Hydraulic hardened body and production method thereof
A hydraulically cured body made from blast furnace slag, silica fume, and alkaline stimulants, combined with pigments, addresses the challenges of color and strength in artificial stones, offering a cost-effective and environmentally friendly alternative to cement-based materials.
Patent Information
- Application Number
- JP2023180914
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-10-20
- Publication Date
- 2025-05-02
AI Technical Summary
Artificial stones that use a large amount of cement struggle to express vivid colors due to the gray color of cement, and existing alternatives like white cement are expensive and not domestically manufactured, while concrete alternatives lack sufficient strength for applications beyond paving.
A hydraulically cured body composed of blast furnace slag, silica fume, an alkaline stimulant, and pigment, which eliminates the need for cement, allowing for excellent color development and strength while being economically viable.
The solution achieves excellent color development and strength comparable to or exceeding that of natural marble and granite, while being more economical and environmentally friendly than traditional cement-based solutions.
Smart Images
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Abstract
Description
[Technical field]
[0001] The present invention relates to a hydraulically hardened product and a method for producing the same. [Background technology]
[0002] Natural stone materials such as marble are becoming difficult to obtain due to resource depletion and restrictions on crushing. For this reason, construction and civil engineering materials that can replace natural stone materials are being considered. A representative artificial stone material is artificial marble called terrazzo. White cement is also used as an alternative material to natural stone materials because it has a strong white color and excellent design properties. Non-Patent Document 1 describes that concrete that is whiter than general concrete can be manufactured by hardening ground granulated blast furnace slag with a calcium-based compound. The same document also describes that concrete manufactured in this way can be mixed with pigments to achieve various textures. [Prior art documents] [Non-patent literature]
[0003] [Non-Patent Document 1] Satoshi Watanabe, Eiji Owaki, Shusuke Kuroiwa, "Development of Architectural Finishing Materials Using Environmentally Friendly Concrete", Proceedings of the Architectural Institute of Japan Annual Meeting, August 2019, P553-554 Summary of the Invention [Problem to be solved by the invention]
[0004] Artificial stone materials that use a large amount of cement have difficulty expressing vivid colors because the cement itself is gray. White cement has excellent color development, but it is not produced domestically and is generally expensive. The concrete described in Non-Patent Document 1 does not have sufficient strength and is limited to applications such as paving.
[0005] An object of the present invention is to provide a hydraulic hardened product which is excellent in color development and strength and is economical. [Means for solving the problem]
[0006] The hydraulic hardened body of the present invention contains a powder and water, and the powder contains blast furnace slag, silica fume, and an alkaline activator. Effect of the Invention
[0007] According to the present invention, it is possible to provide an economical hydraulic hardened product which is excellent in color development and strength. [Brief description of the drawings]
[0008] [Figure 1] FIG. 1 is a diagram illustrating lightness and saturation. [Diagram 2] FIG. 1 is a diagram showing the relationship between saturation and brightness in Comparative Examples 1 and 2 and Examples 1 to 3. [Diagram 3] FIG. 13 is a diagram showing the relationship between saturation and brightness in Comparative Examples 3 and 4 and Examples 4 to 6. [Figure 4] FIG. 13 is a graph showing the distribution of a and b values for Comparative Examples 3 and 4 and Example 4. [Diagram 5] FIG. 1 is a diagram showing the relationship between bending strength and compressive strength. [Figure 6] This is a photograph of a decorative item made from a water-soluble hardened material containing coarse aggregate and glass cullet. [Figure 7] This is a photo of an ornament made using a silicone mold. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0009] The present invention will be described below based on examples. Table 1 shows the materials used in the water-soluble hardened bodies of Examples 1 to 6 and Comparative Examples 1 to 4, and Table 2 shows the compositions of Examples 1 to 6 and Comparative Examples 1 to 4. Although omitted in Table 2, a high-performance water reducing agent (SF) and an antifoaming agent (AF) shown in Table 1 were added to Examples 1 to 6 and Comparative Examples 1 to 4. The mass ratios in Table 2 are ratios when water is taken as 1. Table 3 shows the presence or absence of pigments and the color patterns of pigments in Examples 1 to 6 and Comparative Examples 1 to 4. As shown in Table 3, samples containing pigments and samples not containing pigments were prepared in Examples 1 to 6 and Comparative Examples 1 to 4, and further, for the samples containing pigments, a plurality of samples with different pigment colors were prepared. The samples in Examples 1 to 6 and Comparative Examples 1 to 4 are flat blocks. The water-powder ratio (W / P) of Comparative Examples 1 and 2 and Examples 1 to 3 is 40, and the W / P of Comparative Examples 3 and 4 and Examples 4 to 6 is 14. The samples in Examples 1 to 6 and Comparative Examples 1 to 4 were prepared by casting the materials into a formwork and then curing them at high temperatures. Specifically, after completion of pouring, the concrete was cured at 20°C for two days, and then heat cured at 90°C for five days.
[0010] [Table 1]
[0011] [Table 2]
[0012] [Table 3]
[0013] Examples 1 to 6 and Comparative Examples 1 to 4 contain powder and water. Comparative Examples 1 to 4 use cement as the powder, while Examples 1 to 6 do not use cement. Comparative Examples 1 and 3 use Portland cement (NC), and Comparative Examples 2 and 4 use white cement (WC). Cement generates carbon dioxide during the manufacturing process, so Comparative Examples 1 to 4 generate carbon dioxide during manufacturing. In contrast, Examples 1 to 6 do not basically generate carbon dioxide during manufacturing, so they have environmentally friendly compositions.
[0014] Examples 1 to 6 contain blast furnace slag (BF4, BF6), silica fume (SF), and an alkaline stimulant as powders, and further contain a pigment (CP). Examples 1 and 4 further contain fly ash as powders, and Examples 2 and 5 further contain calcium carbonate as powders. The blast furnace slag (BF4) used in Examples 1, 2, 5, and 6 is ground granulated blast furnace slag 4000 as specified in JIS A6206:2013 "ground granulated blast furnace slag for concrete", and the blast furnace slag (BF6) used in Examples 3 and 6 is ground granulated blast furnace slag 6000 as specified in the above JIS. The specific surface area of ground granulated blast furnace slag 4000 is 3500 cm 2 / g or more but less than 5000, and the specific surface area of ground granulated blast furnace slag 6000 is 5000 cm 2 / g or more and less than 7000. Comparative Examples 1 and 2 do not contain silica fume, and Comparative Examples 3 and 4 contain silica fume.
[0015] The alkaline stimulant increases the pH of the surface of the ground granulated blast furnace slag, causing a hydration reaction similar to that of cement. The alkaline stimulant is not particularly limited as long as it has the property of increasing the pH, but an expanding agent (Ex) was used in Examples 1 to 6. In Comparative Examples 1 to 4, an alkaline stimulant is not necessary, so no expanding agent was used. A powder-based pigment was used. Therefore, although the powder contains a pigment in Examples 1 to 6 and Comparative Examples 1 to 4, the pigment is not limited to a powder, and may be, for example, a liquid. The pigment may be either inorganic or organic, but an inorganic pigment was used in Examples 1 to 6 and Comparative Examples 1 to 4. The mass ratio of the pigment to the powder is about 5%, but the mass ratio can be selected from a range of 3% to 10%.
[0016] The color development properties of Examples 1 to 6 and Comparative Examples 1 to 4 were measured. Specifically, the lightness and chroma of each sample were measured using a spectrophotometer CR-20 manufactured by Konica Minolta. Here, lightness and chroma will be briefly explained. * a * b * It shows the concept of color space. * a * b *The color space is specified in JIS 8781-4 "Colorimetry - Part 4: CIE 1976 L*a*b* Color Space". The hue is a * and b * and saturation C is expressed as √(a 2 +b 2 ) is expressed as L * represents the lightness, and is specified by a value ranging from 0, which is the darkest, to 100, which is the brightest. Therefore, saturation C and lightness L * The larger the value, the more vivid the color and the better the color development.
[0017] FIG. 2 shows the relationship between chroma and lightness for Comparative Examples 1 and 2 and Examples 1 to 3 when W / P=40%. FIG. 2(a) shows the results for a sample that does not contain pigment, and FIGS. 2(b) to 2(g) show the results for samples that contain pigments of each color (white, yellow, black, red, brown, and green, respectively). If both chroma and lightness are higher than Comparative Example 1, which used Portland cement (NC), the color development can be evaluated as good, and even if only one of them is higher than Comparative Example 1, the color development can be evaluated as equivalent to Comparative Example 1. Regardless of the presence or absence of pigment, Examples 1 to 3 generally showed color development equal to or better than Comparative Example 1, which used Portland cement (NC).
[0018] FIG. 3 shows the relationship between chroma and lightness for Comparative Examples 3 and 4 and Examples 4 to 6 when W / P=14%. FIG. 3(a) shows the results for a sample that does not contain pigment, and FIGS. 3(b) to 3(g) show the results for samples that contain pigments of each color (white, yellow, black, red, brown, and green, respectively). If both chroma and lightness are higher than Comparative Example 4, which used Portland cement (NC), the color development can be evaluated as good, and even if only one of them is higher than Comparative Example 1, the color development can be evaluated as being equivalent to Comparative Example 4. Even when W / P=14%, Examples 4 to 6 generally showed color development equal to or better than Comparative Example 4, which used Portland cement (NC).
[0019] Examples 1 to 6 showed similar color development compared to Comparative Examples 2 and 4 using white cement (WC). In particular, when W / P=14%, many samples showed better color development than Comparative Example 4. Comparing W / P=40% and W / P=14%, W / P=40% was slightly better in color development. However, W / P=14% is more advantageous in terms of strength and quality of the hydraulic hardened body. It is believed that the structure was densified and strength was increased by reducing W / P and curing at high temperature. It is believed that the same color development and strength can be secured even if W / P is slightly lower than 14% in Examples 4 to 6, so W / P is preferably selected from the range of 12% to 40%, and more preferably selected from the range of 12% to 20%.
[0020] Figure 4 shows the distribution of a-values and b-values for Comparative Examples 3 and 4 and Example 4. Specifically, the a-values and b-values for samples containing pigments of each color are plotted and connected with a line. Group A is samples containing red pigment, group B is samples containing yellow pigment, and group C is samples containing green pigment. When viewed by color, it can be seen that Example 4 is equal to or better than Comparative Example 3, which used Portland cement (NC), and is also roughly equal to Comparative Example 4, which used white cement (WC).
[0021] Next, the strength of the water-soluble hardened body was evaluated. Table 4 shows the materials used for the water-soluble hardened body of Examples 7 and 8, and Table 5 shows the composition of Examples 7 and 8. Although omitted in Table 5, the high-performance water reducing agent (SF) and antifoaming agent (AF) shown in Table 4 were added to Examples 7 and 8. The W / P was set to 14%. Example 7 corresponds to Example 4 without fly ash, and Example 8 corresponds to Example 4. Although no pigment was added in Examples 7 and 8, the presence or absence of pigment is considered to have no significant effect on the strength. Figure 5 shows the relationship between the bending strength and compressive strength (material age 4 weeks) of Examples 7 and 8. The comparative example is the bending strength and compressive strength of concrete described in Non-Patent Document 1, and the bending strength and compressive strength of marble and granite are plotted from the data described in "Standard Specifications for Building Construction and Commentary JASS9 Stonework" by the Architectural Institute of Japan, and the average values of these are also shown. From this, it can be seen that the bending strength and compressive strength of Examples 7 and 8 are equal to or greater than those of natural marble and granite, and are superior to the comparative examples.
[0022] [Table 4]
[0023] [Table 5]
[0024] As described above, the water-soluble hardened body of this embodiment is excellent in color development and strength. The materials used are relatively inexpensive, so it is also economical. The water-soluble hardened body contains powder, water, and pigment, but it is not essential to contain pigment. That is, as shown in Figures 2(a) and 3(a), it may show the same brightness and chroma as white cement even without pigment, and it is a substitute for expensive white cement. In addition, it is needless to say that the combination of pigments is not limited at all, and various color tones can be realized by combining two or more of the above-mentioned white, yellow, black, red, brown, and green pigments.
[0025] The water-soluble hardened product of the present invention is generally used containing aggregate as shown in Examples 7 and 8, but may be used as a cement paste without containing aggregate as shown in Examples 1 to 6. The presence or absence of aggregate is considered not to have a significant effect on color development. Although Examples 1 to 6 do not contain cement, a small amount of cement may be contained. Since the base color of cement is gray, the color development deteriorates when used in large amounts. However, it is possible to use an amount of cement that is sufficient to replace an expansive agent (approximately 3% to 10% by mass relative to the powder). The water-soluble hardened product of the present invention can be used as mortar containing only fine aggregate as aggregate, or as concrete containing fine aggregate and coarse aggregate as aggregate. When used as concrete, the water-soluble hardened product of the present invention can also be used as a structural material for buildings and the like. The fine aggregate can contain ferronickel slag fine aggregate to prevent shrinkage and cracking.
[0026] The water-soluble hardened body of the present invention may also contain glass cullet. Glass cullet is crushed waste glass and is used for paving blocks, etc. In addition to transparent cullet, there are also colored types, and by combining these with pigments (or by using them alone without combining them with pigments), it is possible to express a variety of colors. Figure 6 shows a ball-shaped decorative item made from a water-soluble hardened body containing coarse aggregate and glass cullet. There are no limitations on the aggregate to be contained in the water-soluble hardened body, and it is sufficient that it contains at least either fine aggregate or coarse aggregate.
[0027] The water-soluble hardened material of the present invention can be applied not only to architectural finishing materials, but also to new fields such as ornaments, for example, by filling a silicon-based formwork and hardening it. Figure 7(a) shows the back of a silicon formwork and an ornament made from the water-soluble hardened material filled in the formwork, and Figure 7(b) shows a partial front view of an ornament made from the hardened water-soluble hardened material. Dimension A in Figure 7(b) is about 1 cm, but the water-soluble hardened material of the present invention has good fluidity, so it is possible to express even the smallest details.
Claims
1. A hydraulic hardening body comprising a powder and water, the powder comprising blast furnace slag, silica fume and an alkaline activator.
2. The hydraulically cured body according to claim 1 , further comprising a pigment.
3. The hydraulic hardened body according to claim 1 or 2, wherein the powder contains fly ash.
4. The hydraulic hardened body according to claim 1 or 2, wherein the powder contains calcium carbonate.
5. The hydraulically hardened body according to claim 1 or 2, wherein the powder does not contain cement.
6. The hydraulic hardened body according to claim 2 , wherein the powder contains the pigment, and a mass ratio of the water to the powder is 12% or more and 40% or less.
7. The hydraulic hardened body according to claim 2 , wherein the powder contains the pigment, and a mass ratio of the water to the powder is 12% or more and 20% or less.
8. The hydraulic hardened body according to claim 2 , wherein the powder contains the pigment, and a mass ratio of the pigment to the powder is 10% or less.
9. 3. The hydraulic hardened body according to claim 1, further comprising glass cullet and at least one of fine aggregate and coarse aggregate.
10. 3. The hydraulic hardened body according to claim 1 or 2, which contains ferronickel slag fine aggregate.
11. A method for producing a hydraulically hardened product, comprising filling the hydraulically hardened product according to claim 1 or 2 into a silicone mold and hardening the product.