KR101081830B1 - Environment friendly polymer cement mortar for conservation and reinforcement using powder type inorganic antibiotic and circulation aggregate - Google Patents

Abstract

The present invention relates to an environmentally friendly repair and reinforcement polymer cement mortar using inorganic inorganic antibacterial agent and high purity circulating fine aggregate, comprising: cement mortar used in concrete sewage system; By weight, portland cement: 34-37%; Powdered illite: 1-8%; Powdery inorganic antibacterial: 1-2%; EVA polymer: 0.5-1.0%; Admixture: 3.5-6.5%; And the balance circulating fine aggregate.

According to the present invention, while compressive strength, flexural strength, and adhesive strength meet or exceed the standard value, concrete corrosion by hydrogen sulfide and sulfuric acid is prevented, which is useful for cross-sectional repair and reinforcement work of concrete structures and improves construction, and extends the life of concrete structures. In addition, it is possible to obtain an environmentally friendly polymer cement mortar that also prevents air pollution due to the discharge of hydrogen sulfide.

Powdery, Antibacterial, Cyclic aggregate, Polymer, Cement, Mortar, Corrosion

Description

ENVIRONMENT FRIENDLY POLYMER CEMENT MORTAR FOR CONSERVATION AND REINFORCEMENT USING POWDER TYPE INORGANIC ANTIBIOTIC AND CIRCULATION AGGREGATE}

The present invention relates to an environmentally friendly repair and reinforcement polymer cement mortar using an inorganic antibacterial agent and high purity recycled fine aggregate, and more particularly, to recycle recycled fine aggregate obtained from waste concrete, contributing to the promotion of recycling of resources and environmental preservation. The present invention relates to an environmentally friendly repair and reinforcement polymer cement mortar using powdered inorganic antibacterial agent and high purity circulating fine aggregate which can be used to prevent corrosion by hydrogen sulfate using powdered inorganic antibacterial agent.

In general, the concrete sewage system is known that sulfuric acid produced by the action of sulfated bacteria reacts with alkali of concrete and is corroded due to neutralization. More than 10 species of sulfated bacteria exist among them, including thiobacilli. Novellus is representative.

For example, organic sulfur oxides contained in sulfur (S) or excreta, which are contained in the form of inorganic sulfate or sulfide in a large amount in the domestic wastewater, are reduced to sulfur sulfide (hydrogen sulfide) by sulfate reducing bacteria using an organic material as an energy source. The sulfuric acid cycle associated with is the same as the example of FIG. 1.

In _{^{particular, SO 4 2 - + 2C +}} 2H 2 O → 2HCO 3 - + H 2 as S (toxic gas), and is reduced to hydrogen sulfide by the ion sulfuric acid contained in the wastewater sulfate-reducing bacteria, the hydrogen sulfide is an acid environment Molecular hydrogen sulphide is transformed into and is diffused into the air by turbulent sewage, contaminating the surrounding atmosphere.

In addition, hydrogen sulfide in the air dissolves in water droplets of condensation or splash water on the concrete surface, and the dissolved hydrogen sulfide is oxidized to sulfuric acid by the action of sulfur oxidizing bacteria. In response,

Ca (OH) ₂ + H ₂ SO ₄ → CaSO ₄ 2H ₂ O in the same form, calcium sulfate (gypsum) is produced.

However, the calcium sulfate reacts with the calcium aluminate of cement to form an expandable substance, Ettringite, and the product rapidly progresses in the form of cracking or peeling as the concrete expands, thereby shortening its lifespan. .

As such, the sulfate reducing bacteria (main species Desulfovibrio desulfuricans) and sulfur oxidizing bacteria (main species Thiobacillus thiooxidans), which are involved in the corrosion of concrete, optimally proliferate around 30 ° C. In the case of sulfur oxidizing bacteria, in particular, as shown in the graph of FIG. 2, pH is rapidly dropped from the neutral zone to the acid zone on the concrete surface by continuous supply of sulfuric acid, which is regeneration of gypsum from ethringite. It can be seen that to further promote the concrete corrosion rate is sharply increased.

In order to prevent the lifespan of sewage pipes from being shortened due to these problems, a method of suppressing the generation of sulfides, a method of suppressing the generation of hydrogen sulfide, and the like have been proposed.

However, these methods have a problem in economical efficiency because the efficacy is secured by adding a large amount of hydrogen peroxide, chlorine compounds or metal salts such as iron, zinc, lead, copper, etc. in sewage.

Alternatively, Japanese Patent Application Laid-Open No. 9-60768, Japanese Patent Application Laid-Open No. 11-156839, etc. may be used to reduce the concentration of hydrogen sulfide in sewage pipes by suppressing the production of sulfuric acid from hydrogen sulfide. Although disclosed, the manufacturing method of the inorganic powder and anti-corrosion agent containing antimicrobial metal ions for use in the fume pipe is complicated, there is a problem in the economical situation is required to develop a new product to improve this.

Recently, a method of inhibiting sulfated bacteria using an antimicrobial agent has been disclosed, and since the antimicrobial agent is usually prepared in powder form, the antimicrobial efficacy of the prepared concrete structure is prevented evenly mixed with cement and aggregate when the concrete structure is mixed. There was a problem that this was not exhibited uniformly.

On the other hand, according to the development priority policy and the policy of high-growthism, the domestic environment has not considered the adverse function, but it can no longer be delayed due to the increase of various wastes and pollutants by-products and the strengthening of international environmental regulations. A desperate time point was reached.

In particular, the construction industry wastes of various construction and civil works show a sharp increase, mainly due to the redevelopment, revitalization of reconstruction, and the dismantling of structures, which are actively progressed due to the aging and deterioration of urban and local buildings.

Here, construction waste refers to soil, sand, gravel, earth or mixed soil mixed with trash and waste materials, concrete lumps, waste wood, asphalt concrete lumps, and construction sludge, etc. One of the characteristics is that most of the construction waste is composed of inorganic materials, and it is harmless to the human body, and various kinds of waste are discharged in a mixed state, and the treatment is complicated and difficult. It is said to provide the cause of indifference between the government and the industry regarding treatment.

Such indifference entailed a waste of valuable resources and caused deterioration of the quality of the recycled aggregates, and most of the utilization of the recycled aggregates was only used for earthworks, such as fill, cover, and landfill.

Therefore, it is necessary to actively promote recycling through the management of such waste, minimizing environmental pollution, replacing scarce resources, and reducing the cost of the construction industry base.

The present invention was created in view of the above-mentioned problems in the prior art as described above, and recycles recycled fine aggregates that are disposed of as well as inhibits the growth of sulfated bacteria using inorganic antibacterial agents and prevents the production of sulfuric acid. By providing the environmentally friendly maintenance and reinforcement polymer cement mortar using powdered inorganic antibacterial agent and high purity circulating aggregate, which prevents corrosion of sewage concrete structure and extends its life and ensures easy reinforcement. There is a challenge.

The present invention as a means for achieving the above object, in the cement mortar used in concrete sewage; By weight, portland cement: 34-37%; Powdered illite: 1-8%; Powdery inorganic antibacterial: 1-2%; EVA polymer: 0.5-1.0%; Admixture: 3.5-6.5%; And it provides an environmentally friendly repair and reinforcement polymer cement mortar using powdered inorganic antibacterial agent and high-purity recycled fine aggregates, characterized in that consisting of residual circulating fine aggregates.

At this time, the powder-based inorganic antimicrobial agent is ground to a particle size of 20nm-10㎛ by mixing a water-tight material with nickel, tungsten obtained as a by-product during metal smelting; Powdered activated carbon mixed with nickel-zinc-tungsten and ground to a particle size of 20 nm-10 탆; The salts of the amine acid derivatives are ground to a particle size of 20 nm-10 탆; The salts of the oxyquinoline derivatives are ground to a particle size of 20 nm-10 탆; Grinding the silver supported catalyst which is a by-product obtained in the production of ethylene oxide into a particle size of 20 nm-10 탆; It is also characterized by being any one selected from among pulverized activated carbons ion-exchanged with silver to a particle size of 20 nm-10 탆.

In addition, the admixture is made of a mixture of the expansion material, the fast hard material, silica fume, it is also characterized in that the composition in the same ratio.

According to the present invention, while compressive strength, flexural strength, and adhesive strength meet or exceed the standard value, concrete corrosion by hydrogen sulfide and sulfuric acid is prevented, which is useful for cross-sectional repair and reinforcement work of concrete structures and improves construction, and extends the life of concrete structures. In addition, it is possible to obtain an environmentally friendly polymer cement mortar that also prevents air pollution due to the discharge of hydrogen sulfide.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment according to the present invention.

3 is a schematic structural diagram showing an example of an inorganic antimicrobial agent according to the present invention, Figures 4 to 6 are photographs showing an experimental example according to the present invention.

The present invention is a cement mortar completed by mixing the recovered recycled aggregate and powdery inorganic antimicrobial agent with Portland cement together with Portland cement, so as to prevent the formation of hydrogen sulfide and sulfuric acid while securing compressive strength, bending strength and adhesion strength above the standard value. It is composed.

At this time, the cement mortar is more preferably configured to increase the hydration, miscibility, and dispersion efficiency during the production of the mortar by adding an expansion material, a fast hard material, silica fume at a predetermined ratio.

To this end, the cement mortar according to the present invention is composed of the composition (wt%) as shown in Table 1.

ingredient

Portland
cement
Powdery
Illite
Powder Inorganic Antibacterial Agent
EVA polymer
Admixture
Circulating aggregate
Creation costs

34-37%
1-8%
1-2%
0.5-1.0%
3.5-6.5%
Bal.

Referring to the reason for numerical limitation of the components of the present invention made of such a composition is as follows.

(Portland Cement: 34-37 wt%)

Portland cement is mainly obtained by mixing calcite and clay stocks in suitable proportions (sometimes adding siliceous and iron oxide raw materials to control the composition) and then calcination until some of them melt (about 1,450 ° C). The clinker is prepared by adding a little gypsum as a coagulation regulator and grinding it.

Such portland cement is suitable for use according to the present invention, namely, maintenance, repair and reinforcement because of its roughness, and is particularly limited to the above range in consideration of the blendability with the circulating fine aggregate and the curing time after the mortar is manufactured.

(Powder illite: 1-8% by weight)

The illite is a fine mica mineral belonging to monoclinic system. The illite is 1 ~ 2, the specific gravity is 2.6 ~ 2.9, and the streak color is white. Calculated in tuff sedimentary rock and produced as altered minerals of hydrothermal deposits, which are mainly SiO ₂ : 55 ~ 80wt%, Al ₂ O ₃ : 5 ~ 30wt%, Fe ₂ O ₃ : 3 ~ 20wt% And, broadly belong to primary clay, and the particle size refers to the assembled mineral.

In the present invention, the elite is pulverized and manufactured in the form of a powder having a particle size of 100 to 500 mesh, and then mixed with the Portland cement at a ratio of 1 to 8% by weight, which is air through far infrared rays and anions emitted from the elite. It is to perform the purification function.

At this time, the powdered illite has a higher grinding processing cost as the particle size is smaller and the adsorption effect of harmful components occurs over a short period of time, so that after 10 years or more, the adsorption and anion emission functions are drastically deteriorated. It is particularly preferable to have a size of the above-mentioned particle size because it is long lasting but weak, and the homogeneity of the product is lowered and the air permeability of the mortar is reduced to lower the harmful substance blocking performance.

In addition, even if the addition amount is less than 1% by weight, the adsorption effect and the harmful substance blocking effect is sharply lowered, the adhesion strength is also lowered, when added to more than 8% by weight, the strength is lowered, so the addition is limited to the above range desirable.

(Powdered inorganic antibacterial agent: 1-2 wt%)

Antibacterial agents are substances that inhibit or inhibit the growth of bacteria, and are classified into organic and inorganic antibacterial agents. Inorganic antimicrobial agents are mainly made of silver, zinc, copper, etc., which are metals that perform antimicrobial action on inorganic substances such as zeolite, calcium phosphate, zirconium phosphate, silica gel, etc. by substitution, support, or coating with nanoparticles (see FIG. 3). Compared to organic antimicrobial agents, although low in human stability, resistant bacteria do not appear, and the antimicrobial duration is almost semi-permanent, its use is expanding.

In particular, since the inorganic antimicrobial agent must solve the problem of dispersibility when applied to the polymer material, the range that can be applied according to the atomization of particles and the complexation technology with the polymer is expanding.

However, the known inorganic antimicrobial agent has a disadvantage in that the cost is increased because it has to be prepared by coating with substitution, support, and nanoparticles.

Therefore, in the present invention, in consideration of the aspects of resource recycling while having ease of processing and equivalent effects, by mixing the water-tight material (eg silica, fly ash) with nickel, tungsten obtained as a by-product during metal smelting, grinding to a certain particle size which; Powdered activated carbon mixed with nickel-zinc-tungsten and ground to a predetermined particle size; The salts of the amine acid derivatives are ground to a certain particle size; The salts of the oxyquinoline derivatives are ground to a certain particle size; Grinding the silver supported catalyst, which is a by-product obtained in the production of ethylene oxide, to a certain particle size; Grinding of activated carbon ion-exchanged with silver to a certain particle size is utilized as an inorganic antibacterial agent.

At this time, the inorganic antimicrobial agent added according to the present invention inhibits the activity of the sulfated bacteria to block the production of sulfuric acid to inhibit the corrosion of the concrete structure.

In particular, in the present invention, in consideration of dispersion in portland cement, the above-described inorganic antimicrobial agent is more preferably formed in a powder form having a particle size of 20 nm-10 μm, and when it is added below 1% by weight, the antimicrobial effect is rapidly increased. It is preferable to limit the amount of mortar to the above range because the adhesion strength of the mortar falls.

(EVA polymer: 0.5-1.0 wt%)

EVA (Ethylene-Vinyl Acetate copolymer) is a generic name for polymer compound made by copolymerization of polyethylene and poly vinylacetate, and it is a thermoplastic material that is more environmentally friendly than conventional polymers such as polystyrene. Has

The EVA polymer forms a film inside the hardened cement paste to improve warpage, tensile and adhesion strength, and improve water retention to improve durability such as neutralization, chloride ion penetration, and freezing and thawing, and to be added at less than 0.5% by weight. In this case, interfacial oxidation and dew condensation caused by organic acids caused by bacteria, fungi, and other microorganisms, such as sulfated bacteria, which may grow at the interface, may be deteriorated. It is preferable to limit the thickness to the above range because it causes a decrease in adhesion strength by delaying the curing time.

(Mixed material: 3.5-6.5 wt%)

Admixtures are components added to improve compressive strength, flexural strength, and adhesion strength, and in the present invention, the expanded material, the fast hard material, and the silica fume do not have the same ratio or any of the three components to be less than twice the one of the other two. The sum within the range may be formulated to conform to the range.

In this case, the expander reduces the required unit quantity necessary for securing the consistency of cement paste, and reduces the excess amount other than the amount required for cement hydration, thereby densifying the internal structure of the cement hardened body, thereby improving watertightness and freeze-thawing. In order to improve resistance and increase durability, fast hardwood is added to promote hydration, and silica fume is added to reduce the increase in the amount of air due to the generation of entrained air.

(Circulating fine aggregate: balance)

As described above, the recycled fine aggregate is recycled from concrete lumps in construction waste. In the present invention, it is required to have a particle size of 2.5 mm or less, an absorption rate of 2.6 or less, and an absolute dry density of 2.3 or less in consideration of dispersibility and miscibility.

In addition, the recycled fine aggregate has a very great value in terms of recycling resources, the main component is added to the above range in consideration of the composition ratio of the Portland cement and illite, and the inorganic inorganic antimicrobial agent and EVA polymer, admixture, etc. desirable.

Mortar made of such a component composition is mixed (mixed) in a conventional manner to be prepared as a mortar for repairing concrete, reinforcement.

Hereinafter, an Example is described.

[Example]

In order to confirm that the polymer cement mortar prepared according to the present invention meets the necessary standards for repair and reinforcement, several samples were prepared within the composition range of Table 1 and then constructed, and then the physical properties thereof were checked. Table 3 shows.

In this case, the measurement experiments on the measurement items generally used well-known conventional measurement method (compression strength and bending strength test according to KS F 2477, adhesion strength test according to JIS A 6916) as it is, and for the samples 1, 2, 3 Composition is shown in Table 2.

ingredient

Portland
cement
Powdery
Illite
Powder Inorganic Antibacterial Agent
EVA polymer
Admixture
Circulating aggregate
Sample 1
34%
4%
1.2%
0.5%
3.8%
Bal.
Sample 2
35%
7%
1.5%
0.6%
5.0%
Bal.
Sample 3
36%
6%
1.5%
0.6%
4.5%
Bal.

Item Reference value Sample 1 Sample 2 Sample 3 Flexural strength (kgf / ㎠) 60 or more 72 74 73 Compressive strength (kgf / ㎠) More than 200 215 213 214 Adhesion strength
(kgf / cm2) Standard Time over 10 18 17 16 After hot and cold repeat over 10 15 17 18 Permeability (g) 20 or less 12 15 14 Absorption amount (mL / ㅎ) 0.5 or less 0.2 0.3 0.1 Length change (%) 0.15 or less 0.1 0.11 0.05

As shown in Table 3, it was confirmed that all of the samples 1,2,3 according to the present invention achieve all the reference values necessary for concrete reinforcement and repair.

Subsequently, in order to confirm the inhibitory ability of the sulfated bacteria through the samples 1,2 and 3 according to the present invention, the samples 1,2 and 3 were respectively placed in a chamber maintained at 30 ° C. which is the temperature of the sulfated bacteria having the highest activity ( Sufficient oxygen supply), and the sulfated bacteria were sprayed on the surfaces of samples 1,2 and 3, and left for 30 days. Then, the presence or absence of calcium sulfate according to the activity of sulfated bacteria on the surfaces of samples 1,2 and 3 was confirmed. .

As a result, as shown in Figures 4 to 6, it was confirmed that the sulfate was suppressed to the extent that it is visually confirmed.

Thus, the mortar according to the present invention can be used for the maintenance and reinforcement of the sewage facility or the facility, thereby prolonging its life and suppressing the generation of hydrogen sulfide, contributing to the recycling of recycled fine aggregates as well as air pollution. It was confirmed that it can be done.

1 is an explanatory diagram showing a sulfuric acid cycle of a general life drainage,

2 is a graph showing the relationship between the general sulfur oxidizing bacteria and pH,

3 is a schematic structural diagram showing an example of an inorganic antimicrobial agent according to the present invention;

4 to 6 is a photograph showing an experimental example according to the present invention.

Claims (3)

In cement mortar used in concrete sewage systems; In weight percent, Portland cement: 34-37%; Powdered illite: 1-8%; Powdery inorganic antibacterial: 1-2%; EVA polymer: 0.5-1.0%; Admixture: 3.5-6.5%; And balance circulating fine aggregates, The powdery inorganic antimicrobial agent is pulverized to a particle size of 20nm-10㎛ by mixing a water-tight material with nickel, tungsten obtained as a by-product of metal smelting; Powdered activated carbon mixed with nickel-zinc-tungsten and ground to a particle size of 20 nm-10 탆; The salts of the amine acid derivatives are ground to a particle size of 20 nm-10 탆; The salts of the oxyquinoline derivatives are ground to a particle size of 20 nm-10 탆; Grinding the silver supported catalyst which is a by-product obtained in the production of ethylene oxide into a particle size of 20 nm-10 탆; An environmentally friendly repair and reinforcement polymer cement mortar using powdered inorganic antimicrobial agent and high-purity recycled fine aggregate, which is selected from pulverized activated carbon ion-exchanged with silver to a particle size of 20 nm-10 μm. delete The method of claim 1, further comprising: The admixture is made of a mixture of expandable material, fastwood material, silica fume, environmentally friendly maintenance and reinforcement polymer cement mortar using a powdered inorganic antimicrobial agent and a high purity circulating aggregate, characterized in that the composition is formed in the same ratio.

Images