JP2013241306A - Cement admixture, cement composition and method for producing the same - Google Patents
Cement admixture, cement composition and method for producing the same Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011575 calcium Substances 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- -1 calcium aluminate compound Chemical class 0.000 claims description 35
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 15
- 239000010419 fine particle Substances 0.000 claims description 6
- 210000004556 brain Anatomy 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 30
- 239000004567 concrete Substances 0.000 abstract description 15
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 13
- 238000002386 leaching Methods 0.000 abstract description 11
- 230000003014 reinforcing effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 48
- 239000003153 chemical reaction reagent Substances 0.000 description 37
- 239000000292 calcium oxide Substances 0.000 description 26
- 235000012255 calcium oxide Nutrition 0.000 description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 238000005984 hydrogenation reaction Methods 0.000 description 16
- 230000002265 prevention Effects 0.000 description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000035515 penetration Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 150000003839 salts Chemical group 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 230000001629 suppression Effects 0.000 description 5
- 239000011398 Portland cement Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 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
- 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
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 238000001816 cooling Methods 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
- SHFAFEZLBIWABL-UHFFFAOYSA-L disilver 2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Ag+].[Ag+].[O-]C(=O)c1ccccc1-c1c2ccc([O-])cc2oc2cc(=O)ccc12 SHFAFEZLBIWABL-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000000887 hydrating effect 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver nitrate Substances [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
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混和材及びセメント組成物に関する。 The present invention mainly relates to a cement admixture and a cement composition used in the civil engineering and construction industries.
近年、土木や建築分野において、コンクリート構造物の耐久性向上に対する要望が高まっている。 In recent years, there has been an increasing demand for improving the durability of concrete structures in the civil engineering and construction fields.
コンクリート構造物の劣化要因の１つとして、塩化物イオンの存在によって鉄筋腐食が顕在化する塩害があり、その塩害を抑制するための方法として、コンクリート構造物に塩化物イオン浸透抵抗性を付与する手法がある。 As one of the deterioration factors of concrete structures, there is salt damage in which rebar corrosion becomes obvious due to the presence of chloride ions, and as a method to suppress the salt damage, impart chloride ion penetration resistance to concrete structures. There is a technique.
コンクリート硬化体の内部への塩化物イオン浸透を抑制し、塩化物イオン浸透抵抗性を与える方法としては、水／セメント比を小さくする方法が知られている（非特許文献１参照）。しかしながら、水／セメント比を小さくする方法では、施工性が損なわれるだけでなく、抜本的な対策とはならない場合があった。 As a method for suppressing chloride ion penetration into the inside of a hardened concrete and imparting chloride ion penetration resistance, a method of reducing the water / cement ratio is known (see Non-Patent Document 1). However, in the method of reducing the water / cement ratio, not only the workability is impaired but also a drastic measure may not be provided.
また、セメントコンクリートに早強性を付与し、かつ、鉄筋の腐食を防止するなどの目的で、ＣａＯ・２Ａｌ２Ｏ３とセッコウを主体とし、ブレーン比表面積値が８，０００ｃｍ２／ｇ以上の微粉を含有するセメント混和材を使用する方法が提案されている（特許文献１参照）。 In addition, for the purpose of imparting early strength to cement concrete and preventing corrosion of reinforcing bars, CaO · 2Al 2 O 3 and gypsum are the main components, and the Blaine specific surface area value is 8,000 cm 2 / g or more. A method of using a cement admixture containing fine powder has been proposed (see Patent Document 1).
さらに、ＣａＯ／Ａｌ２Ｏ３モル比が０．３〜０．７、ブレーン比表面積が２０００〜７０００ｃｍ２／ｇのカルシウムアルミネートを含有するセメント混和材を使用し，優れた塩化物イオン浸透抵抗性を持ち，マスコンの温度ひび割れ抑制する方法が提案されている（特許文献２参照）。
しかしながら、この方法では、混和材中の微粒子がセメントの水和に影響を及ぼし、フローダウンや強度の低下および乾燥収縮の増大を引き起こし、ひび割れが入りやすくなる等の課題を有していた。
Furthermore, using a cement admixture containing calcium aluminate with a CaO / Al 2 O 3 molar ratio of 0.3 to 0.7 and a Blaine specific surface area of 2000 to 7000 cm 2 / g, excellent chloride ion penetration resistance A method for suppressing temperature cracks in mascons has been proposed (see Patent Document 2).
However, in this method, the fine particles in the admixture affect the hydration of the cement, causing problems such as flow down, a decrease in strength and an increase in drying shrinkage, and cracks are easily generated.
さらに、可使時間や初期強度の確保を目的として、カルシウムアルミネートとセッコウから成るセメント急硬材に対して水を０．５〜２質量部含有させたセメント混和材が提案されている（特許文献３参照）。 Furthermore, for the purpose of ensuring the pot life and initial strength, a cement admixture in which 0.5 to 2 parts by mass of water is contained in a cement rapid hardening material composed of calcium aluminate and gypsum has been proposed (patent) Reference 3).
他方、鉄筋の防錆を目的として、亜硝酸塩などを添加する方法も提案されている（特許文献４、特許文献５参照）。
しかしながら、亜硝酸塩は、防錆効果を発揮するものの、外部から侵入する塩化物イオンの遮蔽効果を発揮するものではなく、また、亜硝酸型ハイドロカルマイトは、防錆効果を発揮するものの、これを混和したセメント硬化体が多孔質になりやすく、むしろ、外部からの塩化物イオンの浸透を許容しやすいという課題を有していた。
On the other hand, a method of adding nitrite or the like has also been proposed for the purpose of rust prevention of reinforcing bars (see Patent Document 4 and Patent Document 5).
However, although nitrite exhibits a rust prevention effect, it does not exert a shielding effect against chloride ions entering from the outside, and nitrite hydrocalumite exhibits a rust prevention effect. However, the hardened cement paste containing the material tends to be porous, but rather has a problem that it easily allows permeation of chloride ions from the outside.
本発明は、セメントコンクリート硬化体内部の鉄筋に優れた防錆効果を付与し、外部から侵入するセメントコンクリート硬化体への塩化物イオン浸透の遮蔽効果を有し、セメントコンクリート硬化体からのＣａイオンの溶脱も少ないため多孔化も抑制でき、乾燥収縮量やフローダウンが小さく、さらに発生したひび割れを自ら閉塞する自己治癒効果を有するため、長期に渡り優れた遮塩性を発揮するセメント混和材、セメント組成物及びその製造方法を提供する。 The present invention provides an excellent rust prevention effect to the reinforcing steel inside the cement concrete cured body, has a shielding effect of chloride ion penetration into the cement concrete cured body entering from the outside, and Ca ions from the cement concrete cured body Cement admixture that exhibits excellent salt-blocking properties over a long period of time because it has a self-healing effect that can reduce the amount of drying shrinkage and flow down, and further clogs the generated cracks. A cement composition and a method for producing the same are provided.
本発明は、（１）ＣａＯ／Ａｌ２Ｏ３モル比が０．１５〜０．７でＦｅ２Ｏ３の含有量が０．５〜２０質量％のカルシウムフェロアルミネート化合物と水を含有してなり、カルシウムフェロアルミネート化合物１００質量部に対して水が０．１〜３質量部であるセメント混和材、（２）カルシウムフェロアルミネート化合物の粉末度が、ブレーン比表面積２０００〜７０００ｃｍ２／ｇである（１）のセメント混和材、（３）セメントと、（１）又は（２）のセメント混和材を含有してなるセメント組成物、（４）セメントと、ＣａＯ／Ａｌ２Ｏ３モル比が０．１５〜０．７でＦｅ２Ｏ３の含有量が０．５〜２０質量％のカルシウムフェロアルミネート化合物と水とを含有してなり、カルシウムフェロアルミネート化合物１００質量部に対して水が０．１〜３質量部であるセメント組成物、（５）ＣａＯ／Ａｌ２Ｏ３モル比が０．１５〜０．７でＦｅ２Ｏ３の含有量が０．５〜２０質量％のカルシウムアルミネート化合物１００質量部に対して水を０．１〜３質量部攪拌混合しながら、噴霧器等を用いて１０μｍ以下の微粒子に優先的に吸着するよう添加したブレーン比表面積２０００〜７０００ｃｍ２／ｇのセメント混和材に、セメントを混合するセメント組成物の製造方法、である。 The present invention includes (1) a calcium ferroaluminate compound having a CaO / Al 2 O 3 molar ratio of 0.15 to 0.7 and a Fe 2 O 3 content of 0.5 to 20% by mass and water. A cement admixture in which water is 0.1 to 3 parts by mass with respect to 100 parts by mass of the calcium ferroaluminate compound, and (2) the fineness of the calcium ferroaluminate compound is a Blaine specific surface area of 2000 to 7000 cm 2 / g (1) cement admixture, (3) cement, (1) or a cement composition containing the cement admixture (2), (4) cement, and 3 mol of CaO / Al 2 O ratio and also contains a water content of calcium ferro-aluminate compounds of 0.5 to 20% by weight of Fe 2 O 3 at 0.15 to 0.7, calcium ferro-aluminate compound 100 quality Cement composition of water is 0.1-3 parts by weight with respect to parts, the content of Fe 2 O 3 in (5) CaO / Al 2 O 3 molar ratio of 0.15 to 0.7 0.5 Brain specific surface area added to preferentially adsorb to fine particles of 10 μm or less using a sprayer or the like while stirring and mixing 0.1 to 3 parts by mass of water to 100 parts by mass of calcium aluminate compound of ˜20% by mass It is a manufacturing method of the cement composition which mixes a cement with 2000-7000 cm < 2 > / g cement admixture.
本発明のセメント混和材及びセメント組成物を使用することにより、優れた防錆効果と、外部から侵入する塩化物イオンの遮蔽効果を持ち、セメントコンクリート硬化体からのＣａイオンの溶脱も少ないことから、多孔化も抑制でき、乾燥収縮量やフローダウンが小さく、さらに発生したひび割れを自ら閉塞する自己治癒効果を有するため、長期に渡り優れた遮塩性を発揮するなどの効果を奏する。 By using the cement admixture and the cement composition of the present invention, it has an excellent rust prevention effect and a shielding effect of chloride ions entering from the outside, and there is little leaching of Ca ions from the cement concrete hardened body. Further, it can suppress porosity, has a small amount of drying shrinkage and a small flow-down, and has a self-healing effect of blocking the generated cracks by itself.
以下、本発明を詳細に説明する。
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、本発明で云うセメントコンクリートとは、セメントペースト、セメントモルタル、及びコンクリートの総称である。
Hereinafter, the present invention will be described in detail.
In the present invention, “parts” and “%” are based on mass unless otherwise specified.
The cement concrete referred to in the present invention is a general term for cement paste, cement mortar, and concrete.
本発明で使用するカルシウムフェロアルミネート化合物（以下、ＣＦＡ化合物という）とは、カルシアを含む原料、アルミナを含む原料、フェライトを含む原料等を混合して、キルンでの焼成や電気炉での溶融等の熱処理をして得られる、ＣａＯ、Ａｌ２Ｏ３、Ｆｅ２Ｏ３を主成分とする化合物を総称するものである。
ＣＦＡ化合物の組成は、ＣａＯ／Ａｌ２Ｏ３モル比が０．１５〜０．７でＦｅ２Ｏ３含有量が０．５〜２０％である。ＣａＯ／Ａｌ２Ｏ３モル比が０．４〜０．６がより好ましい。０．１５未満では、塩化物イオンの遮蔽効果が充分に得られない場合があり、逆に、０．７を超えると急硬性が現れるようになり、可使時間が確保できない場合がある。ＣＦＡ化合物のＦｅ２Ｏ３の含有量は、０．５〜２０％が好ましく、１〜１０％がより好ましく、３〜７％が最も好ましい。０．５％未満では、キルンで焼成した場合に未反応の酸化アルミニウムが多く残ったり、初期強度の増進の効果は期待できない。２０％を越えても効率的に反応を進行させる効果は頭うちとなり、塩化物イオン浸透抵抗性が悪くなる場合がある。
The calcium ferroaluminate compound (hereinafter referred to as CFA compound) used in the present invention is a mixture of a raw material containing calcia, a raw material containing alumina, a raw material containing ferrite, etc., and firing in a kiln or melting in an electric furnace. This is a generic term for compounds obtained by heat treatment such as CaO, Al 2 O 3 , and Fe 2 O 3 as main components.
The composition of the CFA compound is such that the CaO / Al 2 O 3 molar ratio is 0.15 to 0.7 and the Fe 2 O 3 content is 0.5 to 20%. The CaO / Al 2 O 3 molar ratio is more preferably 0.4 to 0.6. If it is less than 0.15, the chloride ion shielding effect may not be sufficiently obtained. Conversely, if it exceeds 0.7, rapid hardening may appear, and the pot life may not be secured. The content of Fe 2 O 3 in the CFA compound is preferably 0.5 to 20%, more preferably 1 to 10%, and most preferably 3 to 7%. If it is less than 0.5%, a large amount of unreacted aluminum oxide remains when fired in a kiln, and the effect of increasing the initial strength cannot be expected. Even if it exceeds 20%, the effect of allowing the reaction to proceed efficiently becomes a head, and the chloride ion penetration resistance may deteriorate.
ＣＦＡ化合物１００部に対して含有させる水分（以下、水添率と称する。）は０．１〜３部が好ましく、より好ましくは０．３〜２部である。０．１部未満では乾燥収縮量の低減、フローの経時低下の抑制効果や乾燥収縮量の改善効果が十分ではなく、３部を超えると混和材中に均一に分散させることが困難となり、遮塩性や強度発現性に悪影響を及ぼす場合がある。本発明における水添効果は従来の可使時間の確保や超早期強度発現性の向上を目的とした水添効果とは異なる。
従来、活性の高いカルシウムアルミネートに水分を添加して粒子の表面を水和物で覆うことで、可使時間の確保や早期の強度発現性を向上させることが行われていた。
一方、本発明はＣＦＡ化合物に水分を添加するものであるが、特に反応性の高い１０μｍ以下の微粒子と優先的に水和させることによって、乾燥収縮量が大幅に改善され、塩化物イオン浸透抵抗性や防錆効果にはほとんど影響を及ぼさないことを見出したものである。
ＣＦＡ化合物中に水分を含有させる方法は、優先的に１０μｍ以下の微粒子と反応させる方法が好ましく、例えば、ボールミル等で粉砕混合しながら水を噴霧器や水蒸気等で添加する方法や、Ｖブレンダーなどで撹拌混合しながら、噴霧器や水蒸気等で添加する方法がある。粉砕や攪拌を行いながら水を添加することで１０μｍ以下の微粒子が空気中に舞い上がり、優先的に水分が吸着する。水分を加えてから攪拌混合を始めると、１０μｍ以上の粒子にも水が吸着し、塩化物イオン浸透抵抗性や防錆効果が低下する場合がある。
The water content (hereinafter referred to as the hydrogenation rate) contained in 100 parts of the CFA compound is preferably 0.1 to 3 parts, more preferably 0.3 to 2 parts. If it is less than 0.1 part, the amount of drying shrinkage is not sufficiently reduced, the effect of suppressing the deterioration of the flow over time and the effect of improving the amount of drying shrinkage are insufficient. The saltiness and strength development may be adversely affected. The hydrogenation effect in the present invention is different from the conventional hydrogenation effect for the purpose of securing the pot life and improving the ultra-early strength development.
Conventionally, it has been carried out to secure the pot life and improve the early strength development by adding water to calcium aluminate having high activity and covering the surface of the particles with a hydrate.
On the other hand, according to the present invention, water is added to the CFA compound. By preferentially hydrating with fine particles of 10 μm or less that are particularly highly reactive, the amount of drying shrinkage is greatly improved, and chloride ion permeation resistance. It has been found that it has little effect on the properties and rust prevention effect.
As a method of incorporating water into the CFA compound, a method of preferentially reacting with fine particles of 10 μm or less is preferable. For example, a method of adding water with a sprayer or steam while pulverizing and mixing with a ball mill or the like, a V blender, etc. There is a method of adding with a sprayer or steam while stirring and mixing. By adding water while pulverizing and stirring, fine particles of 10 μm or less rise in the air, and moisture is preferentially adsorbed. When stirring and mixing is started after adding water, water adsorbs even to particles of 10 μm or more, and the chloride ion permeation resistance and the antirust effect may be reduced.
ＣＦＡ化合物の粉末度は、ブレーン比表面積（以下、ブレーン値という）で２０００〜７０００ｃｍ２／ｇが好ましく、３０００〜６０００ｃｍ２／ｇがより好ましく、３０００〜４０００ｃｍ２／ｇが最も好ましい。２０００ｃｍ２／ｇ未満では充分な塩化物イオンの遮蔽効果が得られない場合があり、７０００ｃｍ２／ｇを超える微粉では、急硬性が現れるようになり、可使時間が確保できない場合がある。 Fineness of CFA compounds, Blaine specific surface area (hereinafter, referred to as Blaine value) is preferably 2000~7000cm 2 / g, the more preferred 3000~6000cm 2 / g, 3000~4000cm 2 / g being most preferred. If it is less than 2000 cm 2 / g, a sufficient chloride ion shielding effect may not be obtained, and if it exceeds 7000 cm 2 / g, rapid hardening appears and the pot life may not be secured.
ＣＦＡ化合物の製造に使用する原料について説明する。
カルシアを含む原料は、特に限定されないが、工業原料として市販されている例えば、生石灰（ＣａＯ）、消石灰（Ｃａ（ＯＨ）２）、石灰石（ＣａＣＯ３）等が挙げられる。
アルミナを含む原料は、特に限定されないが、工業原料として市販されている例えばＡｌ２Ｏ３や水酸化アルミニウム、ボーキサイト等が挙げられる。特にボーキサイトはＡｌ２Ｏ３と共にＦｅ２Ｏ３を含んでいるため望ましい。
フェライトを含む原料は、特に限定されないが、工業原料として市販されている鉄鉱石を粉砕、加工、精製したＦｅ２Ｏ３や鋼材洗浄廃塩酸から回収、精製して得られるＦｅ２Ｏ３等が挙げられる。
さらに、例えば、ＳｉＯ２やＲ２Ｏ（Ｒはアルカリ金属）を併用しても、本発明の目的を損なわない限り使用可能である。
The raw material used for manufacture of a CFA compound is demonstrated.
Material containing calcia is not particularly limited, for example, are commercially available as an industrial raw material, quick lime (CaO), slaked lime (Ca (OH) 2), limestone (CaCO 3), and the like.
Material containing alumina is not particularly limited, for example, Al 2 O 3 or aluminum hydroxide is commercially available as an industrial raw material, bauxite, and the like. Particularly bauxite desirable because it contains Fe 2 O 3 with Al 2 O 3.
Material containing ferrite is not particularly limited, crushing the iron ore which is commercially available as an industrial raw material, processed, purified Fe 2 O 3 and steel washing waste recovered from the hydrochloric, or the like Fe 2 O 3 obtained by purification Can be mentioned.
Furthermore, for example, even when SiO 2 or R 2 O (R is an alkali metal) is used in combination, it can be used as long as the object of the present invention is not impaired.
ＣＦＡ化合物は、カルシアを含む原料、アルミナを含む原料、フェライトを含む原料等を混合して、キルンでの焼成や電気炉での溶融等の熱処理をして得られる。焼成温度は原料の配合にもよるが１４００℃以上が好ましく、１５００℃以上がより好ましい。１４００℃未満では効率良く反応が進まず未反応のＡｌ２Ｏ３が残る可能性がある。 The CFA compound is obtained by mixing a raw material containing calcia, a raw material containing alumina, a raw material containing ferrite, and the like, and performing a heat treatment such as firing in a kiln or melting in an electric furnace. The firing temperature is preferably 1400 ° C. or higher, more preferably 1500 ° C. or higher, although it depends on the composition of the raw materials. If it is less than 1400 ° C., the reaction does not proceed efficiently, and unreacted Al 2 O 3 may remain.
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や、これらポルトランドセメントに、高炉スラグ、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、石灰石粉末や高炉徐冷スラグ微粉末等を混合したフィラーセメント、並びに、都市ゴミ焼却灰や下水汚泥焼却灰を原料として製造された環境調和型セメント（エコセメント）等のポルトランドセメントが挙げられ、これらのうちの一種又は二種以上が使用可能である。 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 these portland cements with blast furnace slag, fly ash, or silica, Examples include filler cement mixed with limestone powder, blast furnace slow-cooled slag fine powder, etc., and portland cement such as environmentally friendly cement (eco-cement) manufactured from municipal waste incineration ash and sewage sludge incineration ash. 1 type or 2 types or more can be used.
セメント混和材の使用量は特に限定されるものではないが、通常、セメントとセメント混和材からなるセメント組成物１００部中、１〜３０部が好ましく、５〜１５部がより好ましい。セメント混和材の使用量が少ないと充分な防錆効果、塩化物イオンの遮蔽効果、Ｃａイオンの溶脱抑制効果が得られない場合があり、過剰に使用すると急硬性が現れるようになり、充分な可使時間が確保できない場合がある。 Although the usage-amount of a cement admixture is not specifically limited, Usually, 1-30 parts are preferable in a cement composition which consists of cement and a cement admixture, and 5-15 parts are more preferable. If the amount of cement admixture is small, sufficient rust prevention effect, chloride ion shielding effect, Ca ion leaching suppression effect may not be obtained, and if used excessively, rapid hardening will appear and sufficient The pot life may not be secured.
本発明では、セメントとセメント混和材を配合して、また、セメント、ＣＦＡ化合物を配合してセメント組成物とする。 In the present invention, cement and a cement admixture are blended, and cement and a CFA compound are blended to obtain a cement composition.
本発明のセメント組成物の水／セメント組成物比は、２５〜７０％が好ましく、３０〜６５％がより好ましい。水の配合量が少ないと、ポンプ圧送性や施工性が低下したり、収縮等の原因となる場合があり、水の配合量が過剰では強度発現性が低下する場合がある。 The water / cement composition ratio of the cement composition of the present invention is preferably 25 to 70%, more preferably 30 to 65%. If the blending amount of water is small, the pumpability and workability may be reduced or shrinkage may be caused. If the blending amount of water is excessive, the strength development may be degraded.
本発明のセメント混和材やセメント組成物は、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支えない。 In the cement admixture and cement composition of the present invention, the respective materials may be mixed at the time of construction, or a part or all of them may be mixed in advance.
本発明では、セメント、セメント混和材、及び砂等の細骨材や砂利等の粗骨材の他に、膨張材、急硬材、減水剤、ＡＥ減水剤、高性能減水剤、高性能ＡＥ減水剤、消泡剤、増粘剤、従来の防錆剤、防凍剤、収縮低減剤、凝結調整剤、ベントナイト等の粘土鉱物、ハイドロタルサイト等のアニオン交換体、高炉水砕スラグ微粉末や高炉徐冷スラグ微粉末等のスラグ、石灰石微粉末等の混和材料からなる群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併用することが可能である。 In the present invention, in addition to cement, cement admixture, and fine aggregates such as sand and coarse aggregates such as gravel, expansion material, rapid hardener, water reducing agent, AE water reducing agent, high performance water reducing agent, high performance AE Water reducing agent, antifoaming agent, thickener, conventional rust preventive agent, antifreeze agent, shrinkage reducing agent, setting modifier, clay minerals such as bentonite, anion exchanger such as hydrotalcite, ground granulated blast furnace slag, It is possible to use one or two or more of the group consisting of admixtures such as slag such as blast furnace slow-cooled slag fine powder and limestone fine powder in a range that does not substantially impair the object of the present invention.
混合装置としては、既存の如何なる装置も使用可能であり、例えば、傾胴ミキサ、オムニミキサ、ヘンシェルミキサ、Ｖ型ミキサ、及びナウタミキサ等の使用が可能である。 As the mixing device, any existing device can be used, and for example, a tilting mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used.
以下、実施例、比較例を挙げてさらに詳細に内容を説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example and a comparative example are given and the contents are explained in detail, the present invention is not limited to these.
「実験例１」
表１に示すＣＦＡ化合物を、セメントとセメント混和材からなるセメント組成物１００部中、セメント混和材を１０部配合してセメント組成物を調製し、水／セメント組成物比０．５のモルタルをＪＩＳ Ｒ ５２０１に準じて調製した。このモルタルを用いて、防錆効果、圧縮強さ、フロー保持率、長さ変化率、塩化物浸透深さ、Ｃａイオンの溶脱および自己治癒能力を調べた。結果を表１に併記する。
"Experiment 1"
A CFA compound shown in Table 1 is mixed with 10 parts of a cement admixture in 100 parts of a cement composition composed of cement and a cement admixture to prepare a cement composition, and a mortar having a water / cement composition ratio of 0.5 is prepared. It was prepared according to JIS R 5201. Using this mortar, the antirust effect, compressive strength, flow retention, length change rate, chloride penetration depth, Ca ion leaching and self-healing ability were examined. The results are also shown in Table 1.
（使用材料）
ＣＦＡ化合物Ａ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１５５０℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、Ｖブレンダーで攪拌混合しながらＣＦＡ化合物１００部に対して水を０．５部噴霧器を用いて添加した。ＣａＯ／Ａｌ２Ｏ３モル比０．１、ブレーン値３０００ｃｍ２／ｇ、水添率０．５％
ＣＦＡ化合物Ｂ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１５５０℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、Ｖブレンダーで攪拌混合しながらＣＦＡ化合物１００部に対して水を０．５部噴霧器を用いて添加した。ＣａＯ／Ａｌ２Ｏ３モル比０．１５、ブレーン値３０００ｃｍ２／ｇ、水添率０．５％
ＣＦＡ化合物Ｃ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１５００℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、Ｖブレンダーで攪拌混合しながらＣＦＡ化合物１００部に対して水を０．５部噴霧器を用いて添加した。ＣａＯ／Ａｌ２Ｏ３モル比０．４、ブレーン値３０００ｃｍ２／ｇ、水添率０．５％
ＣＦＡ化合物Ｄ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１４５０℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、Ｖブレンダーで攪拌混合しながらＣＦＡ化合物１００部に対して水を０．５部噴霧器を用いて添加した。ＣａＯ／Ａｌ２Ｏ３モル比０．６、ブレーン値３０００ｃｍ２／ｇ、水添率０．５％
ＣＦＡ化合物Ｅ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１４００℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、Ｖブレンダーで攪拌混合しながらＣＦＡ化合物１００部に対して水を０．５部噴霧器を用いて添加した。ＣａＯ／Ａｌ２Ｏ３モル比０．７、ブレーン値３０００ｃｍ２／ｇ、水添率：０．５％
ＣＦＡ化合物Ｆ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１４００℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、Ｖブレンダーで攪拌混合しながらＣＦＡ化合物１００部に対して水を０．５部噴霧器を用いて添加した。ＣａＯ／Ａｌ２Ｏ３モル比０．９、ブレーン値３０００ｃｍ２／ｇ、水添率：０．５％
ＣＦＡ化合物Ｇ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１４５０℃で電気炉において焼成した後、徐冷して合成し、ボールミルで粉砕混合しながらＣＦＡ化合物１００部に対して水を０．５部噴霧器を用いて添加した。ＣａＯ／Ａｌ２Ｏ３モル比０．６、ブレーン値３０００ｃｍ２／ｇ、水添率０．５％
ＣＦＡ化合物Ｈ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１４５０℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、ＣＦＡ化合物１００部に対して水を０．５部噴霧器を用いて添加し、直ちにＶブレンダーで攪拌混合を行った。ＣａＯ／Ａｌ２Ｏ３モル比０．６、ブレーン値３０００ｃｍ２／ｇ、水添率０．５％
ＣＦＡ化合物Ｉ：試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムを所定割合で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１４５０℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、Ｖブレンダーで攪拌混合しながらＣＦＡ化合物１００部に対して水を０．５部手投入で添加した。ＣａＯ／Ａｌ２Ｏ３モル比０．６、ブレーン値３０００ｃｍ２／ｇ、水添率０．５％
セメント：普通ポルトランドセメント、市販品
細骨材：ＪＩＳ Ｒ ５２０１で使用する標準砂
水：水道水
(Materials used)
CFA compound A: Reagent primary calcium carbonate and reagent primary aluminum oxide are blended at a predetermined ratio, and reagent primary iron oxide is blended so that the Fe 2 O 3 content is 5%, at 1550 ° C. After calcination in an electric furnace, the mixture was gradually cooled and synthesized, pulverized using a vibration mill, and water was added to 100 parts of the CFA compound using a sprayer while stirring and mixing with a V blender. CaO / Al 2 O 3 molar ratio 0.1, Blaine value 3000 cm 2 / g, Hydrogenation rate 0.5%
CFA compound B: Reagent primary calcium carbonate and reagent primary aluminum oxide are blended at a predetermined ratio, and reagent primary iron oxide is blended so that the Fe 2 O 3 content is 5%, at 1550 ° C. After calcination in an electric furnace, the mixture was gradually cooled and synthesized, pulverized using a vibration mill, and water was added to 100 parts of the CFA compound using a sprayer while stirring and mixing with a V blender. CaO / Al 2 O 3 molar ratio 0.15, Blaine value 3000 cm 2 / g, Hydrogenation rate 0.5%
CFA compound C: Reagent primary calcium carbonate and reagent primary aluminum oxide are mixed in a predetermined ratio, and reagent primary iron oxide is mixed so that the Fe 2 O 3 content is 5%. After calcination in an electric furnace, the mixture was gradually cooled and synthesized, pulverized using a vibration mill, and water was added to 100 parts of the CFA compound using a sprayer while stirring and mixing with a V blender. CaO / Al 2 O 3 molar ratio 0.4, Blaine value 3000 cm 2 / g, Hydrogenation rate 0.5%
CFA compound D: Reagent primary calcium carbonate and reagent primary aluminum oxide are blended at a predetermined ratio, and reagent primary iron oxide is blended so that the Fe 2 O 3 content is 5%, at 1450 ° C. After calcination in an electric furnace, the mixture was gradually cooled and synthesized, pulverized using a vibration mill, and water was added to 100 parts of the CFA compound using a sprayer while stirring and mixing with a V blender. CaO / Al 2 O 3 molar ratio 0.6, Blaine value 3000 cm 2 / g, Hydrogenation rate 0.5%
CFA compound E: Reagent primary calcium carbonate and reagent primary aluminum oxide are mixed in a predetermined ratio, and reagent primary iron oxide is mixed so that the Fe 2 O 3 content is 5%. After calcination in an electric furnace, the mixture was gradually cooled and synthesized, pulverized using a vibration mill, and water was added to 100 parts of the CFA compound using a sprayer while stirring and mixing with a V blender. CaO / Al 2 O 3 molar ratio 0.7, brane value 3000 cm 2 / g, hydrogenation rate: 0.5%
CFA compound F: Reagent primary calcium carbonate and reagent primary aluminum oxide are mixed in a predetermined ratio, and reagent primary iron oxide is mixed so that the Fe 2 O 3 content is 5%. After calcination in an electric furnace, the mixture was gradually cooled and synthesized, pulverized using a vibration mill, and water was added to 100 parts of the CFA compound using a sprayer while stirring and mixing with a V blender. CaO / Al 2 O 3 molar ratio 0.9, Blaine value 3000 cm 2 / g, Hydrogenation rate: 0.5%
CFA compound G: Reagent primary calcium carbonate and reagent primary aluminum oxide are mixed at a predetermined ratio, and reagent primary iron oxide is mixed so that the content of Fe 2 O 3 is 5%, at 1450 ° C. After firing in an electric furnace, the mixture was slowly cooled and synthesized, and water was added to 100 parts of the CFA compound using a 0.5 part sprayer while pulverizing and mixing with a ball mill. CaO / Al 2 O 3 molar ratio 0.6, Blaine value 3000 cm 2 / g, Hydrogenation rate 0.5%
CFA compound H: Reagent primary calcium carbonate and reagent primary aluminum oxide are mixed at a predetermined ratio, and reagent primary iron oxide is mixed so that the Fe 2 O 3 content is 5%, at 1450 ° C. After firing in an electric furnace, synthesize by slow cooling, pulverize using a vibration mill, add 0.5 parts of water to 100 parts of CFA compound using a sprayer, and immediately stir and mix in a V blender. It was. CaO / Al 2 O 3 molar ratio 0.6, Blaine value 3000 cm 2 / g, Hydrogenation rate 0.5%
CFA Compound I: Reagent primary calcium carbonate and reagent primary aluminum oxide are blended at a predetermined ratio, and reagent primary iron oxide is blended so that the Fe 2 O 3 content is 5%, at 1450 ° C. After firing in an electric furnace, the mixture was slowly cooled and synthesized, pulverized using a vibration mill, and 0.5 parts of water was manually added to 100 parts of the CFA compound while stirring and mixing with a V blender. CaO / Al 2 O 3 molar ratio 0.6, Blaine value 3000 cm 2 / g, Hydrogenation rate 0.5%
Cement: Ordinary Portland cement, commercially available fine aggregate: Standard sand water used in JIS R 5201: Tap water
（評価方法）
防錆効果：モルタルに内在塩化物イオンとして、１０ｋｇ／ｍ３となるように試薬１級の塩化ナトリウムを加え、丸鋼の鉄筋を入れて５０℃に加温養生することによる促進試験で防錆効果を確認した。鉄筋に錆が発生しなかった場合は良、１／１０の面積以内で錆が発生した場合は可、１／１０の面積を超えて錆が発生した場合は不可とした。
圧縮強さ：ＪＩＳ Ｒ ５２０１に準じて材齢１日と２８日圧縮強さを測定。
長さ変化率：ＪＩＳ Ａ １１２９−３ ダイヤルゲージ法に準じて測定。４×４×１６ｃｍのゲージプラグ付き型枠にモルタルを打設し、４８時間後まで型枠内で養生後、型枠を脱型し、速やかに基長を測定し、２０℃/ＲＨ６０％の環境下における２８日後の長さ変化率を測定した。
フロー保持率：ＪＩＳ Ｒ ５２０１に準じて練り上がり直後と1時間後のフローを測定。以下の式に準じてフロー保持率を算出した。
フロー保持率（％）＝１時間後のフロー（ｍｍ）/練り上がり直後のフロー(ｍｍ)×１００
塩化物浸透深さ：塩化物イオン浸透抵抗性を評価。塩化物イオンの遮蔽効果を示す１０ｃｍφ×２０ｃｍの円柱状のモルタル供試体を作製し、作製したモルタル供試体を、材齢２８日まで２０℃の水中養生を施し、３０℃の塩分濃度３．５％である擬似海水に１２週間浸漬した後、塩化物浸透深さを測定。塩化物浸透深さはフルオロセイン−硝酸銀法により、モルタル供試体断面の茶変しなかった部分を塩化物浸透深さと見なし、ノギスで８点測定して平均値を求めた。
Ｃａイオンの溶脱：４×４×１６ｃｍのモルタル供試体を１０リットルの純水に２８日間浸漬し、液相中に溶解したＣａイオン濃度を測定することにより判定した。
自己治癒能力：６ｍｍのナイロン繊維を０．１５％混合した１０×１０×４０ｃｍのモルタル供試体を作製し、曲げ応力によって幅０．３ｍｍのひび割れを導入した。擬似海水に１８０日間浸漬した後、ひび割れ幅を測定した。◎は完全にひび割れが塞がった、○は０．１ｍｍ以下にひび割れ幅が縮小化した、△は０．２ｍｍ程度までひび割れ幅が縮小。×はひび割れ幅が縮小化されないか、あるいは逆に広がったことを示す。
(Evaluation method)
Rust prevention effect: Rust prevention by accelerated test by adding reagent grade 1 sodium chloride as internal chloride ion to mortar to 10kg / m 3 , putting round steel bar and heat curing at 50 ° C The effect was confirmed. The case where rust did not occur in the reinforcing bars was good, the case where rust occurred within an area of 1/10 was acceptable, and the case where rust occurred beyond an area of 1/10 was deemed impossible.
Compressive strength: Measures compressive strength at 1 day and 28 days of age according to JIS R 5201.
Length change rate: Measured according to JIS A 1129-3 dial gauge method. Mortar is placed in a 4 × 4 × 16 cm mold with a gauge plug, and after curing in the mold until 48 hours, the mold is removed, and the base length is measured immediately. The rate of change in length after 28 days in the environment was measured.
Flow retention: Measured immediately after kneading and after 1 hour according to JIS R 5201. The flow retention was calculated according to the following formula.
Flow retention (%) = flow after 1 hour (mm) / flow immediately after kneading (mm) × 100
Chloride penetration depth: Evaluate chloride ion penetration resistance. A 10 cmφ × 20 cm cylindrical mortar specimen showing the shielding effect of chloride ions was produced, and the produced mortar specimen was subjected to water curing at 20 ° C. until the age of 28 days, and a salt concentration of 30 ° C. was 3.5. % And then immersed in simulated seawater for 12 weeks and then measured the chloride penetration depth. The chloride penetration depth was determined by the fluorescein-silver nitrate method, the portion of the cross section of the mortar specimen where the tea did not change was regarded as the chloride penetration depth, and the average value was obtained by measuring 8 points with calipers.
Ca ion leaching: Determination was made by immersing a 4 × 4 × 16 cm mortar specimen in 10 liters of pure water for 28 days and measuring the concentration of Ca ions dissolved in the liquid phase.
Self-healing ability: A 10 × 10 × 40 cm mortar specimen in which 0.15% of 6 mm nylon fiber was mixed was produced, and a crack having a width of 0.3 mm was introduced by bending stress. After immersing in simulated seawater for 180 days, the crack width was measured. ◎ indicates that the crack is completely closed, ○ indicates that the crack width is reduced to 0.1 mm or less, and △ indicates that the crack width is reduced to about 0.2 mm. X indicates that the crack width has not been reduced or has expanded.
表１より、攪拌混合しながら、水添率を０．５％としたＣａＯ／Ａｌ２Ｏ３モル比が０．１５〜０．７のＣＦＡ化合物を使用することで、防錆効果、塩化物イオン浸透抑制効果を維持し、初期及び長期強度の低下、フローの経時低下及び乾燥収縮量を抑制することができ、Ｃａイオンの溶脱抵抗性及び自己治癒能力を向上することが分かる。 From Table 1, using a CFA compound having a CaO / Al 2 O 3 molar ratio of 0.15 to 0.7 with a hydrogenation rate of 0.5% while stirring and mixing, rust prevention effect, chloride It can be seen that the effect of suppressing ion permeation can be maintained, initial and long-term strength decreases, flow deterioration with time and drying shrinkage can be suppressed, and Ca ion leaching resistance and self-healing ability are improved.
「実験例２」
試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムをＣａＯ／Ａｌ２Ｏ３モル比０．６で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、１４５０℃で電気炉において焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、表２に示すような水添率としたこと以外は実験例１と同様に行った。結果を表２に併記する。
"Experimental example 2"
Reagent grade calcium carbonate and reagent grade aluminum oxide are blended at a CaO / Al 2 O 3 molar ratio of 0.6, and reagent grade iron oxide is blended so that the Fe 2 O 3 content is 5%. Then, after calcination in an electric furnace at 1450 ° C., synthesis was carried out by slow cooling, pulverization using a vibration mill, and the same hydrogenation rate as shown in Table 2 was followed. The results are also shown in Table 2.
表２より、水添率を調整することで、防錆効果、塩化物イオン浸透抑制効果を維持し、初期及び長期強度の低下、フローの経時低下及び乾燥収縮量を抑制することができ、さらにＣａイオンの溶脱抵抗性及び自己治癒能力を向上することが分かる。 From Table 2, by adjusting the hydrogenation rate, it is possible to maintain the rust prevention effect and the chloride ion permeation suppression effect, and to suppress the initial and long-term strength reduction, flow deterioration with time, and drying shrinkage, It can be seen that the leaching resistance and self-healing ability of Ca ions are improved.
「実験例３」
試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムをＣａＯ／Ａｌ２Ｏ３モル比０．６で配合し、試薬１級の酸化鉄を表３に示すＦｅ２Ｏ３含有量となるように配合し、実験例１と同様に電気炉で焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、Ｖブレンダーで攪拌混合しながらＣＦＡ化合物１００部に対して水を０．５部添加噴霧器を用いて添加したＣＦＡ化合物を併用したこと以外は実験例１と同様に行った。結果を表３に併記する。
"Experiment 3"
Reagent grade calcium carbonate and reagent grade aluminum oxide are blended at a CaO / Al 2 O 3 molar ratio of 0.6 so that the reagent grade iron oxide has the Fe 2 O 3 content shown in Table 3. After blending and firing in an electric furnace in the same manner as in Experimental Example 1, the mixture was slowly cooled and synthesized, pulverized using a vibration mill, and mixed with 100 parts of CFA compound while stirring and mixing with a V blender. This was carried out in the same manner as in Experimental Example 1 except that the CFA compound added using a partial addition sprayer was used in combination. The results are also shown in Table 3.
表３より、Ｆｅ２Ｏ３の含有量を調整することで、防錆効果、塩化物イオン浸透抑制効果を維持し、初期及び長期強度の低下、フローの経時低下及び乾燥収縮量を抑制することができ、さらにＣａイオンの溶脱抵抗性及び自己治癒能力を向上することが分かる。 From Table 3, by adjusting the content of Fe 2 O 3 , the rust prevention effect and chloride ion permeation suppression effect are maintained, and the initial and long-term strength decrease, the flow deterioration with time, and the amount of drying shrinkage are suppressed. It can be seen that the leaching resistance and self-healing ability of Ca ions are further improved.
「実験例４」
試薬１級の炭酸カルシウムと試薬１級の酸化アルミニウムをＣａＯ／Ａｌ２Ｏ３モル比０．６で配合し、Ｆｅ２Ｏ３含有量が５％となるように試薬１級の酸化鉄を配合し、実験例１と同様に電気炉で焼成した後、徐冷して合成し、振動ミルを用いて粉砕後、水添率を０．５％とし、表３に示すブレーン比表面積となるように調整したＣＦＡ化合物を併用したこと以外は実験例１と同様に行った。結果を表４に併記する。
"Experimental example 4"
Reagent grade calcium carbonate and reagent grade aluminum oxide are blended at a CaO / Al 2 O 3 molar ratio of 0.6, and reagent grade iron oxide is blended so that the Fe 2 O 3 content is 5%. In the same manner as in Experimental Example 1, after baking in an electric furnace, slowly cooling and synthesizing, pulverizing using a vibration mill, the hydrogenation rate is 0.5%, and the Blaine specific surface area shown in Table 3 is obtained. The same procedure as in Experimental Example 1 was conducted except that the CFA compound prepared in the above was used together. The results are also shown in Table 4.
表４より、ＣＦＡ化合物の粉末度を調整することで、防錆効果、塩化物イオン浸透抑制効果を維持し、フローの経時低下及び乾燥収縮量を抑制することができ、さらにＣａイオンの溶脱抵抗性及び自己治癒能力を向上することが分かる。 From Table 4, by adjusting the fineness of the CFA compound, it is possible to maintain the rust prevention effect and the chloride ion permeation suppression effect, to suppress the flow deterioration with time and the amount of drying shrinkage, and further the Ca ion leaching resistance. It can be seen that it improves sex and self-healing ability.
「実験例５」
ＣＦＡ化合物Ｄを使用して表５に示す使用量としたこと以外は実験例１と同様に行った。比較のために、従来の防錆材を用いて同様に行った。結果を表５に併記する。
“Experimental Example 5”
The same procedure as in Experimental Example 1 was conducted except that the CFA compound D was used and the amount used was as shown in Table 5. For comparison, a conventional rust preventive material was used in the same manner. The results are also shown in Table 5.
（使用材料）
従来の防錆材イ：亜硝酸リチウム、市販品
従来の防錆材ロ：亜硝酸型ハイドロカルマイト、市販品
(Materials used)
Conventional rust-proofing material A: Lithium nitrite, commercial product Conventional rust-proofing material B: Nitrite-type hydrocalumite, commercial product
表５より、ＣＦＡ化合物の使用量を調整することで、防錆効果、塩化物イオン浸透抑制効果を維持し、フローの経時低下及び乾燥収縮量を抑制することができ、さらにＣａイオンの溶脱抵抗性及び自己治癒能力を向上することが分かる。 From Table 5, by adjusting the amount of CFA compound used, it is possible to maintain the rust prevention effect and the chloride ion permeation suppression effect, and to suppress the flow deterioration with time and the amount of drying shrinkage, and further the Ca ion leaching resistance. It can be seen that it improves sex and self-healing ability.
本発明のセメント混和材及びセメント組成物を使用することにより、優れた防錆効果と、外部から侵入する塩化物イオンの遮蔽効果を持ち、セメントコンクリート硬化体からのＣａイオンの溶脱も少ないことから、多孔化も抑制でき、乾燥収縮量やフローダウンが小さく、さらに発生したひび割れを自ら閉塞する自己治癒効果を有するため、長期に渡り優れた遮塩性を発揮するなどの効果を奏するため、主に、土木・建築業界等において海洋や河川の水利構造物、水槽、床版コンクリートなど広範な用途に適する。 By using the cement admixture and the cement composition of the present invention, it has an excellent rust prevention effect and a shielding effect of chloride ions entering from the outside, and there is little leaching of Ca ions from the cement concrete hardened body. Since it can suppress porosity, has a small amount of drying shrinkage and flow down, and has a self-healing effect that blocks the generated cracks by itself, it has the effect of exhibiting excellent salt barrier properties over a long period of time. In addition, it is suitable for a wide range of applications such as marine and river irrigation structures, water tanks, floor slab concrete in the civil engineering and construction industries.
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| JP2006182568A (en) * | 2004-12-24 | 2006-07-13 | Taiheiyo Material Kk | Hardening accelerator and quick-hardening cement composition |
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| JP7132846B2 (en) | 2018-12-27 | 2022-09-07 | 宇部興産建材株式会社 | Repair method for salt-blocking mortar |
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