JP4287685B2 - How to select fly ash for hardened cement - Google Patents
How to select fly ash for hardened cement Download PDFInfo
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- JP4287685B2 JP4287685B2 JP2003084678A JP2003084678A JP4287685B2 JP 4287685 B2 JP4287685 B2 JP 4287685B2 JP 2003084678 A JP2003084678 A JP 2003084678A JP 2003084678 A JP2003084678 A JP 2003084678A JP 4287685 B2 JP4287685 B2 JP 4287685B2
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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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
-
- 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
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00112—Mixtures characterised by specific pH values
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/05—Materials having an early high strength, e.g. allowing fast demoulding or formless casting
-
- 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
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- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Ceramic Engineering (AREA)
- Combustion & Propulsion (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、セメントの硬化を阻害せず、安定かつ速やかなセメントの凝結が得られるセメント硬化体用として好適なフライアッシュの選択方法に関する。
【０００２】
【従来の技術】
フライアッシュは、微粉炭燃焼の火力発電所で、ボイラーの燃焼ガス中の微粉炭灰分を集塵機で捕集したものであり、球状粒子であるため、流動性を改善する等の目的で、セメントに混合して用いられている。また、得られる硬化体の透水性は低く、乾燥収縮も小さく抑えられるため、廃棄物の有効利用の観点からも、近年、多量に用いられるようになってきた。
【０００３】
しかしながら、フライアッシュをセメントに混合すると、セメントの硬化が阻害され、凝結時間が遅延するという問題が生じる。これは、フライアッシュに含まれるホウ素が、凝結に大きく影響を与えるためである（非特許文献１）。しかして、ホウ素の分析は、ＪＩＳ Ｋ ０４００−５２−３０：２００１「水質・誘導結合プラズマ発光分光分析による３３元素の定量」により行なうことができるが、大変精密な分析で、用いる誘導結合プラズマ発酵分光分析装置は非常に高価なものである。
【０００４】
フライアッシュを用いたセメント硬化体の強度を早期に確保し、速やかに脱型するためには、用いるフライアッシュの性質を正確に把握する必要がある。
入手したフライアッシュが実際に使用できるかどうかは、従来、混練、流し込み、硬化体作成等の予備試験を行ない、曲げ強度、圧縮強度等を測定する必要があり、時間と手間のかかるものであった。また、逐次に性質が変化するフライアッシュの全てについて、このような試験を行なって使用可否を判断することは、困難であった。
【０００５】
【非特許文献１】
笠井芳夫、外３名，「フライアッシュ中の微量成分による凝結遅延作用の究明」，第１６回セメント・コンクリート研究討論会研究報告集，平成元年，ｐ．１９−２４
【０００６】
【発明が解決しようとする課題】
従って、本発明の目的は、凝結遅延がなく、安定かつ速やかなセメントの凝結が得られるセメント硬化体用として好適なフライアッシュを選択する方法を提供することにある。
【０００７】
【課題を解決するための手段】
かかる実情において、本発明者らは鋭意検討を行った結果、水に分散させたときの濾液が特定のｐＨであるフライアッシュを用いれば、セメントの硬化が阻害されず、セメントが安定かつ速やかに凝結することを見出し、本発明を完成した。
【０００８】
すなわち、本発明は、フライアッシュ２５０重量部を水５００重量部に分散させて攪拌し、攪拌直後に得た濾液のｐＨが６以上、及び攪拌直後に得た濾液のｐＨ（Ａ）と、攪拌後３０分放置後に得た濾液のｐＨ（Ｂ）により求められるｐＨ変化度、（Ｂ）／（Ａ）が１．２以下であるフライアッシュを選択することを特徴とするセメント硬化体用として好適なフライアッシュの選択方法を提供するものである。
【０００９】
【発明の実施の形態】
本発明において、セメント硬化体用として好適なフライアッシュは、フライアッシュ２５０重量部を水５００重量部に分散させて攪拌し、攪拌直後に得た濾液のｐＨ（Ａ）が６以上のものである。
例えば、水１００〜１０００ｇにフライアッシュ５０〜５００ｇを上記のような割合で均一に分散するよう、ミキサーを用いて５０００〜１５０００ｒｐｍで１〜３分間攪拌する。その直後に濾紙を用いて濾液を得、そのｐＨが６以上、好ましくはｐＨ７〜１３のものである。濾液のｐＨが６未満では、セメントの硬化を著しく遅らせてしまう。
【００１０】
また、本発明において、セメント硬化体用として好適なフライアッシュは、前記攪拌直後に得た濾液のｐＨ（Ａ）と、攪拌後３０分放置した後に得た濾液のｐＨ（Ｂ）により求められるｐＨ変化度、（Ｂ）／（Ａ）が１．２以下、好ましくは０．９〜１．１のものである。この比が１．２を超えるものは、特にセメントの硬化が遅れる。これは、セメントとフライアッシュ、水の混合物の混練初期のｐＨが大きく変動することを意味し、硬化反応が安定しないためである。
【００１１】
本発明において、セメント硬化体用として好適なフライアッシュは、セメントに混合して用いられる。用いるセメントとしては、セメントの硬化を阻害しないことから、特に、速硬性セメント又は早強性セメントを主成分とするものが好ましい。
早強性セメントとは、例えばＪＩＳ Ｒ ５２１０−１９７９に従う１日の圧縮強さが６５ｋｇｆ／ｃｍ2程度以上のものであり、早強ポルトランドセメント、超早強ポルトランドセメントがある。これらは、普通ポルトランドセメントに比べ、１日の圧縮強さがより強く、あるいは流し込み数時間後の圧縮強度が速やかに発現するため、より好ましい。
【００１２】
速硬性セメントとしては、例えば、C11A7・CaCl2、C11A7・CaF2等のカルシウムハロアルミネート類、C12A7、CA等のカルシウムアルミネート類及び／又はC3A3・CaSO4等のカルシウムスルホアルミネート類のような各種の速硬性又は急硬性のセメント成分を主体とするもののほか、ポルトランドセメント類に上記した各種の速硬性又は急硬性のセメント成分を混合した混合セメント等が挙げられる。これらは、速硬エコセメント、ジェットセメント、スーパージェットセメント、ＳＱセメント、ＧＲＣ用セメント等として市販されている。
同様に、早強性セメントとしては、上述した早強ポルトランドセメントや超早強ポルトランドセメントのほか、普通ポルトランドセメント、中庸熱ポルトランドセメントに急結剤、速硬化剤等を併用した混合セメントを使用することもできる。
【００１３】
セメントとフライアッシュの混合割合は、重量比で８５：１５〜４０：６０、特に７５：２５〜５０：５０であるのが、長期強度ののびが良好であるので好ましい。
【００１４】
実施例１
表１に示すNo.１〜１１のフライアッシュ（太平洋セメント社製、中電スーパーフローSF-20）について、強熱減量、攪拌直後の濾液のｐＨ（Ａ）、攪拌後３０分放置後の濾液のｐＨ（Ｂ）、ｐＨ変化度、速硬エコセメントによる硬化度、及び早強ポルトランドセメントによる１日養生曲げ強度を測定した。結果を表１に併せて示す。
【００１５】
（測定方法）
（１）強熱減量：
ＪＩＳ Ａ ６２０１：１９９９「コンクリート用フライアッシュ」に準拠して、強熱減量を測定した。
【００１６】
（２）攪拌直後の濾液のｐＨ（Ａ）：
蒸留水５００ｇ及びフライアッシュ２５０ｇを、内容積１５００cc、１２０００rpmの家庭用ミキサーに入れ、２分間攪拌した後、１分間の間に分析用５Ａ濾紙及びブフナーロートを用い、洗浄液を濾別して得た。この濾液を１００mLビーカーに採取し、マグネットスターラーで攪拌しながら、オリオンリサーチ社製、ｐＨ／イオン・メーターModel 720A、ROSS精密複合ｐＨ電極により、１分後のｐＨを測定した。
【００１７】
（３）攪拌後３０分放置後の濾液のｐＨ（Ｂ）：
（２）と同様に、蒸留水及びフライアッシュを攪拌したものを、３０分間そのまま放置した後、同様に濾過して得た濾液のｐＨを測定した。
【００１８】
（４）ｐＨ変化度：
（２）及び（３）で得られたｐＨより、濾液のｐＨ変化度＝（Ｂ）／（Ａ）を求めた。
【００１９】
（５）速硬エコセメントによる硬化度：
速硬エコセメント（太平洋セメント社製）６０重量部、No.１〜No.１１のフライアッシュ４０重量部、水６５重量部、乾式粉砕パルプ（レッテンマイヤー社製、アーボセルPWC-500）５重量部、減水剤（太平洋マテリアル社製、コアフローCP-300）１重量部、増粘剤（信越化学工業社製、メチルセルロースhi90SH-4000）０．２重量部を材料とし、２０℃に保温して用いた。
速硬エコセメント、フライアッシュ、乾式粉砕パルプ及び増粘剤の合計１０５０．２ｇを、ビニール袋内で予め混合し、水及び減水剤の合計６６０ｇの混合液中に投入し、ハンドミキサーを用いて２分間攪拌して得られたスラリーを、型枠に流し込んだ。これを６０℃で３０分間加熱養生し、ＪＩＳ Ｋ ６２５３「加硫ゴム及び熱可塑性ゴムの硬さ試験方法」で用いられる、高分子計器社製、タイプＣデュロメーターを用いて硬化体表面の硬さを測定し、これを硬化度とした。
【００２０】
（６）早強ポルトランドセメントによる１日養生曲げ強度：
早強ポルトランドセメント（太平洋セメント社製）６０重量部、No.１〜No.１１のフライアッシュ４０重量部、水６５重量部、乾式粉砕パルプ（レッテンマイヤー社製、アーボセルPWC-500）５重量部、減水剤（太平洋マテリアル社製、コアフローCP-300）１重量部、増粘剤（信越化学工業社製、メチルセルロースhi90SH-4000）０．２重量部を材料とし、２０℃に保温して用いた。
早強ポルトランドセメント、フライアッシュ、乾式粉砕パルプ及び増粘剤の合計１０５０．２ｇを、ビニール袋内で予め混合し、水及び減水剤の合計６６０ｇの混合液中に投入し、ハンドミキサーを用いて２分間攪拌して得られたスラリーを、２×２×８cmの砲金製型枠３本に流し込んだ。これを２０℃で４時間養生し、その後３０℃で２０時間養生した後、脱型し、インストロン万能試験機を用い、スパン７cm、載荷速度０．５mm／分、中央載荷３点曲げにて、曲げ強度を測定した。
【００２１】
【表１】
表１の結果より、ｐＨ（Ａ）が６以上、及びｐＨ変化度が１．２以下であるNo.１〜３、５〜８及び１０のフライアッシュは、速硬性セメント及び早強性セメントの硬化を阻害せず、速やかにセメントが凝結し、十分な強度のセメント硬化体を得ることができた。
【００２３】
【発明の効果】
本発明によれば、セメントの硬化を阻害せず、安定かつ速やかなセメントの凝結が得られるセメント硬化体用として好適なフライアッシュを選択することができる。 [0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for selecting fly ash suitable for use in a hardened cement body that does not inhibit hardening of the cement and provides stable and rapid setting of the cement .
[0002]
[Prior art]
Fly ash is a pulverized coal-fired thermal power plant that collects pulverized coal ash in boiler combustion gas with a dust collector.Since it is a spherical particle, it is used in cement for the purpose of improving fluidity. It is used as a mixture. Moreover, since the water permeability of the hardened | cured body obtained is low and drying shrinkage | contraction is also restrained small, it has come to be used in large quantities in recent years also from a viewpoint of effective utilization of a waste material.
[0003]
However, when fly ash is mixed with cement, the hardening of the cement is hindered and the setting time is delayed. This is because boron contained in fly ash greatly affects the condensation (Non-patent Document 1). Boron can be analyzed by JIS K 0400-52-30: 2001 "Quantification of 33 elements by water quality and inductively coupled plasma emission spectroscopy". Inductively coupled plasma fermentation used in a very precise analysis. The spectroscopic analyzer is very expensive.
[0004]
In order to ensure the strength of the hardened cement body using fly ash at an early stage and quickly remove the mold, it is necessary to accurately grasp the properties of the fly ash used.
Whether or not the obtained fly ash can actually be used has previously been subjected to preliminary tests such as kneading, pouring, and making a cured body, and it is necessary to measure bending strength, compressive strength, etc., which is time consuming and laborious. It was. In addition, it is difficult to determine whether or not the fly ash whose properties are sequentially changed by performing such a test.
[0005]
[Non-Patent Document 1]
Yoshio Kasai and three others, "Study on setting delay action by trace components in fly ash", 16th Cement and Concrete Research Conference Report, 1989, p. 19-24
[0006]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a method for selecting a fly ash suitable for a hardened cement body that does not have a setting delay and that provides stable and quick setting of cement .
[0007]
[Means for Solving the Problems]
In such a situation, as a result of intensive studies, the present inventors have determined that if the fly ash having a specific pH as the filtrate when dispersed in water is used, the hardening of the cement is not inhibited, and the cement is stably and rapidly. The present invention was completed by finding that it condenses.
[0008]
That is, according to the present invention, 250 parts by weight of fly ash is dispersed in 500 parts by weight of water and stirred. The pH of the filtrate obtained immediately after stirring is 6 or more, and the pH (A) of the filtrate obtained immediately after stirring is stirred. PH change degree determined by pH (B) of filtrate obtained after standing for 30 minutes after that, suitable for use in hardened cement body, wherein fly ash having (B) / (A) of 1.2 or less is selected A method for selecting a proper fly ash is provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a fly ash suitable for a hardened cement body is one in which 250 parts by weight of fly ash is dispersed in 500 parts by weight of water and stirred, and the pH (A) of the filtrate obtained immediately after stirring is 6 or more. .
For example, 50 to 500 g of fly ash is uniformly dispersed in 100 to 1000 g of water at a ratio as described above, and stirred at 5000 to 15000 rpm for 1 to 3 minutes using a mixer. Immediately thereafter, a filtrate is obtained using filter paper, and the pH is 6 or more, preferably pH 7-13. If the pH of the filtrate is less than 6, the hardening of the cement is significantly delayed.
[0010]
In the present invention, a fly ash suitable for a cemented body is determined by the pH (A) of the filtrate obtained immediately after the stirring and the pH (B) of the filtrate obtained after standing for 30 minutes after stirring. The degree of change (B) / (A) is 1.2 or less, preferably 0.9 to 1.1. When this ratio exceeds 1.2, the hardening of the cement is particularly delayed. This means that the initial pH of the mixture of cement, fly ash and water fluctuates greatly, and the curing reaction is not stable.
[0011]
In the present invention, fly ash suitable for hardened cement bodies is used by mixing with cement. As the cement to be used, a cement containing a fast-hardening cement or a fast-strength cement as a main component is particularly preferable because it does not inhibit the hardening of the cement.
The early-strength cement is, for example, one having a daily compressive strength of about 65 kgf / cm 2 or more according to JIS R 5210-1979, and includes early-strength Portland cement and ultra-early-strength Portland cement. These are more preferable because the compressive strength of one day is stronger or the compressive strength after several hours of pouring is rapidly developed as compared with ordinary Portland cement.
[0012]
Examples of the fast-curing cement include calcium haloaluminates such as C 11 A 7 · CaCl 2 and C 11 A 7 · CaF 2 , calcium aluminates such as C 12 A 7 and CA, and / or C 3 A 3・ In addition to those mainly composed of various quick-hardening or quick-hardening cement components such as calcium sulfoaluminates such as CaSO 4 and the like, Portland cements are mixed with the above-mentioned various quick-hardening or quick-hardening cement components. Cement etc. are mentioned. These are commercially available as fast-hardening eco-cement, jet cement, super jet cement, SQ cement, cement for GRC, and the like.
Similarly, as early-strength cement, in addition to the above-mentioned early-strength Portland cement and ultra-early-strength Portland cement, use mixed cement that combines ordinary Portland cement and medium-heated Portland cement with quick setting agent, fast curing agent, etc. You can also
[0013]
The mixing ratio of cement and fly ash is preferably 85:15 to 40:60, particularly 75:25 to 50:50 in terms of weight ratio, because long-term strength is good.
[0014]
Example 1
For No. 1 to 11 fly ash (manufactured by Taiheiyo Cement Co., Ltd., Chuden Super Flow SF-20) shown in Table 1, loss on ignition, pH of filtrate immediately after stirring (A), filtrate after standing for 30 minutes after stirring PH (B), degree of pH change, degree of cure with fast-curing ecocement, and daily curing bending strength with early-strength Portland cement were measured. The results are also shown in Table 1.
[0015]
(Measuring method)
(1) Loss on ignition:
The ignition loss was measured in accordance with JIS A 6201: 1999 “Fly Ash for Concrete”.
[0016]
(2) pH (A) of the filtrate immediately after stirring:
Distilled water (500 g) and fly ash (250 g) were placed in a household mixer with an internal volume of 1500 cc and 12000 rpm, stirred for 2 minutes, and then washed with a 5A filter paper for analysis and a Buchner funnel for 1 minute. The filtrate was collected in a 100 mL beaker, and the pH after 1 minute was measured with a pH / ion meter Model 720A, ROSS precision composite pH electrode manufactured by Orion Research, while stirring with a magnetic stirrer.
[0017]
(3) pH (B) of the filtrate after standing for 30 minutes after stirring:
In the same manner as (2), a solution obtained by stirring distilled water and fly ash was allowed to stand for 30 minutes, and then the pH of the filtrate obtained by filtration in the same manner was measured.
[0018]
(4) pH change degree:
From the pH obtained in (2) and (3), the pH change of the filtrate = (B) / (A) was determined.
[0019]
(5) Curing degree with fast-curing eco-cement:
60 parts by weight of fast-curing ecocement (manufactured by Taiheiyo Cement), 40 parts by weight of No. 1 to No. 11 fly ash, 65 parts by weight of water, 5 parts by weight of dry pulverized pulp (Arbocel PWC-500, manufactured by Rettenmeier) , 1 part by weight of a water reducing agent (manufactured by Taiheiyo Materials Co., Coreflow CP-300) and 0.2 part by weight of a thickener (manufactured by Shin-Etsu Chemical Co., Ltd., methylcellulose hi90SH-4000) were used by keeping them at 20 ° C. .
A total of 1050.2g of quick-hardening eco-cement, fly ash, dry pulverized pulp and thickener is pre-mixed in a plastic bag, put into a mixed solution of 660g of water and water reducing agent, and using a hand mixer. The slurry obtained by stirring for 2 minutes was poured into a mold. This was heated and cured at 60 ° C. for 30 minutes, and the hardness of the cured body surface was measured using a type C durometer manufactured by Kobunshi Keiki Co., Ltd., used in JIS K 6253 “Hardness test method for vulcanized rubber and thermoplastic rubber”. Was measured and this was taken as the degree of cure.
[0020]
(6) Daily curing bending strength with early strength Portland cement:
60 parts by weight of early strength Portland cement (manufactured by Taiheiyo Cement), 40 parts by weight of No. 1 to No. 11 fly ash, 65 parts by weight of water, 5 parts by weight of dry-pulverized pulp (Arbocel PWC-500, manufactured by Rettenmeier) , 1 part by weight of a water reducing agent (manufactured by Taiheiyo Materials Co., Coreflow CP-300) and 0.2 part by weight of a thickener (manufactured by Shin-Etsu Chemical Co., Ltd., methylcellulose hi90SH-4000) were used by keeping them at 20 ° C. .
A total of 1050.2g of early strength Portland cement, fly ash, dry pulverized pulp and thickener are pre-mixed in a plastic bag, put into a total of 660g of water and a water reducing agent, and using a hand mixer. The slurry obtained by stirring for 2 minutes was poured into three 2 × 2 × 8 cm gunmetal molds. This was cured at 20 ° C. for 4 hours, then cured at 30 ° C. for 20 hours, then demolded, using an Instron universal testing machine, with a span of 7 cm, a loading speed of 0.5 mm / min, and a central loading of 3 points. The bending strength was measured.
[0021]
[Table 1]
From the results of Table 1, the fly ash Nos. 1-3, 5-8, and 10 having a pH (A) of 6 or more and a pH change of 1.2 or less are those of fast-hardening cement and early-strength cement. The cement quickly set without inhibiting the hardening, and a hardened cement body with sufficient strength could be obtained.
[0023]
【The invention's effect】
According to the present invention, it is possible to select a fly ash suitable for a hardened cement body that does not inhibit the hardening of the cement and can obtain a stable and quick setting of the cement.
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