JP5313623B2 - Cement admixture and cement composition - Google Patents

Description

  The present invention mainly relates to a cement admixture and a cement composition used in the civil engineering and construction industries.

  In recent years, there has been an increasing demand for improving the durability of concrete structures in the civil engineering and construction fields.

  One of the causes of deterioration of concrete structures is salt damage in which reinforcing steel corrosion becomes obvious due to the presence of chloride ions. A method to give chloride ion penetration resistance to concrete structures as a method to suppress the salt damage. There is.

  As a method for suppressing chloride ion penetration into the inside of a hardened concrete and imparting chloride ion penetration resistance, a method of reducing the water / cement ratio is known (see Non-Patent Document 1). However, the method of reducing the water / cement ratio has a problem that not only the workability is impaired but also a drastic measure is not taken.

In addition, for the purpose of imparting early strength to cement concrete and preventing corrosion of reinforcing steel bars, it is a fine powder mainly composed of CaO.2Al ₂ O ₃ and gypsum and having a brain specific surface area value of 8,000 cm ² / g. Chloride ion infiltration using a cement admixture containing calcium aluminate with a CaO / Al ₂ O ₃ molar ratio of 0.3 to 0.7 (see Patent Document 1) A method for improving resistance (see Patent Document 2) has been proposed.

  On the other hand, activated silica such as silica fume and fly ash can improve the penetration resistance of chlorine ions without lowering the initial strength with a relatively small addition amount. One of the common reasons for suppressing the penetration of chloride ions in these admixtures is related to the reduction of calcium hydroxide in the hardened cementitious body, and several dozens that are formed when calcium hydroxide is leached into seawater. It is considered that the generation of voids of μm to several hundred μm is suppressed. However, even when activated silica is used, the pozzolanic reaction takes place over a long period of time. Therefore, when immersed in seawater at a young age, there is a problem that the resistance to penetration of chloride ions decreases and the concrete deteriorates. Therefore, in order to improve durability, that is, seawater resistance, it is necessary to suppress the leaching due to the action of seawater by suppressing the generation of calcium hydroxide in the hardened cement body as much as possible from the initial age.

  On the other hand, a method of adding nitrite or nitrite-type hydrocalumite has also been proposed for the purpose of rust prevention of reinforcing bars (see Patent Documents 3 to 5). However, although nitrite exhibits a rust prevention effect, it does not exert a shielding effect against chloride ions entering from the outside, and nitrite hydrocalumite exhibits a rust prevention effect. However, the hardened cement paste containing the material tends to be porous, but rather has a problem that it easily allows permeation of chloride ions from the outside.

Koichi Kishitani, Noriaki Nishizawa et al., “Durability series of concrete, salt damage (I)”, Gihodo Publishing, pp. 49-54, May 1986 JP 47-035020 A JP 2005-104828 A JP-A-53-003423 Japanese Patent Laid-Open No. 01-103970 Japanese Patent Laid-Open No. 04-154648

  Provides excellent rust prevention effect to the reinforcing steel bars inside the hardened cement concrete, shielding effect of chloride ion penetration into the hardened cement concrete from the outside, neutralization suppressing effect of hardened cement concrete, wear resistance Furthermore, the present invention provides a cement admixture and a cement composition that can suppress porosity due to less leaching of Ca ions from the hardened cement concrete.

The present invention is, (1) cement and, CaO / _Al 2 _{O 3} molar ratio of 4000~5000cm ² / g calcium aluminate compounds and naphthalene sulfonate in Blaine specific surface area value of 0.5 to 0.7 It contains a water reducing agent that is one or more selected from a formalin condensate, a formalin condensate of melamine sulfonate, and a polycarboxylate polymer compound, and a calcium aluminate compound and a water reducing agent, The mixing ratio is 50 to 500 parts by mass of a water reducing agent with respect to 100 parts by mass of the calcium aluminate compound, and the cement admixture is 100 parts by mass of cement and cement admixture. during parts, 10 to 20 parts by weight, the cement composition, (2) cement and CaO / _Al 2 _{O 3} molar ratio 0.5 to 0.7 Calcium aluminate compounds of 4000~5000cm 2 / ^g in Blaine specific surface area and formalin condensate of naphthalene sulfonate, formalin condensate of melamine sulfonate, one selected from the group consisting of a polycarboxylic acid salt-based polymer compound Or containing two or more water reducing agents, and the blending ratio of the calcium aluminate compound and the water reducing agent is 50 to 500 parts by weight of the water reducing agent with respect to 100 parts by weight of the calcium aluminate compound. the total of the compound and water reducing agent, in a total of 100 parts by weight of cement and calcium aluminate compounds and water-reducing agent, 10 to 20 parts by weight, the cement composition is.

  By using the cement admixture and the cement composition of the present invention, it gives an excellent rust prevention effect to the reinforcing steel inside the cement concrete hardened body, and shields the chloride ion penetration into the cement concrete hardened body entering from the outside. In addition, it has an effect of suppressing the neutralization of the hardened cement concrete, and further has an effect of suppressing the porous formation because Ca ions are hardly leached from the hardened cement concrete.

The present invention will be described in detail below.
In the present invention, “parts” and “%” are based on mass unless otherwise specified.
The cement concrete referred to in the present invention is a general term for cement paste, cement mortar, and concrete.

The calcium aluminate compound (hereinafter referred to as CA compound) used in the present invention is a mixture of calcia-containing raw material and alumina-containing raw material, and heat treatment such as firing in a kiln or melting in an electric furnace. resulting Te is intended to generically compounds mainly containing CaO and _Al 2 _{O 3,} present invention has a composition, in CaO / _Al 2 _{O 3} molar ratio in the range of 0.15 to 0.7 It is what. Even if the CA compound contains, for example, SiO ₂ or R ₂ O (R is an alkali metal), it can be used as long as the object of the present invention is not impaired. The CaO / Al ₂ O ₃ molar ratio of the CA compound is 0.15 to 0.7, preferably 0.4 to 0.6. If it is less than 0.15, the chloride ion shielding effect may not be sufficiently obtained. Conversely, if it exceeds 0.7, rapid hardening may appear, and the pot life may not be secured.
Fineness of CA compound, Blaine specific surface area value (hereinafter, referred to as Blaine value) is preferably 2000~7000cm ² / g, the more preferred ^{3000~6000cm 2 / g, 4000~5000cm 2 /} g being most preferred. If the CA compound is coarse, a sufficient chloride ion shielding effect may not be obtained, and if it is a fine powder exceeding 7000 cm ² / g, rapid hardening will appear and the pot life may not be ensured.

In the present invention, a water reducing agent is used in combination with a CA compound having a CaO / Al ₂ O ₃ molar ratio of 0.15 to 0.7.
The water reducing agent is not particularly limited as long as it includes an AE water reducing agent, a high performance water reducing agent, a high performance AE water reducing agent, and a fluidizing agent and is commercially available that can be mixed with concrete or mortar. For example, when classified by chemical component, lignin sulfonate and derivatives thereof, oxycarboxylate, polyol derivative, polyoxyethylene alkyl allyl ether, alkyl allyl sulfonate formalin condensate, naphthalene sulfonate formalin condensate, Examples thereof include amino sulfonate compounds, formalin condensates of melamine sulfonate, and polycarboxylic acid polymer compounds. Especially, it is preferable that it is 1 type, or 2 or more types chosen from the formalin condensate of naphthalene sulfonate, the formalin condensate of melamine sulfonate, and a polycarboxylate-type high molecular compound.
These water reducing agents may be liquid or powdery in which the water reducing agent component is dissolved in water.

  As for the compounding ratio of a CA compound and a water reducing agent, 5-1000 parts of a water reducing agent are preferable normally with respect to 100 parts of CA compounds by mass ratio, and 10-500 parts is more preferable. If the amount of water reducing agent is excessive, the setting may be delayed, and if the amount of water reducing agent is small, sufficient fluidity may not be obtained.

  As the cement, various portland cements such as normal, early strength, super early strength, low heat, and moderate heat, various mixed cements in which blast furnace slag, fly ash, or silica is mixed with these portland cements, limestone powder and blast furnace slow Portland cement such as filler cement mixed with fine powder of cold slag, etc., and environmentally friendly cement (eco-cement) manufactured using municipal waste incineration ash and sewage sludge incineration ash as raw materials are listed. Or 2 or more types can be used.

  Although the usage-amount of a cement admixture is not specifically limited, Usually, 1-30 parts are preferable in a cement composition which consists of cement and a cement admixture, and 5-15 parts are more preferable. If the amount of cement admixture is small, sufficient rust prevention effect, chloride ion shielding effect, Ca ion leaching suppression effect may not be obtained, and if used excessively, rapid hardening will appear and sufficient The pot life may not be secured.

  In the present invention, cement and a cement admixture are blended, and cement, the present CA compound, and a water reducing agent are blended to obtain a cement composition.

The water / binder ratio of the cement composition of the present invention is preferably 25 to 70%, more preferably 30 to 65%. If the blending amount of water is small, the pumpability and workability may be reduced or shrinkage may be caused. If the blending amount of water is excessive, the strength development may be degraded.
Here, the binder refers to the total of cement, CA compound, and water reducing agent.

  In the cement admixture and cement composition of the present invention, the respective materials may be mixed at the time of construction, or a part or all of them may be mixed in advance.

  In the present invention, in addition to cement, cement admixture, and fine aggregates such as sand and coarse aggregates such as gravel, expansion material, rapid hardening material, AE agent, antifoaming agent, thickener, conventional rust prevention , Slag such as granulated blast furnace slag fine powder and blast furnace slow-cooled slag fine powder, limestone fine powder, etc. It is possible to use together 1 type or 2 types or more of the group which consists of admixtures in the range which does not inhibit the objective of this invention substantially.

  As the mixing device, any existing device can be used, and for example, a tilting mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used.

  Hereinafter, the contents will be described in more detail, but the present invention is not limited to these.

"Experiment 1"
A cement admixture was prepared by mixing 50 parts of the water reducing agent A with 100 parts of the CA compound shown in Table 1. Using the prepared cement admixture, a cement composition is prepared by blending 10 parts of cement admixture in 100 parts of cement composition composed of cement and cement admixture, and mortar with a water / binder ratio of 35% is prepared according to JIS. Prepared according to R 5201. Using this mortar, the rust prevention effect, compressive strength, chloride penetration depth, and Ca ion leaching were examined. The results are also shown in Table 1.

<Materials used>
CA compound A: Reagent primary calcium carbonate and reagent primary aluminum oxide were blended at a predetermined ratio, baked at 1650 ° C. in an electric furnace, and then slowly cooled to synthesize. CaO / Al ₂ O ₃ molar ratio 0.1, Blaine value 4000 cm ² / g
CA compound B: synthesized in the same manner as CA compound A, CaO / Al ₂ O ₃ molar ratio 0.15, Blaine value 4000 cm ² / g
CA compound C: Reagent primary calcium carbonate and reagent primary aluminum oxide were blended in a predetermined ratio, baked at 1550 ° C. in an electric furnace, and then slowly cooled to synthesize. CaO / Al ₂ O ₃ molar ratio 0.4, Blaine value 4000 cm ² / g
CA compound D: synthesized in the same manner as CA compound C, CaO / Al ₂ O ₃ molar ratio 0.5, Blaine value 4000 cm ² / g
CA compound E: synthesized in the same manner as CA compound C, CaO / Al ₂ O ₃ molar ratio 0.6, Blaine value 4000 cm ² / g
CA compound F: Reagent grade 1 calcium carbonate and reagent grade 1 aluminum oxide are blended at a predetermined ratio, baked at 1450 ° C. in an electric furnace, and then slowly cooled to synthesize. CaO / Al ₂ O ₃ molar ratio 0.7, Blaine value 4000 cm ² / g
CA compound G: synthesized in the same manner as CA compound F, CaO / Al ₂ O ₃ molar ratio 0.9, Blaine value 4000 cm ² / g
Water reducing agent A: Polycarboxylic acid compound, Commercial cement: Normal Portland cement, Commercial fine aggregate: Standard sand water used in JIS R 5201: Tap water

Corrosion protection: as mortar endogenous chloride ions, confirm the anticorrosive effect in accelerated test by the 10 kg / m ³ and comprising as the chloride ion addition, it puts reinforcing steel round bars heated curing in 50 ° C. did. The case where rust did not occur in the reinforcing bars was good, the case where rust occurred within an area of 1/10 was acceptable, and the case where rust occurred beyond an area of 1/10 was deemed impossible.
Compressive strength: Measure compressive strength at age 28 days according to JIS R 5201.
Chloride penetration depth: Evaluate chloride ion penetration resistance. A 10 cmφ × 20 cm cylindrical mortar specimen showing the shielding effect of chloride ions was produced, and the produced mortar specimen was subjected to water curing at 20 ° C. until the age of 28 days, and a salt concentration of 30 ° C. was 3.5. After immersing for 12 weeks in simulated seawater, which is a 10% salt solution, the chloride penetration depth was measured. The chloride penetration depth was determined by the fluorescein-silver nitrate method, the portion of the cross section of the mortar specimen where the tea did not change was regarded as the chloride penetration depth, and the average value was obtained by measuring 8 points with calipers.
Neutralization depth: Measured according to JIS A 1171.
Ca ion leaching: Determination was made by immersing a 4 × 4 × 16 cm mortar specimen in 10 liters of pure water for 28 days and measuring the concentration of Ca ions dissolved in the liquid phase.

"Experimental example 2"
It carried out similarly to Experimental example 1 except having used CA compound D of the fineness shown in Table 2. The results are also shown in Table 2.

"Experiment 3"
The same operation as in Experimental Example 1 was conducted except that CA compound D was used and the water reducing agent shown in Table 3 was used in combination. The results are also shown in Table 3.

<Materials used>
Water reducing agent B: Lignin sulfonate, commercial water reducing agent C: Naphthalene sulfonate formalin condensate, commercial water reducing agent D: Melamine sulfonic acid formalin condensate, commercial water reducing agent E: Water reducing agent a and water reduction Mixture of water-reducing agent, mixing ratio is 100 parts of water-reducing agent i 300 parts of water-reducing agent h Water-reducing agent G: Water-reducing agent C and water-reducing agent D mixture, mixing ratio is 100 parts water-reducing agent A water-reducing agent C 200 parts Water-reducing agent H: Water-reducing agent I, water-reducing agent C The mixing ratio is 200 parts water reducing agent and 200 parts water reducing agent for 100 parts water reducing agent.

"Experimental example 4"
It was carried out in the same manner as in Experimental Example 1 except that the water reducing agent A was blended in the proportion shown in Table 4 to 100 parts of the CA compound D to obtain an admixture.

“Experimental Example 5”
The experiment was performed in the same manner as in Experiment Example 1 except that the cement admixture of Experiment No. 1-5 was used. For comparison, a conventional rust preventive material was used in the same manner. The results are also shown in Table 5.

<Materials used>
Conventional rust-proofing material A: Lithium nitrite, commercial product Conventional rust-proofing material B: Nitrite-type hydrocalumite, commercial product

  By using the cement admixture and the cement composition of the present invention, it gives an excellent rust prevention effect to the reinforcing steel inside the cement concrete hardened body, and shields the chloride ion penetration into the cement concrete hardened body entering from the outside. In addition, it has the effect of suppressing the neutralization of hardened cement concrete, and also has the effect of suppressing the formation of porosity because there is little leaching of Ca ions from the hardened cement concrete. Suitable for marine structures, seawall structures, floor slab concrete, etc. in the civil engineering and construction industries.

Claims (2)

Cement and, CaO / _Al 2 _{O 3} calcium aluminate compounds of 4000~5000cm ² / g mole ratio in Blaine specific surface area value of 0.5 to 0.7 and formalin condensate of naphthalene sulfonate, melamine sulfonate Containing a water reducing agent that is one or more selected from the formalin condensates and polycarboxylate polymer compounds, and the blending ratio of the calcium aluminate compound and the water reducing agent is a calcium aluminate compound It contains a cement admixture that is 50 to 500 parts by mass of a water reducing agent with respect to 100 parts by mass , and the cement admixture is 10 to 20 parts by mass in 100 parts by mass of a cement composition comprising cement and a cement admixture. A cement composition. Cement and CaO / _Al 2 _{O 3} calcium aluminate compounds of 4000~5000cm ² / g mole ratio in Blaine specific surface area value of 0.5 to 0.7 and formalin condensate of naphthalene sulfonate, melamine sulfonate It contains one or more water reducing agents selected from formalin condensates and polycarboxylate polymer compounds, and the blending ratio of calcium aluminate compound and water reducing agent is a calcium aluminate compound. It is 50-500 mass parts of water reducing agents with respect to 100 mass parts, and the sum total of a calcium aluminate compound and a water reducing agent is 10-20 mass parts in a total of 100 mass parts of a cement, a calcium aluminate compound, and a water reducing agent. , Cement composition.