JP4593353B2 - Mortar composition - Google Patents

Description

  The present invention mainly relates to a mortar composition used in the civil engineering and construction industry, and more particularly to a mortar composition having acid resistance, antibacterial and antifungal properties.

  In the present invention, “parts” and “%” are based on mass unless otherwise specified.

Today, there is a strong demand for the development of antibacterial and antifungal materials in order to live in a more comfortable, safe and clean environment.
Conventionally, calcined colemanite powder obtained by firing colemanite 2CaO.3B ₂ O ₃ .5H ₂ O is known as a substance having antibacterial and antifungal properties (see Patent Document 1).
It is also known that antibacterial and antifungal properties can be imparted to the hardened cement by mixing the powder of calcined colemanite with cement (see Non-Patent Document 1).
However, since this calcined colemanite is mainly composed of a boric acid component that significantly delays the setting of the cement, there has been a problem that it causes poor curing when mixed in a large amount.

  On the other hand, many antibacterial agents have been proposed in addition to calcined colemanite, but there is still an unclear point as to whether or not the performance of the antibacterial agents in the hardened cement body is exhibited.

  In recent years, deterioration of concrete structures due to sulfuric acid has been increasing, mainly in sewage treatment facilities. Against this background, more research on sulfuric acid degradation of concrete has been seen than ever before.

It is known that the cause of sulfuric acid generation in sewage treatment facilities is due to the activity of microorganisms.
Therefore, in addition to using acid-resistant materials as countermeasures against acid degradation in sewage treatment facilities, application of antibacterial agents is effective.
And it is thought that a double measure can be taken by combining an acid-resistant hydraulic material and an antibacterial agent, and it becomes possible to prepare mortar and concrete highly resistant to sulfuric acid degradation.

As acid-resistant materials, mortar and concrete in which a large amount of blast furnace slag, fly ash, silica fume, or the like is mixed with Portland cement has been proposed (see Patent Document 2).
However, the acid resistance has not yet reached a sufficient level.

On the other hand, environmental problems are also becoming apparent, and there is a great interest in the effective use of by-products, but there are still many by-products with low utilization rates. One example is non-ferrous smelting slag.
Non-ferrous smelting slag has been studied for use as an aggregate in the cement / concrete field, and JIS has been established for some of them, but it has not been widely spread.

  Therefore, the present inventor has made various efforts for the development of a material having both acid resistance and antibacterial action that suppresses the activity of sulfur-oxidizing bacteria. As a result, the present inventor has achieved excellent acid resistance by using a specific mortar composition. And the antibacterial action that suppresses the activity of sulfur-oxidizing bacteria, and it has been found that the material has excellent adhesion and crack resistance, and the present invention has been completed.

JP 2002-020210 A "Effect of calcined colemanite on concrete corrosive bacteria", Masakazu Okouchi et al., Abstracts of the 106th Academic Lecture Meeting of Inorganic Materials Society, pp54-55, 2003 JP 2000-128618 A

  The present invention provides a cement composition that has both excellent acid resistance and antibacterial action that suppresses the activity of sulfur-oxidizing bacteria, and is excellent in adhesion and crack resistance.

The present invention is a mortar composition containing cement that is ordinary Portland cement or low heat Portland cement, latent hydraulic material that is ground granulated blast furnace slag, pozzolanic material that is fly ash and / or silica fume , and aggregate. In total 100 parts of cement, latent hydraulic substance and pozzolanic material, cement is 20 to 40 parts, latent hydraulic substance is 20 to 40 parts, pozzolanic substance is 30 to 50 parts, and aggregate is 100 parts The mortar composition comprising a mortar composition containing a nonferrous smelted slag aggregate that is one or more selected from the group consisting of 25 to 100 parts of copper slag, zinc slag, and lead slag , and the non-ferrous smelting slag aggregate is a copper slug, zinc slag, and one or the mortar composition is two or more selected from the group consisting of lead slag.

  The cement composition of the present invention has both excellent acid resistance and antibacterial action that suppresses the activity of sulfur-oxidizing bacteria, and is excellent in adhesion and crack resistance, so that it can be widely used in the civil engineering and construction fields.

  Hereinafter, the present invention will be described in detail.

As the cement used in the present invention, various portland cements such as normal, early strength, very early strength, low heat, and moderate heat, various mixed cements obtained by mixing blast furnace slag, fly ash, or silica with these portland cements, and In addition, filler cement mixed with limestone powder or blast furnace slow-cooled slag fine powder, waste-use type cement, so-called eco-cement, and the like, one or more of these can be used.
The fineness of the cement is not particularly limited, but is usually in the range of 3,000 to 6,000 cm ² / g in terms of the specific surface area of the brane (hereinafter referred to as the brane value). If it is less than 3,000 cm ² / g, strength development may not be sufficient, and if it exceeds 6,000 cm ² / g, handling may be difficult.

The latent hydraulic substance used in the present invention is a generic term for substances that exhibit potential hydraulic properties due to their stimulating effects when calcium compounds and alkali metal compounds coexist. And blast furnace granulated slag fine powder.
Blast furnace granulated slag fine powder bears acid resistance.
The fineness of the granulated blast furnace slag powder is not particularly limited, but is usually in the range of about 3,000 to 9,000 cm ² / g in terms of brain value.

The pozzolanic substance used in the present invention is a general term for substances that react with calcium compounds to produce calcium silicate hydrate.
The pozzolanic substance plays a role of promoting the effect of improving acid resistance.
The pozzolanic material is not particularly limited, and specific examples thereof include fly ash, silica fume, pulp sludge incineration ash, sewage sludge incineration ash, waste glass powder, and the like. Of these, the use of fly ash or silica fume is preferred.
The fineness of fly ash and silica fume is not particularly limited, but usually fly ash is in the range of about 3,000 to 9,000 cm ² / g as a brain value, and silica fume has a BET specific surface area of ² to 20 m ^2. It is in the range of about / g.

Latent hydraulic substances and pozzolanic substances are clearly distinguished academically because of their different reaction mechanisms.
In other words, calcium compounds and alkali metal compounds in latent hydraulic substances act as stimulants and play a catalytic role, whereas calcium compounds in pozzolanic substances act as reactants, so the SiO ₂ possessed by pozzolanic substances. An amount of calcium commensurate with the minute amount is required, and if the calcium content is insufficient, the pozzolanic reaction will stagnate.

  In the present invention, it is preferable from the viewpoint of acid resistance that blast furnace granulated slag fine powder is selected as the latent hydraulic material, fly ash and silica fume are selected as the pozzolanic material, and these are used in combination.

The mortar composition of the present invention is composed of a cement composition made of cement, a latent hydraulic material, and a pozzolanic material, and an aggregate containing non-ferrous smelted slag aggregate.
The blending ratio of each material in the cement composition is not particularly limited, but usually 20 to 40 parts of cement is preferable, and 25 to 35 parts is more preferable. The latent hydraulic substance is preferably 20 to 40 parts, more preferably 25 to 35 parts. Furthermore, the pozzolanic material is preferably 30 to 50 parts, more preferably 35 to 45 parts. If the cement is less than 20 parts, the initial strength development may be poor, whereas if it exceeds 40 parts, the acid resistance may not be sufficient. If the latent hydraulic substance is less than 20 parts, the acid resistance may not be sufficient. Conversely, if it exceeds 40 parts, the initial strength development may be deteriorated or the dimensional stability may be deteriorated. Furthermore, if the pozzolan substance is less than 30 parts, the acid resistance may not be sufficient, while if it exceeds 50 parts, the initial strength development may be deteriorated.

In the present invention, aggregate is used in addition to the cement composition.
The aggregate contains non-ferrous smelting slag, and part or all of the aggregate is composed of non-ferrous smelting slag. When a part of the aggregate is composed of non-ferrous smelting slag, the other aggregate is not particularly limited. Specific examples thereof include a silica sand system, a limestone system, a blast furnace granulated slag system, and a recycled aggregate system. In the present invention, it is preferable to select a silica sand aggregate in terms of acid resistance and the like. It is also possible to use heavy aggregate having a density of 3.0 g / cm ³ or more.

  Specific examples of heavy aggregates include, for example, blast furnace slow-cooled slag fine aggregate and electric furnace oxidation period slag fine aggregate as artificial aggregate, and as natural aggregate, peridotite (peridotite). ) System fine aggregate, emery ore, etc., and the solilite type fine aggregate includes so-called olivine sand. In the present invention, one or more of these can be used in combination.

The non-ferrous smelt aggregate used in the present invention is a general term for aggregates, mainly ferronickel slag, ferrochrome slag, copper slag, zinc slag, lead slag, etc. used as fine aggregate.
Ferronickel slag is a slag generated when smelting and collecting ferronickel from nickel ore. Ferrochrome slag is a slag generated when smelting and collecting ferrochrome from chromium ore. Copper slag is produced from copper ore. This is slag generated when copper is refined and extracted. Zinc slag is generated when zinc is refined and extracted from zinc ore. Lead slag is generated when lead is refined and extracted from sulfide ore. It is slag to do. Of these, JIS has been established for ferronickel slag and copper slag (JIS A 5011).
In this invention, use of copper slag, zinc slag, and lead slag is preferable from the surface of an antibacterial effect among these.

  Although the usage-amount of nonferrous smelting aggregate is not specifically limited, 10-100 parts are preferable in 100 parts of aggregates, and 25-75 parts are more preferable. If it is less than 10 parts, the antibacterial effect may not be obtained.

  The amount of aggregate used is not particularly limited, but is usually preferably 50 to 300 parts and more preferably 100 to 200 parts with respect to 100 parts of the cement composition. If it is less than 50 parts, antibacterial properties and dimensional stability may not be sufficient, and if it exceeds 300 parts, further improvement of the effect cannot be expected.

In the present invention, it is preferable to use a polymer in combination from the viewpoint of further improving the acid resistance and from the viewpoint of improving the adhesion strength.
Here, the polymer is not particularly limited.
The polymers are roughly classified into four types: aqueous polymer dispersions, water-soluble polymers, liquid polymers, and re-emulsifying powder resins.
Specific examples thereof include, for example, natural rubber latex, synthetic rubber latex, resin emulsion, and mixed dispersion as aqueous polymer dispersion. Among these, styrene butadiene rubber, chloroprene rubber, methyl methacrylate butadiene rubber, acrylonitrile butadiene rubber, polyacrylate, ethylene vinyl acetate, styrene acrylate, vinyl polypropionate, polypropylene, epoxy resin, asphalt, paraffin, Examples thereof include mixed latex and mixed emulsion.
Examples of the water-soluble polymer include methyl cellulose hydroxypropyl methyl cellulose, polyvinyl alcohol, calcium acrylate, and magnesium acrylate.
Examples of the liquid polymer include unsaturated polyester resins and epoxy resins.
Examples of the re-emulsifying powder resin include styrene butadiene rubber, ethylene vinyl acetate, vinyl acetate vinyl versatate, styrene acrylate, and polyacrylate.

  Although the usage-amount of a polymer is not specifically limited, Usually, 1-10 parts are preferable and 3-7 parts are more preferable in conversion of solid content with respect to 100 parts of cement compositions. If the amount is less than 1 part, the effect of improving the adhesion strength, the substance barrier property, and the crack resistance may not be sufficiently obtained. If the amount exceeds 10 parts, the setting delay and the initial strength may be deteriorated.

In the present invention, it is preferable to use a fiber material in combination from the viewpoint of improving crack resistance.
Here, the fiber material is not particularly limited, and specific examples thereof include, for example, organic fibers such as vinylon fiber, cellulose fiber, and acrylic fiber, carbon fiber, steel fiber, wollastonite fiber, and glass. Examples thereof include inorganic fibers such as fibers. In the present invention, one or more of these can be used.
The amount of the fiber material used is not particularly limited, but usually 0.1 to 3 parts is preferable and 0.3 to 2 parts is more preferable with respect to 100 parts of the cement composition. If it is less than 0.1 part, sufficient crack resistance may not be obtained, and if it exceeds 3 parts, further enhancement of the effect cannot be expected, and dispersibility may deteriorate.

The particle size of the cement composition of the present invention is not particularly limited because it depends on the purpose and application to be used. Usually, the brain value is preferably 3,000 to 8,000 cm ² / g, and 4,000 to 6,000 cm ² / g. Is more preferable. If it is less than 3,000 cm ² / g, sufficient strength development may not be obtained, and if it exceeds 8,000 cm ² / g, workability may deteriorate.

  In the present invention, in addition to cement, latent hydraulic material, pozzolanic material, aggregate, polymer, and fiber material, limestone fine powder, blast furnace annealed slag fine powder, water reducing agent, AE water reducing agent, high-performance water reducing agent, high Performance AE Water reducing agent, antifoaming agent, thickener, rust inhibitor, antifreeze agent, shrinkage reducing agent, setting agent, antibacterial agent, clay minerals such as bentonite, anion exchangers such as hydrotalcite, etc. It is possible to use 1 type, or 2 or more types in the range which does not inhibit substantially the objective of this invention.

  In the present invention, the mixing method of each material is not particularly limited, and the respective materials may be mixed at the time of construction, or a part or all of them may be mixed in advance.

  Any existing apparatus can be used as the mixing apparatus, and for example, a tilting cylinder mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used.

Experimental example 1
A cement composition was prepared by blending 30 parts of cement α, 30 parts of latent hydraulic material and 40 parts of pozzolanic material shown in Table 1.
Next, mortar was prepared according to JIS R 5201, and the mold was tested for mold resistance, compressive strength, and acid resistance. The results are also shown in Table 1.
In addition, 200 parts of the aggregate obtained by replacing 50 parts of the aggregate with 100 parts of the nonferrous smelted aggregate slag was added to 100 parts of the cement composition.

<Materials used>
Cement α: Commercially available ordinary Portland cement, brain value 3,000 cm ² / g
Latent hydraulic material: Commercial ground granulated blast furnace slag, Blaine value 4,000cm ² / g
Pozzolanic substance A: Commercially available fly ash, brain value 4,000 cm ² / g
Pozzolanic material B: Commercially available silica fume, BET specific surface area 15 m ² / g
Pozzolanic substance C: Commercially available pulp sludge incineration ash, brain value 4,000cm ² / g
Pozzolanic substance D: Commercial sewage sludge incineration ash, brain value 9,000cm ² / g
Pozzolanic substance E: Commercial waste glass powder, brain value 4,000cm ² / g
Pozzolanic substance F: Mixture of pozzolanic substance A75 parts and pozzolanic substance B25 parts, Blaine value 9,000 cm ² / g
Non-ferrous smelted slag aggregate a: Commercially available copper slag fine aggregate, density 3.46g / cm ³
Water: Tap water fine aggregate: Standard sand used in JIS R 5201

<Measurement method>
Mold resistance: A mortar cured body having a length of 30 cm, a width of 30 cm, and a height of 3 cm was prepared and carbonized for 7 days under the conditions of 30 ° C., carbon dioxide concentration of 5%, and relative humidity of 60%. A spore suspension of mold species A (Cladosporium cladosporioides) and mold species B (Aspergillus niger) was applied to the surface of the cured mortar, and a mold resistance test was conducted over a period of 4 weeks according to JIS Z 2911. It went according to. “No” for mold resistance is when mold is generated over an area of more than 1/3, “Yes” is when mold is generated in an area of 1/3 or less, and “Good” is when mold is not generated.
Compressive strength: mortar is packed in a mold to create a specimen of 4cm x 4cm x 16cm, and compressive strength at 28 days of age is measured according to JIS R 5201. Strength ratio: Accelerated conversion test, 20 until age 28 Specimens subjected to water curing at ℃ were placed in warm water at 50 ℃ for 28 days for accelerated conversion. The ratio of strength after compressive conversion before compressive conversion to accelerated strength is expressed as a relative value. Acid resistance: The specimen is immersed in a 5% strength sulfuric acid solution for 3 months, and the appearance of the specimen changes. The acid resistance was evaluated from the weight loss. "No" for acid resistance has a significant change in appearance, and when the weight change rate is ± 10% or more, "Yes" has a significant change in appearance, and the weight change rate is ± (5% or more, 10% Less than), if “good” has a significant change in appearance, or if the weight change rate satisfies ± (5% or more, less than 10%), “excellent” indicates a change in appearance and weight. If neither of the above conditions is met.

Experimental example 2
The experiment was performed in the same manner as in Experimental Example 1 except that 30 parts of cement, 30 parts of latent hydraulic material, and 40 parts of pozzolanic material F were mixed to prepare a cement composition. The results are also shown in Table 2.

<Materials used>
Cement β: Commercial early strong Portland cement, Blaine value 5,000cm ² / g
Cement γ: Commercially available low heat Portland cement, Blaine value 4,000cm ² / g

Experimental example 3
The experiment was conducted in the same manner as in Experimental Example 1 except that a cement composition was prepared by blending cement α, latent hydraulic material, and pozzolanic material F shown in Table 3. The results are also shown in Table 3.

実験例４
セメントα30部、潜在水硬性物質30部、及びポゾラン物質Ｆ40部を配合してセメント組成物を調製し、骨材100部中、表４に示す非鉄精錬スラグ骨材を配合した骨材を、セメント組成物100部に対して、200部混合したこと以外は実験例１と同様に行った。結果を表４に併記する。

Experimental Example 4
A cement composition was prepared by blending 30 parts of cement α, 30 parts of latent hydraulic substance, and 40 parts of pozzolanic substance F. In 100 parts of aggregate, aggregate containing nonferrous smelted aggregate shown in Table 4 was cemented. The test was conducted in the same manner as in Experimental Example 1 except that 200 parts were mixed with 100 parts of the composition. The results are also shown in Table 4.

<Materials used>
Non-ferrous refining slag aggregate b: fine ferronickel slag fine aggregate, density 2.85g / cm ³
Non-ferrous refining slag aggregate C: Fine ferrochrome slag fine aggregate, density 3.20g / cm ³
Non-ferrous refining slag aggregate d: Commercially available zinc slag fine aggregate, density 3.30g / cm ³
Non-ferrous refining slag aggregate e: fine aggregate of commercial lead slag, density 3.35g / cm ³
Non-ferrous smelted aggregate: Non-ferrous smelted aggregate and non-ferrous smelted aggregate equal density, density 3.38g / cm ³

<Materials used>
Polymer α: Commercially available styrene butadiene rubber-based polymer β: Commercially available polyacrylate polymer γ: Commercially available ethylene vinyl acetate polymer δ: Commercially available vinyl vinyl acetate versatate

<Measurement method>
Adhesion test: Measures adhesion strength at 28 days of age according to JIS A 1171

Experimental Example 6
A cement composition was prepared by mixing 30 parts of cement α, 30 parts of latent hydraulic material and 40 parts of pozzolanic material F, and 100 parts of the cement composition was mixed with the fiber material shown in Table 6 to form mold resistance of mortar. The test was conducted in the same manner as in Experimental Example 1 except that the test for confirming the property, the compressive strength, the acid resistance, and the crack condition was conducted. The results are also shown in Table 6.

<Materials used>
Fiber material I: Commercial vinylon fiber fiber material II: Commercial acrylic fiber fiber material III: Commercial cellulose fiber fiber material IV: Commercial carbon fiber

<Measurement method>
Cracking condition: Crack resistance test, mortar was applied to a 50cm x 50cm concrete plate with a thickness of 10mm, left in an environment of temperature 20 ° C and relative humidity 40% for one day, and the occurrence of cracking was observed. “Excellent” means no cracks, “Good” means that only one crack has occurred, and “Yes” means that multiple cracks have occurred.

  The cement composition of the present invention has both excellent acid resistance and antibacterial action that suppresses the activity of sulfur-oxidizing bacteria, and is also excellent in adhesion and cracking resistance. Therefore, it is suitable for civil engineering and construction applications.

Claims (1)

A mortar composition comprising a cement that is ordinary Portland cement or low heat Portland cement, a latent hydraulic material that is ground granulated blast furnace slag, a pozzolanic material that is fly ash and / or silica fume , and an aggregate , Of the total of 100 parts of the latent hydraulic substance and the pozzolanic substance, 20 to 40 parts of cement, 20 to 40 parts of the latent hydraulic substance, 30 to 50 parts of the pozzolanic substance , 25 to 100 in 100 parts of the aggregate A mortar composition comprising a non-ferrous smelt aggregate that is one or more selected from the group consisting of copper slag, zinc slag, and lead slag .