WO2017045181A1 - 一种金属氧化物宏观纤维及其制备方法 - Google Patents

一种金属氧化物宏观纤维及其制备方法 Download PDF

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WO2017045181A1
WO2017045181A1 PCT/CN2015/089816 CN2015089816W WO2017045181A1 WO 2017045181 A1 WO2017045181 A1 WO 2017045181A1 CN 2015089816 W CN2015089816 W CN 2015089816W WO 2017045181 A1 WO2017045181 A1 WO 2017045181A1
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Prior art keywords
metal oxide
oxide
fiber
aqueous solution
macrofiber
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PCT/CN2015/089816
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English (en)
French (fr)
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耿凤霞
侯俊宇
郑远川
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苏州大学张家港工业技术研究院
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Priority to PCT/CN2015/089816 priority Critical patent/WO2017045181A1/zh
Priority to US15/760,254 priority patent/US10655245B2/en
Publication of WO2017045181A1 publication Critical patent/WO2017045181A1/zh

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Definitions

  • the present invention relates to a method for preparing a fiber, and more particularly to a metal oxide macrofiber and a method of preparing the same.
  • Fiber devices have a unique one-dimensional structure and diverse functions, and are widely used in many fields such as smart textiles, sensors, drives, lithium-ion batteries, and dye-sensitized batteries. Therefore, research on fibers and their preparation methods has become one of the most active development directions in the current scientific and technological field.
  • the preparation methods of the fibers mainly include wet spinning, dry spinning, melt spinning, gel spinning, and electrospinning. Among them, the wet spinning method has the advantages of simple method, easy control of the preparation process, wide range of materials that can be prepared, and the like, which is commonly used in the fiber preparation process.
  • the preparation process of the wet spinning method comprises: (1) preparing a spinning dope; (2) extruding the spinning dope from the spinning hole; (3) forming the primary fiber in the coagulation bath containing the flocculating agent (4) Post-treatment of nascent fibers.
  • Metal oxides have unique physicochemical properties, and researchers generally coat them on the surface of polymer nanofibers or blend with polymer nanofiber raw materials to prepare polymer/metal oxide nanoparticles by wet spinning.
  • Composite fibers which can improve the performance of polymer nanofibers.
  • the single metal oxide macrofibers it has not been reported, and the prior art generally adopts the electrospinning method to prepare only metal oxide nanofibers, and the precursor synthesis is complicated, and it is necessary to use an organic substance such as PVA, and the subsequent sintering removes the PVA. The process can cause unstable fiber properties and can also pollute the environment.
  • the metal oxide macrofiber cannot be prepared by the existing electrospinning method, and the existing wet spinning method can only prepare the polymer/metal oxide composite fiber, and can not prepare the metal.
  • Oxide macro fiber [0005]
  • the metal oxide nanofibers prepared by the prior preparation methods have poor orientation, resulting in poor mechanical properties and structural instability, which makes the application of metal oxide fibers difficult; and the existing methods do not satisfy the preparation of metal oxides. Macroscopic fiber requirements. Therefore, it is necessary to develop a simple and efficient preparation method to obtain a metal oxide macro fiber having good mechanical properties, stable structural properties, and favorable industrial production, thereby obtaining a fiber device with higher degree of functionalization assembled therefrom. It not only expands the research and application range of metal oxides, but also provides a new idea for the research of flexible sensors and flexible energy storage devices.
  • the object of the present invention is to provide a simple and controllable method for preparing metal oxide macrofibers, which can change the metal oxide-containing composite nanofibers which can only be obtained by the existing preparation method, and the nanofiber mechanics thereof. Poor performance, unstable structural performance, and difficult application.
  • a method for preparing a metal oxide macro fiber comprises the following steps:
  • the anionic metal oxide colloidal aqueous solution is placed in a wet spinning apparatus, and then wet-spun in a coagulation bath to obtain nascent fibers; the nascent fibers are washed by deionized water and dried to obtain metal oxidation. Macroscopic fiber; the coagulation bath contains a flocculant having a mass fraction of 0.5 to 5%; the wet spinning speed is 0.1 to 5 mIJmin ; and the total concentration of the metal oxide in the anionic metal oxide colloidal aqueous solution is 0.1 to 20 mg/mL.
  • the anionic metal oxide is one of manganese oxide, titanium oxide, cerium oxide, cerium oxide, cerium oxide, tungsten oxide, tungsten oxide cerium, calcium cerium oxide, titanium cerium oxide or a mixture of several; wherein the manganese oxide is ⁇ -, 0 ⁇ ⁇ ⁇ 1, or A 2 Na y - 3 Mn0 3y + r, wherein A is Ca, Sr, Ba, 3 ⁇ y ⁇ 6; Is TaO 3 -, SrTa 2 0 7 2 -, La 0 . 7 Tb 0 . 3 Ta 2 0 7 - or Eu .
  • the tungsten oxide is W 2 0 7 2- ; the tungsten oxide ruthenium is Cs 4 W lake 0 36 2- ; the yttrium oxide is RuO ⁇ - or Ru0 2 z -, 0 ⁇ 1;
  • the cerium oxide is Nb 6 0 17 4 -, Nb 3 0 8 -, LaNb 2 0 7 or La 0 . 9 Eu 0 . 05 Nb 2 O 7 - ; n O -, 0 ⁇ n ⁇ l; Ti 0 . 8 Co 0 . 2 ⁇ 2 ⁇ 4 -; Bi 4 Ti 3 0 12 2 -; Ti o.eFe 0 .
  • the anionic metal oxide is ⁇ ⁇ 87 0 2 ° ⁇ 52 -, W 2 0 7 2 -, TiNb 6 0 5 5 -, Ca 2 Nb 3O 10 , TaO 3 , Nb 6 0 17
  • the invention names an anionic metal oxide with a main element in a metal oxide, including a metal oxide consisting only of the main element and oxygen, such as W 2 0 7 2- ; also includes a miscellaneous element and the main A metal oxide composed of an element or oxygen, such as 11. . 8 0. . 2 0 2 .
  • an aqueous solution of salts include metal oxides of a single crystal by high temperature sintering; In Inserting a guest molecule into a metal oxide salt single crystal; peeling off a single metal oxide salt crystal inserted into a guest molecule to obtain a metal oxide having a rigid structure; and centrifuging the stripped metal oxide with deionized water to obtain an anion Type of metal oxide colloidal aqueous solution.
  • the general process of preparing anionic metal oxide colloidal aqueous solution of the cationic metal oxide includes manganese oxide; cerium oxide; cerium oxide; tungsten oxide, including miscellaneous tungsten oxide; cerium oxide, including exotic Hetero-type cerium oxide; titanium oxide, including miscellaneous titanium oxide; and perovskite-type oxide; different anionic metal oxide colloidal aqueous solutions can be prepared by changing the metal oxide raw material.
  • a metal oxide colloidal aqueous solution refers to a solid anionic gold of a certain size. Oxide dispersed in the resulting solution in water.
  • the coagulation bath comprises one or a mixture of water, methanol, ethanol, propanol, acetone;
  • the flocculating agent is a barium salt, an aluminum salt, an iron salt, a copper salt, Calcium, magnesium, zinc, sodium, lithium, potassium, acetic acid, polyvinyl alcohol, polyethylene glycol, cellulose, chitosan, sodium dodecyl sulfate, cetyl bromide
  • ammonium and concentrated sulfuric acid preferably barium chloride, aluminum chloride, iron nitrate, copper sulfate, calcium chloride, magnesium sulfate, zinc chloride, sodium chloride, lithium fluoride, sulfur a mixture of one or more of potassium acid, acetic acid, cellulose, polyethylene glycol, chitosan, sodium dodecyl sulfate, and cetyl ammonium bromide.
  • the flocculating agent added in the coagulation bath with a mass fraction of 0.5 to 5% means that the mass of the flocculating agent accounts for 0.5 to 5% of the total mass of the coagulation bath and the flocculating agent; this condition is advantageous for the formation of the metal oxide fiber of the present invention. Ensure the structural and mechanical strength of the fiber.
  • the nascent fiber is subjected to traction stretching and then subjected to deionized water washing; the traction stretching of the traction stretching makes the nascent fiber easy to be oriented under the applied tension, and the traction stretching ratio is 2-8. Times.
  • Deionized water washing removes residual impurities on the surface of the fiber and prevents the fiber properties from being affected during the drying process.
  • the present invention preferably uses deionized water to wash the wastewater to a pH of 7.
  • the drying condition is dry at 15 ⁇ 80 ° C 0.5 ⁇ 72.0
  • the diameter of the metal oxide macrofiber prepared by the method of the invention is ⁇ 0.1 ⁇ , and the diameter and the fiber length can be respectively controlled by the diameter of the spinneret and the tensile traction device in the wet spinning device, and the obtained metal oxide macroscopically
  • the fiber has excellent mechanical properties and stable structural properties, and strongly expands the application of metal oxides; therefore, the present invention also discloses metal oxide macrofibers prepared according to the above preparation method.
  • the present invention has the following advantages over the prior art:
  • the invention firstly uses an anionic metal oxide aqueous solution as a spinning dope, and reasonable setting of a raw liquid concentration, a spinning rate, a coagulation bath and a drying temperature, and the like, and successfully preparing a metal oxide macrofiber by wet spinning;
  • the obtained metal oxide macro fiber has excellent mechanical properties, and combined with the special physical and chemical properties of the metal oxide itself, a fiber device having a higher degree of functionalization can be assembled, thereby realizing the industrial application of the pure metal oxide fiber.
  • an anisotropic solution is formed at a suitable solution concentration and temperature in a metal oxide having a rigid structure in an anionic metal oxide aqueous solution; In the process, they are easy to orient under shear and tensile flow, and the anisotropic metal oxide undergoes phase transformation to form a highly crystalline solid during cooling and solidification, thereby obtaining high degree of orientation and high crystallinity. Degree of fiber.
  • the method for preparing a metal oxide macro fiber of the present invention is efficient, simple and easy
  • the metal oxide fiber can be prepared in large quantities and has low cost and less pollution, and is suitable for industrial mass production.
  • FIG. 1 is an optical photograph of a titanium oxide macrofiber prepared in an embodiment
  • the mixture was mixed at a mass ratio of 1.73:1.67:0.13:1.27, heated at 1073 K for 0.5 h, and cooled to room temperature, and then the product was heated at 1473 K for 20 h; washed with deionized water to finally obtain K. . 8 [Ti 1 . 73 Li. 27 ] 0 4 crystal; K 0 . 8 [Ti L73 Li 027 ]O 4 crystal was reacted in a 0.5 mol/L HCl solution for 48 h, and filtered to obtain H L07 Ti 1 7 3 ⁇ 4 ; 11 1 . 7 11 1 . 73 0 4 was placed in tetramethylammonium hydroxide solution, shaken, and reacted for 7 days. After centrifugation, the solid was washed with water to obtain Ti ⁇ , 7 0 2 . ⁇ 52 -; Other metal oxides can be obtained by replacing raw materials.
  • a Ti 0. 87 ⁇ 2 ⁇ ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to a wet spinning apparatus, and injected into an aqueous solution containing 0.6% of chitosan at a spinning speed of 0.5 mIJmin.
  • the fibers were stretched and oriented at a stretching speed of 2 times to obtain nascent fibers.
  • the nascent fibers were washed three times with deionized water until the waste liquid was neutral, and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 87 0 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to a wet spinning apparatus, and injected into a mass fraction of 0.6% chitosan at a spinning speed of 1.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 2 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • Embodiment 4 A Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to a wet spinning apparatus, and injected at a spinning speed of 1.5 mL/min to a shell containing 1.2% by mass. In the aqueous solution coagulation bath of the polysaccharide, the fibers are stretched and oriented at a stretching rate of 2 times to obtain nascent fibers. The nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 87 0 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to a wet spinning apparatus, and a mass fraction of 1.2% chitosan was injected at a spinning speed of 1.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 8 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to the wet spinning apparatus, and injected at a spinning speed of 1.5 mL/min to a shell containing 1.2% by mass.
  • the fibers were stretched and oriented at a stretching speed of 8 times to obtain nascent fibers.
  • the nascent fibers were washed three times with deionized water and dried at 65 ° C for 12 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to the wet spinning apparatus, and injected at a spinning speed of 1.5 mL/min to a shell containing 4.5% by mass.
  • the fibers are stretched and oriented at a stretching rate of 2 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 87 0 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to a wet spinning apparatus, and a mass fraction of 0.6% chitosan was injected at a spinning speed of 4.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 2 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 h to obtain a well-oriented titanium oxide. Fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to the wet spinning apparatus, and was injected at a spinning speed of 1.5 mL/min to a mass fraction of 1.2%.
  • the fibers were stretched and oriented at a stretching speed of 2 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 87 0 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to a wet spinning apparatus, and a mass fraction of 1.2% chitosan was injected at a spinning speed of 1.5 mL/min.
  • a coagulation bath of an aqueous solution of 4% acetic acid the fibers were stretched and oriented at a stretching rate of 2 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ⁇ ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to a wet spinning apparatus, and injected at a spinning speed of 1.5 mL/min to a chlorine content of 4% by mass.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ⁇ ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to the wet spinning apparatus, and injected into a mass fraction of 1.3% chlorine at a spinning speed of 1.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 87 0 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to a wet spinning apparatus, and the mass fraction was injected at a spinning speed of 2.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 5 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • FIG. 1 is an optical photograph of the above-mentioned titanium oxide macrofiber, wherein a is the second embodiment, b is the seventh embodiment, c is the embodiment IX, and d is the thirteenth embodiment;
  • the fiber sample has a length of about 15 cm and a diameter of about 500 ⁇ m, and the fiber is well entangled, which proves to be very flexible.
  • the metal oxide macro fiber provided by the invention has excellent mechanical properties and is suitable for industrial applications of flexible devices.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to the wet spinning apparatus, and injected at a spinning speed of 2.5 mL/min to a mass fraction of 3%.
  • the fibers are stretched and oriented at a stretching rate of 2 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 0.8 mg/mL was added to the wet spinning apparatus, and injected at a spinning speed of 2.5 mL/min to a mass fraction of 2.5%.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 87 0 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 3.6 mg/mL was added to a wet spinning apparatus, and a mass fraction of 2.5% chitosan was injected at a spinning speed of 2.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fiber was washed five times with deionized water and dried at 25 ° C for 24 h to obtain a well-oriented titanium oxide. Fiber.
  • a Ti 0 . 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 8 mg/mL was added to a wet spinning apparatus, and injected into an aqueous solution containing 2.5% by mass of chitosan at a spinning speed of 4 mIJmin.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti ⁇ . 87 0 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 15 mg/mL was added to a wet spinning apparatus, and injected into an aqueous solution containing 2.5% by mass of chitosan at a spinning speed of 4 mIJmin.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 15 mg/mL was added to the wet spinning apparatus, and injected at a spinning speed of 4 mIJmin to a mass fraction of 2.5% sodium chloride and 0.5.
  • the fibers were stretched and oriented at a stretching speed of 5 times to obtain nascent fibers.
  • the nascent fibers were washed three times with deionized water and dried at 60 ° C for 12 hours to obtain a well-oriented titanium oxide fiber.
  • a W 2 0 -colloid aqueous solution having a mass fraction of 12 mg/mL was added to a wet spinning apparatus, and injected into an aqueous solution coagulation bath containing 0.2% by mass of calcium chloride at a spinning speed of 3 mL/min.
  • the fibers were stretch oriented at a draw speed of 4 times to obtain nascent fibers.
  • the nascent fibers were washed three times with deionized water and dried at 45 ° C for 14 hours to obtain a tungsten oxide fiber having good orientation.
  • a TiNb 6 0 5 5 -colloid aqueous solution having a mass fraction of 8 mg/mL was added to a wet spinning apparatus, and injected into an aqueous solution containing 0.5% by mass of chitosan at a spinning speed of 1.5 mL/min.
  • the fiber is stretched and oriented at a stretching speed of 4 times to obtain a nascent Fiber.
  • the nascent fibers were washed three times with deionized water and dried at 55 ° C for 12 hours to obtain a well-oriented titanium cerium oxide fiber.
  • a Ca 2 Nb 3 0 10 -colloid aqueous solution having a mass fraction of 4 mg/mL was placed in a wet spinning apparatus, and injected into an aqueous solution containing a mass fraction of 1.8% of chitosan at a spinning speed of 1.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fibers were washed three times with deionized water and dried at 25 ° C for 24 hours to obtain well-oriented calcium cerium oxide fibers.
  • a TaO 3 -colloid aqueous solution having a mass fraction of 5 mg/mL was placed in a wet spinning apparatus, and injected into an aqueous solution coagulation bath containing 4% by mass of polyethylene glycol at a spinning speed of 2.5 mL/min.
  • the fiber was stretch oriented at a stretching speed of 5 times to obtain a nascent fiber.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented cerium oxide fiber.
  • a SrTa 2 0 7 2 -colloid aqueous solution having a mass fraction of 2.5 mg/mL was placed in a wet spinning apparatus, and injected into an aqueous solution containing 2% of calcium chloride at a spinning speed of 1.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 2 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 65 ° C for 8 hours to obtain a well-oriented cerium oxide fiber.
  • a LaNb 2 0 7 -colloid aqueous solution having a mass fraction of 12 mg/mL was added to a wet spinning apparatus, and injected into an aqueous solution coagulation bath containing 1.5% by mass of chitosan at a spinning speed of 3 mIJmin.
  • the fiber was stretched and oriented at a stretching speed of 4 times to obtain a nascent fiber.
  • the nascent fibers were washed three times with deionized water and dried at 80 ° C for 2 hours to obtain a well-oriented cerium oxide fiber.
  • a mass fraction of 8 mg/mL of Cs 4 W Volunteer 0 36 2 - colloidal aqueous solution was added to the wet spinning apparatus, and the mass fraction was injected at a spinning speed of 1.5 mL/min.
  • the fibers were stretch oriented at a draw speed of 6 times to obtain nascent fibers.
  • the nascent fibers were washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented tungsten oxide ruthenium fiber.
  • a mass fraction of 5 mg/mL of Nb 6 0 17 4 -colloid aqueous solution was added to the wet spinning apparatus, and injected into an aqueous solution coagulation bath containing 2.5% by mass of cellulose at a spinning speed of 4 mL/min.
  • the fiber was stretch oriented at a stretching speed of 4 times to obtain a nascent fiber.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented cerium oxide fiber.
  • a RuO 2 ° ⁇ 2 -colloid aqueous solution having a mass fraction of 4 mg/mL was added to a wet spinning apparatus, and injected into an aqueous solution coagulation bath containing 1.5% potassium sulfate at a spinning rate of 2.5 mL/min.
  • the fibers were stretch oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the primary fibers were washed three times with deionized water, 45. C was dried for 16 h to obtain a well-oriented cerium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 4 mg/mL was added to the wet spinning apparatus, and injected at a spinning speed of 1.5 mL/min to a chlorination content of 1.2% by mass.
  • the fibers were stretched and oriented at a stretching speed of 5 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 35 ° C for 18 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0 . 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 4 mg/mL was added to the wet spinning apparatus, and injected into a mass fraction of 1.8% ferric nitrate at a spinning speed of 1.5 mL/min.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 4 mg/mL was added to the wet spinning apparatus, and injected at a spinning speed of 1.2 mL/min to a chlorination content of 2.4% by mass.
  • the fibers were stretched and oriented at a stretching speed of 4 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 4 mg/mL was added to the wet spinning apparatus, and injected at a spinning speed of 1.5 mL/min to a 5% fluorinated mass.
  • the fibers were stretched and oriented at a stretching speed of 6 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti 0. 87 ⁇ 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 4 mg/mL was added to a wet spinning apparatus, and injected at a spinning speed of 1.7 mL/min to a cellulose fraction containing 2.3% by mass.
  • the fibers were stretched and oriented at a stretching speed of 8 times to obtain nascent fibers.
  • the nascent fibers were washed three times with deionized water and dried at 45 ° C for 18 hours to obtain a well-oriented titanium oxide fiber.
  • a Ti ⁇ . 87 0 2 ° ⁇ 52 - colloidal aqueous solution having a mass fraction of 4 mg/mL was added to a wet spinning apparatus, and injected at a spinning speed of 1.2 mL/min to a mass fraction of 5%.
  • an aqueous solution coagulation bath of an alkylammonium bromide the fibers are stretched and oriented at a draw speed of 2 times to obtain nascent fibers.
  • the nascent fiber was washed three times with deionized water and dried at 25 ° C for 24 hours to obtain a well-oriented titanium oxide fiber.

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Abstract

一种金属氧化物宏观纤维及其制备方法，该方法包括：将阴离子型金属氧化物胶体水溶液作为纺丝原液加入到湿法纺丝设备中；将纺丝原液从湿法纺丝设备中挤出细流；将挤出细流注入到含有絮凝剂的凝固浴中得到初生纤维；将得到的初生纤维使用去离子水反复清洗，干燥，得金属氧化物纤维。该方法过程简单可控，适于大批量生产。首次制备出的具有特殊物理化学性质的金属氧化物纤维在智能纺织、生物医学、能源回收与转化以及微电子器件领域等方面有广泛应用。

Description

说明书 发明名称：一种金属氧化物宏观纤维及其制备方法 技术领域
[0001] 本发明涉及一种纤维的制备方法， 具体涉及一种金属氧化物宏观纤维及其制备 方法。
背景技术
[0002] 纤维器件具有独特的一维结构和多样化的功能， 在智能纺织品、 传感器、 驱动 器、 锂离子电池以及染料敏化电池等众多领域有着越加广泛的应用。 因此， 关 于纤维及其制备方法的研究已成为当前科技领域最为活跃的发展方向之一。 目 前， 纤维的制备方法主要有湿法纺丝、 干法纺丝、 融熔纺丝法、 凝胶纺丝法以 及静电纺丝法。 其中， 湿法纺丝法具有方法简单、 制备过程易于控制、 可制备 的材料范围广泛等优点， 是纤维制备过程中普遍采用的方法。 湿法纺丝法的制 备过程包括： （1)制备纺丝原液； （2)将纺丝原液从喷丝孔中挤出； （3)纺丝原液在 含有絮凝剂的凝固浴中形成初生纤维； （4)对初生纤维进行后期处理。
[0003] 随着科技的不断发展进步， 具有多功能的柔性可穿戴纤维器件越来越受到人们 的关注， 而目前的碳纤维器件 （如： 石墨烯纤维器件、 碳纳米管纤维器件等） 、 碳基金属氧化物复合纤维器件的制备过程复杂， 功能化程度不高， 不能满足 人们日益增长的需求。 因此， 我们需要寻求一种简单高效的制备多功能纤维器 件的方法。
[0004] 金属氧化物具有独特的物理化学性质， 研究人员一般将其涂覆在聚合物纳米纤 维表面， 或者与聚合物纳米纤维原料共混， 通过湿法纺丝制备聚合物 /金属氧化 物纳米复合纤维， 从而可以改善聚合物纳米纤维性能。 关于单一金属氧化物宏 观纤维还没有报道， 而且现有技术一般采用静电纺丝的方法只能制备金属氧化 物纳米纤维， 且其前驱体合成复杂， 需要用到 PVA等有机物， 而且后续烧结去 除 PVA的过程会造成纤维性能不稳定， 还会污染环境。 需要指出的是采用现有 的静电纺丝的方法不能制备出金属氧化物宏观纤维， 同吋现有的湿法纺丝方法 只能制备出聚合物 /金属氧化物复合纤维， 也不能制备出金属氧化物宏观纤维。 [0005] 特别的， 现有制备方法制备的金属氧化物纳米纤维取向性差， 导致其力学性能 差、 结构性能不稳定， 而使得金属氧化物纤维应用存在难度； 并且现有方法不 满足制备金属氧化物宏观纤维的要求。 所以， 需要研发一种简单、 高效的制备 方法， 以获得良好力学性能、 结构性能稳定、 且利于工业化生产的金属氧化物 宏观纤维， 从而得到由其组装的具有更高的功能化程度的纤维器件， 不仅仅扩 展了金属氧化物的研究和应用范围， 也为柔性传感器、 柔性储能设备等领域的 研究提供了一种新的思路。
技术问题
[0006] 现有的湿法纺丝方法只能制备出聚合物 /金属氧化物复合纤维， 也不能制备出 金属氧化物宏观纤维。 特别的， 现有制备方法制备的金属氧化物纳米纤维取向 性差， 导致其力学性能差、 结构性能不稳定， 而使得金属氧化物纤维应用存在 难度； 并且现有方法不满足制备金属氧化物宏观纤维的要求。
问题的解决方案
技术解决方案
[0007] 本发明的目的是提供一种过程简单、 可控的金属氧化物宏观纤维的制备方法， 以改变现有制备方法只能得到的含金属氧化物的复合纳米纤维， 且其纳米纤维 力学性能差、 结构性能不稳定、 应用难度大等缺点。
[0008] 为达到上述目的， 本发明采用的技术方案如下：
[0009] 一种金属氧化物宏观纤维的制备方法， 包括如下步骤：
[0010] 将阴离子型金属氧化物胶体水溶液放入湿法纺丝装置中， 然后在凝固浴中进行 湿法纺丝， 得到初生纤维； 所述初生纤维经去离子水洗、 干燥后， 得到金属氧 化物宏观纤维； 所述凝固浴含有质量分数为 0.5〜5%的絮凝剂； 所述湿法纺丝速 度为 0.1〜5mIJmin; 所述阴离子型金属氧化物胶体水溶液中， 金属氧化物的总 浓度为 0.1〜20mg/mL。
[0011] 上述制备方法中， 所述阴离子型金属氧化物为氧化锰、 氧化钛、 氧化铌、 氧化 钽、 氧化钌、 氧化钨、 氧化钨铯、 氧化铌钙、 氧化铌钛中的一种或者几种的混 合物； 其中所述氧化锰为 ΜηΟ -， 0<χ<1 , 或者 A 2Na y— 3Mn0 3y+r， 其中 A为 Ca 、 Sr、 Ba， 3<y<6; 所述氧化钽为 TaO 3-、 SrTa 20 7 2-、 La 0.7Tb 0.3Ta 20 7-或者 Eu 。.56Ta2072-; 所述氧化钨为 W2072-; 所述氧化钨铯为 Cs4W„0362-; 所述氧化钌 为 RuO^ -或者 Ru02 z-， 0<ζ<1; 所述氧化铌为 Nb 6017 4-、 Nb 308-、 LaNb 207 或者 La0.9Eu0.05Nb2O7-; 所述氧化钛为 Ti ^ nO -， 0<n<l; Ti 0.8Co 0.2Ο 2。·4-； Bi4 Ti 3012 2-； Ti o.eFe 0.4O 2 0·4-； Ti 0.8-m/4Fe ^Co o.2-m/402 0·4-， 0≤m<0.8; Ti (5.2— 2i)/6Mn i/2 O 2(3.2— 9/6— 0≤i≤0.4或者 RE2Ti 3010 2-， 其中 RE为 La、 Pr、 Sm、 Nd、 Eu、 Gd、 Tb 或者 Dy; 所述氧化铌钙为 Ca2Nb30 HT; 所述氧化铌钛为 TiNbO 5 -、 Ti 2NbO 7_或 者 Ti 5NbO 14 3-。
[0012] 优选的， 所述阴离子型金属氧化物为 Ήα8702°·52-、 W207 2-、 TiNb 605 5-、 Ca 2Nb 3O10、 TaO3 、 Nb 6017 4 、 Nb 308 、 RuO21 02 、 RuO 2 02 、 SrTa 207 2 、 LaNb 20 7 -、 Cs4W„036 2-中的一种或者几种。
[0013] 发明以金属氧化物中主要元素来命名阴离子型金属氧化物， 包括仅为该主要元 素与氧构成的金属氧化物， 比如 W2072-; 也包括由惨杂元素与该主要元素、 氧 构成的金属氧化物， 比如11。.80。.202。 ; 还包括由几种主要金属元素与氧组成 的金属氧化物， 比如 Cs4W„0362-。 阴离子型金属氧化物胶体水溶液的一般过程 包括通过高温烧结制备金属氧化物盐单晶； 在金属氧化物盐单晶中插入客体分 子； 将插入客体分子的金属氧化物盐单晶进行剥离， 得到具有刚性结构的金属 氧化物； 使用去离子水离心洗涤上述剥离后的金属氧化物， 得到阴离子型金属 氧化物胶体水溶液。 制备阴离子型金属氧化物胶体水溶液的一般过程中的阳离 子金属氧化物包括氧化锰； 氧化钽； 氧化钌； 氧化钨， 包括惨杂型的氧化钨； 氧化铌， 包括惨杂型的氧化铌； 氧化钛， 包括惨杂型的氧化钛； 以及钙钛矿型 氧化物； 可以通过变换金属氧化物原料的方式制备不同的阴离子型金属氧化物 胶体水溶液。 本发明的阴离子型金属氧化物胶体水溶液是指一定大小的固体阴 离子型金属氧化物分散在水中所形成的溶液。
[0014] 上述技术方案中， 所述凝固浴包括水、 甲醇、 乙醇、 丙醇、 丙酮中的一种或者 几种的混合物； 所述絮凝剂为镧盐、 铝盐、 铁盐、 铜盐、 钙盐、 镁盐、 锌盐、 钠盐、 锂盐、 钾盐、 醋酸、 聚乙烯醇、 聚乙二醇、 纤维素、 壳聚糖、 十二烷基 磺酸钠、 十六烷基溴化铵、 浓硫酸中的一种或者几种的混合物， 优选为氯化镧 、 氯化铝、 硝酸铁、 硫酸铜、 氯化钙、 硫酸镁、 氯化锌、 氯化钠、 氟化锂、 硫 酸钾、 醋酸、 纤维素、 聚乙二醇、 壳聚糖、 十二烷基磺酸钠、 十六烷基溴化铵 中的一种或者几种的混合物。 本发明在凝固浴添加质量分数为 0.5〜5%的絮凝剂 是指絮凝剂的质量占凝固浴与絮凝剂总质量的 0.5〜5%； 此条件有利于本发明的 金属氧化物纤维的成型， 保证纤维的结构和力学强度。
[0015] 优选的技术方案中， 所述初生纤维经过牵引拉伸后再经去离子水洗； 牵引拉伸 的牵引拉伸使得初生纤维在外加张力作用下易于取向， 牵引拉伸比为 2-8倍。 去 离子水洗可以去除纤维表面残余的杂质， 避免干燥过程纤维性能受到影响， 本 发明优选用去离子水洗至水洗废水的 pH为 7。
[0016] 上述技术方案中， 干燥的条件为 15〜80°C下干燥 0.5〜72.0
h; 优选 25°C下干燥 24 h。
[0017] 本发明方法制备的金属氧化物宏观纤维的直径≥0.1μηι， 其直径和纤维长度可分 别通过湿法纺丝装置中喷丝口直径和拉伸牵引装置控制， 得到的金属氧化物宏 观纤维力学性能优异、 结构性能稳定， 有力拓展了金属氧化物的应用； 因此本 发明还公幵了根据上述制备方法制备的金属氧化物宏观纤维。
发明的有益效果
有益效果
[0018] 由于上述技术方案运用， 本发明与现有技术相比具有下列优点：
[0019] 1 . 本发明首次以阴离子型金属氧化物水溶液为纺丝原液， 合理设置原液浓度 、 纺丝速率、 凝固浴和干燥温度等条件， 成功采用湿法纺丝制备金属氧化物宏 观纤维； 所得金属氧化物宏观纤维具有优异的力学性能， 结合金属氧化物自身 的特殊物理化学性质， 可组装具有更高的功能化程度的纤维器件， 从而真正实 现纯金属氧化物纤维的工业化应用。
[0020] 2. 本发明公幵的制备金属氧化物宏观纤维的方法中， 阴离子型金属氧化物水 溶液中具有刚性结构的金属氧化物在适当的溶液浓度和温度下形成各向异性溶 液； 纤维制备过程中， 它们在剪切和拉伸流动下易于取向， 同吋在冷却、 凝固 过程中各向异性的金属氧化物又会发生相变形成高结晶性的固体， 从而得到高 取向度和高结晶度的纤维。
[0021] 3. 本发明公幵的制备金属氧化物宏观纤维的方法， 制备过程高效、 简单易行 ， 制备条件可控， 可大量制备的金属氧化物纤维， 成本低， 污染少， 适于工业 化批量生产。
对附图的简要说明
附图说明
[0022] 图 1为实施例制备的氧化钛宏观纤维的光学照片图；
[0023] 图 2为实施例制备的氧化钛宏观纤维的力学试验照片图。
本发明的实施方式
[0024] 下面结合附图以及实施例对本发明作进一步描述：
[0025] 实施例一
[0026] 将 Ti0 2、 K 2C0 3、 Li 2C0 3、 和 MoO 3
以 1.73:1.67:0.13:1.27的质量比例混合， 在 1073K下加热 0.5h， 冷却至室温后， 再 将产物在 1473K下加热 20h; 使用去离子水洗涤， 最终得到K。.8[Ti 1.73Li。.27]0 4晶 体； 将 K 0.8[Ti L73Li 027]O 4晶体于 0.5 mol/L的 HC1溶液中反应 48h， 过滤得到 H L07Ti 1 73θ 4 ; 将11 1.。711 1.730 4置于四甲基氢氧化铵溶液中， 震荡， 反应 7d， 离心后固体 经水洗涤得 Ti ο,70 2。·52-； 其他金属氧化物可以更换原料而得到。
[0027] 实施例二
[0028] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2 ΰ·52- 胶体水溶液加入湿法纺丝设备中， 以 0.5mIJmin的纺丝速度注入到含有 0.6^%壳 聚糖的水溶液中， 以 2倍的拉伸速度将纤维拉伸取向， 得到初生纤维。 将初生纤 维用去离子水洗涤三次至废液为中性， 25°C干燥 24h， 得到取向良好的氧化钛纤 维。
[0029] 实施例三
[0030] 将质量分数为 0.8mg/mL的 Ti 870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 0.6%壳聚糖的水溶液中， 以 2倍的拉伸速度将纤维拉伸取向， 得到初生纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛纤维。
[0031] 实施例四 [0032] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.2%壳聚糖的水溶液凝固浴中， 以 2倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0033] 实施例五
[0034] 将质量分数为 0.8mg/mL的 Ti 870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.2%壳聚糖的水溶液凝固浴中， 以 8倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0035] 实施例六
[0036] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.2%壳聚糖的水溶液凝固浴中， 以 8倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 65°C干燥 12h， 得到取向良好的氧化钛 纤维。
[0037] 实施例七
[0038] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 4.5%壳聚糖的水溶液凝固浴中， 以 2倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0039] 实施例八
[0040] 将质量分数为 0.8mg/mL的 Ti 870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 4.5mL/min的纺丝速度注入到含有质量分数 为 0.6%壳聚糖的水溶液凝固浴中， 以 2倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0041] 实施例九
[0042] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.2%壳聚糖的水、 乙醇混合溶液的凝固浴中， 以 2倍的拉伸速度将纤维拉伸取 向， 得到初生纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向 良好的氧化钛纤维。
[0043] 实施例十
[0044] 将质量分数为 0.8mg/mL的 Ti 870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.2%壳聚糖和 4%醋酸的水溶液凝固浴中， 以 2倍的拉伸速度将纤维拉伸取向， 得到初生纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好 的氧化钛纤维。
[0045] 实施例十一
[0046] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2 ΰ·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 4%氯化钠的乙醇溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0047] 实施例十二
[0048] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2 ΰ·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.3%氯化镧的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0049] 实施例十三
[0050] 将质量分数为 0.8mg/mL的 Ti 870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 2.5mL/min的纺丝速度注入到含有质量分数 为 2.5%氯化钙的水溶液凝固浴中， 以 5倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0051] 附图 1为上述氧化钛宏观纤维的光学照片， 其中 a为实施例二， b为实施例七， c 为实施例九， d为实施例十三； 可以看出本发明制备的宏观纤维试样长度约为 15c m， 直径约为 500μηι， 纤维可很好的缠绕， 证明其具有很好的柔性。
[0052] 附图 2为上述氧化钛宏观纤维的力学试验照片图， 其中 a为实施例二， b为实施 例七， c为实施例九， d为实施例十三； 可以看出单根纤维就能够承受 20g标准砝 码的重量， 其拉伸强度分别为 160MPa、 150MPa、 150MPa、 165MPa。 说明本发 明提供的金属氧化物宏观纤维具有优异的力学性能， 适合柔性器件的工业应用
[0053] 实施例十四
[0054] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 2.5mL/min的纺丝速度注入到含有质量分数 为 3%十二烷基磺酸钠的水溶液凝固浴中， 以 2倍的拉伸速度将纤维拉伸取向， 得到初生纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好 的氧化钛纤维。
[0055] 实施例十五
[0056] 将质量分数为 0.8mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 2.5mL/min的纺丝速度注入到含有质量分数 为 2.5%聚乙二醇的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初 生纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化 钛纤维。
[0057] 实施例十六
[0058] 将质量分数为 3.6mg/mL的 Ti 870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 2.5mL/min的纺丝速度注入到含有质量分数 为 2.5%壳聚糖的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤五次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0059] 实施例十七
[0060] 将质量分数为 8mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 4mIJmin的纺丝速度注入到含有质量分数为 2.5%壳聚糖的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生纤 维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛纤 维。
[0061] 实施例十八
[0062] 将质量分数为 15mg/mL的 Ti ο.870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 4mIJmin的纺丝速度注入到含有质量分数为 2.5%壳聚糖的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生纤 维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛纤 维。
[0063] 实施例十九
[0064] 将质量分数为 15mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 4mIJmin的纺丝速度注入到含有质量分数为 2.5%氯化钠和 0.5%氯化钙的水溶液凝固浴中， 以 5倍的拉伸速度将纤维拉伸取向 ， 得到初生纤维。 将初生纤维用去离子水洗涤三次， 60°C干燥 12h， 得到取向良 好的氧化钛纤维。
[0065] 实施例二十
[0066] 将质量分数为 12mg/mL的 W 20 -胶体水溶液加入湿法纺丝设备中， 以 3mL/min 的纺丝速度注入到含有质量分数为 0.2%氯化钙的水溶液凝固浴中， 以 4倍的拉伸 速度将纤维拉伸取向， 得到初生纤维。 将初生纤维用去离子水洗涤三次， 45°C干 燥 14h， 得到取向良好的氧化钨纤维。
[0067] 实施例二十一
[0068] 将质量分数为 8mg/mL的 TiNb 60 5 5- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 0.5%壳聚糖的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 55°C干燥 12h， 得到取向良好的氧化铌 钛纤维。
[0069] 实施例二十二
[0070] 将质量分数为 4mg/mL的 Ca 2Nb 30 10- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.8%壳聚糖的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化铌 钙纤维。
[0071] 实施例二十三
[0072] 将质量分数为 5mg/mL的 TaO 3-胶体水溶液加入湿法纺丝设备中， 以 2.5mL/min 的纺丝速度注入到含有质量分数为 4%聚乙二醇的水溶液凝固浴中， 以 5倍的拉伸 速度将纤维拉伸取向， 得到初生纤维。 将初生纤维用去离子水洗涤三次， 25°C干 燥 24h， 得到取向良好的氧化钽纤维。
[0073] 实施例二十四
[0074] 将质量分数为 2.5mg/mL的 SrTa 20 7 2- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 2%氯化钙的水溶液凝固浴中， 以 2倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 65°C干燥 8h， 得到取向良好的氧化钽锶 纤维。
[0075] 实施例二十五
[0076] 将质量分数为 12mg/mL的 LaNb 20 7 - 胶体水溶液加入湿法纺丝设备中， 以 3mIJmin的纺丝速度注入到含有质量分数为 1.5%壳聚糖的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生纤 维。 将初生纤维用去离子水洗涤三次， 80°C干燥 2h， 得到取向良好的氧化铌镧纤 维。
[0077] 实施例二十六
[0078] 将质量分数为 8mg/mL的 Cs 4W„0 36 2- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 2.5%聚乙二醇的水溶液凝固浴中， 以 6倍的拉伸速度将纤维拉伸取向， 得到初 生纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化 钨铯纤维。
[0079] 实施例二十七
[0080] 将质量分数为 5mg/mL的 Nb 60 17 4-胶体水溶液加入湿法纺丝设备中， 以 4mL/min 的纺丝速度注入到含有质量分数为 2.5%纤维素的水溶液凝固浴中， 以 4倍的拉伸 速度将纤维拉伸取向， 得到初生纤维。 将初生纤维用去离子水洗涤三次， 25°C干 燥 24h， 得到取向良好的氧化铌纤维。
[0081] 实施例二十八
[0082] 将质量分数为 4mg/mL的 RuO 2°·2 - 胶体水溶液加入湿法纺丝设备中， 以 2.5mL/min的纺丝速度注入到含有质量分数 为 1.5%硫酸钾的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 45。C干燥 16h， 得到取向良好的氧化钌 纤维。
[0083] 实施例二十九
[0084] 将质量分数为 4mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.2%氯化铝的水溶液凝固浴中， 以 5倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 35°C干燥 18h， 得到取向良好的氧化钛 纤维。
[0085] 实施例三十
[0086] 将质量分数为 4mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 1.8%硝酸铁的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0087] 实施例三十一
[0088] 将质量分数为 4mg/mL的 Ti ο.870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 2.1%硫酸铜的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0089] 实施例三十二
[0090] 将质量分数为 4mg/mL的 Ti。.870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.2mL/min的纺丝速度注入到含有质量分数 为 1.7%硫酸镁的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0091] 实施例三十三
[0092] 将质量分数为 4mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.2mL/min的纺丝速度注入到含有质量分数 为 2.4%氯化锌的水溶液凝固浴中， 以 4倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0093] 实施例三十四
[0094] 将质量分数为 4mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 5%氟化锂的水溶液凝固浴中， 以 6倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。
[0095] 实施例三十五
[0096] 将质量分数为 4mg/mL的 Ti。.870 2 ΰ·52- 胶体水溶液加入湿法纺丝设备中， 以 1.5mL/min的纺丝速度注入到含有质量分数 为 5%硫酸钾的水溶液凝固浴中， 以 5倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的氧化钛 纤维。 [0097] 实施例三十五
[0098] 将质量分数为 4mg/mL的 Ti 0.87Ο 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.7mL/min的纺丝速度注入到含有质量分数 为 2.3%纤维素的水溶液凝固浴中， 以 8倍的拉伸速度将纤维拉伸取向， 得到初生 纤维。 将初生纤维用去离子水洗涤三次， 45°C干燥 18h， 得到取向良好的氧化钛 纤维。
[0099] 实施例三十六
[0100] 将质量分数为 4mg/mL的 Ti ο.870 2°·52- 胶体水溶液加入湿法纺丝设备中， 以 1.2mL/min的纺丝速度注入到含有质量分数 为 5%十六烷基溴化铵的水溶液凝固浴中， 以 2倍的拉伸速度将纤维拉伸取向， 得 到初生纤维。 将初生纤维用去离子水洗涤三次， 25°C干燥 24h， 得到取向良好的 氧化钛纤维。

Claims

权利要求书
一种金属氧化物宏观纤维的制备方法， 其特征在于， 包括如下步骤： 将阴离子型金属氧化物胶体水溶液放入湿法纺丝装置中， 然后在凝固 浴中进行湿法纺丝， 得到初生纤维； 所述初生纤维经去离子水洗、 干 燥后， 得到金属氧化物宏观纤维； 所述凝固浴含有质量分数为 0.5〜5 <¾的絮凝剂； 所述湿法纺丝速度为 0.1〜5mIJmin; 所述阴离子型金属 氧化物胶体水溶液中， 金属氧化物的总浓度为 0.1〜20mg/mL。
根据权利要求 1所述金属氧化物宏观纤维的制备方法， 其特征在于， 所述阴离子型金属氧化物为氧化锰、 氧化钌、 氧化钛、 氧化铌、 氧化 钽、 氧化钨、 氧化钨铯、 氧化铌钙、 氧化铌钛中的一种或者几种的混 合物。
根据权利要求 2所述金属氧化物宏观纤维的制备方法， 其特征在于， 所述氧化锰为 MnO -， 0<χ<1, 或者 A2Nay— 3Mn03y+1 -， 其中 A为 Ca 、 Sr、 Ba， 3<y<6; 所述氧化钽为 TaO3-、 SrTa207 2-、 La。.7Tb。.3Ta 2 07-或者 Eu。.56Ta207 2-； 所述氧化钨为 W207 2-； 所述氧化钨铯为 Cs4 W„0362-; 所述氧化钌为 Ru02. 或者 Ru02 z-， 0<ζ<1; 所述氧化铌 为 Nb 6017 4-、 Nb 308-、 LaNb207-或者 La0.9Eu0.05Nb2O7-; 所述氧化 钛为 Τ^— nO -， 0<η<1; Ti 0.8Co 0.2θ 2°·4-; Bi4Ti 3012 2- ; Ti。.6Fe。,402 0·4- ; Ti o.8-m/4Fe
Figure imgf000016_0001
0≤m<0.8; Ti (5.2— 2i)/6Mn i/202(3.2- ， 0 ≤i≤0.4或者 RE2Ti30 H)2-， 其中 RE为 La、 Pr、 Sm、 Nd、 Eu、 Gd、 Tb 或者 Dy; 所述氧化铌钙为 C^Nl^Oi。-; 所述氧化铌钛为 TiNbO 5_ 、 Ti 2NbO 7-或者 Ti 5NbO 14 3-。
根据权利要求 3所述金属氧化物宏观纤维的制备方法， 其特征在于， 所述阴离子型金属氧化物为 Ή。.8702°·52-、 W207 2-、 TiNb 605 5-、 Ca2 Nb3O10、 TaO3 、 Nb 6017 4 、 Nb 308 、 RuO21 02 、 RuO 2 02 、 SrTa 2 07 2-、 LaNb 207-、 Cs4W„036 2-中的一种或者几种。
根据权利要求 1所述金属氧化物宏观纤维的制备方法， 其特征在于， 所述凝固浴包括水、 甲醇、 乙醇、 丙醇、 丙酮中的一种或者几种的混 [权利要求 6] 根据权利要求 1所述金属氧化物宏观纤维的制备方法， 其特征在于： 所述絮凝剂为镧盐、 铝盐、 铁盐、 铜盐、 钙盐、 镁盐、 锌盐、 钠盐、 锂盐、 钾盐、 醋酸、 聚乙烯醇、 聚乙二醇、 纤维素、 壳聚糖、 十二烷 基磺酸钠、 十六烷基溴化铵、 浓硫酸中的一种或者几种的混合物。
[权利要求 7] 根据权利要求 6所述金属氧化物宏观纤维的制备方法， 其特征在于： 所述絮凝剂为氯化镧、 氯化铝、 硝酸铁、 硫酸铜、 氯化钙、 硫酸镁、 氯化锌、 氯化钠、 氟化锂、 硫酸钾、 醋酸、 纤维素、 聚乙二醇、 壳聚 糖、 十二烷基磺酸钠、 十六烷基溴化铵中的一种或者几种的混合物。
[权利要求 8] 根据权利要求 1所述金属氧化物宏观纤维的制备方法， 其特征在于： 所述初生纤维经过牵弓 I拉伸后再经去离子水洗； 所述牵弓 I拉伸比为 2 〜8°
[权利要求 9] 根据权利要求 1所述金属氧化物宏观纤维的制备方法， 其特征在于： 初生纤维经去离子水洗至水洗废水的 pH为 7; 所述干燥的条件为 15〜 80°C下干燥 0.5〜72.0。
[权利要求 10] 根据权利要求 1〜9所述任意一种金属氧化物宏观纤维的制备方法制备 得到的金属氧化物宏观纤维。
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