JP2008063162A - Sulfuric acid-resistant cement composition and method for repairing therewith - Google Patents

Sulfuric acid-resistant cement composition and method for repairing therewith Download PDF

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JP2008063162A
JP2008063162A JP2006240263A JP2006240263A JP2008063162A JP 2008063162 A JP2008063162 A JP 2008063162A JP 2006240263 A JP2006240263 A JP 2006240263A JP 2006240263 A JP2006240263 A JP 2006240263A JP 2008063162 A JP2008063162 A JP 2008063162A
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sulfuric acid
cement composition
mass
cement
resistant cement
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JP5089943B2 (en
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Takumi Kushihashi
巧 串橋
Akitoshi Araki
昭俊 荒木
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/23—Acid resistance, e.g. against acid air or rain
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72—Repairing or restoring existing buildings or building materials
    • 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

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cement composition excellent in sulfuric acid resistance, strength development, etc., and to provide a method for repairing a concrete structure therewith. <P>SOLUTION: Provided is a sulfuric acid-resistant cement composition comprising cement, a water-soluble, organic, metal sulfonate-substituted compound and an inorganic alkali metal sulfate. It is desirable that 0.5-10 pts.mass water-soluble, organic, alkali metal sulfonate-substituted compound is present per 100 pts.mass cement. It is desirable that the cement composition further contains one or more inorganic powders selected from among silica fume, slag, and fly ash. Also provided are a method for repairing a concrete structure with the sulfuric acid-resistant cement composition and a secondary concrete product lined with the sulfuric acid-resistant cement composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、主に、下水道や温泉地帯などにおける、硫酸によるコンクリート構造物の劣化箇所の修復をするための耐硫酸性に優れたセメント組成物およびそれを用いた補修方法に関する。   The present invention mainly relates to a cement composition excellent in sulfuric acid resistance for repairing a deteriorated portion of a concrete structure due to sulfuric acid in a sewer or a hot spring area, and a repair method using the same.

下水道や温泉地帯などでは、微生物や火山ガスの影響で硫化水素が発生し、これに水が介在すると硫酸となる。このような箇所では、硫酸や硫酸塩によるコンクリート構造物の腐食が問題となっている。コンクリートなどのセメント硬化体は、硫酸のような酸に接触すると、硬化体中に存在する水酸化カルシウムとの反応によってニ水石膏が生じ、さらにはエトリンガイトが生成し劣化が起きる。
このような劣化箇所の補修方法としては、劣化部をウォータージェットにより除去し断面修復してから樹脂ライニングを行う方法が多く実施されている。これに用いる断面修復材としては、高炉水砕スラグにポリマーを配合した材料（特許文献１）、アルミナセメントからなる材料（特許文献２、３）、高炉水砕スラグやシリカフュームなどの微粉末を多量に混和したセメントモルタルが使用されている（特許文献４）。また、アルミナセメントと高炉スラグ微粉末を用いた材料で、５μｍ以下のアルミナセメント粒子を２５重量％以下とし、リチウム塩を含有する材料（特許文献５）、置換基としてスルホン酸のアルカリ金属塩を有する水溶性有機化合物を含有する材料（特許文献６）などが提案されている。 In sewage and hot spring areas, hydrogen sulfide is generated due to the influence of microorganisms and volcanic gas, and when water intervenes, it becomes sulfuric acid. In such places, corrosion of concrete structures due to sulfuric acid or sulfate is a problem. When a cemented body such as concrete is brought into contact with an acid such as sulfuric acid, dihydrate gypsum is generated by reaction with calcium hydroxide present in the cured body, and ettringite is further generated and deteriorated.
As a method for repairing such a deteriorated portion, a method of performing resin lining after removing the deteriorated portion with a water jet and repairing the cross section is often performed. As a cross-sectional restoration material used for this, a material in which a polymer is blended with blast furnace granulated slag (Patent Document 1), a material made of alumina cement (Patent Documents 2 and 3), and a large amount of fine powder such as blast furnace granulated slag and silica fume. Cement mortar blended with the above is used (Patent Document 4). In addition, a material using alumina cement and fine powder of blast furnace slag, alumina cement particles of 5 μm or less are 25 wt% or less, a material containing lithium salt (Patent Document 5), an alkali metal salt of sulfonic acid as a substituent A material (Patent Document 6) containing a water-soluble organic compound has been proposed.

特開平０３−２９０３４８号公報Japanese Patent Laid-Open No. 03-290348 特開２００３−８９５６５号公報JP 2003-89565 A 特開２００４−２９２２４５号公報JP 2004-292245 A 特開２０００−１２８６１８号公報JP 2000-128618 A 特開２００２−２９３６０３号公報JP 2002-293603 A 特開２００３−２９２３６２号公報JP 2003-292362 A

また、下水道に使用されるヒューム管などの二次製品においては、耐酸性を付与する目的でヒューム管内面に耐酸性に優れたシートや耐酸モルタルをライニングすることが提案されている（特許文献７）。   In addition, in secondary products such as fume pipes used in sewers, it has been proposed to line a sheet having excellent acid resistance and acid-resistant mortar on the inner surface of the fume pipe for the purpose of imparting acid resistance (Patent Document 7). ).

特開２００１−８８１１４号公報JP 2001-88114 A

本発明は、耐硫酸性、強度発現性などに優れたセメント組成物およびそれを用いたコンクリート構造物の補修方法を提供する。   The present invention provides a cement composition excellent in sulfuric acid resistance, strength development and the like, and a method for repairing a concrete structure using the cement composition.

すなわち、本発明は、（１）セメント、スルホン酸の金属塩を置換基として有する水溶性有機化合物、およびアルカリ金属無機硫酸塩を含有する耐硫酸性セメント組成物、（２）セメント１００質量部に対して、スルホン酸の金属塩を置換基として有する水溶性有機化合物が０．５〜１０質量部である（１）の耐硫酸性セメント組成物、（３）さらに、シリカフューム、スラグ、フライアッシュから選ばれる１種または２種以上の無機粉末を含有することを特徴とする（１）または（２）の耐硫酸性セメント組成物、（４）（１）〜（３）のいずれかの耐硫酸性セメント組成物を使用したコンクリート構造物の補修方法、（５）（１）〜（３）のいずれかの耐硫酸性セメント組成物をライニングしたコンクリート二次製品、である。   That is, the present invention provides (1) a sulfate-resistant cement composition containing cement, a water-soluble organic compound having a metal salt of sulfonic acid as a substituent, and an alkali metal inorganic sulfate, and (2) 100 parts by mass of cement. On the other hand, the sulfuric acid-resistant cement composition according to (1), wherein the water-soluble organic compound having a metal salt of sulfonic acid as a substituent is 0.5 to 10 parts by mass, (3) further from silica fume, slag, fly ash (1) or (2) a sulfuric acid resistant cement composition characterized by containing one or two or more selected inorganic powders; (4) a sulfuric acid resistant material according to any one of (1) to (3) A method for repairing a concrete structure using a basic cement composition, and a secondary concrete product lined with a sulfuric acid resistant cement composition according to any one of (5), (1) to (3).

本発明の耐硫酸性セメント組成物およびそれを用いたコンクリート構造物の補修方法により、硫酸で劣化したコンクリート構造物の耐硫酸性、強度発現性などに優れた補修が可能となる。さらに、コンクリート二次製品に適用することにより、耐硫酸性に優れたコンクリート製品が得られる。   According to the sulfuric acid resistant cement composition of the present invention and the concrete structure repairing method using the same, it is possible to repair the concrete structure deteriorated by sulfuric acid with excellent sulfuric acid resistance and strength development. Furthermore, a concrete product excellent in sulfuric acid resistance can be obtained by applying it to a concrete secondary product.

以下、本発明を詳細に説明する。   Hereinafter, the present invention will be described in detail.

本発明で使用するセメントとは、ＪＩＳ Ｒ ５２１０に規定されている各種ポルトランドセメント、ＪＩＳ Ｒ ５２１１、ＪＩＳ Ｒ ５２１２、およびＪＩＳ Ｒ ５２１３に規定された各種混合セメント、ＪＩＳに規定された以上の混和材混入率で製造した高炉セメント、フライアッシュセメントおよびシリカセメント、石灰石粉末などを混合したフィラーセメントから選ばれる１種又は２種以上や、アルミナセメントなどである。   The cement used in the present invention includes various portland cements defined in JIS R 5210, various mixed cements defined in JIS R 5211, JIS R 5212, and JIS R 5213, and more admixtures defined in JIS. One type or two or more types selected from filler cement mixed with blast furnace cement, fly ash cement and silica cement, limestone powder and the like manufactured at a mixing rate, and alumina cement.

本発明で使用するスルホン酸の金属塩を置換基として有する水溶性有機化合物とは、ナフタレンスルホン酸、メラミンスルホン酸、リグニンスルホン酸、含窒素スルホン酸などのリチウム、ナトリウム、カリウムのアルカリ金属塩が挙げられる。これらの中で、遅延作用が少ないナフタレンスルホン酸のアルカリ金属塩の使用が好ましい。また、ナフタレンスルホン酸のナトリウム塩は、通常、水溶液あるいは粉体として市販されているものが使用できる。   The water-soluble organic compound having a sulfonic acid metal salt as a substituent used in the present invention includes lithium, sodium, and potassium alkali metal salts such as naphthalene sulfonic acid, melamine sulfonic acid, lignin sulfonic acid, and nitrogen-containing sulfonic acid. Can be mentioned. Among these, the use of an alkali metal salt of naphthalene sulfonic acid having a small delay action is preferable. As the sodium salt of naphthalene sulfonic acid, those commercially available as an aqueous solution or powder can be used.

スルホン酸の金属塩を置換基として有する水溶性有機化合物の使用量は、セメント１００質量部に対して、固形分で０．５〜１０質量部が好ましく、４質量部を超え１０質量部以下であることが耐硫酸性と強度発現性の点でより好ましい。   The amount of the water-soluble organic compound having a metal salt of sulfonic acid as a substituent is preferably 0.5 to 10 parts by mass in terms of solid content with respect to 100 parts by mass of cement, and more than 4 parts by mass and 10 parts by mass or less. It is more preferable in terms of sulfuric acid resistance and strength development.

本発明で使用するアルカリ金属無機硫酸塩とは、耐硫酸性の向上および初期強度発現性の改善を行うことを目的に使用する。スルホン酸の金属塩を置換基として有する水溶性有機化合物は、配合量が多いほど耐硫酸性が向上する傾向にあるが、多量に添加すると流動性が増加しすぎて材料分離を起こしたり、強度低下を起こす場合がある。
アルカリ金属無機硫酸塩の種類としては、硫酸リチウム、硫酸ナトリウム、硫酸カリウム、硫酸アルミニウムカリウムなどのミョウバン類などが挙げられる。これらの中で、硫酸ナトリウムが耐硫酸性の向上および強度発現性の点で好ましい。 The alkali metal inorganic sulfate used in the present invention is used for the purpose of improving the sulfuric acid resistance and improving the initial strength. A water-soluble organic compound having a metal salt of sulfonic acid as a substituent tends to improve the sulfuric acid resistance as the amount is increased. However, if added in a large amount, the fluidity increases too much, causing material separation or strength. May cause a drop.
Examples of the alkali metal inorganic sulfate include alums such as lithium sulfate, sodium sulfate, potassium sulfate, and aluminum potassium sulfate. Among these, sodium sulfate is preferable from the viewpoint of improvement in sulfuric acid resistance and strength development.

アルカリ金属無機硫酸塩の使用量は、セメント１００質量部に対して、０．００５〜２質量部が好ましく、０．０２〜１質量部がより好ましい。０．００５質量部未満では、耐硫酸性、強度発現性の改善が少なく、２質量部を超えると改善効果の向上が少ない。   The amount of the alkali metal inorganic sulfate used is preferably 0.005 to 2 parts by mass and more preferably 0.02 to 1 part by mass with respect to 100 parts by mass of cement. When the amount is less than 0.005 parts by mass, improvement in sulfuric acid resistance and strength development is small, and when the amount exceeds 2 parts by mass, the improvement effect is small.

本発明で使用する無機粉末とは、シリカフューム、スラグ、フライアッシュから選ばれる１種または２種以上であり、ポゾラン反応性や潜在水硬性を利用し硬化体を形成させるために使用する。セメント分が少ないことは、水和反応で生成する水酸化カルシウム量を抑制することができるので、酸（硫酸）による劣化に対し有利に働く。
スラグとしては、高炉水砕スラグ、転炉スラグ、高炉徐冷スラグ、脱リンスラグ、下水汚泥や都市ゴミなどの廃棄物に必要により粘土や石灰等を配合し高温で溶融し急冷して得られる下水汚泥溶融スラグや都市ゴミ焼却灰溶融スラグなどが上げられる。フライアッシュとしては、火力発電所などで発生するものが挙げられる。シリカフュームとしては、フェロシリコン製造時に発生するフェロシリコン起源のシリカフューム、電融ジルコニアの製造時に発生するシリカフューム、金属シリコン製造時に発生するシリカフューム、珪石を原料とし高温で溶融し微粉砕した溶融シリカなどが挙げられる。また、これらの無機粉末を２種以上混合して使用してもよい。 The inorganic powder used in the present invention is one or more selected from silica fume, slag, and fly ash, and is used for forming a cured body utilizing pozzolanic reactivity and latent hydraulic properties. Since the amount of cement is small, the amount of calcium hydroxide generated by the hydration reaction can be suppressed, and this works advantageously against deterioration due to acid (sulfuric acid).
As slag, sewage obtained by blast furnace granulated slag, converter slag, blast furnace slow-cooled slag, dephosphorization slag, wastewater such as sewage sludge and municipal waste, and clay and lime, etc. Sludge melting slag and municipal waste incineration ash melting slag can be raised. Examples of fly ash include those generated at thermal power plants. Examples of silica fume include silica fume derived from ferrosilicon produced during the production of ferrosilicon, silica fume produced during the production of electrofused zirconia, silica fume produced during the production of metallic silicon, and fused silica that is melted and pulverized at high temperatures from silica. It is done. Two or more of these inorganic powders may be mixed and used.

無機粉末の粒度は、特に限定されるものではないが、スラグおよびフライアッシュについては３０００ｃｍ２／ｇ以上が好ましく、シリカフュームについては、ＢＥＴ比表面積で８ｍ２/g以上のものが好ましい。 The particle size of the inorganic powder is not particularly limited, but 3000 cm 2 / g or more is preferable for slag and fly ash, and 8 m 2 / g or more in terms of BET specific surface area is preferable for silica fume.

無機粉末の使用量は、セメント１００質量部に対して、５０〜９００質量部が好ましく、１５０質量部を超え〜６００質量部がより好ましく、２００〜４００質量部がさらに好ましい。５０質量部未満では、耐硫酸性の向上が充分でない場合があり、９００質量部を超えると強度発現性に影響する場合がある。   The amount of the inorganic powder used is preferably 50 to 900 parts by weight, more preferably 150 parts by weight to 600 parts by weight, and further preferably 200 to 400 parts by weight with respect to 100 parts by weight of cement. If it is less than 50 parts by mass, the sulfuric acid resistance may not be sufficiently improved, and if it exceeds 900 parts by mass, strength development may be affected.

本発明の耐硫酸性セメント組成物は、骨材を併用したモルタルやコンクリートとすること好ましい。
本発明で使用する骨材は、砂、砂利の他に、例えば、ケイ砂系や石灰石系などの天然骨材、高炉水砕スラグ系、高炉徐冷スラグ系、再生骨材系などの人工骨材が挙げられる。耐酸性などの観点からは、ケイ砂系を選定することが好ましい。また、比重３．０ｇ／ｃｍ３以上の重量骨材を使用することもでき、その具体例としては、例えば、人工骨材として、電気炉酸化期スラグ系骨材や、フェロニッケルスラグ、フェロクロムスラグ、銅スラグ、亜鉛スラグおよび鉛スラグなどを総称する非鉄精錬スラグ骨材などが、また、天然骨材としては、橄欖岩（かんらん岩）系骨材、いわゆるオリビンサンドや、エメリー鉱などが挙げられる。本発明では、これらの１種または２種以上を併用できる。 The sulfuric acid resistant cement composition of the present invention is preferably mortar or concrete combined with aggregate.
In addition to sand and gravel, the aggregate used in the present invention is, for example, natural bone such as silica sand or limestone, blast furnace granulated slag system, blast furnace slow-cooled slag system, regenerated aggregate system, etc. Materials. From the viewpoint of acid resistance and the like, it is preferable to select a silica sand system. In addition, a heavy aggregate having a specific gravity of 3.0 g / cm 3 or more can be used, and specific examples thereof include, for example, an electric furnace oxidation period slag-based aggregate, ferronickel slag, ferrochrome slag as an artificial aggregate. Non-ferrous smelted aggregates such as copper slag, zinc slag and lead slag, and natural aggregates include peridotite aggregates, so-called olivine sand and emery ore. It is done. In this invention, these 1 type (s) or 2 or more types can be used together.

本発明では、耐硫酸性に影響を与えない範囲で、耐久性能や付着性能等を改善する目的でセメント混和用ポリマーディスパージョン、ひび割れ抵抗性や曲げじん性を改善する目的で短繊維、作業性等を改善する目的に粘土鉱物、凝結時間を速めることを目的に硬化促進剤の他に各種要求される性能を付与する目的で消泡剤、防錆剤、防凍剤、撥水剤、増粘剤、抗菌剤などの各種セメント混和剤を使用することができる。   In the present invention, in the range not affecting the sulfuric acid resistance, cement dispersion polymer dispersion for the purpose of improving durability performance and adhesion performance, short fiber for improving crack resistance and bending toughness, workability In addition to clay minerals for the purpose of improving the setting time, in addition to hardening accelerators for the purpose of accelerating the setting time, antifoaming agents, rust preventives, antifreezing agents, water repellents, thickening agents for the purpose of imparting various required performances. Various cement admixtures such as an agent and an antibacterial agent can be used.

本発明の補修方法としては特に限定されるものではないが、例えば、圧搾空気を用いた湿式・乾式吹付け工法やグラウト工法、コテ塗りによる補修方法等が挙げられる。   Although it does not specifically limit as a repair method of this invention, For example, the repair method by the wet and dry spraying method using a compressed air, a grout method, a trowel coating, etc. are mentioned.

本発明の耐硫酸性セメント組成物は、硫酸による劣化が懸念されるコンクリート構造物に適用でき、例えば、下水道処理施設の改修工事、温泉地帯でのコンクリート構造物の改修工事、下水道等で使用するヒューム管内の耐酸ライニング、硫酸劣化が起こることが想定される新設コンクリート構造物の予防保全工事等が挙げられる   The sulfuric acid resistant cement composition of the present invention can be applied to a concrete structure that is likely to be deteriorated by sulfuric acid. Examples include acid-resistant lining in fume pipes and preventive maintenance work for new concrete structures where sulfuric acid deterioration is expected to occur.

以下、実施例で詳細に説明する。   Examples will be described in detail below.

セメント１００質量部に対して、水溶性有機化合物の種類と量を表１に示すように配合し、さらに、アルカリ金属無機硫酸塩（α）を０．５質量部配合しセメント組成物を調製した。このセメント組成物１００質量部に対して細骨材を２００質量部配合し、さらに、水／セメント組成物比が４５質量％となるよう水を加えてモルタルを作製した。硬化したモルタルについて、耐硫酸性、浸透深さ、圧縮強度の試験を行った。結果を表１に示す。   The type and amount of the water-soluble organic compound were blended as shown in Table 1 with respect to 100 parts by mass of cement, and 0.5 parts by mass of alkali metal inorganic sulfate (α) was blended to prepare a cement composition. . A mortar was prepared by adding 200 parts by mass of fine aggregate to 100 parts by mass of the cement composition and adding water so that the water / cement composition ratio was 45% by mass. The cured mortar was tested for sulfuric acid resistance, penetration depth, and compressive strength. The results are shown in Table 1.

（使用材料）
セメント：普通ポルトランドセメント、電気化学工業社製
水溶性有機化合物（Ａ）：スルホン酸の金属塩を置換基として有する、第一工業社製、商品名「セルフロー１１０Ｐ」、粉末タイプ
水溶性有機化合物（Ｂ）：スルホン酸の金属塩を置換基として有する、花王社製、商品名「マイティー１００」、粉末タイプ
水溶性有機化合物（Ｃ）：スルホン酸の金属塩を置換基として有しない、ポリビニルアルコール、電気化学工業社、商品名「Ｂ−１７」、粉末タイプ
細骨材 ：ケイ砂、日瓢鉱業社製、商品名「Ｎ−５０」、最大粒子径０．８ｍｍ
アルカリ金属無機硫酸塩（α）：市販の硫酸ナトリウム、試薬 (Materials used)
Cement: Ordinary Portland cement, water-soluble organic compound manufactured by Denki Kagaku Kogyo Co., Ltd. (A): product name “Cell Flow 110P”, powder type water-soluble organic compound (made by Daiichi Kogyo Co., Ltd.) B): having a metal salt of sulfonic acid as a substituent, manufactured by Kao Corporation, trade name “Mighty 100”, powder type water-soluble organic compound (C): polyvinyl alcohol having no metal salt of sulfonic acid as a substituent, Denki Kagaku Kogyo Co., Ltd., trade name “B-17”, powder type fine aggregate: silica sand, manufactured by Nippon Steel Mining Co., Ltd., trade name “N-50”, maximum particle size 0.8 mm
Alkali metal inorganic sulfate (α): Commercially available sodium sulfate, reagent

（試験方法）
耐硫酸性：モルタルを型枠に詰めてφ７．５ｃｍ×１５ｃｍの成形体を作製し、１日後に脱型した後、材齢２８日まで２０℃の水中で養生を行い、５質量％濃度の硫酸溶液に供試体を１ヶ月間浸漬し、供試体の外観の変化や質量減少から耐酸性を評価した。評価基準は、×は外観の変化が著しく、かつ、質量変化率が±５％以上の場合、△は外観の変化が著しいか、あるいは、質量変化率が±５％以上のいずれか一方を満たす場合、○は外観の変化と質量変化ともに上記条件に該当しない場合とした。
浸透深さ：モルタルを型枠に詰めてφ７．５ｃｍ×１５ｃｍの成形体を作製し、１日後に脱型した後、材齢２８日まで２０℃の水中で養生を行い５％濃度の硫酸溶液に供試体を１ヶ月間浸漬した。浸漬後の供試体を輪切りにし、フェノールフタレインを用いて硫酸の浸透深さを測定した。
圧縮強度：モルタルを型枠に詰めて４ｃｍ×４ｃｍ×１６ｃｍの成形体を作製し、材齢２８日の圧縮強度をＪＩＳ Ｒ ５２０１に準じて測定した。 (Test method)
Sulfuric acid resistance: A molded body of φ7.5 cm × 15 cm was prepared by filling mortar into a mold, and after demolding after 1 day, it was cured in water at 20 ° C. until the age of 28 days. The specimen was immersed in a sulfuric acid solution for one month, and the acid resistance was evaluated from the change in the appearance of the specimen and the decrease in mass. As for the evaluation criteria, × indicates that the appearance change is remarkable and the mass change rate is ± 5% or more, and Δ indicates that the appearance change is significant or the mass change rate is ± 5% or more. In the case, ◯ indicates that neither the change in appearance nor the change in mass meets the above conditions.
Penetration depth: A molded body of φ7.5 cm × 15 cm was prepared by filling a mortar into a mold, and after demolding after 1 day, it was cured in water at 20 ° C. until the age of 28 days, and a 5% strength sulfuric acid solution. The specimen was immersed for 1 month. The specimen after immersion was cut into round pieces, and the penetration depth of sulfuric acid was measured using phenolphthalein.
Compressive strength: A molded body of 4 cm × 4 cm × 16 cm was prepared by filling a mortar into a mold, and the compressive strength at the age of 28 days was measured according to JIS R 5201.

Figure 2008063162
Figure 2008063162

表１より、本発明の耐硫酸性セメント組成物は、耐硫酸性に優れ、硫酸の浸透深さが小さく、さらに、強度発現性が良好であることが分かる。   From Table 1, it can be seen that the sulfuric acid resistant cement composition of the present invention is excellent in sulfuric acid resistance, has a small penetration depth of sulfuric acid, and has good strength development.

実施例１の実験No.1-9において、セメント１００質量部に対して、アルカリ金属無機硫酸塩の種類と使用量を表２に示すように変化したこと以外は実施例１と同様に行った。結果を表２に示す。   In Experiment No. 1-9 of Example 1, the same procedure as in Example 1 was performed except that the type and amount of alkali metal inorganic sulfate were changed as shown in Table 2 with respect to 100 parts by mass of cement. . The results are shown in Table 2.

（使用材料）
アルカリ金属無機硫酸塩（β）：市販の硫酸リチウム、試薬
アルカリ金属無機硫酸塩（γ）：市販の硫酸カリウム、試薬 (Materials used)
Alkali metal inorganic sulfate (β): Commercially available lithium sulfate, reagent Alkali metal inorganic sulfate (γ): Commercially available potassium sulfate, reagent

Figure 2008063162
Figure 2008063162

表２より、本発明の耐硫酸性セメント組成物は、耐硫酸性に優れ、硫酸の浸透深さが小さく、さらに、強度発現性が良好であることが分かる。   From Table 2, it can be seen that the sulfuric acid resistant cement composition of the present invention is excellent in sulfuric acid resistance, has a small penetration depth of sulfuric acid, and has good strength development.

実施例１の実験No.1-9において、セメント１００質量部に対して、さらに、無機粉末の種類と使用量を表３に示すように配合したこと以外は実施例１と同様に行った。結果を表３に示す。   In Experiment No. 1-9 of Example 1, the same procedure as in Example 1 was conducted, except that 100 parts by mass of cement was further blended with inorganic powders as shown in Table 3. The results are shown in Table 3.

（使用材料）
無機粉末（イ）：市販の高炉水砕スラグ、ブレーン比表面積４０００ｃｍ２／ｇ
無機粉末（ロ）：市販のフライアッシュ、ブレーン比表面積４３００ｃｍ２／ｇ
無機粉末（ハ）：無機粉末（イ）と無機粉末（ロ）の等量混合物
無機粉末（ニ）：市販のシリカフューム、ＢＥＴ比表面積で１０ｍ２/g
無機粉末（ホ）：炭酸カルシウム、平均粒径３．７μｍ、常陸砕石社製、粉末タイプ (Materials used)
Inorganic powder (I): Commercial blast furnace granulated slag, Blaine specific surface area 4000 cm 2 / g
Inorganic powder (b): Commercially available fly ash, Blaine specific surface area 4300 cm 2 / g
Inorganic powder (C): Equivalent mixture of inorganic powder (I) and inorganic powder (B) Inorganic powder (D): Commercially available silica fume, 10 m 2 / g in BET specific surface area
Inorganic powder (e): calcium carbonate, average particle size 3.7 μm, manufactured by Hitachi Crushed stone, powder type

Figure 2008063162
Figure 2008063162

表３より、本発明の耐硫酸性セメント組成物は、無機粉末を加えることにより、より耐硫酸性に優れ、より硫酸の浸透深さが小さくなることが分かる。   From Table 3, it can be seen that the sulfuric acid resistant cement composition of the present invention is more excellent in sulfuric acid resistance and has a smaller penetration depth of sulfuric acid by adding inorganic powder.

本発明の耐硫酸性セメント組成物および補修方法により、硫酸で劣化したコンクリート構造物の耐硫酸性、強度発現性などに優れた補修が可能となる。さらに、コンクリート二次製品に適用することにより、耐硫酸性に優れたコンクリート製品が得られるので、土木、建築分野で幅広く適用できる。   By the sulfuric acid resistant cement composition and the repairing method of the present invention, it becomes possible to repair the concrete structure deteriorated by sulfuric acid with excellent sulfuric acid resistance and strength development. Furthermore, by applying to a secondary concrete product, a concrete product excellent in sulfuric acid resistance can be obtained, so that it can be widely applied in the civil engineering and construction fields.

Claims (5)

セメント、スルホン酸の金属塩を置換基として有する水溶性有機化合物、およびアルカリ金属無機硫酸塩を含有する耐硫酸性セメント組成物。 A sulfuric acid resistant cement composition containing cement, a water-soluble organic compound having a metal salt of sulfonic acid as a substituent, and an alkali metal inorganic sulfate. セメント１００質量部に対して、スルホン酸の金属塩を置換基として有する水溶性有機化合物が０．５〜１０質量部である請求項１記載の耐硫酸性セメント組成物。 The sulfuric acid resistant cement composition according to claim 1, wherein the water-soluble organic compound having a metal salt of sulfonic acid as a substituent is 0.5 to 10 parts by mass with respect to 100 parts by mass of cement. さらに、シリカフューム、スラグ、フライアッシュから選ばれる１種または２種以上の無機粉末を含有することを特徴とする請求項１または２記載の耐硫酸性セメント組成物。 The sulfate-resistant cement composition according to claim 1 or 2, further comprising one or more inorganic powders selected from silica fume, slag, and fly ash. 請求項１〜３のいずれか１項に記載の耐硫酸性セメント組成物を使用したコンクリート構造物の補修方法。 The repair method of the concrete structure using the sulfuric-resistant cement composition of any one of Claims 1-3. 請求項１〜３のいずれか１項に記載の耐硫酸性セメント組成物をライニングしたコンクリート二次製品。 A concrete secondary product lined with the sulfuric acid resistant cement composition according to any one of claims 1 to 3.
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