WO2005082813A1 - Modificateur de béton silicieux: - Google Patents

Modificateur de béton silicieux: Download PDF

Info

Publication number
WO2005082813A1
WO2005082813A1 PCT/JP2005/003122 JP2005003122W WO2005082813A1 WO 2005082813 A1 WO2005082813 A1 WO 2005082813A1 JP 2005003122 W JP2005003122 W JP 2005003122W WO 2005082813 A1 WO2005082813 A1 WO 2005082813A1
Authority
WO
WIPO (PCT)
Prior art keywords
modifier
concrete
alkali metal
test
water
Prior art date
Application number
PCT/JP2005/003122
Other languages
English (en)
Japanese (ja)
Inventor
Toyoharu Nawa
Yoshiro Yamakita
Miki Suzuki
Hiroshi Naganuma
Original Assignee
B-Brain Corporation
Hokkaido Technology Licensing Office Co., Ltd.
Minamigumi Co., Ltd.
Urakawa Namaconcrete Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by B-Brain Corporation, Hokkaido Technology Licensing Office Co., Ltd., Minamigumi Co., Ltd., Urakawa Namaconcrete Corporation filed Critical B-Brain Corporation
Priority to JP2006510461A priority Critical patent/JP4484872B2/ja
Publication of WO2005082813A1 publication Critical patent/WO2005082813A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/06—Oxides, Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/65—Coating or impregnation with inorganic materials
    • C04B41/68—Silicic acid; Silicates

Definitions

  • the present invention relates to a silicate-based concrete reforming system that prevents or suppresses deterioration due to freezing and thawing or salt damage of concrete, and prevents or suppresses deterioration due to a combination thereof, thereby contributing to a reduction in life cycle cost.
  • Agent surface modifier
  • composition of cement that constitutes new concrete is changed and the unit water volume is reduced, aggregate components are specified.
  • existing concrete a method of coating the deteriorated surface with polymer cement, and mortar containing a siliceous waterproofing agent is used.
  • a coating method using an organic resin, cement, or water glass based material is used.
  • Patent document 1 JP-A-2000-44317
  • water-glass based materials harden at the surface layer of the cracks (1-2 mm from the surface layer) and cannot penetrate into concrete, so the effect is limited.
  • cement-based materials use ultra-fine cement. Even 0.2mm Only the above cracks can be filled, the surface strength of concrete is improved, and the aqueous solution of lithium silicate, which is known as an alkali imparting agent, has a high viscosity and is difficult to penetrate.
  • the conventional method has a number of problems, such as the fact that it is only about 1-2 mm, and it is inferior in durability and needs to be rebuilt in several years.
  • the present invention prevents or suppresses deterioration due to freezing and thawing or salt damage, or a composite deterioration due to them by a relatively simple construction method of simply applying the composition to the surface of a new or existing concrete structure, and also provides a surface design. It is an object of the present invention to provide a concrete modifier which penetrates deep into the concrete (maintains the condition of the concrete surface immediately after casting) without changing the concrete, and has high durability and high durability.
  • the present invention (1) is a concrete modifier characterized by blending an alkali metal ion source with a lithium silicate aqueous solution.
  • the present invention (2) is the modifier of the above-mentioned invention (1), wherein the alkali metal ion source is a water-soluble alkali metal-containing substance.
  • the present invention (3) is the modifier according to the above (1) or (2), which is an alkali metal ion force sodium ion and potassium ion from an alkali metal ion source.
  • the molar specific force of all alkali metal ions including lithium ions derived from an aqueous solution of lithium silicate to SiO is 0.4.2-1. 1 (preferably, 0.6.1.4. )
  • the present invention (6) relates to the specific power molar ratio of potassium ion to sodium ion of 0.02 to 2
  • the present invention (7) when added to a saturated aqueous calcium hydroxide solution according to the measuring method 1 in the specification, a two-phase structure of a cloudy gel phase and a transparent solution phase is formed, more preferably
  • the turbid gel is one of the modifiers according to the invention (1)-(6), which is separated into a force layer (a floating layer and a sedimentation layer).
  • the present invention (8) is the modifier according to any one of the aforementioned inventions (1)-(7), which is a concrete surface application type.
  • the “concrete surface application type” includes not only a mode of applying to a concrete surface but also a mode of injecting a concrete surface force (for example, from a crack).
  • the present invention (9) is a stock solution of the modifier according to any one of the inventions (1) and (8), which is obtained by mixing an alkali metal ion source with a lithium silicate aqueous solution.
  • SiO and Li 2 O (equivalent oxide equivalent) in the lithium silicate aqueous solution are the total amount of them.
  • the present invention provides the above-mentioned invention (1)-(6), wherein the modifying agent obtained by diluting the undiluted solution of the invention (9) with water is:
  • This is a method for preventing or suppressing deterioration of concrete, including a step of applying (for example, applying) one or more times to a concrete surface.
  • the dilution ratio of the stock solution with water varies depending on the surface condition of the concrete, and is, for example, 115 times.
  • the present invention (11) is to apply an aqueous solution of calcium hydroxide to the concrete surface before or during the one or more times of applying the modifying agent (for example, applying the modifying agent) (for example, The method according to the invention (10), further comprising the step of:
  • the present invention (12) is a concrete in which deterioration is prevented or suppressed by the method of the invention (10) or (11).
  • the concrete modifier according to the present invention imparts a property of reducing concrete to moisture permeability and salt permeability.
  • the alkali metal-containing lithium silicate in the agent reacts with water present on the interface of the aggregate or in the internal voids or calcium hydroxide, which is a pore solution component of concrete, to form a gel.
  • the pores are densified.
  • the intrusion of water which is a factor promoting various kinds of deterioration, is hindered.
  • diffusion on the surface of the gel is suppressed by making the charge on the gel surface negative and electrically repelling.
  • the concrete modifier according to the present invention has a property that, when compared with a conventional alkali imparting agent, penetrates deeper into the concrete (for example, to a depth of about 40 mm). Then! It is understood that the reason for this is that the reaction rate is much slower than that of conventional ones (such as a water glass-based modifier) (it can penetrate deep into the concrete). In various conventional research reports, there are many reports that lithium compounds are effective in preventing various types of concrete deterioration. However, since this component can penetrate only about 1-2 mm from the surface, it could only be used as a concrete admixture / surface coating material.
  • the present invention is epoch-making in that it provides a penetrating surface coating agent based on this second property of deep penetration.
  • FIG. 1 (a) is a schematic diagram of a concrete section, in which a mortar matrix 1 containing fine aggregate, coarse aggregate 2, pores and cracks 3 are shown.
  • Figure 1 (b)-(d) is an enlarged pictorial diagram of the square box in Fig. 1 (a).
  • 3 also shows the fragile tissue portion at the aggregate interface
  • 4 is fine aggregate
  • 5 is cement paste.
  • a pore solution containing ions such as calcium Inside 3 is a pore solution containing ions such as calcium.
  • FIG. 1 (c) shows a state in which the present modifier 6 has penetrated into voids and the like.
  • the modifier that has penetrated into the voids reacts with the hydroxide and water in the pore solution to form a gel.
  • FIG. 1 (d) shows the appearance of gel 7 produced from the present modifier.
  • Fig. 1 (e) shows the actual state of the square box in Fig. 1 (d).
  • the chemical power containing the alkali metal-containing lithium silicate as a main component will penetrate deep into the concrete through the interface between the crack and the aggregate. In addition, it penetrates into fine voids in the rough portion of the composition in contact with the interface. In addition, when gelling in response to water and calcium hydroxide present on the interface or in the void, the reaction rate is much slower than in the past, so that it can penetrate deep into the concrete.
  • the present invention provides a table of new and existing concrete structures. With a relatively simple construction method that only applies to the surface, it is possible to prevent or suppress deterioration due to freezing and thawing and salt damage, and composite deterioration due to them, without changing the surface design.
  • the modifier according to the present invention is a completely inorganic material containing substantially no organic components, it also has the effect of having durability against ultraviolet deterioration.
  • the modifier according to the present invention has an effect that the conventional one is effective and can be applied to a structure in which deterioration is progressing.
  • an aqueous solution of calcium hydroxide is applied to the concrete in advance, or the calcium hydroxide is added between the steps of applying the modifier. It is more effective to apply an aqueous solution.
  • the concrete modifier according to the present invention is characterized in that a lithium silicate aqueous solution is mixed with an alkali metal ion source.
  • a lithium silicate aqueous solution is mixed with an alkali metal ion source.
  • Lithium silicate aqueous solution refers to a type of colloidal silica in which the alkali portion is lithium.
  • aqueous solution does not mean that these raw material components are completely dissolved, but refers to a state in which at least a part of the raw material is dissolved in some form. Therefore, even if one of the raw materials (especially SiO 2) exists in colloidal form,
  • the aqueous solution of lithium silicate according to the present invention can be produced by boiling silica in an aqueous solution of sodium hydroxide or potassium hydroxide, and replacing Na and K in the obtained colloidal silica with Li.
  • Examples of commercially available products include, for example, Nitrogen Lithium Silicate 45 (manufactured by Nissan Chemical Industries, Ltd.) SiO 20.0-21.0 parts by weight, LiO 2.1-2.4 parts by weight per 100 parts by weight of aqueous solution.
  • SiO / Li O molar ratio 4.5 ⁇ , lithium silicate 75 ⁇ aqueous solution 100 parts Si
  • Lithium silicate 35 (100 parts by weight of aqueous solution, SiO 20.0—21.0 parts by weight, Li O
  • the “alkali metal ion source” according to the present invention is not particularly limited as long as the alkali metal ion is present in the aqueous solution of lithium silicate when added to water.
  • Substances that dissociate into alkali metal ions for example, water-soluble alkali metal-containing substances such as alkali metal hydroxides, alkali metal oxides or alkali metal salts (for example, alkali metal carbonates), alkali metals themselves and alkali metal ions Aqueous solutions can be mentioned.
  • the “alkali metal ion” is not particularly limited, and may be any of lithium, sodium, potassium, rubidium, and cesium.
  • the alkali metal ion source to be added to the aqueous solution of lithium silicate is not limited to one type but may be a plurality of types (for example, a combination of sodium hydroxide and sodium carbonate) in which the same alkali metal ion is present in the aqueous solution of lithium silicate.
  • a plurality of different alkali metal ions may be present in the aqueous lithium silicate solution (for example, a combination of sodium hydroxide and potassium hydroxide).
  • Suitable alkali metal ions are those obtained by combining sodium ions and potassium ions.
  • the specific molar ratio of potassium ion to sodium ion is preferably 0.02 to 2.7, and more preferably 0.04 to 1.8.
  • a suitable alkali metal ion source is a combination of sodium hydroxide and potassium hydroxide.
  • the preferred compounding ratio of sodium hydroxide and potassium hydroxide is 1.3-2.5 (by weight ratio). More preferably, it is 1.7-2.2.2).
  • the added amount of alkali metal ion source in the alkali metal ion source is preferably 0.08-1.8 with respect to SiO 2 in terms of molar ratio (in terms of alkali metal ion), and more preferably. It is 0.12-1.2.
  • the modifier according to the present invention forms a two-phase structure of a cloudy gel phase and a transparent solution phase when added to a saturated aqueous sodium hydroxide solution according to the following measurement method 1. It is preferred that there be.
  • the stock solution of the modifier according to the present invention is produced by mixing an alkali metal ion source with an aqueous solution of lithium silicate. It should be noted that, if the order is changed and an alkali metal ion source is added to water and then an aqueous solution of lithium silicate is added, gelling may occur.
  • a preferable aqueous solution of lithium silicate is SiO and Li 2 O 3 based on the total weight of the aqueous solution.
  • An alkali metal ion source is added to the aqueous solution of lithium silicate, and the mixture is stirred well, and then a necessary amount of water is removed to obtain a stock solution of the modifier according to the present invention.
  • the addition of water is performed for the purpose of lowering the viscosity.
  • the water used is preferably pure water or ion-exchanged water.
  • the aqueous solution of lithium silicate as a raw material is stored at +5 to 125 ° C., and a material that has been gelled in a subzero environment is not used as much as possible. Further, it is preferable to perform temperature control of +5 to 25 ° C. even in the production.
  • Hydroxide (granular or aqueous) was added in the order of (i) sodium and potassium, (ii) potassium and sodium, and (iii) sodium and potassium were injected at the same time. Any solution
  • the amount of the hydroxide (particulate or aqueous solution) to be charged is either (i) the solution that is added little by little, or (ii) the solution that is added all at once.
  • (i) When adding ion-exchanged water, (i) first adjust the concentration of each raw material to be a stock solution, and then dilute the stock solution to a predetermined dilution ratio (for example, 2 times); A solution prepared from the beginning to a concentration at a specified dilution ratio (for example, 2 times)
  • the stock solution thus obtained preferably contains water in an amount of 65 to 85% by weight (more preferably 70 to 80% by weight) based on the total weight of the stock solution.
  • the preferred viscosity of the stock solution is 1.0 to 15 mPa's (more preferably 1.5 to 10 lOmPa's).
  • the pH of the stock solution thus obtained is preferably in the range of 12.0 to 13.5, and more preferably in the range of 12.4 to 12.9. Further, it is preferable that the pH of the diluent is also generally within the above range.
  • step 1 the stock solution of the modifier according to the present invention is stirred as necessary (step 1), where necessary (hereinafter, a two-fold dilution will be described as an example). Then, before applying this modifier to the concrete, water is sprayed to keep the concrete on the application surface wet (step 2). After that, check the wet condition of the concrete and apply the modifier diluted twice with water using a low-pressure sprayer, brush, roller, etc. (select according to the construction site conditions) (Step 3).
  • the amount of the modifier per concrete lm 2 is, for example, 200cc / m 2 (2 times those diluted), the undiluted base is lOOccZm 2.
  • water is sprayed at a low pressure after application and before drying (step 4). At this time, if drying is quick with wet curing (basic 90 minutes), watering should be performed (Step 5).
  • Step 7 Check if the modifying agent remains on the surface (Step 7). Watering is performed at a low pressure as the final step, and if residual is confirmed in step 6, it is washed by brushing or the like so that it does not remain on the concrete surface (step 8). Then, air dry (Step 9).
  • the outside air temperature is + 5 ° C or higher, and when it is lower than + 5 ° C, it is preferable to control the temperature by heating and curing. If the coating is coated with a coating material that inhibits permeation, such as paint or polymer cement, apply this modifier after removing the coating material.
  • the type of concrete in which the modifier according to the present invention can be used is not particularly limited, and is effective for all types of concrete in which the type and composition of cement are changed.
  • examples of the cement include ordinary Portland cement, early-strength Portland cement, belite cement, eco cement, blast furnace cement, fly ash cement, and low heat cement.
  • Concrete includes, for example, ordinary concrete, high-strength concrete, low-heating concrete, underwater non-separable concrete, underwater concrete, factory concrete, marine concrete, shotcrete, fiber reinforced concrete, pre-knocked concrete, Examples include fluidized concrete, light (aggregate) concrete, steel-concrete composite structures, prestressed concrete, and recycled aggregate concrete.
  • admixtures such as fly ash, blast furnace slag fine powder, and silica fume may be mixed.
  • Lithium silicate 45 (manufactured by Nissan Chemical Industries, Ltd.
  • Lithium silicate 75 (manufactured by Nissan Chemical Industries, Ltd.
  • Lithium silicate 35 (Nissan Chemical Industries, Ltd.
  • Lithium silicate 75 (manufactured by Nissan Chemical Industries, Ltd., SiO 20.0-21.0 parts by weight, Li O 1.2-1.4 parts by weight, SiO 2 / Li O molar ratio 7.5 per 100 parts by weight of aqueous solution) 88.84 g was weighed into a beaker, and sodium hydroxide (Kanto Chemical Co., Ltd., purity: 97%) was added.4.12 g was mixed well with a glass rod. . After the sodium hydroxide was completely dissolved, 0.39 g of potassium hydroxide (Kanto Chemical Co., Ltd., purity: 86%) was added little by little, and 6.65 g of ion-exchanged water was gently added to the place where it was completely dissolved. In addition, the mixture was stirred well with a glass rod to obtain a stock solution of the concrete modifier according to this production example. Table 4 shows the composition of each component.
  • Lithium silicate 45 (manufactured by Nissan Chemical Industries, Ltd.
  • Lithium silicate 45 (manufactured by Nissan Chemical Industries, Ltd., SiO 20.0-21.0 parts by weight, Li O 2.1-2.4 parts by weight, SiO / Li O molar ratio 4.5 with respect to 100 parts by weight of aqueous solution) 80.15g is weighed into a beaker and sodium hydroxide (manufactured by Kanto Chemical Co., Ltd., purity: 97%) 8. While mixing well with 25g with a glass rod, the input amount is dissolved little by little and added.
  • Lithium silicate 75 (manufactured by Nissan Chemical Industries, Ltd., SiO 20.0-21.0 parts by weight, Li O 1.2-1.4 parts by weight, SiO 2 / Li O molar ratio 7. 5) Weigh 81.72g into a beaker, mix sodium hydroxide (manufactured by Kanto Idani Kagaku Co., Ltd., purity 97%). Carapara was added sequentially. After sodium hydroxide is completely dissolved, potassium hydroxide (Kanto Chemical Co., Ltd., purity 8
  • Table 8 shows the molar ratio of each component in each of the modifier stock solutions according to Production Examples 1 to 7. “Two-layer separation” in the table means whether the cloudy gel is separated into two layers (floating layer and sedimentary layer).
  • the mortar specimen coated with the modifier was cut out in the direction perpendicular to the casting surface, and observed by SEM at each depth from the casting surface.
  • the product obtained by mixing the modifier with a saturated calcium hydroxide aqueous solution simulating a pore solution was also observed by SEM.
  • OPC mortar with an ice cement ratio of 60% fine aggregate / mortar volume ratio of 55% was cast into a mold with a diameter of 5 cm and a height of 10 cm. The mold was removed after 24 hours, and then cured in water. Four days after casting, it was molded to a height of 5 cm.
  • FIG. 2 (a) to (g) show the specimens of the mortar coated with the modifier ⁇ depth from the casting surface (a) lmm, (b) 20mm, (c) 30mm, (d) 40mm ⁇ .
  • Figs. 2 (e) and (f) are SEM images of the uncoated mortar specimen ⁇ depth of the casting surface force (e) 5mm, (i) 20mm ⁇ . ) Is an SEM image of the product obtained from the modifier and saturated Ca (OH) solution. As can be seen from these electrophotographs, a rod-like substance with a thickness of about 0.3 micron was formed inside the specimen coated with the modifier ⁇ Fig. 2 (a) to (d) ⁇ .
  • ⁇ LN gel J '' the gel obtained by dropping the modifier into a saturated calcium hydroxide aqueous solution
  • XRF fluorescent dilute analyzer
  • the gel produced by mixing the filtered saturated calcium hydroxide aqueous solution and the modifier at a volume ratio of 9: 1 was first separated from the liquid phase by a centrifuge. Then, the sample was washed with ion-exchanged water and force dried to remove unreacted calcium ions.
  • Fig. 3 shows the measured spectrum
  • Table 9 shows the analytical results converted to oxides
  • Table 10 shows the values of Ca / Si and Ca / Al of the main components of the hardened cement.
  • Test Example 3 (Test for confirming immersion by alkali component analysis)
  • a powder sample obtained by polishing the same specimen as in Test Example 1 from the coated surface for every lmm thickness was mixed and filtered with 2 md / L hydrochloric acid, and the filtrate was analyzed by ion chromatography.
  • Fig. 4 shows the content of each ion species per lg of calcium. Mg reached almost the same value, whereas values of Li, Na and K decreased as the content became larger and closer to the coated surface. Since Li, Na and K are components contained in the modifier, it is presumed that the modifier gradually penetrates into the specimen. Since Mg is a component derived from cement and fine aggregate, it is considered that the values are almost uniform.
  • Kw permeability coefficient (cm)
  • P applied pressure (kgf / cm 2 )
  • A cross-sectional area of specimen (cm 2 )
  • h thickness of specimen (Cm)
  • ⁇ Unit volume mass of water (kg m 3 )
  • Q Water permeability (cmVs).
  • Mortar made of ordinary Portland cement with a water cement ratio of 60% (hereinafter referred to as ⁇ M60J) was used as the test piece.
  • the composition is shown in Table 11.
  • the mortar was prepared using a mold with a diameter of 10 cm and a height of 1.4 cm.After removal from the mold, the casting surface and the bottom surface were polished to a height of lcm, and a siliceous modifier (Linack and RC) was applied. .
  • a siliceous modifier Licoack and RC
  • Each specimens was by Ri wet watering 0. 15L / m 2 was coated, subjected to water spray curing after 90 minutes, and further coated again watering cured after 90 minutes 0. lL / m 2, 24 Watering was continued after hours. After that, it was wet-cured for 10 days and dried in an oven at 80 ° C. until the mass no longer changed (24 hours). After that, the test was performed after 1 hour in indoor air.
  • M60 mortar was used to confirm the change in permeability in the depth direction due to the penetration of the modifier.
  • Figure 6 shows the change in permeability in the depth direction.
  • the permeability increased at a distance of 5 mm from the surface layer where the permeability was greatest at the surface layer of 5 mm. This is considered to be due to the change in permeability due to the increase in WZC near the surface due to the breathing and sedimentation of cement particles and aggregates.
  • the permeability of the surface is rather low, and there is no significant change due to the depth that can be seen without coating.
  • the permeability of this modifier is less than that of no application at about 40 mm, which is consistent with the depth at which permeability was confirmed in Test Example 1.
  • the hydration force generated inside the mortar by the application of this modifier had a significant effect of improving the water barrier properties, especially at the surface layer.
  • the value was lower than that of this modifier only at the depth of 5 mm, and at a depth of 20 mm or less showing the hydraulic conductivity, the value was larger than that of the non-coated.
  • Test Example 6 chloride ion electrophoresis 3 ⁇ 4: scattering test
  • Specimens include water-cement ratio (W / C) 50% ordinary concrete (OPC50), W / C50% blast furnace type B concrete (BB50), W / C30% low heat concrete (LH30) and W / C30% / C60% ordinary mortar (hereinafter M60) was used.
  • Table 12 shows the formulations.
  • the present modifier obtained by diluting the stock solution obtained in Production Example 1 twice with water, and a commercially available concrete modifier (RC) as a comparative example
  • Concrete is 5cm from a 10cm diameter, 20cm high formwork.
  • the mortar was prepared using a mold having a diameter of 10 cm and a height of 10 cm, cut out to a thickness of 2 cm, and applied with a siliceous concrete modifier or the like. Regardless of the application conditions, no application (NO), and as a comparative example, 0.15 L each of a commercially available siliceous concrete modifier (trade name: RC Guard (RC)) and this modifier (Linack) 90 minutes after the application of / m 2 , watering and curing were performed. Further, 0.1 l / m 2 was applied, and after 90 minutes, watering and curing were performed again. Watering was performed 24 hours later.
  • NO no application
  • RC Guard RC Guard
  • Table 13 shows the effective diffusion coefficients.
  • Fig. 7 (b) (Concrete blend) and Fig. 7 (c) Rutar blend) show the ratio to no coating.
  • Table 3 shows that the effective diffusion coefficient differs greatly depending on the type of cement and the difference in water cement ratio.
  • the application of this modifier (Linack) confirmed the effect of suppressing salt penetration regardless of the type of cement and the ratio of water cement.
  • the ratio of the specimen coated with the RC guard (comparative example) to the uncoated effective diffusion coefficient in OPC50 is 80%, which is much lower than that of the specimen coated with the modifier (Linack). It was a very low figure of 20%.
  • the lower the W / C ratio of concrete the higher the salt-shielding property.
  • the diffusion coefficient of W / C is 40%, The ratio of C50% is 43%, and that of WZC60% is 22%.
  • the value of 20% for the non-application of OPC50 by applying this modifier (Linack) is 40% of W / C, which is thought to prevent salt penetration, compared to 60% of W / C, which is considered to be easy for salt penetration. It can be said that the salt permeation suppression effect is very high. Since BB50 mixed with blast furnace slag has a high effect of suppressing salt penetration, this experiment also showed a low diffusion coefficient of less than lPC of OPC50.
  • the chloride ion concentration on the surface of the structure was set at three levels depending on the distance of the coastal force. Taking the harshest spray zone as an example of the salt environment, a replacement sheet until chloride ions reach the reinforcing bar position (Rule 26)
  • the number of years is only 3 years without general OPC50 application. However, when this modifier is applied, it will be 17 years, and the durability will be about 6 times. With LH30 and BB50, the same spray zone is applied for 30 years and 50 years without application, respectively.
  • the application of this modifier can greatly extend the useful life of concrete with such a high salt-shielding property.
  • LH30 is 1.6 times 50 years and BB50 is 1.9 times 151 Year. Note that there is no significant change in RC guard application. In this case, the concentration of the salt ion on the concrete surface was not considered, and it is estimated that the number of years in the actual environment will be longer.
  • Test example 7 (Surface potential measurement test)
  • This test simply measures the penetration depth of all chloride ions diffused into the hardened cement body.
  • a 1171 Polymer cement mortar was tested in accordance with the test method.
  • the specimen is immersed in salt water (artificial seawater) for 14 days, and the reagent (silver nitrate solution and peranine aqueous solution) is sprayed on the section of the cracked specimen, and the discolored part is measured as the penetration depth.
  • the measurement points were 3 points per cross section, for a total of 6 points.
  • a 4 X 4 X 16 cm OPC mortar (WZC 50%) specimen aged in water up to the specified age is cut into 4 X 4 X 4 cm, completely covered with a sealing agent except one side, and coated with a modifier. After the moist curing for a predetermined number of days, the test was performed.
  • test piece The dimensions of the test piece were 100 x 100 x 400 mm for concrete and 40 x 40 x 160 mm for mortar.
  • the modifier was applied to the concrete only on the casting surface and to the mortar on all surfaces except the bottom.
  • the RDM started to decrease at a force of 300 cycles, which showed a high value.
  • Deterioration due to freezing and thawing means that the moisture that has entered from the outside freezes on the surface of the concrete as the temperature decreases, and the expansion pressure causes the structure to break down inside the concrete.
  • Concrete coated with this modifier (Linack) is densified by the gel generated from the surface layer to the inside, and prevents moisture from entering from the outside.
  • the internal water is consumed when the gel is formed, voids that are not filled with water are maintained in the concrete, and the expansion pressure due to freezing can be reduced. From these, it is considered that the application of this modifier (Linack) brings high frost resistance to concrete.
  • BB forms a denser structure than OPC due to the pozzolanic reaction of the mixed blast furnace slag and also consumes water, so it has high frost resistance.
  • the RDM maintained a value of 100% or more for this modifier (Linack) coated specimen up to 300 cycles.
  • the RC guard application showed a value of 100% or less from the start of the test, and decreased slightly at 300 cycles.
  • LN733 maintained a high dynamic elasticity of 92%.
  • the mass rapidly decreased after 100 cycles, and decreased by 10% at 200 cycles, and the tissue was greatly damaged.
  • the present modifier when the present modifier was applied, no mass reduction was observed up to 150 cycles in any of the formulations.
  • LN422 has no loss of mass up to 200 cycles.As shown in Fig. 13, the force completely loses the surface layer without application.With the application of this modifier (LN422), it remains almost the same as at the start of the test. And showed high scaling resistance. In the case of the RC guard coating of the comparative example, the middle of the surface layer was lost, and the improvement in scaling resistance was lower than that of the present modifier.
  • the modifier for example, Linack
  • Linack produces a gel with a rod-shaped or massive solid structure in the voids in concrete, and improves the water-blocking performance by densifying the voids.
  • the RC guard which is a comparative example, also exhibits the same properties. Due to the difference in force penetration depth, the effect of the comparative product is several millimeters on the surface.
  • this modifier for example, Linack
  • the RC guard of the comparative example has a lower effect of improving the salt-shielding property than the present modifier.
  • This modifier for example, Linack
  • Linack improved the frost resistance regardless of the cement type and water-cement ratio.
  • it exhibited high durability against combined deterioration with salt damage, and also exhibited high scaling resistance.
  • RC guard in the comparative example showed an improvement in frost damage resistance, the performance was lower than that of this modifier (Linack), and the same applies to scaling resistance.
  • this modifier for example, Linack
  • this modifier penetrates deep into the concrete and improves the water-blocking performance, salt-blocking performance, and frost-resistance performance by the generated gel. Therefore, it is considered to be effective as a preventive or preventive measure against the deterioration of concrete due to salt damage and frost damage and their combined deterioration.
  • FIG. 1 (a) is a schematic cross-sectional view of concrete.
  • FIGS. 1 (b)-(e) are enlarged views of a portion surrounded by a square in FIG. 1 (a).
  • FIG. 1 (c) is a diagram showing a state in which the present modifier has penetrated into the microvoids or the fragile tissue portion at the interface of the aggregate shown as 5 in FIG. 1 (b).
  • FIG. 1 (d) is a view showing that the present modifier that has permeated into the voids has reacted with calcium hydroxide and water in the pore solution to form a gel.
  • Fig. 1 (e) is an electrophotograph showing the actual state of the portion enclosed by the square in Fig. 1 (d).
  • 2 coarse aggregate
  • 3 pores and cracks
  • 4 fine aggregate
  • 5 cement paste
  • 6 this modifier
  • 7 gel generated from this modifier Are shown respectively.
  • FIG. 2 is an SEM image (electrophotograph) of Test Example 1 (the test for confirming the permeability of the modifier).
  • Fig. 2 (a)-(d) shows the specimen of the mortar coated with the modifier ⁇ depth of the casting surface (a) lmm, (b) 20mm, (c) 30mm, (d) 40mm ⁇ .
  • Fig. 2 (e) and (f) are SEM images of the uncoated mortar specimen (depth from the casting surface (e) 5mm, (f) 20mm), and Fig. 2 (g) Is a SEM image of the product for which the modifier and saturated Ca (OH) solution power were also obtained.
  • FIG. 3 is a measurement spectrum of an LN gel in Test Example 2 (XRF elemental analysis).
  • FIG. 4 is a diagram showing the relationship between the content of various alkali metals and the depth of the coated surface in Test Example 3 (permeability confirmation test by alkali component analysis).
  • FIG. 5 is a diagram showing an apparatus and results in Test Example 4 ⁇ water permeability test (1) ⁇ .
  • FIG. 5 (a) is a diagram showing an outline of the test apparatus
  • FIG. 5 (b) is a diagram showing the effect of coating conditions on the hydraulic conductivity.
  • FIG. 6 is a diagram showing a change in water permeability in the depth direction due to the application of a modifier in Test Example 5 ⁇ water permeability test (2) ⁇ .
  • FIG. 7 is a diagram showing an apparatus and results in Test Example 6 (chloride diffusion test by electrophoresis).
  • Fig. 7 (a) is a diagram showing an outline of the apparatus according to this test
  • Fig. 7 (b) shows the effective diffusion coefficient (ratio to no application) of various types of concrete by applying the modifier.
  • FIG. 7 (c) is a diagram showing the effective diffusion coefficient (ratio to no application) of various mortars by applying a modifier.
  • FIG. 8 is a diagram showing an apparatus and a result in Test Example 7 (surface potential measurement test).
  • FIG. 8 (a) is a diagram showing an outline of an apparatus according to the present test
  • FIG. 8 (b) is a diagram showing a surface potential of various cements by applying a modifier.
  • FIG. 9 is a diagram showing the relationship between various modifiers and the total salt penetration depth in Test Example 8 (salinity immersion ion penetration test by immersion in seawater). Application, 7 days after immersion in seawater, (b) 14 days of age, 14 days after immersion in seawater ⁇ .
  • Figure 10 shows the relative kinetic elasticity change of OPC50 when various modifiers were applied in the normal cycle test of Test Example 9 (freeze-thaw test) ⁇ Figure 10 (a) ⁇ and the relative dynamics of BB60.
  • FIG. 11 is a diagram showing a coefficient of change ⁇ FIG. 10 (b) ⁇ .
  • FIG. 11 is a diagram showing a change in relative kinetic elastic modulus when the present modifier was applied in an initial frost damage cycle test of Test Example 9 (freeze-thaw test).
  • Figure 12 shows the change in the relative kinematic elastic modulus of nonAE when various modifiers were applied in the seawater cycle test in Test Example 9 (freeze-thaw test) ⁇ Figure 12 (a) ⁇ and the mass loss rate ⁇ Fig. 12 (b) ⁇ , the change in the relative kinematic elasticity of AE ⁇ Fig. 12 (c) ⁇ , and the mass loss rate ⁇ Fig. 12 (d) ⁇ .
  • FIG. 13 is a diagram showing a scaling state at the end of a test on a test piece casting surface in a freeze-thaw test in artificial seawater of Test Example 9 (c).
  • Figure 14 shows the change in relative kinetic elasticity of the modified agent after degradation to RMD 70% in the cycle test after frost damage deterioration in Test Example 9 (freeze-thaw test) ⁇ Figure 14 (a) ⁇ And the mass loss rate ⁇ Fig. 14 (b) ⁇ and the change in the relative kinematic modulus of AE when this modifier is applied after degradation to RDM 50% ⁇ Fig. 14 (c) ⁇ and the mass loss rate ⁇ Fig. FIG.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Modificateur de béton dont la caractéristique est qu’il comprend une solution de silicate de lithium aqueuse et une source d’ion de métal alcalin. Le modificateur de béton permet d’empêcher ou de retarder la détérioration par congélation ou par fonte, par attaque du sel ou par combinaison de ces éléments, grâce à l’utilisation d’un procédé relativement simple, appliqué seulement sur la surface d’un béton fraîchement fait ou sur une structure de béton existante. Ce modificateur s’infiltre dans une partie profonde de la structure de béton sans changer les plans de surface de celle-ci (par rétention de l’état de la surface immédiatement après la pose) et fait preuve d’une grande durabilité.
PCT/JP2005/003122 2004-02-26 2005-02-25 Modificateur de béton silicieux: WO2005082813A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006510461A JP4484872B2 (ja) 2004-02-26 2005-02-25 珪酸質系コンクリート改質剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004052493 2004-02-26
JP2004-052493 2004-02-26

Publications (1)

Publication Number Publication Date
WO2005082813A1 true WO2005082813A1 (fr) 2005-09-09

Family

ID=34908707

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/003122 WO2005082813A1 (fr) 2004-02-26 2005-02-25 Modificateur de béton silicieux:

Country Status (2)

Country Link
JP (1) JP4484872B2 (fr)
WO (1) WO2005082813A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007197308A (ja) * 2005-12-26 2007-08-09 Abc Kenzai Kenkyusho:Kk コンクリート表面改質剤
JP2007246353A (ja) * 2006-03-17 2007-09-27 Denki Kagaku Kogyo Kk 補修工法
JP2007256178A (ja) * 2006-03-24 2007-10-04 Univ Nihon コンクリート防水層の試験方法およびこの方法で使用する試験装置
JP2010001195A (ja) * 2008-06-20 2010-01-07 Asuton:Kk コンクリートの補修方法
JP2010070403A (ja) * 2008-09-17 2010-04-02 Linack Co Ltd 新規コンクリートの乾燥収縮ひび割れ抑制方法及びひび割れ抑制剤、並びに既設コンクリートのひび割れ閉塞方法及びひび割れ閉塞剤
JP2011256065A (ja) * 2010-06-08 2011-12-22 Shimoda Gijutsu Kenkyusho:Kk コンクリート構造物の劣化防止方法
CN106007801A (zh) * 2016-05-30 2016-10-12 江苏名和集团有限公司 一种混凝土用表面增强密封剂及其制备方法
JP2019172564A (ja) * 2018-03-26 2019-10-10 国立大学法人山口大学 コンクリート補修剤
JP7311215B1 (ja) * 2023-03-20 2023-07-19 株式会社リナック八千代 コンクリート補修材、及び、コンクリートの補修方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10139568A (ja) * 1996-11-11 1998-05-26 Mitsubishi Chem Corp 吸水防止材組成物
JP2001302961A (ja) * 2000-04-18 2001-10-31 Touyoko Giken Kk セメント系硬化物表層の着色および改質塗料
JP2002187787A (ja) * 2000-12-15 2002-07-05 Ashford Kk 無機質基材の表面処理方法
JP2002211988A (ja) * 2001-01-11 2002-07-31 Ashford Kk カルシウム系無機質基材用塗工組成物およびそれを用いた着色カルシウム系無機質基材の製造方法
JP2004323333A (ja) * 2003-04-28 2004-11-18 Soma Takafumi コンクリート改質材

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0670206B2 (ja) * 1986-07-09 1994-09-07 義和 遊垣 無機質系建材保護剤及びその調製方法
JPH075401B2 (ja) * 1986-07-15 1995-01-25 日本ユニカー株式会社 建材の保護膜形成法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10139568A (ja) * 1996-11-11 1998-05-26 Mitsubishi Chem Corp 吸水防止材組成物
JP2001302961A (ja) * 2000-04-18 2001-10-31 Touyoko Giken Kk セメント系硬化物表層の着色および改質塗料
JP2002187787A (ja) * 2000-12-15 2002-07-05 Ashford Kk 無機質基材の表面処理方法
JP2002211988A (ja) * 2001-01-11 2002-07-31 Ashford Kk カルシウム系無機質基材用塗工組成物およびそれを用いた着色カルシウム系無機質基材の製造方法
JP2004323333A (ja) * 2003-04-28 2004-11-18 Soma Takafumi コンクリート改質材

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007197308A (ja) * 2005-12-26 2007-08-09 Abc Kenzai Kenkyusho:Kk コンクリート表面改質剤
JP2007246353A (ja) * 2006-03-17 2007-09-27 Denki Kagaku Kogyo Kk 補修工法
JP2007256178A (ja) * 2006-03-24 2007-10-04 Univ Nihon コンクリート防水層の試験方法およびこの方法で使用する試験装置
JP2010001195A (ja) * 2008-06-20 2010-01-07 Asuton:Kk コンクリートの補修方法
JP2010070403A (ja) * 2008-09-17 2010-04-02 Linack Co Ltd 新規コンクリートの乾燥収縮ひび割れ抑制方法及びひび割れ抑制剤、並びに既設コンクリートのひび割れ閉塞方法及びひび割れ閉塞剤
JP2011256065A (ja) * 2010-06-08 2011-12-22 Shimoda Gijutsu Kenkyusho:Kk コンクリート構造物の劣化防止方法
CN106007801A (zh) * 2016-05-30 2016-10-12 江苏名和集团有限公司 一种混凝土用表面增强密封剂及其制备方法
JP2019172564A (ja) * 2018-03-26 2019-10-10 国立大学法人山口大学 コンクリート補修剤
JP7243982B2 (ja) 2018-03-26 2023-03-22 国立大学法人山口大学 コンクリート補修剤
JP7311215B1 (ja) * 2023-03-20 2023-07-19 株式会社リナック八千代 コンクリート補修材、及び、コンクリートの補修方法

Also Published As

Publication number Publication date
JP4484872B2 (ja) 2010-06-16
JPWO2005082813A1 (ja) 2007-10-25

Similar Documents

Publication Publication Date Title
WO2005082813A1 (fr) Modificateur de béton silicieux:
Wang et al. A novel treatment method for recycled aggregate and the mechanical properties of recycled aggregate concrete
Yıldırım et al. Self-healing performance of aged cementitious composites
KR100814962B1 (ko) 천연광물이 함유된 단면복구용 모르타르 및 이를 이용한단면복구공법
CN110818366B (zh) 清水混凝土及其制备工艺
Ichikawa Alkali–silica reaction, pessimum effects and pozzolanic effect
Hay et al. On utilization and mechanisms of waste aluminium in mitigating alkali-silica reaction (ASR) in concrete
JP7243982B2 (ja) コンクリート補修剤
JP5751499B2 (ja) ケイ酸塩系表面含浸工法に用いる反応促進材及びコンクリート補強方法
KR102087707B1 (ko) 수산화칼슘 수용액과 친환경 탄산나노버블수 및 보수용 모르타르 조성물을 이용한 자기치유에 의한 콘크리트 구조물 단면의 보수 보강 공법
KR100919493B1 (ko) 수성발수제로 피복된 순환골재와 이를 이용한 콘크리트조성물
JP5388519B2 (ja) 新規コンクリートの乾燥収縮ひび割れ抑制方法及びひび割れ抑制剤
Li et al. Leaching resistance of alkali-activated slag and fly ash mortars exposed to organic acid
Shafaatian et al. Performance of recycled soda–lime glass powder in mitigating alkali–silica reaction
CN114409341B (zh) 一种抗碳化耐腐蚀混凝土及其制备方法及衬砌管片
Szeles et al. Mitigation of alkali–silica reaction by hydrated alumina
CA2398022C (fr) Procede de protection de l'armature dans du beton arme
Lu et al. Mitigating sulfate ions migration in concrete: A targeted approach to address recycled concrete aggregate's impact
JP5092134B2 (ja) カルシウムイオン水の製造方法、セメント硬化体及びその製造方法
KR100696987B1 (ko) 보수용 방청 몰탈 조성물
Shang et al. EVA enhanced cementitious materials based coatings for the improvement of steel reinforcement corrosion protection performance
JP2013107284A (ja) 硬化体及びその製造方法
Prabhu et al. Durability properties of fly ash and silica fume blended concrete for marine environment
Gorlenko et al. Fine-grained concrete fibre-reinforced by secondary mineral wool raw material
Edwards et al. Pozzolanic properties of glass fines in lime mortars

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006510461

Country of ref document: JP

122 Ep: pct application non-entry in european phase