KR101152361B1 - Eco-friendly admixture of concret using water containing anion - Google Patents

Abstract

PURPOSE: An environmentally-friendly concrete additives using anion water is provided to reduce smell of ammonia and hexavalent chrome which are harmful material among concrete by including methoxy polyethylene glycol methacrylic acid, graft polymer, water reducing agent, air-entraining agent, and strength enhancer. CONSTITUTION: An environmentally-friendly concrete additives using anion water comprises 20-30 parts by weight of water reducing agent, 6-10 parts by weight of air entraining agent, 4-10 parts by weight of strength development material based on 100.0 parts by weight of negative ion water. The water reducing agent is methoxypolyethylene glycol - methacrylic acid graft-copolymer. The air entraining agent is alky benzene sulfonate Fe salt, olefin sulfonate Fe salt, or a mixture thereof. The strength enhancer is triethanol amine, lithium nitrate, or a mixture thereof. The negative ion water contains (CO3)10-300mg/liter, (HCO3)20-500mg/liter, and (SO4) 10-500mg/liter.

Description

Eco-friendly admixture of concret using water containing anion}

The present invention relates to concrete additives using concrete admixtures and anionic water.

Concrete admixtures are materials that are added as a component of concrete when needed when mixing with concrete or mortar as components other than cement, water and aggregates, and improve the properties of unconsolidated concrete, hardened concrete or mortar, It is used to obtain properties that are difficult to obtain when it is not added by adding it, and air-entraining agents or water reducing agents are known as admixtures.

The present invention uses mortar by using water additives containing a large amount of anions and concrete additives composed of water reducing agents, air entrainers, strength enhancers, etc., which are methoxy polyethylene glycol methacrylic acid graft polymers. It is a concrete (lemicon) additive for improving workability and resistance to freezing, improving strength and durability of hardened materials, and preventing sick house syndrome.

The mixed materials of cement or concrete are classified according to the amount of use, the effect of action of the materials, the purpose of use, and the composition of the materials. Industrial by-products such as fine powders are classified as admixtures, and organic liquids used in small amounts, such as chemicals having a mixing ratio of about 3% by weight or less, such as air emulsifiers or water reducing agents, are classified as admixtures.

Concrete does not immediately harden in contact with water and maintains fluidity for a certain period of time, and loses fluidity as it is hydrated by an exothermic reaction. This is because the clinker minerals constituting the cement particles react with water to develop new tissue, and this reaction time is called setting. It hardens slowly after condensation and develops strength. This step is called hardening. The hardening reaction takes a considerable time, and the gel of cement hydrate produced during hardening is a fine aggregate, filling the pores with time. In addition, the early strength of concrete is closely related to the rate of hydration of cement, and the use of admixture among the factors affecting the rate of hydration has a great influence. As described above, the concrete admixture exhibits sufficient dispersibility even when the concrete composition is sensitized to secure its fluidity and workability, and maintains stable dispersibility over time, thereby minimizing condensation delay and It improves the properties of concrete to increase strength and durability.

On the other hand, in recent years, casting sand of industrial steel mills, slag (sewage or water purification sludge), incinerators for incineration plants, dust collectors for thermal power plant dust collectors, etc. have been used as cement raw materials. During the firing process, some of the chromium contained in industrial waste is converted to hexavalent chromium and included in the final product cement, which is inhaled and penetrated into the human body, causing disorders in the skin and mucous membranes, causing various cancers, skin diseases, atopy, allergies, In case of new construction of concrete, due to strong alkali nitrogen compound which contains ascending asthma or curing of concrete and reacts with organic impurities or moisture, and releases basic harmful ammonia gas, the specific smell is so-called sick house syndrome. Problem that is caused by conk Improve the performance of the agent admixture, while the last has become an urgent need for the development of functional additives with environmentally friendly features that problematization and 6 are reduced or reduction of ammonia gas, known as sick building syndrome chrome.

However, the concrete additives developed so far have not been studied for the development of concrete additives having both an improved performance and eco-friendly functions of admixtures. For example, Japanese Patent Application Laid-Open No. 2004-182583 and Korean Patent Application Publication No. 10-979768 include polyoxygen. Cement admixtures using copolymers such as ethylenic monomers and unsaturated organic acid monomers having alkylene groups are disclosed, and Korean Patent Nos. 10-0760586 and 616176 include cement compositions containing polycarboxylic acid polymers. Cement admixture is disclosed that improves susceptibility, fluidity, and excellent slump retention performance. Korean Patent Publication No. 1986-6922 discloses a cationic polyhydride selected from the group consisting of ammonium, alkylammonium and alkanolammonium as admixtures for hydraulic cement compositions Roxy compounds are disclosed, all of which relate to admixtures However, the function of reducing hexavalent chromium contained in cement or reducing ammonia gas known as sick house syndrome is not suggested at all, and Korean Patent Laid-Open No. 1998-39042 discloses a method for removing hexavalent chromium present in cement. Reduction of hexavalent chromium in the cement into trivalent chromium by adding a reducing agent such as ferrous sulfate (FeSO'H2O) or ferrous sulfate (FHSO7'H2O) during cement grinding. The present invention, Korean Patent Publication No. 10-2006-61316 discloses a technique for suppressing the release of hexavalent chromium by re-coated with a surface treatment composition on the cement floor, the domestic Patent No. 10-1046557 ( A technique for preparing ready-mixed concrete using water containing anions such as CO 3) ^2- , (HCO₃) ^1- , and (SO₄) ^2- has been disclosed. It is not disclosed at all.

Japanese Patent Publication No. 2001-220417 : Domestic Patent Publication No. 979768 : Domestic Patent Publication No. 0760586 : Domestic Patent Publication No. 0615376 : Korean Patent Publication No. 1986-6922 : Korean Patent Publication No. 1998-39042 : Domestic Publication No. 2006-61316 : Domestic Patent Publication No. 1046557

An object of the present invention is to use water containing anions such as (CO₃) ^2- , (HCO₃) ^1- , (SO₄) ^2- and methoxy polyethylene glycol methacrylic acid graft polymer It is a concrete additive composed of phosphorus reducing agent, air entrainer and strength enhancer to reduce the odor of hexavalent chromium and ammonia, which are harmful substances in concrete, and exhibit sufficient dispersibility even when water is reduced. It is to provide a concrete additive to increase the strength and durability by improving the physical properties of the concrete by minimizing the condensation delay and maintaining a stable dispersibility over time.

In order to achieve the above object, the concrete additive of the present invention is (CO₃) ^2- , (HCO₃) ^1- , (SO ₄) ^2- and water containing an anion such as methoxy polyethylene glycol methacrylic acid graft copolymer (Methoxy Polyethylene Air binder, triethanol amine and lithium nitrate, composed of glycol methacrylic acid graft polymer, water sensitizer, alkyl benzene sulfonate Fe and olefin sufonate Fe Characterized in that it contains a strength enhancer composition.

When the concrete additive of the present invention is added to the concrete composition, the workability can be increased to reduce the cement and aggregate while securing fluidity and workability, minimizing condensation delay, and improving durability and strength due to water reduction, and at the same time, By maintaining a stable dispersibility, thereby improving the physical properties of the concrete to increase the strength and durability.

In addition, the anion-containing water in the present invention is present in the cement by a chemical reaction with a sensitizer, which is a methoxy polyethylene glycol methacrylic acid graft polymer mainly composed of Fe sulfonate salt. Hexavalent chromium is reduced to trivalent chromium, which is harmless to the human body, and ammonia forms complex salts to remove cement poisons, thereby enabling eco-friendly functions.

According to the present invention, the anion-containing water is present in the cement by chemical reaction with a sensitizer, which is a methoxy polyethylene glycol methacrylic acid graft polymer composed mainly of Fe sulfonate salts. The chromium is reduced to trivalent chromium, which is harmless to the human body, and the ammonia forms a complex salt to remove cement poisons to remove side effects such as sick house syndrome, and exhibits sufficient dispersibility to secure fluidity and workability. By minimizing the delay and realizing the durability and strength improvement by the supervision, while maintaining a stable dispersibility over time, it has the effect of improving the physical properties of the concrete to increase the strength and durability.

Concrete additive of the present invention is a methoxy polyethylene glycol methacrylic acid graft polymer (Methoxy Polyethylene glycol methacrylic acid graft polymer) in order to increase the dispersibility and fluidity, and the sulfonic acid-based Alkylbenzene sulfonate Fe salt and olefin sulfonate Fe salt It is composed of air entrainer and strength enhancer consisting of Triethanol amine and lithium nitrate. The water used is underground water containing large amount of (CO₃) ^2- , (HCO₃) ^1- , and (SO₄) ^2-. It is done.

The water reducing agent electrostatically activates and disperses the cement particles in the concrete, so that the cement particles repel each other to improve workability, and are used for the purpose of reducing the unit quantity and unit cement amount in order to obtain a predetermined consistency and strength. The sensitizer component is generally lignin-based, naphthylene-based, melamine-based or polycarboxylic acid-based.

Among these components, the lignin system has the disadvantage of causing curing delay and strength deterioration when used excessively, and the melamine system has a disadvantage that a relatively large amount is used. Its use is limited.

In the present invention, a carboxylic acid-based methoxy polyethylene glycol methacrylic acid graft polymer having excellent dispersibility, fluidity, water resistance, and excellent slump retention capacity was used as a water reducing agent. .

Air emulsifier (AE agent) generates many independent micro-foams in concrete and acts as a bearing around fine sand, improving workability and freeze-melting resistance. Are anionic surfactants (fatty acid soap type, sulfate ester type, sulfonic acid type, phosphate ester type, etc.) and nonionic surfactant type, but in the present invention, Alkylbenzene sulfonate Fe salt and olefin sulfonate in sulfonate type, which is a kind of anionic surfactant Fe salt was used.

Strength enhancers include inorganic salts (carbonates, sulfates, nitrates, chlorides, etc.) and organic compounds (Amines, organic salts, etc.), but in the present invention, triethanol amine and lithium nitrate were used. . As the mixed water, groundwater around the royal palace hot spring in Wanggung-myeon, Iksan-si, Jeonbuk, which contains large amounts of anions such as (CO₃) ^2- , (HCO₃) ^1- , and (SO₄) ^2- , was used.

The mixing ratio of the concrete additive according to the present invention is as follows.

① 100 parts by weight of anion water

② 20 to 30 parts by weight of a water reducing agent which is a methoxy polyethylene glycol methacrylic acid graft copolymer (Methoxy Polyethylene glycol methacrylic acid graft polymer)

(Methoxy Polyethylene glycol methacrylic acid graft Polymer)

③ Air entrainment

Alky benzene Sulfonate Fe salt 3 to 10 parts by weight

3 to 10 parts by weight of olefin sufonate Fe salt

④ strength enhancer

2 to 5 parts by weight of triethanol amine

lithium nitrate 2 to 5 parts by weight

In the cement additive according to the present invention, hexavalent chromium and ammonia contained in cement react as follows.

○ Reaction of Anion with Ammonia in Water

   2NH₄ + SO₄² → (NH₄) ₂SO₄

○ Reaction of Fe salt with ammonia

   Fe² + 2NH₄ → Fe (NH₄) ²

○ Reaction of Fe Salt with Hexavalent Chromium

6Fe² + Cr₂O² + 14H₂O → 2Cr³ + 6Fe³ + 7H₂O

That is, the ammonia generated during the construction of concrete structures reacted with anions in water to form complex salts, and hexavalent chromium reacted with Fe salts to reduce trivalent chromium, which is harmless to humans.

Hereinafter, examples and comparative examples according to the formulation of the ready-mixed concrete composition of the present invention are shown, but the present invention is not limited by the following examples.

≪ Example 1 >

 Cement: 10 kg

 Fine Aggregate: 15kg

 Coarse aggregate: 17 kg

Water containing anions: 7.0 kg

Methoxy Polyethylene glycol methacrylic acid graft Polymer: 2kg

Alky benzene Sulfonate Fe salt and olefin sufonate Fe salt: 0.8kg

Triethanol amine and lithium nlitrate: 0.6 kg

<Example 2>

 Cement: 10 kg

 Fine Aggregate: 15kg

 Coarse aggregate: 17 kg

Water containing anions: 7.0 kg

Poly stylene sulfonate Fe salt: 0.5kg

Methoxy Polyethylene glycol methacrylic acid graft Polymer: 2kg

Alky benzene Sulfonate Fe Salt: 0.8kg

Triethanol amine: 0.6kg

<Example 3>

 Cement: 10 kg

 Fine Aggregate: 15kg

 Coarse aggregate: 17 kg

Water containing anions: 7.0 kg

Methoxy Polyethylene glycol methacrylic acid graft Polymer: 2kg

olefin sufonate Fe salt: 0.8kg

lithium nlitrate: 0.6kg

 Comparative Example 1

 Cement: 10 kg

 Fine Aggregate: 15kg

 Coarse aggregate: 17 kg

General water: 7.0kg

Comparative Example 2

 Cement: 10 kg

 Fine Aggregate: 15kg

 Coarse aggregate: 17 kg

 General water: 7.0kg

Lignin-based sensitizer: 2kg

Sulfate ester air binder: 0.8kg

Examples 1 to 3 and Comparative Examples 1 and 2 are components used for preparing ready-mixed concrete in a conventional ready-mixed concrete manufacturing process. Examples 1 to 3 added water containing an anion as water and additives of the present invention. In Comparative Examples 1 and 2, no admixture was added to general water (ground water or industrial water), and Comparative Example 2 added a conventional admixture to commercial water (ground water or industrial water) to prepare ready-mixed concrete. Prepared.

As a result of measuring the physical properties of the concrete and the amount of detection of hexavalent chromium and ammonia for the ready-mixed concrete compositions of Examples 1 to 3 and Comparative Examples 1 and 2, it is as shown in [Table 1].

division slump
(cm) Air volume
(%) Reduction rate
(%) Bleeding ratio
(%) Compressive strength ratio
(Standard 100) Hexavalent chrome
(mg / kg) ammonia
ppm 3 days 7 days 28 days Example 1 19.20 4.5 25.2 48 146 131 121 3 Not detected Example 2 18.00 4.2 24.7 53 140 128 120 4 Not detected Example 3 18.31 4.3 24.5 49 141 129 118 4 Not detected Comparative Example 1 9.53 1.8 - 58 140 128 125 15 4 Comparative Example 2 14.65 3.5 17.5 40 105 103 100 14 3

The physical property test of the concrete of [Table 1] was conducted according to the standard of KSF2560 (2007), the hexavalent chromium detection test was the test according to the IEC62321 Ed 1.06 (2006), the ammonia detection test was a gas It was measured using a detector (GV-100SDML, Gastec).

As can be seen from Table 1, ammonia was not detected in the product prepared according to the method of the present invention, and hexavalent chromium was also detected in a small amount compared to the existing products, Comparative Examples 1 and 2, which are environmentally friendly products. Although the air flow rate and slump susceptibility were high, the bleeding ratio was not significantly different from existing products, and it was confirmed that the fluidity was high and the durability and the compressive strength were excellent.

Claims (5)

20 to 30 parts by weight of a water reducing agent which is a methoxy polyethylene glycol methacrylic acid graft polymer, Alky benzene Sulfonate Fe salt or Olefin sufonate Fe salt, or 100 parts by weight of anionic water Concrete additive composition comprising 6 to 10 parts by weight of an air entrainer which is a mixture of 3 to 10 parts by weight of one or a mixture of triethanol amine or lithium nitrate. delete The method of claim 1,
The air entrainer is an alkyl benzene sulfonate salt, and the strength enhancer is triethanol amine. The method of claim 1,
The anionic water is an anionic water containing 10 to 300 mg / l of (CO₃) ^2- , 20 to 500 mg / l of (HCO₃) ¹ , and 10 to 500 mg / l of (SO₄) ^2-. . 100 to 150 parts by weight of fine aggregate, 100 to 200 parts by weight of coarse aggregate, 50 to 70 parts by weight of water containing an anion, methoxy polyethylene glycol methacrylic acid graft concrete) comprising 2 to 6 parts by weight of a water reducing agent which is a polymer), 1 to 3 parts by weight of an alky benzene sulfonate salt of an air entrainer, and 1 to 2 parts by weight of triethanol amine, which is a strength enhancer. Composition.