JP2000290058A - Inorganic material caked body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inorganic material caked body without heating to a high temperature. SOLUTION: Slaked lime and powder of weathered granite are mixed and caked by carbonation and hydration. The composition of the powder of weathered granite consists of 7-17 mass % Al2O3, 2-10 mass % alkali metal oxides and/or alkaline earth metal oxides, 1-6 mass % ignition loss and the balance substantially SiO2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid inorganic material usable for building materials such as interior materials and exterior materials, roadbeds, skeleton floors, skeleton walls, buildings and the like.

[0002]

2. Description of the Related Art Conventional ceramic products such as ceramics such as tiles used for interior and exterior materials and refractories such as bricks are generally made of inorganic materials such as clay which are naturally produced. Is mixed and kneaded with water at a predetermined ratio to form a predetermined shape, and the thus obtained molded body is heated to a high temperature to cause a solid phase reaction, sintering, melting, crystal growth and the like to be solidified.

[0003] In addition, cement used for forming a block or constructing a skeleton floor or a skeleton wall as ready-mixed concrete is generally made of SiO ₂ , Al ₂ O ₃ , Fe ₂ O.
_3. A raw material containing CaO is blended at a predetermined ratio, and the resulting blend is heated to a high temperature until it is melted to form a clinker.
₄ · 2H ₂ O) with formed by crushed into powder. This cement uses sand, pebbles, etc. as aggregate, and is kneaded with water or the like to form a cement paste. The cement paste is composed of C ₂ S (2CaO · SiO ₂ ), C ₃
Compounds such as S (3CaO.SiO ₂ ) undergo a hydration reaction to form C ₃
Produces solid hydrates such as S ₂ H ₃ (3CaO.2SiO ₂ .3H ₂ O) and solidifies by coagulation and hardening. At this time, the gypsum adjusts the setting time.

[0004]

However, conventional ceramic products must be heated to a high temperature in order to solidify them in a predetermined shape and cement to obtain clinker. For this reason, by these, interior material, exterior material, roadbed,
When trying to obtain a solidified body such as a skeleton floor, a skeleton wall, a building, etc., a large amount of energy is consumed, which is environmentally unfavorable.

The present invention has been made in view of the above-mentioned conventional situation, and has as an object to provide a solid inorganic material which can be obtained without heating to a high temperature.

[0006]

The solidified inorganic material according to the present invention is characterized in that slaked lime and weathered granite powder are mixed and solidified by a carbonation reaction and a hydration reaction. In this solidified inorganic material (hereinafter, simply referred to as solidified), slaked lime (calcium hydroxide, Ca (OH) ₂ ) is subjected to calcium carbonate (CaCO ₃ ) by a carbonation reaction under a temperature condition of room temperature to less than 120 ° C. A) has been solidified. In a temperature range from room temperature to less than 120 ° C., weathered granite powders (Saba clay, Masago soil,
Also called henna soil. ) Undergoes a hydration reaction and CSH (CxSyH
z; is the meaning of _{xCaO · ySiO 2 · zH 2 O} . x, y
And z are positive numbers that can exist as a solid hydrate. ), CAH
_{(CxAyHz; xCaO · yAl 2 O} 3 · zH 2 O meaning a is .x of, y and z may be present as a solid hydrate positive number.), CASH (CwAxSyHz; wCaO · xA
It means l ₂ O ₃ .ySiO ₂ .zH ₂ O. w, x, y and z are positive numbers that can exist as solid hydrates. ) And solidified. The hydration product is 120
A temperature condition of less than 120 ° C. is preferable because a phase change accompanied by dehydration occurs at around ° C. and cracks are easily generated. It is considered that such a carbonation reaction and a hydration reaction proceed at the same time or almost at the same time, and promote the other reaction with each other.
Therefore, one of the calcium carbonate and the solid hydrate generated by these reactions reinforces the other phase,
It is believed that it produces a new solid hydrate or a hydrate carbonate intermediate in composition between calcium carbonate and solid hydrate. In addition, hydrate carbonate is CSH, CAH, CA
In some cases, Ca, Si or Al in a solid hydrate such as SH may be partially substituted with an alkali metal, an alkaline earth metal, a nonmetal element, or a transition element. Also,
The hydrate carbonate may be amorphous as well as crystalline.

As described above, since the solidified material is formed under the temperature condition of a normal temperature to less than 120 ° C., it is not necessary to heat it to a high temperature. For this reason, the consumption of energy for obtaining a solidified body such as an interior material, an exterior material, a roadbed, a skeleton floor, a skeleton wall, and a building can be suppressed as much as possible, and excellent environmental conservation can be exhibited. The solidified body of the present invention can be formed into a block shape such as an interblocking block or a tile shape such as an interior tile or an exterior tile. In such a block-shaped or tile-shaped solidified body, natural surface roughness exhibits the design of the structure. In addition, when exposed to rainwater or the like outdoors, the surface collapses relatively easily, further increasing the natural surface roughness, and providing an aesthetic appearance. On this occasion,
Alkali components such as Ca ²⁺ are eluted, which fertilizes the soil as a fertilizer, and also has an effect of not causing an adverse effect on the environment.

[0008] The solidified body may contain an aggregate so as to exhibit a desired strength. This aggregate includes sand, pebbles,
In addition to glass fibers and the like, concrete waste, ceramic waste and cullet can be used. Further, according to the test results of the inventors, the solidified product of the present invention is NaCl, MgCl ₂ , Fe ₂ O ₃ and Al (OH) ₃
It is preferable to include at least one of the following. NaCl and MgCl ₂ improve the strength of the solidified body.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As slaked lime, industrial lime can be employed. On the other hand, Table 1 shows the composition (% by mass) of those easily available as weathered granite powder.

[0010]

[Table 1]

From Table 1, the composition of the weathered granite powder is such that Al ₂ O ₃ is 7 to 17% by mass, alkali metal oxide and / or alkaline earth metal oxide is 2 to 10% by mass, and the ignition loss ( Ignition loss.
It is called ss. ) Is 1-6 wt%, SiO ₂ is substantially the balance, it can be recognized. Substantially means that it may contain Fe ₂ O ₃ , TiO _{2 and the} like. Among these, according to the test results of the inventors, the composition of the weathered granite powder is such that Al ₂ O ₃ is 9-1.
5% by mass, 3 to 9% by mass of alkali metal oxide and / or alkaline earth metal oxide, 1 to 3% by mass of Igloss, and substantially the remainder of SiO ₂ are preferable from the viewpoint of securing the strength of the solidified body. . The weathered granite powder contains Na ₂ O and K ₂ O as alkali metal oxides and CaO and MgO as alkaline earth metal oxides.
In addition, those containing Li ₂ O as an alkali metal oxide,
BeO, SrO or Ba as alkaline earth metal oxide
Those containing O may also be employed. According to XRD observation, the main constituent phases of the weathered granite powder are quartz, soda feldspar, orthoclase, mica, kaolin mineral and chlorite.
The powder may also include amphibolite as a constituent phase. FIG. 1 shows the particle size distribution (frequency (%), integrated amount (%)) of a part of the weathered granite powder shown in Table 1.

As a result of confirmation by the inventors, it is preferable that the granite powder has a small degree of weathering from the viewpoint of securing the strength of the solidified body. Weathering is a process in which rocks are altered and decomposed due to the effects of wind and rain, changes in temperature, and the presence of plants and bacteria. This weathering is thought to be manifested as partial clayification of the constituent phases. Partial calcification of the constituent phases firstly results in the formation of hydrates on the surface of the larger particle size powder, thereby producing a smaller particle size powder, and furthermore the hydrate formation on the entire powder surface. It is thought to proceed. For this reason, it is considered that Igloss shown in Table 1 relatively indicates the amount of hydrate present on the surface of the powder.
It is considered that the greater the amount of loss, the more weathering has progressed. In addition, the inventors confirmed the dehydration behavior of the granite powder by TG-DTA observation. As a result, dehydration reactions having peaks at around 60 ° C. and around 150 ° C. were obtained. It is believed that weathering is proceeding by forming halloysite or montmorillonite on the surface of the powder.

Further, it is considered that the solidified body of the present invention can improve the strength by including aggregates such as sand, pebbles, glass fibers, tile waste, and cullet. In this sense,
The maximum particle size of the weathered granite powder is preferably about 1/5 of the dimension in the load direction acting on the solidified body from the viewpoint of ensuring the strength of the solidified body. Since the solidified body usually needs a compressive strength of 5 MPa or more, it is preferable that the solidified body of the present invention is solidified by mixing slaked lime with 5% by weight or more. On the other hand, slaked lime is relatively expensive, and when the slaked lime is about 30% by weight, the compressive strength of the solidified body is almost saturated. Therefore, the solidified body of the present invention is solidified by mixing the slaked lime with 30% by weight or less. Is preferred.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments 1 and 2 embodying the present invention will be described below with reference to the drawings. (Example 1) "Preparation of preparation" Raw material 1 and slaked lime were mixed at a ratio (% by mass) shown in Table 2 using a mixer for mortar mixing,
Obtain each formulation 1-17. At this time, the amount to be mixed at a time was 5 kg at the maximum. Here, the raw material 1 is a weathered granite powder having a composition shown in Table 1.

However, in the preparations 13 and 14, 5 parts by mass of the powdery aluminum hydroxide was added to 85 parts by mass of the raw materials 1 and 1
It was simultaneously added to 0 parts by mass of slaked lime.

[0016]

[Table 2]

"Preparation of kneaded material"
Water and the like are added to Compounds 1 to 17. At this time, each formulation 1
The water content is set to 8% by mass with respect to 〜17. So
Then, knead with a mixer, corresponding to each formulation 1-17
To obtain the kneaded materials 1 to 17. However, Formulations 3, 6, 14
Then, 82.5 g of water and 15 g of NaCl and MgCl
_TwoNaCl and MgC as an aqueous solution dissolving 2.5 g
l_TwoWas added. This aqueous solution is close to the concentrated seawater.
Effective use of inexhaustible seawater
It is used to reduce manufacturing costs.

In formulation 5, 96.5 g of water was added to NaCl 3
g and 0.5 g of MgCl ₂ as an aqueous solution
Cl and MgCl ₂ were added. This aqueous solution also has a composition close to that of seawater. In formulation 7, 96.5 g of water contained M
MgCl ₂ was added as an aqueous solution in which 3.5 g of gCl ₂ was dissolved.

In Formulation 8, MgCl ₂ was added to 82.5 g of water.
MgCl ₂ was added as an aqueous solution in which 17.5 g was dissolved. In formulation 9 was added silicate ions as an aqueous solution containing SiO ₂ in water at a concentration 0.12%. This aqueous solution is a high Si solution generated by treating slag. In Formulation 10, 96.5 g of the high Si solution was mixed with 3 g of NaCl and MgC.
silicate ions as an aqueous solution obtained by dissolving l ₂ 0.5 g, Na
Cl and MgCl ₂ were added.

In formulation 11, 82.5 g of the above high Si liquid
Silicate ions, NaCl and MgCl ₂ were added as an aqueous solution in which 15 g of NaCl and 2.5 g of MgCl ₂ were dissolved. In Formulation 12, 82.5 g of the high Si liquid was added to Na
Cl 15 g, MgCl ₂ 2.5 g and NH ₃ at a concentration of 30%
Silicate ions, NaCl, MgCl ₂ and NH ₄ OH were added as an aqueous solution in which 2 g of aqueous ammonia containing the above was dissolved.

The curing agent added to the formulation 15 is liquid (about pH10.5 used for hardening of the concrete, Cl in water ^{-, Na +, K +,} NH 4 +, NO 3 - include such , Which has a pH buffering capacity), and is used to prevent the kneaded product 15 of the formulation 15 from becoming difficult to produce calcium carbonate and solid hydrate under acidic conditions. A commercially available stock solution was added at the time of kneading so that the water content in the curing agent was 3 parts by mass with respect to 100 parts by mass of Formulation 15.

Formulation 16 has a concentration of 50% and a commercially available water glass (a soda-based water glass according to JIS K1408 No. 3; 28 to 30% by mass of SiO _{2 and} 9 to 10% of Na ₂ O).
Water glass was added as an aqueous solution containing 0.1% by mass, Fe ₂ O ₃ less than 0.02% by mass, and water as the balance. In formulation 17, 82.5 g of water, 15 g of NaCl, and 2.5 Cl of MgCl ₂
NaCl, MgCl ₂ and NH ₄ OH as an aqueous solution in which 2 g of ammonia water containing NH ₃ at a concentration of 30% are dissolved.
Was added. “Molding and solidification of kneaded material” Each of the kneaded materials 1 to 17 is filled in a triple mold for mortar test with the same mass, and the mixture is mixed with a hydraulic press.
Uniaxial pressure molding is performed at 0 MPa. Thereby, each kneaded material 1
The gap between particles 17 is reduced to bring the particle interface closer. Thus, 200 × 1 corresponding to each kneaded material 1 to 17
00 × molding 1 of tile shape of the molded body 1 to 17 and 160 × 40 × about 20 mm ³ of block-shaped about 60 mm ³
~ 17.

Then, a temperature of 25 ° C. and a humidity (RH) of 80
% In a constant temperature / humidity chamber for 7 to 28 days.
Perform curing of ~ 17. In this way, block-shaped and tile-shaped solidified bodies 1 to 17 corresponding to the respective molded bodies 1 to 17 are obtained. [Evaluation] For each of the solidified bodies 1 to 17, the bending strength (MPa), the compressive strength (MPa) and the bulk density (g / cm ³ ) with the increase in the curing days were measured, and the formed phase was confirmed.

The bending strength was measured using a material testing machine (A
& D TENSILON RTM-500)
Support point interval 120mm, crosshead speed 0.5mm
/ Min by three-point bending. The compression strength was measured using an electronic universal testing machine (CATY YONEKURA), using one solidified body after the bending strength test, at a crosshead speed of 0.5 mm / min. Confirmation of the generated phase is as follows: powder X
XR using X-ray diffractometer (RIGAKU RAD-B)
D.

The measured bending strength is shown in Table 3 and FIG.

[0026]

[Table 3]

The measured compressive strength is shown in Table 4 and FIG.

[0028]

[Table 4]

From Tables 3 and 4 and FIGS. 2 and 3, it can be seen that the compression strength of the solidified product increases with time in other formulations compared to Formulation 1 in which no additive is added. I understand. In addition, solidified bodies 3, 5, 6, 7, 8, 10, 1
In Examples 1, 12, 14, and 17, it is also understood that chloride can be added to these preparations, so that high compressive strength can be exhibited. Further, by adding an alkali metal compound or an alkaline earth metal compound, it is possible to secure a stable compressive strength of the solidified body by promoting the carbonation reaction while reducing the degree of improvement in the compressive strength of the solidified body over time. Understand. It can also be seen that the addition of silicate or aluminate increases the degree of improvement in the compressive strength of the solidified body over time and ensures a stable solidified compressive strength by accelerating the hydration reaction.

The measured densities are shown in Table 5 and FIG.

[0031]

[Table 5]

From Table 5 and FIG. 4, it can be seen that when the amount of slaked lime with respect to the raw material 1 increases, the bulk specific gravity of the solidified body decreases due to the true specific gravity of slaked lime. Also, 10% by mass of raw material 1
In the solidified product obtained by mixing slaked lime, after curing for 28 days, the bulk density is 1.97 to 2.02 g / c.
m ³ , and if the slaked lime is mixed at 10% by mass, the bulk density of the solidified product seems to be settled at 1.95 to 2.05 g / cm ³ . If 10% by mass of slaked lime is mixed in this way, the bulk density of the solidified body does not change much, but the strength of the solidified body is significantly increased by the addition of other components, especially by the addition of Al (OH) ₃ . Thereby, other components, in particular, Al (OH) ₃
May be due to the formation of a solid hydrate.

When the formed phase was confirmed, the total solids 1 to 1
7, the formation of Ca ₄ Al ₂ O ₆ CO ₃ 11H ₂ O was confirmed. Thus, it is considered that these solidified bodies 1 to 17 exhibit a new solid hydrate that cannot be originally produced from the raw material 1 and exhibit high strength. In addition, solidified bodies 1, 2, 4
, The peak intensities of Ca (OH) ₂ and CaCO ₃ increased. This is because the content ratio of slaked lime is increasing. On the other hand, solidified bodies 3, 5, 6, 7, 8, 10, 1
In 1, 12, 14, and 17, Ca ₄ Al ₂ O ₆ Cl ₂ 10H
Generation of ₂ O was confirmed. This is because chloride is added. Further, the peak intensity of CaCO _3, appears to qualitatively generation of CaCO ₃ by the addition of chloride is promoted.

Therefore, according to each of the formulations 1 to 17,
It can be seen that solidification proceeds at room temperature and solidified bodies 1 to 17 can be obtained. For this reason, by using such formulations 1 to 17, it is possible to obtain a solidified body such as an interior material without heating to a high temperature, and it is possible to suppress the consumption of energy for obtaining the solidified body as much as possible. Environmental protection can be demonstrated.

The solids 1 and 8 on the 7th day of curing were subjected to CO ₂
Quantification (JIS R9011) was performed to evaluate whether or not the additive promotes carbonation. The amount of CO _{2 was} determined for each solid 1, 8
Of CO _{2 by} mass (%). Further, the molar reaction rate (%) of Ca and CO ₂ calculated on the assumption that all of the CO ₂ in each of the solidified bodies 1 and 8 had reacted with Ca was also obtained.
Table 6 shows the results.

[0036]

[Table 6]

From Table 6 and the like, it can be seen that the strength of the solidified body due to chloride tends to be increased by adding chloride, and by increasing the amount of chloride added, the strength of solidified body in the early stage of curing is increased. It can be seen that it can be promoted. It is considered that the reason for this is that the addition of chloride to the preparation promotes the formation of carbonate in the solidified product. Generation of carbonate in the sea is caused alkali such as dissolved CO ₂
Is believed to occur because of the increase in solubility of Na, Mg in the formulation to which chloride is added, so that the solubility of CO _{2 in} the formulation increases, and Ca ²⁺ and CO ₃ ^2- It is considered that the reaction precipitation was promoted. (Example 2) "Preparation of preparation" As in Example 1, the raw material 1 and slaked lime were mixed at the ratio (% by mass) shown in Table 7, and each of the preparations 18 to 2 was prepared.
Get 3. Here, the raw material 1 is a weathered granite powder having a composition shown in Table 1.

[0038]

[Table 7]

"Preparation of kneaded material" Then, as in Example 1, water was added to each of the preparations 18 to 23 so that water was 8% by mass with respect to each of the preparations 18 to 23. ~ 2
The respective kneaded materials 18 to 23 are obtained corresponding to 3. "Molding and solidification of kneaded material" Further, similarly to Example 1, the respective kneaded materials 18 to 23 are uniaxially press-molded to obtain molded bodies 18 to 23 corresponding to the respective kneaded materials 18 to 23.

Then, a temperature of 25 ° C. and a humidity (RH) of 80
% In a constant temperature / humidity chamber for 7 days.
Perform 3 curing. Thus, solidified bodies 18 to 23 are obtained corresponding to the respective molded bodies 18 to 23 (n = 3). "Evaluation" The relationship between the ratio (mass%) of slaked lime and the compressive strength (MPa) was determined from each of the solidified bodies 18 to 23. The results are shown in Table 7 and FIG. The error bars in FIG. 5 indicate the maximum value and the minimum value at n = 3. The compression strength was measured using an electronic universal tester (CATY YONEKUR).
A) was performed at a crosshead speed of 0.5 mm / min.

As shown in Table 7 and FIG. 5, the compression strength of the solidified product 18 was 1.0 MPa, which was not practical, whereas the solidified product 1 had a compressive strength of 1.0 MPa.
In the case of 9 to 23, the compressive strength is 5 MPa or more which is practical.
The compressive strength is almost saturated near the solidified body 21 in which slaked lime is 30% by weight. For this reason, it turns out that it is preferable to manufacture a solidified body by using a formulation in which slaked lime is mixed at 5% by weight or more. In particular, since slaked lime is relatively expensive, it can be seen that it is preferable to produce a solidified body by using a mixture in which slaked lime is mixed at 30% by weight or less.

[Brief description of the drawings]

FIG. 1 shows the particle size distribution of weathered granite powder.
(A) is a graph showing the relationship between the particle size and the frequency, and (B) is a graph showing the relationship between the particle size and the integrated amount.

FIG. 2 is a graph showing a change in bending strength of a solidified body with an increase in the number of curing days according to Example 1.

FIG. 3 is a graph showing a change in compressive strength of a solidified body with an increase in the number of curing days in Example 1.

FIG. 4 is a graph showing a change in bulk density of a solidified body with an increase in the number of curing days in Example 1.

FIG. 5 is a graph showing a relationship between a ratio of slaked lime and a compressive strength of a solidified body according to Example 2.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Hiroto Susumu 5-1-1 Koiehonmachi, Tokoname-shi, Aichi F-term in Inax Corporation (reference) 4G012 PA04 PB03 PC01

Claims (6)

[Claims] 1. A solidified inorganic material obtained by mixing slaked lime and weathered granite powder and solidifying them by a carbonation reaction and a hydration reaction. 2. The composition of weathered granite powder is Al ₂ O ₃
Is 7 to 17% by mass, alkali metal oxide or / and alkaline earth metal oxide is 2 to 10% by mass, and ignition loss is 1 to
6 wt%, the inorganic material solidified body according to claim 1, wherein SiO ₂ is characterized by a substantially balance. 3. The composition of the weathered granite powder is Al ₂ O ₃
Is 9 to 15% by mass, alkali metal oxide and / or alkaline earth metal oxide is 3 to 9% by mass, and ignition loss is 1 to 3%.
The solidified inorganic material according to claim ₂ , wherein the mass% and SiO2 are substantially the balance. 4. The constituent phase of the weathered granite powder is quartz,
The solidified inorganic material according to claim 1, 2 or 3, wherein the solid is soda feldspar, feldspar, mica, kaolin mineral and chlorite. 5. The solidified inorganic material according to claim 1, wherein the inorganic material has a block shape. 6. The solidified inorganic material according to claim 1, wherein the inorganic material has a tile shape.