JP2010155734A - Acid resistant cement composition - Google Patents
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- JP2010155734A JP2010155734A JP2008333883A JP2008333883A JP2010155734A JP 2010155734 A JP2010155734 A JP 2010155734A JP 2008333883 A JP2008333883 A JP 2008333883A JP 2008333883 A JP2008333883 A JP 2008333883A JP 2010155734 A JP2010155734 A JP 2010155734A
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- 239000002253 acid Substances 0.000 title claims abstract description 55
- 239000004568 cement Substances 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000002893 slag Substances 0.000 claims abstract description 39
- 229910021487 silica fume Inorganic materials 0.000 claims abstract description 38
- 239000011398 Portland cement Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000006386 neutralization reaction Methods 0.000 abstract description 15
- 239000004570 mortar (masonry) Substances 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 239000013585 weight reducing agent Substances 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000010881 fly ash Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- 235000012241 calcium silicate Nutrition 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002699 waste material Substances 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)
Abstract
Description
本発明は、酸性環境下で使用されるコンクリートやモルタル等の製造に好適に用いることができる耐酸性セメント組成物に関する。 The present invention relates to an acid-resistant cement composition that can be suitably used for producing concrete, mortar, and the like used in an acidic environment.
下水道関連施設などの酸性環境下でコンクリートが使用されると、コンクリートはアルカリ性のため、セメントの水和生成物である水酸化カルシウムと硫酸などの酸との中和反応が起こる。この反応により、コンクリートの膨張の原因となる硫酸カルシウムが生成したり、中性化により鉄筋保護能力が低下したりすることに起因してコンクリート構造物の劣化が起こる。その対策のため、従来から結合材として種々の耐酸性セメント組成物が用いられている。中でも、フライアッシュ、高炉スラグ、シリカフュームといった材料は広くセメントコンクリートの分野で使用されており、入手し易く安価であり、廃棄物利用にもなるので、種々検討されている。 When concrete is used in an acidic environment such as a sewerage facility, since the concrete is alkaline, a neutralization reaction occurs between calcium hydroxide, which is a hydration product of cement, and an acid such as sulfuric acid. By this reaction, deterioration of the concrete structure occurs due to the generation of calcium sulfate that causes the expansion of the concrete or the reduction of the reinforcing bar protection ability due to neutralization. For this purpose, various acid-resistant cement compositions have been conventionally used as binders. Among them, materials such as fly ash, blast furnace slag, and silica fume are widely used in the field of cement concrete, are easily available, are inexpensive, and are used as waste.
例えば、特許文献１には、セメント組成物を、ポルトランドセメント、フライアッシュ、高炉スラグ微粉末、シリカフュームの４成分からなるようにするとともに、セメント組成物１００重量部に対して、ポルトランドセメントを１５〜２５重量部、フライアッシュを４０〜６０重量部、高炉スラグ微粉末を１０〜３０重量部、シリカフュームを５〜１５重量部とする防蝕モルタルが記載されている。また、水酸化カルシウム生成量を抑制すべく、高ビーライト系のセメントを用いたものも知られている。
このような４成分系のセメント組成物を用いたコンクリートやモルタルは、水和反応で水酸化カルシウムがポゾラン反応によって消費されているので、所定材齢まで水中養生した試験体を硫酸水溶液に浸漬して重量の減少率を測定する耐酸性試験（試験方法１）においては、硫酸カルシウムの生成が抑えられ、浸漬材齢２８日までの重量減少率が小さくなることから、優れた耐酸性を有すると評価されている。しかしながら、このような４成分系のセメント組成物を用いたコンクリートやモルタルは、短中期材齢では耐酸性を有するものの、表面からの硫酸浸透が速く進み、この硫酸浸透により重量減少には至らないまでも、コンクリートやモルタルの表面だけでなく深い位置でも容易に中性化が起こることから、長期材齢でのコンクリートやコンクリート構造物の劣化が懸念され、長期にわたって耐酸性に優れているとは一概に言えないという問題があることが判明した。そして、上記耐酸性試験（試験方法１）のみの評価では不十分であり、硫酸浸透による中性化深さを測定する耐酸性試験（試験方法２）も行ったことが良いことが判明した。 In concrete and mortar using such a four-component cement composition, calcium hydroxide is consumed by the pozzolanic reaction in the hydration reaction, so the test specimen cured in water until a predetermined age is immersed in an aqueous sulfuric acid solution. In the acid resistance test (test method 1) for measuring the weight reduction rate, the production of calcium sulfate is suppressed, and the weight reduction rate until the soaking material age of 28 days is reduced. It is evaluated. However, although concrete and mortar using such a four-component cement composition have acid resistance at short and medium-term ages, sulfuric acid permeation from the surface proceeds rapidly, and this sulfuric acid permeation does not lead to weight reduction. In addition, since neutralization occurs easily not only on the surface of concrete and mortar but also at deep positions, there is concern about deterioration of concrete and concrete structures at long-term ages, and it is said that it has excellent acid resistance for a long time It turned out that there was a problem that could not be said in general. And it became clear that the evaluation of only the acid resistance test (test method 1) was not sufficient, and that an acid resistance test (test method 2) for measuring the depth of neutralization by sulfuric acid permeation was also performed.
一方、上記４成分系では、均一に混合する手間がかかるとともに、比重や粒径が異なるので、材料分離を起こし易く、均一性を維持するのが難しいという問題もある。また、高ビーライト系セメントを用いたものは、入手が容易とは言えず、価格も普通ポルトランドセメントよりも高価であり、シリカフュームは更に高価なので、高ビーライト系セメントとシリカフュームを併用する場合は大量には使用し難い。 On the other hand, the above four-component system has the problem that it takes time and effort to uniformly mix, and the specific gravity and particle size are different, so that it is easy to cause material separation and it is difficult to maintain uniformity. Also, it is not easy to obtain the one using high belite cement, the price is more expensive than ordinary Portland cement, and silica fume is more expensive, so if you use high belite cement and silica fume together It is difficult to use in large quantities.
そこで本発明は、上記の問題に鑑み、コンクリートやモルタル等の硬化体にした場合に、酸と接しても容易に劣化しないだけでなく、酸による硬化体内部への中性化進行も同時に抑えることができ、長期にわたって良好な耐酸性を有するとともに、できるだけ使用材料の種類を少なく抑えることができ、安価で入手の容易な耐酸性セメント組成物を提供することを目的とする。 Therefore, in view of the above problems, the present invention does not easily deteriorate even if it comes into contact with an acid when it is made into a hardened body such as concrete or mortar, and simultaneously suppresses the progress of neutralization inside the hardened body by an acid. An object of the present invention is to provide an acid-resistant cement composition that is inexpensive and readily available, having good acid resistance over a long period of time and having as few types of materials as possible.
上記目的を達成するために、試験方法１および２を用いて、上記４成分系のセメント組成物について改良を試みた結果、フライアッシュを用いないことにより、一般的な普通ポルトランドセメントを用いた場合でも、目に見える劣化（重量減少）だけでなく、酸による硬化体内部への中性化進行も同時抑えることができることを見出し、本発明を完成させた。すなわち、本発明に係る耐酸性セメント組成物は、普通ポルトランドセメントと、シリカフュームと、高炉水砕スラグ粉とからなる３成分系の耐酸性セメント組成物であって、前記高炉水砕スラグ粉の含有量が、前記普通ポルトランドセメントの含有量と同等か又はそれより多く、普通ポルトランドセメントが３０〜４０質量％、シリカフュームが１２〜２５質量％、高炉水砕スラグ粉が４０〜５８質量％で、これら３成分で１００質量％となることを特徴とするものである。 In order to achieve the above object, as a result of attempting to improve the above four-component cement composition using Test Methods 1 and 2, the case where general ordinary Portland cement was used by not using fly ash However, the inventors have found that not only visible deterioration (weight reduction) but also the progress of neutralization inside the cured product by acid can be suppressed at the same time, and the present invention has been completed. That is, the acid-resistant cement composition according to the present invention is a three-component acid-resistant cement composition composed of ordinary Portland cement, silica fume, and blast furnace granulated slag powder, which contains the blast furnace granulated slag powder. The amount is equal to or more than the content of the ordinary Portland cement, the ordinary Portland cement is 30 to 40% by mass, the silica fume is 12 to 25% by mass, the granulated blast furnace slag powder is 40 to 58% by mass, The three components are 100% by mass.
前記シリカフュームと前記高炉水砕スラグ粉との割合は、質量比で、高炉水砕スラグ粉／シリカフューム＝２．０〜３．２とすることが好ましい。前記普通ポルトランドセメントと前記シリカフュームとの割合は、質量比で、普通ポルトランドセメント／シリカフューム＝１．９〜２．５とすることが好ましい。前記高炉水砕スラグ粉は、ブレーン比表面積が４０００〜１００００ｃｍ2／ｇのものが好ましい。 The ratio of the silica fume and the blast furnace granulated slag powder is preferably a mass ratio of blast furnace granulated slag powder / silica fume = 2.0 to 3.2. It is preferable that the ratio of the said ordinary Portland cement and the said silica fume is mass ratio, and sets it as ordinary Portland cement / silica fume = 1.9-2.5. The granulated blast furnace slag powder preferably has a Blaine specific surface area of 4000 to 10000 cm 2 / g.
本発明によれば、セメント組成物を普通ポルトランドセメントと、シリカフュームと、高炉水砕スラグ粉の３成分のみにするとともに、前記高炉水砕スラグ粉の含有量が、前記普通ポルトランドセメントの含有量と同等か又はそれより多くなるように、これら３成分を上記の所定の配合量にすることで、実用上の必要な強度や流動性を維持しつつ、セメント組成物によって得られる硬化体においては、硬化体の硫酸侵食による重量減少を抑えるだけでなく、硬化体内部への硫酸浸透速度をも抑え、中性化進行も同時に抑えることができる。また、３成分系であるので混合し易い。更に、一般的な材料からなるので、入手も容易で比較的安価である。 According to the present invention, the cement composition includes only ordinary Portland cement, silica fume, and blast furnace granulated slag powder, and the content of the granulated blast furnace slag powder includes the content of the ordinary Portland cement. In the cured product obtained by the cement composition while maintaining the strength and fluidity necessary for practical use by making these three components the above-mentioned predetermined blending amount so as to be equivalent or more, Not only can the weight reduction due to sulfuric acid erosion of the cured body be suppressed, but also the rate of sulfuric acid penetration into the cured body can be suppressed, and the progress of neutralization can be suppressed simultaneously. Moreover, since it is a three component system, it is easy to mix. Further, since it is made of a general material, it is easily available and relatively inexpensive.
以下、本発明に係る耐酸性セメント組成物の一実施の形態を説明する。本発明に係る耐酸性セメント組成物は、普通ポルトランドセメントと、シリカフュームと、高炉水砕スラグ粉とのみからなる３成分系の耐酸性セメント組成物である。 Hereinafter, an embodiment of an acid-resistant cement composition according to the present invention will be described. The acid-resistant cement composition according to the present invention is a three-component acid-resistant cement composition composed of ordinary Portland cement, silica fume, and granulated blast furnace slag.
本発明では、普通ポルトランドセメントを使用する。ポルトランドセメントには、その他に、早強、中庸熱、低熱がある。しかしながら、早強では、Ｃ3Ｓの量が多いので水酸化カルシウムの生成量が多くなり易く好ましくない。中庸熱や、低熱では、高炉水砕スラグ粉が十分に活性化されず、短期強度の確保も難しい。よって、普通ポルトランドセメント以外では、本発明のような３成分系で目的とする耐酸性セメント組成物を得るのが難しい。 In the present invention, ordinary Portland cement is used. Portland cement has other high strength, moderate heat and low heat. However, early strength is not preferable because the amount of calcium hydroxide is likely to increase because the amount of C 3 S is large. At moderate heat and low heat, blast furnace granulated slag powder is not activated sufficiently, and it is difficult to ensure short-term strength. Therefore, it is difficult to obtain a target acid-resistant cement composition in a three-component system as in the present invention except for ordinary Portland cement.
なお、普通ポルトランドセメントは、ＪＩＳ規格のものが好ましい。 The normal Portland cement is preferably JIS standard.
シリカフュームは、シリカ質を主成分とする超微粒子の活性シリカ材料であり、高強度セメント製品に広く用いられている。本発明に使用するシリカフュームは、ＪＩＳ Ａ６２０７に規定される「コンクリート用シリカフューム」の品質規格を満足するものが好ましいが、特に限定されない。また、シリカフュームのＢＥＴ比表面積は、１５〜２２ｍ2／ｇが好ましい。シリカフュームは、ポゾラン反応によりＣ−Ｓ−Ｈゲルの生成に寄与する他、コンクリート等の硬化体マトリクスの緻密化にも寄与し、中性化進行を抑制する。 Silica fume is an ultrafine active silica material mainly composed of siliceous material, and is widely used in high-strength cement products. The silica fume used in the present invention preferably satisfies the quality standard of “silica fume for concrete” defined in JIS A6207, but is not particularly limited. Silica fume preferably has a BET specific surface area of 15 to 22 m 2 / g. Silica fume contributes to the formation of C—S—H gel by the pozzolanic reaction, and also contributes to densification of a hardened matrix such as concrete and suppresses the progress of neutralization.
高炉水砕スラグ粉は、高炉から生成する溶融スラグに多量の圧力水を噴射することにより急冷した砂状のスラグの粉砕物である。本発明に使用する高炉水砕スラグ粉は、高炉セメントや従来のセメント混和材に用いられているものなら使用できるが、中でも、ＪＩＳ Ａ６２０６に規定される「コンクリート用高炉スラグ微粉末」の品質規格を満足するものが好ましい。また、高炉水砕スラグ粉はブレーン比表面積が４０００〜１００００ｃｍ2／ｇのものが好ましい。ブレーン比表面積をこの範囲内にすることで、適度な流動性を維持しつつ、必要強度も確保し易い。４０００ｃｍ2／ｇ未満では、十分な強度が得られず、１００００ｃｍ2／ｇを超えると、硬化体の緻密性を維持しつつ流動性も維持することが、難しくなる。ブレーン値をこの範囲にするには、例えば、高炉水砕スラグ粉をチューブミル又はローラーミル等で粉砕し、セパレーター等で分級する。 Blast furnace granulated slag powder is a crushed product of sandy slag that has been quenched by injecting a large amount of pressure water into molten slag generated from the blast furnace. The granulated blast furnace slag powder used in the present invention can be used as long as it is used in blast furnace cement and conventional cement admixtures. Those satisfying the above are preferable. Also, blast furnace slag powder Blaine specific surface area preferably from 4000~10000cm 2 / g. By setting the Blaine specific surface area within this range, it is easy to ensure the required strength while maintaining appropriate fluidity. If it is less than 4000 cm 2 / g, sufficient strength cannot be obtained, and if it exceeds 10,000 cm 2 / g, it becomes difficult to maintain fluidity while maintaining the denseness of the cured product. In order to make the brane value within this range, for example, blast furnace granulated slag powder is pulverized with a tube mill or a roller mill, and classified with a separator or the like.
本発明に係る３成分系の耐酸性セメント組成物は、高炉水砕スラグ粉の含有量を普通ポルトランドセメントの含有量と同等か又はそれより多くする必要がある。そうでないと、普通ポルトランドセメントを用いた３成分系のセメント組成物では目的とする耐酸性が得られ難い。普通ポルトランドセメントよりも高炉水砕スラグの含有量を多くした方がより好ましい。本発明に係る３成分系の耐酸性セメント組成物の具体的な配合割合は、前記条件を満たしつつ、普通ポルトランドセメントを３０〜４０質量％、シリカフュームを１２〜２５質量％、高炉水砕スラグ粉を４０〜５８質量％含むものであり、これら３成分で１００質量％となる。 In the three-component acid resistant cement composition according to the present invention, the content of granulated blast furnace slag powder needs to be equal to or more than the content of ordinary Portland cement. Otherwise, the target acid resistance is difficult to obtain with a three-component cement composition using ordinary Portland cement. It is more preferable to increase the content of granulated blast furnace slag than normal Portland cement. The specific blending ratio of the three-component acid-resistant cement composition according to the present invention is 30-40% by mass of ordinary Portland cement, 12-25% by mass of silica fume, and granulated blast furnace slag powder while satisfying the above conditions. 40 to 58 mass%, and these three components make up 100 mass%.
普通ポルトランドセメントが３０質量％未満では、実用上十分な強度が確保できない。一方、普通ポルトランドセメントが４０質量％を超えると、目的とする耐酸性が得られ難い。好ましくは３３〜３６質量％である。また、シリカフュームが１２質量％未満では、前述のシリカフューム作用効果が十分に得られず、硬化体マトリクスの緻密性、必要強度の確保、目的とする耐酸性などの点で不十分となる場合が生じる。一方、シリカフュームが２５質量％を超えると、流動性が悪くなり、作業性が悪くなる。好ましくは１５〜１７質量％である。さらに、高炉水砕スラグ粉が４０質量％未満では、目的とする耐酸性が得られない。一方、高炉水砕スラグ粉が５８質量％を超えると、実用上必要な強度が確保し難く、耐酸性も悪くなる。好ましくは４７〜５２質量％であり、この範囲で普通ポルトランドセメントの１．３〜１．６倍の量となっていることがより好ましい。 When ordinary Portland cement is less than 30% by mass, a practically sufficient strength cannot be secured. On the other hand, when ordinary Portland cement exceeds 40% by mass, it is difficult to obtain the desired acid resistance. Preferably it is 33-36 mass%. Further, if the silica fume is less than 12% by mass, the above-mentioned silica fume action effect cannot be obtained sufficiently, and the case may be insufficient in terms of the denseness of the cured product matrix, ensuring the required strength, and the desired acid resistance. . On the other hand, when silica fume exceeds 25 mass%, fluidity | liquidity will worsen and workability | operativity will worsen. Preferably it is 15-17 mass%. Furthermore, if the blast furnace granulated slag powder is less than 40% by mass, the intended acid resistance cannot be obtained. On the other hand, if the granulated blast furnace slag powder exceeds 58% by mass, it is difficult to ensure the practically required strength and the acid resistance also deteriorates. The amount is preferably 47 to 52% by mass, and more preferably 1.3 to 1.6 times that of ordinary Portland cement in this range.
以上から、特に好ましいのは、普通ポルトランドセメントを３３〜３６質量％、シリカフュームを１５〜１７質量％、高炉水砕スラグ粉を４７〜５２質量％であり、且つ高炉水砕スラグ粉／普通ポルトランドセメント＝１．３〜１．６（質量比）である。 From the above, it is particularly preferable that 33 to 36% by mass of ordinary Portland cement, 15 to 17% by mass of silica fume, 47 to 52% by mass of granulated blast furnace slag, and blast furnace granulated slag powder / ordinary Portland cement. = 1.3 to 1.6 (mass ratio).
一方、ポゾラン物質であり、共に水酸化カルシウムの生成を抑制するシリカフュームと高炉水砕スラグ粉との割合を、質量比で、高炉水砕スラグ粉／シリカフューム＝２．０〜３．２とすることも好ましい。ポゾラン活性や粉末度の異なる高炉水砕スラグ粉をシリカフュームに対して、この割合の範囲内にすることで、適度な流動性を維持しつつ、目的とする耐酸性（重量減少の抑制、中性化進行の抑制）を長期にわたって維持することができる。 On the other hand, the ratio of silica fume and blast furnace granulated slag powder, both of which are pozzolanic substances and suppress the formation of calcium hydroxide, is blast furnace granulated slag powder / silica fume = 2.0 to 3.2 in terms of mass ratio. Is also preferable. By making blast furnace granulated slag powder with different pozzolanic activity and fineness within this range of silica fume, the desired acid resistance (suppression of weight loss, neutrality while maintaining appropriate fluidity) Can be maintained over a long period of time.
一方、普通ポルトランドセメントとシリカフュームとの割合を、質量比で、普通ポルトランドセメント／シリカフューム＝１．９〜２．５とすることも好ましい。普通ポルトランドセメントをシリカフュームに対して、この割合の範囲内にすることで、目的とする耐酸性を得つつ、短期材齢での強度の確保や混練時の適度な流動性が得られ易くなる。 On the other hand, it is also preferable that the ratio of ordinary Portland cement and silica fume is, as a mass ratio, ordinary Portland cement / silica fume = 1.9 to 2.5. By making ordinary Portland cement within the range of this ratio with respect to silica fume, it becomes easy to secure strength at short-term ages and obtain appropriate fluidity during kneading while obtaining the desired acid resistance.
本発明に係る耐酸性セメント組成物は、耐酸性のコンクリートやモルタルの製造に用いることができる。コンクリートを製造する場合、例えば、本発明に係る耐酸性セメント組成物１００質量部に対して、細骨材を９０〜３５０質量部、粗骨材を２００〜４００質量部加えることが好ましい。骨材は、石灰石以外の一般的なコンクリート用骨材を使用できるが、公知の耐酸性骨材を用いることが好ましい。また、水／耐酸性セメント組成物比（質量比）は３０〜６０％とすることが好ましい。このコンクリートを用いて、下水管やマンホール、杭等のコンクリート製品を製造できる。モルタルを製造する場合、例えば、本発明に係る耐酸性セメント組成物１００質量部に対して、細骨材を９０〜３５０質量部加えることが好ましい。また、水／耐酸性セメント組成物比（質量比）は２５〜５５％とすることが好ましい。このモルタルは、耐酸被覆材として使用できる。 The acid-resistant cement composition according to the present invention can be used for the production of acid-resistant concrete and mortar. When producing concrete, for example, it is preferable to add 90 to 350 parts by mass of fine aggregate and 200 to 400 parts by mass of coarse aggregate with respect to 100 parts by mass of the acid-resistant cement composition according to the present invention. As the aggregate, a general concrete aggregate other than limestone can be used, but a known acid-resistant aggregate is preferably used. Moreover, it is preferable that water / acid-resistant cement composition ratio (mass ratio) shall be 30 to 60%. Using this concrete, concrete products such as sewage pipes, manholes and piles can be manufactured. When manufacturing a mortar, it is preferable to add 90-350 mass parts of fine aggregates with respect to 100 mass parts of acid-resistant cement compositions which concern on this invention, for example. The water / acid resistant cement composition ratio (mass ratio) is preferably 25 to 55%. This mortar can be used as an acid resistant coating.
本発明に係る耐酸性セメント組成物は、例えば、工場で上記材料を従来通りの方法で既調合（プレミックス）して、通常袋詰めなどの形態で施工現場に供給し、施工現場でミキサを用いて水と混練して使用することが好ましい。混練方法は特に限定されない。また、混練に用いる装置も特に限定されるものではなく、ハンドミキサ、パン型ミキサ、二軸練りミキサ、傾胴ミキサ等の慣用のミキサなどを使用することができる。 The acid-resistant cement composition according to the present invention is prepared by pre-mixing the above materials by a conventional method at a factory, for example, and usually supplied to the construction site in the form of bagging or the like. It is preferable to use and knead with water. The kneading method is not particularly limited. Moreover, the apparatus used for kneading is not particularly limited, and a conventional mixer such as a hand mixer, a pan-type mixer, a biaxial kneading mixer, and a tilting mixer can be used.
以下に、本発明に係る耐酸性セメント組成物の実施例および比較例について記載する。表１に示すように、実施例１〜９及び比較例１〜７のセメント組成物をプレミックスし調製した。 Below, the Example and comparative example of an acid-resistant cement composition which concern on this invention are described. As shown in Table 1, the cement compositions of Examples 1-9 and Comparative Examples 1-7 were premixed and prepared.
なお、実施例および比較例に用いた材料は、以下の通りである。
（１）普通ポルトランドセメント：太平洋セメント社製。計算による鉱物組成は、エーライトが６０％、ビーライトが１４％。比表面積は３３４０ｃｍ2／ｇで、密度は３．１６ｇ／ｃｍ3であった。
（２）シリカフューム：エルケム社製。ＢＥＴ比表面積は、１６．７ｍ2／ｇであった。
（３）高炉水砕スラグ粉：デイ・シイ社製。ブレーン比表面積が４４００ｃｍ2／ｇで、密度が２．９１ｇ／ｃｍ3であるＡと、ブレーン比表面積が８７６０ｃｍ2／ｇで、密度が２．９１ｇ／ｃｍ3であるＢを用いた。
（４）フライアッシュ：電源開発社製。
In addition, the material used for the Example and the comparative example is as follows.
(1) Ordinary Portland cement: manufactured by Taiheiyo Cement. The calculated mineral composition is 60% for alite and 14% for belite. The specific surface area was 3340 cm 2 / g and the density was 3.16 g / cm 3 .
(2) Silica fume: manufactured by Elchem. The BET specific surface area was 16.7 m 2 / g.
(3) Blast furnace granulated slag powder: manufactured by Dei Shi. Blaine specific surface area of at 4400cm 2 / g, density and A is 2.91 g / cm 3, Blaine specific surface area of at 8760cm 2 / g, density was used B is 2.91 g / cm 3.
(4) Fly ash: manufactured by Power Supply Development Company.
（１．セメントペースト供試体による耐酸性試験）
次に、これら実施例および比較例の各セメント組成物について、ＪＩＳ Ｒ５２０１に準拠して、水を混合して調製したセメントペーストから供試体を成形した。そして、各供試体について、以下の耐酸性試験を行った。先ず、マクロ的な耐酸性を見るために、供試体を材齢２８日まで水中養生した後、５％硫酸水溶液に５６日間浸漬し、その間の供試体の重量変化率（重量減少）を測定した。また、供試体内部への硫酸浸透（中性化）の進行度を見るために、重量変化率を測定した供試体を切断し、現れた断面にフェノールフタレイン溶液を塗布し、非呈色部分の表面からの深さ（すなわち、硫酸が浸透して中性化した深さ）を測定した。これらの結果を表２に示す。なお、実施例および比較例のいずれの供試体についても、水セメント組成物比（質量比）は５０％とした。
(1. Acid resistance test with cement paste specimen)
Next, for each of the cement compositions of these examples and comparative examples, specimens were molded from cement paste prepared by mixing water in accordance with JIS R5201. And the following acid resistance tests were done about each specimen. First, in order to observe the macro acid resistance, the specimen was cured in water until the age of 28 days, and then immersed in a 5% sulfuric acid aqueous solution for 56 days, and the weight change rate (weight reduction) of the specimen during that period was measured. . In addition, in order to see the progress of sulfuric acid penetration (neutralization) into the specimen, the specimen whose weight change rate was measured was cut, and a phenolphthalein solution was applied to the resulting cross section, and the non-colored part The depth from the surface (namely, the depth at which the sulfuric acid penetrated and became neutralized) was measured. These results are shown in Table 2. In addition, the water cement composition ratio (mass ratio) was set to 50% for any of the specimens of Examples and Comparative Examples.
表２に示すように、重量変化率の測定では、実施例１〜９の供試体は、浸漬開始から７日後は、硫酸カルシウム（石膏）が形成されるために重量が増加するものの、浸漬開始から５６日後でも重量の減少は見られず、マクロ的には耐酸性に優れた結果となった。一方、比較例１、４、５の各供試体は、硫酸水溶液浸漬による重量の減少が見られ、マクロ的にも耐酸性に劣る結果となった。また、表２に示すように、中性化深さの測定では、実施例１〜９の供試体は、浸漬開始から５６日経っても中性化深さが１．１ｍｍ以下で、進行速度も減少しており、中性化進行に対しても耐酸性に優れた結果となった。これに対し、比較例２、３、６、７では、重量変化率の測定で重量の減少はみられないものの、中性化深さの測定では、浸漬開始から５６日後で１．４ｍｍ以上と中性化深さがかなり進行しており、進行も止まる傾向が見られないことから、長期的な耐酸性に懸念が生ずる結果となった。 As shown in Table 2, in the measurement of the rate of change in weight, the specimens of Examples 1 to 9 increased in weight because calcium sulfate (gypsum) was formed after 7 days from the start of immersion, but the start of immersion. No reduction in weight was observed even after 56 days, and the result was excellent in acid resistance macroscopically. On the other hand, each specimen of Comparative Examples 1, 4, and 5 showed a decrease in weight due to immersion in a sulfuric acid aqueous solution, resulting in inferior acid resistance macroscopically. Moreover, as shown in Table 2, in the measurement of the neutralization depth, the specimens of Examples 1 to 9 had a neutralization depth of 1.1 mm or less even after 56 days from the start of immersion, and the progression rate. As a result, the acid resistance was excellent with respect to the progress of neutralization. On the other hand, in Comparative Examples 2, 3, 6, and 7, no weight decrease was observed in the weight change rate measurement, but in the neutralization depth measurement, it was 1.4 mm or more after 56 days from the start of immersion. Since the depth of neutralization has progressed considerably and there is no tendency to stop the progress, this has resulted in concerns over long-term acid resistance.
また、参考として、実施例の各供試体について、示差熱分析（リガク社ＴＧ８１２０）により供試体中の水酸化カルシウムの含有率を調べる試験を行った。すなわち、供試体を室温から１０００℃まで１０℃／分で加熱して、その間の重量を測定した。４００℃から５００℃の間の重量減少が全て水酸化カルシウムの分解によるものとして、その重量減少率からＣａ(ＯＨ)2の含有率を求めた。その結果を表３に示す。なお、供試体は、水中養生での材齢７日と材齢２８日のものを用いた。 For reference, a test for examining the content of calcium hydroxide in the specimen by differential thermal analysis (Rigaku TG8120) was performed on each specimen in the examples. That is, the specimen was heated from room temperature to 1000 ° C. at 10 ° C./min, and the weight during that time was measured. Assuming that the weight loss between 400 ° C. and 500 ° C. was all due to the decomposition of calcium hydroxide, the content of Ca (OH) 2 was determined from the weight reduction rate. The results are shown in Table 3. The specimens used were 7 days old and 28 days old under water curing.
表３に示すように、材齢とともにＣａ（ＯＨ）2含有率は減少し、材齢２８日では１．８〜３．２％程度となった。 As shown in Table 3, the Ca (OH) 2 content decreased with the age of the material, and was about 1.8 to 3.2% at the age of 28 days.
（２．セメントペースト供試体による圧縮強度の試験）
表１の実施例および比較例の各セメント組成物につき、ＪＩＳ Ｒ５２０１に準じて、所定の材齢まで水中養生したセメントペースト供試体での圧縮強度試験を行った。その結果を表４に示す。表４に示すように、実施例１〜９のいずれの供試体も、実用上の必要な強度を得られることがわかった。
(2. Compressive strength test with cement paste specimen)
For each of the cement compositions of the examples and comparative examples in Table 1, a compressive strength test was performed on a cement paste specimen cured in water until a predetermined age according to JIS R5201. The results are shown in Table 4. As shown in Table 4, it was found that any of the specimens of Examples 1 to 9 can obtain a practically required strength.
（３．コンクリート供試体によるフレッシュ性状と圧縮強度の確認試験）
表１の実施例１、４、８および比較例３の各セメント組成物につき、表５に示す骨材と表６に示す混和剤を用いて、表７に示すコンクリート配合でＪＩＳ規格に準じてフレッシュ性状試験と、所定の材齢まで水中養生した供試体による圧縮強度試験を行った。その結果を表８に示す。表８に示すように、実施例１、４、８のいずれの供試体も、良好なフレッシュ性と強度発現性を有することを確認した。
(3. Confirmation test of fresh properties and compressive strength with concrete specimens)
For each of the cement compositions of Examples 1, 4, 8 and Comparative Example 3 in Table 1, the aggregate shown in Table 5 and the admixture shown in Table 6 were used, and the concrete composition shown in Table 7 was used in accordance with JIS standards. A fresh property test and a compressive strength test using a specimen cured in water until a predetermined age were performed. The results are shown in Table 8. As shown in Table 8, it was confirmed that any of the specimens of Examples 1, 4, and 8 had good freshness and strength development.
Claims (4)
The granulated blast furnace slag powder, acid-resistant cement composition according to any one of claims 1-3 Blaine specific surface area of 4000~10000cm 2 / g.
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