JP3549635B2 - Stimulant for mixed cement and mixed cement composition - Google Patents
Stimulant for mixed cement and mixed cement composition Download PDFInfo
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- JP3549635B2 JP3549635B2 JP20946495A JP20946495A JP3549635B2 JP 3549635 B2 JP3549635 B2 JP 3549635B2 JP 20946495 A JP20946495 A JP 20946495A JP 20946495 A JP20946495 A JP 20946495A JP 3549635 B2 JP3549635 B2 JP 3549635B2
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- 239000004568 cement Substances 0.000 title claims description 56
- 239000000203 mixture Substances 0.000 title claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 30
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 25
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 20
- 239000004571 lime Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 229910052920 inorganic sulfate Inorganic materials 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 6
- 230000004936 stimulating effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 239000004567 concrete Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000021 stimulant 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
- 235000019738 Limestone Nutrition 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
- 239000011398 Portland cement Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000011400 blast furnace cement Substances 0.000 description 2
- 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 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- -1 hemihydrate gypsum Chemical compound 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000006072 paste Substances 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
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、主に、土木・建築業界において使用される混合セメントの刺激材及びそれを用いた混合セメント組成物に関する。
【０００２】
【従来技術とその課題】
近年、地球の環境保護問題が大きくクローズアップされており、セメント分野においても環境保護に関連して様々な試みが検討され、例えば、セメントクリンカーの製造過程において排気される炭酸ガスは地球を温暖化へと導き、自然環境のつりあいを大きく崩す原因であることが問題視されている。
【０００３】
このような問題に対して、セメント分野では、製造するセメントクリンカーの使用量を抑えることができることから、高炉スラグ、フライアッシュ、及びシリカフューム等の産業廃棄物を混合した混合セメントに注目している。
高炉スラグ、フライアッシュ、及びシリカフューム等の産業廃棄物は、潜在水硬性を有しており、セメントの水和過程で生成する水酸化カルシウムと反応し、強度発現性やセメント硬化体の緻密化に寄与することが知られている。
ここで、セメント硬化体とは、セメントペースト、モルタル、又はコンクリートの硬化体を総称するものである。
ところが、これら潜在水硬性物質を混合した混合セメントは、普通ポルトランドセメントに比較し、初期の強度発現性が乏しく、また、セメント硬化体組織が緻密化しにくいことから炭酸化反応も著しく速いという課題があった。
【０００４】
このような混合セメントの課題を解決するために、水酸化カルシウム生成量の多い早強ポルトランドセメントを刺激材料として、高炉セメントＢ種の強度を増進させる方法が提案された（安永、中村、鍬崎、第４９回セメント技術大会講演集、ｐ１０８〜１１３ １９９５年）。
しかしながら、この方法では、強度発現性やセメント硬化体の緻密化の効果が充分でなく、また、高炉スラグの含有率を５０重量％程度までしか増加させることができないため、セメントクリンカー量を低減することができず、５５重量％を超える含有率になると、強度発現性が低下してしまうという課題があった。
【０００５】
本発明者は、これらの課題を解消するために、鋭意努力を重ねた結果、特定の混合セメントの刺激材を使用することにより、初期の強度発現性が改善されるだけでなく、セメント硬化体の組織を緻密化し、炭酸化反応を著しく抑制することができるとの知見を得て本発明を完成するに至った。
【０００６】
【課題を解決するための手段】
即ち、本発明は、CaO原料、Al２O３原料、及びCaSO４原料を含有する配合物を熱処理して生成するもので、遊離石灰、アウイン、及び無水セッコウを有効成分とする鉱物群からなり、遊離石灰が 41.8 〜 65.7 ％で、CaSO４／Al２O３モル比が1.6〜４である混合セメントの刺激材であり、さらに、無機硫酸塩を含有してなる混合セメントの刺激材であり、セメントと該混合セメントの刺激材とを含有してなる混合セメント組成物である。
【０００７】
以下、本発明をさらに詳しく説明する。
【０００８】
本発明で使用する混合セメントの刺激材（以下本刺激材という）は、ＣａＯ原料、Ａｌ２Ｏ３原料、及びＣａＳＯ４原料を含有する配合物を熱処理して生成するものであり、遊離石灰、アウイン、及び無水セッコウを有効成分とする鉱物群からなる熱処理生成物であり、ＣａＯ、アウイン、及び無水セッコウを単に混合したものとは異なるものである。単に混合したものでは本発明の効果は得られない。
本刺激材の原料は純度やコストにより任意に選択されうるもので特に限定されるものではないが、例えば、ＣａＯ原料として石灰石や消石灰などのＣａＣＯ３質やＣａ（ＯＨ）２質などが、Ａｌ２Ｏ３原料としてボーキサイトやアルミ残灰などが、また、ＣａＳＯ４原料として無水セッコウ、半水セッコウ、及び二水セッコウ等が挙げられる。
各原料中に存在するＳｉＯ２、Ｆｅ２Ｏ３、ＭｇＯ、ＴｉＯ２、及びＣａＦ２等の不純物の存在は、本発明の目的を実質的に阻害しない範囲では特に限定されるものではない。
【０００９】
本発明の混合セメントの刺激材の有効成分である遊離石灰、アウイン、及び無水セッコウの成分割合は、遊離石灰１０〜７０重量％、アウイン１０〜５０重量％、及び無水セッコウ１０〜５０重量％程度の範囲にあるものが好ましい。
【００１０】
本発明における原料は、熱処理生成物中のＣａＯ／Ａｌ２Ｏ３モル比が７．５〜１８で、ＣａＳＯ４／Ａｌ２Ｏ３モル比が１．６〜４となるように配合するもので、ＣａＯ／Ａｌ２Ｏ３モル比が８〜１２で、ＣａＳＯ４／Ａｌ２Ｏ３モル比が２〜３となるように配合することが好ましい。熱処理生成物中のＣａＯ／Ａｌ２Ｏ３モル比が７．５未満、あるいは、ＣａＳＯ４／Ａｌ２Ｏ３モル比が４超では充分な中性化抑制効果が得られない場合があり、熱処理生成物中のＣａＯ／Ａｌ２Ｏ３モル比が１８超、あるいは、ＣａＳＯ４／Ａｌ２Ｏ３モル比が１．６未満では充分な初期の強度発現性が得られない場合がある。
【００１１】
本発明では、熱処理温度は特に限定されるものではないが、通常、１，１００〜１，６００℃程度が好ましい。
原料の混合方法は特に限定されるものではなく、通常の方法が可能である。
本刺激材を製造する熱処理方法としては特に限定されるものではなく、例えば、ロータリーキルンによる焼成法等がある。
【００１２】
本刺激材の粒度は、ブレーン値３，０００ｃｍ２／ｇ以上が好ましく、ブレーン値４，０００ｃｍ２／ｇ以上がより好ましく、５，０００ｃｍ２／ｇ以上が最も好ましい。本刺激材の粒度がブレーン値３，０００ｃｍ２／ｇ未満では本刺激材を用いたセメント硬化体が膨張性を呈し、充分な強度発現性や中性化抑制効果が得られない場合がある。
【００１３】
本刺激材の使用量は、セメントと本刺激材からなる結合材１００重量部中、１〜７重量部が好ましく、２〜５重量部がより好ましい。１重量部未満では使用する効果が充分でなく、７重量部を越えると本刺激材を使用したセメント硬化体が膨張性を呈し、充分な強度発現性や中性化抑制効果が得られない場合がある。
【００１４】
本発明では、本刺激材と無機硫酸塩とを併用することにより、本発明の効果をより顕著にすることが可能である。
【００１５】
本発明で使用する無機硫酸塩とは特に限定されるものではないが、例えば、無水セッコウ、半水セッコウ、及び二水セッコウ等のセッコウ類、硫酸ナトリウムや硫酸カリウムなどのアルカリ金属硫酸塩、硫酸アルミニウム、硫酸マグネシウム、及びミョウバン類等が挙げられ、本発明の効果が顕著であることから、また、経済性の面から、セッコウ類の使用が好ましく、特に、無水セッコウの使用がより好ましい。
無機硫酸塩の粒度は、通常、ブレーン値３，０００ｃｍ２／ｇ以上が好ましく、ブレーン値５，０００ｃｍ２／ｇ以上がより好ましい。３，０００ｃｍ２／ｇ未満では充分な強度発現性が得られない場合がある。
無機硫酸塩の使用量は特に限定されるものではないが、本刺激材と無機硫酸塩との混合物１００重量部中、５〜８０重量部が好ましく、１０〜６０重量部がより好ましい。５重量部未満では強度増進効果が得られない場合があり、８０重量部を越えると充分な中性化効果が得られない場合や長期耐久性が低下する場合がある。
【００１６】
また、本刺激材と無機硫酸塩との混合物の使用量は、セメントとこの混合物からなる結合材１００重量部中、１〜１０重量部が好ましく、３〜７重量部がより好ましい。１重量部未満では使用する効果が充分でなく、１０重量部超では本刺激材を使用したセメント硬化体が膨張性を呈し、充分な強度発現性や中性化抑制効果が得られない場合がある。
【００１７】
本発明では、セメントと本刺激材に、さらに、必要に応じ無機硫酸塩に、水を混合してセメント混練物を作製する。
本発明のセメント混練物を製造時に使用する混合装置としては、既存のいかなる撹拌装置も使用可能であり、例えば、傾胴ミキサー、オムニミキサー、Ｖ型ミキサー、ヘンシェルミキサー、及びナウターミキサー等が使用可能である。
また、混合方法は、それぞれの材料を施工時に混合してもよいし、あらかじめ一部を、あるいは全部を混合しておいても差し支えない。
【００１８】
本発明で使用する水の量は特に限定されるものではなく、通常の使用量、例えば、水／結合材比で２５〜１００％程度の範囲であり、３０〜６０％程度が好ましく、４０〜５０％程度がより好ましい。２５％程度未満では作業性が低下する場合があり、１００％程度超では充分な強度発現性や中性化抑制効果が得られない場合がある。
【００１９】
本発明では、本刺激材や本発明の混合セメント組成物の他に、必要に応じて、減水剤、ＡＥ剤、ＡＥ減水剤、高性能減水剤、高性能ＡＥ減水剤、凝結調整剤、セメント急硬材、砂や砂利などの骨材、水酸化カルシウム等のアルカリ性物質、並びに、炭酸カルシウム等の無機粉末等を本発明の目的を実質的に阻害しない範囲で併用することが可能である。
【００２０】
【実施例】
以下、実施例により本発明を詳細に説明する。
【００２１】
実施例１
表１に示す本刺激材が得られるように、ＣａＯ原料、Ａｌ２Ｏ３原料、及びＣａＳＯ４原料を配合し、ロータリーキルンを用い、最高温度１，４００℃の条件で熱処理して得られたクリンカーを粉砕し、ブレーン値３，５００±２００ｃｍ２／ｇに調整して表１に示す各種本刺激材を得た。
本刺激材を粉末Ｘ線回折法により同定し、遊離石灰、アウイン、及び無水セッコウを有効成分とする鉱物群から構成されていることを確認した。また、本刺激材の組成は、ＪＩＳ Ｒ ５２０２に従って、ＣａＯ、Ａｌ２Ｏ３、及びＳＯ３量を分析し、さらに、ＳＯ３量をＣａＳＯ４に換算して求めた。
各種本刺激材を、セメントαと本刺激材からなる結合材１００重量部中、３重量部配合し、結合材単位量３３０ｋｇ／ｍ３、水／結合材比５５％、細骨材率４５％としたコンクリートを調製し、圧縮強度の測定と促進中性化試験を実施した。結果を表１に併記する。
【００２２】
＜使用材料＞
CaO原料 ：電気化学工業社青海鉱山産石灰石粉末
Al２O３原料 ：アルミ残灰、日本海水化工社製
CaSO４原料 ：新秋田化成社製無水セッコウ
本刺激材ａ：CaO／Al２O３／CaSO４(モル比)＝ 4 ／１／2.5、遊離石灰 25.2 ％、アウイン 30.5 ％、及び無水セッコウ 44.2 ％
本刺激材ｂ：CaO／Al２O３／CaSO４(モル比)＝ 7.5／１／2.5、遊離石灰 42.2 ％、アウイン 23.6 ％、及び無水セッコウ 34.2 ％
本刺激材ｃ：CaO／Al２O３／CaSO４(モル比)＝ 8 ／１／2.5、遊離石灰 44.0 ％、アウイン 22.9 ％、及び無水セッコウ 33.1 ％
本刺激材ｄ：CaO／Al２O３／CaSO４(モル比)＝10 ／１／2.5、遊離石灰 50.3 ％、アウイン 20.3 ％、及び無水セッコウ 29.4 ％
本刺激材ｅ：CaO／Al２O３／CaSO４(モル比)＝12 ／１／2.5、遊離石灰 55.3 ％、アウイン 18.3 ％、及び無水セッコウ 26.5 ％
本刺激材ｆ：CaO／Al２O３／CaSO４(モル比)＝18 ／１／2.5、遊離石灰 65.7 ％、アウイン 14.0 ％、及び無水セッコウ 20.3 ％
本刺激材ｇ：CaO／Al２O３／CaSO４(モル比)＝20 ／１／2.5、遊離石灰 68.1 ％、アウイン 13.0 ％、及び無水セッコウ 18.9 ％
本刺激材ｈ：CaO／Al２O３／CaSO４(モル比)＝10 ／１／1 、遊離石灰 63.2 ％、アウイン 25.5 ％、及び無水セッコウ 11.4 ％
本刺激材ｊ：CaO／Al２O３／CaSO４(モル比)＝10 ／１／1.6、遊離石灰 57.3 ％、アウイン 23.1 ％、及び無水セッコウ 19.6 ％
本刺激材ｋ：CaO／Al２O３／CaSO４(モル比)＝10 ／１／2 、遊離石灰 51.5 ％、アウイン 20.8 ％、及び無水セッコウ 27.8 ％
本刺激材ｌ：CaO／Al２O３／CaSO４(モル比)＝10 ／１／3 、遊離石灰 47.1 ％、アウイン 19.0 ％、及び無水セッコウ 33.9 ％
本刺激材ｍ：CaO／Al２O３／CaSO４(モル比)＝10 ／１／4 、遊離石灰 41.8 ％、アウイン 16.9 ％、及び無水セッコウ 41.3 ％
本刺激材ｎ：CaO／Al２O３／CaSO４(モル比)＝10 ／１／5 、遊離石灰 37.6 ％、アウイン 15.2 ％、及び無水セッコウ 47.3 ％
セメントα：電気化学工業社製高炉セメントＢ種
細骨材 ：新潟県姫川産、比重2.63
粗骨材 ：新潟県姫川産、比重2.67、Ｇmax＝20mm
水 ：水道水
【００２３】
＜測定方法＞
圧縮強度 ：１０φ×２０ｃｍの供試体を作製し、ＪＩＳ Ａ １１０８に準じて測定
促進中性化試験：１０φ×２０ｃｍの供試体を作製し、７日間２０℃の水中養生後、３０℃湿度６０％、炭酸ガス濃度７％の環境試験室内で３ヵ月養生し、供試体内部への中性化深さを供試体断面にフェノールフタレインを塗布し測定
【００２４】
【表１】
実施例２
本刺激材ｄを、結合材１００重量部中、表２に示すように配合したこと以外は実施例１と同様に行った。結果を表２に併記する。
【００２６】
【表２】
実施例３
セメント９７重量部と本刺激材ｄ３重量部とを配合し、セメントの種類を表３に示すようにしたこと以外は実施例１と同様に行った。結果を表３に併記する。
【００２８】
＜使用材料＞
セメントβ：秩父小野田セメント社製フライアッシュセメントＢ種
【００２９】
【表３】
実施例４
セメントα、本刺激材ｄ、及び本刺激材ｄと無機硫酸塩からなる混合物１００重量部中、表４に示す量の無機硫酸塩を使用し、該混合物を、セメントαと混合物からなる結合材１００重量部中、５重量部配合し、単位結合材量３８０ｋｇ／ｍ３、水／結合材比５０％、及び細骨材率４５％としたコンクリートを調製したこと以外は実施例１と同様に行った。結果を表４に併記する。
【００３１】
＜使用材料＞
無機硫酸塩：天然無水セッコウ、ブレーン値５，５３０ｃｍ２／ｇ
【００３２】
【表４】
実施例５
セメントαと本刺激材ｄを使用し、本刺激材ｄと無機硫酸塩からなる混合物１００重量部中、無機硫酸塩を３０重量部使用し、セメントαと混合物材からなる結合材１００重量部中の混合物の使用量を表５に示すように配合したこと以外は実施例４と同様に行った。結果を表５に併記する。
【００３４】
【表５】
実施例６
セメントを変えたこと以外は実施例５と同様に行った。結果を表６に示す。
【００３６】
【表６】
【発明の効果】
本発明の混合セメントの刺激材を使用することにより、初期の強度発現性が良好となり、しかも、中性化抑制効果が大である混合セメント組成物とすることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention mainly relates to a mixed cement stimulant used in the civil engineering and construction industries and a mixed cement composition using the same.
[0002]
[Prior art and its problems]
In recent years, the environmental protection problem of the earth has been greatly highlighted, and various attempts have been considered in the field of cement in connection with environmental protection.For example, carbon dioxide gas exhausted during the manufacturing process of cement clinker warms the earth. It has been considered a problem that it causes the natural environment to be largely unbalanced.
[0003]
In view of such problems, in the cement field, attention has been paid to mixed cement in which industrial wastes such as blast furnace slag, fly ash, and silica fume are mixed because the amount of cement clinker to be manufactured can be suppressed.
Industrial wastes such as blast furnace slag, fly ash, and silica fume have latent hydraulic properties and react with calcium hydroxide generated during the hydration process of cement to produce strength and densify hardened cement. It is known to contribute.
Here, the hardened cement is a general term for hardened cement paste, mortar, or concrete.
However, compared to ordinary Portland cement, the mixed cement containing these latent hydraulic substances has a problem that the initial strength development is poor and the carbonation reaction is extremely fast because the hardened cementitious structure is difficult to densify. there were.
[0004]
In order to solve such a problem of the mixed cement, a method has been proposed to increase the strength of blast furnace cement B type by using an early-strength Portland cement which generates a large amount of calcium hydroxide as a stimulating material (Yasunaga, Nakamura, Hoezaki) Proceedings of the 49th Cement Technology Conference, pp. 108-113, 1995).
However, in this method, the effect of strength development and the effect of densification of the cement hardened body are not sufficient, and the content of the blast furnace slag can be increased only up to about 50% by weight, so that the amount of cement clinker is reduced. However, when the content exceeds 55% by weight, there is a problem that strength developability is reduced.
[0005]
The present inventor has made intensive efforts to solve these problems, and as a result, by using a stimulant of a specific mixed cement, not only the initial strength developability is improved, but also the cement hardened body The present inventors have found that the structure of the above can be densified and the carbonation reaction can be remarkably suppressed, thereby completing the present invention.
[0006]
[Means for Solving the Problems]
That is, the present invention is produced by heat-treating a composition containing a CaO raw material, an Al 2 O 3 raw material, and a CaSO 4 raw material, and is composed of a mineral group containing free lime, auwin, and anhydrous gypsum as active ingredients. A stimulant for a mixed cement having a free lime content of 41.8 to 65.7 % and a CaSO 4 / Al 2 O 3 molar ratio of 1.6 to 4 ; and a stimulant for a mixed cement containing inorganic sulfate. , A mixed cement composition comprising cement and a stimulant for the mixed cement.
[0007]
Hereinafter, the present invention will be described in more detail.
[0008]
The stimulant for the mixed cement used in the present invention (hereinafter referred to as the present stimulant) is produced by heat-treating a compound containing a CaO raw material, an Al 2 O 3 raw material, and a CaSO 4 raw material. It is a heat-treated product consisting of a mineral group containing hauin and anhydrous gypsum as an active ingredient, and is different from a mixture obtained by simply mixing CaO, hauin and anhydrous gypsum. The effect of the present invention cannot be obtained with a simple mixture.
The raw material of the present stimulating material can be arbitrarily selected according to the purity and cost, and is not particularly limited. For example, as a CaO raw material, CaCO 3 material such as limestone or slaked lime, or Ca (OH) 2 material, Bauxite and residual aluminum ash are used as the 2 O 3 raw material, and anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum are used as the CaSO 4 raw material.
The presence of impurities such as SiO 2 , Fe 2 O 3 , MgO, TiO 2 and CaF 2 present in each raw material is not particularly limited as long as the object of the present invention is not substantially impaired.
[0009]
The proportions of free lime, eauin and anhydrous gypsum, which are active ingredients of the stimulant of the mixed cement of the present invention, are about 10 to 70% by weight of free lime, 10 to 50% by weight of eauin and 10 to 50% by weight of anhydrous gypsum. Are preferred.
[0010]
Raw material in the present invention is a CaO / Al 2 O 3 molar ratio in the heat treatment product is from 7.5 to 18, in which CaSO 4 / Al 2 O 3 molar ratio is formulated to be 1.6 to 4 , CaO / Al 2 O 3 molar ratio is preferably 8 to 12, and CaSO 4 / Al 2 O 3 molar ratio is preferably 2 to 3 . If the molar ratio of CaO / Al 2 O 3 in the heat-treated product is less than 7.5, or if the molar ratio of CaSO 4 / Al 2 O 3 is more than 4, a sufficient neutralization suppressing effect may not be obtained. If the CaO / Al 2 O 3 molar ratio in the product exceeds 18 or the CaSO 4 / Al 2 O 3 molar ratio is less than 1.6, sufficient initial strength development may not be obtained.
[0011]
In the present invention, the heat treatment temperature is not particularly limited, but is usually preferably about 1,100 to 1,600 ° C.
The method of mixing the raw materials is not particularly limited, and an ordinary method can be used.
The heat treatment method for producing the present stimulating material is not particularly limited, and includes, for example, a firing method using a rotary kiln.
[0012]
The particle size of the stimulus material is preferably more than Blaine 3,000 cm 2 / g, more preferably at least Blaine value 4,000cm 2 / g, 5,000cm 2 / g or more is most preferred. If the particle size of the present stimulating material is less than 3,000 cm 2 / g, the cured cement body using the present stimulating material may exhibit swelling properties, and may not be able to obtain sufficient strength development and neutralization suppressing effect.
[0013]
The amount of the stimulant used is preferably 1 to 7 parts by weight, more preferably 2 to 5 parts by weight, per 100 parts by weight of the binder composed of cement and the stimulant. When the amount is less than 1 part by weight, the effect of use is not sufficient, and when the amount exceeds 7 parts by weight, the cured cement using the present stimulant exhibits expandability, and sufficient strength expression and neutralization suppressing effect cannot be obtained. There is.
[0014]
In the present invention, by using the present stimulant and an inorganic sulfate together, it is possible to make the effect of the present invention more remarkable.
[0015]
The inorganic sulfate used in the present invention is not particularly limited. For example, anhydrous gypsum, gypsum such as hemihydrate gypsum, and gypsum such as dihydrate, alkali metal sulfate such as sodium sulfate and potassium sulfate, and sulfuric acid Aluminum, magnesium sulfate, alum, and the like can be mentioned, and from the viewpoint of remarkable effects of the present invention and from the viewpoint of economy, use of gypsum is preferable, and particularly, use of anhydrous gypsum is more preferable.
Usually, the particle size of the inorganic sulfate is preferably not less than 3,000 cm 2 / g, more preferably not less than 5,000 cm 2 / g. If it is less than 3,000 cm 2 / g, sufficient strength development may not be obtained.
The amount of the inorganic sulfate used is not particularly limited, but is preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, per 100 parts by weight of the mixture of the present stimulant and the inorganic sulfate. If the amount is less than 5 parts by weight, the strength increasing effect may not be obtained, and if it exceeds 80 parts by weight, a sufficient neutralizing effect may not be obtained or the long-term durability may be reduced.
[0016]
The amount of the mixture of the present stimulant and the inorganic sulfate is preferably 1 to 10 parts by weight, more preferably 3 to 7 parts by weight, based on 100 parts by weight of the cement and the binder comprising the mixture. If the amount is less than 1 part by weight, the effect to be used is not sufficient, and if the amount is more than 10 parts by weight, the cement hardened body using the present stimulant exhibits swelling properties, so that sufficient strength development and neutralization suppressing effect may not be obtained. is there.
[0017]
In the present invention, a cement kneaded product is produced by mixing water with cement and the present stimulant and, if necessary, inorganic sulfate.
As the mixing device used for producing the cement kneaded material of the present invention, any existing stirring device can be used, for example, a tilting mixer, an omni mixer, a V-type mixer, a Henschel mixer, a Nauter mixer, etc. are used. It is possible.
Further, in the mixing method, the respective materials may be mixed at the time of construction, or a part or all of them may be mixed in advance.
[0018]
The amount of water used in the present invention is not particularly limited, and is usually used, for example, in a range of about 25 to 100% by water / binder ratio, preferably about 30 to 60%, and more preferably about 40 to 60%. About 50% is more preferable. If it is less than about 25%, the workability may be reduced, and if it is more than about 100%, a sufficient strength developing property and a neutralization suppressing effect may not be obtained.
[0019]
In the present invention, in addition to the stimulant and the mixed cement composition of the present invention, if necessary, a water reducing agent, an AE agent, an AE water reducing agent, a high-performance water reducing agent, a high-performance AE water reducing agent, a setting modifier, a cement A hardened material, an aggregate such as sand or gravel, an alkaline substance such as calcium hydroxide, an inorganic powder such as calcium carbonate, and the like can be used in combination within a range that does not substantially impair the object of the present invention.
[0020]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples.
[0021]
Example 1
A clinker obtained by blending a CaO raw material, an Al 2 O 3 raw material, and a CaSO 4 raw material so as to obtain the present stimulant shown in Table 1, and heat-treating the mixture at a maximum temperature of 1,400 ° C. using a rotary kiln. Was crushed and adjusted to a Blaine value of 3,500 ± 200 cm 2 / g to obtain various stimulants shown in Table 1.
The stimulant was identified by a powder X-ray diffraction method, and it was confirmed that the stimulant was composed of a mineral group containing free lime, eauin, and anhydrous gypsum as active ingredients. Further, the composition of the present stimulant was determined by analyzing the amounts of CaO, Al 2 O 3 , and SO 3 according to JIS R5202, and further converting the amount of SO 3 into CaSO 4 .
3 parts by weight of various stimulants were mixed with 100 parts by weight of a binder composed of cement α and the stimulants, a binder unit amount of 330 kg / m 3 , a water / binder ratio of 55%, and a fine aggregate ratio of 45% Concrete was prepared, and the compressive strength was measured and accelerated neutralization test was performed. The results are also shown in Table 1.
[0022]
<Material used>
CaO raw material: Limestone powder from Aomi mine, Denki Kagaku Kogyosha
Al 2 O 3 raw material: Aluminum residual ash, manufactured by Nihon Kaisui Kako
CaSO 4 raw material: Shin-Akita Kasei Co., Ltd. anhydrous gypsum main stimulant a: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 4/1 / 2.5 , free lime 25.2 %, auyne 30.5 %, and anhydrous gypsum 44.2 %
The present stimulant b: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 7.5 / 1 / 2.5 , free lime 42.2 %, auyne 23.6 %, and anhydrous gypsum 34.2 %
The present stimulant c: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 8/1 / 2.5 , free lime 44.0 %, auyne 22.9 %, and anhydrous gypsum 33.1 %
The present stimulant d: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 10/1 / 2.5 , free lime 50.3 %, auyne 20.3 %, and anhydrous gypsum 29.4 %
The present stimulant e: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 12/1 / 2.5 , free lime 55.3 %, auyne 18.3 %, and anhydrous gypsum 26.5 %
The present stimulant f: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 18/1 / 2.5 , free lime 65.7 %, auyne 14.0 %, and anhydrous gypsum 20.3 %
This stimulant g: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 20/1 / 2.5 , free lime 68.1 %, auyne 13.0 %, and anhydrous gypsum 18.9 %
The present stimulant h: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 10/1/1 , free lime 63.2 %, auyne 25.5 %, and anhydrous gypsum 11.4 %
The present stimulant j: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 10/1 / 1.6 , free lime 57.3 %, auyne 23.1 %, and anhydrous gypsum 19.6 %
The present stimulant k: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 10/1/2 , free lime 51.5 %, auyne 20.8 %, and anhydrous gypsum 27.8 %
This stimulant 1: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 10/1/3 , free lime 47.1 %, auyne 19.0 %, and anhydrous gypsum 33.9 %
The present stimulant m: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 10/1/4 , free lime 41.8 %, auyne 16.9 %, and anhydrous gypsum 41.3 %
This stimulant n: CaO / Al 2 O 3 / CaSO 4 (molar ratio) = 10/1/5 , free lime 37.6 %, auyne 15.2 %, and anhydrous gypsum 47.3 %
Cement α: Blast furnace cement B fine aggregate made by Denki Kagaku Kogyo Co., Ltd .: Specific gravity 2.63 from Himekawa, Niigata
Coarse aggregate: from Himekawa, Niigata, specific gravity 2.67, Gmax = 20mm
Water: tap water [0023]
<Measurement method>
Compressive strength: A specimen of 10φ × 20cm was prepared, and a measurement-promoted neutralization test according to JIS A 1108: A specimen of 10φ × 20cm was prepared. After curing in water at 20 ° C for 7 days, 30% humidity of 60% After curing for 3 months in an environmental test chamber with a carbon dioxide concentration of 7%, the depth of neutralization inside the specimen is measured by applying phenolphthalein to the cross section of the specimen.
[Table 1]
Example 2
The procedure was performed in the same manner as in Example 1 except that the stimulant d was blended as shown in Table 2 in 100 parts by weight of the binder. The results are also shown in Table 2.
[0026]
[Table 2]
Example 3
The procedure was performed in the same manner as in Example 1 except that 97 parts by weight of cement and 3 parts by weight of the present stimulant d were mixed and the types of cement were as shown in Table 3. The results are also shown in Table 3.
[0028]
<Material used>
Cement β: Fly ash cement type B manufactured by Chichibu Onoda Cement Co. [0029]
[Table 3]
Example 4
In the cement α, the present stimulant d, and 100 parts by weight of a mixture of the present stimulant d and inorganic sulfate, the amount of the inorganic sulfate shown in Table 4 was used, and the mixture was mixed with the cement α and the binder. Same as Example 1 except that 5 parts by weight of 100 parts by weight was mixed to prepare a concrete having a unit binder amount of 380 kg / m 3 , a water / binder ratio of 50%, and a fine aggregate ratio of 45%. went. The results are shown in Table 4.
[0031]
<Material used>
Inorganic sulfate: natural anhydrous gypsum, Blaine value 5,530 cm 2 / g
[0032]
[Table 4]
Example 5
Using cement α and the present stimulant d, in 100 parts by weight of a mixture comprising the present stimulant d and inorganic sulfate, using 30 parts by weight of inorganic sulfate, and in 100 parts by weight of a binder comprising the cement α and the mixture material Example 4 was carried out in the same manner as in Example 4 except that the amount of the mixture was mixed as shown in Table 5. The results are also shown in Table 5.
[0034]
[Table 5]
Example 6
The same operation as in Example 5 was performed except that the cement was changed. Table 6 shows the results.
[0036]
[Table 6]
【The invention's effect】
By using the stimulant for the mixed cement of the present invention, the initial cement strength can be improved and a mixed cement composition having a large neutralization suppressing effect can be obtained.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20946495A JP3549635B2 (en) | 1995-08-17 | 1995-08-17 | Stimulant for mixed cement and mixed cement composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20946495A JP3549635B2 (en) | 1995-08-17 | 1995-08-17 | Stimulant for mixed cement and mixed cement composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0952748A JPH0952748A (en) | 1997-02-25 |
| JP3549635B2 true JP3549635B2 (en) | 2004-08-04 |
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| JP20946495A Expired - Fee Related JP3549635B2 (en) | 1995-08-17 | 1995-08-17 | Stimulant for mixed cement and mixed cement composition |
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| JP3747988B2 (en) * | 1998-04-23 | 2006-02-22 | 電気化学工業株式会社 | Expandable material composition and expanded cement composition |
| JP4816451B2 (en) * | 2006-12-28 | 2011-11-16 | 宇部興産株式会社 | Concrete admixture, concrete composition, and hardened concrete |
| EP2767521B1 (en) * | 2011-10-13 | 2018-02-28 | Denka Company Limited | Method for manufacturing rapid-hardening agent and concrete product |
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| JPH0952748A (en) | 1997-02-25 |
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