JPH08166492A - Inorganic builder for cement - Google Patents
Inorganic builder for cementInfo
- Publication number
- JPH08166492A JPH08166492A JP33237394A JP33237394A JPH08166492A JP H08166492 A JPH08166492 A JP H08166492A JP 33237394 A JP33237394 A JP 33237394A JP 33237394 A JP33237394 A JP 33237394A JP H08166492 A JPH08166492 A JP H08166492A
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- weight
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- cement
- added
- paste
- 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.)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、たとえば原子力施設で
発生する廃棄物に添加して使用するのに適したセメント
用無機混和材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic admixture for cement, which is suitable for use by adding it to waste generated in a nuclear facility, for example.
【０００２】[0002]
【従来の技術】原子力発電所の様な原子力施設で発生す
る廃棄物としては、濃縮廃液を乾燥して得られた粉体を
ペレット状に成形した物や、金属の切断片、フィルタ
ー、パッキンの様な雑廃棄物がある。特に雑廃棄物につ
いては、その種類が多く、形状も複雑である。2. Description of the Related Art Waste generated in a nuclear facility such as a nuclear power plant is formed by pelletizing powder obtained by drying concentrated waste liquid, metal cut pieces, filters, packings. There is such miscellaneous waste. Especially, there are many kinds of miscellaneous wastes and their shapes are complicated.
【０００３】この様な雑廃棄物は２００リットルドラム
缶に充填可能な様に適当な大きさに切断して保管される
ことになっている。そこで、固型化のために、廃棄物を
充填した２００リットルドラム缶中にセメント系材料を
ペースト状にして流し込み、ドラム缶と廃棄物間の空間
や廃棄物同志の空間を固型化材で埋めてしまう方法が提
案されている。[0003] Such miscellaneous waste is to be cut and stored in an appropriate size so that it can be filled in a 200-liter drum. Therefore, for solidification, the cement-based material is poured into a 200-liter drum that is filled with waste in a paste form, and the space between the drum and the waste and the space between the wastes are filled with a solidifying material. A method of closing is proposed.
【０００４】セメント系材料は、セメントに水を混ぜて
ペーストを作成して使用する方法、セメントに砂と水を
混ぜモルタルのペーストにして使用する方法、あるいは
セメントに砂と砂利と水を混ぜてコンクリートのペース
トにして使用する方法等が提案されている。その場合、
建築土木業界で使用されるセメント系材料が有力視され
ている。The cement-based material is used by mixing cement with water to form a paste, by using sand with water by mixing it with mortar paste, or by mixing sand with gravel and water with cement. A method of using it as a concrete paste has been proposed. In that case,
Cement-based materials used in the construction and civil engineering industry are regarded as promising.
【０００５】[0005]
【発明が解決しようとする課題】セメント系材料は前述
の空隙を完全に充填する必要がある。それゆえ、一般的
なセメントペースト、砂、砂利を添加したモルタルやコ
ンクリートペーストでは流動性が悪いために空隙を完全
に充填することは不可能であった。このため、一般建築
や土木業界では、セメント系材料の流動性を良くするた
めに混和材としてリグニンスルホン酸、ナフタリンスル
ホン酸等の有機系添加剤が使用されている。The cement-based material must completely fill the above-mentioned voids. Therefore, general cement paste, sand, mortar to which gravel is added, and concrete paste have poor fluidity, so that it is impossible to completely fill the voids. Therefore, in the general construction and civil engineering industries, organic additives such as ligninsulfonic acid and naphthalenesulfonic acid are used as admixtures in order to improve the fluidity of cement materials.
【０００６】放射性廃棄物の充填材として、このような
有機混和材を添加したセメントが現在検討されている。As a filling material for radioactive waste, cement containing such an organic admixture is currently under study.
【０００７】しかし、長期安定性が最大の要求項目であ
るセメントにとっては、有機系混和材の添加は耐久性と
共に放射性核種の吸着性を低下させる原因となると言わ
れている。However, it is said that the addition of the organic admixture causes not only the durability but also the adsorptivity of the radionuclide for the cement, which has the longest-term stability as the maximum requirement.
【０００８】前述のように、建築土木業界で用いられて
いる混和材あるいは固化材は主に有機物からなっている
が、有機系の分散剤は、長期的に見ると劣化しやすく、
かつ、その際にガスを発生し構造物自体の緻密性を低下
させる恐れがある。それと同時に核種吸着性も欠如す
る。As described above, the admixture or solidifying material used in the construction and civil engineering industry is mainly made of organic matter, but the organic dispersant is apt to deteriorate in the long term,
In addition, at that time, gas may be generated, which may reduce the denseness of the structure itself. At the same time, it lacks nuclide adsorption.
【０００９】そこで、本発明者等は、縮合リン酸ナトリ
ウム塩やリン酸ガラスを混和材として使用することを知
見した特開昭６２−２６７６９９号、特開昭６２−２６
７７００号、特開昭６３−１６７２９７号および特願平
５−１３７４６９号に示す様な放射性廃棄物の固化処理
技術を提案した。Therefore, the present inventors have found that condensed sodium phosphate or phosphate glass is used as an admixture, JP-A-62-267699 and JP-A-62-26.
No. 7,700, JP-A-63-167297 and Japanese Patent Application No. 5-137469, solidification treatment techniques for radioactive waste have been proposed.
【００１０】しかし、これらによって提供される固型化
材では、ポットライフの問題や亀裂発生の問題、また、
凝結時間が著しく長くなるなどの問題が完全に解消され
ず、そのためシステム構成が非常に複雑となったり、シ
ステム化が不可能であるという問題がある。However, in the solidifying material provided by these, the problems of pot life, cracking, and
Problems such as a significantly long setting time are not completely solved, and therefore, there are problems that the system configuration becomes very complicated and systematization is impossible.
【００１１】本発明の目的は、長期的に見て劣化等の変
質が少なく、また仮に変質が生じても、ガスなどが発生
しない無機の混和材を提供することである。It is an object of the present invention to provide an inorganic admixture which is less likely to be deteriorated or deteriorated in the long term and does not generate gas or the like even if the deterioration occurs.
【００１２】[0012]
【課題を解決するための手段】本発明の要旨は、縮合リ
ン酸ナトリウム０．１〜２重量部、炭酸塩化合物０．１
〜２重量部、ホウ酸０．０５〜１重量部、ベントナイト
０．５〜５重量部、アルミナセメント０．５〜４重量部
からるセメント用無機混和材である。The gist of the present invention is to provide 0.1 to 2 parts by weight of condensed sodium phosphate and 0.1 to 100 parts of a carbonate compound.
˜2 parts by weight, boric acid 0.05 to 1 part by weight, bentonite 0.5 to 5 parts by weight, and alumina cement 0.5 to 4 parts by weight is an inorganic admixture for cement.
【００１３】[0013]
【実施例】本発明者等はシステム構成化を容易に行える
セメントの開発を主眼として検討を行った。そして多大
の研究の結果、以下に示す様なシステム構成上まったく
問題を生ぜず、優れた特性を有するセメント用無機混和
材を発明した。[Examples] The inventors of the present invention conducted a study with a focus on the development of a cement that can be easily configured into a system. As a result of a great deal of research, the inventors have invented an inorganic admixture for cement which has excellent characteristics without causing any problems in the system configuration as shown below.
【００１４】本発明の放射性廃棄物の固型化材料は、主
として縮合リン酸ナトリウム、炭酸塩、ホウ酸、ベント
ナイト、アルミナセメントの５種を混合してなる混和材
をセメント（たとえば高炉セメント）に添加して、セメ
ントペーストの流動性を著しく改善せしめる、有機物を
全く含有しない無機系の混和材である。The solidification material for radioactive waste according to the present invention is mainly composed of an admixture made by mixing 5 kinds of condensed sodium phosphate, carbonate, boric acid, bentonite and alumina cement into cement (for example, blast furnace cement). It is an inorganic admixture containing no organic matter, which is added to remarkably improve the fluidity of the cement paste.
【００１５】本発明のセメント用混和材は、普通セメン
トや高炉セメントなどの水硬性セメントと混合して用い
るだけでなく、水硬性セメントの一部を耐火骨材（例え
ばシャモット質、鋳物砂等）で置き換えて用いて放射性
廃棄物用充填固化材としてもよい。The cement admixture of the present invention is used not only by mixing it with a hydraulic cement such as ordinary cement or blast furnace cement, but also by using a part of the hydraulic cement as a refractory aggregate (for example, chamotte, foundry sand, etc.). It may be replaced with and used as a filling and solidifying material for radioactive waste.
【００１６】本発明の混和材は粉末状であり、前述のよ
うに主として５種の原料から構成されている。各原料の
主な添加役割は次のとおりである。The admixture of the present invention is in powder form and, as mentioned above, is mainly composed of five kinds of raw materials. The main addition roles of each raw material are as follows.
【００１７】縮合リン酸ナトリウムはセメントに分散性
を付与するために添加する添加剤である。一般にポルト
ランドセメントや高炉セメントに水を添加して得られた
ペーストは著しく流動性に欠け、狭い間隙を充填する機
能は有しない。従って放射性廃棄物の固型化のためには
流動性を付与するための添加剤が必要となってくる。そ
のために分散剤としてヘキサメタリン酸ナトリウム、ウ
ルトラポリリン酸ナトリウムの名称で知られる縮合リン
酸ナトリウムが添加される。これは、試薬並びに工業用
のいずれのグレードのものを添加してもよい。また、そ
の添加量は０．１〜２重量部であり、好ましくは０．３
〜１．０重量部が添加される。添加量の範囲を０．１〜
２重量部に限定した理由は、０．１重量部未満では流動
性は全く示さず、また２重量部超では著しい硬化遅延を
及ぼし、硬化に７日間以上の時間を要するためである。Condensed sodium phosphate is an additive added to impart dispersibility to cement. Generally, a paste obtained by adding water to Portland cement or blast furnace cement has a remarkably low fluidity and does not have a function of filling narrow gaps. Therefore, an additive for imparting fluidity is required for solidification of radioactive waste. Therefore, as the dispersant, sodium hexametaphosphate and condensed sodium phosphate known as sodium ultrapolyphosphate are added. This may be added to any grade of reagent as well as industrial grade. The amount added is 0.1 to 2 parts by weight, preferably 0.3.
~ 1.0 parts by weight are added. The range of addition amount is 0.1
The reason for limiting the amount to 2 parts by weight is that if the amount is less than 0.1 parts by weight, no fluidity is exhibited, and if the amount exceeds 2 parts by weight, a significant retardation of curing occurs, and it takes 7 days or more for curing.
【００１８】炭酸塩は流動可使時間を著しく延長させる
目的で添加される。上記縮合リン酸ナトリウムを添加し
たセメントペーストは、初期粘度を１５分間保持する
が、更に時間が経過すると粘性が急激に増して、３０分
経過すると自然流動が困難となる。例えばセメントペー
ストの充填注入度の評価方法の手段として行われるＰロ
ート（すなわち土木学会基準のロート）を用いた流下値
の測定においては、混練後ペーストの流下時間が１６秒
であったものがペーストの放置時間が経過すると共に粘
性が次第に上昇し、混練１５分後ではロートから全量流
出するのに６０秒以上を要し、混練３０分後ではロート
から流出しないという事態が生じる。Carbonate is added for the purpose of prolonging the working life of the fluid. The cement paste to which the condensed sodium phosphate has been added retains the initial viscosity for 15 minutes, but the viscosity increases sharply with the lapse of time, and the natural flow becomes difficult after 30 minutes. For example, in the measurement of the flow-down value using a P funnel (that is, the funnel of the standard of the Japan Society of Civil Engineers) performed as a means for evaluating the filling and injecting degree of cement paste, the paste having a flow-down time of 16 seconds after kneading is the paste. The viscosity gradually increases with the lapse of the standing time, and it takes 60 seconds or more for the entire amount to flow out from the funnel after 15 minutes of kneading, and it does not flow out from the funnel after 30 minutes of kneading.
【００１９】このように、縮合リン酸ナトリウムの添加
においては、セメントの分散性に効果は示すものの、２
００リットルドラム缶を完全に均一に充填するのに必要
な流動可使時間を得るには縮合リン酸ナトリウム単独の
添加によっては困難である。Thus, although the addition of condensed sodium phosphate has an effect on the dispersibility of cement,
It is difficult to add the condensed sodium phosphate alone to obtain the fluid pot life required to completely and uniformly fill a 00 liter drum.
【００２０】そこで、流動可使時間を延長させる目的で
種々の添加剤を検討した結果、縮合リン酸ナトリウムと
炭酸塩を併用添加すると、分散性が更に向上すると共に
流動可使時間が著しく延びることが判明したのである。Then, as a result of studying various additives for the purpose of extending the fluid pot life, when the condensed sodium phosphate and the carbonate are added together, the dispersibility is further improved and the fluid pot life is remarkably extended. Was found.
【００２１】炭酸塩としては炭酸カリウム及び炭酸ナト
リウムが使用される。これは、試薬と工業用のいずれに
ついても限定がなく、両方とも使用が可能である。その
添加量は０．１〜２重量部である。好ましくは、炭酸塩
は、縮合リン酸ナトリウムと同様に０．３〜１．０重量
部が添加される。炭酸塩の添加量の範囲を０．１〜２重
量部に限定した理由を述べると、０．１重量部未満では
全く効をなさず、縮合リン酸ナトリウムを単独添加した
ペーストの特性しか得られない。また、逆に添加量が２
重量部を超えると、縮合リン酸ナトリウム単独の添加品
よりもペースト流動可使時間が短かくなったり、異常硬
化（たとえば瞬結）を招くというトラブルが生じた。Potassium carbonate and sodium carbonate are used as carbonates. It is not limited to either reagent or industrial use and both can be used. The amount added is 0.1 to 2 parts by weight. Preferably, 0.3 to 1.0 part by weight of carbonate is added as in the case of condensed sodium phosphate. The reason why the range of the addition amount of the carbonate is limited to 0.1 to 2 parts by weight is as follows. If the addition amount is less than 0.1 parts by weight, no effect is obtained, and only the characteristics of the paste to which the condensed sodium phosphate is added are obtained. Absent. On the contrary, the addition amount is 2
If it exceeds the weight part, there is a problem that the pot life of the paste flow becomes shorter than that of the additive containing only condensed sodium phosphate, or abnormal curing (eg, instantaneous setting) occurs.
【００２２】縮合リン酸ナトリウムと炭酸塩を併用添加
したセメントペーストは、分散性の向上と流動可使時間
の延長が図られ、混練直後と３０分静置保持したペース
トの流下値はいずれも１６秒という結果であった。しか
し、６０分静置保持したペーストには流下特性の低下が
認められ、ロート中のペーストが完全に流下するまでに
３０秒以上の時間を要した。The cement paste to which the condensed sodium phosphate and the carbonate are added in combination has improved dispersibility and extended fluid pot life, and the flow-down values of the paste immediately after kneading and left standing for 30 minutes are 16 The result was seconds. However, deterioration of the flow-down characteristics was observed in the paste that had been left standing for 60 minutes, and it took 30 seconds or more for the paste in the funnel to completely flow down.
【００２３】ホウ酸は流動可使時間を更に延長する目的
で添加する。放射性廃棄物の固型化材は、充填性（流動
性）が要求されるだけでなく、流動可使時間が長いこと
が強く要求される。仮に、流動可使時間が短く、硬化時
間が速い固型化材を使用した場合、充填中や充填後にミ
キサー内やペースト搬送ホース中においてセメントが硬
化してしまうというトラブルを招きかねない。また、硬
化したセメントの除去も、管理区域内での作業を強いら
れるために簡単には行えず、装置全体の稼動を中止して
行うという大きなトラブルを誘発する原因ともなりかね
ない。Boric acid is added for the purpose of further extending the pot life. The solidifying material for radioactive waste is not only required to have a filling property (fluidity), but is also strongly required to have a long flow pot life. If a solidifying material having a short fluid pot life and a fast curing time is used, cement may harden during or after filling in the mixer or in the paste transfer hose. Further, the removal of the hardened cement cannot be easily performed because the work in the controlled area is forced, which may cause a big trouble that the operation of the entire apparatus is stopped.
【００２４】従って、セメントペーストは、流動可使時
間が長ければ長いほど、安心して使用できるわけであ
る。そのため混練後３時間程度初期の流動性（流下値）
を有する様なセメントが最適である。Therefore, the longer the pot life of the cement paste, the safer it can be used. Therefore, the initial fluidity (downflow value) about 3 hours after kneading
Cement having the following is most suitable.
【００２５】ホウ酸は、ペーストの流動可使時間を著し
く延長させるのに大きな効果を持たらす添加剤である。
その添加量は０．０５〜１重量部である。０．０５重量
部未満だと、期待された流動可使時間の延長は認められ
ず、逆に１重量部を超えて添加すると、固化体の収縮率
が大きくなり、亀裂発生の原因となりやすい。ホウ酸添
加における流動可使時間について述べると、１．５時間
以上の初期流動性を可能とすると共に、３時間経過した
ペーストにおいても僅かに流下値が上昇するに留るもの
が好ましい。Boric acid is an additive which has a great effect on prolonging the flow pot life of the paste.
The amount added is 0.05 to 1 part by weight. If it is less than 0.05 parts by weight, the expected extension of the fluid pot life is not observed, and if it is added in excess of 1 part by weight, the shrinkage rate of the solidified product becomes large and cracks are likely to occur. With respect to the flow pot life in boric acid addition, it is preferable that the initial flowability of 1.5 hours or more is possible and the flow-down value is increased only slightly after 3 hours.
【００２６】ペーストの体積収縮や空隙を充填すること
を目的としてベントナイトが添加される。ベントナイト
は白亜紀から第三期層の大昔に海底や湖底に堆積した火
山灰が火山性の熱水作用や地圧続成作用などにより生成
されたもので、粘土鉱物モンモリロナイト結晶を主成分
とするものである。ベントナイトは、潤滑性、懸濁性、
粘性、チクソトロピー性の性質に優れ、土木建築工事
用、鋳物砂粘結剤用、農業土木用として広く使用されて
いる。これを添加すると、粘度が細かくてセメントミル
クのみでは浸透し得ない空隙部にも浸透するため、高い
充填性が得られやすい。ベントナイトの添加量は０．５
〜５重量部である。０．５重量部未満では上記添加効果
は認められず、５重量部を超えて添加すると、ペースト
の粘性が異常に上昇し、流動性が極端に低下する結果を
招く。Bentonite is added for the purpose of shrinking the volume of the paste and filling voids. Bentonite is the volcanic ash deposited on the sea floor and lake bottom from the Cretaceous to the Third Age, which was produced by volcanic hydrothermal action and geodiagenesis, and is mainly composed of clay mineral montmorillonite crystals. Is. Bentonite has lubricity, suspension,
It has excellent viscous and thixotropy properties and is widely used for civil engineering and construction work, casting sand binder, and agricultural civil engineering. When this is added, since it penetrates into voids that have a low viscosity and cannot be penetrated only by cement milk, high filling property is easily obtained. The amount of bentonite added is 0.5
~ 5 parts by weight. If it is less than 0.5 parts by weight, the above addition effect is not observed, and if it exceeds 5 parts by weight, the viscosity of the paste is abnormally increased and the fluidity is extremely lowered.
【００２７】前述のセメントペーストによって充填固化
したドラム缶は、ある所定の時間静置養生した後（たと
えば２４〜３６時間後）、所定の保管個所へ移動され
る。The drum can filled and solidified with the above-mentioned cement paste is allowed to stand and cure for a predetermined time (for example, after 24 to 36 hours), and then moved to a predetermined storage location.
【００２８】移動保管時は、ドラム缶に若干の振動や衝
撃が加わることが予測されることから、固化体として十
分な強度を発現しておく必要がある。仮りに硬化せず十
分な強度を発現していない固化体を移動したりすると、
亀裂割れの発生と共に廃棄物がドラム缶中を移動する等
の問題が発生する。それは、放射性核種の洩れにつなが
り、安定性に欠ける固化体となってしまう。Since it is expected that a slight vibration or shock will be applied to the drum during storage during movement, it is necessary to exhibit sufficient strength as a solidified body. If you move a solidified body that does not cure and does not express sufficient strength,
Along with the occurrence of cracks, problems such as waste moving in the drum can occur. It leads to the leakage of radionuclides and becomes a solidified body lacking stability.
【００２９】アルミナセメントはセメントペーストにド
ラム缶移動が可能な強度を付与するために添加される。
アルミナセメントは急硬性セメントの分類に属し、普通
ポルトランドセメントの２８日強度が僅か１日で得られ
る。アルミナセメントは、カルシウム・アルミネートを
主成分とするため耐熱性に優れるという特性から耐火物
用結合バインダーを主に急硬性という点で見直されて、
様々な用途の展開が検討されている材料である。本来、
ポルトランドセメントや高炉セメントにアルミナセメン
トまたはその混合鉱物系を添加すると、急結性を示すこ
とが知られており、アルミナセメントの添加量によって
は数分にて粘性を失い、発熱して固結する。Alumina cement is added to the cement paste in order to give it strength that allows drum can movement.
Alumina cement belongs to the class of rapid hardening cement, and the 28-day strength of ordinary Portland cement can be obtained in only 1 day. Alumina cement has been reconsidered mainly in terms of rapid hardening of binder binders for refractories because of its excellent heat resistance because it contains calcium aluminate as a main component.
It is a material that is being studied for various applications. Originally,
It is known that when alumina cement or its mixed minerals is added to Portland cement or blast furnace cement, it shows a quick setting property. Depending on the amount of alumina cement added, the viscosity is lost in a few minutes, and heat builds up to solidify. .
【００３０】このようなことを勘案して、本発明のセメ
ント用無機混和材は、縮合リン酸ナトリウム、炭酸カル
シウム、ホウ酸の相互作用やそれらの添加量を詳細に検
討した結果発明されたものであり、３時間に及ぶ流動可
使時間を有しながらも２４時間後には移動可能な強度
（たとえば貫入抵抗強度が３００ｋｇｆ／ｃｍ2 以上）
を示したり、凝結時間をアルミナセメントの添加で容易
に調整したりすることを可能とした。In consideration of the above, the inorganic admixture for cement of the present invention was invented as a result of detailed study of the interaction of condensed sodium phosphate, calcium carbonate, boric acid and their addition amounts. And has a flowable working time of 3 hours and is movable after 24 hours (for example, penetration resistance strength of 300 kgf / cm 2 or more).
And the setting time can be easily adjusted by adding alumina cement.
【００３１】アルミナセメントは、０．５〜４重量部が
添加される。この範囲を逸脱すると、セメントペースト
の流動性と凝結時間に大きな影響を与え、０．５重量部
未満では凝結時間の調整にさしたる効果が認められず、
４重量部を超えると凝結時間が極端に短くなると共に流
動可使時間の短縮にも影響する結果となる。0.5 to 4 parts by weight of alumina cement is added. If it deviates from this range, the fluidity of the cement paste and the setting time will be greatly affected, and if it is less than 0.5 part by weight, no effect of adjusting the setting time will be observed.
If the amount exceeds 4 parts by weight, the setting time becomes extremely short and the flow pot life is also shortened.
【００３２】アルミナセメントは、ＪＩＳで規格されて
いる１級〜５級のいずれのグレードのものも使用が可能
である。As the alumina cement, any grade of grades 1 to 5 standardized by JIS can be used.
【００３３】本発明のセメント用無機混和材は粉末状で
あるが、それについて説明する。The inorganic admixture for cement of the present invention is in the form of powder, which will be described below.
【００３４】予め縮合リン酸塩と炭酸塩を水溶液として
添加するのではなく、粉末状の無機混和材を添加する
と、分散作用が良好となる。たとえば、縮合リン酸ナト
リウムと炭酸塩を同時に加え、強いアルカリ性を保持
し、流動性を著しく延長させる。When the powdered inorganic admixture is added instead of previously adding the condensed phosphate and the carbonate as an aqueous solution, the dispersing action becomes good. For example, condensed sodium phosphate and carbonate are added at the same time to maintain strong alkalinity and significantly extend fluidity.
【００３５】本発明の混和材の粉末の粒度は特に限定す
るものではないが、好ましくは０．２５ｍｍ以下とす
る。さらに、縮合リン酸ナトリウムは、白色結晶の粉末
又は結晶粒が好ましく、特に１００メッシュ以下の粉末
が最適であり、炭酸塩は、粒径３００ミクロン以下の白
色粒状物又は１００メッシュ以下の白色微粉末が好まし
く、とくに溶解性の観点から白色微粉末が最適であり、
ホウ酸は粒径３００ミクロン以下の白色結晶粉末が好ま
しく、ベントナイトは粒径３００メッシュ以下の黄白色
微粉末が細密充填の観点から好ましく、アルミナセメン
トはグレー白色や白色微粉末が好ましい。The particle size of the powder of the admixture of the present invention is not particularly limited, but preferably 0.25 mm or less. Further, the condensed sodium phosphate is preferably a powder of white crystals or crystal grains, and a powder of 100 mesh or less is particularly suitable, and a carbonate is a white granular material having a particle size of 300 microns or less or a white fine powder of 100 mesh or less. Is preferable, white fine powder is most suitable from the viewpoint of solubility,
The boric acid is preferably a white crystalline powder having a particle size of 300 μm or less, the bentonite is preferably a yellowish white fine powder having a particle size of 300 mesh or less from the viewpoint of close packing, and the alumina cement is preferably a gray white or white fine powder.
【００３６】また、本発明のセメント用混和材を耐火骨
材と一緒に用いるのであれば、セメント用混和材１．２
５〜１４重量部、水硬性セメント４０〜６０重量部およ
び耐火骨材６０重量部以下を混合し、放射性廃棄物用充
填固化材とすることが望ましい。If the cement admixture of the present invention is used together with the refractory aggregate, the cement admixture 1.2
It is desirable to mix 5 to 14 parts by weight, hydraulic cement 40 to 60 parts by weight, and fire resistant aggregate 60 parts by weight or less to prepare a filling and solidifying material for radioactive waste.
【００３７】この場合、放射性廃棄物用充填固化材の各
原料の主な添加役割は、次の通りである。In this case, the main addition role of each raw material of the filling and solidifying material for radioactive waste is as follows.
【００３８】セメント用無機混和材の役割は前記の通り
である。１．２５〜１４重量部の範囲をはずれると、セ
メント用無機混和材の十分な効果が得られない。The role of the inorganic admixture for cement is as described above. If the amount is out of the range of 1.25 to 14 parts by weight, the sufficient effect of the inorganic admixture for cement cannot be obtained.
【００３９】本発明で用いる水硬性セメントとは、例え
ば普通ポルトランドセメントや高炉セメント等であり、
特にＪＩＳＲ５２１０、ＪＩＳＲ５２１１等が好まし
い。The hydraulic cement used in the present invention is, for example, ordinary Portland cement or blast furnace cement,
Particularly, JISR5210 and JISR5211 are preferable.
【００４０】水硬性セメントは４０〜６０重量部とする
ことが望ましい。４０重量部以下では、水硬性セメント
の機能が十分得られず、６０重量部以上ではセメント用
無機混和材の効果が十分に得られない。The hydraulic cement is preferably 40-60 parts by weight. If it is 40 parts by weight or less, the function of hydraulic cement cannot be sufficiently obtained, and if it is 60 parts by weight or more, the effect of the inorganic admixture for cement cannot be sufficiently obtained.
【００４１】耐火骨材が６０重量部以下であることが好
ましいとしたのは、６０重量部より多いと低水分化はは
かれるものの骨材が沈降し、材料分離を発生する原因に
なるからである。It is preferable that the amount of the refractory aggregate is 60 parts by weight or less because if the amount is more than 60 parts by weight, the water content can be reduced, but the aggregate precipitates and causes the material separation. .
【００４２】耐火骨材として例えばシャモット質耐火骨
材を用いるならば、その組成はＡｌ2 Ｏ3 ３５〜５５重
量％、ＳｉＯ2 ６５〜４５重量％であることが好まし
い。本発明のシャモット質耐火骨材は、例えばＡｌ2 Ｏ
3 ３５〜５５重量％、ＳｉＯ2６５〜４５重量％の組成
からなる粘土を１０００℃以上の高温で焼固して緻密化
させたのち任意の粒径にクラッシャーやミルで粉砕した
もの等である。本発明のシャモット質耐火骨材の粒径
は、最大粒径１．０ｍｍ以下、粒径０．５〜１．０ｍｍ
のものが５５％以上であることがのぞましい。この粉度
構成からはずれると添加水量が増減するなど固型化した
際の特性にバラツキを生じやすい。嵩比量は、２．４５
〜２．６５、見掛気孔率１．５〜３．５％であることが
好ましい。嵩比量がこの範囲からはずれるとシャモット
質耐火骨材の沈降やペーストの流動性の定価を生じやす
くなり、気孔率がこの範囲をはずれるとペースト特性、
固化体特性に悪影響を与える原因になりやすい。If, for example, chamotte refractory aggregate is used as the refractory aggregate, its composition is preferably 35 to 55% by weight of Al 2 O 3 and 65 to 45% by weight of SiO 2 . The chamotte refractory aggregate of the present invention is, for example, Al 2 O.
3 Clay consisting of 35-55% by weight of SiO 2 and 65-45% by weight of SiO 2 is fired at a high temperature of 1000 ° C. or higher to be densified and then crushed by a crusher or a mill to an arbitrary particle size. . The chamotte refractory aggregate of the present invention has a maximum particle size of 1.0 mm or less and a particle size of 0.5 to 1.0 mm.
It is desirable that more than 55% of them. If it deviates from this fineness constitution, the characteristics when solidified such as an increase or decrease in the amount of added water are likely to occur. The bulk ratio is 2.45.
˜2.65 and apparent porosity 1.5 to 3.5% are preferred. If the volume ratio is out of this range, settling of chamotte refractory aggregates and paste flowability tend to occur, and if the porosity is out of this range, paste characteristics,
It is likely to cause adverse effects on the properties of the solidified body.
【００４３】以下、実施例１〜１７と比較例１〜１７を
示し、本発明のセメント用無機混和材についてさらに具
体的に説明する。Hereinafter, Examples 1 to 17 and Comparative Examples 1 to 17 will be shown to more specifically describe the inorganic admixture for cement of the present invention.
【００４４】実施例１ ＪＩＳＢ種高炉セメント１００重量部に、ヘキサメタリ
ン酸ナトリウム、炭酸カリウム各々０．５重量部、ホウ
酸０．２重量部、ベントナイト２．５重量部、アルミナ
セメント１重量部を予め混合した混和材を添加して混合
し、さらに外率にて水４５重量部を添加し、セメントペ
ーストを得た。このセメントペーストの粘度は１０Ｐａ
・ｓで、フロー値３２０ｍｍ、Ｐロートによる流下時間
については、混練直後で１４秒を示し、１８０分後にて
も１６秒と特性的な低下はほとんど認められなかった。
固化体の２８日経過後の強度は４４．１ＭＰａを示し、
ＪＩＳＲ５２１１の規格値を上回った。 Example 1 To 100 parts by weight of JIS B type blast furnace cement, 0.5 parts by weight each of sodium hexametaphosphate and potassium carbonate, 0.2 parts by weight of boric acid, 2.5 parts by weight of bentonite, and 1 part by weight of alumina cement were previously prepared. The mixed admixture was added and mixed, and 45 parts by weight of water was added at an external ratio to obtain a cement paste. The viscosity of this cement paste is 10 Pa
Regarding s, the flow value was 320 mm, and the flow-down time by the P funnel was 14 seconds immediately after kneading, and 16 seconds even after 180 minutes, showing almost no characteristic deterioration.
The strength of the solidified body after 28 days shows 44.1 MPa,
It exceeded the standard value of JIS R5211.
【００４５】実施例２ 高炉セメントＢ種１００重量部に、ヘキサメタリン酸ナ
トリウム、炭酸カリウム各々１．０重量部、ホウ酸０．
５重量部、ベントナイト１．５重量部、アルミナセメン
ト２．０重量部を予め混合した混和材を添加して混合し
た。それに外率にて水４５重量部を添加しセメントペー
ストを得た。このセメントペーストの粘度は１２Ｐａ・
ｓで、フロー値３２０ｍｍ、Ｐロートによる流下時間に
ついては、混練直後１６秒で流下して、１８０分経過し
ても１８秒と良好な流下特性を示し、固化体強度も２８
日で４２．４ＭＰａであった。 Example 2 100 parts by weight of blast furnace cement type B, 1.0 part by weight each of sodium hexametaphosphate and potassium carbonate, and 0.
An admixture in which 5 parts by weight, bentonite 1.5 parts by weight, and alumina cement 2.0 parts by weight were mixed in advance was added and mixed. 45 parts by weight of water was added thereto at an external rate to obtain a cement paste. The viscosity of this cement paste is 12 Pa
s, the flow value was 320 mm, and the flow-down time by the P funnel was 16 seconds immediately after the kneading and 18 seconds even after 180 minutes, showing a good flow-down property and a solidified body strength of 28.
It was 42.4 MPa in a day.
【００４６】実施例３ ＪＩＳＲ５２１０の普通セメント１００重量部に、ウル
トラポリリン酸ナトリウム１．０重量部、炭酸カリウム
１．５重量部、ホウ酸０．１重量部、ベントナイト２．
０重量部、アルミナセメント１．０重量部の構成にて混
合したものを添加して混合し、さらに外率にて水４５重
量部を加え、セメントペーストを得た。このセメントペ
ーストの特性は、１５Ｐａ・ｓの粘度で、フロー値３０
０ｍｍ、流下時間は混練直後１８秒で、１８０分後でも
２０秒の特性を示した。また固化体の圧縮強度も２８日
経過後で４３．５ＭＰａであった。 Example 3 100 parts by weight of JIS R5210 ordinary cement, 1.0 part by weight of sodium ultrapolyphosphate, 1.5 parts by weight of potassium carbonate, 0.1 part by weight of boric acid, and bentonite 2.
A mixture containing 0 parts by weight and 1.0 part by weight of alumina cement was added and mixed, and 45 parts by weight of water was added at an external ratio to obtain a cement paste. The characteristics of this cement paste are a viscosity of 15 Pa · s and a flow value of 30.
The characteristics were 0 mm, the flowing time was 18 seconds immediately after kneading, and the characteristic was 20 seconds even after 180 minutes. The compressive strength of the solidified body was 43.5 MPa after 28 days.
【００４７】実施例４ 高炉セメントＢ種１００重量部に、ヘキサメタリン酸ナ
トリウム、炭酸ナトリウム各々０．２重量部、ホウ酸
０．０７５重量部、ベントナイト１．０重量部、アルミ
ナセメント０．５重量部を予め混合したものを添加混合
して、外率にて４５重量部の水を添加してセメントペー
ストを得た。粘度は１１Ｐａ・ｓで、フロー値３１０ｍ
ｍで、流下時間は混練直後１５秒で３時間経過後も２０
秒という流下特性を示した。また、圧縮強度も２８日経
過後で４４．５ＭＰａを示した。 Example 4 100 parts by weight of blast furnace cement type B, 0.2 parts by weight each of sodium hexametaphosphate and sodium carbonate, 0.075 parts by weight of boric acid, 1.0 part by weight of bentonite, 0.5 part by weight of alumina cement. Was mixed in advance, and 45 parts by weight of water was added at an external ratio to obtain a cement paste. Viscosity is 11 Pa · s, flow value is 310 m
The flow-down time is 15 seconds immediately after kneading and 20 even after 3 hours have passed.
It showed a run-down characteristic of seconds. The compressive strength was 44.5 MPa after 28 days.
【００４８】実施例５ 高炉Ｂ種セメントに、ヘキサメタリン酸ナトリウム２重
量部、炭酸カリウム２重量部、ホウ酸０．７５重量部、
ベントナイト２．０重量部、アルミナセメント３．０重
量部を予め混合したものを添加混合して、外率にて４５
重量部の水を添加してセメントペーストを得た。ペース
トの粘度は１２Ｐａ・ｓ、フロー値は３００ｍｍを示し
た。Ｐロートによる流下時間は混練直後で１８秒の特性
を示し、１８０分経過してもその特性はほとんど変化せ
ず２０秒という結果であった。固化体特性としては、２
８日経過した固体化に４２．１ＭＰａの圧縮強度を得
た。 Example 5 2 parts by weight of sodium hexametaphosphate, 2 parts by weight of potassium carbonate, 0.75 parts by weight of boric acid were added to B type cement of blast furnace.
A mixture of 2.0 parts by weight of bentonite and 3.0 parts by weight of alumina cement was added and mixed, and the external ratio was 45.
Cement paste was obtained by adding parts by weight of water. The viscosity of the paste was 12 Pa · s and the flow value was 300 mm. The flow-down time by the P funnel showed a characteristic of 18 seconds immediately after kneading, and even after 180 minutes, the characteristic hardly changed and was 20 seconds. The characteristics of the solidified body are 2
A compression strength of 42.1 MPa was obtained upon solidification after 8 days.
【００４９】実施例６ 高炉Ｂ種セメント１００重量部に、ヘキサメタリン酸ナ
トリウム０．１重量部、炭酸カリウム０．１重量部、ホ
ウ酸０．０５重量部、ベントナイト５．０重量部、アル
ミナセメント０．５重量部を予め混合したものを添加混
合して、外率にて４５重量部の水を添加してセメントペ
ーストを得た。ペーストの粘度は１１Ｐａ・ｓ、フロー
値は３００ｍｍで、流下時間は混練直後が１８秒、１８
０分後で２３秒の結果を示した。固化体の圧縮強度は、
２８日養生後にて４５．２ＭＰａであった。 Example 6 100 parts by weight of blast furnace type B cement, 0.1 part by weight of sodium hexametaphosphate, 0.1 part by weight of potassium carbonate, 0.05 part by weight of boric acid, 5.0 parts by weight of bentonite, 0 parts of alumina cement A premix of 0.5 parts by weight was added and mixed, and 45 parts by weight of water was added at an external ratio to obtain a cement paste. The viscosity of the paste is 11 Pa · s, the flow value is 300 mm, and the flowing time is 18 seconds immediately after kneading, 18
The result of 23 seconds was shown 0 minutes later. The compressive strength of the solidified body is
After curing for 28 days, it was 45.2 MPa.
【００５０】実施例７ 普通セメント１００重量部に、ヘキサメタリン酸ナトリ
ウム０．５重量部、炭酸ナトリウム０．５重量部、ホウ
酸０．２重量部、ベントナイト２．５重量部、アルミナ
セメント１．０重量部を予め混合したものを添加混合し
て外率にて４５重量部の水を添加してセメントペースト
を得た。ペースト粘度は１０Ｐａ・ｓ、フロー値３２０
ｍｍであり、流下時間は混練直後で１５秒、１８０分後
にて１６秒という結果を示し、固化体の圧縮強度も２８
日養生後で４３．８ＭＰａという結果を得た。 Example 7 0.5 part by weight of sodium hexametaphosphate, 0.5 part by weight of sodium carbonate, 0.2 part by weight of boric acid, 2.5 parts by weight of bentonite, and 1.0 part of alumina cement to 100 parts by weight of ordinary cement. Premixed parts by weight were added and mixed, and 45 parts by weight of water was added at an external ratio to obtain a cement paste. Paste viscosity is 10 Pa · s, flow value is 320
The flow-down time was 15 seconds immediately after kneading and 16 seconds after 180 minutes, and the compressive strength of the solidified product was 28.
The result of 43.8 MPa was obtained after the day curing.
【００５１】実施例８ 高炉Ｂ種セメント１００重量部に、ウルトラポリリン
酸、炭酸ナトリウムを各々０．５重量部、ホウ酸０．２
重量部、ベントナイト２．５重量部、アルミナセメント
１．０重量部を予め混合したものを添加混合し、外率に
て４５重量部の水を添加してセメントペーストを得た。
ペースト粘度は１０Ｐａ・ｓ、フロー値３２０ｍｍで、
流下時間は混練直後で１６秒、１８０分後で１８秒とい
う結果を示した。固化体の２８日養生後の圧縮強度は４
４．４ＭＰａであった。 Example 8 To 100 parts by weight of blast furnace type B cement, 0.5 parts by weight each of ultrapolyphosphoric acid and sodium carbonate and 0.2 parts of boric acid were added.
A mixture in which 1 part by weight of bentonite, 2.5 parts by weight of bentonite, and 1.0 part by weight of alumina cement were mixed in advance was added and mixed, and 45 parts by weight of water was added at an external ratio to obtain a cement paste.
Paste viscosity is 10Pa · s, flow value is 320mm,
The flow-down time was 16 seconds immediately after kneading and 18 seconds after 180 minutes. The compressive strength of the solidified body after curing for 28 days is 4
It was 4.4 MPa.
【００５２】比較例１ 高炉Ｂ種セメント１００重量部に、外率にて水４５重量
部を添加してセメントペーストを得た。ペーストの粘度
２５Ｐａ・ｓで、フロー値２３０ｍｍを示し、流下時間
は混練直後で２３秒を示したものの、時間経過と共に流
下時間も長くなり、１８０分後にはロートから流出しな
いという結果に終わった。尚、圧縮強度は２８日養生後
で４２．７ＭＰａの特性を示した。 Comparative Example 1 45 parts by weight of water was added to 100 parts by weight of blast furnace type B cement at an external ratio to obtain a cement paste. The viscosity of the paste was 25 Pa · s, the flow value was 230 mm, and the flow-down time was 23 seconds immediately after kneading, but the flow-down time increased with the passage of time, and after 180 minutes, the flow did not flow out from the funnel. The compressive strength showed a characteristic of 42.7 MPa after curing for 28 days.
【００５３】比較例２ 高炉Ｂ種セメント１００重量部に、ヘキサメタリン酸ナ
トリウム０．５重量部、ホウ酸０．２重量部、ベントナ
イト２．５重量部、アルミナセメント１重量部を予め混
合したものを添加混合し、外率にて４５重量部の水を添
加してセメントペーストを得た。 Comparative Example 2 100 parts by weight of blast furnace type B cement were mixed in advance with 0.5 parts by weight of sodium hexametaphosphate, 0.2 parts by weight of boric acid, 2.5 parts by weight of bentonite, and 1 part by weight of alumina cement. The mixture was added and mixed, and 45 parts by weight of water was added at an external ratio to obtain a cement paste.
【００５４】１４Ｐａ・ｓの粘度と２８０ｍｍのフロー
値を示し、流下特性は混練直後１４秒という結果を示し
たものの１５分後では４５秒を要し、３０分後ではロー
ト中から流下はなくなった。圧縮強度は２８日養生後で
２５．６ＭＰａという結果であった。It showed a viscosity of 14 Pa · s and a flow value of 280 mm, and the flow-down characteristics showed a result of 14 seconds immediately after kneading, but it took 45 seconds after 15 minutes and no flow-down from the funnel after 30 minutes. . The compressive strength was 25.6 MPa after curing for 28 days.
【００５５】比較例３ 高炉Ｂ種セメント１００重量部に、炭酸カリウム０．５
重量部、ホウ酸０．２重量部、ベントナイト２．５重量
部、アルミナセメント１．０重量部を予め混合したもの
を添加混合し、外率にて４５重量部の水を添加しセメン
トペーストを得た。粘度５５Ｐａ・ｓ、フロー値２００
ｍｍで、混練直後の流下値は４５秒であったが、１５分
後には凝結し経時変化における流下値は得られなかっ
た。固化体の圧縮強度は２８日養生後で４３．７ＭＰａ
であった。 Comparative Example 3 100 parts by weight of blast furnace type B cement was mixed with 0.5 parts of potassium carbonate.
Parts by weight, 0.2 parts by weight of boric acid, 2.5 parts by weight of bentonite, 1.0 part by weight of alumina cement were added and mixed, and 45 parts by weight of water was added at an external ratio to obtain a cement paste. Obtained. Viscosity 55 Pa · s, flow value 200
In mm, the flow-down value immediately after kneading was 45 seconds, but after 15 minutes, coagulation occurred and no flow-down value due to aging was obtained. The compressive strength of the solidified body is 43.7 MPa after curing for 28 days.
Met.
【００５６】比較例４ 普通セメント１００重量部に、ヘキサメタリン酸ナトリ
ウム、炭酸カリウムを各々０．５重量部、ベントナイト
２．５重量部、アルミナセメント１．０重量部を予め混
合したものを添加混合し、外率にて水４５重量部を添加
してセメントペーストを得た。ペーストの粘度は１０Ｐ
ａ・ｓ、フロー値３１０ｍｍの特性を示し、流下時間は
混練直後〜１５分後までは１４秒の流下時間を示したも
のの、３０分後では７５秒と長くなり、１８０分後では
ロートに付着して流下しなかった。圧縮強度は、２８日
養生後で４３．８ＭＰａの値であった。 Comparative Example 4 To 100 parts by weight of ordinary cement, 0.5 parts by weight of sodium hexametaphosphate and potassium carbonate, 2.5 parts by weight of bentonite, and 1.0 part by weight of alumina cement were added and mixed in advance. Then, 45 parts by weight of water was added at an external ratio to obtain a cement paste. Paste viscosity is 10P
It shows a characteristic of a · s and flow value of 310 mm, and the flow-down time shows a flow-down time of 14 seconds from immediately after kneading to 15 minutes after, but it becomes long at 75 seconds after 30 minutes and adheres to the funnel after 180 minutes. And did not flow down. The compressive strength was 43.8 MPa after 28 days of curing.
【００５７】比較例５ 高炉Ｂ種セメント１００重量部に、一般的に市販されて
いる有機混和材（ナフタリンスルフォン酸系）を１．０
重量部と水を外率にて３５重量部添加してセメントペー
ストを得た。ペーストの粘度は１０．５Ｐａ・ｓ、フロ
ー値３００ｍｍで流下時間は混練直後〜３０分後迄は１
５〜１７秒の流下時間を示したのに対し、１８０分後に
はロートに付着して流下しなかった。圧縮強度は２８日
養生後で４５．４ＭＰａの特性を示した。 Comparative Example 5 100 parts by weight of blast furnace type B cement were mixed with 1.0 of a commercially available organic admixture (naphthalene sulfonic acid type).
35 parts by weight of water and 35 parts by weight of water were added to obtain a cement paste. The viscosity of the paste is 10.5 Pa · s, the flow value is 300 mm, and the flow-down time is 1 from immediately after kneading to after 30 minutes.
It showed a flow-down time of 5 to 17 seconds, but after 180 minutes, it adhered to the funnel and did not flow down. The compressive strength showed a characteristic of 45.4 MPa after curing for 28 days.
【００５８】以下に実施例と比較例を示し、本発明の固
型化材について表７と表８を参照して説明する。Examples and comparative examples will be shown below, and the solidifying material of the present invention will be described with reference to Tables 7 and 8.
【００５９】[0059]
【表７】 [Table 7]
【００６０】[0060]
【表８】 実施例９ 耐火性シャモット４０重量部、ＪＩＳＢ種高炉セメント
６０重量部にヘキサメタリン酸ナトリウム、炭酸カリウ
ムそれぞれ０．４重量部、硼酸０．１５重量部、ベント
ナイト２重量部、アルミナセメント０．５重量部を予め
混合した混和剤を添加混合して外率にて水２８重量部を
添加し、ペーストを得た。ペーストの粘度は１０ｄＰａ
・ｓでＰロートによる流下時間は混練直後で１６秒を示
し、１８０分後においても１８秒と特性的な低下はほと
んど認められなかった。硬化時間は始発で１０時間、終
結で２２時間を示し、圧縮強度は２８日後で４１．７Ｍ
Ｐａの特性を示した。[Table 8] Example 9 40 parts by weight of refractory chamotte, 60 parts by weight of JIS B type blast furnace cement, 0.4 parts by weight of sodium hexametaphosphate and potassium carbonate, 0.15 parts by weight of boric acid, 2 parts by weight of bentonite, 0.5 part by weight of alumina cement. 28% by weight of water was added at an external ratio to obtain a paste. Paste viscosity is 10 dPa
In s, the flow-down time by the P funnel was 16 seconds immediately after kneading, and was 18 seconds even after 180 minutes, showing almost no characteristic deterioration. The setting time was 10 hours at the beginning and 22 hours at the end, and the compressive strength was 41.7M after 28 days.
The characteristics of Pa are shown.
【００６１】実施例１０ 耐火性シャモット４０重量部、高炉セメントＢ種６０重
量部にヘキサメタリン酸ナトリウム１重量部、炭酸ナト
リウム０．８重量部、硼酸０．３重量部、ベントナイト
１重量部、アルミナセメント２重量部を予め混合した混
和剤を添加混合して外率にて水２８重量部を添加し、ペ
ーストを得た。ペーストの粘度は８ｄＰａ・ｓでＰロー
トによる流下時間は混練直後で１４秒、１８０分後で１
６秒であった。硬化時間は始発で８時間、終結で２０時
間を示し、圧縮強度は２８日後で４４．３ＭＰａという
特性を示した。[0061]Example 10 Refractory chamotte 40 parts by weight, blast furnace cement type B 60 weight
1 part by weight of sodium hexametaphosphate and sodium carbonate
0.8 parts by weight of lithium, 0.3 parts by weight of boric acid, bentonite
1 part by weight, 2 parts by weight of alumina cement were mixed in advance.
28 parts by weight of water is added at an external ratio and the mixture is added.
I got the most. The viscosity of the paste is 8 dPa · s and P low.
The flow-down time is 14 seconds immediately after kneading and 1 after 180 minutes.
It was 6 seconds. Curing time is 8 hours at the beginning and 20:00 at the end
And the compressive strength is 44.3 MPa after 28 days.
Characterized.
【００６２】実施例１１ 耐火性シャモット４０重量部、高炉セメントＢ種６０重
量部にウルトラポリリン酸ナトリウム０．４重量部、炭
酸カリウム０．１重量部、硼酸０．５重量部、ベントナ
イト１．５重量部、アルミナセメント１重量部を予め混
合した混和剤を添加混合して外率にて水２８重量部を添
加し、ペーストを得た。ペーストの粘度は１１ｄＰａ・
ｓでＰロートによる流下時間は混練直後で１７秒、１８
０分後で２０秒となった。硬化時間は始発で１１時間、
終結で２４時間、また圧縮強度は２８日後で４２．５Ｍ
Ｐａとなった。 Example 11 40 parts by weight of refractory chamotte, 60 parts by weight of blast furnace cement type B, 0.4 part by weight of sodium ultrapolyphosphate, 0.1 part by weight of potassium carbonate, 0.5 part by weight of boric acid, 1.5 parts of bentonite An admixture prepared by previously mixing 1 part by weight of alumina cement with 1 part by weight of alumina cement was added and mixed, and 28 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 11 dPa
s The P run-down time was 17 seconds immediately after kneading, 18 seconds
It was 20 seconds after 0 minutes. The initial curing time is 11 hours,
24 hours at the end and 42.5M in compressive strength after 28 days
It became Pa.
【００６３】実施例１２ 耐火性シャモット４０重量部、普通ポルトランドセメン
ト６０重量部にヘキサメタリン酸ナトリウム０．６重量
部、炭酸カリウム０．２重量部、硼酸０．１重量部、ベ
ントナイト０．５重量部、アルミナセメント０．３重量
部を予め混合した混和剤を添加混合して、外率にて水２
８重量部を添加し、ペーストを得た。ペーストの粘度は
１０ｄＰａ・ｓでＰロートによる流下時間は混練直後で
１６秒、１８０分後で１９秒となった。硬化時間は始発
で１４時間、終結で２５時間、圧縮強度においては２８
日後で４３．２ＭＰａとなった。 Example 12 40 parts by weight of refractory chamotte, 60 parts by weight of ordinary Portland cement, 0.6 part by weight of sodium hexametaphosphate, 0.2 part by weight of potassium carbonate, 0.1 part by weight of boric acid, 0.5 part by weight of bentonite. , 0.3 parts by weight of alumina cement were mixed in advance, and the admixture was mixed.
8 parts by weight was added to obtain a paste. The viscosity of the paste was 10 dPa · s, and the flow time by the P funnel was 16 seconds immediately after kneading and 19 seconds after 180 minutes. The curing time is 14 hours at the beginning and 25 hours at the completion, and the compressive strength is 28 hours.
After 4 days, it became 43.2 MPa.
【００６４】実施例１３ 耐火性シャモット５０重量部、高炉セメントＢ種５０重
量部にヘキサメタリン酸ナトリウム０．３重量部、炭酸
カリウム０．３重量部、硼酸０．１重量部、ベントナイ
ト２重量部、アルミナセメント０．５重量部を予め混合
した混和剤を添加混合して、外率にて水２７重量部を添
加し、ペーストを得た。ペーストの粘度は９ｄＰａ・ｓ
でＰロートを用いた流下時間は混練直後で１５秒、１８
０分後で１７秒となった。硬化時間は始発で１０時間、
終結で２３時間、圧縮強度においては２８日後で４０．
９ＭＰａとなった。 Example 13 50 parts by weight of refractory chamotte, 50 parts by weight of blast furnace cement type B, 0.3 part by weight of sodium hexametaphosphate, 0.3 part by weight of potassium carbonate, 0.1 part by weight of boric acid, 2 parts by weight of bentonite, An admixture in which 0.5 parts by weight of alumina cement was mixed in advance was added and mixed, and 27 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 9 dPa · s
The flow-down time using the P funnel was 15 seconds immediately after kneading, 18
It was 17 seconds after 0 minutes. The first curing time is 10 hours,
23 hours at the end and 40 days after 28 days in compressive strength.
It became 9 MPa.
【００６５】実施例１４ 耐火性シャモット５０重量部、高炉セメントＢ種５０重
量部にヘキサメタリン酸ナトリウム１重量部、炭酸カリ
ウム１重量部、硼酸０．０２５重量部、ベントナイト
０．３重量部、アルミナセメント０．３重量部を予め混
合した混和剤を添加混合して、外率にて水２７重量部を
添加し、ペーストを得た。ペーストの粘度は８ｄＰａ・
ｓでＰロートを用いた流下時間は混練直後で１４秒、１
８０分後で１８秒であった。硬化時間は始発で１２時
間、終結で２５時間となり、圧縮強度は２８日後で４
０．６ＭＰａであった。 Example 14 50 parts by weight of refractory chamotte, 50 parts by weight of blast furnace cement type B, 1 part by weight of sodium hexametaphosphate, 1 part by weight of potassium carbonate, 0.025 part by weight of boric acid, 0.3 part by weight of bentonite, alumina cement An admixture in which 0.3 parts by weight was previously mixed was added and mixed, and 27 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 8 dPa
The flow-down time using the P funnel was 14 seconds immediately after kneading, 1
It was 18 seconds after 80 minutes. The curing time was 12 hours at the beginning and 25 hours at the completion, and the compressive strength was 4 after 28 days.
It was 0.6 MPa.
【００６６】実施例１５ 耐火性シャモット５０重量部、普通ポルトランドセメン
ト５０重量部にヘキサメタリン酸ナトリウム０．６重量
部、炭酸ナトリウム０．５重量部、硼酸０．１重量部、
ベントナイト１重量部、アルミナセメント１重量部を予
め混合した混和剤を添加混合して、外率にて水２７重量
部を添加し、ペーストを得た。ペーストの粘度は９ｄＰ
ａ・ｓでＰロートを用いた流下時間は混練直後で１５
秒、１８０分後で１７秒であった。硬化時間は始発で９
時間、終結で２２時間、圧縮強度は４０．２ＭＰａであ
った。 Example 15 50 parts by weight of refractory chamotte, 50 parts by weight of ordinary Portland cement, 0.6 part by weight of sodium hexametaphosphate, 0.5 part by weight of sodium carbonate, 0.1 part by weight of boric acid,
An admixture in which 1 part by weight of bentonite and 1 part by weight of alumina cement were mixed in advance was added and mixed, and 27 parts by weight of water was added at an external ratio to obtain a paste. Paste viscosity is 9 dP
Flow time using P funnel in ass was 15 immediately after kneading.
Second, 180 minutes later was 17 seconds. Hardening time is 9
Hours, 22 hours after termination, the compressive strength was 40.2 MPa.
【００６７】実施例１６ 耐火性シャモット６０重量部、高炉セメントＢ種４０重
量部にヘキサメタリン酸ナトリウム０．２重量部、炭酸
カリウム０．３重量部、硼酸０．２重量部、ベントナイ
ト１．５重量部、アルミナセメント０．４重量部を予め
混合した混和剤を添加混合して、外率にて水２６重量部
を添加し、ペーストを得た。ペーストの粘度は８ｄＰａ
・ｓでＰロートを用いた流下時間は混練直後で１４秒、
１８０分後で２０秒であった。硬化時間は始発で１２時
間、終結で２４時間、圧縮強度は２８日後で３８．８Ｍ
Ｐａであった。 Example 16 60 parts by weight of refractory chamotte, 40 parts by weight of blast furnace cement type B, 0.2 parts by weight of sodium hexametaphosphate, 0.3 parts by weight of potassium carbonate, 0.2 parts by weight of boric acid, 1.5 parts by weight of bentonite Parts and 0.4 parts by weight of alumina cement were previously mixed and mixed, and 26 parts by weight of water was added at an external ratio to obtain a paste. Paste viscosity is 8 dPa
・ The flow-down time using the P funnel in s is 14 seconds immediately after kneading,
It was 20 seconds after 180 minutes. Hardening time is 12 hours at the beginning, 24 hours at the end, compressive strength is 38.8M after 28 days
It was Pa.
【００６８】実施例１７ 耐火性シャモット６０重量部、高炉セメントＢ種４０重
量部にウルトラポリリン酸ナトリウム０．６重量部、炭
酸ナトリウム０．４重量部、硼酸０．８重量部、ベント
ナイト０．８重量部、アルミナセメント１．５重量部を
予め混合した混和剤を添加混合して、外率にて水２７重
量部を添加し、ペーストを得た。ペーストの粘度は６ｄ
Ｐａ・ｓでＰロートを用いた流下時間は混練直後で１４
秒、１８０分後で１７秒であった。硬化時間は始発で１
０時間、終結で２４時間、圧縮強度は２８日後で３９．
７ＭＰａであった。 Example 17 60 parts by weight of refractory chamotte, 40 parts by weight of blast furnace cement type B, 0.6 part by weight of sodium ultrapolyphosphate, 0.4 part by weight of sodium carbonate, 0.8 part by weight of boric acid, 0.8 part of bentonite By weight, an admixture in which 1.5 parts by weight of alumina cement was previously mixed was added and mixed, and 27 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 6d
Flow time using P funnel at Pa · s was 14 immediately after kneading.
Second, 180 minutes later was 17 seconds. 1 time for curing
0 hours, 24 hours at termination, compressive strength after 28 days 39.
It was 7 MPa.
【００６９】比較例６ 耐火性シャモット７０重量部、高炉セメントＢ種３０重
量部にヘキサメタリン酸ナトリウム、炭酸カリウムそれ
ぞれ０．２重量部、硼酸０．０５重量部、ベントナイト
１重量部、アルミナセメント０．３重量部を予め添加し
たものを混合添加し、外率にて水２４重量部を添加して
ペーストを得た。ペーストの粘度、Ｐロートによる流下
時間は骨材の沈殿が大きく、測定できなかった。硬化時
間は始発で９時間、終結で２３時間であった。２８日後
の圧縮強度は３０．８ＭＰａで低い値となった。 Comparative Example 6 70 parts by weight of refractory chamotte, 30 parts by weight of blast furnace cement type B, 0.2 parts by weight each of sodium hexametaphosphate and potassium carbonate, 0.05 parts by weight of boric acid, 1 part by weight of bentonite, and 0. A mixture was prepared by adding 3 parts by weight in advance, and 24 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste and the flow-down time by the P funnel could not be measured because the aggregate was largely precipitated. The curing time was 9 hours at the start and 23 hours at the end. The compressive strength after 28 days was 30.8 MPa, which was a low value.
【００７０】比較例８ 耐火性シャモット４０重量部、高炉セメントＢ種６０重
量部にヘキサメタリン酸ナトリウム２重量部、炭酸ナト
リウム０．４重量部、硼酸０．１５重量部、ベントナイ
ト２重量部、アルミナセメント０．５重量部を予め添加
したものを混合添加し、外率にて水２８重量部を添加し
てペーストを得た。ペーストの粘度は６ｄＰａ・ｓでＰ
ロートを用いた流下時間は混練直後で１２秒、１８０分
後で１３秒であった。硬化時間は始発で２２時間、終結
で４３時間で、大幅な硬化遅延を示した。２８日後の圧
縮強度は３７．３ＭＰａであった。 Comparative Example 8 Refractory chamotte 40 parts by weight, blast furnace cement type B 60 parts by weight, sodium hexametaphosphate 2 parts by weight, sodium carbonate 0.4 parts by weight, boric acid 0.15 parts by weight, bentonite 2 parts by weight, alumina cement A mixture was prepared by adding 0.5 parts by weight in advance, and 28 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 6 dPa · s and P
The flow-down time using the funnel was 12 seconds immediately after kneading and 13 seconds after 180 minutes. The curing time was 22 hours at the beginning and 43 hours at the termination, showing a significant curing delay. The compressive strength after 28 days was 37.3 MPa.
【００７１】比較例９ 耐火性シャモット４０重量部、普通ポルトランドセメン
ト６０重量部にヘキサメタリン酸ナトリウム０．１重量
部、炭酸カリウム０．４重量部、硼酸０．１５重量部、
ベントナイト２重量部、アルミナセメント０．５重量部
を予め添加したものを混合添加し、外率にて水２８重量
部を添加してペーストを得た。ペーストの粘度は１７ｄ
Ｐａ・ｓでＰロートによる流下時間は混練直後で２３
秒、１８０分後には完全に流下しなかった。硬化時間は
始発で９時間、終結で２１時間、また、圧縮強度は２８
日後で４２．１ＭＰａであった。 Comparative Example 9 40 parts by weight of refractory chamotte, 60 parts by weight of ordinary Portland cement, 0.1 part by weight of sodium hexametaphosphate, 0.4 part by weight of potassium carbonate, 0.15 part by weight of boric acid,
2 parts by weight of bentonite and 0.5 parts by weight of alumina cement were added in advance, mixed and added, and 28 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 17d
Pa · s P run time is 23 immediately after kneading.
After 180 seconds, it did not completely flow down. The curing time was 9 hours at the beginning and 21 hours at the end, and the compressive strength was 28.
After 4 days, it was 42.1 MPa.
【００７２】比較例１０ 耐火性シャモット５０重量部、高炉セメントＢ種５０重
量部にヘキサメタリン酸ナトリウム０．３重量部、炭酸
カリウム２重量部、硼酸０．１重量部、ベントナイト
１．５重量部、アルミナセメント０．３重量部を予め添
加したものを混合添加し、外率にて水２７重量部を添加
してペーストを得た。ペーストの粘度は１０ｄＰａ・ｓ
でＰロートによる流下時間は混練直後で１６秒、３０分
後にはロートへの付着が大きく完全に流化しなかった。
硬化時間は始発で６時間、終結で１９時間、２８日後の
圧縮強度は４２．２ＭＰａであった。 Comparative Example 10 50 parts by weight of refractory chamotte, 50 parts by weight of blast furnace cement type B, 0.3 part by weight of sodium hexametaphosphate, 2 parts by weight of potassium carbonate, 0.1 part by weight of boric acid, 1.5 parts by weight of bentonite, A paste containing 0.3 parts by weight of alumina cement was mixed and added, and 27 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 10 dPa · s
The flow-down time by the P funnel was 16 seconds immediately after kneading, and the adhesion to the funnel was great after 30 minutes, and the solution was not completely flown.
The initial curing time was 6 hours, the final curing time was 19 hours, and the compressive strength after 28 days was 42.2 MPa.
【００７３】比較例１１ 耐火性シャモット５０重量部、高炉セメントＢ種５０重
量部にヘキサメタリン酸ナトリウム０．４重量部、炭酸
カリウム０．４重量部、硼酸０．２重量部、ベントナイ
ト４重量部、アルミナセメント０．５重量部を予め添加
したものを混合添加し、外率にて水２７重量部を添加し
てペーストを得た。ペーストの粘度は２２ｄＰａ・ｓで
Ｐロートによる流下時間は混練直後で２４秒、３０分後
では完全に流化しなかった。硬化時間は始発で１１時
間、終結で２３時間、２８日後の圧縮強度は３８．５Ｍ
Ｐａであった。 Comparative Example 11 50 parts by weight of refractory chamotte, 50 parts by weight of blast furnace cement type B, 0.4 parts by weight of sodium hexametaphosphate, 0.4 parts by weight of potassium carbonate, 0.2 parts by weight of boric acid, 4 parts by weight of bentonite, A paste in which 0.5 parts by weight of alumina cement was added in advance was mixed and added, and 27 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste was 22 dPa · s, and the P funnel flowed down for 24 seconds immediately after kneading, and did not completely flow after 30 minutes. The curing time was 11 hours at the beginning and 23 hours at the end, and the compressive strength after 28 days was 38.5M.
It was Pa.
【００７４】比較例１２ 耐火性シャモット６０重量部、高炉セメントＢ種４０重
量部にヘキサメタリン酸ナトリウム、炭酸ナトリウムそ
れぞれ０．２５重量部、硼酸０．１重量部、ベントナイ
ト１．５重量部、アルミナセメント３重量部を予め添加
したものを混合添加し、外率にて水２６重量部を添加し
てペーストを得た。ペーストの粘度は８ｄＰａ・ｓでＰ
ロートによる流下時間は混練直後で１５秒、３０分後に
２８秒を示したが、その後流動性を失った。硬化時間は
始発で６時間、終結で１９時間、２８日後の圧縮強度は
４５．０ＭＰａであった。 Comparative Example 12 60 parts by weight of refractory chamotte, 40 parts by weight of blast furnace cement type B, 0.25 parts by weight of sodium hexametaphosphate and sodium carbonate, 0.1 part by weight of boric acid, 1.5 parts by weight of bentonite, alumina cement 3 parts by weight was added in advance, mixed and added, and 26 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 8 dPa · s and P
The flow-down time by the funnel was 15 seconds immediately after kneading and 28 seconds after 30 minutes, but thereafter the fluidity was lost. The initial curing time was 6 hours, the final curing time was 19 hours, and the compressive strength after 28 days was 45.0 MPa.
【００７５】比較例１３ 耐火性シャモット６０重量部、高炉セメントＢ種４０重
量部にヘキサメタリン酸ナトリウム０．２５重量部、炭
酸カリウム０．２５重量部、硼酸０．１重量部、ベント
ナイト１．５重量部、アルミナセメント０．１重量部を
予め添加したものを混合添加し、外率にて水２６重量部
を添加してペーストを得た。ペーストの粘度は８ｄＰａ
・ｓでＰロートによる流下時間は混練直後で１５秒、１
８０分後に１７秒であった。硬化時間は始発で２７時
間、終結で４５時間を要し、大幅な硬化遅延を示した。
圧縮強度は２８日後で３９．４ＭＰａであった。 Comparative Example 13 60 parts by weight of refractory chamotte, 40 parts by weight of blast furnace cement type B, 0.25 part by weight of sodium hexametaphosphate, 0.25 part by weight of potassium carbonate, 0.1 part by weight of boric acid, 1.5 parts by weight of bentonite. Part, 0.1 part by weight of alumina cement were added in advance, and 26 parts by weight of water was added at an external ratio to obtain a paste. Paste viscosity is 8 dPa
・ In s, the flow-down time by P funnel is 15 seconds immediately after kneading.
It was 17 seconds after 80 minutes. The curing time was 27 hours at the beginning and 45 hours at the completion, showing a significant curing delay.
The compressive strength was 39.4 MPa after 28 days.
【００７６】比較例１４ 耐火性シャモット４０重量部、高炉セメントＢ種６０重
量部にヘキサメタリン酸ナトリウム０．４重量部、炭酸
カリウム０．４重量部、硼酸０．０２重量部、ベントナ
イト２重量部、アルミナセメント０．５重量部を予め添
加したものを混合添加し、外率にて水２６重量部を添加
してペーストを得た。ペーストの粘度は１０ｄＰａ・ｓ
でＰロートによる流下時間は混練直後で１６秒、１８０
分後では完全に流下しなかった。硬化時間は始発で１０
時間、終結で２３時間、２８日後の圧縮強度は４１．２
ＭＰａであった。 Comparative Example 14 Refractory chamotte 40 parts by weight, blast furnace cement type B 60 parts by weight, sodium hexametaphosphate 0.4 parts by weight, potassium carbonate 0.4 parts by weight, boric acid 0.02 parts by weight, bentonite 2 parts by weight, A paste in which 0.5 parts by weight of alumina cement had been added in advance was mixed and added, and 26 parts by weight of water was added at an external ratio to obtain a paste. The viscosity of the paste is 10 dPa · s
The P run-down time was 16 seconds immediately after kneading, 180
After a minute, it did not completely flow down. Cure time is 10
The compressive strength after 4 hours and 23 hours and 28 days after termination is 41.2.
It was MPa.
【００７７】比較例１５ 耐火性シャモット４０重量部、高炉セメントＢ種６０重
量部に外率にて水２８重量部を添加してペーストを得
た。ペーストの粘度は２１ｄＰａ・ｓでＰロートによる
流下時間は混練直後で１９秒、１８０分後では完全に流
下しなかった。硬化時間は始発で８時間、終結で１６時
間、２８日後の圧縮強度は４３．５ＭＰａであった。 Comparative Example 15 28 parts by weight of water was added to 40 parts by weight of refractory chamotte and 60 parts by weight of blast furnace cement type B at an external ratio to obtain a paste. The viscosity of the paste was 21 dPa · s, and the flow-down time by the P funnel was 19 seconds immediately after kneading, and did not flow completely after 180 minutes. The initial curing time was 8 hours, the final curing time was 16 hours, and the compressive strength after 28 days was 43.5 MPa.
【００７８】比較例１６ 耐火性シャモット４０重量部、高炉セメントＢ種６０重
量部に有機系混和剤（β−ナフタリンスルホン酸、ホル
マリン高縮合物）を０．５重量部を添加し、外率にて水
２６重量部を添加し、ペーストを得た。ペーストの粘度
は１３ｄＰａ・ｓでＰロートを用いた流下時間は混練直
後で１５秒、１８０分後には完全に流下しなかった。硬
化時間は始発で６時間、終結で１５時間、２８日後の圧
縮強度は４４．３ＭＰａであった。 Comparative Example 16 To 40 parts by weight of refractory chamotte and 60 parts by weight of blast furnace cement type B, 0.5 parts by weight of an organic admixture (β-naphthalenesulfonic acid, high-condensation product of formalin) was added, and the external ratio was adjusted. 26 parts by weight of water was added to obtain a paste. The viscosity of the paste was 13 dPa · s, and the flow time using the P funnel was 15 seconds immediately after kneading, and it did not flow completely after 180 minutes. The initial curing time was 6 hours, the final curing time was 15 hours, and the compressive strength after 28 days was 44.3 MPa.
【００７９】比較例１７ 高炉セメント１００重量部に外率にて水４５重量部を添
加し、ペーストを得た。ペーストの粘度は１９ｄＰａ・
ｓでＰロートを用いた流下時間は混練直後で２０秒、１
８０分後には完全に流下しなかった。硬化時間は始発で
７時間、終結で１０時間、２８日後の圧縮強度は４２．
７ＭＰａであった。 Comparative Example 17 45 parts by weight of water was added to 100 parts by weight of blast furnace cement at an external ratio to obtain a paste. The viscosity of the paste is 19 dPa
In Ps, the run-down time was 20 seconds immediately after kneading, 1
It did not completely flow down after 80 minutes. The curing time was 7 hours at the beginning and 10 hours at the termination, and the compressive strength after 28 days was 42.
It was 7 MPa.
【００８０】本発明の固型化材と高炉セメントＢ種単味
の２種を用いて模擬廃棄物を用いて充填固化を行った。
２００リットルドラム缶に予め金属パイプを配置し、上
記２種のセメントペーストをそれぞれ充填し、充填状況
と効果後の状態を観察した。条件及び結果は下記の表６
に示す通りである。The solidifying material of the present invention and the two types of blast furnace cement, Class B alone, were used to fill and solidify using simulated waste.
A metal pipe was placed in advance in a 200-liter drum and the above-mentioned two types of cement pastes were respectively filled, and the filling state and the state after the effect were observed. Conditions and results are shown in Table 6 below.
As shown in.
【００８１】[0081]
【表６】 上記表６の結果が示すように本発明の固型化材は凹凸や
亀裂の発生も全く確認されず、良好な固化体が得られ
た。しかし、骨材、混和剤を添加しないセメントの固化
体には表面の凹凸や表面、側面の亀裂の発生が認めら
れ、密封性に欠けることが明かになった。[Table 6] As shown by the results in Table 6 above, the solidified material of the present invention showed no irregularities or cracks, and a good solidified body was obtained. However, it was revealed that the solidified body of cement without addition of the aggregate and the admixture had surface irregularities and cracks on the surface and side surfaces, and lacked in hermeticity.
【００８２】以上をまとめると、表１及び２のようにな
る。Tables 1 and 2 summarize the above.
【００８３】[0083]
【表１】 [Table 1]
【００８４】[0084]
【表２】 本発明の混和材を添加混合した高炉Ｂ種セメントと全く
添加しない高炉Ｂ種セメントの２種を用いて模擬廃棄体
を用いて充填固化の実験を行った。[Table 2] Experiments of filling and solidification were conducted using a simulated waste using two types of blast furnace type B cement to which the admixture of the present invention was added and mixed, and blast furnace type B cement to which no admixture was added.
【００８５】複数の２００リットルドラム缶に予め金属
パイプを配置し、上記２種のセメントペーストを各々充
填し、充填情況と硬化後の状態を観察した。Metal pipes were previously placed in a plurality of 200-liter drums, and the above-mentioned two kinds of cement pastes were respectively filled therein, and the filling situation and the state after curing were observed.
【００８６】実験の条件並びに結果は表３に示す通りで
ある。The experimental conditions and results are shown in Table 3.
【００８７】[0087]
【表３】 表３の結果が示す様に、本発明の混和材を添加したセメ
ントは凸凹の亀裂の発生が全く認められず、良好な固化
体が得られた。[Table 3] As shown by the results in Table 3, the cement containing the admixture of the present invention did not show any uneven cracks, and a good solidified product was obtained.
【００８８】しかし、混和材を添加しないセメントによ
る固化体においては、表面の凸凹と共に亀裂の発生が認
められ、密封性に欠けることが明らかとなった。However, in the solidified product of cement without the addition of the admixture, the occurrence of cracks as well as the surface unevenness was observed, and it was revealed that the hermeticity was insufficient.
【００８９】充填の様子を具体的に調べるために、直径
５ｃｍの円柱体の模擬廃棄物を２００リットルドラム缶
に密充填した状態で上からセメント材を流し込むと、従
来ではドラム缶の半分の高さから底部にかけて中心部に
２０〜３０ｃｍ径ほどの全く充填されない部分が存在し
たが、本願発明ではそのような空隙は全く生じなかっ
た。In order to specifically examine the state of filling, when the cement waste was poured from the top in a state in which a simulated waste of a cylindrical body having a diameter of 5 cm was densely packed in a 200-liter drum, from the half height of the drum in the conventional case. Although there was a portion of about 20 to 30 cm in diameter that was not filled at all in the central portion extending to the bottom portion, such voids did not occur at all in the present invention.
【００９０】また、深さ５ｃｍの５ｍｍ幅のスリットを
無数に有する１０ｃｍ角の角材を２０〜３０ｃｍに切断
したものを２００リットルドラム缶にランダムに入るだ
け詰め、セメント材を流し込むと、従来では、ドラム缶
上部のスリットは約８０％充填され、下部のスリットは
約２０％ほど充填されたのに対し、本願発明によれば、
上部ではほぼ１００％、下部でも約９５％充填できた。Further, if a square piece of 10 cm square having an infinite number of slits of 5 mm width of 5 cm in depth is cut into 20 to 30 cm, it is packed randomly into a 200 liter drum and the cement material is poured. The upper slit is about 80% filled and the lower slit is about 20% filled, whereas according to the present invention,
Almost 100% was filled in the upper part, and about 95% was filled in the lower part.
【００９１】さらに、実際の廃材を想定した３０〜４０
ｍｍ大のゴム栓材、７５〜１２５ｍｍ径×３００〜５０
０ｍｍの金属パイプ、１５〜４０ｍｍの樹脂性ペレット
をほぼ均等の割合で混合し、ドラム缶に振動を加えなが
ら、３／４まで詰め、その後上からセメント剤を充填す
ると、従来品は廃材間に３ｍｍ以下の空隙を生じやす
く、また、下方部では全く充填されていないところもあ
り、全体の充填率は約８０％であったが、本願発明で
は、２ｍｍ以上の空隙はほとんど無く、また、全く充填
されていないところは無く、全体の充填率は約９６％で
あった。Furthermore, 30 to 40 assuming actual waste materials
mm-sized rubber plug material, 75-125 mm diameter x 300-50
By mixing 0 mm metal pipe and 15-40 mm resin pellets at an almost even ratio, filling the drum can with vibration until it is 3/4 filled, and then filling the cement agent from above, the conventional product is 3 mm between waste materials. The following voids are apt to occur, and there are some places that are not filled at all in the lower part, and the overall filling rate was about 80%. However, in the present invention, there are almost no voids of 2 mm or more, and there is no filling. There was nothing left unfilled, and the total filling rate was about 96%.
【００９２】[0092]
【表４】 [Table 4]
【００９３】[0093]
【表５】 表５に示す組成を有する混和材を添加したセメントにつ
いて核種吸着性を示す分配係数を測定した結果、本発明
による無機混和材を添加したセメントの核種吸着性能は
表４に示すように一般の普通セメントのものと比較して
格段に優れていることが判明した。[Table 5] As a result of measuring the partition coefficient showing the nuclide adsorbability of the cement to which the admixture having the composition shown in Table 5 is added, the nuclide adsorbing performance of the cement to which the inorganic admixture according to the present invention is added is as shown in Table 4. It was found to be significantly superior to that of cement.
【００９４】[0094]
【発明の効果】このように、本発明による無機混和材
は、有機系分散剤（長期的にみると劣化の恐れがあり、
かつ、その際にガスを発生し構造物自体の緻密性を低下
させる恐れのある有機系分散剤）を全く添加せず、ま
た、現在までに全くと言っていいほど例を見ない無機系
材料のみのセメント用混和材であるので、放射性廃棄物
の固型化材料として使用する場合は、セメントに混和材
を添加するだけで、流動性の極めて高いセメントが容易
に得られ、放射性廃棄物を完全に充填固化できる。した
がって、十分なポットライフが確保でき、亀裂が発生し
がたく、かつ、凝結時間を短縮できる。その結果、シス
テム構成を簡単なものにでき、システム化が容易であ
る。As described above, the inorganic admixture according to the present invention is an organic dispersant (which may deteriorate in the long term,
In addition, no inorganic dispersant that may generate gas at that time and may reduce the denseness of the structure itself) is not added at all, and there is no example of an inorganic material to date. Since it is only an admixture for cement, when it is used as a solidifying material for radioactive waste, it is possible to easily obtain cement with extremely high fluidity by simply adding the admixture to the cement and to eliminate radioactive waste. Can be completely filled and solidified. Therefore, a sufficient pot life can be secured, cracks hardly occur, and the setting time can be shortened. As a result, the system configuration can be simplified and systematization is easy.
───────────────────────────────────────────────────── 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 28/02 28/06 Ｇ２１Ｆ 9/16 ５２１ Ｆ (72)発明者 稲熊 正彦 神奈川県横浜市磯子区新杉田町８番地 株 式会社東芝横浜事業所内 (72)発明者 豊原 尚実 神奈川県川崎市幸区小向東芝町１番地 株 式会社東芝研究開発センター内 (72)発明者 佐藤 龍明 神奈川県川崎市幸区小向東芝町１番地 株 式会社東芝研究開発センター内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication C04B 28/02 28/06 G21F 9/16 521 F (72) Inventor Masahiko Inuma Isogo, Yokohama, Kanagawa Shin-Sugita-cho, Ward 8 Incorporation company Toshiba Yokohama Works (72) Inventor Naomi Toyohara Komukai-shi, Kawasaki-shi, Kanagawa 1 Komukai Toshiba-cho, Toshiba Research & Development Center (72) Inventor Tatsuaki Sato Kawasaki, Kanagawa Komukai Toshiba-cho, Sachi-ku, Yokohama-shi Incorporated company Toshiba Research and Development Center
Claims (1)
部、炭酸塩化合物０．１〜２重量部、ホウ酸０．０５〜
１重量部、ベントナイト０．５〜５重量部、アルミナセ
メント０．５〜４重量部からなるセメント用無機混和
材。1. Condensed sodium phosphate 0.1-2 parts by weight, carbonate compound 0.1-2 parts by weight, boric acid 0.05-
An inorganic admixture for cement comprising 1 part by weight, bentonite 0.5 to 5 parts by weight, and alumina cement 0.5 to 4 parts by weight.
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|---|---|---|---|
| JP33237394A JP3372684B2 (en) | 1994-12-14 | 1994-12-14 | Cement inorganic admixture for nuclear waste |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33237394A JP3372684B2 (en) | 1994-12-14 | 1994-12-14 | Cement inorganic admixture for nuclear waste |
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| Publication Number | Publication Date |
|---|---|
| JPH08166492A true JPH08166492A (en) | 1996-06-25 |
| JP3372684B2 JP3372684B2 (en) | 2003-02-04 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09211194A (en) * | 1996-01-30 | 1997-08-15 | Toshiba Corp | Method for solidifying radioactive waste |
| JPH1172594A (en) * | 1997-08-29 | 1999-03-16 | Toshiba Corp | Solidification method of radioactive waste |
| GB2404378A (en) * | 2003-07-30 | 2005-02-02 | Bj Services Co | Storable cementitious slurries containing boric acid and method of using the same |
| JP2005315641A (en) * | 2004-04-27 | 2005-11-10 | Toshiba Corp | Treating method and treating device of decontamination waste liquid |
| JP2006199821A (en) * | 2005-01-20 | 2006-08-03 | Mitsubishi Materials Corp | Quick hardening grouting material |
| JP2008024925A (en) * | 2006-06-23 | 2008-02-07 | Chikosha:Kk | Plastic grout material and method for producing the same |
| CN108585890A (en) * | 2018-05-30 | 2018-09-28 | 雷春生 | a kind of ceramic dispersants |
-
1994
- 1994-12-14 JP JP33237394A patent/JP3372684B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09211194A (en) * | 1996-01-30 | 1997-08-15 | Toshiba Corp | Method for solidifying radioactive waste |
| JPH1172594A (en) * | 1997-08-29 | 1999-03-16 | Toshiba Corp | Solidification method of radioactive waste |
| GB2404378A (en) * | 2003-07-30 | 2005-02-02 | Bj Services Co | Storable cementitious slurries containing boric acid and method of using the same |
| US6907928B2 (en) | 2003-07-30 | 2005-06-21 | Bj Services Company | Storable cementitious slurries containing boric acid and method of using the same |
| GB2404378B (en) * | 2003-07-30 | 2007-06-20 | Bj Services Co | Storable cementitious slurries containing boric acid and method of using the same |
| JP2005315641A (en) * | 2004-04-27 | 2005-11-10 | Toshiba Corp | Treating method and treating device of decontamination waste liquid |
| JP2006199821A (en) * | 2005-01-20 | 2006-08-03 | Mitsubishi Materials Corp | Quick hardening grouting material |
| JP2008024925A (en) * | 2006-06-23 | 2008-02-07 | Chikosha:Kk | Plastic grout material and method for producing the same |
| CN108585890A (en) * | 2018-05-30 | 2018-09-28 | 雷春生 | a kind of ceramic dispersants |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3372684B2 (en) | 2003-02-04 |
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