CN112601726A - Hardening agent for quick-hardening concrete delivered in ready-mixed concrete mode, quick-hardening concrete material delivered in ready-mixed concrete mode, quick-hardening concrete composition delivered in ready-mixed concrete mode and preparation method thereof - Google Patents
Hardening agent for quick-hardening concrete delivered in ready-mixed concrete mode, quick-hardening concrete material delivered in ready-mixed concrete mode, quick-hardening concrete composition delivered in ready-mixed concrete mode and preparation method thereof Download PDFInfo
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- CN112601726A CN112601726A CN201980054389.9A CN201980054389A CN112601726A CN 112601726 A CN112601726 A CN 112601726A CN 201980054389 A CN201980054389 A CN 201980054389A CN 112601726 A CN112601726 A CN 112601726A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28C7/00—Controlling the operation of apparatus for producing mixtures of clay or cement with other substances; Supplying or proportioning the ingredients for mixing clay or cement with other substances; Discharging the mixture
- B28C7/04—Supplying or proportioning the ingredients
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- 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
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- 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
- C04B22/10—Acids or salts thereof containing carbon in the anion
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- 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
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
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- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
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- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
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- Ceramic Engineering (AREA)
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- Structural Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
Abstract
A hardening agent for quick-hardening concrete delivered as ready-mixed concrete, wherein the hardening agent is added to a composition containing cement, a quick-hardening material and a setting agent, and the aluminum ion concentration in a liquid phase obtained by solid-liquid separating a composition containing no hardening agent, which composition is obtained by adding no hardening agent to the composition at 5 ℃, is 1.1 times or more the aluminum ion concentration in a liquid phase obtained by solid-liquid separating a composition containing a hardening agent, which composition is obtained by adding the hardening agent to the composition at 5 ℃ for 30 minutes.
Description
Technical Field
The present invention relates to a hardening agent for quick-hardening concrete delivered in the form of ready-mixed concrete, a quick-hardening concrete material delivered in the form of ready-mixed concrete, a quick-hardening concrete composition delivered in the form of ready-mixed concrete, and a method for preparing the same.
Background
Worldwide, the production of cement is increasing and infrastructure construction is rapidly advancing. Especially, the construction heat tide in China and southeast Asia is still continued. In infrastructure construction, the construction of roads occupies an important place. Since it is desired to start use as soon as possible both at the time of building a road and at the time of maintenance, a material that can be used as soon as possible is also required as a material to be used. As an example thereof, fast hardening concrete is cited.
The pot life is also an important property as a property required for fast hardening concrete. In view of the time taken to produce and transport ready-mixed concrete to a construction site in a ready-mixed concrete plant, the time taken for construction, and the washing time of a mixer truck as a ready-mixed concrete transport truck, it is desirable to ensure a minimum usable time of 120 minutes or more and as long as 180 minutes or more. However, ensuring a long pot life lengthens the curing time, and thus the strength required for a short-term age cannot be satisfied. Therefore, it is difficult to satisfy the strength expression required for the initial age while securing a sufficient usable time by the conventional technique.
It is currently the case that quick-hardening concrete is prepared at the construction site. In the construction with less pouring amount, 0.1-0.2 m is used3The left mixer and the right mixer mix the fast hardening concrete, and the fast hardening concrete is modulated and poured through the man-sea tactics. In this method, a large amount of manual labor is required, the work time is long, the cost is high, and the volume of the quick hardening concrete which can be supplied is limited. In addition, in construction where the amount of casting is large, quick-hardening concrete is continuously supplied using a concrete casting truck. However, this method requires a concrete-pouring truck, and sometimes requires a long time for carrying out the process such as loading fine aggregate and coarse aggregate into a flexible container bag with a predetermined amount of moisture being controlled in advance and carrying them to the site, or loading quick-hardening cement into a flexible container bag and carrying them to the site for later use, and thus has a problem of significantly increasing the cost of quick-hardening concrete. In addition, the concrete pouring trucks are also equipped with limits.
There is now a strong desire to develop fast hardening concrete that can be shipped from ready mixed concrete plants. If the quick-hardening concrete can be delivered from a ready-mix concrete workshop, the existing mixing equipment and the carrying system can be directly utilized to supply a large amount of quick-hardening concrete to a construction site.
On the other hand, in Spackman in the united states, addition of calcium aluminate for the purpose of imparting quick hardening to portland cement and further addition of gypsum have been studied for a long time (for example, see patent document 1). It is also known to use a mixture of amorphous calcium aluminate and gypsum as a rapid hardening material (see, for example, patent documents 2 and 3).
Patent documents 4 to 8 disclose a quick setting concrete in which a quick setting agent is added after the quick setting concrete is delivered from a ready-mixed concrete plant and arrives at a construction site.
Patent documents 9 to 11 disclose a quick-setting concrete prepared by adding a setting retarder and calcium hydroxide to a ready-mixed concrete together with β naphthalenesulfonic acid, and adding a quick-setting agent after the ready-mixed concrete arrives at a construction site.
Patent documents 12 and 13 disclose a method for producing a quick-hardening concrete, which is characterized in that a setting retarder comprising a hydroxycarboxylic acid or a salt thereof and lithium carbonate is added to a base concrete during or after mixing, and CaO · Al is added to the mixed base concrete during construction2O3A rapid hardening material with crystal as main component.
Documents of the prior art
Patent document
Patent document 1 U.S. Pat. No. 903019
Patent document 2 Japanese laid-open patent publication No. Sho 48-1024
Patent document 3, Japanese patent application laid-open No. H04-97932
Patent document 4 Japanese patent laid-open No. 2000-264712
Patent document 5 Japanese laid-open patent publication No. 2000-327394
Patent document 6, Japanese patent laid-open No. 2001-213655
Patent document 7, Japanese patent laid-open No. 2001-253753
Patent document 8 Japanese patent laid-open publication No. 2002-037654
Patent document 9 Japanese patent application laid-open No. 11-24074
Patent document 10 Japanese patent laid-open publication No. 2002-321958
Patent document 11 Japanese laid-open patent publication No. 2002-321959
Patent document 12, Japanese patent laid-open No. 2007-045654
Patent document 13 Japanese patent laid-open No. 2012 and 139897
Disclosure of Invention
Problems to be solved by the invention
However, only by the techniques using the conventional rapid hardening materials of patent documents 1 to 3, it is impossible to prepare rapid hardening concrete that can be shipped from ready-mixed concrete. That is, conventional quick-hardening concrete is a material using a quick-hardening material and a retarder in combination with portland cement, and when strength expression in a short-term age is required, the usable time must be set within 60 minutes. Moreover, in this case, shipment from ready mix concrete plants is virtually impossible. On the other hand, if a large amount of retarder is added to achieve shipment from a ready-mixed concrete plant and the available time is set to 120 minutes or more, the strength cannot be expressed in a short term age. In addition, in actual construction, there is a possibility that various accidents such as construction stoppage due to traffic jam and construction problems occur. In the case of fast-hardening concrete, which is shipped as ready-mixed concrete, it is important to ensure that such a long time-to-use, which is at risk, is allowed.
Therefore, at a construction site where the transportation time is short, the minimum available time needs to be 120 minutes or more, and in any case, when the traffic volume is large and the transportation distance is long, it is desirable to secure an available time of 180 minutes or more. Thus, the reason why quick-hardening concrete delivered in the ready-mixed concrete form has not been realized so far is because: it is extremely difficult to technically trade off the long availability time and the short intensity performance.
It is desired to develop a quick hardening concrete which can be mixed in a ready mixed concrete plant, transported to a construction site by a mixer truck, and rapidly exhibit strength after casting even if a long usable time such as a time required to allow casting, a time required for washing, and all accidents such as construction stoppage due to traffic jam and construction problems is set.
In addition, since the techniques of patent documents 4 to 8 are used for the tunnel preliminary bracing method, alkali aluminate, aluminum sulfate, sodium silicate, and the like are used as the rapid coagulant, and the operation time cannot be secured after the rapid coagulant is added. In the guide of the civil institute of technology, as a definition of the rapid coagulating agent, a quality standard of the rapid coagulating material is specified in a guide (draft) of spray concrete. According to this standard, the start of the coagulation time is defined to be within 5 minutes and the end is defined to be within 15 minutes. That is, if a quick coagulant is used, a usable time of 15 minutes or more cannot be secured.
Further, the techniques of patent documents 9 to 11 also use a quick coagulating agent, and therefore, it is not possible to secure a usable time of 15 minutes or more after the addition of the quick coagulating agent.
In addition, in the techniques of patent documents 12 and 13, a large amount of rapid hardening material must be added after the technique arrives at a construction site, and therefore, the technique is not practical. Specifically, 10 to 60 parts of a quick-hardening material is added to 40 to 90 parts of a silicate cement. In order to add a large amount of rapid hardening materials later and mix them with a mixer truck, only 3/8(37.5 vol%) or less of ready-mixed concrete was charged into the mixer tank and transported.
Further, if the initial strength expression is good even at a low temperature (for example, about 5 ℃), it is effective in terms of improvement of workability, but the above document does not mention the initial strength at a low temperature.
In view of the above, an object of the present invention is to provide a quick-hardening concrete composition which can ensure a sufficient usable time and which is excellent in initial strength expression even in a low-temperature environment and which is shipped as ready-mixed concrete. It is another object of the present invention to provide a hardening agent for quick-hardening concrete delivered in ready-mixed concrete, which can satisfactorily exhibit the effects of the quick-hardening concrete composition delivered in ready-mixed concrete. It is still another object of the present invention to provide a method for preparing the ready-mixed concrete ready-to-deliver quick-hardening concrete composition, which can be used to produce the ready-mixed concrete ready-to-deliver quick-hardening concrete composition.
Means for solving the problems
Accordingly, the present inventors have made various efforts to solve the above problems, and as a result, have found that a quick-hardening concrete which can ensure a sufficient usable time and has excellent initial strength expression even in a low-temperature environment can be prepared by preparing a concrete prepared by combining a specific quick-hardening material and a specific setting agent in a ready-mixed concrete plant, transporting the concrete to the site, and then adding a specific setting agent thereto, and have completed the present invention. Namely, the present invention is as follows.
[1] A hardening agent for quick-hardening concrete delivered as ready-mixed concrete, wherein the hardening agent is added to a composition containing cement, a quick-hardening material and a setting agent, and the aluminum ion concentration in a liquid phase obtained by subjecting a composition containing no hardening agent, which composition is obtained by not adding the hardening agent to the composition at 5 ℃, to solid-liquid separation is 1.1 times or more the aluminum ion concentration in a liquid phase obtained by subjecting a composition containing the hardening agent, which composition is obtained by adding the hardening agent to the composition at 5 ℃ and then subjecting the composition to solid-liquid separation for 30 minutes.
[2] The hardener for quick hardening concrete shipped as ready mixed concrete according to [1], which contains a calcium aluminate-based compound.
[3] The hardener for quick hardening concrete shipped as ready mixed concrete according to [2], further comprising gypsum.
[4]According to [2]]Or [3]]The hardening agent for quick hardening concrete delivered in the form of ready mixed concrete comprises 30-60 mass% of CaO in the calcium aluminate compound and Al2O330 to 60 mass% of SiO2In the range of 1 to 18 mass%.
[5] The hardener for quick-hardening concrete delivered as ready-mixed concrete according to any one of [2] to [4], wherein the calcium aluminate compound has an amorphousness of 70% or more.
[6] A ready-to-harden concrete material of the two-pack type delivered in ready-mixed concrete form, comprising: material A containing cement, quick-hardening material and dormancy agent; and a material B containing the curing agent for a quick-hardening concrete for shipment in the ready-mixed concrete form according to any one of [1] to [5 ].
[7] A quick-hardening concrete composition which is delivered by the ready-mixed concrete method, wherein a material B containing a hardening agent for quick-hardening concrete delivered by the ready-mixed concrete method as described in any one of [1] to [5] is added to a material A containing cement, a quick-hardening material and a dormant agent.
[8] The quick-hardening concrete composition according to [7], which is shipped as ready-mixed concrete, wherein the quick-hardening material contains a calcium aluminate compound and gypsum.
[9]According to [8]The quick-hardening concrete composition shipped in the form of ready-mixed concrete, the aluminumThe calcium acid compound contains CaO-Al2O3-SiO2A compound of the series CaO-Al2O3-SiO2The amorphous degree of the compound is 70% or more and SiO2In the range of 1 to 18 mass%.
[10] The quick-hardening concrete composition shipped as ready-mixed concrete according to any one of [7] to [9], wherein the dormant agent contains a hydroxycarboxylic acid or a mixture of an alkali metal carbonate other than lithium and a hydroxycarboxylic acid.
[11] The quick-hardening concrete composition delivered in the ready-mixed concrete form according to any one of [7] to [10], wherein the content of the curing agent in the quick-hardening concrete delivered in the ready-mixed concrete form is 0.5 to 7 parts by mass with respect to 100 parts by mass of the total of the cement and the quick-hardening material.
[12] A preparation method of fast-hardening concrete delivered in a ready-mixed concrete mode sequentially comprises the following steps: mixing at least cement, a rapid hardening material, and a dormant agent with mixing water in a mixing vessel; and a step of further mixing the curing agent for quick hardening concrete for shipment in the ready-mixed concrete system according to any one of [1] to [5 ].
[13] The method for preparing quick-hardening concrete delivered as ready-mixed concrete according to [12], wherein in the step of mixing, the volume of the base concrete containing at least the cement, the quick-hardening material, the setting agent, the aggregate, and the mixing water is set to 40% or more of the internal volume of the mixing container.
[14] The method for preparing ready-mixed concrete ready-to-use concrete for shipment according to [12] or [13], wherein the type and the amount of the hardening agent for ready-mixed concrete ready-to-use concrete are determined in such a manner that a usable time after the hardening agent for ready-mixed concrete ready-to-use concrete can be secured for 15 minutes or more.
[15] The method for preparing quick-hardening concrete delivered as ready-mixed concrete according to any one of [12] to [14], wherein the amount of the dormant agent used is 0.3 to 5 parts by mass based on 100 parts by mass of the total of the cement and the quick-hardening material.
Effects of the invention
According to the present invention, it is possible to provide a quick-hardening concrete composition which can ensure a sufficient usable time and is excellent in initial strength expression even in a low-temperature environment and which is shipped as ready-mixed concrete. In addition, it is possible to provide a hardening agent for quick-hardening concrete delivered in the ready-mixed concrete system, which can satisfactorily exhibit the effect of the quick-hardening concrete composition delivered in the ready-mixed concrete system. Further, a method for preparing the ready-mixed concrete shipped fast-hardening concrete composition can be provided for manufacturing the ready-mixed concrete shipped fast-hardening concrete composition.
In view of the above-described effects, the present invention is particularly suitable for use in the civil engineering and construction field.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the embodiments. Unless otherwise specified, "part" and "%" in the present specification are based on mass. In the present specification, the term "composition" is a generic name of cement compositions, mortar compositions and concrete compositions.
[1] Hardener for quick-hardening concrete for shipment as ready-mixed concrete
The hardening agent (sometimes simply referred to as "hardening agent") for quick-hardening concrete delivered as ready-mixed concrete is a hardening agent added to a composition containing cement, a quick-hardening material and a setting agent, and the concentration of aluminum ions (Y) in a liquid phase obtained by solid-liquid separation of a composition containing no hardening agent, which is obtained by not adding the hardening agent to the composition under a condition of 5 ℃. (Y) is5℃) The aluminum ion concentration (X) in the liquid phase obtained by solid-liquid separation of a hardener-containing composition obtained by adding a hardener to the composition at 5 ℃ for 30 minutes5℃) Is 1.1 times (X)5℃/Y5℃1.1) or more.
The compositions containing and not containing the hardener were the same except for the presence of the hardener. In this case, the amount of the hardening agent to be added is preferably about 0.5 to 7 parts by mass based on 100 parts by mass of the total of the cement and the quick-hardening material.
X is above5℃/Y5℃This means the dissolution rate of aluminum ions which contributes greatly to the improvement of the initial strength, and a large value means that a large amount of aluminum ions can be present in the initial stage, the formation of ettringite in the initial stage is excellent, and the strength expression is easily obtained. Thus, in X5℃/Y5℃If the content is less than 1.1, it is difficult to obtain initial strength expression in a low-temperature environment of 5 ℃ and it is difficult to produce a quick-hardening concrete composition that is delivered as ready-mixed concrete. X5℃/Y5℃Preferably 1.2 to 4.0. As described in the examples, the aluminum ion concentration in the liquid phase can be measured by inductively coupled plasma emission spectrometry (ICP-AES) or the like, and X can be calculated from the measured value5℃/Y5℃。
To make X5℃/Y5℃The content of the calcium aluminate compound is 1.1 or more, and for example, a component which promotes the production of ettringite, for example, a calcium aluminate compound may be added, and further, gypsum or the like may be added to the curing agent in view of long-term strength expression.
Similarly, it is preferable that the concentration of aluminum ions (Y) in a liquid phase obtained by solid-liquid separation of a composition containing no hardener and obtained without adding the hardener to the composition at 20 ℃20℃) The aluminum ion concentration (X) in the liquid phase obtained by solid-liquid separation of a hardener-containing composition obtained by adding a hardener to the composition at 20 ℃ for 30 minutes20℃) Is 1.2 times (X)20℃/Y20℃1.2), more preferably 1.2 to 4.0 times.
By X20℃/Y20℃The amount of the inorganic filler is 1.2 times or more, whereby the formation of ettringite in the initial stage is excellent and the strength expression property can be easily obtained.
Further, X5℃/X20℃Preferably 0.65 or more, more preferably 0.75 or more. The upper limit is actually 1. By X5℃/X20℃Being 0.65 or more, the curing agent for quick-hardening concrete delivered in the ready-mixed concrete system can exhibit a function without variation at low and high temperatures, and therefore can be used almost regardless of the working temperature.
The components and the like will be described in detail below.
In the embodiment of the hardening agent for quick hardening concrete delivered by the ready-mixed concrete method according to the present invention, the hardening agent for quick hardening concrete delivered by the ready-mixed concrete method means a material which reminds the hydration hardening again of the quick hardening concrete (concrete whose hydration hardening is almost stopped) which is dormant by adding a large amount of a dormant agent described later. Specific examples thereof include calcium aluminate compounds.
Here, the "quick-hardening concrete delivered in the ready-mixed concrete form" in the present embodiment means the following concrete: ready-mixed concrete (ready-mixed concrete) is mixed in a ready-mixed concrete factory, a ready-mixed concrete plant, or the like, transported by a mixer truck, shipped to a construction site such as a civil engineering construction site or a construction site, and rapidly hardened after a watering operation. In the case of quick-hardening concrete delivered in the ready-mixed concrete system, the minimum available time from delivery to completion of work requires 120 minutes or more because of the transportation time, and when the transportation distance is long, it is desirable to secure an available time of 180 minutes or more. This embodiment is specifically used for such a purpose.
The "mixer truck" is a truck having a mixing tank (mixing container) in a loading platform part, which can transport freshly mixed concrete while mixing, and the functions thereof are not greatly different, but a mixer truck having a maximum loading capacity of 2 to 11t is available, and can be used according to the application.
However, it is necessary to secure the working time even after adding the curing agent for the quick-hardening concrete delivered in the ready-mixed concrete system, and it is necessary to select the type of the curing agent capable of securing the usable time of at least 15 minutes or more and set the addition amount. From this viewpoint, as the hardening agent, it is necessary to avoid selecting a rapid coagulant such as sodium aluminate, aluminum sulfate, sodium silicate, or the like. These rapid coagulants exhibit rapid coagulability immediately after addition, and it is difficult to ensure a usable time of 10 minutes or more. Therefore, these quick setting agents are preferably set to 30 parts or less, more preferably not used at all, relative to 100 parts of the setting agent for quick hardening concrete delivered in the ready-mixed concrete manner.
The hardening agent is preferably used for quick-hardening concrete delivered as ready-mixed concrete, and has a screening residue content of, for example, 300 μm of 5% or less and a screening residue content of 100 μm of 10% or less.
The hardening agent according to the present invention preferably contains a calcium aluminate compound. In the present invention, the calcium aluminate compound is also used in the quick-hardening material described later, but the calcium aluminate compound used in the hardening agent is preferably CaO/Al2O3The molar ratio is in the range of 0.5-2.4. Through CaO/Al2O3The molar ratio is 0.5 or more, and the effect of improving the temperature dependence can be more fully exerted; when the amount is 2.4 or less, the hardening speed can be suppressed when the hardening agent is used in the slurry.
In the above-described preferred range, from the viewpoint of extending the usable time, the range is more preferably 0.5 to 1.2, and still more preferably 0.75 to 1.0. From the viewpoint of initial strength expression, the range is more preferably 1.2 to 2.4, and still more preferably 1.25 to 2.3.
In the calcium aluminate compound, 30 to 60 mass% of CaO and Al are preferable2O330 to 60 mass% of SiO2In the range of 1-18 mass%, more preferably 40-50 mass% CaO and Al2O340 to 50 mass% of SiO2In the range of 3 to 10 mass%. Through CaO and Al2O3、SiO2Within the above range, the effect of improving the temperature dependence can be more sufficiently exhibited, and the hardening speed can be suppressed when the hardening agent is used in the slurry.
Further, calcium aluminate compounds are roughly classified into amorphous calcium aluminate compounds and crystalline calcium aluminate compounds, and amorphous calcium aluminate compounds are preferably used from the viewpoint of the expression of long-term strength. From the above viewpoint, the degree of amorphousness is preferably 70% or more, more preferably 80% or more. The method for measuring the degree of amorphousness is described below.
In addition, from the viewpoint of effectively exerting the effect, the calcium aluminate compound in the hardener for quick-hardening concrete delivered as ready-mixed concrete is preferably 70% or more, and more preferably 80% or more.
The presence of substances (other components) other than the above-exemplified curing agent may be contained in a range of 30% or less as long as the dispersibility of the curing agent can be improved or the effect of the curing agent can be contributed to and the effect of the present invention is not impaired.
The hardening agent according to the present invention is preferably constituted by further containing gypsum, more preferably a calcium aluminate compound and gypsum, in any of the above components.
As the gypsum used, any of anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum can be used. Further, chemical gypsum such as natural gypsum, gypsum by-product of phosphoric acid, desulfurized gypsum, and gypsum by-product of hydrogen fluoride, or gypsum obtained by heat-treating these may be used. Among them, anhydrous gypsum and/or hemihydrate gypsum are preferable in terms of strength expression; from the viewpoint of cost, anhydrous gypsum is preferably selected, and type II anhydrous gypsum and/or natural anhydrous gypsum are preferred. The particle size of gypsum is preferably 3000cm in terms of Blaine value2More preferably 4000 to 7000 cm/g2(ii) in terms of/g. Passing through 3000cm2More than g, the initial strength expression property can be well exerted.
The amount of the gypsum used is preferably 10 to 200 parts, more preferably 15 to 150 parts, and still more preferably 90 to 130 parts, per 100 parts of the curing agent (preferably, a calcium aluminate compound). Within these ranges, the long-term strength expression and durability can be improved.
The amount of the curing agent used for quick-hardening concrete delivered in the ready-mixed concrete form is not particularly limited, but is preferably 0.5 to 7 parts, more preferably 1 to 5 parts, based on 100 parts of the total of the cement and the quick-hardening material to be described later. By 0.5 to 7 parts, the strength of the short-term material can be sufficiently expressed, and the usable time can be secured. The curing agent may be slurried and added to various base concrete or the like. In this case, from the viewpoint of strength expression, it is desirable to mix a slurry in which a part of the water used for mixing is used as a hardening agent in concrete mixing and subtract a corresponding amount of water from the base concrete.
[2] Quick-hardening concrete material delivered in ready-mixed concrete mode and quick-hardening concrete composition delivered in ready-mixed concrete mode
The invention relates to a fast-hardening concrete material which is delivered in a ready-mixed concrete mode, and the implementation mode of the fast-hardening concrete material is a double-material type fast-hardening concrete material which is delivered in a ready-mixed concrete mode, and the fast-hardening concrete material comprises the following components: material A containing cement, quick-hardening material and dormancy agent; and a material B containing the hardening agent for the fast-hardening concrete delivered in the ready-mixed concrete mode.
In addition, an embodiment of the quick-hardening concrete composition delivered as ready-mixed concrete according to the present invention is obtained by adding and mixing the material B to the material a.
In this embodiment, the rapid hardening agent and the dormancy agent need to be added and mixed in advance in the cement in the ready-mixed concrete plant, and the hardening agent needs to be added and mixed after being transported to the site. If the hardener is mixed in advance in a ready-mixed concrete plant, the usable time cannot be ensured. Further, if both the quick-hardening material and the hardening agent are added in the ready-mixed concrete plant, the usable time becomes extremely short, and the concrete can be discarded only in the middle of transportation. When a hardening agent is added in a ready-mixed concrete factory and a rapid hardening material is added in a construction site, the usable time after the rapid hardening material is added is extremely short, and the time is less than 10 minutes, so that construction cannot be performed. When the rapid hardening material and the hardening agent are added at the construction site, the usable time is shortened, the value of the compressive strength is lowered, the abrasion resistance tends to be deteriorated, and only about 30% of the volume of the agitation tank can be transported. Thus, the timing of the addition of the rapid hardening material and the hardening agent is extremely important.
Therefore, in the present embodiment, the ready-mixed concrete shipment quick-hardening concrete composition of the present embodiment can be manufactured by preparing a two-pack type including the material a containing cement, a quick-hardening material and a setting agent and the material B containing a setting agent for quick-hardening concrete shipment in the ready-mixed concrete shipment line, and specifically, by transporting the material a and the material B from the ready-mixed concrete shop to the construction site, respectively, and mixing them at the construction site. The components and the like according to the present embodiment will be described in detail below.
(Cement)
The "cement" in the present embodiment is not particularly limited, and examples thereof include all cements such as ordinary, early strength, medium heat, and low heat portland cements prescribed in Japanese Industrial Standards (JIS), various mixed cements obtained by mixing blast furnace slag, fly ash, and silica, Eco cement (Eco cement) produced using municipal refuse incineration ash and sewage sludge incineration ash as raw materials, and filler cement, sulphoaluminate cement, and alumina cement obtained by mixing limestone powder, fine blast furnace slag powder, and the like, which are not prescribed in Japanese Industrial Standards (JIS). Further, cement prescribed in EN197-2000 from abroad and all cement prescribed in GB standard of China can be cited. One or two or more of these cements may be used.
The Portland cement is composed of a mixture of alite (3 CaO. SiO)2) Belite (belite) (2CaO · SiO)2) Aluminate (3 CaO. Al)2O3) Ferrite (4 CaO. Al)2O3·Fe2O3) And further mixed with dihydrate gypsum (sometimes a part of which becomes hemihydrate gypsum). In the present embodiment, from the viewpoint of strength expression, it is preferable to select cement that does not contain a mixed material such as blast furnace slag, fly ash, silica, and fine limestone powder, and among them, it is preferable to select cement having a high alite content and a high powder content (fine particle size). Examples of the cement suitable for this purpose include Japanese cement, early strength cement, and ordinary cement. Further, as examples of cement of china, PII52.5 and PII42.5 are listed.
(Rapid hardening Material)
The quick-hardening material of the present embodiment preferably contains a calcium aluminate compound and gypsum. Here, the calcium aluminate compound is represented byCaO and Al2O3The general name of the compound as the main component is not particularly limited. Specific examples thereof include CaO & Al2O3、12CaO·7Al2O3、11CaO·7Al2O3·CaF2、3CaO·Al2O3、3CaO·3Al2O3·CaSO4Further, CaO and Al are included2O3Amorphous substance as a main body (e.g. CaO-Al)2O3-SiO2A series of compounds), and the like. Among them, from the viewpoint of strength expression, an amorphous substance is preferably selected. Among them, sulphoaluminate cement and alumina cement specified in GB20472-2006 in china are themselves rapid hardening cements, and therefore can be used without adding a rapid hardening material in accordance with the required initial strength expression.
Here, the degree of amorphousness in the present embodiment is defined as follows. The object was annealed at 1000 ℃ for 2 hours, and then slowly cooled at a cooling rate of 5 ℃/min to crystallize the object. Then, the crystallized substance was measured by powder X-ray diffraction method to determine the area S of the main peak of the crystal mineral0. Next, the degree of amorphousness X is determined from the main peak area S of the crystal of the material before annealing by the following equation.
X(％)＝100×(1-S/S0)
Although the general industrial raw material contains SiO2、MgO、Fe2O3、TiO2、K2O、Na2O, but these impurities have a function of promoting amorphization of the calcium aluminate compound, and the total amount thereof is not limited to 20% or less. Wherein, SiO2May be contained in a range of 1 to 18% for the purpose of obtaining amorphous calcium aluminate.
Therefore, the rapid hardening material preferably contains CaO-Al2O3-SiO2A compound of the series, gypsum, the CaO-Al2O3-SiO2The amorphous degree of the compound is 70% or more, and SiO is2In the range of 1 to 18 mass%. By setting to thisIn this manner, the usable time before the addition of the curing agent can be made sufficient, and the initial strength after the addition of the curing agent can be made excellent. More preferably CaO-Al2O3-SiO2The amorphous degree of the compound is 80% or more, and SiO is2In the range of 2 to 13 mass%.
The calcium aluminate compound is preferably prepared by pulverizing the calcium aluminate compound to 4000 to 9000cm in terms of Blaine specific surface area2A more preferable range is 5000 to 8000 cm/g2(ii) in terms of/g. The powder size (Blaine specific surface area) of the calcium aluminate compound is 4000 to 9000cm2And/g, thereby making it easy to obtain sufficient quick hardening properties and to obtain strength expression properties at low temperatures.
The rapid hardening material according to the present embodiment is preferably prepared by pulverizing the material to 4000 to 9000cm in terms of Blaine specific surface area2A more preferable range is 5000 to 8000 cm/g2(ii) in terms of/g. The powder passing through the rapid hardening material is 4000-9000 cm2And/g, sufficient super-rapid hardness can be easily obtained, and strength expression at low temperature can be easily obtained.
The amount of the rapid hardening agent used is preferably 10 to 35 parts, more preferably 15 to 30 parts, and still more preferably 20 to 25 parts, based on 100 parts of the total of the cement and the rapid hardening agent. By using 10 to 35 parts, good initial strength expression is easily obtained, and long-term strength reduction is also less likely to occur.
(dormancy agent)
The dormancy agent used in the present embodiment has a function of dormant (almost stopping hydration hardening) the quick hardening concrete delivered from the ready-mixed concrete, and is a substance that avoids the quick hardening problem in the ready-mixed concrete plant and the quick hardening problem when transported by a mixer truck. Examples of the dormant agent include hydroxycarboxylic acids, salts thereof, combinations thereof with alkali metal carbonates, saccharides, boric acid, and the like. It is preferable to use a hydroxycarboxylic acid and an alkali metal carbonate in combination, from the viewpoint of the effect of making the quick-hardening concrete dormant and the viewpoint of the strength expression after adding the curing agent. Among them, the alkali metal carbonate is preferably selected from alkali metal carbonates other than lithium. From the viewpoint of ensuring a sufficient usable time of the base concrete, ensuring a certain usable time even after adding the curing agent, and further improving the strength expression, it is not preferable to use lithium carbonate.
The sleep inhibitor preferably contains hydroxycarboxylic acid or a mixture of alkali metal carbonate other than lithium and hydroxycarboxylic acid, and more preferably contains a mixture of alkali metal carbonate other than lithium and hydroxycarboxylic acid. The mixing ratio of the alkali metal carbonate other than lithium to the hydroxycarboxylic acid is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, in terms of the alkali metal carbonate other than lithium/hydroxycarboxylic acid.
Examples of the hydroxycarboxylic acid or salt thereof include citric acid, gluconic acid, tartaric acid, malic acid, and the like; examples of the salt include sodium salt, potassium salt, calcium salt, and magnesium salt. 1 or 2 or more of them may be used in combination.
The amount of the dormant agent used is preferably 0.3 to 5 parts, more preferably 0.3 to 4.5 parts, based on 100 parts of the total of the cement and the rapid hardening material. By using 0.3 to 5 parts, the transportation time and the sufficient operation time before arriving at the site can be easily ensured. Furthermore, when a hardening agent is added, the hydration hardening is also easily resumed.
(Gypsum)
The gypsum used in the present embodiment may be any of anhydrous, semi-hydrated and dihydrate gypsum. Among them, anhydrous gypsum and/or hemihydrate gypsum are preferable in terms of strength expression, but from the viewpoint of cost, it is desirable to select anhydrous gypsum, and type II anhydrous gypsum and/or natural anhydrous gypsum are preferable. The particle size of gypsum is preferably 3000cm in terms of Blaine value2More preferably 4000 to 7000 cm/g2(ii) in terms of/g. Passing through 3000cm2More than g, the initial strength expression property can be well exerted.
The amount of the gypsum is preferably 10 to 200 parts, more preferably 15 to 150 parts, and still more preferably 20 to 130 parts, based on 100 parts of the calcium aluminate compound (preferably, the calcium aluminate compound used for the rapid hardening material). When the amount is within these ranges, the strength expression property can be exhibited well.
In the present embodiment, in addition to the above-mentioned rapid hardening material, dormancy agent and hardening agent, one or more of an expanding material, a water reducing agent, an AE water reducing agent, a high performance water reducing agent, slag such as fine powder of blast furnace slag and fine powder of blast furnace slag, a mixed material such as fine powder of limestone, fly ash and silica fume, a defoaming agent, a thickener, a rust preventive, an antifreeze, a shrinkage reducing agent, a polymer, a clay mineral such as bentonite, and an anion exchanger such as hydrotalcite may be used within a range that does not substantially impair the object of the present invention.
[3] Method for preparing quick-hardening concrete delivered in premixed concrete mode
The embodiment of the preparation method of the quick hardening concrete delivered in the ready-mixed concrete mode sequentially comprises the following steps: mixing at least cement, a rapid hardening material, and a dormant agent with mixing water in a mixing vessel; and a step of further mixing a hardening agent for quick hardening concrete for shipment as ready-mixed concrete, for example, at a construction site.
In the step of kneading, the volume of the base concrete including at least cement, a rapid hardening agent, a setting agent, aggregate, and water for kneading is preferably 40% (volume%) or more, more preferably 50 (volume%) or more of the internal volume of the kneading vessel.
Here, the mixing container is a container that is mounted on a ready-mixed concrete truck, such as a tank of a mixer truck, and can hold ready-mixed concrete while mixing.
Further, it is preferable to determine the kind and the mixing amount of the hardening agent for the fast-hardening concrete shipped in the ready-mixed concrete manner so that the available time after mixing the hardening agent for the fast-hardening concrete shipped in the ready-mixed concrete manner can be secured for 10 minutes or more, preferably 15 minutes or more.
As described above, the hardening agent for quick hardening concrete delivered as ready-mixed concrete according to the present embodiment is suitable as a mixed material to be added after mixing ready-mixed concrete (ready-mixed concrete), transporting the mixture to a construction site, and delivering the mixture after pouring. Similarly, the quick-hardening concrete material delivered as ready-mixed concrete according to the present embodiment is also suitable as a mixed material to be added after a pouring operation, similarly to the hardening agent. The usable time may be, for example, 120 minutes or more, preferably 180 minutes or more.
Examples
The present invention will be described in further detail below based on experimental examples, but the present invention is not limited to these experimental examples.
(Experimental example 1)
Mixing 380kg/m cement3120kg/m of rapid hardening material3Quick-hardening concrete having a water/binder ratio of 32%, an s/a of 42% and an air amount of 2.0 ± 1.5% by volume was mixed in a mixing vessel to prepare a concrete mixture. At this time, 1.5 parts of the setting agent was mixed with 100 parts of the binder composed of cement and rapid hardening material, and the volume after mixing was 85% of the inner volume of the kneading vessel so as not to be hardened by hydration for 24 hours or more (material a). Assuming that a transport time before arrival at a site and a waiting time after arrival at a construction site are generated, 5 parts of each curing agent (material B) shown in table 1 below (a quick-hardening concrete composition shipped as ready-mixed concrete) was added to 100 parts of a binder after 120 minutes. The pot life after the addition of the curing agent was measured, and the compressive strength 6 hours after the addition of the curing agent (8 hours after completion of the kneading) was measured. A series of test temperatures were either 5 ℃ or 20 ℃.
Further, 76 parts of cement excluding the fine aggregate and the coarse aggregate from the concrete mixture, 24 parts of a rapid hardening agent, 32 parts of water, and 1.5 parts of a setting agent were mixed, and a cement paste was prepared at 5 ℃ or 20 ℃. After preparing a cement paste at 5 ℃ or 20 ℃ for 120 minutes, 5 parts of a curing agent I, II was added to 100 parts of the total of cement and rapid hardening agent, and after 30 minutes from this time, solid-liquid separation was performed by filtration under reduced pressure to measure the concentration of aluminum ions contained in the liquid phase, and the concentration was compared with the concentration of aluminum ions when no addition was made. The results are shown in table 1 below.
S/a is a fine aggregate fraction, and is a value in which the absolute volume ratio of the amount of fine aggregate to the total amount of aggregate in concrete is expressed by percentage.
< use of Material >
(1) Hardener I, II
Hardening agent I: calcium hydroxide, commercially available product, has a residual content of 300 μm less than 1%, and a residual content of 100 μm 5%
And (2) hardening agent II: calcium aluminate compound with CaO content of 47% and Al content2O353% of SiO20% of the total amount of the components, the specific surface area of Blaine was 5,000cm2(iv)/g, degree of amorphousness: 85 percent of
(2) Rapid hardening material
The rapid hardening material A: CaO-Al2O3-SiO2An equivalent mixture of a calcium aluminate based compound and anhydrous gypsum. CaO-Al2O3-SiO2The CaO content of the calcium aluminate compound was 43%, and Al content was2O344% of SiO210% and the others 3%. Blaine specific surface area 5000cm2(ii)/g, degree of amorphousness 90%
(3) Dormancy agent
Dormancy agent 1: mixture of 75 parts of first-order reagent potassium carbonate and 25 parts of first-order reagent citric acid
(4) Others
Cement: ordinary portland cement (manufactured by Denka corporation, density 3.15 g/cm)3)
Anhydrous gypsum: type II anhydrite, pH3.0, Blaine specific surface area 5000cm2/g
Water: tap water
Fine aggregate: natural river sand
Coarse aggregate: crushing stone
< method of measurement >
Available time: the time to start coagulation was measured according to JIS A1147 as a usable time.
Compressive strength: measured according to JIS A1108.
Concentration of aluminum ions in the liquid phase: the collected liquid phase was analyzed by ICP-AES. Table 1 also shows the ratios when the additive was not added at each test temperature and was 1.0(1.0 times).
[ Table 1]
As can be seen from table 1, when the concentration of aluminum ions in the liquid phase after 30 minutes from the addition of the hardening agent was 1.2 times or more the concentration of aluminum ions in the liquid phase without the addition of the hardening agent, the strength was excellent in the strength for 6 hours and the strength for 1 day after a certain usable time was obtained. It is also found that the use of a calcium aluminate compound can reduce the temperature dependence and provide excellent strength expression even in a low-temperature environment.
(Experimental example 2)
The procedure of experimental example 1 was repeated, except that the curing agent II was used as the curing agent and that anhydrous gypsum was added to 100 parts of the curing agent II as shown in the following table. The results are shown in Table 2 below.
Wherein the anhydrous gypsum has a Blaine specific surface area of 5000cm2The type II natural anhydrous gypsum is produced in Thailand in a mode of per gram.
[ Table 2]
As can be seen from table 2, the addition of anhydrite to the curing agent improved the expression of the compressive strength after 1 day old.
(Experimental example 3)
The procedure of experimental example 2 was repeated, except that the chemical composition of the calcium aluminate-based compound as the curing agent II was mixed as shown in the following table, and the curing agent II was used so as to prepare a slurry having a water/curing agent ratio of 0.3 (wherein 1 part of the dormant agent was added to 100 parts of the curing agent II). The results are also shown in table 3 below.
The chemical composition was confirmed by JIS R5202 "chemical analysis method for portland cement".
[ Table 3]
By appropriately changing the chemical composition of the calcium aluminate compound in accordance with table 3, the effect of improving the temperature dependence can be more sufficiently exhibited, and rapid hardening can be suppressed when the hardening agent is used in the slurry.
Industrial applicability
The quick-hardening concrete composition shipped as ready-mixed concrete of the present invention ensures a sufficient usable time and, at the same time, is excellent in initial strength expression even under a low-temperature environment, and is therefore particularly suitable for use in the field of civil engineering and construction.
Claims (15)
1. A hardener for quick-hardening concrete delivered in the form of ready-mixed concrete,
which is a hardening agent added to a composition containing cement, a rapid hardening material and a dormant agent,
the aluminum ion concentration in a liquid phase obtained by solid-liquid separating a composition containing no hardener, which composition is obtained by adding no hardener to the composition at 5 ℃, is 1.1 times or more the aluminum ion concentration in a liquid phase obtained by solid-liquid separating a hardener-containing composition obtained by adding the hardener to the composition at 5 ℃ for 30 minutes.
2. Hardener for fast-hardening concrete for outgoing as ready-mixed concrete according to claim 1, which contains a calcium aluminate based compound.
3. Hardener for fast-hardening concrete for shipment as ready mixed concrete in accordance with claim 2, further comprising gypsum.
4. The hardener for quick-hardening concrete to be shipped as ready-mixed concrete according to claim 2 or 3, wherein CaO in the calcium aluminate compound is 30 to 60 mass%, Al2O330 to 60 mass% of SiO2In 1A range of about 18% by mass.
5. The hardener for quick-hardening concrete delivered as ready-mixed concrete according to any one of claims 2 to 4, wherein the calcium aluminate compound has an amorphousness of 70% or more.
6. A ready-to-mix concrete ready-to-harden concrete material of the two-part type, comprising: material A containing cement, quick-hardening material and dormancy agent; and a material B containing the hardener for quick-hardening concrete shipped as ready-mixed concrete according to any one of claims 1 to 5.
7. A quick-hardening concrete composition which is delivered as ready-mixed concrete, comprising a material A containing cement, a quick-hardening agent and a dormant agent, and a material B containing the hardening agent for quick-hardening concrete delivered as ready-mixed concrete according to any one of claims 1 to 5.
8. The ready-to-mix concrete ready-to-deliver quick-hardening concrete composition according to claim 7, wherein said quick-hardening material comprises a calcium aluminate compound and gypsum.
9. The ready-mixed concrete ready-to-deliver fast-hardening concrete composition according to claim 8, wherein said calcium aluminate compound contains CaO-Al2O3-SiO2A compound of the series CaO-Al2O3-SiO2The amorphous degree of the compound is 70% or more, and SiO is2In the range of 1 to 18 mass%.
10. The ready-to-mix concrete shipped quick-hardening concrete composition according to any one of claims 7 to 9, wherein the dormant agent comprises a hydroxycarboxylic acid or a mixture of an alkali metal carbonate other than lithium and a hydroxycarboxylic acid.
11. The quick-hardening concrete composition for ready-mixed concrete shipment according to any one of claims 7 to 10, wherein the content of the hardening agent for quick-hardening concrete for ready-mixed concrete shipment is 0.5 to 7 parts by mass relative to 100 parts by mass of the total of the cement and the quick-hardening material.
12. A preparation method of fast-hardening concrete delivered in a ready-mixed concrete mode sequentially comprises the following steps: mixing at least cement, a rapid hardening material, and a dormant agent with mixing water in a mixing vessel; and a step of further mixing the hardener for quick-hardening concrete to be shipped as ready-mixed concrete according to any one of claims 1 to 5.
13. The method for preparing quick-hardening concrete delivered as ready-mixed concrete according to claim 12, wherein in the step of mixing, the volume of the base concrete containing at least the cement, the quick-hardening material, the setting agent, the aggregate, and the mixing water is set to 40% or more of the internal volume of the mixing container.
14. The method for preparing ready-mixed concrete for quick hardening concrete according to claim 12 or 13, wherein the kind and the mixing amount of the hardening agent for quick hardening concrete shipped in ready-mixed concrete are determined in such a manner that an available time after mixing the hardening agent for quick hardening concrete shipped in ready-mixed concrete can be secured for 15 minutes or more.
15. The method for preparing a quick-hardening concrete delivered as ready-mixed concrete according to any one of claims 12 to 14, wherein the amount of the dormant agent used is 0.3 to 5 parts by mass based on 100 parts by mass of the total of the cement and the quick-hardening material.
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| JP2018155805 | 2018-08-22 | ||
| JP2018-155805 | 2018-08-22 | ||
| PCT/JP2019/030708 WO2020039908A1 (en) | 2018-08-22 | 2019-08-05 | Hardening agent for ready-mix shipped rapid-hardening concrete, ready-mix shipped rapid-hardening concrete material, ready-mix shipped rapid-hardening concrete composition, and method for preparing same |
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| CN112601726A true CN112601726A (en) | 2021-04-02 |
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| JP (1) | JP7319984B2 (en) |
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2019
- 2019-08-05 CN CN201980054389.9A patent/CN112601726A/en active Pending
- 2019-08-05 WO PCT/JP2019/030708 patent/WO2020039908A1/en active Application Filing
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