WO2023120206A1 - Cement composition and method for producing same - Google Patents
Cement composition and method for producing same Download PDFInfo
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- WO2023120206A1 WO2023120206A1 PCT/JP2022/045241 JP2022045241W WO2023120206A1 WO 2023120206 A1 WO2023120206 A1 WO 2023120206A1 JP 2022045241 W JP2022045241 W JP 2022045241W WO 2023120206 A1 WO2023120206 A1 WO 2023120206A1
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- mass
- cement
- portland cement
- mgo
- alkanolamine
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- 239000004568 cement Substances 0.000 title claims abstract description 158
- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000011398 Portland cement Substances 0.000 claims abstract description 90
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 12
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 abstract description 32
- 230000007774 longterm Effects 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 239000010440 gypsum Substances 0.000 description 18
- 229910052602 gypsum Inorganic materials 0.000 description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 description 17
- 239000011707 mineral Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 14
- 235000019738 Limestone Nutrition 0.000 description 13
- 239000006028 limestone Substances 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 12
- 239000006104 solid solution Substances 0.000 description 11
- 238000003991 Rietveld refinement Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000010881 fly ash Substances 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004567 concrete Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 3
- 241001504564 Boops boops Species 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 Nn-butylethanolamine Chemical compound 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007730 finishing process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229940102253 isopropanolamine Drugs 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- XKQMKMVTDKYWOX-UHFFFAOYSA-N 1-[2-hydroxypropyl(methyl)amino]propan-2-ol Chemical compound CC(O)CN(C)CC(C)O XKQMKMVTDKYWOX-UHFFFAOYSA-N 0.000 description 1
- AZQZJVVZBGCHSV-UHFFFAOYSA-N 2-(3,5-dimethylpyrazol-1-yl)-n-[2-(3,5-dimethylpyrazol-1-yl)ethyl]ethanamine Chemical compound N1=C(C)C=C(C)N1CCNCCN1C(C)=CC(C)=N1 AZQZJVVZBGCHSV-UHFFFAOYSA-N 0.000 description 1
- CMWUSCNTMPWOKZ-UHFFFAOYSA-N 2-(methylamino)propan-2-ol Chemical compound CNC(C)(C)O CMWUSCNTMPWOKZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 102100027340 Slit homolog 2 protein Human genes 0.000 description 1
- 101710133576 Slit homolog 2 protein Proteins 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Definitions
- the present invention relates to a cement composition and a method for producing the same.
- Clinker contains minor components such as Mg, Na, and K depending on raw material conditions, and the content varies.
- Mg cement under high MgO conditions
- Ca which is also an alkaline earth metal.
- long-term strength such as 28-day age decreases due to the decrease in .
- Non-Patent Document 3 has found that increasing SO 3 may improve strength even with high MgO.
- Patent Document 1 if the MgO content in the cement clinker after firing exceeds 1.0% by mass, the strength expression in the long-term material age of the cement decreases. It is disclosed that the raw materials are prepared by adjusting the MgO content to 1.0% by mass or less. Furthermore, in Patent Document 2, a cement clinker having a 2CaO ⁇ SiO 2 content of 30 to 60% by mass calculated by the Borg formula, wherein the cement clinker has a MgO content of 1.2% by mass or more, less than 1.9% by weight and a cement clinker characterized by a SO 3 content of 0.4-1.2% by weight.
- Non-Patent Documents 1 to 3 cannot stably maintain long-term strength.
- the problem is that the mines that produce limestone, which is the raw material, sometimes contain a large amount of dolomite, and the produced cement has a high MgO content, causing variations in the quality performance of concrete and the like. Therefore, as in Patent Document 1, it was necessary to reduce the MgO content.
- Patent Document 2 it is explained that even if the content of MgO in cement is high, it is possible to prevent deterioration of the long-term strength development of cement. had to be less than
- the present invention provides a cement composition excellent in long-term strength of mortar even when the MgO content in Portland cement is high, and a cement composition capable of improving long-term strength of mortar even when the MgO content in Portland cement is high.
- the object is to provide a manufacturing method.
- the present invention provides the following ⁇ 1> to ⁇ 10>.
- ⁇ 1> Portland cement that satisfies the following (1) and (2); With respect to 100 parts by mass of the Portland cement, 0.001 to 0.025 parts by mass of alkanolamine, A cement composition comprising: ( 1 ) 0.55 ⁇ MgO/ Fe2O3 + CL'SO3 / SO3 ⁇ 0.95 (2) 0 ⁇ C 4 AF
- MgO represents the mass (% by mass) of MgO in the Portland cement
- Fe 2 O 3 represents the mass (% by mass) of Fe 2 O 3 in the Portland cement
- SO 3 represents the mass (% by mass) of It represents the SO 3 equivalent amount (mass%) of Portland cement
- CL'SO 3 represents the SO 3 equivalent amount (mass%) of the clinker of the Portland cement.
- ⁇ C 4 AF is The mass (% by mass) of C 4 AF and B. It represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF.
- the R.I. C 4 AF represents the C 4 AF value of the Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 .
- the above B. Fe 2 O 3 in C 4 AF represents the mass (% by mass) of Fe 2 O 3 in the Portland cement.
- the Portland cement contains 45 to 75% by mass of C 3 S, 5 to 25% by mass of C 2 S, 7 to 11% by mass of C 3 A, and 7 to 7% by mass of C 4 AF calculated by the Borg formula.
- ⁇ 4> The cement composition according to any one of ⁇ 1> to ⁇ 3>, wherein the alkanolamine content is 0.005 to 0.02 parts by mass with respect to 100 parts by mass of the Portland cement.
- the alkanolamine is at least one selected from the group consisting of diethanolisopropanolamine, triisopropanolamine, ethanoldiisopropanolamine, triethanolamine, N-methyldiethanolamine, and Nn-butyldiethanolamine.
- the cement composition according to any one of 1> to ⁇ 4>.
- ⁇ C 4 AF is The mass (% by mass) of C 4 AF and B. It represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF.
- the R.I. C 4 AF represents the C 4 AF value of the Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 .
- the above B. Fe 2 O 3 in C 4 AF represents the mass (% by mass) of Fe 2 O 3 in the Portland cement.
- ⁇ 7> The method for producing a cement composition according to ⁇ 6>, wherein the MgO/Fe 2 O 3 in (1) exceeds 0.35.
- the Portland cement contains 45 to 75% by mass of C 3 S, 5 to 25% by mass of C 2 S, 7 to 11% by mass of C 3 A, and 7 to 7% by mass of C 4 AF calculated by the Borg formula.
- ⁇ 9> The cement composition according to any one of ⁇ 6> to ⁇ 8>, wherein the amount of the alkanolamine added is 0.005 to 0.02 parts by mass with respect to 100 parts by mass of the Portland cement. Production method.
- the alkanolamine is at least one selected from the group consisting of diethanolisopropanolamine, triisopropanolamine, ethanoldiisopropanolamine, triethanolamine, N-methyldiethanolamine, and Nn-butyldiethanolamine. 6> A method for producing a cement composition according to any one of ⁇ 9>.
- a method for manufacturing an object can be provided.
- FIG. 4 is a graph plotting the values of ⁇ C 4 AF against the conditions ** of Examples and Comparative Examples.
- FIG. It is the graph which plotted the value of the mortar enhancement strength difference with respect to conditions ** in the 7-day age and 28-day age of an Example and a comparative example.
- the cement composition of the present invention contains Portland cement satisfying the following (1) and (2) and 0.001 to 0.025 parts by mass of alkanolamine per 100 parts by mass of the Portland cement.
- MgO represents the mass (mass%) of MgO in Portland cement
- Fe2O3 represents the mass (mass%) of Fe2O3 in Portland cement
- SO3 represents SO of Portland cement. 3 equivalent amount (% by mass)
- CL'SO 3 represents the SO 3 equivalent amount (% by mass) of Portland cement clinker.
- ⁇ C 4 AF is the The mass (% by mass) of C 4 AF and B.
- R.C.sub.4 AF- B.C.sub.4 AF represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF.
- R.I. C 4 AF represents the C 4 AF value of Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 .
- B. Fe 2 O 3 in C 4 AF represents the mass (mass %) of Fe 2 O 3 in Portland cement.
- Portland cement that satisfies the above (1) and (2) is hereinafter referred to as "portland cement in the present invention” or simply "cement in the present invention”.
- the cement composition of the present invention contains clinker, gypsum and alkanolamine, Portland cement containing clinker and gypsum satisfies the above (1) and (2), and the alkanolamine content is Range.
- the MgO content in the cement is high, for example, 1.30% by mass or more, the hydration of calcium decreases, which relatively reduces the strength of the mortar.
- an auxiliary agent such as alkanolamine.
- the long-term strength of the mortar can be improved by making the content of the cement composition as described above.
- Condition (1) is that "MgO/Fe 2 O 3 +CL'SO 3 /SO 3 " is 0.55 to 0.95. Although the details are not clear, it is possible that the mass of MgO relative to the mass of Fe 2 O 3 increases, and the SO 3 equivalent amount (mass standard) in clinker relative to the SO 3 equivalent amount (mass standard) in cement increases. , which is thought to be related to the solid solution of the ferrite phase. “MgO/Fe 2 O 3 +CL′SO 3 /SO 3 ” can be considered as an indicator of the solid solution amount of the ferrite phase.
- the alkanolamine contained together with the Portland cement in the present invention dissolves iron and the like in the ferrite phase, dissolves it in the gel, promotes watertightness by uniformly permeating, and has the function of increasing the strength of the mortar. It is considered that the solid solution of SO 3 in the ferrite phase further enhances the mortar strength enhancing effect of the alkanolamine, thereby improving the long-term strength of the mortar.
- MgO/Fe 2 O 3 +CL'SO 3 /SO 3 " is less than 0.55, the solid solution amount of the ferrite phase is small, and the mortar strength enhancing effect due to the alkanolamine cannot be sufficiently obtained, and the long-term strength of the mortar is low. Not good for When “MgO/Fe 2 O 3 +CL'SO 3 /SO 3 " exceeds 0.95, it becomes difficult to obtain the strength increasing effect of alkanolamine, and alkanolamine, unreacted MgO and MgSO 4 become excessive. It causes expansion cracks and the mortar strength cannot be maintained. From the viewpoint of further improving the long-term strength of the mortar, "MgO/Fe 2 O 3 +CL'SO 3 /SO 3 " is preferably 0.60 to 0.90, more preferably 0.70 to 0.80. is more preferred.
- MgO/Fe 2 O 3 preferably exceeds 0.35.
- the mass of MgO with respect to the mass of Fe 2 O 3 in the cement is considered to represent the solid solution amount of C 4 AF.
- MgO/Fe 2 O 3 is preferably 0.36 to 0.60, more preferably 0.40 to 0.50.
- the mass of MgO in the condition (1) is preferably 3.5% by mass or less, and 0.5 to 3.0% by mass. and more preferably 1.0 to 2.5% by mass.
- the mass of Fe 2 O 3 in the condition (1) is preferably 2.0 to 4.0 mass%, It is more preferably 2.5 to 3.5% by mass, even more preferably 2.7 to 3.4% by mass.
- CL'SO 3 that is, the SO 3 equivalent amount of clinker is preferably 2.5% by weight or less, and 0 .2 to 2.0% by mass, more preferably 0.5 to 1.5% by mass.
- the range of SO 3 which is the denominator of CL'SO 3 /SO 3 that is, the SO 3 equivalent amount of cement is 3.5% by weight or less. It is preferably from 0.5 to 3.0% by mass, and even more preferably from 1.5 to 2.5% by mass.
- Condition (2) is that ⁇ C 4 AF is 0 points or more. Note that the 0 point is, for example, when the C 4 AF (R.C 4 AF) obtained by Rietveld analysis is 10.1% by mass, the C 4 AF (B.C 4 AF) calculated by the Borg formula is also 10.1% by mass. ⁇ C 4 AF was determined by R. The mass of C 4 AF and B. Represents the difference (RC 4 AF-BC 4 AF) from the mass of C 4 AF, and C 4 AF obtained by Rietveld analysis (RC 4 AF) and C 4 calculated by the Borg formula This is the difference from AF (B.C 4 AF).
- the solid solution amount of MgO can be estimated from ⁇ C 4 AF, and ⁇ C 4 AF increases as the MgO content in cement increases.
- ⁇ C 4 AF is 0 or more. Since the increase in the amount of dissolved ferrite phase in which MgO is dissolved by alkanolamine affects the increase in strength, ⁇ C 4 AF is preferably 0.3 to 1.5 points, and 0.5 to 1.5 points. It is more preferable to have
- C 4 AF is determined by the following steps. First, X-ray diffraction measurement of cement is performed to obtain a profile. The obtained profile is analyzed by the Rietveld method to quantify cement minerals. 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), C 3 A-ortho (orthorhombic), and C 4 AF. In the Rietveld analysis, based on the basic crystal structure data of each mineral, refinement operation is performed so that the measured profile and the theoretical profile are fitted with parameters such as lattice constant and scale factor. From the finally refined scale factor, the mass ratio of each of the above minerals was calculated. Obtain the C 4 AF content (% by mass). Specific measurement conditions for the X-ray diffractometer are shown in Examples.
- Portland cement in the present invention is not particularly limited as long as it satisfies the above conditions (1) and (2).
- Portland cement, blast-furnace slag, fly ash, siliceous mixed material (pozzolana), etc. can also be used, and special cement such as alumina cement can be used. preferred.
- the Portland cement used in the cement composition of the present invention contains 45 to 75% by mass of C 3 S (3CaO.SiO 2 ) calculated by the Bogue formula, C 2 S (2CaO.SiO 2 ) is 5 to 25% by mass, C 3 A (3CaO.Al 2 O 3 ) is 7 to 11% by mass, and C 4 AF (4CaO.Al 2 O 3 .FeO 3 ) is 7 to 11% by mass. It is preferred that the Moreover, the Portland cement used in the cement composition of the present invention preferably has a C 4 AF (R.C 4 AF) obtained by Rietveld analysis of 7.5 to 12% by mass.
- C 4 AF R.C 4 AF
- the mechanism of strength enhancement by the addition of alkanolamine is that the selective dissolution of C 4 AF in the clinker increases the opportunity for C 4 AF adjacent to C 4 AF to come into contact with water, promoting hydration and increasing strength. will increase.
- the addition of the alkanolamine tends to increase the strength.
- the content of C 3 S in cement is more preferably 50 to 70% by mass.
- the total of C 4 AF and C 3 A is constant at about 18% by mass, and if the content of C 4 AF in cement increases, the content of C 3 A decreases, The content of 3A increases. From the viewpoint of enhancing strength and fluidity, the content of C 4 AF in cement is preferably 7-9% by mass, more preferably 8-9% by mass.
- the cement composition of the present invention contains 0.001 to 0.025 parts by mass of alkanolamine per 100 parts by mass of Portland cement clinker of the present invention.
- Alkanolamines also act as strength enhancers. If the content of alkanolamine in the cement composition of the present invention is less than 0.001 parts by mass with respect to 100 parts by mass of Portland cement clinker, the effect of increasing strength cannot be obtained. When the content of alkanolamine in the cement composition of the present invention exceeds 0.025 parts by mass with respect to 100 parts by mass of Portland cement clinker, the effect of increasing the initial strength is remarkable. Due to the active hydration activity, the hydrated structure becomes coarse and the strength increasing effect cannot be obtained. From the above viewpoint, the alkanolamine content in the cement composition of the present invention is preferably 0.005 to 0.02 parts by mass per 100 parts by mass of the Portland cement clinker of the present invention.
- Alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, methylethanolamine, methylisopropanolamine, Nn-butylethanolamine, N-methyldiethanolamine, N- n-butyldiethanolamine, N-methyldiisopropanolamine, diethanolisopropanolamine, diisopropanolethanolamine, tetrahydroxyethylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, tris(2-hydroxy Butyl) amine and the like can be exemplified. Only one type of alkanolamine may be used, or two or more types may be used.
- alkanolamines are diethanolisopropanolamine (DEIPA), triisopropanolamine (TIPA), ethanoldiisopropanolamine (EDIPA), triethanolamine (TEA), N-methyldiethanolamine (MDEA), and Nn-butyldiethanolamine.
- BDEA preferably at least one selected from the group consisting of diethanolisopropanolamine (DEIPA), triisopropanolamine (TIPA), ethanoldiisopropanolamine (EDIPA) and triethanolamine (TEA) More preferably, it is at least one more selected, and more preferably diethanol isopropanolamine (DEIPA).
- Alkanolamine is generally difficult to mix due to its high viscosity, and is not suitable for adding during mortar production. Therefore, it is preferable to add it as a grinding aid in the finishing process of cement production. Further, when the alkanolamine is diluted and dissolved in water and used, it becomes easy to mix with cement, and the cement composition of the present invention can be produced efficiently.
- the cement composition of the present invention contains gypsum.
- gypsum any of anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum can be used.
- the content of gypsum in the cement composition is preferably 0.5-2.5% by mass in terms of SO 3 .
- the drying shrinkage of the cement composition can be made appropriate, and the strength exhibited by the cement composition can be increased.
- the content of gypsum in the cement composition is more preferably 1.0 to 1.8% by mass in terms of SO 3 .
- the ratio of SO 3 in gypsum can be measured according to JIS R 5202:2010 "Method for chemical analysis of Portland cement".
- the ratio of the SO3 - equivalent mass of gypsum in the cement composition can be obtained from the compounding amount of gypsum and the ratio of SO3 contained in the gypsum.
- the cement composition of the present invention may contain limestone for the purpose of improving short-term strength and reducing CO2 emissions through pulverization.
- the content of limestone in the cement composition is specified in JIS R 5210: 2009 "Portland cement", but in the present invention, even if limestone is added beyond the range specified in the JIS standard good.
- the content of limestone in the cement composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, even more preferably 2 to 5% by mass.
- the limestone content of 0% by mass means that limestone is not added to the production of the cement composition.
- fly ash to the cement composition of the present invention, fly ash, blast-furnace slag, silica fume, or the like can be further added for adjusting fluidity, hydration rate, strength development, and the like.
- the cement composition of the present invention preferably has a Blaine specific surface area of 3000 to 3400 cm 2 /g.
- the Blaine specific surface area is 3000 cm 2 /g or more, the mortar strength is less likely to decrease, and when it is 3400 cm 2 /g or less, the decrease in fluidity is suppressed, and the dissolution of C 4 AF due to alkanolamine is reduced. can be suppressed to maintain the strength enhancement effect.
- the Blaine specific surface area of the cement composition is more preferably 3100 to 3300 cm 2 /g.
- the Blaine specific surface area of the cement composition may be measured according to JIS R 5201:2015 "Methods for Physical Testing of Cement".
- ⁇ C 4 AF is R.C.
- R.I. C 4 AF represents the C 4 AF value of Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 .
- B. Fe 2 O 3 in C 4 AF represents the mass (mass %) of Fe 2 O 3 in Portland cement.
- the Portland cement used in the method for producing the cement composition of the present invention is the same as the Portland cement contained in the cement composition of the present invention, and preferred embodiments are also the same. That is, MgO/Fe 2 O 3 preferably exceeds 0.35, and the Portland cement in the present invention contains 45 to 75% by mass of C 3 S and 5 to 25% by mass of C 2 S calculated by the Bogue formula. %, 7-11% by weight of C 3 A and 7-11% by weight of C 4 AF.
- the amount of alkanolamine to be blended is the same as the content of alkanolamine in the cement composition of the present invention, and the preferred range is also the same. That is, the amount of alkanolamine to be added is preferably 0.005 to 0.02 parts by mass with respect to 100 parts by mass of Portland cement in the present invention.
- the amount of limestone to be blended is synonymous with the limestone content described above, and the preferred range is also the same.
- the alkanolamine used in the method for producing the cement composition of the present invention is the same as the alkanolamine contained in the cement composition of the present invention, and preferred embodiments are also the same. That is, the alkanolamine used in the method for producing the cement composition of the present invention is selected from the group consisting of diethanolisopropanolamine, triisopropanolamine, ethanoldiisopropanolamine, triethanolamine, N-methyldiethanolamine, and Nn-butyldiethanolamine. At least one is preferably selected.
- Alkanolamine is generally highly viscous and difficult to mix, so it is unsuitable to add during mortar production. Therefore, it is preferable to add it as a grinding aid in the finishing process of cement production. Further, when the alkanolamine is diluted and dissolved in water and used, it becomes easy to mix with cement, and the cement composition of the present invention can be produced efficiently.
- the means for mixing each component in the method for producing the cement composition of the present invention is not particularly limited. Examples include mixers, ball mills, roche mills, and air blending silos.
- the mixing time can be set within a range in which it is determined that sufficient mixing is performed in the normal production of cement compositions.
- pulverization is preferably carried out so that the Blaine specific surface area of the cement composition is 3000 to 3400 cm 2 /g.
- blast furnace slag, siliceous admixture and fly ash can be further added.
- blast furnace slag and siliceous admixture specified in JIS R 5210:2009 "Portland cement” can be used.
- fly ash in addition to fly ash type I and fly ash type II defined in JIS R 5210:2009 "Portland cement", fly ash type III and fly ash type IV can also be used.
- the mineral composition was calculated from the obtained mass ratios of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 using the following Borg formula.
- 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
- C3A ( 2.65 x Al2O3 ) - ( 1.69 x Fe2O3 )
- C4AF 3.04 x Fe2O3
- Alkanolamine/DEIPA diethanol isopropanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.]
- ⁇ TEA Triethanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.]
- TIPA triisopropanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.]
- ⁇ EDIPA ethanol diisopropanolamine [manufactured by Sigma-Aldrich Japan LLC]
- Gypsum Hemihydrate gypsum was used. Specifically, chemical gypsum (CaSO 4 (97.8 mol %)) held in a dryer at 120° C. for 12 hours was used. The SO 3 equivalent amount in gypsum was measured according to JIS R 5202:2015 "Method for chemical analysis of cement". The composition of chemical gypsum is as shown in Table 3.
- FIG. 1 shows a graph plotting the values of ⁇ C 4 AF against the conditions ** of the examples and comparative examples.
- each of the amine-free cement composition and the amine-added cement composition was mixed and pulverized in a test ball mill so that the Blaine specific surface area value was 3300 cm 2 /g, and each cement composition of Example 1 was obtained. Obtained.
- Examples 20 to 22 The cements shown in Tables 5, 6 and 9 were used as amine-free cement compositions.
- An amine-added cement composition was obtained in the same manner as in Example 7, except that an alkanolamine shown in "Amine species" in Table 9 was used as the alkanolamine instead of DEIPA.
- each of the amine-free cement composition and the amine-added cement composition was mixed and pulverized in a test ball mill so that the Blaine specific surface area value was 3300 cm 2 /g, and each cement composition of Examples 20 to 22. got stuff
- test materials were formed in accordance with JIS R 5201: 2015 "Physical test method for cement", and mortar Compressive strength test was measured.
- the mixing ratio of the test material is 11.1% by mass of water, 66.7% by mass of aggregate, and 22.2% by mass of cement.
- the test material was wrapped in vinyl chloride resin and cured.
- the compressive strength of the mortar obtained using the amine-free cement composition is shown in the "Material age (no addition) (a)” column in Tables 7 to 9, and the mortar obtained using the amine-added cement composition.
- the compressive strength of the mortar obtained is shown in Tables 7 to 9 in the "Age (Amine addition) (b)” column.
- a higher numerical value means a higher compressive strength of mortar.
- FIG. 2 shows a graph plotting the difference in mortar enhancement strength against conditions ** at 7-day age and 28-day age.
- "Condition **” is a numerical value shown in the "Condition ** " column of Tables 7 to 9, and corresponds to "MgO/Fe 2 O 3 +CL'SO 3 /SO 3 ”.
- the difference in mortar strength shown in the " ⁇ (b-a)" column in Tables 7 to 9 is the difference between the mortar obtained using the amine-added cement composition and the mortar obtained using the amine-free cement composition. It shows how much the strength is increased compared to , and the greater the positive value, the greater the strength enhancement effect. Comparing the results of the 3-day age with the results of the 7-day and 28-day ages, it can be seen that the value of ⁇ (b ⁇ a) is larger for the 7-day and older samples, indicating that the strength enhancement effect is greater. A comparison of the 7-day age and 28-day age is shown in FIG.
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Abstract
Description
例えば、非特許文献1には、高MgO条件のセメントは同じアルカリ土類金属であるCaと置換されることが知られており、それにより、非特許文献2に示す通り相対的にビーライト量が減少することから28日材齢等の長期強度が低下することが知られている。非特許文献3にてSO3を増加させることで高MgOでも強さを改善させる可能性があるという知見が得られている。 Clinker contains minor components such as Mg, Na, and K depending on raw material conditions, and the content varies.
For example, in Non-Patent
更に、特許文献2では、ボーグ式で算出される2CaO・SiO2の含有率が30~60質量%のセメントクリンカであって、該セメントクリンカ中、MgOの含有率が1.2質量%以上、1.9質量%未満であり、SO3の含有率が0.4~1.2質量%であることを特徴とするセメントクリンカを開示している。 In addition, in
Furthermore, in
<1> 下記(1)及び(2)を満たすポルトランドセメントと、
前記ポルトランドセメント100質量部に対し、0.001~0.025質量部のアルカノールアミンと、
を含むセメント組成物。
(1)0.55≦MgO/Fe2O3+CL’SO3/SO3≦0.95
(2)0≦△C4AF
前記(1)中、MgOは前記ポルトランドセメント中のMgOの質量(質量%)を表し、Fe2O3は前記ポルトランドセメント中のFe2O3の質量(質量%)を表し、SO3は前記ポルトランドセメントのSO3換算量(質量%)を表し、CL’SO3は前記ポルトランドセメントのクリンカのSO3換算量(質量%)を表す。
前記(2)中、△C4AFは、R.C4AFの質量(質量%)とB.C4AFの質量(質量%)との差分(R.C4AF-B.C4AF)を表す。ここで、前記R.C4AFは、粉末X線回析装置で測定した前記ポルトランドセメントのC4AF値を表し、前記B.C4AFは、3.04×Fe2O3を表す。前記B.C4AFにおけるFe2O3は前記ポルトランドセメント中のFe2O3の質量(質量%)を表す。 The present invention provides the following <1> to <10>.
<1> Portland cement that satisfies the following (1) and (2);
With respect to 100 parts by mass of the Portland cement, 0.001 to 0.025 parts by mass of alkanolamine,
A cement composition comprising:
( 1 ) 0.55≤MgO/ Fe2O3 + CL'SO3 / SO3≤0.95
(2) 0≦ΔC 4 AF
In (1) above, MgO represents the mass (% by mass) of MgO in the Portland cement, Fe 2 O 3 represents the mass (% by mass) of Fe 2 O 3 in the Portland cement, and SO 3 represents the mass (% by mass) of It represents the SO 3 equivalent amount (mass%) of Portland cement, and CL'SO 3 represents the SO 3 equivalent amount (mass%) of the clinker of the Portland cement.
In (2) above, ΔC 4 AF is The mass (% by mass) of C 4 AF and B. It represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF. Here, the R.I. C 4 AF represents the C 4 AF value of the Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 . The above B. Fe 2 O 3 in C 4 AF represents the mass (% by mass) of Fe 2 O 3 in the Portland cement.
<3> 前記ポルトランドセメントは、ボーグ式で算出されるC3Sが45~75質量%、C2Sが5~25質量%、C3Aが7~11質量%、C4AFが7~11質量%である普通ポルトランドセメントである<1>または<2>に記載のセメント組成物。
<4> 前記アルカノールアミンの含有量が、前記ポルトランドセメント100質量部に対し、0.005~0.02質量部である<1>~<3>のいずれか1つに記載のセメント組成物。
<5> 前記アルカノールアミンが、ジエタノールイソプロパノールアミン、トリイソプロパノールアミン、エタノールジイソプロパノールアミン、トリエタノールアミン、N-メチルジエタノールアミン、及びN-n-ブチルジエタノールアミンからなる群より選択される少なくとも1つである<1>~<4>のいずれか1つに記載のセメント組成物。 <2> The cement composition according to <1>, wherein the MgO/Fe 2 O 3 in (1) exceeds 0.35.
<3> The Portland cement contains 45 to 75% by mass of C 3 S, 5 to 25% by mass of C 2 S, 7 to 11% by mass of C 3 A, and 7 to 7% by mass of C 4 AF calculated by the Borg formula. The cement composition according to <1> or <2>, which is 11% by mass of ordinary Portland cement.
<4> The cement composition according to any one of <1> to <3>, wherein the alkanolamine content is 0.005 to 0.02 parts by mass with respect to 100 parts by mass of the Portland cement.
<5> The alkanolamine is at least one selected from the group consisting of diethanolisopropanolamine, triisopropanolamine, ethanoldiisopropanolamine, triethanolamine, N-methyldiethanolamine, and Nn-butyldiethanolamine. The cement composition according to any one of 1> to <4>.
前記ポルトランドセメント100質量部に対し、0.001~0.025質量部のアルカノールアミンと、
を混合するセメント組成物の製造方法。
(1)0.55≦MgO/Fe2O3+CL’SO3/SO3≦0.95
(2)0≦△C4AF
前記(1)中、MgOは前記ポルトランドセメント中のMgOの質量(質量%)を表し、Fe2O3は前記ポルトランドセメント中のFe2O3の質量(質量%)を表し、SO3は前記ポルトランドセメントのSO3換算量(質量%)を表し、CL’SO3は前記ポルトランドセメントのクリンカのSO3換算量(質量%)を表す。
前記(2)中、△C4AFは、R.C4AFの質量(質量%)とB.C4AFの質量(質量%)との差分(R.C4AF-B.C4AF)を表す。ここで、前記R.C4AFは、粉末X線回析装置で測定した前記ポルトランドセメントのC4AF値を表し、前記B.C4AFは、3.04×Fe2O3を表す。前記B.C4AFにおけるFe2O3は前記ポルトランドセメント中のFe2O3の質量(質量%)を表す。 <6> Portland cement that satisfies the following (1) and (2);
With respect to 100 parts by mass of the Portland cement, 0.001 to 0.025 parts by mass of alkanolamine,
A method for producing a cement composition by mixing
( 1 ) 0.55≤MgO/ Fe2O3 + CL'SO3 / SO3≤0.95
(2) 0≦ΔC 4 AF
In (1) above, MgO represents the mass (% by mass) of MgO in the Portland cement, Fe 2 O 3 represents the mass (% by mass) of Fe 2 O 3 in the Portland cement, and SO 3 represents the mass (% by mass) of It represents the SO 3 equivalent amount (mass%) of Portland cement, and CL'SO 3 represents the SO 3 equivalent amount (mass%) of the clinker of the Portland cement.
In (2) above, ΔC 4 AF is The mass (% by mass) of C 4 AF and B. It represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF. Here, the R.I. C 4 AF represents the C 4 AF value of the Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 . The above B. Fe 2 O 3 in C 4 AF represents the mass (% by mass) of Fe 2 O 3 in the Portland cement.
<8> 前記ポルトランドセメントは、ボーグ式で算出されるC3Sが45~75質量%、C2Sが5~25質量%、C3Aが7~11質量%、C4AFが7~11質量%である普通ポルトランドセメントである<6>または<7>に記載のセメント組成物の製造方法。
<9> 前記アルカノールアミンの添加量が、前記ポルトランドセメント100質量部に対し、0.005~0.02質量部である<6>~<8>のいずれか1つに記載のセメント組成物の製造方法。
<10> 前記アルカノールアミンが、ジエタノールイソプロパノールアミン、トリイソプロパノールアミン、エタノールジイソプロパノールアミン、トリエタノールアミン、N-メチルジエタノールアミン、及びN-n-ブチルジエタノールアミンからなる群より選択される少なくとも1つである<6>~<9>のいずれか1つに記載のセメント組成物の製造方法。 <7> The method for producing a cement composition according to <6>, wherein the MgO/Fe 2 O 3 in (1) exceeds 0.35.
<8> The Portland cement contains 45 to 75% by mass of C 3 S, 5 to 25% by mass of C 2 S, 7 to 11% by mass of C 3 A, and 7 to 7% by mass of C 4 AF calculated by the Borg formula. The method for producing a cement composition according to <6> or <7>, which is 11% by mass of ordinary Portland cement.
<9> The cement composition according to any one of <6> to <8>, wherein the amount of the alkanolamine added is 0.005 to 0.02 parts by mass with respect to 100 parts by mass of the Portland cement. Production method.
<10> The alkanolamine is at least one selected from the group consisting of diethanolisopropanolamine, triisopropanolamine, ethanoldiisopropanolamine, triethanolamine, N-methyldiethanolamine, and Nn-butyldiethanolamine. 6> A method for producing a cement composition according to any one of <9>.
本発明のセメント組成物は、下記(1)及び(2)を満たすポルトランドセメントと、前記ポルトランドセメント100質量部に対し、0.001~0.025質量部のアルカノールアミンと、を含む。
(1)0.55≦MgO/Fe2O3+CL’SO3/SO3≦0.95
(2)0≦△C4AF
(1)中、MgOはポルトランドセメント中のMgOの質量(質量%)を表し、Fe2O3はポルトランドセメント中のFe2O3の質量(質量%)を表し、SO3はポルトランドセメントのSO3換算量(質量%)を表し、CL’SO3はポルトランドセメントのクリンカのSO3換算量(質量%)を表す。
(2)中、△C4AFは、R.C4AFの質量(質量%)とB.C4AFの質量(質量%)との差分(R.C4AF-B.C4AF)を表す。ここで、R.C4AFは、粉末X線回析装置で測定したポルトランドセメントのC4AF値を表し、B.C4AFは、3.04×Fe2O3を表す。B.C4AFにおけるFe2O3はポルトランドセメント中のFe2O3の質量(質量%)を表す。
以下、上記(1)及び(2)を満たすポルトランドセメントを「本発明におけるポルトランドセメント」又は単に「本発明におけるセメント」と称する。
本発明のセメント組成物は、換言すると、クリンカと、石膏と、アルカノールアミンとを含み、クリンカ及び石膏を含むポルトランドセメントが上記の(1)及び(2)を満たし、アルカノールアミンの含有量が上記範囲である。 <Cement composition>
The cement composition of the present invention contains Portland cement satisfying the following (1) and (2) and 0.001 to 0.025 parts by mass of alkanolamine per 100 parts by mass of the Portland cement.
( 1 ) 0.55≤MgO/ Fe2O3 + CL'SO3 / SO3≤0.95
(2) 0≦ΔC 4 AF
In (1), MgO represents the mass (mass%) of MgO in Portland cement, Fe2O3 represents the mass (mass%) of Fe2O3 in Portland cement, and SO3 represents SO of Portland cement. 3 equivalent amount (% by mass), and CL'SO 3 represents the SO 3 equivalent amount (% by mass) of Portland cement clinker.
In (2), ΔC 4 AF is the The mass (% by mass) of C 4 AF and B. It represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF. Here, R.I. C 4 AF represents the C 4 AF value of Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 . B. Fe 2 O 3 in C 4 AF represents the mass (mass %) of Fe 2 O 3 in Portland cement.
Portland cement that satisfies the above (1) and (2) is hereinafter referred to as "portland cement in the present invention" or simply "cement in the present invention".
In other words, the cement composition of the present invention contains clinker, gypsum and alkanolamine, Portland cement containing clinker and gypsum satisfies the above (1) and (2), and the alkanolamine content is Range.
強度を向上するために、アルカノールアミン等の助剤を用いることが知られているが、アルカノールアミンによる強度増が期待されるのは、7日材齢未満の短期強度であり、長期強度は、むしろ低下させる傾向にあった。
しかし、セメント組成物の内容を上記構成とすることで、モルタル長期強度を向上することができる。かかる理由は定かではないが、次の理由によるものと推察される。 If the MgO content in the cement is high, for example, 1.30% by mass or more, the hydration of calcium decreases, which relatively reduces the strength of the mortar.
In order to improve strength, it is known to use an auxiliary agent such as alkanolamine. On the contrary, it tended to decrease.
However, the long-term strength of the mortar can be improved by making the content of the cement composition as described above. Although the reason for this is not clear, it is presumed to be due to the following reasons.
条件(1)は「MgO/Fe2O3+CL’SO3/SO3」が0.55~0.95であることである。
詳細は定かではないが、Fe2O3の質量に対するMgOの質量が大きくなったり、セメント中のSO3換算量(質量基準)に対するクリンカ中のSO3換算量(質量基準)が大きくなることは、フェライト相の固溶に関連していると考えられる。「MgO/Fe2O3+CL’SO3/SO3」は、いわば、フェライト相の固溶量の指標と考えることができる。
本発明におけるポルトランドセメントと共に含まれるアルカノールアミンはフェライト相中の鉄等を溶かしてゲル中に溶解させ、均一に浸透することで水密性を促進、モルタル強度を増進する機能を有することから、マグネシウムとSO3がフェライト相に固溶することにより、アルカノールアミンによるモルタル強度増強効果を更に向上することとなり、モルタル長期強度を向上することができると考えられる。 [Condition (1)]
Condition (1) is that "MgO/Fe 2 O 3 +CL'SO 3 /SO 3 " is 0.55 to 0.95.
Although the details are not clear, it is possible that the mass of MgO relative to the mass of Fe 2 O 3 increases, and the SO 3 equivalent amount (mass standard) in clinker relative to the SO 3 equivalent amount (mass standard) in cement increases. , which is thought to be related to the solid solution of the ferrite phase. “MgO/Fe 2 O 3 +CL′SO 3 /SO 3 ” can be considered as an indicator of the solid solution amount of the ferrite phase.
The alkanolamine contained together with the Portland cement in the present invention dissolves iron and the like in the ferrite phase, dissolves it in the gel, promotes watertightness by uniformly permeating, and has the function of increasing the strength of the mortar. It is considered that the solid solution of SO 3 in the ferrite phase further enhances the mortar strength enhancing effect of the alkanolamine, thereby improving the long-term strength of the mortar.
「MgO/Fe2O3+CL’SO3/SO3」が0.95を超えると、アルカノールアミンによる強度増進効果が得られにくくなり、アルカノールアミン、未反応のMgO及びMgSO4それぞれが過剰となって膨張ひび割れを起こし、モルタル強度を維持することができない。
モルタル長期強度をより向上する観点から、「MgO/Fe2O3+CL’SO3/SO3」は、0.60~0.90であることが好ましく、0.70~0.80であることがより好ましい。 When "MgO/Fe 2 O 3 +CL'SO 3 /SO 3 " is less than 0.55, the solid solution amount of the ferrite phase is small, and the mortar strength enhancing effect due to the alkanolamine cannot be sufficiently obtained, and the long-term strength of the mortar is low. Not good for
When "MgO/Fe 2 O 3 +CL'SO 3 /SO 3 " exceeds 0.95, it becomes difficult to obtain the strength increasing effect of alkanolamine, and alkanolamine, unreacted MgO and MgSO 4 become excessive. It causes expansion cracks and the mortar strength cannot be maintained.
From the viewpoint of further improving the long-term strength of the mortar, "MgO/Fe 2 O 3 +CL'SO 3 /SO 3 " is preferably 0.60 to 0.90, more preferably 0.70 to 0.80. is more preferred.
セメント中のFe2O3の質量に対するMgOの質量は、C4AFの固溶量を表すものと考えられ、MgO/Fe2O3が0.35を超えることで、C4AFの固溶を促進することができる。
フェライト相の固溶量増加の観点から、MgO/Fe2O3は、0.36~0.60であることが好ましく、0.40~0.50であることがより好ましい。 Furthermore, in condition (1), MgO/Fe 2 O 3 preferably exceeds 0.35.
The mass of MgO with respect to the mass of Fe 2 O 3 in the cement is considered to represent the solid solution amount of C 4 AF. can promote
From the viewpoint of increasing the solid solution amount of the ferrite phase, MgO/Fe 2 O 3 is preferably 0.36 to 0.60, more preferably 0.40 to 0.50.
条件(2)は、△C4AFが0ポイント以上であることである。
なお、0ポイントとは、例えば、リートベルト解析により得られるC4AF(R.C4AF)が10.1質量%のとき、ボーグ式により算出されるC4AF(B.C4AF)も10.1質量%であるような場合を意味する。
△C4AFは、R.C4AFの質量とB.C4AFの質量との差分(R.C4AF-B.C4AF)を表し、リートベルト解析により得られるC4AF(R.C4AF)と、ボーグ式により算出されるC4AF(B.C4AF)との差分である。ボーグ式ではマグネシウムを考慮しないため、△C4AFからMgOの固溶量を見積もることができ、セメント中のMgO含有量が多くなると、△C4AFも増える。本発明では、高MgO条件でのモルタル長期強度を向上するという観点から、△C4AFが0以上であることを条件とする。
アルカノールアミンによりMgOが固溶したフェライト相の溶解量増加が強度増進に影響するため、△C4AFは0.3~1.5ポイントであることが好ましく、0.5~1.5ポイントであることがより好ましい。 [Condition (2)]
Condition (2) is that ΔC 4 AF is 0 points or more.
Note that the 0 point is, for example, when the C 4 AF (R.C 4 AF) obtained by Rietveld analysis is 10.1% by mass, the C 4 AF (B.C 4 AF) calculated by the Borg formula is also 10.1% by mass.
ΔC 4 AF was determined by R. The mass of C 4 AF and B. Represents the difference (RC 4 AF-BC 4 AF) from the mass of C 4 AF, and C 4 AF obtained by Rietveld analysis (RC 4 AF) and C 4 calculated by the Borg formula This is the difference from AF (B.C 4 AF). Since the Borg formula does not consider magnesium, the solid solution amount of MgO can be estimated from ΔC 4 AF, and ΔC 4 AF increases as the MgO content in cement increases. In the present invention, from the viewpoint of improving the long-term strength of mortar under high MgO conditions, it is a condition that ΔC 4 AF is 0 or more.
Since the increase in the amount of dissolved ferrite phase in which MgO is dissolved by alkanolamine affects the increase in strength, ΔC 4 AF is preferably 0.3 to 1.5 points, and 0.5 to 1.5 points. It is more preferable to have
まず、セメントのX線回折測定を行い、プロファイルを得る。得られたプロファイルを、リートベルト法により解析し、セメント鉱物の定量を行う。解析対象の鉱物は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とする。リートベルト解析では、各鉱物の基本結晶構造データに基づき、格子定数、スケールファクター等をパラメータとして、実測プロファイルと理論プロファイルとがフィッティングするように精密化操作を行う。最終的に精密化されたスケールファクターから、上記各鉱物の質量割合を算出し、更にR.C4AFの含有率(質量%)を得る。
X線回析装置の具体的な測定条件は、実施例にて示す。 R. C 4 AF is determined by the following steps.
First, X-ray diffraction measurement of cement is performed to obtain a profile. The obtained profile is analyzed by the Rietveld method to quantify cement minerals. 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), C 3 A-ortho (orthorhombic), and C 4 AF. In the Rietveld analysis, based on the basic crystal structure data of each mineral, refinement operation is performed so that the measured profile and the theoretical profile are fitted with parameters such as lattice constant and scale factor. From the finally refined scale factor, the mass ratio of each of the above minerals was calculated. Obtain the C 4 AF content (% by mass).
Specific measurement conditions for the X-ray diffractometer are shown in Examples.
また、本発明のセメント組成物に使用されるポルトランドセメントは、リートベルト解析により得られるC4AF(R.C4AF)が、7.5~12質量%であることが好ましい。 More specifically, the Portland cement used in the cement composition of the present invention contains 45 to 75% by mass of C 3 S (3CaO.SiO 2 ) calculated by the Bogue formula, C 2 S (2CaO.SiO 2 ) is 5 to 25% by mass, C 3 A (3CaO.Al 2 O 3 ) is 7 to 11% by mass, and C 4 AF (4CaO.Al 2 O 3 .FeO 3 ) is 7 to 11% by mass. It is preferred that the
Moreover, the Portland cement used in the cement composition of the present invention preferably has a C 4 AF (R.C 4 AF) obtained by Rietveld analysis of 7.5 to 12% by mass.
セメント中のC3Sの含有量が45質量%以上であることで、アルカノールアミンの添加による強度増進効果が大きく、モルタル強さに優れ、また、流動性に優れる。セメント中のC3Sの含有量が45質量%以上であることで、相対的に被粉砕性が劣るC2Sの含有量が少なくなる。その結果、セメント組成物を一定のブレーン比表面積にするまでに要する粉砕時間が短くなり、主に被粉砕性がよいC2S以外の鉱物(C3S、C3A、及びC4AF)の過粉砕が抑制され、ブレーン比表面積の増大が抑えられる。また、アルカノールアミンの添加による強度増進メカニズムは、クリンカ中のC4AFを選択的に溶解させることでC4AFに近隣するC4AFの水との接触機会が増大し水和が促進され強度増進することになる。クリンカの過粉砕が抑制されることで、もともと各鉱物が複合して存在しているクリンカ粒子が単独の鉱物として存在しにくくなり、C4AFの溶解がC4AFの水和促進に繋がり易く、したがって、アルカノールアミンの添加による強度増進効果が得られやすい。
セメント中のC3Sの含有量が75質量%以下であることで、コンクリートの長期圧縮強度を十分維持することができる。
セメント中のC2Sの含有量が5質量%以上であることで、コンクリートの長期圧縮強度を十分維持することができる。
セメント中のC2Sの含有量が25質量%以下であることで、コンクリートの初期圧縮強度を十分維持することができる。 ( C3S , C2S )
When the content of C 3 S in the cement is 45% by mass or more, the addition of alkanolamine has a large strength-enhancing effect, resulting in excellent mortar strength and excellent fluidity. When the content of C 3 S in cement is 45% by mass or more, the content of C 2 S, which is relatively poor in grindability, is reduced. As a result, the pulverization time required for the cement composition to have a certain Blaine specific surface area is shortened, and minerals other than C2S ( C3S , C3A , and C4AF ) that have good pulverizability are mainly used. Excessive pulverization of is suppressed, and an increase in Blaine specific surface area is suppressed. In addition, the mechanism of strength enhancement by the addition of alkanolamine is that the selective dissolution of C 4 AF in the clinker increases the opportunity for C 4 AF adjacent to C 4 AF to come into contact with water, promoting hydration and increasing strength. will increase. By suppressing excessive pulverization of clinker, clinker particles, which are originally composed of various minerals, are less likely to exist as individual minerals, and the dissolution of C 4 AF tends to lead to the promotion of hydration of C 4 AF. Therefore, the addition of the alkanolamine tends to increase the strength.
When the content of C 3 S in cement is 75% by mass or less, the long-term compressive strength of concrete can be sufficiently maintained.
When the content of C 2 S in cement is 5% by mass or more, the long-term compressive strength of concrete can be sufficiently maintained.
When the content of C 2 S in cement is 25% by mass or less, the initial compressive strength of concrete can be sufficiently maintained.
セメント中のC4AFの含有量が7質量%以上であることで、アルカノールアミンの添加によるC4AFの溶解が促進され、C3Sの反応が促進されることにより、顕著な強度増進効果を発揮することができる。
セメント中のC4AFの含有量が11質量%以下であることで、C4AF中のFeイオンの溶解によって生じた水酸化鉄ゲル量を抑制することができ、クリンカ粒子表面の被覆を抑制することができるため、水和の遅延を防止することができる。
C4AFとC3Aの合計は約18質量%で一定であり、セメント中のC4AFの含有量が増えればC3Aの含有量は減り、C4AFの含有量が減ればC3Aの含有量は増加する。
強度と流動性を増進する観点から、セメント中のC4AFの含有量は、7~9質量%であることが好ましく、8~9質量%であることがより好ましい。 ( C4AF , C3A )
When the content of C 4 AF in cement is 7% by mass or more, the dissolution of C 4 AF is promoted by the addition of alkanolamine, and the reaction of C 3 S is promoted, resulting in a remarkable strength enhancement effect. can be demonstrated.
When the content of C 4 AF in cement is 11% by mass or less, the amount of iron hydroxide gel generated by the dissolution of Fe ions in C 4 AF can be suppressed, and the coating of the clinker particle surface can be suppressed. delay in hydration can be prevented.
The total of C 4 AF and C 3 A is constant at about 18% by mass, and if the content of C 4 AF in cement increases, the content of C 3 A decreases, The content of 3A increases.
From the viewpoint of enhancing strength and fluidity, the content of C 4 AF in cement is preferably 7-9% by mass, more preferably 8-9% by mass.
本発明のセメント組成物は、本発明におけるポルトランドセメントクリンカ100質量部に対し、0.001~0.025質量部のアルカノールアミンを含む。
アルカノールアミンは、また、強度増進剤として作用する。
本発明のセメント組成物中のアルカノールアミンの含有量が、ポルトランドセメントクリンカ100質量部に対し、0.001質量部未満であると、強度増進効果が得られない。本発明のセメント組成物中のアルカノールアミンの含有量がポルトランドセメントクリンカ100質量部に対し、0.025質量部を超えると、初期強度の増進効果は顕著であるが、28日材齢では、初期の水和活性が活発であったことに起因して水和組織が粗となり強度増進効果が得られなくなる。
上記観点から、本発明のセメント組成物中のアルカノールアミンの含有量は、本発明におけるポルトランドセメントクリンカ100質量部に対し、0.005~0.02質量部であることが好ましい。 [Alkanolamine]
The cement composition of the present invention contains 0.001 to 0.025 parts by mass of alkanolamine per 100 parts by mass of Portland cement clinker of the present invention.
Alkanolamines also act as strength enhancers.
If the content of alkanolamine in the cement composition of the present invention is less than 0.001 parts by mass with respect to 100 parts by mass of Portland cement clinker, the effect of increasing strength cannot be obtained. When the content of alkanolamine in the cement composition of the present invention exceeds 0.025 parts by mass with respect to 100 parts by mass of Portland cement clinker, the effect of increasing the initial strength is remarkable. Due to the active hydration activity, the hydrated structure becomes coarse and the strength increasing effect cannot be obtained.
From the above viewpoint, the alkanolamine content in the cement composition of the present invention is preferably 0.005 to 0.02 parts by mass per 100 parts by mass of the Portland cement clinker of the present invention.
アルカノールアミンは1種のみを用いてもよいし、2種以上を用いてもよい。 Alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, methylethanolamine, methylisopropanolamine, Nn-butylethanolamine, N-methyldiethanolamine, N- n-butyldiethanolamine, N-methyldiisopropanolamine, diethanolisopropanolamine, diisopropanolethanolamine, tetrahydroxyethylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, tris(2-hydroxy Butyl) amine and the like can be exemplified.
Only one type of alkanolamine may be used, or two or more types may be used.
本発明のセメント組成物は、石膏を含む。
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。
セメント組成物中の石膏の含有量は、SO3換算で0.5~2.5質量%であることが好ましい。
セメント組成物中の石膏の含有量が上記範囲であることにより、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。
セメント組成物中の石膏の含有量は、上記の観点から、SO3換算で、1.0~1.8質量%であることがより好ましい。
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。 〔plaster〕
The cement composition of the present invention contains gypsum.
As gypsum, any of anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum can be used.
The content of gypsum in the cement composition is preferably 0.5-2.5% by mass in terms of SO 3 .
When the content of gypsum in the cement composition is within the above range, the drying shrinkage of the cement composition can be made appropriate, and the strength exhibited by the cement composition can be increased.
From the above viewpoint, the content of gypsum in the cement composition is more preferably 1.0 to 1.8% by mass in terms of SO 3 .
The ratio of SO 3 in gypsum can be measured according to JIS R 5202:2010 "Method for chemical analysis of Portland cement". The ratio of the SO3 - equivalent mass of gypsum in the cement composition can be obtained from the compounding amount of gypsum and the ratio of SO3 contained in the gypsum.
本発明のセメント組成物は、微粉末化による短期強度の向上とCO2排出量削減を目的として、石灰石を含んでいてもよい。
セメント組成物中の石灰石の含有量は、JIS R 5210:2009「ポルトランドセメント」で規定されているが、本発明においては該JIS規格に規定されている範囲を超えて石灰石が添加されていてもよい。
セメント組成物中の石灰石の含有量は、0~20質量%であることが好ましく、0~10質量%であることがより好ましく、2~5質量%であることが更に好ましい。なお、石灰石の含有量が0質量%とは、セメント組成物の製造に石灰石を添加しないことを意味する。 [Limestone]
The cement composition of the present invention may contain limestone for the purpose of improving short-term strength and reducing CO2 emissions through pulverization.
The content of limestone in the cement composition is specified in JIS R 5210: 2009 "Portland cement", but in the present invention, even if limestone is added beyond the range specified in the JIS standard good.
The content of limestone in the cement composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, even more preferably 2 to 5% by mass. The limestone content of 0% by mass means that limestone is not added to the production of the cement composition.
本発明のセメント組成物には、流動性、水和速度、強度発現性等の調節用として、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。 [Other ingredients]
To the cement composition of the present invention, fly ash, blast-furnace slag, silica fume, or the like can be further added for adjusting fluidity, hydration rate, strength development, and the like.
本発明のセメント組成物は、ブレーン比表面積が3000~3400cm2/gであることが好ましい。
ブレーン比表面積が3000cm2/g以上であることでモルタル強さが低下しにくく、3400cm2/g以下であることで、流動性が低下を抑制し、また、アルカノールアミンによるC4AFの溶解低下を抑えて、強度増進効果を維持することができる。
強度をより増進する観点から、セメント組成物のブレーン比表面積は、3100~3300cm2/gであることがより好ましい。
セメント組成物のブレーン比表面積は、JIS R 5201:2015「セメントの物理試験方法」に準じて測定すればよい。 (Blaine specific surface area)
The cement composition of the present invention preferably has a Blaine specific surface area of 3000 to 3400 cm 2 /g.
When the Blaine specific surface area is 3000 cm 2 /g or more, the mortar strength is less likely to decrease, and when it is 3400 cm 2 /g or less, the decrease in fluidity is suppressed, and the dissolution of C 4 AF due to alkanolamine is reduced. can be suppressed to maintain the strength enhancement effect.
From the viewpoint of further increasing strength, the Blaine specific surface area of the cement composition is more preferably 3100 to 3300 cm 2 /g.
The Blaine specific surface area of the cement composition may be measured according to JIS R 5201:2015 "Methods for Physical Testing of Cement".
本発明のセメント組成物の製造方法は、下記(1)及び(2)を満たすポルトランドセメントと、ポルトランドセメント100質量部に対し、0.001~0.025質量部のアルカノールアミンと、を混合し、本発明のセメント組成物を製造する方法である。
(1)0.55≦MgO/Fe2O3+CL’SO3/SO3≦0.95
(2)0≦△C4AF
(1)中、MgOはポルトランドセメント中のMgOの質量(質量%)を表し、Fe2O3はポルトランドセメント中のFe2O3の質量(質量%)を表し、SO3はポルトランドセメントのSO3換算量(質量%)を表し、CL’SO3はポルトランドセメントのクリンカのSO3換算量(質量%)を表す。
(2)中、△C4AFは、R.C4AFの質量(質量%)とB.C4AFの質量(質量%)との差分(R.C4AF-B.C4AF)を表す。ここで、R.C4AFは、粉末X線回析装置で測定したポルトランドセメントのC4AF値を表し、B.C4AFは、3.04×Fe2O3を表す。B.C4AFにおけるFe2O3はポルトランドセメント中のFe2O3の質量(質量%)を表す。 <Method for producing cement composition>
In the method for producing a cement composition of the present invention, Portland cement satisfying the following (1) and (2) and 0.001 to 0.025 parts by mass of alkanolamine are mixed with 100 parts by mass of Portland cement. , a method of making the cement composition of the present invention.
( 1 ) 0.55≤MgO/ Fe2O3 + CL'SO3 / SO3≤0.95
(2) 0≦ΔC 4 AF
In (1), MgO represents the mass (mass%) of MgO in Portland cement, Fe2O3 represents the mass (mass%) of Fe2O3 in Portland cement, and SO3 represents SO of Portland cement. 3 equivalent amount (% by mass), and CL'SO 3 represents the SO 3 equivalent amount (% by mass) of Portland cement clinker.
In (2), ΔC 4 AF is R.C. The mass (% by mass) of C 4 AF and B. It represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF. Here, R.I. C 4 AF represents the C 4 AF value of Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 . B. Fe 2 O 3 in C 4 AF represents the mass (mass %) of Fe 2 O 3 in Portland cement.
また、石灰石の配合量は、既述の石灰石含有量と同義であり、好ましい範囲も同様である。 The amount of alkanolamine to be blended is the same as the content of alkanolamine in the cement composition of the present invention, and the preferred range is also the same. That is, the amount of alkanolamine to be added is preferably 0.005 to 0.02 parts by mass with respect to 100 parts by mass of Portland cement in the present invention.
In addition, the amount of limestone to be blended is synonymous with the limestone content described above, and the preferred range is also the same.
すなわち、本発明のセメント組成物の製造方法で用いるアルカノールアミンは、ジエタノールイソプロパノールアミン、トリイソプロパノールアミン、エタノールジイソプロパノールアミン、トリエタノールアミン、N-メチルジエタノールアミン、及びN-n-ブチルジエタノールアミンからなる群より選択される少なくとも1つであることが好ましい。
アルカノールアミンは、一般的に高粘度なため混合が難しく、モルタル生成時に添加するのは不向きである。従って、セメント製造の仕上げ工程にて粉砕助剤として添加することが好ましい。また、アルカノールアミンを水に希釈及び溶解して使用するとセメントとの混合が容易になり、効率よく本発明のセメント組成物を製造することができる。 The alkanolamine used in the method for producing the cement composition of the present invention is the same as the alkanolamine contained in the cement composition of the present invention, and preferred embodiments are also the same.
That is, the alkanolamine used in the method for producing the cement composition of the present invention is selected from the group consisting of diethanolisopropanolamine, triisopropanolamine, ethanoldiisopropanolamine, triethanolamine, N-methyldiethanolamine, and Nn-butyldiethanolamine. At least one is preferably selected.
Alkanolamine is generally highly viscous and difficult to mix, so it is unsuitable to add during mortar production. Therefore, it is preferable to add it as a grinding aid in the finishing process of cement production. Further, when the alkanolamine is diluted and dissolved in water and used, it becomes easy to mix with cement, and the cement composition of the present invention can be produced efficiently.
本発明では、JIS R 5210:2009「ポルトランドセメント」に規定される高炉スラグ及びシリカ質混合材を使用することができる。フライアッシュに関しては、JIS R 5210:2009「ポルトランドセメント」に規定されるフライアッシュI種及びフライアッシュII種の他、フライアッシュIII種及びフライアッシュIV種も使用することができる。 In the method for producing the cement composition of the present invention, in addition to the Portland cement clinker, gypsum, limestone and alkanolamine of the present invention, blast furnace slag, siliceous admixture and fly ash can be further added. .
In the present invention, blast furnace slag and siliceous admixture specified in JIS R 5210:2009 "Portland cement" can be used. Regarding fly ash, in addition to fly ash type I and fly ash type II defined in JIS R 5210:2009 "Portland cement", fly ash type III and fly ash type IV can also be used.
セメント組成物の製造に下記の材料を使用した。
1.クリンカ
表1~2に示す化学組成及び鉱物組成の普通ポルトランドセメントクリンカ〔住友大阪セメント(株)製〕を用いた。表1~2中、HMは水硬率、SMは珪酸率、IMは鉄率を意味する。なお、表1~2中の「%」は質量基準(質量%)である。
クリンカの化学組成は、JIS R 5204:2019「セメントの蛍光X線分析方法」に準じて蛍光X線測定装置(PRIMUS IV、株式会社リガク製)を用いて、ガラスビード法にて成分分析を行った。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。
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 <Components of cement composition>
The following materials were used in the preparation of cement compositions.
1. Clinker Ordinary Portland cement clinker [manufactured by Sumitomo Osaka Cement Co., Ltd.] having the chemical and mineral compositions shown in Tables 1 and 2 was used. In Tables 1 and 2, HM means hydraulic modulus, SM means silicic acid modulus, and IM means iron modulus. "%" in Tables 1 and 2 is based on mass (% by mass).
The chemical composition of clinker is analyzed by the glass bead method using a fluorescent X-ray measuring device (PRIMUS IV, manufactured by Rigaku Co., Ltd.) in accordance with JIS R 5204:2019 "Method for fluorescent X-ray analysis of cement". rice field. The mineral composition was calculated from the obtained mass ratios of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 using the following Borg formula.
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)
C3A = ( 2.65 x Al2O3 ) - ( 1.69 x Fe2O3 )
C4AF = 3.04 x Fe2O3
クリンカの化学組成と鉱物組成を表1~2に示す。 (Chemical composition and mineral composition of clinker)
The chemical and mineral compositions of clinker are shown in Tables 1-2.
・DEIPA:ジエタノールイソプロパノールアミン〔東京化成工業(株)製〕
・TEA:トリエタノールアミン〔東京化成工業(株)製〕
・TIPA:トリイソプロパノールアミン〔東京化成工業(株)製〕
・EDIPA:エタノールジイソプロパノールアミン
〔シグマ アルドリッチ ジャパン合同会社製〕 2. Alkanolamine/DEIPA: diethanol isopropanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.]
・ TEA: Triethanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.]
・ TIPA: triisopropanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.]
・EDIPA: ethanol diisopropanolamine [manufactured by Sigma-Aldrich Japan LLC]
関東化学(株)製、炭酸カルシウム 特級、CaCO3:99.5% 3. Limestone manufactured by Kanto Chemical Co., Ltd., special grade calcium carbonate, CaCO 3 : 99.5%
半水石膏を用いた。具体的には、化学石膏(CaSO4(97.8モル%))を乾燥機内で120℃、12時間保持したものを使用した。石膏中のSO3換算量は、JIS R 5202:2015「セメントの化学分析法」に従って測定した。化学石膏の組成は表3に示すとおりである。 4. Gypsum Hemihydrate gypsum was used. Specifically, chemical gypsum (CaSO 4 (97.8 mol %)) held in a dryer at 120° C. for 12 hours was used. The SO 3 equivalent amount in gypsum was measured according to JIS R 5202:2015 "Method for chemical analysis of cement". The composition of chemical gypsum is as shown in Table 3.
表1~2に示すクリンカに対し、石灰石を、得られるセメント中3.2質量%となるように、また、石膏(上記半水石膏)を表4の配合となるように、それぞれ添加して、ミキサーで混合し、セメントを得た。なお、表4中、CLはクリンカを表す。また「%」は質量基準である。 <Production of cement>
To the clinker shown in Tables 1 and 2, limestone was added so as to be 3.2% by mass in the cement obtained, and gypsum (the above-mentioned hemihydrate gypsum) was added so as to have the composition shown in Table 4. , and mixed in a mixer to obtain cement. In Table 4, CL represents clinker. Also, "%" is based on mass.
クリンカの化学組成と同様の方法でセメントの化学組成を測定し、クリンカの鉱物組成と同様の方法でセメントの鉱物組成を算出した。結果を表5~9に示す。なお、表5~9中の「%」は質量基準(質量%)である。
なお、表6中の「C4AF」の値は、本発明におけるB.C4AFであり、表7~9中の「C4AF(%)」欄の「Bogue」欄に示す値を参照する。表7~9中の「C4AF(%)」欄の「Rietveld」欄の値は、本発明におけるR.C4AFであり、粉末X線回析装置で測定したセメントのC4AF値である。具体的には、粉末X線回折を利用したリートベルト解析方法を用いて次の測定条件で測定した。 (Chemical composition and mineral composition of cement)
The chemical composition of cement was measured by the same method as the chemical composition of clinker, and the mineral composition of cement was calculated by the same method as the mineral composition of clinker. The results are shown in Tables 5-9. "%" in Tables 5 to 9 is based on mass (% by mass).
In addition, the value of "C 4 AF" in Table 6 is the B.I. C 4 AF, refer to the values shown in the "Bogue" column of the "C 4 AF (%)" column in Tables 7-9. The values in the "Rietveld" column in the "C 4 AF (%)" column in Tables 7 to 9 are the R.I. C 4 AF, which is the C 4 AF value of cement measured with a powder X-ray diffractometer. Specifically, it was measured under the following measurement conditions using the Rietveld analysis method using powder X-ray diffraction.
・粉末X線回折装置:パナリティカル社製、X’PartPowder
・リートベルト解析ソフト:パナリティカル社製、X’Part High Score Plusversion 2.1b
・X線管球:Cu(管電圧;45kV、管電流;40mA)
・スリット:divergence slit-可変(照射幅- 12mm、Antiscatter slit- 2°)
・測定範囲:2θ=10~70°(ステップ幅:0.017°)
・スキャン速度:0.1012°/s (Measurement condition)
・ Powder X-ray diffractometer: X'PartPowder manufactured by PANalytical
・ Rietveld analysis software: X'Part High Score Plus version 2.1b manufactured by PANalytical
・X-ray tube: Cu (tube voltage: 45 kV, tube current: 40 mA)
・ Slit: divergence slit - variable (irradiation width - 12 mm, Antiscatter slit - 2 °)
・Measuring range: 2θ = 10 to 70° (step width: 0.017°)
・Scanning speed: 0.1012°/s
また、図1に、実施例及び比較例の条件**に対する△C4AFの値をプロットしたグラフを示す。 The values in the " △ * " column in the "C AF (%)" column in Tables 7 to 9 are the values ( B .C 4 AF) and the difference (R.C 4 AF- B.C 4 AF).
Also, FIG. 1 shows a graph plotting the values of ΔC 4 AF against the conditions ** of the examples and comparative examples.
〔実施例1〕
アミン無添加のセメント組成物として、表5~7に示すセメントを用いた。
アミン添加のセメント組成物として、表7に示すアルカノールアミン(DEIPA)と、表5及び7に示すセメントからなる組成物を調製した。具体的には、セメントとアルカノールアミンとの合計中、アルカノールアミンの濃度が10ppm(セメント100質量部に対し、0.001質量部)となる量のアルカノールアミンを、セメントと共に混合した。
次いで、アミン無添加のセメント組成物及びアミン添加のセメント組成物のそれぞれを、ブレーン比表面積値が3300cm2/gとなるようにテスト用ボールミルで混合粉砕し、実施例1の各セメント組成物を得た。 <Manufacture of cement composition>
[Example 1]
Cements shown in Tables 5 to 7 were used as amine-free cement compositions.
A composition comprising alkanolamine (DEIPA) shown in Table 7 and cement shown in Tables 5 and 7 was prepared as an amine-added cement composition. Specifically, alkanolamine was mixed with cement in an amount such that the concentration of alkanolamine was 10 ppm (0.001 part by mass with respect to 100 parts by mass of cement) in the total amount of cement and alkanolamine.
Next, each of the amine-free cement composition and the amine-added cement composition was mixed and pulverized in a test ball mill so that the Blaine specific surface area value was 3300 cm 2 /g, and each cement composition of Example 1 was obtained. Obtained.
アミン無添加のセメント組成物として、表5~8に示すセメントを用いた。
表5~8に示すセメントを用い、DEIPAを、セメントとDEIPAとの合計中、表7又は8に示す濃度となる量で用いた他は、実施例1と同様にしてアミン添加のセメント組成物を得た。
次いで、アミン無添加のセメント組成物及びアミン添加のセメント組成物のそれぞれを、ブレーン比表面積値が3300cm2/gとなるようにテスト用ボールミルで混合粉砕し、実施例2~19及び比較例1~7の各セメント組成物を得た。 [Examples 2 to 19, Comparative Examples 1 to 7]
Cements shown in Tables 5 to 8 were used as amine-free cement compositions.
An amine-added cement composition was prepared in the same manner as in Example 1, except that the cements shown in Tables 5 to 8 were used, and DEIPA was used in an amount that gave the concentration shown in Table 7 or 8 in the total amount of cement and DEIPA. got
Next, each of the amine-free cement composition and the amine-added cement composition was mixed and pulverized in a test ball mill so as to have a Blaine specific surface area of 3300 cm 2 /g. -7 cement compositions were obtained.
アミン無添加のセメント組成物として、表5、6及び9に示すセメントを用いた。
アルカノールアミンとして、DEIPAに代えて、表9の「アミン種」に示すアルカノールアミンを用いた他は、実施例7と同様にして、アミン添加のセメント組成物を得た。
次いで、アミン無添加のセメント組成物及びアミン添加のセメント組成物のそれぞれを、ブレーン比表面積値が3300cm2/gとなるようにテスト用ボールミルで混合粉砕し、実施例20~22の各セメント組成物を得た。 [Examples 20 to 22]
The cements shown in Tables 5, 6 and 9 were used as amine-free cement compositions.
An amine-added cement composition was obtained in the same manner as in Example 7, except that an alkanolamine shown in "Amine species" in Table 9 was used as the alkanolamine instead of DEIPA.
Next, each of the amine-free cement composition and the amine-added cement composition was mixed and pulverized in a test ball mill so that the Blaine specific surface area value was 3300 cm 2 /g, and each cement composition of Examples 20 to 22. got stuff
各実施例及び各比較例のアミン無添加のセメント組成物及びアミン添加のセメント組成物を用い、JIS R 5201:2015の「セメントの物理試験方法」に準拠して供試材を形成し、モルタル圧縮強さ試験を測定した。
なお、供試材の配合比率は、水11.1質量%、骨材66.7質量%、セメント22.2質量%であり、寸法は40mm×40mm×160mmの直方体、供試材の作成後は、供試材を塩化ビニル製の樹脂で包み養生した。 <Evaluation of cement composition>
Using the amine-free cement composition and the amine-added cement composition of each example and each comparative example, test materials were formed in accordance with JIS R 5201: 2015 "Physical test method for cement", and mortar Compressive strength test was measured.
The mixing ratio of the test material is 11.1% by mass of water, 66.7% by mass of aggregate, and 22.2% by mass of cement. The test material was wrapped in vinyl chloride resin and cured.
また、図2に、7日材齢と28材齢における条件**に対するモルタル増進強度差の値をプロットしたグラフを示す。ここで、「条件**」は表7~9の「条件**」欄に示す数値であり、本発明におけるポルトランドセメントの条件(1)の「MgO/Fe2O3+CL’SO3/SO3」である。 In the "△ (ba)" column of Tables 7 to 9, the compressive strength of the mortar obtained using the amine-added cement composition is compared to the compression strength of the mortar obtained using the amine-free cement composition. The intensity subtracted difference (intensity difference) is shown. It means that the larger the numerical value of the intensity difference, the higher the intensity enhancing effect.
Also, FIG. 2 shows a graph plotting the difference in mortar enhancement strength against conditions ** at 7-day age and 28-day age. Here, "Condition ** " is a numerical value shown in the "Condition ** " column of Tables 7 to 9, and corresponds to "MgO/Fe 2 O 3 +CL'SO 3 /SO 3 ”.
Claims (8)
- 下記(1)及び(2)を満たすポルトランドセメントと、
前記ポルトランドセメント100質量部に対し、0.001~0.025質量部のアルカノールアミンと、
を含み、
前記ポルトランドセメントは、ボーグ式で算出されるC3Sが45~75質量%、C2Sが5~25質量%、C3Aが7~11質量%、C4AFが7~11質量%である普通ポルトランドセメントであるセメント組成物。
(1)0.55≦MgO/Fe2O3+CL’SO3/SO3≦0.95
(2)0≦△C4AF
前記(1)中、MgOは前記ポルトランドセメント中のMgOの質量(質量%)を表し、Fe2O3は前記ポルトランドセメント中のFe2O3の質量(質量%)を表し、SO3は前記ポルトランドセメントのSO3換算量(質量%)を表し、CL’SO3は前記ポルトランドセメントのクリンカのSO3換算量(質量%)を表す。
前記(2)中、△C4AFは、R.C4AFの質量(質量%)とB.C4AFの質量(質量%)との差分(R.C4AF-B.C4AF)を表す。ここで、前記R.C4AFは、粉末X線回析装置で測定した前記ポルトランドセメントのC4AF値を表し、前記B.C4AFは、3.04×Fe2O3を表す。前記B.C4AFにおけるFe2O3は前記ポルトランドセメント中のFe2O3の質量(質量%)を表す。 Portland cement that satisfies the following (1) and (2);
With respect to 100 parts by mass of the Portland cement, 0.001 to 0.025 parts by mass of alkanolamine,
including
The Portland cement contains 45 to 75% by mass of C 3 S, 5 to 25% by mass of C 2 S, 7 to 11% by mass of C 3 A, and 7 to 11% by mass of C 4 AF calculated by the Borg formula. A cement composition which is ordinary Portland cement.
( 1 ) 0.55≤MgO/ Fe2O3 + CL'SO3 / SO3≤0.95
(2) 0≦ΔC 4 AF
In (1) above, MgO represents the mass (% by mass) of MgO in the Portland cement, Fe 2 O 3 represents the mass (% by mass) of Fe 2 O 3 in the Portland cement, and SO 3 represents the mass (% by mass) of It represents the SO 3 equivalent amount (mass%) of Portland cement, and CL'SO 3 represents the SO 3 equivalent amount (mass%) of the clinker of the Portland cement.
In (2) above, ΔC 4 AF is The mass (% by mass) of C 4 AF and B. It represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF. Here, the R.I. C 4 AF represents the C 4 AF value of the Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 . The above B. Fe 2 O 3 in C 4 AF represents the mass (% by mass) of Fe 2 O 3 in the Portland cement. - 前記(1)中、前記MgO/Fe2O3は、0.35を超える請求項1に記載のセメント組成物。 The cement composition according to claim 1, wherein said MgO/ Fe2O3 in (1) exceeds 0.35.
- 前記アルカノールアミンの含有量が、前記ポルトランドセメント100質量部に対し、0.005~0.02質量部である請求項1又は2に記載のセメント組成物。 The cement composition according to claim 1 or 2, wherein the alkanolamine content is 0.005 to 0.02 parts by mass with respect to 100 parts by mass of the Portland cement.
- 前記アルカノールアミンが、ジエタノールイソプロパノールアミン、トリイソプロパノールアミン、エタノールジイソプロパノールアミン、トリエタノールアミン、N-メチルジエタノールアミン、及びN-n-ブチルジエタノールアミンからなる群より選択される少なくとも1つである請求項1~3のいずれか1項に記載のセメント組成物。 wherein the alkanolamine is at least one selected from the group consisting of diethanolisopropanolamine, triisopropanolamine, ethanoldiisopropanolamine, triethanolamine, N-methyldiethanolamine, and Nn-butyldiethanolamine; 4. The cement composition according to any one of 3.
- 下記(1)及び(2)を満たすポルトランドセメントと、
前記ポルトランドセメント100質量部に対し、0.001~0.025質量部のアルカノールアミンと、
を混合し、
前記ポルトランドセメントは、ボーグ式で算出されるC3Sが45~75質量%、C2Sが5~25質量%、C3Aが7~11質量%、C4AFが7~11質量%である普通ポルトランドセメントであるセメント組成物の製造方法。
(1)0.55≦MgO/Fe2O3+CL’SO3/SO3≦0.95
(2)0≦△C4AF
前記(1)中、MgOは前記ポルトランドセメント中のMgOの質量(質量%)を表し、Fe2O3は前記ポルトランドセメント中のFe2O3の質量(質量%)を表し、SO3は前記ポルトランドセメントのSO3換算量(質量%)を表し、CL’SO3は前記ポルトランドセメントのクリンカのSO3換算量(質量%)を表す。
前記(2)中、△C4AFは、R.C4AFの質量(質量%)とB.C4AFの質量(質量%)との差分(R.C4AF-B.C4AF)を表す。ここで、前記R.C4AFは、粉末X線回析装置で測定した前記ポルトランドセメントのC4AF値を表し、前記B.C4AFは、3.04×Fe2O3を表す。前記B.C4AFにおけるFe2O3は前記ポルトランドセメント中のFe2O3の質量(質量%)を表す。 Portland cement that satisfies the following (1) and (2);
With respect to 100 parts by mass of the Portland cement, 0.001 to 0.025 parts by mass of alkanolamine,
and mix
The Portland cement contains 45 to 75% by mass of C 3 S, 5 to 25% by mass of C 2 S, 7 to 11% by mass of C 3 A, and 7 to 11% by mass of C 4 AF calculated by the Borg formula. A method for producing a cement composition that is ordinary Portland cement.
( 1 ) 0.55≤MgO/ Fe2O3 + CL'SO3 / SO3≤0.95
(2) 0≦ΔC 4 AF
In (1) above, MgO represents the mass (% by mass) of MgO in the Portland cement, Fe 2 O 3 represents the mass (% by mass) of Fe 2 O 3 in the Portland cement, and SO 3 represents the mass (% by mass) of It represents the SO 3 equivalent amount (mass%) of Portland cement, and CL'SO 3 represents the SO 3 equivalent amount (mass%) of the clinker of the Portland cement.
In (2) above, ΔC 4 AF is The mass (% by mass) of C 4 AF and B. It represents the difference ( R.C.sub.4 AF- B.C.sub.4 AF) from the mass (% by mass) of C.sub.4 AF. Here, the R.I. C 4 AF represents the C 4 AF value of the Portland cement measured with a powder X-ray diffractometer; C4AF stands for 3.04xFe2O3 . The above B. Fe 2 O 3 in C 4 AF represents the mass (% by mass) of Fe 2 O 3 in the Portland cement. - 前記(1)中、前記MgO/Fe2O3は、0.35を超える請求項5に記載のセメント組成物の製造方法。 6. The method for producing a cement composition according to claim 5 , wherein said MgO/ Fe2O3 in (1) exceeds 0.35.
- 前記アルカノールアミンの添加量が、前記ポルトランドセメント100質量部に対し、0.005~0.02質量部である請求項5又は6に記載のセメント組成物の製造方法。 The method for producing a cement composition according to claim 5 or 6, wherein the amount of alkanolamine added is 0.005 to 0.02 parts by mass with respect to 100 parts by mass of Portland cement.
- 前記アルカノールアミンが、ジエタノールイソプロパノールアミン、トリイソプロパノールアミン、エタノールジイソプロパノールアミン、トリエタノールアミン、N-メチルジエタノールアミン、及びN-n-ブチルジエタノールアミンからなる群より選択される少なくとも1つである請求項5~7のいずれか1項に記載のセメント組成物の製造方法。 wherein the alkanolamine is at least one selected from the group consisting of diethanolisopropanolamine, triisopropanolamine, ethanoldiisopropanolamine, triethanolamine, N-methyldiethanolamine, and Nn-butyldiethanolamine; 8. A method for producing a cement composition according to any one of 7.
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JPH03183647A (en) * | 1989-10-06 | 1991-08-09 | W R Grace & Co | Reinforced blended cement composition and reinforced portland cement composition |
JP2008241442A (en) * | 2007-03-27 | 2008-10-09 | Sumitomo Osaka Cement Co Ltd | Determination method for c3a and c4af contents in cement clinker |
JP6966012B1 (en) * | 2021-03-26 | 2021-11-10 | 住友大阪セメント株式会社 | Cement composition and its manufacturing method |
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JP2009013023A (en) | 2007-07-06 | 2009-01-22 | Tokuyama Corp | Portland cement clinker and its manufacturing method |
JP6517384B2 (en) | 2018-02-01 | 2019-05-22 | 太平洋セメント株式会社 | Cement clinker and cement |
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2022
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JPH03183647A (en) * | 1989-10-06 | 1991-08-09 | W R Grace & Co | Reinforced blended cement composition and reinforced portland cement composition |
JP2008241442A (en) * | 2007-03-27 | 2008-10-09 | Sumitomo Osaka Cement Co Ltd | Determination method for c3a and c4af contents in cement clinker |
JP6966012B1 (en) * | 2021-03-26 | 2021-11-10 | 住友大阪セメント株式会社 | Cement composition and its manufacturing method |
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Title |
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JP2023094091A (en) | 2023-07-05 |
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