CN115093155B - High-strength high-fluidity composite additive for concrete and preparation method thereof - Google Patents
High-strength high-fluidity composite additive for concrete and preparation method thereof Download PDFInfo
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- CN115093155B CN115093155B CN202210749542.3A CN202210749542A CN115093155B CN 115093155 B CN115093155 B CN 115093155B CN 202210749542 A CN202210749542 A CN 202210749542A CN 115093155 B CN115093155 B CN 115093155B
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of 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
- 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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention relates to the technical field of building materials, in particular to a high-strength high-fluidity composite additive for concrete and a preparation method thereof, wherein the composite additive comprises zinc sulfide doped nano powder, a composite nano material and a water reducer according to the weight ratio of 5-10:1-6: 0.5-1.5. The composite additive provided by the invention has excellent strength and fluidity, can obviously improve the strength and fluidity of concrete when applied to the concrete, can greatly improve the working performance of the concrete, and can be applied to building construction with ultrahigh-level flow and high strength requirements.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a high-strength high-fluidity composite additive for concrete and a preparation method thereof.
Background
The concrete is one of the most main civil engineering materials in the current generation, and is an artificial stone prepared by uniformly stirring, compacting, shaping, curing and hardening by using a cementing material, granular aggregate (also called aggregate), water and additives and admixtures added if necessary according to a certain proportion.
In the existing concrete, in order to improve the use strength of the concrete to a greater extent in the production process, more additives are selectively added while the use amount of the cementing material is improved, so that the strength of the concrete is enhanced and the fluidity is improved. For example, chinese patent No. 2019101852571 discloses a high-strength high-fluidity ceramsite concrete comprising, by weight, 10-30 parts of cement, 20-40 parts of sand, 10-40 parts of high-strength coarse aggregate, 20-60 parts of ceramsite, 6-10 parts of mineral powder, 1-3 parts of an additive and 1-3 parts of a polycarboxylic acid additive; the additive comprises polyacrylamide, cellulose ether and dispersible rubber powder, wherein the mass ratio of the polyacrylamide to the cellulose ether to the dispersible rubber powder is 2:2:1; in the technical scheme, through adding haydite and high-strength aggregate, although the improvement of concrete strength and fluidity is realized, the lifting range is limited, the concrete working performance is difficult to realize greatly improved, and as the haydite is high in water absorption rate, particularly under the action of pumping pressure, the haydite can be blocked at the front end or the bent pipe of a pump pipe due to the fact that the haydite is flushed forward under the action of pressure, meanwhile, water in the concrete is pressed into the haydite in the pumping process, so that the mixing performance is greatly influenced, local concrete agglomeration is caused, and pumping difficulty and even pipe blockage are extremely easy to occur.
Therefore, the method is an important problem which needs to be solved in the building field in terms of how to comprehensively perfect the high strength and the high fluidity of the concrete.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the high-strength high-fluidity composite additive for the concrete and the preparation method thereof, and the composite additive has excellent strength and fluidity, can remarkably improve the strength and fluidity of the concrete, and can greatly improve the working performance of the concrete.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the high-strength high-fluidity composite additive for concrete is prepared from zinc sulfide doped nano powder, a composite nano material and a water reducer according to the weight ratio of 5-10:1-6: 0.5-1.5.
As a further preferred scheme of the invention, the preparation method of the zinc sulfide doped nano powder comprises the following steps:
(1) Respectively ultrasonically cleaning a silicon wafer in acetone, absolute ethyl alcohol and deionized water for 10-20min, placing the cleaned silicon wafer in a drying oven, drying at 60-80 ℃ for 2-5h for standby, and performing metal spraying treatment on the standby silicon wafer by adopting an ion sputtering instrument, wherein the thickness of a metal layer is 4-6nm to obtain a pretreated silicon wafer;
(2) Placing S powder and Zn powder along the air flow direction of Ar gas, placing S powder at the front end of a quartz boat, placing Zn powder at the tail end of the quartz boat, placing a pretreatment silicon wafer between the S powder and the Zn powder, and dripping Ga between the S powder and the pretreatment silicon wafer after melting the Ga, wherein the distance between the S powder and the pretreatment silicon wafer is 2-3cm;
(3) Putting the quartz boat into a quartz tube, introducing 150-200sccm of high-purity Ar gas for 50-80min to exhaust air, heating to 500-550 ℃, preserving heat for 30-40min, stopping heating, protecting the high-purity Ar gas with the flux of 80-100sccm in the whole process, cooling to normal temperature, closing the high-purity Ar gas, taking out the quartz boat, scraping the product on the pretreated silicon wafer, and grinding to obtain the zinc sulfide doped nano powder.
As a further preferred embodiment of the present invention, the molar ratio of the S powder to the Zn powder is 2.0 to 2.5:1, a step of;
the Ga accounts for 9.0-9.8% of the mass of the S powder.
As a further preferred scheme of the invention, in the quartz boat, the distance between S powder and Zn powder is 8-12cm;
the distance between the pretreated silicon chip and Zn powder is 1-2cm.
As a further preferred embodiment of the present invention, the zinc sulfide doped nano powder is further subjected to surface modification treatment, specifically including carboxylation and amination treatment, before use.
As a further preferred embodiment of the present invention, the surface modification treatment of the zinc sulfide doped nano powder specifically includes the following steps:
(1) Adding zinc sulfide doped nano powder and beta-mercaptoethylamine into absolute ethyl alcohol together, controlling the concentration of the zinc sulfide doped nano powder to be 5-15mg/mL, introducing nitrogen after mixing, then reacting for 12-18h at 20-50 ℃ under stirring, centrifuging after the reaction is finished, repeatedly cleaning a product with ethanol, and drying to obtain aminated zinc sulfide doped nano powder;
(2) Adding the aminated zinc sulfide doped nano powder and polyacrylic acid into dimethylformamide solution together, controlling the concentration of the aminated zinc sulfide doped nano powder to be 5-15mg/mL, introducing nitrogen after mixing, then reacting for 1-3h under the condition of 120-160 ℃ under the stirring effect, centrifuging after the reaction is finished, repeatedly cleaning the product with ethanol, and drying.
As a further preferred scheme of the invention, the mass ratio of the zinc sulfide doped nano powder to the beta-mercaptoethylamine is 1:1-5;
the mass ratio of the aminated zinc sulfide doped nano powder to the polyacrylic acid is 1:0.3-0.8.
As a further preferred embodiment of the present invention, the preparation method of the composite nanomaterial is as follows:
(1) Dissolving polyvinylpyrrolidone in deionized water to obtain a solution with the concentration of 30-80mg/mL, adding ferric nitrate nonahydrate into the solution, heating to 70-80 ℃ after complete dissolution, stirring to a complete dry state, transferring into a tubular sintering furnace, sintering for 2-5h at 750-800 ℃ under the protection of argon, grinding and mixing the obtained precursor product with selenium powder, placing into the tubular furnace, preserving heat for 3-6h at 300-320 ℃ under the protection of argon, cooling to room temperature, and grinding to obtain the three-dimensional large-skeleton nano material;
(2) Dissolving antimony potassium tartrate in deionized water, magnetically stirring to dissolve the antimony potassium tartrate, sequentially adding polyvinylpyrrolidone and three-dimensional large-framework nano materials, continuously stirring for 10-20min, adding thioacetamide into the mixed solution, magnetically stirring for 10-15min, transferring the formed mixture solution into a reaction kettle, sealing, placing the reaction kettle in a 180-200 ℃ oven, heating at constant temperature for 12-16h, cooling to room temperature after the reaction is completed, taking out the product, repeatedly cleaning with deionized water, and drying to obtain the composite nano material.
As a further preferred embodiment of the present invention, the mass ratio of polyvinylpyrrolidone to ferric nitrate nonahydrate is 1:1.2-1.8;
the mass ratio of the precursor product to the selenium powder is 1:3-5;
the proportion of the antimony potassium tartrate, the deionized water, the polyvinylpyrrolidone, the three-dimensional large-framework nano material and the thioacetamide is (12.3-18.4) g: (30-60) mL: (0.2-0.5) g: (3-8) g: (3.2-5.3) g.
The preparation method of the high-strength high-fluidity composite additive for concrete comprises the following specific steps:
and (3) compounding the zinc sulfide doped nano powder, the composite nano material and the water reducer according to the weight ratio to obtain the required composite additive, wherein the water reducer is a polycarboxylate water reducer.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, through carrying out metal spraying treatment after cleaning a silicon wafer, depositing nano gold particles on the silicon wafer, forming a nano gold deposition layer which can be used as a catalyst for the growth of a subsequent zinc sulfide micro-nano structure, then adopting a low-temperature chemical vapor deposition method, utilizing the characteristic of Ga low melting point to quickly melt and release Ga vapor in the early stage, leading the concentration of the early-stage vapor in a quartz tube to be uniformly distributed, leading the concentration to be uneven, causing stress existence, and because the stress is not released in the interior of the nano wire, only being released through the bending of the nano wire, finally forming a worm-shaped nano wire with shorter length, leading the internal stress of the nano wire to be reduced, leading the nano wire to be smooth and flat, leading the length to be increased, and finally forming the zinc sulfide doped nano powder with a larger nano rod structure, the nano rod structure of the zinc sulfide doped nano powder has smooth surface, can play a role of rolling rods when being added into concrete, reduces the friction force among raw material particles in the concrete, reduces the flow resistance of the raw material particles, thereby improving the fluidity of the concrete, and because the nano rod structure is formed by stacking a large number of nano wires, a small number of nano wires with shorter size exist on the surface of the zinc sulfide doped nano powder of the nano rod structure, the zinc sulfide doped nano powder flows around in the concrete in the flowing process of the raw material of the concrete and is gradually connected with each other through the nano wires, finally, a continuous phase nano rod connecting structure is formed in the leveled concrete, the supporting effect can be realized in the concrete, the resistance of the concrete to various damage factors is improved, thereby contributing to the enhancement of the strength of the concrete.
Meanwhile, in order to avoid the agglomeration phenomenon of the zinc sulfide doped nano powder in the concrete, thereby affecting the fluidity of the concrete, the zinc sulfide doped nano powder is subjected to functional surface modification treatment, and carboxyl and amino groups are connected to the zinc sulfide doped nano powder, so that the dispersion stability of the zinc sulfide doped nano powder in a concrete medium can be remarkably improved, the zinc sulfide doped nano powder is uniformly distributed in a large range in the concrete, a large number of independent rolling rods are formed in the concrete, a multi-point low-friction flowing area is formed in the concrete, and the further improvement of the fluidity of the concrete is promoted.
According to the invention, the characteristic that a large amount of gas can be released in the reaction process of ferric nitrate and polyvinylpyrrolidone is utilized, a material with a three-dimensional large framework structure is blow molded, in order to improve the stability of the framework structure, selenizing treatment is carried out on the material, so that a three-dimensional large framework nano material with a stable structure is obtained, then the nano material is taken as a matrix, antimony potassium tartrate and thioacetamide are respectively taken as an antimony source and a sulfur source, through hydrothermal reaction, the aggregation phenomenon between antimony sulfide nano particles attached to the three-dimensional large framework nano material occurs, a plurality of net structures grow out from the surface, along with the progress of the hydrothermal reaction, the antimony sulfide nano particles gradually decrease until completely disappear, a large number of protruding net structures grow out on the three-dimensional large framework, and through adding the prepared composite nano material into concrete, a large number of aggregates constructed by the independent three-dimensional large framework nano material are formed in the concrete, the formed aggregates have the framework structure, a good supporting effect can be achieved, a large number of independent supporting structures are formed in the concrete, the concrete can be further improved, the external strength is further improved, and the external strength is further improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the effect of the amount of the composite admixture on the compressive strength of concrete 7 d.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The high-strength high-fluidity composite additive for the concrete is prepared from zinc sulfide doped nano powder, a composite nano material and a water reducer according to a weight ratio of 5:1:0.5, mixing;
the preparation method of the zinc sulfide doped nano powder comprises the following steps:
(1) Respectively ultrasonically cleaning a silicon wafer in acetone, absolute ethyl alcohol and deionized water for 10min, placing the cleaned silicon wafer in a drying oven, drying at 60 ℃ for 2h for standby, and performing metal spraying treatment on the standby silicon wafer by adopting an ion sputtering instrument, wherein the thickness of a metal layer is 4nm, so as to obtain a pretreated silicon wafer;
(2) The molar ratio was set to 2.0:1, placing S powder and Zn powder along the air flow direction of Ar gas, placing the S powder at the front end of a quartz boat, placing the Zn powder at the tail end, wherein the distance between the S powder and the Zn powder is 8cm, placing a pretreatment silicon wafer between the S powder and the Zn powder, wherein the distance between the pretreatment silicon wafer and the Zn powder is 1cm, melting Ga accounting for 9% of the mass of the S powder, and then dripping the Ga between the S powder and the pretreatment silicon wafer, and the distance between the Ga and the pretreatment silicon wafer is 2cm;
(3) Putting a quartz boat into a quartz tube, introducing high-purity Ar gas of 150sccm for 50min to exhaust air, heating to 500 ℃, preserving heat for 30min, stopping heating, protecting the high-purity Ar gas with the flux of 80sccm in the whole process, closing the high-purity Ar gas after cooling to normal temperature, taking out the quartz boat, scraping the product on the pretreated silicon wafer, and grinding to obtain the zinc sulfide doped nano powder.
The zinc sulfide doped nano powder is subjected to surface modification treatment before use, comprising carboxylation and amination treatment, and the specific operation steps are as follows:
(1) Adding zinc sulfide doped nano powder and beta-mercaptoethylamine into absolute ethyl alcohol together according to the mass ratio of 1:1, controlling the concentration of the zinc sulfide doped nano powder to be 5mg/mL, introducing nitrogen for 30min after mixing, then reacting for 12h at 20 ℃ under the stirring effect of 30r/min, centrifuging after the reaction is finished, repeatedly cleaning a product with ethanol, and drying to obtain aminated zinc sulfide doped nano powder;
(2) The mass ratio is 1: and 0.3, adding the aminated zinc sulfide doped nano powder and polyacrylic acid into dimethylformamide solution together, controlling the concentration of the aminated zinc sulfide doped nano powder to be 5mg/mL, introducing nitrogen for 1h after mixing, then reacting for 1h under the condition of 120 ℃ under the stirring effect of 30r/min, centrifuging after the reaction is finished, repeatedly cleaning the product with ethanol, and drying.
The preparation method of the composite nano material comprises the following steps:
(1) According to the mass ratio of 1:1.2 respectively weighing polyvinylpyrrolidone and ferric nitrate nonahydrate, dissolving polyvinylpyrrolidone in deionized water to obtain a solution with the concentration of 30mg/mL, adding ferric nitrate nonahydrate into the solution, heating to 70 ℃ after complete dissolution, stirring to a complete dry state, transferring into a tubular sintering furnace, sintering for 2 hours at 750 ℃ under the protection of argon, grinding and mixing the obtained precursor product in selenium powder according to the mass ratio of 1:3, placing into the tubular furnace, preserving heat for 3 hours at 300 ℃ under the protection of argon, cooling to room temperature, and grinding to obtain the three-dimensional large-skeleton nanomaterial;
(2) Dissolving 12.3g of antimony potassium tartrate in 30mL of deionized water, magnetically stirring for 10min, sequentially adding 0.2g of polyvinylpyrrolidone and 3g of three-dimensional large-framework nano material after dissolving, continuously stirring for 10min, adding 3.2g of thioacetamide into the mixed solution, magnetically stirring for 10min, transferring the formed mixture solution into a reaction kettle, sealing, placing in a 180 ℃ oven, heating at constant temperature for 12h, cooling to room temperature after the reaction is completed, repeatedly cleaning the product with deionized water after taking out, and drying to obtain the composite nano material
The preparation method of the high-strength high-fluidity composite additive for concrete comprises the following specific steps:
and (3) compounding the zinc sulfide doped nano powder, the composite nano material and the water reducer according to the weight ratio to obtain the required composite additive, wherein the water reducer is a polycarboxylate water reducer.
Example 2
The high-strength high-fluidity composite additive for the concrete is prepared from zinc sulfide doped nano powder, a composite nano material and a water reducer according to the weight ratio of 7:3:1, mixing and preparing;
the preparation method of the zinc sulfide doped nano powder comprises the following steps:
(1) Respectively ultrasonically cleaning a silicon wafer in acetone, absolute ethyl alcohol and deionized water for 15min, placing the cleaned silicon wafer in a drying oven, drying at 70 ℃ for 3h for standby, and performing metal spraying treatment on the standby silicon wafer by adopting an ion sputtering instrument, wherein the thickness of a metal layer is 5nm, so as to obtain a pretreated silicon wafer;
(2) The molar ratio was set to 2.3:1, placing S powder and Zn powder along the air flow direction of Ar gas at the front end of a quartz boat, placing Zn powder at the tail end of the quartz boat, wherein the distance between the S powder and the Zn powder is 10cm, placing a pretreatment silicon wafer between the S powder and the Zn powder, wherein the distance between the pretreatment silicon wafer and the Zn powder is 1.5cm, melting Ga accounting for 9.5% of the mass of the S powder, and then dripping the Ga between the S powder and the pretreatment silicon wafer, and the distance between the Ga and the pretreatment silicon wafer is 2.5cm;
(3) Putting a quartz boat into a quartz tube, introducing high-purity Ar gas of 180sccm for 70min to exhaust air, heating to 520 ℃, preserving heat for 35min, stopping heating, protecting the high-purity Ar gas with the flow rate of 90sccm in the whole process, closing the high-purity Ar gas after cooling to normal temperature, taking out the quartz boat, scraping the product on the pretreated silicon wafer, and grinding to obtain the zinc sulfide doped nano powder.
The zinc sulfide doped nano powder is subjected to surface modification treatment before use, comprising carboxylation and amination treatment, and the specific operation steps are as follows:
(1) Adding zinc sulfide doped nano powder and beta-mercaptoethylamine into absolute ethyl alcohol together according to the mass ratio of 1:3, controlling the concentration of the zinc sulfide doped nano powder to be 10mg/mL, introducing nitrogen for 40min after mixing, then reacting for 15h at 40 ℃ under the stirring effect of 50r/min, centrifuging after the reaction is finished, repeatedly cleaning a product with ethanol, and drying to obtain aminated zinc sulfide doped nano powder;
(2) The mass ratio is 1: and 0.5, adding the aminated zinc sulfide doped nano powder and polyacrylic acid into dimethylformamide solution together, controlling the concentration of the aminated zinc sulfide doped nano powder to be 10mg/mL, introducing nitrogen for 2 hours after mixing, then reacting for 1-3 hours under the condition of 150 ℃ under the stirring effect of 50r/min, centrifuging after the reaction is finished, repeatedly cleaning the product with ethanol, and drying.
The preparation method of the composite nano material comprises the following steps:
(1) According to the mass ratio of 1:1.5 respectively weighing polyvinylpyrrolidone and ferric nitrate nonahydrate, dissolving polyvinylpyrrolidone in deionized water to obtain a solution with the concentration of 50mg/mL, adding ferric nitrate nonahydrate into the solution, heating to 75 ℃ after complete dissolution, stirring to a complete dry state, transferring into a tubular sintering furnace, sintering for 3h at 760 ℃ under the protection of argon, grinding and mixing the obtained precursor product in selenium powder according to the mass ratio of 1:4, placing into the tubular furnace, preserving heat for 5h at 310 ℃ under the protection of argon, cooling to room temperature, and grinding to obtain the three-dimensional large-skeleton nanomaterial;
(2) Dissolving 15.5g of antimony potassium tartrate in 50mL of deionized water, magnetically stirring for 20min, sequentially adding 0.3g of polyvinylpyrrolidone and 5g of three-dimensional large-framework nano material after dissolving, continuously stirring for 15min, adding 4.6g of thioacetamide into the mixed solution, magnetically stirring for 10min, transferring the formed mixture solution into a reaction kettle, sealing, placing in a baking oven at 190 ℃ for constant temperature heating for 15h, cooling to room temperature after the reaction is completed, repeatedly cleaning the product with deionized water after taking out, and drying to obtain the composite nano material
The preparation method of the high-strength high-fluidity composite additive for concrete comprises the following specific steps:
and (3) compounding the zinc sulfide doped nano powder, the composite nano material and the water reducer according to the weight ratio to obtain the required composite additive, wherein the water reducer is a polycarboxylate water reducer.
Example 3
The high-strength high-fluidity composite additive for concrete is prepared from zinc sulfide doped nano powder, a composite nano material and a water reducer according to the weight ratio of 10:6:1.5, mixing and preparing;
the preparation method of the zinc sulfide doped nano powder comprises the following steps:
(1) Respectively ultrasonically cleaning a silicon wafer in acetone, absolute ethyl alcohol and deionized water for 20min, placing the cleaned silicon wafer in a drying oven, drying at 80 ℃ for 5h for standby, and performing metal spraying treatment on the standby silicon wafer by adopting an ion sputtering instrument, wherein the thickness of a metal layer is 6nm to obtain a pretreated silicon wafer;
(2) The molar ratio was set to 2.5:1, placing S powder and Zn powder along the air flow direction of Ar gas at the front end of a quartz boat, placing Zn powder at the tail end of the quartz boat, wherein the distance between the S powder and the Zn powder is 12cm, placing a pretreatment silicon wafer between the S powder and the Zn powder, wherein the distance between the pretreatment silicon wafer and the Zn powder is 2cm, melting Ga accounting for 9.8% of the mass of the S powder, and then dripping the Ga between the S powder and the pretreatment silicon wafer, and the distance between the Ga and the pretreatment silicon wafer is 3cm;
(3) Putting a quartz boat into a quartz tube, introducing high-purity Ar gas of 200sccm for 80min to exhaust air, heating to 550 ℃, preserving heat for 40min, stopping heating, protecting the high-purity Ar gas with the flow rate of 100sccm in the whole process, closing the high-purity Ar gas after cooling to normal temperature, taking out the quartz boat, scraping the product on the pretreated silicon wafer, and grinding to obtain the zinc sulfide doped nano powder.
The zinc sulfide doped nano powder is subjected to surface modification treatment before use, comprising carboxylation and amination treatment, and the specific operation steps are as follows:
(1) Adding zinc sulfide doped nano powder and beta-mercaptoethylamine into absolute ethyl alcohol together according to the mass ratio of 1:5, controlling the concentration of the zinc sulfide doped nano powder to be 15mg/mL, introducing nitrogen for 50min after mixing, then reacting for 18h at 50 ℃ under the stirring effect of 80r/min, centrifuging after the reaction is finished, repeatedly cleaning a product with ethanol, and drying to obtain aminated zinc sulfide doped nano powder;
(2) The mass ratio is 1: and 0.8, adding the aminated zinc sulfide doped nano powder and polyacrylic acid into dimethylformamide solution together, controlling the concentration of the aminated zinc sulfide doped nano powder to be 15mg/mL, introducing nitrogen for 3 hours after mixing, then reacting for 3 hours under the condition of 160 ℃ under the stirring effect of 80r/min, centrifuging after the reaction is finished, repeatedly cleaning the product with ethanol, and drying.
The preparation method of the composite nano material comprises the following steps:
(1) According to the mass ratio of 1:1.8 respectively weighing polyvinylpyrrolidone and ferric nitrate nonahydrate, dissolving polyvinylpyrrolidone in deionized water to obtain a solution with the concentration of 80mg/mL, adding ferric nitrate nonahydrate into the solution, heating to 80 ℃ after complete dissolution, stirring to a complete dry state, transferring into a tubular sintering furnace, sintering for 5 hours at 800 ℃ under the protection of argon, grinding and mixing the obtained precursor product in selenium powder according to the mass ratio of 1:5, placing into the tubular furnace, preserving heat for 6 hours at 320 ℃ under the protection of argon, cooling to room temperature, and grinding to obtain the three-dimensional large-skeleton nanomaterial;
(2) Dissolving 18.4g of antimony potassium tartrate in 60mL of deionized water, magnetically stirring for 30min, sequentially adding 0.5g of polyvinylpyrrolidone and 8g of three-dimensional large-framework nano material after dissolving, continuously stirring for 20min, then adding 5.3g of thioacetamide into the mixed solution, magnetically stirring for 15min, transferring the formed mixture solution into a reaction kettle, sealing, placing in a baking oven at 200 ℃ for constant temperature heating for 16h, cooling to room temperature after the reaction is completed, repeatedly cleaning the product with deionized water after taking out, and drying to obtain the composite nano material
The preparation method of the high-strength high-fluidity composite additive for concrete comprises the following specific steps:
and (3) compounding the zinc sulfide doped nano powder, the composite nano material and the water reducer according to the weight ratio to obtain the required composite additive, wherein the water reducer is a polycarboxylate water reducer.
Comparative example 1: this comparative example is substantially the same as example 1 except that the composite admixture does not contain zinc sulfide doped nano-powder.
Comparative example 2: this comparative example is substantially the same as example 1 except that the zinc sulfide doped nano powder in the composite additive is not subjected to the surface modification treatment.
Comparative example 3: this comparative example is substantially the same as example 1, except that the composite admixture does not contain composite nanomaterial.
Test experiment 1:
1. preparation of concrete samples: adding 900 parts of yellow sand, 750 parts of graded stone and 70 parts of water into a stirrer to be wetted and premixed for 30s, adding 420 parts of cement, 220 parts of mineral powder, 3 parts of an expanding agent, 1 part of an air entraining agent, 0.3 part of a modifier perfluoropolyether carboxylic acid and 260 parts of a composite additive to be stirred for 2min, adding 0.5 part of a defoaming agent and 0.5 part of a retarder, adding 80 parts of water, uniformly stirring in vacuum, and discharging to obtain a concrete pattern;
wherein the mass parts of the stones with the grain diameters of 1-5mm, 10-15mm and 20-25mm in the graded stone are 150 parts, 500 parts and 100 parts respectively; the air entraining agent is prepared by mixing and compounding triterpenoid saponin, sodium alkyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate (AES) and alpha-alkenyl sodium sulfonate (AOS) according to the mass ratio of 1:2:1.5:1.5; the thickener is prepared by mixing and grinding bentonite, hydroxypropyl methyl cellulose ether, xanthan gum and polyacrylamide resin according to the mass ratio of 3:2:5:10.
2. Test standard: testing strength according to GB/T50107-2010 concrete strength test evaluation Standard; slump expansion was measured according to the standard of ordinary concrete mechanical property test method GB/T50081-2002, and the measurement results are shown in Table 1 below.
Table 1 concrete test results
As can be seen from Table 1, the composite additive provided by the invention is applied to concrete, so that the concrete has the properties of high strength and good fluidity, and can be applied to building construction with ultra-high laminar flow and high strength requirements.
Test experiment 2:
based on the sample of example 1, the influence of different addition amounts of the composite additive on the compressive strength performance of the concrete 7d is compared, as can be seen from fig. 1, the compressive strength of the concrete 7d is gradually enhanced with the increase of the addition amount of the composite additive, but the compressive strength of the concrete 7d is in a decreasing trend when the addition amount of the nano composite additive exceeds a certain value.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (6)
1. The high-strength high-fluidity composite additive for concrete is characterized in that the composite additive is prepared from zinc sulfide doped nano powder, a composite nano material and a water reducer according to the weight ratio of 5-10:1-6: 0.5-1.5;
the preparation method of the zinc sulfide doped nano powder comprises the following steps:
(1) Respectively ultrasonically cleaning a silicon wafer in acetone, absolute ethyl alcohol and deionized water for 10-20min, placing the cleaned silicon wafer in a drying oven, drying at 60-80 ℃ for 2-5h for standby, and performing metal spraying treatment on the standby silicon wafer by adopting an ion sputtering instrument, wherein the thickness of a metal layer is 4-6nm to obtain a pretreated silicon wafer;
(2) Placing S powder and Zn powder along the air flow direction of Ar gas, placing S powder at the front end of a quartz boat, placing Zn powder at the tail end of the quartz boat, placing a pretreatment silicon wafer between the S powder and the Zn powder, and dripping Ga between the S powder and the pretreatment silicon wafer after melting the Ga, wherein the distance between the S powder and the pretreatment silicon wafer is 2-3cm;
(3) Putting a quartz boat into a quartz tube, introducing 150-200sccm of high-purity Ar gas for 50-80min to exhaust air, heating to 500-550 ℃, preserving heat for 30-40min, stopping heating, stopping the whole process, protecting the high-purity Ar gas with the flux of 80-100sccm, closing the high-purity Ar gas after cooling to normal temperature, taking out the quartz boat, scraping the product on a pretreated silicon wafer, and grinding to obtain zinc sulfide doped nano powder;
the zinc sulfide doped nano powder is subjected to surface modification treatment before use, and specifically comprises carboxylation and amination treatment;
the surface modification treatment of the zinc sulfide doped nano powder specifically comprises the following steps:
(1) Adding zinc sulfide doped nano powder and beta-mercaptoethylamine into absolute ethyl alcohol together, controlling the concentration of the zinc sulfide doped nano powder to be 5-15mg/mL, introducing nitrogen after mixing, then reacting for 12-18h at 20-50 ℃ under stirring, centrifuging after the reaction is finished, repeatedly cleaning a product with ethanol, and drying to obtain aminated zinc sulfide doped nano powder;
(2) Adding the aminated zinc sulfide doped nano powder and polyacrylic acid into dimethylformamide solution together, controlling the concentration of the aminated zinc sulfide doped nano powder to be 5-15mg/mL, introducing nitrogen after mixing, then reacting for 1-3 hours under the condition of 120-160 ℃ under the stirring effect, centrifuging after the reaction is finished, repeatedly cleaning the product with ethanol, and drying;
the preparation method of the composite nano material comprises the following steps:
(1) Dissolving polyvinylpyrrolidone in deionized water to obtain a solution with the concentration of 30-80mg/mL, adding ferric nitrate nonahydrate into the solution, heating to 70-80 ℃ after complete dissolution, stirring to a complete dry state, transferring into a tubular sintering furnace, sintering for 2-5h at 750-800 ℃ under the protection of argon, grinding and mixing the obtained precursor product with selenium powder, placing into the tubular furnace, preserving heat for 3-6h at 300-320 ℃ under the protection of argon, cooling to room temperature, and grinding to obtain the three-dimensional large-skeleton nano material;
(2) Dissolving antimony potassium tartrate in deionized water, magnetically stirring to dissolve the antimony potassium tartrate, sequentially adding polyvinylpyrrolidone and three-dimensional large-framework nano materials, continuously stirring for 10-20min, adding thioacetamide into the mixed solution, magnetically stirring for 10-15min, transferring the formed mixture solution into a reaction kettle, sealing, placing the reaction kettle in a 180-200 ℃ oven, heating at constant temperature for 12-16h, cooling to room temperature after the reaction is completed, taking out the product, repeatedly cleaning with deionized water, and drying to obtain the composite nano material.
2. The high-strength high-fluidity composite additive for concrete according to claim 1, wherein the molar ratio of S powder to Zn powder is 2.0 to 2.5:1, a step of;
the Ga accounts for 9.0-9.8% of the mass of the S powder.
3. The high-strength high-fluidity composite admixture for concrete according to claim 1, wherein the distance between S powder and Zn powder in the quartz boat is 8-12cm;
the distance between the pretreated silicon chip and Zn powder is 1-2cm.
4. The high-strength high-fluidity composite additive for concrete according to claim 1, wherein the mass ratio of the zinc sulfide doped nano powder to the beta-mercaptoethylamine is 1:1-5;
the mass ratio of the aminated zinc sulfide doped nano powder to the polyacrylic acid is 1:0.3-0.8.
5. The high-strength high-fluidity composite additive for concrete according to claim 1, wherein the mass ratio of polyvinylpyrrolidone to ferric nitrate nonahydrate is 1:1.2-1.8;
the mass ratio of the precursor product to the selenium powder is 1:3-5;
the proportion of the antimony potassium tartrate, the deionized water, the polyvinylpyrrolidone, the three-dimensional large-framework nano material and the thioacetamide is (12.3-18.4) g: (30-60) mL: (0.2-0.5) g: (3-8) g: (3.2-5.3) g.
6. The method for preparing a high-strength high-fluidity composite additive for concrete according to any one of claims 1 to 5, characterized by comprising the following specific steps:
and (3) compounding the zinc sulfide doped nano powder, the composite nano material and the water reducer according to the weight ratio to obtain the required composite additive, wherein the water reducer is a polycarboxylate water reducer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008254963A (en) * | 2007-04-04 | 2008-10-23 | Mitsubishi Materials Corp | Admixture for cement/concrete and low shrinkage high strength concrete, and high strength cement composition |
| AU2008353901A1 (en) * | 2008-03-31 | 2009-10-08 | Rockwood Italia Spa | Granulate having photocatalytic activity and methods for manufacturing the same |
| CN112299772A (en) * | 2020-11-25 | 2021-02-02 | 安徽滨江新型墙材有限公司 | Processing technology for improving durability of light heat-insulating wall material |
| CN112679132A (en) * | 2021-01-26 | 2021-04-20 | 中建西部建设北方有限公司 | Additive for recycled aggregate concrete and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6832735B2 (en) * | 2002-01-03 | 2004-12-21 | Nanoproducts Corporation | Post-processed nanoscale powders and method for such post-processing |
| US6645289B2 (en) * | 1997-05-26 | 2003-11-11 | Sci Con Technologies, Inc. | Complex admixture and method of cement based materials production |
| WO2004110930A1 (en) * | 2003-06-12 | 2004-12-23 | Matsushita Electric Industrial Co., Ltd. | Composite porous body containing nanoparticle and method for producing same |
| CN104083904B (en) * | 2014-07-02 | 2015-12-09 | 南京中医药大学 | Functionalization porous zinc sulfide nano microballoon solid-phase extraction column and preparation method thereof |
| CN106904860A (en) * | 2017-01-22 | 2017-06-30 | 上海每天生态科技发展有限公司 | A kind of nano inorganic reinforcing agent |
| CN109461902B (en) * | 2018-09-29 | 2021-07-16 | 大连理工大学 | Preparation method and application of iron diselenide/honeycomb carbon composite material |
| CN110436511B (en) * | 2019-09-10 | 2021-12-10 | 安徽锦华氧化锌有限公司 | Preparation method of nano zinc oxide with net structure |
| CN111960769A (en) * | 2020-08-25 | 2020-11-20 | 岑儒湛 | Novel nano modified high-strength concrete |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008254963A (en) * | 2007-04-04 | 2008-10-23 | Mitsubishi Materials Corp | Admixture for cement/concrete and low shrinkage high strength concrete, and high strength cement composition |
| AU2008353901A1 (en) * | 2008-03-31 | 2009-10-08 | Rockwood Italia Spa | Granulate having photocatalytic activity and methods for manufacturing the same |
| CN112299772A (en) * | 2020-11-25 | 2021-02-02 | 安徽滨江新型墙材有限公司 | Processing technology for improving durability of light heat-insulating wall material |
| CN112679132A (en) * | 2021-01-26 | 2021-04-20 | 中建西部建设北方有限公司 | Additive for recycled aggregate concrete and preparation method thereof |
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