JP2004224698A - Cement composition, and method of producing hardened body obtained by using the same - Google Patents

Cement composition, and method of producing hardened body obtained by using the same Download PDF

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JP2004224698A
JP2004224698A JP2004143956A JP2004143956A JP2004224698A JP 2004224698 A JP2004224698 A JP 2004224698A JP 2004143956 A JP2004143956 A JP 2004143956A JP 2004143956 A JP2004143956 A JP 2004143956A JP 2004224698 A JP2004224698 A JP 2004224698A
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cement
cement composition
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JP4301076B2 (en
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Hideaki Igarashi
秀明 五十嵐
Koichiro Yamato
功一郎 大和
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Ube Corp
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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
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a cement composition which gives a hardened body having improved releasing strength from a mold even if precuring time is reduced to ≤1 hr, and to provide a method of producing a hardened body having improved releasing strength from a mold performed by using the cement composition. <P>SOLUTION: The cement composition consists of portland cement, and insoluble anhydrous gypsum in 1 to 3 wt.% of the whole composition, and the total fluorine content in the insoluble anhydrous gypsum is ≤1.0 wt.%. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

本発明は、初期強度の高いセメント二次製品を与えるセメント組成物と、それを使用して高い初期強度を有する硬化体を製造する方法に関するものである。   The present invention relates to a cement composition that provides a secondary cement product having a high initial strength, and a method for producing a cured product having a high initial strength using the same.

セメントボード、コンクリート二次製品等のセメント二次製品は、混練、成形、前養生、蒸気養生、仕上げ工程を経て製造されるが、生産速度の向上、エネルギーコストの削減のために、前養生と蒸気養生時間の短縮が大きな課題の一つとなっている。蒸気養生時間については、セメントの初期水和反応性を向上させることがその短縮に有効な方法であることから種々の方法が検討されているが、中でも、セメント中のせっこう量を増すことがその最も有力な方法の一つであり、これ迄に多くの研究が為されている。例えば、特許文献１には、混合セメントにせっこうをＳＯ3 換算で２．１重量％添加することで、蒸気養生後の圧縮強度が増大することが報告されている。同様な報告は昭和４８年にも既に見られ、高炉セメントから調製した硬化体の蒸気養生後の圧縮強度がせっこう量に依存することが報告されている（非特許文献１を参照）。 Cement secondary products such as cement boards and concrete secondary products are manufactured through kneading, molding, pre-curing, steam curing, and finishing processes.To improve production speed and reduce energy costs, Reduction of steam curing time is one of the major issues. Regarding the steam curing time, various methods have been studied because improving the initial hydration reactivity of the cement is an effective method for shortening it, but among them, increasing the amount of gypsum in the cement is This is one of the most influential methods, and much research has been done so far. For example, Patent Literature 1 reports that adding 2.1% by weight of gypsum to a mixed cement in terms of SO 3 increases the compressive strength after steam curing. A similar report was already found in 1973, and it was reported that the compressive strength of a cured product prepared from blast furnace cement after steam curing was dependent on the amount of gypsum (see Non-Patent Document 1).

一方、前養生時間（混練終了から養生までの時間、前置時間とも言う）については、セメント硬化体を蒸気養生する場合、２〜４時間の前養生時間を取らないと強度発現性が低下することは良く知られている。例えば、上述した、せっこうを添加して初期水和反応性を向上させる方法を実際の工程に適用したところ、前養生時間を２時間以上取れば、確かに所期の効果を発現するが、前養生時間を１時間にすると、所期の効果を発現しないことが確かめられている。この前養生時間は、セメント硬化体の生産速度を向上させる上での一つの障害となっており、この時間を１時間以内とすることが望まれるが、短縮された前養生時間で強度発現性を改善する方法については、報告がないのが現状である。
特開平８−２６８７３６号公報 セメント技術年報，Ｎｏ．２１，ｐ．７５〜７９，１９７３ On the other hand, as for the pre-curing time (time from completion of kneading to curing, also referred to as pre-heating time), when the cured cement is steam-cured, the strength development property is reduced unless the pre-curing time is 2 to 4 hours. It is well known. For example, when the above-mentioned method of adding gypsum to improve the initial hydration reactivity was applied to an actual process, if the pre-curing time was set to 2 hours or more, the intended effect was certainly exhibited, It has been confirmed that the desired effect is not exhibited when the pre-curing time is set to 1 hour. This pre-curing time is one of the obstacles to improving the production speed of the hardened cement, and it is desired that the time be within one hour. There is no report on how to improve the situation.
JP-A-8-268736 Annual Report on Cement Technology, No. 21, p. 75-79,1973

本発明は、前養生時間を１時間以内に短縮しても、脱型強度の改善された硬化体を与えるセメント組成物、及び、該セメント組成物を使用して行なう脱型強度の改善された硬化体製造方法の提供を目的とする。   The present invention provides a cement composition that gives a cured product having improved demolding strength even if the pre-curing time is reduced to within 1 hour, and an improved demolding strength performed using the cement composition. It is intended to provide a method for producing a cured product.

本発明者等は、所定量のフッ素を含有する不溶性無水せっこう添加が、前養生時間を短縮しても、蒸気養生後の圧縮強度の増加に効果があることを見出し、本発明を完成した。 すなわち、本発明は、ポルトランドセメント及び組成物全体の１〜３重量％の不溶性無水せっこうよりなり、該不溶性無水せっこう中の全フッ素含有量が１．０重量％以下であるセメント組成物に関する。また、本発明は、ポルトランドセメント及び組成物全体の１〜３重量％の不溶性無水せっこうよりなり、該不溶性無水せっこう中の全フッ素含有量が１．０重量％以下であるセメント組成物、骨材、化学混和剤及び水との混合物を成形後、２０〜６０分間の前養生を行なった後、２〜５時間蒸気養生することを特徴とする、セメント硬化体の製造方法に関する。
以下に、本発明を詳細に説明する。 The present inventors have found that the addition of insoluble anhydrous gypsum containing a predetermined amount of fluorine, even if shortening the pre-curing time, is effective in increasing the compressive strength after steam curing, and completed the present invention. . That is, the present invention relates to Portland cement and a cement composition comprising 1-3% by weight of insoluble anhydrous gypsum of the whole composition, wherein the total fluorine content in the insoluble anhydrous gypsum is 1.0% by weight or less. . The present invention also provides a cement composition comprising Portland cement and 1 to 3% by weight of insoluble anhydrous gypsum of the whole composition, wherein the total fluorine content in the insoluble anhydrous gypsum is 1.0% by weight or less, The present invention relates to a method for producing a hardened cement body, comprising forming a mixture of an aggregate, a chemical admixture, and water, pre-curing for 20 to 60 minutes, and then steam-curing for 2 to 5 hours.
Hereinafter, the present invention will be described in detail.

本発明のセメント組成物は、従来２時間以上は必要であった前養生時間の１時間以内への短縮を可能にした。これは、セメント二次製品の生産速度を向上させる上での課題の一つを解決したことを意味する。   The cement composition of the present invention has made it possible to shorten the pre-curing time to one hour or less, which was conventionally required for two hours or more. This means that one of the issues in improving the production speed of cement secondary products has been solved.

本発明のセメント組成物は、セメントに無水せっこうを添加して成る。セメントとしては、ＪＩＳ Ｒ ５２１０「ポルトランドセメントの品質規定」に記載されているものは何れも問題なく使用できるが、初期強度の面から、早強ポルトランドセメントの使用が特に好ましい。   The cement composition of the present invention is obtained by adding anhydrous gypsum to cement. As the cement, any of those described in JIS R 5210 "Portland Cement Quality Regulation" can be used without any problem, but from the viewpoint of initial strength, use of early-strength Portland cement is particularly preferred.

一方、せっこうは、不溶性無水せっこうを使用することが必須要件であり、半水せっこう及び二水せっこうでは効果がない。また、不溶性無水せっこう中に含まれるフッ素の量は１重量％以下であることも必要である。不溶性無水せっこうは、フッ素の含有量が１重量％以下であれば、天然無水せっこう或いはふっ酸無水せっこうの何れもが問題なく使用できる。   On the other hand, for gypsum, it is an essential requirement to use insoluble anhydrous gypsum, and hemihydrate gypsum and dihydrate gypsum have no effect. Further, the amount of fluorine contained in the insoluble anhydrous gypsum must be 1% by weight or less. As the insoluble anhydrous gypsum, as long as the fluorine content is 1% by weight or less, either natural anhydrous gypsum or hydrofluoric anhydride gypsum can be used without any problem.

不溶性無水せっこうの添加量は、セメント組成物全体の１〜３重量％とする。不溶性無水せっこうの添加量が１重量％より少ないと十分な添加効果が発現せず、３重量％より大であると、機構は分からないが、マイナス効果が大きくなり、何れに於ても、蒸気養生後の圧縮強度の向上を図ることは出来ない。   The amount of the insoluble anhydrous gypsum is 1 to 3% by weight of the whole cement composition. If the amount of the insoluble anhydrous gypsum is less than 1% by weight, no sufficient effect is obtained, and if it is more than 3% by weight, the mechanism is unknown, but the negative effect is large. It is not possible to improve the compressive strength after steam curing.

本発明のセメント組成物は、ポルトランドセメントに、特定のスペックのせっこうを特定量添加した組成より成るが、これ等必須成分に加えて１５〜４０重量％の量で、高炉スラグ微粉末、フライアッシュ、石灰石微粉末等、公知の無機系混和材を添加することもできる。これ等の無機系混和材は、強度、流動性に影響を与えることなくコスト低減に繋がり、特に、早強ポルトランドセメントを使用する場合にその効果が大きい。無機系混和材は、２０００〜１００００ｃｍ2 ／ｇのブレーン比表面積を有する微粉末の使用が好ましく、初期強度発現性の点から、高炉スラグ微粉末或いは石灰石微粉末の添加が最も好ましい。 The cement composition of the present invention comprises a composition obtained by adding a specific amount of gypsum of a specific specification to Portland cement. In addition to these essential components, 15 to 40% by weight of blast furnace slag fine powder, fly Known inorganic admixtures such as ash and limestone fine powder can also be added. These inorganic admixtures lead to cost reduction without affecting strength and fluidity, and are particularly effective when using early-strength Portland cement. As the inorganic admixture, it is preferable to use a fine powder having a Blaine specific surface area of 2000 to 10000 cm 2 / g, and from the viewpoint of initial strength development, it is most preferable to add a blast furnace slag fine powder or a limestone fine powder.

ポルトランドセメントおよび不溶性無水せっこうを必須成分とし、必要に応じて無機系混和材を添加する本発明のセメント組成物は、使用に際して、それを構成する各成分を、骨材、減水剤、高性能ＡＥ減水剤等の化学混和剤等の、モルタルまたはコンクリート調製の際に一般に使用される他の材料とを混合しても良いが、予めセメント組成物のみを混合調製して置き、使用に当たって骨材、混和剤等の他の材料と混合するのが最も好ましい方法である。化学混和剤はＪＩＳ Ｒ ６２０４「コンクリート用化学混和剤」に記載されている、スルフォン酸系、メラミン系、ポリカルボン酸系の何れもが使用できるが、中でもポリカルボン酸系の減水剤あるいは高性能ＡＥ減水剤が特に好ましい結果を与える。   Portland cement and insoluble anhydrous gypsum are essential components, and the cement composition of the present invention to which an inorganic admixture is added as necessary, when used, uses each component constituting the aggregate, aggregate, water reducing agent, high performance It may be mixed with other materials generally used in the preparation of mortar or concrete, such as a chemical admixture such as an AE water reducing agent. The most preferable method is to mix with other materials such as an admixture. As the chemical admixture, any of sulfonic acid type, melamine type and polycarboxylic acid type described in JIS R 6204 “Chemical admixture for concrete” can be used. Among them, polycarboxylic acid type water reducing agent or high performance AE water reducing agents give particularly favorable results.

本発明のセメント組成物と、骨材、化学混和剤及び水とを混練して調製したモルタルまたはコンクリートは、成形、蒸気養生してセメント硬化体とすることができるが、従来行なわれていた方法と大きく異なる点は、蒸気養生に先立って行なう前養生時間の１時間以内への短縮が可能なことである。本発明のセメント組成物は、使用するポルトランドセメント種、組成比にもよるが、２０〜６０分の前養生時間を取れば、２〜５時間の蒸気養生後に、強度特性に優れたセメント硬化体を与える。前養生時間をこれより長く設定しても、生成するモルタルまたはコンクリートに特性面での問題は生じないが、大きな意味はない。以下に、具体的例を挙げて、本発明を更に詳しく説明する。   The mortar or concrete prepared by kneading the cement composition of the present invention, an aggregate, a chemical admixture and water can be molded and steam-cured to obtain a hardened cement body. The major difference is that the pre-curing time performed prior to steam curing can be reduced to within one hour. Although the cement composition of the present invention depends on the type of Portland cement used and the composition ratio, if a pre-curing time of 20 to 60 minutes is taken, a cured cement body having excellent strength properties after steam curing for 2 to 5 hours. give. Setting the pre-curing time longer than this does not cause any problem in the properties of the resulting mortar or concrete, but has no significant significance. Hereinafter, the present invention will be described in more detail with reference to specific examples.

実施例１
セメント組成物構成成分としての普通ポルトランドセメントおよびフッ素含有量０．５重量％のふっ酸無水せっこう、細骨材、および３．１重量％のナフタレン系減水剤を含む水道水を、２０℃の恒温室においてホバートミキサーで３分間混練し、モルタル中の単位量が、セメント組成物（せっこう含有量２重量％）：６５１ｋｇ／ｍ3 、水：２７６ｋｇ／ｍ3 、細骨材：１２７２ｋｇ／ｍ3 であるモルタルを調製した。得られたモルタルは、ＪＩＳ Ｒ ５２０１「セメントの物理試験方法」記載のフローコーンを用いて０打でのフローを測定後、径５０ｍｍ×高さ１００ｍｍの円筒形鋼製型枠に打ち込んだ。混練開始から３０分間の前養生時間が経過した後、温度７０℃、相対湿度９８％に保った恒温恒湿器に入れ３時間の蒸気養生を行なった。養生終了後、恒温恒湿器より硬化体を取り出し、ＪＩＳ Ａ １１０８「コンクリートの圧縮試験方法」に規定されている方法に準じて、圧縮強度（脱型強度）を測定した。結果を表１に示す。 Example 1
Normal portland cement as a component of the cement composition and tap water containing 0.5% by weight of hydrofluoric anhydride gypsum, fine aggregate, and 3.1% by weight of a naphthalene-based water reducing agent were added at 20 ° C. The mixture is kneaded in a constant temperature room for 3 minutes using a Hobart mixer, and the unit amount in the mortar is a cement composition (gypsum content 2% by weight): 651 kg / m 3 , water: 276 kg / m 3 , fine aggregate: 1272 kg / m A mortar of 3 was prepared. The obtained mortar was measured for flow at 0 strokes using a flow cone described in JIS R 5201 “Physical Testing Method of Cement”, and was then poured into a cylindrical steel mold having a diameter of 50 mm and a height of 100 mm. After a 30-minute pre-curing time had elapsed from the start of kneading, the mixture was placed in a thermo-hygrostat maintained at a temperature of 70 ° C. and a relative humidity of 98%, and subjected to steam curing for 3 hours. After the curing, the cured product was taken out from the thermo-hygrostat, and the compressive strength (demolding strength) was measured according to the method specified in JIS A 1108 “Method of compressive test for concrete”. Table 1 shows the results.

Figure 2004224698
Figure 2004224698

比較例１〜４
ここでは、せっこうとして半水または二水せっこうを使用した例（比較例１、２）及びフッ素含有量の多い無水せっこうを使用した例（比較例３）を示す。せっこう種を変えた以外は実施例１と同様の方法でモルタルおよび硬化体を調製し、モルタルフローと脱型強度を測定した。結果を表１に示す。 Comparative Examples 1-4
Here, examples using hemihydrate or dihydrate gypsum (Comparative Examples 1 and 2) and examples using anhydrous gypsum having a high fluorine content (Comparative Example 3) are shown. A mortar and a cured product were prepared in the same manner as in Example 1 except that the gypsum species was changed, and the mortar flow and the demolding strength were measured. Table 1 shows the results.

実施例２及び比較例５〜６
ここでは、不溶性無水せっこう添加量を変化させた例を示す。ふっ酸無水せっこうの添加量を変えた以外は実施例１と同様の方法でモルタルおよび硬化体を調製し、モルタルフローと脱型強度を測定した。結果を表１に示す。 Example 2 and Comparative Examples 5 to 6
Here, an example in which the amount of insoluble anhydrous gypsum is changed is shown. A mortar and a cured body were prepared in the same manner as in Example 1 except that the amount of the added hydrofluoric anhydride gypsum was changed, and the mortar flow and demolding strength were measured. Table 1 shows the results.

実施例３〜５
ここでは、セメント種を早強ポルトランドセメントに変え且つ、無機系混和材を添加した例を、モルタル及びコンクリートについて示す。モルタル（実施例３、４）については、モルタル中の単位量が、セメント組成物（ポルトランドセメント、不溶性無水せっこう、高炉スラグ（ブレーン比表面積４０００ｃｍ2 ／ｇ、実施例３）または石灰石（ブレーン比表面積４５００ｃｍ2 ／ｇ、実施例４）微粉末の合量）：６５１ｋｇ／ｍ3 、水：２７７ｋｇ／ｍ3 、細骨材：１２５８ｋｇ／ｍ3 となるようにした他は実施例１と同様にモルタルおよび硬化体を調製し、モルタルフローと脱型強度を測定した。一方、コンクリート（実施例５）については、原料を２０℃の恒温室でパン型ミキサーを用いて２分間混練し、単位量を、セメント組成物（ポルトランドセメント、不溶性無水せっこう、高炉スラグ粉末の合量）：４００ｋｇ／ｍ3 、水：１７０ｋｇ／ｍ3 、細骨材：７７３ｋｇ／ｍ3 、粗骨材：１０２０ｋｇ／ｍ3 としたコンクリートのスランプを測定した後、径１００ｍｍ×高さ２００ｍｍの円筒型枠に打ち込んだ。混練開始から３０分経過後、蒸気養生室に入れ、４０℃／時間の速度で７０℃まで昇温した。混練開始から３．５時間経過後、蒸気養生室から取り出し、ＪＩＳ Ａ １１０８「コンクリートの圧縮試験方法」に規定されている方法により、圧縮強度（脱型強度）を測定した。結果を表１に示す。 Examples 3 to 5
Here, an example in which the cement type is changed to early-strength Portland cement and an inorganic admixture is added will be described for mortar and concrete. As for the mortar (Examples 3 and 4), the unit amount in the mortar was determined by the cement composition (Portland cement, insoluble anhydrous gypsum, blast furnace slag (Brain specific surface area 4000 cm 2 / g, Example 3) or limestone (Brain ratio Example 4) Same as Example 1 except that the surface area was 4500 cm 2 / g, the total amount of fine powder) was 651 kg / m 3 , the water was 277 kg / m 3 , and the fine aggregate was 1258 kg / m 3. A mortar and a cured product were prepared, and the mortar flow and the demolding strength were measured. On the other hand, for the concrete (Example 5), the raw materials were kneaded for 2 minutes using a pan-type mixer in a constant temperature room at 20 ° C., and the unit amount was changed to the cement composition (Portland cement, insoluble anhydrous gypsum, blast furnace slag powder). Total weight): 400 kg / m 3 , water: 170 kg / m 3 , fine aggregate: 773 kg / m 3 , coarse aggregate: 1020 kg / m 3 After measuring the slump of concrete, the diameter was 100 mm × height 200 mm. Driving into cylindrical formwork. After a lapse of 30 minutes from the start of kneading, the mixture was placed in a steam curing room and heated to 70 ° C. at a rate of 40 ° C./hour. After 3.5 hours from the start of kneading, the mixture was taken out of the steam curing room, and the compressive strength (demolding strength) was measured by the method specified in JIS A 1108 “Method of compressive test for concrete”. Table 1 shows the results.

実施例として示した本発明のセメント組成物は何れも、僅か３０分の前養生時間でも、蒸気養生直後の圧縮強度（脱型強度）発現性に優れたモルタルまたはコンクリート硬化体を与えることが分かる。それに対し、せっこう種、せっこう量、せっこう中のフッ素含有量何れかの要因が本発明の範囲を外れたセメント組成物では、蒸気養生直後のモルタル硬化体の脱型強度は低い。尚、これ等についても、前養生を２時間以上行なえば、十分な脱型強度の発現したモルタル硬化体を与えものがあることも考えられる。   It can be seen that all of the cement compositions of the present invention shown as examples give a mortar or concrete hardened body having excellent compressive strength (demolding strength) development immediately after steam curing even with a pre-curing time of only 30 minutes. . On the other hand, in the cement composition in which any of the gypsum species, the amount of gypsum, and the fluorine content in the gypsum are out of the range of the present invention, the demolding strength of the mortar hardened body immediately after steam curing is low. It should be noted that it is conceivable that, in these cases, if the pre-curing is performed for 2 hours or more, a mortar cured product having sufficient demolding strength may be provided.

Claims (5)

ポルトランドセメント及び組成物全体の１〜３重量％の不溶性無水せっこうよりなり、該不溶性無水せっこう中の全フッ素含有量が１．０重量％以下であるセメント組成物。   A portland cement and a cement composition comprising 1 to 3% by weight of insoluble anhydrous gypsum of the whole composition, wherein the total fluorine content in the insoluble anhydrous gypsum is 1.0% by weight or less. 請求項１に記載の成分に加え、組成物全体の１５〜４０重量％の無機系混和材を含むセメント組成物。   A cement composition comprising, in addition to the components of claim 1, 15 to 40% by weight of the total composition of the inorganic admixture. 無機系混和材が高炉スラグ微粉末もしくは石灰石微粉末である、請求項２に記載のセメント組成物。   The cement composition according to claim 2, wherein the inorganic admixture is blast furnace slag fine powder or limestone fine powder. ポルトランドセメントが、早強ポルトランドセメントである、請求項１から３までの何れかに記載のセメント組成物。   The cement composition according to any one of claims 1 to 3, wherein the Portland cement is an early-strength Portland cement. 請求項１から４までの何れかに記載のセメント組成物、骨材、化学混和剤及び水との混合物を成形後、２０〜６０分間の前養生を行なった後、２〜５時間蒸気養生する、セメント硬化体の製造方法。
After molding the mixture with the cement composition, aggregate, chemical admixture and water according to any one of claims 1 to 4, after pre-curing for 20 to 60 minutes, steam curing is performed for 2 to 5 hours. , A method for producing a cured cement body.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006282455A (en) * 2005-03-31 2006-10-19 Sumitomo Osaka Cement Co Ltd Cement and method for manufacturing the same
JP2015083526A (en) * 2013-10-25 2015-04-30 太平洋セメント株式会社 Method of producing cement composition
JP2019131416A (en) * 2018-01-29 2019-08-08 太平洋セメント株式会社 Cement composition and method for producing the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006282455A (en) * 2005-03-31 2006-10-19 Sumitomo Osaka Cement Co Ltd Cement and method for manufacturing the same
JP2015083526A (en) * 2013-10-25 2015-04-30 太平洋セメント株式会社 Method of producing cement composition
JP2019131416A (en) * 2018-01-29 2019-08-08 太平洋セメント株式会社 Cement composition and method for producing the same
JP7231980B2 (en) 2018-01-29 2023-03-02 太平洋セメント株式会社 Cement composition and its manufacturing method
JP7372491B2 (en) 2018-01-29 2023-10-31 太平洋セメント株式会社 Cement composition and its manufacturing method

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