JP3871601B2 - Fine aggregate for cement concrete, cement composition, and cement concrete using the same - Google Patents
Fine aggregate for cement concrete, cement composition, and cement concrete using the same Download PDFInfo
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- JP3871601B2 JP3871601B2 JP2002108855A JP2002108855A JP3871601B2 JP 3871601 B2 JP3871601 B2 JP 3871601B2 JP 2002108855 A JP2002108855 A JP 2002108855A JP 2002108855 A JP2002108855 A JP 2002108855A JP 3871601 B2 JP3871601 B2 JP 3871601B2
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- cement
- slag
- cement concrete
- concrete
- sulfur
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- 239000004568 cement Substances 0.000 title claims description 49
- 239000004567 concrete Substances 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 title claims description 8
- 239000002893 slag Substances 0.000 claims description 57
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 23
- YALHCTUQSQRCSX-UHFFFAOYSA-N sulfane sulfuric acid Chemical compound S.OS(O)(=O)=O YALHCTUQSQRCSX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004017 vitrification Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 5
- 238000010583 slow cooling Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000003638 chemical reducing agent Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- -1 sulfur ions Chemical class 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000011372 high-strength concrete Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910001719 melilite Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001720 Åkermanite Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- PDMKBIZYOLJQFE-UHFFFAOYSA-N S.OS(O)(=O)=S Chemical compound S.OS(O)(=O)=S PDMKBIZYOLJQFE-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- FGZBFIYFJUAETR-UHFFFAOYSA-N calcium;magnesium;silicate Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])([O-])[O-] FGZBFIYFJUAETR-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-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
- 229910052907 leucite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- 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セメントコンクリート用細骨材、セメント組成物、及びそれを用いたセメントコンクリートに関する。
なお、本発明における部や%は特に規定しない限り質量基準で示す。
また、本発明でいうセメントコンクリートとはモルタルとコンクリートを総称するものである。
【0002】
【従来の技術と課題】
製鉄所から副生される高炉スラグには大別して高炉水砕スラグと高炉徐冷スラグが存在する。
高炉水砕スラグは潜在水硬性を示し、セメントクリンカーに多量混和しても長期強度は低下しないという優れた特性を有していることから、高強度コンクリートや高流動コンクリートなど様々な分野での研究がなされている(安戸賢一他、「高炉スラグ微粉末の高強度コンクリートへの適用性について」、第45回セメント技術大会講演集、pp.184-189、1991など参照)。
【0003】
一方、高炉徐冷スラグは別名結晶化スラグとも呼ばれ水硬性を示さない。そのため、主に路盤材として利用されてきたが、最近では再生骨材が路盤材へ優先的に利用されるようになり、従来の用途を失いつつある。このため、その有効利用方法については未だに模索状態にある(依田彰彦、「高炉スラグのセメント・コンクリートへの利用」、無機マテリアル、Vol.6、pp.62-67、1999、「再生資源の利用促進に関する法律、いわゆるリサイクル法」、平成3年10月)。
【0004】
本発明者は、すでに高炉徐冷スラグの粉末がブリーディングや中性化抑制機能を有することを見出し、さらに、高流動コンクリートに適用すると、材料分離抵抗性や流動性の保持性能に優れ、自己収縮が小さく、かつ、水和発熱の小さい高流動コンクリートとすることができ、低環境負荷型のコンクリートを調製できることを提案した(特願2000-077683号)。
しかしながら、コンクリート全体に占める高流動コンクリートの割合は少ないこと、また、高流動コンクリートに必要な材料分離抵抗性を付与するためには微粉末である必要があることなどから、処理できる徐冷スラグの量が限定されるという課題があった。
【0005】
本発明者は、高炉徐冷スラグの有効利用についてさらに種々検討を重ねた結果、特定の高炉徐冷スラグを細骨材としてセメントコンクリートに用いることにより、セメントコンクリートの流動性の保持性能が向上することを知見し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、粒子径が0.1 〜5 mmで、非硫酸態イオウとして存在するイオウが0.3%以上である高炉徐冷スラグを含有してなるセメントコンクリート用細骨材であり、高炉徐冷スラグのガラス化率が30%以下である該セメントコンクリート用細骨材であり、骨材のふるい通過率が、呼び寸法4.75mmで100%、2.36mmで95〜100%、1.18mmで80〜100%、0.6mmで35〜80%、0.3mmで15〜50%、及び0.15mmで2〜20%である該セメントコンクリート用細骨材であり、FMが2.26未満である該セメントコンクリート用細骨材であり、セメントと該セメントコンクリート用細骨材とを含有してなるセメント組成物であり、該セメント組成物を用いてなるセメントコンクリートである。
【0007】
本発明で使用する高炉徐冷スラグ(以下、本スラグという)は、徐冷されて結晶化した高炉スラグの粉末である。
本スラグの成分は、高炉水砕スラグと同様の組成を有しており、具体的にはSiO2、CaO、Al2O3、及びMgOなどを主要な化学成分とし、その他の成分として、TiO2、MnO、Na2O、S、P2O5、及びFe2O3などが挙げられる。
また、化合物としては、ゲーレナイト2CaO・Al2O3・SiO2とアケルマナイト2CaO・MgO・2SiO2の混晶である、いわゆる、メリライトを主成分とし、その他、ダイカルシウムシリケート2CaO・SiO2、ランキナイト3CaO・2SiO2、及びワラストナイトCaO・SiO2などのカルシウムシリケート、メルビナイト3CaO・MgO・2SiO2やモンチセライトCaO・MgO・SiO2などのカルシウムマグネシウムシリケート、アノーサイトCaO・Al2O3・2SiO2、リューサイト(K2O、Na2O)・Al2O3・SiO2、スピネルMgO・Al2O3、マグネタイトFe3O4、さらに、硫化カルシウムCaSや硫化鉄FeSなどの硫化物等を含む場合がある。
【0008】
本スラグの粒子径は0.1 〜5 mm であり、 0.3 〜 4.0mm が好ましい。 0.1mm 未満では練り混ぜたセメントコンクリートの粘性が増加し、良好な流動性を示さない場合があり、5mmを超えると細骨材としての機能が得られず、練り混ぜたセメントコンクリートがペースト部分と分離しやすくなり、耐久性が低下する場合がある。
【0009】
本スラグの非硫酸態イオウの含有量は、0.3 %以上であり、0.5%以上が好ましい。0.5%未満では、所定の流動性の保持性能が得られない場合がある。
非硫酸態イオウ量は、全イオウ量、単体イオウ量、硫化物態イオウ量、チオ硫酸態イオウ量、及び硫酸態イオウ(三酸化イオウ)量を山口と小野の方法で定量することによって、また、硫酸態イオウ量(三酸化イオウ)と硫化物態イオウ量については、JIS R 5202に定められた方法で定量することによっても求めることができる(「高炉スラグ中硫黄の状態分析」、山口直治、小野昭紘:製鉄研究、第301号、pp.37-40、1980参照)。
本徐冷スラグは、非硫酸態イオウを含有することにより、長期にわたる流動性の保持性能を発揮するものであるが、単に、非硫酸態イオウを含まないスラグに、多硫化物、硫化物、チオ硫酸塩、及び亜硫酸塩等を添加したのでは、本発明の持続性に優れた流動性の保持性能は得られない。
【0010】
本スラグのガラス化率は、30%以下が好ましく、10%以下がより好ましい。この範囲外では所定の流動性の保持性能が得られない場合がある。ガラス化率が高い場合、ほぼ同量の非硫酸態イオウを含有していても、結晶質である徐冷スラグに比して、チオ硫酸イオウなどの溶出が極めて少なく、流動性の保持性能が期待できない。
本発明でいうガラス化率(X)は、X(%)=(1−S/S0)×100として求められる。ここで、Sは粉末X線回折法により求められる本スラグ中の主要な結晶性化合物であるメリライト(ゲーレナイト2CaO・Al2O3・SiO2とアケルマナイト2CaO・MgO・2SiO2の混晶)のメインピークの面積であり、S0は本スラグを1,000℃で3時間加熱し、その後、5℃/分の冷却速度で冷却したもののメリライトのメインピークの面積を表す。
【0011】
また、本スラグから溶出する非硫酸態イオウイオン濃度(以下、溶解性イオウ濃度という)は20mg/l以上が好ましい。溶解性イオウ濃度がこの範囲にないと、所定のコンクリートの流動性の保持性能が得られない場合がある。
溶解性イオウ濃度としては、イオウイオン(S2-)、多硫化物イオン(Sn2-,n≧2)、チオ硫酸イオン(S2O3 2-)、亜硫酸イオン(SO3 2-)、及び硫酸イオン(SO4 2-)などが挙げられる。
本発明でいう溶解性イオウ濃度とは、本スラグ20gを20℃の水100ml中に入れ、30分間攪拌した後、固液分離した液相中に含まれる非硫酸態イオウイオンの濃度をいう。
これらイオウ濃度はIPC発光分析法やイオンクロマトグラフィ−によって定量することができる。
【0012】
本発明のセメントコンクリート用細骨材(以下、本骨材という)のふるい通過率は、呼び寸法4.75mmで100%、2.36mmで95〜100%、1.18mmで80〜100%、0.6mmで35〜80%、0.3mmで15〜50%、及び0.15mmで2〜20%であることが好ましい。本骨材の粒度がこの範囲外では、セメントコンクリートの流動性が低下したり、材料分離が生じ、セメントコンクリート構造物の耐久性が低下する場合がある。
なお、ふるい通過率の測定に使用するふるいの呼び寸法は、それぞれJIS Z 8801に規定する網ふるいの呼び寸法4.75mm、2.36mm、1.18mm、600μm、300μm、及び150μmである。
【0013】
本骨材は、特定の徐冷スラグを含有してなるものである。
本骨材の使用量は特に限定されるものではないが、通常、セメント100部に対して、100〜400部が好ましく、150〜300部がより好ましい。この範囲外ではセメントコンクリートの流動性が低下する場合がある。
【0014】
本発明で使用するセメントとしては、普通、早強、超早強、低熱、及び中庸熱等の各種ポルトランドセメント、これらポルトランドセメントに、高炉水砕スラグ、フライアッシュ、又はシリカを混合した各種混合セメント、並びに、石灰石微粉末を混合したフィラーセメントなどが挙げられ、これらのうちの一種又は二種以上が使用可能である。
【0015】
本発明のセメント組成物は、セメントと本骨材とを含有してなるものである。
【0016】
本骨材は、他の材料と施工時に混合しても良いし、あらかじめ一部あるいは全部を混合しておいても差し支えない。
【0017】
本発明のセメントコンクリートには汎用の減水剤、AE減水剤、高性能減水剤、及び高性能AE減水剤等の減水剤を用いて高流動化することが好ましい。
減水剤は液状や粉末状のいずれも使用可能である。
減水剤はナフタレン系、メラミン系、アミノスルホン酸系、及びポリカルボン酸系に大別される。
減水剤の使用量は、各メーカーの指定する範囲内であればよく、特に限定されるものではないが、通常、セメント100部に対して、0.5〜3.0部が好ましい。0.5部未満では使用効果のない場合があり、3.0部を超えると材料分離などを引き起こす場合がある。
【0018】
本発明において、水の使用量は特に限定されるものではないが、通常、セメント100部に対して、30〜60部が好ましく、40〜50部がより好ましい。30部未満では流動性が大幅に低下し、ジャンカなどの欠陥が生じる場合があり、60部を超えると材料分離等を引き起こす場合がある。
【0019】
本発明では、セメント、本骨材、及び減水剤のほかに、従来、セメントコンクリートで用いられてきた高炉水砕スラグ微粉末、高炉徐冷スラグ微粉末、石灰石微粉末、フライアッシュ、及びシリカフュームなどの混和材料、消泡剤、増粘剤、防錆剤、防凍剤、収縮低減剤、高分子エマルジョン、凝結調整剤、ベントナイトなどの粘土鉱物、並びに、ハイドロタルサイトなどのアニオン交換体等のうちの一種又は二種以上を、本発明の目的を実質的に阻害しない範囲で使用することが可能である。
【0020】
本発明において、各材料の混合方法は特に限定されるものではなく、それぞれの材料を施工時に混合しても良いし、あらかじめ一部あるいは全部を混合しておいても差しつかえない。
混合装置としては、既存のいかなる装置も使用可能であり、例えば、傾動ミキサ、オムニミキサ、ヘンシェルミキサ、V型ミキサ、及びナウタミキサなどの使用が可能である。
【0021】
【実施例】
以下、本発明の実験例に基づいてさらに詳細に説明する。
【0022】
実施例1
セメント/砂=1/3、水セメント比50%、本骨材のふるい通過率を、呼び寸法4.75mmで100%、2.36mmで97%、1.18mmで90%、0.6mmで50%、0.3mmで35%、及び0.15mmで10%に固定し、表1に示す、本スラグを含むスラグを用いモルタルを調製し、モルタルフローの経時変化をみるためにテーブルフローを測定した。結果を表1に併記する。
なお、比較のため、ケイ砂Aを使用した場合も同様に実験した。結果を表1に併記する。
【0023】
<使用材料>
スラグa :本スラグ、ガラス化率5%、非硫酸態イオウ0.9%、溶解性イオウ濃度90mg/l、密度3.00g/cm3
スラグb :本スラグ、ガラス化率5%、非硫酸態イオウ0.7%、溶解性イオウ濃度77mg/l、密度3.00g/cm3
スラグc :本スラグ、ガラス化率5%、非硫酸態イオウ0.5%、溶解性イオウ濃度53mg/l、密度3.00g/cm3
スラグd :本スラグ、ガラス化率5%、非硫酸態イオウ0.3%、溶解性イオウ濃度28mg/l、密度3.00g/cm3
スラグe :本スラグ、ガラス化率5%、非硫酸態イオウ0.1%、溶解性イオウ濃度12mg/l、密度3.00g/cm3
スラグf :本スラグ、ガラス化率10%、非硫酸態イオウ0.7%、溶解性イオウ濃度65mg/l、密度2.97g/cm3
スラグg :本スラグ、ガラス化率30%、非硫酸態イオウ0.5%、溶解性イオウ濃度47mg/l、密度2.94g/cm3
スラグh :高炉水砕スラグ、ガラス化率95%、非硫酸態イオウ0.9%、溶解性イオウ濃度2mg/l、密度2.90g/cm3
セメント :普通ポルトランドセメント、電気化学工業社製、密度3.15g/cm3
ケイ砂A :JIS標準砂
水 :水道水
【0024】
<測定方法>
骨材のふるい通過率:JIS A1102 骨材のふるい分け試験方法に準拠
テーブルフロー:練り混ぜ直後、30分後、60分後、及び90分後にJIS R 5201に準拠して測定。
【0025】
【表1】
【0026】
実施例2
スラグaを使用し、表2に示すふるい通過率の本骨材を用いたこと以外は実験例1と同様に行った。
【0027】
【表2】
【0028】
実施例3
ふるい通過率が呼び寸法4.75mmで100%、2.36mmで97%、1.18mmで90%、0.6mmで50%、0.3mmで35%、及び0.15mmで10%のスラグaを細骨材として用い、単位セメント量336kg/m3、単位水量180kg/m3、単位細骨材量757kg/m3、単位粗骨材量989kg/m3、及び空気量4.5±1.5%のコンクリートを調製し、スランプの経時変化をみるためにスランプを測定した。結果を表3に示す。
また、比較例として、同様のふるい通過率を持つスラグhとケイ砂Bを細骨材として用いて同様に実験した。結果を表3に併記する。
なお、練り上がりのスランプはAE減水剤により18cmに調整した。
【0029】
<使用材料>
ケイ砂B :新潟県姫川産川砂、粒度調整品
粗骨材 :新潟県姫川産砂利
AE減水剤:ポリカルボン酸系AE減水剤、市販品
【0030】
<測定方法>
スランプ:JIS A 1101に準拠
【0031】
【表3】
【0032】
【発明の効果】
本発明のセメントコンクリート用細骨材を用いることにより、流動性の保持性能が良好なモルタルやコンクリートを提供することが可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention mainly relates to a fine aggregate for cement concrete used in the civil engineering and construction industry, a cement composition, and cement concrete using the same.
In the present invention, “parts” and “%” are based on mass unless otherwise specified.
In addition, the cement concrete referred to in the present invention is a general term for mortar and concrete.
[0002]
[Prior art and issues]
Blast furnace slag produced as a by-product from steelworks is roughly classified into blast furnace granulated slag and blast furnace slow-cooled slag.
Since granulated blast furnace slag has latent hydraulic properties and has excellent properties that long-term strength does not decrease even when mixed with a large amount of cement clinker, research in various fields such as high-strength concrete and high-fluidity concrete (See Kenichi Yado et al., “Applicability of blast furnace slag fine powder to high-strength concrete”, Proc. 45th Cement Technology Conference, pp.184-189, 1991).
[0003]
On the other hand, blast furnace slow-cooled slag is also called crystallization slag and does not show hydraulic properties. For this reason, it has been mainly used as a roadbed material, but recently, recycled aggregate has been preferentially used as a roadbed material and is losing its conventional use. For this reason, there is still a search for effective use (Akihiko Yoda, “Use of Blast Furnace Slag for Cement and Concrete”, Inorganic Materials, Vol. 6, pp. 62-67, 1999, “Use of Recycled Resources” Law on promotion, so-called recycling law ", October 1991).
[0004]
The present inventor has already found that the powder of blast furnace chilled slag has a function of suppressing bleeding and neutralization, and when applied to high-fluidity concrete, it has excellent material separation resistance and fluidity retention performance, and is self-shrinking. It was proposed that high-fluidity concrete with small hydration heat generation and low environmental load type concrete can be prepared (Japanese Patent Application No. 2000-077683).
However, since the proportion of high-fluidity concrete in the whole concrete is small, and because it needs to be fine powder to give the material separation resistance necessary for high-fluidity concrete, it is necessary to treat slowly cooled slag that can be processed. There was a problem that the amount was limited.
[0005]
As a result of further various studies on effective utilization of the blast furnace slow cooling slag, the present inventor improves the fluidity retention performance of cement concrete by using a specific blast furnace slow cooling slag as a fine aggregate in cement concrete. As a result, the present invention has been completed.
[0006]
[Means for Solving the Problems]
That is, the present invention is a fine aggregate for cement concrete comprising a blast furnace annealed slag having a particle size of 0.1 to 5 mm and sulfur present as non-sulfate sulfur of 0.3% or more. The cement concrete fine aggregate has a vitrification rate of slag of 30% or less. The aggregate sieve passing rate is 100% at a nominal size of 4.75 mm, 95 to 100% at 2.36 mm, and 80 to 80 at 1.18 mm. 100%, 35-80% at 0.6mm, 15-50% at 0.3mm, and 2-20% at 0.15mm, and fine aggregate for cement concrete with FM less than 2.26 It is an aggregate, a cement composition comprising cement and the fine aggregate for cement concrete, and cement concrete using the cement composition.
[0007]
The blast furnace slow-cooled slag used in the present invention (hereinafter referred to as the present slag) is a powder of blast furnace slag that has been cooled and crystallized.
The components of this slag have the same composition as granulated blast furnace slag, specifically, SiO 2 , CaO, Al 2 O 3 , MgO, etc. are the main chemical components, and the other components are TiO 2 2 , MnO, Na 2 O, S, P 2 O 5 , Fe 2 O 3 and the like.
In addition, as compounds, so-called melilite, which is a mixed crystal of gelenite 2CaO · Al 2 O 3 · SiO 2 and akermanite 2CaO · MgO · 2SiO 2 , other than that, dicalcium silicate 2CaO · SiO 2 , lanquinite 3CaO · 2SiO 2, and calcium silicates, such as wollastonite CaO · SiO 2, Merubinaito 3CaO · MgO · 2SiO 2 and calcium magnesium silicate, such as Monte celite CaO · MgO · SiO 2, anorthite CaO · Al 2 O 3 · 2SiO 2 , Leucite (K 2 O, Na 2 O) / Al 2 O 3 / SiO 2 , spinel MgO / Al 2 O 3 , magnetite Fe 3 O 4 , sulfides such as calcium sulfide CaS and iron sulfide FeS, etc. May be included.
[0008]
Particle size of the slag is 0.1 to 5 mm, preferably 0.3 ~ 4.0 mm. If it is less than 0.1 mm , the viscosity of the cemented concrete increases and may not show good fluidity. If it exceeds 5 mm, the function as a fine aggregate cannot be obtained. It becomes easy to separate, and durability may be reduced.
[0009]
The content of non-sulfate sulfur in the slag is 0.3 % or more, preferably 0.5% or more. If it is less than 0.5%, a predetermined fluidity retention performance may not be obtained.
The amount of non-sulfuric sulfur can be determined by quantifying the total sulfur amount, elemental sulfur amount, sulfide sulfur amount, thiosulfate sulfur amount, and sulfate sulfur (sulfur trioxide) amount by the method of Yamaguchi and Ono. The amount of sulfate sulfur (sulfur trioxide) and the amount of sulfide sulfur can also be determined by quantifying by the method specified in JIS R 5202 ("Situation analysis of sulfur in blast furnace slag", Naoji Yamaguchi (See Shogo Ono: Steel Research, No. 301, pp. 37-40, 1980).
Although this slow-cooled slag exhibits non-sulfate sulfur and exhibits long-term fluidity retention performance, the slag does not contain non-sulfate sulfur. If thiosulfate, sulfite, or the like is added, the fluidity retention performance excellent in sustainability of the present invention cannot be obtained.
[0010]
The vitrification rate of the slag is preferably 30% or less, and more preferably 10% or less. Outside this range, a predetermined fluidity holding performance may not be obtained. When the vitrification rate is high, even if it contains almost the same amount of non-sulfuric sulfur, elution of sulfur thiosulfate and the like is extremely less than that of crystalline slow-cooled slag, and fluidity retention performance is achieved. I can't expect it.
The vitrification rate (X) referred to in the present invention is determined as X (%) = (1−S / S 0 ) × 100. Here, S is the main crystalline compound in this slag obtained by powder X-ray diffraction method (mixed crystal of gelenite 2CaO · Al 2 O 3 · SiO 2 and akermanite 2CaO · MgO · 2SiO 2 ). S 0 represents the area of the main peak of melilite after the slag was heated at 1,000 ° C. for 3 hours and then cooled at a cooling rate of 5 ° C./min.
[0011]
Further, the concentration of non-sulfuric sulfur ions eluted from the slag (hereinafter referred to as soluble sulfur concentration) is preferably 20 mg / l or more. If the soluble sulfur concentration is not in this range, the fluidity retention performance of a predetermined concrete may not be obtained.
Soluble sulfur concentrations include sulfur ion (S 2- ), polysulfide ion (Sn 2- , n ≧ 2), thiosulfate ion (S 2 O 3 2- ), sulfite ion (SO 3 2- ), And sulfate ion (SO 4 2- ).
The soluble sulfur concentration referred to in the present invention refers to the concentration of non-sulfuric sulfur ions contained in the liquid phase obtained by solid-liquid separation after 20 g of this slag is placed in 100 ml of water at 20 ° C. and stirred for 30 minutes.
These sulfur concentrations can be quantified by IPC emission spectrometry or ion chromatography.
[0012]
The fine aggregate for cement concrete of the present invention (hereinafter referred to as this aggregate) has a sieve passing rate of 100% at a nominal size of 4.75 mm, 95-100% at 2.36 mm, 80-100% at 1.18 mm, and 0.6 mm. 35 to 80%, 0.3 to 15 to 50%, and 0.15 to 2 to 20% are preferable. If the particle size of the aggregate is outside this range, the fluidity of the cement concrete may decrease, or material separation may occur, and the durability of the cement concrete structure may decrease.
In addition, the nominal size of the sieve used for measuring the sieve passage rate is the nominal size of the mesh sieve specified in JIS Z 8801, 4.75 mm, 2.36 mm, 1.18 mm, 600 μm, 300 μm, and 150 μm, respectively.
[0013]
This aggregate contains a specific slow-cooled slag.
The amount of the aggregate used is not particularly limited, but is usually preferably 100 to 400 parts, more preferably 150 to 300 parts with respect to 100 parts of cement. Outside this range, the fluidity of cement concrete may decrease.
[0014]
As the cement used in the present invention, various portland cements such as normal, early strength, super early strength, low heat, and moderate heat, and various mixed cements obtained by mixing blast furnace granulated slag, fly ash, or silica with these portland cements. As well as filler cement mixed with fine limestone powder, one or more of these can be used.
[0015]
The cement composition of the present invention contains cement and the present aggregate.
[0016]
This aggregate may be mixed with other materials at the time of construction, or a part or all of them may be mixed in advance.
[0017]
The cement concrete of the present invention is preferably fluidized using a general water reducing agent, an AE water reducing agent, a high performance water reducing agent, a water reducing agent such as a high performance AE water reducing agent.
The water reducing agent can be used in liquid or powder form.
Water reducing agents are roughly classified into naphthalene series, melamine series, aminosulfonic acid series, and polycarboxylic acid series.
The amount of water reducing agent used is not particularly limited as long as it is within the range specified by each manufacturer, but is usually preferably 0.5 to 3.0 parts with respect to 100 parts of cement. If it is less than 0.5 part, there may be no use effect, and if it exceeds 3.0 part, it may cause material separation.
[0018]
In the present invention, the amount of water used is not particularly limited, but is usually preferably 30 to 60 parts, more preferably 40 to 50 parts, relative to 100 parts of cement. If it is less than 30 parts, the fluidity is significantly lowered, and defects such as jumpers may occur. If it exceeds 60 parts, material separation may be caused.
[0019]
In the present invention, blast furnace granulated slag fine powder, blast furnace annealed slag fine powder, limestone fine powder, fly ash, silica fume, and the like conventionally used in cement concrete, in addition to cement, main aggregate, and water reducing agent Admixture materials, antifoaming agents, thickeners, rust inhibitors, antifreeze agents, shrinkage reducing agents, polymer emulsions, setting modifiers, clay minerals such as bentonite, and anion exchangers such as hydrotalcite It is possible to use 1 type (s) or 2 or more types in the range which does not inhibit substantially the objective of this invention.
[0020]
In the present invention, the mixing method of each material is not particularly limited, and the respective materials may be mixed at the time of construction, or a part or all of them may be mixed in advance.
Any existing device can be used as the mixing device, and for example, a tilting mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used.
[0021]
【Example】
Hereinafter, it demonstrates still in detail based on the experiment example of this invention.
[0022]
Example 1
Cement / sand = 1/3, water cement ratio 50%, sieve passage rate of this aggregate is 100% at nominal size 4.75mm, 97% at 2.36mm, 90% at 1.18mm, 50% at 0.6mm, 0.3 The mortar was prepared using the slag containing the present slag shown in Table 1 and fixed to 35% for mm and 10% for 0.15 mm, and the table flow was measured in order to see the aging of the mortar flow. The results are also shown in Table 1.
For comparison, the same experiment was performed when silica sand A was used. The results are also shown in Table 1.
[0023]
<Materials used>
Slag a: This slag, vitrification rate 5%, non-sulfate sulfur 0.9%, soluble sulfur concentration 90mg / l, density 3.00g / cm 3
Slag b: This slag, vitrification rate 5%, non-sulfate sulfur 0.7%, soluble sulfur concentration 77mg / l, density 3.00g / cm 3
Slag c: This slag, vitrification rate 5%, non-sulfate sulfur 0.5%, soluble sulfur concentration 53 mg / l, density 3.00 g / cm 3
Slag d: This slag, vitrification rate 5%, non-sulfate sulfur 0.3%, soluble sulfur concentration 28 mg / l, density 3.00 g / cm 3
Slag e: This slag, vitrification rate 5%, non-sulfate sulfur 0.1%, soluble sulfur concentration 12mg / l, density 3.00g / cm 3
Slag f: This slag, vitrification rate 10%, non-sulfate sulfur 0.7%, soluble sulfur concentration 65mg / l, density 2.97g / cm 3
Slag g: This slag, vitrification rate 30%, non-sulfate sulfur 0.5%, soluble sulfur concentration 47mg / l, density 2.94g / cm 3
Slag h: Blast furnace granulated slag, 95% vitrification, 0.9% non-sulfate sulfur, soluble sulfur concentration 2mg / l, density 2.90g / cm 3
Cement: Ordinary Portland cement, Denki Kagaku Kogyo, density 3.15g / cm 3
Silica A: JIS standard sand water: Tap water [0024]
<Measurement method>
Aggregate sieve passage rate: Conforms to JIS A1102 Aggregate sieving test method Table flow: Measured according to JIS R 5201 immediately after mixing, after 30 minutes, 60 minutes, and 90 minutes.
[0025]
[Table 1]
[0026]
Example 2
The experiment was performed in the same manner as in Experimental Example 1 except that the slag a was used and the aggregate having the sieve passing rate shown in Table 2 was used.
[0027]
[Table 2]
[0028]
Example 3
Slag a with a sieve passing rate of 100% at nominal size 4.75mm, 97% at 2.36mm, 90% at 1.18mm, 50% at 0.6mm, 35% at 0.3mm, and 10% at 0.15mm as fine aggregate used, the unit amount of cement 336kg / m 3, unit water 180 kg / m 3, the unit fine aggregate weight 757kg / m 3, the unit coarse aggregate content 989kg / m 3, and the air amount 4.5 ± 1.5% of the concrete were prepared, The slump was measured to see the change of the slump with time. The results are shown in Table 3.
As a comparative example, a similar experiment was performed using slag h and silica sand B having the same sieve passing rate as fine aggregates. The results are also shown in Table 3.
The kneaded slump was adjusted to 18 cm with an AE water reducing agent.
[0029]
<Materials used>
Silica sand B: River sand from Himekawa, Niigata Prefecture, particle size adjusted coarse aggregate: Gravel AE water reducing agent from Himekawa, Niigata Prefecture: Polycarboxylic acid-based AE water reducing agent, commercial product [0030]
<Measurement method>
Slump: Conforms to JIS A 1101 [0031]
[Table 3]
[0032]
【The invention's effect】
By using the fine aggregate for cement concrete of the present invention, it becomes possible to provide mortar and concrete having good fluidity retention performance.
Claims (6)
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