CN113735481A - Composite early strength mineral admixture and preparation method and application thereof - Google Patents

Composite early strength mineral admixture and preparation method and application thereof Download PDF

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CN113735481A
CN113735481A CN202110996212.XA CN202110996212A CN113735481A CN 113735481 A CN113735481 A CN 113735481A CN 202110996212 A CN202110996212 A CN 202110996212A CN 113735481 A CN113735481 A CN 113735481A
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composite
early strength
mineral admixture
cement
admixture
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CN113735481B (en
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王雨利
孙路义
王水山
杨宇杰
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Henan University of Technology
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • C04B40/0042Powdery mixtures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10Accelerators; Activators
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/05Materials having an early high strength, e.g. allowing fast demoulding or formless casting
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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

Abstract

The invention belongs to the technical field of building materials, and particularly relates to a composite early strength mineral admixture as well as a preparation method and application thereof. The composite early strength mineral admixture comprises fly ash, mineral powder, fluorgypsum and a composite additive, wherein the composite early strength mineral admixture comprises the following components in percentage by mass: fly ash: mineral powder: fluorine gypsum: the composite additive is (30-50): (30-50): (10-20): (10-20); wherein, the composite admixture comprises the following components in parts by weight: 20-30 parts of calcium formate, 20-30 parts of aluminum sulfate, 10-20 parts of sodium carbonate and 20-30 parts of hydrated lime. The composite early-strength mineral admixture not only can realize the utilization of solid wastes and avoid environmental pollution, but also is beneficial to improving the compressive strength of cement concrete and improving the service performance of the concrete.

Description

Composite early strength mineral admixture and preparation method and application thereof
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a composite early strength mineral admixture as well as a preparation method and application thereof.
Background
The solid waste, especially bulk solid waste, has the characteristics of large amount, wide range, outstanding environmental influence and the like, but due to the characteristics of the solid waste, when the solid waste is singly used in concrete, certain performances of the concrete are often influenced, for example, the early strength of the concrete is influenced by fly ash, water secretion and shrinkage are increased by mineral powder, and the like, so that the using amount of the solid waste is influenced.
Therefore, further research on solid wastes is needed to improve the service performance of concrete while recycling the solid wastes and avoiding the environmental pollution caused by the solid wastes.
Disclosure of Invention
The invention aims to provide a composite early strength mineral admixture to solve the problems of environmental pollution caused by solid wastes and poor concrete performance caused by single use.
The second purpose of the invention is to provide a preparation method of the composite early strength mineral admixture.
The invention also aims to provide the application of the composite early-strength mineral admixture.
One of the purposes of the invention is realized by adopting the following technical scheme: a composite early strength mineral admixture comprises fly ash, mineral powder, fluorgypsum and a composite additive;
the composite early strength mineral admixture comprises the following components in percentage by mass: fly ash: mineral powder: fluorine gypsum: the composite additive is (30-50): (30-50): (10-20): (10-20);
wherein, the composite admixture comprises the following components in parts by weight: 20-30 parts of calcium formate, 20-30 parts of aluminum sulfate, 10-20 parts of sodium carbonate and 20-30 parts of hydrated lime.
Preferably, the fluorgypsum is a byproduct of preparing hydrogen fluoride by using sulfuric acid and fluorspar, and the specific surface area is not less than 300m2/kg。
Preferably, the fly ash is power plant dry discharge ash.
Preferably, the ore powder is ore powder above grade S95.
Preferably, the calcium formate is commercial industrial grade calcium formate, and is solid powder, and the content of the calcium formate is 98% (mass percentage) or more.
Preferably, the aluminum sulfate is solid powder particles of aluminum sulfate I or II in chemical industry Standard "Industrial aluminum sulfate" HG/T2225-2010;
more preferably, the sodium sulfate is anhydrous sodium sulfate solid powder particles in Table 1 which accords with chemical industry standard cosmetic sodium sulfate HG/T4535-.
Preferably, the sodium carbonate is industrial sodium carbonate (both II and III) meeting the requirements of first-class products and/or qualified products in the national standard 'industrial sodium carbonate' GB 210-1992;
more preferably, the slaked lime powder is a slaked lime powder meeting the requirements of first-class products and/or qualified products in building material industry standard JC/T481-92.
The second purpose of the invention is realized by adopting the following technical scheme: the preparation method of the composite early strength mineral admixture comprises the following steps:
step S1, uniformly mixing calcium formate, aluminum sulfate, sodium carbonate and hydrated lime according to a proportion to obtain a composite additive;
and step S2, uniformly mixing the fly ash, the mineral powder, the fluorgypsum and the composite additive according to a proportion to obtain the composite early strength mineral admixture.
The third purpose of the invention is realized by adopting the following technical scheme: the application of the composite early-strength mineral admixture in concrete.
Preferably, the concrete comprises portland cement and a composite early strength mineral admixture, and the mass ratio of the portland cement to the composite early strength mineral admixture is (20-80): (20-80).
Preferably, the concrete further comprises a water reducing agent and sand.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the composite early strength mineral admixture of the invention mainly comprises solid wastes (fly ash, mineral powder and fluorgypsum), not only can effectively realize the utilization of the solid wastes and avoid environmental pollution, but also can play a role in improving the compressive strength of cement.
The cementing material prepared by compounding the composite early-strength mineral admixture and the Portland cement according to the mass ratio of (20-80) to (20-80) has better compressive strength compared with the Portland cement.
The composite early strength mineral admixture of the invention not only greatly improves the 1d compressive strength of concrete, but also improves the 28d compressive strength of concrete when the composite early strength mineral admixture replaces portland cement by a larger proportion.
The cement concrete of the invention has low requirements on production equipment and personnel, short production period and low production cost, does not generate three wastes in the whole process, can utilize solid wastes and does not influence the environment.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a flow chart of the preparation of the composite admixture in the embodiment of the present invention;
FIG. 2 is a flow chart of the preparation of the composite early strength mineral admixture in an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The invention provides a composite early-strength mineral admixture aiming at the problems that solid wastes (coal ash, mineral powder, fluorgypsum and the like) influence the environment and the use performance of concrete is deteriorated when the solid wastes are independently applied to the concrete. The composite early-strength mineral admixture is not only beneficial to realizing the reutilization of solid wastes, but also can play a role in improving the performance of cement and/or concrete.
The composite early-strength mineral admixture comprises fly ash, mineral powder, fluorgypsum and a composite additive; the mass ratio of the fly ash to the mineral powder to the fluorgypsum to the composite additive is, by weight: minerals: fluorine gypsum: the composite admixture is (30-50) and (30-50): (10-20): (10-20). For example, 30:30:10:10, 30:50:20:20, 40:30:10:10, 50:30:10:10, 45:50:10:10, 45:30:20:10, 45:40:10:20, 40:50:15:15, or 40:50:20: 15.
The composite additive comprises the following components in parts by weight: 20 to 30 parts (for example, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts or 30 parts) of calcium formate, 20 to 30 parts (for example, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts or 30 parts) of aluminum sulfate, 10 to 20 parts (for example, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 20 parts) of sodium carbonate and 20 to 30 parts (for example, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts or 30 parts) of hydrated lime.
The fly ash is fine ash collected from flue gas in a coal-fired power plant, and the main chemical component of the fly ash comprises SiO2、Al2O3And the fly ash is used for preparing concrete and has the following effects: firstly, the fly ash has the 'shape effect', the fly ash contains more than 70% of glass beads, the particle shape is complete, the surface is smooth, the texture is compact, and the effect of reducing water can be achieved; the second is the 'activity effect' of the fly ash, namely SiO in the fly ash2、Al2O3Can be mixed with cement hydration products Ca (OH)2Calcium silicate hydrate and calcium aluminate hydrate are generated by reaction, but the early strength of the concrete is influenced due to the slow reaction speed; thirdly, the micro-aggregate effect of the fly ash, and the tiny micro-beads and fragments in the fly ash can perfect the micro-fine particles in the cement concreteAnd (4) granule components. However, if the fly ash contains a large amount of unburned carbon particles, the performance of the concrete is adversely affected.
The mineral powder (blast furnace slag micropowder) is high-fineness and high-activity powder obtained by water quenching blast furnace slag and carrying out drying, grinding and other processes, and its main chemical component is SiO2、Al2O3And CaO and the like. The mineral powder can generate a synergistic hydration reaction with Portland cement, and can optimize the particle size of a cementing material, so that the compressive strength of concrete is effectively improved, the cost of the concrete is reduced, and meanwhile, the mineral powder has better effects of inhibiting alkali aggregate reaction, reducing hydration heat and the like, but is independently used, and the segregation of concrete mixtures, the shrinkage cracking in a hardening stage and the like are easily caused.
The fluorgypsum is a byproduct of hydrogen fluoride prepared from sulfuric acid and fluorspar, is mainly anhydrous calcium sulfate, has low self-activity, but can generate ettringite with calcium aluminate minerals in silicate cement and mineral powder, thereby playing a role in optimizing hydration products of the cementing material.
The composite additive can provide Ca2+、SO4 2-、CO3 2-、Na+、OH-And the method is beneficial to the excitation of the activity of the fly ash and the mineral powder and the generation of early hydration products.
According to the invention, the fly ash, the mineral powder and the fluorgypsum are proportioned according to a specific proportion, the composite additive with the specific proportion is added, and the calcium formate, the aluminum sulfate, the sodium carbonate and the hydrated lime in the composite additive are matched according to the specific proportion for use, so that the calcium formate can shorten the hydration induction period of the portland cement, accelerate the hydration induction period of the portland cement, and advance the occurrence time of a hydration temperature peak, thereby increasing the hydration heat release rate and heat release amount at the early stage; aluminum sulfate provides SO for system4 2-And Al3+Thereby being beneficial to the generation of early ettringite; sodium sulfate is used for providing SO for the system4 2-Is beneficial to the generation of early ettringite; second, Na is provided for the system+The excitation of the activity of the fly ash and the mineral powder is facilitated; sodium carbonate is firstly used for providing CO for the system3 2-And Ca in the system2+Reaction to form CaCO3Thus contributing to early strength; second, Na is provided for the system+The excitation of the activity of the fly ash and the mineral powder is facilitated; slaked lime provides Ca to the system at an early stage2+And OH-First, it helps ettringite and CaCO3Early generation; and secondly, the activity of the fly ash and the mineral powder is stimulated. The components in the composite additive act synergistically, so that the service performance of the fly ash, the mineral powder and the fluorgypsum is improved, and the reuse of solid wastes is realized.
In the preferred embodiment of the invention, the fluorgypsum is a byproduct of preparing hydrogen fluoride from sulfuric acid and fluorite, and the specific surface area is not less than 300m2In terms of/kg, the smaller the particle size of the fluorogypsum is, the more beneficial the fluorogypsum is to hydrate with the silicate cement and the calcium aluminate mineral powder in the mineral powder to generate hydration products such as ettringite and the like.
In the preferred embodiment of the invention, the fly ash is dry ash discharged from a power plant, and only the dry ash is selected because the finished product of the composite early-strength mineral admixture is powder.
In the preferred embodiment of the invention, the mineral powder meets the S95 grade and above in the table 1 of the national standard GB/T18046-2017 granulated blast furnace slag powder used in cement, mortar and concrete, and the higher the grade of the mineral powder is, the better the activity of the mineral powder is.
In a preferred embodiment of the invention, the calcium formate is commercially available industrial grade calcium formate, is in the form of solid powder, and has a content of 98% or more.
In the preferred embodiment of the invention, the aluminum sulfate is solid powder particles of aluminum sulfate I or aluminum sulfate II in chemical industry standard HG/T2225-2010 industrial aluminum sulfate.
In the preferred embodiment of the invention, the sodium sulfate is anhydrous sodium sulfate solid powder particles in Table 1 which meet the chemical industry standard HG/T4535-.
In the preferred embodiment of the invention, the sodium carbonate is industrial soda ash meeting the requirements of first-class products and/or qualified products in the national standard GB210-1992 Industrial sodium carbonate.
In the preferred embodiment of the invention, the slaked lime powder is the slaked lime powder meeting the requirements of first-class products and/or qualified products in building material industry standard JC/T481-92.
The preparation method of the composite early strength mineral admixture comprises the following steps: the method comprises the following steps:
step S1, uniformly mixing the calcium formate, the aluminum sulfate, the sodium carbonate and the hydrated lime according to a ratio to obtain the composite additive;
and step S2, uniformly mixing the fly ash, the mineral powder, the fluorgypsum and the composite additive according to a ratio to obtain the composite early strength mineral admixture.
In a preferred embodiment of the method for preparing the composite early strength mineral admixture of the present invention, in the step S1, calcium formate, aluminum sulfate, sodium carbonate and hydrated lime are proportionally added into a mixer to be uniformly mixed, and the specific surface area reaches 350m2And/kg, according to the detection of national standard GB 8076 + 2008 of concrete admixture, the composite admixture is obtained after the detection is qualified (see the attached figure 1 of the specification).
In the preferred embodiment of the preparation method of the composite early strength mineral admixture of the invention, in the step S2, the fly ash, the mineral powder, the fluorgypsum and the composite admixture are proportionally added into a mixer (or a stirrer) and stirred uniformly, the detection is carried out according to the building industry standard JG/T486-.
The invention also provides application of the composite early-strength mineral admixture in concrete.
In a preferred embodiment of the application of the composite early strength mineral admixture of the invention, the concrete comprises Portland cement and the composite early strength mineral admixture, and the mass ratio of the Portland cement to the composite early strength mineral admixture is (20-80) - (20-80) (for example, 20:80, 20:60, 20:40, 20:20, 40:60, 60:40, 80: 20) so that the 1d compressive strength of the cementing material can be improved by more than 10% (28d compressive strength is improved by more than 7%) relative to the Portland cement.
In one preferred embodiment of the application of the composite early strength mineral admixture of the invention, in order to improve the 1d compressive strength of the cementing material by more than 20 percent (improve the 28d compressive strength by more than 10 percent) relative to the portland cement, the mass ratio of the portland cement to the composite early strength mineral admixture is (40-80): (20-60) (e.g., 40:60, 80:20, 60:40, etc.).
In one preferred embodiment of the application of the composite early strength mineral admixture of the invention, in order to improve the 1d compressive strength of the cementing material by more than 21 percent (improve the 28d compressive strength by more than 14 percent) relative to the portland cement, the mass ratio of the portland cement to the composite early strength mineral admixture is (40-60): 40-60) (for example, 60:40, 40:60, etc.).
In one preferred embodiment of the application of the composite early strength mineral admixture of the invention, in order to improve the 1d compressive strength of the cementing material by more than 43 percent (more than 19 percent improvement of 28d compressive strength) relative to the portland cement, the mass ratio of the portland cement to the composite early strength mineral admixture is 60: 40.
In one preferred embodiment of the application of the composite early strength mineral admixture, the raw materials for preparing the concrete comprise a water reducing agent and sand besides the cementing material, wherein the water reducing agent is a naphthalene water reducing agent or a polycarboxylic acid water reducing agent; the sand is natural sand or machine-made sand 1 or 2 region sand which meets the regulation in the national standard GB/T14684-2011 construction sand table 1.
The composite early strength mineral admixture of the present invention, and the preparation method and application thereof are described in detail by the following specific examples.
In the following examples:
the fly ash is dry discharged ash of a power plant;
the mineral powder is slag powder above the S95 level in GB/T18046-2017 granulated blast furnace slag powder for cement, mortar and concrete;
the fluorgypsum is a by-product of preparing hydrogen fluoride from sulfuric acid and fluorspar, and has a specific surface area of not less than 300m2/kg;
The calcium formate is commercial industrial grade calcium formate, is solid powder and has the content of 98 percent or more;
the aluminum sulfate is qualified aluminum sulfate solid powder particles which meet the II class in the chemical industry standard of industrial aluminum sulfate HG/T2225-2010;
the sodium sulfate used is anhydrous sodium sulfate solid powder particles in Table 1 which meet the chemical industry standard of cosmetic sodium sulfate HG/T4535-;
the sodium carbonate is industrial sodium carbonate meeting the requirements of qualified products of class III in the national standard 'industrial sodium carbonate' GB 210-1992;
the used slaked lime powder is slaked lime powder meeting the first-class and/or qualified product requirements of calcareous slaked lime powder in JC/T481-92 of building material industry standard;
the adopted water reducing agent is a naphthalene water reducing agent;
the adopted sand is the sand in region 1 of natural sand which meets the regulation in the national standard GB/T14684-2011 'construction sand' table 1.
Example 1
The composite early strength mineral admixture in the embodiment comprises: 4000g of fly ash, 3500g of mineral powder, 1000g of fluorgypsum and 1500g of composite additive; wherein the compound additive comprises 2500g of calcium formate, 2500g of aluminum sulfate, 1500g of sodium carbonate and 2000g of hydrated lime.
The preparation method of the composite early strength mineral admixture of the embodiment comprises the following steps:
step S1, adding 2500g of calcium formate, 2500g of aluminum sulfate, 1500g of sodium carbonate and 2000g of hydrated lime into a mixer, and uniformly mixing until the specific surface area reaches 350m2The amount of the additive is/kg, and the composite additive is obtained after the detection is qualified according to the detection of national standard GB 8076 + 2008 of concrete additive;
and step S2, adding 4000g of fly ash, 3500g of mineral powder, 1000g of fluorgypsum and 1500g of composite admixture into a stirrer, stirring uniformly, detecting according to the building industry standard JG/T486-2015 composite admixture for concrete, and obtaining the composite early-strength mineral admixture of the invention after the detection is qualified.
The application of the composite early strength mineral admixture of the embodiment is as follows:
taking portland cement as a cementing material 1; portland cement was mixed with the composite early strength mineral admixture of the example in different proportions to prepare a cement 2 (cement 2 containing silicate cement 80 wt% and composite early strength mineral admixture of example 1 20 wt%), a cement 3 (cement 3 containing silicate cement 60 wt% and composite early strength mineral admixture of example 1 40 wt%), a cement 4 (cement 4 containing silicate cement 40 wt% and composite early strength mineral admixture of example 1 60 wt%), and a cement 5 (cement 5 containing silicate cement 20 wt% and composite early strength mineral admixture of example 180 wt%).
The above-mentioned cement 1, cement 2, cement 3, cement 4 and cement 5 were used for the preparation of concrete, respectively: the concrete is prepared by mixing a cementing material 1, a cementing material 2, a cementing material 3, a cementing material 4 and a cementing material 5 with a water reducing agent (the amount is 1 wt% of the cementing material), the sand rate is 40% (the sand rate is sand/(sand + gravel), the amounts of the sand and the gravel are calculated by mass), water (the water-cement ratio is 0.4, the water-cement ratio is water/(cement + composite early strength mineral admixture), and the amounts of the cement and the composite early strength mineral admixture are calculated by mass), respectively, concrete numbers 1-1, 1-2, 1-3, 1-4 and 1-5 are prepared, the compressive strength of the prepared concrete is detected (according to the standard GB/T7897-.
TABLE 1 Effect of the composite early strength mineral admixtures of the present invention on the compressive strength of concrete
Figure BDA0003234152960000081
As can be seen from Table 1, as the mass proportion of the composite early strength mineral admixture increases, the 1d compressive strength and the 28d compressive strength of the concrete tend to increase first and then decrease, wherein when the mass proportion of the composite early strength mineral admixture is between 20% and 60%, the 1d compressive strength and the 28d compressive strength are both better, wherein the improvement range of the 1d compressive strength is between 20% and 50%, and the improvement range of the 28d compressive strength is between 10% and 30%.
Example 2
The difference from the embodiment 1 lies in that the raw material components of the composite early strength mineral admixture are different, and specifically: comprises 3000g of fly ash, 4000g of mineral powder, 1500g of fluorgypsum and 1500g of composite additive; wherein the composite additive comprises 2000g of calcium formate, 3000g of aluminum sulfate, 1000g of sodium carbonate and 3000g of hydrated lime.
The preparation method of the composite early strength mineral admixture of the embodiment comprises the following steps: the same as in example 1.
The application of the composite early strength mineral admixture of the embodiment is as follows: taking portland cement as a cementing material 1; portland cement was mixed with the composite early strength mineral admixture of the example in different proportions to prepare a cement 2 (cement 2 containing silicate cement 80 wt% and composite early strength mineral admixture of example 1 20 wt%), a cement 3 (cement 3 containing silicate cement 60 wt% and composite early strength mineral admixture of example 1 40 wt%), a cement 4 (cement 4 containing silicate cement 40 wt% and composite early strength mineral admixture of example 1 60 wt%), and a cement 5 (cement 5 containing silicate cement 20 wt% and composite early strength mineral admixture of example 180 wt%).
The above-mentioned cement 1, cement 2, cement 3, cement 4 and cement 5 were used for the preparation of concrete, respectively: the concrete numbers 2-1, 2-2, 2-3, 2-4 and 2-5 are respectively prepared by mixing the gelled material 1, the gelled material 2, the gelled material 3, the gelled material 4 and the gelled material 5 with a water reducing agent (the dosage is 1 wt% of the gelled material), a sand rate is 40% and water (the water-to-cement ratio is 0.4), the compressive strength of the prepared concrete is detected, and the detection results are shown in the following table 2.
TABLE 2 Effect of the composite early strength mineral admixtures of the present invention on the compressive strength of concrete
Figure BDA0003234152960000101
The dosage of each component of the composite early strength mineral admixture is changed within the range of the admixture, and the influence of different admixture on the compressive strength is detected. As can be seen from the data in Table 2, the compressive strength of 1d and 28d tends to increase and decrease with the increase of the mixing amount of the composite early-strength mineral admixture, wherein the increase of the compressive strength of each age is the largest at the mixing amount of 40%, and the increase of the compressive strength of each age is smaller although the increase of the compressive strength is increased at the mixing amount of more than 80%.
Example 3
The difference from the embodiment 1 lies in that the raw material components of the composite early strength mineral admixture are different, specifically, the composite early strength mineral admixture comprises: 5000g of fly ash, 3000g of mineral powder, 1000g of fluorgypsum and 1000g of composite additive; wherein the composite additive comprises 3000g of calcium formate, 2000g of aluminum sulfate, 1000g of sodium sulfate, 2000g of sodium carbonate and 2000g of hydrated lime.
The preparation method of the composite early strength mineral admixture of the embodiment comprises the following steps: the same as in example 1.
The application of the composite early strength mineral admixture of the embodiment is as follows: taking portland cement as a cementing material 1; portland cement was mixed with the composite early strength mineral admixture of the example in different proportions to prepare a cement 2 (cement 2 containing silicate cement 80 wt% and composite early strength mineral admixture of example 1 20 wt%), a cement 3 (cement 3 containing silicate cement 60 wt% and composite early strength mineral admixture of example 1 40 wt%), a cement 4 (cement 4 containing silicate cement 40 wt% and composite early strength mineral admixture of example 1 60 wt%), and a cement 5 (cement 5 containing silicate cement 20 wt% and composite early strength mineral admixture of example 180 wt%).
The above-mentioned cement 1, cement 2, cement 3, cement 4 and cement 5 were used for the preparation of concrete, respectively: the concrete numbers 3-1, 3-2, 3-3, 3-4 and 3-5 are respectively prepared by mixing the gelled material 1, the gelled material 2, the gelled material 3, the gelled material 4 and the gelled material 5 with a water reducing agent (the dosage is 1 wt% of the gelled material), sand 40% and water (the water-to-cement ratio is 0.4), the compression strength of the prepared concrete is detected, and the detection results are shown in the following table 3.
TABLE 3 Effect of the composite early strength mineral admixtures of the present invention on the compressive strength of concrete
Figure BDA0003234152960000111
The dosage of each component of the composite early strength mineral admixture is changed within the range of the admixture, and the influence of different admixture on the compressive strength is detected. As can be seen from the data in Table 3, the compressive strength of 1d and 28d tends to increase and decrease with the increase of the mixing amount of the composite early-strength mineral admixture, wherein the increase of the compressive strength of each age is the largest at the mixing amount of 40%, and the increase of the compressive strength of each age is smaller although the increase of the compressive strength is increased at the mixing amount of more than 80%.
Example 4
The difference from the embodiment 1 lies in that the raw material components of the composite early strength mineral admixture are different, specifically, the composite early strength mineral admixture comprises: 3500g of fly ash, 3500g of mineral powder, 1500g of fluorgypsum and 1500g of composite additive; wherein the composite additive comprises 2000g of calcium formate, 3000g of aluminum sulfate, 1000g of sodium sulfate, 2000g of sodium carbonate and 2000g of hydrated lime.
The preparation method of the composite early strength mineral admixture of the embodiment comprises the following steps: the same as in example 1.
The application of the composite early strength mineral admixture of the embodiment is as follows: taking portland cement as a cementing material 1; portland cement was mixed with the composite early strength mineral admixture of the example in different proportions to prepare a cement 2 (cement 2 containing silicate cement 80 wt% and composite early strength mineral admixture of example 1 20 wt%), a cement 3 (cement 3 containing silicate cement 60 wt% and composite early strength mineral admixture of example 1 40 wt%), a cement 4 (cement 4 containing silicate cement 40 wt% and composite early strength mineral admixture of example 1 60 wt%), and a cement 5 (cement 5 containing silicate cement 20 wt% and composite early strength mineral admixture of example 180 wt%).
The above-mentioned cement 1, cement 2, cement 3, cement 4 and cement 5 were used for the preparation of concrete, respectively: the concrete numbers 4-1, 4-2, 4-3, 4-4 and 4-5 are respectively prepared by mixing the gelled material 1, the gelled material 2, the gelled material 3, the gelled material 4 and the gelled material 5 with a water reducing agent (the dosage is 1 wt% of the gelled material), sand 40% and water (the water-to-cement ratio is 0.4), the compressive strength of the prepared concrete is detected, and the detection results are shown in the following table 4.
TABLE 4 Effect of the composite early strength mineral admixtures of the present invention on the compressive strength of concrete
Figure BDA0003234152960000121
As can be seen from Table 4, as the mass percentage of the composite early strength mineral admixture increases, the compressive strength of 1d and 28d increases and then decreases, wherein the mixing amount is preferably between 20% and 60%.
Example 5
The composite early strength mineral admixture in this example comprises: 3000g of fly ash, 3500g of mineral powder, 1500g of fluorgypsum and 2000g of composite additive; wherein the compound additive comprises 2500g of calcium formate, 2500g of aluminum sulfate, 1500g of sodium carbonate and 2000g of hydrated lime.
The preparation method of the composite early strength mineral admixture of this example is the same as that of example 1.
The application of the composite early strength mineral admixture of the embodiment is as follows: taking portland cement as a cementing material 1; portland cement was mixed with the composite early strength mineral admixture of the example in different proportions to prepare a cement 2 (cement 2 containing silicate cement 80 wt% and composite early strength mineral admixture of example 1 20 wt%), a cement 3 (cement 3 containing silicate cement 60 wt% and composite early strength mineral admixture of example 1 40 wt%), a cement 4 (cement 4 containing silicate cement 40 wt% and composite early strength mineral admixture of example 1 60 wt%), and a cement 5 (cement 5 containing silicate cement 20 wt% and composite early strength mineral admixture of example 180 wt%).
The above-mentioned cement 1, cement 2, cement 3, cement 4 and cement 5 were used for the preparation of concrete, respectively: the concrete is prepared by mixing the gelled material 1, the gelled material 2, the gelled material 3, the gelled material 4 and the gelled material 5 with a water reducing agent (the dosage is 1 wt% of the gelled material), sand 40% and water (the water-to-gel ratio is 0.4) respectively to obtain concrete numbers 5-1, 5-2, 5-3, 5-4 and 5-5, and the compression strength of the prepared concrete is detected, wherein the detection results are shown in the following table 5:
TABLE 5 Effect of the composite early Strength mineral admixtures of the present invention on the compressive Strength of concrete
Figure BDA0003234152960000131
Similarly, the dosage of each component of the composite early strength mineral admixture is changed within the blending amount range, and the influence of different blending amounts on the compressive strength is detected. As can be seen from Table 5, the cement concretes 1d and 28d each have a different increase in compressive strength, particularly between 20% and 60%, in the mass range between 20% and 80% in place of portland cement.
Comparative example 1
Comparative example 1 differs from example 1 in that: the mineral admixture does not comprise the composite admixture, and the rest is the same as that in the example 1, and the description is omitted. The results are shown in Table 6.
TABLE 6 Effect of mineral admixtures not incorporating the Complex Admixture on the compressive Strength of concrete
Figure BDA0003234152960000141
As can be seen from Table 6, when the complex admixture is not included in the mineral admixture, the compressive strengths of 1d and 28d gradually decrease with the increase of the mineral admixture, and the larger the amount of the complex admixture, the larger the magnitude of the decrease.
Comparative example 2
Comparative example 2 differs from example 1 in that: the mixing amounts of other components of the fixed mineral admixture are changed, namely the mixing amounts of 4000g of fixed fly ash, 3500g of mineral powder and 1000g of fluorgypsum are changed, the mixing amounts of the composite admixture are respectively 0g, 500g, 1000g, 1500g, 2000g and 3000g (the mixture ratio of the raw materials in the composite admixture is the same as that in example 1), and the rest is the same as that in example 1, and the details are not repeated. The results are shown in Table 7.
TABLE 7 influence of the amount of the composite admixture on the compressive strength of concrete
Figure BDA0003234152960000151
As can be seen from Table 7, the compressive strengths of 1d and 28d increased gradually with increasing incorporation of the composite admixture, wherein the maximum compressive strength of the composite admixture for 1d was 2000 g; the maximum mixing amount of the composite admixture is 1500g for the compressive strength of 28 d.
Comparative example 3
Comparative example 3 differs from example 1 in that: the mineral admixture is prepared when the composite admixture does not contain calcium formate, aluminum sulfate, sodium carbonate and hydrated lime respectively, and the rest is the same as that in the embodiment 1 and is not repeated. The results are shown in Table 8.
TABLE 8 influence of the composition of the Compound Admixture on the compressive Strength of concrete
Figure BDA0003234152960000161
As can be seen from the data in Table 8, when the admixture composition does not contain a specific component, the compressive strengths of 1d and 28d, although they are increased significantly, are decreased to different degrees when they are contained relatively. The components in the composite additive can improve the compressive strength under the synergistic effect.
Comparative example 4
Comparative example 4 differs from example 1 in that: the fluorgypsum has different surface areas, i.e. the specific surface areas are respectively 200m2/kg、300m2/kg、380m2/kg、450m2Impact of fluorgypsum on compressive strength at/kg.
The rest is the same as that in embodiment 1, and is not described again.
TABLE 9 influence of the specific surface area of fluorgypsum on the compressive strength of concrete
Figure BDA0003234152960000171
As can be seen from the data in Table 9, the compressive strengths of the concretes 1d and 28d gradually increased with the increase of the specific surface area of the fluorogypsum, wherein the specific surface area was 200m2At/kg, the compressive strength of 1d and 28d is increased, but the increase is relatively small; when the specific surface area of the fluorgypsum is more than 380m2And/kg, the increasing amplitude of the compressive strength of the 1d and the 28d is gradually reduced when the pressure is increased.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The composite early strength mineral admixture is characterized by comprising fly ash, mineral powder, fluorgypsum and a composite additive;
the composite early strength mineral admixture comprises the following components in percentage by mass: fly ash: mineral powder: fluorine gypsum: the composite additive is (30-50): (30-50): (10-20): (10-20);
wherein, the composite admixture comprises the following components in parts by weight: 20-30 parts of calcium formate, 20-30 parts of aluminum sulfate, 10-20 parts of sodium carbonate and 20-30 parts of hydrated lime.
2. The composite early strength mineral admixture according to claim 1, wherein said fluorogypsum is a by-product of hydrogen fluoride production from sulfuric acid and fluorite, and has a specific surface area of not less than 300m2/kg。
3. The composite early strength mineral admixture of claim 1, wherein said fly ash is power plant dry ash.
4. The composite early strength mineral admixture of claim 1 wherein said ore fines are ore fines above the S95 grade.
5. The composite early strength mineral admixture according to claim 1, wherein said calcium formate is commercially available technical grade calcium formate in solid powder form and has a content of 98% or more;
preferably, the aluminum sulfate is solid powder particles of aluminum sulfate I or II in chemical industry Standard "Industrial aluminum sulfate" HG/T2225-2010;
more preferably, the sodium sulfate is anhydrous sodium sulfate solid powder particles in Table 1 of HG/T4535-2013, which conforms to chemical industry standard cosmetic sodium sulfate.
6. The composite early strength mineral admixture according to claim 1, wherein said sodium carbonate is industrial soda ash meeting the requirements of first-class products and/or qualified products in the national standard "industrial sodium carbonate" GB 210-1992;
more preferably, the slaked lime powder is a slaked lime powder meeting the requirements of first-class products and/or qualified products in building material industry standard JC/T481-92.
7. The method of any one of claims 1 to 6, wherein the method comprises the steps of:
step S1, uniformly mixing calcium formate, aluminum sulfate, sodium carbonate and hydrated lime according to a proportion to obtain a composite additive;
and step S2, uniformly mixing the fly ash, the mineral powder, the fluorgypsum and the composite additive according to a proportion to obtain the composite early strength mineral admixture.
8. Use of the composite early strength mineral admixture according to any one of claims 1 to 6 in concrete.
9. The use of the composite early strength mineral admixture in concrete according to claim 8, wherein the concrete comprises portland cement and the composite early strength mineral admixture, and the mass ratio of the portland cement to the composite early strength mineral admixture is (20-80) to (20-80).
10. The use of a composite early strength mineral admixture in concrete according to claim 9 wherein said concrete further comprises a water reducing agent and sand.
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