CN102515744B - CaCu3Ti4O12 micro nano sized fiber and its preparation method - Google Patents
CaCu3Ti4O12 micro nano sized fiber and its preparation method Download PDFInfo
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- CN102515744B CN102515744B CN 201110411790 CN201110411790A CN102515744B CN 102515744 B CN102515744 B CN 102515744B CN 201110411790 CN201110411790 CN 201110411790 CN 201110411790 A CN201110411790 A CN 201110411790A CN 102515744 B CN102515744 B CN 102515744B
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Abstract
The invention discloses a CaCu3Ti4O12 micro nano sized fiber and its preparation method, which belongs to the inorganic material technical field. The CaCu3Ti4O12 micro nano sized fiber comprises the elements of Ca, Cu, Ti and O with the mol ratio of 13412, and the diameter is 200-300 nanometers. The preparation method comprises the following steps mixing anhydrous ethyl alcohol, calcium nitrate tetrahydrate and copper acetate monohydrate to obtain a solution A; mixing anhydrous ethanol, butyl titanate and a spinning auxiliary agent to obtain a solution B; slowly adding the solution B in the solution A, and using a static spinning technology to prepare the CaCu3Ti4O12 micro nano sized fiber. The method of the invention can effectively control the hydrolysis process of the raw materials by selecting and adjusting the ratio of raw materials and the spinning auxiliary agent, the obtained static spinning solution possesses spinnability, and the method of the invention provides the novel CaCu3Ti4O12 micro nano sized fiber. The preparation method has the advantages of simple process, mild condition, easy control and wide applicability.
Description
Technical field
The present invention relates to a kind of inorganic fibers technology, be specifically related to a kind of micro-nano level ceramic fiber and preparation method thereof.
Background technology
High dielectric constant materials can be used for the manufacturing of the capacitive device of small volume, for the electron device microminiaturization provides very big possibility, therefore it has purposes very widely, the important effect of play more and more in microelectronics industry in fields such as microresonator, wave filter, portable phones.
People such as Subramanian (M.A. Subramanian, Dong Li, et al. J. Solid State Chemistry, 2000,151:323-325) found to have the CaCu of perovskite-like structure in 2000
3
Ti
4
O
12
(being abbreviated as CCTO) has very high specific inductivity (generalized case is greater than 10000) in the temperature range of 100～500K, and in very wide temperature range, do not have structural phase transition and ferroelectric phase transition, therefore, this material has broad prospects in the application of electron trade.
The one dimension micro-nano level material that with the fiber is representative has particular optical performance, electric property and space geometry structure, is the ideal material that research and development have novel electron transport property, optical characteristics and mechanical property.But, present CaCu
3
Ti
4
O
12
Be confined to existence forms such as ceramic sintered bodies, powder and film, yet there are no about CaCu
3
Ti
4
O
12
The report of micro-nano level fiber makes it limited in the application of the contour frontier of transmitter.
At present, preparation CaCu
3
Ti
4
O
12
The method of sample mainly is solid sintering process, sol-gel method and pulsed laser deposition.Solid sintering process prepares the superfine powder of each component by mechanical milling method, is prepared into fine and close micro-crystalline ceramic by high temperature solid-phase sintering then; But preparation technology is harsh for this method, has only accurate control, could obtain the stable CaCu of specific inductivity
3
Ti
4
O
12
Pottery.Characteristics such as sol-gel method is the effective ways of preparation even superfine powder, has the purity height, and each component molecular level chemistry evenly, granular size is controlled, equipment is simple.Pulsed laser deposition can the growth in situ high-temperature superconducting thin film, is all having broad application prospects aspect the preparation thin-film material or the material of nanostructure.But also having no small difficulty aspect the higher-quality nano material of preparation, and because search time is shorter, how to be more prone to, to control simply the growth mechanism of formation nanostructure and nanostructure, all needing further to explore.Above-mentioned three kinds of methods all can't obtain CaCu
3
Ti
4
O
12
Micro-nano level fiber.
In recent years, electrostatic spinning technique gets more and more people's extensive concerning, and it is a kind ofly to obtain the method for fiber by high pressure static electricity, and its core is that charged spinning solution is flowed in electrostatic field and distortion, along with the cooling of solvent evaporation or melt and solidify, thereby obtain fiber.Compare with additive method, electrostatic spinning has remarkable advantages.For example, the fiber length-to-diameter ratio of preparation is very big, and staple length can reach macro-scale; Preparation condition gentleness, speed are very fast, output is bigger, and applicable surface is extensive, and preparation process is very simple, is to prepare very effective, the easy method of fiber.Before the present invention makes, Chinese invention patent (CN102084044A) discloses the method that a kind of electrostatic spinning by solution is produced inorganic nano-fiber, and this solution comprises and being dissolved in based on the metal in the solvent system of alcohol or semi-metal or nonmetallic alcoxylates.Solution is prevented from the sequestrant institute stabilization of the hydrolysis of alcoxylates, after homogenizing this solution with mix by poly-(vinyl pyrrolidone) solution in alcohol, gained solution is transported to electrostatic field then, carry out electrostatic spinning therein continuously, the result of spinning is the production of organic-inorganic nano fiber, and this fiber is being calcined in air atmosphere under 500～1300 ℃ temperature outside the spinning equipment then.Chinese invention patent " a kind of electrostatic spinning prepares the method for alumina nano fiber " (CN 101982581A) is dissolved in polymkeric substance in the solvent, again aluminium acetylacetonate is joined in the polymers soln, the preparation spinning solution through electrostatic spinning and sintering processes, obtains alumina nano fiber.Technique scheme provides the fiber of preparation simple oxide, and CaCu
3
Ti
4
O
12
Pottery is made up of by fixed proportion three kinds of metallic elements, in order to the inorganic salt of the alkoxy compound of titanium and calcium and copper correspondence during as raw material, owing to contain crystal water and water-absorbent that itself had in the inorganic salt of calcium and copper, to cause metal alkoxide compound hydrolysis and polymerization apace, even generation partial gel, make the viscosity of spinning solution be the geometricprogression rising, can carry out the scope of electrostatic spinning head and shoulders above, this phenomenon is as easy as rolling off a log occur in spinning before, bring difficulty to electrostatic spinning process, even electrostatic spinning can't be carried out, therefore, not seeing at present has CaCu
3
Ti
4
O
12
The use of nanofiber in the prior art, is not seen about electrospinning process to prepare CaCu yet
3
Ti
4
O
12
The report of micro-nano level fiber.
Summary of the invention
In order to overcome the deficiency that prior art exists, the object of the present invention is to provide a kind of CaCu
3
Ti
4
O
12
Micro-nano level fiber, and a kind of technology is simple, mild condition, widely applicable CaCu
3
Ti
4
O
12
Micro-nano level fiber preparation method.
Realize that the technical scheme that the object of the invention adopted provides a kind of CaCu
3
Ti
4
O
12
Micro-nano level fiber, it comprises Elements C a, Cu, Ti and O, they be 1:3:4:12 in molar ratio; , Fibre diameter is 200～300 nanometers.
A kind of CaCu
3
Ti
4
O
12
Micro-nano level fiber preparation method comprises the steps:
1, under agitation condition, by weight, 100～200 parts of dehydrated alcohols, 1～5 part of calcium nitrate tetrahydrate and 2～10 part of one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1～5 hour under 20～50 ℃ temperature condition, obtains solution A;
2, under agitation condition, by weight, 5～30 parts of polyvinylpyrrolidones, 100～200 parts of dehydrated alcohols, 3～15 parts of spin finish aids and 3～15 parts of butyl (tetra) titanates are joined in the reaction vessel, and isothermal reaction is 1～3 hour under 20～50 ℃ temperature condition, obtains solution B;
3, under agitation condition, solution B slowly is added drop-wise in the solution A, obtain electrostatic spinning solution;
4, adopt electrostatic spinning process to obtain fiber;
5, the fiber that electrostatic spinning is obtained 50～70 ℃ dry 12～18 hours down, be heated to 900～1000 ℃ with 5～10 ℃/minute temperature rise rate again, and constant temperature 2～5 hours, obtain CaCu
3
Ti
4
O
12
Micro-nano level fiber.
Described spin finish aid is acetate, Tetramethylammonium hydroxide, or a kind of in the potassium hydroxide.
Electrostatic spinning process is 15～30 kilovolts of voltages, solidifies 5～15 centimetres of distances, and receiving trap is an aluminium foil.
Compared with prior art, the beneficial effect that has of the present invention is: a kind of CaCu is provided
3
Ti
4
O
12
Fiber, it is CaCu
3
Ti
4
O
12
A kind of new existence form.The present invention controls the hydrolytic process of raw material effectively by adjusting proportioning, addition manner and the spin finish aid of each experimental raw, and the electrostatic spinning process is carried out smoothly.The preparation method who is proposed has that technology is simple, mild condition, be easy to control, widely applicable characteristics.
Description of drawings
Fig. 1 is the CaCu that the embodiment of the invention 1 provides
3
Ti
4
O
12
The SEM figure of micro-nano level fiber;
Fig. 2 is the CaCu that the embodiment of the invention 1 provides
3
Ti
4
O
12
The XRD figure of micro-nano level fiber;
Fig. 3 is the CaCu that the embodiment of the invention 5 provides
3
Ti
4
O
12
The SEM figure of micro-nano level fiber;
Fig. 4 is the CaCu that the embodiment of the invention 5 provides
3
Ti
4
O
12
The XRD figure of micro-nano level fiber;
Fig. 5 is the CaCu that the embodiment of the invention 8 provides
3
Ti
4
O
12
The SEM figure of micro-nano level fiber;
Fig. 6 is the CaCu that the embodiment of the invention 8 provides
3
Ti
4
O
12
The XRD figure of micro-nano level fiber.
Embodiment
Below in conjunction with drawings and Examples technical solution of the present invention is further described.
Embodiment 1
1, under agitation condition, 10 milliliters of dehydrated alcohols, 1.04 gram calcium nitrate tetrahydrates and 2.63 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 2 hours under 30 ℃ temperature condition, obtains solution A;
2, under agitation condition, 1.5 gram polyvinylpyrrolidones, 10 milliliters of dehydrated alcohols, 3 milliliters of acetate and 6 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 1 hour under 30 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 100 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 16.50 kilovolts, and sample rate is 6.5 milliliters/hour, and solidifying distance is 12 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 3 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 60 ℃ dry 15 hours down, be heated to 900 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 3 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Referring to accompanying drawing 1 is the CaCu that embodiment 1 provides
3
Ti
4
O
12
The SEM figure of fiber, as can be seen, CaCu
3
Ti
4
O
12
For fibers form exists, diameter is about 200～300 nanometers.
Referring to accompanying drawing 2 are present embodiment CaCu
3
Ti
4
O
12
The XRD figure of fiber, therefrom as can be seen, CaCu
3
Ti
4
O
12
The structure of fiber is pure CaCu
3
Ti
4
O
12
Phase.
Embodiment 2
1, under agitation condition, 15 milliliters of dehydrated alcohols, 1.04 gram calcium nitrate tetrahydrates and 2.63 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution A;
2, under agitation condition, 2.5 gram polyvinylpyrrolidones, 15 milliliters of dehydrated alcohol 1.5 gram Tetramethylammonium hydroxide and 6 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 19.50 kilovolts, and sample rate is 8.5 milliliters/hour, and solidifying distance is 15 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 70 ℃ dry 18 hours down, be heated to 950 ℃ with 10 ℃/minute temperature rise rate then, and constant temperature 5 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 3
1, under agitation condition, 20 milliliters of dehydrated alcohols, 2.08 gram calcium nitrate tetrahydrates and 5.26 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1 hour under 50 ℃ temperature condition, obtains solution A;
2, under agitation condition, 3 gram polyvinylpyrrolidones, 20 milliliters of dehydrated alcohol 3 gram Tetramethylammonium hydroxide and 12 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 1 hour under 50 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 150 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 23.50 kilovolts, and sample rate is 9.5 milliliters/hour, and solidifying distance is 15 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 50 ℃ dry 12 hours down, be heated to 1000 ℃ with 7 ℃/minute temperature rise rate then, and constant temperature 2 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 4
1, under agitation condition, 15 milliliters of dehydrated alcohols, 1.56 gram calcium nitrate tetrahydrates and 3.95 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1 hour under 20 ℃ temperature condition, obtains solution A;
2, under agitation condition, 1.9 gram polyvinylpyrrolidones, 18 milliliters of dehydrated alcohol 1 gram potassium hydroxide and 9 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 1 hour under 20 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 27.50 kilovolts, and sample rate is 8.5 milliliters/hour, and solidifying distance is 12 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 70 ℃ dry 18 hours down, be heated to 1000 ℃ with 9 ℃/minute temperature rise rate then, and constant temperature 3 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 5
1, under agitation condition, 20 milliliters of dehydrated alcohols, 1.56 gram calcium nitrate tetrahydrates and 3.95 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1 hour under 50 ℃ temperature condition, obtains solution A;
2, under agitation condition, 3 gram polyvinylpyrrolidones, 20 milliliters of dehydrated alcohol 1.5 gram potassium hydroxide and 9 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 20 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 30 kilovolts, and sample rate is 10 milliliters/hour, and solidifying distance is 15 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 70 ℃ dry 18 hours down, be heated to 1000 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 3 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Referring to accompanying drawing 3 and 4 is respectively the CaCu that present embodiment provides
3
Ti
4
O
12
The SEM figure and the XRD figure of fiber, as can be seen, CaCu
3
Ti
4
O
12
For fibers form exists and is pure CaCu
3
Ti
4
O
12
Phase, diameter are about 200～300 nanometers.
Embodiment 6
1, under agitation condition, 20 milliliters of dehydrated alcohols, 1.56 gram calcium nitrate tetrahydrates and 3.95 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 5 hours under 20 ℃ temperature condition, obtains solution A;
2, under agitation condition, 1.3 gram polyvinylpyrrolidones, 20 milliliters of dehydrated alcohol 0.5 gram potassium hydroxide and 9 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 20 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 15 kilovolts, and sample rate is 1 milliliter/hour, and solidifying distance is 5 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 5 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 50 ℃ dry 12 hours down, be heated to 900 ℃ with 10 ℃/minute temperature rise rate then, and constant temperature 5 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 7
1, under agitation condition, 10 milliliters of dehydrated alcohols, 0.78 gram calcium nitrate tetrahydrate and 1.98 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 5 hours under 20 ℃ temperature condition, obtains solution A;
2, under agitation condition, 0.5 gram polyvinylpyrrolidone, 0.8 milliliter of acetate of 10 milliliters of dehydrated alcohols and 4.5 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 20 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 100 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 15 kilovolts, and sample rate is 2.3 milliliters/hour, and solidifying distance is 10 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 5 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 60 ℃ dry 12 hours down, be heated to 950 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 2 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 8
1, under agitation condition, 20 milliliters of dehydrated alcohols, 2.08 gram calcium nitrate tetrahydrates and 5.26 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1 hour under 30 ℃ temperature condition, obtains solution A;
2, under agitation condition, 2.5 gram polyvinylpyrrolidones, 15 milliliters of dehydrated alcohol 1.5 gram Tetramethylammonium hydroxide and 12 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 1 hour under 50 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 150 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 23.50 kilovolts, and sample rate is 9.5 milliliters/hour, and solidifying distance is 15 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 50 ℃ dry 12 hours down, be heated to 950 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 2 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Referring to accompanying drawing 5 and 6, be respectively the CaCu that present embodiment provides
3
Ti
4
O
12
The SEM figure and the XRD figure of fiber, as can be seen, CaCu
3
Ti
4
O
12
For fibers form exists and is pure CaCu
3
Ti
4
O
12
Phase, diameter are about 200～300 nanometers.
Embodiment 9
1, under agitation condition, 18 milliliters of dehydrated alcohols, 1.04 gram calcium nitrate tetrahydrates and 2.63 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 3 hours under 35 ℃ temperature condition, obtains solution A;
2, under agitation condition, 2.1 gram polyvinylpyrrolidones, 18 milliliters of dehydrated alcohol 1.8 gram Tetramethylammonium hydroxide and 6 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 100 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 22.50 kilovolts, and sample rate is 7.5 milliliters/hour, and solidifying distance is 17 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 70 ℃ dry 18 hours down, be heated to 900 ℃ with 10 ℃/minute temperature rise rate then, and constant temperature 4 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 10
1, under agitation condition, 13 milliliters of dehydrated alcohols, 1.04 gram calcium nitrate tetrahydrates and 2.63 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution A;
2, under agitation condition, 1.9 gram polyvinylpyrrolidones, 13 milliliters of dehydrated alcohol 1.1 gram Tetramethylammonium hydroxide and 6 milliliters of butyl (tetra) titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 21.50 kilovolts, and sample rate is 9.5 milliliters/hour, and solidifying distance is 16 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 65 ℃ dry 15 hours down, be heated to 950 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 4 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Claims (3)
1. CaCu
3Ti
4O
12Micro-nano level fiber preparation method is characterized in that comprising the steps:
(1) under agitation condition, by weight, 100～200 parts of dehydrated alcohols, 1～5 part of calcium nitrate tetrahydrate and 2～10 part of one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1～5 hour under 20～50 ℃ temperature condition, obtains solution A;
(2) under agitation condition, by weight, 5～30 parts of polyvinylpyrrolidones, 100～200 parts of dehydrated alcohols, 3～15 parts of spin finish aids and 3～15 parts of butyl (tetra) titanates are joined in the reaction vessel, and isothermal reaction is 1～3 hour under 20～50 ℃ temperature condition, obtains solution B;
(3) under agitation condition, solution B slowly is added drop-wise in the solution A, obtain electrostatic spinning solution;
(4) adopt electrostatic spinning process to obtain fiber;
(5) fiber that electrostatic spinning is obtained 50～70 ℃ dry 12～18 hours down, be heated to 900～1000 ℃ with 5～10 ℃/minute temperature rise rate again, and constant temperature 2～5 hours, obtain CaCu
3Ti
4O
12Micro-nano level fiber, described CaCu
3Ti
4O
12Micro-nano level fiber comprises Elements C a, Cu, Ti and O, and they are 1:3:4:12 in molar ratio; Fibre diameter is 200～300 nanometers.
2. CaCu according to claim 1
3Ti
4O
12Micro-nano level fiber preparation method is characterized in that: described spin finish aid is acetate, Tetramethylammonium hydroxide, or a kind of in the potassium hydroxide.
3. CaCu according to claim 1
3Ti
4O
12Micro-nano level fiber preparation method is characterized in that: electrostatic spinning process is 15～30 kilovolts of voltages, solidifies 5～15 centimetres of distances, and receiving trap is an aluminium foil.
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| CN103172363B (en) * | 2012-09-10 | 2014-08-13 | 常州大学 | Preparation method of high-dielectric-constant perovskite CaCu3Ti4O12 (CCTO) pressure-sensitive material |
| CN103396548B (en) * | 2013-08-14 | 2015-09-16 | 武汉一海数字工程有限公司 | A kind of preparation method of high dielectric polyimide/CaCu 3 Ti 4 O nanowire composite |
| CN104357955B (en) * | 2014-10-28 | 2017-02-01 | 浙江大学 | Preparation method of one-dimensional hollow porous structure calcium titanate nanofiber |
| CN105803579A (en) * | 2016-04-06 | 2016-07-27 | 中国科学院深圳先进技术研究院 | CaCu3Ti4O12 micro/nano-fibers and manufacturing method thereof |
| CN106111209B (en) * | 2016-06-17 | 2019-04-26 | 江苏纳佰成纳米科技有限公司 | The preparation method of tail gas denitration sub-micron fibers material |
| JP6864263B2 (en) * | 2017-03-30 | 2021-04-28 | Jnc株式会社 | Titanate metal salt fiber manufacturing method |
| CN108017861A (en) * | 2017-10-09 | 2018-05-11 | 南通洪明电工科技有限公司 | A kind of polymer-based dielectric composite material of coated with silica CaCu 3 Ti 4 O nanofiber and preparation method thereof |
| CN108017913B (en) * | 2018-01-09 | 2021-03-02 | 哈尔滨理工大学 | Silicone rubber-based direct current cable accessory material and preparation method thereof |
| CN117758507A (en) * | 2023-09-08 | 2024-03-26 | 江苏国望高科纤维有限公司 | Application of modified copper calcium titanate nanofiber as dielectric filler in preparation of dielectric composite material |
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