阅读说明：本技术 红外辐射涂料及其制备方法 (Infrared radiation coating and preparation method thereof ) 是由 樊河雲 刘功国 秦洁 倪伟 于 2021-10-27 设计创作，主要内容包括：本发明公开了一种红外辐射涂料及其制备方法,属于红外节能材料领域。红外辐射涂料,其主要制备原料按质量百分比为高炉渣90-95％、过渡金属氧化物A5-10％；制备原料还包括过渡金属氧化物B和高温粘结剂,所述过渡金属氧化物B的质量为高炉渣和过渡金属氧化物A总质量的5-10％,所述高温粘结剂的质量为高炉渣、过渡金属氧化物A和过渡金属氧化物B总质量的5-10％。本发明制备的红外辐射涂料,高温粘结性较好,软化温度不低于1400℃,综合发射率不低于0.9,其低波段发射率(1-5μm)不低于0.95,综合性能优异,本发明利用冶金固废为原料制备得到红外辐射涂料,生产成本低廉,可有效解决现有高温条件下红外辐射涂料辐射性能较差、使用成本较高的问题。(The invention discloses an infrared radiation coating and a preparation method thereof, belonging to the field of infrared energy-saving materials. The infrared radiation coating is prepared from 90-95% of blast furnace slag and 78-10% of transition metal oxide A5 by mass percent; the preparation raw materials also comprise a transition metal oxide B and a high-temperature binder, wherein the mass of the transition metal oxide B is 5-10% of the total mass of the blast furnace slag and the transition metal oxide A, and the mass of the high-temperature binder is 5-10% of the total mass of the blast furnace slag, the transition metal oxide A and the transition metal oxide B. The infrared radiation coating prepared by the invention has better high-temperature cohesiveness, the softening temperature is not lower than 1400 ℃, the comprehensive emissivity is not lower than 0.9, the low-band emissivity (1-5 mu m) is not lower than 0.95, and the comprehensive performance is excellent.)

1. The infrared radiation coating is characterized in that: the main preparation raw materials comprise 90-95% of blast furnace slag and 5-10% of transition metal oxide A by mass percent; the preparation raw materials also comprise a transition metal oxide B and a high-temperature binder, wherein the mass of the transition metal oxide B is 5-10% of the total mass of the blast furnace slag and the transition metal oxide A, and the mass of the high-temperature binder is 5-10% of the total mass of the blast furnace slag, the transition metal oxide A and the transition metal oxide B.

2. The infrared radiation paint of claim 1, wherein: the blast furnace slag is produced after blast furnace smelting by taking vanadium titano-magnetite as a raw material, and comprises the chemical components of 20-30% of CaO and SiO by mass percent₂19-32％，Al₂O₃13-17％，TiO₂6-31％，MgO 7-9％，MnO₂0.3-1.2%, FeO 1.2-1.9%, and inevitable impurities.

3. The infrared radiation paint of claim 1, wherein: the transition metal oxide A is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂One of (1); the transition metal oxide B is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂Except one kind of transition metal oxide A.

4. The infrared radiation paint of claim 1, wherein: the high-temperature binder is water glass, and the modulus is 2.0-2.5.

5. The preparation method of the infrared radiation coating is characterized by comprising the following steps:

a. mechanically crushing the blast furnace slag until the proportion of the blast furnace slag with the granularity of 200 meshes is more than or equal to 80 percent, mixing the blast furnace slag with the proportion of 90-95 percent and 5-10 percent of transition metal oxide A by mass percent, sintering the mixture at the temperature of 1000-1200 ℃, and cooling the mixture to obtain an intermediate product;

b. crushing the intermediate product A until the proportion of the intermediate product A with the granularity of-200 meshes is more than or equal to 80%, adding the transition metal oxide B according to 5-10% of the mass of the intermediate product A, fully mixing, sintering at 1300-1400 ℃ for 1-3h, cooling, crushing the cooled product to-300 meshes, and obtaining the infrared radiation coating powder;

c. and fully mixing the infrared radiation coating powder with a high-temperature binder and hot water to obtain the infrared radiation coating, wherein the addition amount of the high-temperature binder is 5-10% of the mass of the infrared radiation coating powder.

6. The method for preparing an infrared radiation paint according to claim 5, characterized in that: in the step a, the blast furnace slag is generated after blast furnace smelting by taking vanadium titano-magnetite as a raw material, and the blast furnace slag comprises 20-30% of CaO and SiO by mass percent₂19-32％，Al₂O₃13-17％，TiO₂6-31％，MgO 7-9％，MnO₂0.3-1.2%, FeO 1.2-1.9%, and inevitable impurities.

7. The method for preparing an infrared radiation paint according to claim 5, characterized in that: in the step a, the transition metal oxide A is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂One kind of (1).

8. The method for preparing an infrared radiation paint according to claim 5, characterized in that: in step B, the transition metal oxide B is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂Except one kind of transition metal oxide A.

9. The method for preparing an infrared radiation paint according to claim 5, characterized in that: in the step c, the high-temperature binder is water glass, and the modulus is 2.0-2.5.

Technical Field

The invention belongs to the field of infrared energy-saving materials, and relates to an infrared radiation coating and a preparation method thereof.

Background

The technological level of fuel furnaces in China has been widely developed since the improvement and the opening of the technological level, but the overall utilization rate of the fuel furnaces is still not high, the average thermal efficiency is only 30-45%, and is far lower than that of industrial furnaces in developed countries (more than 50%). However, the shortage of resources in China urgently needs to promote the advanced energy-saving technology of the industrial furnace and promote the technical progress of the industrial furnace, and particularly, the heat efficiency of the industrial furnace can be directly reflected on the cost of products, so that the competitiveness of the products is influenced, and therefore, the improvement and the improvement of the heat efficiency of the industrial furnace are important in the development of the industrial furnace industry.

The infrared radiation coating is a novel heat-resistant protective coating with infrared radiation capability, mainly plays a role in energy conservation and consumption reduction, is widely applied to the fields of industries such as metallurgy, petrifaction, ceramics, medicine and the like in China, can be directly sprayed or painted on the heating surfaces or the inner sides of furnace bodies of various industrial boilers, power station boilers, flame furnaces and the like, and can strengthen the radiation heat exchange between a heat source and the heating surfaces or the heating bodies so as to achieve the purposes of improving the heat utilization rate of the furnaces and saving energy. However, the existing high-emissivity infrared coating material is expensive, so that the cost of the infrared coating material applied to industrial furnaces on a large scale is very high, and the existing infrared radiation coating material has poor heat resistance, so that the research on the infrared radiation coating material with excellent performance and low production and use cost is urgently needed.

Disclosure of Invention

The invention aims to solve the technical problems of poor radiation performance and high use cost of the existing infrared radiation coating under the high-temperature condition.

The technical scheme adopted by the invention for solving the technical problems is as follows: the infrared radiation coating comprises 90-95% of blast furnace slag and 5-10% of transition metal oxide by mass percent; the preparation raw materials also comprise a transition metal oxide B and a high-temperature binder, wherein the mass of the transition metal oxide B is 5-10% of the total mass of the blast furnace slag and the transition metal oxide A, and the mass of the high-temperature binder is 5-10% of the total mass of the blast furnace slag, the transition metal oxide A and the transition metal oxide B.

The blast furnace slag is produced after blast furnace smelting by using vanadium titano-magnetite as a raw material, and comprises the chemical components of 20-30% of CaO and SiO by mass percent₂ 19-32％，Al₂O₃ 13-17％，TiO₂ 6-31％，MgO 7-9％，MnO₂0.3-1.2%, FeO 1.2-1.9%, and inevitablyThe impurities of (1).

The transition metal oxide A is CuO, CoO, or Cr₂O₃、MnO₂、ZrO₂One kind of (1).

The transition metal oxide B is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂Except one kind of transition metal oxide A.

The high-temperature binder is water glass, and the modulus is 2.0-2.5.

The preparation method of the infrared radiation coating comprises the following steps:

a. mechanically crushing the blast furnace slag until the proportion of the blast furnace slag with the granularity of 200 meshes is more than or equal to 80 percent, mixing the blast furnace slag with the proportion of 90-95 percent and 5-10 percent of transition metal oxide A by mass percent, sintering the mixture at the temperature of 1000-1200 ℃, and cooling the mixture to obtain an intermediate product;

b. crushing the intermediate product A until the proportion of the intermediate product A with the granularity of-200 meshes is more than or equal to 80%, adding the transition metal oxide B according to 5-10% of the mass of the intermediate product A, fully mixing, sintering at 1300-1400 ℃ for 1-3h, cooling, crushing the cooled product to-300 meshes, and obtaining the infrared radiation coating powder;

c. and fully mixing the infrared radiation coating powder with a high-temperature binder and hot water to obtain the infrared radiation coating, wherein the addition amount of the high-temperature binder is 5-10% of the mass of the infrared radiation coating powder.

In the step a, the blast furnace slag is generated after blast furnace smelting by taking vanadium titano-magnetite as a raw material, and the blast furnace slag comprises 20-30% of CaO and SiO by mass percent₂ 19-32％，Al₂O₃ 13-17％，TiO₂ 6-31％，MgO 7-9％，MnO₂0.3-1.2%, FeO 1.2-1.9%, and inevitable impurities.

In the step a, the transition metal oxide A is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂One kind of (1).

The transition metal oxide B is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂Except one kind of transition metal oxide A.

In the step c, the high-temperature binder is water glass, and the modulus is 2.0-2.5.

The invention has the beneficial effects that: the invention utilizes TiO in the blast furnace slag component₂CaO and the transition metal oxide are subjected to high-temperature solid-phase melting reaction at the temperature of 1000-1200 ℃ to obtain the perovskite composite oxide, so that the infrared radiation performance of the material can be greatly improved; secondly, by Al in the blast furnace slag component₂O₃、SiO₂MgO is synthesized into cordierite (Mg) in 1300-1400 ℃ high-temperature melting state₂Al₄Si₅O₁₈) And then the transition metal oxide is used for modifying the cordierite so that the cordierite has stronger corresponding characteristics of infrared radiation.

The preparation method of the invention utilizes the blast furnace slag active ingredient in the vanadium-titanium smelting process to mix with transition metal oxide, adopts two-step high-temperature solid-phase melting reaction to prepare hybrid cordierite and perovskite composite oxide, and simultaneously combines the control and coordination of high-temperature binder to prepare cordierite-perovskite crystal, namely infrared radiation coating, the crystal material has good heat resistance and high rate of generation, the softening temperature is not lower than 1400 ℃, the high-temperature cohesiveness is good, the comprehensive emissivity is not lower than 0.9, the low-band emissivity (1-5 mu m) is not lower than 0.95, the comprehensive performance is excellent, the infrared radiation coating is prepared by using metallurgical solid waste as raw material, the production cost is low, and the infrared radiation coating can be produced and applied in large scale.

Detailed Description

The technical solution of the present invention can be specifically implemented as follows.

The infrared radiation coating is prepared from 90-95% of blast furnace slag and 78-10% of transition metal oxide A5 by mass percent; the preparation raw materials also comprise a transition metal oxide B and a high-temperature binder, wherein the mass of the transition metal oxide B is 5-10% of the total mass of the blast furnace slag and the transition metal oxide A, and the mass of the high-temperature binder is 5-10% of the total mass of the blast furnace slag, the transition metal oxide A and the transition metal oxide B.

The preparation method of the infrared radiation coating comprises the following steps:

a. mechanically crushing the blast furnace slag until the proportion of the blast furnace slag with the granularity of 200 meshes is more than or equal to 80 percent, mixing the blast furnace slag with the proportion of 90-95 percent and 5-10 percent of transition metal oxide A by mass percent, sintering the mixture at the temperature of 1000-1200 ℃, and cooling the mixture to obtain an intermediate product;

b. crushing the intermediate product A until the proportion of the intermediate product A with the granularity of-200 meshes is more than or equal to 80%, adding the transition metal oxide B according to 5-10% of the mass of the intermediate product A, fully mixing, sintering at 1300-1400 ℃ for 1-3h, cooling, crushing the cooled product to-300 meshes, and obtaining the infrared radiation coating powder;

c. and fully mixing the infrared radiation coating powder with a high-temperature binder and hot water to obtain the infrared radiation coating, wherein the addition amount of the high-temperature binder is 5-10% of the mass of the infrared radiation coating powder.

In the step a, the blast furnace slag is generated after blast furnace smelting by taking vanadium titano-magnetite as a raw material, and the blast furnace slag comprises 20-30% of CaO and SiO by mass percent₂ 19-32％，Al₂O₃ 13-17％，TiO₂ 6-31％，MgO 7-9％，MnO₂0.3-1.2%, FeO 1.2-1.9%, and inevitable impurities.

In the step a, the transition metal oxide A is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂One kind of (1).

Perovskite type composite oxide ABO₃The inorganic non-metal material has unique physical and chemical properties, the A site is RE or alkali earth element ion, the B site is transition element ion, and the A site and the B site may be partially replaced with other metal ion of similar radius to maintain the crystal structure unchanged basically.

The invention adopts TiO in the blast furnace slag component₂CaO can generate CaTiO when being sintered for one time under the high temperature condition of 1000-1200 DEG C₃The crystal, the invention utilizes the metal ion of the transition metal oxide to react with CaTiO under the same high temperature condition₃The crystal reaction can replace B-site ions in the crystal to form the perovskite composite oxide. The perovskite composite oxide has a unique crystal structure, particularly a crystal defect structure and performance formed after doping, and is caused by introduction of impuritiesThe crystal lattice is distorted, the vibration absorption of the crystal lattice is enhanced, and the infrared radiation performance of the material can be greatly improved, especially the short wave band (1-5 mu m).

In the step B, the transition metal oxide B is CuO, CoO or Cr₂O₃、MnO₂、ZrO₂Except one transition metal oxide A, namely, the transition metal oxide A and the transition metal oxide B are different.

And the cordierite is a cyclic silicate mineral material, the crystal structure of the cordierite is an orthorhombic system, internal silicon-oxygen tetrahedrons are in a hexahydric ring shape and are arranged along the c axis to form a certain internal channel, and the internal channel has a larger space. Due to the untight crystal structure, ions inside the crystal structure are easy to generate non-simple harmonic vibration so as to distort the crystal lattice. Secondly, the non-compact structure is easily replaced by transition metal elements, further causes lattice distortion and enhances the absorption of lattice vibration. Therefore, it has a high infrared radiation capability. In addition, cordierite has the advantages of good thermal stability and small thermal expansion coefficient, and is used as a framework of chemical compositions of infrared radiation materials.

Al in the blast furnace slag component of the present invention₂O₃、SiO₂When MgO is sintered for the second time at 1300-1400 ℃, cordierite (Mg) can be synthesized in a high-temperature molten state₂Al₄Si₅O₁₈) Meanwhile, the added transition metal oxide can replace metal elements in cordierite, and the cordierite is modified under the high-temperature condition, so that the symmetry of the cordierite is poor, the dipole moment change is large when the crystal lattice vibrates, and the cordierite has strong corresponding infrared radiation characteristics.

The modulus of water glass is an important parameter of water glass and is generally between 1.5 and 3.5. The larger the modulus of the water glass is, the more insoluble the solid water glass is in water, n is 1, the solid water glass can be dissolved by warm water at all times, when n is increased, the solid water glass can be dissolved by hot water, and when n is more than 3, the solid water glass can be dissolved by steam with the pressure of more than 4 atmospheres. The larger the modulus of the water glass is, the more the silicon oxide content is, the viscosity of the water glass is increased, the water glass is easy to decompose and harden, and the binding power is increased. Therefore, in the step c, the high-temperature binder is preferably water glass, and the modulus is 2.0-2.5. The invention adopts the water glass with the modulus of 2.0-2.5, is for industrial large-scale preparation, the mixing by hot water is beneficial to large-scale preparation, the modulus is too low to be decomposed and hardened, the high-temperature caking property can be reduced, and the range of 2.0-2.5 is determined after tests. The medium silica component of the water glass further promotes the formation of heterocordierite-perovskite crystals at high temperatures in the furnace.

The technical solution and effects of the present invention will be further described below by way of practical examples.

Examples

The invention provides a group of examples for preparing infrared radiation coating by adopting the method of the invention, and the blast furnace slag adopted in the examples comprises the following chemical components in percentage by mass: CaO 20.2%, SiO₂ 27.1％，Al₂O₃ 16.4％，TiO₂26.9％，MgO 7.1％，MnO₂0.8%, FeO 1.0%, and inevitable impurities.

The specific experimental steps for preparing the infrared radiation coating are as follows:

a. after the blast furnace slag is mechanically crushed to the proportion of more than or equal to 80 percent of the granularity of 200 meshes, 90 percent of the blast furnace slag and 10 percent of Cr are mixed according to the mass percentage₂O₃Uniformly mixing, placing into a muffle furnace, roasting at the high temperature of 1100 ℃, preserving heat for 1h, cooling with the furnace, and taking out to obtain a sample A;

b. crushing the sample A until the granularity of-200 meshes is more than or equal to 80%, uniformly mixing 90% of the sample A and 10% of CoO according to the mass percentage, putting the mixture into a muffle furnace, roasting at the high temperature of 1400 ℃, preserving heat for 1h, cooling along with the furnace, taking out the mixture, and crushing the mixture to-300 meshes to obtain infrared radiation powder;

c. mixing 90% of infrared radiation powder and 10% of high-temperature binder according to the mass percentage, and adding hot water for stirring to obtain the infrared radiation coating.

The infrared radiation powder and the coating prepared in the examples are detected as follows:

1. the infrared radiation powder prepared by the embodiment is detected by a melting point tester and an emissivity tester, and the result is as follows: the softening temperature is larger than 1450 ℃, the average emissivity in a 1-22 mu m wave band is 0.91, and the emissivity in a 1-5 mu m short wave band is 0.96.

2. The infrared radiation coating prepared in the example was applied to the surface of a substrate and then tested:

(1) coating the infrared radiation coating on the bottom of a 1L beaker filled with 500ml of water, and then carrying out flame heating on the bottom of the beaker;

(2) coating infrared radiation paint on 1 polished 300mm × 300mm refractory brick, putting the refractory brick into a muffle furnace, heating the refractory brick to 1000 ℃ from normal temperature, cooling the refractory brick along with the furnace, repeating the process for 25 times, and observing the appearance of the coating.

Meanwhile, the present invention prepared paints according to the methods of patent nos. CN101302365A and CN155279A, and also conducted the experiments of (1) and (2), and comparative analysis was conducted as comparative examples, and the results of the experiments are shown in table 1.

TABLE 1 Infrared radiation coatings test results

As can be seen from table 1, the time required for heating water to boiling in the beaker coated with the infrared radiation coating prepared in the example of the present invention is 27% faster than that in the beaker without coating, and 12.5% faster than that in the CN 101302365A-sample 2 with the shortest time in the comparative example, so that the infrared radiation coating prepared by the method of the present invention has excellent energy saving and consumption reduction properties; after the infrared radiation coating disclosed by the embodiment of the invention is subjected to 25 thermal shock experiments, the high-temperature cohesiveness is good, the heat-resistant temperature is 1480 ℃, the average emissivity is 0.91, and the comprehensive performance is superior to that of similar products.