# Patent

## Title
Binder for monolithic refractories, monolithic refractory, and construction method of monolithic refractories

## Abstract

This binder for monolithic refractories includes a solid solution obtained by dissolving Ca components in α-SrAl2O4 or β-SrAl2O4, wherein when the Ca components are dissolved in the α-SrAl2O4, a crystallite diameter of the solid solution is from 40 nm to 75 nm, and when the Ca components are dissolved in the β-SrAl2O4, a crystallite diameter of the solid solution is from 35 nm to 70 nm.

## Background
FIELD OF THE INVENTION
The present invention relates to a binder for monolithic refractories, which is used for the lining or repair of furnaces, a monolithic refractory, and a construction method of monolithic refractories.
This application is a national stage application of International Application No. PCT/JP2011/060452, filed Apr. 28, 2011, which claims priority to Japanese Patent Application No. 2010-104559, filed Apr. 28, 2010, the content of which is incorporated herein by reference.
RELATED ART
As a binder for the lining refractories of furnaces used for a variety of high temperature processes, best exemplified by steel processes, a number of organic and inorganic compounds, such as sodium phosphate, sodium silicate, a furan resin, a phenol resin, pitch, aluminum lactate, sodium aluminate, silica sol, alumina sol, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, ethylsilicate, alumina cement, hydraulic alumina, or the like, are used.
In recent years, refractories have become unshaped for improvement in constructability, ease of repair, or the like, and monolithic refractories have become widely used even in parts that come into contact with molten iron or high temperature slag, for which shaped bricks were used in the past.
The manufacture of monolithic refractories does not include a high pressure press, which is performed in the manufacture of shaped refractories. Therefore, the characteristics of raw materials or binders for a filling property, firmness, and development of strength are particularly important. Among them, alumina cement (major chemical compounds: CaO.Al2O3, CaO.2Al2O3, 12CaO.7Al2O3) is used for a wide range of uses as a binder for refractories of degassing and secondary refining facilities such as a blast furnace runner, a molten steel ladle, or RH; a tundish; a heating furnace; heat treatment furnace; and the like.
Furthermore, investigations are also ongoing with alumina-based binders including chemical components other than CaO—Al2O3.
For examples, Patent Documents 1 and 2 disclose mixtures of raw materials for the manufacture of refractory alumina cement including barium or strontium and alumina as the main chemical components. Specifically, the mixtures of raw materials for the manufacture of cement are obtained by appropriately performing a thermal treatment on mixtures of carbonates and chlorides.
Non-Patent Document 1 discloses a material produced by adding a commercial high-purity reagent to CaO—SrO—Al2O3-based cement and then blending and firing the mixture, which shows a property of being hardened with an addition of water.
In addition, Patent Document 3 discloses a binder for monolithic refractories using mixtures of raw materials for the manufacture of cement having CaO—SrO—Al2O3 composition, which shows improved high-temperature slag resistance, compared to binders with CaO—Al2O3 composition.
REFERENCE DOCUMENTS
Patent Documents


    [Patent Document 1] Japanese Unexamined Patent Application, First Publication No. S52-148524
    [Patent Document 2] Japanese Unexamined Patent Application, First Publication No. S58-26079
    [Patent Document 3] Japanese Unexamined Patent Application, First Publication No. 2008-290934


Non-Patent Documents


    [Non-Patent Document 1] Ito, Mizuno, Kawano, Suzuki: Journal of the Ceramic Society of Japan, 89, 10, P. 572-577, 1981
    [Non-Patent Document 2] Prodjosantoso, A. K. and B. J. Kennedy, Journal of Solid State Chemistry, 2002, Vol. 168, No. 1, pp. 229-236


DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
However, the demand for improvement in steel quality tends to make conditions, such as operation temperature, or the like, more severe and thus high temperature corrosion resistance, or the like is continuously becoming insufficient in conventional binders. Compared to chemical components in refractory aggregates for monolithic refractories, binders including alumina cement, which are generally used, have problems in that they are liable to form low melting point materials due to ferric oxides in molten iron or slag, and wear or infiltration proceeds from binder portions in refractories, which makes it impossible to sufficiently develop the intrinsic tolerance of chemical components in the refractory aggregates.
That is, Patent Document 1 supplies the mixtures of raw materials for the manufacture of refractory alumina cement including barium or strontium and alumina as the main chemical components, and studies the strength, or the like of clinker binders using the mixtures of raw materials. However, the compressive strength is not sufficiently developed 3 days and 7 days after the manufacture and eventually reaches the maximum on the 28 days after the manufacture.
Generally, monolithic refractories are subjected to drying and heating 1 day after the manufacture and are often placed under the operating environment. From such a viewpoint, development of the maximum strength within 24 hours is strongly required. As a result, binders whose maximum strength is eventually developed on the 28 days after manufacture cannot be adopted for monolithic refractories.
In addition, Patent Document 1 discloses nothing about high temperature characteristics of higher than 1000° C. and furthermore is not clear about corrosion resistance with respect to high temperature molten iron or slag and discloses nothing about methods for the application to monolithic refractories with excellent high temperature corrosion resistance.
In addition, Patent Document 2 supplies heat-insulating castable mixtures using strontium aluminate as a binder, with which heat-insulating materials with high temperature strength can be obtained. However, the document is about heat-insulating uses for which the mixtures are lined on the rear surface of furnaces, and therefore is not clear about corrosion resistance with respect to high temperature molten iron or slag, which is an essential characteristic for the wear lining of furnaces. In addition, when strontium aluminate is used as a binder, strontium ions are liable to be eluted during mixing, which easily leads to agglomeration. Accordingly, it becomes clear that there are cases where the construction of the heat-insulating castable mixtures using strontium aluminate as a binder is difficult.
In addition, Non-Patent Document 1 shows that CaO—SrO—Al2O3-based cement is produced and the strength of hardened bodies becomes extremely great at an amount of Sr-substitution of from 0.3 mol to 0.4 mol. However, the document discloses nothing about high temperature characteristics of higher than 1000° C., and also shows nothing about methods for the application to monolithic refractories with excellent high temperature corrosion resistance.
Due to the above limitations, as binders for monolithic refractories in actual industrial uses, alumina cement including CaO.Al2O3, as the major chemical component, α-Al2O3 or CaO.2Al2O3, 12CaO.7Al2O3 and a variety of additives are used.
In addition, Non-Patent Document 2 shows that a crystal structure of a CaAl2O4—SrAl2O4 solid solution varies depending on the amount of Ca or Sr solidified. The Introduction thereof shows that CaAl2O4 is the major chemical component of high alumina cement used for a heat-resistant castable in the steel industry. However, the document discloses or suggests nothing relating to performance, for example, the strength or corrosion resistance of monolithic refractories when the CaAl2O4—SrAl2O4 solid solution is used as a binder for monolithic refractories.
That is, as of now, examples of alumina cement used as binders for monolithic refractories include “high alumina cement ES”, “high alumina cement VS-2”, “high alumina cement super 90”, “high alumina cement super G”, “high alumina cement super 2”, “high alumina cement super”, or the like (all product names, manufactured by Denki Kagaku Kogyo Kabushiki Kaisha); “SECAR 71”, “SECAR 80”, or the like (all product names, manufactured by Kerneos Inc.); or the like. Any of the above includes CaO.Al2O3, as the major chemical component, α-Al2O3 or CaO.2Al2O3, 12CaO.7Al2O3, and a small amount of additives depending on required characteristics.
As a result, there has been a strong demand for the development of binders for monolithic refractories with excellent corrosion resistance with respect to high temperature molten iron or slag because conditions such as operation temperature continuously become more severe.
On the other hand, Patent Document 3 discloses CaxSr1-xAl2O4 as binders having excellent corrosion resistance with respect to slag or molten iron, compared to alumina cement in the conventional technology. However, in order for CaxSr1-xAl2O4 to be widely used as binders of monolithic refractories of furnaces having various thicknesses and shapes and the like, further improvement of hardened strength is required.
An object of the present invention is to provide a binder for monolithic refractories having excellent corrosion resistance with respect to slag or molten iron and excellent characteristics in the early development of hardened strength and the stability thereof, compared to binders such as alumina cement in the conventional technology; a monolithic refractory using the binder; and a construction method of the monolithic refractory.
Methods for Solving the Problem
The inventors paid attention to substituting Ca in a binder for monolithic refractories with a metal atom from the viewpoint of improving the refractoriness of a monolithic refractory, and newly found that, by dissolving SrO in CaO.Al2O3 which is a component of alumina cement in the conventional technology (in other words, by dissolving Ca components in SrAl2O4 to obtain a solid solution), a composition has a high melting point, corrosion resistance with respect to slag or molten iron is excellent, and constructability and high temperature stability can be improved (refer to Patent Document 3). In addition, the inventors also found that due to the solidification of SrO, a time taken to develop strength of a monolithic refractory can be shortened and thus high strength can be realized (refer to Patent Document 3).
The inventors newly paid attention to a crystallite diameter of the above-described solid solution and vigorously studied and discussed; and as a result, found that, when the crystallite diameter is set to be a predetermined size or less smaller than that in the conventional technology, corrosion resistance and a strength developing property can be further improved and completed the present invention.
Here, the solidification represents two or more kinds of elements (which may be metal or non-metal) dissolving each other such that the entire mixture is uniformly solid. In addition, the solid solution represents a phase of a crystalline material which is formed by two or more kinds of elements becoming uniformly solid.
The summary of the present invention is as follows.
(1) A binder for monolithic refractories including a solid solution obtained by dissolving Ca components in α-SrAl2O4 or β-SrAl2O4, wherein when the Ca components are dissolved in the α-SrAl2O4, a crystallite diameter of the solid solution is from 40 nm to 75 nm, and when the Ca components are dissolved in the β-SrAl2O4, a crystallite diameter of the solid solution is from 35 nm to 70 nm.
(2) The binder for monolithic refractories according to (1) above, wherein an amount of the solid solution obtained by dissolving Ca components in the α-SrAl2O4 or the β-SrAl2O4 is from 10 mass % to 60 mass %, and 40 mass % to 90 mass % of Al2O3 is blended thereinto.
(3) The binder for monolithic refractories according to (1) above, further including, as a mixture, a solid solution obtained by dissolving Sr components in CaAl2O4, wherein a crystallite diameter of the solid solution is from 25 nm to 60 nm.
(4) The binder for monolithic refractories according to (3) above, wherein an amount of the solid solution obtained by dissolving Ca components in the α-SrAl2O4 or the β-SrAl2O4 and the solid solution obtained by dissolving Sr components in the CaAl2O4 is from 10 mass % to 60 mass %, and 40 mass % to 90 mass % of Al2O3 is blended thereinto.
(5) The binder for monolithic refractories according to (1) above, wherein both of a solid solution obtained by dissolving Ca components in the α-SrAl2O4 and a solid solution obtained by dissolving Ca components in the β-SrAl2O4 are included as a mixture.
(6) The binder for monolithic refractories according to (5) above, wherein a total amount of both of the solid solution obtained by dissolving Ca components in the α-SrAl2O4 and the solid solution obtained by dissolving Ca components in the β-SrAl2O4 is from 10 mass % to 60 mass %, and 40 mass % to 90 mass % of Al2O3 is blended thereinto.
(7) The binder for monolithic refractories according to (5) above, further including, as a mixture the solid solution obtained by dissolving Sr components in the CaAl2O4.
(8) The binder for monolithic refractories according to (7) above, wherein a total amount of the solid solution obtained by dissolving Ca components in the α-SrAl2O4, the solid solution obtained by dissolving Ca components in the β-SrAl2O4, and the solid solution obtained by dissolving Sr components in the CaAl2O4 is from 10 mass % to 60 mass %, and 40 mass % to 90 mass % of Al2O3 is blended thereinto.
(9) The binder for monolithic refractories according to (1) above, wherein one kind or two or more kinds selected from a group consisting of SiO2, TiO2, Fe2O3, MgO, and BaO are included in the binder for monolithic refractories and an amount thereof is 12 mass % or less.
(10) The binder for monolithic refractories according to (1) above, wherein at least one of a dispersant and a hardening retardant is blended into the binder for monolithic refractories.
(11) A monolithic refractory obtained by blending the binder for monolithic refractories according to any one of (1) to (10) above into a refractory aggregate.
(12) The monolithic refractory according to (11) above, wherein the refractory aggregate includes an ultrafine alumina powder with a particle diameter of from 0.8 nm to 1 μm.
(13) The monolithic refractory according to (11) above, wherein an amount of the binder for monolithic refractories is from 0.3 mass % to 20 mass % with respect to 100 mass % of a total amount of the binder for monolithic refractories and the refractory aggregate.
(14) The monolithic refractory according to (13) above, wherein the amount of the binder for monolithic refractories is from 0.5 mass % to 12 mass % with respect to 100 mass % of the total amount of the binder for monolithic refractories and the refractory aggregate.
(15) The monolithic refractory according to (11) above, wherein further at least one of a dispersant, a hardening retardant, and a hardening accelerator is added.
(16) The monolithic refractory according to (15) above, wherein the dispersant is one kind or two or more kinds selected from a group consisting of a polycarbonate-based dispersant, a phosphate-based dispersant, an oxycarboxylic acid, a melamine-based dispersant, a naphthalene-based dispersant, and a lignin sulfonic acid-based dispersant, the hardening accelerator is at least one of an alkali metal salt and aluminate, and the hardening retardant is at least one of boric acid group and silicofluoride.
(17) A construction method of monolithic refractories including: blending and mixing the binder for monolithic refractories according to any one of (1) to (10) above and a refractory aggregate including an ultrafine alumina powder with a particle diameter of 1 μm or less to obtain a monolithic refractory; and constructing the monolithic refractory.
Effects of the Invention
According to a binder for monolithic refractories of the present invention, since a favorable strength developing property is developed within a shorter period of time compared to that of the conventional technology, a time taken to remove a frame can be reduced and construction efficiency can be improved. In addition, it is possible to develop the effects of excellent corrosion resistance with respect to slag or molten iron, and of expansion of the service life of monolithic refractories lined in furnaces used at a high temperature.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing a shape of an evaluation specimen.
FIG. 2 is a perspective view showing an external appearance of a rotary corrosion furnace.
FIG. 3 is a cross-sectional view of the rotary corrosion furnace.



EMBODIMENTS OF THE INVENTION
Hereinafter, some embodiments of the present invention will be described.
According to a first embodiment of the present invention, a binder includes a solid solution obtained by dissolving Ca components in SrAl2O4 therein. At this time, when SrAl2O4 is α-SrAl2O4, a crystallite diameter of the solid solution is from 40 nm to 75 nm; or when SrAl2O4 is β-SrAl2O4, a crystallite diameter of the solid solution is from 35 nm to 70 nm.
A binder, which includes a solid solution having a crystallite diameter in the above-described predetermined range, has a higher melting point than that of alumina cement (major chemical component: CaO.Al2O3) in the conventional technology, and has excellent high temperature stability when it reacts with water so as to form the hardened body. In addition, in particular, when the crystallite diameter is in the above-described predetermined range, by using the present binder, an appropriate operation time can be secured when manufacturing monolithic refractories. Furthermore, since hardening rate is improved compared to that in the conventional technology, corrosion resistance and strength can be improved. As a result, the present binder can be used for a wide range of uses as a binder.
However, in order to facilitate the effects, it is preferable that an amount of the solid solution be 10 mass % or higher in the binder. In addition, the upper limit of the amount may be 100 mass %. The composition of a balance in the binder is typically Al2O3, and also includes examples of SiO2, TiO2, Fe2O3, MgO, BaO, or the like. With regard to how they can intrude into the binders of the present invention, in the case of Al2O3, it may be intentionally added in order to impart a high level of fireproofness thereto. In the case of other components, a case in which they have already been included in raw materials to be used or a case in which the binders are contaminated from a crushing apparatus, a transportation apparatus, a firing apparatus, or the like of binder raw materials or products during the manufacturing process can be considered. In addition, a solid solution according to the following embodiment can be included in the binder as a mixture.
In a binder for monolithic refractories according to a second embodiment of the present invention, a solid solution, obtained by dissolving SrO as Sr components in CaO.Al2O3, is blended into a binder including the solid solution according to the first embodiment obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm, or into a binder including the solid solution according to the first embodiment obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm. In this case, a crystallite diameter of the solid solution obtained by dissolving SrO in CaO.Al2O3 is from 25 nm to 60 nm.
With regard to the existence form of these solid solutions in the binder, they are not present as a single solid solution obtained by being solidified with each other but are present as independent solid solutions. The binder is present in the form of a mixture.
A content ratio of the solid solution obtained by dissolving SrO in CaO.Al2O3 included in the binder is not limited. However, in order to facilitate the effects thereof, it is preferable that an amount of a mixture of the solid solution in the binder be 10 mass % or higher. In addition, the upper limit of the amount may be 100 mass %. If there is a balance in the binder, the composition of the balance is typically Al2O3, and also includes examples of SiO2, TiO2, Fe2O3, MgO, BaO, or the like. With regard to how they can intrude into the binders of the present invention, as in the case of the first embodiment, Al2O3 may be intentionally added in order to impart a high level of fireproofness thereto. In the case of other components, a case in which they have already been included in raw materials to be used or a case in which the binders are contaminated from a crushing apparatus, a transportation apparatus, a firing apparatus, or the like of binder raw materials or products during the manufacturing process can be considered.
The solid solution obtained by dissolving SrO in CaO.Al2O3 is hydraulic, has a higher melting point than that of CaO.Al2O3 of alumina cement in the conventional technology, and has excellent high temperature stability when it reacts with water so as to form the hardened body. Therefore, it is possible to obtain a greater effect than that with a binder in the conventional technology. In addition, the solid solution obtained by dissolving SrO in CaO.Al2O3 is more preferable because a crystallite diameter of the solid solution is from 25 nm to 60 nm and thus an appropriate operation time and hardening rate can be obtained.
According to a third embodiment of the present invention, both of the solid solution according to the first embodiment obtained by dissolving Ca components in α-SrAl2O4 which has a crystallite diameter in the predetermined range and the solid solution according to the first embodiment obtained by dissolving Ca components in β-SrAl2O4 which has a crystallite diameter in the predetermined range, are included in a binder. The third embodiment is different from the first embodiment in that both of the solutions are included, not either of them. This binder may further include the solid solution according to the second embodiment obtained by dissolving Sr components in CaO.Al2O3. With regard to the existence form of these solid solutions in the binder, they are not present as a single solid solution obtained by being solidified with each other but are present as independent solid solutions. The binder is present in the form of a mixture. In addition, according to the third embodiment, as in the cases of the first embodiment and the second embodiment, it is possible to obtain a greater effect than that with a binder in the conventional technology.
A ratio of two or three kinds of solid solutions as a mixture in the binder is not particularly limited. However, in order to facilitate the effects thereof, it is preferable that a total amount of a mixture of these solid solutions in the binder be 10 mass % or higher. In addition, the upper limit of the amount may be 100 mass %. The composition of a balance in the binder is typically Al2O3, and also includes examples of SiO2, TiO2, Fe2O3, MgO, BaO, or the like. With regard to how they can intrude into the binders of the present invention, as in the cases of the first and second embodiments, Al2O3 may be intentionally added in order to impart a high level of fireproofness thereto. In the case of other components, a case in which they have already been included in raw materials to be used or a case in which the binders are contaminated from a crushing apparatus, a transportation apparatus, a firing apparatus, or the like of binder raw materials or products during the manufacturing process can be considered.
By performing the maintenance and optimization of the selection and manufacturing processes of industrially used raw materials, an amount of SiO2, TiO2, Fe2O3, MgO, BaO, and the like, which are impurities in the binders of the first to third embodiment, can be reduced to a level with no influence on the effects of the present invention. The amount is preferably 12 mass % or less and more preferably 5 mass % or less with respect to the total mass of the binders of the present invention in the total amount of chemical components, which is the converted amount of the oxides of the respective chemical components. If the amount is more than 12 mass %, there are cases in which performance degradation, such as degradation of the strength developing property and corrosion resistance of monolithic refractories using the binders, occurs.
In addition, when the amount of SiO2, TiO2, Fe2O3, MgO, and BaO is 12 mass % or less, the cured strength of monolithic refractories may increase. The reason is considered that minerals containing these components generate amorphous materials and ions are liable to be eluted when it reacts with water. Strength increases greatly when the amount is 5 mass % or less and the increase continues until 12 mass %. However, when the amount exceeds 12 mass %, conversely, there are cases in which strength is reduced maybe because the minerals containing the components generate crystalline materials having a low solubility in water. In addition, there are cases where high temperature corrosion resistance is degraded maybe because a melting point of impurities is lowered.
Furthermore, the present inventors also reviewed a case where no Ca components are included in a solid solution of SrAl2O4 in comparison, but found that there were differences in the functions of a binder, from the case where Ca components are included as in the present invention. Therefore, in order to study the functions of the binders, an ion elution test was conducted to compare reaction processes with water of both of the cases to each other. As a result, in a case where the composition of a solid solution is represented by CaxSr1-xAl2O4, it was found that the initial amount of ions eluted of a solid solution in which X=0 and no Ca components were included was extremely greater than that of a solid solution in which Ca components was included (for example, X=0.15). Therefore, in the case where no Ca components were included, the elution speed of ions was extremely fast. After a saturated solubility was reached, hydration products were precipitated in a supersaturated solution. A cross-linked structure was generated between particles so as to contribute to binding and strength development for hardening.
In detail, the rate of Sr ions eluted from the SrAl2O4 composition, in which no Ca components were included, into mixing water and the rate of Sr and Ca ions eluted from the above-described various solid solutions according to the present invention were compared. For the comparison, 200 g of a specimen was fed into 400 g of distilled water and stirred for a predetermined period of time using a magnetic stirrer, and then the solution was extracted and analyzed with inductively-coupled plasma (ICP) optical emission spectrometry, thereby measuring the amount of elements in the solution. The elements in the solution were presumed to be present in a variety of ion states. As a result of comparing the amounts for the same stirring time, it was quantitatively found that the rate of Sr ions eluted from SrAl2O4, in which no Ca components were included, into mixing water was greater than the rate of Sr and Ca ions eluted from the above-described various solid solutions according to the present invention.
Therefore, when the solid solution in which X=0 is used for the binder for monolithic refractories, agglomeration of materials occurs easily due to a large amount of ions eluted. As a result, the necessary time for hardening is shortened and an amount of monolithic refractories to be constructed is large. For example, when an hour or longer is necessary for construction, there is a possibility of problems such as the hardening of a material during mixing and during pouring. To suppress this, it is necessary that a large amount of additives which have an effect of sequestering initially eluted ions, that is, a large amount of boric acid, borax, sodium gluconate, silicofluorides, or the like be added as a hardening retardant compared to the case where Ca components are included (for example, X=0.15). Still, when the function of the hardening retardant which suppresses ion elution does not work, hardening proceeds immediately.
Therefore, when a long period of time is necessary for construction, for example, in furnace facilities where there is a large amount to be constructed, it was found that the case where Ca components are included is preferable from the viewpoint of more stable construction.
Since a binder is usually used in the powder state, it is preferable that the above-described solid solutions according to the present invention be present in the powder state in the binders.
In addition, crystallite diameters of all the solid solutions can be calculated by the Scherrer method after obtaining the full-width at half maximum from the diffraction peak obtained by powder X-ray diffractometry. The solid solutions according to the present invention have a characteristic that a diffraction line thereof changes depending on the blending ratio of Ca and Sr. The respective crystallite diameters can be calculated by obtaining the full-width at half maximum: from the diffraction peak of (−2 1 1) plane with 2θ of about 28.4° in the case of the solid solution obtained by dissolving Ca components in α-SrAl2O4; from the diffraction peak of (1 0 2) plane with 2θ of about 29.5° in the case of the solid solution obtained by dissolving Ca components in β-SrAl2O4; and from the diffraction peak of (1 2 3) plane with 2θ of about 30.0° in the case of the solid solution obtained by dissolving Sr components in CaAl2O4.
In detail, in the various solid solutions, for which a variety of raw materials are prepared and synthesized by a firing method, when a batch furnace is used, samples are taken from various places, such as the surface, interior, or the like of a fired body; and when a continuous furnace such as a rotary kiln is used, samples are taken on a predetermined time interval basis (for example, on a minute basis) to obtain average evaluation samples. Then, the samples (for example, n=10) are sampled, divided, and then crushed by a crusher so that the 50% average diameter becomes 10 μm or less. The samples are measured using a powder X-ray diffractometer (for example, JDX-3500, trade name, manufactured by JEOL Ltd.), and it is possible to calculate the crystallite diameter using JADE 6, a powder X-ray diffraction pattern analyzing software.
The measurement of crystallite diameters using an X-ray diffractometer may be performed under the conditions of an X-ray source of CuKα, a tube voltage of 40 kV, a tube current of 300 mA, a step angle of 0.02°, and a spectroscopy with a measurement condition of monochromator of 2θ from 15° to 40°. With regard to the X-ray diffractometer-derived full-width at half maximum used for the analysis of crystallite diameter, it is possible to use values obtained by measuring silicon powder specimens with the same diffractometer under the same conditions and then obtaining the full-width at half maximum curves.
Next, a manufacturing method of the binders according to the present invention will be described.
In the manufacture of the solid solution obtained by dissolving Ca components in α-SrAl2O4, the solid solution obtained by dissolving Ca components in β-SrAl2O4, and the solid solution obtained by dissolving Sr components in CaAl2O4, these can be respectively manufactured according to the firing temperature by changing the blending ratio of starting materials so as to be a predetermined molar ratio.
As the starting materials, any raw materials can be used as long as CaO, SrO, and Al2O3 are used as the major chemical components. However, since there is a possibility that CaO and SrO may be hydrated in the atmosphere, CaCO3, SrCO3, and Al2O3 are preferably used. The kind of raw materials will be described in detail.
The blending ratio of CaO:SrO:Al2O3 is set by weighing and blending the raw materials so that CaxSr1-xAl2O4 has a predetermined X in terms of molar ratio.
As the crystal phase obtained after firing the mixture at, for example 1450° C., when X is equal to 1.0, CaAl2O4 is obtained; when X is from about 0.8 to 0.9, the solid solution obtained by dissolving Sr components in CaAl2O4 is obtained; when X is from about 0.5 to 0.7, a mixture of the solid solution obtained by dissolving Sr components in CaAl2O4 and the solid solution obtained by dissolving Ca components in β-SrAl2O4 is obtained; when X is from about 0.3 to 0.4, the solid solution obtained by dissolving Ca components in β-SrAl2O4 is obtained; when X is from about 0.1 to 0.2, a mixture of the solid solution obtained by dissolving Ca components in β-SrAl2O4 and the solid solution obtained by dissolving Ca components in α-SrAl2O4 is obtained; and when X is more than 0 and equal to or less than 0.1, the solid solution obtained by dissolving Ca components in α-SrAl2O4 is obtained.
At this time, along with the increase in the molar ratio of Sr, the lattice constants of a-axis, b-axis, and c-axis increase. This is because of, for example, the ionic radii of Ca and Sr. Referring to the ionic radii during pouring, the ionic radius of Ca is 0.099 nm and the ionic radius of Sr is 0.113 nm and Sr has a larger ionic radius. It is presumed that, due to the substitution with Sr having a larger ionic radius, the lattice expands and the lattice spacing expands.
Therefore, these crystal phases can be identified using the powder X-ray diffractometry (XRD) and can be respectively obtained while checking a desired solid solution and a mixture thereof. As the device, for example, a RAD-B system equipped with a curved crystal monochromator (manufactured by Rigaku Corporation) can be used. The XRD measurement is performed under the conditions of an anticathode of Cu (CuKα), 2θ from 15° to 70°, a tube voltage of 40 kV, a tube current of 20 mA, a scan step of 0.010 deg, a scan speed of 4°/min, a divergence slit of 1⁄2 deg, a receiving slit of 0.15 nm, and a scattering slit of 1⁄2 deg. However, the conditions for the XRD measurement are not limited thereto. When the crystal phases are precisely measured, it is preferable that silicon, aluminum, and magnesium be used as primary standards and an internal standard method be used.
In addition, the solid solutions and the mixtures of the solid solutions may be further blended to obtain a desired mixture of the solid solutions.
In addition, as a method of making a crystallite diameter a predetermined size, in cases where the crystallite diameter of the solid solution obtained by dissolving Ca components in α-SrAl2O4 is made to be from 40 nm to 75 nm; where the crystallite diameter of the solid solution obtained by dissolving Ca components in β-SrAl2O4 is made to be from 35 nm to 70 nm; and where the crystallite diameter of the solid solution obtained by dissolving Sr components in CaAl2O4 is made to be from 25 nm to 60 nm, firing is performed at a temperature of preferably from 1300° C. to 1600° C. and more preferably from 1400° C. to 1500° C. using a firing apparatus, such as an electric furnace, a reverberating furnace, an open-hearth furnace, a shaft furnace, a shuttle kiln, or a rotary kiln.
When the firing temperature is lower than 1300° C., unreacted raw materials are liable to remain and there are cases in which the amount of a target solid solution generated is reduced. In addition, when the firing temperature is higher than 1600° C., there are cases in which the crystal of a solid solution is excessively grown, the crystallite diameter thereof becomes large beyond the predetermined range, and therefore the strength developing property deteriorates. At a temperature of from 1400° C. to 1500° C., it is possible to shorten the firing time to obtain a predetermined crystallite diameter and it becomes difficult for the crystallite diameter to be excessively increased due to excessive firing. Therefore, this temperature range is preferable.
The time period of firing may be adjusted so that a target crystallite diameter is obtained at each temperature, and, for example, is from about 1 hour to 24 hours at 1400° C. and from about 0.5 hours to 12 hours at 1500° C. When firing is performed for longer than 24 hours at 1400° C. and for longer than 12 hours at 1500° C., the crystallite diameter of a solid solution becomes too large beyond the predetermined range of crystallite diameter. Therefore, the hardened strength after a short-term curing time deteriorates, which is not preferable. It is more preferable that the firing temperature and the firing time be 1400 to 1500° C. and 1 to 5 hours.
The above-described appropriate temperature and firing time varies to some extent depending on the specification of a furnace, such as the volume or heating capacity. Therefore, it is preferable to check phases generated in specimens after firing through X-ray diffraction measurement and check whether or not a solid solution having a target crystallite diameter range has been generated for the manufacture, from the viewpoint of reliably obtaining a desired solid solution.
In all of the first to third embodiments, it is preferable that Al2O3 be blended thereinto in a case in which there is a demand for a further increase in the strength or refractoriness of hardened bodies when the solid solutions react with water so as to form the hardened body. The preferable amount of the solid solutions in the binder is from 10 mass % to 60 mass %, and the preferable amount of Al2O3 blended thereinto is from 40 mass % to 90 mass %.
With the amount of the solid solutions of less than 10 mass %, depending on the chemical components or particle size distribution of the aggregates in monolithic refractories, there are cases in which it becomes difficult to develop a sufficient hardened strength.
On the other hand, with the amount of the solid solutions of higher than 60 mass %, depending on the chemical components or particle size distribution of the aggregates in monolithic refractories, there are cases in which the hardening rate is too fast and it becomes difficult to secure a sufficient usable life for construction.
In addition, if the amount of Al2O3 in the binder is 40 mass % or higher, the strength or refractoriness of hardened bodies increases sufficiently, which is preferable. However, if the amount of Al2O3 to be blended thereinto is more than 90 mass %, the amount of the solid solutions becomes relatively small, and thus it may become difficult to be uniformly hardened. Therefore, the amount of Al2O3 to be blended thereinto is preferably 90 mass % or less.
Next, a monolithic refractory used for the binder for monolithic refractories according to the present invention will be described. In the present invention, the blending ratio of the binder and refractory aggregates in a monolithic refractory is not particularly specified, and it has been confirmed that, even with an arbitrary blending ratio, the effects of the present invention can be obtained.
However, in a case in which the binder for monolithic refractories of the present invention is used to manufacture actual monolithic refractories, with regard to the blending ratio of the binder and refractory aggregates, it is suggested that the amount of the binder is preferably from 0.3 mass % to 20 mass %, and further preferably from 0.5 mass % to 12 mass % with respect to 100 mass % of the total amount of the binder and refractory aggregates.
This is because, with an amount of less than 0.3 mass %, there are cases in which binding is not sufficient and therefore the strength is not sufficient even after the binder has been hardened. In addition, it is because, with an amount of more than 20 mass %, there are cases in which volume change, or the like generated during the hydration or dehydration process of the binder adversely affects the entire monolithic refractories, and therefore cracking, or the like occurs.
As the refractory aggregates of monolithic refractories, fused alumina, fused bauxite, sintered alumina, calcined alumina, fused mullite, synthesized mullite, melted silica, fused zirconia, fused zirconia mullite, zircon, magnesia clinker, fused magnesia, fused magnesite-chrome, sintered spinel, fused spinel, silicon nitride, silicon carbide, squamation graphite, earthy graphite, sillimanite, kyanite, andalusite, agalmatolite, shale, dolomite clinker, silica rock, clay, chamotte, lime, chrome, melted quartz, calcium aluminate, calcium silicate, or silica flower can be used. They may be used alone or in combination of two or more kinds thereof.
In a case in which the binder of the present invention is used as a binder for monolithic refractories, the amount of water or water-containing solvent used for construction is not particularly specified. However, the amount is dependent on the particle size distribution of aggregates or the type and amount of dispersants, and therefore it is preferable that the amount is roughly from about 2 mass % to 10 mass % with respect to the refractory aggregates in outer percentage.
This is because, if the amount is less than 2 mass %, it becomes difficult to harden the binder. In addition, it is because, if the amount is more than 10 mass %, the amount relating to the formation of hardened structures becomes relatively large, and volume change, or the like during hardening reactions becomes liable to adversely affect the quality of refractories.
In addition, if the binder of the present invention is used as a binder for monolithic refractories, in order to appropriately control the rate of the hydration and hardening reactions according to the atmospheric temperature or humidity, it is preferable to add a dispersant or a hardening adjuster.
As the dispersant, carbonates, such as sodium carbonate, sodium hydrogen carbonate, or the like; oxycarboxylic acids, such as citric acid, sodium citrate, tartaric acid, sodium tartrate acid, or the like; polyacrylic acid or methacrylic acid and salts thereof; condensed phosphates, such as sodium tripolyphosphate or sodium hexametaphosphate, or the like, and/or alkali metals thereof; alkaline-earth metal salts, or the like are mainly used.
As the hardening adjuster, a hardening retardant or a hardening accelerator can be used. As the hardening retardant, it is possible to use boric acid, borax, sodium gluconate, silicofluorides, or the like. On the other hand, as the hardening accelerator, it is possible to use lithium salts, such as lithium carbonate or the like; slaked lime or the like; and aluminates or the like.
In addition, a method also can be used that increases the ventilation rate of materials by adding an explosion preventer, such as an organic fiber, such as vinylon, or the like, metallic aluminum powder, aluminum lactate, or the like.
Furthermore, it is also possible to add ultrafine powder in order to achieve improvement in the flow property, a filling property or sinterability. Examples of the ultrafine powder include inorganic fine powder with a particle diameter of from about 0.01 μm to 100 μm, such as silica fume, colloidal silica, well-sinterable alumina, amorphous silica, zirconia, silicon carbide, silicon nitride, chrome oxide, titanium oxide, or the like.
In a case in which a basic aggregate, such as magnesia, or the like, is blended thereinto, there is a possibility of the generation of cracking caused by hydration swelling of magnesia. In order to suppress such a phenomenon, it is preferable to add a highly surface-active additive, such as fumed silica.
Furthermore, since the monolithic refractories of the present invention are used to manufacture dense hardened bodies, during mixing with water, it is possible to use chemical admixtures, such as a water reducing agent, such as a polycarbonate-based water reducing agent, a lignin-based water reducing agent, or the like, a high performance water reducing agent, a high performance AE water reducing agent, or the like. The type and amount added of the above chemical admixtures can be properly selected according to the type or amount of refractory aggregates to be blended thereinto and conditions, such as the construction temperature, or the like.
As raw materials used for manufacturing the solid solution obtained by dissolving Ca components in α-SrAl2O4, the solid solution obtained by dissolving Ca components in β-SrAl2O4, and the solid solution obtained by dissolving Sr components in CaAl2O4, which are the binders for monolithic refractories according to the present invention, lime stone (mainly CaCO3), calcined lime (mainly CaO), purified alumina (α-Al2O3, Al(OH)3) or bauxite (a raw material of Al2O3), strontianite (SrCO3) or celestite (SrSO4) are preferably used. Before firing, it is preferable to crush the raw material with a crusher so as to have a 50% average diameter (median diameter) of from about 0.5 μm to 15 μm. This is because, if the raw material includes particles coarser than the above, there are cases in which a large number of unreacted parts remain or a composition other than the solid solutions according to the present invention is partially generated, and therefore there are cases in which the intrinsic effects of the present invention become difficult to develop.
As the composition other than the solid solutions according to the present invention, there are cases in which, if alumina components are rich in the raw material, a solid solution such as CaxSr1-xAl4O7 is generated, and if CaO components and SrO components are rich in the raw material, a solid solution such as (CaxSr1-x)12Al14O33 or (CaxSr1-x)3Al2O6 is generated. However, if the raw materials are prepared, crushed, and blended as described above so as to obtain the target solid solution according to the present invention, the amount of the above generation is small and has less effect on the binder characteristics.
Furthermore, the raw material to be used is preferably a high purity material with 98 mass % or more of a total amount of CaO, Al2O3 and SrO in the raw material. Impurities included in bauxite, strontianite or celestite, such as SiO2, TiO2, MgO, Fe2O3, or the like, have a possibility of degrading high temperature properties, and it is preferable to suppress these to an extremely small amount.
Since the particle size of solid solution powder in the binders affects hydration reaction or hardening rate, it is preferable to control particles to be from about 1 μm to 20 μm by a crusher after firing for manufacturing a solid solution. The particle size is a measurement result by a particle size analyzer used for a laser diffractometry, a laser scattering method, a sedimentation balance method, or the like and indicates the 50% average diameter. The raw material can be uniformly blended using a mixer, such as an Eirich mixer, a rotary drum, a cone blender, a V-shape blender, an omni mixer, a nauta mixer, a pan-type mixer, or the like.
As the crusher, it is possible to use an industrial crusher, such as an oscillating mill, a tube mill, a ball mill, a roller mill, a jet mill or the like.
The binders, in which from 10 mass % to 60 mass % of the solid solutions according to the first to third embodiment are included and from 40 mass % to 90 mass % of Al2O3 is blended, can be manufactured by blending α-alumina powder into the various solid solutions obtained by the above-described method.
α-alumina powder refers to high purity alumina including 90 mass % or more of Al2O3, and generally alumina is manufactured by the Bayer process. In this method, firstly, bauxite is washed in a hot solution of sodium hydroxide (NaOH) at 250° C. In this process, alumina is transformed to aluminum hydroxide (Al(OH3)) and dissolved by a reaction shown in the following formula (1).

Al2O3+2OH−+3H2O→2[Al(OH)4]−  (1)

At this time, other chemical components in the bauxite are not dissolved and can be removed through filtering as solid impurities. Subsequently, if the solution is cooled, the dissolved aluminum hydroxide is precipitated as a white fluffy solid. If the solid is subjected to a firing treatment at 1050° C. or higher using a rotary kiln, or the like, dehydration shown in the following formula (2) occurs and therefore alumina is generated.

2Al(OH)3→Al2O3+3H2O  (2)

Since binders are highly dependent on the specific surface area of α-Al2O3 blended into the binders in terms of the flow property, the BET specific surface area of α-Al2O3 is preferably from about 0.1 m2/g to 20 m2/g.
α-Al2O3 can be blended thereinto in a state of being made into fine particles or by blending and crushing it with the various solid solutions.
When α-Al2O3 to be blended into the binder is crushed and then blended, it is preferable that refinement be performed so that the 50% average diameter be from about 0.3 μm to 10 μm. In addition, fine alumina powder with the above-described particle diameter can be blended. In addition, when the components of the solid solutions and α-Al2O3 are crushed and blended, it is preferable to set crushing conditions so that the 50% average diameter of α-Al2O3 be in the same range.
When the 50% average diameter of α-Al2O3 is in the above-described range, sinterability with respect to aggregates to be blended into binders or monolithic refractories is improved and a dense structure having excellent corrosion resistance can be obtained.
In addition, the higher the purity of Al2O3, the superior the refractoriness. Therefore, the purity of α-Al2O3 is preferably 95 mass % or higher and more preferably 99 mass % or higher.
This α-Al2O3 is uniformly blended with hydraulic components by blending it in the binder in advance. When the resultant is blended into a monolithic refractory, the hydraulic components can be more uniformly blended and it is possible to obtain a structure of refractory having excellent strength developing property and corrosion resistance of hardened bodies.
In the present invention, the manner in which α-Al2O3 is blended with the binder and crushed is preferable since α-Al2O3 is uniformly blended into the binder composition and therefore the microstructure of the hardened bodies is liable to become uniform when used for monolithic refractories, and this manner has a tendency of improving performance, such as corrosion resistance, or the like.
In addition, in the monolithic refractory according to the present invention, a construction method of refractories used for the lining or repair of furnaces may be the same as a general construction method of monolithic refractories. However, particularly when an aggregate including an ultrafine alumina powder with a particle diameter of from 0.8 nm to 1 μm and the binders according to the present invention are blended and mixed for construction, binding is further improved due to the synergistic effect with the binders according to the present invention. As a result, a favorable strength developing property is developed within a short period of time, construction efficiency is improved, corrosion resistance with respect to slag and molten iron is further improved, and the effect of service life expansion of furnaces can be more strongly exhibited. Therefore, the above-described manner is preferable.
It is preferable that the blending ratio of the ultrafine alumina powder with a particle diameter of 1 μm or less in the monolithic refractory (other than moisture) be from 2 mass % to 70 mass %
EXAMPLES
Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to the examples.
In the following examples, as the raw materials, CaCO3 with a purity of 99 mass % (manufactured by Ube Material Co., Ltd.), SrCO3 with a purity of 98 mass % (manufactured by Sakai Chemical Industry Co., Ltd.), and high purity α-alumina with a purity of 99 mass % (manufactured by Nippon Light Metal Co., Ltd.) were used.
Each of the raw materials was weighed with scales so as to have the chemical compositions in the following tables, and then blended and crushed with a mortar. 15 mass % of water was added to the blended and crushed raw materials in outer percentage, was granulated into spherical pellets, were fed into an alumina container, and then subjected to a heating treatment at the maximum temperature in the air atmosphere using an electric furnace (with a furnace volume of 130 L) while changing the holding time thereof. After that, the resultant were cooled to room temperature and placed in the air, and then crushed with a batch type ball mill so as to obtain various solid solutions and binders shown in the examples.
Furthermore, with regard to examples in which α-Al2O3 is blended, high purity α-alumina (manufactured by Nippon Light Metal Co., Ltd.) was added to the obtained solid solutions and binders so as to obtain a predetermined chemical component.
In addition, in order to study the effects of impurities, barium oxide was used which was obtained by heating at 1400° C. a variety of reagents with a purity of 99 mass %, such as silicon oxide, titanium oxide, magnesium oxide and ferric oxide and a barium carbonate reagent with a purity of 99%. The raw materials were blended according to the contents of the respective following tables to prepare the binders in the same manner described above.
8 mass % of the binder, 92 mass % of refractory aggregates (50 mass % of sintered alumina with a particle size by sieving of 1 μm or lower, 43 mass % of fused alumina with a particle size of from 75 μm to 5 mm, 6 mass % of magnesia, 0.8 mass % of silica flower, and 0.15 mass % of vinylon fiber), and 0.05 mass % of boric acid powder were blended for 1 minute with an omni mixer, and, furthermore, 6.8 mass % of water was added to 100 mass % of the mixture thereof in a constant temperature room of 20° C. and then blended and mixed with a mortar mixer for 3 minutes, thereby obtaining monolithic refractory specimens.
In order to evaluate the operability of the prepared monolithic refractory specimens, the flow test was carried out according to JIS R2521, “Physical testing methods of aluminous cement for refractories” to measure spreading diameters of samples immediately after mixing and 2 hours after the start of blending, in which the samples were subjected to falling motion 15 times.
The flexural strength after curing was measured according to JIS 82553, “Testing method for crushing strength and modulus of rupture of castable refractories” after the monolithic refractory specimens were poured into a 40×40×160 mm mold form and then cured in a constant temperature room at 20° C. for a predetermined time. In addition, the curing time was set to 6, 12, and 24 hours after the start of blending of monolithic refractories.
In addition, the monolithic refractory specimens were cured in a constant temperature room at 20° C. for a predetermined time to manufacture hardened bodies of the refractories and provide specimens for a test for the evaluation of corrosion resistance with respect to slag at a high temperature.
The rotary corrosion method was used for the evaluation of corrosion resistance with respect to slag at a high temperature. Specimens (refractory 1) cut out into the shape as in FIG. 1 were manufactured, and, as shown in FIG. 2, 8 pieces of the refractory 1 were lined and embedded in a rotary furnace. The size thereof was a=67 mm, b=41 mm, c=48 mm, and d=114 mm. In addition, a cylindrical protection plate 2 (with a diameter of about 150 mmφ) was embedded on the inner side on which 8 pieces of the refractory 1 were lined.
As shown in FIG. 3, the embedded refractory 1 was installed in the rotary furnace, and the temperature was increased by the burning of a burner 3 from the inside of the rotary furnace while rotating the refractory 1. As the burning gas, a gas with a volume ratio of 1 LPG to 5 oxygen was used. Further, the reference number 4 indicates slag, and the reference number 5 indicates a filling material.
The wear amount of each specimen was obtained from the average value obtained by measuring the remaining dimensions (which are the thicknesses of a non-oxidation layer in the case of the thicknesses of a decarburized layer) at 5 points every 20 mm and calculating the difference from the initial thickness (48 mm). The composition of the slag 4 includes 50.5 mass % of CaO, 16.8 mass % of SiO2, 7 mass % of MgO, 2 mass % of Al2O3, 3.5 mass % of MnO, and 20.2 mass % of FeO, and, with the test temperature of 1600° C. and 1 charge of 25 minutes, 500 g of the slag 4 was subjected to 1 charge of the test for a replacement, and the test was performed for a total of 6 charges for 2 hours 30 minutes. The old charge of the slag 4 was replaced with a new charge of the slag 4 by tilting a horizontal type drum.
[1] Example relating to a binder for monolithic refractories including a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm or a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including a solid solution for which all the components of a binder had been controlled so as to solidify Ca components in α-SrAl2O4 and firing conditions had been set so that a crystallite diameter thereof was a value in the tables in Examples 1 to 8 and Reference Examples 1 to 6; monolithic refractories manufactured with binders including a solid solution for which all the components of a binder had been controlled so as to solidify Ca components in β-SrAl2O4 and firing conditions had been set so that a crystallite diameter thereof was a value in the tables in Examples 9 to 16 and Reference Examples 7 to 12; monolithic refractories manufactured with binders including no Sr components in Comparative Examples 1 to 3; and monolithic refractories manufactured with binders including no Ca components in Reference Examples 13 to 16. Tables 1 to 3 show the composition of the raw materials of the binder, the crystallite diameter of the solid solution, the firing conditions, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the examples.
In addition, when the monolithic refractory manufactured with the binder including no Ca components was used in Reference Example 15, the test results were obtained after 0.3 mass % of boric acid powder to be blended into the monolithic refractory was added with respect to the mass of castable in outer percentage so as to obtain a predetermined flow property 2 hours after the start of mixing.















TABLE 1









Reference
Example
Example
Example
Example
Reference
Reference




Example 1
1
2
3
4
Example 2
Example 3





Raw materials of solid
CaCO3
2
2
2
2
2
2
2


solution obtained by
SrCO3
57
57
57
57
57
57
57


dissolving Ca components
α-Al2O4
41
41
41
41
41
41
41


in α- or β-SrAl2O4










(mass %)






















X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution
30
38
47
59
76
81
86


obtained by dissolving Ca components









in SrAl2O4 (nm)









Firing conditions (maximum
1200° C.-
1300° C.-
1400° C.-
1500° C.-
1600° C.-
1400° C.-
1500° C.-


temperature-holding time)
2 hr
2 hr
2 hr
2 hr
1 hr
48 hr
48 hr















15 tap-flow value
After mixing
187
181
176
179
173
162
165


(mm)
After 2 hours
102
118
129
131
134
135
131














Bending strength after
1.8
1.6
1.5
1.3
1.1
0.7
0.6


curing of 6 hours (MPa)









Bending strength after
1.9
1.8
1.8
1.7
1.6
1
0.9


curing of 12 hours (MPa)









Bending strength after
2.2
2.2
2.1
2.1
2.1
1.5
1.3


curing of 24 hours (MPa)









Wear amount in rotary
6.4
6.5
6.6
6.4
6.6
6.9
6.9


corrosion test (mm)




















Reference
Example
Example
Example
Example





Example 4
5
6
7
8






Raw materials of solid
CaCO3
6.2
6.2
6.2
6.2
6.2



solution obtained by
SrCO3
52.2
52.2
52.2
52.2
52.2



dissolving Ca components
α-Al2O4
41.6
41.6
41.6
41.6
41.6



in α- or β-SrAl2O4









(mass %)




















X value of CaxSr1−xAl2O4
0.15
0.15
0.15
0.15
0.15



Crystallite diameter of solid solution
28
36
44
56
73



obtained by dissolving Ca components








in SrAl2O4 (nm)








Firing conditions (maximum
1200° C.-
1300° C.-
1400° C.-
1500° C.-
1600° C.-



temperature-holding time)
2 hr
2 hr
2 hr
2 hr
1 hr















15 tap-flow value
After mixing
182
179
179
175
171



(mm)
After 2 hours
105
122
126
135
136














Bending strength after
1.5
1.6
1.5
1.3
1.2



curing of 6 hours (MPa)








Bending strength after
2
2
1.9
1.7
1.5



curing of 12 hours (MPa)








Bending strength after
2.5
2.4
2.4
2.3
2



curing of 24 hours (MPa)








Wear amount in rotary
6.6
6.4
6.5
6.4
6.5



corrosion test (mm)
























TABLE 2









Reference
Reference
Reference
Example
Example
Example
Example




Example 5
Example 6
Example 7
9
10
11
12





Raw materials of solid
CaCO3
6.2
6.2
12.7
12.7
12.7
12.7
12.7


solution obtained by
SrCO3
52.2
52.2
44.2
44.2
44.2
44.2
44.2


dissolving Ca components
α-Al2O3
41.6
41.6
43.1
43.1
43.1
43.1
43.1


in α- or β-SrAl2O4










(mass %)






















X value of CaxSr1−xAl2O4
0.15
0.15
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution
77
81
31
35
47
54
70


obtained by dissolving Ca components









in SrAl2O4 (nm)









Firing conditions (maximum
1400° C.-
1500° C.-
1200° C.-
1300° C.-
1400° C.-
1500° C.-
1600° C.-


temperature-holding time)
48 hr
48 hr
2 hr
2 hr
2 hr
2 hr
1 hr















15 tap-flow value
After mixing
171
165
176
172
172
169
164


(mm)
After 2 hours
142
135
107
123
125
123
129














Bending strength after
0.6
0.5
1.5
1.5
1.3
1.2
1


curing of 6 hours (MPa)









Bending strength after
1
0.8
1.9
2
1.9
1.7
1.5


curing of 12 hours (MPa)









Bending strength after
1.4
1.3
2.1
2.2
2.3
2.4
2.3


curing of 24 hours (MPa)









Wear amount in rotary
6.6
6.9
6.6
6.4
6.5
6.4
6.5


corrosion test (mm)




















Reference
Reference
Reference
Example
Example





Example 8
Example 9
Example 10
13
14






Raw materials of solid
CaCO3
12.7
12.7
24.6
24.6
24.6



solution obtained by
SrCO3
44.2
44.2
30.1
30.1
30.1



dissolving Ca components
α-Al2O3
43.1
43.1
45.2
45.2
45.2



in α- or β-SrAl2O4









(mass %)




















X value of CaxSr1−xAl2O4
0.3
0.3
0.55
0.55
0.55



Crystallite diameter of solid solution
74
79
24
36
45



obtained by dissolving Ca components








in SrAl2O4 (nm)








Firing conditions (maximum
1400° C.-
1500° C.-
1200° C.-
1300° C.-
1400° C.-



temperature-holding time)
48 hr
48 hr
2 hr
2 hr
2 hr















15 tap-flow value
After mixing
165
160
186
175
174



(mm)
After 2 hours
134
131
109
124
127














Bending strength after
0.6
0.5
1.4
1.3
1.3



curing of 6 hours (MPa)








Bending strength after
0.9
0.8
1.8
1.8
1.7



curing of 12 hours (MPa)








Bending strength after
1.7
1.7
2
2.4
2.4



curing of 24 hours (MPa)








Wear amount in rotary
6.6
6.5
6.6
6.6
6.4



corrosion test (mm)























TABLE 3









Example
Example
Reference
Reference
Reference
Reference




15
16
Example 11
Example 12
Example 13
Example 14





Raw materials of solid solution
CaCO3
24.6
24.6
24.6
24.6
0
0


obtained by dissolving Ca
SrCO3
30.1
30.1
30.1
30.1
59.4
59.4


components in α- or β-
α-Al2O3
45.2
45.2
45.2
45.2
40.6
40.6


SrAl2O4 (mass %)




















X value of CaxSr1−xAl2O4
0.55
0.55
0.55
0.55
0
0


Crystallite diameter of solid solution obtained by
53
65
72
76
41
64


dissolving Ca components in SrAl2O4 (nm)








Firing conditions (maximum
1500° C.-
1600° C.-
1400° C.-
1500° C.-
1300° C.-
1500° C.-


temperature-holding time)
2 hr
1 hr
48 hr
48 hr
2 hr
2 hr














15 tap-flow value
After mixing
171
168
163
159
188
183


(mm)
After 2 hours
126
133
131
134
Solidified
Solidified













Bending strength after
1.2
1.1
0.5
0.5
—
—


curing of 6 hours (MPa)








Bending strength after
1.6
1.5
0.9
0.8
—
—


curing of 12 hours (MPa)








Bending strength after
2.3
2.4
1.8
1.5
—
—


curing of 24 hours (MPa)








Wear amount in rotary
6.5
6.5
6.6
6.8
—
—


corrosion test (mm)




















Reference
Reference
Comparative
Comparative
Comparative





Example 15
Example 16
Example 1
Example 2
Example 3






Raw materials of solid solution
CaCO3
0
0
49.5
49.5
49.5



obtained by dissolving Ca
SrCO3
59.4
59.4
0
0
0



components in α- or β-
α-Al2O3
40.6
40.6
50.5
50.5
50.5



SrAl2O4 (mass %)




















X value of CaxSr1−xAl2O4
0
0
1
1
1



Crystallite diameter of solid solution obtained by
64
76
38
48
49



dissolving Ca components in SrAl2O4 (nm)








Firing conditions (maximum
1500° C.-
1600° C.-
1300° C.-
1500° C.-
1600° C.-



temperature-holding time)
2 hr
2 hr
2 hr
2 hr
2 hr















15 tap-flow value
After mixing
172
177
181
172
173



(mm)
After 2 hours
121
Solidified
122
148
153














Bending strength after
1.4
—
0.6
0.6
0.5



curing of 6 hours (MPa)








Bending strength after
1.8
—
1.1
1.1
1



curing of 12 hours (MPa)








Bending strength after
2.3
—
1.7
1.6
1.7



curing of 24 hours (MPa)








Wear amount in rotary
6.3
—
8.4
8.2
8.4



corrosion test (mm)









The evaluation results are as shown in Tables 1 to 3. In Examples 1 to 16, the flow values suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 1 to 16 can be applied to furnaces with a large volume or the like. Furthermore, Examples 1 to 16 show larger values than Comparative Examples 1 to 3 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 1 to 16 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 1 to 16 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 1 to 16 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In Reference Examples 1, 4, 7, and 10 in which the crystallite diameters of the solid solution obtained by dissolving Ca components in α-SrAl2O4 and the solid solution obtained by dissolving Ca components in β-SrAl2O4 are less than the range of the present invention and in Reference Examples 13, 14, and 16 in which the binder including no Ca components was used, a large amount of deterioration in the flow property after 2 hours or the hardening of the monolithic refractories occurred, and therefore it has been confirmed that it is difficult for Reference Examples 1, 4, 7, and 10 and Reference Examples 13, 14, and 16 be applied to furnaces with a large volume or the like. As described in Reference Example 15, by increasing the amount of boric acid powder as the hardening retardant added, the flow property after 2 hours can be secured. However, it is necessary that the amount of the hardening retardant added be increased to a large degree, which leads to a rise in manufacturing costs. In addition, in Reference Examples 2, 3, 5, 6, 8, 9, 11, and 12 in which the crystallite diameters are more than the range of the present invention, it has been confirmed that, compared to the case where the crystallite diameter is in the range of the present invention, the strength after curing deteriorates, it is difficult for a frame to be removed early, and the risk of explosion increases due to insufficient strength when the monolithic refractories are dried.
From these test results, it has been clarified that, by using the binder including a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm or a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[2] Examples relating to a binder for monolithic refractories including a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm or a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm, into which Al2O3 is blended
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.05, into which α-Al2O3 was blended with a predetermined ratio, in Examples 17 to 21; monolithic refractories manufactured with binders including a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.30, into which α-Al2O3 was blended with a predetermined ratio, in Examples 22 to 26; and monolithic refractories manufactured with binders obtained by blending raw materials so that the composition of a binder is CaAl2O4 and blending the resultant and α-Al2O3 with a predetermined ratio in Comparative Examples 4 to 6. Tables 4 and 5 show the compositions of the solid solutions, the crystallite diameters of the solid solutions, the blending ratio of the solid solutions, CaAl2O4, and α-Al2O3, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples. All of the solid solutions and the binders were subjected to firing for 2 hours at the maximum temperature of 1500° C. for manufacture.















TABLE 4







Example
Example
Example
Example
Example
Example
Example



Example 3
17
18
19
20
21
11
22























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.3
0.3


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
54
54


dissolving Ca components in SrAl2O4 (nm)










Blending ratio of solid solution obtained by dissolving
100
62
60
40
10
8
100
62


Ca components in SrAl2O4 (mass %)










Blending ratio of CaAl2O4 (mass %)
0
0
0
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
38
40
60
90
92
0
38
















15 tap-flow value
After mixing
179
180
175
169
163
158
169
172


(mm)
After 2 hours
131
133
135
134
132
138
123
128















Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.2
1.1
1
0.9
1.2
1.1


Bending strength after curing of 12 hours (MPa)
1.7
1.6
1.6
1.4
1.2
1.2
1.7
1.5


Bending strength after curing of 24 hours (MPa)
2.1
2.2
2.1
1.9
1.7
1.6
2.4
2.2


Wear amount in rotary corrosion test (mm)
6.4
6.1
6
5.7
5.3
5.3
6.4
6.2





Note)


*1Al2O3 other than solid solution and CaAl2O4





















TABLE 5












Compar-
Compar-



Example
Example
Example
Example
Comparative
Comparative
ative
ative



23
24
25
26
Example 2
Example 4
Example 5
Example 6























X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
1
1
1
1


Crystallite diameter of solid solution obtained by
54
54
54
54
—
—
—
—


dissolving Ca components in SrAl2O4 (nm)










Blending ratio of solid solution obtained by
60
40
10
8
—
—
—
—


dissolving Ca components in SrAl2O4 (mass %)










Blending ratio of CaAl2O4 (mass %)
0
0
0
0
100
60
40
10


Blending ratio of α-Al2O3 (mass %)*1
40
60
90
92
0
40
60
90
















15 tap-flow value
After mixing
172
168
163
161
172
170
167
159


(mm)
After 2 hours
131
130
132
135
148
133
135
141















Bending strength after curing of 6 hours (MPa)
1.1
1
0.8
0.8
0.6
0.5
0.5
0.3


Bending strength after curing of 12 hours (MPa)
1.5
1.4
1.2
1.2
1.1
1.1
0.9
0.6


Bending strength after curing of 24 hours (MPa)
2.2
1.9
1.6
1.5
1.6
1.6
1.5
1.1


Wear amount in rotary corrosion test (mm)
6.1
5.7
5.3
5.2
8.2
8
7.9
7.6





Note)


*1Al2O3 other than solid solution and CaAl2O4






The evaluation results are as shown in Tables 4 and 5. In Examples 17 to 26, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 17 to 26 can be applied to furnaces with a large volume or the like. Furthermore, Examples 17 to 26 show larger values than Comparative Examples 1 to 6 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 17 to 26 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 17 to 26 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 17 to 26 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In addition, in Examples 17 to 26, it is possible to further decrease the wear amount in the rotary corrosion test using slag, compared to Examples 3 and 11 including no Al2O3, since Examples 17 to 26 include Al2O3, which clarifies that Examples 17 to 26 are superior in terms of slag resistance at a high temperature.
From these test results, it has been clarified that, by using the binder for monolithic refractories including a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm or a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm, into which Al2O3 is blended, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[3] Examples relating to a binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 or a solid solution obtained by dissolving Ca components in β-SrAl2O4; and a solid solution obtained by dissolving Sr components in CaAl2O4 in which a crystallite diameter of the solid solution is from 25 nm to 60 nm.
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including a mixture of a solid solution for which all the components of a binder had been controlled so as to solidify Ca components in α-SrAl2O4 and a solid solution for which all the components of a binder had been controlled so as to solidify Sr components in CaAl2O4, in which firing conditions had been set so that a crystallite diameter thereof was a value in the tables in Examples 27 to 37 and Reference Examples 17 to 19; and monolithic refractories manufactured with binders including a mixture of a solid solution for which all the components of a binder had been controlled so as to solidify Ca components in β-SrAl2O4 and a solid solution for which all the components of a binder had been controlled so as to solidify Sr components in CaAl2O4, in which firing conditions had been set so that a crystallite diameter thereof was a value in the tables in Examples 38 to 48 and Reference Examples 20 to 22. The solid solution obtained by dissolving Ca components in α-SrAl2O4 and the solid solution obtained by dissolving Ca components in β-SrAl2O4 were subjected to firing for 2 hours at the maximum temperature of 1500° C. for manufacture. Tables 6 to 8 show the composition of the raw materials, the firing conditions, the crystallite diameters of the solid solutions, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples.













TABLE 6









Reference
Example
Example
Example
Example




Example 17
27
28
29
30





Raw materials of solid solution obtained by dissolving
CaCO3
2
2
2
2
2


Ca components in α- or β-SrAl2O4 (mass %)
SrCO3
57
57
57
57
57



α-Al2O3
41
41
41
41
41


X value of CaxSr1−xAl2O4

0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by

59
59
59
59
59


dissolving Ca components in SrAl2O4 (nm)








Blending ratio of solid solution obtained by dissolving

50
50
50
50
50


Ca components in SrAl2O4 (mass %)








Raw materials of solid solution obtained by dissolving
CaCO3
32.3
32.3
32.3
32.3
32.3


Sr components in CaAl2O4 (mass %)
SrCO3
20.6
20.6
20.6
20.6
20.6



α-Al2O3
47
47
47
47
47


X value of CaxSr1−xAl2O4

0.7
0.7
0.7
0.7
0.7


Crystallite diameter of solid solution obtained by

24
29
42
51
59


dissolving Sr components in CaAl2O4 (nm)








Firing conditions (maximum temperature-holding time)

1200° C.-
1300° C.-
1400° C.-
1500° C.-
1600° C.-




2 hr
2 hr
2 hr
2 hr
1 hr


Blending ratio of solid solution obtained by dissolving

50
50
50
50
50


Sr components in CaAl2O4 (mass %)








15 tap-flow value (mm)
After mixing
184
182
183
176
174



After 2 hours
102
119
124
136
132


Bending strength after curing of 6 hours (MPa)

1.6
1.5
1.3
1.3
1.2


Bending strength after curing of 12 hours (MPa)

1.9
1.8
1.7
1.6
1.6


Bending strength after curing of 24 hours (MPa)

2.1
2.2
2.3
2.3
2.3


Wear amount in rotary corrosion test (mm)

6.5
6.6
6.8
6.6
6.7


















Example
Reference
Reference
Example
Example




31
Example 18
Example 19
32
33





Raw materials of solid solution obtained by dissolving
CaCO3
2
2
2
2
2


Ca components in α- or β-SrAl2O4 (mass %)
SrCO3
57
57
57
57
57



α-Al2O3
41
41
41
41
41


X value of CaxSr1−xAl2O4

0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by

59
59
59
59
59


dissolving Ca components in SrAl2O4 (nm)








Blending ratio of solid solution obtained by dissolving

50
50
50
50
50


Ca components in SrAl2O4 (mass %)








Raw materials of solid solution obtained by dissolving
CaCO3
32.3
32.3
46.5
46.5
46.5


Sr components in CaAl2O4 (mass %)
SrCO3
20.6
20.6
3.7
3.7
3.7



α-Al2O3
47
47
49.9
49.9
49.9


X value of CaxSr1−xAl2O4

0.7
0.7
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by

63
68
21
25
39


dissolving Sr components in CaAl2O4 (nm)








Firing conditions (maximum temperature-holding time)

1400° C.-
1500° C.-
1200° C.-
1300° C.-
1400° C.-




48 hr
48 hr
2 hr
2 hr
2 hr


Blending ratio of solid solution obtained by dissolving

50
50
50
50
50


Sr components in CaAl2O4 (mass %)








15 tap-flow value (mm)
After mixing
171
172
181
180
179



After 2 hours
124
131
104
121
134


Bending strength after curing of 6 hours (MPa)

1
0.6
1.6
1.6
1.4


Bending strength after curing of 12 hours (MPa)

1.5
1.1
2
1.9
1.9


Bending strength after curing of 24 hours (MPa)

2.4
2.1
2.2
2.3
2.1


Wear amount in rotary corrosion test (mm)

6.6
6.7
6.7
6.6
6.5

























TABLE 7






Example
Example
Example
Example
Reference
Example
Example
Example
Example



34
35
36
37
Example 20
38
39
40
41

























Raw materials of solid
CaCO3
2
2
2
2
2
12.7
12.7
12.7
12.7


solution obtained by
SrCO3
57
57
57
57
57
44.2
44.2
44.2
44.2


dissolving Ca
α-Al2O3
41
41
41
41
41
43.1
43.1
43.1
43.1


components in α- or












β-SrAl2O4 (mass %)


























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution
59
59
59
59
54
54
54
54
54


obtained by dissolving Ca components











in SrAl2O4 (nm)











Blending ratio of solid solution obtained
50
50
50
50
50
50
50
50
50


by dissolving Ca components











in SrAl2O4 (mass %)


























Raw materials of solid
CaCO3
46.5
46.5
46.5
46.5
32.3
32.3
32.3
32.3
32.3


solution obtained by
SrCO3
3.7
3.7
3.7
3.7
20.6
20.6
20.6
20.6
20.6


dissolving Sr components
α-Al2O3
49.9
49.9
49.9
49.9
47
47
47
47
47


in CaAl2O4 (mass %)


























X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.7
0.7
0.7
0.7
0.7


Crystallite diameter of solid solution
50
55
59
65
24
29
42
51
59


obtained by dissolving Sr











components in CaAl2O4 (nm)











Firing conditions (maximum
1500° C.-
1600° C.-
1400° C.-
1500° C.-
1200° C.-
1300° C.-
1400° C.-
1500° C.-
1600° C.-


temperature-holding time)
2 hr
1 hr
48 hr
48 hr
2 hr
2 hr
2 hr
2 hr
1 hr


Blending ratio of solid solution obtained
50
50
50
50
50
50
50
50
50


by dissolving Sr components in











CaAl2O4 (mass %)


























15 tap-flow value (mm)
After mixing
181
176
172
167
178
180
176
172
167



After 2 hours
135
137
134
134
103
117
122
132
132
















Bending strength after curing of
1.3
1.2
1.1
1.1
1.5
1.4
1.3
1.2
1.1


6 hours (MPa)











Bending strength after curing of
1.6
1.6
1.5
1.4
1.8
1.7
1.7
1.6
1.6


12 hours (MPa)











Bending strength after curing of
2.4
2.5
2.5
2.4
2.4
2.3
2.4
2.3
2.4


24 hours (MPa)











Wear amount in rotary corrosion
6.7
6.7
6.8
6.9
6.6
6.6
6.7
6.6
6.7


test (mm)

























TABLE 8







Reference
Reference









Example
Example
Example
Example
Example
Example
Example
Example
Example



42
21
22
43
44
45
46
47
48

























Raw materials of solid
CaCO3
12.7
12.7
12.7
12.7
12.7
12.7
12.7
12.7
12.7


solution obtained by
SrCO3
44.2
44.2
44.2
44.2
44.2
44.2
44.2
44.2
44.2


dissolving Ca components
α-Al2O3
43.1
43.1
43.1
43.1
43.1
43.1
43.1
43.1
43.1


in α- or β-SrAl2O4 












(mass %)


























X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution
54
54
54
54
54
54
54
54
54


obtained by dissolving Ca components











in SrAl2O4 (nm)











Blending ratio of solid solution obtained
50
50
50
50
50
50
50
50
50


by dissolving Ca components in











SrAl2O4 (mass %)


























Raw materials of solid
CaCO3
32.3
32.3
46.5
46.5
46.5
46.5
46.5
46.5
46.5


solution obtained
SrCO3
20.6
20.6
3.7
3.7
3.7
3.7
3.7
3.7
3.7


by dissolving Sr
α-Al2O3
47
47
49.9
49.9
49.9
49.9
49.9
49.9
49.9


components in CaAl2O4












(mass %)


























X value of CaxSr1−xAl2O4
0.7
0.7
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution
63
68
21
25
39
50
55
59
65


obtained by dissolving Sr











components in CaAl2O4 (nm)











Firing conditions (maximum
1400° C.-
1500° C.-
1200° C.-
1300° C.-
1400° C.-
1500° C.-
1600° C.-
1400° C.-
1500° C.-


temperature-holding time)
48 hr
48 hr
2 hr
2 hr
2 hr
2 hr
1 hr
48 hr
48 hr


Blending ratio of solid solution obtained
50
50
50
50
50
50
50
50
50


by dissolving Sr components in











CaAl2O4 (mass %)


























15 tap-flow value
After mixing
162
163
185
176
172
172
173
169
167


(mm)
After 2 hours
135
131
103
118
124
128
131
134
134
















Bending strength after curing of
0.8
0.6
1.6
1.4
1.3
1.1
1.1
1
1


6 hours (MPa)











Bending strength after curing of
1.4
1
1.9
1.8
1.8
1.6
1.4
1.5
1.4


12 hours (MPa)











Bending strength after curing of
2
1.8
2.1
2.4
2.4
2.5
2.5
2.5
2.4


24 hours (MPa)











Wear amount in rotary corrosion
6.7
6.9
6.8
6.7
6.6
6.7
6.6
6.9
6.9


test (mm)









The evaluation results are as shown in Tables 6 to 8. In Examples 27 to 48, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 27 to 48 can be applied to furnaces with a large volume or the like. Furthermore, Examples 27 to 48 show larger values than Comparative Examples 1 to 3 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 27 to 48 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of Comparative Examples 1 to 3, and therefore it has been confirmed that Examples 27 to 48 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples 1 to 3, Examples 27 to 48 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In Reference Examples 17, 19, 20, and 22 in which the crystallite diameter of the solid solution obtained by dissolving Sr components in CaAl2O4 is less than the range of the present invention, a large amount of deterioration in the flow property after 2 hours occurred, and therefore it has been confirmed that it is difficult for Reference Examples 17, 19, 20, and 22 to be applied to furnaces with a large volume or the like. In addition, in Reference Examples 18 and 21 in which the crystallite diameters are more than the range of the present invention, it has been confirmed that, compared to the case where the crystallite diameter is in the range of the present invention, the flexural strength after curing deteriorates, it is difficult for a frame to be removed early, and the risk of explosion increases due to insufficient strength when the monolithic refractories are dried.
From these test results, it has been clarified that, by using the binder including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm or a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm; and a solid solution obtained by dissolving Sr components in CaAl2O4 in which a crystallite diameter of the solid solution is from 25 nm to 60 nm, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[4] Examples relating to a binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 or β-SrAl2O4 and a solid solution obtained by dissolving Sr components in CaAl2O4, into which Al2O3 is blended
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.05 and a solid solution obtained by dissolving Sr components in CaAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.95, into which α-Al2O3 was blended with a predetermined ratio, in Examples 49 to 53; and monolithic refractories manufactured with binders obtained including a mixture of a solid solution obtained by dissolving Ca components in 13-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.30 and a solid solution obtained by dissolving Sr components in CaAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.95, into which α-Al2O3 was blended with a predetermined ratio, in Examples 54 to 58. Table 9 shows the compositions of the solid solutions, the crystallite diameters, the blending ratio of the solid solutions and α-Al2O3, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples. All of the solid solutions were subjected to firing for 2 hours at the maximum temperature of 1500° C. for manufacture.













TABLE 9








Example
Example
Example
Example
Example
Example



34
49
50
51
52
53





X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by dissolving
59
59
59
59
59
59


Ca components in SrAl2O4 (nm)








Blending ratio of solid solution obtained by dissolving Ca
50
31
30
20
5
4


components in SrAl2O4 (mass %)








X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by dissolving
50
50
50
50
50
50


Sr components in CaAl2O4 (nm)








Blending ratio of solid solution obtained by dissolving Sr
50
31
30
20
5
4


components in CaAl2O4 (mass %)








Blending ratio of α-Al2O3 (mass %)*1
0
38
40
60
90
92














15 tap-flow value
After mixing
181
174
173
170
166
165


(mm)
After 2 hours
135
133
131
138
134
131













Bending strength after curing of 6 hours (MPa)
1.3
1.1
1.1
1.1
1
0.8


Bending strength after curing of 12 hours (MPa)
1.6
1.5
1.5
1.4
1.2
1.2


Bending strength after curing of 24 hours (MPa)
2.4
2.1
2.1
2
1.9
1.8


Wear amount in rotary corrosion test (mm)
6.7
6.2
6.2
5.8
5.4
5.3






Example
Example
Example
Example
Example
Example



45
54
55
56
57
58





X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by dissolving
54
54
54
54
54
54


Ca components in SrAl2O4 (nm)








Blending ratio of solid solution obtained by dissolving Ca
50
31
30
20
5
4


components in SrAl2O4 (mass %)








X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by dissolving
50
50
50
50
50
50


Sr components in CaAl2O4 (nm)








Blending ratio of solid solution obtained by dissolving Sr
50
31
30
20
5
4


components in CaAl2O4 (mass %)








Blending ratio of α-Al2O3 (mass %)*1
0
38
40
60
90
92














15 tap-flow value
After mixing
172
170
168
166
166
165


(mm)
After 2 hours
128
130
132
135
134
131













Bending strength after curing of 6 hours (MPa)
1.1
1
1
0.9
0.8
0.8


Bending strength after curing of 12 hours (MPa)
1.6
1.4
1.4
1.4
1.3
1.2


Bending strength after curing of 24 hours (MPa)
2.5
2.3
2.2
2
1.9
1.9


Wear amount in rotary corrosion test (mm)
6.7
6.3
6.3
5.7
5.5
5.4





Note)


*1Al2O3 other than solid solution and CaAl2O4






The evaluation results are as shown in Table 9. In Examples 49 to 58, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 49 to 58 can be applied to furnaces with a large volume or the like. Furthermore, Examples 49 to 58 show larger values than Comparative Examples 1 to 6 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 49 to 58 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 49 to 58 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 49 to 58 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In addition, in Examples 49 to 58, it is possible to further decrease the wear amount in the rotary corrosion test using slag, compared to Examples 34 and 45 including no Al2O3, since Examples 49 to 58 include Al2O3, which clarifies that Examples 49 to 58 are superior in terms of slag resistance at a high temperature.
From these test results, it has been clarified that, by using the binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm or a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm; and a solid solution obtained by dissolving Sr components in CaAl2O4 in which a crystallite diameter of the solid solution is from 25 nm to 60 nm, into which Al2O3 is blended, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[5] Examples relating to a binder for monolithic refractories including a mixture of both of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm and a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including a mixture of both of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.05 or 0.15 and a crystallite diameter of the solid solution is from 40 nm to 75 nm and a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.30 or 0.55 and a crystallite diameter of the solid solution is from 35 nm to 70 nm in Examples 59 to 94. Tables 10 to 13 show the compositions of the solid solutions, the crystallite diameters of the solid solutions, the firing conditions, the blending ratio of the solid solutions, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples. In each solid solution, firing conditions had been set so that a crystallite diameter thereof was a value in the tables.












TABLE 10








Example 59
Example 60
Example 61
Example 62
Example 63





X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
38
38
38
38
38


dissolving Ca components in α-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1300° C.-2 hr
1300° C.-2 hr
1300° C.-2 hr
1300° C.-2 hr
1300° C.-2 hr


Blending ratio of solid solution obtained by dissolving
50
50
50
50
50


Ca components in α-SrAl2O4 (mass %)







X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.55
0.55


Crystallite diameter of solid solution obtained by
35
54
70
36
53


dissolving Ca components in β-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1300° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr
1300° C.-2 hr
1500° C.-2 hr


Blending ratio of solid solution obtained by
50
50
50
50
50


dissolving Ca components in β-SrAl2O4 (mass %)


















15 tap-flow value
After mixing
184
181
182
179
178


(mm)
After 2 hours
119
122
121
125
125












Bending strength after curing of 6 hours (MPa)
1.5
1.5
1.4
1.4
1.4


Bending strength after curing of 12 hours (MPa)
2
1.9
1.9
1.9
1.8


Bending strength after curing of 24 hours (MPa)
2.4
2.3
2.4
2.3
2.3


Wear amount in rotary corrosion test (mm)
6.4
6.4
6.5
6.5
6.4

















Example 64
Example 65
Example 66
Example 67






X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05



Crystallite diameter of solid solution obtained by
38
59
59
59



dissolving Ca components in α-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1300° C.-2 hr
1500° C.-2 hr
1500° C.-2 hr
1500° C.-2 hr



Blending ratio of solid solution obtained by dissolving
50
50
50
50



Ca components in α-SrAl2O4 (mass %)







X value of CaxSr1−xAl2O4
0.55
0.3
0.3
0.3



Crystallite diameter of solid solution obtained by
65
35
54
70



dissolving Ca components in β-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1600° C.-1 hr
1300° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr



Blending ratio of solid solution obtained by
50
50
50
50



dissolving Ca components in β-SrAl2O4 (mass %)


















15 tap-flow value
After mixing
176
173
171
170



(mm)
After 2 hours
124
124
127
124













Bending strength after curing of 6 hours (MPa)
1.3
1.4
1.3
1.1



Bending strength after curing of 12 hours (MPa)
1.7
1.8
1.7
1.6



Bending strength after curing of 24 hours (MPa)
2.3
2.4
2.3
2.4



Wear amount in rotary corrosion test (mm)
6.5
6.4
6.6
6.6





















TABLE 11








Example 68
Example 69
Example 70
Example 71
Example 72





X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
76
76


dissolving Ca components in α-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1500° C.-2 hr
1500° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr
1600° C.-1 hr


Blending ratio of solid solution obtained by dissolving
50
50
50
50
50


Ca components in α-SrAl2O4 (mass %)







X value of CaxSr1−xAl2O4
0.55
0.55
0.55
0.3
0.3


Crystallite diameter of solid solution obtained by
36
53
65
35
54


dissolving Ca components in β-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1300° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr
1300° C.-2 hr
1500° C.-2 hr


Blending ratio of solid solution obtained by dissolving
50
50
50
50
50


Ca components in β-SrAl2O4 (mass %)


















15 tap-flow value
After mixing
172
171
168
166
165


(mm)
After 2 hours
129
128
131
125
134












Bending strength after curing of 6 hours (MPa)
1.2
1.2
1.1
1.3
1.1


Bending strength after curing of 12 hours (MPa)
1.7
1.7
1.6
1.8
1.6


Bending strength after curing of 24 hours (MPa)
2.2
2.3
2.4
2.1
2.3


Wear amount in rotary corrosion test (mm)
6.5
6.6
6.4
6.6
6.6

















Example 73
Example 74
Example 75
Example 76






X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05



Crystallite diameter of solid solution obtained by
76
76
76
76



dissolving Ca components in α-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1600° C.-1 hr
1600° C.-1 hr
1600° C.-1 hr
1600° C.-1 hr



Blending ratio of solid solution obtained by dissolving
50
50
50
50



Ca components in α-SrAl2O4 (mass %)







X value of CaxSr1−xAl2O4
0.3
0.55
0.55
0.55



Crystallite diameter of solid solution obtained by
70
36
53
65



dissolving Ca components in β-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1600° C.-1 hr
1300° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr



Blending ratio of solid solution obtained by dissolving
50
50
50
50



Ca components in β-SrAl2O4 (mass %)


















15 tap-flow value
After mixing
161
168
165
161



(mm)
After 2 hours
134
127
132
136













Bending strength after curing of 6 hours (MPa)
1
1.2
1.1
1



Bending strength after curing of 12 hours (MPa)
1.5
1.6
1.5
1.5



Bending strength after curing of 24 hours (MPa)
2.3
2.2
2.4
2.3



Wear amount in rotary corrosion test (mm)
6.7
6.6
6.7
6.5





















TABLE 12








Example 77
Example 78
Example 79
Example 80
Example 81





X value of CaxSr1−xAl2O4
0.15
0.15
0.15
0.15
0.15


Crystallite diameter of solid solution obtained by
36
36
36
36
36


dissolving Ca components in α-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1300° C.-2 hr
1300° C.-2 hr
1300° C.-2 hr
1300° C.-2 hr
1300° C.-2 hr


Blending ratio of solid solution obtained by dissolving
50
50
50
50
50


Ca components in α-SrAl2O4(mass %)







X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.55
0.55


Crystallite diameter of solid solution obtained by
35
54
70
36
53


dissolving Ca components in β-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1300° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr
1300° C.-2 hr
1500° C.-2 hr


Blending ratio of solid solution obtained by dissolving
50
50
50
50
50


Ca components in β-SrAl2O4 (mass %)


















15 tap-flow value
After mixing
180
181
173
182
175


(mm)
After 2 hours
119
124
127
120
122












Bending strength after curing of 6 hours (MPa)
1.4
1.4
1.2
1.3
1.2


Bending strength after curing of 12 hours (MPa)
1.9
1.8
1.7
1.8
1.7


Bending strength after curing of 24 hours (MPa)
2.4
2.3
2.4
2.2
2.3


Wear amount in rotary corrosion test (mm)
6.6
6.7
6.7
6.8
6.6

















Example 82
Example 83
Example 84
Example 85






X value of CaxSr1−xAl2O4
0.15
0.15
0.15
0.15



Crystallite diameter of solid solution obtained by
36
56
56
56



dissolving Ca components in α-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1300° C.-2 hr
1500° C.-2 hr
1500° C.-2 hr
1500° C.-2 hr



Blending ratio of solid solution obtained by dissolving
50
50
50
50



Ca components in α-SrAl2O4(mass %)







X value of CaxSr1−xAl2O4
0.55
0.3
0.3
0.3



Crystallite diameter of solid solution obtained by
65
35
54
70



dissolving Ca components in β-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1600° C.-1 hr
1300° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr



Blending ratio of solid solution obtained by dissolving
50
50
50
50



Ca components in β-SrAl2O4 (mass %)


















15 tap-flow value
After mixing
169
179
169
167



(mm)
After 2 hours
132
123
127
127













Bending strength after curing of 6 hours (MPa)
1.1
1.3
1.3
1.1



Bending strength after curing of 12 hours (MPa)
1.6
1.7
1.7
1.6



Bending strength after curing of 24 hours (MPa)
2.4
2.3
2.4
2.3



Wear amount in rotary corrosion test (mm)
6.5
6.7
6.6
6.6





















TABLE 13








Example 86
Example 87
Example 88
Example 89
Example 90





X value of CaxSr1−xAl2O4
0.15
0.15
0.15
0.15
0.15


Crystallite diameter of solid solution obtained by
56
56
56
73
73


dissolving Ca components in α-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1500° C.-2 hr
1500° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr
1600° C.-1 hr


Blending ratio of solid solution obtained by dissolving
50
50
50
50
50


Ca components in α-SrAl2O4 (mass %)







X value of CaxSr1−xAl2O4
0.55
0.55
0.55
0.3
0.3


Crystallite diameter of solid solution obtained by
36
53
65
35
54


dissolving Ca components in β-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1300° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr
1300° C.-2 hr
1500° C.-2 hr


Blending ratio of solid solution obtained by dissolving
50
50
50
50
50


Ca components in β-SrAl2O4 (mass %)


















15 tap-flow value
After mixing
177
169
164
179
170


(mm)
After 2 hours
121
126
130
125
131












Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.1
1.3
1.2


Bending strength after curing of 12 hours (MPa)
1.8
1.7
1.5
1.6
1.6


Bending strength after curing of 24 hours (MPa)
2.2
2.4
2.3
2.1
2.3


Wear amount in rotary corrosion test (mm)
6.8
6.5
6.9
6.8
6.6

















Example 91
Example 92
Example 93
Example 94






X value of CaxSr1−xAl2O4
0.15
0.15
0.15
0.15



Crystallite diameter of solid solution obtained by
73
73
73
73



dissolving Ca components in α-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1600° C.-1 hr
1600° C.-1 hr
1600° C.-1 hr
1600° C.-1 hr



Blending ratio of solid solution obtained by dissolving
50
50
50
50



Ca components in α-SrAl2O4 (mass %)







X value of CaxSr1−xAl2O4
0.3
0.55
0.55
0.55



Crystallite diameter of solid solution obtained by
70
36
53
65



dissolving Ca components in β-SrAl2O4 (nm)







Firing conditions (maximum temperature-holding time)
1600° C.-1 hr
1300° C.-2 hr
1500° C.-2 hr
1600° C.-1 hr



Blending ratio of solid solution obtained by dissolving
50
50
50
50



Ca components in β-SrAl2O4 (mass %)


















15 tap-flow value
After mixing
169
177
173
169



(mm)
After 2 hours
134
124
130
136













Bending strength after curing of 6 hours (MPa)
1.1
1.3
1.2
1.1



Bending strength after curing of 12 hours (MPa)
1.6
1.8
1.7
1.6



Bending strength after curing of 24 hours (MPa)
2.5
2.3
2.4
2.3



Wear amount in rotary corrosion test (mm)
6.7
6.5
6.8
6.6









The evaluation results are as shown in Tables 10 to 13. In Examples 59 to 94, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 59 to 94 can be applied to furnaces with a large volume or the like. Furthermore, Examples 59 to 94 show larger values than Comparative Examples 1 to 3 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 59 to 94 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 59 to 94 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples 1 to 3, Examples 59 to 94 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
From these test results, it has been clarified that, by using the binder for monolithic refractories including a mixture of both of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm and a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[6] Examples relating to a binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 and a solid solution obtained by dissolving Ca components in β-SrAl2O4, into which Al2O3 is blended
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.05 and a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.30, into which α-Al2O3 was blended with a predetermined ratio, in Examples 95 to 99. Table 14 shows the compositions of the solid solutions, the crystallite diameters of the solid solutions, the blending ratio of the solid solutions, the binder, and α-Al2O3, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples. All of the solid solutions were subjected to firing for 2 hours at the maximum temperature of 1500° C. for manufacture.













TABLE 14






Example
Example







66
95
Example 96
Example 97
Example 98
Example 99





















X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained
59
59
59
59
59
59


by dissolving Ca components in α-SrAl2O4 (nm)








Blending ratio of solid solution obtained by
50
31
30
20
5
4


dissolving Ca components in α-SrAl2O4 (mass %)








X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained
54
54
54
54
54
54


by dissolving Ca components in β-SrAl2O4 (nm)








Blending ratio of solid solution obtained by
50
31
30
20
5
4


dissolving Ca components in β-SrAl2O4 (mass %)








Blending ratio of α-Al2O3 (mass %)*1
0
38
40
60
90
92














15 tap-flow value (mm)
After mixing
171
173
175
175
169
165



After 2 hours
127
130
132
135
132
127













Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.2
1.1
1
0.9


Bending strength after curing of 12 hours (MPa)
1.7
1.6
1.6
1.5
1.4
1.4


Bending strength after curing of 24 hours (MPa)
2.3
2.4
2.2
2.3
2.1
2


Wear amount in rotary corrosion test (mm)
6.6
6.2
6.1
5.6
5.2
5.3





Note)


*1Al2O3 other than solid solution and CaAl2O4






The evaluation results are as shown in Table 14. In Examples 95 to 99, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 95 to 99 can be applied to furnaces with a large volume or the like. Furthermore, Examples 95 to 99 show larger values than Comparative Examples 1 to 6 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 95 to 99 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 95 to 99 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 95 to 99 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In addition, in Examples 95 to 99, it is possible to further decrease the wear amount in the rotary corrosion test using slag, compared to Example 66 including no Al2O3, since Examples 95 to 99 include Al2O3, which clarifies that Examples 95 to 99 are superior in terms of slag resistance at a high temperature.
From these test results, it has been clarified that, by using the binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm and a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm, into which Al2O3 is blended, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[7] Examples relating to a binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4, a solid solution obtained by dissolving Ca components in β-SrAl2O4, and a solid solution obtained by dissolving Sr components in CaAl2O4 
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a X value of CaxSr1-xAl2O4Al2O4 is 0.05, a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.30, and a solid solution obtained by dissolving Sr components in CaAl2O4 in which a X value of CaxSr1-xAl2O4 is 0.95 in Examples 100 to 104. Table 15 shows the compositions of the solid solutions, the crystallite diameters of the solid solutions, the blending ratio of the solid solutions, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples. All of the solid solutions were subjected to firing for 2 hours at the maximum temperature of 1500° C. for manufacture.













TABLE 15







Example 100
Example 101
Example 102
Example 103
Example 104





















X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
40
35
30
20
10


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
40
35
30
20
10


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
20
30
40
60
80


dissolving Sr components in CaAl2O4 (mass %)













15 tap-flow value (mm)
After mixing
167
165
166
163
163



After 2 hours
129
133
131
134
137












Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.2
1.1
0.9


Bending strength after curing of 12 hours (MPa)
1.6
1.6
1.5
1.5
1.3


Bending strength after curing of 24 hours (MPa)
2.4
2.5
2.5
2.5
2.5


Wear amount in rotary corrosion test (mm)
6.7
6.6
6.7
6.8
7





Note)


*1Al2O3 other than solid solution and CaAl2O4






The evaluation results are as shown in Table 15. In Examples 100 to 104, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 100 to 104 can be applied to furnaces with a large volume or the like. Furthermore, Examples 100 to 104 show larger values than Comparative Examples 1 to 6 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 100 to 104 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 100 to 104 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 100 to 104 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
From these test results, it has been clarified that, by using the binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm, a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm, and a solid solution obtained by dissolving Sr components in CaAl2O4 in which a crystallite diameter of the solid solution is from 25 nm to 60 nm, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[8] Examples relating to a binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4, a solid solution obtained by dissolving Ca components in β-SrAl2O4, and a solid solution obtained by dissolving Sr components in CaAl2O4, into which Al2O3 is blended
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which an X value of CaxSr1-xAl2O4 is 0.05, a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which an X value of CaxSr1-xAl2O4 is 0.30, and a solid solution obtained by dissolving Sr components in CaAl2O4 in which an X value of CaxSr1-xAl2O4 is 0.95, into which α-Al2O3 is blended, in Examples 105 to 109. Table 16 shows the compositions of the solid solutions, the crystallite diameters of the solid solutions, the blending ratio of the solid solutions and α-Al2O3, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples. All of the solid solutions were subjected to firing for 2 hours at the maximum temperature of 1500° C. for manufacture.













TABLE 16






Example 101
Example 105
Example 106
Example 107
Example 108
Example 109





















X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4(nm)








Blending ratio of solid solution obtained by
35
21.7
21
14
3.5
2.8


dissolving Ca components in α-SrAl2O4 (mass %)








X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained
54
54
54
54
54
54


by dissolving Ca components in β-SrAl2O4 (nm)








Blending ratio of solid solution obtained by
35
21.7
21
14
3.5
2.8


dissolving Ca components in β-SrAl2O4 (mass %)








X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained
50
50
50
50
50
50


by dissolving Sr components in CaAl2O4 (nm)








Blending ratio of solid solution obtained by
30
18.6
18
12
3
2.4


dissolving Sr components in CaAl2O4 (mass %)








Mixing ratio of α-Al2O3 (mass %)*1
0
38
40
60
90
92














15 tap-flow value (mm)
After mixing
166
169
167
166
162
160



After 2 hours
131
134
133
137
133
131













Bending strength after curing of 6 hours (MPa)
1.2
1.1
1.1
1
0.7
0.7


Bending strength after curing of 12 hours (MPa)
1.5
1.5
1.5
1.4
1.2
1.1


Bending strength after curing of 24 hours (MPa)
2.5
2.3
2.2
2
1.9
1.8


Wear amount in rotary corrosion test (mm)
6.7
6.3
6.3
5.9
5.4
5.3





Note)


*1Al2O3 other than solid solution and CaAl2O4






The evaluation results are as shown in Table 16. In Examples 105 to 109, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 105 to 109 can be applied to furnaces with a large volume or the like. Furthermore, Examples 105 to 109 show larger values than Comparative Examples 1 to 6 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 105 to 109 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 105 to 109 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 105 to 109 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In addition, in Examples 105 to 109 it is possible to further decrease the wear amount in the rotary corrosion test using slag, compared to Example 101 including no Al2O3, since Examples 105 to 109 include Al2O3, which clarifies that Examples 105 to 109 are superior in terms of slag resistance at a high temperature.
From these test results, it has been clarified that, by using the binder for monolithic refractories including a mixture of a solid solution obtained by dissolving Ca components in α-SrAl2O4 in which a crystallite diameter of the solid solution is from 40 nm to 75 nm, a solid solution obtained by dissolving Ca components in β-SrAl2O4 in which a crystallite diameter of the solid solution is from 35 nm to 70 nm, and a solid solution obtained by dissolving Sr components in CaAl2O4 in which a crystallite diameter of the solid solution is from 25 nm to 60 nm, into which Al2O3 is blended, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[9] Examples relating to a binder for monolithic refractories according to the present invention including one kind or two or more kinds selected from a group consisting of SiO2, TiO2, Fe2O3, MgO, and BaO in which an amount thereof is 12 mass % or less
Characteristics were evaluated using monolithic refractories manufactured with binders including a solid solution obtained by blending various combinations of one kind or two or more kinds selected from a group consisting of SiO2, TiO2, Fe2O3, MgO, and BaO in Examples 110 to 221 in order to verify the effects of the contamination amount of the raw materials to be used and inevitable impurities generated during the manufacturing process. Characteristics were evaluated using monolithic refractories manufactured with binders having amounts of a variety of contamination components, which were out of the range of the invention, blended thereinto in Comparative Examples 7 to 30.
Characteristics were evaluated using monolithic refractories manufactured with binders including a solid solution for which the chemical components of a binder had been controlled to solidify Ca components in α-SrAl2O4 or β-SrAl2O4 in Examples 110 to 137 and Comparative Examples 7 to 14; monolithic refractories manufactured with binders including a solid solution for which the chemical components of a binder had been controlled to solidify Ca components in α-SrAl2O4 or β-SrAl2O4, into which Al2O3 was blended, in Examples 138 to 149; monolithic refractories manufactured with binders including a mixture of two or three kinds selected from a group consisting of a solid solution for which the chemical components of a binder had been controlled to solidify Ca components in α-SrAl2O4, a solid solution for which the chemical components of a binder had been controlled to solidify Ca components in β-SrAl2O4, and a solid solution for which the chemical components of a binder had been controlled to solidify Sr components in CaAl2O4 in Examples 150 to 197 and Comparative Examples 15 to 30; and monolithic refractories manufactured with binders including a mixture of two or three kinds selected from a group consisting of a solid solution for which the chemical components of a binder had been controlled to solidify Ca components in α-SrAl2O4, a solid solution for which the chemical components of a binder had been controlled to solidify Ca components in β-SrAl2O4, and a solid solution for which the chemical components of a binder had been controlled to solidify Sr components in CaAl2O4, into which Al2O3 was blended, in Examples 198 to 221.
Tables 17 to 43 show the chemical composition and chemical components, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of Examples and Comparative Examples. All of the solid solutions were subjected to firing for 2 hours at the maximum temperature of 1500° C. for manufacture. In addition, the chemical components of the manufactured binders were measured using X-ray fluorescence analysis (“ZSX-Primus II”, a scanning X-ray fluorescence analyzer manufactured by Rigaku Corporation).












TABLE 17






Example 110
Example 111
Example 112
Example 113
Example 114





















Raw materials of solid
CaCO3
2
2
1.9
1.9
1.9


solution A obtained by
SrCO3
55.6
55.6
54.5
54.5
54.5


dissolving Ca
α-Al2O3
40.4
40.4
39.6
39.6
39.6


components in α-SrAl2O4
SiO2
2
0
4
0
0


including various impurity
MgO
0
2
0
4
0


components (mass %)
BaO
0
0
0
0
4



TiO2
0
0
0
0
0



Fe2O3
0
0
0
0
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
58
59
56
61
56


Blending ratio of solid solution A (mass %)
100
100
100
100
100













Raw materials of solid
CaCO3
—
—
—
—
—


solution B obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in β-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution B (nm)
—
—
—
—
—


Blending ratio of solid solution B (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
1.4
1.3
1.3
1.2
1.3


of chemical
SrO
47
47.1
46
45.9
45.9


components of
Al2O3
49.1
49
47.9
48
47.9


binder (mass %)
Total amount of SiO2,
2.4
2.5
4.7
4.8
4.8



MgO, BaO, TiO2, and Fe2O3







15 tap-flow
After mixing
181
180
183
182
185


value (mm)
After 2 hours
133
134
130
129
123












Bending strength after curing of 6 hours (MPa)
1.5
1.5
1.5
1.4
1.4


Bending strength after curing of 12 hours (MPa)
1.9
2
1.9
1.8
2


Bending strength after curing of 24 hours (MPa)
2.2
2.2
2.3
2
2.3


Wear amount in rotary corrosion test/mm
6.3
6.2
6.5
6.2
6.2





Note)


*1Components other than solid solution and CaAl2O4


















TABLE 18






Example 115
Example 116
Example 117
Example 118
Example 119





















Raw materials of solid
CaCO3
1.9
1.9
1.9
1.8
1.8


solution A obtained by
SrCO3
54.5
54.5
53.9
51.7
51.7


dissolving Ca
α-Al2O3
39.6
39.6
39.2
37.5
37.5


components in α-SrAl2O4
SiO2
0
0
1
9
0


including various impurity
MgO
0
0
1
0
9


components (mass %)
BaO
0
0
1
0
0



TiO2
4
0
1
0
0



Fe2O3
0
4
1
0
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
61
56
58
55
63


Blending ratio of solid solution A (mass %)
100
100
100
100
100













Raw materials of solid
CaCO3
—
—
—
—
—


solution B obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in β-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution B (nm)
—
—
—
—
—


Blending ratio of solid solution B (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
1.3
1.3
1.3
1.2
1.3


of chemical
SrO
45.9
45.9
45.4
43.1
43.1


components of
Al2O3
47.9
48
47.4
44.9
45


binder (mass %)
Total amount of SiO2,
4.8
4.7
5.8
10.7
10.5



MgO, BaO, TiO2, and Fe2O3







15 tap-flow
After mixing
180
183
182
179
180


value (mm)
After 2 hours
133
130
134
136
135












Bending strength after curing of 6 hours (MPa)
1.5
1.5
1.4
1.4
1.5


Bending strength after curing of 12 hours (MPa)
1.9
1.9
1.8
1.8
1.8


Bending strength after curing of 24 hours (MPa)
2.2
2.4
2.2
2
2.1


Wear amount in rotary corrosion test/mm
6.4
6.6
6.5
6.7
6.1





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 19











Comparative



Example 120
Example 121
Example 122
Example 123
Example 7






















Raw materials of solid
CaCO3
1.8
1.8
1.8
1.8
1.8


solution A obtained by
SrCO3
51.7
51.7
51.7
51.1
49.9


dissolving Ca
α-Al2O3
37.5
37.5
37.5
37.1
36.3


components in α-SrAl2O4
SiO2
0
0
0
2
12


including various impurity
MgO
0
0
0
2
0


components (mass %)
BaO
9
0
0
2
0



TiO2
0
9
0
2
0



Fe2O3
0
0
9
2
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
60
55
54
57
54


Blending ratio of solid solution A (mass %)
100
100
100
100
100













Raw materials of solid
CaCO3
—
—
—
—
—


solution B obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in β-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution B (nm)
—
—
—
—
—


Blending ratio of solid solution B (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
1.3
1.2
1.2
1.2
1.2


of chemical
SrO
43.1
43.1
43.2
42.3
41.3


components of
Al2O3
45
44.9
44.7
44.4
43.1


binder (mass %)
Total amount of SiO2,
10.6
10.7
10.8
12
14.3



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
175
183
186
184
177


value (mm)
After 2 hours
121
136
122
126
141












Bending strength after curing of 6 hours (MPa)
1.6
1.3
1.5
1.3
0.9


Bending strength after curing of 12 hours (MPa)
2
1.7
1.9
1.8
1.4


Bending strength after curing of 24 hours (MPa)
2.3
2
2.1
2.1
1.9


Wear amount in rotary corrosion test/mm
6.2
6.6
6.9
6.3
7.5





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 20







Comparative
Comparative
Comparative





Example 8
Example 9
Example 10
Example 124
Example 125






















Raw materials of solid
CaCO3
1.8
1.7
1.6
—
—


solution A obtained by
SrCO3
49.9
48.3
45.4
—
—


dissolving Ca
α-Al2O3
36.3
35
33
—
—


components in α-SrAl2O4
SiO2
0
3
4
—
—


including various impurity
MgO
12
3
4
—
—


components (mass %)
BaO
0
3
4
—
—



TiO2
0
3
4
—
—



Fe2O3
0
3
4
—
—












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
—
—


Crystallite diameter of solid solution A (nm)
62
60
52
—
—


Blending ratio of solid solution A (mass %)
100
100
100
0
0













Raw materials of solid
CaCO3
—
—
—
12.5
12.5


solution B obtained by
SrCO3
—
—
—
43
43


dissolving Ca
α-Al2O3
—
—
—
42.5
42.5


components in β-SrAl2O4
SiO2
—
—
—
2
0


including various impurity
MgO
—
—
—
0
2


components (mass %)
BaO
—
—
—
0
0



TiO2
—
—
—
0
0



Fe2O3
—
—
—
0
0












X value of CaxSr1−xAl2O4
—
—
—
0.3
0.3


Crystallite diameter of solid solution B (nm)
—
—
—
54
55


Blending ratio of solid solution B (mass %)
0
0
0
100
100













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
1.3
1.1
0.9
8.5
8.6


of chemical
SrO
41.3
39.8
37.2
36.7
36.7


components of
Al2O3
43.2
41.5
38.7
52.2
52.2


binder (mass %)
Total amount of SiO2,
14.1
17.5
23.1
2.5
2.4



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
177
180
172
175
174


value (mm)
After 2 hours
134
125
118
126
128












Bending strength after curing of 6 hours (MPa)
0.6
1
0.7
1.4
1.3


Bending strength after curing of 12 hours (MPa)
1
1.4
1.1
1.8
1.8


Bending strength after curing of 24 hours (MPa)
1.5
1.8
1.7
2.4
2.3


Wear amount in rotary corrosion test/mm
6.6
7.6
8.2
6.4
6.3





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 21







Example 126
Example 127
Example 128
Example 129
Example 130






















Raw materials of solid
CaCO3
—
—
—
—
—


solution A obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in α-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution A (nm)
—
—
—
—
—


Blending ratio of solid solution A (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
12.3
12.3
12.3
12.3
12.3


solution B obtained by
SrCO3
42.2
42.2
42.2
42.2
42.2


dissolving Ca
α-Al2O3
41.5
41.5
41.5
41.5
41.5


components in β-SrAl2O4
SiO2
4
0
0
0
0


including various impurity
MgO
0
4
0
0
0


components (mass %)
BaO
0
0
4
0
0



TiO2
0
0
0
4
0



Fe2O3
0
0
0
0
4












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
54
56
56
53
53


Blending ratio of solid solution B (mass %)
100
100
100
100
100













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
8.4
8.4
8.4
8.4
8.3


of chemical
SrO
35.9
35.9
35.9
35.9
35.9


components of
Al2O3
50.8
50.8
50.9
50.8
50.8


binder (mass %)
Total amount of SiO2,
4.9
4.9
4.7
4.9
5



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
177
173
171
170
170


value (mm)
After 2 hours
126
129
125
136
131












Bending strength after curing of 6 hours (MPa)
1.4
1.4
1.4
1.3
1.5


Bending strength after curing of 12 hours (MPa)
1.9
1.9
1.9
1.8
1.9


Bending strength after curing of 24 hours (MPa)
2.3
2.4
2.3
2.3
2.4


Wear amount in rotary corrosion test/mm
6.5
6.3
6.3
6.4
6.7





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 22







Example 131
Example 132
Example 133
Example 134
Example 135






















Raw materials of solid
CaCO3
—
—
—
—
—


solution A obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in α-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution A (nm)
—
—
—
—
—


Blending ratio of solid solution A (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
12.1
11.6
11.6
11.6
11.6


solution B obtained by
SrCO3
41.7
40
40
40
40


dissolving Ca
α-Al2O3
41.2
39.4
39.4
39.4
39.4


components in β-SrAl2O4
SiO2
1
9
0
0
0


including various impurity
MgO
1
0
9
0
0


components (mass %)
BaO
1
0
0
9
0



TiO2
1
0
0
0
9



Fe2O3
1
0
0
0
0












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
54
52
58
58
52


Blending ratio of solid solution B (mass %)
100
100
100
100
100













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
8.1
7.8
8
7.8
7.9


of chemical
SrO
35.4
33.6
33.8
33.6
33.6


components of
Al2O3
50.2
47.6
47.5
47.6
47.8


binder (mass %)
Total amount of SiO2,
6.3
10.8
10.7
10.8
10.6



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
174
174
172
168
173


value (mm)
After 2 hours
134
133
137
122
131












Bending strength after curing of 6 hours (MPa)
1.5
1.4
1.4
1.5
1.3


Bending strength after curing of 12 hours (MPa)
1.9
1.8
1.7
2
1.8


Bending strength after curing of 24 hours (MPa)
2.5
2.3
2.4
2.5
2.4


Wear amount in rotary corrosion test/mm
6.5
6.6
6.2
6.2
6.3





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 23









Comparative
Comparative
Comparative



Example 136
Example 137
Example 11
Example 12
Example 13






















Raw materials of solid
CaCO3
—
—
—
—
—


solution A obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in α-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution A (nm)
—
—
—
—
—


Blending ratio of solid solution A (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
11.6
11.5
11.2
11.2
10.8


solution B obtained by
SrCO3
40
39.5
38.7
38.7
37.4


dissolving Ca
α-Al2O3
39.4
39
38.1
38.1
36.8


components in β-SrAl2O4
SiO2
0
2
12
0
3


including various impurity
MgO
0
2
0
12
3


components (mass %)
BaO
0
2
0
0
3



TiO2
0
2
0
0
3



Fe2O3
9
2
0
0
3












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
50
52
54
56
50


Blending ratio of solid solution B (mass %)
100
100
100
100
100













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
7.8
7.8
7.5
7.6
7.2


of chemical
SrO
33.6
33.1
32.3
32.3
31


components of
Al2O3
47.6
47.1
45.6
45.7
43.9


binder (mass %)
Total amount of SiO2,
10.8
12
14.5
14.3
17.8



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
167
173
169
163
170


value (mm)
After 2 hours
123
131
140
143
129












Bending strength after curing of 6 hours (MPa)
1.4
1.4
0.7
0.6
0.8


Bending strength after curing of 12 hours (MPa)
1.8
1.9
1.2
1.1
1.2


Bending strength after curing of 24 hours (MPa)
2.5
2.4
1.7
1.7
1.6


Wear amount in rotary corrosion test/mm
6.9
6.5
7.6
6.7
7.7





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 24







Comparative







Example 14
Example 138
Example 139
Example 140
Example 141






















Raw materials of solid
CaCO3
—
1.8
1.8
1.8
1.8


solution A obtained by
SrCO3
—
51.7
51.7
51.7
51.1


dissolving Ca
α-Al2O3
—
37.5
37.5
37.5
37.1


components in α-SrAl2O4
SiO2
—
9
0
0
2


including various impurity
MgO
—
0
9
0
2


components (mass %)
BaO
—
0
0
9
2



TiO2
—
0
0
0
2



Fe2O3
—
0
0
0
2












X value of CaxSr1−xAl2O4
—
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
—
55
63
60
57


Blending ratio of solid solution A (mass %)
0
40
40
40
40













Raw materials of solid
CaCO3
10.2
—
—
—
—


solution B obtained by
SrCO3
35.1
—
—
—
—


dissolving Ca
α-Al2O3
34.7
—
—
—
—


components in β-SrAl2O4
SiO2
4
—
—
—
—


including various impurity
MgO
4
—
—
—
—


components (mass %)
BaO
4
—
—
—
—



TiO2
4
—
—
—
—



Fe2O3
4
—
—
—
—












X value of CaxSr1−xAl2O4
0.3
—
—
—
—


Crystallite diameter of solid solution B (nm)
48
—
—
—
—


Blending ratio of solid solution B (mass %)
100
0
0
0
0













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
60
60
60
60













Measured value
CaO
6.8
0.5
0.6
0.5
0.5


of chemical
SrO
28.8
17
17.2
17.2
16.8


components of
Al2O3
41
78.1
78
78
77.7


binder (mass %)
Total amount of SiO2,
23.3
4.3
4.2
4.3
4.9



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
161
172
174
175
177


value (mm)
After 2 hours
120
132
137
133
135












Bending strength after curing of 6 hours (MPa)
0.7
1.2
1.3
1.3
1.3


Bending strength after curing of 12 hours (MPa)
1
1.5
1.6
1.7
1.6


Bending strength after curing of 24 hours (MPa)
1.4
2
2.1
1.9
2.1


Wear amount in rotary corrosion test/mm
8.1
5.8
5.7
5.7
5.7





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 25







Example 142
Example 143
Example 144
Example 145
Example 146






















Raw materials of solid
CaCO3
1.7
1.6
—
—
—


solution A obtained by
SrCO3
48.3
45.4
—
—
—


dissolving Ca
α-Al2O3
35
33
—
—
—


components in α-SrAl2O4
SiO2
3
4
—
—
—


including various impurity
MgO
3
4
—
—
—


components (mass %)
BaO
3
4
—
—
—



TiO2
3
4
—
—
—



Fe2O3
3
4
—
—
—












X value of CaxSr1−xAl2O4
0.05
0.05
—
—
—


Crystallite diameter of solid solution A (nm)
60
52
—
—
—


Blending ratio of solid solution A (mass %)
40
40
0
0
0













Raw materials of solid
CaCO3
—
—
11.6
11.6
11.6


solution B obtained by
SrCO3
—
—
40
40
40


dissolving Ca
α-Al2O3
—
—
39.4
39.4
39.4


components in β-SrAl2O4
SiO2
—
—
9
0
0


including various impurity
MgO
—
—
0
9
0


components (mass %)
BaO
—
—
0
0
9



TiO2
—
—
0
0
0



Fe2O3
—
—
0
0
0












X value of CaxSr1−xAl2O4
—
—
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
—
—
52
58
58


Blending ratio of solid solution B (mass %)
0
0
40
40
40













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60













Measured value
CaO
0.4
0.4
3
3.1
3.1


of chemical
SrO
15.8
14.6
13.3
13.4
13.5


components of
Al2O3
76.5
75.4
79.2
78.9
79


binder (mass %)
Total amount of SiO2,
7.1
9.5
4.4
4.5
4.3



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
173
171
170
169
172


value (mm)
After 2 hours
130
133
132
130
131












Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.2
1.2
1.3


Bending strength after curing of 12 hours (MPa)
1.8
1.7
1.6
1.5
1.6


Bending strength after curing of 24 hours (MPa)
2
2.1
2
2.1
2.1


Wear amount in rotary corrosion test/mm
6.1
6.7
5.7
5.7
5.9





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 26







Example 147
Example 148
Example 149
Example 150
Example 151






















Raw materials of solid
CaCO3
—
—
—
1.9
1.9


solution A obtained by
SrCO3
—
—
—
54.5
54.5


dissolving Ca
α-Al2O3
—
—
—
39.6
39.6


components in α-SrAl2O4
SiO2
—
—
—
4
0


including various impurity
MgO
—
—
—
0
4


components (mass %)
BaO
—
—
—
0
0



TiO2
—
—
—
0
0



Fe2O3
—
—
—
0
0












X value of CaxSr1−xAl2O4
—
—
—
0.05
0.05


Crystallite diameter of solid solution A (nm)
—
—
—
56
61


Blending ratio of solid solution A (mass %)
0
0
0
50
50













Raw materials of solid
CaCO3
11.5
10.8
10.2
—
—


solution B obtained by
SrCO3
39.5
37.4
35.1
—
—


dissolving Ca
α-Al2O3
39
36.8
34.7
—
—


components in β-SrAl2O4
SiO2
2
3
4
—
—


including various impurity
MgO
2
3
4
—
—


components (mass %)
BaO
2
3
4
—
—



TiO2
2
3
4
—
—



Fe2O3
2
3
4
—
—












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
—
—


Crystallite diameter of solid solution B (nm)
52
50
48
—
—


Blending ratio of solid solution B (mass %)
40
40
40
0
0













Raw materials of solid
CaCO3
—
—
—
44.7
44.7


solution C obtained by
SrCO3
—
—
—
3.4
3.4


dissolving Sr
α-Al2O3
—
—
—
47.9
47.9


components in CaAl2O4
SiO2
—
—
—
4
0


including various impurity
MgO
—
—
—
0
4


components (mass %)
BaO
—
—
—
0
0



TiO2
—
—
—
0
0



Fe2O3
—
—
—
0
0












X value of CaxSr1−xAl2O4
—
—
—
0.95
0.95


Crystallite diameter of solid solution C (nm)
—
—
—
49
52


Blending ratio of solid solution C (mass %)
0
0
0
50
50


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
0
0













Measured value
CaO
3.1
2.9
2.7
16.2
16.1


of chemical
SrO
13.1
12.4
11.5
24.9
24.9


components of
Al2O3
78.8
77.5
76.4
54.2
54.1


binder (mass %)
Total amount of SiO2,
4.9
7.3
9.4
4.7
4.9



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
174
171
174
183
181


value (mm)
After 2 hours
131
127
127
137
138












Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.2
1.4
1.4


Bending strength after curing of 12 hours (MPa)
1.6
1.6
1.5
1.7
1.7


Bending strength after curing of 24 hours (MPa)
2
2.1
1.9
2.6
2.5


Wear amount in rotary corrosion test/mm
6.1
6.4
6.9
6.7
6.6





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 27







Example 152
Example 153
Example 154
Example 155
Example 156






















Raw materials of solid
CaCO3
1.9
1.9
1.9
1.9
1.9


solution A obtained by
SrCO3
54.5
54.5
54.5
53.9
51.7


dissolving Ca
α-Al2O3
39.6
39.6
39.6
39.2
37.5


components in α-SrAl2O4
SiO2
0
0
0
1
9


including various impurity
MgO
0
0
0
1
0


components (mass %)
BaO
4
0
0
1
0



TiO2
0
4
0
1
0



Fe2O3
0
0
4
1
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
56
61
56
58
55


Blending ratio of solid solution A (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
—
—
—
—
—


solution B obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in β-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution B (nm)
—
—
—
—
—


Blending ratio of solid solution B (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
44.7
44.7
44.7
44.2
44.3


solution C obtained by
SrCO3
3.4
3.4
3.4
3.4
3.3


dissolving Sr
α-Al2O3
47.9
47.9
47.9
47.9
45.4


components in CaAl2O4
SiO2
0
0
0
1
9


including various impurity
MgO
0
0
0
1
0


components (mass %)
BaO
4
0
0
1
0



TiO2
0
4
0
1
0



Fe2O3
0
0
4
1
0












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
51
48
46
49
48


Blending ratio of solid solution C (mass %)
50
50
50
50
50


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
16.1
16
16.1
15.9
15


of chemical
SrO
24.9
24.9
24.7
24.6
23.2


components of
Al2O3
54.1
54.3
54.1
53.4
50.7


binder (mass %)
Total amount of SiO2,
4.9
4.8
5
6
11



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
179
184
181
183
180


value (mm)
After 2 hours
137
136
135
134
139












Bending strength after curing of 6 hours (MPa)
1.6
1.5
1.4
1.4
1.4


Bending strength after curing of 12 hours (MPa)
2
1.9
1.9
1.8
1.8


Bending strength after curing of 24 hours (MPa)
2.4
2.3
2.5
2.4
2.3


Wear amount in rotary corrosion test/mm
6.9
6.6
6.7
6.9
7.1





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 28







Example 157
Example 158
Example 159
Example 160
Example 161






















Raw materials of solid
CaCO3
1.8
1.8
1.8
1.8
1.8


solution A obtained by
SrCO3
51.7
51.7
51.7
51.7
51.1


dissolving Ca
α-Al2O3
37.5
37.5
37.5
37.5
37.1


components in α-SrAl2O4
SiO2
0
0
0
0
2


including various impurity
MgO
9
0
0
0
2


components (mass %)
BaO
0
9
0
0
2



TiO2
0
0
9
0
2



Fe2O3
0
0
0
9
2












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
63
60
55
54
57


Blending ratio of solid solution A (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
—
—
—
—
—


solution B obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in β-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution B (nm)
—
—
—
—
—


Blending ratio of solid solution B (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
42.3
42.3
42.3
42.3
42.3


solution C obtained by
SrCO3
3.3
3.3
3.3
3.3
3.2


dissolving Sr
α-Al2O3
45.4
45.4
45.4
45.4
44.9


components in CaAl2O4
SiO2
0
0
0
0
2


including various impurity
MgO
9
0
0
0
2


components (mass %)
BaO
0
9
0
0
2



TiO2
0
0
9
0
2



Fe2O3
0
0
0
9
2












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
53
54
48
44
46


Blending ratio of solid solution C (mass %)
50
50
50
50
50


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
15
14.9
15.2
15
14.9


of chemical
SrO
23.3
23.4
23.3
23.3
23


components of
Al2O3
50.6
50.6
50.7
50.6
50.1


binder (mass %)
Total amount of SiO2,
10.9
11
10.7
10.9
11.9



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
184
181
178
182
180


value (mm)
After 2 hours
138
125
140
130
134












Bending strength after curing of 6 hours (MPa)
1.4
1.5
1.3
1.4
1.4


Bending strength after curing of 12 hours (MPa)
1.7
1.9
1.7
1.7
1.8


Bending strength after curing of 24 hours (MPa)
2.4
2.5
2.4
2.4
2.5


Wear amount in rotary corrosion test/mm
6.8
6.8
6.9
7.1
6.9





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 29







Comparative
Comparative
Comparative
Comparative




Example 15
Example 16
Example 17
Example 18
Example 162






















Raw materials of solid
CaCO3
1.8
1.8
1.7
1.6
—


solution A obtained by
SrCO3
49.9
49.9
48.3
45.4
—


dissolving Ca
α-Al2O3
36.3
36.3
35
33
—


components in α-SrAl2O4
SiO2
12
0
3
4
—


including various impurity
MgO
0
12
3
4
—


components (mass %)
BaO
0
0
3
4
—



TiO2
0
0
3
4
—



Fe2O3
0
0
3
4
—












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
—


Crystallite diameter of solid solution A (nm)
54
62
60
52
—


Blending ratio of solid solution A (mass %)
50
50
50
50
0













Raw materials of solid
CaCO3
—
—
—
—
12.3


solution B obtained by
SrCO3
—
—
—
—
42.2


dissolving Ca
α-Al2O3
—
—
—
—
41.5


components in β-SrAl2O4
SiO2
—
—
—
—
4


including various impurity
MgO
—
—
—
—
0


components (mass %)
BaO
—
—
—
—
0



TiO2
—
—
—
—
0



Fe2O3
—
—
—
—
0












X value of CaxSr1−xAl2O4
—
—
—
—
0.3


Crystallite diameter of solid solution B (nm)
—
—
—
—
54


Blending ratio of solid solution B (mass %)
0
0
0
0
50













Raw materials of solid
CaCO3
40.9
40.9
39.6
37.3
44.7


solution C obtained by
SrCO3
3.2
3.2
3.1
2.9
3.4


dissolving Sr
α-Al2O3
43.9
43.9
42.3
39.8
47.9


components in CaAl2O4
SiO2
12
0
3
4
4


including various impurity
MgO
0
12
3
4
0


components (mass %)
BaO
0
0
3
4
0



TiO2
0
0
3
4
0



Fe2O3
0
0
3
4
0












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
46
49
47
45
49


Blending ratio of solid solution C (mass %)
50
50
50
50
50


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
14.5
14.3
14
12.9
19.8


of chemical
SrO
22.4
22.5
21.6
19.9
19.7


components of
Al2O3
48.6
48.6
46.5
43.3
55.5


binder (mass %)
Total amount of SiO2,
14.5
14.5
17.8
23.8
5



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
176
169
178
166
174


value (mm)
After 2 hours
126
121
129
123
130












Bending strength after curing of 6 hours (MPa)
0.6
0.5
0.7
0.6
1.3


Bending strength after curing of 12 hours (MPa)
0.9
0.7
1
1
1.7


Bending strength after curing of 24 hours (MPa)
1.1
1
1.3
1.3
2.5


Wear amount in rotary corrosion test/mm
7.5
7
7.6
8
6.2





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 30







Example 163
Example 164
Example 165
Example 166
Example 167






















Raw materials of solid
CaCO3
—
—
—
—
—


solution A obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in α-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution A (nm)
—
—
—
—
—


Blending ratio of solid solution A (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
12.3
12.3
12.3
12.3
12.1


solution B obtained by
SrCO3
42.2
42.2
42.2
42.2
41.7


dissolving Ca
α-Al2O3
41.5
41.5
41.5
41.5
41.2


components in β-SrAl2O4
SiO2
0
0
0
0
1


including various impurity
MgO
4
0
0
0
1


components (mass %)
BaO
0
4
0
0
1



TiO2
0
0
4
0
1



Fe2O3
0
0
0
4
1












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
56
56
53
53
54


Blending ratio of solid solution B (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
44.7
44.7
44.7
44.7
44.2


solution C obtained by
SrCO3
3.4
3.4
3.4
3.4
3.4


dissolving Sr
α-Al2O3
47.9
47.9
47.9
47.9
47.4


components in CaAl2O4
SiO2
0
0
0
0
1


including various impurity
MgO
4
0
0
0
1


components (mass %)
BaO
0
4
0
0
1



TiO2
0
0
4
0
1



Fe2O3
0
0
0
4
1












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
52
51
48
46
49


Blending ratio of solid solution C (mass %)
50
50
50
50
50


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
19.9
19.8
19.6
19.6
19.5


of chemical
SrO
19.5
19.7
19.8
19.5
19.5


components of
Al2O3
55.6
55.7
55.5
55.8
54.8


binder (mass %)
Total amount of SiO2,
4.9
4.8
5
5.1
6.1



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
176
171
175
174
176


value (mm)
After 2 hours
131
129
134
131
131












Bending strength after curing of 6 hours (MPa)
1.3
1.4
1.3
1.4
1.4


Bending strength after curing of 12 hours (MPa)
1.7
1.8
1.7
1.8
1.9


Bending strength after curing of 24 hours (MPa)
2.6
2.5
2.5
2.5
2.6


Wear amount in rotary corrosion test/mm
6.1
6.2
6.2
6.7
6.3





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 31







Example 168
Example 169
Example 170
Example 171
Example 172






















Raw materials of solid
CaCO3
—
—
—
—
—


solution A obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in α-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution A (nm)
—
—
—
—
—


Blending ratio of solid solution A (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
11.6
11.6
11.6
11.6
11.6


solution B obtained by
SrCO3
40
40
40
40
40


dissolving Ca
α-Al2O3
39.4
39.4
39.4
39.4
39.4


components in β-SrAl2O4
SiO2
9
0
0
0
0


including various impurity
MgO
0
9
0
0
0


components (mass %)
BaO
0
0
9
0
0



TiO2
0
0
0
9
0



Fe2O3
0
0
0
0
9












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
52
58
58
52
50


Blending ratio of solid solution B (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
42.3
42.3
42.3
42.3
42.3


solution C obtained by
SrCO3
3.3
3.3
3.3
3.3
3.3


dissolving Sr
α-Al2O3
45.4
45.4
45.4
45.4
45.4


components in CaAl2O4
SiO2
9
0
0
0
0


including various impurity
MgO
0
9
0
0
0


components (mass %)
BaO
0
0
9
0
0



TiO2
0
0
0
9
0



Fe2O3
0
0
0
0
9












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
48
53
54
48
44


Blending ratio of solid solution C (mass %)
50
50
50
50
50


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
18.5
18.5
18.4
18.5
18.4


of chemical
SrO
18.2
18.3
18.3
18.4
18.4


components of
Al2O3
52.1
52.1
52.3
52
51.9


binder (mass %)
Total amount of SiO2,
11.1
11
10.9
11
11.2



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
173
177
170
169
173


value (mm)
After 2 hours
133
134
127
139
133












Bending strength after curing of 6 hours (MPa)
1.3
1.3
1.4
1.2
1.2


Bending strength after curing of 12 hours (MPa)
1.8
1.7
1.9
1.7
1.7


Bending strength after curing of 24 hours (MPa)
2.6
2.5
2.5
2.4
2.4


Wear amount in rotary corrosion test/mm
6.5
6.3
6.4
6.5
7





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 32








Comparative
Comparative
Comparative
Comparative



Example 173
Example 19
Example 20
Example 21
Example 22






















Raw materials of solid
CaCO3
—
—
—
—
—


solution A obtained by
SrCO3
—
—
—
—
—


dissolving Ca
α-Al2O3
—
—
—
—
—


components in α-SrAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution A (nm)
—
—
—
—
—


Blending ratio of solid solution A (mass %)
0
0
0
0
0













Raw materials of solid
CaCO3
11.5
11.2
11.2
10.8
10.2


solution B obtained by
SrCO3
39.5
38.7
38.7
37.4
35.1


dissolving Ca
α-Al2O3
39
38.1
38.1
36.8
34.7


components in β-SrAl2O4
SiO2
2
12
0
3
4


including various impurity
MgO
2
0
12
3
4


components (mass %)
BaO
2
0
0
3
4



TiO2
2
0
0
3
4



Fe2O3
2
0
0
3
4












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
52
54
56
50
48


Blending ratio of solid solution B (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
41.9
40.9
40.9
39.6
37.3


solution C obtained by
SrCO3
3.2
3.2
3.2
3.1
2.9


dissolving Sr
α-Al2O3
44.9
43.9
43.9
42.3
39.8


components in CaAl2O4
SiO2
2
12
0
3
4


including various impurity
MgO
2
0
12
3
4


components (mass %)
BaO
2
0
0
3
4



TiO2
2
0
0
3
4



Fe2O3
2
0
0
3
4












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
46
46
49
47
45


Blending ratio of solid solution C (mass %)
50
50
50
50
50


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
18.3
17.7
17.9
17
15.8


of chemical
SrO
18.1
17.6
17.7
17.1
15.8


components of
Al2O3
51.4
50
49.7
47.8
44.7


binder (mass %)
Total amount of SiO2,
12
14.6
14.6
18
23.7



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
172
167
162
170
164


value (mm)
After 2 hours
131
132
127
126
120












Bending strength after curing of 6 hours (MPa)
1.3
0.6
0.5
0.6
0.6


Bending strength after curing of 12 hours (MPa)
1.8
0.9
0.8
0.9
0.8


Bending strength after curing of 24 hours (MPa)
2.5
1.3
1.3
1.4
1.2


Wear amount in rotary corrosion test/mm
6.8
7.5
7.1
7.7
8.1





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 33







Example 174
Example 175
Example 176
Example 177
Example 178






















Raw materials of solid
CaCO3
1.9
1.9
1.9
1.9
1.9


solution A obtained by
SrCO3
54.5
54.5
54.5
54.5
54.5


dissolving Ca
α-Al2O3
39.6
39.6
39.6
39.6
39.6


components in α-SrAl2O4
SiO2
4
0
0
0
0


including various impurity
MgO
0
4
0
0
0


components (mass %)
BaO
0
0
4
0
0



TiO2
0
0
0
4
0



Fe2O3
0
0
0
0
4












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
56
61
56
61
56


Blending ratio of solid solution A (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
12.3
12.3
12.3
12.3
12.3


solution B obtained by
SrCO3
42.2
42.2
42.2
42.2
42.2


dissolving Ca
α-Al2O3
41.5
41.5
41.5
41.5
41.5


components in β-SrAl2O4
SiO2
4
0
0
0
0


including various impurity
MgO
0
4
0
0
0


components (mass %)
BaO
0
0
4
0
0



TiO2
0
0
0
4
0



Fe2O3
0
0
0
0
4












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
54
56
56
53
53


Blending ratio of solid solution B (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
4.8
4.9
4.8
4.8
4.7


of chemical
SrO
41
41
40.9
40.9
41.1


components of
Al2O3
49.4
49.4
49.4
49.6
49.4


binder (mass %)
Total amount of SiO2,
4.7
4.6
4.8
4.6
4.8



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
173
175
170
173
170


value (mm)
After 2 hours
127
130
125
131
134












Bending strength after curing of 6 hours (MPa)
1.4
1.5
1.4
1.3
1.5


Bending strength after curing of 12 hours (MPa)
1.9
1.9
1.9
1.8
1.8


Bending strength after curing of 24 hours (MPa)
2.3
2.4
2.3
2.4
2.3


Wear amount in rotary corrosion test/mm
6.6
6.5
6.6
6.5
6.8





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 34







Example 179
Example 180
Example 181
Example 182
Example 183






















Raw materials of solid
CaCO3
1.9
1.8
1.8
1.8
59 1.8


solution A obtained by
SrCO3
53.9
51.7
51.7
51.7
51.7


dissolving Ca
α-Al2O3
39.2
37.5
37.5
37.5
37.5


components in α-SrAl2O4
SiO2
1
9
0
0
0


including various impurity
MgO
1
0
9
0
0


components (mass %)
BaO
1
0
0
9
0



TiO2
1
0
0
0
9



Fe2O3
1
0
0
0
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
58
55
63
60
55


Blending ratio of solid solution A (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
12.1
11.6
11.6
11.6
11.6


solution B obtained by
SrCO3
41.7
40
40
40
40


dissolving Ca
α-Al2O3
41.2
39.4
39.4
39.4
39.4


components in β-SrAl2O4
SiO2
1
9
0
0
0


including various impurity
MgO
1
0
9
0
0


components (mass %)
BaO
1
0
0
9
0



TiO2
1
0
0
0
9



Fe2O3
1
0
0
0
0












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
54
52
58
58
52


Blending ratio of solid solution B (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of as α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
Cao
4.7
4.4
4.5
4.5
4.5


of chemical
SrO
40.3
38.4
38.4
38.4
38.4


components of
Al2O3
49
46.4
46.2
46.3
46.3


binder (mass %)
Total amount of SiO2,
5.9
10.7
10.9
10.8
10.8



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
175
170
173
169
172


value (mm)
After 2 hours
135
137
135
126
139












Bending strength after curing of 6 hours (MPa)
1.5
1.4
1.4
1.5
1.3


Bending strength after curing of 12 hours (MPa)
1.9
1.8
1.9
1.9
1.8


Bending strength after curing of 24 hours (MPa)
2.5
2.3
2.4
2.5
2.3


Wear amount in rotary corrosion test/mm
6.7
6.9
6.7
6.7
6.7





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 35









Comparative
Comparative
Comparative



Example 184
Example 185
Example 23
Example 24
Example 25






















Raw materials of solid
CaCO3
1.8
1.8
1.8
1.8
1.7


solution A obtained by
SrCO3
51.7
51.1
49.9
49.9
48.3


dissolving Ca
α-Al2O3
37.5
37.1
36.3
36.3
35


components in α-SrAl2O4
SiO2
0
2
12
0
3


including various impurity
MgO
0
2
0
12
3


components (mass %)
BaO
0
2
0
0
3



TiO2
0
2
0
0
3



Fe2O3
9
2
0
0
3












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
54
57
54
62
60


Blending ratio of solid solution A (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
11.6
11.5
11.2
11.2
10.8


solution B obtained by
SrCO3
40
39.5
38.7
38.7
37.4


dissolving Ca
α-Al2O3
39.4
39
38.1
38.1
36.8


components in β-SrAl2O4
SiO2
0
2
12
0
3


including various impurity
MgO
0
2
0
12
3


components (mass %)
BaO
0
2
0
0
3



TiO2
0
2
0
0
3



Fe2O3
9
2
0
0
3












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
50
52
54
56
50


Blending ratio of solid solution B (mass %)
50
50
50
50
50













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
4.3
4.4
4.3
4.3
4.1


of chemical
SrO
38.5
37.9
36.9
36.8
35.3


components of
Al2O3
46.1
45.7
44.3
44.6
42.6


binder (mass %)
Total amount of SiO2,
11
11.9
14.4
14.2
17.9



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
167
172
167
164
172


value (mm)
After 2 hours
134
136
130
135
132












Bending strength after curing of 6 hours (MPa)
1.3
1.4
0.6
0.5
0.7


Bending strength after curing of 12 hours (MPa)
1.8
1.9
0.9
0.8
1


Bending strength after curing of 24 hours (MPa)
2.4
2.3
1.3
1.3
1.4


Wear amount in rotary corrosion test/mm
7.1
6.9
7.2
6.9
7.3





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 36







Comparative







Example 26
Example 186
Example 187
Example 188
Example 189






















Raw materials of solid
CaCO3
1.6
1.9
1.9
1.9
1.9


solution A obtained by
SrCO3
45.4
54.5
54.5
54.5
54.5


dissolving Ca
α-Al2O3
33
39.6
39.6
39.6
39.6


components in α-SrAl2O4
SiO2
4
4
0
0
0


including various impurity
MgO
4
0
4
0
0


components (mass %)
BaO
4
0
0
4
0



TiO2
4
0
0
0
4



Fe2O3
4
0
0
0
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
52
56
61
56
61


Blending ratio of solid solution A (mass %)
50
35
35
35
35













Raw materials of solid
CaCO3
10.2
12.3
12.3
12.3
12.3


solution B obtained by
SrCO3
35.1
42.2
42.2
42.2
42.2


dissolving Ca
α-Al2O3
34.7
41.5
41.5
41.5
41.5


components in β-SrAl2O4
SiO2
4
4
0
0
0


including various impurity
MgO
4
0
4
0
0


components (mass %)
BaO
4
0
0
4
0



TiO2
4
0
0
0
4



Fe2O3
4
0
0
0
0












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
48
54
56
56
53


Blending ratio of solid solution B (mass %)
50
35
35
35
35













Raw materials of solid
CaCO3
—
44.7
44.7
44.7
44.7


solution C obtained by
SrCO3
—
3.4
3.4
3.4
3.4


dissolving Sr
α-Al2O3
—
47.9
47.9
47.9
47.9


components in CaAl2O4
SiO2
—
4
0
0
0


including various impurity
MgO
—
0
4
0
0


components (mass %)
BaO
—
0
0
4
0



TiO2
—
0
0
0
4



Fe2O3
—
0
0
0
0












X value of CaxSr1−xAl2O4
—
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
—
49
52
51
48


Blending ratio of solid solution C (mass %)
0
30
30
30
30


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
3.8
12.6
12.5
12.8
12.7


of chemical
SrO
32.7
29.7
29.8
29.6
29.8


components of
Al2O3
39.9
52.6
52.7
52.7
52.6


binder (mass %)
Total amount of SiO2,
23.5
5
4.9
4.8
4.8



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
165
166
169
163
170


value (mm)
After 2 hours
122
134
136
128
135












Bending strength after curing of 6 hours (MPa)
0.5
1.4
1.4
1.5
1.3


Bending strength after curing of 12 hours (MPa)
0.9
1.7
1.8
1.8
1.6


Bending strength after curing of 24 hours (MPa)
1.3
2.6
2.6
2.5
2.6


Wear amount in rotary corrosion test/mm
7.5
6.7
6.8
6.7
6.6





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 37







Example 190
Example 191
Example 192
Example 193
Example 194






















Raw materials of solid
CaCO3
1.9
1.9
1.8
1.8
1.8


solution A obtained by
SrCO3
54.5
53.9
51.7
51.7
51.7


dissolving Ca
α-Al2O3
39.6
39.2
37.5
37.5
37.5


components in α-SrAl2O4
SiO2
0
1
9
0
0


including various impurity
MgO
0
1
0
9
0


components (mass %)
BaO
0
1
0
0
9



TiO2
0
1
0
0
0



Fe2O3
4
1
0
0
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
56
58
55
63
60


Blending ratio of solid solution A (mass %)
35
35
35
35
35













Raw materials of solid
CaCO3
12.3
12.1
11.6
11.6
11.6


solution B obtained by
SrCO3
42.2
41.7
40
40
40


dissolving Ca
α-Al2O3
41.5
41.2
39.4
39.4
39.4


components in β-SrAl2O4
SiO2
0
1
9
0
0


including various impurity
MgO
0
1
0
9
0


components (mass %)
BaO
0
1
0
0
9



TiO2
0
1
0
0
0



Fe2O3
4
1
0
0
0












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
53
54
52
58
58


Blending ratio of solid solution B (mass %)
35
35
35
35
35













Raw materials of solid
CaCO3
44.7
44.2
42.3
42.3
42.3


solution C obtained by
SrCO3
3.4
3.4
3.3
3.3
3.3


dissolving Sr
α-Al2O3
47.9
47.4
45.4
45.4
45.4


components in CaAl2O4
SiO2
0
1
9
0
0


including various impurity
MgO
0
1
0
9
0


components (mass %)
BaO
0
1
0
0
9



TiO2
0
1
0
0
0



Fe2O3
4
1
0
0
0












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
46
49
48
53
54


Blending ratio of solid solution C (mass %)
30
30
30
30
30


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
12.6
12.4
11.8
11.8
11.9


of chemical
SrO
29.8
29.3
27.9
27.9
27.9


components of
Al2O3
52.5
51.9
49.3
49.3
49.3


binder (mass %)
Total amount of SiO2,
5
6.3
10.9
10.9
10.8



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
168
171
170
172
163


value (mm)
After 2 hours
134
135
137
136
124












Bending strength after curing of 6 hours (MPa)
1.4
1.4
1.3
1.3
1.5


Bending strength after curing of 12 hours (MPa)
1.7
1.8
1.7
1.6
1.9


Bending strength after curing of 24 hours (MPa)
2.7
2.6
2.5
2.4
2.5


Wear amount in rotary corrosion test/mm
7
6.8
7
6.5
6.8





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 38










Comparative
Comparative



Example 195
Example 196
Example 197
Example 27
Example 28






















Raw materials of solid
CaCO3
1.8
1.8
1.8
1.8
1.8


solution A obtained by
SrCO3
51.7
51.7
51.1
49.9
49.9


dissolving Ca
α-Al2O3
37.5
37.5
37.1
36.3
36.3


components in α-SrAl2O4
SiO2
0
0
2
12
0


including various impurity
MgO
0
0
2
0
12


components (mass %)
BaO
0
0
2
0
0



TiO2
9
0
2
0
0



Fe2O3
0
9
2
0
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
55
54
57
54
62


Blending ratio of solid solution A (mass %)
35
35
35
35
35













Raw materials of solid
CaCO3
11.6
11.6
11.5
11.2
11.2


solution B obtained by
SrCO3
40
40
39.5
38.7
38.7


dissolving Ca
α-Al2O3
39.4
39.4
39
38.1
38.1


components in β-SrAl2O4
SiO2
0
0
2
12
0


including various impurity
MgO
0
0
2
0
12


components (mass %)
BaO
0
0
2
0
0



TiO2
9
0
2
0
0



Fe2O3
0
9
2
0
0












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
52
50
52
54
56


Blending ratio of solid solution B (mass %)
35
35
35
35
35













Raw materials of solid
CaCO3
42.3
42.3
41.9
40.9
40.9


solution C obtained by
SrCO3
3.3
3.3
3.2
3.2
3.2


dissolving Sr
α-Al2O3
45.4
45.4
44.9
43.9
43.9


components in CaAl2O4
SiO2
0
0
2
12
0


including various impurity
MgO
0
0
2
0
12


components (mass %)
BaO
0
0
2
0
0



TiO2
9
0
2
0
0



Fe2O3
0
9
2
0
0












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
48
44
46
46
49


Blending ratio of solid solution C (mass %)
30
30
30
30
30


Blending ratio of α-Al2O3 (mass %)*1
0
0
0
0
0













Measured value
CaO
11.8
11.8
11.7
11.4
11.3


of chemical
SrO
27.9
27.9
27.5
26.6
26.7


components of
Al2O3
49.3
49.3
48.7
47.2
47.4


binder (mass %)
Total amount of SiO2,
10.9
10.9
12
14.7
14.5



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
170
166
168
166
161


value (mm)
After 2 hours
140
138
137
141
131












Bending strength after curing of 6 hours (MPa)
1.3
1.3
1.4
0.6
0.5


Bending strength after curing of 12 hours (MPa)
1.6
1.6
1.7
0.9
0.8


Bending strength after curing of 24 hours (MPa)
2.5
2.6
2.4
1.4
1.2


Wear amount in rotary corrosion test/mm
6.7
7.1
7
7.6
7.1





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 39







Comparative
Comparative






Example 29
Example 30
Example 198
Example 199
Example 200






















Raw materials of solid
CaCO3
1.7
1.6
1.8
1.8
1.8


solution A obtained by
SrCO3
48.3
45.4
51.7
51.7
51.7


dissolving Ca
α-Al2O3
35
33
37.5
37.5
37.5


components in α-SrAl2O4
SiO2
3
4
9
0
0


including various impurity
MgO
3
4
0
9
0


components (mass %)
BaO
3
4
0
0
9



TiO2
3
4
0
0
0



Fe2O3
3
4
0
0
0












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
60
52
55
63
60


Blending ratio of solid solution A (mass %)
35
35
20
20
20













Raw materials of solid
CaCO3
10.8
10.2
—
—
—


solution B obtained by
SrCO3
37.4
35.1
—
—
—


dissolving Ca
α-Al2O3
36.8
34.7
—
—
—


components in β-SrAl2O4
SiO2
3
4
—
—
—


including various impurity
MgO
3
4
—
—
—


components (mass %)
BaO
3
4
—
—
—



TiO2
3
4
—
—
—



Fe2O3
3
4
—
—
—












X value of CaxSr1−xAl2O4
0.3
0.3
—
—
—


Crystallite diameter of solid solution B (nm)
50
48
—
—
—


Blending ratio of solid solution B (mass %)
35
35
0
0
0













Raw materials of solid
CaCO3
39.6
37.3
42.3
42.3
42.3


solution C obtained by
SrCO3
3.1
2.9
3.3
3.3
3.3


dissolving Sr
α-Al2O3
42.3
39.8
45.4
45.4
45.4


components in CaAl2O4
SiO2
3
4
9
0
0


including various impurity
MgO
3
4
0
9
0


components (mass %)
BaO
3
4
0
0
9



TiO2
3
4
0
0
0



Fe2O3
3
4
0
0
0












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
47
45
48
53
54


Blending ratio of solid solution C (mass %)
30
30
20
20
20


Blending ratio of α-Al2O3 (mass %)*1
0
0
60
60
60













Measured value
CaO
10.9
10.2
5.9
6
6


of chemical
SrO
25.6
23.7
9.3
9.3
9.3


components of
Al2O3
45.2
42.3
80.2
80.2
80.4


binder (mass %)
Total amount of SiO2,
18.2
23.7
4.5
4.4
4.3



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
167
160
172
170
168


value (mm)
After 2 hours
130
123
138
140
133












Bending strength after curing of 6 hours (MPa)
0.6
0.5
1.3
1.4
1.2


Bending strength after curing of 12 hours (MPa)
0.9
0.8
1.6
1.7
1.6


Bending strength after curing of 24 hours (MPa)
1.3
1.1
2.2
2
2.1


Wear amount in rotary corrosion test/mm
7.6
8
5.8
5.7
5.7





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 40







Example 201
Example 202
Example 203
Example 204
Example 205






















Raw materials of solid
CaCO3
1.8
1.7
1.6
—
—


solution A obtained by
SrCO3
51.1
48.3
45.4
—
—


dissolving Ca
α-Al2O3
37.1
35
33
—
—


components in α-SrAl2O4
SiO2
2
3
4
—
—


including various impurity
MgO
2
3
4
—
—


components (mass %)
BaO
2
3
4
—
—



TiO2
2
3
4
—
—



Fe2O3
2
3
4
—
—












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
—
—


Crystallite diameter of solid solution A (nm)
57
60
52
—
—


Blending ratio of solid solution A (mass %)
20
20
20
0
0













Raw materials of solid
CaCO3
—
—
—
11.6
11.6


solution B obtained by
SrCO3
—
—
—
40
40


dissolving Ca
α-Al2O3
—
—
—
39.4
39.4


components in β-SrAl2O4
SiO2
—
—
—
9
0


including various impurity
MgO
—
—
—
0
9


components (mass %)
BaO
—
—
—
0
0



TiO2
—
—
—
0
0



Fe2O3
—
—
—
0
0












X value of CaxSr1−xAl2O4
—
—
—
0.3
0.3


Crystallite diameter of solid solution B (nm)
—
—
—
52
58


Blending ratio of solid solution B (mass %)
0
0
0
20
20













Raw materials of solid
CaCO3
41.9
39.6
37.3
42.3
42.3


solution C obtained by
SrCO3
3.2
3.1
2.9
3.3
3.3


dissolving Sr
α-Al2O3
44.9
42.3
39.8
45.4
45.4


components in CaAl2O4
SiO2
2
3
4
9
0


including various impurity
MgO
2
3
4
0
9


components (mass %)
BaO
2
3
4
0
0



TiO2
2
3
4
0
0



Fe2O3
2
3
4
0
0












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
46
47
45
48
53


Blending ratio of solid solution C (mass %)
20
20
20
20
20


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60













Measured value
CaO
5.9
5.6
5.4
7.4
7.4


of chemical
SrO
9.1
8.4
7.8
7.3
7.5


components of
Al2O3
80.1
78.8
77.1
80.8
80.7


binder (mass %)
Total amount of SiO2,
4.8
7.1
9.6
4.4
4.3



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
173
167
166
168
170


value (mm)
After 2 hours
140
134
130
135
139












Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.1
1.1
1.2


Bending strength after curing of 12 hours (MPa)
1.7
1.6
1.5
1.6
1.8


Bending strength after curing of 24 hours (MPa)
2
2
2.1
2.2
2


Wear amount in rotary corrosion test/mm
5.9
6.2
6.6
5.9
5.7





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 41







Example 206
Example 207
Example 208
Example 209
Example 210






















Raw materials of solid
CaCO3
—
—
—
—
1.8


solution A obtained by
SrCO3
—
—
—
—
51.7


dissolving Ca
α-Al2O3
—
—
—
—
37.5


components in α-SrAl2O4
SiO2
—
—
—
—
9


including various impurity
MgO
—
—
—
—
0


components (mass %)
BaO
—
—
—
—
0



TiO2
—
—
—
—
0



Fe2O3
—
—
—
—
0












X value of CaxSr1−xAl2O4
—
—
—
—
0.05


Crystallite diameter of solid solution A (nm)
—
—
—
—
55


Blending ratio of solid solution A (mass %)
0
0
0
0
20













Raw materials of solid
CaCO3
11.6
11.5
10.8
10.2
11.6


solution B obtained by
SrCO3
40
39.5
37.4
35.1
40


dissolving Ca
α-Al2O3
39.4
39
36.8
34.7
39.4


components in β-SrAl2O4
SiO2
0
2
3
4
9


including various impurity
MgO
0
2
3
4
0


components (mass %)
BaO
9
2
3
4
0



TiO2
0
2
3
4
0



Fe2O3
0
2
3
4
0












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
58
52
50
48
52


Blending ratio of solid solution B (mass %)
20
20
20
20
20













Raw materials of solid
CaCO3
42.3
41.9
39.6
37.3
—


solution C obtained by
SrCO3
3.3
3.2
3.1
2.9
—


dissolving Sr
α-Al2O3
45.4
44.9
42.3
39.8
—


components in CaAl2O4
SiO2
0
2
3
4
—


including various impurity
MgO
0
2
3
4
—


components (mass %)
BaO
9
2
3
4
—



TiO2
0
2
3
4
—



Fe2O3
0
2
3
4
—












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
—


Crystallite diameter of solid solution C (nm)
54
46
47
45
—


Blending ratio of solid solution C (mass %)
20
20
20
20
0


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60













Measured value
CaO
7.7
7.4
6.9
6.3
1.9


of chemical
SrO
7.4
7.2
6.8
6.2
15.2


components of
Al2O3
80.4
80.3
79
77.9
78.6


binder (mass %)
Total amount of SiO2,
4.4
5
7.3
9.5
4.2



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
166
171
167
163
177


value (mm)
After 2 hours
132
135
130
133
135












Bending strength after curing of 6 hours (MPa)
1.1
1.1
1
1
1.3


Bending strength after curing of 12 hours (MPa)
1.7
1.6
1.5
1.4
1.7


Bending strength after curing of 24 hours (MPa)
2
2.1
2.1
2
2.4


Wear amount in rotary corrosion test/mm
5.8
6
6.4
6.9
5.8





Note)


*1Components other than solid solution and CaAl2O4



















TABLE 42







Example 211
Example 212
Example 213
Example 214
Example 215






















Raw materials of solid
CaCO3
1.8
1.8
1.8
1.7
1.6


solution A obtained by
SrCO3
51.7
51.7
51.1
48.3
45.4


dissolving Ca
α-Al2O3
37.5
37.5
37.1
35
33


components in α-SrAl2O4
SiO2
0
0
2
3
4


including various impurity
MgO
9
0
2
3
4


components (mass %)
BaO
0
9
2
3
4



TiO2
0
0
2
3
4



Fe2O3
0
0
2
3
4












X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
63
60
57
60
52


Blending ratio of solid solution A (mass %)
20
20
20
20
20













Raw materials of solid
CaCO3
11.6
11.6
11.5
10.8
10.2


solution B obtained by
SrCO3
40
40
39.5
37.4
35.1


dissolving Ca
α-Al2O3
39.4
39.4
39
36.8
34.7


components in β-SrAl2O4
SiO2
0
0
2
3
4


including various impurity
MgO
9
0
2
3
4


components (mass %)
BaO
0
9
2
3
4



TiO2
0
0
2
3
4



Fe2O3
0
0
2
3
4












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
58
58
52
50
48


Blending ratio of solid solution B (mass %)
20
20
20
20
20













Raw materials of solid
CaCO3
—
—
—
—
—


solution C obtained by
SrCO3
—
—
—
—
—


dissolving Sr
α-Al2O3
—
—
—
—
—


components in CaAl2O4
SiO2
—
—
—
—
—


including various impurity
MgO
—
—
—
—
—


components (mass %)
BaO
—
—
—
—
—



TiO2
—
—
—
—
—



Fe2O3
—
—
—
—
—












X value of CaxSr1−xAl2O4
—
—
—
—
—


Crystallite diameter of solid solution C (nm)
—
—
—
—
—


Blending ratio of solid solution C (mass %)
0
0
0
0
0


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60













Measured value
CaO
1.8
1.8
1.8
1.7
1.4


of chemical
SrO
15.2
15.3
14.9
14
13


components of
Al2O3
78.5
78.3
78.3
76.9
75.9


binder (mass %)
Total amount of SiO2,
4.4
4.5
4.9
7.3
9.6



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
179
173
180
176
173


value (mm)
After 2 hours
136
129
139
136
127












Bending strength after curing of 6 hours (MPa)
1.3
1.4
1.3
1.2
1.1


Bending strength after curing of 12 hours (MPa)
1.8
1.8
1.7
1.7
1.6


Bending strength after curing of 24 hours (MPa)
2.3
2.3
2.4
2.3
2.3


Wear amount in rotary corrosion test/mm
5.6
5.7
5.8
6.3
6.8





Note)


*1Components other than solid solution and CaAl2O4




















TABLE 43







Example 216
Example 217
Example 218
Example 219
Example 220
Example 221























Raw materials of solid
CaCO3
1.8
1.8
1.8
1.8
1.7
1.6


solution A obtained by
SrCO3
51.7
51.7
51.7
51.1
48.3
45.4


dissolving Ca
α-Al2O3
37.5
37.5
37.5
37.1
35
33


components in α-SrAl2O4
SiO2
9
0
0
2
3
4


including various impurity
MgO
0
9
0
2
3
4


components (mass %)
BaO
0
0
9
2
3
4



TiO2
0
0
0
2
3
4



Fe2O3
0
0
0
2
3
4













X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution A (nm)
55
63
60
57
60
52


Blending ratio of solid solution A (mass %)
14
14
14
14
14
14














Raw materials of solid
CaCO3
11.6
11.6
11.6
11.5
10.8
10.2


solution B obtained by
SrCO3
40
40
40
39.5
37.4
35.1


dissolving Ca
α-Al2O3
39.4
39.4
39.4
39
36.8
34.7


components in β-SrAl2O4
SiO2
9
0
0
2
3
4


including various impurity
MgO
0
9
0
2
3
4


components (mass %)
BaO
0
0
9
2
3
4



TiO2
0
0
0
2
3
4



Fe2O3
0
0
0
2
3
4













X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution B (nm)
52
58
58
52
50
48


Blending ratio of solid solution B (mass %)
14
14
14
14
14
14














Raw materials of solid
CaCO3
42.3
42.3
42.3
41.9
39.6
37.3


solution C obtained by
SrCO3
3.3
3.3
3.3
3.2
3.1
2.9


dissolving Sr
α-Al2O3
45.4
45.4
45.4
44.9
42.3
39.8


components in CaAl2O4
SiO2
9
0
0
2
3
4


including various impurity
MgO
0
9
0
2
3
4


components (mass %)
BaO
0
0
9
2
3
4



TiO2
0
0
0
2
3
4



Fe2O3
0
0
0
2
3
4













X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution C (nm)
48
53
54
46
47
45


Blending ratio of solid solution C (mass %)
12
12
12
12
12
12


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60














Measured value
CaO
4.7
4.7
4.8
4.7
4.4
4


of chemical
SrO
11
11.1
10.9
10.8
10.3
9.3


components of
Al2O3
79.7
79.6
79.8
79.4
78.1
77


binder (mass %)
Total amount of SiO2,
4.5
4.5
4.4
5
7.2
9.6



MgO, BaO, TiO2, and Fe2O3


15 tap-flow
After mixing
165
162
162
167
164
165


value (mm)
After 2 hours
140
135
130
138
131
128













Bending strength after curing of 6 hours (MPa)
1.2
1.2
1.3
1.2
1.1
1


Bending strength after curing of 12 hours (MPa)
1.5
1.6
1.7
1.6
1.6
1.5


Bending strength after curing of 24 hours (MPa)
2.2
2.1
2
2
1.9
2


Wear amount in rotary corrosion test/mm
6.1
6
6.1
6.2
6.4
6.9





Note)


*1Components other than solid solution and CaAl2O4






The evaluation results are as shown in Tables 17 to 43. Comparative Examples 7 to 30 show degradation in the cured flexural strength and an increase in the wear amount in the rotary corrosion test using slag since they include from 14.8 mass % to 23.8 mass % of one kind or two or more kinds of components selected from a group consisting of SiO2, TiO2, Fe2O3, MgO, and BaO other than SrO, CaO, and Al2O3 in the binders of the present invention. Examples 110 to 221 show a superior strength developing property compared to a case not including the above-described components and superior high temperature slag resistance compared to CaO—Al2O3-based binders of the conventional technique, which clarifies that favorable characteristics can be obtained by including preferably 12 mass % or less and more preferably 5 mass % or less of one kind or two or more kinds of components selected from a group consisting of SiO2, TiO2, Fe2O3, MgO, and BaO in the binders.
From these test results, it has been clarified that, by using the binder for monolithic refractories according to the present invention including a solid solution including one kind or two or more kinds selected from a group consisting of SiO2, TiO2, Fe2O3, MgO, and BaO in which an amount thereof is 12 mass % or less, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained. Therefore, in the binder for monolithic refractories according to the present invention, when low purity raw materials including impurities such as SiO2, TiO2, Fe2O3, MgO, and BaO are used or when various contaminations of impurities are generated during the manufacturing process, by adjusting an amount thereof to be 12 mass % or less in a binder, superior characteristics can be obtained compared to CaO—Al2O3-based binders of the conventional technique.
[10] Examples relating to a monolithic refractory obtained by blending at least either a dispersant or a hardening retardant in the binders according to the present invention
Measurement of the flow value and the flexural strength after curing and rotary corrosion tests using slag were performed using monolithic refractories manufactured with binders including various solid solutions for which raw materials had been controlled to obtain an X value of CaxSr1-xAl2O4 of 0.05, 0.30, or 0.95 and firing had been performed for 2 hours at the maximum temperature of 1500° C. for manufacture, into which α-Al2O3 was blended with a predetermined ratio and one or two kinds of either a dispersant or a hardening retardant were blended, in Examples 222 to 257. In addition, the same tests were performed using monolithic refractories manufactured with binders including a solid solution for which raw materials had been controlled to obtain a composition of CaAl2O4 and firing had been performed for 2 hours at the maximum temperature of 1500° C. for manufacture, into which α-Al2O3 was blended with a predetermined ratio, in Comparative Examples 31 to 36. Monolithic refractories were manufactured with an amount of water added reduced to 6.2 mass % with respect to 100 mass % of a mixture of the binder and refractory aggregates. Tables 44 to 47 show the compositions of the solid solutions, the crystallite diameters of the solid solutions, the blending ratio of the solid solutions, CaAl2O4, α-Al2O3, the dispersant, and the hardening retardant, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples. In the tables, the amounts of the dispersant and the hardening retardant blended are represented by the ratio (mass ratio) to the binders.
A commercially available powder polycarboxylic acid-based dispersant was used as the dispersant, and boric acid (primary reagent) was crushed to 200 mesh or lower and used as the hardening retardant.













TABLE 44








Example
Example
Example
Example
Example
Example



222
223
224
225
226
227





X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by dissolving Ca
59
59
59
59
59
59


components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by dissolving Ca
40
40
40
40
40
40


components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by dissolving Ca
54
54
54
54
54
54


components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by dissolving Ca
0
0
0
0
0
0


components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by dissolving Sr
50
50
50
50
50
50


components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by dissolving Sr
0
0
0
0
0
0


components in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60


Dispersant (part by mass)
0.5
1
—
—
0.5
1


Hardening retardant (part by mass)
—
—
0.3
0.6
0.3
0.3














15 tap-flow value
After mixing
166
184
159
152
171
189


(mm)
After 2 hours
121
132
129
133
133
141













Bending strength after curing of 6 hours (MPa)
1.6
1.7
1.4
1.2
1.5
1.3


Bending strength after curing of 12 hours (MPa)
1.9
1.9
1.7
1.5
1.6
1.7


Bending strength after curing of 24 hours (MPa)
2.5
2.5
2.5
2.4
2.5
2.4


Wear amount in rotary corrosion test (mm)
5.4
5.3
5.4
5.5
5.3
5.3


















Example
Example
Example
Example
Example




228
229
230
231
232







X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05



Crystallite diameter of solid solution obtained by dissolving Ca
59
59
59
59
59



components in α-SrAl2O4 (nm)



Blending ratio of solid solution obtained by dissolving Ca
0
0
0
0
0



components in α-SrAl2O4 (mass %)



X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3



Crystallite diameter of solid solution obtained by dissolving Ca
54
54
54
54
54



components in β-SrAl2O4 (nm)



Blending ratio of solid solution obtained by dissolving Ca
40
40
40
40
40



components in β-SrAl2O4 (mass %)



X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95



Crystallite diameter of solid solution obtained by dissolving Sr
50
50
50
50
50



components in CaAl2O4 (nm)



Blending ratio of solid solution obtained by dissolving Sr
0
0
0
0
0



components in CaAl2O4 (mass %)



Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—



Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60



Dispersant (part by mass)
0.5
1
—
—
0.5



Hardening retardant (part by mass)
—
—
0.3
0.6
0.3















15 tap-flow value
After mixing
163
177
156
151
164



(mm)
After 2 hours
128
131
124
130
131














Bending strength after curing of 6 hours (MPa)
1.5
1.5
1.3
1.2
1.4



Bending strength after curing of 12 hours (MPa)
1.9
1.8
1.7
1.5
1.7



Bending strength after curing of 24 hours (MPa)
2.6
2.7
2.7
2.6
2.7



Wear amount in rotary corrosion test (mm)
5.5
5.5
5.4
5.6
5.2







Note)



*1Al2O3 other than solid solution and CaAl2O4



















TABLE 45








Example
Example
Example
Example
Example
Example



233
234
235
236
237
238





X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained
59
59
59
59
59
59


by dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
20
20
20
20
20


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
40
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained
50
50
50
50
50
50


by dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained
0
20
20
20
20
20


by dissolving Sr components in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60


Dispersant (part by mass)
1
0.5
1
—
—
0.5


Hardening retardant (part by mass)
0.3
—
—
0.3
0.6
0.3














15 tap-flow value (mm)
After mixing
178
164
181
162
158
171



After 2 hours
138
128
133
133
135
132













Bending strength after curing of 6 hours (MPa)
1.3
1.5
1.5
1.3
1.2
1.5


Bending strength after curing of 12 hours (MPa)
1.6
1.9
1.8
1.8
1.7
1.8


Bending strength after curing of 24 hours (MPa)
2.6
2.6
2.6
2.5
2.6
2.5


Wear amount in rotary corrosion test (mm)
5.3
5.5
5.4
5.6
5.5
5.4


















Example
Example
Example
Example
Example




239
240
241
242
243







X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05



Crystallite diameter of solid solution obtained
59
59
59
59
59



by dissolving Ca components in α-SrAl2O4 (nm)



Blending ratio of solid solution obtained by
20
0
0
0
0



dissolving Ca components in α-SrAl2O4 (mass %)



X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3



Crystallite diameter of solid solution obtained by
54
54
54
54
54



dissolving Ca components in β-SrAl2O4 (nm)



Blending ratio of solid solution obtained by
0
20
20
20
20



dissolving Ca components in β-SrAl2O4 (mass %)



X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95



Crystallite diameter of solid solution obtained
50
50
50
50
50



by dissolving Sr components in CaAl2O4 (nm)



Blending ratio of solid solution obtained
20
20
20
20
20



by dissolving Sr components in CaAl2O4 (mass %)



Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—



Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60



Dispersant (part by mass)
1
0.5
1
—
—



Hardening retardant (part by mass)
0.3
—
—
0.3
0.6















15 tap-flow value (mm)
After mixing
185
160
169
152
147




After 2 hours
134
124
127
123
126














Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.2
1.1
1.1



Bending strength after curing of 12 hours (MPa)
1.7
1.5
1.6
1.5
1.5



Bending strength after curing of 24 hours (MPa)
2.4
2.7
2.6
2.6
2.5



Wear amount in rotary corrosion test (mm)
5.5
5.5
5.6
5.7
5.7







Note)



*1Al2O3 other than solid solution and CaAl2O4


















TABLE 46








Example
Example
Example
Example
Example



244
245
246
247
248





X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained
59
59
59
59
59


by dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
20
20
20


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained
50
50
50
50
50


by dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained
20
20
0
0
0


by dissolving Sr components in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60


Dispersant (part by mass)
0.5
1
0.5
1
—


Hardening retardant (part by mass)
0.3
0.3
—
—
0.3













15 tap-flow value (mm)
After mixing
162
166
168
179
159



After 2 hours
129
131
127
132
122












Bending strength after curing of 6 hours (MPa)
1.2
1.2
1.6
1.5
1.4


Bending strength after curing of 12 hours (MPa)
1.6
1.6
2
1.9
1.8


Bending strength after curing of 24 hours (MPa)
2.7
2.5
2.7
2.6
2.6


Wear amount in rotary corrosion test (mm)
5.6
5.5
5.4
5.5
5.5






Example
Example
Example
Example
Example



249
250
251
252
253





X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained
59
59
59
59
59


by dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
15
15


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
03
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
15
15


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained
50
50
50
50
50


by dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained
0
0
0
10
10


by dissolving Sr components in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60


Dispersant (part by mass)
—
0.5
1
0.5
1


Hardening retardant (part by mass)
0.6
0.3
0.3
—
—













15 tap-flow value (mm)
After mixing
153
167
177
162
174



After 2 hours
134
128
132
129
135












Bending strength after curing of 6 hours (MPa)
1.3
1.5
1.4
1.2
1.3


Bending strength after curing of 12 hours (MPa)
1.7
1.8
1.7
1.6
1.7


Bending strength after curing of 24 hours (MPa)
2.5
2.5
2.5
2.7
2.6


Wear amount in rotary corrosion test (mm)
5.7
5.3
5.4
5.4
5.5





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 47










Compar-
Compar-
Compar-
Compar-
Compar-
Compar-







ative
ative
ative
ative
ative
ative



Example
Example
Example
Example
Example
Example
Example
Example
Example
Example



254
255
256
257
31
32
33
34
35
36

























X value of CaxSr1-xAl2O4
0.05
0.05
0.05
0.05
 
 
 
 
 
 


Crystallite diameter of solid solution 
59
59
59
59
 
 
 
 
 
 


obtained by dissolving Ca components 












in α-SrAl2O4 (nm)












Blending ratio of solid solution 
15
15
15
15
 
 
 
 
 
 


obtained by dissolving Ca components 












in α-SrAl2O4 (mass %)












X value of CaxSr1-xAl2O4
0.3
0.3
0.3
0.3
 
 
 
 
 
 


Crystallite diameter of solid solution 
54
54
54
54
 
 
 
 
 
 


obtained by dissolving Ca components 












β-SrAl2O4 (nm)












Blending ratio of solid solution 
15
15
15
15
 
 
 
 
 
 


obtained by dissolving Ca components 












in β-SrAl2O4 (mass %)












X value of CaxSr1-xAl2O4
0.95
0.95
0.95
0.95
 
 
 
 
 
 


Crystallite diameter of solid solution 
50
50
50
50
 
 
 
 
 
 


obtained by dissolving Sr components 












in CaAl2O4 (nm)












Blending ratio of solid solution 
10
10
10
10
 
 
 
 
 
 


obtained by dissolving Sr components 












in CaAl2O4 (mass %)












Blending ratio of CaAl2O4 (mass %)
—
 
 
 
40
40
40
40
40
40


Blending ratio of α-Al2O3 (mass %) *1
60
60
60
60
60
60
60
60
60
60


Dispersant (part by mass)
 
 
0.5
1
0.5
1
 
 
0.5
1


Hardening retardant (part by mass)
0.3
0.6
0.3
0.3
 
 
0.3
0.6
0.3
0.3


















15 tap-flow value (mm)
After mixing
151
150
160
177
161
168
153
147
163
173



After 2 hours
130
137
132
134
122
123
121
125
129
131

















Bending strength after curing of 6 
1.2
1.1
1.2
1.2
0.3
0.3
0.4
0.2
0.3
0.2


hours (MPa)












Bending strength after curing of
1.5
1.4
1.6
1.7
0.7
0.6
0.6
0.5
0.7
0.5


12 hours (MPa )












Bending strength after curing of 
2.4
2.5
2.6
2.6
1.8
1.8
1.6
1.3
1.6
1.4


24 hours (MPa)












Wear amount in rotary corrosion 
5.6
5.5
5.5
5.6
7.6
7.5
7.7
7.8
7.5
7.6


test (mm)





Note)


*1 Al2O3 other than solid solution and CaAl2O4






The evaluation results are as shown in Tables 44 to 47. In Examples 222 to 257, regardless of the reduced amount of water added to monolithic refractories, the flow values suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 222 to 257 can be applied to furnaces with a large volume or the like. Furthermore, Examples 222 to 257 show larger values than Comparative Examples 31 to 36 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 222 to 257 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 222 to 257 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 222 to 257 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In addition, since monolithic refractories were manufactured with a reduced amount of water added, a decrease in the wear amount in the rotary corrosion test using slag could be obtained compared to a case where monolithic refractories were manufactured with the same composition of binder.
From these test results, it has been clarified that, by using the dispersant and the hardening retardant in the binder for monolithic refractories according to the present invention, a monolithic refractory in which a favorable operability is secured even after a long period of time has elapsed after pouring and blending water thereinto, a favorable strength developing property is obtained early, and slag resistance at a high temperature is superior compared to the conventional technique can be obtained.
[11] Examples relating to a monolithic refractory including a mixture of the binder for monolithic refractories according to the present invention and a refractory aggregate including an ultrafine alumina powder with a particle diameter of 1 μm or less
The same tests were performed using monolithic refractories manufactured from aggregates in which amounts of the ultrafine alumina powder with a particle diameter of 1 μm or less in the monolithic refractories were varied in a range of 0 to 80 mass % and the binder according to the present invention in Examples 258 to 293 and Reference Examples 23 to 34. In all tests, a binder including 40 mass % of various solid solutions and their mixture and 60 mass % of α-Al2O3 were used, wherein the solid solutions prepared such that raw materials had been controlled to obtain an X value of CaxSr1-xAl2O4 of 0.05, 0.30, or 0.95 and firing had been performed for 2 hours at the maximum temperature of 1500° C. The amount of fused alumina of from 75 μm to 5 mm was adjusted to cover a changed amount of the ultrafine alumina powder of 1 μm or less so as to manufacture monolithic refractories with the same total mass of alumina refractory aggregates. Further, the blending ratio of the binder, magnesia, silica flower, vinylon fiber and the amount of water added was not varied. Tables 48 to 52 show the compositions of the solid solutions, the crystallite diameters of the solid solutions, the blending ratio of the various solid solutions and α-Al2O3, the amount of sintered alumina of 1 μm or less, the amount of fused alumina of from 75 μm to 5 mm, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples.













TABLE 48








Example
Example
Example
Example
Example
Example



258
259
260
261
262
263





X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained
40
40
40
40
40
40


by dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60


Amount of sintered alumina of 1 μm or less*2 (mass %)
2
5
10
30
50
70


Amount of fused alumina of
83.56
80.56
75.56
55.56
35.56
15.56


from 75 μm to 5 mm*2 (mass %)














15 tap-flow value (mm)
After mixing
184
179
176
172
171
162



After 2 hours
131
135
135
133
132
122













Bending strength after curing of 6 hours (MPa)
0.9
1
1
1.1
1.1
1.3


Bending strength after curing of 12 hours (MPa)
1.2
1.3
1.3
1.4
1.4
1.6


Bending strength after curing of 24 hours (MPa)
1.9
1.9
2
1.9
2
2


Wear amount in rotary corrosion test (mm)
6
5.9
5.8
5.8
5.7
5.7

















Reference
Reference
Example
Example




Example 23
Example 24
264
265







X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05



Crystallite diameter of solid solution obtained
40
40
0
0



by dissolving Ca components in α-SrAl2O4 (nm)



Blending ratio of solid solution obtained by
59
59
59
59



dissolving Ca components in α-SrAl2O4 (mass %)



X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3



Crystallite diameter of solid solution obtained by
54
54
54
54



dissolving Ca components in β-SrAl2O4 (nm)



Blending ratio of solid solution obtained by
0
0
40
40



dissolving Ca components in β-SrAl2O4 (mass %)



X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95



Crystallite diameter of solid solution obtained by
50
50
50
50



dissolving Sr components in CaAl2O4 (nm)



Blending ratio of solid solution obtained by
0
0
0
0



dissolving Sr components in CaAl2O4 (mass %)



Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60



Amount of sintered alumina of 1 μm or less*2 (mass %)
0
80
2
5



Amount of fused alumina of
85.56
5.56
83.56
80.56



from 75 μm to 5 mm*2 (mass %)














15 tap-flow value (mm)
After mixing
181
133
180
177




After 2 hours
136
103
133
135













Bending strength after curing of 6 hours (MPa)
0.5
1.3
0.8
0.9



Bending strength after curing of 12 hours (MPa)
0.8
1.6
1.1
1.2



Bending strength after curing of 24 hours (MPa)
1.2
1.9
2
2



Wear amount in rotary corrosion test (mm)
6
6.3
5.9
5.9







Note)



*1Al2O3 other than solid solution and CaAl2O4



*2Mixing ratio with respect to monolithic refractory (total amount of binder and refractory aggregates)























TABLE 49










Refer-
Refer-







Ex-
Ex-
Ex-
Ex-
ence
ence
Ex-
Ex-
Ex-
Ex-



ample
ample
ample
ample
Example
Example
ample
ample
ample
ample



266
267
268
269
25
26
270
271
272
273

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained
0
0
0
0
0
0
20
20
20
20


by dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
40
40
40
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
20
20
20
20


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Amount of sintered alumina of 1 μm or less*2
10
30
50
70
0
80
2
5
10
30


(mass %)












Amount of fused alumina of
75.56
55.56
35.56
15.56
85.56
5.56
83.56
80.56
75.56
55.56


from 75 μm to 5 mm*2 (mass %)




























15 tap-flow value (mm)
After mixing
173
174
167
160
183
141
180
177
175
172



After 2 hours
135
131
128
124
138
105
130
135
132
135

















Bending strength after curing of 6 hours (MPa)
0.9
0.9
1.1
1.2
0.4
1.3
0.9
1
1
1.1


Bending strength after curing of 12 hours (MPa)
1.3
1.4
1.5
1.6
0.8
1.7
1.2
1.3
1.3
1.3


Bending strength after curing of 24 hours (MPa)
2.1
2.2
2.2
2.2
1.8
2.3
1.8
1.9
2
2.1


Wear amount in rotary corrosion test (mm)
5.9
5.7
5.7
5.8
6.2
6.4
6.1
5.9
5.9
5.8





Note)


*1Al2O3 other than solid solution and CaAl2O4


*2Mixing ratio with respect to monolithic refractory (total amount of binder and refractory aggregates)























TABLE 50








Refer-
Refer-









Ex-
Ex-
ence
ence
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-



ample
ample
Example
Example
ample
ample
ample
ample
ample
ample



274
275
27
28
276
277
278
279
280
281

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained
20
20
20
20
0
0
0
0
0
0


by dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
20
20
20
20
20
20


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20
20


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Amount of sintered alumina of 1 μm or less*2
50
70
0
80
2
5
10
30
50
70


(mass %)












Amount of fused alumina of
35.56
15.56
85.56
5.56
83.56
80.56
75.56
55.56
35.56
15.56


from 75 μm to 5 mm*2 (mass %)




























15 tap-flow value (mm)
After mixing
169
160
183
136
178
177
172
170
167
161



After 2 hours
136
129
140
102
146
142
139
139
138
134

















Bending strength after curing of 6 hours (MPa)
1.1
1.2
0.5
1.2
0.8
0.8
0.9
1
1
1


Bending strength after curing of 12 hours (MPa)
1.4
1.4
0.7
1.5
1
1.1
1.2
1.2
1.3
1.4


Bending strength after curing of 24 hours (MPa)
2.1
2
1.3
2
2
2.2
2.2
2.1
2.2
2.2


Wear amount in rotary corrosion test (mm)
5.8
5.7
6.2
6.1
6.3
6.2
6
5.9
5.9
5.8





Note)


*1Al2O3 other than solid solution and CaAl2O4


*2Mixing ratio with respect to monolithic refractory (total amount of binder and refractory aggregates)























TABLE 51






Reference
Reference
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Reference
Reference



Example
Example
ample
ample
ample
ample
ample
ample
Example
Example



29
30
282
283
284
285
286
287
31
32

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution
0
0
20
20
20
20
20
20
20
20


obtained by dissolving Ca components in












α-SrAl2O4 (nm)












Blending ratio of solid solution obtained
59
59
59
59
59
59
59
59
59
59


by dissolving Ca components in α-SrAl2O4












(mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution
54
54
54
54
54
54
54
54
54
54


obtained by dissolving Ca components in












β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20
20


dissolving Ca components in β-SrAl2O4












(mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution
50
50
50
50
50
50
50
50
50
50


obtained by dissolving Sr components in












CaAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4












(mass %)












Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Amount of sintered alumina of 1 μm or
0
80
2
5
10
30
50
70
0
80


less*2 (mass %)












Amount of fused alumina of
85.56
5.56
83.56
80.56
75.56
55.56
35.56
15.56
85.56
5.56


from 75 μm to 5 mm*2 (mass %)




























15 tap-flow value (mm)
After mixing
176
144
184
176
172
173
171
162
184
136



After 2 hours
144
106
131
134
132
135
132
122
139
106

















Bending strength after curing of 6 hours
0.4
1.1
0.8
0.9
0.9
0.9
1
1.2
0.4
1.3


(MPa)












Bending strength after curing of 12 hours
0.6
1.5
1.1
1.2
1.2
1.4
1.4
1.5
0.8
1.6


(MPa)












Bending strength after curing of 24 hours
1.8
2.3
1.8
1.9
2
2.1
2.2
2.2
1.5
2


(MPa)












Wear amount in rotary corrosion test (mm)
6.5
6.1
6.1
5.9
5.9
5.7
5.7
5.8
5.9
6.2





Note)


*1Al2O3 other than solid solution and CaAl2O4


*2Mixing ratio with respect to monolithic refractory (total amount of binder and refractory aggregates)





















TABLE 52






Example
Example
Example
Example
Example
Example
Reference
Reference



288
289
290
291
292
293
Example 33
Example 34























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained
14
14
14
14
14
14
14
14


by dissolving Ca components in α-SrAl2O4 (nm)










Blending ratio of solid solution obtained by
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (mass %)










X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)










Blending ratio of solid solution obtained by
14
14
14
14
14
14
14
14


dissolving Ca components in β-SrAl2O4 (mass %)










X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)










Blending ratio of solid solution obtained by
12
12
12
12
12
12
12
12


dissolving Sr components in CaAl2O4 (mass %)










Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60


Amount of sintered alumina of 1 μm or less*2
2
5
10
30
50
70
0
80


(mass %)










Amount of fused alumina of
83.56
80.56
75.56
55.56
35.56
15.56
85.56
5.56


from 75 μm to 5 mm*2 (mass %)
























15 tap-flow value (mm)
After mixing
184
181
177
174
171
163
186
142



After 2 hours
142
139
139
136
136
131
142
104















Bending strength after curing of 6 hours (MPa)
0.8
0.9
0.9
1
1
1.1
0.5
1.2


Bending strength after curing of 12 hours (MPa)
1.1
1.1
1.2
1.2
1.3
1.3
0.7
1.5


Bending strength after curing of 24 hours (MPa)
1.9
2
2.1
2.1
2.1
2.2
1.4
2.2


Wear amount in rotary corrosion test (mm)
6.1
5.9
5.8
5.7
5.7
5.8
6.3
5.9





Note)


*1Al2O3 other than solid solution and CaAl2O4


*2Mixing ratio with respect to monolithic refractory (total amount of binder and refractory aggregates)






The evaluation results are as shown in Tables 48 to 52. In Examples 258 to 293, the flow values suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 258 to 293 can be applied to furnaces with a large volume or the like. Furthermore, Examples 258 to 293 show favorable values in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 258 to 293 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, Examples 258 to 293 show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
On the other hand, in Reference Examples 23, 25, 27, 29, 31, and 33 including no ultrafine alumina powder with a particle diameter of 1 μm or less, it has been confirmed that the flexural strength after curing of 6 hours is low, it is difficult for a frame to be removed early, and the risk of explosion increases due to insufficient strength when the monolithic refractories are dried. In Reference Examples 24, 26, 28, 30, 32, and 34 including 80 mass % of ultrafine alumina powder with a particle diameter of 1 μm or less, the flow values deteriorated after 2 hours and a large amount of deterioration in the flow property after 2 hours occurred. Therefore, it has been confirmed that it is difficult for Reference Examples 24, 26, 28, 30, 32, and 34 to be applied to furnaces with a large volume or the like.
From these test results, in the binders for monolithic refractories according to the present invention, it has been confirmed that it is preferable to blend a refractory aggregate including an ultrafine alumina powder with a particle diameter of 1 μm or less in which an amount of the ultrafine alumina powder with a particle diameter of 1 μm or less is from 2 mass % to 70 mass %.
[12] Examples relating to a monolithic refractory using a varied amount of the binder for monolithic refractories according to the present invention
In Examples 294 to 337 and Reference Examples 35 to 44, in monolithic refractories manufactured using the binder according to the present invention, the same tests were performed with a varied amount of the binder in a case in which the total of the binder and refractory aggregates was made to be 100 mass %. In all tests, a binder including 40 mass % of various solid solutions and their mixture and 60 mass % of α-Al2O3 were used, wherein the solid solutions prepared such that raw materials had been controlled to obtain an X value of CaxSr1-xAl2O4 of 0.05, 0.30, or 0.95 and firing had been performed for 2 hours at the maximum temperature of 1500° C. Tables 53 to 58 show the compositions of the solid solutions, the crystallite diameters of the solid solutions, the blending ratio of the various solid solutions and α-Al2O3, the amount of the binder added, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples.

















TABLE 53














Refer-
Refer-



Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
ence
ence



ample
ample
ample
ample
ample
ample
ample
ample
Example
Example



294
295
296
297
298
299
300
301
35
36

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
0


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
40


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Amount of binder added (mass %)
0.2
0.3
0.5
5
10
12
16
20
25
0.2


















15 tap-flow value (mass %)
After mixing
161
163
171
168
170
174
176
172
163
161



After 2 hours
133
136
134
129
131
129
127
123
117
133

















Bending strength after curing of 6 hours (MPa)
0.7
0.8
0.9
1.1
1.2
1.2
1.3
1.4
1.5
0.6


Bending strength after curing of 12 hours (MPa)
0.9
1.1
1.2
1.4
1.5
1.5
1.6
1.8
1.9
0.8


Bending strength after curing of 24 hours (MPa)
1.4
1.5
1.5
1.8
2
2.1
2.1
2.2
2.2
1.5



5
5
5.1
5.4
5.8
5.8
6
6.4
7.1
5.2





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 54













Refer-
Refer-




Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
ence
ence
Ex-



ample
ample
ample
ample
ample
ample
ample
Example
Example
ample



302
303
304
305
306
307
308
37
38
309

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
20
20


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
0
0


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
20
20


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Amount of binder added (mass %)
0.3
0.5
5
10
12
16
20
25
0.2
0.3


















15 tap-flow value (mass %)
After mixing
162
167
169
172
170
174
168
169
159
162



After 2 hours
130
135
132
132
129
125
125
120
136
136

















Bending strength after curing of 6 hours (MPa)
0.7
0.8
1
1.1
1.1
1.2
1.3
1.3
0.6
0.7


Bending strength after curing of 12 hours (MPa)
1
1.1
1.3
1.4
1.5
1.6
1.7
1.8
0.8
0.9


Bending strength after curing of 24 hours (MPa)
1.7
1.7
1.9
2
2.2
2.4
2.5
2.5
1.3
1.4



5.1
5.2
5.3
5.6
5.6
6.1
6.6
7.1
5
5.1





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 55












Refer-
Refer-





Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
ence
ence
Ex-
Ex-



ample
ample
ample
ample
ample
ample
Example
Example
ample
ample



310
311
312
313
314
315
39
40
316
317

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
0
0
0


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
20
20
20


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20
20


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Amount of binder added (mass %)
0.5
5
10
12
16
20
25
0.2
0.3
0.5


















15 tap-flow value (mass %)
After mixing
166
170
172
175
173
167
166
160
158
162



After 2 hours
139
135
136
133
133
127
125
132
134
132

















Bending strength after curing of 6 hours (MPa)
0.8
0.9
1.1
1.1
1.2
1.3
1.5
0.5
0.7
0.8


Bending strength after curing of 12 hours (MPa)
0.9
1.2
1.5
1.5
1.6
1.8
1.8
0.8
0.9
0.9


Bending strength after curing of 24 hours (MPa)
1.4
1.8
2.2
2.3
2.3
2.3
2.4
1.2
1.4
1.5



5.2
5.6
5.8
6
6.2
6.6
7.2
5.2
5.2
5.2





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 56







Ex-
Ex-
Ex-
Ex-
Reference
Ex-
Ex-
Ex-
Ex-



Example
ample
ample
ample
ample
Example
ample
ample
ample
ample



318
319
320
321
322
41
323
324
325
326

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
20
20
20
20


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
03
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20
20


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
20
20
20
20
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Amount of binder added (mass %)
5
10
12
16
20
25
0.2
0.3
0.5
5


















15 tap-flow value (mass %)
After mixing
166
169
172
176
171
173
161
163
171
168



After 2 hours
130
137
134
131
129
128
133
136
134
129

















Bending strength after curing of 6 hours (MPa)
0.9
1
1
1.1
1.2
1.2
0.7
0.7
0.8
1


Bending strength after curing of 12 hours (MPa)
1.1
1.3
1.3
1.4
1.5
1.6
0.9
1
1.1
1.2


Bending strength after curing of 24 hours (MPa)
2.2
2.4
2.5
2.5
2.6
2.7
1.5
1.6
1.6
1.8



5.6
5.9
6.1
6.2
6.7
7.3
5.1
5.2
5.1
5.3





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 57










Refer-
Refer-







Ex-
Ex-
Ex-
Ex-
ence
ence
Ex-
Ex-
Ex-
Ex-



ample
ample
ample
ample
Example
Example
ample
ample
ample
ample



327
328
329
330
42
43
331
332
333
334

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
20
20
20
14
14
14
14
14


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
20
20
20
20
20
14
14
14
14
14


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
12
12
12
12
12


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Amount of binder added (mass %)
10
12
16
20
25
0.2
0.3
0.5
5
10


















15 tap-flow value (mass %)
After mixing
170
174
176
172
163
157
156
160
165
171



After 2 hours
131
129
127
123
117
133
135
134
133
135

















Bending strength after curing of 6 hours (MPa)
1.1
1.1
1.2
1.3
1.4
0.6
0.7
0.8
1
1


Bending strength after curing of 12 hours (MPa)
1.4
1.5
1.5
1.9
1.9
0.9
1
1.1
1.2
1.3


Bending strength after curing of 24 hours (MPa)
2
2.1
2.2
2.3
2.4
1.2
1.4
1.5
2
2.2



5.7
5.7
6.1
6.5
7.1
5.1
5.1
5.1
5.5
5.9





Note)


*1Al2O3 other than solid solution and CaAl2O4


















TABLE 58







Example
Example
Example
Reference



335
336
337
Example 44




















X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
14
14
14
14


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
14
14
14
14


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
12
12
12
12


dissolving Sr components in CaAl2O4 (mass %)


Blending ratio of α-Al2O3 (mass %) *1
60
60
60
60


Amount of binder added (mass %)
12
16
20
25












15 tap-flow value
After mixing
173
173
170
169


(mass %)
After 2 hours
130
135
129
127











Bending strength after curing of 6 hours (MPa)
1.1
1.2
1.2
1.2


Bending strength after curing of 12 hours (MPa)
1.4
1.5
1.6
1.6


Bending strength after curing of 24 hours (MPa)
2.3
2.4
2.4
2.5



5.9
6.3
6.8
7.1





Note)


*1 Al2O3 other than solid solution and CaAl2O4






The evaluation results are as shown in Tables 53 to 58. In Examples 294 to 337, the flow values suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 294 to 337 can be applied to furnaces with a large volume or the like. Furthermore, Examples 294 to 337 show favorable values in the flexural strength after curing of 6, 12, and 24 hours. In particular, Examples 294 to 337 show larger values in the flexural strength after curing of 6 hours, and therefore it has been clarified that Examples 294 to 337 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, Examples 294 to 337 show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
On the other hand, in Reference Examples 36, 38, 40, and 43 in which an amount of the binder added was 0.2 mass %, it has been confirmed that the flexural strength after curing of 6 hours is low, it is difficult for a frame to be removed early, and the risk of explosion increases due to insufficient strength when the monolithic refractories are dried. In Reference Examples 35, 37, 39, 41, 42, and 44 in which an amount of the binder added was 25 mass %, it has been confirmed that, compared to other cases, Reference Examples 35, 37, 39, 41, 42, and 44 show an increase in the wear amount in the rotary corrosion test using slag and degradation in the slag resistance at a high temperature.
In Examples in which an amount of the binder added was from 0.5 mass % to 12 mass %, it has been confirmed that Examples are excellent in terms of both of the cured strength and the wear amount in the rotary corrosion test using slag.
From these test results, it has been confirmed that the amount of the binder for monolithic refractories according to the present invention is preferably from 0.3 mass % to 20 mass %, and further preferably from 0.5 mass % to 12 mass % with respect to 100 mass % of the total amount of the binder for monolithic refractories and the refractory aggregates.
[13] Examples relating to a monolithic refractory into which at least one of a dispersant, a hardening retardant, and a hardening accelerator is added
In Examples 338 to 515, monolithic refractories were manufactured by using a binder including 40 mass % of various solid solutions and their mixture and 60 mass % of α-Al2O3, wherein the solid solutions prepared such that raw materials had been controlled to obtain an X value of CaxSr1-xAl2O4 of 0.05, 0.30, or 0.95 and firing had been performed for 2 hours at the maximum temperature of 1500° C., and blending a predetermined amount of at least one kind of a variety of dispersants, hardening retardants and hardening accelerators in outer percentage, and then the tests were performed. In addition, in Comparative Examples 31 to 47, monolithic refractories were manufactured by using a binder including no Sr components and blending at least one kind of a dispersant, a hardening retardant and a hardening accelerator in the same manner, and then the tests were performed. Further, when blending a dispersant, a hardening retardant, or a dispersant and a hardening retardant, the amount of water added was reduced to 6.2 mass % with respect to 100 mass % of the mixture of the binder and refractory aggregates, and then the test was performed. In addition, when blending only a hardening accelerator, as usual, 6.8 mass % of water was added and the test was performed. A powder dispersant, a hardening retardant, and a hardening accelerator were used after being blended with the binder and refractory aggregate using an omni mixer. For liquid dispersants, the mass of solid components included was considered as the amount added, and adjustment was performed so as to obtain a predetermined amount of water by reducing from the amount of water to be added by the mass portion of the solvent parts. In addition, liquid dispersants were used after being blended with mixing water.
Meanwhile, in the embodiments, a sodium polyacrylate reagent, which is a polycarboxylic acid-based dispersant, was used as the dispersant A; “TIGHTLOCK” (trade name, manufactured by Kao Corporation), which is a polyether-based dispersant, was used as the dispersant B; sodium tripolyphosphate (primary reagent), which is a phosphate-based dispersant, was used as the dispersant C; trisodium citrate dihydrate (primary reagent), which is an oxycarboxylic acid, was used as the dispersant D; “FT-3S” (with a solid content of 33 mass %) (trade name, manufactured by Grace Chemical Co., Ltd.), which is a melamine-based dispersant, was used as the dispersant E; “MIGHTY 150” (with a solid content of 40 mass %) (trade name, manufactured by Kao Corporation), which is a naphthalene-based dispersant, was used as the dispersant F; “VANILLEX HW” (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), which is a lignin-based dispersant, was used as the dispersant G; boric acid (special grade chemical), which is one of boric acid groups, was used as the hardening retardant a; sodium silicofluoride (special grade chemical), which is a silicofluoride, was used as the hardening retardant b; lithium citrate (primary reagent), which is one of salts of alkaline metals, was used as the hardening accelerator a; and sodium aluminate (primary reagent), which is one of aluminates, was used as the hardening accelerator 13.
Tables 59 to 78 show the compositions of the solid solutions, the crystallite diameters of the solid solutions, the blending ratio of the various solid solutions and CaAl2O4 and α-Al2O3 for comparison, the type and amount added of the dispersant, the type and amount added of the hardening retardant, the type and amount added of the hardening accelerator, and the measurement results of flow value and flexural strength after curing and results of the rotary corrosion test of the monolithic refractory in each of the Examples. In the tables, the amounts of the dispersant, the hardening retardant, and the hardening accelerator used are represented by the ratio to the total amount of the binders and the refractory aggregates.

















TABLE 59








Ex-
Ex-
Ex-
Ex-
Ex
Ex-
Ex-
Ex-



Example
Example
ample
ample
ample
ample
ample
ample
ample
ample



338
339
340
341
342
343
344
345
346
347

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
40


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Type of dispersant
A
A
A
B
B
B
C
C
C
D


Amount of dispersant added (mass %)
0.05
0.1
0.3
0.05
0.1
0.3
0.05
0.1
0.3
0.05


Type of hardening retardant
—
—
—
—
—
—
—
—
—
—


Amount of hardening retardant added (mass %)
—
—
—
—
—
—
—
—
—
—


Type of hardening accelerator
—
—
—
—
—
—
—
—
—
—


Amount of hardening accelerator added (mass %)
—
—
—
—
—
—
—
—
—
—


















15 tap-flow value (mm)
After mixing
160
172
189
171
182
194
146
153
159
143



After 2 hours
120
122
126
127
131
143
118
122
120
122

















Bending strength after curing of 6 hours (MPa)
1.4
1.5
1.6
1.4
1.3
1
1.4
1.5
1.5
1.3


Bending strength after curing of 12 hours (MPa)
1.8
1.8
1.9
1.9
1.7
1.4
1.8
1.9
1.9
1.6


Bending strength after curing of 24 hours (MPa)
2.4
2.4
2.5
22
2.1
1.9
2.4
2.3
2.4
2.1


Wear amount in rotary corrosion test (mm)
5.3
5.2
5.2
5.3
5.3
5.5
5.4
5.3
5.3
5.6





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 60








Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-



Example
Example
ample
ample
ample
ample
ample
ample
ample
ample



348
349
350
351
352
353
354
355
356
357

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
40


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Type of dispersant
D
D
E
E
E
F
F
F
G
G


Amount of dispersant added (mass %)
0.1
0.3
0.05
0.1
0.3
0.05
0.1
0.3
0.05
0.1


Type of hardening retardant
—
—
—
—
—
—
—
—
—
—


Amount of hardening retardant added (mass %)
—
—
—
—
—
—
—
—
—
—


Type of hardening accelerator
—
—
—
—
—
—
—
—
—
—


Amount of hardening accelerator added (mass %)
—
—
—
—
—
—
—
—
—
—


















15 tap-flow value (mm)
After mixing
149
152
144
146
153
142
151
151
151
157



After 2 hours
127
130
117
121
123
116
118
123
122
128

















Bending strength after curing of 6 hours (MPa)
1.5
1.5
1.4
1.5
1.4
1.2
1.3
1.3
1.4
1.4


Bending strength after curing of 12 hours (MPa)
1.9
2
1.8
1.9
1.8
1.6
1.7
1.6
1.7
1.8


Bending strength after curing of 24 hours (MPa)
2.5
2.5
2.2
2.4
2.4
2
2.2
2.3
2.1
2.3


Wear amount in rotary corrosion test (mm)
5.4
5.4
5.6
5.5
5.4
5.3
5.4
5.3
5.4
5.3





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 61








Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-



Example
Example
ample
ample
ample
ample
ample
ample
ample
ample



358
359
360
361
362
363
364
365
366
367

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
40


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Type of dispersant
G
—
—
—
—
—
—
—
—
—


Amount of dispersant added (mass %)
0.3
—
—
—
—
—
—
—
—
—


Type of hardening retardant
—
a
a
a
b
b
b
—
—
—


Amount of hardening retardant added (mass %)
—
0.01
0.05
0.2
0.01
0.05
0.2
—
—
—


Type of hardening accelerator
—
—
—
—
—
—
—
α
α
α


Amount of hardening accelerator added (mass %)
—
—
—
—
—
—
—
0.01
0.05
0.2


















15 tap-flow value (mm)
After mixing
156
151
161
163
145
141
140
169
174
164



After 2 hours
124
121
124
128
124
129
130
130
123
117

















Bending strength after curing of 6 hours (MPa)
1.5
1.5
1.6
1.6
1.2
1.1
0.9
1.5
1.5
1.7


Bending strength after curing of 12 hours (MPa)
1.9
1.9
1.9
2
1.6
1.5
1.2
1.7
1.8
1.9


Bending strength after curing of 24 hours (MPa)
2.3
2.2
2.2
2.1
2.3
2.2
1.9
2
2.1
2.1


Wear amount in rotary corrosion test (mm)
5.2
5.4
5.3
5.4
5.3
5.4
5.5
5.8
5.9
5.8





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 62






Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-



ample
ample
ample
ample
ample
ample
ample
ample
ample
ample



368
369
370
371
372
373
374
375
376
377

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
40


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Type of dispersant
—
—
—
A
A
A
A
A
A
A


Amount of dispersant added (mass %)
—
—
—
0.1
0.1
0.1
0.1
0.1
0.1
0.1


Type of hardening retardant
—
—
—
a
a
a
b
b
b
—


Amount of hardening retardant added (mass %)
—
—
—
0.01
0.05
0.2
0.01
0.05
0.2
—


Type of hardening accelerator
β
β
β
—
—
—
—
—
—
α


Amount of hardening accelerator added (mass %)
0.01
0.05
0.2
—
—
—
—
—
—
0.01


















15 tap-flow value (mm)
After mixing
173
182
180
171
167
166
169
163
162
173



After 2 hours
132
129
115
127
128
131
133
132
136
125

















Bending strength after curing of 6 hours (MPa)
1.4
1.6
1.7
1.4
1.3
1.3
1.3
1.2
1
1.8


Bending strength after curing of 12 hours (MPa)
1.7
1.9
2
1.9
1.7
1.6
1.6
1.6
1.5
2.1


Bending strength after curing of 24 hours (MPa)
2
2.2
2.1
2.3
2.2
2.3
2.1
2.2
2.2
2.5


Wear amount in rotary corrosion test (mm)
5.8
5.9
6
5.2
5.4
5.4
5.3
5.4
5.2
5.2





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 63






Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-



ample
ample
ample
ample
ample
ample
ample
ample
ample
ample



378
379
380
381
382
383
384
385
386
387

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
40


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Type of dispersant
A
A
A
A
A
—
—
—
—
—


Amount of dispersant added (mass %)
0.1
0.1
0.1
0.1
0.1
—
—
—
—
—


Type of hardening retardant
—
—
—
—
—
a
a
a
a
a


Amount of hardening retardant added (mass %)
—
—
—
—
—
0.05
0.05
0.05
0.05
0.05


Type of hardening accelerator
α
α
β
β
β
α
α
α
β
β


Amount of hardening accelerator added 
0.05
0.2
0.01
0.05
0.2
0.01
0.05
0.2
0.01
0.05


(mass %)




























15 tap-flow value (mm)
After mixing
175
168
169
171
164
145
142
139
142
144



After 2 hours
121
117
124
121
118
134
128
118
131
123

















Bending strength after curing of 6 hours (MPa)
1.9
1.9
1.8
1.9
2
1.5
1.6
1.8
1.7
1.8


Bending strength after curing of 12 hours (MPa)
2.2
2.3
2.1
2.3
2.3
1.9
2
2.2
2.1
2.2


Bending strength after curing of 24 hours (MPa)
2.5
2.4
2.6
2.7
2.7
2.4
2.3
2.4
2.5
2.5


Wear amount in rotary corrosion test (mm)
5.2
5.3
5.2
5.3
5.2
5.4
5.3
5.3
5.4
5.4





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 64









Com-
Com-
Com-
Com-
Com-
Com-
Com-






parative
parative
parative
parative
parative
parative
parative



Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-
Ex-



ample
ample
ample
ample
ample
ample
ample
ample
ample
ample



388
389
390
31
32
33
34
35
36
37

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
—
—
—
—
—
—
—


Crystallite diameter of solid solution obtained by
59
59
59
—
—
—
—
—
—
—


dissolving Ca components in α-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
40
40
40
—
—
—
—
—
—
—


dissolving Ca components in α-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.3
0.3
0.3
—
—
—
—
—
—
—


Crystallite diameter of solid solution obtained by
54
54
54
—
—
—
—
—
—
—


dissolving Ca components in β-SrAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
—
—
—
—
—
—
—


dissolving Ca components in β-SrAl2O4 (mass %)












X value of CaxSr1−xAl2O4
0.95
0.95
0.95
—
—
—
—
—
—
—


Crystallite diameter of solid solution obtained by
50
50
50
—
—
—
—
—
—
—


dissolving Sr components in CaAl2O4 (nm)












Blending ratio of solid solution obtained by
0
0
0
—
—
—
—
—
—
—


dissolving Sr components in CaAl2O4 (mass %)












Blending ratio of CaAl2O4 (mass %)
—
—
—
40
40
40
40
40
40
40


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Type of dispersant
—
A
A
A
B
C
D
E
F
G


Amount of dispersant added (mass %)
—
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1


Type of hardening retardant
a
a
a
—
—
—
—
—
—
—


Amount of hardening retardant added (mass %)
0.05
0.05
0.05
—
—
—
—
—
—
—


Type of hardening accelerator
β
α
β
—
—
—
—
—
—
—


Amount of hardening accelerator added (mass %)
0.2
0.05
0.05
—
—
—
—
—
—
—


















15 tap-flow value (mm)
After mixing
145
173
176
173
182
170
172
166
164
168



After 2 hours
116
137
134
137
142
131
129
131
125
132

















Bending strength after curing of 6 hours (MPa)
2
1.8
2
0.5
0.3
0.5
0.6
0.4
0.6
0.5


Bending strength after curing of 12 hours (MPa)
2.2
2.2
2.2
0.8
0.6
1
1.1
0.8
1
0.9


Bending strength after curing of 24 hours (MPa)
2.6
2.6
2.6
1.4
1.2
1.7
1.6
1.3
1.5
1.6


Wear amount in rotary corrosion test (mm)
5.3
5.1
5.2
7.4
7.7
7.4
7.5
7.6
7.5
7.6





Note)


*1Al2O3 other than solid solution and CaAl2O4
























TABLE 65








Com-
Com-
Com-
Com-
Com-
Com-
Com-
Com-
Com-




parative
parative
parative
parative
parative
parative
parative
parative
parative



Comparative
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-



Example 38
ple 39
ple 40
ple 41
ple 42
ple 43
ple 44
ple 45
ple 46
ple 47


























X value of CaxSr1−xAl2O4
—
—
—
—
—
—
—
—
—
—


Crystallite diameter of solid solution obtained by
—
—
—
—
—
—
—
—
—
—


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
—
—
—
—
—
—
—
—
—
—


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
—
—
—
—
—
—
—
—
—
—


Crystallite diameter of solid solution obtained by
—
—
—
—
—
—
—
—
—
—


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
—
—
—
—
—
—
—
—
—
—


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
—
—
—
—
—
—
—
—
—
—


Crystallite diameter of solid solution obtained by
——
—
—
—
—
—
—
—
—


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
—
—
—
—
—
—
—
—
—
—


dissolving Sr components in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
40
40
40
40
40
40
40
40
40
40


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60


Type of dispersant
—
—
—
—
A
A
A
A
A
A


Amount of dispersant added (mass %)
—
—
—
—
0.1
0.1
0.1
0.1
0.1
0.1


Type of hardening retardant
a
b
—
—
a
b
—
—
a
b


Amount of hardening retardant added (mass %)
0.05
0.05
—
—
0.05
0.05
—
—
0.05
0.05


Type of hardening accelerator
—
—
α
β
—
—
α
β
α
β


Amount of hardening accelerator added (mass %)
—
—
0.05
0.05
—
—
0.05
0.05
0.05
0.05


















15 tap-flow value (mm)
After mixing
151
147
153
150
167
161
164
173
168
173



After 2 hours
126
127
121
119
139
147
119
123
126
119

















Bending strength after curing of 6 hours (MPa)
0.4
0.3
0.9
0.8
0.4
0.3
1
1
0.7
0.7


Bending strength after curing of 12 hours (MPa)
0.7
0.5
1.4
1.4
0.7
0.6
1.5
1.4
1.3
1.2


Bending strength after curing of 24 hours (MPa)
1.1
0.9
1.6
1.5
1.2
0.9
1.7
1.6
1.7
1.6


Wear amount in rotary corrosion test (mm)
7.8
8.1
8.3
8.2
7.5
7.9
7.5
7.6
7.4
7.6





Note)


*1Al2O3 other than solid solution and CaAl2O4

























TABLE 66







Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-



ple
ple
ple
ple
ple
ple
ple
ple
ple
ple
ple



391
392
393
394
395
396
397
398
399
400
401



























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution
59
59
59
59
59
59
59
59
59
59
59


obtained by dissolving Ca components in


α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0
0


dissolving Ca components in α-SrAl2O4


(mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution
54
54
54
54
54
54
54
54
54
54
54


obtained by dissolving Ca components in


β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
40
40


dissolving Ca components in β-SrAl2O4


(mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution
50
50
50
50
50
50
50
50
50
50
50


obtained by dissolving Sr components in


CaAl2O4 (nm)


Blending ratio of solid solution obtained
0
0
0
0
0
0
0
0
0
0
0


by dissolving Sr components in CaAl2O4


(mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60
60


Type of dispersant
A
A
A
B
B
B
C
C
C
D
D


Amount of dispersant added (mass %)
0.05
0.1
0.3
0.05
0.1
0.3
0.05
0.1
0.3
0.05
0.1


Type of hardening retardant
—
—
—
—
—
—
—
—
—
—
—


Amount of hardening retardant added
—
—
—
—
—
—
—
—
—
—
—


(mass %)


Type of hardening accelerator
—
—
—
—
—
—
—
—
—
—
—


Amount of hardening accelerator added
—
—
—
—
—
—
—
—
—
—
—


(mass %)



















15 tap-flow value (mm)
After mixing
158
170
173
167
180
186
148
151
157
151
153



After 2 hours
123
128
133
128
134
143
123
122
124
124
121


















Bending strength after curing of 6 hours
1.3
1.4
1.4
1.3
1.3
0.9
1.2
1.2
1.1
12
1.3


(MPa)


Bending strength after curing of 12 hours
1.6
1.7
1.7
1.7
1.7
1.2
1.7
1.5
1.6
1.6
1.6


(MPa)


Bending strength after curing of 24 hours
2.7
2.6
2.6
2.5
2.4
2.5
2.5
2.3
2.3
2.4
2.5


(MPa)


Wear amount in rotary corrosion test (mm)
5.3
5.4
5.4
5.5
5.3
5.3
5.5
5.5
5.4
5.3
5.5





Note)


*1Al2O3 other than solid solution and CaAl2O4

























TABLE 67







Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-



ple
ple
ple
ple
ple
ple
ple
ple
ple
ple
ple



402
403
404
405
406
407
408
409
410
411
412



























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution
59
59
59
59
59
59
59
59
59
59
59


obtained by dissolving Ca components in


α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0
0


dissolving Ca components in α-SrAl2O4


(mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution
54
54
54
54
54
54
54
54
54
54
54


obtained by dissolving Ca components in


β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
40
40


dissolving Ca components in β-SrAl2O4


(mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution
50
50
50
50
50
50
50
50
50
50
50


obtained by dissolving Sr components in


CaAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4


(mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60
60


Type of dispersant
D
E
E
E
F
F
F
G
G
G
—


Amount of dispersant added (mass %)
0.3
0.05
0.1
0.3
0.05
0.1
0.3
0.05
0.1
0.3
—


Type of hardening retardant
—
—
—
—
—
—
—
—
—
—
a


Amount of hardening retardant added
—
—
—
—
—
—
—
—
—
—
0.01


(mass %)


Type of hardening accelerator
—
—
—
—
—
—
—
—
—
—
—


Amount of hardening accelerator added
—
—
—
—
—
—
—
—
—
—
—


(mass %)



















15 tap-flow value (mm)
After mixing
155
151
153
159
150
153
152
156
161
166
147



After 2 hours
127
121
124
120
121
125
122
124
128
131
126


















Bending strength after curing of 6 hours
1.3
1.4
1.4
1.3
1.3
1.2
1.2
1.3
1.3
1.2
1.3


(MPa)


Bending strength after curing of 12 hours
1.8
1.8
1.7
1.6
1.6
1.7
1.7
1.8
1.7
1.7
1.6


(MPa)


Bending strength after curing of 24 hours
2.5
2.6
2.4
2.4
2.3
2.4
2.4
2.5
2.6
2.4
2.5


(MPa)


Wear amount in rotary corrosion test (mm)
5.5
5.4
5.3
5.4
5.4
5.5
5.4
5.4
5.4
5.5
5.3





Note)


*1Al2O3 other than solid solution and CaAl2O4

























TABLE 68







Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-



ple
ple
ple
ple
ple
ple
ple
ple
ple
ple
ple



413
414
415
416
417
418
419
420
421
422
423



























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution
59
59
59
59
59
59
59
59
59
59
59


obtained by dissolving Ca components in


α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0
0


dissolving Ca components in α-SrAl2O4


(mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
03
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution
54
54
54
54
54
54
54
54
54
54
54


obtained by dissolving Ca components in


β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
40
40
40
40
40
40
40
40
40
40
40


dissolving Ca components in β-SrAl2O4


(mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution
50
50
50
50
50
50
50
50
50
50
50


obtained by dissolving Sr components in


CaAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4


(mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60
60
60


Type of dispersant
—
—
—
—
—
—
—
—
—
—
—


Amount of dispersant added (mass %)
—
—
—
—
—
—
—
—
—
—
—


Type of hardening retardant
a
a
b
b
b
—
—
—
—
—
—


Amount of hardening retardant added
0.05
0.2
0.01
0.05
0.2
—
—
—
—
—
—


(mass %)


Type of hardening accelerator
—
—
—
—
—
α
α
α
β
β
β


Amount of hardening accelerator added
—
—
—
—
—
0.01
0.05
0.2
0.01
0.05
0.2


(mass %)



















15 tap-flow value (mm)
After mixing
153
152
143
140
142
166
172
174
173
176
175



After 2 hours
131
132
125
130
135
127
126
121
125
122
118


















Bending strength after curing of 6 hours
1.3
1.2
1.1
1
0.8
1.4
1.4
1.5
1.3
1.4
1.5


(MPa)


Bending strength after curing of 12 hours
1.5
1.5
1.4
1.3
1.1
1.7
1.8
1.8
1.6
1.7
1.9


(MPa)


Bending strength after curing of 24 hours
2.3
2.3
2.5
2.4
2.2
2.5
2.4
2.2
2.3
2.3
2.2


(MPa)


Wear amount in rotary corrosion test (mm)
5.4
5.4
5.4
5.5
5.3
5.9
6
5.8
5.9
6
5.9





Note)


*1Al2O3 other than solid solution and CaAl2O4
























TABLE 69






Example
Example
Example
Example
Example
Example
Example
Example
Example
Example
Example



424
425
426
427
428
429
430
431
432
433
434


























X value of CaxSr1-xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution 
59
59
59
59
59
59
59
59
59
59
59


obtained by dissolving Ca components 













in α-SrAl2O4 (nm)













Blending ratio of solid solution 
0
0
0
0
0
0
0
0
0
0
0


obtained by dissolving Ca components 













in α-SrAl2O4 (mass %)













X value of CaxSr1-xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution 
54
54
54
54
54
54
54
54
54
54
54


obtained by dissolving Ca components 













β-SrAl2O4 (nm)













Blending ratio of solid solution 
40
40
40
40
40
40
40
40
40
40
40


obtained by dissolving Ca components 













in β-SrAl2O4 (mass %)













X value of CaxSr1-xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution 
50
50
50
50
50
50
50
50
50
50
50


obtained by dissolving Sr components 













in CaAl2O4 (nm)













Blending ratio of solid solution 
0
0
0
0
0
0
0
0
0
0
0


obtained by dissolving Sr components 













in CaAl2O4 (mass %)













Blending ratio of CaAl2O4 (mass %)
 
 
 
 
 
 
 
 
 
 
 


Blending ratio of α-Al2O3 (mass %) *1
60
60
60
60
60
60
60
60
60
60
60


Type of dispersant
A
A
A
A
A
A
A
A
A
A
A


Amount of dispersant added (mass %)
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1


Type of hardening retardant
a
a
a
b
b
b
 
 
 
 
 


Amount of hardening retardant 
0.01
0.05
0.2
0.01
0.05
0.2
 
 
 
 
 


added (mass %)













Type of hardening accelerator
 
 
 
 
 
 
α
α
α
β
β


Amount of hardening accelerator 
 
 
 
 
 
 
0.01
0.05
0.2
0.01
0.05


added (mass %)






























15 tap-flow value (mm)
After mixing
169
167
162
163
160
163
170
172
166
173
175



After 2 hours
131
135
140
133
135
139
129
124
122
124
122


















Bending strength after curing of 
1.3
1.2
1.2
1.3
1.1
0.9
1.7
1.8
1.8
1.6
1.7


6 hours (MPa)













Bending strength after curing of 
1.8
1.6
1.5
1.6
1.4
1.3
2
2.1
2.2
1.9
2


12 hours (MPa)













Bending strength after curing of 
2.5
2.4
2.3
2.4
2.3
2.3
2.6
2.5
2.3
2.6
2.6


24 hours (MPa)













Wear amount in rotary corrosion 
5.3
5.3
5.4
5.3
5.3
5.3
5.4
5.3
5.5
5.4
5.3


test (mm)





Note)


*1 Al2O3 other than solid solution and CaAl2O4






















TABLE 70






Example
Example
Example
Example
Example
Example
Example
Example
Example



435
436
437
438
439
440
441
442
443
























X value of CaxSr1-xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained 
59
59
59
59
59
59
59
59
59


by dissolving Ca components in α-SrAl2O4 (nm)











Blending ratio of solid solution obtained by 
0
0
0
0
0
0
0
0
0


dissolving Ca components in α-SrAl2O4 (mass %)











X value of CaxSr1-xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by 
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)











Blending ratio of solid solution obtained by 
40
40
40
40
40
40
40
40
40


dissolving Ca components in β-SrAl2O4 (mass %)











X value of CaxSr1-xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained 
50
50
50
50
50
50
50
50
50


by dissolving Sr components CaAl2O4 (nm)











Blending ratio of solid solution obtained by 
0
0
0
0
0
0
0
0
0


dissolving Sr components in CaAl2O4 (mass %)











Blending ratio of CaAl2O4 (mass %)
 
 
 
 
 
 
 
 
 


Blending ratio of α-Al2O3 (mass %) *1
60
60
60
60
60
60
60
60
60


Type of dispersant
A
 
 
 
 
 
 
A
A


Amount of dispersant added (mass %)
0.1
 
 
 
 
 
 
0.1
0.1


Type of hardening retardant
 
a
a
a
a
a
a
a
a


Amount of hardening retardant added (mass %)
 
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Type of hardening accelerator
β
α
α
α
β
β
β
α
β


Amount of hardening accelerator added (mass %)
0.2
0.01
0.05
0.2
0.01
0.05
0.2
0.05
0.05

















15 tap-flow value (mm)
After mixing
168
147
142
143
147
153
156
176
172



After 2 hours
118
137
131
125
134
127
121
141
138
















Bending strength after curing of 6 hours (MPa)
1.7
1.4
1.5
1.7
1.5
1.6
1.7
1.7
1.8


Bending strength after curing of 12 hours (MPa)
2.1
1.8
1.8
2
1.8
1.8
2
2
2.1


Bending strength after curing of 24 hours (MPa)
2.5
2.6
2.6
2.5
2.6
2.5
2.6
2.7
2.6


Wear amount in rotary corrosion test (mm)
5.3
5.3
5.4
5.5
5.3
5.4
5.5
5.3
5.2





Note)


*1 Al2O3 other than solid solution and CaAl2O4























TABLE 71







Exam-

Exam-

Exam-







ple
Example
ple
Example
ple
Example
Example
Example
Example



444
445
446
447
448
449
450
451
452

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Sr componentst in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60


Type of dispersant
A
B
C
D
E
F
G
—
—


Amount of dispersant added (mass %)
0.1
0.1
0.1
0.1
0.1
0.1
0.1
—
—


Type of hardening retardant
—
—
—
—
—
—
—
a
b


Amount of hardening retardant added (mass %)
—
—
—
—
—
—
—
0.05
0.05


Type of hardening accelerator
—
—
—
—
—
—
—
—
—


Amount of hardening accelerator added (mass %)
—
—
—
—
—
—
—
—
—

















15 tap-flow value (mm)
After mixing
170
179
157
152
152
159
160
148
148



After 2 hours
125
133
130
131
124
131
131
128
131
















Bending strength after curing of 6 hours (MPa)
1.4
1.1
1.3
1.3
1.3
1.1
1.4
1.2
1


Bending strength after curing of 12 hours (MPa)
1.8
1.4
1.7
1.7
1.8
1.5
1.7
1.5
1.3


Bending strength after curing of 24 hours (MPa)
2.6
2.2
2.4
2.6
2.5
2.5
2.6
2.4
2.2


Wear amount in rotary corrosion test (mm)
5.4
5.3
5.3
5.4
5.4
5.3
5.3
5.3
5.2





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 72







Exam-

Exam-

Exam-







ple
Example
ple
Example
ple
Example
Example
Example
Example



453
454
455
456
457
458
459
460
461

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Sr componentst in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60


Type of dispersant
—
—
A
A
A
A
—
—
A


Amount of dispersant added (mass %)
—
—
0.1
0.1
0.1
0.1
—
—
0.1


Type of hardening retardant
—
—
a
b
—
—
a
a
a


Amount of hardening retardant added (mass %)
—
—
0.05
0.05
—
—
0.05
0.05
0.05


Type of hardening accelerator
α
β
—
—
α
β
α
β
α


Amount of hardening accelerator added (mass %)
0.05
0.05
—
—
0.05
0.05
0.05
0.05
0.05

















15 tap-flow value (mm)
After mixing
169
174
166
166
172
175
140
152
170



After 2 hours
129
130
132
134
126
125
123
130
135
















Bending strength after curing of 6 hours (MPa)
1.5
1.5
1.3
1.1
1.7
1.7
1.6
1.8
1.5


Bending strength after curing of 12 hours (MPa)
1.8
1.9
1.6
1.5
2.1
2.1
1.9
2.1
2


Bending strength after curing of 24 hours (MPa)
2.3
2.3
2.5
2.5
2.6
2.7
2.6
2.6
2.5


Wear amount in rotary corrosion test (mm)
5.8
5.7
5.4
5.3
5.2
5.2
5.4
5.3
5.2





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 73







Exam-

Exam-

Exam-







ple
Example
ple
Example
ple
Example
Example
Example
Example



462
463
464
465
466
467
468
469
470

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Sr componentst in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60


Type of dispersant
A
B
C
D
E
F
G
—
—


Amount of dispersant added (mass %)
0.1
0.1
0.1
0.1
0.1
0.1
0.1
—
—


Type of hardening retardant
—
—
—
—
—
—
—
a
b


Amount of hardening retardant added (mass %)
—
—
—
—
—
—
—
0.05
0.05


Type of hardening accelerator
—
—
—
—
—
—
—
—
—


Amount of hardening accelerator added (mass %)
—
—
—
—
—
—
—
—
—

















15 tap-flow value (mm)
After mixing
163
179
160
157
158
159
162
146
151



After 2 hours
128
136
130
132
132
125
131
126
131
















Bending strength after curing of 6 hours (MPa)
1.1
0.9
1.1
1.1
1
1.2
1
1
0.9


Bending strength after curing of 12 hours (MPa)
1.6
1.3
1.5
1.5
1.4
1.5
1.4
1.3
1.2


Bending strength after curing of 24 hours (MPa)
2.7
2.3
2.6
2.7
2.5
2.7
2.6
2.5
2.5


Wear amount in rotary corrosion test (mm)
5.3
5.3
5.3
5.4
5.5
5.3
5.4
5.4
5.5





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 74







Exam-

Exam-

Exam-







ple
Example
ple
Example
ple
Example
Example
Example
Example



471
472
473
474
475
476
477
478
479

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Sr componentst in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60


Type of dispersant
—
—
A
A
A
A
—
—
A


Amount of dispersant added (mass %)
—
—
0.1
0.1
0.1
0.1
—
—
0.1


Type of hardening retardant
—
—
a
b
—
—
a
a
a


Amount of hardening retardant added (mass %)
—
—
0.05
0.05
—
—
0.01
0.01
0.01


Type of hardening accelerator
α
β
—
—
α
β
α
β
α


Amount of hardening accelerator added (mass %)
0.05
0.05
—
—
0.05
0.05
0.05
0.05
0.05

















15 tap-flow value (mm)
After mixing
160
164
166
160
171
171
146
153
162



After 2 hours
122
126
131
133
125
128
131
126
132
















Bending strength after curing of 6 hours (MPa)
1.5
1.5
1.1
0.9
1.6
1.7
1.5
1.7
1.5


Bending strength after curing of 12 hours (MPa)
1.9
2
1.4
1.3
2
2
1.7
2.1
1.8


Bending strength after curing of 24 hours (MPa)
2.4
2.6
2.5
2.6
2.7
2.6
2.7
2.7
2.7


Wear amount in rotary corrosion test (mm)
5.9
5.7
5.2
5.3
5.3
5.2
5.5
5.3
5.2





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 75







Exam-

Exam-

Exam-







ple
Example
ple
Example
ple
Example
Example
Example
Example



480
481
482
483
484
485
486
487
488

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0


dissolving Sr componentst in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60


Type of dispersant
A
B
C
D
E
F
G
—
—


Amount of dispersant added (mass %)
0.1
0.1
0.1
0.1
0.1
0.1
0.1
—
—


Type of hardening retardant
—
—
—
—
—
—
—
a
b


Amount of hardening retardant added (mass %)
—
—
—
—
—
—
—
0.05
0.05


Type of hardening accelerator
—
—
—
—
—
—
—
—
—


Amount of hardening accelerator added (mass %)
—
—
—
—
—
—
—
—
—

















15 tap-flow value (mm)
After mixing
168
174
161
159
162
157
162
147
146



After 2 hours
126
134
133
131
129
131
137
131
136
















Bending strength after curing of 6 hours (MPa)
1.3
1.2
1.2
1.1
1.2
1
1.2
1.1
1


Bending strength after curing of 12 hours (MPa)
1.7
1.5
1.6
1.6
1.6
1.4
1.6
1.4
1.3


Bending strength after curing of 24 hours (MPa)
2.6
2.4
2.5
2.6
2.7
2.5
2.5
2.5
2.4


Wear amount in rotary corrosion test (mm)
5.5
5.3
5.4
5.6
5.4
5.5
5.5
5.3
5.4





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 76







Exam-

Exam-

Exam-







ple
Example
ple
Example
ple
Example
Example
Example
Example



489
490
491
492
493
494
495
496
497

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
20
20
20
20
20
20
20
20
20


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
0
0
0
0
0
0
0
0
0


dissolving Sr componentst in CaA2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60


Type of dispersant
—
—
A
A
A
A
—
—
A


Amount of dispersant added (mass %)
—
—
0.1
0.1
0.1
0.1
—
—
0.1


Type of hardening retardant
—
—
a
b
—
—
a
a
a


Amount of hardening retardant added (mass %)
—
—
0.05
0.05
—
—
0.05
0.05
0.05


Type of hardening accelerator
α
β
—
—
α
β
α
β
α


Amount of hardening accelerator added (mass %)
0.05
0.05
—
—
0.05
0.05
0.05
0.05
0.05

















15 tap-flow value (mm)
After mixing
169
169
172
169
174
172
148
155
173



After 2 hours
129
127
138
135
130
133
127
134
139
















Bending strength after curing of 6 hours (MPa)
1.3
1.3
1.2
1.1
1.5
1.6
1.4
1.6
1.4


Bending strength after curing of 12 hours (MPa)
1.7
1.7
1.5
1.4
1.9
1.9
1.8
2
1.9


Bending strength after curing of 24 hours (MPa)
2.2
2.3
2.6
2.6
2.6
2.6
2.4
2.5
2.6


Wear amount in rotary corrosion test (mm)
5.9
5.8
5.3
5.5
5.3
5.4
5.6
5.5
5.3





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 77







Exam-

Exam-

Exam-







ple
Example
ple
Example
ple
Example
Example
Example
Example



498
499
500
501
502
503
504
505
506

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
14
14
14
14
14
14
14
14
14


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
14
14
14
14
14
14
14
14
14


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
12
12
12
12
12
12
12
12
12


dissolving Sr componentst in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O4 (mass %)*1
60
60
60
60
60
60
60
60
60


Type of dispersant
A
B
C
D
E
F
G
—
—


Amount of dispersant added (mass %)
0.1
0.1
0.1
0.1
0.1
0.1
0.1
—
—


Type of hardening retardant
—
—
—
—
—
—
—
a
b


Amount of hardening retardant added (mass %)
—
—
—
—
—
—
—
0.05
0.05


Type of hardening accelerator
—
—
—
—
—
—
—
—
—


Amount of hardening accelerator added (mass %)
—
—
—
—
—
—
—
—
—

















15 tap-flow value (mm)
After mixing
167
171
160
155
155
156
157
146
148



After 2 hours
129
135
132
134
130
128
128
129
131
















Bending strength after curing of 6 hours (MPa)
1.3
1.1
1.3
1.2
1.1
1.3
1.1
1.1
0.8


Bending strength after curing of 12 hours (MPa)
1.7
1.4
1.6
1.6
1.5
1.7
1.6
1.5
1.2


Bending strength after curing of 24 hours (MPa)
2.6
2.4
2.6
2.6
2.4
2.6
2.6
2.5
2.1


Wear amount in rotary corrosion test (mm)
5.4
5.3
5.2
5.4
5.2
5.3
5.4
5.3
5.3





Note)


*1Al2O3 other than solid solution and CaAl2O4























TABLE 78







Exam-

Exam-

Exam-







ple
Example
ple
Example
ple
Example
Example
Example
Example



507
508
509
510
511
512
513
514
515

























X value of CaxSr1−xAl2O4
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05


Crystallite diameter of solid solution obtained by
59
59
59
59
59
59
59
59
59


dissolving Ca components in α-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
14
14
14
14
14
14
14
14
14


dissolving Ca components in α-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Crystallite diameter of solid solution obtained by
54
54
54
54
54
54
54
54
54


dissolving Ca components in β-SrAl2O4 (nm)


Blending ratio of solid solution obtained by
14
14
14
14
14
14
14
14
14


dissolving Ca components in β-SrAl2O4 (mass %)


X value of CaxSr1−xAl2O4
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95


Crystallite diameter of solid solution obtained by
50
50
50
50
50
50
50
50
50


dissolving Sr components in CaAl2O4 (nm)


Blending ratio of solid solution obtained by
12
12
12
12
12
12
12
12
12


dissolving Sr componentst in CaAl2O4 (mass %)


Blending ratio of CaAl2O4 (mass %)
—
—
—
—
—
—
—
—
—


Blending ratio of α-Al2O3 (mass %)*1
60
60
60
60
60
60
60
60
60


Type of dispersant
—
—
A
A
A
A
—
—
A


Amount of dispersant added (mass %)
—
—
0.1
0.1
0.1
0.1
—
—
0.1


Type of hardening retardant
—
—
a
b
—
—
a
a
a


Amount of hardening retardant added (mass %)
—
—
0.05
0.05
—
—
0.01
0.01
0.01


Type of hardening accelerator
α
β
—
—
α
β
α
β
α


Amount of hardening accelerator added (mass %)
0.05
0.05
—
—
0.05
0.05
0.05
0.05
0.05

















15 tap-flow value (mm)
After mixing
167
169
160
162
167
177
144
150
167



After 2 hours
129
126
133
136
128
134
133
126
134
















Bending strength after curing of 6 hours (MPa)
1.5
1.4
1.1
0.9
1.6
1.8
1.5
1.7
1.5


Bending strength after curing of 12 hours (MPa)
1.7
1.9
1.4
1.3
2.1
2.1
1.8
2
1.9


Bending strength after curing of 24 hours (MPa)
2.6
2.5
2.6
2.4
2.7
2.6
2.5
2.5
2.6


Wear amount in rotary corrosion test (mm)
5.8
5.7
5.3
5.3
5.2
5.3
5.3
5.4
5.3





Note)


*1Al2O3 other than solid solution and CaAl2O4






The evaluation results are as shown in Tables 59 to 78. In the cases of Examples 338 to 364, 371 to 376, 391 to 417, 424 to 429, 444 to 452, 455, 456, 462 to 470, 473, 474, 480 to 488, 491, 492, 498 to 506, 505, and 506 in which a dispersant and/or a hardening retardant were used, regardless of the reduced amount of water added to monolithic refractories, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 338 to 364, 371 to 376, 391 to 417, 424 to 429, 444 to 452, 455, 456, 462 to 470, 473, 474, 480 to 488, 491, 492, 498 to 506, 505, and 506 can be applied to furnaces with a large volume or the like. Furthermore, Examples 338 to 364, 371 to 376, 391 to 417, 424 to 429, 444 to 452, 455, 456, 462 to 470, 473, 474, 480 to 488, 491, 492, 498 to 506, 505, and 506 show larger values than Comparative Examples 31 to 39, 42, and 43 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 338 to 364, 371 to 376, 391 to 417, 424 to 429, 444 to 452, 455, 456, 462 to 470, 473, 474, 480 to 488, 491, 492, 498 to 506, 505, and 506 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 338 to 364, 371 to 376, 391 to 417, 424 to 429, 444 to 452, 455, 456, 462 to 470, 473, 474, 480 to 488, 491, 492, 498 to 506, 505, and 506 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 338 to 364, 371 to 376, 391 to 417, 424 to 429, 444 to 452, 455, 456, 462 to 470, 473, 474, 480 to 488, 491, 492, 498 to 506, 505, and 506 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In addition, by reducing the amount of water added, compared to Examples in which the same binder was used with the ordinary amount of water added, Examples 338 to 364, 371 to 376, 391 to 417, 424 to 429, 444 to 452, 455, 456, 462 to 470, 473, 474, 480 to 488, 491, 492, 498 to 506, 505, and 506 show an increase in the cured flexural strength and degradation in the wear amount in the rotary corrosion test using slag.
In Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 using only a hardening accelerator, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 can be applied to furnaces with a large volume or the like. Furthermore, Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 show larger values than Comparative Examples 40 and 41 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 including a hardening accelerator added, the cured flexural strength was further increased after 6 hours and 12 hours compared to Examples including no hardening accelerator added, which clarified that Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 are superior in terms of early strength developing property. In addition, the wear amount became almost the same as that of cases including no additive in the rotary corrosion test using slag, which clarified that Examples 365 to 370, 418 to 423, 453, 454, 471, 472, 489, 490, 507, and 508 are excellent in terms of slag resistance at a high temperature.
In Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515 using a hardening accelerator and furthermore at least either a dispersant or a hardening retardant, regardless of the reduced amount of water added to monolithic refractories, the flow values of the monolithic refractories suitable for pouring were obtained 2 hours after the start of mixing. Therefore, it has been confirmed that Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515 can be applied to furnaces with a large volume or the like. Furthermore, Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515 show larger values than Comparative Examples 44 to 47 in the flexural strength after curing of 6, 12, and 24 hours, and therefore it has been clarified that Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515 are excellent in terms of cured strength developing property. In particular, the flexural strength after curing of 6 hours is remarkably greater compared to those of the Comparative Examples, and therefore it has been confirmed that Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515 are excellent in terms of early strength developing property. Furthermore, it has been clarified that, compared to Comparative Examples, Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515 clearly show small wear amounts in the rotary corrosion test using slag and are excellent in terms of slag resistance at a high temperature.
In Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515, the cured flexural strength further increased after 6 hours and 12 hours compared to Examples including at least either a dispersant or a hardening retardant, and no hardening accelerator added, which clarified that Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515 are superior in terms of early strength developing property. In addition, the wear amount became almost the same in the rotary corrosion test using slag, which clarified that Examples 377 to 390, 430 to 443, 457 to 461, 475 to 479, 493 to 497, and 511 to 515 are excellent in terms of slag resistance at a high temperature.
As described above, the binders for monolithic refractories according to the present invention of all Examples obtained more satisfactory flow property suitable for pouring even after a long period of time has elapsed after mixing, were superior to Comparative Examples in terms of early strength developing property, thereby obtaining excellent construction performance. In addition, all Examples obtained more satisfactory slag resistance at 1600° C. than the Comparative Examples, which clarified that the tolerance at places that come into contact with molten iron or slag are improved.
INDUSTRIAL APPLICABILITY
According to the prevention, a binder for monolithic refractories having excellent corrosion resistance with respect to slag or molten iron and excellent characteristics in the early development of hardened strength and the stability thereof, compared to binders such as alumina cement in the conventional technology; a monolithic refractory using the binder; and a construction method of the monolithic refractory, can be provided.
REFERENCE SYMBOL LIST


    
    
        1: REFRACTORY (TEST SPECIMEN)
        2: PROTECTION PLATE
        3: BURNER
        4: SLAG
        5: FILLING MATERIAL

## Claims

1. A binder for monolithic refractories comprising
a solid solution obtained by dissolving Ca components in α-SrAl2O4 or β-SrAl2O4,
wherein when the Ca components are dissolved in the α-SrAl2O4, a crystallite diameter of the solid solution is from 40 nm to 75 nm, and
when the Ca components are dissolved in the β-SrAl2O4, a crystallite diameter of the solid solution is from 35 nm to 70 nm.

2. The binder for monolithic refractories according to claim 1,
wherein an amount of the solid solution obtained by dissolving Ca components in the α-SrAl2O4 or the β-SrAl2O4 is from 10 mass % to 60 mass %, and
40 mass % to 90 mass % of Al2O3 is blended thereinto.

3. The binder for monolithic refractories according to claim 1, further comprising, as a mixture,
a solid solution obtained by dissolving Sr components in CaAl2O4,
wherein a crystallite diameter of the solid solution is from 25 nm to 60 nm.

4. The binder for monolithic refractories according to claim 3,
wherein an amount of the solid solution obtained by dissolving Ca components in the α-SrAl2O4 or the β-SrAl2O4 and the solid solution obtained by dissolving Sr components in the CaAl2O4 is from 10 mass % to 60 mass %, and
40 mass % to 90 mass % of Al2O3 is blended thereinto.

5. The binder for monolithic refractories according to claim 1,
wherein both of a solid solution obtained by dissolving Ca components in the α-SrAl2O4 and a solid solution obtained by dissolving Ca components in the β-SrAl2O4 are included as a mixture.

6. The binder for monolithic refractories according to claim 5,
wherein a total amount of both of the solid solution obtained by dissolving Ca components in the α-SrAl2O4 and the solid solution obtained by dissolving Ca components in the β-SrAl2O4 is from 10 mass % to 60 mass %, and
40 mass % to 90 mass % of Al2O3 is blended thereinto.

7. The binder for monolithic refractories according to claim 5, further comprising, as a mixture
the solid solution obtained by dissolving Sr components in the CaAl2O4.

8. The binder for monolithic refractories according to claim 7,
wherein a total amount of the solid solution obtained by dissolving Ca components in the α-SrAl2O4, the solid solution obtained by dissolving Ca components in the β-SrAl2O4, and the solid solution obtained by dissolving Sr components in the CaAl2O4 is from 10 mass % to 60 mass %, and
40 mass % to 90 mass % of Al2O3 is blended thereinto.

9. The binder for monolithic refractories according to claim 1,
wherein at least one selected from a group consisting of SiO2, TiO2, Fe2O3, MgO, and BaO are included in the binder for monolithic refractories and an amount thereof is 12 mass % or less.

10. The binder for monolithic refractories according to claim 1,
wherein at least one of a dispersant and a hardening retardant is blended into the binder for monolithic refractories.

11. A monolithic refractory obtained by blending the binder for monolithic refractories according to any one of claims 1 to 10 into a refractory aggregate.

12. The monolithic refractory according to claim 11,
wherein the refractory aggregate includes an ultrafine alumina powder with a particle diameter of from 0.8 nm to 1 μm.

13. The monolithic refractory according to claim 11,
wherein an amount of the binder for monolithic refractories is from 0.3 mass % to 20 mass % with respect to 100 mass % of a total amount of the binder for monolithic refractories and the refractory aggregate.

14. The monolithic refractory according to claim 13,
wherein the amount of the binder for monolithic refractories is from 0.5 mass % to 12 mass % with respect to 100 mass % of the total amount of the binder for monolithic refractories and the refractory aggregate.

15. The monolithic refractory according to claim 11,
wherein further at least one of a dispersant, a hardening retardant, and a hardening accelerator is added.

16. The monolithic refractory according to claim 15,
wherein the dispersant is at least one selected from a group consisting of a polycarbonate-based dispersant, a phosphate-based dispersant, an oxycarboxylic acid, a melamine-based dispersant, a naphthalene-based dispersant, and a lignin sulfonic acid-based dispersant,
the hardening accelerator is at least one of an alkali metal salt and aluminate, and
the hardening retardant is at least one of boric acid group and silicofluoride.

17. A construction method of monolithic refractories comprising:
blending and mixing the binder for monolithic refractories according to any one of claims 1 to 10 and a refractory aggregate including an ultrafine alumina powder with a particle diameter of 1 μm or less to obtain a monolithic refractory; and
constructing the monolithic refractory.