KR20040039838A - Method of producing subaqueous non-separated blending material simultaneously having anti-corrosive function - Google Patents

Abstract

PURPOSE: Provided is a method for preparing an anti-washout underwater admixture with anti-corrosive function, by which one-part products having both functions as an admixture for underwater concretes and as an anti-corrosive agent are produced. CONSTITUTION: The method for preparing an anti-washout underwater admixture with anti-corrosive function comprises: providing an anti-washout underwater admixture by mixing a cellulose-based thickener with a high-viscosity acrylic thickener; introducing a strength reinforcing agent, a liquid defoamer and a flowing agent into the admixture and compounding them together; and adding a powdery anti-corrosive agent to the compounded product and then mixing.

Description

TECHNICAL FIELD OF THE INVENTION A method for producing an underwater fire-resistant anti-corrosive admixture having a rust-preventing function at the same time {METHOD OF PRODUCING SUBAQUEOUS NON-SEPARATED BLENDING MATERIAL SIMULTANEOUSLY HAVING

The present invention relates to a method for producing an underwater fire separation anticorrosive admixture having a rust prevention function, and more specifically, to prevent corrosion of reinforcing bars by chloride ions when constructing underwater concrete in the ocean and at the same time washing cement during concrete work in water. The present invention relates to a method for preparing an underwater fire separation anticorrosive admixture having a rust prevention function to prevent a phenomenon and to improve durability of concrete.

Currently, developed countries have not only established and implemented countermeasures against salt damage when constructing concrete structures affected by chloride, but have also taken measures to maintain, diagnose and evaluate the durability of already constructed structures. In particular, the use of anti-corrosive agent for reinforced concrete, which has been evaluated as having an effect of suppressing the corrosion of reinforcing steel in Korea, is used for SOC (Social infrastructure: roads, ports, airports, bridges, etc.) Increasingly, construction is becoming more common.

Similarly, the demand for unsealed concrete has been on the rise since the bridge repair work on the Han River. Underwater unsecured concrete works on bridges such as Busan Gwangan Bridge, Honam Line Double Track Construction, and Namhae Coastal Road Construction were in progress.

However, there is little review of the impact on the salt damage of unsealed concrete in the construction of offshore structures.

According to the literature, undisintegrated concrete in seawater tended to decrease in strength due to the erosion of harmful ions, which is due to the hydration of C ₃ S and C ₂ S in cement-based minerals. _It is believed that 2 deteriorates the structure of concrete by producing gypsum and Mg (OH) ₂ by reacting with SO ⁴ , Mg ²⁺ ions in seawater.

Concrete materials, which occupy the largest share with steel materials, have been applied to semi-permanent structures. Recently, the consumption of seawater is exploding due to the depletion of inland sand, and corrosion of rebar is caused by chloride in seawater. In addition, as marine development becomes more active, many concrete structures, such as bridges, breakwaters, and quaywalls, which are installed near seas, coasts, and seas, have been infiltrated from the outside of structures in high resolution, marine aerodromes, submarine tunnels, and deep-field oilfield exploration bases. Due to the effect of salts, the steel reinforcement buried in concrete becomes rusted and the volume increases about 1.8 to 2.5 times, resulting in deterioration such as cracking or peeling of the concrete structure under this expansion pressure. It is easy to penetrate moisture and oxygen due to the generation, and the corrosion of reinforcing steel is further promoted, and the durability of concrete is considerably lowered, and the destruction of concrete proceeds. Therefore, the issue of securing durability and reliability against reinforcing corrosion of the marine and marine concrete structures is very important.

The deteriorated concrete structure is thought to be easy to penetrate chloride ions, and the countermeasures need to be prepared. Recently, the construction of large concrete structures in seawater, marine environment, etc. has been increasing, causing corrosion of concrete structures. It is a big problem.

Nevertheless, in the past, there has been a separate construction of underwater undecomposed concrete and rust preventive concrete, and in the case of marine concrete, there is no example of simultaneously constructing underwater unseparated and rust prevented.

As a result, deterioration of durability performance by rust prevention is feared in water-indestructive concrete, while in water-resistant concrete, deterioration in water resistance of concrete such as deterioration in strength due to loss of cement in water is feared.

Particularly, in the case of pouring concrete in water from marine concrete, it is impossible to prevent corrosion of reinforcing steel by penetration of chloride ions, which can have a fatal effect on durability.In case of using only rust inhibitor in underwater concrete construction, It is not possible to prevent the decrease in strength and the deterioration of durability due to the loss of cement.

In addition, it is divided into water-incombustible admixture and anti-corrosive agent, so it is very difficult to use both admixtures at the same time in the existing ready-mixed concrete plant equipment. As described above, when two admixtures are used at the same time, the usage amount is 6.4kg / ㎥ ~ 10kg / ㎥. It is very economical and divided into liquid and powder.

Therefore, there has been a continuing need for a 1-type underwater fireproof rust preventive admixture that can be constructed using a single admixture for underwater fireless concrete and a rust preventive.

Therefore, an object of the present invention was devised to solve the above problems, a method for producing an underwater fire separation anti-corrosive admixture having an anti-corrosive function that can be commercialized in 1-type of the admixture for underwater fire-disconnected concrete and anti-rust agent To provide.

It is another object of the present invention to provide a method for preparing an underwater fire separation anti-corrosive admixture having an anti-rust function at the same time to significantly reduce the manufacturing cost by reducing the total weight of the anti- underwater fire-concrete admixture mixed with the anti-rust agent. have.

In order to achieve the above object, the method for producing an underwater fire-resistant sedimentation anticorrosive admixture having a rust preventing function according to the present invention comprises the steps of preparing a water-insoluble admixture by mixing a cellulose-based thickener and a high viscosity acrylic thickener; Blending the admixture with a coarsening agent, a liquid defoamer, and a fluidizing agent; And mixing by adding a powder rust inhibitor to the blend.

The liquid defoaming agent is preferably used 0.01 to 0.03% relative to the input amount of the fluidizing agent.

Hereinafter, a method for preparing an underwater fire-resistant rust preventive admixture having a rust prevention function according to the present invention will be described in detail.

Conventionally, 2.5 kg / m 3 to 3.5 kg / m 3 of the admixture used for water-disintegrated concrete was used, and 3.9 kg / m 3 to 6.5 kg / m 3 of the rust preventive agent was used. In addition, there was no construction example using them at the same time, and their usage increased, so it was not appropriate to use them together economically.

However, the present invention is to invent an economical product that can be used universally by reducing the total weight to 2.6kg / ㎥ by mixing the water-insoluble admixture and rust inhibitor by a new mixing method.

That is, in the past, thickeners, crude agents, powder defoamers, and glidants were used to prepare the water-in-separated admixture, and when these were mixed with the rust-preventing agent for the anti-corrosive function, their total amount of use increased, and thus the manufacturing cost was not economical. . Therefore, the present invention is a study on a method that can significantly reduce the amount of the raw material of the admixture and the rust inhibitor.

Looking at the raw materials for the preparation of the underwater fire-resistant rust preventive admixture having a rust prevention function according to the present invention as follows.

(1) thickener

① HPMC (HYDROXY PROPYL METHYL CELLULOSE)

② HEC (HYDROXY ETHYL CELLULOSE)

③ CMC (CARBOXY METHYL CELLULOSE)

④ EHEC (ETHYL HYDROXY ETHYL CELLULOSE)

⑤ POLY ACRYL AMIDE partial hydrolyzate

⑥ POLY SACCARIDE (curdlan, wellan, xanthan, guar gum)

⑦ HEMC ((HYDROXY ETHYL METHYL CELLULOSE)

⑧ SODIUM POLY ACRYLATE

⑨ PEO (POLY ETHYLENE OXIDE) thickener

⑩ EVA (ETHYLENE VINYL ACETATE) polymer

(2) steel

① amines such as diethanol amine, triethanol amine, organic acids such as silicic acid, acetic acid, acrylic acid, Ca (HCOO) ₂ , Na ₂ CO ₃ , OXALIC ACID, NaOH (strength reduction), sodium gluconate COMPLEX, PROPYONATE, UREA, GLYOXAL

② CALCIUM NITRATE (Ca (NO ₃ ) ₂ ), NaNO ₃ (SODIUM NITRATE)

③ CALCIUM NITRITE (Ca (NO ₂ ) ₂ ), NaNO ₂ ((SODIUM NITRITE)

④ Sulfates such as CaSO ₄ , Na ₂ SO ₄ , K ₂ SO ₄

⑤ carbonates such as CaCO ₃ , Na ₂ CO ₃ , K ₂ CO ₃

⑥ Silicates such as SODIUM SILICATE

⑦ Alumina type such as Al (OH) ₃ , Al ₂ O ₃

(3) antirust agent

① CALCIUM NITRITE (Ca (NO ₂ ) ₂ )

② NaNO ₂ ((SODIUM NITRITE)

③ chromate

④ silicate

Phosphate and organophosphate

⑥ Organic rust inhibitors, such as sulfonic acids, alkyl phenols, amines and organic acid mercaptans

(4) antifoam

① Organic polar antifoaming agents such as 2-ETHYL ETHANOL

② DIBUTHYL CARBONYL

③ POLYPROPYLENE GRYCOL defoamer

④ SORBITAN MONOLAURATE

⑤ SORBITAN MONOOLEATE

⑥ SORBITAN TRIOLEATE

⑦ TRI BUTHYL PHOSPHATE, DIISOBUTHYL CARBINOL, Amyl Alcohol, OLEIC ACID, TALL OIL, POLYPROPYLENE GRYCOL and its derivatives

⑧ Surfactant blend of SILICON RESINE and SILICON RESINE, inorganic powder blend of SILICON RESINE

⑨ Low alcohol such as METHANOL, ETHANOL, n-BUTHANOL

(5) Glidants (High Performance Reducers)

① MELAMINE series high performance water reducing agent

② POLYCARBONE acid high performance water reducing agent

③ modified LIGNINE series high performance water reducing agent

In the present invention, by using a cellulose thickener and a high-viscosity acrylic thickener is mixed to prepare a water-insoluble separation admixture, the amount of the total admixture is greatly reduced. In addition, by applying the liquid defoamer to the fluidizing agent in place of the powder defoamer used previously, the amount of the non-isolated admixture in the total water is reduced.

In addition, the powdered rust inhibitor is used instead of the conventional liquid rust inhibitor to reduce the amount of the predissolved rust inhibitor in water.

Step-by-step description of the step of producing a water-insoluble segregated rust preventing admixture having a rust-preventing function according to the present invention on the basis of such a characteristic method, (1) to prepare a water-insoluble admixture in water by mixing a cellulose-based thickener and a high viscosity acrylic thickener And (2) adding a coarse adjuvant, a liquid defoaming agent and a fluidizing agent to the admixture, and (3) adding a powdered rust inhibitor to the compound to mix the mixture.

According to the manufacturing method of the water-insoluble anti-corrosive admixture of the present invention as described above, while reducing the total weight of the existing admixture and rust inhibitor from 6.4kg / ㎥ to 10kg / ㎥ to 1.8kg / ㎥ ~ 3.0kg / ㎥ The anti-corrosive anti-corrosive admixture in water of 1-type product which is better in rust prevention performance and economical than 2-type product can be prepared.

The following are test results for the specimens obtained through various examples and comparative examples.

<Example 1>

1-type water-insoluble anti-corrosive anticorrosive admixture 2.6kg / ㎥ prepared by mixing a cellulose thickener and a high-viscosity acrylic thickener, and a mixture of a coarse and a powder rust preventive agent, and a fluidizing agent 8.8kg / ㎥ and a liquid antifoaming agent compared to a fluidizing agent. 0.01% was added, cement 440kg / ㎥, aggregate 643kg / ㎥, sand 994kg / ㎥, water 220kg / ㎥ was added to the specimen. At this time, the cement used was one kind of ordinary portland cement, and the maximum aggregate size of sand was 5mm or less, and the maximum size of coarse aggregate was 25mm or less of crushed stone. The air volume, flow, turbidity, pH, and compressive strength of the specimens were measured and the results are shown in Table 2.

<Example 2>

A specimen was prepared in the same manner as in Example 1 except that the amount of the liquid defoamer was 0.02% compared to the fluidizing agent, and the air content, flow, turbidity, pH, and compressive strength of the specimen were measured. It is shown in Table 2.

<Example 3>

A specimen was prepared in the same manner as in Example 1 except that the amount of the liquid defoamer was 0.03% compared to the fluidizing agent, and the air volume, flow, turbidity, pH, and compressive strength of the specimen were measured. It is shown in Table 2.

Comparative Example 1

Powder defoamer was used instead of liquid defoamer, and the specimen was prepared in the same manner as in Example 1 except that the powder defoamer was used 8% of the thickener, and the amount of air, flow, turbidity, pH, And the compressive strength was measured and listed in Table 2.

Comparative Example 2

Except that 10% of the powder defoamer was used compared to the thickener, a specimen was prepared by the same method as in Preparation Example 1, and the air volume, flow, turbidity, pH, and compressive strength of the specimen were measured and described in Table 2. .

Comparative Example 3

A specimen was prepared in the same manner as in Preparation Example 1 except that the powder defoamer was 13% compared to the thickener, and the air volume, flow, turbidity, pH, and compressive strength of the specimen were measured and described in Table 2. .

<Example 4>

Underwater fire separation admixture 0.8kg / ㎥ and powder antirust agent 1kg / ㎥ mixed with water fire separation rust inhibitor 1.8kg / ㎥ and fluidizing agent 8.8kg / ㎥, cement 440kg / ㎥, aggregate 643kg / ㎥, sand 994kg / ㎥ The specimen was prepared by adding to water, 220 kg / m 3, and the flow elapsed time, condensation time, turbidity, pH, compressive strength, and corrosion rate thereof were measured and described in Tables 4 to 8, respectively.

Example 5

A specimen was prepared in the same manner as in Example 4, except that 2.2 kg / ㎥ of the water-free separation anticorrosive admixture prepared by mixing 1.2 kg / ㎥ of the water-insoluble admixture and 1 kg / ㎥ of the powder rust inhibitor was used. The elapsed time, the setting time, the turbidity, the pH, the compressive strength, and the corrosion rate were measured and described in Tables 4 to 8, respectively.

<Example 6>

A specimen was prepared in the same manner as in Example 4 except that 2.6 kg / ㎥ of the water-insoluble anti-corrosive admixture prepared by mixing 1.6 kg / m 3 of the water-insoluble admixture and 1 kg / m 3 of the powder rust inhibitor was used. The elapsed time, the setting time, the turbidity, the pH, the compressive strength, and the corrosion rate were measured and described in Tables 4 to 8, respectively.

<Example 7>

A specimen was prepared in the same manner as in Example 4, except that 3 kg / m 3 of water-insoluble anti-corrosive admixtures prepared by mixing 2.0 kg / m 3 of water-insoluble admixtures and 1 kg / m 3 of powder rust inhibitors were used. The time, setting time, turbidity, pH, compressive strength, and corrosion rate were measured and described in Tables 4 to 8, respectively.

Comparative Example 3

2.6 kg / m3 of water-miscible admixture was mixed with 8.8 kg / m3 of fluidizing agent, and the mixture was added to 440 kg / m3 of aggregate, 643 kg / m3 of aggregate, 994 kg / m3 of sand, and 220 kg / m3 of water to prepare a specimen. The flow elapsed time, the setting time, the turbidity, the pH, the compressive strength, the corrosion rate and the like were measured and described in Tables 4 to 8, respectively.

<Comparative Example 4>

Except for adding 3.9kg / ㎥ of the liquid rust preventive agent was prepared in the same manner as in the manufacturing method of Comparative Example 3 and the flow elapsed time, condensation time, turbidity, pH, compressive strength, and corrosion rate The measurements were shown in Tables 4 to 8, respectively.

TABLE 1

division Antifoam Unit weight (kg / ㎥) 1 type underwater fire separation admixture (kg / ㎥) Liquid defoamer (fluidizing agent ×%) Powder Defoamer (Thickener ×%) cement aggregate sand water Glidants Example 1 0.01 440 643 994 220 8.8 2.6 Example 2 0.02 Example 3 0.03 Comparative Example 1 8 Comparative Example 2 10 Comparative Example 3 13

TABLE 2

division Air volume Flow Turbidity pH Compressive strength (kg / cm ² ) 3 days 7 days 28 days Example 1 3.8 52 49 10.1 158/173 245/270 289/350 Example 2 2.7 50 43 9.5 163/185 253/288 297/355 Example 3 2.5 47 40 9.3 166/191 256/296 301/360 Comparative Example 1 3.7 51 48 9.8 133/160 223/259 283/339 Comparative Example 2 2.6 49 42 9.4 136/163 227/264 287/344 Comparative Example 3 2.3 47 38 9.2 135/164 227/263 288/343

Table 2 shows the results of using the liquid defoamer and powder defoamer. As a result, the powder defoamer was included in the water inseparable admixture, and as the amount used increased, the air volume, flow, turbidity, and pH all decreased, and the compressive strength increased as the amount of the powder defoamer increased from 8% to 10%. 13% of use decreased slightly. The reason for this is that 8% of the antifoaming agent is used to increase the air content, and the compressive strength is lowered at 13% of the antifoaming agent. .

When the amount of liquid defoaming agent was used 0.01 ~ 0.03, the amount of air, flow, turbidity, and pH were decreased as the amount of liquid defoaming agent was used, and the compressive strength was increased. When 0.01% of the liquid defoaming agent is used, the compressive strength is slightly decreased due to the increase in air volume.

Therefore, the liquid defoaming agent proposed in the present invention is not included in the water-incombustible admixture, and even when the water-in-compass admixture is mixed, the amount of the powder defoamer can be increased by increasing the amount or the amount of the water-incombustible admixture can be reduced. It is judged to be suitable for the specification of the heavy fire separation admixture.

TABLE 3

division Underwater fire separation admixture (kg / ㎥) Liquid rust preventive agent (kg / ㎥) Unit weight (kg / ㎥) The present invention (mixing agent + rust inhibitor) Conventional Conventional cement aggregate sand water AD Example 4 1.8 440 643 994 220 8.8 Example 5 2.2 Example 6 2.6 Example 7 3 Comparative Example 4 2.6 Comparative Example 5 2.6 3.9

TABLE 4

division Flow elapsed time Immediately 30 seconds 60 seconds 3 minutes 5 minutes 60 minutes Example 4 43 45 48 52 53 51 Example 5 42 44 45 51 52 50 Example 6 40 42 44 50 52 50 Example 7 38 40 42 48 50 48 Comparative Example 4 38 41 43 48 51 49 Comparative Example 5 37 40 41 47 49 47

As used in Examples 4 to 7, the amount of the water-insoluble anti-corrosive admixture according to the present invention was used in the range of 1.8 to 3.0 kg / m 3, and it was found that the flow was slightly decreased as the amount was increased. It was similar to or better than the sample according to 5.

TABLE 5

division Response time Candle texture Termination Example 4 18: 17 19: 49 Example 5 19: 35 21: 10 Example 6 20: 00 21: 48 Example 7 20: 47 22: 00 Comparative Example 4 21: 10 22: 27 Comparative Example 5 19: 30 21: 11

In order to solve the problem that the condensation time is delayed when the amount of the conventional water-insoluble admixture is increased, in the present invention, the condensation time is measured as in Examples 4 to 7 and Comparative Examples 4 to 5, and is shown in Table 5.

As shown in Table 5, a mixture (1 type) of water-miscible admixture and rust inhibitor was used in the range of 1.8 to 3.0kg / ㎥, and the condensation time was delayed as the amount of use increased. At least 5 hours of initial and 30 hours of termination were all suitable. Rather, it was found that Examples 3 to 6 were faster in early termination than those using only the water-incombustible admixture of Comparative Example 4. This is judged to be due to the crude steel component of the rust preventive agent contained in Examples 3 to 6.

TABLE 6

division Turbidity (ppm) pH Example 4 42 9.5 Example 5 43 9.5 Example 6 42 9.4 Example 7 35 9.3 Comparative Example 4 38 9.2 Comparative Example 5 37 9.2

Table 6 shows turbidity and pH. Compared to using only water-insoluble admixtures, the use of mixed anti-corrosive agent (1 type) showed slightly higher turbidity and pH, but it was found to meet the standards of turbidity of 150ppm or less and pH 12 or less.

TABLE 7

division Compressive strength (kg / cm ² ) 7 days 28 days 91 days 6 months Example 4 195/241 283/327 318/360 340/381 Example 5 227/259 291/340 324/378 367/395 Example 6 229/263 305/347 343/388 377/403 Example 7 238/283 322/370 358/409 387/428 Comparative Example 4 231/267 306/351 321/403 362/416 Comparative Example 5 235/270 307/351 323/405 366/417

Table 7 shows the compressive strength results. In the case of using the water-insoluble admixture alone, the strength of 7 days and 28 days was slightly higher, but it was found that the strength of the mixed type of rust inhibitor proposed by the present invention increases with the long-term age. The underwater / air compressive strength ratio was over 80%, which satisfies the regulations of the Korean Society of Civil Engineers.

TABLE 8

division Corrosion rate Example 4 0.08% Example 5 0.08% Example 6 0.07% Example 7 0.05% Comparative Example 4 5.4% Comparative Example 5 0.1%

Table 8 shows the results of the corrosion promotion test according to KS F 2561. Corrosion rate of using only water-insoluble admixtures was high as 5.4%, and the mixed corrosion inhibitor (1 type) proposed in the present invention was used in the range of 1.8 to 3.0 kg / m 3, and almost no corrosion was achieved at 0.08% to 0.05%. I could see that not.

Therefore, the amount of water fire separation admixture proposed in the present invention and the anti-water fire separation admixture mixed with the anti-corrosive agent as 1-type is compared with the conventional use of the water fire separation admixture alone, which is the same as the conventional use. As a result, the flow elapsed time, the setting time, the turbidity, the pH, the flow, the compressive strength was similar or excellent, the corrosion rate was confirmed that the 1-type underwater fire separation rust preventive admixture proposed in the present invention is much better.

However, in consideration of the compressive strength and the flow economical efficiency of the water-insoluble anti-corrosive admixture prepared according to the present invention, it is determined that it is preferable to use 2.6 kg / m 3 rather than 3.0 kg / m 3.

As mentioned above, the water-in-oil separation anticorrosive admixture having a rust-preventing function simultaneously according to the present invention is easy to use by commercializing the conventional admixture and anti-corrosive agent for water-in-fire separation concrete, respectively, in the 1-type, By reducing the total weight of the rust preventive mixed with the admixture for heavy fire separation concrete, there is an advantage that can significantly reduce the manufacturing cost.

On the other hand, while the above has been described with reference to the preferred embodiments of the present invention, those skilled in the art to which the present invention pertains without departing from the spirit and scope of the present invention described in the claims below It will be understood that modifications and changes can be made.

Claims (2)

Preparing a water-insoluble admixture by mixing a cellulose thickener and a high viscosity acrylic thickener; Blending the admixture with a coarsening agent, a liquid defoamer, and a fluidizing agent; And Method for producing an underwater fire-resistant anti-corrosion admixture having a rust prevention function, characterized in that it comprises the step of adding a powder rust inhibitor to the blend. The liquid antifoaming agent is a method for producing an underwater fire-resistant anti-corrosive admixture having a rust prevention function, characterized in that the use of 0.01 to 0.03% of the amount of the fluidizing agent.