High-temperature-resistant basalt fiber as well as preparation method and application thereof

Abstract

The invention relates to the technical field of basalt fibers, and discloses a high-temperature-resistant basalt fiber and a preparation method and application thereof.The preparation method of the high-temperature-resistant basalt fiber comprises the following steps that basalt, zirconite, potassium feldspar, rutile and molybdenite are mixed and then subjected to melting and wire drawing treatment, and a base material is obtained; mixing a zinc source and a nickel source to obtain a mixed solution; and dipping the matrix material in the mixed solution, curing and pressing to obtain the composite material. The zinc element and the nickel element have high thermal stability, a matrix material is soaked in a mixed solution of a zinc source and a nickel source, and a functional group on the surface of the basalt fiber and two ions form a chemical bond, so that the zinc source-nickel source can be firmly adsorbed on the surface of the fiber, and the high temperature resistance and the oxidation resistance of the basalt fiber are improved; the damage to the basalt fiber is small, the original performance and structural integrity of the basalt fiber can be kept, harmful gas cannot be generated, and the process is environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of basalt fiber, and particularly relates to a high-temperature resistant basalt fiber, a preparation method thereof and an application thereof. Background Art

[0002] Basalt fiber is another high-tech fiber material after carbon fiber, aramid fiber and ultra-high molecular weight polyethylene fiber. It has excellent mechanical properties and high-temperature resistance, and can be widely used in flame retardant materials, high-temperature filtration and other fields. However, the basalt fiber prepared with basalt as the main raw material can withstand temperatures from -269°C to 700°C. When the temperature rises above 700°C, ordinary basalt fiber will be difficult to bear, its performance will decline and be damaged, which limits its application in high-temperature fields. Therefore, how to optimize and improve basalt fiber to improve its high-temperature resistance is one of the technical problems that need to be solved urgently in this field. Summary of the Invention

[0003] In view of this, the present invention provides a preparation method of a high-temperature resistant basalt fiber.

[0004] The present invention also provides a high-temperature resistant basalt fiber.

[0005] The purpose of the present invention is achieved by the following technical solutions: In a first aspect, the present invention provides a preparation method of a high-temperature resistant basalt fiber, including the following steps: (1) Mix basalt, zircon, potassium feldspar, rutile and molybdenite, and then carry out melting and drawing treatment to obtain a matrix material; mix a zinc source and a nickel source to obtain a mixed solution; (2) Immerse the matrix material in the mixed solution, and obtain it after curing and pressing; The mass ratio of the zinc source to the nickel source is 4-9:1.

[0006] In an optional embodiment, the temperature of the immersion is 25°C - 40°C, and the time of the immersion is 0.5h - 2h.

[0007] In an optional embodiment, the zinc source includes at least one of zinc sulfate and zinc fluoborate.

[0008] In an optional embodiment, the nickel source includes at least one of nickel sulfate and nickel nitrate.

[0009] In an optional embodiment, the weight ratio of the basalt, the rutile, the zircon, the potassium feldspar and the molybdenite is 13-43:1-3:1-4:0.5-4:1-5.

[0010] In an alternative embodiment, the pressing method is hot isostatic pressing, the temperature of the hot isostatic pressing is 300°C - 400°C, and the pressure is 50 MPa - 130 MPa.

[0011] In an alternative embodiment, the melting temperature is 1400°C - 1590°C.

[0012] In an alternative embodiment, the wire drawing temperature is 1350°C - 1460°C.

[0013] In an alternative embodiment, the particle size of the basalt is 0.8 mm - 4 mm.

[0014] In an alternative embodiment, the particle size of the rutile is 0.21 μm - 0.25 μm.

[0015] In an alternative embodiment, the particle size of the zircon is 1 mm - 5 mm.

[0016] In an alternative embodiment, the particle size of the potassium feldspar is 0.03 mm - 0.05 mm.

[0017] In an alternative embodiment, the particle size of the molybdenite is 0.03 mm - 0.05 mm.

[0018] Second invention, the present invention provides a high-temperature resistant basalt fiber, comprising a matrix material and a functional coating, and the functional coating comprises a zinc source and a nickel source.

[0019] In an alternative embodiment, the thickness of the functional coating is 5 μm - 10 μm.

[0020] Second invention, the present invention provides an application of the above-mentioned high-temperature resistant basalt fiber in the fields of aerospace, transportation and environmental protection.

[0021] Compared with the prior art, the technical solution of the present invention has the following advantages: 1. The preparation method of the high-temperature resistant basalt fiber provided by the present invention includes the following steps: Mix basalt, zircon, potassium feldspar, rutile and molybdenite, and then melt and draw them to obtain a matrix material; Mix a zinc source and a nickel source to obtain a mixed solution; Immerse the matrix material in the mixed solution, and then cure and press it to obtain. Zinc and nickel elements have high thermal stability. In the present invention, the matrix material is immersed in the mixed solution of the zinc source and the nickel source, and the functional groups (silanol groups (Si-OH), carboxyl groups (–COOH)) on the surface of the basalt fiber can form chemical bonds with the two ions, so that the zinc-nickel source can be more firmly adsorbed on the fiber surface, significantly improving the high-temperature resistance and antioxidant ability of the basalt fiber; And it causes less damage to the basalt fiber itself, helps to maintain the original properties and structural integrity of the basalt fiber, and does not generate harmful gases, and the process is relatively environmentally friendly; By controlling the mass ratio of the zinc source to the nickel source to be 4-9:1, when the proportion of zinc is too large, the exchange reaction between zinc ions and metal ions (Ca 2+ 、Al 3+ ) in the basalt fiber intensifies, destroying the internal network structure of the basalt fiber, resulting in the surface of the basalt fiber becoming rough, thus affecting its mechanical properties and chemical stability; When the proportion of zinc is too small, nickel element dominates in the solution, changing the charge distribution on the surface of the basalt fiber, reducing the binding force between the functional coating and the surface of the basalt fiber, resulting in poor high-temperature resistance, bending strength and corrosion resistance of the basalt fiber; When the proportion of nickel is too large, an oxidation-reduction reaction occurs between the functional coating and the surface of the basalt fiber, changing the structure of the surface of the basalt fiber, greatly reducing the high-temperature resistance performance of the basalt fiber; When the proportion of nickel is too small, zinc ions dominate in the solution, changing the pH value of the solution, thus affecting the mechanical properties and binding force of the basalt fiber, resulting in poor high-temperature resistance, bending strength and corrosion resistance of the basalt fiber; Molybdenite contains abundant molybdenum elements, and zircon contains abundant zirconium elements. Molybdenum and zirconium elements have high melting points, which is beneficial to improving the heat resistance of basalt fiber and enabling it to maintain excellent properties in extremely high-temperature environments; The preparation method of the present invention has a low cost, a simple preparation method, an environmentally friendly production process, and is easy to realize industrial production.

[0022] 2. For the preparation method of the high-temperature resistant basalt fiber provided by the present invention, control the impregnation temperature within the range of 25°C - 40°C. When the temperature is too high, the precipitation rate of the mixed solution on the surface of the basalt fiber is too fast, which is likely to cause uneven thickness of the functional coating and reduce the stability at high temperatures; When the solution temperature is too low, the precipitation rate of the mixed solution on the surface of the basalt fiber is too slow, prolonging the functional coating time, and the binding force and durability of the functional coating are poor, resulting in poor high-temperature resistance, bending strength and corrosion resistance of the basalt fiber.

[0023] 3. The preparation method of the high-temperature resistant basalt fiber provided by the present invention controls the mass ratio of basalt, rutile, zircon, potassium feldspar and molybdenite to be 13-43:1-3:1-4:0.5-4:1-5. The main component of basalt is SiO2, which is beneficial to improving the chemical stability and thermal stability of basalt fiber, thereby improving the high-temperature resistance of basalt fiber; the main component of rutile is TiO2, which can not only improve the chemical stability of basalt fiber, but also increase the surface tension and viscosity of the melt, which is beneficial to increasing the drawing strength of basalt fiber.

[0024] 4. The high-temperature resistant basalt fiber provided by the present invention includes a matrix material and a functional coating, and the functional coating includes a zinc source and a nickel source. Compared with ordinary basalt fiber, the high-temperature resistant basalt fiber prepared by the present invention has better flexibility, a tolerance temperature of 820°C - 980°C, an increase of 120°C - 200°C, and still maintains good stability in high-temperature and corrosive environments, and can be widely applied in the fields of aerospace, transportation and environmental protection, etc. Detailed implementation manners

[0025] The following embodiments are provided to better further understand the present invention. They are not limited to the best implementation manner, and do not constitute a limitation to the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior art features falls within the protection scope of the present invention.

[0026] For those not indicating specific experimental steps or conditions in the embodiments, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For those reagents or instruments not indicating the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0027] The following further describes the present invention in detail with specific embodiments, and these embodiments should not be construed as limiting the scope claimed by the present invention.

[0028] Example 1 This example provides a preparation method of high-temperature resistant basalt fiber, including the following steps: (1) Material selection and pretreatment: Select basalt, zircon, potassium feldspar, rutile and molybdenite, and respectively perform pretreatment steps of crushing, screening and magnetic separation to obtain basalt particles with a particle size of 0.9 mm, zircon particles with a particle size of 2 mm, potassium feldspar particles with a particle size of 0.04 mm, rutile particles with a particle size of 0.23 μm, and molybdenite with a particle size of 0.03 mm; (2) Mixing: Weigh 13 parts by weight of the above-mentioned basalt particles, 1.2 parts by weight of zircon, 1 part by weight of potassium feldspar, 0.5 part by weight of rutile, and 1 part by weight of molybdenite particles. After mixing evenly, a mixed material with a uniformity of 95% is obtained and stored in the raw material storage for standby; (3) Melting the sample: The above-mentioned mixed material enters the tank furnace through a metering feeder and is melted at a temperature of 1500 °C to obtain a basalt fiber melt; (4) Drawing: Transfer the above-mentioned basalt fiber melt to a drawing system, and draw it at 1380 °C through a precision platinum-rhodium-gold drawing bushing and cooled to 75 °C to obtain a matrix material; among them, the composition of the matrix material includes: SiO2 63%, Al2O3 13%, CaO 5%, Fe2O3+FeO 4%, K2O+Na2O 3%, TiO2 3%, ZrO2 5%, MoO2 4%; (5) Surface modification treatment: Mix zinc sulfate and nickel sulfate in a mass ratio of 8.5:1.5 to obtain a mixed solution; immerse all the matrix materials in the mixed solution at 30 °C for 1 h to form a film on the surface of the basalt fiber, and dry and cure it; (6) Hot isostatic pressing treatment: Perform hot isostatic pressing treatment on the coated basalt fiber at 300 °C and 55 MPa to obtain a high-temperature resistant basalt fiber; it includes a matrix material and a functional coating, and the thickness of the functional coating is 8 μm.

[0029] Example 2 This example provides a method for preparing high-temperature resistant basalt fiber, including the following steps: (1) Material selection and pretreatment: Select basalt, zircon, potassium feldspar, rutile, and molybdenite, and respectively perform pretreatment steps of crushing, screening, and magnetic separation to obtain basalt particles with a particle size of 0.9 mm, zircon particles with a particle size of 2 mm, potassium feldspar particles with a particle size of 0.04 mm, rutile particles with a particle size of 0.23 μm, and molybdenite with a particle size of 0.03 mm; (2) Mixing: Weigh 40 parts by weight of the above-mentioned basalt particles, 1 part by weight of zircon, 1.5 parts by weight of potassium feldspar, 1 part by weight of rutile, and 2.5 parts by weight of molybdenite particles. After mixing evenly, a mixed material with a uniformity of not less than 95% is obtained and stored in the raw material storage for standby; (3) Melting the sample: The above-mentioned mixed material enters the tank furnace through a metering feeder and is melted at a temperature of 1400 °C to obtain a basalt fiber melt; (4) Fiber drawing: Transfer the above-mentioned basalt fiber melt to a fiber drawing system, and draw it at 1400 °C through a precision platinum-rhodium-gold fiber drawing bushing, and cool it to 100 °C to obtain a matrix material; wherein, the composition of the matrix material includes: 55% SiO2, 15% Al2O3, 6% CaO, 5% Fe2O3+FeO, 4% K2O+Na2O, 6% TiO2, 4% ZrO2, 5% MoO2; (5) Surface improvement treatment: After mixing zinc sulfate and nickel sulfate in a mass ratio of 8:2, a mixed solution is obtained; Immerse all the matrix materials in the mixed solution at 25 °C for 0.5 h to form a film on the surface of the basalt fiber, and dry and cure it; (6) Hot isostatic pressing treatment: Perform hot isostatic pressing treatment on the basalt fiber after plating at 350 °C and 70 MPa to obtain high-temperature resistant basalt fiber; It includes a matrix material and a functional coating, and the thickness of the functional coating is 5 μm.

[0030] Example 3 This example provides a method for preparing high-temperature resistant basalt fiber, which includes the following steps: (1) Material selection and pretreatment: Select basalt, zircon, potassium feldspar, rutile and molybdenite, and respectively perform pretreatment steps of crushing, screening and magnetic separation to obtain basalt particles with a particle size of 0.9 mm, zircon particles with a particle size of 2 mm, potassium feldspar particles with a particle size of 0.04 mm, rutile particles with a particle size of 0.23 μm, and molybdenite with a particle size of 0.03 mm; (2) Mixing: Weigh 43 parts by weight of the above-mentioned basalt particles, 2 parts by weight of zircon, 4 parts by weight of potassium feldspar, 3 parts by weight of rutile and 5 parts by weight of molybdenite particles. After mixing evenly, a mixed material with a uniformity of not less than 95% is obtained and stored in a raw material storage for later use; (3) Sample melting: Feed the above-mentioned mixed material into a tank furnace through a metering feeder and melt it at a temperature of 1590 °C to obtain a basalt fiber melt; (4) Fiber drawing: Transfer the above-mentioned basalt fiber melt to a fiber drawing system, and draw it at 1450 °C through a precision platinum-rhodium-gold fiber drawing bushing, and cool it to 50 °C to obtain a matrix material; wherein, the composition of the matrix material includes: 59% SiO2, 12% Al2O3, 7% CaO, 3% Fe2O3+FeO, 4% K2O+Na2O, 6% TiO2, 3% ZrO2, 6% MoO2; (5) Surface improvement treatment: After mixing zinc fluoborate and nickel nitrate in a mass ratio of 9:1, a mixed solution is obtained; Immerse the matrix material in the mixed solution at 40 °C for 2 h to form a film on the surface of the basalt fiber, and dry and cure it; (6)Hot isostatic pressing treatment: The basalt fiber after coating is subjected to hot isostatic pressing treatment at 400 °C and 130 MPa to obtain high-temperature resistant basalt fiber; it includes a matrix material and a functional coating, and the thickness of the functional coating is 6 μm.

[0031] Comparative Example 1 This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is basically the same as the steps of Example 1, except that the mass ratio of zinc sulfate to nickel sulfate is 15:1.5.

[0032] Comparative Example 2 This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is basically the same as the steps of Example 1, except that the mass ratio of zinc sulfate to nickel sulfate is 4:1.5.

[0033] Comparative Example 3 This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is basically the same as the steps of Example 1, except that the mass ratio of zinc sulfate to nickel sulfate is 8.5:2.5.

[0034] Comparative Example 4 This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is basically the same as the steps of Example 1, except that the mass ratio of zinc sulfate to nickel sulfate is 8.5:0.5.

[0035] Comparative Example 5 This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is basically the same as the steps of Example 1, except that the impregnation temperature is 20 °C.

[0036] Comparative Example 6 This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is basically the same as the steps of Example 1, except that the impregnation temperature is 45 °C.

[0037] Experimental Example The high-temperature resistant basalt fibers prepared in the above Examples 1 - 3 and Comparative Examples 1 - 6 are subjected to flexibility testing using flexural toughness testing, and high-temperature resistance testing is carried out according to GB / T 25045-2010 "Basalt Fiber Rovings"; the corrosion resistance testing includes the following steps: The basalt fibers prepared in each example and comparative example are cut into samples with uniform size, and are respectively placed in 1 mol / L NaOH solution. After standing for 12 h, the mass retention rate of each sample is calculated respectively, and the results are shown in the following table; among them, the mass retention rate (%) = the mass of the basalt fiber after corrosion / the mass of the basalt fiber before corrosion × 100%.

[0038] Table 1 Performance test results of high-temperature resistant basalt fibers prepared in each example and comparative example

[0039] As can be seen from the above table, the basalt fibers prepared in Examples 1 - 3 have good high-temperature resistance, flexural strength, and corrosion resistance; compared with Example 1, the properties of the basalt fibers of the present invention are higher in Comparative Example 1 because the proportion of zinc in Comparative Example 1 is relatively large, and the exchange reaction between zinc ions and metal ions (Ca 3+ and Al 3+ ) in the basalt fiber intensifies, damaging the internal network structure of the basalt fiber, resulting in a rough surface of the basalt fiber, thus affecting its mechanical properties and chemical stability; in Comparative Example 2, the proportion of zinc is relatively small, and nickel elements dominate in the solution, changing the charge distribution on the surface of the basalt fiber, thereby reducing the bonding force between the functional coating and the surface of the basalt fiber, resulting in poor high-temperature resistance, flexural strength, and corrosion resistance of the basalt fiber; in Comparative Example 3, the proportion of nickel is relatively large, and the solution undergoes a redox reaction with the surface of the basalt fiber, changing the surface structure of the basalt fiber, reducing the bonding force between the functional coating and the surface of the basalt fiber, thus affecting the high-temperature resistance of the basalt fiber; in Comparative Example 4, the proportion of nickel is relatively small, and zinc ions dominate in the solution, changing the pH value of the solution, thus affecting the mechanical properties and bonding force of the basalt fiber, and further resulting in poor high-temperature resistance, flexural strength, and corrosion resistance of the basalt fiber. Compared with Example 1, the properties of the basalt fiber in Comparative Example 5 are reduced because the temperature of the zinc-nickel mixed solution is too low, and the precipitation rate of the solution on the surface of the basalt fiber is too slow, resulting in poor bonding force and durability of the functional coating; compared with Example 1, the properties of the basalt fiber in Comparative Example 6 are reduced because the impregnation temperature is relatively high, and the precipitation rate of the mixed solution on the surface of the basalt fiber is too fast, causing uneven thickness of the functional coating and reducing the stability at high temperatures.

[0040] Obviously, the above examples are merely illustrations for clear explanation and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or variations can be made based on the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or variations derived therefrom are still within the protection scope of the present invention.

Claims

1. A preparation method of high-temperature resistant basalt fiber, characterized in that, It includes the following steps: (1) Mix basalt, zircon, potassium feldspar, rutile and molybdenite, then carry out melting and wire drawing treatments to obtain a matrix material; mix a zinc source and a nickel source to obtain a mixed solution; (2) Immerse the matrix material in the mixed solution, and obtain the product after curing and pressing; The mass ratio of the zinc source to the nickel source is 4-9:

1.

2. The preparation method of basalt fiber according to claim 1, characterized in that The temperature of the immersion is 25°C - 40°C, and the immersion time is 0.5h - 2h.

3. The preparation method of basalt fiber according to claim 1, characterized in that, The zinc source includes at least one of zinc sulfate and zinc fluoroborate; And / or, the nickel source includes at least one of nickel sulfate and nickel nitrate.

4. The preparation method of basalt fiber according to claim 1, characterized in that, The weight ratio of the basalt, the rutile, the zircon, the potassium feldspar and the molybdenite is 13-43:1-3:1-4:0.5-4:1-5.

5. The preparation method of basalt fiber according to claim 1, characterized in that, The pressing method is hot isostatic pressing, the temperature of the hot isostatic pressing is 300°C - 400°C, and the pressure is 50MPa - 130MPa.

6. The preparation method of basalt fiber according to claim 1, characterized in that, The melting temperature is 1400°C - 1590°C; And / or, the wire drawing temperature is 1350°C - 1460°C.

7. The preparation method of basalt fiber according to claim 1 or 4, characterized in that The particle size of the basalt is 0.8mm - 4mm; And / or, the particle size of the rutile is 0.21μm - 0.25μm; And / or, the particle size of the zircon is 1mm - 5mm; And / or, the particle size of the potassium feldspar is 0.03mm - 0.05mm; And / or, the particle size of the molybdenite is 0.03mm - 0.05mm.

8. A heat-resistant basalt fiber, characterized in that, Prepared by the preparation method according to any one of claims 1-7, comprising a matrix material and a functional coating, and the functional coating comprises a zinc source and a nickel source.

9. The heat-resistant basalt fiber according to claim 8, wherein, The thickness of the functional coating is 5μm - 10μm.

10. Application of the high-temperature resistant basalt fiber prepared by the preparation method according to any one of claims 1-7 or the high-temperature resistant basalt fiber according to claim 8 or 9 in the fields of aerospace, transportation and environmental protection.

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