TW200602283A - Cement admixture, cement composition, mortar and concrete - Google Patents

Description

200602283 (1) Description of the Invention [Technical Field] The present invention relates to a cement admixture, a cement composition, and a mortar and concrete using the cement composition. More particularly, the present invention relates to a cement admixture comprising s i1 i C afume and fly ash sized to a size of 20 microns or less, and a cement composition The cement blend is added to the cement. Further, φ, the present invention relates to mortar and concrete which enhance bending strength by using the cement composition. [Prior Art] A problem with mortar or concrete is that its bending strength is substantially lower than its compressive strength, and even when the compressive strength is increased, the bending strength is not increased equally. Therefore, pavements based on flexural strength, trabeculae, girders, and many types of concrete secondary products are prone to over-provisioning of uneconomical blends of φ. In addition, in order to increase the bending strength, the cross section of the element is thickened or prestressed via a PC steel bar. Among the Hume fittings and the like, the expansive material is inserted into the concrete to introduce chemical stress or chemical pre-stress, thereby increasing their external pressure strength. On the other hand, ash has a high condensing activity and is used as a strength enhancer. In addition, the combination of ash and a significant amount of high performance water reducer can increase mortar fluidity, concrete twist or turbulence, and facilitate the manufacture of mortar or concrete having a low water/bond ratio. Therefore, it is often used in the form of admixture -4- 200602283 (2) in high-flow high-strength mortar or concrete. Fly ash is a spherical granulated coal ash containing hollow particles having a size of 100 μm or less, which is obtained as a by-product from a pulverized coal combustion thermal power plant. Fly ash can react for a long time to enhance water tightness, but it has low solidification activity, making it often used as fly ash cement. As shown in Patent Document 1, the fly ash is sieved to a size of 20 μm or less or 10 μm or less to remove large hollow particles to provide good spherical hollow particles. Due to its ball bearing function, when it is mixed with a high performance water reducer or especially a high performance AE water reducer, the mortar fluidity, concrete twist or turbulence will increase and exhibit strong adhesion. Further, it is known that even if the fluidity or the twist is the same, the increased strength of the water reduction exceeds the case where the mortar or concrete of the sieved fly ash is not blended. Further, for example, as shown in Patent Document 2, gypsum is often used in the form of a high-strength blend, whether or not steam curing is carried out, and it is also known that a combination of gypsum and ash can provide higher strength and durability. . Further, as shown in Patent Document 3, there is a method of adding metal fibers as a method of improving bending strength or toughness in the conventional method. It is also known that the toughness improvement using metal fibers can be achieved by adding ash and needle or flat particles to the cement and limiting the maximum aggregate size to a smaller enthalpy.

Patent Document 1: JP 63 — 8248A

Patent Document 2: JP 3 — 40947A

Patent Document 3: JP 1 1 — 24625 5 A However, a general technique in which only ash is blended can increase the compressive strength of concrete, but it has a problem that the concrete becomes brittle and its bend is -5 - 200602283 ( 3) The ratio of the compressive strength to the compressive strength is lower than that without the blended ash. Further, as shown in Patent Document 1, since fly ash sized to a size of 20 μm or less or 1 μm or less originally has low condensing hard activity, its strength is increased by water reduction. However, even if steam curing is carried out, the strength increase is hardly increased in the short term relative to the case where the sieved fly ash is not blended at the same low water/adhesive material ratio. Further, as shown in Patent Document 2, it is easy to exhibit high strength by using gypsum alone or in combination with φ ash, and it is also possible to increase the bending strength with respect to an increase in compressive strength. However, there are still problems, that is, the proportion is not better than that of conventional concrete. As shown in Patent Document 3, the maximum aggregate size is 5 mm or less compared to the fine aggregate or mortar or concrete used in concrete mixing plants or concrete product factories. Limiting to 2 mm or less, or 1 mm or less, has become an indispensable element. Therefore, this method has a problem that it cannot be widely adopted. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) The present invention has been made in an effort to solve the problems in the aforementioned conventional techniques, and an object of the present invention is to provide absolute strength and bending strength versus compressive strength of compressive strength and bending strength. Proportion 値 has increased mortar or concrete. Another object of the present invention is to provide a cement admixture to achieve the above-described mortar or concrete, and a cement composition using the cement admixture. Still another object of the present invention is to provide a cement hardened product obtained from the above mortar or concrete -6 - 200602283 (4). [Means for Solving the Problem] It has been found that by using the so-called ash as far as known, fly ash sized to a size of 20 μm or less, and gypsum, are not separate but combined users, with respect to each individual In the case of use, the ratio of bending strength and bending strength to compressive strength can be synergistically increased. In addition, the fact φ found is that since the bending strength of the matrix mortar or the concrete itself can be increased, even if a conventionally available fine aggregate for mortar or concrete is used, the use of the metal fiber can greatly increase the bending strength. This results in the completion of the present invention. In particular, the present invention relates to the following cement admixtures, cement compositions, mortars, concretes, cement hardened products. (1) A cement admixture comprising ash and fly ash sized to a size of 20 microns or less, wherein the ash weight ratio of the ash to the sieved fly ash is from 95:5 to 10 : 90. (2) The cement admixture according to the above item (1), which further comprises gypsum. (3) a cement composition comprising the cement in an amount of from 1 to 35 parts by weight per 100 parts by weight of the cement admixture according to item (1) above (4) according to the above (3) The cement composition of the item 'further contains gypsum in an amount of from 5 to 12 parts by weight per 1 part by weight per part by weight of the cement composition. -7- 200602283 (5) (5) A mortar comprising the cement composition according to the above item (3) or (4), a fine aggregate, a water reducing agent and a kneaded water. (6) The mortar according to the above item (5), which has a metal fiber added thereto, the metal fiber being externally added in an amount of from 1 to 0.001% by volume per cubic meter of the mortar. (7) A concrete comprising the cement composition of the above item (3) or (4), a fine aggregate, a coarse aggregate, a water reducing agent and a kneaded water. (8) The concrete according to the above item (7), which has the metal fiber added thereto, and the metal fiber is externally added in an amount of from 1 Torr to 4.0 vol% per cubic meter of the concrete. (9) A cement hardened product obtained by hardening the mortar of the above item (5) or (6). (1 〇 ) — A cement hardened product obtained by hardening the concrete of the above item (7) or (8). φ [Effect of the invention] According to the present invention, the fluidity of the kneaded mortar or concrete is improved to obtain good workability. Further, the obtained mortar and concrete have high compressive strength and bending strength, and a high ratio of bending strength to compressive strength can be obtained. In addition, the strengthening effect of the intrusion of the metal fibers can greatly increase the bending strength. This can result in an economical and advantageous design in the manufacture of civil engineering and building structures and concrete secondary products. (Best Mode for Carrying Out the Invention) -8- 200602283 (6) The present invention will be described in detail below. The parts and percentages used in the present invention to indicate the ratio or amount of the formulation are by weight. However, in the case of metal fibers, they are expressed in units of mortar or concrete in volume % per cubic meter. The ash used in the present invention is obtained as a by-product in the production of a niobium alloy and a chromium oxide such as a metal ruthenium or a ferrite in an electric furnace, and is composed of fine spherical particles having a size of 1 μm or less. The main component is amorphous cerium oxide with high reactivity of φ. Although the compressive strength increases as the amount of ash added increases, the ratio of flexural strength to compressive strength decreases with respect to the absence of ash. As described above, ash is not only used as a strength increasing agent. When it is used in an amount of about 1% by weight based on cement and is used in combination with a considerable amount of high-performance water reducing agent, the fluidity will increase dramatically. However, its flow characteristics vary depending on the type of high performance water reducer, and the soot is associated with a so-called slightly high performance water reducer such as polyalkylallyl sulfonate or melamine-formalin resin. When the sulfonate-based water reducing agent is used, it exhibits a high viscous fluidity associated with a low flow enthalpy of the paste. On the other hand, when the ash is used with a so-called high-performance AE water-reducing agent based on polycarboxylate which entrains air, the fluidity increases in a viscous plastic state rather than a slightly viscous state. In the shovel flip, the former produces a heavy feeling while the latter is light. Therefore, the combination of high performance AE water reducer and ash ash is only used in some cases for ease of pumping. As mentioned above, fly ash is a coal ash obtained as a by-product in a pulverized coal-combustion heat power plant, and is a spherical granular residue discarded from the combustion gas from the boiler gas pipe -9 - 200602283 (7). The person who recovered the waste with a dust collector. Usually, fly ash is blended with cement and used in the form of fly ash cement. In the present invention, an indispensable element is the use of fly ash sized to a size of 20 microns or less, while unscreened ones do not provide the advantages of the present invention. There are two types of commercially available paved fly ash products, that is, those that have been sieved to a size of 20 microns or less and that have been sieved to a size of 10 microns or less. φ In the cement admixture of the present invention, the weight ratio of the ash to the fly ash sized to a size of 20 μm or less is from 95:5 to 10:90, preferably from 90:10 to 15: 85, and better from 80: 20 to 70: 30. When the proportion of the sieved fly ash is less than 5%, the effect of increasing the bending strength becomes small. Conversely, when the proportion of the sieved fly ash exceeds 90%, the effect of increasing the bending strength becomes small. Although the compressive strength decreases as the blending ratio of the sieve fly ash increases, the effect of increasing the bending strength has a peak near 60:40. Φ On the other hand, mortar fluidity, temperature or turbulence (hereinafter referred to as "flow M" will also increase with the proportion of sieved fly ash, and fly in the ash / sieve The ash ratio has a peak near 50:50. The moderate viscosity caused by the sieved fly ash inhibits the separation of the aggregate so that it can easily flow even when metal fibers are added. The amount of the substance to be added is preferably from 1 to 35 parts, more preferably from 2 to 30 parts, and particularly preferably from 3 to 25 parts per 100 parts of the cement. Even if the admixture is added in an amount of more than 35 parts, The increase in bending strength still only reaches this peak, so it is economically disadvantageous. -10- 200602283

In the present invention, various types of gypsum such as dihydrate gypsum, hemihydrate gypsum, soluble anhydrite (type I) and insoluble anhydrous gypsum (type II) are used. Among them, preferred are anhydrite and dihydrate gypsum. When adding "flying ash and fly ash sieved to a size of 20 microns or less" to the cement, the compressive strength increases with the proportion of fly ash that is sieved to a size of 20 microns or less. However, the effect of increasing the compressive strength of gypsum is greater than the reduction, so that the absolute enthalpy of both the compressive strength and the flexural φ strength can be increased at the same time. The amount of gypsum added is preferably from 5 to 12 parts on a water-free basis, preferably. It is from 0.8 to 10 parts, and particularly preferably from 1 to 8 parts per 100 parts of cement. Even if the amount of gypsum added exceeds 12 parts, the effect of further increasing the strength cannot be obtained. In the present invention, one is also used. The required amount of high performance water reducing agent or high performance water reducing agent. The high performance water reducing agent mainly includes polyalkyl allyl sulfonate, aromatic amine sulfonate and melamine-formalin resin sulfonate One. These may be used singly or in combination of two or more thereof. The polyalkylallyl sulfonate-based high performance water reducing agent includes methylnaphthalenesulfonic acid-formalin condensation. , naphthalenesulfonic acid-formalin condensate and sulfonate-fu Marlin condensates, and typical examples of their commercially available products include nFT-500" (trade name) and a series of products thereof manufactured by Denki Kagaku Kogyo Κ·Κ, "Mighty-100" (trade name, powder) ), and ''Mighty-150' and its series of products made by Kao Corporation; "Selflow 110P" (trade name, powder) made by Daiich Kogyo Seiyaku Co., Ltd., by Takemoto Oil & Fat Co., Ltd. made by "Polfine 510N" (trade name): and by Nippon Paper Industries -11 - 200602283 (9)

"Sunflow PS" (trade name) manufactured by Co., Ltd. and its series of products. High performance water reducing agent based on aromatic amine sulfonate includes Fujisawa Pharmaceutical Co., Ltd. Paric FP200H" (trade name) and its products; and high-performance water reducer based on melamine-formaldehyde resin sulfonate, including G race C hemica 1 s K. K. '' FT - 3 SM (trade name) ). High-performance AE water reducing agents are generally referred to as polycarboxylate-based water reducing agents, and copolymers or salts thereof containing an unsaturated carboxylic acid monomer as a component. Examples thereof include poly(alkylene glycol) monoacrylate, poly(alkylene glycol) monomethacrylate, copolymer of maleic anhydride and styrene, copolymerization of acrylate or methacrylate And a copolymer derived from a monomer copolymerizable with such monomers. Commercially available is the "Rheobuild SP8N" (trade name) series manufactured by NMB Co., Ltd., and the "Paric FP100S and 300S" (trade name) system manufactured by Fujisawa Pharmaceutical Co., Ltd. ; Takemoto oil & Fat Co·, Ltd. manufactured by "Chupol HP8 and 11" (trade name) series; Grace Chemicals KK· made by ''Dar ex Super 100, 200, 300, and 1000' (trade name) series; and similar. The cement used in the present invention may be any of various Portland cements and various cement or ecological cements (e c 〇 c e m e n t s ). It is also possible to use cement obtained by mixing any amount of them. In the manufacture of the mortar and concrete of the present invention, there is no particular limitation, and fine aggregates and coarse aggregates which are widely used can be used. In addition, they can be selected at will, because the ratio of the bending strength to the compressive strength of the mortar or concrete and their bending, regardless of the ratio of water/adhesive material and the ratio of fine aggregates is -1·2- 200602283 (10) Absolute strength will increase. Further, in the present invention, metal fibers can be used. For metal fibers, it is equally possible to use metal fibers which are generally commercially available for mortar or concrete, and not any special one. The metal fiber is externally added in an amount of 1.0 to 6.0% by volume per cubic meter of mortar or concrete. However, from the viewpoint of increasing the bending strength and operability, the maximum addition amount and the preferred range are different between the sand-slurry condition and the concrete condition. Further, the maximum addition amount and preferred range are also varied depending on a molding method of concrete such as vibration molding or centrifugal molding. In the case of vibration molding, less than 2% by volume for the mortar causes a small increase in the bending strength. However, when the amount of the metal fibers added is 2 vol% or more, the bending strength also increases as the amount of the added metal fibers increases, and the peak enthalpy is reached at 5.5% by volume or more. More than 6.0% by volume can cause flow difficulties and cause molding failure. Therefore, the external addition amount of the metal fiber φ is from 1.0 to 6.0% by volume, preferably from 2.5 to 5.0% by volume. For concrete, it exhibits utility at 1.5% by volume, and more than 4% by volume results in poor operability. Therefore, the external addition amount of the metal fiber is from 1.0 to 4.0% by volume, preferably from 1.5 to 3.5% by volume. In the centrifugally molded article, for both the mortar and the concrete, the amount of addition of the metal fiber at a volume of 1.0% by volume starts to increase the bending tensile strength. In the case of the mortar, from the viewpoint of workability, it is preferably 5% by volume. For concrete, it is preferably 0.001% by volume. In order to increase the strength of the Hume pipe against external pressure, it is economically preferable to concentrate the steel fiber -13-200602283 (11) on the inside of the pipe to reinforce the pipe thickness by about two-thirds or less. There is no particular limitation on the method of adding the blend of the present invention. A mixture of ash and fly ash sieved to a size of 20 microns or less, or a mixture of further mixed gypsum, may be added during kneading of mortar or concrete. Alternatively, the ingredients can be prepared separately and added to the mixer along with other mortar or concrete materials. There is also no particular limitation on the kneading method, and a conventional kneading method can be used. Further, there is no particular limitation on the method of adding the metal fiber φ. However, it is preferred to knead the mortar or concrete under continuous stirring using a mixer while adding metal fibers thereto, since the fiber balls are less likely to be formed. In addition, there is no particular restriction on the method of curing the mortar or concrete, and standard curing, steam curing and autoclave curing can be employed. [Embodiment] [Examples] The materials and methods used in the examples and comparative examples of the present invention are collectively shown below. <Materials used> Cement: Ordinary Portland cement made by Denki Kagaku Kogyo Κ·Κ·5, density: 3.16 g/cm 3 fine aggregate: from H ime R i ν er, N iigata, River sand (5 mm or less), density · 2.62 g / cm 3 coarse aggregate: gravel from Hime River, Niigata, 5 to 13 -14 - 200602283 (12) mm, density: 2.64 Gram/cubic centimeter ash ash · from Russia, made of granules (called SF), density: 2.44 g / cm 3 fly ash: made by Shikoku Electric Power Co., Inc., one is sieved to 20 Micron or smaller size (called FA20), another size to be sieved to 1 〇 micron or smaller (called FA 1 0 ) and an unscreened fly ash (called FA ) , density · 2.44 g / cm3 | gypsum: insoluble anhydrite (natural, density · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Rope MFG, Co. Ltd. made by "Dipac,,, steel products, width: 0.9 mm, thickness: 0.34 mm, long : 30 mm, density: 8.00 g / cm 3 water reducing agent: Grace Chemicals KK ·, made high performance AE water reducing agent WRA (1), "Super 1 000N"; Daiich Kogyo Seiyaku φ Co·, Ltd. Performance water reducing agent WRA ( 2 ) , " Selflow 1 1 0 P,, ° <Inspection items and methods thereof> Measurement of mortar flow The flow rate 拉 when measured on JIS R 5 20 1 is measured. 50x50x2 cm acrylic glass plate on the flow table 0 -15- 200602283 (13) Measurement of mortar strength The bending strength is measured according to JIS R 5 20 1 and the compressive strength is molded into a diameter in a mold. 5 cm and length 10 cm test piece Measurement of concrete fluidity The lateral spread of concrete was measured according to JIS A 1 1 0 1. The flexural strength and compressive strength of concrete were measured at an outer diameter of 20 cm and length. The 30 cm cylindrical mold fills 17.5 kg of concrete and is 2 minutes at the initial speed of 1.5G, 5 minutes at 3G low speed, 1 minute at 8G intermediate speed I, 2 minutes at 1.5G intermediate speed II and 30G under 30G speed. Implemented under 3 minutes Heart molding. After the solidification, the external pressure load and the tube thickness at the time of chipping were measured to calculate the bending tensile strength. When forming a mortar φ containing metal fibers in one third of the inner portion, the mold is filled with 12.5 kg of concrete, then centrifugally molded under the above conditions, and then filled with 5 kg of mortar, followed by similar Centrifugal molding. For the kneading of mortar (or concrete), the cement, the individual components of the blend, the fine aggregate (and the coarse aggregate) are dry-blended for 30 seconds, and then added to the kneaded water in which the water reducing agent is dissolved, followed by Omni - Knead in the mixer for 3 minutes. When metal fibers were to be added, the metal fibers were added little by little without stopping the stirring, followed by further kneading for 3 minutes. -16- 200602283 (14) [Example 1] Mortar will be 100 parts of cement, 100 parts of fine aggregate, ash and fly ash changed according to the individual blending amount shown in Table 1, and 20 parts of kneading Water, wherein 3 parts of high-performance AE water reducing agent are dissolved in 20 parts of water, and kneaded mortar is added based on kneading material (cement or cement + shi ash and/or fly ash). The fluidity 値 of the obtained mortar was measured, and the results are shown in Table 1. The test piece obtained by molding the mortar φ was allowed to stand for 8 hours in advance, and then the temperature was increased to 80 ° C at a rate of increase of 2 (TC / hour). Then, the test piece was kept at this temperature for 5 hours, and the steam valve was closed. The test piece was slowly cooled in the steam curing tank to the next day. The bending strength and compressive strength of the day age were measured, and the results are shown in Table 1. 0 It can be seen from Table 1 that no ash and fly ash were added. Experiment 1 - 1 , in the comparative example experiment 1 - 2 in which only ash was added, the fluidity enthalpy was increased, the operability was improved, and the compressive strength and the bending strength were also increased. φ However, the bending strength was increased. The increase with respect to the compressive strength is slight, and the ratio of the bending strength to the compressive strength is reduced. In addition, in the experiment 1 - 14 in which only the sieved fly ash is added, the improvement of the fluidity enthalpy is also observed, but compression is performed. There is almost no increase in strength and flexural strength. Conversely, in experiments 1 to 3 to 13 and 1 to 26 to 1-30 of the present invention, which further incorporates ash and sieve fly ash, fluidity is shown. The increase in 値. It is clear from this that although The shrinkage decreases with increasing proportion of ash, but the increase in bending strength becomes significant and also increases the ratio of flexural strength to compressive strength. Thereafter, the ash/screen ash ratio is 60:40. The strength reaches the highest '17- 200602283 (15). In addition, it is obvious from the experiment 1 - 15 to 1 - 25 that the fluidity, bending strength and compressive strength increase with the addition of the admixture. However, the bending strength increases from 1 part per 1 part of cement, and the increase in bending strength becomes obvious at 3 parts. However, the flow enthalpy, bending strength and compressive strength all reach peaks. Therefore, in consideration of economic efficiency, the blending amount is preferably 30 parts or less. [Table 1 - 1] Experiment No. Bending amount per 100 parts of cement fluidity 値 Bending strength Compressive strength Bending/compression SF (Parts) FA (parts) (mm) (N/mm2) (N/mm2) Strength ratio 1-1 0 0 198 14.6 133 1/9.1 1-2 16.0(100) 0 293 15.0 156 1/10.4 1 -3 15.2(95) FA20 0.8(5) 294 18.7 158 1/8.4 1-4 14.4(90) FA20 1.6(10) 312 24.8 155 1/6.3 1-5 12.8(80) FA2.0 3.2(20) 342 27.6 152 1/5.5 1-6 11.2(70) FA20 4.8(30) 355 29.2 150 1/5.1 1-7 9.6(60) FA20 6.4(40) 360 29.5 148 1/5.0 1-8 8.0(50) FA20 8.0(50) 368 28.9 145 1/5.0 SF: ash gray FA: fly ash-18- 200602283 (16)

Table 1 - 2] Experimental bending amount per 100 parts of cement fluidity 値 bending strength compressive strength bending/compression number. SF (parts) FA (parts) (mm) (N/mm2) (N/mm2) strength ratio 1 -9 6.4(40) FA20 9.6(60) 364 28.8 142 1/5.1 1-10 4.8(30) FA20 11.2(70) 355 27.1 141 1/5.2 1-11 3.2(20) FA20 12.8(80) 342 25.5 140 1/5.5 M2 2.4(15) FA20 13.6(85) 336 22.7 138 1/6.1 1-13 1.6(10) FA20 14.4(90) 311 17.1 136 1/8.0 1-14 0 FA20 16.0(100) 290 15.3 134 1 /8.8 1-15 0.5(50) FA20 0.5(50) 202 16.7 137 1/8.2 1-16 1.5(50) FA20 1.5(50) 273 19.1 143 1/7.5 1-17 2.5(50) FA20 2.5(50) 296 21.2 140 1/6.6 1-18 3.5(50) FA20 3.5(50) 325 24.7 148 1/6.0 1-19 50(50) FA20 5.0(50) 348 28.0 140 1/5.0 1-20 7.0(50) FA20 70(50) 357 29.6 153 1/5.2 1-21 10.0(50) FA20 10.0(50) 374 31.5 158 1/5.0 1-22 12.5(50) FA20 12.5(50) 380 32.0 160 1/5.0 1-23 15.0 (50) FA20 15.0(50) 385 33.0 162 1/4.9 1-24 17.5(50) FA20 17.5(50) 387 33.4 163 1/4.9 1-25 20.0(50) FA20 20.5(50) 389 31.8 158 1/5.0 1-26 15.2(95) FA10 0.8(5) 305 19.7 160 1/8.1 1-27 14.4(90) FA10 1.6(10) 323 26.0 156 1/6.0 1-28 9.6(60) FA10 6.4(40) 371 30.4 152 1/5.0 1-29 2.4(15) FA10 1.3.6(85) 346 24.1 140 1/5.8 1-30 1.6(10) FA10 14.4(90) 323 17.5 138 1/7.8 1-31 9.6(60) FA6.4(40) 259 16.6 148 1/8.9 Note: Numbers in parentheses Indicates the weight ratio of SF and FA. -19- 200602283 (17) [Example 2] Mortar was examined in the same manner as in Experiments 1 - 1, 1 - 2, 1 - 7 and 1 - 14 of Example 1, except that Table 2 was further blended. Gypsum of the type shown and added (per 100 parts of cement). The results are shown in Table 2, and Table 2 shows that the gypsum can enhance the compressive strength and the bending strength to increase the strength of φ. In this embodiment, when the amount of gypsum added is 0.5 part or more per 100 parts of cement, the effect is exhibited. When the amount of gypsum added is 〇·8 parts or more, or 1.0 part or more, the utility becomes more conspicuous. However, even if the amount of gypsum added exceeds 12 parts, the effect of further increasing the strength cannot be obtained. As a result, it is apparent that when the amount of gypsum added is part by weight or less, preferably from 1 to 8 parts, the absolute enthalpy of both compressive strength and bending strength is improved every time the cement is added.

-20- 200602283 (18) [Table 2]

Experimental Adhesive Material Type Gypsum Blend (Parts) Fluidity 値 Bending Strength Compressive Strength No. Anhydrite Gypsum Dihydrate Gypsum (mm) (N/mm2) (N/mm2) 2-1 Experiment 1-1. 5.0 203 16.6 153 2-2 Experiment 1-2 5.0 299 17.1 168 2-3 Experiment 1-〗 4 5.0 301 15.5 147 2-4 Experiment 1-7 0.5 363 30.0 153 2-5 Experiment 1-7 0.8 366 31.5 158 2 -6 Experiment 1-7 1.0 370 33.8 165 2-7 Experiment 1-7 2.0 374 34.3 171 2-8 Experiment 1-7 3.0 375 35.0 176 2-9 Experiment 1-7 5.0 377 36.4 180 2-10 Experiment 1-7 6.0 368 37.2 186 2-11 Experiment 1-7 8.0 360 37.3 188 2-12 Experiment 1-7 10.0 356 37.2 186 2-13 Experiment 1-7 12.0 342 36.0 184 2-14 Experiment 1 -7 1.0360 31.4 160 2-15 Experiment 1-7 3.0 358 33.9 164 2-16 Experiment 1-7 5.0 342 34.3 167 2-17 Experiment 1-7 6.0 330 35.3 173 2-18 Experiment 1-7 8.0 321 35.6 174 2-19 Experiment 1-7 10.0 308 35.7 172 -21 - 200602283 (19) [Example 3] Mortar-mixed metal fiber mortar with metal fiber and 1 cubic meter (air content: 4%) 1-8 mortar kneading, change The addition of the modified metal fiber was externally added, and the test piece was formed by molding by pouring. In the same manner as in 1, the steam curing was carried out, and then, the test was performed with a single strength. The results are shown in Table 3. φ As shown in Table 3, the metal fiber can greatly increase the mortar, but it has no effect at 5% by volume. The presence of metal fibers begins to show significant effects and the bending strength increases as the metal fibers increase. More than 5% by volume results in a peak 値 product% resulting in poor workability and deterioration in formability. In the case of obtaining a mortar, it is apparent that the optimum range is from 2.% 〇 the amount of Example 1 (the bending strength to the mortar at the age of the embodiment, the addition amount from the 2 vol% dimension, and 6.5 body molded by vibration 5 to 5 volumes

-22- 200602283 (20) [Table 3] Experiment No. Adhesive Material Type Metal Fiber (% by Volume) Bending Strength (N / mm 2) 3-1 Experiment - 0 28.9 3-2 Experiment - 1.5 28.7 3-3 Experiment 2.0 33.2 3-4 ------------ Experimental soil ^- 2.5 42.4 3-5 Experiment I-8 test 30 47.5 3-6 Experiment I·8 %....... 3.5 52.6 3 -7 Experiment I·8 ^...- 4.0 58.0 3-8 Experiment 1 -8 One 4.5 62.4 3-9 Experiment I-8 _ .. 5.0 65.8 3-10 Experiment 1-8 _ 5.5 66.2 3- 11 Experiment 1 - 8 6.0 66.4 3-12 Experiment 1-8 6.5 Cannot be molded [Example 4] Concrete is to obtain a total volume of 1 cubic meter of concrete, and the experiment 1 to 1 to 1 of Example 1 14 and kneading in the same manner as in Experiment 2-5 to 2-13 of Example 2, except that the amount of the coarse aggregate added is 900 kg/m3 per 1 m3 of concrete, and the air content is Adjust to 2 · 5 % and then mold the test piece from it. After 91 days of standard curing, the compressive strength and flexural strength were measured. The results are shown in Table 4. -23- 200602283 (21) It is apparent from Table 4 that the concrete of Experiment 4-2 in which only cement and ash as cement are added, and the concrete of Experiment 4-14 in which only cement and sieving fly ash are added, The rate of increase in bending strength is small. On the other hand, it is apparent that concrete having both fly ash and sieve fly ash, such as the experiment 4 - 3 to 4 - 1 3 , shows a marked increase in bending strength. This is especially true when the ratio of ash to sieved fly ash is 95:5 to 10:90, and particularly 90:10 to 2:80. φ This confirms that the simultaneous use of gypsum increases the compressive strength and flexural strength, as is evident from Experiments 4-15 to 4-23. Further, in the case of concrete in which gypsum is used in combination, in the case of mortar, even if the amount of gypsum added exceeds 12 parts per 1 part of cement, the effect of further increasing the strength cannot be obtained. Therefore, the amount of gypsum added is 1 part or less, and preferably from 1 to 8 parts.

-24- 200602283 (22) [Table 4]

Experiment number Adhesive material type (including gypsum) Bending strength (N/mm2) Compressive strength (N/mm2) Bending/compressive strength ratio 4-1 Experiment 1 -1 - 11.2 123 1/11.0 4-2 Experiment 1-2 12.1 156 1/12.9 4-3 Experiment 1-3. 15.3 155 1/10.1 4-4 Experiment 1-4. 15.9 154 1/9.7 4-5 Experiment 1-5. 18.8 152 1/8.1 4-6 Experiment 1 6 20.8 150 1/7.2 4-7 Experiment 1-7 2 1.2 15 1 1/7.1 4-8 Experiment 1-8 20.5 150 1/7.3 4-9 Experiment 1_9 20.0 149 1/7.5 4-10 Experiment 1 -1 1 18.0 150 1/8.3 4-11 Experiment 1 -1 1 of 17.2 152 1/8.8 4-12 Experiment 1 -1 2 of 15.5 150 1/9.7 4-13 Experiment 1 -1 3 of 13.7 144 1 /10.5 4-14 Experiment 1 -1 4 of 11.9 142 1/11.9 4-15 Experiment 2-5 2 of 1.9 162 1/7.9 4-16 Experiment 2-6 of 23.1 165 1/7.1 4-17 Experiment 2-7 24.9 170 1/6.8 4-18 Experiment 2-8 25.3 1 74 1/6.9 4-19 Experiment 2-9 25.8 178 1/6.9 4-20 Experiment 2-10 26.4 177 1/6.7 4-21 Experiment 2-1 1 26.0 175 1/6.7 4-22 Experiment 2-12 25.9 176 1/6.8 4-23 Experiment 2-13 25.0 173 1/6.9 -25- 200602283 (23) [Example 5] Metal fiber concrete in Table 5 The metal fibers of the amount (externally added to the concrete) were kneaded with 1 m3 of the concrete of the experiment 4-8 of Example 4, and the concrete was poured into a mold placed on a tabletop vibrator while being slightly vibrated to make the metal fibers. Separation does not occur, thereby molding the test piece. Steam solidification was carried out in the same manner as in Example 1, and then, a bending φ strength test of 1 day was performed. The results are shown in Table 5. As can be seen from Table 5, the metal fiber increases the bending strength of the concrete, but does not work at all in an amount of 1.0% by volume. The metal fiber showed a significant effect from the K5 volume ❶/〇, and the bending strength increased as the amount of metal fiber added increased. However, it gradually reaches a peak 値 and 4 · 5 % by volume results in poor operability and molding difficulty. In the case where concrete is obtained by vibration molding, it is apparent that the optimum range is from 2 · 〇 to 4.0 vol%. -26- 200602283 (24) [Table 5] Experiment No. Concrete Type Metal Fiber (External Addition Volume %) (Based on Concrete) Bending Strength (N/mm 2 ) 5-1 Experiment 4-8 1.0 2 1.7 5- 2 Experiment 4-8 1. 5 23.8 5-3 Experiment 4-8 2.0 17.1 5-4 Experiment 4_8 2.5 2.52.4 5-5 Experiment 4-8 3.0 3.0 56.5 5-6 Experiment 4-8 3.5 38.6 5- 7 Experiment 4-8. 4.0 39.1 5-8 Experiment 4-8. 4.5 Cannot be molded [Example 6] Using the formula shown in Table 6 'Knead mortar or concrete with different added amount of metal fiber, and centrifuge A test piece was prepared by molding. Steam solidification was carried out in the same manner as in Example 1, and then the external pressure load at the time of fragmentation was measured at 1 day of age to calculate the bending tensile strength. The central column indicates the formulation of the concrete, the above lists the concrete formulations used for comparison, and the following indicates the mortar formulation obtained from the amount of coarse aggregate of the concrete formulation shown in the central column and converted to several metres per cubic meter. Incidentally, the symbols used in Table 6 indicate the following meanings:

Gmax : Maximum aggregate size Air: Air content -27- 200602283 (25) sL : 坍 s/a : Fine aggregate ratio W / B : Water / binder ratio w · · Water C : Cement S : Fine aggregate G: coarse aggregate g A test piece is prepared by centrifugal molding in which the entire test piece is molded by single-layer molding of concrete or mortar having different amounts of metal fibers, and a mold is prepared via double-layer molding. Plastic test piece, in which the outer 3 - cm portion of the test piece is molded from mortar or concrete without metal fiber, and then the inner 2 - cm portion is molded with a mortar or concrete having a variation of metal fiber . The results are shown in Table 7. [Table 6]

Gmax Air sL s/a W/B Unit quantity (kg/m3) (mm) (%) (cm) (%) (%) WCSG WRA(2) SF FA20 II-CS *13 1.5 65 48.7 28 168 600 799 850 12 0 0 0 13 1.5 65 48.1 28 168 500 782 850 10 48 29 19 • 1.6 35 • 20 234 984 953 · 18 94 56 38 (Note) WRA (2): a high performance water reducing agent, added in powder form and Kneading. II - CS is insoluble anhydrite. As can be seen from Table 7, the addition of 1. 〇 vol% of the metal fiber can increase the tensile strength of -28-200602283 (26), and the flexural tensile strength will vary with the amount of metal fiber added. Increase and increase. In the case of concrete, when 3.5% by volume is added, even when the metal fiber is added to the concrete having high fluidity, the concrete is poorly stretched to cause the fiber ball to float on the inner surface. Therefore, preferably, the amount of the metal fibers added is up to 3.0% by volume. In the case of the mortar, it is impossible to mold at an amount exceeding 5.5 % by volume, and it is apparent that the amount of the metal fibers added is preferably up to 5% by volume. In the case of the Hume tube, the molding in which only the metal fibers are blended into the inner side of the tube clearly provides a higher bending tensile strength than the molding in which the metal fibers are blended into the entire tube. It is more economical.

-29- 200602283 (27) m 7] Experiment No. Metal fiber addition amount (external addition amount, volume %) Molding method Bending tensile strength (N/mm2) 6-1 〇 in concrete mortar, whole tube molding Layer 13.1 6-2 1.0, full tube moulding • Single layer 16.1 6-3 1.5, full tube moulding single layer 19.0 6-4 2.0, full tube moulding • single layer 22.5 6-5 2.5, full tube moulding Layer 27.6 6-6 3.0, single tube molding single layer 27.5 6-7 3.5, single tube molding surface single layer fiber ball 6-8 _ 〇, whole tube molding single layer 17.0 6-9 雠 1.0, whole tube mold Plastic single layer 2 1.0 6-10 嶋1.5, whole tube molding single layer 24.6 6-1 1 surface 2.0, whole tube molding single layer 28.3 6-1 2 ton 3.0, whole tube molding single layer 33.2 6-1 3 Sense 3.5, the whole tube molding single layer 37.2 6-14 嶋4.0, the whole tube molding single layer 40.0 6-15 5.0, the whole tube molding single layer 41.7 6-16 • 6.0, the whole tube molding single layer can not be molded 6-17 1.0, inner molded double layer 19.8 6-1 8 2.0, inner molded double layer 25.8 6-19 3.0, inner molded double layer 30.1 6-2 1 • 1.0, inner molded double layer 24.1 6-22 • 2.0, inner molded double layer 32.5 6-23 • 3.0, inner molded double layer 3 6.2 6-24 4.0, inner molded double layer 44.5 6-25 *〇, whole tube molded double layer 8.2 (Note)*: Experiment 6 - 2 5 is the coagulation indicated by the symbol in the comparative example of the topsoil formula - 30-200602283 (28) Although the present invention has been described in detail with reference to the specific embodiments thereof, various modifications and modifications may be made therein without departing from the spirit and scope of the invention. range. The present application is based on Japanese Patent Application No. 2004-07518, filed on Jan. 17, 2004, the content of which is incorporated herein by reference. The fluidity can be improved to achieve good operability. Further, the obtained mortar and concrete have high compressive strength and bending strength, and high bending strength with respect to compressive strength can be obtained. In addition, the bending strength can be greatly increased by the strengthening action of the blended metal fibers. This can result in an economical and advantageous design in the manufacture of civil engineering and building structures and concrete secondary products. -31 -

Claims (1)

200602283 (1) X. Patent Application 1 • A cement admixture comprising ash and fly ash sized to a size of 20 microns or less, wherein the ash is mixed with sieved fly ash The weight ratio is from 9 5 : 5 to 1 0 : 9 0. 2. The cement admixture of claim 1 further comprising gypsum. 3. A cement composition comprising a cement admixture of claim 1 in an amount of from 1 to 35 parts by weight per 10,000 parts by weight of cement. 4. The cement composition of claim 3, which further comprises gypsum in an amount of from 0.5 to 12 parts by weight per 1 part by weight of the cement composition, calculated on an anhydrous basis. 5. A mortar comprising a cement composition of claim 3 or 4, a fine aggregate, a water reducer and a kneaded water. 6. The mortar of claim 5, which has a metal fiber added thereto, the metal fiber being externally added in an amount of from 1.0 to 6.00 volume Φ% per cubic meter of the mortar. A concrete comprising the cement composition of the third or fourth aspect of the patent application, a fine aggregate, a coarse aggregate, a water reducer and a kneaded water. 8. The concrete of claim 7, which has a metal fiber added thereto, the metal fiber being externally added in an amount of K0 to 4% by volume per cubic meter of the concrete. 9. A cement hardened product obtained by hardening a mortar of claim 5 of the patent application. 1 〇·- Kind of cement hardened product obtained by hardening the concrete of the scope of application of the scope of the patent -32- 200602283 (2). 1 1 . A cement hardened product obtained by hardening concrete of claim 7 of the patent application. 1 2. A cement hardened product obtained by hardening concrete of the application of claim 8th. -33- 200602283 VII. Designated representative circle · (1) The designated representative circle of this case is: None (2), the representative symbol of the representative 简单 is simple: no 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none