JP6960814B2 - Filler and manufacturing method of filler - Google Patents

Description

The present invention relates to a filler and a method for producing a filler that can be used for filling a back cavity such as a tunnel lining body, a retaining wall, a revetment, a mortar spraying surface, a chestnut stone layer, and the like.

Examples of the filler used for filling the back cavity of the tunnel lining body (backfilling) include those containing mortar as an active ingredient and those containing urethane foam as an active ingredient. However, although the filler containing mortar as an active ingredient is excellent in strength, it has drawbacks such as a heavy filler before filling and a large capacity. On the other hand, a filler containing urethane foam as an active ingredient is excellent in terms of weight and capacity, but has drawbacks such as insufficient strength and high cost.

Therefore, in recent years, a filler made by mixing aluminum powder as a foaming agent with mortar has been proposed (see, for example, Patent Document 1 and the like). Aluminum powder has the property of reacting with cement and foaming. Therefore, by using the aluminum powder, the filler before filling can be made lighter, and the capacity can be reduced.

However, aluminum powder is a material designated as Dangerous Goods Class 2, and is dangerous to handle. Aluminum powder is a material that is insoluble in water. Therefore, it is necessary to make it into a fine powder for the reaction. As a result, it becomes easy to fly in the air and it becomes difficult to handle. Further, the gas generated from the aluminum powder is hydrogen gas. Therefore, there is a risk of combustion.

JP-A-2007-051232

A main problem to be solved by the present invention is to provide a filler having sufficient strength and having foamability that is easy to handle, and a method for producing the filler.

The means for solving the above problems are as follows.
(Means according to claim 1)
With at least one of cement and slag, and liquid A containing water,
And B liquid percarbonate sodium is blended,
It is a two-component mixed chemical solution consisting of
The amount of the sodium percarbonate compounded is 0.5 to 20 kg per ^{1 m 3 of the compounded chemical solution.}
At least one of alumina cement and calcium ^{sulphoaluminate was added to the solution B in an amount of 50 to 500 kg per 1 m 3 of the} combination drug solution to adjust the gel time to 3 seconds to 10 minutes.
Manganese oxide is blended in the liquid A at a ratio of 10 to 1000 parts by mass with respect to 100 parts by mass of the sodium percarbonate, and / or at a ratio of 10 to 800 parts by mass with respect to 100 parts by mass of the sodium percarbonate. Contains catalase,
The proportion of sodium carbonate is 2% or less of the total amount of the cement and the slag, and the proportion of calcium hydroxide is 10 kg or less per ^{1 m 3 of the compounded chemical solution.}
A filler characterized by that.

(Means according to claim 2)
At least one of a nonionic surfactant and an anionic surfactant is blended in the liquid A.
The filler according to claim 1.

(Means according to claim 3)
Liquid A containing at least one of cement and slag, at least one of manganese oxide and catalase, and water.
And B solution blended with at least one of percarbonate sodium, and alumina cement and calcium monkeys follower aluminate,
To make a two-component mixed chemical solution.
The amount of the sodium percarbonate compounded is 0.5 to 20 kg per ^{1 m 3 of the compounded chemical solution.}
The gel time was adjusted to 3 seconds to 10 minutes by adjusting the blending of the alumina cement and the calcium ^{sulfoluminate to 50 to 500 kg per 1 m 3 of the blended chemical solution.}
Manganese oxide was added to the solution A at a ratio of 10 to 1000 parts by mass with respect to 100 parts by mass of the sodium percarbonate, and / or at a ratio of 10 to 800 parts by mass with respect to 100 parts by mass of the sodium percarbonate. Contains catalase,
The proportion of sodium carbonate shall be 2% or less of the total amount of the cement and the slag, and the proportion of calcium hydroxide shall be 10 kg or less per ^{1 m 3 of the compounded chemical solution.}
A method for producing a filler.

According to the present invention, there is a filler having sufficient strength and foamability that is easy to handle, and a method for producing the filler.

Next, a mode for carrying out the present invention will be described. This embodiment is an example of the present invention. The scope of the present invention is not limited to the scope of this embodiment.

The filler of this embodiment is formed by mixing at least one of cement and slag, liquid A containing water, and liquid B containing at least one of sodium percarbonate and hydrogen peroxide. ..

(cement)
Cement is a substance having hydraulic property. Cement is usually a powder.

Examples of cement include various Portland cements such as ordinary, early-strength, ultra-fast-strength, low-heat, and moderate-heat, various mixed cements in which these Portland cements are mixed with blast furnace slag, fly ash, silica, etc., limestone powder, and blast furnace. One or more types can be selected and used from filler cement mixed with slow-cooled slag fine powder, etc., and environment-friendly cement (so-called eco-cement) manufactured using various industrial wastes as the main raw materials. can.

(Slag)
Slag is a substance or the like containing a mineral component separated from the metal by melting when the metal is smelted from the ore. Slag is naturally occurring and its chemical composition is usually similar to Portland cement. Slag has the property of hardening when exposed to alkaline stimuli.

As the slag, it is preferable to use hydraulic slag such as steel slag or steelmaking slag. Steel slag contains calcium oxide (CaO, lime) and silica (SiO ₂ ) as main components. In particular, blast furnace slag also contains alumina (Al ₂ O ₃ ), magnesium oxide (MgO), sulfur (S) and the like. Among the blast furnace slags, the blast furnace granulated slag has a latent hydraulic property of being hardened by alkaline stimulation and is widely used in civil engineering applications, so that it can be preferably used. On the other hand, steelmaking slag contains iron oxide (FeO), magnesium oxide (MgO) and the like as components.

The mixing ratio of cement and slag (total amount) is, for example, 50 kg to 800 kg, preferably 100 kg to 700 kg, and particularly preferably 200 kg to 600 kg, per ^{1 m 3 of the mixed chemical solution (solution A + solution B).}

(Sodium percarbonate, hydrogen peroxide)
Sodium percarbonate (sodium percarbonate adduct, sodium percarbonate) is a compound in which sodium carbonate (sodium carbonate) and hydrogen peroxide are mixed at a ratio of 2: 3. The chemical formula of sodium percarbonate is _{2Na 2 CO 3 · 3H 2 O} 2 or _{Na 2 CO 3 · 1.5H 2 O} 2.

When the liquid A and the liquid B are mixed, sodium percarbonate is decomposed to generate hydrogen peroxide. In addition, this hydrogen peroxide is decomposed to generate oxygen. Therefore, sodium percarbonate and hydrogen peroxide function as a foaming agent. Further, when sodium percarbonate or hydrogen peroxide is used as the foaming agent, oxygen is generated as the foaming gas, which is excellent in safety. Furthermore, since sodium percarbonate is water-soluble, it does not need to be made into a fine powder for reaction. Therefore, it is easy to handle.

However, sodium carbonate in sodium percarbonate reacts with cement and slag to produce calcium carbonate. Therefore, when sodium percarbonate is added to the liquid A, the gel time becomes long. Therefore, it is preferable to add sodium percarbonate to the liquid B.

The blending amount of sodium percarbonate is preferably 0.5 to 20 kg, more preferably 0.8 to 15 kg, and particularly preferably ^{1 to 10 kg per 1 m 3} of the blended chemical solution (solution A + solution B).

The amount of hydrogen peroxide compounded is preferably 0.01 to 5 kg, more preferably 0.1 to 4 kg, and particularly preferably ^{1 to 3} kg as H ₂ O ₂ per 1 m 3 of the compounded chemical solution (solution A + solution B). Is.

(Instantaneous material)
It is preferable to add at least one of alumina cement and calcium sulfoluminate as an instant binder to the liquid B. The addition of alumina cement or calcium sulphoaluminate promotes gelation. Therefore, when alumina cement or calcium sulfate is blended, the possibility that the filler is washed away by water is reduced. However, alumina cement and calcium sulphoaluminate promote gelation by reacting with cement and slag. Therefore, alumina cement and calcium sulphoaluminate are preferably blended in the liquid B.

The gel time of the filler is preferably adjusted to 3 seconds to 10 minutes , more preferably 30 seconds to 5 minutes. If the gel time is too short, the filler may not reach the back cavity. On the other hand, if the gel time is too long, the filler may move and settle and be washed away.

The blending amount of the alumina cement is preferably 50 to 500 kg, more preferably 100 to 400 kg, and particularly preferably 150 to 300 kg per ^{1 m 3} of the blended chemical solution (liquid A + liquid B).

The blending amount of calcium sulfoluminate is preferably 50 to 500 kg, more preferably 100 to 400 kg, and particularly preferably 150 to 300 kg per ^{1 m 3} of the blended chemical solution (liquid A + liquid B). As the calcium sulfoluminate, for example, Denka ES manufactured by Denki Kagaku Kogyo Co., Ltd. can be used.

(Catalase)
It is preferable to add catalase to the liquid A. Catalase functions as an enzyme that breaks down hydrogen peroxide produced from sodium percarbonate. Therefore, the addition of catalase promotes foaming. In this regard, if the filler foams after gelling, the strength of the cured product may decrease due to the edge breakage of the consolidated portion. Therefore, it is preferable to add catalase to foam the filler at once before it gels.

The amount of catalase to be blended is preferably 10 to 800 parts by mass, more preferably 50 to 500 parts by mass, and particularly preferably 200 to 400 parts by mass with respect to 100 parts by mass of sodium percarbonate (catalase solution enzyme activity 50,000 u / g). ).

(Manganese oxide)
It is preferable to add manganese oxide to the liquid A. Manganese oxide functions as a catalyst for decomposing hydrogen peroxide produced from sodium percarbonate. Therefore, the addition of manganese oxide promotes foaming. It is preferable to promote foaming as in the case of catalase.

The blending amount of manganese oxide is preferably 10 to 1000 parts by mass, more preferably 100 to 800 parts by mass, and particularly preferably 250 to 500 parts by mass with respect to 100 parts by mass of sodium percarbonate.

(Foaming agent)
It is preferable to add at least one of a nonionic surfactant and an anionic surfactant as a defoaming agent to the liquid A. By blending these defoaming agents, bubbles (oxygen) are retained in the filler and become finer.

As the nonionic surfactant, it is preferable to use Twin 20. Twin 20 is excellent in terms of surface-active effect in alkalinity and environmental impact when spilled. The English name of the twin 20 is Polyoxyethylene sorbitan monolaurate (polyoxyethylene sorbitan monolaurate). The twin 20 is also referred to as polyoxyethylene sorbitan monolaurate.

As the anionic surfactant, it is preferable to use sodium α-olefin sulfonate.

When twin 20 or sodium α-olefin sulfonate is used, the blending amount thereof is preferably 0.01 to 10 kg, more preferably 0.1 to ^{3 kg, particularly preferably 0.1 to 3 kg per 1 m 3 of the blended chemical solution (solution A + solution B).} It is 0.5 to 3 kg.

(Mixing method)
Liquids A and B are mixed when filling the back cavity of the tunnel lining. That is, the filler of this embodiment is a two-component mixed type.

Next, examples of the present invention will be described, and the effects of the present invention will be clarified.
Liquids A and B having the formulations shown in Table 1 were mixed to obtain a filler. The gel time, the change over time of foaming, and the uniaxial compressive strength of the obtained cured product (filler) were examined. The results are shown in Table 2.

The change with time of foaming indicates the change in the foaming rate after mixing the liquid A and the liquid B. The foaming rate is a comparison of the length of a φ52 mm PVC pipe filled with 250 ml of a chemical solution (filler) and the length filled with the chemical solution with the length (118 mm) when a 250 ml volume is filled. .. For example, when the length is 130 mm, it becomes "((130-118) ÷ 118) x 100 = 10%".

(Discussion)
It was found that the strength-enhancing effect was obtained by adding about 1 to 2% of the amount of compounded cement to sodium carbonate (Test Examples 5 and 6). However, it was also found that when sodium carbonate was added excessively, hydrogen peroxide (H ₂ O ₂ ) and sodium carbonate (Na ₂ CO ₃ ) were bound to inhibit foaming. Moreover, it was also found that if catalase was also added at this time, it was inactivated by high alkali and the catalytic effect was lost (Test Example 13).

The gel time can be shortened by adding calcium hydroxide (Ca (OH) ₂ ), but if it is added in excess, hydrogen peroxide will bind to the alkali of calcium hydroxide and foaming will be inhibited. It was also found (Test Example 9).

INDUSTRIAL APPLICABILITY The present invention can be used as a filler and a method for producing a filler that can be used for filling a back cavity such as a tunnel lining body, a retaining wall, a revetment, a mortar spraying surface, a chestnut stone layer, or the like. ..

Claims (3)

With at least one of cement and slag, and liquid A containing water,
And B liquid percarbonate sodium is blended,
It is a two-component mixed chemical solution consisting of
The amount of the sodium percarbonate compounded is 0.5 to 20 kg per ^{1 m 3 of the compounded chemical solution.}
At least one of alumina cement and calcium ^{sulphoaluminate was added to the solution B in an amount of 50 to 500 kg per 1 m 3 of the} combination drug solution to adjust the gel time to 3 seconds to 10 minutes.
Manganese oxide is blended in the liquid A at a ratio of 10 to 1000 parts by mass with respect to 100 parts by mass of the sodium percarbonate, and / or at a ratio of 10 to 800 parts by mass with respect to 100 parts by mass of the sodium percarbonate. Contains catalase,
The proportion of sodium carbonate is 2% or less of the total amount of the cement and the slag, and the proportion of calcium hydroxide is 10 kg or less per ^{1 m 3 of the compounded chemical solution.}
A filler characterized by that. At least one of a nonionic surfactant and an anionic surfactant is blended in the liquid A.
The filler according to claim 1. Liquid A containing at least one of cement and slag, at least one of manganese oxide and catalase, and water.
And B solution blended with at least one of percarbonate sodium, and alumina cement and calcium monkeys follower aluminate,
To make a two-component mixed chemical solution.
The amount of the sodium percarbonate compounded is 0.5 to 20 kg per ^{1 m 3 of the compounded chemical solution.}
The gel time was adjusted to 3 seconds to 10 minutes by adjusting the blending of the alumina cement and the calcium ^{sulfoluminate to 50 to 500 kg per 1 m 3 of the blended chemical solution.}
Manganese oxide was added to the solution A at a ratio of 10 to 1000 parts by mass with respect to 100 parts by mass of the sodium percarbonate, and / or at a ratio of 10 to 800 parts by mass with respect to 100 parts by mass of the sodium percarbonate. Contains catalase,
The proportion of sodium carbonate shall be 2% or less of the total amount of the cement and the slag, and the proportion of calcium hydroxide shall be 10 kg or less per ^{1 m 3 of the compounded chemical solution.}
A method for producing a filler.