JP2012140279A - Calcium aluminate - Google Patents
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Abstract
【課題】 本発明は、急硬性や急結性等の発現作用を損なうことなく、優れた易粉砕性を具備せしめた非晶質カルシウムアルミネートクリンカの提供及びセメントペースト、モルタル又はコンクリート等の表面にポップアウト等を生じさせることなく急結性又は急硬性を付与することができる急硬性や急結性等の発現作用を呈することができる非晶質カルシウムアルミネート系混和材を提供する。
【解決手段】 単位容積あたりの充填嵩密度が０．１〜１．０ｋｇ／Ｌの中空状粒子であることを特徴とする非晶質カルシウムアルミネートクリンカ、および該カルシウムアルミネートクリンカをブレーン比表面積２５００ｃｍ2／ｇ以上に粉砕してなる非晶質カルシウムアルミネート系混和材。
【選択図】 なしPROBLEM TO BE SOLVED: To provide an amorphous calcium aluminate clinker provided with an excellent pulverization property without impairing an action of rapid hardening, quick setting or the like, and a surface of cement paste, mortar, concrete or the like The present invention provides an amorphous calcium aluminate-based admixture that can exhibit rapid hardening or rapid hardening without causing pop-out or the like, and can exhibit effects such as rapid hardening and rapid hardening.
SOLUTION: Amorphous calcium aluminate clinker characterized by being hollow particles having a filling bulk density per unit volume of 0.1 to 1.0 kg / L, and a specific surface area of Blaine using the calcium aluminate clinker An amorphous calcium aluminate-based admixture obtained by grinding to 2500 cm 2 / g or more.
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Description
本発明は、水硬性無機物質に急硬性や急結性を付与したり、耐火性を付与することに活用されるカルシウムアルミネート系物質に関する。 The present invention relates to a calcium aluminate-based material that is utilized for imparting rapid hardening or quick setting to a hydraulic inorganic material or imparting fire resistance.
セメント等の水硬性無機物質に急硬性や急結性を付与する物質として、また不定形耐火材料として用いられるアルミナセメントの有効成分としてカルシウムアルミネート系物質が使用されている。カルシウムアルミネート系物質は構造上、結晶質と非晶質のものに大別され、両者が共存する状態のものも存在する。このうち実質的に非晶質のカルシウムアルミネート系物質は、結晶質または低ガラス化率構造のカルシウムアルミネート系物質よりも反応活性が高く、急結性や急硬性の付与には有利である。（例えば、特許文献１参照）しかるに、非晶質のカルシウムアルミネート系物質は堅く、また従来の原料溶融化プロセス手法においては一般に緻密で比較大きな塊状物（クリンカ）として得られ易い。適度な反応活性の非晶質カルシウムアルミネート系物質を得るには、このようなクリンカを粉砕し、望ましくは整粒する必要があり、またより高い反応活性を得るには粉砕を進め微粉化して比表面積を増大させる必要もあるが（例えば、特許文献２参照）、かかる実情から非晶質カルシウムアルミネートの粉砕性は悪く、粉砕には多大な労力やコストを要した。このように難粉砕性であるが故に、所望のブレーン比表面積（粒度）にすべく粉砕を行っても、ボールミル粉砕等の通常の粉砕手法では３００μｍを超えるグリッド（粗粒）が粉砕物中に混在し易い。グリッドは内部と表面近傍では注水後の水和反応に多大なタイムラグが発生し、凝結終局面で遅れ水和反応が起こし易く、モルタルやコンクリート表面のポップアウトの主たる原因になる。グリッド混入を防ぎ、適度な反応活性の非晶質カルシウムアルミネート系混和材を得るには、粉砕でクリンカをできるだけ斑無く微細化できる必要がある。クリンカ原料を十分溶融させずに急冷すると反応未達原料残存により粉砕し易くなる可能性があるものの、非晶質カルシウムアルミネートの生成も未達となり、所望の凝結・硬化特性が得られない。 Calcium aluminate-based materials have been used as active ingredients of alumina cement used as an amorphous refractory material as a material that imparts rapid hardening and quick setting properties to hydraulic inorganic materials such as cement. Calcium aluminate-based materials are broadly divided into crystalline and amorphous materials in terms of structure, and some exist in a state where both coexist. Of these, the substantially amorphous calcium aluminate material has a higher reaction activity than the crystalline or low vitrification structure calcium aluminate material, and is advantageous for imparting quick setting and hardening properties. . (For example, see Patent Document 1) However, amorphous calcium aluminate-based materials are hard, and are generally easily obtained as dense and comparatively large lumps (clinker) in the conventional raw material melting process method. In order to obtain an amorphous calcium aluminate material having an appropriate reaction activity, it is necessary to pulverize such a clinker, desirably to adjust the particle size, and to obtain a higher reaction activity, the pulverization is advanced to fine powder. Although it is necessary to increase the specific surface area (see, for example, Patent Document 2), the grindability of the amorphous calcium aluminate is poor from such a situation, and much labor and cost are required for grinding. Because of the difficulty in pulverization, even when pulverization is performed to obtain a desired Blaine specific surface area (particle size), a grid (coarse particles) exceeding 300 μm is present in the pulverized product by a normal pulverization method such as ball milling. Easy to mix. In the grid and in the vicinity of the surface, a great time lag occurs in the hydration reaction after water injection, and a delayed hydration reaction tends to occur at the final stage of setting, which is a major cause of pop-out of mortar and concrete surfaces. In order to prevent grid mixing and obtain an amorphous calcium aluminate-based admixture with moderate reaction activity, it is necessary to make the clinker as fine as possible by grinding. If the clinker raw material is quenched without being sufficiently melted, it may be easily pulverized due to the reaction unreachable raw material remaining, but the formation of amorphous calcium aluminate will not be achieved, and the desired setting and hardening characteristics will not be obtained.
本発明は、急硬性や急結性等の発現作用を損なわせることなく、優れた易粉砕性を備えた非晶質カルシウムアルミネートクリンカを提供することであり、またセメントペースト、モルタル又はコンクリート等の表面にポップアウトを生じさせることなく急結性又は急硬性を付与できる非晶質カルシウムアルミネート系混和材の提供を課題とする。 The present invention is to provide an amorphous calcium aluminate clinker having excellent grindability without impairing the effects of rapid hardening, quick setting, etc., and cement paste, mortar, concrete, etc. It is an object of the present invention to provide an amorphous calcium aluminate-based admixture capable of imparting quick setting or quick hardening without causing pop-out on the surface of the material.
本発明者は、前記課題解決のため検討を重ねた結果、加熱溶融を経て得られる非晶質カルシウムアルミネートを特定の形状構造にせしめることで、容易に粉砕できたことから本発明を完成させた。 As a result of repeated investigations for solving the above problems, the present inventor completed the present invention because amorphous calcium aluminate obtained through heating and melting could be easily pulverized by making it into a specific shape structure. It was.
即ち、本発明は、次の（１）〜（３）で表す非晶質カルシウムアルミネートクリンカおよび（４）で表す非晶質カルシウムアルミネート系混和材である。
（１） 単位容積あたりの充填嵩密度が０．１〜１．０（ｋｇ／Ｌ）の中空状粒子であることを特徴とする非晶質カルシウムアルミネートクリンカ。
（２） フリーカーボンを含む原料を溶融発泡させてなる中空状粒子であることを特徴とする前記（１）の非晶質カルシウムアルミネートクリンカ。
（３） フリーカーボン含有量が０．００１〜１質量％の中空状粒子であることを特徴とする前記（１）又は（２）の非晶質カルシウムアルミネートクリンカ。
（４） 前記（１）〜（３）何れかのカルシウムアルミネートクリンカをブレーン比表面積２５００ｃｍ2／ｇ以上に粉砕してなる非晶質カルシウムアルミネート系混和材。
That is, the present invention is an amorphous calcium aluminate clinker represented by the following (1) to (3) and an amorphous calcium aluminate-based admixture represented by (4).
(1) An amorphous calcium aluminate clinker, which is a hollow particle having a filling bulk density per unit volume of 0.1 to 1.0 (kg / L).
(2) The amorphous calcium aluminate clinker according to (1) above, which is hollow particles obtained by melting and foaming a raw material containing free carbon.
(3) The amorphous calcium aluminate clinker according to (1) or (2), wherein the amorphous calcium aluminate clinker is a hollow particle having a free carbon content of 0.001 to 1% by mass.
(4) An amorphous calcium aluminate-based admixture obtained by pulverizing any of the calcium aluminate clinker (1) to (3) to a Blaine specific surface area of 2500 cm 2 / g or more.
本発明によれば、極めて粉砕し易い非晶質カルシウムアルミネートクリンカが容易に得られるため、特殊な粉砕装置の使用や膨大な粉砕エネルギーを要すことなく、また労力や時間も節減でき、所望の粒度に粉砕することができる。しかも、このクリンカ粉砕物は従来の非晶質カルシウムアルミネートに勝るとも劣らない急結性や急硬性を発現することが可能である。 According to the present invention, an amorphous calcium aluminate clinker that is extremely easily pulverized can be easily obtained, so that it does not require the use of a special pulverizing apparatus and enormous pulverizing energy, and labor and time can be reduced, and the desired Can be pulverized to a particle size of. Moreover, this clinker pulverized product can exhibit quick setting and rapid hardening that are not inferior to those of conventional amorphous calcium aluminate.
本発明でいう非晶質カルシウムアルミネートとは、主要化学成分としてＣａＯとＡｌ2Ｏ3を含む水和活性物質のうち、実質的に結晶構造となっていないものである。ただし、予め原料に加えられた結晶質発泡助剤の加熱後の残存物や微量の不可避結晶質物質などの混在は許容される。好ましくは実質的に結晶構造となっていないものの目安として概ね９５％以上のガラス化率のものとする。化学成分としてのＣａＯとＡｌ2Ｏ3の配合上のモル比率は特に限定されないが、急結性や急硬性を十分発現させる上では、ＣａＯとＡｌ2Ｏ3の配合上のモル比；ＣａＯ／Ａｌ2Ｏ3が１．０〜３．０であるものが好ましい。またＣａＯとＡｌ2Ｏ3に加えて他の化学成分が加わったものも広義のカルシウムアルミネートとして本発明では対象となる。このような成分は急結性や急硬性の発現に対し阻害要因とならない限り特に限定されない。具体的には、例えばＳＯ4、ＣａＦ2、Ｎａ2Ｏ、Ｌｉ2Ｏ、Ｋ2Ｏ等が挙げられる。 The amorphous calcium aluminate referred to in the present invention is a substance having substantially no crystal structure among hydration active substances containing CaO and Al 2 O 3 as main chemical components. However, mixing of the crystalline foaming auxiliary added in advance to the raw material after heating or a trace amount of inevitable crystalline substances is allowed. Preferably, it has a vitrification rate of approximately 95% or more as a guide for a material that has substantially no crystal structure. The molar ratio of the compound of CaO and Al 2 O 3 as a chemical component is not particularly limited. However, in order to sufficiently develop the quick setting property or the rapid hardening property, the molar ratio of the compound of CaO and Al 2 O 3 ; CaO / those al 2 O 3 is 1.0 to 3.0 is preferred. The ones in addition to CaO and Al 2 O 3 applied by other chemical components also of interest in the present invention as broadly calcium aluminate. Such a component is not particularly limited as long as it does not become an inhibiting factor for the expression of rapid setting or rapid hardening. Specifically, for example SO 4, CaF 2, Na 2 O, Li 2 O, K 2 O , and the like.
本発明の非晶質カルシウムアルミネートクリンカは、前記のような非晶質カルシウムアルミネートの加熱溶融物を冷却したものであって、単位容積あたりの充填嵩密度が０．１〜１．０（ｋｇ／Ｌ）の中空状粒子である。ここで中空状粒子とは粒子内部に空隙を有し、概ね殻状の構造の粒子をいう。該空隙は粒子表面に開口せずに密閉された空隙であるのが好ましい。空隙は望ましくは１つの密閉空隙が良いが、単数又は複数の隔壁で仕切られた空隙群からなるものでも良い。複数の空隙が粒子内部で連通しているものでも良い。溶融時の中空粒子形成過程で一部が破泡した構造の殻となったもの、また外部に開口した空隙が共存する粒子であっても良い。好ましくはこれらの不完全殻構造の中空粒子は粉砕後の使用時の反応活性が劣る可能性もあることから、その存在が個数で全体の概ね３０％以下となっているものを使用する。また、空隙を隔てる隔壁が多いものほど、また隔壁や殻の厚み又は隔壁や殻の容積は何れも小さいほど粒子としては堅牢化が進んでいないため、粉砕が行い易い。また、本発明の非晶質カルシウムアルミネートクリンカの大きさは特に制限されないが、後の粉砕処理を考慮すると概ね０．０１〜５ｍｍにすれば、高い粉砕効率で粉砕できることから好ましい。クリンカの大きさは加熱方法である程度調整できる。 The amorphous calcium aluminate clinker of the present invention is obtained by cooling a heated melt of amorphous calcium aluminate as described above, and has a filling bulk density per unit volume of 0.1 to 1.0 ( kg / L) hollow particles. Here, the hollow particles refer to particles having a substantially shell-like structure having voids inside the particles. The voids are preferably voids that are sealed without opening on the particle surface. The air gap is desirably one sealed air gap, but may be a group of air gaps partitioned by one or a plurality of partition walls. A plurality of voids communicating with each other inside the particle may be used. It may be a shell having a structure in which a part of the hollow particle is broken during melting, or a particle in which voids opened to the outside coexist. Preferably, these hollow particles having an incomplete shell structure may be inferior in the reaction activity during use after pulverization, so that the number thereof is approximately 30% or less of the total. Further, as the number of partition walls separating the voids increases, and the thickness of the partition wall or shell or the volume of the partition wall or shell decreases, the solidification of the particles does not progress and the pulverization is easy. In addition, the size of the amorphous calcium aluminate clinker of the present invention is not particularly limited, but considering the subsequent pulverization treatment, it is preferably about 0.01 to 5 mm because it can be pulverized with high pulverization efficiency. The size of the clinker can be adjusted to some extent by the heating method.
また、中空殻状構造の殻である粒子表層部の肉厚は、薄い方が好ましいが、特に制限されるものではない。中空状粒子自体の空隙率は粉砕性に影響を及ぼすが、多数の小粒子に対する空隙率の計測は容易ではない。そこで本発明では、粒子の空隙状況の把握可能な代替指標として、該粒子の単位容積あたりの充填嵩密度を規定する。単位容積あたりの充填嵩密度（ρｂ）は、一定の内容積（Ｖ）を有する容器内に、該中空状粒子を振動充填させ、容器上面まで充填させた中空状粒子の質量（Ｗ）から算出した密度（ρｂ＝Ｗ／Ｖ）である。粒径が同様のものでは、この充填嵩密度が低いものほどそれに比例して空隙率が高くなる。本発明では、クリンカ粒子の充填嵩密度を０．１〜１．０（ｋｇ／Ｌ）とする。充填嵩密度が１．０を超えると、概して空隙率が低くなり、厚肉の殻を有すものとなるため粉砕し難くなり好ましくない。また充填嵩密度が０．１未満では、軽量化し過ぎるためクリンカ粉砕時に高い粉砕エネルギーが生じ難く、その結果、実質未粉砕の粒子が採取される可能性があるので好ましくない。 In addition, the thickness of the particle surface layer portion, which is a shell of a hollow shell structure, is preferably thin, but is not particularly limited. The porosity of the hollow particles themselves affects the grindability, but it is not easy to measure the porosity for a large number of small particles. Therefore, in the present invention, the packing bulk density per unit volume of the particles is defined as an alternative index that can grasp the void state of the particles. The filling bulk density (ρb) per unit volume is calculated from the mass (W) of the hollow particles in which the hollow particles are vibrated and filled up to the upper surface of the container in a container having a constant internal volume (V). Density (ρb = W / V). When the particle size is the same, the lower the filling bulk density, the higher the porosity in proportion. In the present invention, the filling bulk density of the clinker particles is 0.1 to 1.0 (kg / L). When the filling bulk density exceeds 1.0, the porosity is generally low and a thick shell is formed, which makes it difficult to pulverize. Further, if the filling bulk density is less than 0.1, it is not preferable because the weight is excessively reduced, so that high pulverization energy is hardly generated at the time of clinker pulverization.
また、本発明の非晶質カルシウムアルミネートクリンカは、このような中空状粒子からなるクリンカであって、フリーカーボン（化合物でないＣ単体）を含む原料を溶融発泡させてなる中空状粒子である。溶融に供される原料に加えられるフリーカーボンは、例えばグラファイト、無定形炭素、カーボンブラック、活性炭などを挙げることができる。また、原料中のフリーカーボン含有量は、好ましくは総原料中０．００１〜１質量％とする。総原料中の含有量が０．００１質量％未満だと非晶質カルシウムアルミネートクリンカが中空殻状になり難いので適当でなく、また１質量％を超えると急結性や急硬性が低下することがあるので適当でない。溶融に供される原料のうち、フリーカーボン以外は、非晶質カルシウムアルミネート製造に際して通常使用されるような原料であれば特に限定されない。具体例を挙げれば、ＣａＯ源として炭酸カルシウム、消石灰、生石灰など、Ａｌ2Ｏ3源としてアルミナ、バン土頁岩、ボーキサイト、ベーマイト、ギブサイトなど、またＣａＯとＡｌ2Ｏ3をの両者を化学成分として含有する高炉スラグ等も使用可能である。さらにＣａＯやＡｌ2Ｏ3以外の化学成分として、ＳＯ4、ＣａＦ2、Ｎａ2Ｏ、Ｌｉ2Ｏ、Ｋ2Ｏ、ＭｇＯ、Ｆｅ2Ｏ3等が原料中に含まれているものでも良い。ＣａＯ源とＡｌ2Ｏ3源の含有割合は特に制限されないが、好ましくは、ＣａＯとＡｌ2Ｏ3の化学成分としての含有モル比；ＣａＯ／Ａｌ2Ｏ3で１．０〜３．０とする。含有モル比；ＣａＯ／Ａｌ2Ｏ3が１．０未満あるいはＣａＯ／Ａｌ2Ｏ3が３．０を超えると急結性や急硬性が低下することがあるので適当でない。 Further, the amorphous calcium aluminate clinker of the present invention is a clinker composed of such hollow particles, and is a hollow particle formed by melting and foaming a raw material containing free carbon (a C simple substance which is not a compound). Examples of the free carbon added to the raw material to be melted include graphite, amorphous carbon, carbon black, activated carbon and the like. The free carbon content in the raw material is preferably 0.001 to 1% by mass in the total raw material. If the content in the total raw material is less than 0.001% by mass, the amorphous calcium aluminate clinker is not suitable because it is difficult to form a hollow shell, and if it exceeds 1% by mass, the quick setting property and the rapid hardening property are deteriorated. This is not appropriate. Of the raw materials used for melting, materials other than free carbon are not particularly limited as long as they are raw materials usually used in the production of amorphous calcium aluminate. Specific examples include calcium carbonate, slaked lime, quicklime, etc. as the CaO source, alumina, van earth shale, bauxite, boehmite, gibbsite, etc. as the Al 2 O 3 source, and both CaO and Al 2 O 3 as chemical components. The contained blast furnace slag can also be used. Furthermore, as a chemical component other than CaO and Al 2 O 3 , SO 4 , CaF 2 , Na 2 O, Li 2 O, K 2 O, MgO, Fe 2 O 3 and the like may be contained in the raw material. The content ratio of the CaO source and the Al 2 O 3 source is not particularly limited, but preferably the molar ratio of CaO and Al 2 O 3 as chemical components; 1.0 to 3.0 as CaO / Al 2 O 3 To do. Containing molar ratio: When CaO / Al 2 O 3 is less than 1.0 or CaO / Al 2 O 3 exceeds 3.0, the quick setting property and the rapid hardening property may be deteriorated.
本発明では非晶質カルシウムアルミネートクリンカに中空殻状構造形成に寄与する主たる物質（発泡助剤）としてフリーカーボンを用いるのが好ましいが、フリーカーボン以外の発泡助剤も本発明の効果を喪失させない限り使用しても良い。このような物質としてＳｉＣが例示される。 In the present invention, it is preferable to use free carbon as the main substance (foaming aid) contributing to the formation of the hollow shell structure in the amorphous calcium aluminate clinker, but foaming aids other than free carbon also lose the effect of the present invention. It may be used as long as it is not. SiC is exemplified as such a substance.
また、本発明の非晶質カルシウムアルミネートクリンカは、単位容積あたりの充填嵩密度が０．１〜１．０（ｋｇ／Ｌ）の中空状粒子であって、あるいはフリーカーボンを含む原料を溶融発泡させてなる単位容積あたりの充填嵩密度が０．１〜１．０（ｋｇ／Ｌ）であって、フリーカーボン含有量が０．００１〜１質量％の中空状粒子である。本発明ではフリーカーボンを溶融時の主たる発泡起源に用いた場合、該フリーカーボンは発砲後も気化離脱せずに一部がクリンカ中に残留する。非晶質カルシウムアルミネートクリンカ中に適量のフリーカーボンが残留すれば、残留フリーカーボンは該クリンカにおいては脆弱な破壊源となりうるので、易粉砕性のクリンカを得る上では有利である。一方で過剰にフリーカーボンを含有したクリンカは急結性や急硬性が低下することがある。クリンカ中のフリーカーボン含有量が１質量％を超えるものでは過剰フリーカーボン量となるので適当ではない。またクリンカ中のフリーカーボンが０．００１質量％未満ではその含有効果が実質得られない。 The amorphous calcium aluminate clinker of the present invention is a hollow particle having a filling bulk density of 0.1 to 1.0 (kg / L) per unit volume, or a raw material containing free carbon is melted. It is a hollow particle having a filling bulk density per unit volume of 0.1 to 1.0 (kg / L) and having a free carbon content of 0.001 to 1% by mass. In the present invention, when free carbon is used as the main foaming origin at the time of melting, the free carbon does not separate from vaporization even after firing and a part thereof remains in the clinker. If an appropriate amount of free carbon remains in the amorphous calcium aluminate clinker, the residual free carbon can be a fragile fracture source in the clinker, which is advantageous in obtaining an easily pulverized clinker. On the other hand, a clinker containing excessive free carbon may deteriorate its quick setting property and quick hardening property. If the free carbon content in the clinker exceeds 1% by mass, the excess free carbon amount is not suitable. Further, if the free carbon in the clinker is less than 0.001% by mass, the content effect cannot be obtained.
本発明では非晶質カルシウムアルミネートクリンカの製造方法の好適な一例を述べる。
少なくとも前記のようなＣａＯ源とＡｌ2Ｏ3源となる原料にフリーカーボンを加えた原料混合物を電気炉、反射炉又は気流炉などの加熱装置で最高温度１３００〜１８００℃で加熱する。加熱後は急冷が必要で、急冷方法は冷水と直接接触させる水中急冷などは不適であるが、それ以外の急冷方法なら特に制限されない。一例として比較的簡易で実効性のある急冷方法として加熱溶融温度下の溶融物を加熱炉から直ちに室温環境下に取り出す方法が挙げられる。また、急冷して得たクリンカは、例えばボールミル、ロッドミル又はピンミル等の通常の粉砕手段でも容易に粉砕できる。
In this invention, a suitable example of the manufacturing method of an amorphous calcium aluminate clinker is described.
At least a raw material mixture obtained by adding free carbon to the raw material to be the CaO source and Al 2 O 3 source as described above is heated at a maximum temperature of 1300 to 1800 ° C. by a heating device such as an electric furnace, a reflection furnace or an airflow furnace. Rapid cooling is necessary after heating, and the rapid cooling method is not suitable for underwater rapid cooling in direct contact with cold water, but other rapid cooling methods are not particularly limited. As an example, a relatively simple and effective quenching method is a method in which a melt at a heating and melting temperature is immediately taken out from a heating furnace to a room temperature environment. Further, the clinker obtained by rapid cooling can be easily pulverized by a normal pulverizing means such as a ball mill, a rod mill or a pin mill.
また、本発明の非晶質カルシウムアルミネート系混和材は前記の中空殻状の非晶質カルシウムアルミネートクリンカをブレーン比表面積２５００ｃｍ2／ｇ以上に粉砕したものである。このようなブレーン比表面積にすることでセメント、モルタル又はコンクリートに急硬性や急結性を付与するに適した非晶質カルシウムアルミネート系混和材を得ることができる。特にブレーン比表面積４０００ｃｍ2／ｇ以上に微粉砕した粉末粒子は高い急結・急硬性の付与が可能である。 The amorphous calcium aluminate-based admixture of the present invention is obtained by pulverizing the hollow shell-like amorphous calcium aluminate clinker to a Blaine specific surface area of 2500 cm 2 / g or more. By using such a Blaine specific surface area, it is possible to obtain an amorphous calcium aluminate-based admixture suitable for imparting rapid hardening or rapid setting to cement, mortar or concrete. In particular, powder particles finely pulverized to a Blaine specific surface area of 4000 cm 2 / g or more can impart high rapid setting and rapid hardening.
以下、本発明を実施例によって具体的に説明するが、本発明は記載された実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the described examples.
［カルシウムアルミネートクリンカ製造原料］
市販石灰石粉（ＣａＯ含有量５４％、ＣＯ2含有量４５％、Ａｌ2Ｏ3、ＳｉＯ2及びＦｅ2Ｏ3は実質無含有）、市販仮焼ボーキサイト（Ａｌ2Ｏ3含有量８７％、ＳｉＯ2含有量５％、Ｆｅ2Ｏ3含有量１％）及び黒鉛粉末（市販試薬、純度＞９９．９％）を表１で表される化学成分割合となるよう配合し、混合することでクリンカ製造原料を作製した。尚、クリンカ製造原料の粒径は、約１〜１０μｍ程度のものを使用した。
[Calcium aluminate clinker production raw material]
Commercial limestone powder (CaO content 54%, CO 2 content 45%, Al 2 O 3 , SiO 2 and Fe 2 O 3 substantially free), commercial calcined bauxite (Al 2 O 3 content 87%, SiO 2 2 content 5%, Fe 2 O 3 content 1%) and graphite powder (commercially available reagent, purity> 99.9%) were mixed so as to have the chemical component ratio shown in Table 1 and mixed to obtain a clinker. Production raw materials were prepared. In addition, the particle size of the clinker manufacturing raw material used about 1-10 micrometers.
次いで、カーボン電極を具備したアーク式電気炉（加熱室容積２００リットル）を用い、該クリンカ製造原料をアーク式電気炉中で、１５００℃±約１００℃に加熱し、当該温度から直ちに、溶融物を１０ｍ／℃の速度の気流中に投入することで溶融発泡させた。溶融物はそのまま炉外常温下に設置したフィルター付回収装置に気流搬送することで急冷され、表２に表すカルシウムアルミネートクリンカを得た。尚、表２のガラス化率は、粉末Ｘ線回折により、カルシウムアルミネートクリンカ中のＣａＯ・Ａｌ2Ｏ3及び１２ＣａＯ・７Ａｌ2Ｏ3の結晶存在量（Ｗ１）を測定した後、このカルシウムアルミネートクリンカを電気炉で１５００℃で再溶融し、炉内で自然放冷することで実質的に全相結晶化させ、粉末Ｘ線回折によって自然放冷物中のＣａＯ・Ａｌ2Ｏ3及び１２ＣａＯ・７Ａｌ2Ｏ3の結晶生成量（Ｗ２）を測定し、１００×（Ｗ１／Ｗ２）で算出される。また、カルシウムアルミネートクリンカ中のフリーカーボンの含有量は、熱重量分析による方法によって求めた。さらに、カルシウムアルミネートクリンカの形状構造はＳＥＭ（走査型電子顕微鏡）観察によって調べた。観察領域において概ね８０％以上の粒子が呈した形状構造に共通性があることをもって特定した。形状構造に当該水準での共通性が見られない場合は不定形とした。 Next, using an arc electric furnace (heating chamber volume 200 liters) equipped with a carbon electrode, the clinker production raw material is heated to 1500 ° C. ± about 100 ° C. in the arc electric furnace, and immediately from that temperature, the melt Was melted and foamed by introducing it into an air stream at a speed of 10 m / ° C. The melt was quenched as it was by carrying it in an air stream to a recovery device with a filter installed at room temperature outside the furnace, and calcium aluminate clinker shown in Table 2 was obtained. The vitrification rate in Table 2 is determined by measuring the amount of crystals (W1) of CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 in the calcium aluminate clinker by powder X-ray diffraction, and then measuring the calcium aluminum content. Nate clinker is remelted at 1500 ° C. in an electric furnace and allowed to cool naturally in the furnace to crystallize substantially all phases. By powder X-ray diffraction, CaO.Al 2 O 3 and 12CaO -The crystal production amount (W2) of 7Al 2 O 3 is measured and calculated by 100 × (W1 / W2). The free carbon content in the calcium aluminate clinker was determined by a method based on thermogravimetric analysis. Furthermore, the shape structure of the calcium aluminate clinker was examined by SEM (scanning electron microscope) observation. It was specified by the commonality in the shape structure exhibited by approximately 80% or more of the particles in the observation region. If the shape structure does not have the same level of commonality, it was determined to be indefinite.
得られたカルシウムアルミネートクリンカは４ｋｇずつ内容積５０リットルのボールミルと直径１５、３０および５０ｍｍの鋼球を等重量ずつ混合したボールを用い、回転速度４０ｒｐｍで所定のブレーン比表面積（３０００±２００ｃｍ2／ｇ又は５０００±２００ｃｍ2／ｇ）になるよう粉砕し、粉砕に要した時間を測定した。また、ブレーン比表面積５０００±２００ｃｍ2／ｇに粉砕したものについて、グリッド残存量を把握するため粉砕物の３００μｍ篩上残存量も調べた。これらの結果を表３に表す。 The obtained calcium aluminate clinker was used by mixing 4 kg each of a ball mill having an internal volume of 50 liters and a ball in which steel balls having a diameter of 15, 30 and 50 mm were mixed in equal weights at a rotational speed of 40 rpm and a predetermined specific surface area (3000 ± 200 cm 2). / G or 5000 ± 200 cm 2 / g), and the time required for grinding was measured. Moreover, about what was grind | pulverized to the brain specific surface area 5000 +/- 200cm < 2 > / g, in order to grasp | ascertain the residual amount of a grid, the residual amount on a 300 micrometer sieve was also investigated. These results are shown in Table 3.
また、かような方法でブレーン比表面積５０００±２００ｃｍ2／ｇに粉砕したクリンカ粉砕物をベースモルタルに混和させ、ＪＩＳ Ａ １１４７「コンクリートの凝結時間試験方法」に準拠した方法でモルタルの凝結時間を測定し、終結時間をもって急硬性を把握した。また、モルタル表面のポップアウト発生有無を目視で調べた。ベースモルタルは、市販の普通ポルトランドセメント１ｋｇ、ＪＩＳ Ｒ ５２０１で規定するセメント強さ試験用標準砂１．３５ｋｇ及び水０．４０５ｋｇをホバートミキサに投入し、混合して作製した。クリンカ粉砕物の当該ベースモルタルへの添加量は１００ｇとした。この結果を表４に表す。 In addition, the clinker pulverized material pulverized to a brain specific surface area of 5000 ± 200 cm 2 / g by such a method is mixed with the base mortar, and the setting time of the mortar is determined by a method in accordance with JIS A 1147 “Concrete setting time test method”. Measured and grasped rapid hardness with the termination time. In addition, the presence or absence of pop-out on the mortar surface was examined visually. The base mortar was prepared by putting 1 kg of commercially available ordinary Portland cement, 1.35 kg of standard sand for cement strength test specified in JIS R 5201 and 0.405 kg of water into a Hobart mixer and mixing them. The amount of clinker pulverized product added to the base mortar was 100 g. The results are shown in Table 4.
以上の結果から、本発明による非晶質カルシウムアルミネートクリンカは、通常の粉砕手段で従来の非晶質カルシウムアルミネートクリンカに比べてかなり短時間で所定の粒度（ブレーン比表面積）まで容易に粉砕することが出来（表３参照。）、また急結・急硬性に関連する凝結特性も従来の非晶質カルシウムアルミネート系混和材と遜色ない発現状況が確保されていることがわかる。（表４参照。） From the above results, the amorphous calcium aluminate clinker according to the present invention can be easily pulverized to a predetermined particle size (brain specific surface area) in a considerably shorter time than the conventional amorphous calcium aluminate clinker by conventional pulverization means. It can be seen (see Table 3), and the setting characteristics that are comparable to conventional amorphous calcium aluminate admixtures are also secured for the setting characteristics related to rapid setting and hardening. (See Table 4.)
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