Alkali-resistant basalt fiber and its preparation method and application

Abstract

The present invention relates to the technical field of basalt fibers and discloses an alkali-resistant basalt fiber and a preparation method and application thereof. The chemical composition of the basalt fiber comprises, by weight percentage, SiO2 40%-70%, Al2O3 4%-11%, CaO+MgO 2%-8%, Fe2O3+FeO 2%-9%, K2O+Na2O 4%-13%, TiO2 4%-10%, ZrO2 2%-9%, B2O3 1%-6%, MoO2 1%-6%, and Ta2O5+Nb2O5 1%-4%. The basalt fiber of the present invention can maintain high stability under alkaline conditions, thereby extending its service life.

Description

Technical Field

[0001] The present invention relates to the technical field of basalt fibers, and in particular to an alkali-resistant basalt fiber and a preparation method and application thereof. Background Art

[0002] Basalt fiber is low in cost, cost-effective, energy-saving and environmentally friendly in the production process, and non-toxic and harmless. It is known as the pollution-free "green material and new material" of the 21st century. Compared with glass fiber, basalt fiber has higher mechanical properties (high elastic modulus, high fracture strength), good insulation performance, excellent temperature resistance and thermal stability, strong radiation resistance and other excellent properties, making it widely used in national defense and military industry, transportation, construction, vehicle and ship manufacturing, petrochemical industry, environmental protection equipment, electronic information, aerospace and other fields. However, since natural basalt ore is used as raw material, the performance of the prepared basalt fiber is relatively simple. Under alkaline conditions, the Si element, Al element, B element in the fiber material reacts with OH - Therefore, how to effectively improve the alkali resistance of basalt fiber is one of the key issues that the industry in this field needs to solve urgently.

[0003] To this end, the relevant technology discloses a method, product and equipment for manufacturing alkali-resistant basalt fiber. Although the method discloses that after being immersed in a saturated Ca(OH)2 solution at 100°C for 4 hours, the tensile strength of the fiber can still be maintained at more than 800MPa, and the retention rate of the single fiber strength exceeds 75%; however, the total content of SiO2 and Al2O3 is too high, resulting in unsatisfactory alkali resistance; and the raw materials include fluorite, which decomposes to produce fluorine-containing gas during the production process of the fiber, which not only pollutes the air, but may also affect the growth environment of surrounding organisms. Cause adverse effects; related technology discloses a formula for alkali-resistant basalt fiber with a multi-mineral combination, the formula is 40-60 weight parts of basalt, 5-15 weight parts of dolomite, 10-18 weight parts of white chrysocolla, 6-8 weight parts of zircon, 2-5 weight parts of ilmenite, 5-10 weight parts of celestite, 6-14 weight parts of calcite, 3-9 weight parts of diopside, 8-11 weight parts of kaolin, the finished product is soaked in an alkaline solution for 28 days, however, the calculated loss rate of SiO2 in the fiber is high.

[0004] Therefore, how to optimize and improve basalt fiber to improve the alkali resistance of basalt fiber is one of the technical problems that need to be solved urgently in this field. Summary of the Invention

[0005] In view of this, the present invention provides an alkali-resistant basalt fiber.

[0006] The present invention also provides a method for preparing the alkali-resistant basalt fiber.

[0007] In a first aspect, the present invention provides an alkali-resistant basalt fiber. The chemical composition of the basalt fiber includes, by mass percentage, SiO2 40%-70%, Al2O3 4%-11%, CaO+MgO 2%-8%, Fe2O3+FeO 2%-9%, K2O+Na2O 4%-13%, TiO2 4%-10%, ZrO2 2%-9%, B2O3 1%-6%, MoO2 1%-6%, and Ta2O5+Nb2O5 1%-4%.

[0008] In an optional embodiment, the chemical composition of the basalt fiber includes: SiO2 45%-69%, Al2O3 5%-10%, CaO+MgO 4%-6%, Fe2O3+FeO 3%-6%, K2O+Na2O 5%-9%, TiO2 6%-7%, ZrO2 4%-6%, B2O3 2%-4%, MoO2 1%-4%, Ta2O5+Nb2O5 1%-3%.

[0009] In an optional embodiment, the chemical composition of the basalt fiber includes: SiO2 54%, Al2O3 10%, CaO+MgO 5%, Fe2O3+FeO 6%, K2O+Na2O 7%, TiO27%, ZrO25%, B2O33%, MoO22%, Ta2O5+Nb2O51%.

[0010] In an optional embodiment, the chemical composition of the basalt fiber includes: SiO2 56%, Al2O 39%, CaO+MgO 4%, Fe2O3+FeO 4%, K2O+Na2O 6%, TiO26%, ZrO26%, B2O 34%, MoO 23%, Ta2O5+Nb2O 52%.

[0011] In an optional embodiment, the chemical composition of the basalt fiber includes: SiO2 59%, Al2O 35%, CaO+MgO 6%, Fe2O3+FeO 3%, K2O+Na2O 8%, TiO26%, ZrO 24%, B2O 32%, MoO 24%, Ta2O5+Nb2O 53%.

[0012] In a second aspect, the present invention provides a method for preparing the above-mentioned alkali-resistant basalt fiber, comprising the following steps:

[0013] (1) mixing and stirring the raw materials of the alkali-resistant basalt fiber to obtain a mixed material;

[0014] (2) The mixed material is sequentially melted and drawn to obtain the alkali-resistant basalt fiber;

[0015] The raw materials of the alkali-resistant basalt fiber include basalt, rutile, zircon, boraxite, potassium feldspar, molybdenite, and tantalum-niobium ore tailings.

[0016] In an optional embodiment, the melting temperature is 1450°C-1600°C.

[0017] In an optional embodiment, the wire drawing temperature is 1320°C-1450°C.

[0018] In an optional embodiment, in step (1), grinding and magnetic separation are further performed in sequence before mixing and stirring.

[0019] In an optional embodiment, the mass ratio of the basalt, the rutile, the zircon, the boraxite, the potassium feldspar, the molybdenite, and the tantalum-niobium ore tailings is 60-100:5-13:5-15:3-10:3-40:2-8:20-50.

[0020] In a third aspect, the present invention provides applications of the above-mentioned alkali-resistant basalt fiber in civil engineering and aerospace.

[0021] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0022] 1. The alkali-resistant basalt fiber provided by the present invention has a chemical composition comprising: SiO2 40%-70%, Al2O3 4%-11%, CaO+MgO 2%-8%, Fe2O3+FeO 2%-9%, K2O+Na2O 4%-13%, TiO2 4%-10%, ZrO2 2%-9%, B2O3 1%-6%, MoO2 1%-6%, and Ta2O5+Nb2O5 1%-4%. The basalt fiber provided by the present invention can maintain high stability under alkaline conditions, thereby extending its service life. Specifically: the main component of potassium feldspar is potassium aluminum silicate, which is a common feldspar mineral, mainly providing potassium and silicate components. Potassium feldspar has a low melting point and a long melting time, which can improve the melting performance of basalt fiber raw materials and make it easier to draw into fiber yarns; MgO, Na2O, and CaO can fill and supplement the network structure inside the basalt fiber, which is beneficial to improve the fiber's resistance to alkaline corrosion; the main component of rutile is TiO2, which can improve the corrosion resistance and waterproof performance of basalt fiber; ZrO2 can improve the alkaline corrosion resistance of basalt fiber, and also improve the heat resistance of basalt fiber; the main components of borax include magnesium, boron and other elements, which is a common boron mineral. Borax is used to extract Boron is a mineral that provides boron. The addition of boron can improve the chemical stability of basalt fiber and make it exhibit good corrosion resistance in different chemical environments. Molybdenite is rich in molybdenum, which has excellent corrosion resistance. Adding molybdenum to basalt fiber can help enhance the corrosion resistance of basalt fiber under alkaline conditions. Tantalum-niobium tailings are rich in tantalum and niobium, which have strong corrosion resistance and high melting points. Adding them to basalt fiber can enhance the adaptability of basalt fiber to corrosive environments and extend the service life of the fiber. At the same time, it is beneficial to improve the heat resistance and mechanical properties (tensile strength, elastic modulus) of basalt fiber, enabling it to maintain excellent performance in extreme high temperature environments.

[0023] Compared with common basalt fiber materials, the alkali-resistant basalt fiber provided by the present invention has lower cost and longer service life and is suitable for use under extreme conditions.

[0024] 2. The preparation method of the alkali-resistant basalt fiber of the present invention has simple raw material composition, mature preparation technology, and is easy to realize industrial production and popularize and apply.

[0025] 3. The preparation method of the alkali-resistant basalt fiber of the present invention further includes grinding and magnetic separation before the stirring and mixing step, which can effectively remove impurities in the raw materials. DETAILED DESCRIPTION

[0026] 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.

[0027] 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.

[0028] 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.

[0029] Example 1

[0030] This embodiment provides a method for preparing alkali-resistant basalt fiber, comprising the following steps:

[0031] (1) Weigh 79 parts by weight of basalt, 7 parts by weight of rutile, 10 parts by weight of zircon, 3 parts by weight of magnesia, 3 parts by weight of potassium feldspar, 3 parts by weight of molybdenite, and 20 parts by weight of tantalum-niobium ore tailings, grind them finely, perform magnetic separation treatment, and stir and mix to obtain a mixed material;

[0032] (2) Melting the above-mentioned mixed material in a high-temperature furnace at 1500°C to obtain a basalt fiber melt;

[0033] (3) The basalt fiber melt is pulled and drawn through a platinum-rhodium alloy bushing at 1320°C; wherein the composition of the basalt fiber includes: SiO2 54%, Al2O3 10%, CaO+MgO 5%, Fe2O3+FeO 6%, K2O+Na2O 7%, TiO27%, ZrO25%, B2O33%, MoO22%, Ta2O5+Nb2O51%; and then, under the action of the impregnating agent, the basalt fiber passes through a bundler, a fiber tensioner, and an automatic winding machine to finally be formed into a tube.

[0034] Example 2

[0035] This embodiment provides a method for preparing alkali-resistant basalt fiber, comprising the following steps:

[0036] (1) Weighing 82 parts by weight of basalt, 6 parts by weight of rutile, 8 parts by weight of zircon, 9 parts by weight of magnesia, 9 parts by weight of potassium feldspar, 4 parts by weight of molybdenite, and 40 parts by weight of tantalum-niobium ore tailings, finely grinding, magnetically separating, and stirring to obtain a mixed material;

[0037] (2) Melting the above-mentioned mixed material in a high-temperature furnace at 1550°C to obtain a basalt fiber melt;

[0038] (3) The basalt fiber melt is pulled and drawn through a platinum-rhodium alloy bushing at 1380°C; wherein the composition of the basalt fiber includes: SiO2 56%, Al2O3 9%, CaO+MgO 4%, Fe2O3+FeO 4%, K2O+Na2O 6%, TiO26%, ZrO26%, B2O34%, MoO23%, Ta2O5+Nb2O52%; and then, under the action of the impregnating agent, the basalt fiber passes through a bundler, a fiber tensioner, and an automatic winding machine to finally be formed into a tube.

[0039] Example 3

[0040] This embodiment provides a method for preparing alkali-resistant basalt fiber, comprising the following steps:

[0041] (2) Weighing 84 parts by weight of basalt, 9 parts by weight of rutile, 8 parts by weight of zircon, 5 parts by weight of magnesia, 30 parts by weight of potassium feldspar, 8 parts by weight of molybdenite, and 30 parts by weight of tantalum-niobium ore tailings, and subjecting them to fine grinding, magnetic separation, and stirring to obtain a mixed material;

[0042] (2) Melting the above-mentioned mixed material in a high-temperature furnace at 1600°C to obtain a basalt fiber melt;

[0043] (3) The basalt fiber melt is pulled and drawn through a platinum-rhodium alloy bushing at 1450°C; wherein the composition of the basalt fiber includes: SiO2 59%, Al2O3 5%, CaO+MgO 6%, Fe2O3+FeO 3%, K2O+Na2O 8%, TiO26%, ZrO24%, B2O32%, MoO24%, Ta2O5+Nb2O53%; and then, under the action of the impregnating agent, the basalt fiber passes through a bundler, a fiber tensioner, and an automatic winding machine to finally be formed into a tube.

[0044] Example 4

[0045] This embodiment provides a method for preparing alkali-resistant basalt fiber, comprising the following steps:

[0046] (1) Weighing 89 parts by weight of basalt, 7 parts by weight of rutile, 10 parts by weight of zircon, 3 parts by weight of magnesia, 40 parts by weight of potassium feldspar, 5 parts by weight of molybdenite, and 50 parts by weight of tantalum-niobium ore tailings, and subjecting them to fine grinding, magnetic separation, and stirring to obtain a mixed material;

[0047] (2) melting the above-mentioned mixture in a high-temperature furnace at 1450°C to obtain a basalt fiber melt;

[0048] (3) The basalt fiber melt is pulled and drawn through a platinum-rhodium alloy bushing at 1350°C; wherein the composition of the basalt fiber includes: SiO2 60%, Al2O3 11%, CaO+MgO 2%, Fe2O3+FeO 2%, K2O+Na2O 9%, TiO24%, ZrO22%, B2O31%, MoO25%, Ta2O5+Nb2O54%; and then, under the action of the impregnating agent, it passes through a bundler, a fiber tensioner, and an automatic winding machine to finally be formed into a tube.

[0049] Example 5

[0050] This embodiment provides a method for preparing alkali-resistant basalt fiber, comprising the following steps:

[0051] (1) Weigh 65 parts by weight of basalt, 5 parts by weight of rutile, 15 parts by weight of zircon, 10 parts by weight of magnesia, 20 parts by weight of potassium feldspar, 2 parts by weight of molybdenite, and 50 parts by weight of tantalum-niobium ore tailings, grind them finely, perform magnetic separation treatment, and stir and mix them to obtain a mixed material;

[0052] (2) Melting the above-mentioned mixed material in a high-temperature furnace at 1600°C to obtain a basalt fiber melt;

[0053] (3) The basalt fiber melt is pulled and drawn through a platinum-rhodium alloy bushing at 1450°C; wherein the composition of the basalt fiber includes: SiO247%, Al2O34%, CaO+MgO 7%, Fe2O3+FeO 2%, K2O+Na2O 13%, TiO25%, ZrO27%, B2O35%, MoO26%, Ta2O5+Nb2O54%; and then, under the action of an impregnating agent, the basalt fiber passes through a bundler, a fiber tensioner, and an automatic winding machine to finally be formed into a tube.

[0054] Example 6

[0055] This embodiment provides a method for preparing alkali-resistant basalt fiber, comprising the following steps:

[0056] (1) Weigh 60 parts by weight of basalt, 10 parts by weight of rutile, 5 parts by weight of zircon, 3 parts by weight of magnesia, 17 parts by weight of potassium feldspar, 6 parts by weight of molybdenite, and 50 parts by weight of tantalum-niobium ore tailings, grind them finely, perform magnetic separation treatment, and stir and mix them to obtain a mixed material;

[0057] (2) Melting the above-mentioned mixed material in a high-temperature furnace at 1580°C to obtain a basalt fiber melt;

[0058] (3) The basalt fiber melt is pulled and drawn through a platinum-rhodium alloy bushing at 1425°C; wherein the composition of the basalt fiber includes: SiO2 41%, Al2O3 11%, CaO+MgO 8%, Fe2O3+FeO 8%, K2O+Na2O 10%, TiO2 10%, ZrO 22%, B2O 31%, MoO 25%, Ta2O5+Nb2O 54%; and then, under the action of the impregnating agent, the basalt fiber passes through a bundler, a fiber tensioner, and an automatic winding machine to finally be formed into a tube.

[0059] Comparative Example 1

[0060] This comparative example provides a preparation method of alkali-resistant basalt fiber, which is basically the same as the steps in Example 1, except that the raw material composition includes: 80 parts by weight of basalt, 10 parts by weight of rutile, 10 parts by weight of zircon, 3 parts by weight of borax, 6 parts by weight of potassium feldspar, 4 parts by weight of molybdenite, and 41 parts by weight of tantalum-niobium ore tailings; the composition of the basalt fiber includes: SiO2 55%, Al2O3 8%, CaO+MgO 3%, Fe2O3+FeO 5%, K2O+Na2O 4%, TiO2 10%, ZrO 25%, B2O 31%, MoO2 4%, and Ta2O5+Nb2O 55%.

[0061] Comparative Example 2

[0062] This comparative example provides a preparation method of alkali-resistant basalt fiber, which is basically the same as the steps in Example 1, except that the raw material composition includes: 83 parts by weight of basalt, 6 parts by weight of rutile, 7 parts by weight of zircon, 9 parts by weight of magnesite, 28 parts by weight of potassium feldspar, 2 parts by weight of molybdenite, and 18 parts by weight of tantalum-niobium ore tailings; the composition of the basalt fiber includes: SiO2 57%, Al2O3 10%, CaO+MgO 8%, Fe2O3+FeO 2%, K2O+Na2O 10%, TiO24%, ZrO23%, B2O33%, MoO22.5%, and Ta2O5+Nb2O50.5%.

[0063] Comparative Example 3

[0064] This comparative example provides a preparation method of alkali-resistant basalt fiber, which is basically the same as the steps in Example 1, except that 80 parts by weight of basalt, 10 parts by weight of rutile, 9 parts by weight of zircon, 4 parts by weight of magnesite, 5 parts by weight of potassium feldspar, 11 parts by weight of molybdenite, and 22 parts by weight of tantalum-niobium ore tailings are used. The composition of the basalt fiber includes: SiO2 55%, Al2O3 5%, CaO + MgO 2%, Fe2O3 + FeO 3%, K2O + Na2O 4%, TiO2 9%, ZrO2 8%, B2O3 6%, MoO2 7%, and Ta2O5 + Nb2O 51%.

[0065] Comparative Example 4

[0066] This comparative example provides a preparation method of alkali-resistant basalt fiber, which is basically the same as the steps in Example 1, except that the raw material composition includes: 86 parts by weight of basalt, 9 parts by weight of rutile, 9 parts by weight of zircon, 4 parts by weight of magnesia, 4 parts by weight of potassium feldspar, 1 part by weight of molybdenite, and 28 parts by weight of tantalum-niobium ore tailings, and the composition of the basalt fiber includes: SiO2 59%, Al2O3 5%, CaO + MgO 2%, Fe2O3 + FeO 2%, K2O + Na2O 4%, TiO2 9%, ZrO2 9%, B2O 36%, MoO2 0.5%, and Ta2O5 + Nb2O5 3.5%.

[0067] Experimental Example 1

[0068] The basalt fibers prepared in each embodiment and comparative example were cut into samples of uniform size and evenly divided into four groups. The samples were placed in 0.1 mol / L NaOH solution and 1 mol / L NaOH solution, respectively. After standing for 12 h, 24 h, and 36 h, the loss rate of each sample was calculated.

[0069] Under alkaline environmental conditions, the following reactions occur on the surface of basalt fiber samples:

[0070]

[0071] The loss rate of basalt fiber in NaOH solutions of different concentrations was calculated according to the following formula. The results are shown in Table 1:

[0072]

[0073] Among them, m1 is the mass of basalt fiber before corrosion, and m2 is the mass of basalt fiber after corrosion.

[0074] Table 1 Loss rate of basalt fiber in different concentrations of NaOH solution in each embodiment and comparative example (%)

[0075]

[0076] As can be seen from the above table, the loss rate of the basalt fibers prepared in Examples 1 to 6 is 3.04%-5.23% in 12 hours, 3.33%-5.58% in 24 hours, and 3.76%-5.83% in 36 hours; in the basalt fibers prepared in Comparative Example 1, the content of Ta2O5+Nb2O5 is too high, which destroys the silicon-oxygen tetrahedral structure in the basalt fibers, causes the silicate network to break, and reduces its alkali resistance; in the basalt fibers prepared in Comparative Example 2, T The content of a2O5+Nb2O5 is too small, and the alkali resistance of the basalt fiber cannot be significantly changed; in the basalt fiber prepared in Comparative Example 3, the content of MoO2 is too large, which destroys the network structure of the basalt fiber, accelerates the erosion in the alkaline solution, and causes the mass loss of the basalt fiber to increase; in the basalt fiber prepared in Comparative Example 4, the content of MoO2 is relatively small, and the performance of the basalt fiber cannot be significantly changed. Due to its poor alkali resistance, it has a large mass loss rate in the alkaline solution.

[0077] 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. An alkali-resistant basalt fiber, characterized in that: Calculated by mass percentage, the chemical composition of the basalt fiber is: SiO2 40%-70%, Al2O3 4%-11%, CaO+MgO 2%-8%, Fe2O3+FeO 2%-9%, K2O+Na2O 4%-13%, TiO2 4%-10%, ZrO2 2%-9%, B2O3 1%-6%, MoO2 1%-6%, Ta2O5+Nb2O5 1%-4%; The raw materials of the alkali-resistant basalt fiber include basalt, rutile, zircon, boraxite, potassium feldspar, molybdenite, and tantalum-niobium ore tailings.

2. The alkali-resistant basalt fiber according to claim 1, characterized in that: The chemical composition of the basalt fiber is: SiO2 45%-69%, Al2O3 5%-10%, CaO+MgO 4%-6%, Fe2O3+FeO 3%-6%, K2O+Na2O 5%-9%, TiO26%-7%, ZrO2 4%-6%, B2O3 2%-4%, MoO2 1%-4%, Ta2O5+Nb2O5 1%-3%.

3. The alkali-resistant basalt fiber according to claim 1 or 2, characterized in that: The chemical composition of the basalt fiber is: SiO2 54%, Al2O3 10%, CaO+MgO 5%, Fe2O3+FeO 6%, K2O+Na2O 7%, TiO2 7%, ZrO2 5%, B2O3 3%, MoO2 2%, Ta2O5+Nb2O5 1%.

4. The alkali-resistant basalt fiber according to claim 1 or 2, characterized in that: The chemical composition of the basalt fiber is: SiO2 56%, Al2O3 9%, CaO+MgO 4%, Fe2O3+FeO 4%, K2O+Na2O 6%, TiO2 6%, ZrO2 6%, B2O34%, MoO2 3%, Ta2O5+Nb2O5 2%.

5. The alkali-resistant basalt fiber according to claim 1 or 2, characterized in that: The chemical composition of the basalt fiber is: SiO2 59%, Al2O3 5%, CaO+MgO 6%, Fe2O3+FeO 3%, K2O+Na2O 8%, TiO2 6%, ZrO2 4%, B2O32%, MoO2 4%, Ta2O5+Nb2O5 3%.

6. A method for preparing the alkali-resistant basalt fiber according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) mixing and stirring the raw materials of the alkali-resistant basalt fiber to obtain a mixed material; (2) The mixed material is sequentially melted and drawn to obtain the alkali-resistant basalt fiber; The raw materials of the alkali-resistant basalt fiber include basalt, rutile, zircon, boraxite, potassium feldspar, molybdenite, and tantalum-niobium ore tailings.

7. The method for preparing alkali-resistant basalt fiber according to claim 6, characterized in that: The melting temperature is 1450°C-1600°C; And / or, the wire drawing temperature is 1320°C-1450°C.

8. The method for preparing alkali-resistant basalt fiber according to claim 6 or 7, characterized in that: In step (1), grinding and magnetic separation are also performed in sequence before mixing and stirring.

9. The method for preparing alkali-resistant basalt fiber according to claim 6 or 7, characterized in that: The mass ratio of the basalt, the rutile, the zircon, the magnesite, the potassium feldspar, the molybdenite, and the tantalum-niobium ore tailings is 60-100:5-13:5-15:3-10:3-40:2-8:20-50.

10. Use of the alkali-resistant basalt fiber according to any one of claims 1 to 5 or the alkali-resistant basalt fiber prepared by the preparation method according to any one of claims 6 to 9 in civil engineering and aerospace.

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