JP2017116267A - Prediction method of methylene blue adsorption amount of fly ash, and cement composition containing fly ash - Google Patents
Prediction method of methylene blue adsorption amount of fly ash, and cement composition containing fly ash Download PDFInfo
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- 239000010881 fly ash Substances 0.000 title claims abstract description 94
- 229960000907 methylthioninium chloride Drugs 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 25
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 title claims abstract 7
- 239000004568 cement Substances 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 title claims description 12
- 230000001678 irradiating effect Effects 0.000 claims abstract description 10
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 42
- 238000005259 measurement Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000000611 regression analysis Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010883 coal ash Substances 0.000 description 4
- 238000007655 standard test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 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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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、フライアッシュによるメチレンブルーの吸着量を、短時間で予測する方法等に関する。 The present invention relates to a method for predicting the amount of methylene blue adsorbed by fly ash in a short time.
フライアッシュセメントは、火力発電所などの微粉炭ボイラーの燃焼排ガス中から回収された、微細な石炭灰であるフライアッシュを混合材として含むセメントである。フライアッシュは、非晶質の二酸化けい素を主成分とする球状の微粒子であり、コンクリートのワーカビリティーを改善するとともに、セメントの水和によって生じた水酸化カルシウムと反応（ポゾラン反応）して緻密な硬化体組織を形成する。
このように、高いポゾラン活性を有するフライアッシュは、コンクリート材料として非常に有用であるため、ＪＩＳ規格化され（ＪＩＳ Ａ ６２０１「コンクリート用フライアッシュ」）、また、フライアッシュが特定量使用されたフライアッシュセメント等はグリーン購入法の特定調達品目に指定されている。
The fly ash cement is a cement containing fly ash, which is fine coal ash, collected from the combustion exhaust gas of a pulverized coal boiler such as a thermal power plant as a mixture. Fly ash is a spherical fine particle mainly composed of amorphous silicon dioxide. It improves the workability of concrete and reacts with calcium hydroxide generated by hydration of cement (pozzolanic reaction) and is dense. A hardened body structure is formed.
As described above, fly ash having high pozzolanic activity is very useful as a concrete material. Therefore, the fly ash has been standardized by JIS (JIS A 6201 “Fly Ash for Concrete”), and a fly ash with a specific amount of fly ash is used. Ash cement is designated as a specific procurement item under the Green Purchasing Law.
しかし、一般社団法人石炭エネルギーセンターの石炭灰全国実態調査報告書によれば、平成２５年度に国内で発生した石炭灰の内、セメント混合材やコンクリート混和材（フライアッシュ）として有効利用されている量は約１８万トンで、これは石炭灰発生量全体の１．４％に過ぎない。この理由の１つに、フライアッシュ中に残存する未燃炭素がコンクリート中のＡＥ剤（空気連行剤）を吸着して空気連行性を阻害し、コンクリートのフレッシュ性状を悪化させることが挙げられる。 However, according to the coal ash national fact-finding report of the Japan Coal Energy Center, it is effectively used as cement admixture or concrete admixture (fly ash) among the coal ash generated in Japan in FY2013. The amount is about 180,000 tons, which is only 1.4% of the total amount of coal ash generated. One reason for this is that the unburned carbon remaining in the fly ash adsorbs the AE agent (air entraining agent) in the concrete to inhibit air entrainment and deteriorate the fresh properties of the concrete.
ＪＩＳ Ａ ６２０１「コンクリート用フライアッシュ」では、未燃炭素量の指標として、強熱減量（ＬＯＩ）が定められている。しかし、フライアッシュの強熱減量は、フライアッシュに含まれる水和物からの脱水や、炭酸塩が分解して生じる炭酸ガス等の揮発による減量も含まれるため、強熱減量と未燃炭素量は同じではない。
フライアッシュ中の未燃炭素は、ＡＥ剤と同様に、メチレンブルー（ＭＢ）も吸着することが知られている。染料であるメチレンブルーの吸着量は、吸着前後の溶液中のメチレンブルーの濃度（色調）の変化から容易に定量できるため、フライアッシュによるメチレンブルーの吸着量は、強熱減量に代わる、フライアッシュの未燃炭素の含有量を示す指標になる。
公益社団法人土木学会の「コンクリートライブラリー９４ フライアッシュを用いたコンクリートの施工指針（案）（１９９９）」によると、フレッシュコンクリート中の空気量の管理において、ＡＥ剤の種類や使用量の調整が不要とされるメチレンブルー吸着量の上限値は、０．４ｍｇ／ｇである。
メチレンブルー吸着量の測定方法は、一般社団法人セメント協会の標準試験方法（ＪＣＡＳ Ｉ−６１：２００８）および電源開発法（電発法）が広く用いられており、両方法の測定値の間には大きな違いはない。ただし、これらの試験方法は、メチレンブルー吸着量の測定に約１時間要するため、より短時間に結果が得られ、且つ、測定者間でバラツキが生じない方法が求められている。
この課題に対し、特許文献１と特許文献２ではメチレンブルー吸着量の自動測定装置が提案されている。しかし、両装置ともに複雑な機構を有する専用装置であり、汎用的な測定装置とは言い難い。
In JIS A 6201 “Fly Ash for Concrete”, loss on ignition (LOI) is defined as an index of the amount of unburned carbon. However, the loss on ignition of fly ash includes dehydration from the hydrates contained in fly ash and the loss due to volatilization of carbon dioxide gas generated by decomposition of carbonates. Are not the same.
It is known that unburned carbon in fly ash adsorbs methylene blue (MB) as well as the AE agent. The amount of methylene blue adsorbed as a dye can be easily determined from the change in the concentration (color tone) of methylene blue in the solution before and after the adsorption, so the amount of methylene blue adsorbed by fly ash is an unburned fly ash instead of loss of ignition It becomes an index indicating the carbon content.
According to the “Concrete Library 94 Guidelines for Construction of Concrete Using Fly Ash (Draft)” (1999) of the Japan Society of Civil Engineers, the type and amount of AE agent can be adjusted in the management of the amount of air in fresh concrete. The upper limit of the unnecessary amount of methylene blue adsorbed is 0.4 mg / g.
As a method for measuring the amount of methylene blue adsorbed, the standard test method (JCAS I-61: 2008) and the power source development method (electric generation method) of the Japan Cement Association are widely used. There is no big difference. However, since these test methods require about 1 hour to measure the amount of methylene blue adsorbed, there is a demand for a method in which results can be obtained in a shorter time and variations do not occur between measurers.
In response to this problem,
そこで、本発明は、フライアッシュのメチレンブルー吸着量を、簡易な装置を用いて短時間で予測できる方法等を提供することを目的とする。 Then, an object of this invention is to provide the method etc. which can estimate the methylene blue adsorption amount of fly ash in a short time using a simple apparatus.
本発明者は、簡易な装置を用いたメチレンブルー吸着量の予測方法を鋭意検討した結果、特定の範囲の波長の光をフライアッシュに照射して得られる拡散反射率と、特定の１点の波長の光をフライアッシュに照射して得られる拡散反射率の比が、フライアッシュのメチレンブルー吸着量を予測するための指標となることを見出し、本発明を完成させた。
すなわち、本発明は下記の構成を有するフライアッシュのメチレンブルー吸着量予測方法等である。
As a result of intensive studies on a method for predicting the amount of methylene blue adsorbed using a simple device, the present inventor has obtained a diffuse reflectance obtained by irradiating fly ash with light in a specific range of wavelengths and a specific single wavelength. The ratio of diffuse reflectance obtained by irradiating the fly ash with the above light was found to be an index for predicting the methylene blue adsorption amount of fly ash, and the present invention was completed.
That is, the present invention is a methylene blue adsorption amount prediction method for fly ash having the following configuration.
［１］下記（１）式を用いて算出したＲｓ値に基づき、フライアッシュのメチレンブルーの吸着量を予測する、フライアッシュのメチレンブルー吸着量予測方法。
Ｒｓ＝Ｒ３８０〜４１０／Ｒ４９０ ・・・（１）
（ただし、（１）式中、Ｒ３８０〜４１０は３８０〜４１０ｎｍの範囲から任意に選ばれる１つの波長の光を、フライアッシュに照射して得られる拡散反射率を表し、Ｒ４９０は４９０ｎｍの波長の光を、フライアッシュに照射して得られる拡散反射率を表す。）
［２］前記［１］に記載のフライアッシュのメチレンブルー吸着量予測方法を用いて算出したＲｓ値が、０．６以下であるフライアッシュを含む、フライアッシュ含有セメント組成物。
[1] A method for predicting the amount of methylene blue adsorbed on fly ash, which predicts the amount of methylene blue adsorbed on fly ash based on the Rs value calculated using the following equation (1).
Rs = R 380-410 / R 490 (1)
(However, in the formula (1), R 380 to 410 represents a diffuse reflectance obtained by irradiating fly ash with light having one wavelength arbitrarily selected from the range of 380 to 410 nm, and R 490 is 490 nm. (This represents the diffuse reflectance obtained by irradiating fly ash with light of a wavelength.)
[2] A fly ash-containing cement composition containing fly ash having an Rs value calculated using the methylene blue adsorption amount prediction method for fly ash according to [1] above of 0.6 or less.
本発明のフライアッシュのメチレンブルー吸着量予測方法は、フライアッシュのメチレンブルー吸着量を、簡易な装置を用いて短時間で予測できる。また、本発明のフライアッシュ含有セメント組成物は、ＡＥ剤の空気連行性に与える影響が少ない。 The method for predicting the amount of methylene blue adsorbed on fly ash according to the present invention can predict the amount of methylene blue adsorbed on fly ash in a short time using a simple device. Moreover, the fly ash containing cement composition of this invention has little influence which it has on the air entrainment property of AE agent.
本発明は、前記（１）式を用いて算出したＲｓ値に基づき、フライアッシュのメチレンブルーの吸着量を予測する方法、およびフライアッシュ含有セメント組成物である。
以下、本発明について、フライアッシュのメチレンブルー吸着量予測方法と、フライアッシュ含有セメント組成物に分けて、詳細に説明する。
The present invention is a method for predicting the amount of methylene blue adsorbed on fly ash based on the Rs value calculated using the formula (1), and a fly ash-containing cement composition.
Hereinafter, the present invention will be described in detail by dividing it into a methylene blue adsorption amount prediction method for fly ash and a fly ash-containing cement composition.
１、フライアッシュのメチレンブルー吸着量予測方法
本発明のフライアッシュのメチレンブルー吸着量予測方法で用いる指標は、前記（１）式に示すように、４９０ｎｍの波長の光をフライアッシュに照射して得られる拡散反射率（Ｒ４９０）に対する、３８０〜４１０ｎｍの範囲から任意に選ばれる１つの波長の光をフライアッシュに照射して得られる拡散反射率（Ｒ３８０〜４１０）の比（Ｒｓ）である。後掲の図４に示すように、フライアッシュに照射した光の波長と、フライアッシュのメチレンブルー吸着量およびＲｓの間で単回帰分析を行って求めた相関係数は、３８０〜４１０ｎｍの範囲で最大値（０．８）を取るから、他の範囲の波長を用いた場合よりも予測精度は高くなる。
前記拡散反射率は、市販の色差計を用いて、例えば、ＪＩＳ Ｐ ８１５２「紙、板紙及びパルプ−拡散反射率係数の測定方法」に準拠して測定できる。
1. Method for predicting the amount of methylene blue adsorbed on fly ash The index used in the method for predicting the amount of methylene blue adsorbed on fly ash according to the present invention is obtained by irradiating fly ash with light having a wavelength of 490 nm as shown in the above equation (1). It is a ratio (Rs) of diffuse reflectance (R 380-410 ) obtained by irradiating fly ash with light of one wavelength arbitrarily selected from the range of 380-410 nm with respect to diffuse reflectance (R 490 ). As shown in FIG. 4 below, the correlation coefficient obtained by performing a single regression analysis between the wavelength of light irradiated on fly ash, the amount of methylene blue adsorbed on fly ash, and Rs is in the range of 380 to 410 nm. Since the maximum value (0.8) is taken, the prediction accuracy is higher than when other wavelengths are used.
The diffuse reflectance can be measured using a commercially available color difference meter in accordance with, for example, JIS P 8152 “Paper, paperboard and pulp—Method of measuring diffuse reflectance coefficient”.
２．フライアッシュ含有セメント組成物
本発明のフライアッシュ含有セメント組成物は、前記フライアッシュのメチレンブルー吸着量予測方法を用いて算出したＲｓ値が、０．６以下であるフライアッシュを含むセメント組成物である。フライアッシュのＲｓ値が０．６以下であれば、一般的なＡＥ剤の調整が不要となる目安であるメチレンブルー吸着量が０．４ｍｇ／ｇ以下を満たすため、フレッシュコンクリートの空気量の管理において、ＡＥ剤の種類や使用量の調整が必要ない。
また、本発明のフライアッシュ含有セメント組成物に用いるセメントは、特に制限されず、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント、高炉セメント、シリカセメント、およびエコセメントから選ばれる１種以上である。また、前記セメントと前記フライアッシュの混合装置は、例えば、ボールミルやヘンシェルミキサ等が挙げられる。また、フライアッシュ含有セメント組成物中のフライアッシュの含有率は、強度発現性およびコンクリートのワーカビリティの向上の観点から、５〜３０質量％である。
2. Fly ash containing cement composition The fly ash containing cement composition of this invention is a cement composition containing the fly ash whose Rs value computed using the methylene blue adsorption amount prediction method of the said fly ash is 0.6 or less. . If the Rs value of fly ash is 0.6 or less, the amount of methylene blue adsorbed, which is a standard that eliminates the need for adjustment of a general AE agent, satisfies 0.4 mg / g or less. It is not necessary to adjust the type or amount of AE agent used.
The cement used in the fly ash-containing cement composition of the present invention is not particularly limited, and is selected from ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, low heat Portland cement, blast furnace cement, silica cement, and ecocement. One or more types. Examples of the cement and fly ash mixing device include a ball mill and a Henschel mixer. Moreover, the content rate of the fly ash in a fly ash containing cement composition is 5-30 mass% from a viewpoint of an intensity | strength expression and the improvement of workability of concrete.
以下、実施例を用いて本発明を説明するが、本発明はこれらの実施例に限定されない。
１．使用材料
（１）フライアッシュ
７つの石炭火力発電所の９ラインから採取した１９種のフライアッシュを試料として用いた。同一ラインから複数の試料を採取する場合、試料の採取日を変えた。また、全ての試料は、ＪＩＳ Ａ ６２０１「コンクリート用フライアッシュ」のフライアッシュII種またはフライアッシュIII種に分類される。
これらのフライアッシュのメチレンブルー吸着量は、一般社団法人セメント協会の標準試験方法（ＪＣＡＳ Ｉ−６１：２００８）に準拠して測定し、強熱減量、密度、ブレーン比表面積、および４５μｍふるい残分は、ＪＩＳ Ａ ６２０１「コンクリート用フライアッシュ」に準拠して測定した。また化学分析値は、蛍光Ｘ線分析法（検量線法）により測定した。これらの結果を表１に示す。
EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these Examples.
1. Materials used (1)
The amount of methylene blue adsorbed by these fly ash was measured according to the standard test method (JCAS I-61: 2008) of the Japan Cement Association. The loss on ignition, density, brain specific surface area, and 45 μm sieve residue were , Measured according to JIS A 6201 “Fly Ash for Concrete”. The chemical analysis value was measured by fluorescent X-ray analysis (calibration curve method). These results are shown in Table 1.
２．メチレンブルー吸着量と相関性の高い指標の探索
メチレンブルー吸着量と相関性の高い指標を見い出すために、下記（１）に従いフライアッシュの拡散反射率を測定して、下記（２）〜（４）の探索を行なった。
（１）フライアッシュの拡散反射率の測定
試料１〜１９を５．０±０．１ｇ計量して、色差計の測定セルに入れた。測定セルに蓋をした後、測定セルを５cmの高さから１５回落下させて、フライアッシュを測定セルに充填して測定用試料とした。次に、前記測定用試料を分光色差計（日本電色工業社製 ＳＥ６０００）に装着して、３８０〜７８０ｎｍの波長の範囲で１０ｎｍおきに拡散反射率を測定した。その結果を図１に示す。
図１に示すように、どの試料も照射した光の波長が長くなる程、拡散反射率が高くなる傾向がある。
2. Search for an index highly correlated with the amount of adsorption of methylene blue In order to find an index highly correlated with the amount of adsorption of methylene blue, the diffuse reflectance of fly ash was measured according to the following (1), and the following (2) to (4) A search was conducted.
(1) Measurement of diffuse reflectance of
As shown in FIG. 1, the diffuse reflectance tends to increase as the wavelength of light irradiated on any sample increases.
（２）メチレンブルー吸着量と拡散反射率の間の関係
試料１〜１９の前記メチレンブルー吸着量、および前記拡散反射率の間で単回帰分析を行い、相関係数を求めた。次に、該相関係数とフライアッシュに照射した光の波長（１０ｎｍ間隔）の関係をグラフにプロットした。その結果を図２に示す。
図２から、照射した光の波長は長くなるにつれて、前記相関係数は単調に減少してプラスからマイナスに転じ、相関係数がゼロになる特異な波長（４９０ｎｍ）が存在することが分かる。
(2) Relationship between Methylene Blue Adsorption Amount and Diffuse Reflectance A single regression analysis was performed between the methylene blue adsorption amount of
From FIG. 2, it can be seen that as the wavelength of the irradiated light becomes longer, the correlation coefficient decreases monotonously and turns from positive to negative, and there is a specific wavelength (490 nm) at which the correlation coefficient becomes zero.
（３）フライアッシュに照射した光の波長とＲｓの関係
そこで、メチレンブルー吸着量と最も相関が低い４９０ｎｍの波長の光を使って測定した拡散反射率を分母に置き、３８０〜７８０ｎｍの波長の範囲において１０ｎｍおきに測定した各フライアッシュの拡散反射率を分子に置いて、比（Ｒｓ）を求めた。
そして、Ｒｓと、フライアッシュに照射した光の波長（１０ｎｍ間隔）の関係をグラフにプロットした。その結果を図３に示す。
(3) Relationship between wavelength of light irradiated to fly ash and Rs Therefore, a diffuse reflectance measured using light having a wavelength of 490 nm having the lowest correlation with the amount of adsorption of methylene blue is placed in the denominator, and a wavelength range of 380 to 780 nm. The ratio (Rs) was determined by placing the diffuse reflectance of each fly ash measured every 10 nm in the molecule.
And the relationship between Rs and the wavelength (10 nm interval) of the light irradiated to fly ash was plotted on a graph. The result is shown in FIG.
（４）メチレンブルー吸着量とＲｓの間の関係
試料１〜１９の前記メチレンブルー吸着量、および前記Ｒｓの間で単回帰分析を行い、相関係数を求めた。次に、該相関係数とフライアッシュに照射した光の波長（１０ｎｍ間隔）の関係をグラフにプロットした。その結果を図４に示す。
図２と図４の相関係数を比べると、前記Ｒｓの分母に採用した波長４９０ｎｍ以外の全ての測定点で、図４に示す相関係数が、図２に示す相関係数よりも高いこと、特に、３８０〜４１０ｎｍの範囲で高いことが分かる。そこで、最も相関係数の高かった波長３８０ｎｍの拡散反射率を分子に採用した場合の、Ｒｓとメチレンブルー吸着量の関係をグラフにプロットした。その結果を図５に示す。
図５に示すように、決定係数（Ｒ２）は０．６７と高く、Ｒｓを指標に用いた本発明のフライアッシュのメチレンブルー吸着量予測方法は、実用可能な予測精度を有していることが分かる。
また、従来の標準試験方法（ＪＣＡＳ １−６１：２００８）は試験に約１時間かかるのに対し、本発明のフライアッシュのメチレンブルー吸着量予測方法は、数分で終了した。
(4) Relationship between Methylene Blue Adsorption Amount and Rs A single regression analysis was performed between the Methylene Blue adsorption amount of
When the correlation coefficients of FIG. 2 and FIG. 4 are compared, the correlation coefficient shown in FIG. 4 is higher than the correlation coefficient shown in FIG. 2 at all measurement points other than the wavelength of 490 nm adopted as the denominator of Rs. In particular, it can be seen that it is high in the range of 380 to 410 nm. Therefore, the relationship between Rs and the amount of methylene blue adsorbed when the diffuse reflectance at a wavelength of 380 nm, which had the highest correlation coefficient, was adopted for the molecule was plotted on a graph. The result is shown in FIG.
As shown in FIG. 5, the coefficient of determination (R 2 ) is as high as 0.67, and the fly ash methylene blue adsorption amount prediction method of the present invention using Rs as an index has a practical prediction accuracy. I understand.
The conventional standard test method (JCAS 1-61: 2008) takes about 1 hour for the test, whereas the fly ash methylene blue adsorption amount prediction method of the present invention was completed in a few minutes.
本発明の予測値のみでも、メチレンブルー吸着性能に関するフライアッシュの良否を判断できるが、本発明の予測方法を１次評価試験として用い、該一次評価試験の結果、さらに詳細な確認が必要と判断されたフライアッシュに絞って、前記標準試験方法等の従来の方法によりメチレンブルー吸着量を測定すれば、より確実なフライアッシュの品質評価を、少ない作業量で迅速に行うことができる。 Although only the predicted value of the present invention can determine the quality of fly ash related to methylene blue adsorption performance, the prediction method of the present invention is used as a primary evaluation test, and as a result of the primary evaluation test, further detailed confirmation is determined to be necessary. By focusing on fly ash and measuring the amount of methylene blue adsorbed by conventional methods such as the standard test method, more reliable fly ash quality evaluation can be performed quickly with a small amount of work.
Claims (2)
Ｒｓ＝Ｒ３８０〜４１０／Ｒ４９０ ・・・（１）
（ただし、（１）式中、Ｒ３８０〜４１０は３８０〜４１０ｎｍの範囲から任意に選ばれる１つの波長の光を、フライアッシュに照射して得られる拡散反射率を表し、Ｒ４９０は４９０ｎｍの波長の光を、フライアッシュに照射して得られる拡散反射率を表す。） A method for predicting the amount of fly ash methylene blue that predicts the amount of fly ash methylene blue adsorbed based on the Rs value calculated using the following equation (1).
Rs = R 380-410 / R 490 (1)
(However, in the formula (1), R 380 to 410 represents a diffuse reflectance obtained by irradiating fly ash with light having one wavelength arbitrarily selected from the range of 380 to 410 nm, and R 490 is 490 nm. (This represents the diffuse reflectance obtained by irradiating fly ash with light of a wavelength.)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107247048A (en) * | 2017-06-06 | 2017-10-13 | 济南四建（集团）有限责任公司 | A kind of method of flyash and water reducer compatibility in measure concrete |
| JP2019178034A (en) * | 2018-03-30 | 2019-10-17 | 三菱マテリアル株式会社 | Injection material for rapid hardening semi-flexible pavement, and injection milk using the same |
| JP2019178033A (en) * | 2018-03-30 | 2019-10-17 | 三菱マテリアル株式会社 | Injection material for semi-flexible pavement, and injection milk for semi-flexible pavement |
| JP2021160963A (en) * | 2020-03-31 | 2021-10-11 | 三菱マテリアル株式会社 | Manufacture management method of concrete |
| CN114425303A (en) * | 2022-03-01 | 2022-05-03 | 广东石油化工学院 | Preparation method and application of alkali-soluble fly ash modified straw stalk biochar |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09225441A (en) * | 1996-02-26 | 1997-09-02 | Chichibu Onoda Cement Corp | Treatment of fly ash and application thereof |
| JPH11262749A (en) * | 1998-03-16 | 1999-09-28 | Sumitomo Osaka Cement Co Ltd | Method and apparatus for measuring quantity of unburned carbon of classified fly ash |
| JP2000226245A (en) * | 1999-02-03 | 2000-08-15 | Taiheiyo Cement Corp | Air-entraining agent for cement position and curing of cement composition containing the air-entraining agent |
| JP2002047051A (en) * | 2000-07-31 | 2002-02-12 | Taiheiyo Cement Corp | Composition having self-leveling ability |
| JP2002323412A (en) * | 2001-04-27 | 2002-11-08 | Mitsubishi Heavy Ind Ltd | Instrument and method for measuring reacting weight to reagent |
| JP2006300627A (en) * | 2005-04-19 | 2006-11-02 | Shikoku Res Inst Inc | Measuring method of adsorption amount of reagent, adsorption amount measuring instrument and measuring implement |
| JP2007217244A (en) * | 2006-02-17 | 2007-08-30 | Umetani Shoji:Kk | Quality control method of concrete admixture |
| JP2010030885A (en) * | 2008-06-30 | 2010-02-12 | Mitsubishi Materials Corp | Method for reducing unburnt carbon content in coal ash |
| JP2010043933A (en) * | 2008-08-12 | 2010-02-25 | Shimizu Corp | Quality evaluation method of fly ash |
| JP2012522103A (en) * | 2009-03-30 | 2012-09-20 | ダウ グローバル テクノロジーズ エルエルシー | Hybrid dispersion and method for producing the same |
| CN102712533A (en) * | 2010-01-15 | 2012-10-03 | 拉法基公司 | Method for producing a hydraulic composition having entrained air |
| JP2015124136A (en) * | 2013-12-27 | 2015-07-06 | 住友大阪セメント株式会社 | Concrete composition having initial-stage and long-term high strength developability and high crack resistance, and concrete body using the composition |
-
2015
- 2015-12-21 JP JP2015248452A patent/JP6630145B2/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09225441A (en) * | 1996-02-26 | 1997-09-02 | Chichibu Onoda Cement Corp | Treatment of fly ash and application thereof |
| JPH11262749A (en) * | 1998-03-16 | 1999-09-28 | Sumitomo Osaka Cement Co Ltd | Method and apparatus for measuring quantity of unburned carbon of classified fly ash |
| JP2000226245A (en) * | 1999-02-03 | 2000-08-15 | Taiheiyo Cement Corp | Air-entraining agent for cement position and curing of cement composition containing the air-entraining agent |
| JP2002047051A (en) * | 2000-07-31 | 2002-02-12 | Taiheiyo Cement Corp | Composition having self-leveling ability |
| JP2002323412A (en) * | 2001-04-27 | 2002-11-08 | Mitsubishi Heavy Ind Ltd | Instrument and method for measuring reacting weight to reagent |
| JP2006300627A (en) * | 2005-04-19 | 2006-11-02 | Shikoku Res Inst Inc | Measuring method of adsorption amount of reagent, adsorption amount measuring instrument and measuring implement |
| JP2007217244A (en) * | 2006-02-17 | 2007-08-30 | Umetani Shoji:Kk | Quality control method of concrete admixture |
| JP2010030885A (en) * | 2008-06-30 | 2010-02-12 | Mitsubishi Materials Corp | Method for reducing unburnt carbon content in coal ash |
| JP2010043933A (en) * | 2008-08-12 | 2010-02-25 | Shimizu Corp | Quality evaluation method of fly ash |
| JP2012522103A (en) * | 2009-03-30 | 2012-09-20 | ダウ グローバル テクノロジーズ エルエルシー | Hybrid dispersion and method for producing the same |
| CN102712533A (en) * | 2010-01-15 | 2012-10-03 | 拉法基公司 | Method for producing a hydraulic composition having entrained air |
| US20120304893A1 (en) * | 2010-01-15 | 2012-12-06 | Lafarge | Process for production of a hydraulic composition with entrained air |
| JP2015124136A (en) * | 2013-12-27 | 2015-07-06 | 住友大阪セメント株式会社 | Concrete composition having initial-stage and long-term high strength developability and high crack resistance, and concrete body using the composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107247048A (en) * | 2017-06-06 | 2017-10-13 | 济南四建（集团）有限责任公司 | A kind of method of flyash and water reducer compatibility in measure concrete |
| CN107247048B (en) * | 2017-06-06 | 2020-06-30 | 济南四建（集团）有限责任公司 | Method for determining compatibility of fly ash and water reducing agent in concrete |
| JP2019178034A (en) * | 2018-03-30 | 2019-10-17 | 三菱マテリアル株式会社 | Injection material for rapid hardening semi-flexible pavement, and injection milk using the same |
| JP2019178033A (en) * | 2018-03-30 | 2019-10-17 | 三菱マテリアル株式会社 | Injection material for semi-flexible pavement, and injection milk for semi-flexible pavement |
| JP2021160963A (en) * | 2020-03-31 | 2021-10-11 | 三菱マテリアル株式会社 | Manufacture management method of concrete |
| JP7429588B2 (en) | 2020-03-31 | 2024-02-08 | Ｕｂｅ三菱セメント株式会社 | Concrete manufacturing control method |
| CN114425303A (en) * | 2022-03-01 | 2022-05-03 | 广东石油化工学院 | Preparation method and application of alkali-soluble fly ash modified straw stalk biochar |
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