JP2018016504A - High belite-based cement composition - Google Patents
High belite-based cement composition Download PDFInfo
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- JP2018016504A JP2018016504A JP2016146144A JP2016146144A JP2018016504A JP 2018016504 A JP2018016504 A JP 2018016504A JP 2016146144 A JP2016146144 A JP 2016146144A JP 2016146144 A JP2016146144 A JP 2016146144A JP 2018016504 A JP2018016504 A JP 2018016504A
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- 239000004568 cement Substances 0.000 title claims abstract description 88
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 235000012241 calcium silicate Nutrition 0.000 title claims abstract description 34
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 34
- 239000010440 gypsum Substances 0.000 claims abstract description 19
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 19
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 15
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 15
- 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 claims abstract description 15
- 239000004571 lime Substances 0.000 claims abstract description 15
- 239000006104 solid solution Substances 0.000 claims description 26
- 238000011161 development Methods 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 30
- 239000000395 magnesium oxide Substances 0.000 description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 24
- 239000002994 raw material Substances 0.000 description 23
- 238000010304 firing Methods 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 11
- 235000010755 mineral Nutrition 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000002699 waste material Substances 0.000 description 10
- 238000010276 construction Methods 0.000 description 9
- 238000006703 hydration reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000011398 Portland cement Substances 0.000 description 8
- 239000004567 concrete Substances 0.000 description 8
- 230000036571 hydration Effects 0.000 description 8
- 239000002689 soil Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 150000004683 dihydrates Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000004904 shortening Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000002076 thermal analysis method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- MYLBTCQBKAKUTJ-UHFFFAOYSA-N 7-methyl-6,8-bis(methylsulfanyl)pyrrolo[1,2-a]pyrazine Chemical compound C1=CN=CC2=C(SC)C(C)=C(SC)N21 MYLBTCQBKAKUTJ-UHFFFAOYSA-N 0.000 description 2
- 241001504564 Boops boops Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- -1 and the like Chemical compound 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 239000011335 coal coke Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、凝結が促進された高ビーライト系セメント組成物に関するものである。 The present invention relates to a high belite cement composition with accelerated setting.
低熱ポルトランドセメント等の高ビーライト系セメントは、水和発熱量が極めて小さいという品質上の特徴を活かしたマスコンクリート用途に適していることに加えて、良好な流動性や施工性を有するとともに、長期材齢の強度発現性や耐久性にも優れる。また、セメントクリンカの焼成工程において熱エネルギーを多量に消費するエーライト（Ｃ３Ｓ）量が少ないため、理論的にはセメント製造におけるエネルギー使用量の少ない、いわゆる低炭素セメントとしての機能を発揮する。そのため、近年では、有用性の高い水硬性材料として、建築分野やコンクリート製品分野での需要が増加する一方、こうしたエーライト量が少ない高ビーライト系セメントは、７日材齢までの短期材齢の強度発現性に劣る上に凝結時間が長いため、所定の硬化強度を得るまでに時間を要するという品質上の課題も有している。 In addition to having good fluidity and workability, high belite-based cements such as low heat Portland cement are suitable for mass concrete applications that take advantage of the quality characteristics of extremely low hydration calorific value, Excellent strength and durability of long-term ages. In addition, since the amount of alite (C 3 S) that consumes a large amount of heat energy in the cement clinker firing process is small, it functions theoretically as a so-called low-carbon cement that consumes less energy in cement production. . For this reason, in recent years, demand for building materials and concrete products has increased as highly useful hydraulic materials, while high belite cement with a low amount of alite is a short-term material age up to 7 days. In addition to being inferior in strength development property, the setting time is long, so there is a quality problem that it takes time to obtain a predetermined curing strength.
こうしたなか、ポルトランドセメントについては、その凝結を確実に促進させる方法として、セメント中のフリーライム（以下、「ＦＬ」とも称する。）量を増加させる方法がよく知られてはいるものの、通常セメント中のＦＬ量を増加させるためには、焼成温度を下げる等の手段によってセメントクリンカの焼成度を下げたり、或いは粒度の粗いセメントクリンカ原料を使用したりする必要がある。しかも、こうして得られるＦＬ量の多いセメントは、水と接触した際にＦＬから溶出されるＣａ成分により、セメント初期水和反応への刺激が強まってセメントの凝結が促進される反面、ＦＬ量が多い分エーライト量が少なくなるので、短期材齢における強度発現性に劣る結果となる。そのため、そもそも短期材齢の強度発現性が低いという特有の課題を有する高ビーライト系セメントに、こうしたＦＬ量を増加させる方法を採用することは必ずしも適切ではないと考えられており、十分な検討がなされることなく他の手段を採用した種々の技術が開発されている。 Under these circumstances, although it is well known to increase the amount of free lime (hereinafter also referred to as “FL”) in cement as a method for surely promoting the setting of Portland cement, In order to increase the amount of FL, it is necessary to lower the degree of firing of the cement clinker by means such as lowering the firing temperature or to use a cement clinker raw material having a coarse particle size. Moreover, the cement with a large amount of FL obtained in this way is stimulated by the Ca component eluted from the FL when contacted with water, which stimulates the cement initial hydration reaction and promotes the setting of the cement. Since the amount of alite is reduced by a large amount, it results in inferior strength development in a short age. Therefore, it is considered that it is not always appropriate to adopt such a method to increase the amount of FL in high belite cement, which has the specific problem that strength development of short-term ages is low. Various techniques that employ other means have been developed without the above.
例えば、特許文献１には、高ビーライトセメントと、硫酸カリウム、硫酸ナトリウム、硫酸マグネシウム、硫酸アルミニウム、硫酸カリウムアルミニウム及び硫酸ナトリウムアルミニウムからなる硬化促進剤を０．３〜４．０％含有する低熱セメント組成物が開示されており、これによって短期材齢におけるコンクリートの強度発現を試みている。また、特許文献２には、半水石膏をＳＯ３換算量で少なくとも０．５質量％含有する低熱ポルトランドセメントに、オキシカルボン酸及びその塩からなる群より選ばれた少なくとも１種を主成分とする低熱ポルトランドセメント用凝結促進剤を０．０１〜０．５質量％添加する技術が開示されており、かかる技術を用いて低熱ポルトランドセメントの凝結の始発時間及び終結時間の短縮化を図っている。 For example, Patent Document 1 discloses low heat containing 0.3 to 4.0% of a hardening accelerator composed of high belite cement and potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, potassium aluminum sulfate, and sodium aluminum sulfate. A cement composition is disclosed, which attempts to develop the strength of concrete at short ages. Patent Document 2 discloses a low heat Portland cement containing at least 0.5% by mass of hemihydrate gypsum in terms of SO 3 , and at least one selected from the group consisting of oxycarboxylic acids and salts thereof as a main component. A technology for adding 0.01 to 0.5% by mass of a setting accelerator for low heat Portland cement is disclosed, and by using such a technology, the start time and setting time of setting of low heat Portland cement are shortened. .
しかしながら、上記特許文献に記載のいずれの技術においても、別途所定の凝結促進剤を所定の量で添加する必要があり、その量を誤るとかえって凝結が遅延してしまうおそれもあることも知られているため、実際の使用場面では、凝結促進剤の最適添加量に関する事前確認試験がかかせず、工程の煩雑化を招くこととなる。特に、工期の短縮化や型枠の使用回転数の向上を図りつつ、建築分野やコンクリート製品分野における需要の増加に対応するには、凝結時間を確実に短縮することが望まれてはいるものの、上記いずれの技術を採用しても、短期材齢における強度発現性を良好に保持しながら、有効に凝結時間の短縮化を図るには至らない状況である。 However, in any of the techniques described in the above-mentioned patent documents, it is necessary to add a predetermined setting accelerator separately in a predetermined amount, and it is also known that if the amount is wrong, the setting may be delayed. Therefore, in an actual use situation, a prior confirmation test regarding the optimum addition amount of the setting accelerator is indispensable, and the process becomes complicated. In particular, while shortening the construction period and increasing the number of rotations of the formwork, it is desirable to reduce the setting time to meet the increasing demand in the construction and concrete products fields. Even if any of the above-described techniques is employed, the setting time cannot be effectively shortened while maintaining the strength development in a short age.
したがって、本発明の課題は、凝結促進剤等の特別な添加剤を用いることなく、短期材齢の強度発現性を良好に保持しながら、凝結時間の短縮化を有効に図ることのできる高ビーライト系セメント組成物を提供することにある。 Therefore, an object of the present invention is to achieve a high bead capable of effectively shortening the setting time while maintaining good strength development of short-term ages without using a special additive such as a setting accelerator. The object is to provide a light cement composition.
そこで本発明者らは、種々検討したところ、フリーライム等が特定量であるセメントクリンカと特定量の半水石膏を含む特定量の石膏を含有することにより、良好な短期材齢の強度発現性を有しつつ、凝結時間の短縮化をも図ることのできる高ビーライト系セメント組成物が得られることを見出した。 Therefore, the present inventors have conducted various studies, and by including a specific amount of gypsum including a cement clinker having a specific amount of free lime and a specific amount of hemihydrate gypsum, a good short-term strength development property is obtained. It has been found that a high belite-based cement composition capable of shortening the setting time can be obtained.
すなわち、本発明は、次の成分（Ｘ）、並びに（Ｙ）：
（Ｘ）フリーライムを１．５〜２．５質量％、Ｃ３Ｓを２３〜３１質量％、Ｃ２Ｓを５４〜６２質量％、Ｃ３Ａを１〜３質量％、Ｃ４ＡＦを８〜１３質量％、ＭｇＯを０．５〜１．０質量％、及びＳＯ３を０．１０〜０．３１質量％含み、かつＣ３ＡとＣ４ＡＦの合計量が１１〜１５質量％であるセメントクリンカ、並びに
（Ｙ）ＳＯ３換算量で１．２〜４．０質量％の石膏
を含有し、かつ
成分（Ｙ）中における半水石膏のＳＯ３換算量が、２０〜８０質量％である高ビーライト系セメント組成物を提供するものである。
That is, the present invention includes the following components (X) and (Y):
(X) 1.5 to 2.5% by mass of free lime, 23 to 31% by mass of C 3 S, 54 to 62% by mass of C 2 S, 1 to 3% by mass of C 3 A, and C 4 AF 8 to 13% by mass, MgO 0.5 to 1.0% by mass, SO 3 0.10 to 0.31% by mass, and the total amount of C 3 A and C 4 AF is 11 to 15% by mass cement clinker, and (Y) containing 1.2 to 4.0 mass% of gypsum with SO 3 equivalent amount, and SO 3 equivalent amount of hemihydrate gypsum in the component (Y) is 20 to 80 mass is % High belite cement composition.
本発明の高ビーライト系セメント組成物によれば、フリーライム量が多いながらも短期材齢において高い強度発現性を保持し、かつ凝結時間を効果的に短縮することができる。また、実際の使用場面においても、凝結促進剤を用いることなく、工程の簡略化を図ることもできる。 According to the high belite type cement composition of the present invention, high strength development can be maintained in a short-term material age while the amount of free lime is large, and the setting time can be shortened effectively. Further, even in actual use situations, the process can be simplified without using a setting accelerator.
以下、本発明について詳細に説明する。
本発明の高ビーライト系セメント組成物は、次の成分（Ｘ）のセメントクリンカ、並びに成分（Ｙ）の石膏：
（Ｘ）フリーライムを１．５〜２．５質量％、Ｃ３Ｓ（エーライト：３ＣａＯ・ＳｉＯ２）を２３〜３１質量％、Ｃ２Ｓ（ビーライト：２ＣａＯ・ＳｉＯ２）を５４〜６２質量％、Ｃ３Ａ（３ＣａＯ・Ａｌ２Ｏ３）を１〜３質量％、Ｃ４ＡＦ（４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３）を８〜１３質量％、ＭｇＯを０．５〜１．０質量％、及びＳＯ３を０．１０〜０．２５質量％含み、かつＣ３ＡとＣ４ＡＦの合計量が１１〜１５質量％であるセメントクリンカ、並びに
（Ｙ）ＳＯ３換算量で１．２〜４．０質量％の石膏
を含有し、かつ
成分（Ｙ）中における半水石膏のＳＯ３換算量が、２０〜８０質量％である。
Hereinafter, the present invention will be described in detail.
The high belite cement composition of the present invention comprises the following component (X) cement clinker and component (Y) gypsum:
(X) free lime 1.5-2.5 mass%, C 3 S (alite: 3CaO · SiO 2) and 23 to 31 mass%, C 2 S (belite: 2CaO · SiO 2) and 54 to 62 wt%, C 3 a (3CaO · Al 2 O 3) 1-3% by weight, C 4 to AF (4CaO · Al 2 O 3 · Fe 2 O 3) 8~13 wt%, the MgO 0.5 A cement clinker containing ˜1.0% by mass and 0.10˜0.25% by mass of SO 3 and the total amount of C 3 A and C 4 AF is 11˜15% by mass, and (Y) SO 3 It contains 1.2 to 4.0% by mass of gypsum in terms of conversion amount, and the SO 3 conversion amount of hemihydrate gypsum in component (Y) is 20 to 80% by mass.
本発明の高ビーライト系セメント組成物は、成分（Ａ）として、フリーライム（ＦＬ）を１．５〜２．５質量％、Ｃ３Ｓ（エーライト：３ＣａＯ・ＳｉＯ２）を２３〜３１質量％、Ｃ２Ｓ（ビーライト：２ＣａＯ・ＳｉＯ２）を５４〜６２質量％、Ｃ３Ａ（３ＣａＯ・Ａｌ２Ｏ３）を１〜３質量％、Ｃ４ＡＦ（４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３）を８〜１３質量％、ＭｇＯを０．５〜１．０質量％、及びＳＯ３を０．１０〜０．３１質量％含み、かつＣ３ＡとＣ４ＡＦの合計量が１１〜１５質量％であるセメントクリンカを含有する。 The high belite cement composition of the present invention contains, as component (A), 1.5 to 2.5 mass% of free lime (FL) and 23 to 31 of C 3 S (Alite: 3CaO · SiO 2 ). % By mass, 54 to 62% by mass of C 2 S (Belite: 2CaO · SiO 2 ), 1 to 3% by mass of C 3 A (3CaO · Al 2 O 3 ), C 4 AF (4CaO · Al 2 O 3) Fe 2 O 3 ) 8-13% by mass, MgO 0.5-1.0% by mass, SO 3 0.10-0.31% by mass, and the sum of C 3 A and C 4 AF Contains cement clinker in an amount of 11-15% by weight.
Ｃ３Ｓ量は、成分（Ａ）中に２３〜３１質量％であり、凝結時間、短期材齢の強度発現性及び水和発熱特性に影響を与える極めて重要な値である。かかるＣ３Ｓ量が２３質量％に満たないと、後述するＣ３Ａ量や石膏量を調整しても、凝結時間の短縮効果が充分に得られず、さらに短期材齢における良好な強度発現性も保持できないおそれがある。一方、Ｃ３Ｓ量が３１質量％を超えると、高ビーライト系セメント組成物として水和発熱量が増大しすぎるおそれがある。 The amount of C 3 S is 23 to 31% by mass in the component (A), and is an extremely important value that affects the setting time, the strength development of short-term ages, and the hydration exothermic characteristics. If the amount of C 3 S is less than 23% by mass, the effect of shortening the setting time cannot be sufficiently obtained even if the amount of C 3 A or gypsum described later is adjusted, and further, good strength expression at a short age. It may not be possible to maintain the sex. On the other hand, when the amount of C 3 S exceeds 31% by mass, the calorific value of hydration may increase excessively as a high belite cement composition.
Ｃ２Ｓ量は、成分（Ａ）中に５４〜６２質量％である。Ｃ２Ｓは下記式（ｘ）で表される、セメントクリンカの焼成工程中におけるＣ３Ｓ生成反応の中間相として位置付けられるため、基本的にＣ２Ｓ量とＣ３Ｓ量は、一方の増大に連動して逆に減少するという関係にあるが、成分（Ａ）のセメントクリンカ中におけるＣ２Ｓ量は、特に長期材齢の強度発現性及び水和発熱特性に影響を与える極めて重要な値である。かかるＣ２Ｓ量が５４質量％に満たないと、長期材齢における良好な強度発現性と水和発熱特性を確保することができないおそれがある。
Ｃ２Ｓ＋ＦＬ → Ｃ３Ｓ ・・・（ｘ）
The amount of C 2 S is 54 to 62% by mass in the component (A). Since C 2 S is positioned as an intermediate phase of the C 3 S formation reaction in the cement clinker firing step represented by the following formula (x), basically, the C 2 S amount and the C 3 S amount are The amount of C 2 S in the cement clinker of component (A) is extremely important because it particularly affects the strength development of long-term ages and the hydration exothermic properties. Value. If the amount of C 2 S is less than 54% by mass, good strength development and hydration exothermic properties may not be ensured in the long-term age.
C 2 S + FL → C 3 S (x)
Ｃ３Ａ量は、成分（Ａ）中に１〜３質量％であり、Ｃ４ＡＦ量は、成分（Ａ）中に８〜１３質量％であり、かつこれらＣ３ＡとＣ４ＡＦの合計量は１１〜１５質量％である。かかるＣ３Ａ量が３質量％を超えると、流動性や施工性のみならず、水和発熱特性も悪化してしまうおそれがあり、またＣ４ＡＦ量が１３質量％を超えると、流動性や施工性が悪化するおそれがある。そして、これらＣ３ＡとＣ４ＡＦの合計量が１１質量％に満たないと、セメントクリンカの焼成工程における液相量が少なすぎるために、セメントクリンカの焼成が困難となるおそれがあり、本来ビーライト系セメント組成物が有する低炭素セメントとしての効果が低減してしまうこととなる。 The amount of C 3 A is 1 to 3% by mass in component (A), the amount of C 4 AF is 8 to 13% by mass in component (A), and the amount of C 3 A and C 4 AF is The total amount is 11-15% by mass. When the amount of C 3 A exceeds 3% by mass, not only the fluidity and workability but also the hydration exothermic property may be deteriorated. When the amount of C 4 AF exceeds 13% by mass, the fluidity And workability may be deteriorated. If the total amount of C 3 A and C 4 AF is less than 11% by mass, the amount of liquid phase in the cement clinker firing step is too small, which may make firing of the cement clinker difficult. The effect as a low carbon cement which a belite type cement composition has will reduce.
フリーライム量は、成分（Ａ）中に１．５〜２．５質量％である。かかるフリーライム量が１．５質量％に満たないと、凝結の促進効果が低減するとともに、短期材齢における良好な強度発現性を保持することができなくなるおそれがある。一方、フリーライム量が２．５質量％を超えると、水和発熱量が増大しすぎるおそれがある。したがって、フリーライム量が上記所定の量となるよう、焼成温度を調整する等の手段を用い、上記式（ｘ）に表されるセメントクリンカの焼成工程でのＣ３Ｓ生成反応を抑制するのが好ましい。 The amount of free lime is 1.5 to 2.5% by mass in component (A). If the amount of free lime is less than 1.5% by mass, the effect of accelerating the setting may be reduced, and good strength development at a short age may not be maintained. On the other hand, if the amount of free lime exceeds 2.5% by mass, the hydration heat value may increase excessively. Therefore, by using means such as adjusting the firing temperature so that the amount of free lime becomes the predetermined amount, the C 3 S formation reaction in the cement clinker firing step represented by the above formula (x) is suppressed. Is preferred.
上記Ｃ３ＳやＣ２Ｓ等の、いわゆるセメントクリンカの鉱物組成は、Ｘ線回折−リートベルト法により得られる値であり、例えば特開２００７−７６９３１号公報に記載の方法等を用いることができる。なお、かかるセメントクリンカの鉱物組成の算出方法として、化学分析値から見積るボーグ式がよく用いられるが、ボーグ式による見積値は、理想的な化学平衡を前提として得られる値であるため、実際のセメントクリンカの鉱物組成から乖離しており、本発明に用いることは好ましくない。 The mineral composition of so-called cement clinker, such as C 3 S and C 2 S, is a value obtained by the X-ray diffraction-Riet belt method. For example, the method described in JP 2007-76931 A can be used. it can. As a method for calculating the mineral composition of such cement clinker, the Bogue equation estimated from the chemical analysis value is often used, but the estimated value based on the Bogue equation is a value obtained on the assumption of an ideal chemical equilibrium. It deviates from the mineral composition of cement clinker and is not preferred for use in the present invention.
ＭｇＯ量は、成分（Ａ）中に０．５〜１．０質量％である。かかるＭｇＯ含有量が、０．５質量％に満たないと、凝結の促進効果が低下するおそれがあり、１．０質量％を超えると、短期材齢の強度発現性に劣るＭIII型のＣ３Ｓ量が増加してしまうため、短期材齢における良好な強度発現性が得られなくなるおそれがある。かかるＭｇＯ量は、成分（Ａ）中に、好ましくは０．６〜０．９質量％である。
なお、成分（Ａ）中におけるＭIII型のＣ３Ｓ量は、Ｘ線回折−リートベルト法を用いることにより、簡便に求めることができる。また、成分（Ａ）中におけるＭｇＯ量の調整は、ドロマイト系石灰石、徐冷スラグ及び苦鉄質〜超苦鉄質系の岩石類等の高ＭｇＯ原料等の原単位調整により行うのが好ましい。
The amount of MgO is 0.5 to 1.0% by mass in component (A). If the MgO content is less than 0.5% by mass, the effect of accelerating the condensation may be reduced. If the MgO content exceeds 1.0% by mass, the MIII type C 3 is inferior in strength development in short-term ages. Since the amount of S increases, there is a possibility that good strength development in short-term ages cannot be obtained. The amount of MgO is preferably 0.6 to 0.9% by mass in component (A).
The amount of MIII type C 3 S in the component (A) can be easily determined by using an X-ray diffraction-Riet belt method. The MgO content in the component (A) is preferably adjusted by adjusting the basic unit of high MgO raw materials such as dolomite limestone, slow-cooled slag, and mafic to supermafic rocks.
ＳＯ３量は、成分（Ａ）中にＳＯ３を０．１０〜０．３１質量％である。かかるＳＯ３含有量が０．１０質量％に満たないと、短期材齢における良好な強度発現性を保持することができなくなるおそれがあり、０．３１質量％を超えると、凝結の促進効果が低減するおそれがある。成分（Ａ）中のＳＯ３は、優先的に、全量の半分以上のＳＯ３がアルカリ硫酸塩を形成した後、II型無水石膏の形成とクリンカシリケート相（Ｃ３Ｓ及びＣ２Ｓ）への固溶が生じる。本発明において、成分（Ａ）中のＳＯ３量が一般的なポルトランドセメントよりも少量であるのは、Ｃ３Ｓ及びＣ２ＳへのＳＯ３固溶量を有効に抑制するためである。
なお、成分（Ａ）中におけるＳＯ３量の調整は、セメントクリンカ原料に硫黄含有量の少ない原料を使用するとともに、硫黄分の少ない石炭や石油コークスなどをセメントクリンカの焼成に使用することにより行うのが好ましい。かかるＳＯ３量は、成分（Ａ）中に、好ましくは０．１５〜０．３１質量％である。
SO 3 content is 0.10 to 0.31 wt% of SO 3 in component (A). If the SO 3 content is less than 0.10% by mass, there is a risk that good strength development in short-term ages may not be maintained. There is a risk of reduction. The SO 3 in the component (A) is preferentially formed into a type II anhydrous gypsum and a clinker silicate phase (C 3 S and C 2 S) after more than half of the total amount of SO 3 forms an alkali sulfate. This results in solid solution. In the present invention, the amount of SO 3 in the component (A) is smaller than that of general Portland cement in order to effectively suppress the SO 3 solid solution amount in C 3 S and C 2 S.
The amount of SO 3 in the component (A) is adjusted by using a raw material having a low sulfur content as a cement clinker raw material and using coal or petroleum coke having a low sulfur content for the firing of the cement clinker. Is preferred. The amount of SO 3 is preferably 0.15 to 0.31% by mass in component (A).
なお、成分（Ａ）中のＭｇＯ量及びＳＯ３量は、ＪＩＳ Ｒ ５２０２「ポルトランドセメントの化学分析方法」、又はＪＩＳ Ｒ ５２０４「セメントの蛍光Ｘ線分析方法」等の公定方法を用いてえられる分析値を意味する。 The amount of MgO and the amount of SO 3 in the component (A) can be obtained using an official method such as JIS R 5202 “Chemical analysis method for Portland cement” or JIS R 5204 “Method for fluorescent X-ray analysis of cement”. Mean analytical value.
本発明において、Ｃ３Ｓ中におけるＭｇＯ固溶量（ａＭ）は、０．６〜０．８質量％であるのが好ましく、０．７〜０．８質量％であるのがより好ましく、かつＳＯ３固溶量（ａＳ）は０．０５質量％以下であるのが好ましく、０．０１〜０．０４質量％であるのがより好ましい。また、Ｃ２Ｓ中におけるＭｇＯ固溶量（ｂＭ）は、０．２〜０．４質量％であるのが好ましく、０．２〜０．３質量％であるのがより好ましく、かつＳＯ３固溶量（ｂＳ）は０．１〜０．３質量％であるのが好ましく、０．１〜０．２５質量％であるのがより好ましい。これら２つのクリンカ鉱物相であるＣ３Ｓ及びＣ２ＳへのＭｇＯ及びＳＯ３の固溶量は、上記鉱物組成、及びＭｇＯ量とＳＯ３量が成分（Ａ）に含まれるよう、調合又は設計されたセメントクリンカ原料や燃料を使用して、後述する製造方法等を用いることにより、成分（Ａ）中のフリーライム量が上記所定の量となるよう、セメントクリンカを焼成することによって得るのが好ましい。 In the present invention, the MgO solid solution amount (aM) in C 3 S is preferably 0.6 to 0.8% by mass, more preferably 0.7 to 0.8% by mass, and The SO 3 solid solution amount (aS) is preferably 0.05% by mass or less, and more preferably 0.01 to 0.04% by mass. Further, the MgO solid solution amount (bM) in C 2 S is preferably 0.2 to 0.4% by mass, more preferably 0.2 to 0.3% by mass, and SO 3. The solid solution amount (bS) is preferably from 0.1 to 0.3% by mass, and more preferably from 0.1 to 0.25% by mass. The solid solution amount of MgO and SO 3 in C 3 S and C 2 S, which are these two clinker mineral phases, is adjusted so that the component (A) contains the above-mentioned mineral composition and the amount of MgO and SO 3. By using the designed cement clinker raw material and fuel and using the production method described later, the cement clinker is obtained by firing so that the amount of free lime in the component (A) becomes the above predetermined amount. Is preferred.
上記Ｃ３Ｓ及びＣ２Ｓ中のＭｇＯ固溶量及びＳＯ３固溶量（ａＭ、ａＳ、ｂＭ、ｂＳ）は、ＥＰＭＡ（電子線マイクロアナライザ）や、元素分析用の検出器や分光器を有する走査電子顕微鏡（ＳＥＭ）等を用いることにより測定できる。なお、これら固溶量の値としては、鉱物相毎に１０個以上の粒子を測定した平均値を用いる。 The MgO solid solution amount and SO 3 solid solution amount (aM, aS, bM, bS) in the above C 3 S and C 2 S are EPMA (electron beam microanalyzer), detector and spectrometer for elemental analysis. It can be measured by using a scanning electron microscope (SEM) or the like. In addition, as a value of these solid solution amounts, an average value obtained by measuring 10 or more particles for each mineral phase is used.
さらに、成分（Ｘ）中におけるＭｇＯ量（ｘＭ）及びＳＯ３量（ｘＳ）は、Ｃ３Ｓ中におけるＭｇＯ固溶量（ａＭ）及びＳＯ３固溶量（ａＳ）、並びにＣ２Ｓ中におけるＭｇＯ固溶量（ｂＭ）及びＳＯ３固溶量（ｂＳ）とともに、下記式（１）及び式（２）を満たすのが好ましい。
ｘＭ×０．５＜Ａ×ａＭ＋Ｂ×ｂＭ・・・（１）
ｘＳ×０．５＞Ａ×ａＳ＋Ｂ×ｂＳ・・・（２）
上記式（１）及び式（２）中、Ａは成分（Ｘ）中におけるＣ３Ｓの含有量（質量％）を示し、Ｂは成分（Ｘ）中におけるＣ２Ｓの含有量（質量％）を示し、ｘＭ及びｘＳの単位はいずれも質量％である。
Further, MgO content in the component (X) (xM) and SO 3 amount (xS) is, MgO solid solution amount in the C 3 S (aM) and SO 3 solid solution amount (aS), and in C 2 in S The following formula (1) and formula (2) are preferably satisfied together with the MgO solid solution amount (bM) and the SO 3 solid solution amount (bS).
xM × 0.5 <A × aM + B × bM (1)
xS × 0.5> A × aS + B × bS (2)
The formula (1) and formula (2), A represents the content of C 3 S in the component (X) (wt%), B is the content of C 2 S in the component (X) (wt% The unit of xM and xS is mass%.
これら成分（Ａ）の鉱物組成中におけるＭｇＯ量及びＳＯ３量とＣ３Ｓ又はＣ２Ｓ中のＭｇＯ固溶量又はＳＯ３固溶量とが上記式（１）及び式（２）を満たすことにより、より容易かつ効果的に、強度発現性を悪化させることなく、凝結が速い高ビーライト系セメント組成物を得ることができる。 The amount of MgO and SO 3 in the mineral composition of these components (A) and the amount of MgO solid solution or SO 3 solid solution in C 3 S or C 2 S satisfy the above formulas (1) and (2). As a result, it is possible to obtain a high belite-based cement composition having a quick setting without easily and effectively deteriorating strength development.
本発明の高ビーライト系セメント組成物は、成分（Ｙ）の石膏を、ＳＯ３換算量で１．２〜４．０質量％含有し、好ましくは１．５〜２．５質量％含有する。かかる成分（Ｙ）としては、二水石膏、半水石膏及び無水石膏が挙げられ、成分（Ｙ）の石膏全量中（ＳＯ３換算量）に含まれる半水石膏量（ＳＯ３換算量）が、２０〜８０質量％であるのが好ましい。成分（Ｙ）の石膏全量中に含まれる半水石膏量が８０質量％を超えると、モルタルやコンクリートの初期流動性が低下するおそれがあり、半水石膏量が２０質量％に満たないと、モルタルやコンクリートの流動性の経時変化が大きくなるおそれがある。 The high belite type cement composition of the present invention contains 1.2 to 4.0% by mass, preferably 1.5 to 2.5% by mass, in terms of SO 3 , of the gypsum component (Y). . Such component (Y), gypsum dihydrate, hemihydrate gypsum and anhydrous gypsum, and the like, hemihydrate gypsum content in the gypsum total amount (SO 3 equivalent amount) of the component (Y) (SO 3 equivalent amount) of It is preferable that it is 20-80 mass%. If the amount of hemihydrate gypsum contained in the total amount of gypsum of component (Y) exceeds 80% by mass, the initial fluidity of mortar and concrete may be reduced. If the amount of hemihydrate gypsum is less than 20% by mass, There is a risk that the change in fluidity of mortar and concrete will increase over time.
なお、かかる石膏量の測定方法としては、熱分析（熱重量分析（ＴＧ）、示差走査熱量測定（ＤＳＣ）等）、Ｘ線回折−リートベルト法等が挙げられるが、無水石膏を含めた、より正確な分析をする観点から、熱重量分析による二水石膏及び半水石膏の測定結果をＸ線回折−リートベルト法に反映する、熱分析とＸ線回折−リートベルト法の併用法を用いるのが好ましい。また、熱分析に使用される熱分析用試料容器としては、特開平６−２４２０３５号公報に記載されている容器（容器の蓋体に径が５〜６０μｍである穴のみを有し、かかる穴以外は密封した状態となる金属質容器）を用いることが好ましい。 Examples of the method for measuring the amount of gypsum include thermal analysis (thermogravimetric analysis (TG), differential scanning calorimetry (DSC), etc.), X-ray diffraction-Rietveld method, etc., including anhydrous gypsum, From the viewpoint of more accurate analysis, a combined method of thermal analysis and X-ray diffraction-Rietbelt method is used to reflect the measurement results of dihydrate gypsum and hemihydrate gypsum by thermogravimetric analysis to the X-ray diffraction-Rietbelt method Is preferred. In addition, as a sample container for thermal analysis used for thermal analysis, a container described in JP-A-6-242035 (having only a hole having a diameter of 5 to 60 μm in the lid of the container, the hole Other than the above, it is preferable to use a metal container in a sealed state.
本発明の高ビーライト系セメント組成物のブレーン比表面積は、好ましくは３，１００〜３，８００ｃｍ２／ｇであり、より好ましくは３，２００〜３，６００ｃｍ２／ｇである。かかるブレーン比表面積の値が３，８００ｃｍ２／ｇを超えると、流動性や施工性が低下するおそれがあり、さらに水和発熱量が大きくなり過ぎる傾向にある。一方、かかるブレーン比表面積の値が３，１００ｃｍ２／ｇに満たないと、凝結時間の短縮効果が低下するおそれがある。
なお、ブレーン比表面積の測定は、ＪＩＳ Ｒ ５２０１「セメントの物理試験方法」記載の方法に準じて行えばよい。
The Blaine specific surface area of the high belite system cement composition of this invention becomes like this. Preferably it is 3,100-3,800 cm < 2 > / g, More preferably, it is 3,200-3,600 cm < 2 > / g. When the value of the specific surface area of branes exceeds 3,800 cm 2 / g, the fluidity and workability may be lowered, and the hydration heat value tends to be too large. On the other hand, if the value of the Blaine specific surface area is less than 3,100 cm 2 / g, the effect of shortening the setting time may be reduced.
The Blaine specific surface area may be measured according to the method described in JIS R 5201 “Cement physical test method”.
本発明で用いる成分（Ａ）のセメントクリンカの原料として、ポルトランドセメントクリンカの製造に用いられる一般的な原料を用いることができる。かかるセメントクリンカの原料としては、具体的には、石灰石、生石灰、消石灰等のＣａＯ原料、珪石、粘土等のＳｉＯ２原料、粘土等のＡｌ２Ｏ３原料、鉄滓、製鉄スラッジ等のＦｅ２Ｏ３原料が挙げられる。
さらに、本発明では、これらの原料に加え、ＭｇＯ原料を使用するのが好ましい。かかるＭｇＯ原料としては、具体的には、ドロマイト系石灰石、徐冷スラグ等の高炉スラグ類、製鋼スラグ、焼却灰類、及び蛇紋岩等の岩石類を使用することができる。
As a raw material of the component (A) cement clinker used in the present invention, a general raw material used for the production of Portland cement clinker can be used. Specific examples of such cement clinker raw materials include CaO raw materials such as limestone, quicklime and slaked lime, SiO 2 raw materials such as silica and clay, Al 2 O 3 raw materials such as clay, Fe 2 such as iron slag and iron sludge. O 3 raw material is mentioned.
Furthermore, in this invention, it is preferable to use a MgO raw material in addition to these raw materials. As such MgO raw material, concretely, blast furnace slag such as dolomite limestone and slow-cooled slag, steelmaking slag, incineration ash, and rocks such as serpentinite can be used.
さらに、上記原料のほか、さらに産業廃棄物、一般廃棄物、及び建設発生土から選ばれる一種以上を原料の一部として使用することができる。かかる原料としては、具体的には、石炭灰、生コンスラッジ、各種汚泥（例えば、下水汚泥、浄水汚泥、建設汚泥、製鉄汚泥等）、ボーリング廃土、各種焼却灰、鋳物砂、ロックウール、廃ガラス、高炉二次灰、建築廃材、コンクリート廃材等の産業廃棄物；下水汚泥乾粉、都市ごみ焼却灰、貝殻等の一般廃棄物；建設現場または工事現場等から発生する土壌、残土、及び廃土壌等の建設発生土が挙げられる。なかでも、使用の容易性等の観点から、石炭灰を用いるのが好ましい。
上記廃棄物（産業廃棄物、一般廃棄物、及び建設発生土から選ばれる一種以上）の使用量は、廃棄物の有効利用を図り、かつセメントにおける所望の品質を確保するという観点から、上記焼成物１ｔｏｎ当たり、好ましくは２００ｋｇ以下である。
Furthermore, in addition to the above raw materials, one or more selected from industrial waste, general waste, and construction generated soil can be used as part of the raw materials. Specific examples of such raw materials include coal ash, ready-mixed sludge, various sludges (for example, sewage sludge, purified water sludge, construction sludge, iron sludge, etc.), boring waste soil, various incineration ash, foundry sand, rock wool, waste Industrial waste such as glass, blast furnace secondary ash, construction waste, concrete waste; general waste such as sewage sludge dry powder, municipal waste incineration ash, shells; soil generated from construction sites or construction sites, residual soil, and waste soil For example, construction soils such as Of these, coal ash is preferably used from the viewpoint of ease of use.
The amount of the waste (one or more selected from industrial waste, general waste, and construction generated soil) is used from the viewpoint of effective use of waste and ensuring the desired quality of cement. It is preferably 200 kg or less per ton of the object.
本発明で用いる成分（Ａ）のセメントクリンカの焼成工程に使用する石炭や石油コークス等の燃料は、硫黄分の少ないもの程好ましく、燃料の硫黄含有量（ドライベース）は、好ましくは０．５質量％以下であり、より好ましくは０．３質量％以下である。
なお、燃料中の硫黄含有量の測定は、ＪＩＳ Ｍ ８８１３「石炭類及びコークス類−元素分析方法」記載の方法に準じて行えばよい。
The fuel such as coal and petroleum coke used in the firing step of the cement clinker of component (A) used in the present invention is preferably as low as the sulfur content, and the sulfur content (dry base) of the fuel is preferably 0.5. It is less than mass%, more preferably less than 0.3 mass%.
The measurement of the sulfur content in the fuel may be performed according to the method described in JIS M 8813 “Coal and cokes—elemental analysis method”.
本発明で用いる成分（Ａ）のセメントクリンカを製造する方法としては、上述した各原料を所望のクリンカ鉱物組成となるように調合及び混合し、得られた混合物を、好ましくは１，２００〜１，５００℃、より好ましくは１，２５０〜１，４５０℃の温度で焼成する方法が挙げられる。この際、セメントクリンカのフリーライム量が所定の値となるように、石炭等燃料の焚量調整等の操作によって、焼成温度を適宜制御すればよい。焼成温度の制御の目安として、焼成温度（例えば、キルン落口温度）が５０℃上昇した場合、セメントクリンカ中のフリーライム量は１質量％減少する。 As a method for producing the cement clinker of component (A) used in the present invention, the above-mentioned raw materials are prepared and mixed so as to have a desired clinker mineral composition, and the resulting mixture is preferably 1,200 to 1 , 500 ° C., more preferably a method of firing at a temperature of 1,250 to 1,450 ° C. At this time, the firing temperature may be appropriately controlled by an operation such as adjustment of the amount of fuel such as coal so that the amount of free lime of the cement clinker becomes a predetermined value. As a guide for controlling the firing temperature, when the firing temperature (for example, kiln drop temperature) is increased by 50 ° C., the amount of free lime in the cement clinker is reduced by 1% by mass.
以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
［製造例１：セメントクリンカの製造］
特級試薬の炭酸カルシウム、酸化ケイ素、酸化アルミニウム、酸化鉄（III）、酸化マグネシウムおよび三酸化硫黄を、表１の化学組成になるように調合後、振動型ディスクミルを使用して１８０μｍ篩残分量が１．２質量％まで粉砕した調合原料を、一旦、電気炉を使用して１０００℃で６０分間仮焼して脱炭酸を行った後、ペレット状（φ２５×ｈ１０ｍｍ）に加圧成形して焼成用原料（表１に示す「原料」）を作成した。
なお、ふるい分け試験は、ＪＩＳ Ｚ ８８１５「ふるい分け試験方法通則」に準じて行った。
[Production Example 1: Production of cement clinker]
After preparing the special grades of calcium carbonate, silicon oxide, aluminum oxide, iron (III) oxide, magnesium oxide and sulfur trioxide to the chemical composition shown in Table 1, 180μm sieve residue using a vibrating disc mill The raw material was pulverized to 1.2% by mass, temporarily calcined at 1000 ° C. for 60 minutes using an electric furnace, decarboxylated, and then pressed into pellets (φ25 × h10 mm). A raw material for firing ("raw material" shown in Table 1) was prepared.
The screening test was conducted according to JIS Z 8815 “General rules of screening test method”.
次いで、得られた焼成用原料を用い、表１に示す各焼成温度に保持された電気炉に３０分間静置した後、炉外気中放冷による冷却を行って、各セメントクリンカ（ＣＬ−１〜ＣＬ−５）を得た。得られたセメントクリンカの化学組成及び鉱物組成を下記方法にしたがって求めた。結果を表１に示す。
なお、各セメントクリンカは、焼成後に１ｋｇ以上得られるよう調整した。
Next, using the obtained raw material for firing, it was allowed to stand in an electric furnace maintained at each firing temperature shown in Table 1 for 30 minutes, and then cooled by cooling in the outside air, and each cement clinker (CL-1 To CL-5). The chemical composition and mineral composition of the obtained cement clinker were determined according to the following method. The results are shown in Table 1.
In addition, each cement clinker was adjusted so that 1 kg or more could be obtained after baking.
《セメントクリンカの化学組成》
ＪＩＳ Ｒ ５２０４「セメントの蛍光Ｘ線分析方法」に準拠して、蛍光Ｘ線分析装置ＺＳＸ１００ｅ（リガク社製）による測定値とした。
<Chemical composition of cement clinker>
In accordance with JIS R 5204 “Method for fluorescent X-ray analysis of cement”, the measured value was measured with a fluorescent X-ray analyzer ZSX100e (manufactured by Rigaku Corporation).
《セメントクリンカの鉱物組成》
Ｘ線回折−リートベルト法により、具体的には以下の刊行物の方法に準拠した測定値とした。なお、Ｘ線回折装置として、Ｄ８ ＡＤＶＡＮＣＥ（ブルカー・エイエックスエス社製）を用い、解析ソフトウェアとして、ＤＩＦＦＲＡＣｐｌｕｓ ＴＯＰＡＳ(Ver.3) （ブルカー・エイエックスエス社製）を用いた。
星野清一他；非晶質混和材を含むセメントの鉱物の定量におけるＸ線回折／リートベルト法の適用，セメント・コンクリート論文集，No.59，pp.14-21（2005）
<Mineral composition of cement clinker>
Specifically, the measured values were based on the method of the following publications by the X-ray diffraction-Rietbelt method. In addition, D8 ADVANCE (made by Bruker AXS) was used as an X-ray diffractometer, and DIFFRAC plus TOPAS (Ver.3) (made by Bruker AXS) was used as analysis software.
Hoshino, Seiichi et al .: Application of X-ray diffraction / Rietbelt method in the determination of cement minerals containing amorphous admixtures, Papers on cement and concrete, No.59, pp.14-21 (2005)
次に、製造例１で得られた各セメントクリンカ（ＣＬ−１〜ＣＬ−５）中におけるＣ３Ｓ及びＣ２Ｓの結晶粒子の化学組成について、以下の手順にしたがってＥＰＭＡを用いて測定を行った。
結果を表２に示す。
Next, the chemical composition of C 3 S and C 2 S crystal particles in each cement clinker (CL-1 to CL-5) obtained in Production Example 1 was measured using EPMA according to the following procedure. went.
The results are shown in Table 2.
《Ｃ３Ｓ及びＣ２Ｓの結晶粒子の化学組成（ＭｇＯ固溶量及びＳＯ３固溶量）》
ＥＰＭＡ測定試料は、５ｍｍ以下に粗砕した高ビーライト系セメントクリンカをエポキシ樹脂中に埋め、樹脂硬化後に表面研磨を施した。ＥＰＭＡの測定にはＪＸＡ−８１００（日本電子社製）を使用した。加速電圧１５ｋＶ、試料電流５×１０−８Ａでの点分析を、各試料で１５点測定後に平均値を算出した。
<< Chemical composition of crystal particles of C 3 S and C 2 S (MgO solid solution amount and SO 3 solid solution amount) >>
For the EPMA measurement sample, high belite cement clinker coarsely crushed to 5 mm or less was embedded in an epoxy resin, and surface polishing was performed after the resin was cured. For measurement of EPMA, JXA-8100 (manufactured by JEOL Ltd.) was used. In the point analysis at an acceleration voltage of 15 kV and a sample current of 5 × 10 −8 A, an average value was calculated after measuring 15 points in each sample.
［製造例２：高ビーライト系セメント組成物の製造］
製造例１で得られた各セメントクリンカ（ＣＬ−１〜ＣＬ−５）と、以下に示す石膏を用いて、高ビーライト系セメント組成物（ＨＢＣ−１〜ＨＢＣ−５）を製造した。
次いで、石膏として、排脱二水石膏（住友金属社製）と、該排脱二水石膏を１４０℃で加熱して得られた半水石膏とを用い、高ビーライト系セメント組成物１００質量％中におけるこれら石膏（二水石膏＋半水石膏）の合計がＳＯ３換算で２．０質量％の量となるよう添加した後、バッチ式ボールミルを用いてブレーン比表面積が３４００±１００ｃｍ２／ｇとなるよう同時粉砕した。
なお、二水石膏及び半水石膏の合計量（ＳＯ３換算）に対する半水石膏の割合（ＳＯ３換算）は、全て高ビーライト系セメント組成物中に６０質量％となるよう調製した。
[Production Example 2: Production of high belite-based cement composition]
Using each cement clinker (CL-1 to CL-5) obtained in Production Example 1 and gypsum shown below, high belite cement compositions (HBC-1 to HBC-5) were produced.
Next, 100 g of high belite cement composition is used by using drained dihydrate gypsum (manufactured by Sumitomo Metal Co., Ltd.) and hemihydrate gypsum obtained by heating the drained dihydrate gypsum at 140 ° C. % So that the total of these gypsum (dihydrate gypsum + hemihydrate gypsum) is 2.0% by mass in terms of SO 3 , and using a batch type ball mill, the brain specific surface area is 3400 ± 100 cm 2 / Simultaneously pulverized to g.
Incidentally, the total amount of gypsum and hemihydrate gypsum (SO 3 conversion) rate of hemihydrate gypsum for (SO 3 equivalent) was prepared so that all the 60 wt% to a high belite cement composition.
得られた高ビーライト系セメント組成物を用いて、以下の方法にしたがって各特性を評価した。なお、比較例３として、市販の低熱セメント（太平洋セメント製）を用いた。 Each characteristic was evaluated according to the following method using the obtained high belite type cement composition. In addition, as Comparative Example 3, a commercially available low heat cement (manufactured by Taiheiyo Cement) was used.
《凝結性状》
各高ビーライト系セメント組成物の凝結時間について、ＪＩＳ Ｒ ５２０１「セメントの物理試験方法」に準拠して測定を行った。結果を表３に示す。
《Condensation properties》
The setting time of each high belite cement composition was measured according to JIS R 5201 “Physical Test Method for Cement”. The results are shown in Table 3.
《モルタル圧縮強さ》
強度発現性はモルタル圧縮強さで評価した。ただし、試料量が少なかったため、以下の手順で行った。
《Mortar compressive strength》
Strength development was evaluated by mortar compressive strength. However, since the sample amount was small, the following procedure was performed.
i）モルタル混練
高ビーライト系セメント組成物４５ｇ、標準砂（ＪＩＳ Ｒ ５２０１「セメントの物理試験方法」付属書２の５．１．３節）１３５ｇ、及び水（上水道水）２２．５ｇを、練り匙で６０秒間混練した後、注水から９５秒後にソルダーペーストミキサー（回転数：３００ｒｐｍ、シンキー社製）で３０秒間混練し、その後再び練り匙で１５秒間混練した。
i) mortar kneading 45 g of high belite cement composition, 135 g of standard sand (section 5.1.3 of Appendix 2 of JIS R 5201 “Physical Test Method for Cement”) and 22.5 g of water (tap water) After kneading with a kneader for 60 seconds, 95 seconds after pouring water, the mixture was kneaded for 30 seconds with a solder paste mixer (rotation speed: 300 rpm, manufactured by Shinky Corp.), and then again kneaded with a kneader for 15 seconds.
ii）モルタル成形
２×２×３ｃｍの型枠に、上記モルタルを１層で詰め、テーブルバイブレーターで３０秒間加振した後、金属製ストレートエッジを用いて供試体上面を平滑にした。その後、ガラス板で供試体表面を覆った後、湿気箱（２０±１℃、相対湿度９０％以上）に静置して所定期間養生した。
ii) Mortar Molding The above mortar was packed in a 2 × 2 × 3 cm mold with one layer, and was shaken with a table vibrator for 30 seconds, and then the upper surface of the specimen was smoothed using a metal straight edge. Then, after covering the surface of the specimen with a glass plate, it was allowed to stand in a humidity box (20 ± 1 ° C., relative humidity 90% or more) and cured for a predetermined period.
iii）モルタル圧縮強さの測定
荷重用加圧板を用いて、供試体中央部に６００±５０Ｎ／ｓの載荷速度で、圧壊までの最大荷重（Ｎ）を測定した。
iii) Measurement of mortar compressive strength The maximum load (N) until crushing was measured at a loading speed of 600 ± 50 N / s at the center of the specimen using a pressure plate for loading.
iv）モルタル圧縮強さの算出
モルタル圧縮強さは、下式より得られる。結果を表３に示す。
モルタル圧縮強さ（Ｎ／ｍｍ２）＝ 最大荷重（Ｎ）／４００
iv) Calculation of mortar compressive strength Mortar compressive strength is obtained from the following equation. The results are shown in Table 3.
Mortar compressive strength (N / mm 2 ) = Maximum load (N) / 400
表３より、本発明の高ビーライト系セメント組成物である実施例１〜３は、比較例１〜２に比して、比較例３の市販セメントと同等の強度発現性を保持しながら、凝結の始発時間及び終結時間ともに有効に短縮できることが分かる。 From Table 3, Examples 1-3 which are the high belite system cement composition of the present invention maintain intensity development property equivalent to the commercial cement of Comparative Example 3 compared with Comparative Examples 1-2, It can be seen that both the start time and the end time of condensation can be effectively shortened.
Claims (5)
（Ｘ）フリーライムを１．５〜２．５質量％、Ｃ３Ｓを２３〜３１質量％、Ｃ２Ｓを５４〜６２質量％、Ｃ３Ａを１〜３質量％、Ｃ４ＡＦを８〜１３質量％、ＭｇＯを０．５〜１．０質量％、及びＳＯ３を０．１０〜０．３１質量％含み、かつＣ３ＡとＣ４ＡＦの合計量が１１〜１５質量％であるセメントクリンカ、並びに
（Ｙ）ＳＯ３換算量が１．２〜４．０質量％である石膏
を含有し、かつ
成分（Ｘ）中における半水石膏のＳＯ３換算量が、２０〜８０質量％である高ビーライト系セメント組成物。 The following components (X) and (Y):
(X) 1.5 to 2.5% by mass of free lime, 23 to 31% by mass of C 3 S, 54 to 62% by mass of C 2 S, 1 to 3% by mass of C 3 A, and C 4 AF 8 to 13% by mass, MgO 0.5 to 1.0% by mass, SO 3 0.10 to 0.31% by mass, and the total amount of C 3 A and C 4 AF is 11 to 15% by mass in a cement clinker, and (Y) converted to SO 3 amount contained gypsum is 1.2 to 4.0 wt%, and SO 3 equivalent amount of hemihydrate gypsum in the component (X) is 20 to 80 High belite cement composition which is mass%.
ｘＭ×０．５＜Ａ×ａＭ＋Ｂ×ｂＭ・・・（１）
ｘＳ×０．５＞Ａ×ａＳ＋Ｂ×ｂＳ・・・（２）
（式中、Ａは成分（Ｘ）中におけるＣ３Ｓの含有量（質量％）を示し、Ｂは成分（Ｘ）中におけるＣ２Ｓの含有量（質量％）を示し、ｘＭ及びｘＳの単位はいずれも質量％である。） The amount of MgO (xM) and the amount of SO 3 (xS) in component (X) are the amounts of MgO solid solution (aM) and SO 3 solid solution (aS) in C 3 S, and MgO solid solution in C 2 S. The high belite cement composition according to any one of claims 1 to 3, wherein the following formula (1) and formula (2) are satisfied together with the dissolved amount (bM) and the SO 3 solid solution amount (bS).
xM × 0.5 <A × aM + B × bM (1)
xS × 0.5> A × aS + B × bS (2)
(In the formula, A represents the content (mass%) of C 3 S in the component (X), B represents the content (mass%) of C 2 S in the component (X), and xM and xS (All units are mass%.)
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