Basalt fiber based on phase transformation toughening of zirconia, and preparation method therefor

Abstract

The present invention belongs to the field of inorganic fiber materials with high performance, and provides a basalt fiber based on the phase transformation toughening of zirconia, and a preparation method therefor. The basalt fiber based on the phase transformation toughening of zirconia comprises the following components in parts by mass: 100 parts of basalt, 5-10 parts of a phase transformation toughening material, and 0.5-1.5 parts of inorganic reinforcing whiskers, wherein the phase transformation toughening material comprises a metallic oxide carrier, yttrium-oxide-doped tetragonal nano-zirconia, and a grinding aid. The preparation method comprises: crushing, grinding and sieving basalt, then heating the basalt to melt same, and maintaining the temperature thereof; adding the phase transformation toughening material, performing ultrasonic dispersion, and then cooling same; and adding inorganic reinforcing whiskers, performing ultrasonic dispersion, and then drawing same to obtain a basalt fiber based on the phase transformation toughening of zirconia. The basalt fiber based on the phase transformation toughening of zirconia has better tensile strength and a better tensile modulus of elasticity, and meets the requirements of performance indexes of high-modulus basalt fibers.

Description

A basalt fiber toughened by zirconium oxide phase change and its preparation method

[0001] This application claims priority to a Chinese patent application filed with the Patent Office of China on April 2, 2024, with application number CN202410395420.8 and invention name “A basalt fiber toughened by zirconia phase change and its preparation method”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The present application belongs to the field of high-performance inorganic fiber materials, and specifically relates to a basalt fiber toughened by zirconium oxide phase change and a preparation method thereof. Background Art

[0003] Basalt fiber is a high-performance inorganic fiber made by rapidly drawing basalt stone through a bushing after melting it at high temperatures. It exhibits excellent physical and chemical properties, including heat resistance, single-filament mechanical strength, elastic modulus, density, creep rupture stress, and chemical stability. Its corrosion resistance surpasses that of ordinary glass fiber. Furthermore, its production process generates minimal waste, and its discarded product poses no environmental hazards, making it a truly green and environmentally friendly material. Currently, basalt fiber is used in a wide range of fields, including national defense and military industry, civil engineering, building reinforcement, marine engineering, ultra-high voltage power transmission, rail transit vehicles, lightweight automobiles, fire protection, and environmental protection.

[0004] However, many emerging fields have further increased their demands for the strength of fiber materials. At the same time, the performance of basalt fiber based on the current production process cannot meet the new requirements. It is urgent to develop new technologies and processes to improve the strength of basalt fiber to adapt to the technological development of emerging fields.

[0005] Summary of the Invention

[0006] In response to the problems and shortcomings of the existing technology, the present application provides a basalt fiber toughened by zirconium oxide phase change and a preparation method thereof.

[0007] Based on the above objectives, this application adopts the following technical solutions:

[0008] In a first aspect, the present application provides a basalt fiber based on zirconium oxide phase change toughening, which comprises, by weight: 100 parts of basalt, 5-10 parts of phase change toughening material, and 0.5-1.5 parts of inorganic reinforcing whiskers;

[0009] The phase change toughening material comprises a metal oxide carrier, yttria-doped tetragonal nano zirconium oxide and a grinding aid.

[0010] Preferably, the basalt comprises the following chemical components by mass fraction: SiO2+Al2O3 69% to 83%, Fex O y 10% to 15%, CaO + MgO 5% to 10%, NaO + K2O 2% to 5%, others 0% to 1%. x O y represents iron oxides, including Fe2O3 and / or FeO.

[0011] Preferably, the phase change toughening material comprises the following components in parts by mass: 100 parts of a metal oxide carrier, 5 to 10 parts of yttria-doped tetragonal nano-zirconia, and 1 to 2 parts of a grinding aid.

[0012] More preferably, the metal oxide carrier is at least one of calcium oxide (CaO), magnesium oxide (MgO), cerium oxide (CeO2) and yttrium oxide (Y2O3), and has an average particle size of 1 to 10 μm.

[0013] More preferably, the mass fraction of yttrium oxide in the yttrium oxide-doped tetragonal nano-zirconia is 4% to 8%.

[0014] More preferably, the average particle size of the yttria-doped tetragonal nano-zirconia is 10 to 100 nm.

[0015] More preferably, the grinding aid is at least one of sodium hexametaphosphate, sodium tripolyphosphate and sodium polyacrylate.

[0016] Furthermore, the phase change toughening material is prepared by the following method: a metal oxide carrier, yttria-doped tetragonal nano-zirconium oxide, and a grinding aid are ball-milled and mixed.

[0017] Furthermore, the ball milling medium is alumina ceramic balls.

[0018] Furthermore, the ball milling has a rotation speed of 200 to 400 r / min and a duration of 30 to 60 min.

[0019] Preferably, the inorganic reinforcing whiskers are at least one of zirconium oxide whiskers, boron nitride whiskers and silicon carbide whiskers.

[0020] Preferably, the diameter of the inorganic reinforcing whisker is 0.1-3 μm, and the aspect ratio is 20-100.

[0021] In a second aspect, the present application provides a method for preparing basalt fiber toughened by zirconium oxide phase change, comprising the following steps:

[0022] (1) ball-milling a metal oxide support, yttria-doped tetragonal nano-zirconia, and a grinding aid to obtain a phase change toughening material;

[0023] (2) crushing, grinding, and sieving the basalt, heating and melting the basalt to obtain a basalt melt, adding the phase change toughening material to the basalt melt, performing a first ultrasonic dispersion, and then cooling, and then adding the inorganic reinforcing whiskers and performing a second ultrasonic dispersion to obtain a mixed melt;

[0024] (3) Drawing the mixed melt to obtain the zirconia-based phase-change toughened basalt fiber.

[0025] Furthermore, the screening in step (2) is performed using a 100-mesh square-hole sieve.

[0026] Furthermore, the temperature of the heating and melting in step (2) is set to 1500°C to 1700°C.

[0027] Furthermore, the insulation time in step (2) is 1 to 2 hours.

[0028] Furthermore, in step (2), the duration of the first ultrasonic dispersion is 30 to 60 minutes, the duration of the second ultrasonic dispersion is 20 to 40 minutes, and the frequencies of the first ultrasonic dispersion and the second ultrasonic dispersion are independently 20 kHz to 80 kHz.

[0029] Furthermore, the cooling temperature in step (2) is reduced to 1400°C to 1500°C.

[0030] Furthermore, the wire drawing speed in step (3) is 4 to 8 m / s.

[0031] Compared with the prior art, the present invention has the following advantages:

[0032] 1. The present application adds a phase change toughening material to the basalt fiber, wherein the tetragonal nano-zirconia particles can improve the fracture toughness of the fiber through stress-induced phase change toughening and other mechanisms when microcracks occur in the fiber, thereby improving the tensile strength and tensile elastic modulus of the basalt fiber; using metal oxides as carriers of the phase change toughening material can reduce the agglomeration of nano-zirconia in the basalt melt, thereby obtaining a uniformly dispersed melt and further improving the mechanical properties of the basalt fiber, especially when using metal oxides such as CaO, MgO, CeO2, and Y2O3, which can better infiltrate with nano-zirconia.

[0033] 2. This application incorporates inorganic reinforcing whiskers into basalt fiber and distributes them evenly throughout the basalt melt through ultrasonic dispersion. After drawing, the whiskers slow the growth of crack tips within the fiber through bridging and crack deflection mechanisms, thereby improving the fracture toughness of the basalt fiber.

[0034] 3. The basalt fiber based on zirconium oxide phase change toughening provided in this application has better tensile strength and tensile elastic modulus. Under the combined action of phase change toughening material and inorganic reinforcing whiskers, the tensile strength of the basalt fiber is as high as 4525MPa, and the tensile elastic modulus is as high as 107GPa, which meets the performance index requirements of high-strength and high-modulus basalt fiber in GB / T38111-2019. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of this application clearer and more specific, the following further describes this application in detail through examples. It should be understood that the specific examples described herein are only used to explain this application and are not intended to limit this application.

[0036] Example 1

[0037] A basalt fiber based on zirconium oxide phase change toughening comprises the following components, calculated by mass: 100 parts of basalt, 7 parts of phase change toughening material, and 1 part of inorganic reinforcing whisker (with a diameter of 1 μm and an aspect ratio of 30).

[0038] The above-mentioned method for preparing basalt fiber based on zirconium oxide phase change toughening comprises the following steps:

[0039] (1) 100 parts of magnesium oxide (average particle size of 6 μm), 7 parts of yttria-doped tetragonal nano-zirconia (average particle size of 50 nm, Y2O3 mass fraction of 6%), and 1.5 parts of sodium tripolyphosphate were ball-milled using alumina ceramic balls as the ball milling medium at a speed of 300 r / min for 45 min to obtain a phase change toughened material.

[0040] (2) 100 parts of basalt (including chemical composition of SiO2+Al2O3 75%, Fe x O y 12%, CaO+MgO 8.5%, NaO+K2O 4%, and other 0.5%) were crushed and ground, passed through a 100-mesh square-hole sieve, heated to 1600°C to melt and kept warm for 1.5 hours to obtain a basalt melt. 7 parts of the phase change toughening material were added to the basalt melt and ultrasonically dispersed for 45 minutes at a frequency of 40 kHz. The mixture was then cooled to 1450°C, and 1 part of zirconia whiskers was added. The mixture was ultrasonically dispersed for 20 minutes at a frequency of 40 kHz to obtain a mixed melt.

[0041] (3) Drawing the mixed melt at a drawing speed of 6 m / s to obtain the zirconia phase-transformation toughened basalt fiber.

[0042] Comparative Example 1

[0043] A basalt fiber preparation method comprises the following steps:

[0044] (1) 100 parts of basalt (including chemical composition of SiO2+Al2O3 75%, Fe x O y 12%, CaO+MgO 8.5%, NaO+K2O 4%, and other 0.5%) were crushed and ground, passed through a 100-mesh square-hole sieve, heated to 1600°C to melt and kept warm for 1.5 hours to obtain basalt melt.

[0045] (2) The basalt melt is drawn at a drawing speed of 6 m / s to obtain a basalt fiber.

[0046] The basalt fibers prepared in Example 1 and Comparative Example 1 were tested for their properties according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 1.

[0047] Table 1 Effect of toughening modification on the properties of basalt fiber

[0048] As can be seen from Table 1, in Comparative Example 1, the tensile strength and tensile elastic modulus of the basalt fiber are lower than those of the basalt fiber in Example 1, indicating that after the toughening material and process used in the present application to toughen and modify the basalt fiber, the tensile strength and tensile elastic modulus of the basalt fiber are significantly improved.

[0049] Example 2

[0050] A basalt fiber based on zirconium oxide phase change toughening, whose composition and preparation method are basically the same as those in Example 1, except that the amount of phase change toughening material used is 5 parts.

[0051] Example 3

[0052] A basalt fiber based on zirconium oxide phase change toughening, whose composition and preparation method are basically the same as those in Example 1, except that the amount of phase change toughening material used is 10 parts.

[0053] Comparative Example 2

[0054] A basalt fiber based on zirconium oxide phase change toughening, whose composition and preparation method are basically the same as those of Example 1, except that no phase change toughening material is added.

[0055] The performance of the basalt fibers prepared in Examples 2 to 3 and Comparative Example 2 was tested according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 2.

[0056] Table 2 Effect of phase change toughening material dosage on basalt fiber properties

[0057] As can be seen from Table 2, in Comparative Example 2, the basalt fiber without adding phase change toughening material has a lower tensile strength and tensile elastic modulus than the basalt fibers of other examples. Among them, in Example 1, when the amount of phase change toughening material is 7 parts by mass, the tensile strength and tensile elastic modulus of the basalt fiber are higher than those of other examples.

[0058] Example 4

[0059] A basalt fiber based on zirconium oxide phase change toughening, whose composition and preparation method are basically the same as those in Example 1, except that the metal oxide carrier in the phase change toughening material is calcium oxide.

[0060] Example 5

[0061] A basalt fiber based on zirconium oxide phase change toughening, whose composition and preparation method are basically the same as those in Example 1, except that the metal oxide carrier in the phase change toughening material is cerium oxide.

[0062] Example 6

[0063] A basalt fiber based on zirconium oxide phase change toughening, whose composition and preparation method are basically the same as those in Example 1, except that the metal oxide carrier in the phase change toughening material is calcium oxide and yttrium oxide mixed in a mass ratio of 4:1.

[0064] The properties of the basalt fibers prepared in Examples 4 to 6 were tested according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 3.

[0065] Table 3 Effect of metal oxide carrier types in phase change toughening materials on the properties of basalt fibers

[0066] As can be seen from Table 3, in Example 1, when the metal oxide carrier in the phase change toughening material is magnesium oxide, its tensile strength and tensile elastic modulus are higher than those of other examples.

[0067] Example 7

[0068] A basalt fiber based on zirconium oxide phase change toughening has a composition and a preparation method that are substantially the same as those in Example 1, except that the amount of yttria-doped tetragonal nano-zirconia in the phase change toughening material is 5 parts.

[0069] Example 8

[0070] A basalt fiber based on zirconium oxide phase change toughening has a composition and a preparation method that is substantially the same as that of Example 1, except that the amount of yttria-doped tetragonal nano-zirconia in the phase change toughening material is 10 parts.

[0071] Comparative Example 3

[0072] A basalt fiber based on zirconium oxide phase change toughening, whose composition and preparation method are basically the same as those of Example 1, except that yttria-doped tetragonal nano-zirconia is not added to the phase change toughening material.

[0073] The performance of the basalt fibers prepared in Examples 7 and 8 and Comparative Example 3 was tested according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 4.

[0074] Table 4 Effect of the amount of yttria-doped tetragonal nanozirconia in phase change toughening materials on the properties of basalt fibers

[0075] As can be seen from Table 4, in Comparative Example 3, in which yttria-doped tetragonal nano-zirconia is not added to the phase change toughening material, the tensile strength and tensile elastic modulus of the basalt fiber are lower than those of the basalt fibers in other examples. In particular, in Example 1, when the amount of yttria-doped tetragonal nano-zirconia in the phase change toughening material is 7 parts by mass, the tensile strength and tensile elastic modulus of the basalt fiber are higher than those of the other examples.

[0076] Example 9

[0077] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those of Example 1, except that the mass fraction of Y2O3 in the yttria-doped tetragonal nano-zirconia is 4%.

[0078] Example 10

[0079] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those of Example 1, except that the mass fraction of Y2O3 in the yttria-doped tetragonal nano-zirconia is 8%.

[0080] The properties of the basalt fibers prepared in Examples 9 and 10 were tested according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 5.

[0081] Table 5 Effect of Y2O3 mass fraction in yttria-doped tetragonal nanozirconia on the properties of basalt fiber

[0082] As shown in Table 5, in Example 1, when the mass fraction of Y2O3 in the yttria-doped tetragonal nano-zirconia is 6%, its tensile strength and tensile elastic modulus are higher than those of other examples.

[0083] Example 11

[0084] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those in Example 1, except that the amount of inorganic reinforcing whiskers used is 0.5 parts.

[0085] Example 12

[0086] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those in Example 1, except that the amount of inorganic reinforcing whiskers used is 1.5 parts.

[0087] Comparative Example 4

[0088] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those of Example 1, except that no inorganic reinforcing whiskers are added.

[0089] The basalt fibers prepared in Examples 11 and 12 and Comparative Example 4 were tested for their properties according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 6.

[0090] Table 6 Effect of the amount of inorganic reinforcing whiskers on the properties of basalt fiber

[0091] As shown in Table 6, in Example 1, when the amount of inorganic reinforcing whiskers is 1 part by mass, the tensile strength and tensile elastic modulus are higher than those of other examples.

[0092] Example 13

[0093] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those of Example 1, except that the inorganic reinforcing whiskers are boron nitride whiskers.

[0094] Example 14

[0095] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those of Example 1, except that the inorganic reinforcing whiskers are silicon carbide whiskers.

[0096] The properties of the basalt fibers prepared in Examples 13 and 14 were tested according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 7.

[0097] Table 7 Effect of inorganic reinforcing whisker types on basalt fiber properties

[0098] As can be seen from Table 7, in Example 1, when the inorganic reinforcing whiskers are zirconia whiskers, the tensile strength and tensile elastic modulus are higher than those of the other examples.

[0099] Example 15

[0100] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those in Example 1, except that in step (2), the heating temperature is 1500°C and the cooling temperature is 1400°C.

[0101] Example 16

[0102] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those in Example 1, except that in step (2), the heating temperature is 1700°C and the cooling temperature is 1500°C.

[0103] The properties of the basalt fibers prepared in Examples 15 and 16 were tested according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 8.

[0104] Table 8 Effect of temperature regime on basalt fiber properties

[0105] As can be seen from Table 8, in Example 1, when the heating temperature in step (2) is 1600°C and the cooling temperature is 1450°C, the tensile strength and tensile elastic modulus are higher than those of other examples.

[0106] Example 17

[0107] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those in Example 1, except that in step (3), the drawing speed is 4 m / s.

[0108] Example 18

[0109] A basalt fiber toughened by zirconium oxide phase change, whose composition and preparation method are basically the same as those in Example 1, except that in step (3), the drawing speed is 8 m / s.

[0110] The properties of the basalt fibers prepared in Examples 17 and 18 were tested according to the test method described in GB / T 20310-2006 “Preparation of Glass Fiber Roving and Dipped Yarn Samples and Determination of Tensile Strength”. The results are shown in Table 9.

[0111] Table 9 Effect of drawing speed on basalt fiber properties

[0112] It can be seen from Table 9 that in Example 1, when the drawing speed in step (3) is 6 m / s, its tensile strength and tensile elastic modulus are higher than those of other examples.

[0113] As shown in Tables 1 to 9, the zirconia phase-transform toughened basalt fiber prepared in this application exhibits higher tensile strength and tensile modulus. The basalt fiber prepared in Example 1 has a tensile strength of up to 4525 MPa and a tensile modulus of up to 107 GPa, meeting the performance requirements for high-strength, high-modulus basalt fibers specified in GB / T38111-2019.

[0114] Although the above embodiment provides a detailed description of the present application, it is only a part of the embodiments of the present application rather than all the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present application.

Claims

1. A basalt fiber toughened by zirconium oxide phase change, characterized in that: The composition comprises the following components by weight: 100 parts of basalt, 5 to 10 parts of phase change toughening material, and 0.5 to 1.5 parts of inorganic reinforcing whiskers; The phase change toughening material comprises a metal oxide carrier, yttria-doped tetragonal nano zirconium oxide and a grinding aid.

2. The zirconia phase-change toughened basalt fiber according to claim 1, characterized in that: The phase change toughening material comprises the following components in parts by mass: 100 parts of a metal oxide carrier, 5-10 parts of yttria-doped tetragonal nano-zirconium oxide, and 1-2 parts of a grinding aid.

3. The zirconia phase-change toughened basalt fiber according to claim 1 or 2, characterized in that: The metal oxide carrier is at least one of calcium oxide, magnesium oxide, cerium oxide and yttrium oxide, and has an average particle size of 1 to 10 μm.

4. The zirconia phase-change toughened basalt fiber according to claim 1 or 2, characterized in that: The mass fraction of yttrium oxide in the yttrium oxide-doped tetragonal nano-zirconium oxide is 4% to 8%.

5. The zirconia phase-change toughened basalt fiber according to claim 1, characterized in that: The inorganic reinforcing whiskers are at least one of zirconium oxide whiskers, boron nitride whiskers and silicon carbide whiskers.

6. The zirconia phase-change toughened basalt fiber according to claim 1 or 5, characterized in that: The inorganic reinforcing whisker has a diameter of 0.1 to 3 μm and an aspect ratio of 20 to 100.

7. The zirconia phase-transform toughened basalt fiber according to claim 1, characterized in that: The basalt includes the following chemical components by mass fraction: SiO2+Al2O369%-83%, Fe x O y 10%~15%, CaO+MgO5%~10%, NaO+K2O2%~5%, others 0%~1%.

8. The zirconia phase-change toughened basalt fiber according to claim 1 or 2, characterized in that: The average particle size of the yttrium oxide-doped tetragonal nano-zirconium oxide is 10-100 nm.

9. The zirconia phase-change toughened basalt fiber according to claim 1 or 2, characterized in that: The grinding aid is at least one of sodium hexametaphosphate, sodium tripolyphosphate and sodium polyacrylate.

10. The zirconia phase change toughened basalt fiber according to claim 1 or 2, characterized in that: The phase change toughening material is prepared by the following method: a metal oxide carrier, yttria-doped tetragonal nano zirconium oxide and a grinding aid are ball-milled and mixed.

11. The zirconia phase-change toughened basalt fiber according to claim 10, characterized in that: The medium of the ball mill is alumina ceramic balls.

12. The zirconia phase-transformation toughened basalt fiber according to claim 10, characterized in that: The ball mill has a rotation speed of 200 to 400 r / min and a duration of 30 to 60 min.

13. The method for preparing basalt fiber toughened by zirconium oxide phase change according to any one of claims 1 to 12, characterized in that: The following steps are involved: (1) ball-milling a metal oxide support, yttria-doped tetragonal nano-zirconia, and a grinding aid to obtain a phase change toughening material; (2) crushing, grinding, and sieving the basalt, heating and melting the basalt to obtain a basalt melt, adding the phase change toughening material to the basalt melt, performing a first ultrasonic dispersion, and then cooling, and then adding the inorganic reinforcing whiskers and performing a second ultrasonic dispersion to obtain a mixed melt; (3) Drawing the mixed melt to obtain the zirconia-based phase-change toughened basalt fiber.

14. The preparation method according to claim 13, wherein The heating and melting temperature in step (2) is set to 1500°C to 1700°C, and the cooling temperature is set to 1400°C to 1500°C.

15. The preparation method according to claim 13, wherein The drawing speed in step (3) is 4 to 8 m / s.

16. The preparation method according to claim 13, wherein The sieving in step (2) is performed using a 100-mesh square-hole sieve.

17. The preparation method according to claim 13 or 14, characterized in that: The insulation time in step (2) is 1 to 2 hours.

18. The preparation method according to claim 13, wherein In step (2), the duration of the first ultrasonic dispersion is 30 to 60 minutes, the duration of the second ultrasonic dispersion is 20 to 40 minutes, and the frequencies of the first ultrasonic dispersion and the second ultrasonic dispersion are independently 20 kHz to 80 kHz.

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