A continuous zirconia fiber with an ion gel coating and its preparation method

Abstract

This invention discloses a continuous zirconia fiber with an ionogel coating and its preparation method, belonging to the field of new continuous inorganic ceramic fiber technology. The ionogel coating, formed by the rapid polymerization of ramie fibers modified with a coupling agent using a eutectic solvent under UV light, effectively protects the fibers while maintaining their thinness, uniform thickness, and flexibility. It imparts a certain degree of self-lubricating property to the fibers, thereby reducing frictional damage during the weaving process of continuous zirconia fibers. Simultaneously, this ionogel coating possesses excellent mechanical properties and self-healing capabilities, is not easily peeled off from the fibers, improves the wear resistance of zirconia fibers, and enhances the stability of products in three-dimensional weaves, demonstrating significant commercial value.

Description

Technical Field

[0001] This invention belongs to the field of new continuous inorganic ceramic fiber technology, specifically relating to a continuous zirconia fiber with an ion gel coating and its preparation method. Background Technology

[0002] Zirconia fiber possesses properties such as high temperature resistance, oxidation resistance, low heat capacity, and lightweight, making it highly sought after in aerospace, military defense, and modern advanced industries. However, continuous zirconia fiber suffers from drawbacks such as poor bundle cohesion and high brittleness of single filaments. During three-dimensional weaving, frequent mechanical friction between multiple layers of yarn causes yarn damage, leading to fuzzing, splitting, and even breakage of the zirconia fiber bundles, thus reducing weaving efficiency.

[0003] Ionogels, as an emerging material, have shown great potential in fields such as artificial skin, soft robots, and biomedical engineering. However, their practical applications are greatly limited by factors such as performance degradation due to water loss upon exposure to air, loss of flexibility due to water crystallization at low temperatures, and water corrosion at the interface between hydrogels and metal electrodes. To overcome these shortcomings, researchers have developed ionogels using ionic liquids as solvents. These ionogels are non-corrosive to metal electrodes and the solvent is non-volatile, but they are costly and highly toxic. Deep eutectic solvents are a novel type of ionic liquid with low volatility, biodegradability, and low cost, attracting widespread attention in the fields of separation and dissolution. However, their enormous potential in the preparation of eutectic gels has not been fully explored, and their mechanical properties are not satisfactory due to the shielding effect of the solvent.

[0004] Currently, there is no domestic technology for preparing iontophoresis coatings to improve the weaveability of continuous zirconia fibers. Therefore, it is of great significance to find a way to modify the surface of long, narrow-diameter / low-surface-energy zirconia fibers with iontophoresis coatings that have excellent environmental stability, high mechanical properties, and self-healing properties, so as to improve the bundleability of zirconia fibers, reduce the coefficient of friction of zirconia fibers, reduce the amount of fuzz generated during processing, and meet the performance requirements of zirconia fibers in the subsequent three-dimensional texture forming process such as weaving, lay-up, and winding. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing continuous zirconia fibers with an ion gel coating.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: including,

[0009] (1) Ramie fiber treatment: The pretreated ramie fiber is soaked in a mixed solution of 2.0-3.0 wt% silane coupling agent, 2-4 wt% deionized water and 93-96 wt% anhydrous ethanol for 1-3 hours, while adjusting the pH value of the solution simultaneously. After the reaction is complete, it is washed and dried.

[0010] (2) Preparation of ion gel prepolymer solution mixture: Mix the eutectic solvent with ramie fiber evenly and stir at 70-90℃ for 1-2 hours. After cooling to room temperature, add the photoinitiator and stir evenly to obtain the ion gel prepolymer solution mixture.

[0011] (3) Preparation of continuous zirconia fiber with ion gel coating: The continuous zirconia fiber is immersed in ion gel prepolymer solution, extracted after 1 to 5 min and polymerized under UV conditions to obtain continuous zirconia fiber with ion gel coating.

[0012] The amount of ramie fiber added is 0 to 1.5% of the total mass of the eutectic solvent.

[0013] In a preferred embodiment of the method for preparing continuous zirconia fiber with ion gel coating according to the present invention, the pretreatment involves mechanically crushing ramie fiber and passing it through a 100-mesh sieve, followed by ball milling for finer pulverization.

[0014] In a preferred embodiment of the method for preparing continuous zirconia fibers with ionogel coating according to the present invention, the length of the pretreated ramie fibers is 40-50 μm.

[0015] In a preferred embodiment of the method for preparing continuous zirconia fibers with ionogel coating according to the present invention, the silane coupling agent includes one or more of KH-550 silane coupling agent, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltri(β-methoxyethoxy)silane.

[0016] In a preferred embodiment of the method for preparing continuous zirconia fibers with ionogel coating according to the present invention, the amount of ramie fiber added in the ionogel prepolymer solution is 1% of the total mass of the eutectic solvent.

[0017] In a preferred embodiment of the method for preparing continuous zirconia fibers with ionogel coating according to the present invention, the photoinitiator includes one or more of 2959 (2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone), ethyl 4-dimethylaminobenzoate, 2-isopropylthioxanthone, ethyl 2,4,6-trimethylbenzoylphosphonate, and 2-hydroxy-2-methyl-1-phenylacetone.

[0018] In a preferred embodiment of the method for preparing continuous zirconia fibers with ionogel coating according to the present invention, the eutectic solvent includes one or more of choline chloride, acrylic acid, and hydroxyethyl acrylate.

[0019] In a preferred embodiment of the method for preparing continuous zirconia fibers with ionogel coating according to the present invention, the zirconia fibers are single-strand fibers.

[0020] In a preferred embodiment of the method for preparing continuous zirconia fibers with ionogel coating according to the present invention, the UV irradiation intensity is 50-100W and the time is 10-60s.

[0021] The purpose of this invention is to overcome the shortcomings of the prior art and provide a continuous zirconia fiber with an ion gel coating.

[0022] Beneficial effects of this invention:

[0023] (1) The present invention uses a novel, designable eutectic solvent to prepare ion gels, overcoming the problems of high cost and toxicity of organic solvent ion gels.

[0024] (2) By incorporating ramie fiber, which is abundant, biodegradable and low-cost, into a low eutectic solvent, the resulting ionogel has excellent self-healing and mechanical properties; by treating ramie fiber with a coupling agent, the dispersibility of the fiber in the prepolymer solution is improved.

[0025] (3) This ion gel achieves multifunctional integration, with good flexibility, high transparency, self-healing and excellent mechanical properties, and has a wide range of application prospects; it has the advantages of easy preparation, green environmental protection and low cost; it provides a new idea for the preparation of ion gels that combine abundant raw materials, biodegradability and low cost with excellent mechanical properties.

[0026] (4) By uniformly forming an ion gel coating on the surface of zirconia fiber, the coefficient of friction of the fiber is reduced, which effectively improves the wear resistance of brittle continuous zirconia fiber and gives it certain lubricating properties. At the same time, it improves the fuzzing and breakage phenomena that occur after fiber friction, and improves the mechanical properties and processing performance of the fiber, thereby improving the weavability, weaving efficiency and product quality of continuous zirconia fiber and zirconia fabric. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0028] Figure 1 Mechanical properties of ionogels prepared from AA, HEA and ChCl at different curing times.

[0029] Figure 2 The fracture stress and elongation at break of ionogels prepared from AA, HEA and ChCl at different curing times are shown.

[0030] Figure 3 The toughness and Young's modulus of ionogels prepared from AA, HEA and ChCl at different curing times are shown.

[0031] Figure 4 Mechanical properties of ionogels prepared with AA, HEA and ChCl at different ratios.

[0032] Figure 5 Fracture stress and elongation at break of ionogels prepared from AA, HEA, and ChCl at different ratios; among which, HCAG x-y This refers to an ionogel prepared using AA, HEA, and ChCl, where x refers to the amount of ChCl and y refers to the molar ratio of HEA and AA.

[0033] Figure 6 This is a schematic diagram of the preparation of the ion gel and a schematic diagram of its network microstructure according to the present invention.

[0034] Figure 7 This is a schematic diagram of the structure of the continuous zirconia fiber with an ion gel coating prepared according to the present invention; wherein: 1, ion gel coating; 2, zirconia fiber. Detailed Implementation

[0035] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0036] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0037] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0038] Unless otherwise specified, all raw materials used in this invention are commercially available.

[0039] The materials obtained in the embodiments of the present invention were subjected to performance testing according to the following method:

[0040] The tensile breaking strength test was conducted according to GB / T3362-2005; the stiffness test was conducted according to GB / T7690.4-2013 Test Methods for Reinforcing Yarns Part 4: Determination of Stiffness; the wear rate test was conducted according to FZ / T01058-1999 Test Methods for Yarn Abrasion Resistance - Reciprocating Roller Method; the coefficient of friction (COF) test was conducted using the UMT-Tribolab tribolab friction and wear tester.

[0041] Example 1

[0042] This invention provides a method for preparing eutectic solvent ionogels:

[0043] (1) Preparation of ion gel prepolymer solution mixture: 0.5g choline chloride (ChCl), 1.33g acrylic acid (AA) and 2.67g hydroxyethyl acrylate (HEA) were mixed at 80℃ and stirred at 300r / min for 1h until a colorless and transparent solution was formed. After cooling to room temperature, 0.05g UV initiator (2959) was added and mixed evenly to obtain the ion gel prepolymer solution mixture.

[0044] (2) Pour the ion gel prepolymer solution into a polytetrafluoroethylene mold, place the mold under an 80W UV light source, and cure for 10 seconds to form an ion gel.

[0045] Example 2

[0046] The difference from Example 1 is that the curing time was adjusted to 20 seconds, while the rest of the preparation process was the same as in Example 1, and an ion gel was obtained.

[0047] Example 3

[0048] The difference from Example 1 is that the curing time was adjusted to 30 seconds, while the rest of the preparation process was the same as in Example 1, and an ion gel was obtained.

[0049] Example 4

[0050] The difference from Example 1 is that the curing time was adjusted to 40 seconds, while the rest of the preparation process was the same as in Example 1, and an ion gel was obtained.

[0051] Example 5

[0052] The difference from Example 1 is that the curing time was adjusted to 50 seconds, while the rest of the preparation process was the same as in Example 1, and an ionogel was obtained.

[0053] Depend on Figures 1-3 Analysis shows that curing for 40 seconds in Example 4 is the optimal solution.

[0054] Example 6

[0055] The difference from Example 4 is that in step (1), the ion gel prepolymer solution mixture is prepared by mixing 0.5g ChCl, 2.0g acrylic acid and 2.0g HEA at 80°C and stirring at 300r / min for 1h until a colorless and transparent solution is formed. After cooling to room temperature, 0.05g UV initiator (2959) is added and mixed evenly to obtain the ion gel prepolymer solution mixture.

[0056] Example 7

[0057] The difference from Example 4 is that in step (1), the ion gel prepolymer solution mixture is prepared by mixing 0.5g ChCl, 0.8g acrylic acid and 3.2g HEA at 80°C and stirring at 300r / min for 1h until a colorless and transparent solution is formed. After cooling to room temperature, 0.05g UV initiator (2959) is added and mixed evenly to obtain the ion gel prepolymer solution mixture.

[0058] Example 8

[0059] The difference from Example 4 is that in step (1), the ion gel prepolymer solution mixture is prepared by mixing 0.5g ChCl, 1.0g acrylic acid and 3.0g HEA at 80°C and stirring at 300r / min for 1h until a colorless and transparent solution is formed. After cooling to room temperature, 0.05g UV initiator (2959) is added and mixed evenly to obtain the ion gel prepolymer solution mixture.

[0060] Figure 4 Mechanical properties of ionogels prepared with AA, HEA and ChCl at different ratios; Figure 5 The fracture stress and elongation at break of ionogels prepared with AA, HEA, and ChCl at different ratios were measured. Example 4 was selected as the optimal ratio for preparing eutectic solvent ionogels.

[0061] Example 9

[0062] This embodiment provides a method for preparing continuous zirconium oxide fibers with an ion gel coating, referring to... Figure 6 Specifically:

[0063] S1: Ramie Fiber Treatment: After washing and drying, the ramie fibers are mechanically pulverized and sieved through a 100-mesh sieve. 15g of the sieved ramie fiber powder is weighed and added to the zirconium jar of a planetary ball mill along with 80 zirconium dioxide balls (10mm in diameter). The milling is carried out at 500 rpm for 5 hours, with a 10-minute interval between milling sessions. The resulting ramie fibers have a length of 42–47 μm. 10g of ramie fiber is then soaked in a mixed solution of 2.5 wt% silane coupling agent (KH-550), 2 wt% deionized water, and 95.5 wt% anhydrous ethanol for 1 hour. While stirring, 0.5 mol / L acetic acid solution is added dropwise to adjust the pH to 3.5. After the reaction is complete, the fiber is washed with deionized water to remove the adsorbed silane coupling agent and ethanol, and then dried at 60°C.

[0064] S2: Preparation of ionogel prepolymer solution mixture: Mix 0.5g choline chloride, 1.33g acrylic acid, 2.67g hydroxyethyl acrylate and ramie fiber evenly (ramie fiber content is 1.0% of the total mass of eutectic solvent), stir at room temperature for 1h, cool to room temperature and add 0.05g UV initiator (2959) to obtain ionogel prepolymer solution mixture.

[0065] S3: Continuous zirconia fibers are immersed in the ionogel prepolymer solution obtained in S2. After 5 minutes, the fibers are extracted and polymerization is initiated under 80W UV light for 40 seconds to obtain continuous zirconia fibers with an ionogel coating. The structural schematic diagram is shown below. Figure 7 As shown.

[0066] In this embodiment, repeated friction under a 1N load results in breakage after approximately 300 wear cycles, producing scratches and debris.

[0067] Example 10

[0068] The difference between this embodiment and Example 9 is that the amount of ramie fiber is adjusted to 0 of the total mass of the eutectic solvent, while the rest of the preparation process is the same as in Example 9, to obtain continuous zirconia fiber with an ion gel coating.

[0069] In this embodiment, repeated friction under a 1N load results in breakage after approximately 200 wear cycles, producing scratches and debris.

[0070] Example 11

[0071] The difference between this embodiment and Example 9 is that the amount of ramie fiber is adjusted to 0.5% of the total mass of the eutectic solvent, while the rest of the preparation process is the same as in Example 9, to obtain continuous zirconia fiber with an ion gel coating.

[0072] In this embodiment, repeated friction under a 1N load results in breakage after approximately 230 wear cycles, producing scratches and debris.

[0073] Example 12

[0074] The difference between this embodiment and Example 9 is that the amount of ramie fiber is adjusted to 1.5% of the total mass of the eutectic solvent, while the rest of the preparation process is the same as in Example 9, to obtain continuous zirconia fiber with an ion gel coating.

[0075] In this embodiment, repeated friction under a 1N load resulted in breakage after approximately 287 wear cycles, producing scratches and debris.

[0076] Comparative Example 1

[0077] Raw fibers.

[0078] The performance of the materials prepared in the above embodiments and comparative examples was tested, and the comparison results with those of Example 9 are shown in Table 1.

[0079] Table 1

[0080]

[0081] As shown in Table 1, compared with the original continuous zirconia fiber, under the condition of a coating thickness of approximately 0.12 mm, the fiber wear rate decreased by 2.1%–6.7%, the coefficient of friction decreased by 2.3%–13.1%, and the wear resistance was significantly improved, achieving self-lubricating properties to a certain extent. The tensile properties of the fiber increased by 0.6%–3.2%, and the stiffness decreased, which helps to improve fiber damage and breakage caused by bending deformation during continuous zirconia fiber weaving. Adjusting the amount of ramie fiber added has a significant impact on the performance of continuous zirconia fiber. This is because ramie fiber has high surface activity and high aspect ratio, and its surface has many hydrophilic groups that react and combine with the polar groups in the ion gel. Strong ionic bonds and multiple hydrogen bonds increase the mechanical strength of the ion gel. In summary, the preferred amount of ramie fiber added is 1.0%.

[0082] This invention utilizes a novel, designable eutectic solvent to prepare ionogels, overcoming the high cost and toxicity issues of organic solvent-based ionogels. By incorporating abundant, biodegradable, and low-cost ramie fibers into the eutectic solvent, the resulting ionogel exhibits excellent self-healing and mechanical properties. Treatment of the ramie fibers with a coupling agent improves their dispersibility in the prepolymer solution. This ionogel achieves multifunctional integration, possessing good flexibility, high transparency, self-healing properties, and excellent mechanical properties, showing broad application prospects. It also boasts advantages such as ease of preparation, environmental friendliness, and low cost. This invention provides a new approach to preparing ionogels that combine abundant raw materials, biodegradability, low cost, and superior mechanical properties.

[0083] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing continuous zirconia fibers with an ion-gel coating, characterized in that: include, Ramie fiber treatment: The pretreated ramie fiber is soaked in a mixed solution of 2.0~3.0wt% silane coupling agent, 2~4wt% deionized water and 93~96wt% anhydrous ethanol for 1~3h, while adjusting the pH value of the solution simultaneously. After the reaction is complete, it is washed and dried. Preparation of ionogel prepolymer solution mixture: Mix the eutectic solvent with ramie fiber evenly and stir at 70~90℃ for 1~2h. After cooling to room temperature, add the photoinitiator and stir evenly to obtain the ionogel prepolymer solution mixture. Preparation of continuous zirconia fibers with ion gel coating: Continuous zirconia fibers are immersed in ion gel prepolymer solution, extracted after 1-5 min and polymerized under UV conditions to obtain continuous zirconia fibers with ion gel coating. The amount of ramie fiber added is 0.5-1.5% of the total mass of the eutectic solvent; The length of the pretreated ramie fibers is 40~50 μm; The eutectic solvent is composed of choline chloride, acrylic acid, and hydroxyethyl acrylate. The ionogel prepared using the eutectic solvent is designated as HCAG. x-y Where x refers to the amount of ChCl, and y refers to the molar ratio of HEA and AA, and the ratio of x to y is 0.358:

1.

2. The method for preparing continuous zirconia fibers with an ion-gel coating as described in claim 1, characterized in that: The pretreatment involves mechanically crushing the ramie fibers, passing them through a 100-mesh sieve, and then ball milling them for finer crushing.

3. The method for preparing continuous zirconia fibers with an ion-gel coating as described in claim 1, characterized in that: The silane coupling agent is selected from one or more of KH-550 silane coupling agent, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltri(β-methoxyethoxy)silane.

4. The method for preparing continuous zirconia fibers with an ion-gel coating as described in claim 1, characterized in that: In the ionogel prepolymer solution mixture, the amount of ramie fiber added is 1% of the total mass of the eutectic solvent.

5. The method for preparing continuous zirconia fibers with an ion-gel coating as described in claim 1, characterized in that: The photoinitiator is selected from one or more of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylpropanone, ethyl 4-dimethylaminobenzoate, 2-isopropylthioxanthone, ethyl 2,4,6-trimethylbenzoylphosphonate, and 2-hydroxy-2-methyl-1-phenylpropanone.

6. The method for preparing continuous zirconia fibers with an ion-gel coating as described in claim 1, characterized in that: The zirconium oxide fiber is a single strand fiber.

7. The method for preparing continuous zirconia fibers with an ion-gel coating as described in claim 1, characterized in that: The UV irradiation intensity is 50–100W and the duration is 10–60s.

8. A continuous zirconia fiber with an ion gel coating prepared by any one of the preparation methods described in claims 1 to 7.

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