JPH01176260A - High-strength hydraulic material composition - Google Patents

Abstract

PURPOSE:To provide the title fluid composition having precise transferability, especially excellent in flexural strength, comprising a hydraulic material consisting mainly of alkaline earth metal oxide and Al2O3, ultrafine powder, metallic aggregate and dispersant. CONSTITUTION:(A) A mixture of (i) 95-50wt.% of a hydraulic material with a particle size of 10-30mu consisting mainly of alkaline earth metal oxide and Al2O3 (e.g. alumina cement consisting mainly of calcium aluminate with a molar ratio: CaO/Al2O3<0.5) and (ii) 5-50wt.% of ultrafine powder with its average particle size smaller than the component (i) by one order or more (e.g. silica fume) is incorporated with (B) <=5wt.% times the mixture A, of metallic aggregate with a granular size of 0.1-5mm (e.g. iron powder), (C) 1-5wt.% of a dispersant (beta-naphthalensulfonate formaldehyde condensate), (D) <=35wt.% of water, and, if needed, (E) curing regulator (e.g. Na2SO4), inert inorganic powder, metallic powder etc. followed by kneading, defoaming treatment under a vacuum and vibration treatment, thus obtaining the title composition.

Description

[Detailed description of the invention]

<Industrial Field of Application> The present invention has excellent workability that allows casting to be performed at room temperature, extremely precise transferability to the casting surface, and excellent heat resistance and high strength properties. In particular, it relates to high strength hydraulic material compositions with improved flexural strength. <Prior art and its problems> The technology of adding ultrafine powder 1 to 2 orders of magnitude smaller than that of a hydraulic inorganic material and using it together with a high-performance water reducing agent to obtain a dense, high-strength cured product is already known (especially Kosho 60-59182
Publication, Special Publication No. 55-500863). Also, stainless steel particles are used as aggregate. A similar technology combining Portland cement hydraulic materials is also known (Special Publication No. 6l-502603). However, among these conventional hydraulic materials, the former has superior density compared to ordinary mortar and concrete. Therefore, explosions occur due to water vapor at high temperatures, and it is difficult to say that they are necessarily heat resistant, and it is said that the upper limit of the temperature at which molded products can be used regularly is about 250°C to 400°C. In addition, temperature cracking due to thermal stress has become a problem that must be solved when making molded products. Furthermore, in both cases, the bending strength decreases during dry curing at 100° C. or higher. On the other hand, hydraulic castable refractory compositions are also known, but although these have no problems with heat resistance, it is difficult to obtain high strength, especially high bending strength, and they maintain excellent fluidity. It is difficult to obtain transferability by pour molding, and furthermore, it is difficult to obtain transferability in the medium temperature range (400 to 900
Many problems remain, such as large strength loss at temperatures (°C) and instability as the hydrate transition temperature is near room temperature. As described above, hydraulic material compositions have excellent workability, allowing pour molding at room temperature, extremely precise transferability to the pouring surface, and excellent heat resistance and high strength properties. There are various problems in ensuring this. <Object of the invention> An object of the present invention is to provide a hydraulic material composition having particularly high bending strength. Another object of the present invention is to provide a high-strength hydraulic material composition that can be cast at room temperature, has excellent workability, and has extremely precise transferability to the casting surface. Still another object of the present invention is to provide a hydraulic material composition that has excellent heat resistance and high strength. According to the present invention, a hydraulic substance containing an alkaline earth metal oxide and aluminum oxide (AQzOs) as main components, and a hydraulic substance having an average particle diameter of at least one order of magnitude smaller than that of the hydraulic substance. A high strength hydraulic material composition is provided that includes an ultrafine powder, a metal aggregate, and a dispersant. The present invention will be explained in more detail below. The hydraulic substance mainly composed of alkaline earth metal oxide and aluminum oxide (agxoi) used in the present invention is mainly composed of Cab, Bad, SrO, or a mixture of two or more thereof, and A Q z O3. It is preferable to use it as a component. Particularly preferable hydraulic substances include alumina cement, and CaO/AI
! Calcium aluminate with a molar ratio of z Os of less than 0.5, a molar ratio of Ca O / A' Q z Oz of 1
．． Mention may be made of calcium aluminates of 5 to 4.0. The alumina cement contains CaO・Al, O, as a main component, and also contains CaO*.
2Afi, 03,12Ca0 7AQ, 03, or mixtures thereof can be used, and also, for example, S
It may contain a small amount of a solid solution such as i oat Fe203. These commercially available products include ``R Denka Alumina Cement No. 1'', ``Denka Alumina Cement No. 2'',
``Denka High Alumina Cement'' (all manufactured by Denki Kagaku Kogyo Co., Ltd. 11, product name), ``Asano Alumina Cement'' (manufactured by Nippon Cement Co., Ltd., product name), r-Asahi Honju'' (Asahi Glass Co., Ltd.) , product name). The calcium aluminate having a molar ratio of C'a O/A Q 203 of less than 0.5 includes: Ca 0 ・2 A Qx Oa-Ca O” 6 A
Examples include those containing a Q z Oa mixture as a main component, and may further contain the above-mentioned alumina cement. In this case, heat resistance is particularly improved. The molar ratio of CaO/AQzOs is 1.5 to 4
．． As calcium aluminate of 0, 12Ca0・7AQ□o3,3CaO-AQ203゜4
C'aO-Au, ○, *p' 6.03゜6Ca0
・2AQ2o3・Fe2O, or a mixture thereof can be mentioned as a main component, and a small amount of solid solution component may be included in addition to these. In this case, it is possible to obtain a material that exhibits high early strength and high bendability. In addition, BaAl2O4 and 5rAQ04 are used as hydraulic substances.
Those containing constituent minerals such as and mixtures thereof as main components can be used. The particle size of the hydraulic substance is not particularly limited, but 1
Those having an average particle size of about 0 to 30 μm are preferable. The ultrafine powder in the present invention has an average particle size at least one order or more, preferably two orders smaller than the average particle size of the hydraulic substance, and is preferably 1 μm or less, preferably 0.5 μm or less. Specifically, silica dust that is produced as a by-product during the production of ferrosilicon and metal silicon, or the above-mentioned hydraulic substances, blast furnace slag, fly ash, alumina and silica that are crushed and classified,
These include the recovered products of each Bacfilter, as well as ultrafine inorganic powders produced by gas phase methods, liquid phase precipitation methods, and the like. The amount of ultrafine powder used is about 5 to 50% by weight, more preferably about 10 to 20% by weight, relative to 95 to 50% by weight of the hydraulic substance, preferably 90 to 80% by weight. If it is less than 5% by weight, the fluidity of the kneaded product becomes dilatantic and sufficient kneading cannot be achieved. Moreover, if it exceeds 50% by weight, it is difficult to obtain fluidity, and in any case, it is difficult to have precise transferability to the pouring surface. In the present invention, metal aggregate is added to the hydraulic material composition. Examples of the metal aggregate include iron powder, stainless steel powder, alloy iron powder such as ferrosilicon, ferromanganese, calcium silicon, etc., especially alloy iron powder that has been washed and dried with water. From the viewpoint of improving bending strength, iron powder and stainless steel powder are preferred, particularly among stainless steel powders, austenitic stainless steel powder and ferromanganese powder are preferred. It is not clear why the bending strength is particularly high when iron powder, austenitic stainless steel powder, or ferromanganese powder is used, but it is thought to be because they themselves have high strength and have excellent adhesion. Normal particle size is 0.1-5111
It is about 1, and although it is not particularly limited, the smaller the particle size is, the better the bending strength is. On the other hand, by increasing the brittle tendency of the material, it is preferable to select the material at a level of about 0.1 to 0.3.The amount of metal aggregate used is 5 weight per total amount of hydraulic material and ultrafine powder. It is used selectively within double the amount, but this does not apply in the case of special molding methods such as pre-packed and post-packed construction methods. Dispersants used in the present invention include oxycarboxylic acids such as citric acid, polycarboxylic acids or salts thereof, formalin condensates of naphthalene or alkylnaphthalenesulfonic acids or salts thereof called super plasticizers, and melamine. Examples include resin sulfonic acid or a salt thereof and high molecular weight polygenin sulfonic acid or a salt thereof, and these can be used alone or in combination. The amount added is desirably 1 to 5 parts by weight, preferably 1.5 to 3 parts by weight, based on 100 parts by weight of the total of the hydraulic substance and ultrafine powder. At this time, if the amount added is less than 1 part by weight, it is difficult to obtain fluidity, and if it exceeds 5 parts by weight, the hydration reaction will be significantly delayed, which is undesirable. It is recommended to use an agent. In the present invention, a hardening modifier can be added to the hydraulic substance if necessary, and particularly good results can be obtained by using a hardening modifier and a high performance water reducing agent in combination. Examples of the hardening modifier include inorganic acids and borates such as sulfuric acid and boric acid, alkali metal sulfates, carbonates, hydrogen carbonates, organic acids and their salts such as citric acid, phosphoric esters, and gypsum. Can be done. The amount of the curing modifier used varies depending on the purpose, but it is usually preferably 3 parts by weight or less per 100 parts by weight of the total of the hydraulic substance and ultrafine powder. In the present invention, inert inorganic powder having a particle size of 1 to 100 μm can also be added to the hydraulic material. The above-mentioned inert inorganic powder used in the present invention means a powder consisting of particles of an inorganic solid material that is inert to hydration reactions. The smaller the particle size, the greater the surface activity of the particles, making it impossible to ensure fluidity unless a large amount of water is used during kneading, and the larger the particle size, the worse the surface transferability. 1 to 100 μm, taking into account
, preferably 5 to 88 μm, more preferably 5 to 44 μm
A μm one is better. There are no particular restrictions on the composition of this inert inorganic powder, and oxides and non-oxide ceramics can be used. For example, silica, alumina, mullite, magnesia, spinel, silicon carbide, and nitride are used. These powders can be prepared by crushing or crushing and classifying various ceramics, refractories, aggregates, etc. Further, it is not appropriate that the inert inorganic powder is easily soluble in water, and it is preferable that the inert inorganic powder has a not very high water absorption rate. Furthermore, if heat resistance is required for the molded article, the inert inorganic powder used must be able to withstand at least a high temperature higher than the required temperature, depending on the degree of heat resistance required. The amount of inert inorganic powder used can be changed arbitrarily with respect to the hydraulic substance, but in order to improve fluidity, it is preferable that the amount of inert inorganic powder is 20 parts by volume or more per 100 parts by volume of both. Preferable from this point of view. From the viewpoint of significant improvement in curing shrinkage, it is preferable to use 50 parts by volume or more, and more preferably 80 parts by volume or more, as a large effect on heat resistance can be seen and is suitable for use in harsh thermal environments such as high temperatures and thermal shock. 90 parts by volume or more is preferred. However, although there is no problem with compressive strength, from the viewpoint of bending strength, it is preferable that the hydraulic substance is contained in an amount of 50 parts by volume or more, more preferably 80 parts by volume or more, per 100 parts by volume of both. This improves other properties and makes it possible to maintain high bending strength. In the present invention, metal particles having a particle size of 1 to 100 μm, which is approximately the same as that of the hydraulic substance, can also be used. In this case, workability and mechanical strength can be improved. If the particle size of the metal particles is too small, the fluidity will decrease, and the amount of water required to obtain a certain level of fluidity will increase, which will reduce the strength of the cured product. In this case, the negative side is that the particles may peel off and the machinability of the system will be reduced. Taking these into consideration, use particles of 100 μm or more and 1 μm or more, that is, approximately the same particle size as the hydraulic material. It is important to. There are no particular restrictions on the components constituting the metal particles, and for example, iron, stainless steel, ferroalloys such as ferrochrome, etc. can be used. The usage ratio of the metal particles is 10 to 5 parts by volume of the hydraulic substance and metal particles in total.
~95 parts by volume can be replaced. However, in order to maintain high bending strength, it is preferable that the hydraulic substance is contained in an amount of 50 parts by volume or more, more preferably 80 parts by volume or more. In addition to the above formulations, various types of fibers and nets can also be incorporated. Fibers include fibers produced by chatter cutting of cast iron, metal fibers such as steel fibers and stainless steel fibers, various natural or synthetic mineral fibers such as asbestos and alumina fibers, carbon fibers, glass fibers, polypropylene, vinylon,
Examples include natural or synthetic organic fibers such as acrylonitrile and cellulose. Further, it is also possible to use conventionally used copper rods, FRP rods, etc. as reinforcing materials, and these reinforcing materials are indispensable especially for large-sized ones. From the point of view of not impairing fluidity, short metal fibers having a length of about 3 mm or shorter whiskers can also be preferably used. Also,
It can also be used as a so-called preform, which is knitted in advance and later impregnated with paste or mortar. Furthermore, when considering use at high temperatures, it is desirable to use heat-resistant fibers. In the present invention, using a smaller amount of water can suppress strength loss due to conversion and obtain high strength, and the weight ratio of the total weight (C) of the hydraulic substance and ultrafine powder to the water weight (W) (W/C) is 0.35 or less, particularly preferably 0.
It is preferably 25 or less. In the present invention, the method of kneading the materials is not particularly limited, but it is preferable to thoroughly knead them. In the present invention, it is effective to further perform vacuum degassing treatment, specifically, a vacuum casting device (manufactured by Takagi Seisakusho Co., Ltd.),
Examples include using a vacuum omnimixer (manufactured by Chiyogiken Kogyo Co., Ltd.) and a vacuum mixer (manufactured by Sanei Seisakusho Co., Ltd.), and a method of forming a thin film to degas. It is preferable to reduce the rotational speed during defoaming, and in particular, the method of defoaming by forming a thin film has a rapid defoaming speed and is highly effective. As for the defoaming conditions, a degree of vacuum of about 50 to 70 mml (g) is appropriate when considering moisture evaporation, etc.
Defoaming time is not particularly limited, but is usually 5 to 3
About 0 minutes is preferable. ASTM C-185-59 by vacuum degassing process
It is preferable that the amount of air measured according to the method is about 1 to 2% or less, and more preferably about 1% or less. Furthermore, it is very effective to combine vacuum defoaming treatment and vibration during molding, and it is possible to provide a molded article made of a high-strength hydraulic material composition with high defoaming efficiency and higher bending strength. To further cure the molded product, normal temperature curing,
Normal pressure steam curing, high temperature and high pressure curing or high temperature water curing can be used. In the present invention, after curing the molded article, it is preferable to further dry and cure it at 100° C. or higher. By performing the dry curing, the mechanical properties can be further improved. In particular, mechanical properties can be significantly improved by high temperature treatment at about 400 to 600°C, but in this case it is preferable to pre-dry at about 110°C. The curing period varies depending on the shape and composition, but is usually about 3 to 7 days, and for higher temperature treatments, it is sufficient to maintain the maximum temperature for several hours. However, due to the size, etc., it is necessary to avoid creating a temperature difference between the inside and outside, and in that case, it will take a long time to raise and lower the temperature.
It takes 1-2 days. <Effects of the Invention> The high-strength hydraulic material composition according to the present invention maintains a high degree of fluidity and transferability, which is impossible with conventional techniques, and has high strength, especially excellent bending strength, and excellent heat resistance. It provides a cured product that can be used as an excellent molding material for various applications. Examples of its use include (1) various metal casting molds and their cores, especially considering the transferability of the surface and ease of molding at room temperature. , (2) Production molds for various metal casting molds and cores that use thermosetting resin as a binder, (3) Gravity molds (low-pressure casting molds), (4) Die-cast molds, (5)
) Molding molds for various heat-resistant resins and engineering plastics, (6) RI M (Reaion I
injectionMold) mold, (7) SMC(
Sheet Molding Compound) mold, B MC (Bulk Molding Compound)
d) FRP molds such as molds and stamping molds; (8) master molds for plasma spraying;
(9) Various powder metallurgy molds for high-temperature firing, (10) molds for glass ceramics, (11) high-temperature press molds, etc. <Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 Using the composition shown in Table 1 below, 2×2×8a
1 sample was prepared by pouring, and the strength test was conducted according to JIS
It was carried out according to R5201. For mixing, use a vacuum omni mixer (Chiyoda Giken Industries, Ltd.)
After kneading and mixing for 10 minutes, vacuum defoaming treatment was performed for 10 minutes at low speed. It was cured in warm water at 50°C for 7 days, then dried at 110°C for 3 days, and the compressive strength after curing was measured. The results are also shown in Table-1. As shown in Table 1, no matter which cement is used,
Dry curing increases compressive strength. Among them, those using alumina cement are preferable in terms of strength. Moreover, in the case of alumina cement alone, a decrease in strength is observed over time, but experiments Nos. 3 and 4 were left indoors for one year. No decrease in strength was observed. The materials used are as follows. (Materials used) White Portland cement: Chichibu Cement Co., Ltd. (average particle size 10.8 μm) Alumina cement: [Product name: Denka High Alumina Cement” Denki Kagaku Kogyo Co., Ltd. 113 (average particle size 10 μm) Ultra-fine powder Nijirika Hue [Manufactured by Japan Heavy Chemical Industry Co., Ltd.] High performance water reducing agent: β-naphthalene sulfonate formaldehyde condensation system [Product name: "Cellflow 110PJ" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] Metal aggregate di-reduced iron powder (Product name: " Metalet” manufactured by Nihon Magnetic Sen Co., Ltd.] (particle size 0.15 mm or less) Fiber: [Product name rsUs430J, (φ50 μm)
× Length 25al (by crack cutting method) Made by Tokyo Steel Co., Ltd.] Mouth

[l] The same treatment as in Example 1 was performed using a composition having the formulation (parts by weight) shown in Table 2 below. Strength test is JIS R
5201, after the specimen was cooled to room temperature. For mixing, use a vacuum omni mixer (Chiyoda Giken Industries, Ltd.)
11], and after kneading and mixing for 10 minutes, vacuum defoaming treatment was performed at low speed for 10 minutes. After curing for 7 days in a sealed thermostatic box at 50°C, dry curing was performed under various dry curing conditions shown in Table 3 below, and the strength was measured. The results are shown in Table-3. Table 2 In addition, in the same formulation as Table 2, the results are shown in Table 4 when the hardening modifier was changed to lithium carbonate and citric acid. It exploded at temperatures between 'C and 300C and was unable to maintain heat resistance. Why did this result occur? Also, why did 3CaO-A, a hydrate that was previously thought to be disadvantageous in terms of strength,
Some explanation will be given regarding the mechanism of whether high strength can also be obtained with N, O, .6H, and O't'. The mechanism was discussed using the paste portion shown in Table 2, excluding metal aggregates and fibers. For comparison, an experiment was conducted using only alumina cement, which is usually used in castable refractories, and setting W/C to 0.35. Figures 1a and 1b are the relative intensity ratios of hydration products and unreacted products by powder line analysis. In addition, in the figure and the following explanation, C is CaO, A is AQ203. H represents H2O, and the number represents the number of moles. When using only alumina cement and setting the W/C ratio (water/hydraulic substance ratio) to 0.35, unreacted cement (C
A, CAm) decreased rapidly, and the hydration products C, AH, and AH3 increased significantly. On the other hand, as shown in Figure 1b, W
/P ratio (water/hydraulic substance + ultrafine powder ratio) of 0.2, unreacted cement (c A,
Although more than 50% of c At) remains in relative strength ratio, and the hydration products are the same as C, AH, and AH3, the amount produced seems to be small. Generally, hydration products such as C and A Hs are considered to be the main cause of strength reduction, but in the composition shown in Table 2, even if the products are C and A H, high strength can be achieved. can be obtained. The cause of this is shown in Figures 2a and 2b as shown in Figures 2a and 2b.
As shown in the -8EM photograph, this can be attributed to the fact that the products are much smaller than in the case of normal alumina cement. In addition, according to the composition shown in Table 2, if silica hume is used as the ultrafine powder, the hydrates will be C, AH, A
In addition to H, calcium silicate hydrate (C-3-H)
Therefore, the production ratios of C3AHG and AH are different. Figure 3 shows Differential S
cannig Calurimetry (D 5-C
) is the result of analysis. As a result, Table-2
In the case of , it is clear that the production peak ratios of AH, and C, AH, are close to each other. This can be considered to be because the following reaction suppresses the production of C, A H, more than in the normal case. (Water) Therefore, the schematic diagram of this hardened body is as shown in Figure 4.
Closely packed unreacted cement CA or CA, 1 is 1n
It acts as a ner-filler, and it can be considered that small C3A H, AH3, and C-8-N2 are solidified. The presence of such a large amount of unreacted cement is considered to be the cause of deterioration of heat resistance even if the unit cement amount in mortar or concrete is considerably larger than that of ordinary castable refractories. This is very important from the viewpoint of high bending strength and heat resistance. Furthermore, the bending strength is significantly improved by firing at a high temperature, but this may be due to the fact that the products are different in the dehydration reaction at 200 to 400°C. C3A H and AH3 start dehydrating at about 200°C to produce C,,A, and CH. However, in the case of the example of the present invention, the generated CH reacts with excess AH3 compared to the normal case. Due to such a recycling reaction, no CH remains. Therefore, at 400°C to 600°C, C
, , A, and amorphous AQ, O, and C-5-H. Furthermore, since C3AHs is small, it is assumed that C1□A7 generated is also very small. (Dehydration decomposition) C3A) Is Cz *
A, + CI In processing at high temperature 5 ordinary portland cement and silica film and superplasticizer (
Super plastiazer) in combination with W/
When P is lowered (for example, experiment number 1 or 2 of Example 1)
) causes an explosion phenomenon when the temperature exceeds 250°C, but this does not occur in the examples of the present invention. This can be considered to be because the pore structures of the cured bodies are different. Figure 5 shows the mercury intrusion of samples obtained by curing the paste portions of experiment numbers 1 and 3 of Example 1 for one day at 50°C, pulverizing them, stopping the hydration with acetone, and drying them in a N2 stream. This is the pore size distribution determined by the method. This results in
It is clear that experiment number 3 of Example 1 has larger pores. Furthermore, in terms of the total porosity (A) during pressure increase and the total porosity (CB) during pressure decrease, the ratio of (A-B)/A in Experiment No. 1 of Example 1 was 75 to 80%, whereas in this case In the invention example, it was about 60%. This is because the Portland cement system of Experiment No. 1 of Example 1 is less likely to release mercury than the present invention, for example, in an ink bottle type or a tort cement type.
It can be considered to have a pore structure with large osity (tortuosity). Such a difference in pore structure is considered to be one of the reasons why the examples of the present invention can be subjected to high-temperature treatment without causing detonation. In addition, metal particles such as iron powder expand due to oxidation during high-temperature treatment, and according to SEM photographs, adhesion tends to increase, and in this sense, it is thought that the examples of the present invention exhibit high bending strength. It will be done. 11. Using the composition shown in Experiment No. 4 in Table 1 of Example 1, it was molded in the same manner as in Example 1, and then cured under various curing conditions shown in Table 5 below. Dry curing was performed at 110°C for 3 days. The compressive strength of each was measured. The results are shown in Table-5. Table 5 As is clear from Table 5, even after curing, dry curing according to the present invention is effective in improving strength. Example 4 Using the formulation shown in Table 6, the mixture was mixed for 10 minutes using a 30Q vacuum omnimixer (manufactured by Chiyoda Giken Kogyo Co., Ltd.), and vacuum defoaming was performed at 50 mHg for another 10 minutes. Thereafter, a 4 x 4 x 16 cn specimen was prepared, placed between polyethylene and cured at 50°C for 7 days, and passed JIS R5.
A strength test was conducted according to 201. The results are also listed in Table-6. (Materials used) Cement: White Portland cement (manufactured by Chichibu Cement) Alumina cement: Product name “Denka Alumina Cement 1”
No.'' (manufactured by Denki Kagaku Kogyo) Ultra-fine powdered rainbow kahiyum (manufactured by Japan Heavy Chemical Industry) High-performance water reducing agent: Product name ``Cellflow 110PJ (manufactured by Dai-Kogyo Seiyaku) Hardening regulator: Sodium sulfate reagent Grade 1 aggregate A: Heavy sulfur Earthen rock, China Great Wall ware 0゜3nn
Bottom (manufactured by Fuji Kozai) B: Metal aggregate, product name rsUs304LJ stainless steel powder (Daido Special) 100 mesh or less C: Metal aggregate, product name rsUs316LJ stainless steel powder (Daido Special) 100 mesh D: Metal aggregate, product Name rs
Us430LJ stainless steel powder (Daido Special) 100 mesh E: Metal aggregate, reduced iron powder, trade name "Metalette" (manufactured by Nihon Magnetic Sen Co., Ltd.) 0.15 nm lower F: Metal aggregate, ferromanganese, (Nippon Heavy Industries, Ltd.) Arrow JLLL Using the formulation shown in Table 7, the bending strength was measured by changing the humid air curing temperature in the same manner as in Example 4. In all cases, the alumina cement type showed a higher value. The material age was 14 days. The results are also listed in Table 7. The materials used were Example 4 and S]0
1. Using the formulation shown in Table 8 at 20°C and 80% RH, mix for 5 minutes with a 5Q Shinkushin mixer (manufactured by Sanei Seisakusho Co., Ltd.), vacuum defoaming at 70 + omHg for a specified time, and pour molding. A 4 x 4 x 16 cym specimen was prepared, sealed at 20° C. and 80% RH, and cured for a predetermined period of time. At that time, 3H128 according to JIS R-5201
A strength test was conducted on the following day. The setting time was defined as the time when the penetration resistance value reached 4 tOOOOpsi using a Broctor penetration tester, and the results are also listed in Table 8. (Materials) CA-A: White Portland cement, (manufactured by Chichibu Cement Co., Ltd.) B: Alumina cement, trade name "Denka High Alumina Cement", (manufactured by Denki Kagaku Kogyo Co., Ltd.) #C: C4AF, CaC0, /Al2O3/Fe2
Blend O, in the ratio of 400/102/160 to 1350
Calcined at ~1360°C for 1H and ground to an average particle size of 12μ. CA A: C,zA4- CaO/AQ203 4
5155, electrolyzed to 1600°C, rapidly cooled, and pulverized to an average particle size of 8μ. Ultra-fine powdered rainbow cahuum (manufactured by Japan Heavy Chemical Industry) High-performance water reducing agent; β-naphthalene sulfonate formaldehyde condensation system, trade name "Cellflow 110PJ (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Metal aggregate: reduced iron powder [Metallet J Q, 15m+ below,
(manufactured by Nippon Magnetic Sensing Co., Ltd.) Fiber: 5US430. φ50μm x length 2.5-
Hardening modifier E: NatSOs (reagent) F by chatter cutting method (manufactured by Tokyo Steel Corporation)
; Boric acid (reagent) G: Citric acid (reagent) Mixing was carried out in the same manner as in Example 6 using the formulation shown in JLIL Table 9, fiber (SUS 631) was mixed, and then during molding. While applying vibration on a vibrator, vacuum degassing was performed to carefully prepare a specimen with dimensions <4X4X16Qm. The specimen was cured in a polyethylene bag at 50° C. for 7 days and then dried at 110° C. for 3 days, and the bending strength of the specimen was 805 kgf/a&. Mix the composition shown in Table 10 with a high-speed stirrer, pour it with a table vibrator, and vibrate mold it to form 2X2X8C11.
A specimen was prepared. Thereafter, it was cured in warm water at 50°C for 7 days and then dried at 110°C for 7 days, and a strength test was conducted according to JISR-5201. (Material) Clinker-A: C4AF, CaCO3/Al2O3/
Fe2O, was blended to a predetermined molar ratio, held at 1350 to 1360°C for 1 hour, fired, and then ground to an average particle size of 12-μm. Clinker B: CAz CAs t Ca C0
3 and Af1201 were blended to a predetermined molar ratio, electrolyzed, rapidly cooled in air, and ground to an average particle size of 10 μm. Clinker C: B a A Q204. B a C
O3 and AQ203 were blended in a predetermined molar ratio, fired at 1500°C for 2 hours, rapidly cooled in air, and pulverized to an average particle size of 11°3 μm. Talin force-D: CA, Ca Co3 and Aj2.
O, which was quenched by electric melting and pulverized to an average particle size of 11 μm. Ultra-fine powder rainbow cahuum (Japan Heavy Chemical Industries) Dispersant: β-naphthalene sulfonate formaldehyde condensate system, trade name: Cellflow 110PJ (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Metal aggregate-E: Iron powder rNcJ ( Particle size 0.15-0゜3m) Metal aggregate manufactured by Dowa Iron Powder Industries Co., Ltd. - F diiron powder "A" (Particle size 0.15+am or less) Hardening modifier manufactured by Dowa Iron Powder Industries Co., Ltd. -〇 : N a 2 S O4 (reagent) H
:boric acid (reagent) ■ = citric acid (reagent)
The composition of each component is (parts by weight) in a 2Q mortar mixer, and the mixture is 4 x 4 x according to JIS-R-5201.
A 16 cm specimen was prepared, subjected to wet curing at 50° C. for 7 days, and then subjected to a compressive strength test. In addition, to confirm machinability, we flattened the surface using a milling machine and drilled holes using a drill press. The results are shown in Table-11. (Materials used) Cement A: Product name "Alumina Cement No. 2 J" manufactured by Denki Kagaku Kogyo Co., Ltd. Cementro: White Portland cement manufactured by Chichibu Cement Co., Ltd. (average particle size 10.3 μm by light transmission method) Reduced iron powder: Dowa Complete set of 200 meshes manufactured by Tetsuko Kogyo Co., Ltd. (
(The sieve fraction is 74 μm or less) Ultra-fine powdered Nijiri flower (average particle size 0 by TEM)
．． 2 μm) High performance water reducing agent: Daiichi Kogyo Seiyaku product name “Cellflow ll”
0PJ (Main component: alkylnaphthalene sulfonic acid formaldehyde metal condensate) Aggregate: Iron powder (0.15~1.0m) Dowa Iron Powder Kogyo (
Co., Ltd. is a mortar mixer at 20°C and 80% RH using river sand (particle size 0.3-1゜2m), Na, SO2: reagent (see the margin below), and Be: Megasu m using the composition shown in Table-12. After mixing for 3 minutes, vacuum defoaming was performed for 2 minutes using a vacuum mixer (manufactured by Sanei Seisakusho), and 2X2X8 was vibrated and molded. It was cured at 50°C for 7 days (in a greenhouse), then heated to 110°C for 7 days, and then fired at 600°C for 3 hours. The compressive strength is shown in Table-13. (Materials used) The same materials as in Example 1 were used except for the materials shown below. Ultrafine powder: Alumina (manufactured by Alcoa) (A-16SG) (average particle size by TEM 0.2-0.
5μm) Dispersant: 1flLi of citric acid (reagent) Table 13 [Compressive strength (kgf/cd)] Using the formulation shown in Table 14, the mixture was kneaded for 5 minutes with a mortar mixer, poured into a 4X4X16a++ mold, and
Dry curing was performed at 0°C for 7 days and at 180°C for 1 day, followed by firing at 600-800°C. Table 1 shows the results.
4. (Materials used) The same materials as in Example 1 were used except as shown below. Inert inorganic powder: Corundum sand, 0.3 to 1 cm ground for one day in a ball mill (average particle size 18.5 μm by light transmission method) Metal aggregate: Iron powder NG, A (manufactured by Dowa Iron Powder Industries) BrO:
Bronze 100 mesh cement: Product name [Alumina cement No. 1] Electricity

[Brief explanation of the drawing]

Figures 1a and 1b are graphs showing the relative intensity ratios of hydrated products and unreacted substances by powder X-ray diffraction. Cryo-3EM photograph of the fractured surface of the hardened material, Figure 2b shows W using alumina cement, silica fume, and high performance water reducing agent.
A cryo-8EM photograph of the fracture surface of the cured product with a /P ratio of 0°20, Figure 3 is a Differential Scan
Fig. 4 is a graph showing the analysis results by ing calorimetry (DSC), and Fig. 5 is a schematic diagram of the cured product.
The figure is a pore size distribution diagram. 1. Unreacted cement (CA or CA,), 2. Hydrate (C, AH,, AI (,, C-3-H), 3. Hydrate layer (C3A) I,, A )! ,). Patent applicant: Denki Kagaku Kogyo Co., Ltd. Representative patent attorney: Sakai
Kane Saka Moka Kane Saka
Engraving of traditional drawing No. 4 Kang@1a Figure! 15'O" (-ma 110'c 1b ffl! No:"M at 150°C (h) Fig. 3 Fig. 5

Claims (1)

[Claims] 1) Alkaline earth metal oxide and aluminum oxide (Al
A high-strength hydraulic substance composition comprising a hydraulic substance mainly composed of _2O_3), ultrafine powder with an average particle size smaller than that of the hydraulic substance by one order or more, a metal aggregate, and a dispersion material. 2) The composition according to claim 1, wherein the hydraulic substance is alumina cement. 3) The hydraulic substance has a CaO/Al_2O_3 molar ratio of 0
．． A composition according to claim 1, characterized in that it has less than 5 calcium aluminates. 4) The hydraulic substance has a CaO/Al_2O_3 molar ratio of 1
．． 5. The composition of claim 1, wherein the composition is a calcium aluminate with a pH of 5 to 4.0. 5) Claim 1, characterized in that the weight ratio (W/C) of the total weight (C) of the hydraulic substance and the ultrafine powder to the water weight (W) is 0.35 or less. Compositions as described. 6) The composition according to claim 1, wherein the hydraulic material composition further contains an inert inorganic powder having a particle size of 1 to 100 μm. 7) The composition according to claim 1, wherein the hydraulic material composition further contains a hardening modifier. 8) The composition according to claim 1, wherein the hydraulic material composition further contains metal particles having a particle size of 1 to 100 μm. 9) The composition according to claim 1, which is obtained by subjecting the high-strength hydraulic material composition to vacuum defoaming treatment and vibration treatment. 10) The composition according to claim 1, wherein the high-strength hydraulic material composition is further dried and cured at 100° C. or higher after curing.