CN116163040B - 一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法 - Google Patents
一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法 Download PDFInfo
- Publication number
- CN116163040B CN116163040B CN202310179726.5A CN202310179726A CN116163040B CN 116163040 B CN116163040 B CN 116163040B CN 202310179726 A CN202310179726 A CN 202310179726A CN 116163040 B CN116163040 B CN 116163040B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- nanofiber yarn
- spinning
- flexible
- yarn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002121 nanofiber Substances 0.000 title claims abstract description 67
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 44
- 239000000919 ceramic Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000009987 spinning Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000013557 residual solvent Substances 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HZCFFZVTOFTEIP-UHFFFAOYSA-N acetic acid;ethanol;methanol Chemical compound OC.CCO.CC(O)=O HZCFFZVTOFTEIP-UHFFFAOYSA-N 0.000 claims description 3
- RFQIWHDNNZFRBL-UHFFFAOYSA-N acetic acid;ethanol;hydrate Chemical compound O.CCO.CC(O)=O RFQIWHDNNZFRBL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 230000021615 conjugation Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920001690 polydopamine Polymers 0.000 description 3
- 239000004964 aerogel Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 titanium alkoxide Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62259—Fibres based on titanium oxide
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/16—Yarns or threads made from mineral substances
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
- D02J13/001—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass in a tube or vessel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/781—Nanograined materials, i.e. having grain sizes below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/95—Products characterised by their size, e.g. microceramics
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
- D10B2101/08—Ceramic
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Mycology (AREA)
- Microbiology (AREA)
- Inorganic Fibers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法:采用溶胶凝胶法制备二氧化钛前驱体溶液,所述前驱体溶胶包含高分子聚合物、钛源、盐酸多巴胺及有机溶剂;将所述的纺丝液转移至两个注射器中进行尖端共轭静电纺纱,其中一个注射器与高压正极相连,另一个与负极相连,加捻转杯接地,得到前驱体纳米纤维纱线;将前驱体纳米纤维纱线置于烘箱中干燥以去除残余溶剂,然后采用阶梯式升温法在空气气氛下煅烧,得到柔性二氧化钛陶瓷纳米纤维纱线。本发明所制备的柔性二氧化钛纳米纤维纱线具有良好的柔韧性和机械性能、光催化效率高、耐氧化、耐酸碱腐蚀、耐高温,且其制备工艺简单,易于加工,环境污染小,有利于规模化应用。
Description
技术领域
本发明涉及一种柔性二氧化钛陶瓷纳米纤维纱线及其制备方法和应用,属于无机材料制备工艺领域。
背景技术
目前陶瓷纳米纤维材料主要以二维膜材料和三维气凝胶的形式存在。研究者们已制备出柔性可折叠的二维膜材料及具有优异压缩回弹性的三维气凝胶,但这些材料内部的纳米纤维取向度较差,其拉伸、弯曲力学性能有待进一步提高,以满足实际应用需求。相比而言,将紧密取向排列的静电纺陶瓷纳米纤维施以一定捻度,构筑陶瓷纳米纤维纱线,可在一定程度上改善拉伸力学性能,拓宽应用范畴。
其中二氧化钛陶瓷半导体可高效吸收紫外光,具有光催化、杀菌抑菌、遮挡紫外线等多重作用,在能源、环境治理等方面具有广阔的应用前景。二氧化钛常负载于无机多孔基体,用以制备负载型光催化剂,但该负载型光催化剂催化效率较低、比表面积较小、制备过程较复杂等。此外,利用钛的醇盐溶液或二氧化钛溶胶与有机聚合物混合制备高分子材料/二氧化钛复合膜,复合膜虽然机械性能较好,但其耐酸碱性、耐热性、催化性能等方面有待改善。通过静电纺丝制备的柔性二氧化钛陶瓷纳米纤维膜一般需加入掺杂剂,这会影响纤维中二氧化钛纯度,且其拉伸、弯曲力学性能限制其应用范围。因此开发柔性二氧化钛陶瓷纳米纤维纱线显得尤为重要。
发明内容
本发明所要解决的问题是:提供一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法。
为了解决上述问题,本发明提供了一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法,包括以下步骤:
步骤1):将高分子聚合物溶解于有机溶剂中,搅拌至溶液澄清透明后,加入钛源得到稳定的溶胶A;将盐酸多巴胺溶解于去离子水或甲醇,得到溶液B,将溶液B加入到溶胶A中,搅拌至混合溶液澄清透明,得到纺丝液;
步骤2):将纺丝液转移至两个注射器中进行尖端共轭静电纺纱,其中一个注射器与高压正极相连,另一个与负极相连,加捻转杯接地,环境温度设置为20~30℃,相对湿度设置为30%~50%,得到前驱体纳米纤维纱线;
步骤3):将前驱体纳米纤维纱线置于烘箱中干燥以去除残余溶剂,然后采用阶梯式升温法在空气气氛下煅烧,得到柔性二氧化钛陶瓷纳米纤维纱线。
优选地,所述步骤1)所得纺丝液中盐酸多巴胺的质量百分数为 10-6~10-4。
优选地,所述步骤1)中的钛源为钛酸异丙酯、钛酸四丁酯及钛酸四乙酯中的至少一种。
优选地,所述步骤1)中的高分子聚合物为聚氧化乙烯,聚氧化乙烯在纺丝液中的质量百分数为1~5%。
优选地,所述步骤1)中的有机溶剂为水-乙醇-乙酸、水-异丙醇-乙酸及甲醇-乙醇-乙酸体系中的至少一种。
所述步骤2)中静电纺纱的工艺参数为:纺丝液灌注速度0.5~1.5mL/h,纺丝电压±6~±10kV,针头与纺纱转杯距离10~15cm,纺纱角30°~45°,转杯速度20~30r/min,转杯材质为不锈钢306,纱线卷绕速度1.0~1.5r/min。
优选地,所述步骤3)中烘箱的温度为40~60℃,干燥时间为8~24h;所述阶梯式升温法具体设置为以1~5℃/min的升温速率升至200~300℃保温1~3h,再以1~5℃/min升温至500~600℃煅烧1~3h。
本发明还提供了一种上述制备方法制备的柔性二氧化钛陶瓷纳米纤维纱线。
优选地,所述柔性二氧化钛纳米纤维纱线的平均直径为140~600μm,纱线中纳米纤维的平均直径为200~500nm,内部平均晶粒尺寸为10~30nm。
本发明还提供了一种上述柔性二氧化钛陶瓷纳米纤维纱线在制备光催化剂、催化剂载体或抗菌材料中的应用。
本发明的柔性二氧化钛陶瓷纳米纤维纱线具有良好的外观、柔韧性及机械性能,耐氧化、耐高温、耐酸碱腐蚀,同时光催化效率高、易回收分离,且制备工艺简便易行、环境污染小,有利于规模化应用。
与现有技术相比,本发明的有益效果在于:
(1)本发明将容易水解的钛源置于含盐酸多巴胺的乙醇等有机溶剂中形成溶液,加入乙酸等物质抑制调节钛源的快速水解,同时弱酸环境抑制多巴胺单体在空气中的氧化自聚反应,而后经水解等过程形成均匀稳定的溶胶。利用尖端共轭静电纺纱技术制备前驱体纳米纤维纱线,电场会加快多巴胺电聚合过程中的氧化还原反应进程,提高反应速率,加速转化为聚多巴胺。聚多巴胺会形成纱线中纤维间粘结点,增强纱线机械强度,同时研究发现聚多巴胺导致煅烧后二氧化钛晶粒间存在碳中间区,可有效降低二氧化钛晶粒尺寸,降低单纤维孔隙率,增加单纤维致密程度,有利于纤维、纱线的柔性及拉伸力学等性能。
(2)本发明的制备方法简便易行、反应温度低、环境污染小、易于控制,且煅烧后二氧化钛晶格中基本无掺杂离子、纯度高、晶粒尺寸小、均匀性好。通过调控纺丝液浓度、电压、转杯速度等静电纺纱参数可制备不同纱线直径、不同纳米纤维直径、不同捻度、不同密度的前驱体纱线,进一步改善后续二氧化钛陶瓷纳米纤维纱线力学等性能,以满足其实际应用需求。
(3)本发明的柔性二氧化钛纳米纤维纱线属于纯无机材料组成的纳米纤维纱线,具有耐高温、耐酸碱腐蚀、耐氧化、比表面积大,活性位点多,催化效率高等优点,且方便回收分离,可多次重复利用,在光催化、杀菌抑菌等领域具有潜在的应用价值。
附图说明
图1为实施例1中所制备的柔性二氧化钛纳米纤维纱线实物图;
图2为实施例1中所制备的柔性二氧化钛纳米纤维纱线的扫描电镜SEM图及局部放大图;其中,a为低倍扫描电镜图,b为局部放大图;
图3为实施例1中所制备的柔性二氧化钛纳米纤维纱线的透射电镜TEM图及局部放大图;其中,a为低倍透射电镜图,b和c为局部放大图;
图4为实施例1中所制备的柔性二氧化钛纳米纤维纱线的X射线衍射谱;
图5为对比例1中所制备的二氧化钛纳米纤维纱线实物图。
具体实施方式
为使本发明更明显易懂,兹以优选实施例,并配合附图作详细说明如下。
实施例1
一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法,具体步骤为:
(1)将0.11g聚氧化乙烯PEO溶解于2.25g乙酸中,搅拌至溶液澄清透明后,加入3.30g无水乙醇搅拌30min,然后向体系中加入1.50g钛酸异丙酯,搅拌30min得到稳定的溶胶;
(2)将0.01g盐酸多巴胺溶解于10g去离子水中,并从中取0.01g加入到上述溶胶中,搅拌至混合溶液澄清透明,得到纺丝液;
(3)将上述纺丝液转移到两个注射器中进行尖端共轭静电纺纱,其中一个注射器与高压正极相连,另一个与负极相连,不锈钢306材质的转杯接地,纺丝液的灌注速度为0.5mL/h,纺丝电压为±6kv,针头与纺纱转杯距离为15cm,夹角为45°,环境温度25℃,相对湿度50%,转杯速度为30r/min纱线卷绕速度为1.0r/min;
(4)将上述前驱体纳米纤维纱线置于40℃烘箱中干燥8h,以去除残余溶剂,将烘干后的杂化纤维纱线置于马弗炉中煅烧,以5℃/min的升温速率升至200℃保温1h,再以5℃/min的升温速率升温至600℃煅烧1h,得到如图1所示的柔性二氧化钛纳米纤维纱线。
上述的二氧化钛纳米纤维纱线通过扫描电子显微镜测量纱线的平均直径为149μm,纤维直径为400~500nm,纳米纤维直径分布较均匀,以一定取向排列加捻形成纳米纤维纱线,如图2所示。透射电镜TEM图及局部放大图(图3)表明单纤维直径470nm,纤维结构致密,孔隙率低,晶粒尺寸较小,二氧化钛晶粒间存在碳中间区。图4是该二氧化钛纳米纤维纱线的X射线衍射(XRD)分析。它反映了产物的晶相、纯度、结晶性等信息。其中,位于25.3°、36.9°、37.8°、38.6°和48.0°的衍射峰分别对应于锐钛矿型二氧化钛(标准卡片编号PDF#21-1272)的(101)、(103)、(004)、(112)和(200)晶面。通过Scherrer公式计算得到内部平均晶粒尺寸为15nm。
实施例2
一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法,类似于实施例1,不同之处在于,所用的有机溶剂为甲醇-乙醇-乙酸体系,具体步骤为:
(1)将0.11g聚氧化乙烯PEO溶解于2.25g乙酸中,搅拌至溶液澄清透明后,加入3.30g无水乙醇搅拌30min,然后向体系中加入1.50g钛酸异丙酯,搅拌30min得到稳定的溶胶;
(2)将0.01g盐酸多巴胺溶解于10g甲醇中,并从中取0.01g加入到上述溶胶中,搅拌至混合溶液澄清透明,得到纺丝液;
(3)将上述纺丝液转移到两个注射器中进行尖端共轭静电纺纱,其中一个注射器与高压正极相连,另一个与负极相连,不锈钢306材质的转杯接地,纺丝液的灌注速度为0.5mL/h,纺丝电压为±6kv,针头与纺纱转杯距离为15cm,夹角为45°,环境温度25℃,相对湿度50%,转杯速度为30r/min纱线卷绕速度为1.0r/min;
(4)将上述前驱体纳米纤维纱线置于40℃烘箱中干燥8h,以去除残余溶剂,将烘干后的杂化纤维纱线置于马弗炉中煅烧,以5℃/min的升温速率升至200℃保温1h,再以5℃/min的升温速率升温至600℃煅烧1h,得到柔性二氧化钛纳米纤维纱线。
上述的二氧化钛纳米纤维纱线通过扫描电子显微镜测量纱线的平均直径为172μm,纤维直径为200~500nm。透射电镜TEM图表明单纤维结构致密,二氧化钛晶粒间存在碳中间区。由X射线衍射(XRD)分析知,实施例2的柔性陶瓷纳米纤维纱线二氧化钛晶体结构基本为锐钛矿相。通过Scherrer公式计算得到内部平均晶粒尺寸为16nm。
实施例3
一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法,类似于实施例1,不同之处在于,煅烧条件不同,具体步骤为:
(1)将0.11g聚氧化乙烯PEO溶解于2.25g乙酸中,搅拌至溶液澄清透明后,加入3.30g无水乙醇搅拌30min,然后向体系中加入1.50g钛酸异丙酯,搅拌30min得到稳定的溶胶;
(2)将0.01g盐酸多巴胺溶解于10g去离子水中,并从中取0.01g加入到上述溶胶中,搅拌至混合溶液澄清透明,得到纺丝液;
(3)将上述纺丝液转移到两个注射器中进行尖端共轭静电纺纱,其中一个注射器与高压正极相连,另一个与负极相连,不锈钢306材质的转杯接地,纺丝液的灌注速度为0.5mL/h,纺丝电压为±6kv,针头与纺纱转杯距离为15cm,夹角为45°,环境温度25℃,相对湿度50%,转杯速度为30r/min纱线卷绕速度为1.0r/min;
(4)将上述前驱体纳米纤维纱线置于40℃烘箱中干燥8h,以去除残余溶剂,将烘干后的杂化纤维纱线置于马弗炉中煅烧,以2℃/min的升温速率升至200℃保温2h,再以2℃/min的升温速率升温至550℃煅烧1h,得到柔性二氧化钛纳米纤维纱线。
上述的二氧化钛纳米纤维纱线通过扫描电子显微镜测量纱线的平均直径为165μm,纤维直径为300~400nm。透射电镜TEM图表明单纤维结构致密,二氧化钛晶粒间存在碳中间区。由X射线衍射(XRD)分析知,实施例3的柔性陶瓷纳米纤维纱线二氧化钛晶体结构基本为锐钛矿相。通过Scherrer公式计算得到内部平均晶粒尺寸为19nm。
对比例1
对比例1的制备方法类似于实施例1,不同之处在于,对比例1制备过程中不加入盐酸多巴胺,所得到的陶瓷纳米纤维纱线弯曲时易碎,不具备较好的柔韧性,如图5所示。
Claims (8)
1.一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法,其特征在于,包括以下步骤:
步骤1):将高分子聚合物溶解于有机溶剂中,搅拌至溶液澄清透明后,加入钛源得到稳定的溶胶A;将盐酸多巴胺溶解于去离子水或甲醇,得到溶液B,将溶液B加入到溶胶A中,搅拌至混合溶液澄清透明,得到纺丝液;有机溶剂为水-乙醇-乙酸、水-异丙醇-乙酸及甲醇-乙醇-乙酸体系中的至少一种;
步骤2):将纺丝液转移至两个注射器中进行尖端共轭静电纺纱,其中一个注射器与高压正极相连,另一个与负极相连,加捻转杯接地,环境温度设置为20~30℃,相对湿度设置为30%~50%,得到前驱体纳米纤维纱线;静电纺纱的工艺参数为:纺丝液灌注速度0.5~1.5mL/h,纺丝电压±6~±10kV,针头与纺纱转杯距离10~15cm,纺纱角30°~45°,转杯速度20~30r/min,转杯材质为不锈钢306,纱线卷绕速度1.0~1.5r/min;
步骤3):将前驱体纳米纤维纱线置于烘箱中干燥以去除残余溶剂,然后采用阶梯式升温法在空气气氛下煅烧,得到柔性二氧化钛陶瓷纳米纤维纱线。
2. 如权利要求1所述的制备方法,其特征在于,所述步骤1)所得纺丝液中盐酸多巴胺的质量百分数为 10-6~10-4。
3.如权利要求1所述的制备方法,其特征在于,所述步骤1)中的钛源为钛酸异丙酯、钛酸四丁酯及钛酸四乙酯中的至少一种。
4.如权利要求1所述的制备方法,其特征在于,所述步骤1)中的高分子聚合物为聚氧化乙烯,聚氧化乙烯在纺丝液中的质量百分数为1~5%。
5.如权利要求1所述的制备方法,其特征在于,所述步骤3)中烘箱的温度为40~60℃,干燥时间为8~24h;所述阶梯式升温法具体设置为以1~5℃/min的升温速率升至200~300℃保温1~3h,再以1~5℃/min升温至500~600℃煅烧1~3h。
6.一种权利要求1-5任一项所述的制备方法制备的柔性二氧化钛陶瓷纳米纤维纱线。
7.如权利要求1所述的柔性二氧化钛陶瓷纳米纤维纱线,其特征在于,所述柔性二氧化钛纳米纤维纱线的平均直径为140~600μm,纱线中纳米纤维的平均直径为200~500nm,内部平均晶粒尺寸为10~30nm。
8.一种权利要求7所述的柔性二氧化钛陶瓷纳米纤维纱线在制备光催化剂、催化剂载体或抗菌材料中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310179726.5A CN116163040B (zh) | 2023-02-27 | 2023-02-27 | 一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310179726.5A CN116163040B (zh) | 2023-02-27 | 2023-02-27 | 一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116163040A CN116163040A (zh) | 2023-05-26 |
CN116163040B true CN116163040B (zh) | 2024-09-10 |
Family
ID=86411309
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310179726.5A Active CN116163040B (zh) | 2023-02-27 | 2023-02-27 | 一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116163040B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116813368B (zh) * | 2023-06-08 | 2024-06-14 | 东华大学 | 弹性层状结构二氧化钛陶瓷纳米纤维体型材料的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107653518A (zh) * | 2017-09-27 | 2018-02-02 | 中南大学 | 一种高取向度连续超细/纳米氧化铝基陶瓷纤维束材料及其制备方法 |
CN110512354A (zh) * | 2019-08-15 | 2019-11-29 | 东华大学 | 一种柔性钛酸钡陶瓷纳米纤维膜的制备方法 |
CN113737395A (zh) * | 2021-08-06 | 2021-12-03 | 华南理工大学 | 一种柔性二氧化钛纳米纤维膜及其制备方法和应用 |
CN115537975A (zh) * | 2022-10-28 | 2022-12-30 | 安徽农业大学 | 一种柔性自支撑氮掺杂碳纤维复合材料的制备方法及应用 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101313898B1 (ko) * | 2012-04-27 | 2013-09-30 | 서울대학교산학협력단 | 히알루론산―도파민 컨쥬게이트로 표면이 개질된 하이드록시아파타이트 나노입자를 포함하는 실크피브로인 나노섬유 및 이를 이용한 지지체 |
CN107604497A (zh) * | 2017-10-09 | 2018-01-19 | 长春理工大学 | 磁光双功能纳米纤维纱线及其制备方法 |
CN108498868B (zh) * | 2018-04-03 | 2020-09-15 | 北京大学口腔医学院 | 具有细胞外基质电学拓扑特征的带电复合膜及其制备方法 |
CN109112728B (zh) * | 2018-08-03 | 2023-11-17 | 东华大学 | 柔性二氧化钛/碳复合多孔纳米纤维膜材料的制备方法 |
CN110241490B (zh) * | 2019-05-16 | 2020-11-10 | 常熟市华坤针纺织有限公司 | 一种低成本制备具有抗菌性能的蚕丝包芯纱的方法 |
CN112300993B (zh) * | 2019-07-24 | 2023-09-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | 基于TiO2纳米纤维的CTC捕获和分离基底及其制备方法与应用 |
CN113249811B (zh) * | 2021-05-13 | 2022-11-08 | 太原理工大学 | 一种中空纳米纤维内部固定化生物酶的制备方法 |
CN114687000A (zh) * | 2022-02-22 | 2022-07-01 | 江西师范大学 | 一种聚多巴胺@TiO2@PI纳米纤维膜及其制备方法 |
-
2023
- 2023-02-27 CN CN202310179726.5A patent/CN116163040B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107653518A (zh) * | 2017-09-27 | 2018-02-02 | 中南大学 | 一种高取向度连续超细/纳米氧化铝基陶瓷纤维束材料及其制备方法 |
CN110512354A (zh) * | 2019-08-15 | 2019-11-29 | 东华大学 | 一种柔性钛酸钡陶瓷纳米纤维膜的制备方法 |
CN113737395A (zh) * | 2021-08-06 | 2021-12-03 | 华南理工大学 | 一种柔性二氧化钛纳米纤维膜及其制备方法和应用 |
CN115537975A (zh) * | 2022-10-28 | 2022-12-30 | 安徽农业大学 | 一种柔性自支撑氮掺杂碳纤维复合材料的制备方法及应用 |
Also Published As
Publication number | Publication date |
---|---|
CN116163040A (zh) | 2023-05-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104153123B (zh) | 一种柔性氧化钛纳米纤维膜及其制备方法 | |
CN109112728B (zh) | 柔性二氧化钛/碳复合多孔纳米纤维膜材料的制备方法 | |
CN101428209B (zh) | 纳米纤维负载二氧化钛光催化剂及其制备方法 | |
CN116163040B (zh) | 一种柔性二氧化钛陶瓷纳米纤维纱线的制备方法 | |
CN101815563B (zh) | 空心多孔微球 | |
CN105126886B (zh) | 一种TiO2/WO3/g-C3N4全介孔纳米纤维的制备方法 | |
CN107099880B (zh) | 一种氧化钴镍/二氧化锡复合纳米管及其制备方法和用途 | |
CN111167455B (zh) | 一种石墨烯负载钴掺杂二氧化钛光催化剂及其制备方法 | |
CN106978652B (zh) | 一种聚醋酸氧钛前驱体溶胶纺丝液及氧化钛纳米纤维光催化剂的制备方法 | |
CN103318956B (zh) | 一种制备二氧化钛纳米线的方法 | |
CN113564916B (zh) | 一种柔性压电光催化纳米纤维的原位制备方法 | |
CN104153125A (zh) | 一种柔性氧化铁纳米纤维膜及其制备方法 | |
CN113737395A (zh) | 一种柔性二氧化钛纳米纤维膜及其制备方法和应用 | |
KR20110075509A (ko) | 은이 첨가된 광촉매용 산화티탄 섬유의 제조방법 | |
CN112973686A (zh) | 一种热释电效应增强异质结构复合材料光催化性能的方法及应用 | |
CN105148965B (zh) | 一种TiO2/WO3/g-C3N4全介孔纳米纤维 | |
CN105126892B (zh) | 一种TiO2/WO3/g-C3N4全介孔纳米纤维在高效光催化剂中的应用 | |
CN103990463A (zh) | 一种NiO/γ-Al2O3复合陶瓷纳米纤维光催化材料的制备方法 | |
CN115467047B (zh) | 一种高效抗菌光催化的连续氧化铝纤维的制备方法 | |
CN114561719B (zh) | 一种纤维交织结构的氧化铈/氧化硅复合纤维材料及其制备方法与应用 | |
KR101007887B1 (ko) | 2단계 열처리를 이용한 SiO2-TiO2계 복합무기섬유의 제조방법 | |
CN114045608B (zh) | 一种柔性多晶氧化钛-氧化铝复合纳米纤维膜及其制备方法 | |
CN113502596A (zh) | 一种自支撑MgTiO3纳米纤维化学战剂降解材料及其制备方法 | |
CN102000577A (zh) | 一种磁性纳米复合纤维及其制备方法和用途 | |
CN109589996B (zh) | 一种TiO2基/二维材料纳米复合光催化纤维膜及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant |