JP6305874B2 - Method for producing hardened cementitious body - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000463 material Substances 0.000 claims description 56
- 239000004568 cement Substances 0.000 claims description 53
- 239000011398 Portland cement Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004898 kneading Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 88
- 238000001723 curing Methods 0.000 description 55
- 239000001569 carbon dioxide Substances 0.000 description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 description 44
- 239000000047 product Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 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 10
- 230000000694 effects Effects 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 239000004576 sand Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000011178 precast concrete Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000011888 autopsy Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Description
本発明は、セメント質硬化体およびその製造方法に関する。 The present invention relates to a cementitious cured body and a method for producing the same.
現在、地球温暖化の抑制のため、二酸化炭素の排出量の低減が重要な課題になっている。セメント質硬化体の製造における、二酸化炭素の排出量を低減する方法として、セメント質硬化体の養生過程において二酸化炭素を吸収させることにより、セメント質硬化体を得るまでに排出される二酸化炭索の総量を低減する方法が知られている。
例えば、特許文献１には、粉体成分として、γ−Ｃ２Ｓ （記号γ）、製鋼スラグ粉末（記号Ｂ）の１種または２種と、ポルトランドセメント（記号Ｃ）を含有し、上記γ、Ｂ、Ｃの合計含有量に占めるγ、Ｂの合計が２５〜９５質量％であり、水セメント比Ｗ／Ｃが８０〜２５０％である配合のコンクリート混練物を硬化させたプレキャストコンクリートであって、硬化過程で炭酸化養生を経ることにより、表面から深さ２０ｍｍ以上の部位（ただし肉厚が２０ｍｍ未満の部分は肉厚全体）に炭酸化領域を形成してなるＣＯ２吸収プレキャストコンクリートが記載されている。
該プレキャストコンクリートは、炭酸化養生による二酸化炭素の吸収を利用することで、コンクリート製品を製造する際に排出される二酸化炭素の総量（ト−タル量）を大幅に低減することができる。
At present, reducing carbon dioxide emissions is an important issue in order to control global warming. In the production of hardened cementitious materials, as a method of reducing the amount of carbon dioxide emitted, by absorbing carbon dioxide during the curing process of hardened cementitious materials, Methods for reducing the total amount are known.
For example, Patent Document 1 contains γ-C 2 S (symbol γ), one or two types of steelmaking slag powder (symbol B), and Portland cement (symbol C) as a powder component. , B and C are precast concrete obtained by curing a concrete kneaded mixture having a total content of γ and B of 25 to 95% by mass and a water-cement ratio W / C of 80 to 250%. Te, through the carbonation curing in the curing process, part (the part below the proviso wall thickness 20mm overall thickness) of the above deep 20mm from the surface CO 2 absorption precast concrete obtained by forming a carbonated regions Have been described.
The precast concrete can significantly reduce the total amount of carbon dioxide (total amount) discharged when producing a concrete product by utilizing the absorption of carbon dioxide by carbonation curing.
特許文献１の実施例では、炭酸化養生を６０℃の温度条件下で行っている。しかし、本発明者らが実験を行ったところ、炭酸化養生を２０℃の温度条件下で行った場合、γ−Ｃ２Ｓを含むセメント質硬化体では、二酸化炭素の排出量の低減効果は小さいことがわかった。また、特許文献１には、γ−Ｃ２Ｓは炭酸化により顕著な強度増進効果を発揮することが確認されたと記載されているが、本発明者らが、特許文献１に記載されているγ−Ｃ２Ｓを含むセメント質硬化体について実験を行ったところ、このような強度増進効果は、室温（２０℃程度）での養生を行ったものについては、認められなかった。
また、γ−Ｃ２Ｓの原料としては、産業廃棄物である副生水酸化カルシウムや、石灰石が挙げられる。しかし、副生水酸化カルシウムは、一般的に入手が困難であるという問題があった。また、石灰石を原料としてγ−Ｃ２Ｓを製造する場合、その製造過程において、二酸化炭索が排出されることから、二酸化炭素の排出量の低減効果が小さくなるという問題があった。
そこで本発明は、ポルトランドセメント以外の粉末材料（特に、ポルトランドセメントに比べて、粉末の製造時の二酸化炭素の排出量が少ないもの）を含むものの、例えば、６０℃等の高温ではなく、常温（２０℃程度）で養生を行った場合であっても、養生過程において多量の二酸化炭素を吸収することにより、排出される二酸化炭素の総量を大幅に低減することができ、かつ、粉末材料の全量がポルトランドセメントからなる場合を基準としたときに、圧縮強さの低下の割合が小さいセメント質硬化体を提供することを目的とする。
In the Example of patent document 1, carbonation curing is performed on the temperature conditions of 60 degreeC. However, when the present inventors conducted experiments, when carbonation curing is performed at a temperature of 20 ° C., the cementitious hardened body containing γ-C 2 S has an effect of reducing the amount of carbon dioxide emission. I found it small. Further, Patent Document 1 describes that γ-C 2 S has been confirmed to exhibit a remarkable strength enhancement effect by carbonation, but the present inventors have described it in Patent Document 1. When an experiment was conducted on a hardened cementitious material containing γ-C 2 S, such a strength enhancement effect was not observed for those cured at room temperature (about 20 ° C.).
Further, as a material for gamma-C 2 S, which is industrial waste and by-product calcium hydroxide, limestone. However, there is a problem that by-product calcium hydroxide is generally difficult to obtain. Further, when γ-C 2 S is produced using limestone as a raw material, there is a problem in that the effect of reducing the amount of carbon dioxide emission is reduced because the carbon dioxide cord is discharged during the manufacturing process.
Therefore, the present invention includes a powder material other than Portland cement (particularly, a material that emits less carbon dioxide during the production of powder compared to Portland cement). Even when curing is performed at about 20 ° C.), the total amount of carbon dioxide discharged can be greatly reduced by absorbing a large amount of carbon dioxide in the curing process, and the total amount of powder material It is an object of the present invention to provide a cementitious hardened body with a small rate of decrease in compressive strength when the case is made of Portland cement.
本発明者は、上記課題を解決するために鋭意検討した結果、特定の粉末状セメント組成物（特定の鉱物成分を含む焼成物の粉砕物と、ポルトランドセメントを含むもの）と水と骨材を含むセメント混練物の硬化体を、炭酸化してなるセメント質硬化体によれば、上記目的を達成できることを見出し、本発明を完成した。
すなわち、本発明は、以下の［１］〜［５］を提供するものである。
［１］（Ａ）Ｃ２Ｓ１００質量部に対して、Ｃ２ＡＳを１０〜２００質量部含有し、かつ、Ｃ３Ａの含有量が２０質量部以下である焼成物の粉砕物（記号α）と、ポルトランドセメントを含む粉末状セメント組成物と、（Ｂ）水と、（Ｃ）骨材、の各材料を含むセメント混練物の硬化体を、炭酸化してなることを特徴とするセメント質硬化体。
［２］上記（Ａ）粉末状セメント組成物中、上記焼成物の粉砕物の割合が１０〜６０質量％であり上記ポルトランドセメントの剖合が４０〜９０質量％である前記［１］に記載のセメント質硬化体。
［３］前記［１］又は［２］に記載のセメント質硬化体を製造するための方法であって、上記（Ａ）〜（Ｃ）の各材料を混練して、上記セメント混練物を調製するセメント混練物調製工程と、上記セメント混練物を型枠内に打設する打設工程と、上記型枠内の上記セメント混練物が硬化した後に、上記セメント混練物の硬化体を上記型枠から脱型する脱型工程と、上記型枠から脱型した上記セメント混練物の硬化体を炭酸化養生して、上記セメント質硬化体を得る炭酸化養生工程、を含むことを特徴とするセメント質硬化体の製造方法。
［４］上記脱型工程と、上記炭酸化養生工程の間に、上記セメント混練物の硬化体の圧縮強さを高めるための高強度化養生工程、を含む前記［３］に記載のセメント質硬化体の製造万法。
［５］上記炭酸化養生工程の開始時における上記セメント混練物の硬化体の圧縮強さが、１５Ｎ／ｍｍ２以上である前記［３］又は［４］に記載のセメント質硬化体の製造方法。
As a result of intensive studies to solve the above problems, the present inventor has obtained a specific powdered cement composition (a pulverized product containing a specific mineral component and a Portland cement), water and aggregate. The present invention has been completed by finding that the above object can be achieved by using a cemented hardened body obtained by carbonizing the hardened body of the cement kneaded product.
That is, the present invention provides the following [1] to [5].
[1] (A) A pulverized product (symbol α) containing 10 to 200 parts by mass of C 2 AS and containing 20 parts by mass or less of C 3 A with respect to 100 parts by mass of C 2 S ), A powdered cement composition containing Portland cement, (B) water, and (C) a cement kneaded material containing a hardened body of a cement kneaded material, which is carbonized. Cured body.
[2] In the above [1], in the powdered cement composition (A), the ratio of the pulverized product of the fired product is 10 to 60% by mass, and the autopsy of the Portland cement is 40 to 90% by mass. Hardened cementitious material.
[3] A method for producing the hardened cementitious body according to [1] or [2], wherein the materials (A) to (C) are kneaded to prepare the cement kneaded material. A cement kneaded material preparation step, a casting step in which the cement kneaded material is cast into a mold, and after the cement kneaded material in the mold is cured, And a carbonation curing step in which a hardened body of the cement kneaded material released from the mold is carbonized and cured to obtain the cementitious hardened body. A method for producing a cured product.
[4] The cementitious material according to [3], including a high-strength curing step for increasing the compressive strength of the hardened body of the cement kneaded material between the demolding step and the carbonation curing step. Manufacture of cured body.
[5] The method for producing a hardened cementitious material according to [3] or [4], wherein the compressive strength of the hardened material of the cement kneaded product at the start of the carbonation curing step is 15 N / mm 2 or more. .
本発明のセメント質硬化体によれば、例えば、６０℃等の高温ではなく、２０℃程度で養生を行った場合であっても、養生過程において多量の二酸化炭素を吸収することにより、二酸化炭素の排出量を大幅に低減することができる。
また、本発明のセメント質硬化体は、ポルトランドセメント以外の粉末材料（特に、ポルトランドセメントに比べて、粉末の製造時の二酸化炭素の排出量が少ないもの）を含むものの、例えば、６０℃等の高温ではなく、２０℃程度で養生を行った場合であっても、粉末材料の全量がポルトランドセメントからなる場合を基準としたときに、圧縮強さの低下の割合が小さいものである。
According to the cementitious hardened body of the present invention, for example, even when curing is performed at about 20 ° C. instead of high temperature such as 60 ° C., carbon dioxide is absorbed by absorbing a large amount of carbon dioxide in the curing process. Emissions can be greatly reduced.
Moreover, although the cementitious hardened body of the present invention includes a powder material other than Portland cement (particularly, a material that emits less carbon dioxide during the production of powder compared to Portland cement), for example, 60 ° C. Even when curing is performed at about 20 ° C. instead of high temperature, the rate of decrease in compressive strength is small when the total amount of the powder material is made of Portland cement.
本発明のセメント質硬化体は、（Ａ）Ｃ２Ｓ１００質量部に対して、Ｃ２ＡＳを１０〜２００質量部含有し、かつ、Ｃ３Ａの含有量が２０質量部以下である焼成物の粉砕物（α）と、ポルトランドセメントを含む粉末状セメント組成物と、（Ｂ）水と、（Ｃ）骨材、の各材料を含むセメント混練物の硬化体を、炭酸化してなるものである。
ここで、「炭酸化」とは、セメント質硬化体中のアルカリ性の成分が、二酸化炭素と反応して、該アルカリ性の成分のｐＨを低下させることをいう。
以下、本発明を詳しく説明する。
The cementitious cured body of the present invention contains (A) 10 to 200 parts by mass of C 2 AS with respect to 100 parts by mass of C 2 S, and a burned product having a C 3 A content of 20 parts by mass or less. A cemented kneaded hardened body containing each of the pulverized product (α), a powdered cement composition containing Portland cement, (B) water, and (C) aggregates is carbonized. is there.
Here, “carbonation” means that the alkaline component in the cementitious cured body reacts with carbon dioxide to lower the pH of the alkaline component.
The present invention will be described in detail below.
［（Ａ）粉末状セメント組成物］
上記粉末状セメント組成物は、Ｃ２Ｓ１００質量部に対して、Ｃ２ＡＳを１０〜２００質量部含有し、かつ、Ｃ３Ａの含有量が２０質量部以下である焼成物の粉砕物（α）とポルトランドセメントを含む。
[(A) Powdered cement composition]
The powdered cement composition contains 10 to 200 parts by mass of C 2 AS with respect to 100 parts by mass of C 2 S, and a pulverized product of a fired product having a C 3 A content of 20 parts by mass or less ( α) and Portland cement.
上記粉砕物（α）は、Ｃ２ＡＳの一部、好ましくはＣ２ＡＳ質量の７０質量％以下がＣ４ＡＦで置換されても良い。また、上記粉砕物（α）は、ムライト、アノーサイト、非晶質相、ＳｉＯ２、クリストバライトやウォラストナイト等を含有してもよい。 The pulverized product (alpha), a part of the C 2 AS, preferably less 70 weight percent of C 2 AS mass may be substituted by C 4 AF. The pulverized product (α) may contain mullite, anorthite, amorphous phase, SiO 2 , cristobalite, wollastonite, and the like.
上記粉砕物（α）のブレーン比表面積は、好ましくは２，５００〜１０，０００ｃｍ２／ｇ、より好ましくは３，０００〜９，０００ｃｍ２／ｇである。該ブレーン比表面積が２，５００ｃｍ２／ｇ以上であれば、二酸化炭素の排出量の低減効果が大きくなる。また、得られるセメント質硬化体の圧縮強さが大きくなる。該ブレーン比表面積が１０，０００ｃｍ２／ｇ以下であれば、粉砕する手間がかからず、製造のコストを低くすることができる。 Blaine specific surface area of the pulverized product (alpha) is preferably 2,500~10,000cm 2 / g, more preferably 3,000~9,000cm 2 / g. If the Blaine specific surface area is 2,500 cm 2 / g or more, the effect of reducing carbon dioxide emission is increased. Moreover, the compressive strength of the obtained cementitious hardened body becomes large. If the Blaine specific surface area is 10,000 cm 2 / g or less, it does not take time to grind, and the manufacturing cost can be reduced.
上記粉末状セメント組成物中、上記粉砕物（α）の割合は、好ましくは１０〜６０質量％、より好ましくは１５〜５５質量％、特に好ましくは２０〜５０質量％である。該割合が１０質量％以上であれば、二酸化炭素の排出量の低減効果が大きくなる。また、得られるセメント質硬化体の圧縮強さが大きくなる。該割合が６０質量％以下であれば、脱型の時期が早くなり、セメント質硬化体からなる製品の生産効率が向上する。 In the powdered cement composition, the ratio of the pulverized product (α) is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and particularly preferably 20 to 50% by mass. If this ratio is 10 mass% or more, the reduction effect of the discharge | emission amount of a carbon dioxide will become large. Moreover, the compressive strength of the obtained cementitious hardened body becomes large. If this ratio is 60 mass% or less, the demolding time will become early and the production efficiency of the product which consists of cementitious hardened bodies will improve.
本発明で用いられるポルトランドセメントは、特に限定されるものではなく、例えば、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等の各種ポルトランドセメントを使用することができる。中でも、強度発現性やコストの観点から、普通ポルトランドセメントまたは早強ポルトランドセメントが好ましい。 The Portland cement used in the present invention is not particularly limited. For example, various Portland cements such as ordinary Portland cement, early-strength Portland cement, medium heat Portland cement, and low heat Portland cement can be used. Among these, ordinary portland cement or early-strength portland cement is preferable from the viewpoint of strength development and cost.
上記粉末状セメント組成物中、上記ポルトランドセメントの割合は、好ましくは４０〜９０質量％、より好ましくは４５〜８５質量％、特に好ましくは５０〜８０質量％である。該割合が４０質量％以上であれば、脱型の時期が早くなり、セメント質硬化体からなる製品の生産効率が向上する。該割合が９０質量％以下であれば、二酸化炭素の排出量の低減効果が大きくなる。また、得られるセメント質硬化体の圧縮強さが大きくなる。 In the powdered cement composition, the proportion of the Portland cement is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and particularly preferably 50 to 80% by mass. When the ratio is 40% by mass or more, the time for demolding is advanced, and the production efficiency of a product made of a cementitious hardened body is improved. If this ratio is 90 mass% or less, the reduction effect of the discharge | emission amount of a carbon dioxide will become large. Moreover, the compressive strength of the obtained cementitious hardened body becomes large.
［（Ｂ）水］
上記セメント混練物において、粉末状セメント組成物１００質量％に対する水の配合比（以下、「水／粉末状セメント組成物の質量比」ともいう。）は、好ましくは３０〜１００質量％、より好ましくは４０〜７０質量％である。該比が３０質量％以上であれば、二酸化炭素の排出量の低減効果が大きくなる。また、セメント混練物のワーカビリティが向上する。該比が１００質量％以下であれば、セメント質硬化体の圧縮強さが大きくなる。
[(B) Water]
In the cement kneaded material, the mixing ratio of water with respect to 100% by mass of the powdered cement composition (hereinafter also referred to as “the mass ratio of the water / powdered cement composition”) is preferably 30 to 100% by mass, and more preferably. Is 40-70 mass%. When the ratio is 30% by mass or more, the effect of reducing the amount of carbon dioxide emission increases. Moreover, the workability of the cement kneaded product is improved. When the ratio is 100% by mass or less, the compressive strength of the cementitious cured body is increased.
［（Ｃ）骨材］
本発明で用いられる骨材としては、細骨材のみ、または、細骨材と粗骨材の組み合わせが挙げられる。
細骨材としては、川砂、山砂、陸砂、海砂、砕砂、珪砂またはこれらの混合物等を使用することができる。粗骨材としては、川砂利、山砂利、陸砂利、砕石またはこれらの混合物等を使用することができる。
骨材の配合量（細骨材と粗骨材を併用する場合はその合計量）は、粉末状セメント組成物１００質量部に対して、好ましくは２００〜７００質量部、より好ましくは２００〜６００質量部である。該配合量が前記範囲内であれば、セメント質硬化体の圧縮強さが大きくなり、また、セメント質硬化体の収縮率が小さくなる。
また、粗骨材を用いる揚合、細骨材率は、好ましくは５〜６０％である。細骨材率が前記範囲内であれば、セメント混練物のワーカビリティや成形のし易さが向上する。
[(C) Aggregate]
Aggregates used in the present invention include only fine aggregates or a combination of fine aggregates and coarse aggregates.
As fine aggregate, river sand, mountain sand, land sand, sea sand, crushed sand, silica sand, or a mixture thereof can be used. As the coarse aggregate, river gravel, mountain gravel, land gravel, crushed stone, or a mixture thereof can be used.
The amount of aggregate (the total amount when fine and coarse aggregates are used together) is preferably 200 to 700 parts by weight, more preferably 200 to 600 parts per 100 parts by weight of the powdered cement composition. Part by mass. When the blending amount is within the above range, the compressive strength of the cementitious cured body is increased, and the shrinkage rate of the cementitious cured body is decreased.
Moreover, the lift using a coarse aggregate and the fine aggregate rate are preferably 5 to 60%. When the fine aggregate ratio is within the above range, the workability of the cement kneaded material and the ease of molding are improved.
［その他の材料］
また、上記セメント混練物には、本発明の目的を阻害しない範囲内で、必要に応じて他の材料を配合してもよい。必要に応じて配合される他の材料としては、減水剤、消泡剤、収縮低減剤等の各種添加剤や、フライアッシュ、シリカフューム、高炉スラグ微粉末等の各種混和材が挙げられる。
[Other materials]
Moreover, you may mix | blend another material with the said cement kneaded material as needed within the range which does not inhibit the objective of this invention. Examples of other materials blended as necessary include various additives such as water reducing agents, antifoaming agents, shrinkage reducing agents, and various admixtures such as fly ash, silica fume, and blast furnace slag fine powder.
［セメント質硬化体の製造方法］
本発明のセメント質硬化体の製造方法は、上述の粉末状セメント組成物と、水と、骨材の各材料を混練して、セメント混練物を調製するセメント混練物調製工程と、上記セメント混練物を型枠内に打設する打設工程と、上記型枠内の上記セメント混練物が硬化した後に、上記セメント混練物の硬化体を上記型枠から脱型する脱型工程と、上記型枠から脱型した上記セメント混練物の硬化体を炭酸化養生して、セメント質硬化体を得る炭酸化養生工程、を含む。
[Method for producing hardened cementitious material]
The method for producing a hardened cementitious material of the present invention includes a cement kneaded material preparation step in which a cement kneaded material is prepared by kneading the above powdered cement composition, water, and aggregate materials, and the cement kneading method. A casting step of casting an object in a mold, a demolding process of demolding a cured body of the cement kneaded material from the mold after the cement kneaded material in the mold is cured, and the mold A carbonation curing step of carbonizing and curing the hardened body of the cement kneaded material released from the frame to obtain a cementitious hardened body.
上記セメント混練物調製工程において、各材料を混練する方法は、特に限定されるものではない。また、混練に用いる装置も特に限定されるものではなく、オムニミキサ、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を使用することができる。 In the cement kneaded material preparation step, the method for kneading each material is not particularly limited. Moreover, the apparatus used for kneading is not particularly limited, and a conventional mixer such as an omni mixer, a pan-type mixer, a biaxial kneading mixer, and a tilting mixer can be used.
上記打設工程において、上記セメント混練物は所望の型枠内に打設される。打設方法としては、特に限定されるものではなく、流し込み成形等の慣用の方法を使用することができる。
上記セメント混練物を型枠内に打設した後、脱型するまでの養生方法としては、特に限定されるものではなく、例えば、気中養生、湿空養生、水中養生、及び蒸気養生等の一般的な養生方法を採用することができる。
In the placing step, the cement kneaded material is placed in a desired mold. The casting method is not particularly limited, and a conventional method such as casting can be used.
The curing method after the cement kneaded material is placed in the mold and before demolding is not particularly limited, and examples thereof include air curing, wet air curing, underwater curing, and steam curing. A general curing method can be employed.
上記炭酸化養生工程における二酸化炭素ガスの濃度は、好ましくは１体積％以上、より好ましくは３体積％以上、特に好ましくは５体積％以上である。該濃度が１体積％以上であれば、炭酸化養生工程における二酸化炭素の吸収量を大きくすることができる。
二酸化炭素ガスの濃度の上限は、特に限定されるものではなく、二酸化炭素ガスの濃度が高いほど、二酸化炭素の吸収量を増加させることができるが、養生設備等のコストを低くする観点から、好ましくは９０体積％以下、より好ましくは７０体積％以下、特に好ましくは５０体積％以下である。
The concentration of carbon dioxide gas in the carbonation curing step is preferably 1% by volume or more, more preferably 3% by volume or more, and particularly preferably 5% by volume or more. If this density | concentration is 1 volume% or more, the absorbed amount of the carbon dioxide in a carbonation curing process can be enlarged.
The upper limit of the concentration of carbon dioxide gas is not particularly limited, and as the concentration of carbon dioxide gas is higher, the amount of carbon dioxide absorbed can be increased, but from the viewpoint of reducing the cost of curing equipment, etc. Preferably it is 90 volume% or less, More preferably, it is 70 volume% or less, Most preferably, it is 50 volume% or less.
また、上記炭酸化養生工程における温度は、特に限定されるものではないが、好ましくは５〜１００℃、より好ましくは１０〜５０℃、特に好ましくは１５〜３５℃である。
炭酸化養生における温度が、上記数値範囲内であれば、セメント質硬化体からなる製品の生産性が向上し、セメント質硬化体の圧縮強さが大きくなる。
また、本発明のセメント質硬化体は、比較的低温（例えば、５〜３０℃）で炭酸化養生を行った場合であっても、二酸化炭素の排出量の低減効果が大きいものである。
また、上記炭酸化養生工程における相対湿度は、特に限定されるものではないが、好ましくは３０〜９０％、より好ましくは４０〜８０％である。該相対湿度が、上記数値範囲内であれば、セメント質硬化体からなる製品の生産性が向上し、セメント質硬化体の圧縮強さが大きくなる。
Moreover, although the temperature in the said carbonation curing process is not specifically limited, Preferably it is 5-100 degreeC, More preferably, it is 10-50 degreeC, Most preferably, it is 15-35 degreeC.
When the temperature in the carbonation curing is within the above numerical range, the productivity of the product made of the cementitious hardened body is improved, and the compressive strength of the cementitious hardened body is increased.
Moreover, the cementitious hardened body of the present invention has a great effect of reducing carbon dioxide emission even when carbonation curing is performed at a relatively low temperature (for example, 5 to 30 ° C.).
Moreover, although the relative humidity in the said carbonation curing process is not specifically limited, Preferably it is 30 to 90%, More preferably, it is 40 to 80%. When the relative humidity is within the above numerical range, the productivity of a product made of a cementitious hardened body is improved, and the compressive strength of the cementitious hardened body is increased.
上記炭酸化養生工程は、脱型工程において、セメント混練物の硬化体を型枠から脱型した直後から行ってもよいが、セメント質硬化体の圧縮強さを高める観点から、上記脱型工程と上記炭酸化養生工程の間に、高強度化養生工程を設けてもよい。
高強度化養生工程において、型枠から脱型したセメント混練物の硬化体を、その圧縮強さが、好ましくは１５Ｎ／ｍｍ２以上、より好ましくは２０Ｎ／ｍｍ２以上、特に好ましくは３０Ｎ／ｍｍ２以上となるまで養生することで、炭酸化養生後のセメント質硬化体の圧縮強さを高めることができる。
上記高強度化養生工程における養生方法としては、特に限定されるものではなく、例えば、気中養生、湿空養生、水中養生、及び蒸気養生等の一般的な養生方法を採用することができる。なお、高強度化養生工程における「養生」には、炭酸化養生は含まれないものとする。
The carbonation curing step may be performed immediately after the hardened body of the cement kneaded product is removed from the mold in the demolding step, but from the viewpoint of increasing the compressive strength of the cementitious hardened body, the demolding step. A high-strength curing process may be provided between the carbonation curing process.
In the high-strength curing process, the cement kneaded cured product released from the mold is preferably 15 N / mm 2 or more, more preferably 20 N / mm 2 or more, and particularly preferably 30 N / mm. By curing to 2 or more, the compressive strength of the cementitious cured body after carbonation curing can be increased.
The curing method in the high-strength curing process is not particularly limited, and for example, general curing methods such as air curing, wet air curing, underwater curing, and steam curing can be adopted. Note that “curing” in the high-strength curing process does not include carbonation curing.
なお、本発明においては、上記製造方法によって得られたセメント質硬化体は、上記焼成物の粉砕物に代えて、上記粉末状セメント組成物に含まれるポルトランドセメントと同じポルトランドセメントを用いた場合に比べて、セメント質硬化体の製造に際して排出される二酸化炭素の量が１５％以上（より好ましくは２０％以上、さらに好ましくは３０％以上、特に好ましくは４０％以上）低減され、かつ、セメント質硬化体の圧縮強さの低下の割合が５０％以下（より好ましくは４０％以下）であるものが好ましい。 In the present invention, the hardened cementitious material obtained by the above production method uses the same Portland cement as the Portland cement contained in the powdered cement composition instead of the pulverized product of the fired product. In comparison, the amount of carbon dioxide discharged during the production of a cementitious hardened body is reduced by 15% or more (more preferably 20% or more, more preferably 30% or more, particularly preferably 40% or more), and the cementum It is preferable that the rate of decrease in the compressive strength of the cured product is 50% or less (more preferably 40% or less).
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
使用材料は、以下に示すとおりである。
（１）α：Ｃ２Ｓ１００質量部に対して、Ｃ２ＡＳを３８質量部、Ｃ４ＡＦ１５質量部含有し、かつ、Ｃ３Ａの含有量が０質量部である焼成物の粉砕物で、ブレーン比表面積６，０００ｃｍ２／ｇのもの
なお、焼成物の原料としては、石灰石、石炭灰、建設発生土、珪石及び粘土を使用した。焼成は、小型ロータリーキルンを用いて１３５０℃で行った。
（２）γ−Ｃ２Ｓ粉末：試薬である炭酸カルシウム粉末と試薬である二酸化珪素粉末を、電気炉で焼成したもの （ブレーン比表面積；６，０００ｃｍ２／ｇ：γ−Ｃ２Ｓ （γ−２ＣａＯ・ＳｉＯ２）の含有率が９５質量％以上のもの）
（３）普通ポルトランドセメント（ＯＰＣ）：太平洋セメント社製
（４）細骨材：「ＪｌＳ Ｒ ５２０１ （セメントの物理試験方法）」の標準砂
（５）水：上水道水
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The materials used are as shown below.
(1) α: A pulverized product of calcined product containing 38 parts by mass of C 2 AS, 15 parts by mass of C 4 AF and 0 part by mass of C 3 A with respect to 100 parts by mass of C 2 S Blane specific surface area of 6,000 cm 2 / g In addition, limestone, coal ash, construction generated soil, silica stone and clay were used as the raw material of the fired product. Firing was performed at 1350 ° C. using a small rotary kiln.
(2) γ-C 2 S powder: a calcium carbonate powder as a reagent and silicon dioxide powder as a reagent fired in an electric furnace (Brain specific surface area: 6,000 cm 2 / g: γ-C 2 S (γ -2CaO · SiO 2 ) content of 95% by mass or more)
(3) Ordinary Portland cement (OPC): Taiheiyo Cement Co., Ltd. (4) Fine aggregate: Standard sand of “JlS R 5201 (Cement physical test method)” (5) Water: Tap water
［実験例１］
上記普通ポルトランドセメントと上記細骨材を１：３の質量比で、ホバートミキサに投入後、空練りして、これらの混合物を得た。得られた混合物と水を、水／粉末状セメント組成物の質量比が５０質量％となるように混合して、モルタルを調製した。得られたモルタルを、４×４×１６ｃｍの型枠内に充填した後、温度２０℃の条件下で２４時間湿空養生を行い、次いで、脱型を行った。その後、脱型したモルタル硬化体を、材齢２８日までは温度２０℃の条件下で水中養生を行い、材齢５６日までは、温度２０℃、相対湿度６０℃の条件下で、促進中性化槽内において炭酸化養生を行った。炭酸化養生における二酸化炭素ガスの濃度は５体積％であった。
[Experimental Example 1]
The ordinary Portland cement and the fine aggregate were put into a Hobart mixer at a mass ratio of 1: 3, and then kneaded to obtain a mixture thereof. The obtained mixture and water were mixed so that the mass ratio of the water / powdered cement composition was 50% by mass to prepare a mortar. After the obtained mortar was filled in a 4 × 4 × 16 cm mold, it was subjected to moisture curing under a temperature of 20 ° C. for 24 hours, and then demolded. Thereafter, the demolded mortar cured body is cured under water at a temperature of 20 ° C. until the age of 28 days, and is promoted at a temperature of 20 ° C. and a relative humidity of 60 ° C. until the age of 56 days. Carbonation curing was performed in the oxidization tank. The concentration of carbon dioxide gas in the carbonation curing was 5% by volume.
水中養生後の供試体、及び、炭酸化養生後の供試体を用いて、「ＪＩＳ Ｒ ５２０１（セメントの物理試験方法）」に準拠して、モルタルの圧縮強さを測定した。それぞれの結果を表１に示す。
また、供試体１本あたりの、二酸化炭素吸収量を、熱重量分析（ＴＧ）から算出した。また、供試体の材料の組成から算出される二酸化炭素排出量から、二酸化炭素吸収量を減じることで、排出される二酸化炭素の総量を算出した。それぞれの結果を表２に示す。
さらに、炭酸化養生後の４×４×１６ｃｍの供試体から、モルタルカッターを用いて、４×４×４ｃｍの立方供試体を３個切り出した。切断は４×４×１６ｃｍの供試休の端面より略２０ｍｍの部分から開始して、供試体の長手方向に垂直な方向に切断面を有するようにして行った。切断の結果、得られた供試体の両端部分の部材については使用せずに処分した。
該立方供試体の切断面にフェノールフタレインを塗布した。その結果、切断面の中央部分が、略正方形状に変色した。このことから、切断面の中央部分は中性化されていないことがわかった。
The compressive strength of the mortar was measured in accordance with “JIS R 5201 (Cement physical test method)” using the specimen after underwater curing and the specimen after carbonation curing. The results are shown in Table 1.
In addition, the amount of carbon dioxide absorbed per specimen was calculated from thermogravimetric analysis (TG). In addition, the total amount of carbon dioxide emitted was calculated by subtracting the carbon dioxide absorption from the carbon dioxide emission calculated from the composition of the specimen material. The results are shown in Table 2.
Further, three 4 × 4 × 4 cm cubic specimens were cut out from the 4 × 4 × 16 cm specimens after carbonation curing using a mortar cutter. The cutting was started from a portion approximately 20 mm from the end face of the test holiday of 4 × 4 × 16 cm, and was carried out so as to have a cut surface in a direction perpendicular to the longitudinal direction of the specimen. As a result of cutting, members at both ends of the obtained specimen were disposed without being used.
Phenolphthalein was applied to the cut surface of the cubic specimen. As a result, the central portion of the cut surface changed to a substantially square shape. From this, it was found that the central portion of the cut surface was not neutralized.
[実験例２]
普通ポルトランドセメントの代わりに、上記普通ポルトランドセメントとαを用いた以外は、実験例１と同様にして、供試体を得た。
得られた供試体について、実験例１と同様にして、モルタルの圧縮強さ、二酸化炭素排出量、及び二酸化炭素吸収量等を測定または算出し、得られた結果から、排出される二酸化炭素の総量、圧縮強さの低減率、及び排出される二酸化炭素の総量の低減率を算出した。それぞれの結果を表１〜２に示す。
なお、圧縮強さの低減率（単位：％）は。下記式（１）によって算出されるものである。
（実験例１の炭酸化養生後の圧縮強さ−供試体の炭酸化養生後の圧縮強さ）／実験例１の炭酸化養生後の圧縮強さ）×１００ （１）
また、排出される二酸化炭素の総量の低減率（単位：％）は、下記式（２）によって算出されるものである。
（実験例１の排出される二酸化炭素の総量−供試体の排出される二酸化炭素の総量）／実験例１の排出される二酸化炭素の総量）×１００ （２）
[Experiment 2]
A specimen was obtained in the same manner as in Experimental Example 1 except that the above ordinary Portland cement and α were used instead of ordinary Portland cement.
For the obtained specimen, the mortar compressive strength, carbon dioxide emission, carbon dioxide absorption, etc. were measured or calculated in the same manner as in Experimental Example 1, and from the obtained results, The total amount, the reduction rate of compressive strength, and the reduction rate of the total amount of discharged carbon dioxide were calculated. Each result is shown to Tables 1-2.
The reduction rate of compressive strength (unit:%). It is calculated by the following formula (1).
(Compressive strength after carbonation curing of Experimental Example 1−Compressive strength after carbonation curing of test sample) / Compressive strength after carbonation curing of Experimental Example 1) × 100 (1)
Moreover, the reduction rate (unit:%) of the total amount of carbon dioxide discharged is calculated by the following formula (2).
(Total amount of carbon dioxide discharged in Experimental Example 1−Total amount of carbon dioxide discharged from the specimen) / Total amount of carbon dioxide discharged in Experimental Example 1) × 100 (2)
また、実験例１と同様にして、４×４×４ｃｍの立方供試体を３個切り出して、フェノールフタレインを塗布したところ、切断面の中央部分が略円形状に変色した。変色部分の面積は、実験例１における変色部分の面積よりも小さかったことから、切断面の中央部分は、中性化されていないものの、実験例１と比べて、中性化が進んでいることがわかった。 Further, in the same manner as in Experimental Example 1, three 4 × 4 × 4 cm cubic specimens were cut out and applied with phenolphthalein, and the central portion of the cut surface was changed to a substantially circular shape. Since the area of the discolored portion was smaller than the area of the discolored portion in Experimental Example 1, the central portion of the cut surface was not neutralized, but was neutralized compared to Experimental Example 1. I understood it.
[実験例３]
αの代わりに、上記γ−Ｃ２Ｓ粉末を用いる以外は実験例２と同様にして、モルタルの圧縮強さ等の測定、及び排出される二酸化炭素の総量等の算出を行った。それぞれの結果を表１〜２に示す。
また、実験例１と同様にして、４×４×４ｃｍの立方供試体を３個切り出して、フェノールフタレインを塗布したところ、切断面の中央部分が略正方形状に変色した。また、変色部分の面積は、実験例１における変色部分の面積よりも若干大きいものであった。このことから、切断面の中央部分は、中性化されておらず、かつ、実験例１と比べて、若干中性化が進んでいないことがわかった。
[Experiment 3]
Instead of α, the measurement of the compressive strength of the mortar and the calculation of the total amount of discharged carbon dioxide and the like were performed in the same manner as in Experimental Example 2 except that the γ-C 2 S powder was used. Each result is shown to Tables 1-2.
Further, in the same manner as in Experimental Example 1, three 4 × 4 × 4 cm cubic specimens were cut out and applied with phenolphthalein, and the central portion of the cut surface was changed to a substantially square shape. Further, the area of the discolored portion was slightly larger than the area of the discolored portion in Experimental Example 1. From this, it was found that the central portion of the cut surface was not neutralized and was not slightly neutralized as compared with Experimental Example 1.
[実験例４]
αを４５質量％に増量して用いる以外は実験例２と同様にして、モルタルの圧縮強さ等の測定、及び排出される二酸化炭素の総量等の算出を行った。それぞれの結果を表１〜２に示す。
また、実験例１と同様にして、４×４×４ｃｍの立方供試体を３個切り出して、フェノールフタレインを塗布したところ、切断面に変色が見られなかった。このことから、供試体の中央部分にまで中性化が進んでいることがわかった。
[Experiment 4]
Except that the α was increased to 45% by mass and used in the same manner as in Experimental Example 2, the compression strength of the mortar and the total amount of carbon dioxide discharged were calculated. Each result is shown to Tables 1-2.
Further, in the same manner as in Experimental Example 1, three 4 × 4 × 4 cm cubic specimens were cut out and phenolphthalein was applied, and no discoloration was observed on the cut surface. From this, it was found that neutralization has progressed to the central part of the specimen.
[実験例５]
αの代わりに、上記γ−Ｃ２Ｓ粉末を用いる以外は実験例４と同様にして、モルタルの圧縮強さ等の測定、及び排出される二酸化炭素の総量等の算出を行った。それぞれの結果を表１〜２に示す。
また、実験例１と同様にして、４×４×４ｃｍの立方供試体を３個切り出して、フェノールフタレインを塗布したところ、切断面の中央部分が、略正方形状に変色した。また、変色部分の面積は、実験例１における変色部分の両積よりも大きいものであった。このことから、切断面の中央部分は、中性化されておらず、かつ、実験例１と比べて、中性化が進んでいないことがわかった。
[Experimental Example 5]
Instead of α, measurement of the compressive strength of the mortar and calculation of the total amount of discharged carbon dioxide and the like were performed in the same manner as in Experimental Example 4 except that the γ-C 2 S powder was used. Each result is shown to Tables 1-2.
Further, in the same manner as in Experimental Example 1, three 4 × 4 × 4 cm cubic specimens were cut out and coated with phenolphthalein, and the central portion of the cut surface was changed to a substantially square shape. Further, the area of the discolored portion was larger than the product of the discolored portions in Experimental Example 1. From this, it was found that the central portion of the cut surface was not neutralized and was not neutralized as compared with Experimental Example 1.
表１〜２より、実験例２のセメント質硬化体の圧縮強さの低減率は、実験例３のセメント質硬化体の圧縮強さの低減率よりも小さいことがわかる。同様に実験例４の圧縮強さの低減率は、実験例５の低減率よりも小さいことがわかる。
また、実験例２のセメント質硬化体の排出される二酸化炭索の総量の低減率は、実験例３のセメント質硬化体の排出される二酸化炭素の総量の低減率より大きいことがわかる。同様に実験例４の二酸化炭索の総量の低減率は、実験例５の低減率よりも大きいことがわかる。
From Tables 1 and 2, it can be seen that the reduction rate of the compressive strength of the hardened cementitious material of Experimental Example 2 is smaller than the reduction rate of the compressive strength of the hardened cementitious material of Experimental Example 3. Similarly, it can be seen that the reduction rate of the compressive strength in Experimental Example 4 is smaller than that in Experimental Example 5.
It can also be seen that the reduction rate of the total amount of carbon dioxide cord discharged from the cementitious hardened body of Experimental Example 2 is larger than the reduction rate of the total amount of carbon dioxide discharged from the cementitious hardened body of Experimental Example 3. Similarly, it can be seen that the reduction rate of the total amount of the carbon dioxide cable of Experimental Example 4 is larger than the reduction rate of Experimental Example 5.
Claims (4)
上記（Ａ）〜（Ｃ）の各材料を混練して、上記セメント混練物を調製するセメント混練物調製工程と、
上記セメント混練物を型枠内に打設する打設丁程と、
上記型枠内の上記セメント混練物が硬化した後に、上記セメント混練物の硬化体を上記型枠から脱型する脱型工程と、
上記型枠から脱型した上記セメント混練物の硬化体を５〜５０℃の炭酸化養生をして、上記セメント質硬化体を得る炭酸化養生工程、を含むことを特徴とするセメント質硬化体の製造方法。 (A) With respect to 100 parts by mass of C 2 S, 38 parts by mass of C 2 AS, 0 part by mass of C 3 A, and 15 parts by mass of C 4 AF are contained. Powdered cement composition containing 25 to 45% by mass of a pulverized product having a Blaine specific surface area of 2,500 to 10,000 cm 2 / g, 55 to 75% by mass of Portland cement, (B) water, and (C) an aggregate A method for producing a cementitious hardened body which is a low-temperature carbonation nourishing body of 5 to 50 ° C. of a cement kneaded material containing each of the materials,
Cement kneaded material preparation step of kneading each material of (A) to (C) to prepare the cement kneaded material,
A placement tool for placing the cement kneaded material in a mold,
A demolding step of demolding the cured body of the cement kneaded material from the mold after the cement kneaded material in the mold is cured;
A cemented hardened body comprising a carbonation curing step for obtaining a cementitious hardened body by subjecting the hardened body of the cement kneaded material released from the mold to carbonation curing at 5 to 50 ° C. Manufacturing method.
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