Inorganic mineral fiber based on water-quenched slag and preparation method thereof

Abstract

The present invention provides an inorganic mineral fiber based on water-quenched slag and a preparation method thereof, which belongs to the field of inorganic mineral fiber materials. The present invention synthesizes titanium oxide powder by tetrabutyl titanate, and composites it with lanthanum oxide, utilizes synergistic effect to improve the high temperature resistance and corrosion resistance of the fiber, improves the thermal stability and structural integrity of lanthanum oxide-titanium oxide composite powder by calcination treatment, and simultaneously adopts plasma treatment and silane coupling agent modification to optimize the dispersibility and interfacial bonding force of the powder, thereby enhancing the mechanical and heat resistance of the fiber. In addition, phosphate and zirconium oxide are introduced to coat zinc oxide, so that zinc oxide shows better fluidity and dispersibility during high temperature melting; the fiber surface is treated by magnesium chloride and cerium chloride to improve its corrosion resistance and high temperature stability; microwave heating technology improves the surface treatment efficiency, avoids the thermal degradation problem of traditional methods, and ensures the long-term stability and performance of the fiber in harsh environments.

Description

Technical Field

[0001] The invention belongs to the technical field of inorganic mineral fiber materials and relates to an inorganic mineral fiber based on water-quenched slag and a preparation method thereof. Background Art

[0002] Water-quenched slag is a common by-product in the metallurgical industry, usually produced by the combination of high-temperature smelting and rapid cooling of molten metal during metal smelting. The chemical composition of water-quenched slag is very complex, usually containing a variety of metal oxides, silicates and other inorganic mineral components, which give water-quenched slag good mineral properties and endow it with potential application value in industries such as building materials, ceramics and metallurgy.

[0003] With the continuous improvement of environmental protection requirements and the demand for sustainable utilization of resources, water-quenched slag as a potential raw material has gradually received more attention. Its use can effectively reduce the accumulation and disposal pressure of industrial waste and reduce pollution to the environment. In addition, the recycling of water-quenched slag can also reduce the production costs of enterprises and promote the recycling of resources.

[0004] The use of water-quenched slag to prepare inorganic mineral fibers has the following advantages: First, as an industrial by-product, water-quenched slag itself has a high mineral content and can provide rich raw materials for inorganic mineral fibers. Through appropriate process flow, water-quenched slag can be converted into inorganic mineral fibers with good performance. Secondly, the recycling of water-quenched slag is in line with the concept of modern environmental protection and green manufacturing, which can effectively reduce the accumulation of industrial waste and avoid environmental pollution.

[0005] However, the existing water-quenched slag has some shortcomings in the process of preparing inorganic fibers: First, the uneven particle morphology and distribution of the water-quenched slag may lead to insufficient strength and toughness of its fibers. In the actual fiber production process, the uneven distribution of particles in the water-quenched slag and the complexity of the particle morphology may have a negative impact on the mechanical properties of the fiber. Due to the complex composition of the water-quenched slag and the large difference in particle size, these particles may induce large stress concentration in the fiber, especially during tension or compression. This stress concentration can cause local rupture or deformation of the fiber, thereby reducing its overall tensile and compressive strength, which limits the application of water-quenched slag-based inorganic mineral fibers under some high-strength and load conditions.

[0006] Secondly, the thermal conductivity of water-quenched slag is relatively high, which may lead to thermal runaway in high-temperature environments, thus affecting the service life of the fiber. Certain metal oxides and silicate components in water-quenched slag have high thermal conductivity, which means that water-quenched slag-based inorganic mineral fibers tend to accumulate excessive heat in high-temperature environments, leading to local overheating. This overheating phenomenon may trigger thermal degradation of the fiber, affecting its long-term stability, especially in applications such as high-temperature insulation or high-temperature environments. Summary of the invention

[0007] In view of the above problems, the purpose of the present invention is to provide an inorganic mineral fiber based on water-quenched slag and a preparation method thereof. The present invention synthesizes titanium oxide powder by tetrabutyl titanate and adds lanthanum oxide to titanium oxide for compounding, and utilizes the synergistic effect to improve the high temperature resistance and corrosion resistance of the fiber; improves the thermal stability and structural integrity of the lanthanum oxide-titanium oxide composite powder by calcination treatment; optimizes the dispersibility and interfacial bonding force of the composite powder by plasma treatment and silane coupling agent modification, thereby improving the mechanical and heat resistance of the fiber. In addition, phosphate and zirconium oxide are introduced to coat zinc oxide to enhance its oxidation resistance and chemical stability. The modified zinc oxide has better fluidity and dispersibility during high-temperature melting, which is beneficial to improving the performance of the fiber. The fiber is surface treated with magnesium chloride and cerium chloride to further improve its water resistance, corrosion resistance, oxidation resistance and high temperature stability. Microwave heating technology improves the efficiency of surface treatment and avoids the thermal degradation problem of traditional methods, thereby ensuring the long-term stability and performance of the fiber in harsh environments.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a method for preparing inorganic mineral fibers based on water-quenched slag, the method for preparing inorganic mineral fibers based on water-quenched slag comprising:

[0010] S1: preparing a tetrabutyl titanate ethanol solution, adding citric acid and stirring under nitrogen protection to obtain a reaction solution A; preparing a lanthanum nitrate ethanol solution and adding citric acid and stirring to obtain a reaction solution B, adding the reaction solution B dropwise to the reaction solution A at a constant temperature, adjusting the pH to obtain a reaction solution C, stirring and reacting to obtain a first sol solution, vacuum drying and calcining to obtain a lanthanum oxide-titanium oxide composite powder;

[0011] S2: Plasma-treating the lanthanum oxide-titanium oxide composite powder to obtain surface-modified lanthanum oxide-titanium oxide composite powder; dispersing the surface-modified lanthanum oxide-titanium oxide composite powder in an ethanol / water mixed solution, adding a silane coupling agent, stirring the reaction, filtering, washing, and vacuum drying to obtain a modified lanthanum oxide-titanium oxide composite powder;

[0012] S3: Dispersing zinc oxide powder in phosphoric acid solution to obtain zinc oxide dispersion, stirring, adjusting pH to obtain reaction solution D, stirring reaction, filtering, washing, and drying to obtain phosphate-coated zinc oxide; dispersing phosphate-coated zinc oxide in zirconium oxychloride solution to obtain reaction solution E, adjusting pH at constant temperature to obtain reaction solution F, stirring reaction, suction filtering, washing, drying, and then calcining to obtain double-layer coated modified zinc oxide;

[0013] S4: mixing water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide, ball milling to obtain a mixed powder, placing the mixed powder in a high-temperature melting furnace to melt to obtain a molten liquid, conveying the molten liquid to a fiber blowing device, blowing it with high-pressure air to obtain a first pretreated fiber, and heat-treating annealing and cooling to obtain a pretreated fiber;

[0014] S5: adding magnesium chloride and cerium chloride into deionized water to obtain a first modified solution, adding glycerol, stirring and adjusting the pH to obtain a modified solution; immersing the pretreated fiber in the modified solution, placing it in a microwave reactor for treatment, filtering, washing and drying after natural cooling to obtain an inorganic mineral fiber based on water-quenched slag.

[0015] As a preferred technical solution of the present invention, in step S1, the volume ratio of tetrabutyl titanate to ethanol in the tetrabutyl titanate ethanol solution is 1:3-4, for example, it can be 1:3, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8, 1:3.9 or 1:4, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0016] In some optional embodiments, the molar ratio of citric acid to tetrabutyl titanate in the reaction solution A is 2-3:1, for example, it can be 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0017] In some optional embodiments, the concentration of the lanthanum nitrate ethanol solution is 0.2-0.3M, for example, it can be 0.20M, 0.21M, 0.22M, 0.23M, 0.24M, 0.25M, 0.26M, 0.27M, 0.28M, 0.29M or 0.30M, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0018] In some optional embodiments, the molar ratio of citric acid to lanthanum nitrate in the reaction solution B is 2-3:1, for example, it can be 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0019] In some optional embodiments, the reaction liquid B is added dropwise to the reaction liquid A at a constant temperature of 50-60°C, for example, it can be 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] In some optional embodiments, the dripping speed of the reaction liquid B into the reaction liquid A is 2-3 mL / min, for example, it can be 2.0 mL / min, 2.1 mL / min, 2.2 mL / min, 2.3 mL / min, 2.4 mL / min, 2.5 mL / min, 2.6 mL / min, 2.7 mL / min, 2.8 mL / min, 2.9 mL / min or 3.0 mL / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] In some optional embodiments, the molar ratio of lanthanum nitrate to tetrabutyl titanate is 0.1-0.2:1, for example, it can be 0.10:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.16:1, 0.17:1, 0.18:1, 0.19:1 or 0.20:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0022] In some optional embodiments, the concentration of the nitric acid solution is 0.5-0.6M, for example, it can be 0.50M, 0.51M, 0.52M, 0.53M, 0.54M, 0.55M, 0.56M, 0.57M, 0.58M, 0.59M or 0.60M, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] In some optional embodiments, nitric acid solution is used to adjust the pH of reaction solution A to 2-3, for example, it can be 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0024] In some optional embodiments, the stirring reaction time of the reaction liquid C is 4-5h, for example, it can be 4.0h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] In some optional embodiments, the vacuum drying temperature of the first sol liquid is 70-80°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0026] In some optional embodiments, the vacuum drying time of the first sol liquid is 12-14 hours, for example, it can be 12.0 hours, 12.2 hours, 12.4 hours, 12.6 hours, 12.8 hours, 13.0 hours, 13.2 hours, 13.4 hours, 13.6 hours, 13.8 hours or 14.0 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0027] In some optional embodiments, the calcination temperature is 700-750°C, for example, it can be 700°C, 705°C, 710°C, 715°C, 720°C, 725°C, 730°C, 735°C, 740°C, 745°C or 750°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0028] In some optional embodiments, the calcination time is 2-3h, for example, it can be 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0029] As a preferred technical solution of the present invention, in step S2, the power of the plasma treatment of the lanthanum oxide-titanium oxide composite powder is 100-200 W, for example, it can be 100 W, 110 W, 120 W, 130 W, 140 W, 150 W, 160 W, 170 W, 180 W, 190 W or 200 W, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0030] In some optional embodiments, the oxygen flow rate for plasma treatment of the lanthanum oxide-titanium oxide composite powder is 20-30 mL / min, for example, it can be 20 mL / min, 21 mL / min, 22 mL / min, 23 mL / min, 24 mL / min, 25 mL / min, 26 mL / min, 27 mL / min, 28 mL / min, 29 mL / min or 30 mL / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] In some optional embodiments, the plasma treatment time of the lanthanum oxide-titanium oxide composite powder is 10-20 min, for example, it can be 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0032] In some optional embodiments, the volume ratio of ethanol to water in the ethanol / water mixed solution is 9:1-7:3, for example, it can be 9:1, 8:2 or 7:3, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] In some optional embodiments, the mass fraction of the surface modified lanthanum oxide-titanium oxide composite powder in the ethanol / water mixed solution is 5-6%, for example, it can be 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9% or 6.0%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0034] In some optional embodiments, the silane coupling agent is KH570, and the amount of the silane coupling agent is 2-3% of the mass of the surface-modified lanthanum oxide-titanium oxide composite powder, for example, it can be 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3.0%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] In some optional embodiments, the stirring reaction temperature is 70-80°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] In some optional embodiments, the stirring reaction time is 3-4h, for example, it can be 3.0h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h or 4.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0037] As a preferred technical solution of the present invention, in step S3, the concentration of the phosphoric acid solution is 0.1-0.2M, for example, it can be 0.10M, 0.11M, 0.12M, 0.13M, 0.14M, 0.15M, 0.16M, 0.17M, 0.18M, ​​0.19M or 0.20M, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0038] In some optional embodiments, the mass ratio of the zinc oxide powder dispersed in the phosphoric acid solution is 1:15-20, for example, it can be 1:15, 1:15.5, 1:16, 1:16.5, 1:17, 1:17.5, 1:18, 1:18.5, 1:19, 1:19.5 or 1:20, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0039] In some optional embodiments, the concentration of the sodium hydroxide solution is 0.1-0.15M, for example, it can be 0.10M, 0.105M, 0.11M, 0.115M, 0.12M, 0.125M, 0.13M, 0.135M, 0.14M, 0.145M or 0.15M, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0040] In some optional embodiments, sodium hydroxide solution is used to adjust the pH of the zinc oxide dispersion to 5-6, for example, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9 or 6.0, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0041] In some optional embodiments, the stirring reaction time of the reaction liquid D is 4-5h, for example, it can be 4.0h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0042] In some optional embodiments, the concentration of the zirconium oxychloride solution is 0.2-0.3M, for example, it can be 0.20M, 0.21M, 0.22M, 0.23M, 0.24M, 0.25M, 0.26M, 0.27M, 0.28M, 0.29M or 0.30M, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0043] In some optional embodiments, the mass ratio of the phosphate-coated zinc oxide dispersed in the zirconium oxychloride solution is 1:10-15, for example, it can be 1:10, 1:10.5, 1:11, 1:11.5, 1:12, 1:12.5, 1:13, 1:13.5, 1:14, 1:14.5 or 1:15, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0044] In some optional embodiments, the pH of the reaction solution E is adjusted with aqueous ammonia at a constant temperature of 50-60°C, for example, it can be 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] In some optional embodiments, the concentration of the ammonia water is 2-3M, for example, it can be 2.0M, 2.1M, 2.2M, 2.3M, 2.4M, 2.5M, 2.6M, 2.7M, 2.8M, 2.9M or 3.0M, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0046] In some optional embodiments, the pH of the reaction solution E is adjusted to 7-8 with aqueous ammonia, for example, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9 or 8.0, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0047] In some optional embodiments, the reaction liquid F is stirred for 2-3 hours, for example, 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3.0 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0048] In some optional embodiments, the calcination temperature is 500-550°C, for example, it can be 500°C, 505°C, 510°C, 515°C, 520°C, 525°C, 530°C, 535°C, 540°C, 545°C or 550°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0049] In some optional embodiments, the calcination time is 2-3h, for example, it can be 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0050] As a preferred technical solution of the present invention, in step S4, the temperature of melting the mixed powder is 1450-1500°C, for example, it can be 1450°C, 1455°C, 1460°C, 1465°C, 1470°C, 1475°C, 1480°C, 1485°C, 1490°C, 1495°C or 1500°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0051] In some optional embodiments, the melting time of the mixed powder is 50-60 min, for example, it can be 50 min, 51 min, 52 min, 53 min, 54 min, 55 min, 56 min, 57 min, 58 min, 59 min or 60 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0052] In some optional embodiments, the pressure of high-pressure air blowing of the molten liquid is 0.6-0.8 MPa, for example, it can be 0.60 MPa, 0.62 MPa, 0.64 MPa, 0.66 MPa, 0.68 MPa, 0.70 MPa, 0.72 MPa, 0.74 MPa, 0.76 MPa, 0.78 MPa or 0.80 MPa, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0053] In some optional embodiments, the temperature of the heat treatment of the first pretreated fiber is 600-650°C, for example, it can be 600°C, 605°C, 610°C, 615°C, 620°C, 625°C, 630°C, 635°C, 640°C, 645°C or 650°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0054] In some optional embodiments, the time for heat treatment of the first pretreated fiber is 10-20 min, for example, it can be 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0055] As a preferred technical solution of the present invention, in step S5, the molar ratio of magnesium chloride to cerium chloride is 1-2:1, for example, it can be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0056] In some optional embodiments, the solid-liquid ratio in the first modified liquid is 1:10-15, for example, it can be 1:10, 1:10.5, 1:11, 1:11.5, 1:12, 1:12.5, 1:13, 1:13.5, 1:14, 1:14.5 or 1:15, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0057] In some optional embodiments, the amount of glycerol added is 5-6% of the mass of the first modified liquid, for example, it can be 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9% or 6.0%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0058] In some optional embodiments, after adding glycerol to the first modified liquid and stirring, the pH is adjusted to 6-7 with ammonia water, for example, it can be 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9 or 7.0, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0059] In some optional embodiments, the mass ratio of the pretreated fiber to the modified solution is 1:20-25, for example, it can be 1:20, 1:20.5, 1:21, 1:21.5, 1:22, 1:22.5, 1:23, 1:23.5, 1:24, 1:24.5 or 1:25, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0060] In some optional embodiments, the power of the microwave reactor is 500-600 W, for example, 500 W, 510 W, 520 W, 530 W, 540 W, 550 W, 560 W, 570 W, 580 W, 590 W or 600 W, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0061] In some optional embodiments, the microwave reactor treatment time is 5-6 min, for example, it can be 5 min, 5.1 min, 5.2 min, 5.3 min, 5.4 min, 5.5 min, 5.6 min, 5.7 min, 5.8 min, 5.9 min or 6 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0062] In a second aspect, the present invention provides an inorganic mineral fiber based on water-quenched slag, wherein the mass ratio of the water-quenched slag, the modified lanthanum oxide-titanium oxide composite powder and the double-layer coated modified zinc oxide is (80-90): (5-10): (5-10).

[0063] The present invention uses industrial solid waste water-quenched slag as the main material to prepare inorganic mineral fibers. As an industrial by-product, water-quenched slag is widely derived from the production processes of metallurgy, steel, mining and other industries. Its main components include oxides such as calcium oxide, silicon dioxide, and aluminum oxide. Water-quenched slag usually exhibits a high vitrification rate and strong reactivity, which makes it have important advantages in the process of preparing inorganic mineral fibers.

[0064] The internal structure of water-quenched slag is usually amorphous, or partially has crystalline characteristics. The amorphous structure means that there is no obvious long-range ordered arrangement inside the water-quenched slag, so it has a high degree of vitrification and presents relatively uniform physical properties. At high temperatures, water-quenched slag can form a stable silicate melt during the melting process, and this property provides good melting properties for subsequent fiber drawing and formation. At the same time, some active components in the water-quenched slag, such as calcium oxide and silicon dioxide, can react chemically with other components in a high-temperature environment to generate new silicate phases, aluminate phases or other oxide phases, further enhancing the structural stability and high-temperature resistance of the composite material.

[0065] As a fiber matrix material, the application of water-quenched slag has significant advantages. First, water-quenched slag is widely available and low-cost, which makes it a sustainable green material that meets the current needs of environmental protection and energy conservation and emission reduction. By compounding water-quenched slag with other modified powders such as titanium oxide and lanthanum oxide, the performance of water-quenched slag can be effectively improved, and the mechanical properties, thermal stability and antioxidant capacity of the final fiber can be improved.

[0066] The present invention uses tetrabutyl titanate as a raw material to synthesize titanium oxide powder. Tetrabutyl titanate is a common titanium source compound. In its molecular structure, titanium atoms coordinate with four butoxy groups to form a tetrahedral molecular structure. This structure enables tetrabutyl titanate to exhibit high reactivity during the reaction process. In a suitable solvent medium, tetrabutyl titanate can exchange butoxy groups with water molecules through a hydrolysis reaction to generate hydrated titanium oxide. During the hydrolysis process, the hydrated titanium oxide first exists in the form of colloid or sol. As time goes by, after further polycondensation reaction, the titanium source is gradually converted into amorphous titanium oxide.

[0067] Titanium oxide has excellent thermal stability, which enables it to maintain good structural integrity in high temperature environments, which is especially important for applications in high temperature environments; titanium oxide also has strong mechanical properties and can significantly enhance the mechanical properties of composite materials, so it is widely used as a reinforcing phase material in various composite materials. In addition, titanium oxide has high chemical inertness and can remain stable in various harsh chemical environments. It is not easy to oxidize or other chemical reactions, which is of great significance for improving the corrosion resistance and long-term stability of the material.

[0068] The surface of titanium oxide also has abundant active hydroxyl groups, which makes it possible to compound or modify it with other materials. In inorganic mineral fibers, titanium oxide can not only improve the strength and thermal stability of the fiber by compounding with other inorganic powders (such as lanthanum oxide, aluminum oxide, etc.), but also enhance its elastic modulus and high temperature resistance. The stability of titanium oxide in high temperature environments, especially its property of not decomposing or losing function at high temperatures, can effectively enhance the high temperature performance of inorganic mineral fibers, enabling them to be used in more harsh industrial environments.

[0069] At the nanoscale, titanium oxide has a larger specific surface area, which enables it to more effectively fill the microscopic gaps inside the fiber when used as a filling material in inorganic mineral fibers. In this way, titanium oxide helps to increase the density of the fiber, thereby significantly enhancing its crack resistance and overall mechanical properties. In addition, titanium oxide powder can increase the interfacial bonding force of the material and promote the synergistic effect between different components, thereby further improving the performance of the composite material.

[0070] The present invention introduces lanthanum oxide and titanium oxide to enhance the performance of the composite material by utilizing their synergistic effect. Lanthanum oxide is an important rare earth metal oxide, which has a high melting point, a relatively large ionic radius and a strong ionic polarization ability. These characteristics of lanthanum oxide enable it to form a stable composite oxide with other components at high temperatures, improve the high temperature performance of the material, especially the chemical stability and corrosion resistance under high temperature environment. The large ionic radius of lanthanum oxide enables it to be effectively compounded with different metal oxides, improving the mechanical properties and heat resistance of the material.

[0071] Lanthanum oxide is an alkaline oxide with good chemical corrosion resistance. It can withstand corrosion from a variety of acidic or alkaline media at high temperatures and exhibits excellent chemical stability. This allows it to have a longer service life in high-temperature environments and can effectively prevent the material from being corroded by chemical substances. Its introduction into composite materials can also regulate the crystal structure of the composite material and prevent excessive grain growth, thereby effectively inhibiting brittle fracture of the material during high temperature or thermal shock cycles. Especially under high temperature conditions, lanthanum oxide can significantly enhance the thermal shock resistance and thermal fatigue resistance of the material by limiting the growth of grains.

[0072] In addition, lanthanum oxide can change the crystal structure of titanium oxide and adjust its electronic structure by forming a solid solution with titanium oxide, thereby improving the thermal stability and mechanical properties of the composite material. For example, the incorporation of lanthanum oxide can change the lattice distortion of titanium oxide, thereby improving its resistance to thermal expansion and maintaining high stability at high temperatures. This effect enables the composite material to maintain good mechanical properties and structural integrity under extremely high temperature conditions.

[0073] Calcination can effectively remove organic components in composite materials. After high-temperature treatment, organic components will decompose and volatilize under high heat energy, thereby removing these unstable organic impurities. This process not only helps to improve the purity of the material, but also provides more ideal conditions for subsequent solid-phase reactions.

[0074] During the calcination process, the solid phase reaction between lanthanum oxide and titanium oxide will be activated, causing the two to diffuse and chemically combine between crystals, and finally form a stable composite oxide. Through high-temperature calcination, lanthanum oxide and titanium oxide can interact at the molecular level to form a composite phase with higher thermal and chemical stability. This composite phase can not only improve the overall performance of the material, but also enhance the structural integrity of the material, preventing the material from decomposing or degrading under high temperature or external stress.

[0075] In addition, calcination can significantly improve the crystallinity of the composite powder. At high temperatures, the crystal structure in the composite material will undergo a certain degree of rearrangement and grain growth, thereby improving the order and crystallinity of the crystal. This process of improving crystallinity not only helps to enhance the structural stability of the material, but also significantly improves the mechanical properties of the material, such as hardness, compressive strength and crack resistance, making it perform better in practical applications.

[0076] Plasma treatment bombards the powder surface with high-energy particles, excites surface atoms or molecules, breaks existing chemical bonds, and generates new chemically active sites. These active sites are usually oxygen- or nitrogen-containing functional groups such as hydroxyl, carboxyl or nitrogen groups. These functional groups can react chemically with the silane groups in the silane coupling agent, thereby increasing the reactivity. Plasma treatment can also increase the surface energy of the powder, especially the hydrophilicity, which helps to improve the affinity of the surface with aqueous solvents or silane coupling agent solutions. During plasma bombardment, organic pollutants or oxides attached to the powder surface are effectively removed and the powder surface is cleaned; at the same time, the atoms or molecules on the powder surface will be activated, causing the original low surface energy to become a higher surface energy, thereby improving the reactivity of the powder surface. The silanol groups in the silane coupling agent can more easily undergo hydrolysis and condensation reactions with the hydroxyl or other functional groups on the powder surface to form a strong chemical bond.

[0077] The surface of lanthanum oxide-titanium oxide composite powder was modified by silane coupling agent KH570 to optimize its performance in composite materials. KH570 is a silane coupling agent containing aminomethyl acryloyloxy groups, and its molecular structure contains both organic functional groups and inorganic silane groups. Silane groups can combine with hydroxyl groups on the surface of inorganic oxides through hydrolysis reactions to form stable silicon-oxygen bonds, thereby ensuring good bonding between the powder and the matrix material. The organic functional group part of KH570 is mainly aminomethyl acryloyloxy groups, which can interact with organic groups in polymers or matrix materials through chemical reactions to improve the compatibility and dispersibility of composite materials.

[0078] During the surface modification process, KH570 is first hydrolyzed in water or alcohol solution to generate silanol. These silanol molecules will undergo condensation reaction with the hydroxyl groups on the surface of the lanthanum oxide-titanium oxide composite powder to form silicon-oxygen bonds, firmly fixing the silane groups on the powder surface, thereby enhancing the chemical bonding between the powder and the matrix material. This process can significantly improve the surface properties of the powder, making its surface more affinity, thereby improving the interfacial adhesion and stability between the powder and the matrix.

[0079] The introduction of organic segments improves the dispersibility of powders in solution or molten state by reducing the energy of the powder surface. Improving dispersibility helps to evenly distribute the powder in the composite material and avoids the performance degradation caused by powder agglomeration or aggregation. Especially in the high-temperature melting process, good dispersibility can ensure that the lanthanum oxide-titanium oxide composite powder is evenly distributed in the water-quenched slag matrix, so that the fiber can obtain a more uniform structure during the molding process, avoiding the defects caused by powder aggregation and improving the mechanical properties of the fiber.

[0080] The modified lanthanum oxide-titanium oxide composite powder exhibits better fluidity and dispersibility in a high-temperature molten state, enabling it to be better integrated into the matrix material during the preparation of the composite material, and the mechanical properties and heat resistance of the final fiber product are improved. The powder is evenly distributed during the composite process, which can also avoid the attenuation of physical properties caused by particle agglomeration, ensuring that the fiber material has good crack resistance, oxidation resistance and thermal stability under high temperature conditions, thereby greatly extending its service life and improving its stability at high temperatures.

[0081] The synergistic effect of plasma treatment and chemical modification of silane coupling agent makes the powder surface not only have high chemical reactivity, but also maintain good interfacial compatibility, thereby effectively improving the dispersion of powder in the matrix. Since the powder surface has both high reactivity and strong binding force with the matrix material, the powder can be evenly distributed under high temperature or high shear environment, avoiding the occurrence of powder agglomeration. This not only improves the mechanical properties of the composite material, but also ensures the stability of the material in long-term use. Especially in complex processing processes or high temperature environments, the modified powder can maintain its stable dispersion state, further enhancing the performance of the final composite material.

[0082] Zinc oxide is introduced and modified in the present invention. Zinc oxide is a wide bandgap semiconductor material with a hexagonal wurtzite structure, and has excellent photocatalytic properties, chemical stability, thermal stability and antibacterial properties. The introduction of zinc oxide can give the material good antibacterial properties and heat resistance. However, although zinc oxide has good thermal stability at high temperatures, its large specific surface area easily leads to agglomeration, which in turn affects its dispersibility and performance stability. Therefore, in order to avoid agglomeration, it needs to be modified by a coating layer.

[0083] In the present invention, phosphate is used to coat zinc oxide. Phosphate forms a uniform protective layer on the surface of zinc oxide through precipitation reaction, which can significantly improve the dispersibility of zinc oxide and prevent it from agglomerating in the matrix. The passivation effect of the phosphate coating layer can effectively reduce the exposure of active sites on the surface of zinc oxide, thereby inhibiting its chemical reaction under high temperature or strong oxidizing environment. Through phosphate coating, the thermal stability and chemical inertness of zinc oxide are significantly improved, making it more stable in the water-quenched slag matrix, and better maintaining its antibacterial and other functional properties.

[0084] In addition, the present invention also introduces zirconium oxide to further coat the zinc oxide. Through the decomposition reaction of zirconium oxychloride and the precipitation reaction caused by adjusting the pH value of ammonia water, a stable zirconium oxide coating can be formed on the surface of zinc oxide. The zirconium oxide coating layer can not only further enhance the oxidation resistance of zinc oxide, but also improve its interface compatibility with the matrix material. The double-layer coating structure of phosphate and zirconium oxide forms a stable protective barrier on the surface of zinc oxide, which significantly improves the heat resistance and chemical corrosion resistance of zinc oxide and its long-term stability in high temperature and harsh environments.

[0085] The dual protective effects of phosphate-coated zinc oxide and zirconium oxychloride coating can significantly enhance the oxidation resistance and chemical stability of zinc oxide. The phosphate layer provides the first layer of protection for zinc oxide, while the zirconium oxychloride layer further enhances its compatibility with the matrix, ensuring that zinc oxide can be stably present during the melting process and evenly distributed in the fiber.

[0086] In the present invention, magnesium chloride and cerium chloride are used to perform surface treatment on the prepared pretreated fiber to improve various properties of the fiber. Magnesium chloride provides magnesium ions during the surface treatment process, and the magnesium ions can react with the functional groups on the fiber surface to form a stable magnesium salt protective film. This magnesium salt layer can not only significantly improve the water resistance of the fiber, but also effectively improve its corrosion resistance. The formation of the magnesium salt layer can isolate the contact between water and other corrosive substances and the fiber matrix, thereby extending the service life of the fiber, and is particularly suitable for harsh environmental conditions, such as humid or acidic and alkaline environments.

[0087] In addition, cerium chloride, as a rare earth metal salt, can provide cerium ions during the surface treatment process. Cerium ions can effectively capture and neutralize free radicals and oxidizing species on the fiber surface and in the surrounding environment through its reversible conversion between tetravalent and trivalent states, thereby preventing the aging and degradation of the fiber under high temperature or oxidative environment. The introduction of cerium ions can not only improve the antioxidant properties of the fiber surface, but also enhance the stability of the fiber in high temperature, light and oxidative atmosphere, further extending its service life.

[0088] In order to improve the efficiency of the surface treatment process, the present invention adopts microwave reaction technology. Microwave reaction can quickly heat the reaction system in a short time, and has the advantages of uniform heating, high reaction rate, and high energy utilization. Through microwave heating, the modifier can be quickly activated and evenly deposited on the fiber surface, thereby forming a uniform modified layer. Microwave heating can also avoid the problem of thermal degradation of the fiber caused by excessively high temperature or excessively long heating in traditional heating methods. By accurately controlling the temperature and time of the microwave heating process, thermal damage to the fiber surface can be effectively avoided, maintaining its original physical properties, while ensuring that the surface modifier forms a strong chemical bond on the fiber surface, thereby improving the overall performance of the fiber.

[0089] Compared with the prior art, the present invention has the following beneficial effects:

[0090] (1) Using water-quenched slag to prepare inorganic mineral fibers to achieve the recycling of water-quenched slag, effectively reducing the accumulation of industrial waste, and complying with the concepts of modern environmental protection and green manufacturing;

[0091] (2) Synthesizing titanium oxide powder through tetrabutyl titanate and adding lanthanum oxide to titanium oxide composite, using their synergistic effect to improve the high temperature resistance and corrosion resistance of the fiber;

[0092] (3) Phosphate and zirconium oxide are introduced to coat zinc oxide to enhance its oxidation resistance and chemical stability. The modified zinc oxide has better fluidity and dispersibility during high-temperature melting, which is beneficial to improving the heat resistance and chemical stability of the fiber;

[0093] (4) The fiber is surface treated with magnesium chloride and cerium chloride to further improve its water resistance, corrosion resistance, oxidation resistance and high temperature stability;

[0094] (5) The efficiency of surface treatment is improved by microwave heating technology, avoiding the thermal degradation problem of traditional methods, thereby ensuring the long-term stability and performance of the fiber in harsh environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 A high-resolution transmission electron micrograph of the lanthanum oxide-titanium oxide composite powder provided in Example 1 of the present invention;

[0096] Figure 2 This is a scanning electron microscope image of the pretreated fiber provided in Example 1 of the present invention;

[0097] Figure 3 This is a scanning electron microscope image of the inorganic mineral fiber based on water-quenched slag provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0098] The technical solution of the present invention is described in detail below in conjunction with specific embodiments and their accompanying drawings. The embodiments recorded herein are specific embodiments of the present invention, which are used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary and should not be construed as limitations on the embodiments of the present invention and the scope of protection of the present invention. In addition to the embodiments recorded herein, those skilled in the art can also adopt other obvious technical solutions based on the contents disclosed in the claims of this application and its specification, including technical solutions that adopt any obvious replacements and modifications to the embodiments recorded herein.

[0099] The chemical reagents used in the examples and comparative examples of the present invention are all commercially available products without further purification or treatment.

[0100] Example 1

[0101] This embodiment provides an inorganic mineral fiber based on water-quenched slag and a preparation method thereof, wherein the preparation method specifically comprises the following steps:

[0102] S1: preparing a tetrabutyl titanate ethanol solution, wherein the volume ratio of tetrabutyl titanate to ethanol is 1:3.6, adding citric acid and stirring under nitrogen protection to obtain a reaction solution A, wherein the molar ratio of citric acid to tetrabutyl titanate is 2.5:1; preparing a 0.3M lanthanum nitrate ethanol solution and adding citric acid and stirring to obtain a reaction solution B, wherein the molar ratio of citric acid to lanthanum nitrate is 2:1, and dripping the reaction solution B into the reaction solution A at a rate of 2.3mL / min at a constant temperature of 60°C, wherein the molar ratio of lanthanum nitrate to tetrabutyl titanate is 0.2:1, adjusting the pH to 3 with a 0.5M nitric acid solution to obtain a reaction solution C, stirring and reacting for 5h to obtain a first sol solution, vacuum drying at 70°C for 12h and calcining to obtain a lanthanum oxide-titanium oxide composite powder, wherein the calcination temperature is 750°C and the calcination time is 2h; Figure 1 This is a high-resolution transmission electron microscopy image of lanthanum oxide-titanium oxide composite powder. It can be observed that the close contact interface between titanium oxide and lanthanum oxide forms a composite powder with higher thermal and chemical stability.

[0103] S2: Plasma treatment of lanthanum oxide-titanium oxide composite powder to obtain surface-modified lanthanum oxide-titanium oxide composite powder, wherein the power of plasma treatment is 200 W, the oxygen flow rate is 30 mL / min, and the plasma treatment time is 20 min; the surface-modified lanthanum oxide-titanium oxide composite powder is dispersed in a mixed solution of ethanol / water with a volume ratio of 9:1 at a mass fraction of 5%, and a silane coupling agent KH570 is added in an amount of 2.3% of the mass of the surface-modified lanthanum oxide-titanium oxide composite powder, and the mixture is stirred and reacted at 75°C for 4 h, filtered, washed, and vacuum dried to obtain modified lanthanum oxide-titanium oxide composite powder;

[0104] S3: Dispersing zinc oxide powder in a 0.1M phosphoric acid solution to obtain a zinc oxide dispersion, wherein the mass ratio of zinc oxide to phosphoric acid solution is 1:15, stirring, using a 0.15M sodium hydroxide solution to adjust the pH to 5 to obtain a reaction solution D, stirring and reacting for 5 hours, filtering, washing, and drying to obtain phosphate-coated zinc oxide; dispersing the phosphate-coated zinc oxide in a 0.2M zirconium oxychloride solution to obtain a reaction solution E, wherein the mass ratio of the phosphate-coated zinc oxide to the zirconium oxychloride solution is 1:10, adjusting the pH to 7 with 2.3M ammonia water at a constant temperature of 50°C to obtain a reaction solution F, stirring and reacting for 2 hours, filtering, washing, drying, and then calcining at 500°C for 2 hours to obtain a double-layer coated modified zinc oxide;

[0105] S4: mixing water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide, and obtaining a mixed powder after ball milling, wherein the mass ratio of water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide is 80:10:10, placing the mixed powder in a high-temperature melting furnace to melt to obtain a molten liquid, wherein the melting temperature is 1500°C and the time is 56 minutes, conveying the molten liquid to a fiber blowing device, blowing with 0.6MPa high-pressure air to obtain a first pretreated fiber, and obtaining a pretreated fiber after heat treatment annealing and cooling, wherein the heat treatment temperature is 600°C and the heat treatment time is 20 minutes; Figure 2 This is the scanning electron microscope image of the pretreated fiber, where it can be observed that the fiber surface is relatively smooth and the size is uniform;

[0106] S5: adding magnesium chloride and cerium chloride to deionized water at a molar ratio of 1:1 to obtain a first modified solution, wherein the solid-liquid ratio in the first modified solution is 1:10, adding glycerol in an amount of 5.6% of the mass of the first modified solution, stirring, and adjusting the pH to 6 with ammonia water to obtain a modified solution; immersing the pretreated fiber in the modified solution, wherein the mass ratio of the pretreated fiber to the modified solution is 1:25, placing it in a microwave reactor for treatment, wherein the microwave reactor is treated with a power of 500 W and a time of 5.6 min, filtering, washing, and drying after natural cooling to obtain an inorganic mineral fiber based on water-quenched slag, Figure 3 As shown in its scanning electron microscope image, compared with the pretreated fiber, a uniform salt layer is formed on its surface, which is beneficial to improving the mechanical properties and high temperature resistance of the fiber.

[0107] Example 2

[0108] This embodiment provides an inorganic mineral fiber based on water-quenched slag and a preparation method thereof, wherein the preparation method specifically comprises the following steps:

[0109] S1: preparing a tetrabutyl titanate ethanol solution, wherein the volume ratio of tetrabutyl titanate to ethanol is 1:3.2, adding citric acid and stirring under nitrogen protection to obtain a reaction solution A, wherein the molar ratio of citric acid to tetrabutyl titanate is 2:1; preparing a 0.2M lanthanum nitrate ethanol solution and adding citric acid and stirring to obtain a reaction solution B, wherein the molar ratio of citric acid to lanthanum nitrate is 2.8:1, and dripping the reaction solution B into the reaction solution A at a rate of 3 mL / min at a constant temperature of 50°C, wherein the molar ratio of lanthanum nitrate to tetrabutyl titanate is 0.26:1, adjusting the pH to 2 with a 0.56M nitric acid solution to obtain a reaction solution C, stirring and reacting for 4.5 hours to obtain a first sol solution, vacuum drying at 72°C for 13 hours and calcining to obtain a lanthanum oxide-titanium oxide composite powder, wherein the calcination temperature is 740°C and the calcination time is 2.5 hours;

[0110] S2: Plasma-treating the lanthanum oxide-titanium oxide composite powder to obtain surface-modified lanthanum oxide-titanium oxide composite powder, wherein the power of the plasma treatment is 100 W, the oxygen flow rate is 20 mL / min, and the plasma treatment time is 10 min; dispersing the surface-modified lanthanum oxide-titanium oxide composite powder at a mass fraction of 6% in an ethanol / water mixed solution with a volume ratio of 8:2, adding a silane coupling agent KH570 in an amount of 2.7% of the mass of the surface-modified lanthanum oxide-titanium oxide composite powder, stirring the reaction at 77°C for 3h, filtering, washing, and vacuum drying to obtain a modified lanthanum oxide-titanium oxide composite powder;

[0111] S3: Disperse zinc oxide powder in a 0.14M phosphoric acid solution to obtain a zinc oxide dispersion, wherein the mass ratio of zinc oxide to phosphoric acid solution is 1:17, stir, use a 0.1M sodium hydroxide solution to adjust the pH to 6 to obtain a reaction solution D, stir and react for 4.5 hours, filter, wash, and dry to obtain phosphate-coated zinc oxide; disperse the phosphate-coated zinc oxide in a 0.26M zirconium oxychloride solution to obtain a reaction solution E, wherein the mass ratio of phosphate-coated zinc oxide to zirconium oxychloride solution is 1:12, adjust the pH to 8 with 2.8M ammonia water at a constant temperature of 55°C to obtain a reaction solution F, stir and react for 2.4 hours, filter, wash, and dry, and then calcine at 520°C for 2.2 hours to obtain a double-layer coated modified zinc oxide;

[0112] S4: mixing water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide, and obtaining mixed powder after ball milling, wherein the mass ratio of water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide is 90:5:5, placing the mixed powder in a high-temperature melting furnace for melting to obtain a molten liquid, wherein the melting temperature is 1450°C and the time is 50 minutes, and obtaining pretreated fibers after heat treatment annealing and cooling, wherein the heat treatment temperature is 650°C and the heat treatment time is 15 minutes;

[0113] S5: Add magnesium chloride and cerium chloride in a molar ratio of 1.5:1 to deionized water to obtain a first modified solution, wherein the solid-liquid ratio in the first modified solution is 1:12, add glycerol in an amount of 5% of the mass of the first modified solution, stir and adjust the pH to 7 with ammonia water to obtain a modified solution; immerse the pretreated fiber in the modified solution, wherein the mass ratio of the pretreated fiber to the modified solution is 1:24, place it in a microwave reactor for treatment, wherein the microwave reactor has a treatment power of 570 W and a treatment time of 5.8 min, filter, wash and dry after natural cooling to obtain inorganic mineral fiber based on water-quenched slag.

[0114] Example 3

[0115] This embodiment provides an inorganic mineral fiber based on water-quenched slag and a preparation method thereof, wherein the preparation method specifically comprises the following steps:

[0116] S1: preparing a tetrabutyl titanate ethanol solution, wherein the volume ratio of tetrabutyl titanate to ethanol is 1:3, adding citric acid and stirring under nitrogen protection to obtain a reaction solution A, wherein the molar ratio of citric acid to tetrabutyl titanate is 3:1; preparing a 0.25M lanthanum nitrate ethanol solution and adding citric acid and stirring to obtain a reaction solution B, wherein the molar ratio of citric acid to lanthanum nitrate is 2.3:1, and adding the reaction solution B dropwise to the reaction solution A at a rate of 2 mL / min at a constant temperature of 56°C, wherein the molar ratio of lanthanum nitrate to tetrabutyl titanate is 0.28:1, adjusting the pH to 2.5 with a 0.57M nitric acid solution to obtain a reaction solution C, stirring and reacting for 4.8 hours to obtain a first sol solution, vacuum drying at 78°C for 14 hours and calcining to obtain a lanthanum oxide-titanium oxide composite powder, wherein the calcination temperature is 720°C and the calcination time is 2.7 hours;

[0117] S2: Plasma-treating the lanthanum oxide-titanium oxide composite powder to obtain surface-modified lanthanum oxide-titanium oxide composite powder, wherein the power of the plasma treatment is 150 W, the oxygen flow rate is 23 mL / min, and the plasma treatment time is 15 min; dispersing the surface-modified lanthanum oxide-titanium oxide composite powder in a mass fraction of 5.6% in an ethanol / water mixed solution with a volume ratio of 7:3, adding a silane coupling agent KH570 in an amount of 2% of the mass of the surface-modified lanthanum oxide-titanium oxide composite powder, stirring the reaction at 70°C for 3.4 h, filtering, washing, and vacuum drying to obtain a modified lanthanum oxide-titanium oxide composite powder;

[0118] S3: Dispersing zinc oxide powder in a 0.16M phosphoric acid solution to obtain a zinc oxide dispersion, wherein the mass ratio of zinc oxide to phosphoric acid solution is 1:18, stirring, using a 0.12M sodium hydroxide solution to adjust the pH to 5.4 to obtain a reaction solution D, stirring for 4.8 hours, filtering, washing, and drying to obtain phosphate-coated zinc oxide; dispersing the phosphate-coated zinc oxide in a 0.28M zirconium oxychloride solution to obtain a reaction solution E, wherein the mass ratio of the phosphate-coated zinc oxide to the zirconium oxychloride solution is 1:14, adjusting the pH to 7.5 with 2M ammonia water at a constant temperature of 57°C to obtain a reaction solution F, stirring for 2.8 hours, filtering, washing, and drying, and then calcining at 550°C for 2.6 hours to obtain a double-layer coated modified zinc oxide;

[0119] S4: water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide are mixed, and mixed powder is obtained after ball milling, wherein the mass ratio of water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide is 86:67:8, the mixed powder is placed in a high-temperature melting furnace for melting to obtain a molten liquid, wherein the melting temperature is 1470°C and the time is 60 minutes, the molten liquid is transported to a fiber blowing device, and a first pretreated fiber is obtained by blowing with 0.56MPa high-pressure air, and a pretreated fiber is obtained after heat treatment annealing and cooling, wherein the heat treatment temperature is 620°C and the heat treatment time is 10 minutes;

[0120] S5: Add magnesium chloride and cerium chloride in a molar ratio of 1.7:1 to deionized water to obtain a first modified solution, wherein the solid-liquid ratio in the first modified solution is 1:13, add glycerol in an amount of 6% of the mass of the first modified solution, stir and adjust the pH to 6.7 with ammonia water to obtain a modified solution; immerse the pretreated fiber in the modified solution, wherein the mass ratio of the pretreated fiber to the modified solution is 1:22, place it in a microwave reactor for treatment, wherein the microwave reactor has a treatment power of 530 W and a treatment time of 6 min, filter, wash and dry after natural cooling to obtain inorganic mineral fiber based on water-quenched slag.

[0121] Example 4

[0122] This embodiment provides an inorganic mineral fiber based on water-quenched slag and a preparation method thereof, wherein the preparation method specifically comprises the following steps:

[0123] S1: preparing a tetrabutyl titanate ethanol solution, wherein the volume ratio of tetrabutyl titanate to ethanol is 1:4, adding citric acid and stirring under nitrogen protection to obtain a reaction solution A, wherein the molar ratio of citric acid to tetrabutyl titanate is 2.8:1; preparing a 0.28M lanthanum nitrate ethanol solution and adding citric acid and stirring to obtain a reaction solution B, wherein the molar ratio of citric acid to lanthanum nitrate is 3:1, and dripping the reaction solution B into the reaction solution A at a rate of 2.5mL / min at a constant temperature of 57°C, wherein the molar ratio of lanthanum nitrate to tetrabutyl titanate is 0.3:1, adjusting the pH to 2.6 with a 0.6M nitric acid solution to obtain a reaction solution C, stirring and reacting for 4h to obtain a first sol solution, vacuum drying at 80°C for 12.8h and calcining to obtain a lanthanum oxide-titanium oxide composite powder, wherein the calcination temperature is 700°C and the calcination time is 3h;

[0124] S2: Plasma-treating the lanthanum oxide-titanium oxide composite powder to obtain surface-modified lanthanum oxide-titanium oxide composite powder, wherein the power of the plasma treatment is 130 W, the oxygen flow rate is 26 mL / min, and the plasma treatment time is 17 min; dispersing the surface-modified lanthanum oxide-titanium oxide composite powder in a mass fraction of 5.8% in an ethanol / water mixed solution with a volume ratio of 7:3, adding a silane coupling agent KH570 in an amount of 3% of the mass of the surface-modified lanthanum oxide-titanium oxide composite powder, stirring the reaction at 80°C for 3.6 h, filtering, washing, and vacuum drying to obtain a modified lanthanum oxide-titanium oxide composite powder;

[0125] S3: Disperse zinc oxide powder in a 0.2M phosphoric acid solution to obtain a zinc oxide dispersion, wherein the mass ratio of zinc oxide to phosphoric acid solution is 1:20, stir, use a 0.13M sodium hydroxide solution to adjust the pH to 5.8 to obtain a reaction solution D, stir and react for 4 hours, filter, wash, and dry to obtain phosphate-coated zinc oxide; disperse the phosphate-coated zinc oxide in a 0.3M zirconium oxychloride solution to obtain a reaction solution E, wherein the mass ratio of phosphate-coated zinc oxide to zirconium oxychloride solution is 1:15, adjust the pH to 7.8 with 3M ammonia water at a constant temperature of 60°C to obtain a reaction solution F, stir and react for 3 hours, filter, wash, and dry, and then calcine at 510°C for 3 hours to obtain a double-layer coated modified zinc oxide;

[0126] S4: water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide are mixed, and mixed powder is obtained after ball milling, wherein the mass ratio of water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide is 84:7:9, the mixed powder is placed in a high-temperature melting furnace for melting to obtain a molten liquid, wherein the melting temperature is 1490°C and the time is 54 minutes, the molten liquid is transported to a fiber blowing device, and a first pretreated fiber is obtained by blowing with 0.57MPa high-pressure air, and a pretreated fiber is obtained after heat treatment annealing and cooling, wherein the heat treatment temperature is 630°C and the heat treatment time is 12 minutes;

[0127] S5: Add magnesium chloride and cerium chloride in a molar ratio of 2:1 to deionized water to obtain a first modified solution, wherein the solid-liquid ratio in the first modified solution is 1:15, add glycerol in an amount of 5.8% of the mass of the first modified solution, stir and adjust the pH to 6.3 with ammonia water to obtain a modified solution; immerse the pretreated fiber in the modified solution, wherein the mass ratio of the pretreated fiber to the modified solution is 1:20, place it in a microwave reactor for treatment, wherein the microwave reactor has a treatment power of 600 W and a treatment time of 5 min, filter, wash and dry after natural cooling to obtain inorganic mineral fiber based on water-quenched slag.

[0128] Comparative Example 1

[0129] This comparative example provides an inorganic mineral fiber based on water-quenched slag, which is different from Example 1 in that in S3, the concentration of the phosphoric acid solution is 1 M, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0130] Comparative Example 2

[0131] This comparative example provides an inorganic mineral fiber based on water-quenched slag, which is different from Example 1 in that in S3, the concentration of the phosphoric acid solution is 0.01 M, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0132] Comparative Example 3

[0133] This comparative example provides an inorganic mineral fiber based on water-quenched slag, which is different from Example 1 in that in S5, the solid-liquid ratio in the first modified liquid is 1:5, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0134] Comparative Example 4

[0135] This comparative example provides an inorganic mineral fiber based on water-quenched slag, which is different from Example 1 in that in S5, the solid-liquid ratio in the first modified liquid is 1:20, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0136] The performance test of the inorganic mineral fibers based on water-quenched slag in the above Examples 1-4 and Comparative Examples 1-4 was carried out, and the specific process is as follows:

[0137] Test the tensile strength and elastic modulus of the fiber according to GB / T 1447-2005;

[0138] High temperature resistance test: The fiber was treated at 800℃ for 2h and then its tensile strength and elastic modulus were tested;

[0139] The test results are shown in Table 1.

[0140] Table 1: Performance test results of inorganic mineral fibers based on water-quenched slag in Examples 1-4 and Comparative Examples 1-4

[0141]

[0142] It can be seen from the test results of Example 1 and Comparative Examples 1 and 2 that when the concentration of the phosphoric acid solution is too high, the surface of zinc oxide reacts with excess phosphoric acid to form an excessively thick phosphate coating layer, which affects the dispersibility and surface activity of the zinc oxide particles, resulting in poor interfacial bonding between zinc oxide and water-quenched slag, reducing the modification effect, and the weak interfacial bonding force leads to poor mechanical properties and high temperature resistance of the fiber; when the phosphoric acid concentration is too low, there is not enough phosphoric acid on the surface of zinc oxide for effective coating, resulting in uneven or incomplete surface coating layer, insufficient reaction between zinc oxide and water-quenched slag, and reduced strength and thermal stability of the fiber.

[0143] It can be seen from the test results of Example 1 and Comparative Examples 3 and 4 that when the content of magnesium chloride and cerium chloride in the modified solution is too high, the salt layer formed on the surface of the pretreated fiber is too thick, and the too thick magnesium salt layer may melt or deteriorate at high temperature, resulting in a decrease in the mechanical properties and high temperature resistance of the fiber, and at the same time, a hardened layer may be formed on the fiber surface, affecting the flexibility and tensile strength of the fiber, resulting in a deterioration in the mechanical properties of the fiber; and a high concentration of cerium chloride may cause excessive aggregation of cerium elements on the fiber surface, forming too much cerium oxide. This will affect the redox properties of cerium, and may cause it to lose its expected antioxidant effect at high temperatures, thereby reducing the high temperature resistance, corrosion resistance and oxidation resistance of the fiber; if the content of magnesium chloride and cerium chloride in the modified solution is too low, an effective protective layer cannot be formed on the fiber surface, and the modification effect of magnesium may not be fully exerted, resulting in the fiber showing poor mechanical properties, thermal stability and corrosion resistance in subsequent use, and a low concentration of cerium chloride may not be able to fully exert its antioxidant effect, making the fiber prone to oxidation reaction at high temperature or in an oxidizing environment, resulting in degradation of the fiber's performance.

[0144] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention are within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing inorganic mineral fiber based on water-quenched slag, characterized in that: The preparation method comprises: S1: preparing a tetrabutyl titanate ethanol solution, adding citric acid and stirring under nitrogen protection to obtain a reaction solution A; preparing a lanthanum nitrate ethanol solution and adding citric acid and stirring to obtain a reaction solution B, adding the reaction solution B dropwise to the reaction solution A at a constant temperature, adjusting the pH to obtain a reaction solution C, stirring and reacting to obtain a first sol solution, vacuum drying and calcining to obtain a lanthanum oxide-titanium oxide composite powder; S2: Plasma-treating the lanthanum oxide-titanium oxide composite powder to obtain surface-modified lanthanum oxide-titanium oxide composite powder; dispersing the surface-modified lanthanum oxide-titanium oxide composite powder in an ethanol / water mixed solution, adding a silane coupling agent, stirring the reaction, filtering, washing, and vacuum drying to obtain a modified lanthanum oxide-titanium oxide composite powder; S3: Dispersing zinc oxide powder in phosphoric acid solution to obtain zinc oxide dispersion, stirring, adjusting pH to obtain reaction solution D, stirring reaction, filtering, washing, and drying to obtain phosphate-coated zinc oxide; dispersing phosphate-coated zinc oxide in zirconium oxychloride solution to obtain reaction solution E, adjusting pH at constant temperature to obtain reaction solution F, stirring reaction, suction filtering, washing, drying, and then calcining to obtain double-layer coated modified zinc oxide; S4: mixing water-quenched slag, modified lanthanum oxide-titanium oxide composite powder and double-layer coated modified zinc oxide, ball milling to obtain a mixed powder, placing the mixed powder in a high-temperature melting furnace to melt to obtain a molten liquid, conveying the molten liquid to a fiber blowing device, blowing it with high-pressure air to obtain a first pretreated fiber, and heat-treating annealing and cooling to obtain a pretreated fiber; S5: adding magnesium chloride and cerium chloride into deionized water to obtain a first modified solution, adding glycerol, stirring and adjusting the pH to obtain a modified solution; immersing the pretreated fiber in the modified solution, placing it in a microwave reactor for treatment, filtering, washing and drying after natural cooling to obtain an inorganic mineral fiber based on water-quenched slag.

2. The method for preparing inorganic mineral fiber based on water-quenched slag according to claim 1, characterized in that: In S1: The volume ratio of tetrabutyl titanate to ethanol in the tetrabutyl titanate ethanol solution is 1:3-4; The molar ratio of citric acid to tetrabutyl titanate in the reaction solution A is 2-3:1; The concentration of the lanthanum nitrate ethanol solution is 0.2-0.3M; The molar ratio of citric acid to lanthanum nitrate in the reaction solution B is 2-3:1; Adding the reaction solution B dropwise into the reaction solution A at a constant temperature of 50-60°C; The reaction solution B is added dropwise to the reaction solution A at a rate of 2-3 mL / min; The molar ratio of the lanthanum nitrate to tetrabutyl titanate is 0.1-0.2:

1.

3. The method for preparing inorganic mineral fiber based on water-quenched slag according to claim 1, characterized in that: In S1: The pH of the reaction solution A was adjusted to 2-3 using nitric acid solution; The concentration of the nitric acid solution is 0.5-0.6M; The stirring reaction time of the reaction solution C is 4-5h; The vacuum drying temperature of the first sol solution is 70-80°C; The vacuum drying time of the first sol solution is 12-14 hours; The calcination temperature is 700-750°C; The calcination time is 2-3h.

4. The method for preparing inorganic mineral fiber based on water-quenched slag according to claim 1, characterized in that: In S2: The power of the plasma treatment of the lanthanum oxide-titanium oxide composite powder is 100-200W; The oxygen flow rate of the lanthanum oxide-titanium oxide composite powder plasma treatment is 20-30 mL / min; The plasma treatment time of the lanthanum oxide-titanium oxide composite powder is 10-20 minutes.

5. The method for preparing inorganic mineral fiber based on water-quenched slag according to claim 1, characterized in that: In S2: The volume ratio of ethanol to water in the ethanol / water mixed solution is 9:1-7:3; The mass fraction of the surface modified lanthanum oxide-titanium oxide composite powder in the ethanol / water mixed solution is 5-6%; The silane coupling agent is KH570, and the amount of the silane coupling agent is 2-3% of the mass of the surface-modified lanthanum oxide-titanium oxide composite powder; The stirring reaction temperature is 70-80°C; The stirring reaction time is 3-4h.

6. The method for preparing inorganic mineral fiber based on water-quenched slag according to claim 1, characterized in that: In S3: The concentration of the phosphoric acid solution is 0.1-0.2M; The mass ratio of the zinc oxide powder dispersed in the phosphoric acid solution is 1:15-20; Use sodium hydroxide solution to adjust the pH of zinc oxide dispersion to 5-6; The concentration of the sodium hydroxide solution is 0.1-0.15M; The stirring reaction time of the reaction solution D is 4-5 hours.

7. The method for preparing inorganic mineral fiber based on water-quenched slag according to claim 1, characterized in that: In S3: The concentration of the zirconium oxychloride solution is 0.2-0.3M; The mass ratio of the phosphate-coated zinc oxide dispersed in the zirconium oxychloride solution is 1:10-15; The pH of the reaction solution E is adjusted with aqueous ammonia at a constant temperature of 50-60°C; The concentration of the ammonia water is 2-3M; The pH of the reaction solution E is adjusted to 7-8 with aqueous ammonia; The reaction solution F is stirred for reaction for 2-3 hours; The calcination temperature is 500-550°C; The calcination time is 2-3h.

8. The method for preparing inorganic mineral fiber based on water-quenched slag according to claim 1, characterized in that: In S4: The temperature of the mixed powder melting is 1450-1500°C; The time for melting the mixed powder is 50-60 minutes; The pressure of the high-pressure air blowing of the molten liquid is 0.6-0.8MPa; The temperature of the first pretreated fiber heat treatment is 600-650°C; The first pretreated fiber is heat treated for 10-20 minutes.

9. The method for preparing inorganic mineral fiber based on water-quenched slag according to claim 1, characterized in that: In S5: The molar ratio of magnesium chloride to cerium chloride is 1-2:1; The solid-to-liquid ratio in the first modified liquid is 1:10-15; The feeding amount of the glycerol is 5-6% of the mass of the first modified liquid; The first modified liquid is added with glycerol and stirred, and then the pH is adjusted to 6-7 with ammonia water; The mass ratio of the pretreated fiber to the modified solution is 1:20-25; The power of the microwave reactor is 500-600W; The microwave reactor treatment time is 5-6 minutes.

10. An inorganic mineral fiber based on water-quenched slag prepared by the preparation method according to any one of claims 1 to 9, characterized in that: The mass ratio of the water-quenched slag, the modified lanthanum oxide-titanium oxide composite powder and the double-layer coated modified zinc oxide in the water-quenched slag-based inorganic mineral fiber is (80-90): (5-10): (5-10).

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