CN114477888A - Slag micro powder cementing material and preparation method thereof - Google Patents
Slag micro powder cementing material and preparation method thereof Download PDFInfo
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- CN114477888A CN114477888A CN202110771196.4A CN202110771196A CN114477888A CN 114477888 A CN114477888 A CN 114477888A CN 202110771196 A CN202110771196 A CN 202110771196A CN 114477888 A CN114477888 A CN 114477888A
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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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Abstract
The invention discloses a slag micropowder cementing material and a preparation method thereof. According to the invention, firstly, nitric acid is used for modifying the fly ash to enable the fly ash to have adsorption capacity, and then the modified fly ash is fully contacted with a sodium gluconate solution through a fluidized bed to enable the sodium gluconate to be adsorbed on the surface of the modified fly ash, so that the self-made water reducing agent is prepared; then carrying out addition reaction on glucose and diethylenetriamine to generate modified glucose, then reacting with a polycarboxylic acid water reducing agent, and grafting the modified glucose into a side chain of the polycarboxylic acid water reducing agent to prepare a self-made water reducing agent; and finally, mixing the slag micro powder, cement, self-made fly ash, self-made water reducing agent and water according to an optimal ratio to prepare the slag micro powder cementing material. The slag micropowder cementing material prepared by the invention has the effects of good adsorption capacity, strong fluidity and good retardation performance.
Description
Technical Field
The invention relates to the technical field of civil engineering materials, in particular to a slag micro powder cementing material and a preparation method thereof.
Background
With the increasing of the energy-saving and environment-friendly strength in recent years in China, energy conservation and emission reduction become a major topic of China, and the recycling of industrial waste residues is the most effective way for energy conservation and emission reduction. The slag micropowder is ultrafine powder obtained by granulating molten slag discharged from an iron-making blast furnace, drying and grinding. The slag micropowder is widely used as a cement mixing material, can reduce enterprise cost and adjust strength grade, and can improve cement particle composition and certain physical properties, so that the slag micropowder becomes one of important development directions of cement concrete technology and is widely applied to a large number of projects at home and abroad.
The cementing material is one of the most widely used and most used building materials in the world at present. It is made up by using water, cement, slag micropowder and chemical additive through a certain preparation process and stirring and forming. The development of cement technology has also met with problems such as high slump loss over time, severe cracking, poor durability, and increased cost. With the development of modern society and science and technology, the use requirement of high-rise buildings and the harsh use environment have higher requirements on the strength, the workability, the durability and the economy of the cementing material. High performance gelling materials were born in the end of the 20 th century 80 s, the primary design criterion being their durability. Compared with the common cementing material, the high-performance cementing material has the advantages of high durability, high workability, high strength and the like, and is the development direction of the cementing material technology in the future.
The additive has a great promoting effect on the development of concrete, can reduce the cement consumption, consume industrial waste residues, improve the durability and the strength of the cementing material and the like, is an essential fifth component for preparing modern cementing materials, and is also an essential material for the development of the cementing material to high-performance cementing materials. The water reducing agent can reduce the water-cement ratio of the cementing material so as to improve the performance of the cementing material, and the function of the high-efficiency water reducing agent cannot be avoided in the development process of the high-performance cementing material. The polycarboxylic acid high-performance water reducing agent is widely applied at present, and the main performance characteristics of the polycarboxylic acid high-performance water reducing agent are as follows: the reinforcing effect potential on the cementing material is large, the mixing amount is low, the water reducing rate is high, the slump loss resistance is good, the concrete shrinkage is low, the total alkali content is extremely low, the environment is friendly, and the like. The high-performance cementing material is popularized in China, is an effective way for reducing cement clinker consumption, cement yield and resource and energy consumption, and is an effective way for strengthening energy conservation, emission reduction and preventing and treating atmospheric pollution.
Disclosure of Invention
The invention aims to provide a slag micropowder cementing material and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the slag micro powder cementing material is characterized by mainly comprising 130-200 parts by weight of slag micro powder, 125-200 parts by weight of cement, 98-150 parts by weight of self-made fly ash, 52-60 parts by weight of self-made water reducing agent and 135-208 parts by weight of water.
Further, the slag micropowder cementing material is characterized in that the self-made fly ash is prepared from fly ash, nitric acid and sodium gluconate.
Further, the slag micropowder cementing material is characterized in that the self-made water reducing agent is prepared from modified glucose and a polycarboxylic acid water reducing agent.
Further, the slag micropowder cementing material is characterized in that the modified glucose is prepared from glucose, diethylenetriamine and phosphorous acid.
Further, the slag micropowder cementing material is characterized by comprising the following raw material components in parts by weight: 140 parts of slag micro powder, 140 parts of cement, 105 parts of self-made fly ash, 56 parts of self-made water reducing agent and 146 parts of water.
Further, the preparation method of the slag micropowder cementing material is characterized by mainly comprising the following preparation steps:
(1) placing fly ash and a nitric acid solution with the mass fraction of 10% and the mass of 12.8 times of that of the fly ash into a mortar, reacting for 2 hours, adding calcium carbonate with the mass of 0.3 time of that of the fly ash and calcium oxide with the mass of 0.08 time of that of the fly ash into the mortar, grinding for 3 minutes to prepare mixed particles, adding hydrogen peroxide with the mass of 3 times of that of the fly ash into the mixed particles, then placing the mixed particles into a muffle furnace, calcining for 60 minutes at 920 ℃, naturally cooling to room temperature, and crushing into powder with the particle size of 5.14 mu m by a steam kinetic energy mill crusher to obtain modified fly ash;
(2) placing a sodium gluconate solution with the mass fraction of 35% and 10 times of the mass of the modified fly ash into an ultrasonic atomization device, and atomizing the sodium gluconate solution into small droplets with the diameter of 1-5 mu m under the condition of 1.7 MHz; then, placing the modified fly ash obtained in the step (1) in a fluidized bed reactor, enabling the modified fly ash to be in a boiling fluidized state in the reactor by using compressed air, introducing an atomized sodium gluconate solution into the reactor, uniformly mixing the atomized sodium gluconate solution with the modified fly ash, and evaporating at 160 ℃ to obtain crystals; finally, blowing the crystals out of the fluidized bed reactor by compressed air, recovering the crystals by a dust collecting device, and drying the crystals for 24 hours at the temperature of 60 ℃ to prepare self-made fly ash;
(3) adding glucose and distilled water with the mass 2 times of that of the glucose into a four-mouth bottle, stirring for 5min under the condition of 150r/min, then adding diethylenetriamine with the mass 1.2 times of that of the glucose into the four-mouth bottle, reacting for 0.5-4 h at 15-60 ℃ to prepare an aminoglucose mixed solution, then dropwise adding phosphorous acid aqueous solution with the mass fraction of 40% and the mass 0.46 time of that of the glucose into the aminoglucose mixed solution under the condition of 25 drops/min, and reacting for 0.5-4 h at 40-80 ℃ to prepare a modified glucose solution;
(4) stirring the modified glucose solution obtained in the step (3) and hydrogen peroxide with the mass of 0.07 time that of the modified glucose solution at 50 ℃ for 5-6 min to obtain a modified glucose-hydrogen peroxide mixed solution for later use; stirring acrylic acid with the mass of 0.1 time of that of the modified glucose solution and distilled water with the mass of 0.12 time of that of the modified glucose solution for 3-5 min under the condition of 150r/min to prepare a mixed solution A; mixing mercaptopropionic acid accounting for 0.02 time of the mass of the modified glucose solution, vitamin C accounting for 0.04 time of the mass of the modified glucose solution and distilled water accounting for 0.18 time of the mass of the modified glucose solution, and stirring for 5-6 min under the condition of 150r/min to prepare a mixed solution B; respectively adding the mixed solution A into the modified glucose-hydrogen peroxide mixed solution at the speed of 0.6mL/min and the mixed solution B at the speed of 1mL/min, uniformly mixing, controlling the adding time to be 2.5-4 h, preserving the heat at 55 ℃ for 1-2 h, and finally adding sodium hydroxide with the mass of 0.09 time of that of the modified glucose and distilled water with the mass of 0.48 time of that of the modified glucose to prepare the self-made water reducing agent;
(5) adding slag micro powder and cement with the mass 1-3 times of that of the slag micro powder into a horizontal concrete mixer at normal temperature, stirring the mixture to be slightly viscous, then adding self-made fly ash with the mass 0.5-1 time of that of the slag micro powder in the step (2), a self-made water reducing agent with the mass 0.1-0.4 time of that of the slag micro powder in the step (4) and water with the mass 1-2 times of that of the slag micro powder into the mixer, and stirring the mixture at the same speed for 4-5 min to prepare the slag micro powder cementing material.
Further, the preparation method of the slag micropowder cementing material is characterized in that the crushing pressure of the steam kinetic energy mill in the step (1) is 0.5MPa, the steam temperature is 260 ℃, and the rotation speed of a grading wheel is 1200 r/min.
Further, the preparation method of the slag micropowder cementing material is characterized in that in the step (2), the feeding speed of the fluidized bed is 450-500 mL/min, the gas fluidization speed is 4-6 m/s, and the gas pressure is 1.27-2.45 MPa.
Further, the preparation method of the slag micro powder cementing material is characterized in that the slag micro powder in the step (5) is S95-grade granulated blast furnace slag micro powder, the particle size is 4 microns, and the cement is portland cement.
Compared with the prior art, the invention has the following beneficial effects:
the slag micro powder cementing material is prepared by using slag micro powder, cement, self-made fly ash and self-made water reducing agent as raw materials.
Firstly, oxidizing the self-made fly ash by nitric acid to modify the fly ash, and dissolving silicon dioxide and aluminum oxide in the fly ash by hydrogen ions to break chains of silicon-oxygen bonds and aluminum-oxygen bonds in the fly ash and form adsorption bridges with the hydrogen ions, so that the adsorption capacity of the cementing material to chloride ions is enhanced.
Secondly, the self-made fly ash adopts a fluidized bed to ensure that the modified fly ash is fully contacted with the vaporized sodium gluconate saturated solution, the sodium gluconate passes through hydroxyl and carboxylic acid groups, reacting with hydrogen ions on the surface of the fly ash, adsorbing sodium gluconate on the surface of the modified fly ash sphere to form a surface hydration film, and the complex salt is generated with hydration products in the cement and is precipitated on the surface of cement particles to inhibit the hydration reaction of the cementing material, and simultaneously, in the hydration process, sodium gluconate on the surface of the self-made fly ash is adsorbed on the crystal surface of a cement hydration product, so that the cement hydration product mostly exists in a gel form, and a compact membrane structure is formed on the surface, so that the further reaction of water molecules and cement hydration products is prevented, the growth of the cement hydration products is inhibited, the hydration heat release rate of the cementing material is reduced, the hydration is delayed, and the durability of the cementing material is improved; in addition, under the excitation effect of the self-made water reducing agent, the self-made fly ash, polyvalent anions generated by water and organic silver ions formed by hydrolysis of the self-made water reducing agent enter a diffusion layer and a compact layer of an electric double layer in the cement together, the structure of the electric double layer is changed, the potential is improved, an auxiliary plasticizing effect is achieved, and the fluidity of the cementing material is increased.
Furthermore, the self-made water reducing agent adopts modified glucose and polycarboxylic acid water reducing agent as raw materials, the modified glucose is glucosamine generated by the addition reaction of the amino group of diethylenetriamine and the aldehyde group of glucose, the imine ions and the alpha hydrogen of phosphorous acid generate condensation reaction to generate modified glucose, the hydroxyl of the modified glucose and the polycarboxylate superplasticizer free radical are polymerized and grafted to the polycarboxylate superplasticizer side chain, the hydroxyl in the side chain and water molecules generate hydrogen bonds to form a hydration film with a certain thickness, so that a lubricating effect is generated among cement particles, the dispersion effect is increased, meanwhile, the diethylenetriamine molecule has nitrogen atoms, which can easily form covalent bonds with metal ions to generate stable complexes, the complexes form a plurality of soluble areas in cement, so that the diffusion rate of cement hydration products is increased, and the early strength of the cementing material is improved; in addition, sodium gluconate and the self-made water reducing agent compete with each other to adsorb the surface of the cementing material, so that more sodium gluconate remains in a liquid phase, the inhibition on cement hydration products is stronger, and the setting time of the cementing material is prolonged.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are given, and the method for testing each index of the fine slag powder cement produced in the following examples is as follows:
chloride ion adsorption amount: 3 groups of parallel tests are carried out according to GB/T11896 silver nitrate titration method for measuring water quality chloride, and an average value is taken.
Heat of hydration: hydration heat release rate test is carried out by adopting a hydration heat tester and a hydration heat tester of model TAM-AlR-C08 produced in Sweden, referring to GB12959 cement hydration heat test method (direct method).
Fluidity: according to GB/T8077 'concrete admixture collusion test method', the net slurry fluidity of the slag micro powder cementing material at 0min, 60min and 120min is respectively measured.
Setting time: and measuring the time required by the slag micro-powder cementing material to solidify by using a stopwatch.
Example 1
The slag micro powder gel material mainly comprises the following components in parts by weight: 140 parts of slag micro powder, 140 parts of cement, 105 parts of self-made fly ash, 56 parts of self-made water reducing agent and 146 parts of water.
A preparation method of a slag micropowder gel material mainly comprises the following preparation steps:
(1) placing fly ash and a nitric acid solution with the mass fraction of 10% and the mass of 12.8 times of that of the fly ash into a mortar, reacting for 2 hours, adding calcium carbonate with the mass of 0.3 time of that of the fly ash and calcium oxide with the mass of 0.08 time of that of the fly ash into the mortar, grinding for 3 minutes to prepare mixed particles, adding hydrogen peroxide with the mass of 3 times of that of the fly ash into the mixed particles, then placing the mixed particles into a muffle furnace, calcining for 60 minutes at 920 ℃, naturally cooling to room temperature, and crushing into powder with the particle size of 5.14 mu m by a steam kinetic energy mill crusher to obtain modified fly ash;
(2) placing a sodium gluconate solution with the mass fraction of 35% and 10 times of the mass of the modified fly ash into an ultrasonic atomization device, and atomizing the sodium gluconate solution into small liquid drops with the diameter of 3.5 mu m under the condition of 1.7 MHz; then, placing the modified fly ash obtained in the step (1) in a fluidized bed reactor, enabling the modified fly ash to be in a boiling fluidized state in the reactor by using compressed air, introducing an atomized sodium gluconate solution into the reactor, uniformly mixing the atomized sodium gluconate solution with the modified fly ash, and evaporating at 160 ℃ to obtain crystals; finally, blowing the crystals out of the fluidized bed reactor by compressed air, recovering the crystals by a dust collecting device, and drying the crystals for 24 hours at the temperature of 60 ℃ to prepare self-made fly ash;
(3) adding glucose and distilled water with the mass 2 times of that of the glucose into a four-mouth bottle, stirring for 5min under the condition of 150r/min, then adding diethylenetriamine with the mass 1.2 times of that of the glucose into the four-mouth bottle, reacting for 2h at 60 ℃ to prepare an aminoglucose mixed solution, then dropwise adding phosphorous acid aqueous solution with the mass fraction 40% and the mass 0.46 time of that of the glucose into the aminoglucose mixed solution under the condition of 25 drops/min, and reacting for 2h at 75 ℃ to prepare a modified glucose solution;
(4) stirring the modified glucose solution obtained in the step (3) and hydrogen peroxide with the mass of 0.07 time that of the modified glucose solution for 6min at 50 ℃ at 150r/min to obtain a modified glucose-hydrogen peroxide mixed solution for later use; stirring acrylic acid with the mass of 0.1 time of that of the modified glucose solution and distilled water with the mass of 0.12 time of that of the modified glucose solution for 4min under the condition of 150r/min to prepare a mixed solution A; mixing mercaptopropionic acid with the mass of 0.02 time that of the modified glucose solution, vitamin C with the mass of 0.04 time that of the modified glucose solution and distilled water with the mass of 0.18 time that of the modified glucose solution, and stirring for 5min under the condition of 150r/min to prepare a mixed solution B; respectively adding the mixed solution A into the modified glucose-hydrogen peroxide mixed solution at the speed of 0.6mL/min and the mixed solution B at the speed of 1mL/min, uniformly mixing, controlling the adding time to be 3h, keeping the temperature at 55 ℃ for 1.5h, and finally adding sodium hydroxide with the quality of 0.09 times that of the modified glucose and distilled water with the quality of 0.48 times that of the modified glucose to prepare the self-made water reducing agent;
(5) adding slag micro powder and cement with the mass of 1 time of that of the slag micro powder into a horizontal concrete mixer at normal temperature, stirring the mixture to be slightly viscous, then adding self-made fly ash with the mass of 0.75 time of that of the slag micro powder in the step (2), a self-made water reducing agent with the mass of 0.4 time of that of the slag micro powder in the step (4) and water with the mass of 1 time of that of the slag micro powder into the mixer, and stirring the mixture for 5min at the same speed to prepare the slag micro powder cementing material.
Further, the preparation method of the slag micropowder cementing material is characterized in that the crushing pressure of the steam kinetic energy mill in the step (1) is 0.5MPa, the steam temperature is 260 ℃, and the rotation speed of a grading wheel is 1200 r/min.
Further, the preparation method of the slag micropowder cementing material is characterized in that the feeding speed of the fluidized bed in the step (2) is 500mL/min, the gas fluidization speed is 5m/s, and the gas pressure is 2.3 MPa.
Further, the preparation method of the slag micropowder cementing material is characterized in that the slag micropowder in the step (5) is S95-grade granulated blast furnace slag micropowder with the particle size of 4 μm, and the cement is portland cement.
Example 2
The slag micro powder gel material mainly comprises the following components in parts by weight: 140 parts of slag micropowder, 140 parts of cement, 105 parts of fluidized bed fly ash, 56 parts of self-made water reducing agent and 146 parts of water.
A preparation method of a slag micropowder gel material mainly comprises the following preparation steps:
(1) putting a sodium gluconate solution with the mass fraction of 35 percent, which is 10 times of the mass of the fly ash, into an ultrasonic atomization device, and atomizing the sodium gluconate solution into small liquid drops with the diameter of 3.5 mu m under the condition of 1.7 MHz; then, placing the fly ash in a fluidized bed reactor, using compressed air to enable the modified fly ash to be in a boiling fluidized state in the reactor, introducing an atomized sodium gluconate solution into the reactor, uniformly mixing the atomized sodium gluconate solution with the fly ash, and evaporating at 160 ℃ to obtain crystals; finally, blowing the crystals out of the fluidized bed reactor by compressed air, recovering by a dust collecting device, and drying for 24 hours at 60 ℃ to prepare fluidized bed fly ash;
(2) adding glucose and distilled water with the mass 2 times of that of the glucose into a four-mouth bottle, stirring for 5min under the condition of 150r/min, then adding diethylenetriamine with the mass 1.2 times of that of the glucose into the four-mouth bottle, reacting for 2h at 60 ℃ to prepare an aminoglucose mixed solution, then dropwise adding phosphorous acid aqueous solution with the mass fraction 40% and the mass 0.46 time of that of the glucose into the aminoglucose mixed solution under the condition of 25 drops/min, and reacting for 2h at 75 ℃ to prepare a modified glucose solution;
(3) stirring the modified glucose solution obtained in the step (2) and hydrogen peroxide with the mass of 0.07 time that of the modified glucose solution for 6min at 50 ℃ at 150r/min to obtain a modified glucose-hydrogen peroxide mixed solution for later use; stirring acrylic acid with the mass of 0.1 time of that of the modified glucose solution and distilled water with the mass of 0.12 time of that of the modified glucose solution for 4min under the condition of 150r/min to prepare a mixed solution A; mixing mercaptopropionic acid with the mass of 0.02 time that of the modified glucose solution, vitamin C with the mass of 0.04 time that of the modified glucose solution and distilled water with the mass of 0.18 time that of the modified glucose solution, and stirring for 5min under the condition of 150r/min to prepare a mixed solution B; respectively adding the mixed solution A into the modified glucose-hydrogen peroxide mixed solution at the speed of 0.6mL/min and the mixed solution B at the speed of 1mL/min, uniformly mixing, controlling the adding time to be 3h, keeping the temperature at 55 ℃ for 1.5h, and finally adding sodium hydroxide with the quality of 0.09 times that of the modified glucose and distilled water with the quality of 0.48 times that of the modified glucose to prepare the self-made water reducing agent;
(4) adding slag micro powder and cement with the mass of 1 time of that of the slag micro powder into a horizontal concrete mixer at normal temperature, stirring the mixture to be slightly viscous, then adding fluidized bed fly ash with the mass of 0.75 time of that of the slag micro powder in the step (1), a self-made water reducing agent with the mass of 0.4 time of that of the slag micro powder in the step (3) and water with the mass of 1 time of that of the slag micro powder into the mixer, and stirring the mixture for 5min at the same speed to prepare the slag micro powder cementing material.
Further, the preparation method of the slag micropowder cementing material is characterized in that the feeding speed of the fluidized bed in the step (1) is 500mL/min, the gas fluidization speed is 5m/s, and the gas pressure is 2.3 MPa.
Further, the preparation method of the slag micro powder cementing material is characterized in that the slag micro powder in the step (4) is S95-grade granulated blast furnace slag micro powder, the particle size is 4 microns, and the cement is portland cement.
Example 3
The slag micro powder gel material mainly comprises the following components in parts by weight: 140 parts of slag micro powder, 140 parts of cement, 105 parts of modified fly ash, 56 parts of self-made water reducing agent and 146 parts of water.
A preparation method of a slag micropowder gel material mainly comprises the following preparation steps:
(1) placing fly ash and a nitric acid solution with the mass fraction of 10% and the mass of 12.8 times of that of the fly ash into a mortar, reacting for 2 hours, adding calcium carbonate with the mass of 0.3 time of that of the fly ash and calcium oxide with the mass of 0.08 time of that of the fly ash into the mortar, grinding for 3 minutes to prepare mixed particles, adding hydrogen peroxide with the mass of 3 times of that of the fly ash and a sodium gluconate solution with the mass of 2 times of that of the fly ash into the mixed particles, placing the mixture into a muffle furnace, calcining for 60 minutes at 920 ℃, naturally cooling to room temperature, and crushing the mixture into powder with the particle size of 5.14 mu m by a steam kinetic energy mill to obtain modified fly ash;
(2) adding glucose and distilled water with the mass 2 times of that of the glucose into a four-mouth bottle, stirring for 5min under the condition of 150r/min, then adding diethylenetriamine with the mass 1.2 times of that of the glucose into the four-mouth bottle, reacting for 2h at 60 ℃ to prepare an aminoglucose mixed solution, then dropwise adding phosphorous acid aqueous solution with the mass fraction 40% and the mass 0.46 time of that of the glucose into the aminoglucose mixed solution under the condition of 25 drops/min, and reacting for 2h at 75 ℃ to prepare a modified glucose solution;
(3) stirring the modified glucose solution obtained in the step (3) and hydrogen peroxide with the mass of 0.07 time that of the modified glucose solution for 6min at 50 ℃ at 150r/min to obtain a modified glucose-hydrogen peroxide mixed solution for later use; stirring acrylic acid with the mass of 0.1 time of that of the modified glucose solution and distilled water with the mass of 0.12 time of that of the modified glucose solution for 4min under the condition of 150r/min to prepare a mixed solution A; mixing mercaptopropionic acid accounting for 0.02 time of the mass of the modified glucose solution, vitamin C accounting for 0.04 time of the mass of the modified glucose solution and distilled water accounting for 0.18 time of the mass of the modified glucose solution, and stirring for 5min under the condition of 150r/min to prepare a mixed solution B; respectively adding the mixed solution A into the modified glucose-hydrogen peroxide mixed solution at the speed of 0.6mL/min and the mixed solution B at the speed of 1mL/min, uniformly mixing, controlling the adding time to be 3h, keeping the temperature at 55 ℃ for 1.5h, and finally adding sodium hydroxide with the quality of 0.09 times that of the modified glucose and distilled water with the quality of 0.48 times that of the modified glucose to prepare the self-made water reducing agent;
(4) adding slag micro powder and cement with the weight 1 time that of the slag micro powder into a horizontal concrete mixer at normal temperature, stirring to be slightly viscous, then adding the modified fly ash with the weight 0.75 time that of the slag micro powder in the step (1), the self-made water reducing agent with the weight 0.4 time that of the slag micro powder in the step (3) and water with the weight 1 time that of the slag micro powder into the mixer, and stirring at the same speed for 5min to prepare the slag micro powder cementing material.
Further, the preparation method of the slag micropowder cementing material is characterized in that the crushing pressure of the steam kinetic energy mill in the step (1) is 0.5MPa, the steam temperature is 260 ℃, and the rotation speed of a grading wheel is 1200 r/min.
Further, the preparation method of the slag micro powder cementing material is characterized in that the slag micro powder in the step (4) is S95-grade granulated blast furnace slag micro powder, the particle size is 4 microns, and the cement is portland cement.
Example 4
The slag micro powder gel material mainly comprises the following components in parts by weight: 140 parts of slag micropowder, 140 parts of cement, 105 parts of self-made fly ash, 56 parts of polycarboxylic acid water reducing agent and 146 parts of water.
A preparation method of a slag micropowder gel material mainly comprises the following preparation steps:
(1) placing fly ash and a nitric acid solution with the mass fraction of 10% and the mass of 12.8 times of that of the fly ash into a mortar, reacting for 2 hours, adding calcium carbonate with the mass of 0.3 time of that of the fly ash and calcium oxide with the mass of 0.08 time of that of the fly ash into the mortar, grinding for 3 minutes to prepare mixed particles, adding hydrogen peroxide with the mass of 3 times of that of the fly ash into the mixed particles, then placing the mixed particles into a muffle furnace, calcining for 60 minutes at 920 ℃, naturally cooling to room temperature, and crushing into powder with the particle size of 5.14 mu m by a steam kinetic energy mill crusher to obtain modified fly ash;
(2) placing a sodium gluconate solution with the mass fraction of 35% and 10 times of the mass of the modified fly ash into an ultrasonic atomization device, and atomizing the sodium gluconate solution into small liquid drops with the diameter of 3.5 mu m under the condition of 1.7 MHz; then, placing the modified fly ash obtained in the step (1) in a fluidized bed reactor, enabling the modified fly ash to be in a boiling fluidized state in the reactor by using compressed air, introducing an atomized sodium gluconate solution into the reactor, uniformly mixing the atomized sodium gluconate solution with the modified fly ash, and evaporating at 160 ℃ to obtain crystals; finally, blowing the crystals out of the fluidized bed reactor by compressed air, recovering the crystals by a dust collecting device, and drying the crystals for 24 hours at the temperature of 60 ℃ to prepare self-made fly ash;
(3) and (3) adding slag micro powder and cement with the mass of 1 time of that of the slag micro powder into a horizontal concrete mixer at normal temperature, stirring to be slightly viscous, adding the self-made fly ash with the mass of 0.75 time of the slag micro powder in the step (2), the polycarboxylic acid water reducing agent with the mass of 0.4 time of the slag micro powder and water with the mass of 1 time of the slag micro powder into the mixer, and stirring at the same speed for 5min to prepare the slag micro powder cementing material.
Further, the preparation method of the slag micropowder cementing material is characterized in that the crushing pressure of the steam kinetic energy mill in the step (1) is 0.5MPa, the steam temperature is 260 ℃, and the rotation speed of a grading wheel is 1200 r/min.
Further, the preparation method of the slag micropowder cementing material is characterized in that the feeding speed of the fluidized bed in the step (2) is 500mL/min, the gas fluidization speed is 5m/s, and the gas pressure is 2.3 MPa.
Further, the preparation method of the slag micro powder cementing material is characterized in that the slag micro powder in the step (3) is S95-grade granulated blast furnace slag micro powder, the particle size is 4 microns, and the cement is portland cement.
Example 5
The slag micro powder gel material mainly comprises the following components in parts by weight: 140 parts of slag micro powder, 140 parts of cement, 60 parts of self-made water reducing agent and 146 parts of water.
A preparation method of a slag micropowder gel material mainly comprises the following preparation steps:
(1) adding glucose and distilled water with the mass 2 times of that of the glucose into a four-mouth bottle, stirring for 5min under the condition of 150r/min, then adding diethylenetriamine with the mass 1.2 times of that of the glucose into the four-mouth bottle, reacting for 2h at 60 ℃ to prepare an aminoglucose mixed solution, then dropwise adding phosphorous acid aqueous solution with the mass fraction 40% and the mass 0.46 time of that of the glucose into the aminoglucose mixed solution under the condition of 25 drops/min, and reacting for 2h at 75 ℃ to prepare a modified glucose solution;
(2) stirring the modified glucose solution obtained in the step (2) and hydrogen peroxide with the mass of 0.07 time that of the modified glucose solution for 6min at 50 ℃ at 150r/min to obtain a modified glucose-hydrogen peroxide mixed solution for later use; stirring acrylic acid with the mass of 0.1 time of that of the modified glucose solution and distilled water with the mass of 0.12 time of that of the modified glucose solution for 4min under the condition of 150r/min to prepare a mixed solution A; mixing mercaptopropionic acid with the mass of 0.02 time that of the modified glucose solution, vitamin C with the mass of 0.04 time that of the modified glucose solution and distilled water with the mass of 0.18 time that of the modified glucose solution, and stirring for 5min under the condition of 150r/min to prepare a mixed solution B; respectively adding the mixed solution A into the modified glucose-hydrogen peroxide mixed solution at the speed of 0.6mL/min and the mixed solution B at the speed of 1mL/min, uniformly mixing, controlling the adding time to be 3h, keeping the temperature at 55 ℃ for 1.5h, and finally adding sodium hydroxide with the quality of 0.09 times that of the modified glucose and distilled water with the quality of 0.48 times that of the modified glucose to prepare the self-made water reducing agent;
(3) and (3) adding the slag micro powder and cement with the weight 1 time that of the slag micro powder into a horizontal concrete mixer at normal temperature, stirring to be slightly viscous, adding the self-made water reducing agent with the weight 0.43 time that of the slag micro powder in the step (2) and water with the weight 1 time that of the slag micro powder into the mixer, and stirring at the same speed for 5min to prepare the slag micro powder cementing material.
Further, the preparation method of the slag micro powder cementing material is characterized in that the slag micro powder in the step (3) is S95-grade granulated blast furnace slag micro powder, the particle size is 4 microns, and the cement is portland cement.
Comparative example
The superfine slag powder gel material mainly comprises the following components in parts by weight: 140 parts of slag micropowder, 140 parts of cement, 105 parts of fly ash, 56 parts of polycarboxylic acid water reducing agent and 146 parts of water.
A preparation method of a slag micropowder gel material mainly comprises the following preparation steps:
(1) adding slag micro powder and cement with the mass of 1 time of that of the slag micro powder into a horizontal concrete mixer at normal temperature, stirring the mixture to be slightly viscous, then adding fly ash with the mass of 0.75 time of the slag micro powder, a polycarboxylic acid water reducing agent with the mass of 0.4 time of the slag micro powder and water with the mass of 1 time of the slag micro powder into the mixer, and stirring the mixture for 5min at the same speed to prepare the slag micro powder cementing material.
Further, the preparation method of the slag micro powder cementing material is characterized in that the slag micro powder in the step (1) is S95-grade granulated blast furnace slag micro powder, the particle size is 4 microns, and the cement is portland cement.
Examples of effects
The following table 1 shows the results of performance analysis of the fine slag powder cements using examples 1 to 5 of the present invention and comparative examples.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example | |
| Chloride ion adsorption capacity (mg/g) | 65.53 | 40.62 | 64.39 | 65.50 | 38.49 | 37.56 |
| Heat of hydration (J/g) | 86.04 | 88.13 | 143.58 | 90.18 | 147.15 | 150.81 |
| 0min fluidity (mm) | 290.10 | 289.91 | 270.19 | 261.74 | 267.55 | 260.88 |
| 60min fluidity (mm) | 253.00 | 252.13 | 250.16 | 250.01 | 250.89 | 249.70 |
| 120min fluidity (mm) | 200.58 | 200.13 | 193.78 | 163.41 | 182.33 | 160.23 |
| Setting time | 9′20″ | 8′36″ | 6′32″ | 5′10″ | 6′15″ | 4′17″ |
Compared with the experimental data of the comparative example, the experimental data of the example 1 shows that the adsorption capacity of the example 1 is large, the hydration heat is low, the fluidity is strong, and the setting time is long, which indicates that in the process of preparing raw materials, the self-made fly ash is oxidized and modified by nitric acid, the activity of silica and alumina in the fly ash is excited, adsorption bridging is formed between the modified fly ash and hydrogen ions, the adsorption capacity of a cementing material to chloride ions is enhanced, then ammonium gluconate is deposited on the surface of the fly ash by a fluidized bed to form a compact surface hydration film, the compact surface hydration film and hydration products in cement generate double salt, the double salt is deposited on the surface of cement particles to prevent further reaction between water molecules and cement hydration products, the hydration heat release rate of the cementing material is reduced, the hydration is delayed, in addition, the hydroxyl in the long side chain of the self-made water reducer molecule and the water molecules generate hydrogen bonds to form a hydration film with a certain thickness, and the nitrogen atom in the amine group and the metal ion form covalent bonds, generating a stable complex, delaying the solidification time of the slag micro-powder, enhancing the fluidity, and exciting the auxiliary plasticizing effect of the self-made fly ash by the mutual synergistic effect of the self-made water reducing agent and the self-made fly ash, so as to enhance the fluidity of the slag micro-powder and delay the solidification time; from the comparison of the experimental data of the example 1 and the example 2, it can be found that the chloride ion adsorption amount of the example 2 is low, which means that the chemical bonds in the silica and the alumina in the fly ash cannot be broken, the activity thereof cannot be excited, and the chloride ions cannot be adsorbed without modifying the fly ash with nitric acid; from the comparison of the experimental data of the embodiment 1 and the embodiment 3, it can be found that the hydration heat is higher, which means that sodium gluconate cannot be adsorbed on the surface of the fly ash to form a hydration film because sodium gluconate is directly added into the fly ash without using a fluidized bed, and the action of sodium gluconate for adsorbing the hydrate cannot be activated, so that the hydration heat is higher and the heat release rate is high; from the comparison of the experimental data of example 1 and example 4, it can be seen that example 4 has low fluidity and short setting time, which means that when the polycarboxylate water reducing agent is not modified by modified glucose, the water reducing agent does not contain hydroxyl and nitrogen atoms in the side chains, and cannot form a hydration film with water, so that the cement particles have poor dispersibility and poor fluidity, and the setting time is short; the experimental data comparison of the embodiment 1 and the embodiment 5 shows that the adsorption capacity is low, the hydration heat is high, and the fluidity is poor, which indicates that the water reducing agent alone cannot enter an electric layer inside cement, cannot change a double electric layer structure of the cement, cannot improve the cement potential, cannot delay the cement hydration, and meanwhile, the self-made fly ash is not available, and cannot compete and adsorb on the surface of the slag micro powder cementing material, so that the self-made water reducing agent is large in using amount and high in cost, the fluidity of the cementing material is low, and the flow loss is large.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. The slag micro powder cementing material is characterized by mainly comprising 130-200 parts by weight of slag micro powder, 125-200 parts by weight of cement, 98-150 parts by weight of self-made fly ash, 52-60 parts by weight of self-made water reducing agent and 135-208 parts by weight of water.
2. The slag micropowder cementitious material of claim 1, wherein the self-made fly ash is prepared from fly ash, nitric acid and sodium gluconate.
3. The slag micropowder cementitious material of claim 2, wherein the self-made water reducer is prepared from modified glucose and a polycarboxylic acid water reducer.
4. The slag micropowder cementitious material of claim 3, wherein the modified glucose is prepared from glucose, diethylenetriamine and phosphorous acid.
5. The slag micropowder cementitious material of claim 4, wherein the slag micropowder cementitious material comprises the following raw materials in parts by weight: 140 parts of slag micro powder, 140 parts of cement, 105 parts of self-made fly ash, 56 parts of self-made water reducing agent and 146 parts of water.
6. The preparation method of the slag micropowder cementing material is characterized by mainly comprising the following preparation steps:
(1) placing fly ash and a nitric acid solution with the mass fraction of 10% and the mass of 12.8 times of that of the fly ash into a mortar, reacting for 2 hours, adding calcium carbonate with the mass of 0.3 time of that of the fly ash and calcium oxide with the mass of 0.08 time of that of the fly ash into the mortar, grinding for 3 minutes to prepare mixed particles, adding hydrogen peroxide with the mass of 3 times of that of the fly ash into the mixed particles, then placing the mixed particles into a muffle furnace, calcining for 60 minutes at 920 ℃, naturally cooling to room temperature, and crushing into powder with the particle size of 5.14 mu m by a steam kinetic energy mill crusher to obtain modified fly ash;
(2) placing a sodium gluconate solution with the mass fraction of 35% and 10 times of the mass of the modified fly ash into an ultrasonic atomization device, and atomizing the sodium gluconate solution into small droplets with the diameter of 1-5 mu m under the condition of 1.7 MHz; then, placing the modified fly ash obtained in the step (1) in a fluidized bed reactor, enabling the modified fly ash to be in a boiling fluidized state in the reactor by using compressed air, introducing an atomized sodium gluconate solution into the reactor, uniformly mixing the atomized sodium gluconate solution with the modified fly ash, and evaporating at 160 ℃ to obtain crystals; finally, blowing the crystals out of the fluidized bed reactor by compressed air, recovering the crystals by a dust collecting device, and drying the crystals for 24 hours at the temperature of 60 ℃ to prepare self-made fly ash;
(3) adding glucose and distilled water with the mass 2 times of that of the glucose into a four-mouth bottle, stirring for 5min under the condition of 150r/min, then adding diethylenetriamine with the mass 1.2 times of that of the glucose into the four-mouth bottle, reacting for 0.5-4 h at 15-60 ℃ to prepare an aminoglucose mixed solution, then dropwise adding phosphorous acid aqueous solution with the mass fraction of 40% and the mass 0.46 time of that of the glucose into the aminoglucose mixed solution under the condition of 25 drops/min, and reacting for 0.5-4 h at 40-80 ℃ to prepare a modified glucose solution;
(4) stirring the modified glucose solution obtained in the step (3) and hydrogen peroxide with the mass of 0.07 time that of the modified glucose solution at 50 ℃ for 5-6 min to obtain a modified glucose-hydrogen peroxide mixed solution for later use; stirring acrylic acid with the mass of 0.1 time that of the modified glucose solution and distilled water with the mass of 0.12 time that of the modified glucose solution for 3-5 min under the condition of 150r/min to prepare a mixed solution A; mixing mercaptopropionic acid with the mass being 0.02 time that of the modified glucose solution, vitamin C with the mass being 0.04 time that of the modified glucose solution and distilled water with the mass being 0.18 time that of the modified glucose solution, and stirring for 5-6 min under the condition of 150r/min to prepare a mixed solution B; respectively adding the mixed solution A into the modified glucose-hydrogen peroxide mixed solution at the speed of 0.6mL/min and the mixed solution B at the speed of 1mL/min, uniformly mixing, controlling the adding time to be 2.5-4 h, keeping the temperature at 55 ℃ for 1-2 h, and finally adding sodium hydroxide with the quality of 0.09 time of that of the modified glucose and distilled water with the quality of 0.48 time of that of the modified glucose to prepare the self-made water reducing agent;
(5) adding slag micro powder and cement with the mass 1-3 times of that of the slag micro powder into a horizontal concrete mixer at normal temperature, stirring the mixture to be slightly viscous, then adding self-made fly ash with the mass 0.5-1 time of that of the slag micro powder in the step (2), a self-made water reducing agent with the mass 0.1-0.4 time of that of the slag micro powder in the step (4) and water with the mass 1-2 times of that of the slag micro powder into the mixer, and stirring the mixture at the same speed for 4-5 min to prepare the slag micro powder cementing material.
7. The method for preparing slag micropowder cementitious material of claim 6, wherein the grinding pressure of the steam kinetic energy mill in the step (1) is 0.5MPa, the steam temperature is 260 ℃, and the rotation speed of a grading wheel is 1200 r/min.
8. The preparation method of slag micropowder cementitious material according to claim 6, characterized in that the feeding speed of the fluidized bed in the step (2) is 450-500 mL/min, the gas fluidization speed is 4-6 m/s, and the gas pressure is 1.27-2.45 MPa.
9. The method for preparing a fine slag powder binding material according to claim 6, wherein the fine slag powder in the step (5) is granulated blast furnace fine slag powder of grade S95, the particle size is 4 μm, and the cement is portland cement.
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