JP2016160146A - Admixture for countermeasure against salt damage and method for countermeasure against salt damage of reinforced concrete - Google Patents
Admixture for countermeasure against salt damage and method for countermeasure against salt damage of reinforced concrete Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 48
- 239000011150 reinforced concrete Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 51
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011575 calcium Substances 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 28
- 239000004571 lime Substances 0.000 claims abstract description 23
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 22
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000004567 concrete Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000010298 pulverizing process Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 239000004568 cement Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 6
- 230000003449 preventive effect Effects 0.000 abstract description 2
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002956 ash 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
- 210000004556 brain Anatomy 0.000 description 1
- 239000000404 calcium aluminium silicate Substances 0.000 description 1
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 1
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 1
- 229940078583 calcium aluminosilicate Drugs 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 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 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
本発明は、土木・建築分野で使用される鉄筋コンクリートの塩害対策方法および塩害対策用混和材に関する。 The present invention relates to a salt damage countermeasure method for reinforced concrete used in the field of civil engineering and architecture and an admixture for salt damage countermeasures.
コンクリートのひび割れは、塩化物の浸透や中性化の進行を加速させ、鉄筋腐食に伴うコンクリート片の剥離や落下を誘発させる。特に沿岸部や道路関連のコンクリートでは、海からの飛来塩分や凍結防止剤の散布によって塩害が生じやすく、コンクリートのひび割れを低減する材料や技術の開発が進んでいる（特許文献１）。
また、塩害対策としてカルシウムフェロアルミネート化合物が有効であることが知られている（特許文献２）。
Cracks in concrete accelerate the progress of chloride penetration and neutralization, and induce the peeling and dropping of concrete pieces due to reinforcement corrosion. In particular, in coastal areas and road-related concrete, salt damage is likely to occur due to flying salt from the sea or spraying of an antifreezing agent, and development of materials and techniques for reducing cracks in the concrete is proceeding (Patent Document 1).
Moreover, it is known that a calcium ferroaluminate compound is effective as a countermeasure against salt damage (Patent Document 2).
本発明は、塩化物浸透抑制効果とひび割れ抵抗性を有する塩害対策用混和材および鉄筋コンクリートの塩害対策方法を提供する。 The present invention provides a salt damage countermeasure admixture having a chloride penetration inhibiting effect and crack resistance and a salt damage countermeasure method for reinforced concrete.
すなわち、本発明は、（１）ＣａＯ原料、Ａｌ２Ｏ３原料、およびＦｅ２Ｏ３原料を混合したものを熱処理して得られ、カルシウムアルミノフェライト、および遊離石灰の合計１００質量部中、カルシウムアルミノフェライトを３０〜９０質量部、遊離石灰を１０〜７０質量部の割合で含有する熱処理物を粉砕してなる塩害対策用混和材、（２）ＣａＯ原料、Ａｌ２Ｏ３原料、およびＦｅ２Ｏ３原料に、さらにＣａＳＯ４原料を混合したものを熱処理または後添加して得られ、カルシウムアルミノフェライト、遊離石灰、および無水石膏の合計１００質量部中、カルシウムアルミノフェライトを２０〜６０質量部、遊離石灰を２０〜７０質量部、無水石膏を１０質量部以下の割合で含有する熱処理物を粉砕してなる（１）の塩害対策用混和材、（３）熱処理物を炭酸化処理してなる（１）または（２）の塩害対策用混和材、（４）（１）〜（３）のいずれかの塩害対策用混和材をコンクリートに配合してなる鉄筋コンクリートの塩害対策方法、（５）塩害対策用混和材をコンクリート中のセメントに対してカルシウムアルミノフェライト含有量が１０〜２０質量％となるようにコンクリートに配合してなる（４）の鉄筋コンクリートの塩害対策方法、である。 That is, the present invention is (1) obtained by heat-treating a mixture of a CaO raw material, an Al 2 O 3 raw material, and an Fe 2 O 3 raw material, and calcium in a total of 100 parts by mass of calcium aluminoferrite and free lime. Admixture for countermeasure against salt damage obtained by grinding a heat-treated product containing 30 to 90 parts by mass of aluminoferrite and 10 to 70 parts by mass of free lime, (2) CaO raw material, Al 2 O 3 raw material, and Fe 2 It is obtained by heat-treating or later adding a mixture of CaSO 4 raw material to O 3 raw material, and 20 to 60 parts by mass of calcium aluminoferrite in a total of 100 parts by mass of calcium aluminoferrite, free lime, and anhydrous gypsum, (1) Salt damage countermeasures obtained by pulverizing a heat-treated product containing 20 to 70 parts by mass of free lime and 10 parts by mass or less of anhydrous gypsum (3) The salt damage countermeasure admixture of (1) or (2) obtained by carbonizing a heat-treated product, or (4) the salt damage countermeasure admixture of any one of (1) to (3) (5) A salt damage countermeasure admixture is blended with concrete so that the calcium aluminoferrite content is 10 to 20% by mass with respect to the cement in the concrete ( 4) A countermeasure method for salt damage of reinforced concrete.
本発明により、塩化物を含む凍結防止材を散布しても鉄筋コンクリートの膨張率が高く、塩害によるひび割れ発生を防止することが可能となるなどの効果を奏する。 According to the present invention, even when spraying an antifreezing material containing chloride, the reinforced concrete has a high expansion rate, and it is possible to prevent the occurrence of cracking due to salt damage.
本発明で使用される、部、％は、特に規定しない限り質量基準である。
また、本発明で云うコンクリートとは、セメントペースト、セメントモルタル、およびセメントコンクリートを総称するものである。
Unless otherwise specified, parts and% used in the present invention are based on mass.
The concrete referred to in the present invention is a general term for cement paste, cement mortar, and cement concrete.
本発明の熱処理物とは、ＣａＯ原料、Ａｌ２Ｏ３原料、およびＦｅ２Ｏ３原料、あるいは、これら原料に、さらにＣａＳＯ４原料を混合したものを熱処理して得られる。 The heat-treated product of the present invention is obtained by heat-treating a CaO raw material, an Al 2 O 3 raw material, an Fe 2 O 3 raw material, or a mixture of these raw materials with a CaSO 4 raw material.
ＣａＯ原料としては、石灰石や消石灰などが挙げられる。Ａｌ２Ｏ３原料としては、ボーキサイトやアルミ残灰などが挙げられる。Ｆｅ２Ｏ３原料としては銅カラミや市販の酸化鉄などが挙げられる。ＣａＳＯ４原料としては二水石膏、半水石膏および無水石膏などが挙げられる。
これらの原料には不純物を含む場合があるが、本発明の効果を阻害しない範囲内では特に問題とはならない。不純物としては、ＳｉＯ２、ＭｇＯ、ＴｉＯ２、ＺｒＯ２、ＭｎＯ、Ｐ２Ｏ５、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ、硫黄、フッ素、塩素などが挙げられる。
Examples of the CaO raw material include limestone and slaked lime. Examples of the Al 2 O 3 raw material include bauxite and aluminum residual ash. Examples of the Fe 2 O 3 raw material include copper calami and commercially available iron oxide. Examples of the CaSO 4 raw material include dihydrate gypsum, hemihydrate gypsum, and anhydrous gypsum.
These raw materials may contain impurities, but are not particularly problematic as long as the effects of the present invention are not impaired. Examples of impurities include SiO 2 , MgO, TiO 2 , ZrO 2 , MnO, P 2 O 5 , Na 2 O, K 2 O, Li 2 O, sulfur, fluorine, and chlorine.
本発明において、ＣａＯ原料、Ａｌ２Ｏ３原料、およびＦｅ２Ｏ３原料、あるいは、ＣａＯ原料、Ａｌ２Ｏ３原料、およびＦｅ２Ｏ３原料に、さらにＣａＳＯ４原料を混合したものを熱処理する方法は、特に限定されるものではない。
例えば、電気炉やキルンなどを用いて、１０００〜１６００℃の温度で焼成することが好ましく、１２００〜１５００℃がより好ましい。１０００℃未満では、練り混ぜ直後のコンクリートの流動性の確保が難しい場合や初期強度の発現性が充分でない場合があり、１６００℃を超えると無水石膏が分解する場合や初期強度の発現性が不十分になる場合がある。熱処理の時間は、その温度にもよるが、最高温度での保持時間は０〜２．０時間が好ましく、０．２５〜１．７５時間がより好ましい。
In the present invention, a CaO raw material, an Al 2 O 3 raw material, and an Fe 2 O 3 raw material, or a CaO raw material, an Al 2 O 3 raw material, and an Fe 2 O 3 raw material further mixed with a CaSO 4 raw material is heat-treated. The method is not particularly limited.
For example, it is preferable to bake at a temperature of 1000 to 1600 ° C using an electric furnace or a kiln, and more preferably 1200 to 1500 ° C. If the temperature is lower than 1000 ° C, it may be difficult to ensure the fluidity of the concrete immediately after mixing, or the initial strength may not be sufficiently developed. If the temperature exceeds 1600 ° C, anhydrous gypsum may decompose or the initial strength may not be sufficiently developed. It may be enough. Although the heat treatment time depends on the temperature, the holding time at the maximum temperature is preferably 0 to 2.0 hours, more preferably 0.25 to 1.75 hours.
本発明の熱処理物には、カルシウムアルミノフェライト、遊離石灰や無水石膏が含まれる。
本発明で云う遊離石灰とは、通常ｆ−ＣａＯと呼ばれるものである。
本発明で云うカルシウムアルミノフェライトとは、４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３（Ｃ４ＡＦと略記）や６ＣａＯ・２Ａｌ２Ｏ３・Ｆｅ２Ｏ３（Ｃ６Ａ２Ｆと略記）や６ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３（Ｃ６ＡＦと略記）で示されるものである。
The heat-treated product of the present invention includes calcium aluminoferrite, free lime and anhydrous gypsum.
The free lime referred to in the present invention is usually called f-CaO.
The calcium aluminoferrite referred to in the present invention is 4CaO.Al 2 O 3 .Fe 2 O 3 (abbreviated as C 4 AF), 6CaO.2Al 2 O 3 .Fe 2 O 3 (abbreviated as C 6 A 2 F), 6CaO.Al 2 O 3 .Fe 2 O 3 (abbreviated as C 6 AF).
本発明の熱処理物に含まれる各成分の含有量は、以下の範囲であることが好ましい。カルシウムアルミノフェライトの含有量は、ＣａＯ原料、Ａｌ２Ｏ３原料、およびＦ
ｅ２Ｏ３原料を混合したものを熱処理する場合、カルシウムアルミノフェライト、遊離
石灰の合計１００部中、カルシウムアルミノフェライトを３０〜９０部、遊離石灰を
１０〜７０部の割合で含有する熱処理物が好ましい。
また、ＣａＯ原料、Ａｌ２Ｏ３原料、およびＦｅ２Ｏ３原料に、さらにＣａＳＯ４原料
を配合する場合には、カルシウムアルミノフェライトの含有量は、カルシウムアルミノフェライト、遊離石灰、無水石膏の合計１００部中、２０〜６０部が好ましく、３０〜５０部がより好ましい。遊離石灰の含有量は、２０〜７０部が好ましく、３０〜６０部がより好ましい。無水石膏の含有量は、遊離石灰、カルシウムアルミノフェライトおよび無水石膏の合計１００部中、１０部以下が好ましく、１〜９部がより好ましい。なお、無水石膏は、カルシウムアルミノフェライト、遊離石灰を含む熱処理物に混合しても良い。
The content of each component contained in the heat-treated product of the present invention is preferably in the following range. The content of calcium aluminoferrite is CaO raw material, Al 2 O 3 raw material, and F
For heating a mixture of e 2 O 3 raw material, a calcium aluminosilicate ferrite, in total 100 parts of free lime, 30 to 90 parts of calcium alumino ferrite, Cook containing free lime in a proportion of 10 to 70 parts of preferable.
In addition, when a CaSO 4 raw material is further added to the CaO raw material, the Al 2 O 3 raw material, and the Fe 2 O 3 raw material, the content of calcium aluminoferrite is a total of 100 of calcium aluminoferrite, free lime, and anhydrous gypsum. In the part, 20 to 60 parts are preferable, and 30 to 50 parts are more preferable. The content of free lime is preferably 20 to 70 parts, more preferably 30 to 60 parts. The content of anhydrous gypsum is preferably 10 parts or less, more preferably 1 to 9 parts, out of a total of 100 parts of free lime, calcium aluminoferrite, and anhydrous gypsum. The anhydrous gypsum may be mixed with a heat-treated product containing calcium aluminoferrite and free lime.
また、本発明の熱処理物を炭酸ガスで処理し、熱処理物中に炭酸カルシウムを生成させることは塩害対策用混和材の性能を確保する上で好ましい。炭酸ガスによる処理温度は４００〜７００℃が好ましい。
炭酸カルシウムの含有量は、炭酸カルシウム、カルシウムアルミノフェライト、遊離石灰、および無水石膏の合計１００部中、０．５〜１０部であることが好ましく、１〜６部がより好ましい。前記範囲外では、塩害抑制性能の向上が見られない場合がある。
In addition, it is preferable to treat the heat-treated product of the present invention with carbon dioxide gas to produce calcium carbonate in the heat-treated product in order to secure the performance of the salt damage countermeasure admixture. The treatment temperature with carbon dioxide gas is preferably 400 to 700 ° C.
The content of calcium carbonate is preferably 0.5 to 10 parts, more preferably 1 to 6 parts, in a total of 100 parts of calcium carbonate, calcium aluminoferrite, free lime, and anhydrous gypsum. Outside the above range, the salt damage suppression performance may not be improved.
上記各成分の含有量は、従来一般の分析方法で確認することができる。例えば、粉砕した試料を粉末Ｘ線回折装置にかけ、生成鉱物を確認するとともにデータをリートベルト法にて解析し、各成分を定量することができる。また、化学成分と粉末Ｘ線回折の同定結果に基づいて、各成分の量を計算によって求めることもできる。
炭酸カルシウムの含有量は、示差熱天秤（ＴＧ−ＤＴＡ）や示差熱熱量測定（ＤＳＣ）などによって、炭酸カルシウムの脱炭酸に伴う質量変化から定量することができる。
The content of each of the above components can be confirmed by a conventional analysis method. For example, the pulverized sample can be applied to a powder X-ray diffractometer to confirm the generated minerals and analyze the data by the Rietveld method to quantify each component. Moreover, the amount of each component can also be obtained by calculation based on the identification result of the chemical component and powder X-ray diffraction.
The content of calcium carbonate can be quantified from a mass change accompanying decarboxylation of calcium carbonate by a differential thermal balance (TG-DTA), differential thermal calorimetry (DSC), or the like.
本発明の塩害対策用混和材の粉末度は、ブレーン比表面積で２５００〜９０００ｃｍ２／ｇが好ましく、３５００〜９０００ｃｍ２／ｇがより好ましい。２５００ｃｍ２／ｇ未満では、塩化物イオンの浸透抑制効果が不十分になる可能性や、初期強度の増進が不十分の場合や長期に亘って後膨張して強度が低下する場合がある。また、９０００ｃｍ２／ｇを超えるとコンクリートの流動性が低下するとともに、塩害抑制性能が不十分となる場合がある。
本発明の塩害対策用混和材の使用量は、コンクリート中のセメントと塩害対策用混和材の合計に対して、カルシウムアルミノフェライト量が１０〜２０％となるようにコンクリートに配合することが好ましい。
The fineness of the admixture for combating salt damage according to the present invention is preferably 2500 to 9000 cm 2 / g, more preferably 3500 to 9000 cm 2 / g in terms of Blaine specific surface area. If it is less than 2500 cm < 2 > / g, the chloride ion permeation suppressing effect may be insufficient, the initial strength may not be sufficiently increased, or the strength may be reduced by post-expansion over a long period of time. Moreover, when it exceeds 9000 cm < 2 > / g, while the fluidity | liquidity of concrete falls, salt damage suppression performance may become inadequate.
The amount of the salt damage countermeasure admixture of the present invention is preferably blended in the concrete so that the amount of calcium aluminoferrite is 10 to 20% with respect to the total amount of cement and salt damage countermeasure admixture in the concrete.
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、および中庸熱などの各種ポルトランドセメント、これらセメントに対して、高炉スラグ、フライアッシュ、およびシリカからなる群から選ばれる少なくとも１種を混合した各種混合セメント、ならびに石灰石粉末を混合したフィラーセメントなどが挙げられる。 The cement used in the present invention is usually at least selected from the group consisting of various Portland cements such as early strength, very early strength, low heat, and moderate heat, and these cements, blast furnace slag, fly ash, and silica. Examples include various mixed cements in which one type is mixed, and filler cements in which limestone powder is mixed.
本発明では、砂、砂利の他、減水剤、高性能減水剤、ＡＥ減水剤、高性能ＡＥ減水剤、流動化剤、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、セメント急硬材、ベントナイトなどの粘土鉱物、ゼオライトなどのイオン交換体、シリカ質微粉末、炭酸カルシウム、水酸化カルシウム、石膏、ケイ酸カルシウム、鋼繊維などを併用することが可能である。有機系材料としては、ビニロン繊維、アクリル繊維、炭素繊維などの繊維状物質などが挙げられる。 In the present invention, in addition to sand and gravel, water reducing agent, high performance water reducing agent, AE water reducing agent, high performance AE water reducing agent, fluidizing agent, antifoaming agent, thickener, rust preventive agent, antifreeze agent, shrinkage reducing agent , Polymer emulsions, setting modifiers, cement hardeners, clay minerals such as bentonite, ion exchangers such as zeolite, siliceous fine powder, calcium carbonate, calcium hydroxide, gypsum, calcium silicate, steel fibers, etc. Is possible. Examples of the organic material include fibrous substances such as vinylon fiber, acrylic fiber, and carbon fiber.
以下、実施例および比較例により本発明を具体的に説明するが、本発明はこれらに限定されないことはもちろんである。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, of course, this invention is not limited to these.
「実験例１」
ＣａＯ原料、Ａｌ２Ｏ３原料、およびＦｅ２Ｏ３原料、あるいは、ＣａＯ原料、Ａｌ２Ｏ３原料、Ｆｅ２Ｏ３原料およびＣａＳＯ４原料を表１、２に記載するような所定の鉱物組成となるように混合した。この混合物を、電気炉を用いて１３５０℃で０．５時間熱処理し、得られた熱処理物をボールミルでブレーン比表面積３，５００ｃｍ２／ｇに粉砕し、塩害対策用混和材とした。
なお、遊離石灰（ｆ−ＣａＯ）５０部、カルシウムアルミノフェライト（Ｃ４ＡＦ）４０部、無水石膏（ＣａＳＯ４）１０部の熱処理物について、炭酸ガス雰囲気下、６００℃で処理を行い、処理時間を変えて、炭酸カルシウム（ＣａＣＯ３）含有量の異なる塩害対策用混和材を調製した。
次に、セメント４５０ｇ、標準砂１３５０ｇ、水２２５ｇを基準配合とし、表１、２に示すように塩害対策用混和材の種類とセメントに対する使用量を変えて、モルタルの膨張率、圧縮強さ、塩分浸透深さ、および曲げひび割れ発生強度比を評価した。塩害対策用混和材は、セメントに内割で配合した。
なお、遊離石灰（ｆ−ＣａＯ）とカルシウムアルミノフェライト（Ｃ４ＡＦ）を含む熱処理物に無水石膏（ブレーン比表面積５０００ｃｍ２/ｇ、市販品）を添加した場合や、遊離石灰（ｆ−ＣａＯ）とカルシウムアルミノフェライト（Ｃ４ＡＦ）をそれぞれ純合成して、ブレーン比表面積３，５００ｃｍ２／ｇに粉砕して混合したものや、市販膨張材に純合成したカルシウムアルミノフェライト（Ｃ４ＡＦ）を添加したものも評価した。
"Experiment 1"
CaO raw material, Al 2 O 3 raw material, and Fe 2 O 3 raw material, or predetermined mineral composition as described in Tables 1 and 2 for CaO raw material, Al 2 O 3 raw material, Fe 2 O 3 raw material and CaSO 4 raw material It mixed so that it might become. This mixture was heat-treated at 1350 ° C. for 0.5 hours using an electric furnace, and the obtained heat-treated product was pulverized with a ball mill to a Blaine specific surface area of 3,500 cm 2 / g to obtain an admixture for preventing salt damage.
Incidentally, free lime (f-CaO) 50 parts, calcium alumino ferrite (C 4 AF) 40 parts of the anhydrous gypsum (CaSO 4) 10 parts of heat-treated product under a carbon dioxide atmosphere, a process at 600 ° C., the treatment time The salt damage countermeasure admixtures having different calcium carbonate (CaCO 3 ) contents were prepared.
Next, 450 g of cement, 1350 g of standard sand, and 225 g of water are used as a reference composition, and as shown in Tables 1 and 2, the type of admixture for preventing salt damage and the amount used for cement are changed, and the expansion rate, compressive strength of mortar, The salt penetration depth and bending cracking strength ratio were evaluated. The admixture for preventing salt damage was blended into the cement.
In addition, when anhydrous gypsum (Brain specific surface area of 5000 cm 2 / g, commercially available product) is added to a heat-treated product containing free lime (f-CaO) and calcium aluminoferrite (C 4 AF), free lime (f-CaO) And calcium aluminoferrite (C 4 AF) were purely synthesized and pulverized to a Blaine specific surface area of 3,500 cm 2 / g and mixed, or calcium aluminoferrite (C 4 AF) purely synthesized into a commercially available expansion material. The added ones were also evaluated.
（使用材料）
ＣａＯ原料：炭酸カルシウム（石灰石微粉末）、１００メッシュ、市販品
Ａｌ２Ｏ３原料：ボーキサイト、９０μｍ篩通過率１００％、市販品
Ｆｅ２Ｏ３原料：酸化鉄粉末、ブレーン比表面積３０００ｃｍ２/ｇ、市販品
ＣａＳＯ４原料：ニ水石膏、ブレーン比表面積５０００ｃｍ２/ｇ、市販品
セメント：普通ポルトランドセメント、市販品、密度３．１６ｇ／ｃｍ３
市販膨張材：ｆ−ＣａＯ５０部、３ＣａＯ・３Ａｌ２Ｏ３、ＣａＳＯ４１２部、ＣａＳＯ４３０部、エトリンガイト・石灰複合型膨張材、電気化学工業社製
砂：ＪＩＳ標準砂
水：水道水
(Materials used)
CaO raw material: Calcium carbonate (fine limestone powder), 100 mesh, commercially available Al 2 O 3 raw material: bauxite, 90 μm sieve passage rate 100%, commercially available Fe 2 O 3 raw material: iron oxide powder, Blaine specific surface area 3000 cm 2 / g Commercially available CaSO 4 raw material: dihydrate gypsum, Blaine specific surface area 5000 cm 2 / g, commercially available cement: ordinary Portland cement, commercially available, density 3.16 g / cm 3
Commercially available expandable material: f-CaO50 parts, 3CaO · 3Al 2 O 3, CaSO 4 12 parts, CaSO 4 30 parts of ettringite-lime composite expanding material, manufactured by Denki Kagaku Kogyo KK sand: JIS standard sand Water: Tap water
（試験方法）
膨張率および圧縮強さ：ＪＩＳ Ａ ６２０２付属書１に準拠した。
塩分浸透深さ：材齢１日で脱型した４０ｍｍ×４０ｍｍ×１６０ｍｍのモルタル試験体を材齢２８日まで２０℃水中で養生し、その後、疑似海水にモルタルを２０℃環境下で浸漬した。浸漬３か月後にモルタル試験体を取り出し、モルタル断面に硝酸銀水溶液を吹きかけて、塩分浸透深さを測定した。測定は８か所測定し、平均値を求めた。
曲げひび割れ発生強度比：膨張率測定で用いた一軸拘束試験体を材齢２８日まで２０℃水中で養生した後、その後、疑似海水にモルタルを２０℃環境下で浸漬した。浸漬３か月後にモルタル試験体を取り出し、端板を取り外した後、曲げ試験を実施した。ひび割れ発生時の荷重を計測し、塩害対策混和材を混和しない試験体との強度比を算出した。
(Test method)
Expansion coefficient and compressive strength: compliant with JIS A 6202 Annex 1.
Salt penetration depth: A 40 mm × 40 mm × 160 mm mortar specimen demolded at 1 day of age was cured in water at 20 ° C. until the age of 28 days, and then the mortar was immersed in simulated seawater in a 20 ° C. environment. After 3 months of immersion, the mortar specimen was taken out and a silver nitrate aqueous solution was sprayed on the cross section of the mortar to measure the salt penetration depth. The measurement was performed at 8 locations and the average value was obtained.
Bending cracking strength ratio: The uniaxial restraint specimen used for the expansion coefficient measurement was cured in 20 ° C. water until the age of 28 days, and then the mortar was immersed in simulated sea water in a 20 ° C. environment. After 3 months of immersion, the mortar specimen was taken out, the end plate was removed, and then a bending test was performed. The load at the time of crack occurrence was measured, and the strength ratio with the test specimen not containing the salt damage countermeasure admixture was calculated.
表１、２より、本発明について以下のことが分かる。
（１）カルシウムアルミノフェライト含有量が高くなるにしたがって塩分浸透が抑制される。（２）熱処理物に無水石膏を共存させると膨張性能が向上するため、無水石膏の含有量を調整することによって、塩分浸透の抑制効果と膨張性能が両立することが可能となる。（３）熱処理物に炭酸カルシウムを生成させることによって、膨張率が向上する。（４）塩害対策混和材を混和しない試験体に比べて、曲げひび割れ発生強度比が高くなり、塩分が浸透してもひび割れ抵抗性に優れる。
From Tables 1 and 2, the following can be understood for the present invention.
(1) Salinity permeation is suppressed as the calcium aluminoferrite content increases. (2) When anhydrous gypsum is allowed to coexist with the heat-treated product, the expansion performance is improved. Therefore, by adjusting the content of anhydrous gypsum, it is possible to achieve both the salt penetration inhibiting effect and the expansion performance. (3) The expansion coefficient is improved by generating calcium carbonate in the heat-treated product. (4) Bending cracking strength ratio is higher than that of specimens that do not contain salt damage countermeasure admixtures, and excellent resistance to cracking even if salt penetrates.
本発明により、塩化物を含む凍結防止材を散布しても鉄筋コンクリートの膨張率が高く塩害によるひび割れ発生を防止することが可能となることから、土木分野などで広範に適用できる。 According to the present invention, even when spraying an antifreezing material containing chloride, the expansion rate of reinforced concrete is high and it is possible to prevent the occurrence of cracks due to salt damage.
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| JPH05294693A (en) * | 1992-04-10 | 1993-11-09 | Denki Kagaku Kogyo Kk | Salt damage-preventing cement additive and salt damage-preventing cement composition |
| JP2001064054A (en) * | 1999-08-25 | 2001-03-13 | Denki Kagaku Kogyo Kk | Cement admixture and cement composition |
| JP2001322848A (en) * | 2000-05-08 | 2001-11-20 | Denki Kagaku Kogyo Kk | Cement admixture and cement composition |
| WO2010143506A1 (en) * | 2009-06-12 | 2010-12-16 | 電気化学工業株式会社 | Expansive admixture and method for producing same |
| WO2012077418A1 (en) * | 2010-12-08 | 2012-06-14 | 電気化学工業株式会社 | Cement admixture, cement composition, and hexavalent chromium reduction method using same |
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| JPH05294693A (en) * | 1992-04-10 | 1993-11-09 | Denki Kagaku Kogyo Kk | Salt damage-preventing cement additive and salt damage-preventing cement composition |
| JP2001064054A (en) * | 1999-08-25 | 2001-03-13 | Denki Kagaku Kogyo Kk | Cement admixture and cement composition |
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| WO2010143506A1 (en) * | 2009-06-12 | 2010-12-16 | 電気化学工業株式会社 | Expansive admixture and method for producing same |
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