JPH0986989A - Crystalline highly hydrated and activated material hardening accelerating material for cement and acceleration of setting and hardening of mortar or concrete - Google Patents

Crystalline highly hydrated and activated material hardening accelerating material for cement and acceleration of setting and hardening of mortar or concrete

Info

Publication number
JPH0986989A
JPH0986989A JP27350695A JP27350695A JPH0986989A JP H0986989 A JPH0986989 A JP H0986989A JP 27350695 A JP27350695 A JP 27350695A JP 27350695 A JP27350695 A JP 27350695A JP H0986989 A JPH0986989 A JP H0986989A
Authority
JP
Japan
Prior art keywords
weight
parts
hardening
cement
highly hydrated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP27350695A
Other languages
Japanese (ja)
Inventor
Yoshifumi Hosokawa
佳史 細川
Shigeru Matsuura
茂 松浦
Minoru Takehiro
実 武広
Yasuhisa Taguma
靖久 田熊
Shunichiro Uchida
俊一郎 宇智田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chichibu Onoda Cement Corp
Original Assignee
Chichibu Onoda Cement Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chichibu Onoda Cement Corp filed Critical Chichibu Onoda Cement Corp
Priority to JP27350695A priority Critical patent/JPH0986989A/en
Publication of JPH0986989A publication Critical patent/JPH0986989A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C04B2103/12—Set accelerators

Landscapes

  • 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)

Abstract

PROBLEM TO BE SOLVED: To obtain an admixture for various kinds of cements capable of remarkably accelerating the setting and hardening of a cement paste, a mortar, a concrete, etc., by blending it in a prescribed amount and stably providing a high initial strength even at normal temperatures or under low-temperature environments in a short time. SOLUTION: This crystalline highly hydrated and activated material containing C2 A3 .CaSO4 , C4 AF, C3 A, C12 A7 and C11 A7 .CaF2 is obtained by baking a CaO-Al2 O3 -Fe2 O3 -SO3 -CaF2 -based composition at 1000-1400 deg.C temperature. The resultant material is then suitably mixed with a gypsum, lime, an alkali carbonate, sodium aluminate, an alkali sulfate and aluminum hydroxide, etc., to provide a hardening accelerator for cements.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】この発明は、トンネル、橋脚
等の天井や壁面にセメントペーストやモルタル、コンク
リートなど（以下コンクリート等と記す）を吹き付ける
際に、これらが自重により剥落しないうちに急速に凝結
硬化させるための急結性混和材料や、コンクリート等に
混合して、初期強度発現性を高めるための速硬性混和材
料（これらをセメント用硬化促進材料という）の基材に
用いる結晶質高水和活性物、及びこの高水和活性物を用
いたセメント用硬化促進材料、及びこのセメント用硬化
促進材料を用いたセメントペースト、モルタル又はコン
クリートの凝結・硬化促進方法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a method for rapidly setting cement paste, mortar, concrete, etc. (hereinafter referred to as concrete) on the ceiling or wall surface of tunnels, bridge piers, etc. before they fall off by their own weight. Crystalline high hydration used as a base material for quick-setting admixtures for hardening and concretes for quick-setting admixtures for enhancing initial strength development (these are called hardening accelerators for cement). The present invention relates to an active substance, a hardening accelerator for cement using the highly hydrated active substance, and a method for promoting setting and hardening of cement paste, mortar or concrete using the hardening accelerator for cement.

【０００２】[0002]

【従来の技術】従来あるセメント用硬化促進材料として
は、アーウィン（Ｃ3Ａ3・ＣａＳＯ4）を主体とするも
の、モノカルシウムアルミネート（ＣａＯ・Ａｌ2Ｏ3、
以下ＣＡと記す）を主体とするもの、Ｃ12Ａ7を主成分
とする非晶質カルシウムアルミネート（以下非晶質Ｃ12
Ａ7と記す）を主体としたもの等が、使用されている。2. Description of the Related Art As a hardening accelerator material for cement with conventional, Erwin (C 3 A 3 · CaSO 4 ) mainly formed of, monocalcium aluminate (CaO · Al 2 O 3,
Amorphous calcium aluminate containing C 12 A 7 as the main component (hereinafter referred to as amorphous C 12)
Such as those mainly composed of referred to as A 7) has been used.

【０００３】しかしながら、アーウィンを主体としたセ
メント用硬化促進材料は、低温時に於ける硬化速度及び
強度発現性が低いという欠点を有している。また、ＣＡ
を主体としたセメント用硬化促進材料は主にアルミナセ
メントが使用されるが、Ｃ12Ａ7を主体としたセメント
用硬化促進材料に比べ、速硬性が劣る、及び速硬性にバ
ラツキが多い傾向があるという欠点を有する。However, the hardening accelerator for cement mainly composed of Erwin has a drawback that the hardening rate and strength development at low temperature are low. Also, CA
Although primarily alumina cement for cement cure accelerator materials mainly are used to compare the C 12 A 7 in cement curing accelerator materials mainly, fast curing poor, and variations in fast curing is often a tendency It has the drawback of being.

【０００４】非晶質Ｃ12Ａ7を主体とするセメント用硬
化促進材料は、低温に於いても速硬性を発揮するもので
ある。しかし、非晶質Ｃ12Ａ7の製造においては、Ｃ12
Ａ7を主成分とするクリンカーを電融炉で溶融する方法
を用いるため多量の電力を要し、その結果電力費が高く
なり製造コストが増大するという問題を有している。The hardening-accelerating material for cement, which is mainly composed of amorphous C 12 A 7 , exhibits a rapid hardening property even at a low temperature. However, in the production of amorphous C 12 A 7 , C 12
Since a method of melting a clinker containing A 7 as a main component in a melting furnace is used, a large amount of electric power is required, resulting in an increase in electric power cost and an increase in manufacturing cost.

【０００５】[0005]

【発明が解決しようとする課題】この発明は、セメント
に所定量を混合することによってコンクリート等の凝結
及び硬化を著しく促進させ、しかも短時間で高い初期強
度が、常温あるいは低温度環境下においても安定して得
られるセメント用硬化促進材料を安価に提供すること、
及びこれを用いてコンクリート等の硬化を促進すること
である。SUMMARY OF THE INVENTION According to the present invention, by mixing a predetermined amount of cement, the setting and hardening of concrete or the like is significantly promoted, and high initial strength can be obtained in a short time even at room temperature or low temperature environment. To provide a stable hardening-promoting material for cement at a low price,
And to use it to accelerate the hardening of concrete and the like.

【０００６】[0006]

【課題を解決するための手段】セメントの硬化速度及び
初期強度を増加させるためには、セメントに硬化促進材
料を添加することによりセメントの水和を促進するとと
もに、添加した組成物がセメントペースト液相中の各イ
オンと反応し急速に凝集性のある水和物を生成する必要
がある。[Means for Solving the Problems] In order to increase the hardening rate and initial strength of cement, the hydration of the cement is promoted by adding a hardening promoting material to the cement, and the added composition is a cement paste liquid. It is necessary to react with each ion in the phase to form a hydrate that rapidly aggregates.

【０００７】本願の第１の発明は、ＣａＯ−Ａｌ2Ｏ3−
ＳＯ3−Ｆｅ2Ｏ3−ＣａＦ2系組成の焼成物で、Ｃ3Ａ3・
ＣａＳＯ4と、Ｃ4ＡＦと、Ｃ3Ａ及び／又はＣ12Ａ7と、
Ｃ11Ａ7・ＣａＦ2とを、含有した結晶質高水和活性物
（請求項１）である。これは、一般に水和活性が低いと
言われるＣ4ＡＦとＣ3Ａ3・ＣａＳＯ4に、ＣａＯ−Ａｌ
2Ｏ3系組成物であるＣ3Ａ及び／又はＣ12Ａ7と、Ｃ11Ａ
7・ＣａＦ2とを含有させることにより、低温度でも水和
活性を高めた結晶質高水和活性物である。特に低温度時
にはＣ3Ａを多く含むほど高水和活性を示す。The first invention of the present application is CaO-Al 2 O 3-.
SO 3 —Fe 2 O 3 —CaF 2 system fired product, C 3 A 3 ·
CaSO 4 , C 4 AF, C 3 A and / or C 12 A 7 ,
A crystalline highly hydrated active substance containing C 11 A 7 .CaF 2 (Claim 1). This is C 4 AF and C 3 A 3 · CaSO 4 generally hydration activity is said to be low, CaO-Al
2 O 3 based composition C 3 A and / or C 12 A 7 and C 11 A
By containing 7 · CaF 2, it is a crystalline highly hydrated active substance having enhanced hydration activity even at low temperature. Particularly, at a low temperature, the higher the content of C 3 A, the higher the hydration activity.

【０００８】第２の発明は、ＣａＯ−Ａｌ2Ｏ3−ＳＯ3
−Ｆｅ2Ｏ3−ＣａＦ2系組成の焼成物で、Ｃ3Ａ3・Ｃａ
ＳＯ4を５０重量％以上と、Ｃ4ＡＦを５重量％以上と、
Ｃ3Ａ及び／又はＣ12Ａ7を１０重量％以上と、Ｃ11Ａ7
・ＣａＦ2を５重量％以上とを、含有した結晶質高水和
活性物である。これは第１の発明のなかで、特に水和活
性に優れた組成の結晶質高水和活性物である。（請求項
２）The second invention is CaO-Al 2 O 3 -SO 3
In the burned material of -Fe 2 O 3 -CaF 2 based composition, C 3 A 3 · Ca
SO 4 is 50 wt% or more, C 4 AF is 5 wt% or more,
When C 3 A and / or C 12 A 7 is 10% by weight or more, C 11 A 7
A crystalline highly hydrated active substance containing 5% by weight or more of CaF 2 . This is a crystalline highly hydrated active substance having a composition particularly excellent in hydration activity in the first invention. (Claim 2)

【０００９】第３の発明は、上記の結晶質高水和活性物
に対し、石膏、石灰、炭酸アルカリ金属塩、アルミン酸
ソーダ、硫酸アルカリ金属塩及び水酸化アルミニウムの
うちの少なくとも１種以上を混合したセメント用硬化促
進材料であり、セメントペースト、モルタル、コンクリ
ート中にエトリンガイトなどの凝集性に優れた水和物を
短期間に生成するように調整したセメント用硬化促進材
料である。（請求項３）A third aspect of the present invention is to add at least one or more of gypsum, lime, alkali metal carbonate, sodium aluminate, alkali metal sulfate and aluminum hydroxide to the above crystalline highly hydrated active substance. It is a mixed hardening accelerator for cement, and is a hardening accelerator for cement that is adjusted to produce a hydrate having excellent cohesiveness such as ettringite in cement paste, mortar, and concrete in a short period of time. (Claim 3)

【００１０】第４の発明は、上記の結晶質高水和活性物
１００重量部に対し、石膏を無水換算で２重量部以上、
石灰を５重量部以上、炭酸アルカリ金属塩を１重量部以
上、アルミン酸ソーダを１重量部以上、硫酸アルカリ金
属塩を１重量部以上及び水酸化アルミニウムを１重量部
以上混合したセメント用硬化促進材料であり、分オーダ
ーでの速硬性及び急結性が必要な場合のセメント用硬化
促進材料である。（請求項４）A fourth aspect of the present invention is based on 100 parts by weight of the above-mentioned crystalline highly hydrated active substance, 2 parts by weight or more of gypsum in anhydrous equivalent,
5 parts by weight or more of lime, 1 part by weight or more of alkali metal carbonate, 1 part by weight or more of sodium aluminate, 1 part by weight or more of alkali metal sulfate and 1 part by weight or more of aluminum hydroxide are used to accelerate hardening of cement. It is a material, and is a hardening-accelerating material for cement when quick hardening and quick setting on the order of minutes are required. (Claim 4)

【００１１】第５及び第６の発明は、特にセメント用硬
化促進材料として優れた急結性能を必要とする場合の急
結材の配合であり、請求項１又は２のいずれかに記載の
結晶質高水和活性物１００重量部に対し、石膏を無水換
算で２〜２００重量部、石灰を５〜１００重量部、炭酸
アルカリ金属塩を２〜５０重量部、アルミン酸ソーダを
２〜５０重量部及び硫酸アルカリ金属塩を２〜２０重量
部混合したセメント用硬化促進材料（請求項５）と、請
求項１又は２のいずれかに記載の結晶質高水和活性物１
００重量部に対し、石膏を無水換算で２〜２００重量
部、石灰を５〜１００重量部、炭酸アルカリ金属塩を２
〜５０重量部、アルミン酸ソーダを１０〜５０重量部、
硫酸アルカリ金属塩を２〜２０重量部及び水酸化アルミ
ニウムを２５重量部以下混合したセメント用硬化促進材
料（請求項６）である。The fifth and sixth inventions are blending of a quick-setting material particularly when a quick-setting property which is excellent as a hardening promoting material for cement is required, and the crystal according to claim 1 or 2. 2 to 200 parts by weight of gypsum, 5 to 100 parts by weight of lime, 2 to 50 parts by weight of alkali metal carbonate, and 2 to 50 parts by weight of sodium aluminate per 100 parts by weight of high-quality hydrated active substance. Part and 2 to 20 parts by weight of an alkali metal sulfate mixed with a hardening accelerator for cement (claim 5), and the crystalline highly hydrated active substance 1 according to claim 1 or 2.
2 to 200 parts by weight of gypsum, 5 to 100 parts by weight of lime, and 2 parts of alkali metal carbonate per 100 parts by weight of anhydrous
~ 50 parts by weight, 10-50 parts by weight of sodium aluminate,
A hardening promoting material for cement (claim 6), wherein 2 to 20 parts by weight of an alkali metal sulfate and 25 parts by weight or less of aluminum hydroxide are mixed.

【００１２】第７の発明はコンクリート等を混練する際
に、請求項３ないし６のいずれかに記載のセメント用硬
化促進材料を、セメントに対し５〜５０重量部添加した
セメントペースト、モルタル又はコンクリートの凝結・
硬化促進方法であり、各セメント用硬化促進材料の配合
や添加量により速硬性及び急結性能が異なる。（請求項
７）A seventh invention is a cement paste, mortar or concrete in which 5 to 50 parts by weight of the hardening accelerator for cement according to any one of claims 3 to 6 is added when kneading concrete or the like. Condensation of
This is a hardening acceleration method, and the quick-hardening property and quick setting performance differ depending on the composition and the amount of addition of each hardening hardening material for cement. (Claim 7)

【００１３】[0013]

【発明の実施の形態】本願発明の結晶質高水和活性物
（請求項１及び２）は、溶融炉等の特殊な設備を用いず
に、キルンや電気炉等の適当な設備で１０００〜１４０
０℃で焼成される。原料としては、ＣａＯ源として生石
灰、炭酸カルシウム、Ａｌ2Ｏ3源としてボーキサイト、
アルミ灰、Ｆｅ2Ｏ3源としてベンガラ、ヘマタイト、ス
クラップ鉄粉、ＳＯ3源として、石膏、ＣａＦ2源として
螢石などが使用できる。微量成分としてはＳｉＯ2、Ｋ2
Ｏ、ＭｇＯ、ＴｉＯ2、等を５％程度含有しても良い。BEST MODE FOR CARRYING OUT THE INVENTION The crystalline highly hydrated active substance of the present invention (Claims 1 and 2) can be used in a suitable equipment such as a kiln or an electric furnace without using special equipment such as a melting furnace. 140
Baking at 0 ° C. As raw materials, quicklime, calcium carbonate as a CaO source, bauxite as an Al 2 O 3 source,
Aluminum ash, red iron oxide, hematite, scrap iron powder as an Fe 2 O 3 source, gypsum as an SO 3 source, and fluorite as a CaF 2 source can be used. As trace components, SiO 2 , K 2
About 5% of O, MgO, TiO 2 , etc. may be contained.

【００１４】また、焼成した結晶質高水和活性物には、
Ｃ3Ａ3・ＣａＳＯ4、Ｃ4ＡＦ、Ｃ3Ａ、Ｃ12Ａ7、Ｃ11Ａ
7・ＣａＦ2等以外にｆｒｅｅ−ＣａＯが存在するが、Ｃ
3Ａ3・ＣａＳＯ4、Ｃ4ＡＦ、Ｃ3Ａ、Ｃ12Ａ7、Ｃ11Ａ7
・ＣａＦ2等を別々に焼成して混合した場合とは異な
り、非常に高い水和活性を示す。すなわち、本発明の結
晶質高水和活性物をコンクリート等に添加することによ
り、コンクリート等の付着性が増大するとともに凝結及
び硬化を促進し、初期強度を高めることができるもので
ある。Further, the calcined crystalline highly hydrated active substance contains
C 3 A 3 · CaSO 4 , C 4 AF, C 3 A, C 12 A 7 , C 11 A
Free-CaO exists in addition to 7・ CaF 2, etc., but C
3 A 3 · CaSO 4 , C 4 AF, C 3 A, C 12 A 7 , C 11 A 7
-Unlike the case where CaF 2 and the like are separately fired and mixed, a very high hydration activity is exhibited. That is, by adding the crystalline highly hydrated active substance of the present invention to concrete or the like, the adhesiveness of concrete or the like can be increased and the setting and hardening can be promoted to increase the initial strength.

【００１５】また、良好な速硬性能を示したセメント用
硬化促進材料について検討を加えた結果、結晶質高水和
活性物を含むセメント用硬化促進材料は、ゲルの生成→
カルシウムアルミネート水和物の生成→エトリンガイ
ト、モノサルフェート水和物の生成の順で水和が進行
し、この反応の形態が非常に良好な速硬性能を示すこと
が明らかになった。しかしながら、この速硬反応メカニ
ズムの性能をより高くするためには、石膏、石灰、炭酸
アルカリ金属塩、アルミン酸ソーダ、硫酸アルカリ金属
塩及び水酸化アルミニウムのうちの一種以上を混合しセ
メントに添加することが有効である（請求項３）。Further, as a result of studying a hardening promoting material for cement showing good rapid hardening performance, a hardening promoting material for cement containing a crystalline highly hydrated active substance is formed into a gel.
Hydration proceeded in the order of formation of calcium aluminate hydrate → formation of ettringite and monosulfate hydrate, and it became clear that the morphology of this reaction shows very good rapid hardening performance. However, in order to improve the performance of this quick-hardening reaction mechanism, one or more of gypsum, lime, alkali metal carbonate, sodium aluminate, alkali metal sulfate and aluminum hydroxide are mixed and added to cement. Is effective (claim 3).

【００１６】ここで石膏は、エトリンガイド及びモノサ
ルフェート水和物の生成のバランスを図るものであり、
速硬性を付与するための重要な構成物であり、その種類
としては不水溶性の〓型無水石膏が最も好ましい。その
添加量は使用温度によって異なるが、速硬性混和材料と
する場合は、結晶質高水和活性物１００重量部に対し無
水石膏換算で２重量部以上が好ましい。使用温度が５〜
１０℃では石膏の配合比は５０〜１００重量部が好まし
い。低温度使用の場合、これらが５０重量部未満或いは
１００重量部以上となるとエトリンガイドの生成量が低
く強度発現が低くなる恐れがあるので上記範囲が好まし
い。また急結性混和材料とする場合の石膏の配合比は、
使用温度によって異なるが、結晶質高水和活性物１００
重量部に対し無水石膏換算で、通常は２〜２００重量部
が、特に５〜１０℃程度の低温度では５０〜８０重量部
が好ましい。配合比がこれらの範囲に満たないか又は越
える場合は、エトリンガイトの生成量が少なく、強度発
現が低くなる恐れがある。Here, gypsum is intended to balance the production of ethrin guide and monosulfate hydrate,
It is an important component for imparting quick-setting property, and the most preferable type is water-insoluble 〓 type anhydrous gypsum. The addition amount varies depending on the use temperature, but in the case of a quick-setting admixture, it is preferably 2 parts by weight or more in terms of anhydrous gypsum per 100 parts by weight of the crystalline highly hydrated active substance. Use temperature is 5
At 10 ° C, the compounding ratio of gypsum is preferably 50 to 100 parts by weight. In the case of using at low temperature, if the amount is less than 50 parts by weight or 100 parts by weight or more, the amount of ethrin guide produced may be low and the strength development may be low, so the above range is preferable. The mixing ratio of gypsum when using a quick-setting admixture is
Crystalline highly hydrated active substance 100 depending on the use temperature
It is usually 2 to 200 parts by weight, especially 50 to 80 parts by weight at a low temperature of about 5 to 10 ° C., in terms of anhydrous gypsum based on parts by weight. If the compounding ratio is less than or exceeds these ranges, the amount of ettringite produced is small and the strength development may be low.

【００１７】石灰は、実質上８０重量部以上のＣａＯ又
はＣａ（ＯＨ）2よりなる。石灰は、エトリンガイドの
生成量及び生成速度を制御する重要な役割と、混合した
セメントの水和を促進する役割を果たす。その配合比
は、速硬性混和材料とする場合は、結晶質高水和活性物
１００重量部に対し５重量部以上が好ましい。また急結
性混和材料とする場合の石灰の配合比は結晶質高水和活
性物１００重量部に対し５〜１００重量部が好ましい。
配合比がこれらの範囲に満たないか又は越える場合は、
エトリンガイトの生成量が少なく強度発現が低くなる恐
れがある。石灰に生石灰を用いる場合は、硬焼としてＣ
ａ2+イオンの溶出を極力低下させたものが良好な性能を
示す。Lime consists essentially of 80 parts by weight or more of CaO or Ca (OH) 2 . Lime plays an important role in controlling the amount and rate of ethrin guide production, and also promotes hydration of the mixed cement. The mixing ratio is preferably 5 parts by weight or more with respect to 100 parts by weight of the crystalline highly hydrated active material when the material is a quick-setting admixture. In the case of a quick-setting admixture, the mixing ratio of lime is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the crystalline highly hydrated active substance.
If the compounding ratio is less than or exceeds these ranges,
There is a risk that the amount of ettringite produced will be small and strength development will be low. When quicklime is used for lime, it is hard burned to C
Good performance is obtained by reducing the elution of a 2+ ions as much as possible.

【００１８】炭酸アルカリ金属塩は、速硬性あるいは急
結性を付与する場合の補完的役割を果たす副材で、炭酸
リチウム、炭酸ソーダ、炭酸カリウムなどを用い、その
配合比は速硬性混和材料とする場合は、結晶質高水和活
性物１００重量部に対し１重量部以上とする。これが１
重量部未満ではＡｌ2Ｏ3イオンの溶出を増進することが
できず、十分な速硬性を示さない。また急結性混和材料
とする場合の炭酸アルカリ金属塩の配合比は、結晶質高
水和活性物１００重量部に対し２〜５０重量部が好まし
い。配合比がこれらの範囲に満たないとＡｌ2Ｏ3イオン
の溶出を増進することができないため十分な急結性を示
さず、またこれらの範囲を超えると長期強度及び耐久性
が低下し、好ましくない。The alkali metal carbonate is an auxiliary material which plays a complementary role in imparting quick-hardening property or quick-setting property. Lithium carbonate, sodium carbonate, potassium carbonate and the like are used, and the mixing ratio thereof is that of the fast-hardening admixture. In that case, it is 1 part by weight or more per 100 parts by weight of the crystalline highly hydrated active substance. This is 1
If the amount is less than about 1 part by weight, the elution of Al 2 O 3 ions cannot be enhanced, and sufficient rapid hardening is not exhibited. The mixing ratio of the alkali metal carbonate in the case of the quick-setting admixture is preferably 2 to 50 parts by weight with respect to 100 parts by weight of the crystalline highly hydrated active substance. If the compounding ratio is less than these ranges, the elution of Al 2 O 3 ions cannot be promoted, so that sufficient quick-setting property is not exhibited, and if it exceeds these ranges, long-term strength and durability are deteriorated, which is preferable. Absent.

【００１９】アルミン酸ソーダは、速硬性混和材料とす
る場合、その配合比は結晶質高水和活性物１００重量部
に対し１重量部以上とする。これを１重量部以上添加す
ると速硬性が著しく増加する。またアルミン酸ソーダ
は、配合により急結性を著しく向上させることができ、
急結性混和材料とする場合の配合比は結晶質高水和活性
物に対し、２〜５０重量部が好ましい。配合比がこれら
の範囲に満たないと急結性が著しく低下し、またこれら
の範囲を超えると、凝結が速すぎてモルタル又はコンク
リートがこわばり、これらを吹き付けた際の性状を悪化
させる。また耐久性も低下する。When sodium aluminate is used as a fast-setting admixture, the compounding ratio is 1 part by weight or more per 100 parts by weight of the crystalline highly hydrated active substance. If this is added in an amount of 1 part by weight or more, rapid hardening will remarkably increase. In addition, sodium aluminate can significantly improve quick setting property by blending,
When used as a quick-setting admixture, the compounding ratio is preferably 2 to 50 parts by weight with respect to the crystalline highly hydrated active substance. If the compounding ratio is less than these ranges, the quick-setting property is remarkably reduced, and if it exceeds these ranges, the setting is too fast and the mortar or concrete becomes stiff and the properties when sprayed with them deteriorate. Also, the durability is reduced.

【００２０】硫酸アルカリ金属塩には、硫酸ソーダ、硫
酸カリウム等を用い、速硬性混和材料とする場合、その
配合比は結晶質高水和活性物１００重量部に対し１重量
部以上が好ましい。また急結性混和材料とする場合、そ
の配合比は結晶質高水和活性物１００重量部に対し、２
〜２０重量部が好ましい。これにより、良好な作業性の
確保及びセメント中の組成物の水和の促進硬化が図られ
る。When sodium sulfate, potassium sulfate or the like is used as the alkali metal sulfate and is used as a fast-setting admixture, the mixing ratio is preferably 1 part by weight or more per 100 parts by weight of the crystalline highly hydrated active substance. When the quick-setting admixture is used, the compounding ratio is 2 with respect to 100 parts by weight of the crystalline highly hydrated active substance.
-20 parts by weight is preferred. This ensures good workability and accelerates hardening of hydration of the composition in cement.

【００２１】水酸化アルミニウムは、配合により速硬性
や急結性を著しく向上させることができる。その配合比
は、速硬性混和材料とする場合、結晶質高水和活性物１
００重量部に対し１重量部以上配合することにより、よ
り速硬性能を向上させることができる。また、急結性混
和材料とする場合、その配合比は結晶質高水和活性物１
００重量部に対し２５重量部以下とする。この水酸化ア
ルミニウムは、アルミン酸ソーダの配合比が多い場合は
可溶性アルミニウムが多く必要としないか、あるいは配
合しても少量でよい。Aluminum hydroxide can remarkably improve quick-hardening property and quick-setting property by blending. The compounding ratio of the crystalline highly hydrated active compound 1 is 1 when a rapid-setting admixture material is used.
By blending 1 part by weight or more with respect to 00 parts by weight, the rapid hardening performance can be further improved. In addition, when it is used as a quick-setting admixture, the compounding ratio is crystalline highly hydrated active substance 1
25 parts by weight or less with respect to 00 parts by weight. This aluminum hydroxide does not require a large amount of soluble aluminum when the blending ratio of sodium aluminate is large, or the aluminum hydroxide may be blended in a small amount.

【００２２】上記の速硬性又は急結性のセメント用硬化
促進材料は、コンクリート等を混練する際に、セメント
１００重量部に対し５〜５０重量部配合してあると、コ
ンクリー等の硬化を著しく促進することができる。即
ち、セメント用硬化促進材料を、セメントに予め混合す
るか、若しくは、コンクリート等の混練に際して添加す
るか、あるいは、混練したコンクリート等に添加して、
コンクリート等の凝結、硬化を促進することができ、緊
急工事等における速硬材や、吹き付け工事における急結
材に用いることができる。配合量が５重量部未満では凝
結、硬化速度が遅く、吹付け工事用としては十分でな
く、またこれが５０重量％を超えると長期強度及び耐久
性及び作業性能が低下し好ましくない。また、ここに用
いるセメントは中庸熱、普通及び、早強ポルトランドセ
メントなどのポルトランドセメントから高炉、フライア
ッシュ等の混合セメント等の全てに使用できる。The above-mentioned quick-hardening or quick-setting hardening accelerator for cement, when 5 to 50 parts by weight of 100 parts by weight of cement are mixed when kneading concrete or the like, the hardening such as concrete becomes remarkable. Can be promoted. That is, the hardening accelerator for cement is premixed with cement, or added during kneading of concrete, or added to kneaded concrete,
It can accelerate the setting and hardening of concrete, etc., and can be used for quick-hardening materials in emergency construction and quick-setting materials in spraying construction. If the blending amount is less than 5 parts by weight, the rate of setting and curing is slow and it is not sufficient for spraying work, and if it exceeds 50% by weight, the long-term strength, durability and workability are deteriorated, which is not preferable. In addition, the cement used here can be used for all of medium-heat, normal- and early-strength Portland cement such as Portland cement to mixed cement such as blast furnace and fly ash.

【００２３】[0023]

【作用】この発明では、Ｃ3Ａ3・ＣａＳＯ4、Ｃ4ＡＦ、
Ｃ3Ａ、Ｃ12Ａ7、Ｃ11Ａ7・ＣａＦ2等を含有する焼成物
の水和活性が著しく高いことを利用して、これに石膏、
石灰、炭酸アルカリ金属塩、アルミン酸ソーダ、硫酸ア
ルカリ金属塩及び水酸化アルミニウム等を適宜配合して
各種の高性能のセメント用硬化促進材料、つまり速硬性
混和材料や急結性混和材料等を安価かつ容易に得ること
ができ、またこれらのセメント用硬化促進材料を用いて
コンクリート等の硬化を促進させることができる。In the present invention, C 3 A 3 · CaSO 4 , C 4 AF,
Taking advantage of the extremely high hydration activity of the fired product containing C 3 A, C 12 A 7 , C 11 A 7 · CaF 2, etc.
Various types of high-performance cement hardening accelerating materials, that is, quick-setting admixtures and quick-setting admixtures, etc., are inexpensively mixed with lime, alkali metal carbonate, sodium aluminate, alkali metal sulfate, aluminum hydroxide, etc. And, it can be easily obtained, and hardening of concrete or the like can be promoted by using these hardening promoting materials for cement.

【００２４】[0024]

【実施例】以下に実施例をあげて説明する。以下に示す
原料を所定量混合して焼成し、表１に示す組成の焼成物
すなわち結晶質高水和活性物を得た。焼成温度は１２５
０〜１４００℃である。 ＣａＯ源 石灰石粉末 Ａｌ2Ｏ3源 日本軽金属（株）Ａ−１３アルミナ ＳＯ3源 天然無水石膏（タイ産） Ｆｅ2Ｏ3源 ベンガラ ＣａＦ2源 ホタル石 また、これとは別に、Ｃ3Ａ3・ＣａＳＯ4、Ｃ4ＡＦ、Ｃ
3Ａ、Ｃ12Ａ7、Ｃ11Ａ7・ＣａＦ2をそれぞれを単独で焼
成し、各成分を混合したものを比較例として表１に示し
た。これらの水和活性度を示す値として、水和１時間及
び１日までの積算水和発熱量を微少熱量計（レスカ社
製）で測定した結果を表２に示した。[Examples] Examples will be described below. A predetermined amount of the following raw materials were mixed and fired to obtain a fired product having the composition shown in Table 1, that is, a crystalline highly hydrated active substance. Firing temperature is 125
It is 0-1400 degreeC. CaO source Limestone powder Al 2 O 3 source Nippon Light Metal Co., Ltd. A-13 Alumina SO 3 source Natural anhydrous gypsum (produced in Thailand) Fe 2 O 3 source Bengal CaF 2 source Fluorite In addition to this, C 3 A 3 source・ CaSO 4 , C 4 AF, C
3 A, C 12 A 7 and C 11 A 7 .CaF 2 were separately fired, and the respective components were mixed and shown in Table 1 as a comparative example. As values showing these hydration activities, Table 2 shows the results of measuring the cumulative heat of hydration for 1 hour and 1 day of hydration using a microcalorimeter (Resca).

【００２５】[0025]

【表１】 [Table 1]

【００２６】[0026]

【表２】 [Table 2]

【００２７】表２に見られるように、焼成物はいずれも
高い水和発熱量を示すことが分かる。また、比較例の混
合物はいずれも溶解熱が低く、特に同一鉱物組成同士を
対比した場合にその違いが一層明らかである。As can be seen from Table 2, all the calcined products show a high calorific value of hydration. Further, the mixtures of Comparative Examples all have a low heat of solution, and the difference is more apparent when the same mineral compositions are compared.

【００２８】表１に示した焼成物及び混合物に、表３に
示す割合で、無水石膏、生石灰、炭酸ソーダ、アルミン
酸ソーダ、硫酸ソーダ及び水酸化アルミニウムを配合し
て、セメント用硬化促進材料とし、これらを早強ポルト
ランドセメント１００重量部に対して３０重量部添加し
たモルタルの３時間、１２時間、１日、３日の圧縮強度
を表３に示した。モルタルの圧縮強度は、セメントの物
理試験方法 ＪＩＳ Ｒ ５２０１−１９８７に準拠し
て測定した。The calcined products and mixtures shown in Table 1 were mixed with anhydrous gypsum, quicklime, sodium carbonate, sodium aluminate, sodium sulfate and aluminum hydroxide in the proportions shown in Table 3 to obtain a hardening accelerator for cement. Table 3 shows the compressive strengths of mortar containing 30 parts by weight of 100 parts by weight of early-strength Portland cement added thereto for 3 hours, 12 hours, 1 day, and 3 days. The compressive strength of mortar was measured according to the physical test method of cement JIS R 5201-1987.

【００２９】[0029]

【表３】 [Table 3]

【００３０】表３に見られるように、実施例のセメント
用硬化促進材料を混合したものは、特に３時間及び１２
時間の初期強度が高い。As can be seen in Table 3, the blends of the example set accelerators for cement are especially useful for 3 hours and 12 hours.
The initial strength of time is high.

【００３１】[0031]

【発明の効果】以上のように、本発明によれば、優れた
結晶質高水和活性物が得られ、これに所定量の石膏、石
灰、炭酸アルカリ金属塩、アルミン酸ソーダ、硫酸アル
カリ金属塩及び水酸化アルミニウム等を添加することに
よって、各種の優れたセメント用硬化促進材料、すなわ
ち様々な用途・性能の速硬性混和材料や急結性混和材料
が安価かつ容易に得られる。そして、このセメント用硬
化促進材料をセメントに所定量配合し、ジェットセメン
トのように時間単位で凝結・硬化の特性を有する速硬性
のセメントや、吹き付けコンクリートなどに用いるよう
な著しく凝結の早い急結性のコンクリート等が容易に得
られる。As described above, according to the present invention, an excellent crystalline highly hydrated active substance is obtained, and a predetermined amount of gypsum, lime, alkali metal carbonate, sodium aluminate, alkali metal sulfate is obtained. By adding salt, aluminum hydroxide, etc., various excellent hardening accelerators for cement, that is, quick-setting admixtures and quick-setting admixtures for various purposes and performances can be obtained inexpensively and easily. Then, a predetermined amount of this hardening accelerator for cement is mixed into cement, and it is a quick-setting quick-setting cement that is used in fast-setting cement, which has the property of setting and hardening in hour units like jet cement, and sprayed concrete. Concrete, etc. can be easily obtained.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 22/10 Ｃ０４Ｂ 22/10 22/12 22/12 // Ｃ０４Ｂ 103:14 (72)発明者 田熊 靖久 千葉県佐倉市大作二丁目４番２号 秩父小 野田株式会社中央研究所内 (72)発明者 宇智田 俊一郎 千葉県佐倉市大作二丁目４番２号 秩父小 野田株式会社中央研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C04B 22/10 C04B 22/10 22/12 22/12 // C04B 103: 14 (72) Inventor Yasuhisa Takuma 2-4 Osaku 2-chome, Sakura City, Chiba Prefecture Chichibu Onoda Central Research Institute (72) Inventor Shunichiro Uchida 2-4-2 Daisaku Sakura City, Chiba Prefecture Chichibu Onoda Central Research Institute

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】 ＣａＯ−Ａｌ2Ｏ3−ＳＯ3−Ｆｅ2Ｏ3−
ＣａＦ2系組成物を焼成してなる、３ＣａＯ・３Ａｌ2Ｏ
3・ＣａＳＯ4（以下Ｃ3Ａ3・ＣａＳＯ4と記す）と、Ｃ
ａ2（ＡｌxＦｅ1-x）2Ｏ5（以下Ｃ4ＡＦと記す）と、３
ＣａＯ・Ａｌ2Ｏ3（以下Ｃ3Ａと記す）及び／又は１２
ＣａＯ・７Ａｌ2Ｏ3（以下Ｃ12Ａ7と記す）と、１１Ｃ
ａＯ・７Ａｌ2Ｏ3・ＣａＦ2（以下Ｃ11Ａ7・ＣａＦ2と
記す）とを、含有する焼成物からなることを特徴とする
結晶質高水和活性物。1. A CaO-Al 2 O 3 -SO 3 -Fe 2 O 3 -
3CaO / 3Al 2 O formed by firing a CaF 2 composition
3・ CaSO 4 (hereinafter referred to as C 3 A 3・ CaSO 4 ) and C
a 2 (Al x Fe 1-x ) 2 O 5 (hereinafter referred to as C 4 AF) and 3
CaO.Al 2 O 3 (hereinafter referred to as C 3 A) and / or 12
CaO · 7Al 2 O 3 (hereinafter referred to as C 12 A 7 ) and 11C
A crystalline highly hydrated active substance comprising a fired product containing aO.7Al 2 O 3 .CaF 2 (hereinafter referred to as C 11 A 7・ CaF 2 ). 【請求項２】 ＣａＯ−Ａｌ2Ｏ3−ＳＯ3−Ｆｅ2Ｏ3−
ＣａＦ2系組成物を焼成してなる、Ｃ3Ａ3・ＣａＳＯ4を
５０重量％以上と、Ｃ4ＡＦを５重量％以上と、Ｃ3Ａ及
び／又はＣ12Ａ7を１０重量％以上と、Ｃ11Ａ7・ＣａＦ
2を５重量％以上とを、含有する焼成物からなることを
特徴とする結晶質高水和活性物。2. CaO—Al 2 O 3 —SO 3 —Fe 2 O 3 —
Made by firing a CaF 2 based composition, C 3 A 3 · CaSO 4 to 50% by weight or more and, C 4 a 5 wt% or more AF, C 3 A and / or C 12 A 7 10% by weight or more And C 11 A 7 · CaF
A crystalline highly hydrated active substance, characterized by comprising a calcined product containing 2 or more 5% by weight or more. 【請求項３】 請求項１又は２のいずれかに記載の結晶
質高水和活性物に対し、石膏、石灰、炭酸アルカリ金属
塩、アルミン酸ソーダ、硫酸アルカリ金属塩及び水酸化
アルミニウムのうちの少なくとも１種以上を混合したこ
とを特徴とするセメント用硬化促進材料。3. The crystalline highly hydrated active substance according to claim 1, of gypsum, lime, alkali metal carbonate, sodium aluminate, alkali metal sulfate, and aluminum hydroxide. A hardening-promoting material for cement, characterized in that at least one kind is mixed. 【請求項４】 請求項１又は２のいずれかに記載の結晶
質高水和活性物１００重量部に対し、石膏を無水換算で
２重量部以上、石灰を５重量部以上、炭酸アルカリ金属
塩を１重量部以上、アルミン酸ソーダを１重量部以上、
硫酸アルカリ金属塩１重量部以上及び水酸化アルミニウ
ムを１重量部以上混合したことを特徴とするセメント用
硬化促進材料。4. Based on 100 parts by weight of the crystalline highly hydrated active substance according to claim 1 or 2, 2 parts by weight or more of gypsum, 5 parts by weight or more of lime, and an alkali metal carbonate are used. 1 part by weight or more, sodium aluminate 1 part by weight or more,
A hardening-accelerating material for cement, characterized by mixing 1 part by weight or more of an alkali metal sulfate and 1 part by weight or more of aluminum hydroxide. 【請求項５】 請求項１又は２のいずれかに記載の結晶
質高水和活性物１００重量部に対し、石膏を無水換算で
２〜２００重量部、石灰を５〜１００重量部、炭酸アル
カリ金属塩を２〜５０重量部、アルミン酸ソーダを２〜
５０重量部及び硫酸アルカリ金属塩を２〜２０重量部混
合したことを特徴とするセメント用硬化促進材料。5. Based on 100 parts by weight of the crystalline highly hydrated active substance according to claim 1, 2 to 200 parts by weight of gypsum, 5 to 100 parts by weight of lime, alkali carbonate 2 to 50 parts by weight of metal salt, 2 to 2 parts of sodium aluminate
A hardening-promoting material for cement, characterized in that 50 parts by weight and 2 to 20 parts by weight of an alkali metal sulfate are mixed. 【請求項６】 請求項１又は２のいずれかに記載の結晶
質高水和活性物１００重量部に対し、石膏を無水換算で
２〜２００重量部、石灰を５〜１００重量部、炭酸アル
カリ金属塩を２〜５０重量部、アルミン酸ソーダを１０
〜５０重量部、硫酸アルカリ金属塩を２〜２０重量部及
び水酸化アルミニウムを２５重量部以下混合したことを
特徴とするセメント用硬化促進材料。6. 100 parts by weight of the crystalline highly hydrated active substance according to claim 1, 2 to 200 parts by weight of gypsum, 5 to 100 parts by weight of lime, alkali carbonate 2 to 50 parts by weight of metal salt and 10 parts of sodium aluminate
-50 parts by weight, 2 to 20 parts by weight of an alkali metal sulfate, and 25 parts by weight or less of aluminum hydroxide are mixed, and a hardening accelerator for cement. 【請求項７】 セメントペースト、モルタル又はコンク
リートを混練する際に、請求項３ないし６のいずれかに
記載のセメント用硬化促進材料を、セメントに対し５〜
５０重量部添加することを特徴とするセメントペース
ト、モルタル又はコンクリートの凝結・硬化促進方法。7. When the cement paste, mortar or concrete is kneaded, the hardening accelerator for cement according to claim 3 is added to the cement in an amount of 5 to 5.
A method for promoting the setting and hardening of cement paste, mortar or concrete, which is characterized by adding 50 parts by weight.
JP27350695A 1995-09-27 1995-09-27 Crystalline highly hydrated and activated material hardening accelerating material for cement and acceleration of setting and hardening of mortar or concrete Pending JPH0986989A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27350695A JPH0986989A (en) 1995-09-27 1995-09-27 Crystalline highly hydrated and activated material hardening accelerating material for cement and acceleration of setting and hardening of mortar or concrete

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27350695A JPH0986989A (en) 1995-09-27 1995-09-27 Crystalline highly hydrated and activated material hardening accelerating material for cement and acceleration of setting and hardening of mortar or concrete

Publications (1)

Publication Number Publication Date
JPH0986989A true JPH0986989A (en) 1997-03-31

Family

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000051947A1 (en) * 1999-03-02 2000-09-08 Italcementi S.P.A. Quick setting cement with lime and aluminates
JP2010150105A (en) * 2008-12-26 2010-07-08 Taiheiyo Cement Corp Quick hardening cement
JP2012056795A (en) * 2010-09-09 2012-03-22 Denki Kagaku Kogyo Kk Spray material and spraying method using same
JP2014058437A (en) * 2012-08-22 2014-04-03 Taiheiyo Cement Corp Hydraulic composition
WO2014021797A3 (en) * 2012-07-30 2014-06-05 Melek Akman A cement material for renewal of damaged dental tissues
JP2021169385A (en) * 2020-04-14 2021-10-28 デンカ株式会社 Cement quick-setting admixture and cement composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000051947A1 (en) * 1999-03-02 2000-09-08 Italcementi S.P.A. Quick setting cement with lime and aluminates
JP2010150105A (en) * 2008-12-26 2010-07-08 Taiheiyo Cement Corp Quick hardening cement
JP2012056795A (en) * 2010-09-09 2012-03-22 Denki Kagaku Kogyo Kk Spray material and spraying method using same
WO2014021797A3 (en) * 2012-07-30 2014-06-05 Melek Akman A cement material for renewal of damaged dental tissues
JP2014058437A (en) * 2012-08-22 2014-04-03 Taiheiyo Cement Corp Hydraulic composition
JP2021169385A (en) * 2020-04-14 2021-10-28 デンカ株式会社 Cement quick-setting admixture and cement composition

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