JPH0450154A - Multimodal spherical hydraulic composition and cured article of multimodal spherical hydraulic composition - Google Patents

Abstract

PURPOSE:To obtain a hydraulic composition giving a cement article having excellent water resistance and fire resistance and high flexural strength by compounding spherical hydraulic cement with silico-carnotite, tetracalcium phosphate or dicalcium gamma-silicate. CONSTITUTION:The objective multimodal spherical hydraulic composition is composed of (A) a spherical hydraulic cement having multimodal particle size distribution and (B) at least one component selected from tricalcium alpha-phosphate, silico-carnotite [a solid solution of SiO2 dissolved in a calcium phosphate compound, i.e., a solid solution of Ca2(PO4)2-Ca2SiO4], tetracalcium phosphate and dicalcium gamma-silicate. Since the above composition gives a hardened product having extremely high flexural strength, a novel hardened article having unusually high flexural strength which cannot be attained by conventional cement and usable beyond the range of conventional cement product market can be produced from the present composition.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" This invention relates to multimodal spherical hydraulic compositions that can be formed in close packing by mixing under low water-cement ratio and shear stress; The present invention relates to a multimode spherical hydraulic composition and a cured product thereof, which enable the production of cement products that are dense and have high bending strength, as well as excellent water resistance and fire resistance.

``Prior Art'' Conventionally, in order to produce cement such as Portland cement, raw materials are pulverized and fired in a rotary kiln, and the resulting cement clinker is then rapidly cooled with air. Then, gypsum powder is added to the cooled cement clinker, and this is further pulverized again using a tube mill or the like to obtain cement of a desired particle size.

By the way, the Portland cement obtained in this way generally has a water-cement ratio of about 60%, a mortar compressive strength of about 400 kg/am'' at 4 weeks of age, and a bending strength of 50 to 70 kg/cm'' ( It was possible to obtain only about 5 to 7 MPa).

``Problems to be Solved by the Invention'' In order to solve the above-mentioned drawbacks, by minimizing the voids in the structure of the hardened cement product using methods such as high shear mixing or calendar molding, it is possible to achieve a bending strength of 50 MPa or more and toughness. A technique for obtaining a large hydraulic cementitious body has been provided. (JP-A-56-9256, JP-A-56-14465, JP-A-56-84349) However, the cement hardened products produced by these techniques have poor water resistance, and moreover, the hardened products naturally disappear after a long period of time. Collapse. Furthermore, these techniques require the addition of a large amount of organic matter, which has a fatal drawback in that the material has poor fire resistance and burns, making it impossible to use as a noncombustible material.

Therefore, it has been extremely difficult to put hydraulic cementitious hardened bodies based on these techniques into practical use.

This invention was made in view of the above circumstances, and has water resistance,
The object of the present invention is to provide a multi-mode spherical hydraulic composition which can provide a cement product having excellent fire resistance and high bending strength.

"Means for Solving the Problems" The multimodal spherical hydraulic composition according to claim 1 of the present invention includes a spherical hydraulic cement having a multimodal particle size distribution configuration, α-tricalcium phosphate, and a calcium phosphate compound. SiO! is formed as a solid solution/Licocar 7tite,
The solution to the above problem is to consist of at least one type of tetracalcium phosphate γ-dicalcium silicate.

Moreover, in the multimode spherical hydraulic composition according to claim 2,
The multimodal spherical hydraulic composition according to claim 1, wherein α-tricalcium phosphate is incorporated.

Silicocarnotite formed by solid solution of SiO2 in calcium phosphate compound, tetracalcium phosphate, gamma dical silicate/
The solution to the above problem was to use a spheroid having a multi-mode particle size distribution structure.

The multimode spherical hydraulic composition according to claim 3 solves the above problem by adding 30 parts by weight or less of water to 100 parts by weight of the multimode spherical hydraulic composition according to claim 1 or 2. It was used as a means.

The multimodal spherical hydraulic composition according to claim 4, which is composed of a spherical hydraulic cement having a multimodal particle size distribution configuration and at least one of silica sol microparticles, silica gel microparticles, and silicic material microparticles, solves the above problem. It was used as a solution.

The multimodal spherical hydraulic composition according to claim 5 includes a spherical hydraulic cement having a multimodal particle size distribution structure, and α-
Tricarium phosphate, calcium phosphate compound with SiO
Means for solving the above problems is made of at least one of silicocarnotite, tetracalcium phosphate, and γ-dicalcium silicate in which 2 is dissolved in solid solution, and at least one of silica sol fine particles, silica gel fine particles, and silicate substance fine particles. And so.

In the multimode spherical hydraulic cement according to claim 6, in the multimode spherical hydraulic composition according to claim 1.2.3 or 5, SiC is solidly dissolved in the α-tricalcium phosphate and calcium phosphate compound to be added. silicocarnotite formed by solid solution of SiOt in at least one of tetracalcium phosphate and γ-dicalcium silicate and α-tricalcium/ium phosphate and calcium phosphate compound; A calcium phosphate compound mixed powder consisting of a mixed powder of at least one kind and tetracarunium phosphate,
And the calcium phosphate compound mixed powder is hydroquine apatite, Ca, o(PO2)6(○H), , Ca5(
The solution to the above problem is that it is obtained by thermally decomposing calcium phosphate compounds such as P○, ), (OH), etc.

In the multimode spherical hydraulic composition according to claim 7, in the multimode spherical hydraulic composition according to claim 1.2.3.4.5 or 6, the spherical hydraulic composition has a multimodal particle size distribution configuration. A means for solving the above problem is that the cement consists of a spherical hydraulic cement clinker obtained by passing the cement clinker through a high-temperature flame to make it molten or semi-molten, and then cooling it.

In the multimodal spherical hydraulic composition according to claim 8, in the multimodal spherical hydraulic composition according to claim 1.2.3.4.5.6 or 7, filler, fiber, reinforcement, aggregate The solution to the above problem is to add at least one of the above.

In the multimode spherical hydraulic composition cured product according to claim 9,
30 parts by weight or less of water is added to 100 parts by weight of the multimode spherical hydraulic composition according to claim 1.2.4.5.6.7 or 8, and after kneading and molding, 40-1 under humidity 20-70% and/or 5-15 atm
The solution to the above problem was obtained by performing a curing treatment at a humidity of 80°C.

Hereinafter, the multimode spherical hydraulic composition of the present invention will be explained in detail.

First, to explain about spherical hydraulic cement, spherical hydraulic cement has spherical particles, for example, the following ■ ~
It is manufactured by the method (2).

■ A method of obtaining cement by passing cement clinker through a high-temperature flame to make it molten or semi-molten, then cooling it, and then adding gypsum powder.

■ A method in which a mixture of cement clinker and gypsum powder is passed through a high-temperature flame to form a molten or semi-molten state, and then the mixture is cooled.

■Cement clinker is passed through a high-temperature flame to melt or semi-melt it, and then it is cooled, and then spherical gypsum powder produced by the same method as the cement clinker or by a conventionally known spheroidizing method is added. How to obtain by adding.

■A method in which cement clinker or a mixture of cement clinker and gypsum powder is spheroidized by an impact method in a high-speed air stream.

In other words, gypsum, which is naturally added as cement, may be added after the cement clinker is spheroidized, or it may be spheroidized together with the cement clinker, or it may be spheroidized separately from the cement clinker. However, it may be mixed with cement tarinker which has been spheroidized afterwards. In addition to the above-mentioned methods, known spheroidizing methods such as pulverization can be used as the method for spheroidizing the hydraulic cement in the present invention.

Also, α-tricalcium phosphate of the present invention, which will be described later.

As mentioned above, the method for spheroidizing silicocarnotite, tetracalcium phosphate, and dicalcium γ silicate, which are formed by solid solution of SiOt in a calcium phosphate compound, is as follows.
They may be passed through a high-temperature flame to become molten or semi-molten and then cooled, or may be obtained by other known methods (high-pressure melt injection, crushing, etc.).

To explain in detail the above method (■), in order to obtain spherical hydraulic cement by this method, first the raw materials are crushed and fired in a rotary kiln in the same way as in the past, and then the obtained cement clinker is quenched with air. . Then, gypsum is added to the cooled cement clinker and pulverized again using a tube mill or the like to adjust to a desired particle size. Finally, a cement barrel with the following classified mode is passed through the high-temperature flame.
The particle size of the multimode spherical hydraulic cement obtained by subsequently adding spherical gypsum is, for example, when the multimode is two modes, the particle size of the coarser mode is 40 to 110.
The cement particles have a diameter of 1 to 10 μm in the mode where the particles are finer. To explain in more detail, the cement tarinker to be introduced into the high-volume flame of the present invention is classified by a known method such as classification to obtain a particle size of 50%.
~120μ shoulder cement talin force-particles and particle size 1~
20 μm cement tarinker particles are obtained respectively.

In this case, the cement clinker particles have a particle size of 50 to 12
The reason for obtaining the 0.11m and 1-20μ particles is that by passing these cement particles through a high-temperature flame to make them spheroidal, the apparent average particle size becomes smaller, and the final This is because the particle size of the spherical cement obtained by adding spherical gypsum to the cement particles is 40 to 110 μl and 1 to 10 μl.

The cement tarinker particles of each particle size classified and produced in this way are, for example, 50% by weight or more of the particles in the coarser mode, and 50% by weight or more of the particles in the finer mode. It is blended so that it accounts for 5% by weight or more of the total weight.

Next, prepare a flame generator that uses flammable gases such as propane, butane, propylene, acetone, and hydrogen, liquid fuels such as heavy oil and light oil, or petroleum, and even solid fuels such as oil coke. Generates flame. Next, a predetermined amount of cement clinker particles, the particle size of which has been adjusted as described above, is fed into the flame to melt or semi-melt it, and then it is cooled.

Here, if necessary, cement clinker particles having a particle size outside the mode are added to the cement clinker particles after particle adjustment and subjected to spheroidization treatment, but the amount of particles added in that case is, for example, It is preferable to add so that the total weight of particles of intermediate particle size in adjacent modes is 20% or less of the total weight of each particle of particle size in adjacent modes, and the above-mentioned 40 to 110 μ shoulder and 1 In the example of two modes with a shoulder of ~10μ, it is preferable to add the particles so that the total weight of particles outside the range of these two modes is 20% or less of the total weight.

When the cement talin car particles are passed through the flame in this manner, the molten or semi-molten cement talin car particles become spherical due to their surface tension.

The flame temperature here varies depending on the type of cement tarinker, but it needs to be at least 1000'C or higher, preferably 1500°C or higher; if it is lower than 1000°C, the cement tarinker particles will not fully melt or be in a semi-molten state. Therefore, the cement talin car particles do not become sufficiently spherical, which is not preferable. Further, the residence time in the flame is preferably about 0.01 to 0.05 seconds. In addition, when using a highly gifted fuel as the fuel for the above-mentioned flame generator, it is necessary to adjust the blend of cement raw materials in advance so that it becomes a cement component or a target component.

Thereafter, about 0 to 5 parts by weight of gypsum powder is added to 100 parts by weight of the obtained spherical cement clinker, and the desired hydraulic speed is adjusted to obtain a spherical hydraulic cement.

In addition, the particle size of the gypsum powder should be adjusted in advance so that it corresponds to the cement curing force - each mode of the particle.
This is preferable in order to improve the close packing and fluidity of the resulting spherical hydraulic cement, and also to improve the bending strength of the hardened cement product obtained therefrom.

Also, the difference between method ■ above and method example ■ is as follows:
The point is that not only cement clinker particles alone but also a mixture of cement clinker particles whose particle size has been adjusted and gypsum powder whose particle size has also been adjusted are fed into the flame of a flame generator and fired and melted. In this case, by taking the cement out of the flame and cooling it, spherical cement can be obtained without adding gypsum powder. Here, unlike the above example, the flame temperature is 1
It is considered to be over 300'C. Further, in this case, it is preferable to mix a larger amount of gypsum powder into the cement clinker than in the above example, since some of the gypsum powder decomposes at temperatures above 1300°C.

Also, the difference between method ■ above and method example ■ is as follows:
The point is that spherical gypsum powder is used as the gypsum powder to be added to the obtained spherical cement aggregate. Here, the spherical gypsum powder used is one that has been passed through a high-temperature flame as in the case of cement talin car, or that has been subjected to spheroidization treatment in the gypsum manufacturing process.

In addition, method (1) above is a completely different method from methods (2) to (2) in which the angular parts of the clinker are simply shaved off by the impact of high-speed airflow without passing the cement clinker into the flame, resulting in spherical cement particles. This is the way to obtain. As described above, the method for producing spherical hydraulic cement clinker or cement according to the present invention is not limited to the above-mentioned method of producing cement clinker or cement by passing it through a high-temperature flame. The cement may be spheroidized by a known method.

In addition, in the present invention, the spheroidization process may be performed after classification into multiple modes, or the spheroidization process may be performed and then converted into multimodes.

Since the spherical hydraulic cements obtained in this way are all spherical, there is less frictional resistance between the particles, and therefore they have a larger flow value than conventional cements at the same water-cement ratio. Become. This also improves fluidity and filling properties, so cement hardens after hardening.

The strength of the body is higher than that of conventional cement.

Next, the multi-mode formation of the above-mentioned spherical hydraulic cement will be explained.

Here, ``multimodal j'' means that there are two or more distinguishable bands, or modes, of grain size in the distribution pattern, and there are intermediate grains between adjacent major bands (i.e., modes). This means that only a very small proportion of the sizes are present, and therefore the overall particle size distribution is not substantially continuous. It is sufficient that the total weight of particles of different diameters does not exceed 20% of the total weight of particles in adjacent major bands (i.e. modes).Also, as for multimode, bimodal is preferable. However, 3 modes may be advantageous,
Furthermore, four modes may be used. However, even if the number of modes is increased beyond this, there is little effect to be obtained, and it is economically disadvantageous in terms of additional costs and labor.

A quantitative example of the desired particle size distribution of the spherical hydraulic cement is as follows regarding the bimodal distribution.

As a first general guideline, the ratio of the weight average particle sizes of the particles in each band (mode) should be as widely separated as practical. The reason for this is that it facilitates achieving the desired properties in cement products made from the hydraulic cement, ie increased flexural strength. Therefore, if the weight average particle size of the coarser mode is , and the weight average particle size of the finer mode is , then the ratio of D: D is preferably 2 or more, more preferably is in the range of 10 or more, more preferably in the range of 20 to 40.

As a second guideline, it is preferable that the range of particle sizes in each mode be narrower than wider. That is, it is preferable that the particle size range for each mode is as narrow as technically and economically possible.

Particularly useful compositions of spherical hydraulic cements with a bimodal distribution include those having the following particle sizes and weight ratios.

(a) The particle size is 40 to 110 μm, and the weight ratio is 50% of the total.
% by weight or more, preferably 70 to 90% by weight, (b) the particle size is 1 to 10 μl, and the weight ratio is 5% to the total weight, preferably 10 to 30% by weight, (C) the above (a) and ( b
) The particle size outside the two ranges is 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less of the total weight.

In addition, in the particle size ranges of (a) and (b) above,
By narrowing the particle size range, it is possible to improve the close packing. That is, for example, in (a), 40 to 90 μm distributed with a width of about 20 to 25 μm
A particle size range of m is preferred, and in (b) a particle size range of order 4 to 8 μm distributed with a width of about 5 μm is preferred.

By applying the first and second guidelines, useful compositions outside the specific particle size ranges (a), (b) and (C) described above can be defined. It should be noted that the optimum composition depends, to a certain extent, on the properties of the spherical hydraulic cement used, its economics (in particular the economics of specifying the desired dimensions and performing the classification), and the degree to which it affects the maximum strength of the hardened cement product. It depends on whether it is required to get as close as possible.

For the 3 modes, guidelines similar to those for the 2 modes above can be applied. If the weight average particle diameters of the three modes, namely coarse, intermediate and fine modes, are DID and D3, then the ratio of D: D and D3 is: D.

It is a special product that satisfies the ratio specified for .

Of course, it may not be practical to make both D, :D, and Dt:Ds the same. Therefore, although there may be considerable differences between the two, it is preferable that at least one of them be within a preferable range. Furthermore, the effect obtained by narrowing the particle size range of each mode in a two-mode distribution is the same in a three-mode distribution, and therefore it is still preferable to narrow the particle size range of each mode. .

Particularly useful compositions of spherical hydraulic cements with a trimodal distribution include those having the following particle sizes and weight ratios.

(a) Particle size is 40 to 150μ, preferably 100 to 1
(b) When the grain size is 7 to 12μ, the weight ratio is 50% or more of the total weight, preferably 10 to 30% by weight, (c) Particle size is 0.5
~2μ shoulder and the weight ratio is 1% or more of the total weight, preferably 3
~8% by weight.

To adjust the multimode distribution of spherical hydraulic cement, as described above, prior to spheroidizing the cement talinker particles, it is possible to classify them in advance and mix them in a desired weight ratio, or by adjusting the particle size. The previous cement talin car particles are spheronized and then classified by sieving or any other conventional means to obtain particles in the desired size range and then mixed in the desired weight ratio. It's okay. Here, the reason why a classification operation is required to adjust the multimode distribution is because conventional granular hydraulic cement is generally manufactured by first grinding a coarse material into granules. This is because the particles have a very wide particle size distribution. That is, conventionally commercially available hydraulic cements typically have a particle size distribution that extends over a broad, substantially continuous particle size band (eg, from 1 μm or more to about 150 μm). Of course, among the cement particles separated by the classification operation, those having a particle size larger than a desired value can be adjusted to the desired particle size by pulverization treatment or remelting treatment.

The thus obtained multimode spherical hydraulic cement is then mixed with a calcium phosphate compound mixed powder formed by mixing α-tricalcium phosphate and tetracalcium phosphate, or γ-nyllucium silicate, silica sol fine particles, The multimode spherical hydraulic composition of the present invention can be obtained by mixing one or both of silica gel particles and at least one type of silicic material particles. When mixing here or when adding water and mixing,
Applying high frequency waves and mixing under high shear stress are preferable because the resulting cured product has even higher bending strength.

In addition, silicocarnotite [Ca3(PO,)2-Ca,Sio, formed by solid solution of α-tricalcium phosphate [α-Cas(PO,), ], IJcalcium phosphate compound in, solid solution]
and at least one of tetracalcium phosphate [Ca, o (
The calcium phosphate compound mixed powder consisting of mixed powder with P O4)z] includes hydroxyapatite, Ca
1o(PO4)6(OH)6, Ca5(PO4)3(
Those obtained by thermally decomposing calcium phosphate compounds such as OH) are preferred. That is, in order to produce such a mixed powder of calcium phosphate compound, for example, hydroxyapatite synthesized by a wet synthesis method and having a molar ratio of calcium to phosphorus of 1.50 to 1.68 is heated at a high temperature of 1200'C or higher. The mixture is dehydrated and thermally decomposed and further pulverized to produce a mixed powder of α-tricalcium phosphate and tetracalcium phosphate. Here, as a method for synthesizing hydroxyapatite, for example, a phosphoric acid solution is dropped into a calcium hydroxide slurry, the reaction is aged, and after filtration and washing,
α-Tricalcium phosphate and tetracalcium phosphate 7 obtained by drying or by treating calcium diphosphate and calcium carbonate at a high temperature of 1200°C or higher.
It is possible to adopt a method in which a mixture with umum is further mixed with water. In particular, in the latter case, a mixture of α-tricalcium phosphate and tetracalcium/ium phosphate, which is obtained by subjecting the synthesized hydroxyapatite to high temperature treatment at 1200°C or higher, is more preferable because it has a homogeneous chemical composition. . In addition, in addition to the hydroxyapatite, phosphoric acid, monocalcium phosphate, dibasic calcium phosphate, tribasic calcium phosphate, calcium carbonate, and calcium, calcium nitrate,
It can also be obtained by mixing ammonium phosphate, calcium hydroxide, etc. in a predetermined ratio and firing at a high temperature of 600° C. or higher.

In addition, as a method for producing γ-silicium silicic acid powder used in the present invention, first, a powder of calcium oxide, calcium hydroxide, or calcium carbonate with a purity of 99 wt% or more and a powder of silicon dioxide, etc. with a purity of 991 t% or more are combined. Cao
/SiOt in a molar ratio of 1.90 to 2.05, calcined at a temperature of 1000 to 1500°C for 30 minutes to 3 hours, and then slowly cooled to room temperature. Obtained by a method for producing sicalcium silicate powder.

γ-Sicalcium silicate powder obtained in this way,
It becomes a fine white powder.

On the other hand, when using silicocarnotite in place of α-tricalcium phosphate, to prepare the silicocarnotite, silicic acid is mixed with a suitable one of the above-mentioned calcium phosphates at a predetermined ratio, It can be obtained by calcining at a high temperature of 5.5ft to form a solid solution.

Furthermore, regarding the preparation of the calcium phosphate compound, Ca,o(PO,)-(OH)= and Cas(PO
4) -(OH) can be obtained by thermal decomposition at 1500'C or higher, or by separately preparing powders of α-tricalcium phosphate or silicocarnotite and tetracalcium/ium phosphate, to increase the ratio of calcium to phosphorus. It is also possible to adopt a method of mixing so that the molar ratio is 1.50 to 1.68.

In addition, the molar ratio of calcium to phosphorus is 150 to 1
．． The reason why hydroxyapatite having No. 68 was used and subjected to dehydrothermal decomposition is that hydroxyapatite is stable within the above molar ratio range.

The calcium phosphate compound mixed powder obtained in this way is also preferably subjected to the spheroidization treatment as described above, but of course only the usual granulation treatment may be applied. The particle size also depends on the blending amount of the calcium phosphate compound mixed powder, but in order not to damage the multi-mode particle size distribution structure of the spherical hydraulic cement mentioned above, the particle size should be determined in advance to be equivalent to the multi-mode particle size distribution structure of the spherical hydraulic cement. It is preferable to adjust the particle size distribution configuration. The amount of the calcium phosphate compound powder to be added to the multimode spherical hydraulic cement is in the range of 99:1 to 1·99 in terms of the ratio of the multimode spherical hydraulic cement to the phosphate compound powder.

Such calcium phosphate compound powder hardens through a hydration reaction to form hydroxyapatite, Ca,o(P 0
-)8(○H)7, Cas(PO4)3(OH), and exhibits high bending strength upon curing and has extremely large adhesive strength. Therefore, a multimode spherical hydraulic composition containing this calcium phosphate compound powder can be obtained by synergistically curing the multimode spherical hydraulic cement and curing the calcium phosphate compound powder (i.e., high adhesiveness). The cured product has extremely high bending strength, and since both the multimode hydraulic cement and the calcium phosphate compound powder are inorganic substances, it has high fire resistance.

On the other hand, as the silica sol fine particles, silica gel fine particles, and silicic acid substance fine particles, those commonly used in the past can be used, and of course commercially available ones can be used. And regarding these fine particles,
It is preferable to subject the powder to spheroidization treatment as in the case of the above-mentioned mixed powder of calcium phosphate compound, but of course it is also possible to use a normal non-treated powder. The particle size also depends on its blending amount, but it is adjusted in advance to a particle size distribution composition equivalent to the multimode particle size distribution composition of the above-mentioned spherical hydraulic cement so as not to damage the multimode particle size distribution composition. It is preferable to do so. The amount of such fine particles to be added to the multimode spherical hydraulic cement is such that the ratio of the multimode spherical hydraulic cement to the phosphate compound powder is 9.
The range is 9:1 to 1°99.

Furthermore, when mixing both the above-mentioned calcium phosphate compound mixed powder and at least one of silica sol fine particles, silica gel fine particles, and silicic material fine particles into a multimode spherical hydraulic cement, the blending amount is as follows: The ratio of the total amount of mixed powder and fine particles in the hydraulic cement to the soil is in the range of 99:1 to 1:99. In addition, each of the silicocarnotite, tetracalcium phosphate, and γ-dicalcium silicate formed by solid solution of SiOt in α-tricarunium phosphate, calcium phosphate compound is a spheroidized body hydraulically having a multimodal particle size distribution structure. It is a composition. Here, multimode formation is performed by the method described above, and spheroidization is also performed by the method described above. 30 parts by weight or less of water and optionally fine aggregate, filler, etc. are added to 100 parts by weight of the powder made of the multimode spherical hydraulic composition optionally mixed with γ-dicalunium silicate, and further, After mixing and molding, the relative humidity is 20-70% and/or 5-70%.
This is a cured product of a multimode spherical hydraulic composition obtained by curing treatment at a humidity of 40 to 180°C under 15 atm.

In order to cure the multimode spherical hydraulic composition thus obtained, 30 parts by weight or less of water is added to 100 parts by weight of the composition.

Here, the amount of water added was set to 30 parts by weight or less, but since the amount of water added should be sufficient to plastically deform the composition, it should be kept as small as possible as long as the composition is plastically deformed. The amount added should preferably be 15 parts by weight or less, more preferably 7 parts by weight or less. In other words, the multi-mode spherical hydraulic cement of the present invention makes it possible to reduce the amount of added water for the first time by using the spherical hydraulic cement, and furthermore, by making the spherical hydraulic cement multimodal, the amount of added water can be further reduced. As a result, the bending strength of the resulting hardened product is significantly improved compared to conventional hardened cement products.

In addition, in the multimode spherical hydraulic composition of the present invention, if necessary, known organic synthetic resins, water-dispersible processing additives, water-soluble processing additives, non-water-dispersible processing additives, water-insoluble processing additives, etc. Approximately 0.1 to 10.0 parts by weight of processing additives may be blended, and by blending and adding these, it is possible to further reduce the amount of water required for the layer, thereby increasing the bending strength of the resulting cured product. etc. can be further improved.

However, since these additives reduce heat resistance, they are added as necessary and are not mandatory. Here, the purpose of adding the processing additive is to promote dispersion and mixing of the multimode spherical hydraulic cement and water, thereby reducing the amount of water added. In addition, the addition amount is set to 0.1 to 10.0 parts by weight because if it is less than 0.1 part by weight, the effect of adding it will not be obtained substantially, whereas if it exceeds 10.0 parts by weight, it will not be formed. This is because the water resistance and fire resistance of the cured product (cement product) deteriorates, which is undesirable.

Furthermore, if necessary, fine aggregates, coarse aggregates, fillers, fibers, and reinforcement materials may be added to the multimode spherical hydraulic composition of the present invention as additives to obtain a cured product.

Further, such a multimode spherical hydraulic composition can be easily and suitably molded and cured by molding under relatively low pressure, but of course it may also be molded under high pressure, such as extrusion molding, press molding, It can also be molded by injection molding. In addition, when molding the multimode spherical hydraulic composition obtained in this way, if particularly high bending strength is required for the molded product (cured product) obtained, the composition should be thoroughly mixed throughout. It is preferable to
For example, it may be desirable to mix the composition under high shear conditions. Here, when mixing under high shear conditions, it can be carried out using, for example, a Banbury mixer or a screw extruder, or it can be carried out by using a twin roll mill and repeatedly passing the composition through the nip between the rolls. It is more preferable to mix by applying a high shearing force to the composition. By this operation, the composition can be well mixed throughout, and the cured product obtained thereby can have sufficiently high bending strength.

In addition, depending on the desired strength of the product (cured product), reinforcing bars, synthetic resin bars, non-ferrous alloys or non-ferrous metals (aluminum etc.), carbon fibers, glass fibers, silicon carbide, etc. may be added to the composition during curing. Streaks of fibers, silicon nitride fibers, glass wool, wood chips, or their fibers may be provided for reinforcement by known methods, and prestressing, chemical prestressing, etc. may be added.

Furthermore, to control the porosity characteristics of the cured product,
It is advantageous to cure the composition under pressure and release the pressure after curing has proceeded at least to the extent that the composition does not relax upon release of pressure (i.e. does not substantially change dimensions upon release of pressure). be. In this case, the applied pressure may be low, for example, 3 MPa or more is sufficient. Regarding pressurization time, the type of hydraulic cement and curing conditions (i.e. curing temperature and humidity)
Therefore, it is desirable to obtain it in advance through a simple experiment.

According to the multimode spherical hydraulic composition of the present invention, since the calcium phosphate compound, silica sol fine particles, silica gel fine particles, and silicic material fine particles are all inorganic, the cured product obtained has extremely high fire resistance, heat resistance, and water resistance. It will be excellent. By adding fine silica sol particles, fine silica gel particles, and fine silicic acid particles, the bending strength of the hydrated hardened product of the present invention is significantly increased. In addition, since the hydraulic cement particles and other compounded compositions are spherical, there is less frictional resistance between the particles, so of course they have a larger flow value than conventional cement at the same water-cement ratio. Since it has good fluidity and good filling properties, it is possible to achieve close packing, and since it is multimodal, it is possible to achieve even tightest packing, and an extremely dense cured product can be obtained.

In addition, calcium phosphate compounds, silica sol fine particles,
By blending and adding silica gel fine particles and silicate substance fine particles, the degree of hardening of the resulting cured product increases synergistically with the hardening of these calcium phosphate compounds, etc., and therefore 3 Q M
It has higher bending strength and compressive strength than a cured product made of a single multimode spherical hydraulic cement, such as a high bending strength of P a or more, and even 50 MPa or more.

The material for the multimode spherical hydraulic cement in the present invention is limited to Portland cement, and other cements such as alumina cement, white cement, early strength cement, and moderate heat cement.

Ultra early strength cement (e.g. jet cement), blast furnace cement, silica cement, fly ash cement, high sulfate cement, seawater cement, oil well cement can be used, as well as Toughrock, quicklime and other soil improvement plasters. , waterproof cement 1, injection cement (including graft cement), and acid-resistant cement can all be used.

"Example" Hereinafter, the present invention will be specifically explained with reference to Examples.

(Example 1) Cement clinker (Portland cement) was produced by a conventional manufacturing method, and the obtained cement clinker was calcined and melted (semi-molten) in a flame at 1500'C, and then cooled to form gypsum. Powder was added to obtain spherical hydraulic cement.

A mortar was prepared by adding standard sand and water to the obtained cement in the following formulation. The compressive strength 1 bending strength and flow value of this mortar were investigated based on JIS standard mortar, and the results are shown in Table 1.

Cement; 540g Standard sand; 1040g Water; 324g (W/C=60%)
For comparison, mortar was prepared using conventional cement with the above formulation, and its compressive strength 1 bending strength and flow value were measured in the same manner as in the above examples, and the results are also listed in Table 1.

From the results shown in Table 1, it was confirmed that the spherical hydraulic cement of the example was superior to that of the comparative example in both compressive strength, bending strength, and flow value.

(Example 2) The spherical cement particles obtained in Example 1 were classified into the following two components according to their particle sizes.

Particle size component ■: Does it pass through a sieve with an opening size of 125 μm?7
Components that do not pass through a sieve with an opening size of 6 μl.

Particle size component ■; Particle classifier [Alpinej 100M
Z R (trademark), a component consisting of particles with a particle size of 10 μl or less (substantially all particle sizes of this component are within the range of 1 to 10 μl, and the peak is 4 μl).

080 parts by weight of the particle size component thus obtained and 020 parts by weight of the particle size component were mixed and stirred to prepare a thoroughly mixed dry mixture. Next, 100 parts by weight of this dry mixture and a mixed powder of a calcium phosphate compound of α-tricalcium phosphate and tetracalcium phosphate obtained by thermally decomposing Ca+o(PO-)a(OH)t at 1500°C were prepared. 3 parts by weight and 15 parts by weight of water were mixed in a planetary mixer while applying ultrasonic waves. The resulting mixture was then placed in a twin roll mill and passed repeatedly through the nip between the rolls of the mill to thoroughly mix the composition and form it into a sheet. Next, the obtained sheet was taken out from the twin roll mill, pressed under a pressure of 4 MPa, and further heated to a temperature of 20
'C1 It was allowed to stand for 7 days in an atmosphere with a relative humidity of 98%, and then left to stand for 7 days under atmospheric conditions to dry.

A cut is made in the sheet-like hardened cement body obtained in this way and the size is 5. A number of pieces of OX 1.7 x 0.3 (cm) were outlined and the pieces were broken apart at the score line and then subjected to a three point bending test on an Instron testing machine. In addition, for the test, the span was 3.2 cm.
The breaking load of the piece was measured with a crosshead speed of 0 and 05 cm/min.

Moreover, the bending strength of the piece was calculated based on the following formula.

a = (1,5W L /d”u) X (0,10
1325/1.0332) [MP a] Here, W - Breaking load (kg) L - Span (cm) d - Thickness (c, w) ω = Width (Cx) σ = Bending strength (MPa) Like this When the bending strength of the test piece was determined, the average value of six measurements was 32±2 MPa.

(Example 3) Particle size component 080 parts by weight obtained in Example 2 and particle size component 020 parts by weight
Parts by weight were mixed and stirred to prepare a thoroughly mixed dry mixture. Next, 1 part of 100 fij of this dry mixture was put into a twin-roll mill, and in the mill was added carunium phosphate compound i6 powder of α-tricalcium phosphate and tetracalcium phosphate obtained by thermally decomposing hydroxyapatite at 1300°C. 15 parts by weight of water and 10 parts by weight of water were added and mixed at a constant speed. Then, the mixture obtained by mixing in the mill became a hard dough (like bread dough). Next, this dough-like material was placed between two polyethylene terephthalate sheets and pressed with a pressure of 5 MPa to form a plate-like material.

The plate-shaped body thus obtained was left in a high-humidity chamber (room temperature, relative humidity 90-100%) for 7 days, and then left under atmospheric conditions for 7 days to obtain a cured plate-shaped cement body.

Using this hardened cement plate as a test piece, a three-point bending test was conducted in the same manner as in Example 2, and the bending strength was 45±
It was 5 MPa.

(Example 4) The operation of Example 2 was repeated, but in this example, α-tricalcium phosphate obtained by thermally decomposing hydroxyapatite at 1300°C and 100 parts by weight of multimode spherical hydraulic cement were added. 5 parts by weight of a calcium phosphate compound mixed powder with tetracalcium phosphate, 5 parts by weight of silica sol, and 1 part by weight of water.
A sheet was produced by pressing the mixture obtained by adding 5 parts by weight under a pressure of 5 MPa.

A test piece was prepared from the obtained sheet and subjected to a three-point bending test in the same manner as in Example 2, and the bending strength was 60±2.
It was MPa.

(Example 5) The spherical hydraulic cement particles obtained in Example 1 were classified into the following two components according to their particle sizes.

Particle size component ■Component consisting of particles with a single particle size exceeding 10 μm.

Particle size component ■: Particles with a particle size of 10 μm or less and a weight average particle size of 5 μm.

080 parts by weight of the particle size component thus adjusted and 020 parts by weight of the particle size component were mixed and stirred to produce a thoroughly mixed dry mixture. Next, 100 parts by weight of this dry mixture was placed in a twin roll mill, and in the mill, a mixed powder of a calcium phosphate compound of α-tricalcium phosphate and tetracalcium phosphate obtained by thermally decomposing hydroxyapatite at 1300°C was added. 5 parts by weight, 5 parts by weight of silica sol,
23 parts by weight of water were added and mixed at a constant speed to obtain a tow-like product. Next, this dough-like material was placed between two polyethylene terephthalate sheets and 3 MPa
It was pressed with the pressure of a hydraulic press to form a plate with a thickness of 3xx.

The plate-shaped body thus obtained was left in a humid box maintained at a temperature of 18±2°C and relative humidity of 100% for 7 days, and then left to dry under atmospheric conditions for 7 days to obtain a cured plate-shaped body. Ta.

This plate-shaped cured body was used as a test piece, and the test was carried out in the same manner as in Example 2.
When a point bending test was conducted, the bending strength was measured 6 times and the average value was 60 MPa.

(Example 6) The operation of Example 3 was repeated, but in this example, as a multimode spherical hydraulic cement, 80 parts by weight of spherical cement with a particle size of 100 to 120 μm and a particle size of 10 μm! Using 20 parts by weight of the following spherical cement (with a peak of 5 μR), Ca, O
3 parts by weight of a mixed powder of a calcium phosphate compound of α-tricalcium phosphate and tetracalcium phosphate obtained by thermally decomposing (PO,)6(OH)- at 1500°C, 3 parts by weight of silica gel, and water. 15 parts by weight were added.

Then, the obtained dough was pressed between polyethylene terephthalate sheets with a pressure of 5 MPa to form a plate.

Thereafter, this plate-like body was left immersed in hot water at 30'C for 7 days, and further left to dry for 7 days under atmospheric conditions to obtain a cured plate-like body.

This plate-shaped cured body was used as a test piece, and the test was carried out in the same manner as in Example 2.
When a point bending test was performed, the bending strength was 50 ± 4 M.
It was P a.

(Example 7) The operation of Example 6 was repeated, but in this example, α-tricalcium phosphate obtained by thermally decomposing hydroxyapatite at 1500'C was added to 100 parts by weight of multimode spherical hydraulic cement. 5 parts by weight of mixed powder of calcium phosphate compound with tetracalcium phosphate and 15 parts by weight of γ-dicalcium silicate powder
parts by weight and 15 parts by weight of water were added. Here, for γ-dicalcium silicate, (CaO)=S io is 98
wt%, Blaine value 1500cm”/g, particle size 88
More than μM or OQ4wt%, more than 63μ contribution is 1.57wt
%, 4.47 wt% for 44 μm or more, 3 for 30 μm or more
0.28wt%, 20uw or more or 58.0wt%, 15
A material having μi or more of 72.44 wt% was used.

Hereinafter, a plate-shaped cured body was prepared by the same operation as in Example 6, and this plate-shaped cured body was used as a test piece, and a 3-point bending test was conducted in the same manner as in Example 2. The bending strength was 5 times. The measured average value was 65 MPa.

(Example 8) The operation of Example 6 was repeated, but in this example, spherical calcium aluminate having the particle size composition (double mode) shown in Example 2 was used as the multimode spherical hydraulic cement.

Then, to this spherical calcium aluminate, Ca,
7 parts by weight of a calcium phosphate compound mixed powder of α-tricalcium phosphate and tetracalcium phosphate obtained by thermally decomposing o(P○, ), (OH)t at 1500°C, and 7 parts by weight of silica sol, 15 parts by weight of water were added.

Hereinafter, a plate-shaped cured body was prepared by the same operation as in Example 6, and this plate-shaped cured body was used as a test piece. When a three-point bending test was conducted in the same manner as in Example 2, the bending strength was 6Q M P
It was a.

"Effects of the Invention" As explained above, the multimodal spherical hydraulic composition of the present invention has a hydraulic cement having a multimodal particle size distribution structure, α-tricarium phosphate, and a calcium phosphate compound of 810. is a solid solution of at least one of silicocarnotite, tetracalcium phosphate, and γ-dicalcium silicate, and at least one of at least one of silica sol fine particles, silica gel fine particles, and silicate substance fine particles, or both are blended and added. It is something.

Therefore, according to this hydraulic composition, since the calcium phosphate compound, silica sol fine particles, silica sol fine particles, and silicic material fine particles are all inorganic, the cured product obtained has extremely excellent fire resistance, heat resistance, and water resistance. becomes. In addition, since the hydraulic cement particles are spherical, there is less frictional resistance between the particles, and as a result, compared to conventional cement, it not only has a larger flow value at the same water-cement ratio, but also has better fluidity. Since the filling properties are also improved, even closer packing can be achieved, and since it is in the upper body mode, even closer packing is possible, and an extremely dense cured product can be obtained.

In addition, calcium phosphate compounds, silica sol fine particles,
By blending and adding silica sol fine particles and silicate substance fine particles, the degree of hardening of the obtained cured product increases synergistically with the curing of these carunium phosphate compounds, etc.
It has higher bending strength and compressive strength than a cured product made of a single multimode spherical hydraulic cement, such as a high bending strength of P a or more, and even 50 MPa or more.

In this way, more than 30 MPa and even 5 Q M
Since the resulting hardened product has an extremely high bending strength of P a or more, it is possible to provide a new hardened product with a high bending strength that does not exist in conventional cement products beyond the scope of the cement product market. It is possible to obtain hardened products with high bending strength that extends beyond the cement field to include plastics, steel, wood, and non-ferrous metals (aluminum and others).

Since this type of cured product has high bending strength, it can be formed into a thin layer, making it possible to replace materials such as plastic, wood, steel, and non-ferrous metals (aluminum and others). It becomes a new material with a lot of properties.

Claims (1)

[Scope of Claims] (1) Spherical hydraulic cement with a multimodal particle size distribution structure, and silicocarnotite made of α-tricalcium phosphate and SiO_2 dissolved in a calcium phosphate compound [
A multimode spherical hydraulic composition comprising at least one of Ca_3(PO_4)_2-Ca_2SiO_4 solid solution], tetracalcium phosphate, and γ-dicalcium silicate. (2) The multimodal spherical hydraulic composition according to claim 1, which comprises α-tricalcium phosphate, silicocarnotite in which SiO_2 is solidly dissolved in the calcium phosphate compound, tetracalcium phosphate, and γ-disilicic acid. A multimodal spherical hydraulic composition in which calcium is a spheroidized body having a multimodal particle size distribution configuration. (3) A multimode spherical hydraulic composition obtained by adding 30 parts by weight or less of water to 100 parts by weight of the multimode spherical hydraulic composition according to claim 1 or 2. (4) A multimodal spherical hydraulic composition comprising a spherical hydraulic cement having a multimodal particle size distribution configuration and at least one of silica sol microparticles, silica gel microparticles, and silicate material microparticles. (5) A spherical hydraulic cement with a multimodal particle size distribution configuration, and a silicocarnotite formed by solidly dissolving SiO_2 in α-tricalcium phosphate and a calcium phosphate compound.
A multimode spherical hydraulic composition comprising at least one of tetracalcium phosphate and γ-dicalcium silicate, and at least one of silica sol fine particles, silica gel fine particles, and silicate substance fine particles. (6) The multimode spherical hydraulic composition according to claim 1, 2, 3, or 5, comprising: silicocarnotite in which SiO_2 is solidly dissolved in the α-tricalcium phosphate and calcium phosphate compound to be added;
At least one of tetracalcium phosphate and γ-dicalcium silicate is made of mixed powder of at least one of silicocarnotite and tetracalcium phosphate, which is formed by solid solution of SiO_2 in α-tricalcium phosphate and a calcium phosphate compound. It is a calcium phosphate compound mixed powder, and the calcium phosphate compound mixed powder is hydroxyapatite, Ca_1_0(PO_4)_6(OH)_2, Ca
A multimode spherical hydraulic composition obtained by thermally decomposing a calcium phosphate compound such as _5(PO_4)_3(OH). (7) The multimodal spherical hydraulic composition according to claim 1, 2, 3, 4, 5, or 6, wherein the spherical hydraulic cement having a multimodal particle size distribution structure passes through a cement clinker in a high-temperature flame. A multimodal spherical hydraulic composition comprising a spherical hydraulic cement clinker obtained by melting or semi-molten the clinker and then cooling the same. (8) The multimodal spherical hydraulic composition according to claim 1, 2, 3, 4, 5, 6, or 7, wherein a filler, a fiber, a reinforcement material,
A multimodal spherical hydraulic composition comprising at least one type of aggregate added thereto. (9) Claim 1, 2, 4, 5, 6, 7 or 8
For 100 parts by weight of the multimodal spherical hydraulic composition described,
After adding 30 parts by weight or less of water and further kneading and molding, the product was cured at a humidity of 40 to 180°C under a relative humidity of 20 to 70% and/or 5 to 15 atm. Multimode spherical hydraulic composition cured product.