A high temperature resistant basalt fiber and its preparation method and application

Abstract

The present invention relates to the field of basalt fiber technology, and discloses a high-temperature resistant basalt fiber and its preparation method and application. The preparation method of the high-temperature resistant basalt fiber provided by the present invention comprises the following steps: mixing basalt, zircon, potassium feldspar, rutile and molybdenite, melting and drawing to obtain a matrix material; mixing a zinc source and a nickel source to obtain a mixed solution; immersing the matrix material in the mixed solution, and solidifying and pressing to obtain. Zinc and nickel elements have high thermal stability. By immersing the matrix material in the mixed solution of the zinc source and the nickel source, the functional groups on the surface of the basalt fiber form chemical bonds with the two ions, so that the zinc source and the nickel source can be firmly adsorbed on the fiber surface, thereby improving the high-temperature resistance and antioxidant capacity of the basalt fiber; and the damage to the basalt fiber itself is small, which helps to maintain the original performance and structural integrity of the basalt fiber, and no harmful gases are generated, and the process is more environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of basalt fibers, and in particular to a high-temperature resistant basalt fiber and a preparation method and 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, basalt fiber prepared with basalt as the main raw material has a temperature resistance of -269°C to 700°C. When the temperature rises above 700°C, ordinary basalt fiber will not be able to withstand it, and its performance will decline and become damaged, limiting 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 urgently need to be solved in this field. Summary of the Invention

[0003] In view of this, the present invention provides a method for preparing high-temperature resistant volcanic rock fiber.

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

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] In a first aspect, the present invention provides a method for preparing high-temperature resistant basalt fiber, comprising the following steps:

[0007] (1) Mixing basalt, zircon, potassium feldspar, rutile and molybdenite, melting them, and drawing them into a wire to obtain a matrix material; mixing a zinc source and a nickel source to obtain a mixed solution;

[0008] (2) dipping the base material into the mixed solution, solidifying and pressing to obtain a base material;

[0009] The mass ratio of the zinc source to the nickel source is 4-9:1.

[0010] In an optional embodiment, the immersion temperature is 25°C-40°C, and the immersion time is 0.5h-2h.

[0011] In an optional embodiment, the zinc source includes at least one of zinc sulfate and zinc fluoroborate.

[0012] In an optional embodiment, the nickel source includes at least one of nickel sulfate and nickel nitrate.

[0013] 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.

[0014] In an optional 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.

[0015] In an optional embodiment, the melting temperature is 1400°C-1590°C.

[0016] In an optional embodiment, the wire drawing temperature is 1350°C-1460°C.

[0017] In an optional embodiment, the particle size of the basalt is 0.8 mm-4 mm.

[0018] In an optional embodiment, the particle size of the rutile is 0.21 μm-0.25 μm.

[0019] In an optional embodiment, the particle size of the zircon is 1 mm-5 mm.

[0020] In an optional embodiment, the particle size of the potassium feldspar is 0.03 mm-0.05 mm.

[0021] In an optional embodiment, the particle size of the molybdenite is 0.03 mm-0.05 mm.

[0022] The second invention provides a high-temperature resistant basalt fiber, comprising a matrix material and a functional coating, wherein the functional coating comprises a zinc source and a nickel source.

[0023] In an optional embodiment, the thickness of the functional coating is 5 μm-10 μm.

[0024] The second invention provides an application of the above-mentioned high-temperature resistant basalt fiber in the fields of aerospace, transportation and environmental protection.

[0025] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0026] 1. The preparation method of high-temperature resistant basalt fiber provided by the present invention comprises the following steps: mixing basalt, zircon, potassium feldspar, rutile and molybdenite, melting and drawing the mixture to obtain a matrix material; mixing a zinc source and a nickel source to obtain a mixed solution; immersing the matrix material in the mixed solution, solidifying and pressing the mixture to obtain a matrix material. Zinc and nickel elements have high thermal stability. The present invention immerses the matrix material in a mixed solution of zinc and nickel sources. The functional groups (silicon hydroxyl groups (Si-OH) and carboxyl groups (-COOH)) on the surface of the basalt fiber can form chemical bonds with the two ions, so that the zinc source and nickel source can be more firmly adsorbed on the fiber surface, significantly improving the high-temperature resistance and antioxidant capacity of the basalt fiber; and the damage to the basalt fiber itself is small, which helps to maintain the original performance and structural integrity of the basalt fiber, and no harmful gases are generated, making the process more environmentally friendly. By controlling the mass ratio of the zinc source to the nickel source to be 4-9:1, when the zinc proportion is too large, the zinc ions and the metal ions (Ca) in the basalt fiber will react with each other. 2+ 、Al 3+ ) exchange reaction intensifies, destroying the internal network structure of basalt fiber, causing the surface of basalt fiber to become rough, thereby affecting its mechanical properties and chemical stability; when the zinc ratio is too small, nickel element occupies a dominant position in the solution, changing the charge distribution on the surface of basalt fiber, reducing the bonding force between functional coating and basalt fiber surface, resulting in poor high temperature resistance, bending strength and corrosion resistance of basalt fiber; when the nickel ratio is too large, redox reaction occurs between functional coating and basalt fiber surface, changing the structure of basalt fiber surface, greatly reducing the high temperature resistance of basalt fiber; when the nickel ratio is too small, zinc ions occupy a dominant position in the solution, changing the pH value of the solution, thereby affecting the mechanical properties and bonding force of basalt fiber, resulting in poor high temperature resistance, bending strength and corrosion resistance of basalt fiber;

[0027] Molybdenite is rich in molybdenum, and zircon is rich in zircon. Molybdenum and zirconium have high melting points, which are beneficial to improving the heat resistance of basalt fiber and enabling it to maintain excellent performance in extremely high temperature environments.

[0028] The preparation method of the present invention has low cost, is simple, has an environmentally friendly production process, and is easy to implement industrial production.

[0029] 2. The preparation method of high-temperature resistant basalt fiber provided by the present invention controls the impregnation temperature within the range of 25°C-40°C. When the temperature is too high, the mixed solution precipitates on the surface of the basalt fiber too quickly, which easily causes uneven thickness of the functional coating and reduces stability at high temperatures. When the solution temperature is too low, the mixed solution precipitates on the surface of the basalt fiber too slowly, which prolongs the functional coating time, resulting in poor bonding strength and durability of the functional coating, resulting in poor high-temperature resistance, bending strength, and corrosion resistance of the basalt fiber.

[0030] 3. The preparation method of high-temperature resistant basalt fiber provided by the present invention controls the mass ratio of basalt, rutile, zircon, potassium feldspar and molybdenite to 13-43:1-3:1-4:0.5-4:1-5. The main component of basalt includes 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.

[0031] 4. The high-temperature resistant basalt fiber provided by the present invention comprises a matrix material and a functional coating, wherein the functional coating comprises a zinc source and a nickel source. Compared with conventional basalt fibers, the high-temperature resistant basalt fiber prepared by the present invention has better flexibility and a temperature tolerance of 820°C-980°C, an improvement of 120°C-200°C. It also maintains good stability in high-temperature, corrosive environments and is widely used in aerospace, transportation, and environmental protection fields. DETAILED DESCRIPTION

[0032] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0033] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0034] The present invention is further described in detail below with reference to specific examples. These examples should not be construed as limiting the scope of protection claimed in the present invention.

[0035] Example 1

[0036] This embodiment provides a method for preparing high-temperature resistant basalt fiber, comprising the following steps:

[0037] (1) Material selection and pretreatment: basalt, zircon, potassium feldspar, rutile and molybdenite were selected and subjected to crushing, screening and magnetic separation pretreatment steps respectively 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;

[0038] (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 parts by weight of rutile and 1 part by weight of molybdenite particles, mix them evenly, and obtain a mixed material with a uniformity of 95%, which is stored in a raw material storage container for later use;

[0039] (3) Melting sample: The above mixed material is fed into the tank kiln through a quantitative feeder and melted at 1500°C to obtain basalt fiber melt;

[0040] (4) Wire drawing: The basalt fiber melt is transferred to a wire drawing system, drawn at 1380°C through a precision platinum-rhodium-gold wire drawing plate, and cooled to 75°C to obtain a matrix material; wherein the matrix material comprises: SiO2 63%, Al2O3 13%, CaO 5%, Fe2O3+FeO 4%, K2O+Na2O 3%, TiO23%, ZrO25%, MoO24%;

[0041] (5) Surface improvement treatment: zinc sulfate and nickel sulfate were mixed in a mass ratio of 8.5:1.5 to obtain a mixed solution; the entire matrix material was immersed in the mixed solution at 30°C for 1 hour to form a film on the surface of the basalt fiber, which was then dried and solidified;

[0042] (6) Hot isostatic pressing: The coated basalt fiber is hot isostatically pressed at 300°C and 55 MPa to obtain high-temperature resistant basalt fiber; including matrix material and functional coating, the thickness of the functional coating is 8 μm.

[0043] Example 2

[0044] This embodiment provides a method for preparing high-temperature resistant basalt fiber, comprising the following steps:

[0045] (1) Material selection and pretreatment: basalt, zircon, potassium feldspar, rutile and molybdenite were selected and subjected to crushing, screening and magnetic separation pretreatment steps respectively 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 basalt molybdenite with a particle size of 0.03 mm;

[0046] (2) Mixing: Weigh 40 parts by weight of the 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, mix them evenly, and obtain a mixed material with a uniformity of not less than 95%, and store it in a raw material storage container for later use;

[0047] (3) Melting sample: The above mixed material is fed into the tank kiln through a quantitative feeder and melted at 1400°C to obtain basalt fiber melt;

[0048] (4) Wire drawing: The basalt fiber melt is transferred to a wire drawing system, drawn at 1400°C through a precision platinum-rhodium-gold wire drawing plate, and cooled to 100°C to obtain a matrix material; wherein the matrix material comprises: SiO2 55%, Al2O3 15%, CaO 6%, Fe2O3+FeO 5%, K2O+Na2O 4%, TiO26%, ZrO24%, MoO25%;

[0049] (5) Surface improvement treatment: zinc sulfate and nickel sulfate are mixed in a mass ratio of 8:2 to obtain a mixed solution; the entire matrix material is immersed in the mixed solution at 25°C for 0.5 h to form a film on the surface of the basalt fiber, which is then dried and solidified;

[0050] (6) Hot isostatic pressing: The coated basalt fiber is hot isostatically pressed at 350°C and 70 MPa to obtain high-temperature resistant basalt fiber; including matrix material and functional coating, the thickness of the functional coating is 5 μm.

[0051] Example 3

[0052] This embodiment provides a method for preparing high-temperature resistant basalt fiber, comprising the following steps:

[0053] (1) Material selection and pretreatment: basalt, zircon, potassium feldspar, rutile and molybdenite were selected and subjected to crushing, screening and magnetic separation pretreatment steps respectively 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 basalt molybdenite with a particle size of 0.03 mm;

[0054] (2) Mixing: Weighing 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, mixing them uniformly to obtain a mixed material with a uniformity of not less than 95%, and storing it in a raw material storage container for later use;

[0055] (3) Melting sample: The above mixed material is fed into a tank kiln through a quantitative feeder and melted at 1590°C to obtain a basalt fiber melt;

[0056] (4) Wire drawing: The basalt fiber melt is transferred to a wire drawing system, drawn at 1450°C through a precision platinum-rhodium-gold wire drawing plate, and cooled to 50°C to obtain a matrix material; wherein the matrix material comprises: SiO2 59%, Al2O3 12%, CaO 7%, Fe2O3+FeO 3%, K2O+Na2O 4%, TiO26%, ZrO23%, MoO26%;

[0057] (5) Surface modification treatment: Zinc borofluoride and nickel nitrate in a mass ratio of 9:1 were combined to obtain a mixed solution; the substrate material was immersed in the mixed solution at 40 °C for 2 h to form a film on the surface of the basalt fiber, which was then dried and solidified;

[0058] (6) Hot isostatic pressing: The coated basalt fiber is hot isostatically pressed at 400°C and 130 MPa to obtain high-temperature resistant basalt fiber; including matrix material and functional coating, the thickness of the functional coating is 6 μm.

[0059] Comparative Example 1

[0060] This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is substantially the same as the steps in Example 1, except that the mass ratio of zinc sulfate to nickel sulfate is 15:1.5.

[0061] Comparative Example 2

[0062] This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is substantially the same as the steps in Example 1, except that the mass ratio of zinc sulfate to nickel sulfate is 4:1.5.

[0063] Comparative Example 3

[0064] This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is substantially the same as the steps in Example 1, except that the mass ratio of zinc sulfate to nickel sulfate is 8.5:2.5.

[0065] Comparative Example 4

[0066] This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is substantially the same as the steps in Example 1, except that the mass ratio of zinc sulfate to nickel sulfate is 8.5:0.5.

[0067] Comparative Example 5

[0068] This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is basically the same as the steps in Example 1, except that the immersion temperature is 20°C.

[0069] Comparative Example 6

[0070] This comparative example provides a method for preparing high-temperature resistant basalt fiber, which is basically the same as the steps in Example 1, except that the immersion temperature is 45°C.

[0071] Experimental example

[0072] The high-temperature resistant basalt fibers prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were tested for flexibility using a bending toughness test, and for high-temperature resistance according to GB / T 25045-2010 "Basalt Fiber Roving." A corrosion resistance test included the following steps: the basalt fibers prepared in each Example and Comparative Example were cut into uniformly sized samples, each placed in a 1 mol / L NaOH solution, and allowed to stand for 12 hours. The mass retention rate of each sample was then calculated, as shown in the table below. Mass retention rate (%) = mass of basalt fiber after corrosion / mass of basalt fiber before corrosion × 100%.

[0073] Table 1 Performance test results of high temperature resistant basalt fibers prepared in various examples and comparative examples

[0074]

[0075] As can be seen from the above table, the basalt fibers prepared in Examples 1 to 3 have good high temperature resistance, flexural strength and corrosion resistance. Compared with the examples, the basalt fibers of the present invention have higher performance in Comparative Example 1. This is because zinc accounts for a large proportion in Comparative Example 1, and the zinc ions react with the metal ions (Ca) in the basalt fibers. 3+ 、Al 3+ ) intensifies the exchange reaction, destroys the internal network structure of the basalt fiber, causes the surface of the basalt fiber to become rough, thereby affecting its mechanical properties and chemical stability; in Comparative Example 2, zinc accounts for a small proportion, and nickel elements occupy a dominant position in the solution, which changes 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, nickel accounts for a large proportion, and the solution and the surface of the basalt fiber undergo an oxidation-reduction reaction, which changes the structure of the surface of the basalt fiber and reduces the bonding force between the functional coating and the surface of the basalt fiber, thereby affecting the high temperature resistance of the basalt fiber; in Comparative Example 4, nickel accounts for a small proportion, and zinc ions occupy a dominant position in the solution, which changes the pH value of the solution, thereby 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 the examples, the performance of the basalt fiber in Comparative Example 5 is reduced. This is 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 strength and durability of the functional coating. Compared with the examples, the performance of the basalt fiber in Comparative Example 6 is reduced. This is because the immersion temperature is high and the precipitation rate of the mixed solution on the surface of the basalt fiber is too fast, resulting in uneven thickness of the functional coating and reduced stability at high temperatures.

[0076] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A method for preparing high temperature resistant basalt fiber, characterized in that: The steps include: (1) Mixing basalt, zircon, potassium feldspar, rutile and molybdenite, melting and drawing the mixture to obtain a matrix material; mixing a zinc source and a nickel source to obtain a mixed solution; (2) dipping the base material into the mixed solution, solidifying and pressing to obtain a base material; The mass ratio of the zinc source to the nickel source is 4-9:1; The immersion temperature is 25°C-40°C.

2. The method for preparing basalt fiber according to claim 1, characterized in that: The soaking time is 0.5h-2h.

3. The method for preparing 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 method for preparing 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 method for preparing 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 50 MPa-130 MPa.

6. The method for preparing 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 method for preparing 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 0.21 μm-0.25 μm; And / or, the particle size of the zircon is 1 mm to 5 mm; And / or, the particle size of the potassium feldspar is 0.03 mm to 0.05 mm; And / or, the particle size of the molybdenite is 0.03 mm to 0.05 mm.

8. A high temperature resistant basalt fiber, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 7, comprising a base material and a functional coating, wherein the functional coating comprises a zinc source and a nickel source.

9. The high temperature resistant basalt fiber according to claim 8, characterized in that: The thickness of the functional coating is 5 μm-10 μm.

10. Use of the high-temperature resistant basalt fiber prepared by the preparation method according to any one of claims 1 to 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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