JP2592887B2 - Inorganic cured product and method for producing the same - Google Patents

Description

The present invention relates to an inorganic cured product and a method for producing the same. More specifically, the present invention aims at effective use of steel slag and the like with high added value, and relates to an inorganic cured product using a hydraulic slag powder containing a boron component as a binder and a component method thereof.

[Conventional technology] Various metallurgical slags such as blast furnace slag, ferroalloy slag, and metal magnesium slag have a main composition of basic calcium silicate, and their powders, especially granulated slag powder, have latent hydraulic properties. It is well-known that it is used as a cement material as represented by blast furnace cement.

However, usually, such slag itself is not practically used simply because the hydraulic reaction itself is slow.

Therefore, when using such slag as a cement material, together with cement such as Portland cement or alumina cement or quick lime, slaked lime, alkali stimulants such as alkali metal compounds, gypsum, calcium chloride, sulfate, other auxiliary agents, etc. The cement composition is extremely diverse and many proposals have been made and put to practical use.

[Problems to be Solved by the Invention] Conventionally, in the use of a typical blast furnace slag for a cement material, a cement composition in a combination use of the slag and other components often has a drawback due to compounding in many cases. Has less characteristics and lower performance than Portland cement.

By the way, the present inventors have found that there is a significant modification of slag by adding boron-containing glass to a slag melt for the purpose of modifying the slag in relation to the so-called powdering problem of steelmaking slag, We succeeded in paving the way for use in cement (Japanese Patent Application No. 61-324881). However, the hydraulic strength of the modified slag itself is insufficient, and there is room for improvement for practical use.

[Means for Solving the Problems] Furthermore, the present inventors have found that the hydraulic slag powder containing a boron component mixed with active silica and hardened has improved strength and surprisingly deteriorated the strength of the molded article. The present inventors have found that they have sufficient fire resistance without performing the present invention, and have completed the present invention.

That is, the present invention relates to a hydraulic composition containing a boron component-containing hydraulic slag powder, activated silica and an aggregate.
The present invention relates to a cured inorganic material characterized by being formed.

Further, the present invention relates to mixing a composition comprising a hydraulic slag powder containing a boron component, activated silica and an aggregate with an appropriate amount of water, and then subjecting the frame filled with the composition to vibration to form a hydraulically molded article. And a method for producing a cured inorganic material.

[Operation] The inorganic hardened product according to the present invention is not a powder of steel slag or the like having ordinary hydraulic properties as described above, but uses a modified hydraulic slag containing a boron component and activated silica as a binder. It is characterized by the fact that it is mixed with an aggregate and hydraulically and molded.

Here, the boron component-containing hydraulic slag powder is not simply a mixture of ordinary steel slag and other powders with a boron component, but a modified slag melt to which the boron component has been added. It was done.

Such slag powder can be applied to any of the slowly cooled crystalline or water-cooled vitreous powders depending on the composition, although they have hydraulic properties. It is preferable from the viewpoint of.

In addition, the slag powder is preferably highly basic in order to have reactivity with active silica and good hydraulic properties, and particularly in a (CaO + MgO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) weight ratio. basicity represented is a 1.5 to 3.0, and the slag powder having a composition 0.1-5.0% by weight boron component in terms _of B ₂ O ₃ and fluorine component contains 0-10% by weight F are preferred.

Further, the slag powder is preferably as fine as possible, and in many cases, the slag powder has a Blaine specific surface area value in the range of 2000 to 6000 m ² / g.

Such slag powder is not particularly limited as long as it is within the range of the above composition, for example, steelmaking slag such as stainless steel, converter slag, ferrochrome, ferroboron, ferroalloy slag such as ferrosilicon, and other slag such as magnesium smelting slag and the like. Which are modified with a boron component.

Whether or not the slag has been modified by the boron component can be grasped by the presence and degree of the powdering phenomenon and the hydraulic property during the slow cooling of the slag.

The powdering phenomenon of highly basic slag is caused by α'-2CaO.
It is thought to be due to volume expansion accompanying the transformation of SiO ₂ component to γ type and hydration reaction of free calcium component (CaO),
When a boron component is contained, the phenomenon is suppressed and hydraulic property is developed.

In the present invention, it is important that the content of B ₂ O ₃ is 0.1 to 5% by weight.
A range of weight percent is preferred. Further, the slag powder may contain a fluorine component due to its properties. When the slag powder contains a fluorine component, the content is preferably 3 to 10% by weight.

Next, active silica is another component of the inorganic cured product according to the present invention, which is an essential component for improving the physical properties of the inorganic cured product.

Here, active silica refers to a silica raw material that causes a so-called hozolan reaction to neutralize the calcium component in the boron component-containing hydraulic slag powder in the presence of water, for example, ferrosilicon dust, fumed silica, silica sol, Activated clay and the like are mentioned, and particularly, ultrafine silica such as ferrosilicon dust and fumed silica is preferable.

The aggregate is not particularly limited, but natural crushed stones such as silica stone and pyroxene, refractory crushed products such as chamotte particles, and slowly cooled crushed slag products are practical. Although it differs depending on the size and use of the body, if it is a panel molded body, it is preferable that 90% or more have a thickness of 0.1 to 10 mm.

Accordingly, the inorganic cured product according to the present invention is a hydraulic / molded product of a formulation composed of the boron component-containing hydraulic slag powder, activated silica and aggregate as described above, and the composition is the same as that of the cured product. It is not uniform depending on the application and the physical properties of the raw material components.

However, in many cases, 5 to 50 parts by weight of activated silica and 10 parts by weight of aggregate per 100 parts by weight of hydraulic slag powder containing boron component
It is a hydraulic product of a composition composed of 10001000 parts by weight.

Therefore, in the inorganic cured product, active silica has undergone a horazone reaction, and it is presumed that free silica is substantially absent, and even if present, it is slight.

Since the inorganic cured product according to the present invention is a hydraulic product, it can be said that it belongs to one type of cement molded product in that sense. However, unlike ordinary cement molded products, water (W) and cement (C ), Which has a small so-called W / C ratio, is hydraulically hardened with a small amount of water, and has a remarkably low heat of hydration.

Also, surprisingly, ordinary cement molded products are hydraulically molded products, so that when heated, strength is deteriorated, so that not only the fire resistance, but also the heat resistance is not common, but the inorganic material according to the present invention is not generally used. The cured body has heat resistance and fire resistance,
Heating at about 1000 ° C. has the property of improving strength rather than thermal degradation.

Therefore, for example, the cured body according to the present invention heated at 800 to 1100 ° C. can be considered to have been converted from hydraulic strength to sintered strength. It can be called a molded body,
In other words, it can be said that this is a unique inorganic cured product that has both cementability and ceramic properties.

Such characteristics exhibit excellent curing in that the cured body according to the present invention is surface-decorated.

For example, it is difficult to apply a glaze to a normal cement molded product with dehydration, but the inorganic cured product according to the present invention has substantially no cracks due to the glaze by the flame spraying as well as the glaze by the ordinary heating furnace. A beautiful hardened glaze can be obtained.

Next, as described above, the inorganic cured product according to the present invention is obtained by mixing the raw material mixture with an appropriate amount of water, then pouring the mixture into a mold, and then vibrating the frame to hydraulically harden. Can be manufactured as a feature.

In this case, the amount of water is 5 to 3 per 100 parts by weight of the raw material mixture.
0 parts by weight, often 6 to 20 parts by weight, which is significantly lower than in the case of ordinary cement.

In addition, when kneading the raw material mixture with water, a known dispersant and / or foaming agent commonly used in the case of cement can be used in combination as necessary.

Further, if necessary, a colorant and an organic or inorganic short fiber can be blended.

Although the raw material mixture can be poured into a frame and cured by static curing to form an inorganic cured product, the present invention effectively promotes the hydraulic reaction by the horazone reaction and the hydration reaction to achieve desired molding. In order to obtain strength, it is important and preferable to perform vibration molding.

In the present invention, since the hydraulic reaction is extremely rapid, efficient work can be performed, and after curing, the product can be demolded and dried by natural standing or, if necessary, cured by heating and drying to obtain a product. .

In the production of the inorganic cured product according to the present invention, the shape is not particularly limited, and a plate-like panel, a rectangular parallelepiped such as a brick, a cube, a cylinder, a column, an arbitrary cured product such as a trapezoid, if necessary. Can be manufactured.

[Examples] Hereinafter, examples will be described in order to specifically explain the present invention.

Example 1 The material used in this example has the following composition.

◎ Modified stainless steel slag Burele specific surface area 3000cm ² / g Composition component wt% CaO 46.4 SiO ₂ 16.8 Al ₂ O ₃ 14.6 MgO 10.7 Fe ₂ O ₃ 2.2 Cr ₂ O ₃ 2.1 F 6.8 B ₂ O ₃ 0.5 ◎ Silica fine powder Dust [commonly known as silica fume: manufactured by Nippon Heavy Chemical Industry Co., Ltd.] Composition component weight% SiO ₂ 91.5 Fe ₂ O ₃ 3.0 K ₂ O 2.0 Al ₂ O ₃ 1.5 C 0.8 MgO 0.7 ◎ Chamotte Composition component weight% SiO ₂ 60.3 Al ₂ O ₃ 34.2 Fe ₂ O ₃ 2.1 K ₂ O 2.0 MgO 0.2 Particle size sieve (mm) passage rate (%) 5.0 100 2.5 90 1.2 65 0.6 35 0.3 20 0.15 12 ◎ Normal bolt land cement Composition component Weight% CaO 64.0 SiO ₂ 22.3 Al ₂ O ₃ 5.5 Fe ₂ O ₃ 2.9 MgO 1.7 A mixture was obtained by mixing the above-mentioned materials in the mixing ratio shown in Table 1 below with the modified stainless slag containing the boron component having the above composition, Further, water and an appropriate amount of a dispersant were added and kneaded for 5 minutes to conduct a flow test.

For comparison, a flow test was performed using ordinary Portland cement.

 The results obtained are shown in Table 1.

From the results in Table 1, it can be seen that the mixture using the modified stainless slag improves the fluidity when silica fume is mixed at 4 to 10%, but the ordinary fluidity of Portland cement deteriorates and the same fluidity is obtained. It can be seen that the amount of water required to obtain is half that of ordinary Portland cement.

After adding water and an appropriate amount of a dispersant to the composition having the compounding ratio shown in Table 1 above and kneading the mixture, the mixture is poured into a mold (width × thickness × length = 40 × 10 × 150 mm), and the table is vibrated. After compacting for about 1 minute with a machine, the mold was covered with a vinyl sheet to prevent evaporation of water from the surface, cured at room temperature for 24 hours and demolded to obtain a cured inorganic material. A bending test was performed under the following conditions. Table 2 shows the obtained results.

Firing material age: 1 day Firing temperature and time: firing at 850 ° C for 5 minutes in an electric furnace, taken out of the electric furnace, cooled to room temperature, and then subjected to a bending test.

Bending test method: Span l = 12 cm, strain rate 0.5 mm / min (constant), and measurement was performed with centrally loaded. The measured values were each an average value of three specimens.

From Table 2 above, in the cured inorganic material of the present invention using the modified stainless slag, the one baked by mixing silica fume shows high bending strength, but the cured inorganic material using ordinary Portland cement has It can be seen that the bending strength after firing is low even when silica fume is mixed or not.

Example 2 Modified stainless slag 85 having the same composition as in Example 1
Parts by weight, silica fume 15 parts by weight, aggregate (chamotte)
An appropriate amount of a dispersant was added to 150 parts by weight of water and 19 parts by weight of water, and molded in the same manner as in Example 1 to obtain an inorganic cured product of the present invention. As shown in FIG.

For comparison, the test results of the inorganic hardened material using ordinary Portland cement are also shown.

Drying (firing) material age: 1 day Drying (firing) temperature / time: 5 hours at the temperature shown in Table 3.

Bending test method: Same as in Example 1.

In addition, the comparative product using ordinary Portland cement was tested on the age of 3 days.

From Table 3, it can be seen that the bending strength of the product of the present invention using the modified stainless slag increases as the drying (sintering) temperature increases, but a peak appears at around 100 ° C for ordinary Portland cement, and the bending exceeds 300 ° C. It can be seen that the strength is significantly reduced.

Example 3 Table 4 and FIG. 2 show the test results of the same formulation as in Example 2 for the fired material age and bending test material age under the following conditions.

Firing material age: 1 day, 7 days, 28 days.

Firing temperature / time: Same as in Example 1.

Bending test material order: Immediately after firing, 28 days and 91 days after firing (leaving indoors).

Bending test method: Same as in Example 1.

From Table 4, it can be seen that there is no effect of the fired material age, and that the long-term strength tends to increase, and the flexural strength on the 91st material age increases by 10 to 15% as compared to immediately after firing.

Example 4 ◎ Modified steel slag Blaine specific surface area value 3500cm ² / g Composition component% by weight CaO 51.5 SiO ₂ 18.1 Al ₂ O ₃ 15.5 MgO 7.5 F 7.0 B ₂ O ₃ 0.5 The above-mentioned modified iron slag powder containing boron, A mixture of fumed silica and the above-mentioned modified slag coarse particles (90% or more of 1 to 5 mm) in a ratio shown in Table 5 below was kneaded with a small amount of a dispersant, and the same as in Example 1 Each of them was molded to obtain an inorganic cured product.

The bending strength of each inorganic cured product was measured in the same manner as in Example 1, and the results shown in Table 6 were obtained.

 The conditions of the specimen are as follows.

Dried product: After demolding, dried at 150 ° C for 5 hours.

Baking product: Material 1 of dried product heated at 850 ° C for 5 minutes
Days, 2 days and 7 days later.

Post-curing: Dried product immersed in water for 1 hour and then 7
What was left in the air for days.

[Effects of the Invention] The inorganic cured product according to the present invention has properties significantly different from those of a cured product using ordinary Portland cement or hydraulic slag cement as a binder.

That is, the cured product is an inorganic cured material having both cementability and ceramic properties, and has high bending strength and excellent strength.

Further, according to the production method of the present invention, since the so-called water / cement (W / C) ratio is extremely small, an efficient and high-strength inorganic cured product can be produced by vibration molding.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the drying (firing) temperature and bending strength of the product of the present invention and the comparative product obtained in Example 2, and FIG. 2 is a graph showing the inorganic curing of the present invention obtained in Example 3. It is a graph which shows the relationship between bending test material age and bending strength of a body.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Haruhiko Waki 225 Yodohoncho, Fushimi-ku, Kyoto-shi, Kyoto (56) References JP-A-61-111947 (JP, A) JP-A-61-21950 (JP, A)

Claims (5)

(57) [Claims] An inorganic cured product obtained by subjecting a composition comprising a hydraulic slag powder containing a boron component, activated silica and an aggregate to hydraulic and molding. 2. A hydraulic slag powder containing a boron component has a basicity of 1.5 to 3.0 represented by (CaO + MgO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) weight ratio, and the boron component is B ₂ O ₃ conversion
0.1 to 5.0% by weight and the fluorine component is 0 to 10% by weight as F
Having a composition containing and having a Blaine specific surface area value of 2000 to 6000
^2. The inorganic cured product according to claim 1, which is a fine powder of m2 / g. 3. The composition is a hydraulic slag powder containing a boron component.
Active silica 5 to 50 parts by weight and aggregate 10 to 1 per 100 parts by weight
2. The inorganic cured product according to claim 1, which has a composition range of 000 parts by weight. 4. A composition comprising a hydraulic slag powder containing a boron component, activated silica and an aggregate is mixed with an appropriate amount of water,
Next, the frame filled with the composition is vibrated to give hydraulic
A method for producing an inorganic cured product, which comprises molding. 5. The method for producing an inorganic cured product according to claim 4, wherein the mixture is mixed with an appropriate amount of water in the presence of a dispersant and / or a foaming agent.