤0.0010 ... (1)
In equation (1),
C Mg-C3A represents the content rate (mass%) of MgO in 3CaO · Al 2 O 3 and represents.
C Ti-C3A represents the content rate (mass%) of TiO 2 in 3CaO · Al 2 O 3 and represents.
C Mn-C3A represents the content rate (mass%) of MnO in 3CaO · Al 2 O 3 and represents.
C Zn—C3A represents the content rate (mass%) of ZnO in 3CaO · Al 2 O 3.
<2> The cement clinker according to <1>, wherein the content of Fe 2 O 3 in the 3 CaO · Al 2 O 3 is less than 6.32% by mass.
<3> The cement clinker according to <1> or <2>, wherein the content of TiO 2 is less than 0.24% by mass.
<4> A cement composition containing the cement clinker according to any one of <1> to <3> and gypsum.
<5> A method for producing cement clinker, which includes a step of blending raw materials and a step of firing the blended raw materials, wherein the cement clinker after firing is 3CaO · SiO 2 calculated by the Borg formula. ratio is 50 to 75 mass%, the fraction of 2CaO · SiO 2 calculated in Borg formulas 5 to 25 mass%, 3CaO · Al 2 O 3 and 4CaO · Al 2 O 3 calculated by Borg formula A production method in which the total ratio of Fe 2 O 3 is 15 to 22% by mass, contains MgO, TiO 2 , MnO and ZnO, and satisfies the following formula (1).
C Mg-C3A x C Ti-C3A x C Mn-C3A x C Zn-C3A ≤0.0010 ... (1)
In equation (1),
C Mg-C3A represents the content rate (mass%) of MgO in 3CaO · Al 2 O 3 and represents.
C Ti-C3A represents the content rate (mass%) of TiO 2 in 3CaO · Al 2 O 3 and represents.
C Mn-C3A represents the content rate (mass%) of MnO in 3CaO · Al 2 O 3 and represents.
C Zn—C3A represents the content rate (mass%) of ZnO in 3CaO · Al 2 O 3.
　本発明に依れば、水和熱を低減させることができるセメントクリンカを得ることができる。本発明のセメントクリンカを用いることにより、水和熱が低いセメント組成物を得ることができる。 According to the present invention, it is possible to obtain a cement clinker capable of reducing the heat of hydration. By using the cement clinker of the present invention, a cement composition having a low heat of hydration can be obtained.
　以下、本発明のセメントクリンカ及びセメント組成物について、詳細に説明する。なお、本明細書中の「ＡＡ～ＢＢ」との数値範囲の表記は、「ＡＡ以上ＢＢ以下」であることを意味する。 Hereinafter, the cement clinker and cement composition of the present invention will be described in detail. The notation of the numerical range of "AA to BB" in this specification means "AA or more and BB or less".
［セメントクリンカ］
　本発明のセメントクリンカは、ボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合が５０～７５質量％であり、ボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合が５～２５質量％であり、ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３の合計の割合が１５～２２質量％であり、ＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯを含み、下記式（１）を満たす、セメントクリンカ。
　　ＣＭｇ－Ｃ３Ａ×ＣＴｉ－Ｃ３Ａ×ＣＭｎ－Ｃ３Ａ×ＣＺｎ－Ｃ３Ａ≦０．００１０　・・・（１）
　式（１）中、
　ＣＭｇ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｇＯの含有率（質量％）を表し、
　ＣＴｉ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＴｉＯ２の含有率（質量％）を表し、
　ＣＭｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｎＯの含有率（質量％）を表し、
　ＣＺｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＺｎＯの含有率（質量％）を表す。
　本発明のセメントクリンカは、好適には普通ポルトランドセメントに使用される。 [Cement clinker]
Cement clinker of the present invention is 50 to 75 mass% ratio of the calculated 3CaO · SiO 2 is in the Borg type, the fraction of 2CaO · SiO 2 calculated in Borg formulas 5 to 25 mass%, Borg The total ratio of 3CaO · Al 2 O 3 and 4 CaO · Al 2 O 3 · Fe 2 O 3 calculated by the formula is 15 to 22% by mass, and includes MgO, TiO 2 , MnO and ZnO, and the following formula ( Cement clinker that satisfies 1).
C Mg-C3A x C Ti-C3A x C Mn-C3A x C Zn-C3A ≤0.0010 ... (1)
In equation (1),
C Mg-C3A represents the content rate (mass%) of MgO in 3CaO · Al 2 O 3 and represents.
C Ti-C3A represents the content rate (mass%) of TiO 2 in 3CaO · Al 2 O 3 and represents.
C Mn-C3A represents the content rate (mass%) of MnO in 3CaO · Al 2 O 3 and represents.
C Zn—C3A represents the content rate (mass%) of ZnO in 3CaO · Al 2 O 3.
The cement clinker of the present invention is preferably commonly used for Portland cement.
　本発明のセメントクリンカは、セメント組成物を構成する主要組成物であり、石灰石（ＣａＯ成分）、粘土（Ａｌ２Ｏ３成分、ＳｉＯ２成分）、ケイ石（ＳｉＯ２成分）及び酸化鉄原料（Ｆｅ２Ｏ３成分）などを配合し、焼成して製造される。本発明のセメントクリンカは、原料として石炭灰、建設発生土、高炉スラグ、転炉スラグ、副産石膏、都市ごみ焼却灰等の産業廃棄物等を含んでいても良い。
　本発明のセメントクリンカは、３ＣａＯ・ＳｉＯ２（略号：Ｃ３Ｓ）、２ＣａＯ・ＳｉＯ２（略号：Ｃ２Ｓ）、３ＣａＯ・Ａｌ２Ｏ３（略号：Ｃ３Ａ）、及び４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３（略号：Ｃ４ＡＦ）を含む。セメントクリンカは、エーライト（Ｃ３Ｓ）及びビーライト（Ｃ２Ｓ）の主要鉱物と、その主要鉱物の結晶間に存在するアルミネート相（Ｃ３Ａ）及びフェライト相（Ｃ４ＡＦ）の間隙相などとから構成される。 The cement clinker of the present invention is a main composition constituting a cement composition, and is a limestone (CaO component), clay (Al 2 O 3 component, SiO 2 component), silica stone (SiO 2 component) and an iron oxide raw material (SiO 2 component). Fe 2 O 3 component) and the like are mixed and fired to produce. The cement cleaner of the present invention may contain industrial waste such as coal ash, construction soil, blast furnace slag, converter slag, by-product plaster, and municipal waste incineration ash as raw materials.
Cement clinker of the present invention, 3CaO · SiO 2 (abbreviation: C 3 S), 2CaO · SiO 2 ( abbreviation: C 2 S), 3CaO · Al 2 O 3 ( abbreviation: C 3 A), and 4CaO · Al 2 Includes O 3 and FeO 3 (abbreviation: C 4 AF). Cement clinker is composed of the main minerals of alite (C 3 S) and belite (C 2 S) and the aluminate phase (C 3 A) and ferrite phase (C 4 AF) existing between the crystals of the main minerals. It is composed of interstitial phases and the like.
　セメントクリンカにおけるＣ３Ｓ、Ｃ２Ｓ、Ｃ３Ａ及びＣ４ＡＦの割合は、ＪＩＳ　Ｒ　５２０４：２０１９「セメントの蛍光Ｘ線分析方法」により測定したセメントクリンカにおけるＣａＯ、ＳｉＯ２、Ａｌ２Ｏ３及びＦｅ２Ｏ３の割合から、セメント化学の分野でボーグ式と呼ばれる計算式により求められる（例えば、大門正機編訳「セメントの科学」、内田老鶴圃（１９８９）、ｐ．１１を参照）。 The ratios of C 3 S, C 2 S, C 3 A and C 4 AF in cement clinker are CaO, SiO 2 , Al 2 O in cement clinker measured by JIS R 5204: 2019 “Method of fluorescent X-ray analysis of cement”. From the ratio of 3 and Fe 2 O 3 , it can be obtained by a calculation formula called the Borg formula in the field of cement chemistry (for example, "Cement Science" edited by Masaki Daimon, Uchida Otsuruho (1989), p.11. reference).
＜３ＣａＯ・ＳｉＯ２（Ｃ３Ｓ）の割合＞
　本発明のセメントクリンカにおけるボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合は、５０～７５質量％である。ボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合が５０質量％未満であると、セメントクリンカによって発現されるコンクリートやモルタルの強度が低下する場合がある。ボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合が７５質量％よりも大きいと、セメント組成物の水和熱が高くなりすぎる場合がある。ボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合は、５０～７０質量％であることが好ましく、５５～７０質量％であることがより好ましく、５５～６７質量％であることが更に好ましい。 <Percentage of 3CaO · SiO 2 (C 3 S )>
The ratio of 3CaO · SiO 2 calculated by the Borg formula in the cement clinker of the present invention is 50 to 75% by mass. If the ratio of 3CaO · SiO 2 calculated by the Borg formula is less than 50% by mass, the strength of concrete or mortar expressed by cement clinker may decrease. If the ratio of 3CaO · SiO 2 calculated by the Borg formula is larger than 75% by mass, the heat of hydration of the cement composition may become too high. The ratio of 3CaO · SiO 2 calculated by the Borg formula is preferably 50 to 70% by mass, more preferably 55 to 70% by mass, and even more preferably 55 to 67% by mass.
＜２ＣａＯ・ＳｉＯ２（Ｃ２Ｓ）の割合＞
　本発明のセメントクリンカにおけるボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合は、５～２５質量％である。ボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合が５質量％未満であると、結果的に、３ＣａＯ・ＳｉＯ２の割合が高くなり、セメント組成物の水和熱が高くなりすぎる場合がある。また、ボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合が２５質量％よりも大きくなると、セメント組成物によって発現されるコンクリートやモルタルの短期強度が低くなりすぎる場合がある。ボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合は、１０～２５質量％であることが好ましく、１１～２３質量％であることがより好ましく、１２～２２質量％であることが更に好ましい。 <Ratio of 2CaO · SiO 2 (C 2 S)>
The ratio of 2CaO · SiO 2 calculated by the Borg formula in the cement clinker of the present invention is 5 to 25% by mass. When the ratio of 2CaO · SiO 2 calculated in Borg formula is less than 5 mass%, resulting in, the higher the proportion of 3CaO · SiO 2, which may heat of hydration of the cement composition becomes too high. Further, when the ratio of 2CaO · SiO 2 calculated by the Borg formula becomes larger than 25% by mass, the short-term strength of concrete or mortar expressed by the cement composition may become too low. The ratio of 2CaO · SiO 2 calculated by the Borg formula is preferably 10 to 25% by mass, more preferably 11 to 23% by mass, and even more preferably 12 to 22% by mass.
＜３ＣａＯ・Ａｌ２Ｏ３（Ｃ３Ａ）及び４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３（Ｃ４ＡＦ）の合計の割合＞
　本発明のセメントクリンカにおけるボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３の合計の割合は、１５～２２質量％である。ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３の合計の割合が１５質量％未満であると、セメントクリンカの焼成時に生成する液相の量が少なくなるため、液相介在による固相－液相反応が速やかに進まなくなり、セメントクリンカの焼成が不十分になる場合がある。また、セメントキルン中にダストが飛散し、バーナーからの輻射熱が遮断されるため、セメントクリンカの焼成を効率よく実施できない場合がある。また、ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３の合計の割合が２２質量％よりも大きいと、操業不良を引き起こしやすくなると同時に、強度に寄与するカルシウムシリケート鉱物の生成が少なくなるため、本発明のセメントクリンカを用いたセメント組成物の強度が低下する場合がある。また、セメント組成物の水和熱が高くなりすぎる場合がある。ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３の合計の割合は、１７～２２質量％であることが好ましく、１８～２２質量％であることがより好ましく、１８～２０質量％であることが更に好ましい。 <Total proportion of 3CaO · Al 2 O 3 (C 3 A) and 4CaO · Al 2 O 3 · FeO 3 (C 4 AF)>
The total percentage of 3CaO · Al 2 O 3 and 4CaO · Al 2 O 3 · FeO 3 calculated by the Borg type in the cement clinker of the present invention is 15-22% by weight. If the total ratio of 3CaO / Al 2 O 3 and 4 CaO / Al 2 O 3 / FeO 3 calculated by the Borg equation is less than 15% by mass, the amount of the liquid phase generated during the firing of the cement clinker is small. In some cases, the solid-phase-liquid phase reaction due to the intervention of the liquid phase does not proceed rapidly, and the calcination of the cement clinker becomes insufficient. In addition, dust is scattered during the cement kiln and radiant heat from the burner is blocked, so that the cement clinker may not be fired efficiently. Further, when the total ratio of 3CaO / Al 2 O 3 and 4 CaO / Al 2 O 3 / FeO 3 calculated by the Borg formula is larger than 22% by mass, calcium is likely to cause poor operation and at the same time contribute to strength. Since the production of silicate minerals is reduced, the strength of the cement composition using the cement clinker of the present invention may be reduced. In addition, the heat of hydration of the cement composition may become too high. The total ratio of 3CaO / Al 2 O 3 and 4 CaO / Al 2 O 3 / FeO 3 calculated by the Borg equation is preferably 17 to 22% by mass, more preferably 18 to 22% by mass. , 18 to 20% by mass, more preferably.
＜３ＣａＯ・Ａｌ２Ｏ３（Ｃ３Ａ）の割合＞
　本発明のセメントクリンカにおけるボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３の割合は、好ましくは５．５～１２．５質量％であり、より好ましくは７～１２質量％であり、さらに好ましくは８～１１質量％である。ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３の割合が上記範囲であると、セメントクリンカの焼成中に生成する液相の粘性低下を抑制し、セメントクリンカの造粒を適切に進行させ、セメントクリンカの粒径が小さくなることによってクリンカークーラー中の層圧が一定しなくなることを抑制するとともに、水和熱を低くすることができる。なお、クリンカークーラー中の層圧が一定しなくなると、セメントクリンカの急冷に支障をきたす場合がある。 <Proportion of 3CaO · Al 2 O 3 (C 3 A)>
Proportion of 3CaO · Al 2 O 3 calculated by the Borg type in the cement clinker of the present invention is preferably 5.5 to 12.5 wt%, more preferably 7-12 wt%, more preferably It is 8 to 11% by mass. If the proportion of 3CaO · Al 2 O 3 calculated by the Borg type is in the above range, to suppress the decrease in viscosity of the liquid phase produced during sintering of the cement clinker, suitably allowed to proceed granulation of the cement clinker, cement By reducing the particle size of the clinker, it is possible to prevent the layer pressure in the clinker cooler from becoming constant and to reduce the heat of hydration. If the layer pressure in the clinker cooler is not constant, it may interfere with the rapid cooling of the cement clinker.
＜４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３（Ｃ４ＡＦ）の割合＞
　本発明のセメントクリンカにおけるボーグ式で算出された４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３の割合は、好ましくは８．５～１２．５質量％であり、より好ましくは９．０～１１．５質量％であり、さらに好ましくは９．５～１１．０質量％である。ボーグ式で算出された４ＣａＯ・Ａｌ２Ｏ３・ＦｅＯ３の割合が上記範囲であると、セメント組成物が発現する強度をより高くすることができるとともに、水和熱をより低くすることができる。 <Proportion of 4CaO · Al 2 O 3 · FeO 3 (C 4 AF)>
Proportion of 4CaO · Al 2 O 3 · FeO 3 calculated by the Borg type in the cement clinker of the present invention is preferably 8.5 to 12.5 wt%, more preferably 9.0 to 11.5 mass %, More preferably 9.5 to 11.0% by mass. When the ratio of 4CaO, Al 2 O 3, and FeO 3 calculated by the Borg formula is in the above range, the strength developed by the cement composition can be further increased, and the heat of hydration can be further reduced. ..
＜微量成分＞
　本発明のセメントクリンカは、微量成分としてＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯを含む。ＭｇＯ、ＴｉＯ２、ＭｎＯの各含有量は、ＪＩＳ　Ｒ　５２０４：２０１９「セメントの蛍光Ｘ線分析方法」に準拠して測定される。ＺｎＯの含有量はＪＣＡＳ　Ｉ－５３：２０１８「セメント中の微量成分の定量方法」に準拠して測定される。
　ＭｇＯは、例えば、ＭｇＯを多く含むスラグをセメントクリンカの原料として用いることにより、セメントクリンカへ導入される。
　ＴｉＯ２は、例えば、チタン石膏やフライアッシュをセメントクリンカの原料として用いることにより、セメントクリンカへ導入される。
　ＭｎＯは、例えば、高炉スラグ、転炉スラグをセメントクリンカの原料として用いることにより、セメントクリンカへ導入される。
　ＺｎＯは、例えば、都市ごみ焼却灰をセメントクリンカの原料として用いることにより、セメントクリンカへ導入される。 <trace components>
The cement clinker of the present invention contains MgO, TiO 2 , MnO and ZnO as trace components. The contents of MgO, TiO 2 , and MnO are measured in accordance with JIS R 5204: 2019 "Fluorescent X-ray Analysis Method for Cement". The ZnO content is measured in accordance with JCAS I-53: 2018 “Method for quantifying trace components in cement”.
MgO is introduced into the cement clinker, for example, by using slag containing a large amount of MgO as a raw material for the cement clinker.
TiO 2 is introduced into cement clinker by using, for example, titanium gypsum or fly ash as a raw material for cement clinker.
MnO is introduced into cement clinker by using, for example, blast furnace slag and converter slag as raw materials for cement clinker.
ZnO is introduced into cement clinker, for example, by using municipal waste incineration ash as a raw material for cement clinker.
＜ＭｇＯの含有量＞
　本発明において、セメントクリンカ中のＭｇＯの含有量は、好ましくは０．５０～２．００質量％、より好ましくは０．８０～１．８０質量％、更に好ましくは０．９５～１．６０質量％である。ＭｇＯの含有量が上記範囲であることにより、セメントクリンカの焼成が良好となるとともに、コンクリートやモルタルの硬化の際の水和膨張を抑制することができる。 <Content of MgO>
In the present invention, the content of MgO in the cement clinker is preferably 0.50 to 2.00% by mass, more preferably 0.80 to 1.80% by mass, and further preferably 0.95 to 1.60% by mass. %. When the MgO content is in the above range, the cement clinker can be fired well and hydration expansion during hardening of concrete or mortar can be suppressed.
　本発明におけるセメントクリンカは、３ＣａＯ・Ａｌ２Ｏ３中のＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯの各含有率（質量％）が、下記式（１）を満たす。
　　ＣＭｇ－Ｃ３Ａ×ＣＴｉ－Ｃ３Ａ×ＣＭｎ－Ｃ３Ａ×ＣＺｎ－Ｃ３Ａ≦０．００１０　・・・（１）
　ＣＭｇ－Ｃ３Ａ：３ＣａＯ・Ａｌ２Ｏ３中のＭｇＯの含有率（質量％）
　ＣＴｉ－Ｃ３Ａ：３ＣａＯ・Ａｌ２Ｏ３中のＴｉＯ２の含有率（質量％）
　ＣＭｎ－Ｃ３Ａ：３ＣａＯ・Ａｌ２Ｏ３中のＭｎＯの含有率（質量％）
　ＣＺｎ－Ｃ３Ａ：３ＣａＯ・Ａｌ２Ｏ３中のＺｎＯの含有率（質量％）
　式（１）中、ＣＭｇ－Ｃ３Ａ、ＣＴｉ－Ｃ３Ａ、ＣＭｎ－Ｃ３Ａ、ＣＺｎ－Ｃ３Ａは、実際のセメントクリンカにおいてＣ３Ａに含まれる各成分の含有率を表している。式（１）は、重回帰分析により求めることができる。 In the cement clinker of the present invention, the content (mass%) of MgO, TiO 2 , MnO and ZnO in 3CaO · Al 2 O 3 satisfies the following formula (1).
C Mg-C3A x C Ti-C3A x C Mn-C3A x C Zn-C3A ≤0.0010 ... (1)
C Mg-C3A : Content of MgO in 3CaO · Al 2 O 3 (mass%)
C Ti-C3A : Content of TiO 2 in 3CaO · Al 2 O 3 (mass%)
C Mn-C3A : Content of MnO in 3CaO · Al 2 O 3 (mass%)
C Zn-C3A : ZnO content (mass%) in 3CaO · Al 2 O 3
Wherein (1), C Mg-C3A , C Ti-C3A, C Mn-C3A, C Zn-C3A represent the content ratio of each component contained in C 3 A in the actual cement clinker. Equation (1) can be obtained by multiple regression analysis.
　ＣＭｇ－Ｃ３Ａ、ＣＴｉ－Ｃ３Ａ、ＣＭｎ－Ｃ３Ａ、ＣＺｎ－Ｃ３Ａは、以下のステップにより求められる。まず、セメントクリンカに所定の処理を施し、電子線マイクロアナライザ（ＥＰＭＡ）によりセメントクリンカ粒子の組成像を観察する。組成像において、以下の特徴に基づいて各鉱物を特定する。
　　（ａ）Ｃ３Ｓ：多角形粒子、明灰色、大きさ数十μｍ。
　　（ｂ）Ｃ２Ｓ：楕円形粒子、暗灰色、大きさ数十μｍ。
　　（ｃ）Ｃ３Ａ：Ｃ３Ｓ及びＣ２Ｓと特定された粒子間に見られる不定形組織、暗灰色、大きさ数μｍ～十数μｍ。
　　（ｄ）Ｃ４ＡＦ：Ｃ３Ｓ及びＣ２Ｓと特定された粒子間に見られる不定形組織、白色、大きさ数μｍ～十数μｍ。
　上記指標で特定されたＣ３Ａについて電子線マイクロアナライザ（ＥＰＭＡ）により特性Ｘ線分析を行い、Ｃ３Ａ中のＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯの含有率（質量％）を求める。なお、本発明では、組成像でＣ３Ａと特定された領域の複数点に対して特性Ｘ線分析を行い、１．３５＜（ＣａＯ含有率）／（Ａｌ２Ｏ３含有率＋Ｆｅ２Ｏ３含有率）＜２．２の範囲内となる点を分析点として採用する。そして、２０点の分析点での各成分の測定値の平均を、それぞれＣＭｇ－Ｃ３Ａ、ＣＴｉ－Ｃ３Ａ、ＣＭｎ－Ｃ３Ａ、ＣＺｎ－Ｃ３Ａとする。 C Mg-C3A , C Ti-C3A , C Mn-C3A , and C Zn-C3A can be obtained by the following steps. First, the cement clinker is subjected to a predetermined treatment, and the composition image of the cement clinker particles is observed with an electron probe microanalyzer (EPMA). In the composition image, each mineral is specified based on the following characteristics.
(A) C 3 S: polygonal particles, light gray, size of several tens [mu] m.
(B) C 2 S: Elliptical particles, dark gray, tens of μm in size.
(C) C 3 A: Atypical structure found between C 3 S and C 2 S and the identified particles, dark gray, a few μm to a dozen μm in size.
(D) C 4 AF: Amorphous structure found between C 3 S and C 2 S and the identified particles, white, several μm to ten and several μm in size.
Characteristic X-ray analysis of C 3 A specified by the above index is performed by an electron probe microanalyzer (EPMA) to determine the content (mass%) of MgO, TiO 2 , MnO and ZnO in C 3 A. In the present invention, characteristic X-ray analysis is performed on a plurality of points in the region specified as C 3 A in the composition image, and 1.35 <(CaO content) / (Al 2 O 3 content + Fe 2 O). 3 Content rate) The points within the range of <2.2 are adopted as analysis points. Then, the average of the measured values of each component at the 20 analysis points is defined as C Mg-C3A , C Ti-C3A , C Mn-C3A , and C Zn-C3A , respectively.
　式（１）を満たすことによって、水和熱が低いセメントクリンカを得ることが可能となる。この理由として、以下の２点が考えられる。
　式（１）は、Ｃ３Ａ中のＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯの含有量が少ないことを表している。Ｃ３Ａ中の微量成分が少ないことにより、Ｃ３Ａの活性が下がり、この結果、水和熱が低減されると推測される。水和熱を低減させるとの観点から、式（１）の左辺は０．０００８以下であることが好ましい。一方で、Ｃ３Ａの活性をある程度確保して、モルタルやコンクリートの凝結時間の遅延を防止するとの観点から、式（１）の左辺は、０．０００１以上であることが好ましい。 By satisfying the formula (1), it becomes possible to obtain a cement clinker having a low heat of hydration. The following two points can be considered as the reason for this.
Equation (1) is, MgO in C 3 A, indicates that the content of TiO 2, MnO and ZnO is small. By minor component in C 3 A is small, decreases the activity of C 3 A, the result is presumed that the heat of hydration is reduced. From the viewpoint of reducing the heat of hydration, the left side of the formula (1) is preferably 0.0008 or less. Meanwhile, to ensure the activity of C 3 A certain degree, with a view to preventing a delay of mortar and concrete setting time, the left side of the equation (1) is preferably 0.0001 or more.
　また、Ｃ３Ａ中に微量成分が式（１）を満たすことは、相対的に他の相にＭｇ，Ｔｉ，Ｍｎ，Ｚｎが多く固溶していることになる。Ｍｇ，Ｔｉ，Ｍｎ，ＺｎがＣ４ＡＦに固溶する際には、ＡｌがＣ４ＡＦに取り込まれやすくなり、相対的に、Ｃ３Ａの析出が少なくなるため水和熱が低減されると考えられる。
　ＭｎＯ及びＺｎＯは、一般的なポルトランドセメントクリンカでは非常に微量な成分であるものの、Ｃ３Ａの相対的な析出量の低減やＣ３Ａ中の結晶構造に関連して水和熱に対する影響を無視できるものではないと考えられる。 Furthermore, the minor component satisfies the formula (1) is in the C 3 A, becomes relatively other phase Mg, Ti, Mn, that Zn is more solid solution. When Mg, Ti, Mn, and Zn are dissolved in C 4 AF, Al is easily incorporated into C 4 AF, and the precipitation of C 3 A is relatively reduced, so that the heat of hydration is reduced. it is conceivable that.
MnO and ZnO, although in a typical Portland cement clinker is a very small amount of components, the effect in relation to the crystal structure in the C 3 A relative amount of precipitation of reduced or C 3 A in respect of hydration heat It is not considered to be negligible.
　本発明において、３ＣａＯ・Ａｌ２Ｏ３（Ｃ３Ａ）中のＦｅ２Ｏ３の含有率（以下、「ＣＦｅ－Ｃ３Ａ」と称する場合がある）が、６．３２質量％未満であることが好ましい。ＣＦｅ－Ｃ３Ａは、ＣＭｇ－Ｃ３Ａ等と同様に、電子線マイクロアナライザ（ＥＰＭＡ）による分析から取得される。具体的に、前述のステップにより、特定されたＣ３Ａについて電子線マイクロアナライザ（ＥＰＭＡ）により特性Ｘ線分析を行い、Ｃ３Ａ中のＦｅ２Ｏ３の含有率（質量％）を求める。そして、２０点の分析点での各成分の測定値の平均をＣＦｅ－Ｃ３Ａとする。
　実際のセメントクリンカ中の鉱物は、上記微量成分や製造条件などの影響により、各相の主成分に対して他の成分が固溶して形成されている。Ｆｅ２Ｏ３は、大部分がＣ４ＡＦに含まれるが、一部はＣ３Ａ、Ｃ３Ｓ及びＣ２Ｓにも固溶する。ここで、上記ボーグ式で表される鉱物組成の範囲では、実鉱物において間隙相であるＣ３Ａ中に含まれるＦｅ２Ｏ３の含有率が少なくなるほど、Ｃ３Ａが析出しにくく、Ｃ４ＡＦが析出やすい状況であると推測される。つまり、セメントクリンカ中のＦｅ２Ｏ３及びＡｌ２Ｏ３は、Ｃ４ＡＦの析出に消費されやすく、相対的にセメントクリンカ中のＣ３Ａの割合が低減することに繋がる。上記のように、Ｃ３Ａ中のＦｅ２Ｏ３の含有率が６．３２質量％未満であることにより、水和熱上昇の原因となるＣ３Ａの析出が抑制されて、水和熱の低減効果を得ることができる。Ｃ３Ａ中のＦｅ２Ｏ３の含有率は、６．００質量％以下であることがより好ましく、５．９０質量％以下であることが更に好ましく、５．８０質量％以下であることが特に好ましい。 In the present invention, the content of Fe 2 O 3 in 3 CaO · Al 2 O 3 (C 3 A) (hereinafter, may be referred to as “C Fe— C 3A”) is less than 6.32% by mass. Is preferable. C Fe-C3A , like C Mg-C3A and the like, is obtained from analysis with an electron probe microanalyzer (EPMA). Specifically, the foregoing steps, carried out characteristic X-ray analysis by electron probe microanalyzer (EPMA) for the identified C 3 A, obtains the content of Fe 2 O 3 in C 3 A (mass%). Then, the average of the measured values of each component at the 20 analysis points is defined as C Fe-C3A .
Minerals in an actual cement clinker are formed by solid-solving other components with respect to the main components of each phase due to the influence of the above-mentioned trace components and production conditions. Most of Fe 2 O 3 is contained in C 4 AF, but some of it is also dissolved in C 3 A, C 3 S and C 2 S. Here, in the range of the mineral composition represented by the Borg equation, the smaller the content of Fe 2 O 3 contained in C 3 A, which is the interstitial phase of the actual mineral, the more difficult it is for C 3 A to precipitate, and the more C 3 A is deposited. 4 It is presumed that AF is likely to precipitate. That is, Fe 2 O 3 and Al 2 O 3 in the cement clinker are easily consumed for the precipitation of C 4 AF, which leads to a relative reduction in the proportion of C 3 A in the cement clinker. As described above, when the content of Fe 2 O 3 in C 3 A is less than 6.32% by mass , the precipitation of C 3 A, which causes an increase in heat of hydration, is suppressed, and the heat of hydration is suppressed. Can be obtained. The content of Fe 2 O 3 in C 3 A is more preferably 6.00% by mass or less, further preferably 5.90% by mass or less, and preferably 5.80% by mass or less. Especially preferable.
　本発明において、上記ＣＴｉ－Ｃ３Ａ（Ｃ３Ａ中のＴｉＯ２の含有率）が、０．２４質量％未満であることが好ましい。Ｃ３Ａ中のＴｉＯ２の含有率が少ない程、Ｃ３Ａ中のＦｅ２Ｏ３の含有量も減少する傾向がある。このため、相対的に、セメントクリンカ中のＣ４ＡＦの割合が増加し、Ｃ４ＡＦの割合が低下する傾向にある。ＣＴｉ－Ｃ３Ａが上記範囲であることにより、Ｃ３Ａの析出を抑制して、水和熱を低減させることができる。 In the present invention, (the content of C 3 TiO 2 in A) above C Ti-C3A is preferably less than 0.24 wt%. The lower the content of TiO 2 in C 3 A, the lower the content of Fe 2 O 3 in C 3 A tends to be. Therefore, relatively, the proportion of C 4 AF in the cement clinker is increased, the proportion of C 4 AF tends to decrease. By C Ti-C3A is within the above range, it is possible to suppress the deposition of C 3 A, reduce the heat of hydration.
　セメントクリンカの実鉱物中の化学組成は、セメントクリンカの化学組成、セメントクリンカ製造時の焼成条件（熱履歴）などにより、調整することができる。 The chemical composition in the actual minerals of cement clinker can be adjusted by the chemical composition of cement clinker, the firing conditions (heat history) at the time of manufacturing cement clinker, and the like.
　式（１）を満たしやすくするために、例えば、セメントクリンカ中のＡｌ２Ｏ３、Ｆｅ２Ｏ３、ＭｇＯ、ＴｉＯ２、ＭｎＯ、及び、ＺｎＯの各含有率が、下記式（２）を満たすことが好ましい。
　　ＣＡｌ２Ｏ３×（３３．０６）＋ＣＦｅ２Ｏ３×（－８．１２）＋ＣＭｇＯ×（－４８．０８）＋ＣＴｉＯ２×（－１６３．６０)＋ＣＭｎＯ×（－３９０．８１）＋ＣＺｎＯ×（１０４．６０）＜４２．９・・・（２）
　式（２）において、ＣＡｌ２Ｏ３はＡｌ２Ｏ３の含有率（質量％）、ＣＦｅ２Ｏ３はＦｅ２Ｏ３の含有率（質量％）、ＣＭｇＯはＭｇＯの含有率（質量％）、ＣＴｉＯ２はＴｉＯ２の含有率（質量％）、ＣＭｎＯはＭｎＯの含有率（質量％）、ＣＺｎＯはＺｎＯの含有率（質量％）である。ＣＡｌ２Ｏ３、ＣＦｅ２Ｏ３、ＣＭｇＯ、ＣＴｉＯ２、ＣＭｎＯは、ＪＩＳ　Ｒ　５２０４：２０１９「セメントの蛍光Ｘ線分析方法」に準拠して測定され、ＣＺｎＯはＪＣＡＳ　Ｉ－５３：２０１８「セメント中の微量成分の定量方法」に準拠して測定される。式（２）は、重回帰分析により求めることができる。 In order to make it easier to satisfy the formula (1), for example, the contents of Al 2 O 3 , Fe 2 O 3 , MgO, TiO 2 , MnO, and ZnO in the cement clinker satisfy the following formula (2). Is preferable.
C Al2O3 × (33.06) + C Fe2O3 × (-8.12) + C MgO × (-48.08) + C TiO2 × (-163.60) + C MnO × (-390.81) + C ZnO × (104. 60) <42.9 ... (2)
In the formula (2), the content of C Al2 O3 is Al 2 O 3 (wt%), C Fe2 O3 content of the Fe 2 O 3 (wt%), C MgO is MgO content (mass%), C TiO2 Is the content of TiO 2 (mass%), C MnO is the content of MnO (% by mass), and C ZnO is the content of ZnO (% by mass). C Al2O3, C Fe2O3, C MgO, C TIO2, C MnO were measured in accordance with JIS R 5204: 2019 "X-ray fluorescence analysis method of cement", and C ZnO was JCAS I-53: 2018 "in cement". It is measured according to "Method for quantifying trace components". Equation (2) can be obtained by multiple regression analysis.
　式（２）の左辺の各項の係数は、その成分の水和熱への寄与に相当する。式（２）は、微量成分であるＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯの複合作用によって、間隙相の鉱物組成が変動することを意味するものである。式（２）では、一般的なポルトランドセメントクリンカでは非常に微量な成分であるＭｎＯ及びＺｎＯの係数が高いので、ＭｎＯ及びＺｎＯが、間隙相の鉱物の構成比にも影響していると言える。本発明において、セメントクリンカの化学組成が式（２）を満たすことにより、式（１）を満たしやすくなる。 The coefficient of each term on the left side of the formula (2) corresponds to the contribution of the component to the heat of hydration. The formula (2) means that the mineral composition of the interstitial phase changes due to the combined action of the trace components MgO, TiO 2, MnO and ZnO. In the formula (2), since the coefficients of MnO and ZnO, which are very trace components, are high in general Portland cement clinker, it can be said that MnO and ZnO also affect the composition ratio of minerals in the interstitial phase. In the present invention, when the chemical composition of the cement clinker satisfies the formula (2), the formula (1) can be easily satisfied.
　焼成条件としては、焼成雰囲気や、焼成温度、冷却速度などが挙げられる。例えば、焼成雰囲気が還元状態である場合や、焼成温度が高い場合、冷却速度が急冷である場合に、式（１）を満たしやすくすることができる。 The firing conditions include the firing atmosphere, firing temperature, cooling rate, and the like. For example, when the firing atmosphere is in a reduced state, the firing temperature is high, and the cooling rate is rapid cooling, the equation (1) can be easily satisfied.
［セメントクリンカの製造方法］
　本発明のクリンカは、例えば、以下のようにして製造することができる。
　クリンカ原料としては、Ｃａ、Ｓｉ、Ａｌ、Ｆｅの他、少なくともＭｇ、Ｔｉ、Ｍｎ、Ｚｎを含むものを用いる。上記元素を含むのであれば、元素単体物、酸化物、炭酸化物などの形態を問わず用いることができ、また、それらの混合物を用いることができる。例えば、天然原料として、石灰石、粘土、珪石、酸化鉄原料が挙げられ、工業的な原料の例として、上記元素を含む廃棄物原料、高炉スラグ、フライアッシュなどが挙げられる。クリンカ原料の混合割合に関しては、目的とするボーグ式値に対応した成分組成となり、かつ、焼成後のセメントクリンカにおいて式（１）ように、原料配合を定める。例えば、セメントクリンカの化学組成が式（２）を満たすように、原料を配合する。 [Manufacturing method of cement clinker]
The clinker of the present invention can be produced, for example, as follows.
As the clinker raw material, in addition to Ca, Si, Al and Fe, those containing at least Mg, Ti, Mn and Zn are used. As long as it contains the above elements, it can be used in any form such as elemental substances, oxides, carbon oxides, etc., and mixtures thereof can be used. For example, natural raw materials include limestone, clay, silica stone, and iron oxide raw materials, and examples of industrial raw materials include waste raw materials containing the above elements, blast furnace slag, fly ash, and the like. Regarding the mixing ratio of the clinker raw materials, the composition of the components corresponds to the target Borg formula value, and the raw material composition is determined as in the formula (1) in the cement clinker after firing. For example, the raw materials are blended so that the chemical composition of the cement clinker satisfies the formula (2).
　そして、目的とするクリンカが得られるような組成で混合されたクリンカ原料を、所定の焼成条件で焼成し、冷却する。焼成は、通常、電気炉やロータリーキルンなどを用いて行われる。焼成方法としては、例えば、クリンカ原料を、所定の第１焼成温度及び第１焼成時間で加熱して焼成を行う第１焼成工程と、該第１焼成工程後、第１焼成温度から所定の第２焼成温度まで所定の昇温時間をかけて昇温させる昇温工程と、該昇温工程後、所定の第２焼成温度及び第２焼成時間で加熱して焼成を行う第２焼成工程と、を含む方法が挙げられる。各工程の温度及び時間は、焼成後のセメントクリンカが式（１）を満たすことを目安として設定することができる。例えば、クリンカ原料を、９５０～１１００℃の焼成温度（第１焼成温度）で３０～６０分間（第１焼成時間）加熱して焼成を行った後（第１焼成工程）、１４２０～１４８０℃（第２焼成温度）まで３０～６０分間（昇温時間）かけて昇温させ（昇温工程）、さらに１４２０～１４８０℃で１５～４５分間（第２焼成時間）加熱して焼成を行った後（第２焼成工程）、焼成物を急冷することにより、クリンカを製造することができる。 Then, the clinker raw material mixed with a composition that can obtain the desired clinker is fired under predetermined firing conditions and cooled. Firing is usually performed using an electric furnace, a rotary kiln, or the like. As a firing method, for example, a first firing step in which a clinker raw material is heated and fired at a predetermined first firing temperature and a first firing time, and after the first firing step, a predetermined first firing temperature is used. 2 A raising step of raising the temperature to a predetermined raising time over a predetermined raising time, and a second firing step of heating and firing at a predetermined second firing temperature and a second firing time after the raising step. Examples include methods including. The temperature and time of each step can be set with the cement clinker after firing satisfying the formula (1) as a guide. For example, the clinker raw material is heated at a firing temperature of 950 to 1100 ° C. (first firing temperature) for 30 to 60 minutes (first firing time) to perform firing (first firing step), and then 1420 to 1480 ° C. (1st firing step). After raising the temperature to the second firing temperature) over 30 to 60 minutes (heating time) (heating step), and further heating at 1420 to 1480 ° C. for 15 to 45 minutes (second firing time) to perform firing. (Second firing step) The clinker can be produced by quenching the fired product.
［セメント組成物］
　本発明のセメント組成物は、上記セメントクリンカと、石膏とを含む。セメントクリンカ及び石膏の混合物のブレーン比表面積は、３０００ｃｍ２／ｇ以上３４００ｃｍ２／ｇ以下であることが好ましく、３１００ｃｍ２／ｇ以上３３００ｃｍ２／ｇ以下であることがより好ましい。
＜石膏＞
　本発明のセメント組成物における石膏の割合は、ＳＯ３換算量で好ましくは０．５～２．５質量％、より好ましくは１．０～１．８質量％である。石膏の割合が上記範囲とすることにより、セメント組成物の乾燥収縮を適切にすることができるとともに、セメント組成物が発現する強度を高くすることができる。石膏中のＳＯ３の割合は、ＪＩＳ　Ｒ　５２０２：２０１０「ポルトランドセメントの化学分析方法」に準じて測定することができる。セメント組成物中の石膏のＳＯ３に換算した質量の割合は、石膏の配合量と石膏に含まれるＳＯ３の割合から求めることができる。
　石膏としては、無水石膏、半水石膏、二水石膏のいずれも使用することができる。 [Cement composition]
The cement composition of the present invention contains the above-mentioned cement clinker and gypsum. A Blaine specific surface area of the mixture of cement clinker and gypsum is preferably from 3000 cm 2 / g or more 3400 cm 2 / g, and more preferably less 3100 cm 2 / g or more 3300cm 2 / g.
<Gypsum>
The proportion of gypsum in the cement compositions of the present invention are preferably converted to SO 3 content from 0.5 to 2.5 mass%, more preferably 1.0-1.8% by weight. By setting the ratio of gypsum to the above range, the drying shrinkage of the cement composition can be made appropriate, and the strength developed by the cement composition can be increased. The ratio of SO 3 in gypsum can be measured according to JIS R 5202: 2010 “Chemical analysis method of Portland cement”. Ratio of the mass in terms of SO 3 gypsum cement composition can be determined from the ratio of SO 3 contained in the amount and gypsum plaster.
As the gypsum, any of anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum can be used.
＜その他の成分＞
　本発明のセメント組成物には、流動性、水和速度または強度発現の調節用として、フライアッシュ、高炉スラグあるいはシリカフュームなどをさらに添加することができる。また、本発明のセメント組成物に、ＡＥ減水剤、高性能減水剤または高性能ＡＥ減水剤、特にポリカルボン酸系高性能ＡＥ減水剤を添加することができる。 <Other ingredients>
Fly ash, blast furnace slag, silica fume and the like can be further added to the cement composition of the present invention for adjusting the fluidity, hydration rate or strength development. Further, an AE water reducing agent, a high-performance water reducing agent or a high-performance AE water reducing agent, particularly a polycarboxylic acid-based high-performance AE water reducing agent, can be added to the cement composition of the present invention.
［モルタル及びコンクリート］
　本発明のセメント組成物を、水と混合することにより、セメントミルクを作製することができる。本発明のセメント組成物を、水及び砂と混合することにより、モルタルを作製することができる。本発明のセメント組成物を、水、砂及び砂利と混合することにより、コンクリートを製造することができる。また、上記セメント組成物からモルタルやコンクリートを作製する際、高炉スラグやフライアッシュなどを添加することもできる。 [Mortar and concrete]
Cement milk can be prepared by mixing the cement composition of the present invention with water. A mortar can be prepared by mixing the cement composition of the present invention with water and sand. Concrete can be produced by mixing the cement composition of the present invention with water, sand and gravel. Further, when producing mortar or concrete from the above cement composition, blast furnace slag, fly ash or the like can be added.
　以下、実施例を挙げて本発明を更に詳細に説明する。但し、本発明は、以下の実施例に何ら限定されるものではない。
１．測定及び評価
１－１．クリンカ組成
　実施例及び比較例のセメントクリンカ中の化学組成（各成分の含有率）を、ＪＩＳ　Ｒ　５２０４：２０１９「セメントの蛍光Ｘ線分析方法」及びＪＣＡＳ　Ｉ－５３：２０１８「セメント中の微量成分の定量方法」に準拠して測定した。鉱物組成は、得られたＣａＯ、ＳｉＯ２、Ａｌ２Ｏ３及びＦｅ２Ｏ３の質量割合から、下記のボーグ式を用いて算出した。結果を表１に示す。
　　Ｃ３Ｓ＝（４．０７×ＣａＯ）－（７．６０×ＳｉＯ２）－（６．７２×Ａｌ２Ｏ３）－（１．４３×Ｆｅ２Ｏ３）
　　Ｃ２Ｓ＝（２．８７×ＳｉＯ２）－（０．７５４×Ｃ３Ｓ）
　　Ｃ３Ａ＝（２．６５×Ａｌ２Ｏ３）－（１．６９×Ｆｅ２Ｏ３）
　　Ｃ４ＡＦ＝３．０４×Ｆｅ２Ｏ３
　更に、得られた各成分の含有率を用い、式（２）の左辺の値を算出した。結果を表２に示す。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
1. 1. Measurement and evaluation 1-1. Clinker Composition The chemical composition (content of each component) in the cement clinker of Examples and Comparative Examples is described in JIS R 5204: 2019 "Fluorescent X-ray analysis method of cement" and JCAS I-53: 2018 "Minor components in cement". It was measured according to the quantification method of. The mineral composition was calculated from the mass ratios of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 obtained by using the following Borg formula. The results are shown in Table 1.
C 3 S = (4.07 × CaO)-(7.60 × SiO 2 )-(6.72 × Al 2 O 3 )-(1.43 × Fe 2 O 3 )
C 2 S = (2.87 x SiO 2 )-(0.754 x C 3 S)
C 3 A = (2.65 x Al 2 O 3 )-(1.69 x Fe 2 O 3 )
C 4 AF = 3.04 x Fe 2 O 3
Further, the value on the left side of the formula (2) was calculated using the content of each component obtained. The results are shown in Table 2.
１－２．ＥＰＭＡ測定
　実施例及び比較例のセメントクリンカを、粒径１～２ｍｍ程度に粉砕し、粒度調整を行った。得られた粒子をエポキシ樹脂に包埋し、その後樹脂表面を鏡面研磨した。鏡面研磨後、樹脂表面に炭素蒸着を行い、ＥＰＭＡ測定用試料を作製した。
　測定装置として日本電子社製、ＥＰＭＡ　ＪＸＡ－８２００を用い、下記条件で上記試料の鏡面におけるセメントクリンカ粒子の組織像を観察した。組織像において、前記（ａ）～（ｄ）の特徴に基づき各鉱物を特定した。
＜ＥＰＭＡ　組織像観察条件＞
　　・加速電圧：１５ｋＶ
　　・照射電流：３．０×１０－８Ａ 1-2. EPMA measurement The cement clinker of Examples and Comparative Examples was pulverized to a particle size of about 1 to 2 mm to adjust the particle size. The obtained particles were embedded in an epoxy resin, and then the resin surface was mirror-polished. After mirror polishing, carbon vapor deposition was performed on the resin surface to prepare a sample for EPMA measurement.
An EPMA JXA-8200 manufactured by JEOL Ltd. was used as a measuring device, and the microstructure image of cement clinker particles on the mirror surface of the above sample was observed under the following conditions. In the histological image, each mineral was specified based on the characteristics of (a) to (d).
<EPMA tissue image observation conditions>
・ Acceleration voltage: 15kV
・ Irradiation current: 3.0 × 10-8 A
　Ｃ３Ａと特定された領域に対して下記条件で特性Ｘ線分析を行い、Ｃ３Ａ中のＭｇＯ含有率（質量％）、ＴｉＯ２含有率（質量％）、ＭｎＯ含有率（質量％）、ＺｎＯ含有率（質量％）、及び、Ｆｅ２Ｏ３含有率（質量％）を求めた。
＜ＥＰＭＡ　組織像観察条件＞
　　・加速電圧：１５ｋＶ
　　・照射電流：３．０×１０－８Ａ
　　・ビーム径：約１μｍ
　　・補正計算法：Ｏｘｉｄｅ－ＺＡＦ法
　試料中の複数のセメントクリンカ粒子について上記分析を行い、計２０点の分析点での各成分の含有率（質量％）を取得し、その平均値をＣ３Ａ中のＣＭｇ－Ｃ３Ａ、ＣＴｉ－Ｃ３Ａ、ＣＭｎ－Ｃ３Ａ、ＣＺｎ－Ｃ３Ａ、及び、ＣＦｅ－Ｃ３Ａとした。更に、得られた各成分の含有率から、式（１）の左辺の値を算出した。結果を表２に示す。 Performs characteristic X-ray analysis under the following conditions with respect to C 3 A with a particular region, MgO content in C 3 A (mass%), TiO 2 content (wt%), MnO content (wt%) , ZnO content (mass%) and Fe 2 O 3 content (mass%) were determined.
<EPMA tissue image observation conditions>
・ Acceleration voltage: 15kV
・ Irradiation current: 3.0 × 10-8 A
・ Beam diameter: Approximately 1 μm
-Correction calculation method: Oxide-ZAF method The above analysis was performed on multiple cement clinker particles in the sample, the content rate (mass%) of each component at a total of 20 analysis points was obtained, and the average value was C 3 It was designated as C Mg-C3A , C Ti-C3A , C Mn-C3A , C Zn-C3A , and C Fe-C3A in A. Further, the value on the left side of the formula (1) was calculated from the content of each component obtained. The results are shown in Table 2.
　また、Ｃ４ＡＦと特定された領域に対して、上記と同様の条件で特性Ｘ線分析を行い、Ｃ４ＡＦ中のＦｅ２Ｏ３の含有率（質量％）を求めた。なお、本発明では、０．８＜（ＣａＯ含有率）／（Ａｌ２Ｏ３含有率＋Ｆｅ２Ｏ３含有率）＜１．３５の範囲内となる点を分析点として、２０点の分析点での平均値を、ＣＦｅ－Ｃ４ＡＦとした。結果を表２に示す。 Further, with respect to C 4 AF and the identified region, performs a characteristic X-ray analysis under the same conditions as described above, was determined the content of Fe 2 O 3 in C 4 AF (mass%). In the present invention, 20 analysis points are set as analysis points in the range of 0.8 <(CaO content) / (Al 2 O 3 content + Fe 2 O 3 content) <1.35. The average value in (C Fe-C4AF) was defined as C Fe-C4AF. The results are shown in Table 2.
１－３．粉末Ｘ線回折測定
　実施例及び比較例のセメントクリンカに対して、粉末Ｘ線回析装置（パナリティカル社製、Ｘ’Ｐａｒｔ　Ｐｏｗｄｅｒ）を用い、測定条件を、測定範囲：２θ＝１０～７０°、ステップサイズ：０．０１７°、スキャンスピード：０．１０１２°／ｓ、電圧：４５ｋＶ、電流：４０ｍＡとして、Ｘ線回折測定を行い、Ｘ線回折プロファイルを得た。
　得られたＸ線回析プロファイルについて、上記粉末Ｘ線回析装置に備えられた結晶構造解析用ソフトウエア（パナリティカル社製、Ｘ’Ｐａｒｔ　Ｈｉｇｈ　Ｓｃｏｒｅ　Ｐｌｕｓ　ｖｅｒｓｉｏｎ　２．１ｂ）を用い、セメントクリンカ鉱物の定量を行った。解析対象のセメントクリンカ鉱物は、Ｃ３Ｓ－Ｍ１（Ｍ１相）、Ｃ３Ｓ－Ｍ３（Ｍ３相）、Ｃ２Ｓ－α’Ｈ（α’Ｈ相）、Ｃ２Ｓ－β（β相）、Ｃ３Ａ－ｃｕｂｉｃ（立方晶）、Ｃ３Ａ－ｏｒｔｈｏ（斜方晶）、Ｃ４ＡＦとした。
　上記ソフトウエアに搭載されたリートベルト法による解析機能を用い、文献「セメント化学専門委員会報告　Ｃ－１２　測定法の違いによるクリンカ鉱物量の差異の検討　第二部　第４章　粉末Ｘ線回折／Ｒｉｅｔｖｅｌｄ解析による定量に関する検討」の共同実験手順書２に準拠して、セメントクリンカの各鉱物の割合（質量％）を得た。また、各鉱物の割合の合計を１００質量％とし、各実施例及び比較例のＣ３Ａの含有率（ＣＣ３Ａ、質量％）及びＣ４ＡＦの含有率（ＣＣ４ＡＦ、質量％）を得た。結果を表２に示す。 1-3. Powder X-ray diffraction measurement For the cement clinker of Examples and Comparative Examples, a powder X-ray diffractometer (X'Part Powerer manufactured by PANalytical Co., Ltd.) was used, and the measurement conditions were set to the measurement range: 2θ = 10 to 70 °. , Step size: 0.017 °, scan speed: 0.1012 ° / s, voltage: 45 kV, current: 40 mA, X-ray diffraction measurement was performed, and an X-ray diffraction profile was obtained.
For the obtained X-ray diffraction profile, cement clinker minerals were used using software for crystal structure analysis (manufactured by PANalytical, X'Part High Score Plus version 2.1b) provided in the powder X-ray diffractometer. Was quantified. The cement clinker minerals to be analyzed are C 3 S-M1 (M1 phase), C 3 S-M3 (M3 phase), C 2 S-α'H (α'H phase), C 2 S-β (β phase). ), C 3 A-cubic (cubic crystal), C 3 A-ortho (orthorhombic crystal), and C 4 AF.
Using the Rietveld analysis function installed in the above software, the document "Cement Chemistry Expert Committee Report C-12 Examination of Differences in Clinker Mineral Amount Due to Differences in Measurement Method Part 2 Chapter 4 Powder X-ray Diffraction / The proportion (% by mass) of each mineral of cement clinker was obtained according to the joint experimental procedure manual 2 of "Study on Quantification by Rietveld Analysis". Further, the sum of the proportions of each mineral is 100 mass%, to obtain Examples and Comparative C 3 A content of Example (C C3A, mass%) and C 4 AF content of the (C C4AF, mass%) rice field. The results are shown in Table 2.
１－４．水和熱測定
　実施例及び比較例のセメントについて、材齢７日及び材齢２８日での水和熱を、ＪＩＳ　Ｒ　５２０３：２０１５「セメントの水和熱測定方法（溶解熱方法）」に準拠して測定した。基準値として、材齢７日での水和熱を３５０Ｊ／ｇ、材料２８日での水和熱を４００Ｊ／ｇに設定した。材齢７日及び材齢２８日いずれも基準値以下の水和熱となったものを「Ａ」評価、いずれかの材齢で基準値を超えるものを「Ｃ」評価とした。結果を表２に示す。 1-4. Heat hydration measurement For the cement of Examples and Comparative Examples, the heat of hydration at the age of 7 days and 28 days is based on JIS R 5203: 2015 "Method for measuring heat of hydration of cement (heat of solution)". And measured. As reference values, the heat of hydration at 7 days of age was set to 350 J / g, and the heat of hydration at 28 days of material was set to 400 J / g. Those having a heat of hydration below the standard value for both 7 days and 28 days of age were evaluated as "A", and those exceeding the standard value at any of the ages were evaluated as "C". The results are shown in Table 2.
１－５．モルタル圧縮強さ
　実施例及び比較例のモルタルから得たモルタル供試体について、材齢３日の圧縮強さを、ＪＩＳ　Ｒ　５２０１：２０１５「セメントの物理試験方法」に準拠して測定した。結果を表２に示す。 1-5. Mortar Compressive Strength For mortar specimens obtained from the mortars of Examples and Comparative Examples, the compressive strength at 3 days of age was measured in accordance with JIS R 5201: 2015 “Physical Test Method for Cement”. The results are shown in Table 2.
２．セメント組成物の作製
２－１．クリンカ
　セメントクリンカの原料として、炭酸カルシウム（キシダ化学（株）製、試薬１級、ＣａＣＯ３）、二酸化珪素（関東化学（株）製、試薬１級、ＳｉＯ２）、酸化アルミニウム（関東化学（株）製、試薬１級、Ａｌ２Ｏ３）、酸化鉄（III）（関東化学（株）製、試薬特級、Ｆｅ２Ｏ３）、塩基性炭酸マグネシウム（キシダ化学（株）製、試薬特級、４ＭｇＣＯ３・Ｍｇ（ＯＨ）２・５Ｈ２Ｏ）、炭酸ナトリウム（キシダ化学（株）製、特級、Ｎａ２ＣＯ３）、炭酸カリウム（関東化学（株）製、試薬１級、Ｋ２ＣＯ３）、硫酸カルシウム２水和物（キシダ化学（株）製、試薬１級、ＣａＳＯ４・２Ｈ２Ｏ）、二酸化チタン（関東化学（株）製、試薬特急、ＴｉＯ２）、リン酸三カルシウム（キシダ化学（株）製、試薬１級、Ｃａ３（ＰＯ４）２）、酸化マンガン（関東化学（株）製、鹿１級、ＭｎＯ２）、及び、酸化亜鉛（関東化学（株）製、試薬特級、ＺｎＯ）を用いた。 2. Preparation of cement composition 2-1. Clinker Cement As raw materials for Clinker, calcium carbonate (manufactured by Kishida Chemical Co., Ltd., reagent first grade, CaCO 3 ), silicon dioxide (manufactured by Kanto Chemical Co., Ltd., reagent first grade, SiO 2 ), aluminum oxide (Kanto Kagaku Co., Ltd.) ), Reagent 1st grade, Al 2 O 3 ), Iron oxide (III) (Kanto Chemical Co., Ltd., Reagent special grade, Fe 2 O 3 ), Basic magnesium carbonate (Kishida Chemical Co., Ltd., Reagent special grade, 4MgCO 3 · Mg (OH) 2 · 5H 2 O), sodium carbonate (manufactured by Kishida chemical Co., Ltd., special grade, Na 2 CO 3), potassium carbonate (Kanto chemical Co., Ltd., first grade reagent, K 2 CO 3 ), calcium sulfate dihydrate (Kishida chemical Co., Ltd., first grade reagent, CaSO 4 · 2H 2 O), titanium dioxide (Kanto chemical Co., Ltd., reagent express, TiO 2), tricalcium phosphate ( Kishida Chemical Co., Ltd., Reagent 1st grade, Ca 3 (PO 4 ) 2 ), Manganese oxide (Kanto Chemical Co., Ltd., Deer 1st grade, MnO 2 ), and Zinc oxide (Kanto Chemical Co., Ltd., Special grade reagent, ZnO) was used.
　配合量を変えて配合した原料を、電気炉に投入して１０００℃で３０分間の焼成を行った．その後、１０００℃から１４５０℃まで４５分間かけて昇温させ、更に１４５０℃で３０分間の焼成を行った。その後、焼成物を大気中に取り出すことによって急冷して、実施例１～９及び比較例１～２のセメントクリンカを作製した。 The raw materials mixed with different amounts were put into an electric furnace and fired at 1000 ° C for 30 minutes. Then, the temperature was raised from 1000 ° C. to 1450 ° C. over 45 minutes, and further calcined at 1450 ° C. for 30 minutes. Then, the fired product was rapidly cooled by taking it out into the atmosphere to prepare cement clinker of Examples 1 to 9 and Comparative Examples 1 and 2.
２－２．セメント組成物の調製
　上記作製したセメントクリンカに、内割でＳＯ３換算量１．５質量％の半水石膏（関東化学（株）製、半水石膏、型番：０７１０８－０１（焼石膏　鹿１級））を配合した。当該配合物を、ブレーン比表面積値が約３２００±２００ｃｍ２／ｇの範囲となるようにボールミルで粉砕して、実施例１～９及び比較例１～２のセメント組成物を作製した。 2-2. Preparation of the above-prepared cement clinker cement composition, the inner split converted to SO 3 of 1.5% by weight of hemihydrate gypsum (Kanto Chemical Co., hemihydrate gypsum, model number: 07108-01 (calcined gypsum deer 1 Grade)) was blended. The compound was pulverized with a ball mill so that the brain specific surface area value was in the range of about 3200 ± 200 cm 2 / g to prepare cement compositions of Examples 1 to 9 and Comparative Examples 1 and 2.
２－３．モルタルの作製
　実施例及び比較例のセメント組成物から、ＪＩＳ　Ｒ　５２０１：２０１５「セメントの物理試験方法」に準拠してモルタルを調整した。得られたモルタルを、４０ｍｍ×４０ｍｍ×１６０ｍｍの金属型枠３個に打設し、２４時間後に脱型して供試体を３個ずつ作製した。その後、２０℃水中で材齢３日まで養生して、各実施例及び比較例のモルタル供試体を得た。 2-3. Preparation of mortar From the cement compositions of Examples and Comparative Examples, mortar was prepared according to JIS R 5201: 2015 “Physical test method for cement”. The obtained mortar was cast into three metal molds having a size of 40 mm × 40 mm × 160 mm, and after 24 hours, the mortar was demolded to prepare three specimens each. Then, the mortar specimens of each Example and Comparative Example were obtained by curing in water at 20 ° C. up to 3 days of age.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１～９はいずれも、式（１）の数値が０．００１０以下であり、材齢７日及び材齢２８日のいずれでも水和熱が基準値以下であった。一方、比較例１～２は、材齢７日での水和熱が基準値を満たしていなかった。つまり、式（１）を満たすことにより、低い水和熱のセメント組成物を得ることができた。 In Examples 1 to 9, the numerical value of the formula (1) was 0.0010 or less, and the heat of hydration was below the reference value in both the age of 7 days and the age of 28 days. On the other hand, in Comparative Examples 1 and 2, the heat of hydration at the age of 7 days did not satisfy the standard value. That is, by satisfying the formula (1), a cement composition having a low heat of hydration could be obtained.
　セメントクリンカの間隙相の組成に着目すると、表２に示すように、実施例のＣ３Ａ中のＦｅ２Ｏ３の含有率は、比較例よりも低い値となった。一方で、本実験ではＣ４ＡＦ中のＦｅ２Ｏ３の含有率（ＣＦｅ－Ｃ４ＡＦ）とＣ３Ａ中のＦｅ２Ｏ３の含有率（ＣＦｅ－Ｃ３Ａ）との相関はあまり見られなかった。しかしながら、リートベルト解析による実鉱物中のＣ３Ａ含有率は、比較例よりも実施例の方が低い傾向が見られている。このことから、実施例のセメントクリンカではＣ３Ａの析出が抑制された結果、水和熱が低減されたと言える。なお、リートベルト解析によるＣ３Ａ含有率が低い実施例１，２，５，７－９では、３日材齢の圧縮強度が比較例と同等または比較例よりも高いという結果が得られた。このことから、リートベルト解析によるＣ３Ａ含有率が低い程、短期強度発現性に優れるセメント組成物となる傾向があると言える。 Focusing on the composition of the gap phase of the cement clinker, as shown in Table 2, the content of Fe 2 O 3 in C 3 A of Example, it was lower than the comparative example. On the other hand, in this experiment, there is not much correlation between the content of Fe 2 O 3 in C 4 AF (C Fe- C 4 AF) and the content of Fe 2 O 3 in C 3 A (C Fe-C 3A). There wasn't. However, C 3 A content of the actual minerals by Rietveld analysis are the observed low tendency towards embodiment than in the comparative example. Therefore, as a result of deposition of C 3 A in the cement clinker is suppressed embodiments, it can be said that the heat of hydration is reduced. Incidentally, lied in belt Analysis C 3 A content less Example 1,2,5,7-9 by, result in higher than equal to or Comparative Examples and Comparative Examples compressive strength of 3 days material age was obtained .. Therefore, the lower the C 3 A content by Rietveld analysis, it can be said that there tends to be a cement composition excellent in the short-term strength development.
　表１に示す化学成分上はＴｉＯ２含有量が同等程度のセメントクリンカを用いた場合であっても、表２によると水和熱が異なる。表２に示すように、ＣＴｉ－Ｃ３Ａが０．２４質量％未満であることにより、水和熱が低減する傾向が見られた。

  In terms of the chemical composition shown in Table 1, even when cement clinker having the same TiO 2 content is used, the heat of hydration is different according to Table 2. As shown in Table 2, when C Ti—C3A was less than 0.24% by mass, the heat of hydration tended to decrease.

Claims (5)

  1. 　ボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合が５０～７５質量％であり、
    　ボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合が５～２５質量％であり、
    　ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３の合計の割合が１５～２２質量％であり、
    　ＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯを含み、
    　下記式（１）を満たす、セメントクリンカ。
    　　ＣＭｇ－Ｃ３Ａ×ＣＴｉ－Ｃ３Ａ×ＣＭｎ－Ｃ３Ａ×ＣＺｎ－Ｃ３Ａ≦０．００１０　・・・（１）
    　式（１）中、
    　ＣＭｇ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｇＯの含有率（質量％）を表し、
    　ＣＴｉ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＴｉＯ２の含有率（質量％）を表し、
    　ＣＭｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｎＯの含有率（質量％）を表し、
    　ＣＺｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＺｎＯの含有率（質量％）を表す。     The ratio of 3CaO · SiO 2 calculated by the Borg formula is 50 to 75% by mass.
    The ratio of 2CaO · SiO 2 calculated by the Borg formula is 5 to 25% by mass.
    The total ratio of 3CaO / Al 2 O 3 and 4 CaO / Al 2 O 3 / Fe 2 O 3 calculated by the Borg equation is 15 to 22% by mass.
    Contains MgO, TiO 2 , MnO and ZnO
    A cement clinker that satisfies the following formula (1).
    C Mg-C3A x C Ti-C3A x C Mn-C3A x C Zn-C3A ≤0.0010 ... (1)
    In equation (1),
    C Mg-C3A represents the content rate (mass%) of MgO in 3CaO · Al 2 O 3 and represents.
    C Ti-C3A represents the content rate (mass%) of TiO 2 in 3CaO · Al 2 O 3 and represents.
    C Mn-C3A represents the content rate (mass%) of MnO in 3CaO · Al 2 O 3 and represents.
    C Zn—C3A represents the content rate (mass%) of ZnO in 3CaO · Al 2 O 3.
  2. 　前記３ＣａＯ・Ａｌ２Ｏ３中のＦｅ２Ｏ３の含有率が、６．３２質量％未満である、請求項１に記載のセメントクリンカ。 The 3CaO · Al 2 O 3 Fe 2 O 3 of content in is less than 6.32 wt%, the cement clinker of claim 1.
  3. 　前記ＴｉＯ２の含有率が、０．２４質量％未満である、請求項１または請求項２に記載のセメントクリンカ。 The cement clinker according to claim 1 or 2 , wherein the content of TiO 2 is less than 0.24% by mass.
  4. 　請求項１乃至請求項３のいずれか１項に記載のセメントクリンカと、石膏とを含むセメント組成物。 A cement composition containing the cement clinker according to any one of claims 1 to 3 and gypsum.
  5. 　原料を配合する工程と、配合された前記原料を焼成する工程と、を含むセメントクリンカの製造方法であって、
    　焼成後のセメントクリンカが、
    　ボーグ式で算出された３ＣａＯ・ＳｉＯ２の割合が５０～７５質量％であり、
    　ボーグ式で算出された２ＣａＯ・ＳｉＯ２の割合が５～２５質量％であり、
    　ボーグ式で算出された３ＣａＯ・Ａｌ２Ｏ３及び４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３の合計の割合が１５～２２質量％であり、
    　ＭｇＯ、ＴｉＯ２、ＭｎＯ及びＺｎＯを含み、
    　下記式（１）を満たす、製造方法。
    　　ＣＭｇ－Ｃ３Ａ×ＣＴｉ－Ｃ３Ａ×ＣＭｎ－Ｃ３Ａ×ＣＺｎ－Ｃ３Ａ≦０．００１０　・・・（１）
    　式（１）中、
    　ＣＭｇ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｇＯの含有率（質量％）を表し、
    　ＣＴｉ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＴｉＯ２の含有率（質量％）を表し、
    　ＣＭｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＭｎＯの含有率（質量％）を表し、
    　ＣＺｎ－Ｃ３Ａは、３ＣａＯ・Ａｌ２Ｏ３中のＺｎＯの含有率（質量％）を表す。

          A method for producing cement clinker, which comprises a step of blending raw materials and a step of firing the blended raw materials.
    Cement clinker after firing
    The ratio of 3CaO · SiO 2 calculated by the Borg formula is 50 to 75% by mass.
    The ratio of 2CaO · SiO 2 calculated by the Borg formula is 5 to 25% by mass.
    The total ratio of 3CaO / Al 2 O 3 and 4 CaO / Al 2 O 3 / Fe 2 O 3 calculated by the Borg equation is 15 to 22% by mass.
    Contains MgO, TiO 2 , MnO and ZnO
    A manufacturing method that satisfies the following formula (1).
    C Mg-C3A x C Ti-C3A x C Mn-C3A x C Zn-C3A ≤0.0010 ... (1)
    In equation (1),
    C Mg-C3A represents the content rate (mass%) of MgO in 3CaO · Al 2 O 3 and represents.
    C Ti-C3A represents the content rate (mass%) of TiO 2 in 3CaO · Al 2 O 3 and represents.
    C Mn-C3A represents the content rate (mass%) of MnO in 3CaO · Al 2 O 3 and represents.
    C Zn—C3A represents the content rate (mass%) of ZnO in 3CaO · Al 2 O 3.

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JP2016190751A (en) * 2015-03-31 2016-11-10 住友大阪セメント株式会社 Cement clinker and cement composition
JP2018016504A (en) * 2016-07-26 2018-02-01 太平洋セメント株式会社 High belite-based cement composition

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