JP5135127B2 - Calcium aluminate - Google Patents

Calcium aluminate Download PDF

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JP5135127B2
JP5135127B2 JP2008219731A JP2008219731A JP5135127B2 JP 5135127 B2 JP5135127 B2 JP 5135127B2 JP 2008219731 A JP2008219731 A JP 2008219731A JP 2008219731 A JP2008219731 A JP 2008219731A JP 5135127 B2 JP5135127 B2 JP 5135127B2
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calcium aluminate
12cao
vitrification
ratio
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JP2010052983A (en
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裕 中島
大輔 矢羽田
和彦 中原
浩司 副島
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Taiheiyo Materials Corp
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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
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • 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
    • C04B2111/00086—Mixtures with prolonged pot-life
    • 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
    • C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Description

本発明は、耐火物、コンクリート製品、建築・土木工事等で水硬質の主材やセメント系材料の助剤等に用いられるカルシウムアルミネートに関する。   The present invention relates to a calcium aluminate used as a refractory material, a concrete product, a water-based main material, a cement-based material auxiliary agent, and the like in construction and civil engineering work.

カルシウムアルミネートは、例えばアルミナセメントとして耐火物、コンクリート製品又は建築土木工事等の主材に使われたり、助剤や混和成分としてポルトランドセメントなどに併用され、建築・土木材料に用いられる。カルシウムアルミネートは、１２ＣａＯ・７Ａｌ2Ｏ3、ＣａＯ・Ａｌ2Ｏ3、３ＣａＯ・Ａｌ2Ｏ3、ＣａＯ・２Ａｌ2Ｏ3などの化学成分としてＣａＯとＡｌ2Ｏ3からなる結晶質又はガラス化が進んだ構造のものの他、他の化学成分も加わった４ＣａＯ・３Ａｌ2Ｏ3・ＳＯ3、１１ＣａＯ・７Ａｌ2Ｏ3・ＣａＦ2、Ｎａ2Ｏ・８ＣａＯ・３Ａｌ2Ｏ3なども広義のカルシウムアルミネートとして扱われている。このうち、２種以上のカルシウムアルミネートを使用する例が知られている。（例えば、特許文献１〜２参照。）構造的にガラス化率が高いカルシウムアルミネートほど水和反応等の活性が高く、初期強度発現性も高くなる。（例えば、特許文献３参照。）実使用に際しては、高い初期強度の発現性のみならず、打設・施工時の作業制約が軽減されることから適度な可使時間が得られること、中・長期強度も安定した発現性を呈すること等の性状がカルシウムアルミネートに望まれる。しかし、カルシウムアルミネートに長い可使時間と高い強度を同時に発現させるのは甚だ困難であり、特に可使時間の確保が難しい。また、組成の異なる２種以上のカルシウムアルミネートを使用しても、その主たる目的は、初期強度発現性に関するものである。（例えば、特許文献４参照。）可使時間の長時間確保のためにカルシウムアルミネート自体を組み合わせで所望の効果を得ることに関しては知られていない。カルシウムアルミネート系材料の可使時間を長くするには、遅延剤を併用すれば可能であることが知られている。（例えば、特許文献５参照。）遅延剤配合量を増すほど可使時間は長くなるが、一方で初期強度は低下する。また分散剤や減水剤を用いる系に遅延剤を併用したカルシウムアルミネート系の水硬性組成物も知られているが（例えば、特許文献６参照。）、分散剤や減水剤による流動性向上作用が阻害されるという問題もあった。更には、適正な可使時間確保のためには施工時の温度に応じて遅延剤配合量を繊細に調整する必要があり、遅延剤併用による影響は安定した強度値を得る上で実施工の問題となっている。
特開昭５４−１３９６３７号公報 特開２００５−１６２５６８号公報 特開平１０−１０１３９０号公報 特開昭４９−３２９２１号公報 特開２０００−１６８４３号公報 特開平９−２５５３９０号公報 Calcium aluminate is used, for example, as an alumina cement as a main material for refractories, concrete products, or construction works, or as an auxiliary or admixture component in Portland cement or the like, and is used as a construction or civil engineering material. Calcium aluminate, 12CaO · 7Al 2 O 3, CaO · Al 2 O 3, 3CaO · Al 2 O 3, crystalline or vitrified consist CaO · 2Al 2 O 3 CaO and for Al 2 O 3 chemical components, such as 4CaO · 3Al 2 O 3 · SO 3 , 11CaO · 7Al 2 O 3 · CaF 2 , Na 2 O · 8CaO · 3Al 2 O 3, etc. in a broad sense with other chemical components added It is treated as an aluminate. Among these, the example which uses 2 or more types of calcium aluminate is known. (For example, refer to Patent Documents 1 and 2.) Calcium aluminate having a structurally high vitrification rate has a higher activity such as a hydration reaction and an initial strength development property. (For example, refer to Patent Document 3.) In actual use, not only high initial strength can be developed, but also work life at the time of placing and construction is reduced, so that a moderate pot life can be obtained. Properties such as exhibiting stable expression with long-term strength are desired for calcium aluminate. However, it is extremely difficult to simultaneously develop a long pot life and high strength in calcium aluminate, and it is particularly difficult to secure a pot life. Even when two or more calcium aluminates having different compositions are used, the main purpose is related to the initial strength development. (For example, refer patent document 4.) It is not known about obtaining a desired effect by combining calcium aluminate itself in order to ensure a long working life. In order to increase the pot life of the calcium aluminate material, it is known that a retarder can be used in combination. (For example, refer to Patent Document 5.) As the amount of retarder is increased, the pot life becomes longer, but the initial strength is lowered. Also known is a calcium aluminate hydraulic composition in which a dispersant or water reducing agent is used in combination with a retarder (see, for example, Patent Document 6), but the fluidity improving effect of the dispersant or water reducing agent is known. There was also a problem that was disturbed. Furthermore, in order to secure an appropriate pot life, it is necessary to finely adjust the amount of retarder added according to the temperature at the time of construction. It is a problem.
Japanese Patent Laid-Open No. 54-139637 JP 2005-162568 A Japanese Patent Laid-Open No. 10-101390 JP 49-32921 A JP 2000-16843 A JP-A-9-255390

本発明は、凝結遅延剤等の遅延成分を特に使用しなくても、長い可使時間と高い初期強度発現性を共に得られ、且つ初期〜長期に渡って強度発現値が安定したカルシウムアルミネート及びこれを含む水硬性組成物を提供することを課題とする。   The present invention provides a calcium aluminate which can obtain both a long pot life and a high initial strength development property, and has a stable strength expression value from the initial stage to a long term, even without using a delay component such as a setting retarder. It is another object of the present invention to provide a hydraulic composition containing the same.

本発明者は、検討を重ねた結果、特定のガラス化率及び含有率の相対的に反応活性の高いカルシウムアルミネートと相対的に反応活性が低いカルシウムアルミネートの二種類のカルシウムアルミネートを特定の含有比率で、かつ特定のガラス化状態にしたものが、初期強度発現性低下原因となる凝結遅延成分を使用せずに、長期に渡って安定した強度発現性が見られ、施工・打設作業を行うに十分な長さの可使時間が確保できるという知見を得、本発明を完成するに至った。   As a result of repeated studies, the present inventor has identified two types of calcium aluminate, a calcium aluminate having a relatively high reaction activity and a calcium aluminate having a relatively low reaction activity. Stable strength development can be seen over a long period of time without using a set retarding component that causes the initial strength development to be reduced. The inventor has obtained knowledge that a pot life sufficient for the work can be secured, and has completed the present invention.

即ち、本発明は、ガラス化率５０％以下のＣａＯ・Ａｌ2Ｏ3とガラス化率１００％以下の１２ＣａＯ・７Ａｌ2Ｏ3を有効成分とし、ＣａＯ・Ａｌ2Ｏ3含有量（Ｄ）と１２ＣａＯ・７Ａｌ2Ｏ3含有量（Ｅ）の質量比（Ｄ／Ｅ）が１．５〜１５であって、含有する１２ＣａＯ・７Ａｌ2Ｏ3のガラス化率（Ｆ）と含有するＣａＯ・Ａｌ2Ｏ3のガラス化率（Ｇ）の和（Ｇ＋Ｆ）が１５〜１５０％、且つガラス化率の比（Ｆ／Ｇ）が１〜３０であることを特徴とするカルシウムアルミネートである。また本発明は、前記カルシウムアルミネートを含有してなる水硬性組成物である。
That is, the present invention comprises CaO · Al 2 O 3 with a vitrification rate of 50% or less and 12CaO · 7Al 2 O 3 with a vitrification rate of 100% or less as an active ingredient, and a CaO · Al 2 O 3 content (D) The mass ratio (D / E) of the 12CaO · 7Al 2 O 3 content (E) is 1.5 to 15, and the vitrification rate (F) of the contained 12CaO · 7Al 2 O 3 and the contained CaO · Al The calcium aluminate is characterized in that the sum (G + F) of vitrification rate (G) of 2 O 3 is 15 to 150% and the ratio of vitrification rate (F / G) is 1 to 30. Moreover, this invention is a hydraulic composition formed by containing the said calcium aluminate.

本発明のカルシウムアルミネートは凝結遅延剤等の遅延成分を用いることなく適度な可使時間を確保できるため、施工・打設作業上の制約が大きく軽減される。また高い初期強度発現性と安定した強度発現状態を中長期に渡って発現できる。さらに、本発明のカルシウムアルミネートは、遅延成分を含まないため減水剤の類と併用しても、カルシウムアルミネート本来の作用が低減されることがなく、適度な流動性を有する水硬性組成物が得られる。   Since the calcium aluminate of the present invention can secure an appropriate pot life without using a retarding component such as a setting retarder, restrictions on construction and placing work are greatly reduced. In addition, high initial strength development and stable strength development can be expressed over the medium to long term. Further, since the calcium aluminate of the present invention does not contain a delay component, even if it is used in combination with a water reducing agent, the original action of calcium aluminate is not reduced, and the hydraulic composition has appropriate fluidity. Is obtained.

本発明のカルシウムアルミネートは、ＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3を有効成分とする。ＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3以外の成分の含有は、本発明の効果を実質喪失させない限り制限されるものではない。このような成分として例えば、カルシウムフェライト、カルシウムサルホアルミネート、ビーライト、ゲーレナイト、ＣａＯ・２Ａｌ2Ｏ3、ＣａＯ・６Ａｌ2Ｏ3等を挙げることができる。本発明のカルシウムアルミネートは、含有するＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3の量が、ＣａＯ・Ａｌ2Ｏ3（Ｄ）と１２ＣａＯ・７Ａｌ2Ｏ3（Ｅ）の質量比（Ｄ／Ｅ）で１．５〜１５の関係を充当するものとする。質量比（Ｄ／Ｅ）が１．５未満では、高活性の１２ＣａＯ・７Ａｌ2Ｏ3の割合が相対的に過多となり、可使時間確保が困難になる。さらに、Ａｌ2Ｏ3成分が低含有のカルシウムアルミネートになることから、強度発現の安定性が低下し、例えば中〜長期強度の低下や、環境により強度値のバラツキが大きくなる可能性もあるので好ましくない。また、（Ｄ／Ｅ）の質量比が１５を超えると、１２ＣａＯ・７Ａｌ2Ｏ3より反応活性が低いＣａＯ・Ａｌ2Ｏ3が多くなり、高い初期強度発現性が得難くなるので好ましくない。 The calcium aluminate of the present invention contains CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 as active ingredients. The inclusion of components other than CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 is not limited as long as the effects of the present invention are not substantially lost. For example, as such a component include calcium ferrite, calcium sulfoaluminate, belite, gehlenite, the CaO · 2Al 2 O 3, CaO · 6Al 2 O 3 or the like. The calcium aluminate of the present invention contains CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 in a mass ratio of CaO · Al 2 O 3 (D) and 12CaO · 7Al 2 O 3 (E) ( D / E) shall satisfy the relationship of 1.5-15. When the mass ratio (D / E) is less than 1.5, the ratio of highly active 12CaO · 7Al 2 O 3 is relatively excessive, and it becomes difficult to ensure the pot life. Furthermore, since the calcium aluminate containing a low content of Al 2 O 3 is used, the stability of strength development is reduced. For example, there is a possibility that the strength value may vary depending on the environment or the environment due to a decrease in medium to long-term strength. Therefore, it is not preferable. Further, if the mass ratio of (D / E) exceeds 15, it is not preferable because CaO · Al 2 O 3 having a lower reaction activity than 12CaO · 7Al 2 O 3 increases and it becomes difficult to obtain high initial strength.

本発明のカルシウムアルミネートは、含有するＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3の構造状態として、ＣａＯ・Ａｌ2Ｏ3のガラス化率（Ｇ）、但し、ＣａＯ・Ａｌ2Ｏ3が複数のガラス化率のＣａＯ・Ａｌ2Ｏ3が混在したものからなるときは、ガラス化率毎のＣａＯ・Ａｌ2Ｏ3の質量割合を考慮したガラス化率の平均値とする、および１２ＣａＯ・７Ａｌ2Ｏ3のガラス化率（Ｆ）、但し、複数のガラス化率の１２ＣａＯ・７Ａｌ2Ｏ3が混在したものからなるときはガラス化率毎の１２ＣａＯ・７Ａｌ2Ｏ3の質量割合を考慮したガラス化率の平均値とする、が、両成分のガラス化率の和（Ｆ＋Ｇ）で１５〜１５０％であって、両成分のガラス化率の比（Ｆ／Ｇ）が１〜３０であることを充当するものとする。また、該ガラス化率の和と比を充当する限り、成分個々のガラス化率を特に制限されない。一般に、結晶質に比べ、ガラス化率が高いものほど水和反応が早く進行し、可使時間を確保し難くなる。ガラス化率の和（Ｆ＋Ｇ）が１５％未満では、反応活性が低く、初期強度発現性が低下するので好ましくない。また、ガラス化率の和（Ｆ＋Ｇ）が１５０％を超えると逆に活性が高くなり過ぎて、所望の可使時間を確保できないことがあるので好ましくない。また、ガラス化率の比（Ｆ／Ｇ）の値が３０を超えると、ＣａＯ・Ａｌ2Ｏ3よりも反応活性の高い１２ＣａＯ・７Ａｌ2Ｏ3がさらに高い活性のものとなるため、可使時間の確保が困難となるので好ましくない。ガラス化率の比（Ｆ／Ｇ）が１未満では、強度発現の安定性を欠くため好ましくない。 The calcium aluminate of the present invention has a vitrification ratio (G) of CaO · Al 2 O 3 as a structural state of CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 to be contained, provided that CaO · Al 2 O 3 Is composed of a mixture of CaO · Al 2 O 3 having a plurality of vitrification rates, and an average value of vitrification rate considering the mass ratio of CaO · Al 2 O 3 for each vitrification rate, and 12CaO・ Vitrification rate of 7Al 2 O 3 (F), but when it consists of a mixture of 12CaO · 7Al 2 O 3 with multiple vitrification rates, the mass ratio of 12CaO · 7Al 2 O 3 for each vitrification rate The average value of the vitrification rate considered is 15 to 150% in terms of the sum of vitrification rates of both components (F + G), and the ratio of vitrification rates of both components (F / G) is 1 to 30. Shall be appropriate. Moreover, as long as the sum and ratio of this vitrification rate are applied, the vitrification rate of each component is not particularly limited. In general, the higher the vitrification rate, the faster the hydration reaction as compared with the crystalline material, and it becomes difficult to secure the pot life. If the sum of vitrification rates (F + G) is less than 15%, the reaction activity is low and the initial strength development is reduced, which is not preferable. On the other hand, if the sum of vitrification rates (F + G) exceeds 150%, the activity becomes too high, and a desired pot life may not be secured. Also, if the ratio of vitrification ratio (F / G) exceeds 30, 12CaO · 7Al 2 O 3, which has a higher reaction activity than CaO · Al 2 O 3 , becomes even higher in activity. It is not preferable because it is difficult to secure time. If the ratio of vitrification rate (F / G) is less than 1, it is not preferable because the stability of strength development is lacking.

本発明のカルシウムアルミネートの製造方法の一例を示すと、ＣａＯ源及びＡｌ2Ｏ3源となるＣａＯ、ＣａＣＯ3、Ａｌ2Ｏ3などの原料をモル比でＣａＯ：Ａｌ2Ｏ3が１：１及び１２：７となるよう秤量混合し、各混合物は、１５００℃以上で大気中で加熱し、当該加熱温度又はそれ以下の所定の温度から急冷することによってガラス化率を調整したＣａＯ・Ａｌ2Ｏ3や１２ＣａＯ・７Ａｌ2Ｏ3を得ることができる。ガラス化率は、一般に、加熱溶融せしめた後、高い温度からの急冷ほど、また急冷速度を速くするほど、高くすることができる。加熱は例えばバッチ式キルン、ロータリーキルン、反射炉などが使用できる。急冷は、例えば炉外への取り出し放置、水中急冷、冷却ガス吹付け等で行うことができる。所望のガラス化率のＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3を前記の所定質量比となるよう混合すれば得ることができる。これ以外の製造方法として、例えばＣａＯ源及びＡｌ2Ｏ3源の原料を混合し、加熱して得たクリンカにＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3を共存生成させたものでも良く、さらに他の方法でも良い。 An example of the method for producing calcium aluminate according to the present invention is as follows. Raw materials such as CaO, CaCO 3 , Al 2 O 3 and the like serving as a CaO source and an Al 2 O 3 source have a CaO: Al 2 O 3 ratio of 1: 1 and 12: 7 are weighed and mixed, and each mixture is heated in air at 1500 ° C. or higher, and the vitrification rate is adjusted by quenching from the heating temperature or a predetermined temperature lower than that. 2 O 3 and 12CaO · 7Al 2 O 3 can be obtained. In general, the vitrification rate can be increased as the material is rapidly melted by heating and then rapidly cooled from a high temperature and the rapid cooling rate is increased. For example, a batch kiln, a rotary kiln, a reflection furnace or the like can be used for heating. The rapid cooling can be performed, for example, by taking it out of the furnace, leaving it in water, quenching it in water, or blowing a cooling gas. It can be obtained by mixing CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 having a desired vitrification ratio so as to achieve the predetermined mass ratio. As other production methods, for example, a clinker obtained by mixing raw materials of a CaO source and an Al 2 O 3 source and heating them may co-produce CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3. Other methods may be used.

また、本発明は、前記のカルシウムアルミネートを含有してなる水硬性組成物である。本発明の水硬性組成物は、カルシウムアルミネートの含有量やカルシウムアルミネート以外の成分の含有は、本発明の効果を実質的に喪失させない限り、何れのものでも良い。含有成分の例としては、普通、早強、中庸熱、低熱等のポルトランドセメント、白色セメント、エコセメント等の特殊セメント、高炉セメントやフライアッシュセメント等の混合セメント、減水剤、膨張材、収縮低減剤、空気連行剤、保水剤、消泡剤、ポゾラン反応性物質、無機微粉、繊維、ポリマー等のモルタルやコンクリートに使用可能な混和材（剤）、砂、砂利、砕石等の天然骨材や人工骨材などを挙げることができる。また、混練水は含有するカルシウムアルミネート１００質量部に対し、１５〜１００質量部加えるのが好ましいが、特に制限されるものではない。該水硬性組成物の製造方法の一例を示すと、前記のカルシウムアルミネートと必要に応じて所望のセメントや混和材（剤）を市販のミキサに投入し、乾式混合してプレミックス体として用いるか、乾式混合物に水を加えて混練することでモルタル、ペースト或いはコンクリートとして水硬性組成物を得ることができる。   Moreover, this invention is a hydraulic composition formed by containing the said calcium aluminate. In the hydraulic composition of the present invention, any content of calcium aluminate or components other than calcium aluminate may be used as long as the effects of the present invention are not substantially lost. Examples of ingredients include normal, early strong, moderately hot, low heat, etc. Portland cement, white cement, special cements such as eco-cement, mixed cements such as blast furnace cement and fly ash cement, water reducing agent, expansion material, shrinkage reduction Additives, air entraining agents, water retention agents, antifoaming agents, pozzolanic reactive materials, inorganic fine powders, fibers, polymers and other mortars and concrete admixtures (agents), sand, gravel, crushed stones and other natural aggregates Artificial aggregates can be mentioned. The kneading water is preferably added in an amount of 15 to 100 parts by mass with respect to 100 parts by mass of the calcium aluminate contained, but is not particularly limited. An example of a method for producing the hydraulic composition is as follows. The calcium aluminate and, if necessary, a desired cement or admixture (agent) are put into a commercially available mixer and dry-mixed for use as a premix body. Alternatively, a hydraulic composition can be obtained as mortar, paste, or concrete by adding water to the dry mixture and kneading.

以下、実施例により本発明を具体的に詳しく説明するが、本発明はここに表す実施例に限定されるものではない。   EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples shown here.

粉末状のＣａＣＯ3とＡｌ2Ｏ3をモル比でそれぞれ１：１及び１２：７に調合し、乾式混合した。各混合物を、電気炉（大気雰囲気）で約１８００℃に加熱し、該温度から加熱物を常温の炉外に取り出し、直ちに冷却用窒素ガスを表面に高速で吹き付ける（冷却方法：Ａ）か、該温度から水中急冷する（冷却方法：Ｂ）か、該温度から加熱物を常温の炉外に取り出し、大気雰囲気下で放置放冷する（冷却方法：Ｃ）か、該温度で加熱を停止し、加熱物をそのまま炉内に留め自然降温させる（冷却方法：Ｄ）かの何れかの冷却方法により冷却物を得た。尚、水中急冷品（Ｂ）は水中で概ね１分間留めた後、水中から回収して乾燥させた。各冷却物はボールミル粉砕し、表１に表すガラス化率の異なるＣａＯ・Ａｌ2Ｏ3及び１２ＣａＯ・７Ａｌ2Ｏ3を作成した。粉砕は、評価時に粒度の影響が現れないようにするため、同じボールミルで被砕物毎に粉砕時間を調整し、さらに篩などによる分級処理することでブレーン比表面積で５０００〜６０００ｃｍ2／ｇの範囲に整粒した。 Powdered CaCO 3 and Al 2 O 3 were mixed at a molar ratio of 1: 1 and 12: 7, respectively, and dry mixed. Each mixture is heated to about 1800 ° C. in an electric furnace (atmosphere), and the heated product is taken out of the room temperature outside the furnace and immediately cooled with nitrogen gas for cooling on the surface (cooling method: A), The water is rapidly cooled from the temperature (cooling method: B), or the heated product is taken out of the room temperature outside the furnace and allowed to cool in the atmosphere (cooling method: C), or the heating is stopped at the temperature. Then, the heated product was kept in the furnace as it was and the temperature was naturally lowered (cooling method: D) to obtain a cooled product. The underwater quenched product (B) was retained in water for approximately 1 minute, then recovered from water and dried. Each cooled product was ball milled to prepare a different CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 glass rate representing in Table 1. In order to prevent the influence of the particle size from appearing at the time of evaluation, the pulverization is carried out by adjusting the pulverization time for each object to be crushed with the same ball mill, and further by classifying with a sieve or the like in the range of 5000 to 6000 cm 2 / g in the brain specific surface area. Sized.

尚、ＣａＯ・Ａｌ2Ｏ3のガラス化率の測定は、他の成分を含まないものでは粉末Ｘ線回折（内部標準法）によりＣａＯ・Ａｌ2Ｏ3の結晶相の量を求め、残部をガラス相とみなしてガラス化率を算出した。他の成分を含まない１２ＣａＯ・７Ａｌ2Ｏ3のガラス化率の測定も同様の方法で行った。また、ＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3が共存生成したカルシウムアルミネートの場合は、粉末Ｘ線回折によりＣａＯ・Ａｌ2Ｏ3及び１２ＣａＯ・７Ａｌ2Ｏ3の結晶生成量を測定した後、これを電気炉で再溶融（１８００℃）し、炉内で溶融温度から約１００℃以下となるまで１２時間以上かけて徐冷することで全相を実質的に結晶化させ、粉末Ｘ線回折でＣａＯ・Ａｌ2Ｏ3及び１２ＣａＯ・７Ａｌ2Ｏ3の生成量を測定した。この測定値と再溶融前の結晶質ＣａＯ・Ａｌ2Ｏ3及び結晶質１２ＣａＯ・７Ａｌ2Ｏ3の生成量との差からガラス化率を算出した。 The measurement of the vitrification ratio of CaO · Al 2 O 3 is intended free of other components to determine the amount of crystalline phase of CaO · Al 2 O 3 by X-ray powder diffraction (internal standard method), the remainder The vitrification rate was calculated by regarding the glass phase. The vitrification rate of 12CaO · 7Al 2 O 3 not containing other components was also measured in the same manner. In the case of calcium aluminate in which CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 coexist, the amount of crystal formation of CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 is measured by powder X-ray diffraction. Then, this is remelted in an electric furnace (1800 ° C.) and gradually cooled in the furnace over 12 hours from the melting temperature to about 100 ° C. The amount of CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 produced was measured by X-ray diffraction. The vitrification rate was calculated from the difference between this measured value and the amount of crystalline CaO · Al 2 O 3 and crystalline 12CaO · 7Al 2 O 3 before remelting.

Figure 0005135127
Figure 0005135127

各ガラス化率のＣａＯ・Ａｌ2Ｏ3及び１２ＣａＯ・７Ａｌ2Ｏ3を表１の配合量となるよう混合し、ＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3からなるカルシウムアルミネート（Ｎｏ．１〜１１）を作製した。また、参考のため、ＣａＯ・Ａｌ2Ｏ3と１２ＣａＯ・７Ａｌ2Ｏ3以外の成分を有効成分とするカルシウムアルミネート系材料も市販品又は上記方法に準じて試製し（Ｎｏ．１２〜１３）、併せて表１に表す。 CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 having respective vitrification ratios are mixed so as to have the blending amounts shown in Table 1, and calcium aluminate composed of CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 (No .1 to 11). Further, for reference, calcium aluminate based material as an active ingredient CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 other components is also in accordance with the commercial product or the method to Shisei (No.12~13) These are also shown in Table 1.

次いで、表１のカルシウムアルミネート（Ｎｏ．１〜１３）、普通ポルトランドセメント（太平洋セメント社製）、ポリカルボン酸系減水剤（商品名「太平洋コアフロー」、太平洋マテリアル社製）、クエン酸（市販試薬）、砂（豊浦標準砂）から選定される材料を、表２に表す配合量となるよう内容積５リットルのホバートミキサ（ホバート社製）に一括投入した。投入材料は、温度約２０℃で１分間乾式混合した後、これに表２に表す量の水を加えて湿式混合を１分間行い、混練物を作製した。   Next, calcium aluminate (Nos. 1 to 13) in Table 1, ordinary Portland cement (manufactured by Taiheiyo Cement), polycarboxylic acid-based water reducing agent (trade name “Pacific Core Flow”, Taiheiyo Materials Co., Ltd.), citric acid (commercially available) Reagents) and sand (Toyoura standard sand) were collectively put into a Hobart mixer (made by Hobart) having an internal volume of 5 liters so as to obtain the blending amounts shown in Table 2. The input material was dry mixed at a temperature of about 20 ° C. for 1 minute, and then the amount of water shown in Table 2 was added thereto for wet mixing for 1 minute to prepare a kneaded product.

Figure 0005135127
Figure 0005135127

湿式混合終了直後の減水剤含有混練物に対し、流動性の評価として２０℃でのフロー値を、ＪＩＳ Ｒ ２５２１「耐火物用アルミナセメントの物理試験方法」に準じた方法で測定した。また、湿式混合終了直後の混練物に対し、ＪＩＳ Ｒ ２５２１に準じて、約２０℃の恒温環境下で凝結及び硬化状況に関する試験を行った。即ち、湿式混合終了直後から凝結開始までの時間を可使時間として測定した。さらに、初期強度発現性評価とし、湿式混合終了直後に内寸４×４×１６ｃｍの角柱状型枠に混練物を充填し、成形を行った材齢１日の供試体の圧縮強度を測った。同様に材齢２８日の供試体の圧縮強度も長期強度発現性の評価として測定した。ただし、可使時間がおよそ１０分以下のものは供試体作製が困難であったことから圧縮強度の測定は行わなかった。以上の評価結果を纏めて表２に表す。さらに、表２に表した本発明品１及び２と参考品１２及び１５については、混練物調合での製造ロットを各５〜６水準にしてそれぞれ供試体を作製し、材齢１日の圧縮強度の測定から、ロット間の強度値のバラツキを調べることで（ロットによる圧縮強度の最大値と最小値の差／全ロットの圧縮強度平均値で表す。）強度発現値の安定性も評価した。この結果を表３に表す。   For the water-reducing agent-containing kneaded material immediately after completion of the wet mixing, the flow value at 20 ° C. was measured as a fluidity evaluation by a method according to JIS R 2521 “Physical test method for alumina cement for refractory”. In addition, the kneaded material immediately after the completion of the wet mixing was tested according to JIS R 2521 for the setting and curing conditions in a constant temperature environment of about 20 ° C. That is, the time from the end of wet mixing to the start of setting was measured as the pot life. Furthermore, as initial strength development evaluation, the kneaded product was filled into a prismatic mold with an inner size of 4 × 4 × 16 cm immediately after the end of wet mixing, and the compressive strength of the specimen of one day after molding was measured. . Similarly, the compressive strength of the specimens with a material age of 28 days was also measured as an evaluation of long-term strength development. However, when the pot life was approximately 10 minutes or less, it was difficult to prepare a specimen, and thus the compression strength was not measured. The above evaluation results are summarized in Table 2. Further, for the inventive products 1 and 2 and the reference products 12 and 15 shown in Table 2, each of the production lots in the kneaded mixture preparation was made into 5 to 6 levels, respectively, and specimens were prepared, respectively, and compression of the material age of 1 day was performed. From the measurement of strength, the stability of strength expression value was also evaluated by examining the variation in strength values between lots (represented by the difference between the maximum and minimum values of compression strength by lot / average compression strength of all lots). . The results are shown in Table 3.

Figure 0005135127
Figure 0005135127

表２の評価結果より、本発明のカルシウムアルミネートは、何れも約６０分以上という比較的長い可使時間を、初期強度発現性を低下させずに確保することができる。また、長期強度も安定した発現性を呈した。さらに、減水剤を併用した場合でも流動性を低減させる様子は見られなかった。これに対し、従来技術の範疇にあるカルシウムアルミネートに凝結遅延成分を加えたものは、何れも初期強度の発現性の低下が見られた。また、表３より、本発明品は参考品よりもロット間の強度値変動が少なくなることがわかる。   From the evaluation results of Table 2, the calcium aluminate of the present invention can ensure a relatively long pot life of about 60 minutes or more without reducing the initial strength development. In addition, long-term strength exhibited stable expression. Further, even when a water reducing agent was used in combination, the fluidity was not reduced. On the other hand, in the case of adding a setting delay component to calcium aluminate in the category of the prior art, a decrease in the expression of the initial strength was observed. Further, it can be seen from Table 3 that the product of the present invention has less variation in strength value between lots than the reference product.

Claims (2)

ガラス化率５０％以下のＣａＯ・Ａｌ2Ｏ3とガラス化率１００％以下の１２ＣａＯ・７Ａｌ2Ｏ3を有効成分とし、ＣａＯ・Ａｌ2Ｏ3含有量（Ｄ）と１２ＣａＯ・７Ａｌ2Ｏ3含有量（Ｅ）の質量比（Ｄ／Ｅ）が１．５〜１５であって、含有する１２ＣａＯ・７Ａｌ2Ｏ3のガラス化率（Ｆ）と含有するＣａＯ・Ａｌ2Ｏ3のガラス化率（Ｇ）の和（Ｇ＋Ｆ）が１５〜１５０％、且つガラス化率の比（Ｆ／Ｇ）が１〜３０であることを特徴とするカルシウムアルミネート。 Vitrification ratio of 50% or less of CaO · Al of 2 O 3 and vitrification ratio of 100% or less 12CaO · 7Al 2 O 3 as an active ingredient, CaO · Al 2 O 3 content (D) and 12CaO · 7Al 2 O 3 Mass ratio (D / E) of content (E) is 1.5 to 15, and vitrification rate (F) of 12CaO · 7Al 2 O 3 contained and vitrification of contained CaO · Al 2 O 3 A calcium aluminate characterized in that the sum (G + F) of the rate (G) is 15 to 150% and the ratio of vitrification rate (F / G) is 1 to 30. 請求項１記載のカルシウムアルミネートを含有してなる水硬性組成物。 A hydraulic composition comprising the calcium aluminate according to claim 1.
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