阅读说明：本技术 一种CaCO3包覆刚玉骨料及其制备方法和应用 (CaCO (calcium carbonate)3Coated corundum aggregate and preparation method and application thereof ) 是由 肖国庆 屈娇阳 丁冬海 雷长坤 于 2021-01-21 设计创作，主要内容包括：本发明公开一种CaCO-3包覆刚玉骨料及其制备方法和应用,该方法首先以有机酸水溶液和钙源为原料制备前驱体浸渍溶液,再将刚玉骨料充分浸渍在所述前驱体浸渍溶液中,最后将浸渍后的刚玉骨料烘干和煅烧后得到CaCO-3包覆刚玉骨料。采用液相浸渍法制备CaCO-3包覆刚玉骨料,制备方法简单且成本低廉；CaCO-3包覆刚玉骨料是在刚玉骨料表面包覆微米级CaCO-3涂层,以制备好的CaCO-3包覆刚玉骨料制备铝镁质浇注料,在高温下浇注料骨料与基质间原位生成性能优越的六铝酸钙(CA-6)界面层,有效的提高了耐火材料的力学性能以及抗热震性能。(The invention discloses CaCO 3 The method comprises the steps of firstly preparing a precursor dipping solution by taking an organic acid aqueous solution and a calcium source as raw materials, then fully dipping corundum aggregate into the precursor dipping solution, and finally drying and calcining the dipped corundum aggregate to obtain CaCO 3 And coating corundum aggregate. Preparation of CaCO by liquid-phase impregnation 3 The corundum aggregate is coated, the preparation method is simple and the cost is low; CaCO 3 The coated corundum aggregate is prepared by coating micron-sized CaCO on the surface of corundum aggregate 3 Coating of prepared CaCO 3 The corundum aggregate is coated to prepare the aluminum-magnesium castable, and calcium hexaluminate (CA) with excellent performance is generated in situ between the castable aggregate and a substrate at high temperature 6 ) The interface layer effectively improves the mechanical property and the thermal shock resistance of the refractory material.)

1. CaCO (calcium carbonate)₃Preparation of coated corundum aggregateThe method is characterized in that firstly, organic acid aqueous solution and calcium source are used as raw materials to prepare precursor dipping solution, then corundum aggregate is fully dipped in the precursor dipping solution, and finally, the dipped corundum aggregate is dried and calcined to obtain CaCO₃And coating corundum aggregate.

2. The CaCO as claimed in claim 1₃The preparation method of the coated corundum aggregate is characterized in that the organic acid aqueous solution is an aqueous solution of citric acid, malic acid, tartaric acid, acetic acid, succinic acid or oxalic acid; the calcium source is CaCO₃Calcium hydroxide or calcium oxide.

3. CaCO as claimed in claim 2₃The preparation method of the coated corundum aggregate is characterized in that the corundum aggregate is plate-shaped corundum aggregate with the particle size of 1-3mm and 3-5 mm.

4. CaCO as claimed in claim 2₃The preparation method of the coated corundum aggregate is characterized in that the molar ratio of the calcium source to the organic acid is 1: 3.

5. The CaCO as claimed in claim 1₃The preparation method of the coated corundum aggregate is characterized in that Ca is added into the precursor dipping solution²⁺The concentration is 0.05-0.35 mol/L.

6. The CaCO as claimed in claim 1₃The preparation method of the coated corundum aggregate is characterized by comprising the following steps:

dissolving organic acid in water to obtain an organic acid aqueous solution, slowly adding a calcium source into the organic acid aqueous solution in several times under ultrasound, and oscillating the mixture with ultrasound for 30min to obtain a precursor dipping solution after the reaction is completed;

step two, putting the corundum aggregate into the precursor dipping solution for full dipping, and then drying and calcining to obtain CaCO₃And coating corundum aggregate.

7. Such as rightCaCO as claimed in claim 6₃The preparation method of the coated corundum aggregate is characterized in that the drying temperature in the second step is 60-100 ℃.

8. CaCO as claimed in claim 6₃The preparation method of the coated corundum aggregate is characterized in that the calcination temperature in the step two is 430-500 ℃.

9. CaCO (calcium carbonate)₃Coated corundum aggregate, characterized in that the CaCO₃CaCO coated with corundum aggregate as claimed in any one of claims 1 to 8₃The coated corundum aggregate is prepared by the preparation method, and the CaCO₃The distribution condition and the granularity of the calcium carbonate particles coated on the surface of the corundum aggregate and with different appearances can be determined according to Ca in the precursor dipping solution²⁺The concentration is regulated and controlled.

10. CaCO as claimed in claim 9₃The application of the coated corundum aggregate in preparing refractory castable; the refractory castable is an aluminum-magnesium ultralow-cement refractory castable.

Technical Field

The invention belongs to the technical field of inorganic non-metallic materials, and particularly relates to CaCO₃Coated corundum aggregate and a preparation method and application thereof.

Background

In recent years, the aluminum-magnesium castable is widely applied to ladle lining materials due to the characteristics of simple preparation process, excellent slag corrosion resistance and the like. After high-temperature heat treatment, three high-melting-point phases of calcium hexaluminate, magnesia-alumina spinel and alumina are alternately distributed and firmly combined in the castable, so that the castable has more excellent high-temperature performance, and the thermal shock stability of the material is improved.

In the case of high-density magnesia-alumina casting materials for steel ladles, cracks are generated at the boundary of the penetration layer on the working surface and the vicinity thereof due to thermal stress impact caused by temperature change in use, and the cracks are finally damaged in a peeling mode along with the expansion of the cracks. And CA₆Because the crystal structure is hexagonal, O is generated^2-Since the diffusion rate in the direction perpendicular to the c-axis is high, the crystal preferentially develops into a plate-like or sheet-like crystal form, and the crack propagation is more likely to proceed along the sheet-like crystal direction due to fracture mechanics, which makes the path of crack propagation tortuous and can well buffer thermal stress, recently, by introducing different forms of Ca²⁺Thereby producing a flake CA at a high temperature₆Further improving the mechanical property and thermal shock resistance of the castable becomes a research hotspot.

Researches show that the residual breaking strength and the residual strength retention rate of a sample subjected to thermal shock can be effectively improved by increasing the addition of the calcium aluminate cement, and the thermal shock resistance stability of the material is improved; the nanometer calcium oxide generated by decomposing the calcium carbonate nanometer powder has large specific surface area, more lattice defects and higher reaction activity, and the calcium aluminate mineral generated in situ reacts more fully, so the castable containing the calcium carbonate nanometer powder has higher cold and hot rupture strength. However, when the calcium aluminate cement or calcium carbonate nanopowder is introduced too much, the performance of the castable is rather reduced. Therefore, the existing research base is combined to find that the Ca is aimed at²⁺The research of the introduction method needs further deepening.

Disclosure of Invention

Aiming at the defects and shortcomings in the prior art, the invention provides CaCO₃Preparation method and application of coated corundum aggregate, and CA with excellent performance is generated in situ between castable aggregate and matrix at high temperature₆The phase interface layer solves the problem of thermal spalling caused by the untight combination of the refractory aggregate and the matrix, and improves the thermal shock resistance stability of the refractory material.

In order to achieve the purpose, the invention adopts the following technical scheme:

CaCO (calcium carbonate)₃The preparation method of the coated corundum aggregate comprises the steps of firstly preparing a precursor dipping solution by taking an organic acid aqueous solution and a calcium source as raw materials, then fully dipping the corundum aggregate into the precursor dipping solution, and finally drying and calcining the dipped corundum aggregate to obtain CaCO₃And coating corundum aggregate.

The invention also comprises the following technical characteristics:

specifically, the organic acid aqueous solution is an aqueous solution of citric acid, malic acid, tartaric acid, acetic acid, succinic acid or oxalic acid; the calcium source is CaCO₃Calcium hydroxide or calcium oxide.

Specifically, the corundum aggregate is plate-shaped corundum aggregate with the particle size of 1-3mm and 3-5 mm.

Specifically, the molar ratio of the calcium source to the organic acid is 1: 3.

Specifically, Ca is contained in the precursor impregnation solution²⁺The concentration is 0.05-0.35 mol/L.

Specifically, the method comprises the following steps:

dissolving organic acid in water to obtain an organic acid aqueous solution, slowly adding a calcium source into the organic acid aqueous solution in several times under ultrasound, and oscillating the mixture with ultrasound for 30min to obtain a precursor dipping solution after the reaction is completed;

step two, putting the corundum aggregate into the precursor dipping solution for full dipping, and then drying and calcining to obtain CaCO₃And coating corundum aggregate.

Specifically, the drying temperature in the second step is 60-100 ℃.

Specifically, the calcination temperature in the second step is 430-500 ℃.

CaCO (calcium carbonate)₃Coated corundum aggregate, the CaCO₃Coating corundum aggregate with the CaCO₃The coated corundum aggregate is prepared by the preparation method, and the CaCO₃The distribution condition and the granularity of the calcium carbonate particles coated on the surface of the corundum aggregate and with different appearances can be determined according to Ca in the precursor dipping solution²⁺The concentration is regulated and controlled.

The CaCO₃Coating ofThe application of corundum aggregate in preparing refractory castable; the refractory castable is an aluminum-magnesium ultralow-cement refractory castable.

Compared with the prior art, the invention has the beneficial technical effects that:

(I) CaCO of the invention₃Coating CaCO in corundum aggregate₃The coating structure is controllable, the aggregate outer coating is sequentially decomposed into a calcium carbonate coating from a mixed coating of calcium hydrogen citrate and citric acid along with the rise of temperature along with the change of temperature, and CaCO can be obtained₃And coating corundum aggregate.

(II) CaCO produced according to the invention₃Coating corundum aggregate, Ca in precursor impregnating solution²⁺At 0.15mol/L, calcium carbonate particles with the size of 0.1-0.3 μm and uniform distribution are generated on the surface of the corundum aggregate and follow Ca²⁺And gradually agglomerating the small calcium carbonate particles into cluster-shaped calcium carbonate aggregates with the size of 20-40 mu m by increasing the concentration. The prepared aggregate is added into the aluminum-magnesium castable, calcium hexaluminate is generated in situ in a bonding area of the aggregate and the matrix, and is alternately distributed and firmly bonded with three high-melting-point phases of magnesium aluminate spinel and alumina in the castable, so that the castable has more excellent mechanical and high-temperature properties, and the thermal shock stability of the material is improved.

(III) CaCO of the invention₃The coated corundum aggregate is added into the aluminum-magnesium castable after being dipped and dried, the preparation process is simple, and the cost is low. The calcium source in the form of micron-grade calcium carbonate is introduced in the form of a coating, and the thermal shock resistance of the aluminum-magnesium castable is obviously improved due to the in-situ generation of a calcium hexaluminate phase interface layer between the aggregate and the matrix.

Drawings

FIG. 1 is a diagram of a manufacturing process of the present invention;

FIG. 2 is an SEM image of the surface of corundum aggregate dried at 80 ℃ according to the invention;

FIG. 3 shows CaCO prepared according to examples 1 to 4 of the present invention₃XRD pattern of the coated corundum aggregate;

FIG. 4 is CaCO prepared according to example 1 of the present invention₃SEM picture of the clad corundum aggregate;

FIG. 5 shows an embodiment of the present inventionCaCO prepared in example 2₃SEM picture of the clad corundum aggregate;

FIG. 6 is CaCO prepared according to example 3 of the present invention₃SEM picture of the clad corundum aggregate;

FIG. 7 is CaCO prepared according to example 4 of the present invention₃SEM picture of the clad corundum aggregate;

FIG. 8 shows CaCO prepared according to examples 1 to 4 of the present invention₃A thermal shock resistance result chart of the aluminum-magnesium castable prepared by coating corundum aggregate;

FIG. 9 is an SEM image of the aluminum-magnesium castable material of the control group after thermal shock treatment;

FIG. 10 is CaCO prepared according to example 2 of the present invention₃SEM picture of the aluminum-magnesium castable prepared by coating corundum aggregate.

Detailed Description

The invention discloses CaCO₃The preparation method of the coated corundum aggregate comprises the steps of firstly preparing a precursor dipping solution by taking an organic acid aqueous solution and a calcium source as raw materials, then fully dipping the corundum aggregate into the precursor dipping solution, and finally drying and calcining the dipped corundum aggregate to obtain CaCO₃And coating corundum aggregate.

The organic acid water solution is water solution of citric acid, malic acid, tartaric acid, acetic acid, succinic acid or oxalic acid; the calcium source is CaCO₃Calcium hydroxide or calcium oxide. The corundum aggregate is plate-shaped corundum aggregate with the particle size of 1-3mm and 3-5 mm.

The molar ratio of the calcium source and the organic acid is 1: 3.

Specifically, in the present embodiment, the preferred organic acid is citric acid, and the calcium source is CaCO₃And CaCO₃And citric acid in a 1:3 molar ratio.

Precursor impregnation of Ca in solution²⁺The concentration is 0.05-0.35 mol/L.

The method specifically comprises the following steps:

dissolving organic acid in water to obtain an organic acid aqueous solution, slowly adding a calcium source into the organic acid aqueous solution in several times under ultrasound, and oscillating the mixture with ultrasound for 30min to obtain a precursor dipping solution after the reaction is completed;

step two, putting the corundum aggregate into the precursor dipping solution for full dipping, and then drying and calcining to obtain CaCO₃And coating corundum aggregate.

The drying temperature in the second step is 60-100 ℃.

The calcination temperature in the second step is 430-500 ℃.

CaCO (calcium carbonate)₃Coated corundum aggregate, the CaCO₃Coated corundum aggregate made of CaCO₃The coated corundum aggregate is prepared by the preparation method, and the CaCO₃The distribution condition and the granularity of the calcium carbonate particles coated on the surface of the corundum aggregate and with different appearances can be determined according to Ca in the precursor dipping solution²⁺The concentration is regulated and controlled.

CaCO (calcium carbonate)₃The application of the coated corundum aggregate in preparing refractory castable; the refractory castable is an aluminum-magnesium ultralow-cement refractory castable.

CaCO according to the invention₃Coating corundum aggregate with organic acid water solution and calcium source as raw materials to prepare dipping solution, preparing a coating on the surface of plate-shaped corundum aggregate with the thickness of 1-3mm and 3-5mm by adopting a liquid phase dipping method, drying at 80 ℃, and preserving heat at 430 ℃ to obtain CaCO₃And coating corundum aggregate. Mixing CaCO₃The coated corundum aggregate is added into the aluminum-magnesium castable, and a calcium hexaluminate phase interface layer is generated in situ between the aggregate and the matrix after high-temperature sintering, so that the thermal shock stability of the aluminum-magnesium castable is improved.

CaCO prepared by the invention₃Coating corundum aggregate, Ca in precursor impregnating solution²⁺At 0.15mol/L, calcium carbonate particles with the size of 0.1-0.3 μm and uniform distribution are generated on the surface of the corundum aggregate and follow Ca²⁺And gradually agglomerating the small calcium carbonate particles into cluster-shaped calcium carbonate aggregates with the size of 20-40 mu m by increasing the concentration. The prepared aggregate is added into the aluminum-magnesium castable, calcium hexaluminate is generated in situ in a bonding area of the aggregate and the matrix, and is alternately distributed and firmly bonded with three high-melting-point phases of magnesium aluminate spinel and alumina in the castable, so that the castable has more excellent mechanical and high-temperature properties, and the thermal shock stability of the material is improved.

The followingThe invention provides an example, the citric acid aqueous solution and calcium carbonate provided by the invention are prepared into solution according to the required proportion, and CaCO is prepared by a liquid phase impregnation method₃The corundum aggregate is coated, and the experimental process is shown in figure 1.

SEM analysis is carried out on the surface of the plate-shaped corundum aggregate to obtain an SEM picture, and referring to fig. 2, the microstructure of the coating is in a cluster structure with the size of 15-25 mu m and is distributed uniformly after the coating is dried at the concentration of 80 ℃.

The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.

Example 1:

this example discloses a CaCO₃The preparation method of the coated corundum aggregate comprises the steps of firstly preparing a precursor dipping solution by taking an organic acid aqueous solution and a calcium source as raw materials, then fully dipping the corundum aggregate into the precursor dipping solution, and finally drying and calcining the dipped corundum aggregate to obtain CaCO₃And coating corundum aggregate.

The organic acid aqueous solution of the embodiment is an aqueous solution of citric acid; the calcium source is CaCO₃(ii) a Wherein CaCO₃The molar ratio of the precursor to the citric acid is 1:3, and Ca in the precursor impregnation solution²⁺The concentration was 0.05mol/L, and the citric acid concentration corresponded to it by molar ratio.

The method comprises the following specific steps:

step one, completely dissolving 0.15mol/L citric acid in 1L deionized water, and gradually and slowly adding 5g of calcium carbonate into the aqueous solution of the citric acid under ultrasound (to obtain Ca in the precursor dipping solution)²⁺The concentration is 0.05mol/L), and ultrasonic oscillation is carried out for 30min until the reaction is completed, so as to obtain a precursor dipping solution, wherein the precursor dipping solution is a mixed solution of calcium hydrogen citrate and citric acid with the pH value of 3.1.

Secondly, putting the tabular corundum aggregate with the size of 1-3mm and 3-5mm into the precursor dipping solution for full dipping, drying at 80 ℃, and then preserving heat at 430 ℃ to obtain CaCO 5₃Coated corundum boneAnd (5) feeding.

CaCO prepared in example 1₃And (3) carrying out X-ray diffraction analysis and SEM analysis on the surface coating of the coated corundum aggregate to obtain an XRD (X-ray diffraction) spectrum and an SEM (scanning Electron microscope) spectrum, and referring to figures 3 and 4.

Example 2:

this example differs from example 1 in that: completely dissolving 0.45mol/L citric acid in 1L deionized water, gradually and slowly adding 15g calcium carbonate into the citric acid water solution under ultrasound (to obtain Ca in the precursor impregnation solution)²⁺The concentration is 0.15mol/L), and ultrasonic oscillation is carried out for 30min until the reaction is completed, so as to obtain a precursor dipping solution, wherein the precursor dipping solution is a mixed solution of calcium hydrogen citrate and citric acid with the pH value of 3.1. The remaining procedure was the same as in example 1, to obtain CaCO numbered C15₃And coating corundum aggregate.

CaCO prepared in example 2₃The coated corundum aggregate is subjected to X-ray diffraction analysis and SEM analysis to obtain an XRD (X-ray diffraction) spectrum and an SEM (scanning Electron microscope) spectrum, and the XRD spectrum and the SEM spectrum are shown in figures 3 and 5.

Example 3:

the present embodiment 3 differs from embodiment 1 in that: completely dissolving 0.75mol/L citric acid in 1L deionized water, and slowly adding 25g calcium carbonate into the citric acid water solution under ultrasonic wave (to obtain precursor impregnation solution, Ca²⁺The concentration is 0.25mol/L), ultrasonic oscillation is carried out for 30min, and after the reaction is completed, a precursor dipping solution can be obtained, wherein the precursor dipping solution is a mixed solution of calcium hydrogen citrate and citric acid with the pH value of 3.0. The remaining procedure was the same as in example 1, to obtain CaCO numbered C25₃And coating corundum aggregate.

CaCO prepared in example 3₃The coated corundum aggregate is subjected to X-ray diffraction analysis and SEM analysis to obtain an XRD (X-ray diffraction) spectrum and an SEM (scanning Electron microscope) spectrum, and the XRD spectrum and the SEM spectrum are shown in figures 3 and 6.

Example 4:

this example 4 differs from example 1 in that: completely dissolving 1.05mol/L citric acid in 1L deionized water, slowly adding 35g calcium carbonate into the citric acid water solution under ultrasonic wave (to obtain precursor impregnation solution, Ca²⁺Concentration of 0.35mol/L), ultrasonic vibrationAnd after the reaction is completed within 20min, a precursor dipping solution can be obtained, wherein the precursor dipping solution is a mixed solution of calcium hydrogen citrate and citric acid with the pH value of 3.0. The remaining procedure was the same as in example 1, to obtain CaCO numbered C35₃And coating corundum aggregate.

CaCO prepared in example 4₃The coated corundum aggregate is subjected to X-ray diffraction analysis and SEM analysis to obtain an XRD (X-ray diffraction) spectrum and an SEM (scanning Electron microscope) spectrum, and the XRD spectrum and the SEM spectrum are shown in figures 3 and 7.

And (I) result characterization:

(1.1) X-ray diffraction analysis:

CaCO prepared in example 1₃The weight gain of the coating in the coated corundum aggregate is 0.19 percent, and the main phase of the coating is Al as shown in figure 3₂O₃And a small amount of CaCO in the calcite form₃And (4) coating. CaCO prepared in examples 2 and 3₃The weight gain of the coating in the coated corundum aggregate is 0.23 percent and 0.29 percent respectively, and the main phase of the coating is calcite type CaCO₃And Al₂O₃. CaCO prepared in example 4₃The weight of the coating in the coated corundum aggregate is 0.36 percent, and the main phase of the coating is calcite type CaCO₃And a small amount of Al₂O₃. It is known that Ca is different from Ca²⁺CaCO generated on the surface of plate-shaped corundum aggregate after dipping by precursor dipping solution with concentration₃All of calcite type, and CaCO₃The content is dependent on Ca²⁺The concentration increases with increasing concentration. When Ca is used²⁺CaCO formed in one coating layer at increased concentrations₃The content is increased; CaCO formed on the other hand₃The binding property of the coating and the aggregate is gradually deteriorated and the coating is easy to scrape off.

(1.2) scanning electron microscopy analysis:

FIG. 4 CaCO prepared in example 1₃SEM image of the surface of the coated corundum aggregate can show that Ca is contained in the precursor dipping solution²⁺CaCO on the surface of the aggregate at a concentration of 0.05mol/L₃CaCO with sparsely distributed and agglomerated coating₃The size is about 3-5 μm.

FIG. 5 CaCO prepared in example 2₃SEM image of coated corundum aggregate surface illustrating Ca in precursor impregnation solution^{2 +}Cubic CaCO with size of 0.1-0.3 μm at concentration of 0.15mol/L₃The particles are in a dispersed state, are more uniformly distributed on the surface of the aggregate and have lower agglomeration degree.

FIG. 6 CaCO prepared in example 3₃SEM image of corundum aggregate surface coated with Ca in precursor dipping solution²⁺CaCO on the surface of the aggregate at a concentration of 0.25mol/L₃The particles are agglomerated into a continuously distributed cluster structure and have a size of about 30-40 μm.

FIG. 7 CaCO prepared in example 4₃SEM image of corundum aggregate surface coated with Ca in precursor dipping solution²⁺CaCO on the surface of the aggregate at a concentration of 0.35mol/L₃The coating is agglomerated into a flower-shaped structure with the diameter of 20-30 mu m and is distributed discontinuously. With Ca in the solution²⁺Increase in Ca adsorption²⁺The quantity of carboxyl on the surface is increased, so that the viscosity of the solution is increased and the solution is easy to agglomerate. The impregnated aggregate is dried at 80 ℃ to generate a cluster structure on the surface of the aggregate, and calcium carbonate is generated by the decomposition of calcium hydrogen citrate in the temperature rising process because of Ca²⁺The calcium carbonate and the citrate radical are mutually adsorbed, and the calcium carbonate is generated by taking calcium hydrogen citrate as a template, so that partial appearance of the calcium hydrogen citrate is kept.

By comparison, CaCO prepared in example 2₃The calcium carbonate particles coated on the surface of the corundum aggregate are distributed most uniformly, and the coating property is strong.

(1.3) analysis of thermal shock resistance of castable

The invention also discloses CaCO₃The coated corundum aggregate is used for preparing refractory castable. CaCO prepared in example 2₃The formula of applying the coated corundum aggregate to the aluminum-magnesium ultra-low cement castable and using the untreated blank corundum aggregate to prepare the aluminum-magnesium ultra-low cement castable as the castable is shown in table 1.

TABLE 1 ingredient composition of aluminum-magnesium low-cement castable

Weighing the materials according to the table 1, dry-mixing in a stirrer for 1min, sequentially adding a polycarboxylic acid water reducing agent and water, wet-mixing for 3min, pouring the castable in a mould with the size of 40mm multiplied by 160mm in a vibration mode, and vibrating for 4 min; and (3) curing the test mold at room temperature for 24 hours, demolding, curing the castable at room temperature for 24 hours, drying at 110 ℃ for 24 hours, and then respectively preserving heat for 3 hours at 1600 ℃ under the air condition. The casting material of the control group was designated as S0, and the CaCO obtained in example 2 was used₃The preparation castable of the coated corundum aggregate is numbered as S15.

The thermal shock resistance of the sample after heat preservation at 1600 ℃ for 3h (delta T is 1100 ℃, water cooling is carried out for 3 times) is measured by a water cooling method, the thermal shock resistance of the material is evaluated by the breaking strength and the breaking strength retention rate after thermal shock, and the breaking strength and the residual strength retention rate after thermal shock are shown in figure 8. And (3) analyzing and characterizing the microstructure of the refractory castable thermal shock resistance sample by using a SU6600 type field emission scanning electron microscope, wherein an SEM image of a blank sample S0 castable is shown in a figure 9, and an SEM image of an S15 castable is shown in a figure 10.

The castable material of S0 in FIG. 8 has poor thermal shock resistance, the retention rate of the residual strength after thermal shock is only 17%, and the thermal shock resistance of other castable materials is obviously improved compared with that of the S0 sample. Sample S15 CaCO on aggregate surface₃The particles are distributed in a dispersive and uniform way and basically do not agglomerate, so that more continuous CA is generated₆The coating has the highest breaking strength before and after thermal shock, the retention rate of the residual strength is improved from 17% to 28.5% compared with that of an S0 sample, and the performance is improved most obviously.

As can be seen from fig. 9 and 10, the S0 sample has transgranular fracture and large crack size, and no obvious Ca element aggregation region is found at the crack as can be seen from the Al and Ca element distribution in fig. 9; the S15 sample has no transgranular fracture, the cracks disappear at the joint of the aggregate and the matrix, the disappearance of the cracks can be seen by combining the distribution condition of Al and Ca elements in figure 10, and the more concentrated distribution of the Ca element shows that the CA is generated in situ at the position₆The interface layer plays a good role in buffering stress in the crack propagation process, so that the thermal shock resistance of the material is improved.