CN114920549B - Method for preparing oxide ceramic nanofiber membrane by using precursor liquid as binder - Google Patents
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Abstract
The invention discloses a method for preparing an oxide ceramic nanofiber membrane by taking precursor liquid as a binder, which comprises the steps of preparing electrostatic spinning precursor liquid; diluting the precursor liquid, adding ethanol, acetone and acetic acid, and stirring to obtain an adhesive; preparing a compact nanofiber membrane by an electrostatic spinning technology, tiling at least two prepared nanofiber membranes, overlapping edges, covering a layer of prepared strip nanofiber membrane at the overlapping position as a connecting layer, finally dipping an adhesive, spot-coating the adhesive on the connecting layer, and bonding two adjacent tiled nanofiber membranes through the connecting layer; roasting the bonded nanofiber membrane to obtain an oxide ceramic nanofiber membrane; the precursor liquid is used as the binder to realize the bonding and splicing of the fiber membranes, and the performance of the joint of the fiber membranes is not affected on the premise of not introducing impurities and after calcination, so that the large-area fiber membranes without changing the flexibility and the functionality of the fiber membranes are obtained, and the large-scale mass production of the fiber membranes is realized.
Description
Technical Field
The invention belongs to the technical field of ceramic nanofiber membranes, and relates to a method for preparing an oxide ceramic nanofiber membrane by using a precursor solution as a binder.
Background
The nanofiber membrane prepared by the electrostatic spinning technology has the excellent performances of large specific surface area, high porosity, good flexibility, easy functionalization of the fiber surface, good separation performance, recycling and the like, so that the nanofiber membrane has remarkable development in the field of filtration and purification. The electrostatic spinning process has relatively low cost and simple maintenance and processing process, is a main method for laboratory research and industrialized production of the nanofiber, but is limited by conditions such as solvent selection, needle number, uniformity of fiber structure and the like, and the mass production is still a subject for restricting the mass industrialized production of the electrostatic spinning.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention aims to provide a method for preparing an oxide ceramic nanofiber membrane by taking precursor liquid as a binder, wherein the fiber membrane is adhered in a small-amount dipping and spot coating mode by utilizing the viscosity of spinning liquid, so that a large-area fiber membrane without changing the flexibility and the functionality of the fiber membrane is obtained, and the large-scale mass production of the fiber membrane is realized.
The technical scheme is as follows: the method for preparing the oxide ceramic nanofiber membrane by using the precursor liquid as the binder comprises the following steps of:
(1) Preparing an electrostatic spinning precursor liquid: firstly preparing an ethanol solution of polyvinylpyrrolidone, then sequentially adding ceramic raw materials, a good solvent and an auxiliary agent into the ethanol solution of polyvinylpyrrolidone, and stirring to fully mix the materials to obtain an electrostatic spinning precursor solution;
(2) Preparing an adhesive: diluting the precursor liquid, adding ethanol, acetone and acetic acid into the precursor liquid, and uniformly stirring to obtain an adhesive;
(3) Spraying the electrostatic spinning precursor liquid prepared in the step (1) out of the nanofiber by an electrostatic spinning technology, and forming a compact nanofiber membrane on a receiving plate;
(4) Tiling at least two nanofiber membranes prepared in the step (3), only overlapping edges of two adjacent nanofiber membranes, then covering a layer of strip-shaped nanofiber membrane prepared in the step (3) at the overlapping part of the adjacent nanofiber membranes as a connecting layer, finally dipping an adhesive, spot-coating the adhesive on the connecting layer, and bonding the two adjacent tiled nanofiber membranes through the connecting layer;
(5) Crimping, folding and roasting the nanofiber membrane prepared in the step (4) to obtain aluminum oxide (Al) 2 O 3 ) Titanium dioxide (TiO) 2 ) Ceramic nanofiber membranes.
In the step (1), the ceramic material is a mixture of aluminum acetylacetonate and isopropyl titanate, wherein the mass fraction of the aluminum acetylacetonate in the ceramic material is 10-60%.
In the step (1), ethanol is used as a solvent in an ethanol solution of polyvinylpyrrolidone to disperse the whole system, good solvent is acetone, the acetone is used for dissolving aluminum acetylacetonate, auxiliary agent is acetic acid, and the acetic acid is used for inhibiting the hydrolysis of isopropyl titanate; the volume ratio of the ethanol to the acetone to the acetic acid is 8-10: 8-10: 6.
in the step (2), the precursor solution: good solvents for ethanol and acetone: the mixing volume ratio of acetic acid as an auxiliary agent is 2-2.5:1:1.
Wherein, in the step (3), the thickness of the prepared compact nanofiber membrane is 5-50 μm.
Wherein in the step (5), the roasting is carried out at a roasting temperature of 500-700 ℃, a heating rate of 1.5-2.0 ℃/min and a roasting time of 1-2 h.
Wherein, the prepared ceramic nanofiber membrane is ventilated, the humidity of the ventilation environment is 30-50%, and the standing time is 1-2 h.
The beneficial effects are that: the invention prepares large-area Al by electrostatic spinning, in-situ self-assembly and high-temperature roasting 2 O 3 /TiO 2 The ceramic nanofiber membrane is prepared by diluting a spinning solution by using the viscosity of PVP high polymer substances in an electrospinning precursor solution, the volatility of a good solvent and an auxiliary agent to obtain an adhesive with certain viscosity, and bonding and splicing the nanofiber membrane by dipping a small amount of adhesive in a spot coating manner, wherein the process ensures that a proper amount of adhesive is dipped; the precursor liquid is used as the binder to realize the bonding and splicing of the fiber membranes, and the performance of the joint of the fiber membranes is not affected on the premise of not introducing impurities and after calcination, so that the large-area fiber membranes without changing the flexibility and the functionality of the fiber membranes are obtained, and the large-scale mass production of the fiber membranes is realized.
Drawings
FIG. 1 is a process flow diagram of a bondable flexible oxide ceramic nanofiber membrane;
FIG. 2 is a diagram of three fiber membranes stacked;
FIG. 3 is a view of an adhesive dispensing article;
FIG. 4 is a physical diagram of the bonded fiber membranes;
FIG. 5 is a mechanical test chart of a single layer fiber membrane;
FIG. 6 is a graph of a mechanical test of a fibrous membrane at a three-layer bond;
FIG. 7 is a flexible representation of a fibrous membrane at a three-layer bond;
fig. 8 shows a fiber film calcined using polyvinyl alcohol as a binder.
Detailed Description
Example 1
The invention relates to a method for preparing an oxide ceramic nanofiber membrane by taking a precursor liquid as a binder, which comprises the following steps:
step 1, preparing an electrostatic spinning precursor solution: 0.6g of polyvinylpyrrolidone (PVP) powder was mixed with 4.5mL of ethanol and mixed for 12h under magnetic stirring to obtain a uniform and transparent solution; after 5mL of acetone was added and uniformly dispersed, 0.73g of aluminum Acetylacetonate (AP) was further added; adding 3mL of acetic acid, dispersing uniformly, adding 2.5mL of Titanium Tetraisopropoxide (TTIP), stirring uniformly at room temperature, and fully mixing to obtain a pale yellow transparent precursor solution;
step 2, preparing an adhesive: 1mL of the precursor solution is taken for dilution, 0.3mL of ethanol, 0.2mL of acetone and 0.5mL of acetic acid are added into 1mL of the precursor solution, and the mixture is stirred uniformly at room temperature to obtain an adhesive;
step 3, under the conditions that the spinning environment temperature is 25 ℃, the humidity is 30% -40%, the voltage is 18.5kV, the distance between a metal needle head and a receiver is 12.5cm, the liquid supply speed is 0.5mL/h, and a ceramic fiber membrane is obtained on a receiving plate after spinning for 2 h;
step 4, taking three fiber membranes prepared in the step 3, overlapping and placing two fiber membrane edges with larger areas, covering a third fiber membrane at the joint of the two fiber membranes, carrying out spot coating on the third fiber membrane by using an adhesive, wherein the strength is light, only the first fiber membrane is soaked visually, thus obtaining a large-area fiber membrane, ventilating and standing the large-area fiber membrane, and measuring the thickness of a spliced part and a main body of the fiber membrane by using a thickness meter;
step 5, folding and stacking the fiber membrane roll obtained in the step 4 in a muffle furnace at 600 ℃ for roasting for 2 hours, wherein the heating rate is 2.0 ℃/min, and obtaining Al 2 O 3 /TiO 2 Ceramic nanofiber membranes.
Step 6, spreading the fiber membrane obtained in the step 5 in an environment with humidity of 30-50%, and then ventilating and standing for 2 hours again to obtain flat flexible Al 2 O 3 /TiO 2 A fibrous membrane.
The invention obtains the micro-nano fiber membrane by an electrostatic spinning method, and the micro-nano fiber membrane is slowly calcined to remove macromolecule PVP, good solvent and auxiliary agent in the fiber, and the amorphous Al is generated along with multiphase chemical reactions such as evaporation of polymer/solvent, crystal growth and the like in the process 2 O 3 Along TiO 2 Grain boundary dispersion, effective inhibition of grain growth, al 2 O 3 Densification, anchoring at TiO 2 On the grooves on the surfaces of the nano particles, the defects on the surfaces of the fibers are repaired, the stress is effectively dispersed, and the TiO is weakened 2 The thermal driving force of particle sintering improves the thermal stability and mechanical properties of the fibers, so that after bonding with the precursor liquid, al is present in the bonding site 2 O 3 Still tend to be distributed in TiO 2 In the crystal, the bridge function is achieved, and the fiber strength is toughened. If other pure polymer solution, such as polyvinyl alcohol liquid, is used as the adhesive, the fiber film is bonded by the spot coating method in the step 4, and after calcination, the bonding place TiO can not be ensured due to the reduction of inorganic matters at the bonding place 2 Crystal growth and Al 2 O 3 Repairing the defect, causing brittle fracture, reducing strength of the fiber membrane, and calcining the product with polyvinyl alcohol liquid as binder is shown in fig. 8.
Adhesive spliced Al obtained in example 1 2 O 3 /TiO 2 The fiber membrane was subjected to mechanical testing.
Cutting 4 x 2cm from the above fiber film 2 A binder clip having a mass of 1.1132g was used at the lower end of the single-layer fiber film without breaking the fiber film; when two long tail clips are used to clip the ends of a single-layer fiber membrane, the fiber membrane breaks. I.e., the single layer fibrous membrane can withstand a gravitational pull of 0.011N (less than 0.022N). As shown in FIG. 5Shown.
And (3) carrying out mechanical test on the spliced part of the three-layer fiber membranes with the bonding part, sequentially clamping 1-5 long tail clamps at the lower end of the three-layer fiber membranes, and finding that when the 5 th long tail clamp is clamped, the three-layer fiber membranes break, namely the three-layer fiber membranes can bear the weight of 4 long tail clamps and is 0.044N (less than 0.55N). As shown in fig. 6.
By bonding and splicing, the mechanical strength of the fiber membrane at the bonding position can be increased, and the fiber form can be maintained in the folding process.
The three-layer fibrous membrane with the bond is folded and bent, and the shape of the bond is still maintained after the bond is unfolded, as shown in fig. 7.
Example 2
The invention relates to a method for preparing an oxide ceramic nanofiber membrane by taking a precursor liquid as a binder, which comprises the following steps:
step 1, preparing an electrostatic spinning precursor solution: 0.6g of polyvinylpyrrolidone (PVP) powder was mixed with 4.5mL of ethanol and mixed for 12h under magnetic stirring to obtain a uniform and transparent solution; after 5mL of acetone was added and uniformly dispersed, 0.73g of aluminum Acetylacetonate (AP) was further added; adding 3mL of acetic acid, dispersing uniformly, adding 2.5mL of Titanium Tetraisopropoxide (TTIP), stirring uniformly at room temperature, and fully mixing to obtain a pale yellow transparent precursor solution;
step 2, preparing an adhesive: taking 1mL of the precursor liquid as an adhesive, and placing the adhesive into a 2mL centrifuge tube for standby;
step 3, under the conditions that the spinning environment temperature is 25 ℃, the humidity is 30% -40%, the voltage is 18.5kV, the distance between a metal needle head and a receiver is 12.5cm, the liquid supply speed is 0.5mL/h, and a ceramic fiber membrane is obtained on a receiving plate after spinning for 2 h;
step 4, taking three fiber membranes prepared in the step 3, overlapping and placing two fiber membrane edges with larger areas, covering a third fiber membrane at the joint of the two fiber membranes, carrying out spot coating on the third fiber membrane by using an adhesive, wherein the strength is light, only the first fiber membrane is soaked visually, thus obtaining a large-area fiber membrane, ventilating and standing the large-area fiber membrane, and measuring the thickness of a spliced part and a main body of the fiber membrane by using a thickness meter;
step 5, folding and stacking the fiber membrane roll obtained in the step 4 in a muffle furnace at 600 ℃ for roasting for 2 hours, wherein the heating rate is 2.0 ℃/min, and obtaining Al 2 O 3 /TiO 2 A ceramic nanofiber membrane;
step 6, spreading the fiber membrane obtained in the step 5 in an environment with humidity of 30-50%, and then ventilating and standing for 2 hours again to obtain flat flexible Al 2 O 3 /TiO 2 A fibrous membrane. The thickness of the fiber film splice and the fiber film body was measured using a thickness gauge.
The thickness of the fiber film before and after firing was measured by a thickness meter, and the shrinkage thereof was recorded.
Thickness tests show that the shrinkage rates of the fiber main body and the fiber interface are similar, which indicates that the fiber precursor liquid at the adhesion part does not influence oxide crystallization in the high-temperature sintering process, so that the fiber can still maintain the structural characteristics. And the phenomenon of fracture at the bonding position does not occur, and the structure of the fiber membrane is not influenced after the fibers are spliced through the adhesion process.
Example 3
The invention relates to a method for preparing an oxide ceramic nanofiber membrane by taking a precursor liquid as a binder, which comprises the following steps:
step 1, preparing an electrostatic spinning precursor solution: 0.6g of polyvinylpyrrolidone (PVP) powder was mixed with 4.5mL of ethanol and mixed for 12h under magnetic stirring to obtain a uniform and transparent solution; after 5mL of acetone was added and uniformly dispersed, 0.73g of aluminum Acetylacetonate (AP) was further added; adding 3mL of acetic acid, dispersing uniformly, adding 2.5mL of Titanium Tetraisopropoxide (TTIP), stirring uniformly at room temperature, and fully mixing to obtain a pale yellow transparent precursor solution;
step 2, preparing an adhesive: 1mL of the precursor solution is taken for dilution, 0.3mL of ethanol, 0.2mL of acetone and 0.5mL of acetic acid are added into 1mL of the precursor solution, and the mixture is stirred uniformly at room temperature to obtain an adhesive;
step 3, under the conditions that the spinning environment temperature is 25 ℃, the humidity is 30% -40%, the voltage is 18.5kV, the distance between a metal needle head and a receiver is 12.5cm, the liquid supply speed is 0.5mL/h, and a ceramic fiber membrane is obtained on a receiving plate after spinning for 2 h;
step 4, taking three fiber membranes prepared in the step 3, overlapping two fiber membrane edges with larger area, then covering a third fiber membrane at the joint of the two fiber membranes, and carrying out spot coating on the third fiber membrane by using an adhesive, wherein the strength is light, and only the first fiber membrane is soaked visually, so that the fiber membrane with large area is obtained;
step 5, folding and stacking the fiber membrane roll obtained in the step 4 in a muffle furnace at 600 ℃ for roasting for 2 hours, wherein the heating rate is 2.0 ℃/min, and obtaining Al 2 O 3 /TiO 2 A ceramic nanofiber membrane;
step 6, spreading the fiber membrane obtained in the step 5 in an environment with humidity of 30-50%, and then ventilating and standing for 2 hours again to obtain flat flexible Al 2 O 3 /TiO 2 A fibrous membrane. The thickness of the fiber film splice and the fiber film body was measured using a thickness gauge.
The thickness of the fiber film before and after firing was measured by a thickness meter, and the shrinkage thereof was recorded.
Thickness tests show that the shrinkage rates of the fiber main body and the fiber interface are similar, which indicates that the fiber precursor liquid at the adhesion part does not influence oxide crystallization in the high-temperature sintering process, so that the fiber can still maintain the structural characteristics. And the phenomenon of fracture at the bonding position does not occur, and the structure of the fiber membrane is not influenced after the fibers are spliced through the adhesion process. The shrinkage at the interface is increased compared to example 2, because the addition of the good solvent and the adjuvant dilutes the concentration of the oxide precursor at the interface, and both types of solvents are decomposed during high temperature calcination, resulting in a relative reduction of the oxide at the interface, thereby increasing shrinkage.
Experiments show that the original precursor liquid or diluted precursor liquid is used as an adhesive to generate an oxide structure at the interface, and the three-layer fiber membrane is bonded, so that the purpose of expanding the area without changing the properties of the fiber is achieved.
Claims (6)
1. The method for preparing the oxide ceramic nanofiber membrane by using the precursor liquid as the binder is characterized by comprising the following steps of:
(1) Preparing an electrostatic spinning precursor liquid: firstly preparing an ethanol solution of polyvinylpyrrolidone, then sequentially adding ceramic raw materials, a good solvent and an auxiliary agent into the ethanol solution of polyvinylpyrrolidone, and stirring to fully mix the materials to obtain an electrostatic spinning precursor solution;
(2) Preparing an adhesive: diluting the precursor liquid, adding ethanol, acetone and acetic acid into the precursor liquid, and uniformly stirring to obtain an adhesive, wherein the precursor liquid is prepared by the following steps: good solvents for ethanol and acetone: the mixing volume ratio of acetic acid as an auxiliary agent is 2-2.5:1:1;
(3) Spraying the electrostatic spinning precursor liquid prepared in the step (1) out of the nanofiber by an electrostatic spinning technology, and forming a compact nanofiber membrane on a receiving plate;
(4) Tiling at least two nanofiber membranes prepared in the step (3), only overlapping edges of two adjacent nanofiber membranes, then covering a layer of strip-shaped nanofiber membrane prepared in the step (3) at the overlapping part of the adjacent nanofiber membranes as a connecting layer, finally dipping an adhesive, spot-coating the adhesive on the connecting layer, and bonding the two adjacent tiled nanofiber membranes through the connecting layer;
(5) And (3) crimping, folding and roasting the nanofiber membrane prepared in the step (4) to obtain the ceramic nanofiber membrane of aluminum oxide/titanium dioxide, wherein the roasting temperature is 500-700 ℃, the heating speed is 1.5-2.0 ℃/min, and the roasting time is 1-2 h.
2. The method for preparing the oxide ceramic nanofiber membrane by using the precursor liquid as a binder according to claim 1, wherein the method comprises the following steps of: in the step (1), the ceramic material raw material is a mixture of aluminum acetylacetonate and isopropyl titanate, and the mass fraction of the aluminum acetylacetonate in the ceramic material raw material is 10-60%.
3. The method for preparing the oxide ceramic nanofiber membrane by using the precursor liquid as a binder according to claim 1, wherein the method comprises the following steps of: in the step (1), ethanol is used as a solvent in an ethanol solution of polyvinylpyrrolidone to disperse the whole system, good solvent is acetone, the acetone is used for dissolving aluminum acetylacetonate, auxiliary agent is acetic acid, and the acetic acid is used for inhibiting the hydrolysis of isopropyl titanate; the volume ratio of the ethanol to the acetone to the acetic acid is 8-10: 8-10: 6.
4. the method for preparing the oxide ceramic nanofiber membrane by using the precursor liquid as a binder according to claim 1, wherein the method comprises the following steps of: in the step (3), the thickness of the prepared dense nanofiber membrane is 5-50 μm.
5. The method for preparing the oxide ceramic nanofiber membrane by using the precursor liquid as a binder according to claim 1, wherein the method comprises the following steps of: and (3) carrying out ventilation treatment on the prepared ceramic nanofiber membrane, wherein the humidity of a ventilation environment is 30-50%, and the standing time is 1-2 h.
6. A flexible oxide ceramic nanofiber membrane made based on the method of claim 1.
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| WO2015027769A1 (en) * | 2013-08-29 | 2015-03-05 | 天津工业大学 | Novel enhancing electrostatic spinning nanofiber membrane, producing method thereof, and device applied to method |
| AU2020103787A4 (en) * | 2020-11-30 | 2021-02-11 | Junada (qingdao) Technology Co., Ltd. | SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application |
| CN113149615A (en) * | 2021-01-16 | 2021-07-23 | 东南大学 | Super-elastic flexible three-dimensional composite ceramic nanofiber block and preparation method and application thereof |
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| DE102005005467A1 (en) * | 2005-02-04 | 2006-08-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composites of ceramic hollow fibers, process for their preparation and their use |
| CN102965848B (en) * | 2012-11-15 | 2016-06-22 | 广州市香港科大霍英东研究院 | A kind of nano-porous ceramic film and preparation method thereof |
| CN103721578B (en) * | 2013-12-17 | 2016-05-04 | 杭州创享环境技术有限公司 | The preparation method of the pure matter silicon carbide film of a kind of multichannel unsymmetric structure |
| CN104909798B (en) * | 2015-05-25 | 2017-07-28 | 航天材料及工艺研究所 | A kind of silicon carbide fibre lightweight high temperature insulating material and preparation method thereof |
| CN110760994B (en) * | 2018-07-25 | 2022-02-01 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional cross-linked super-wetting nanofiber membrane and preparation method thereof |
| CN111187092B (en) * | 2019-05-20 | 2021-10-01 | 中国科学院上海硅酸盐研究所 | Suspension slurry and method for reactive joining of silicon carbide ceramics |
| CN111809252A (en) * | 2020-06-10 | 2020-10-23 | 南京金思博纳米科技有限公司 | Composite ceramic nanofiber membrane and preparation method and application thereof |
| CN114045608B (en) * | 2021-11-10 | 2023-05-09 | 东华大学 | Flexible polycrystalline titanium oxide-aluminum oxide composite nanofiber membrane and preparation method thereof |
| CN114349508B (en) * | 2022-01-14 | 2022-11-29 | 中国科学院青岛生物能源与过程研究所 | Preparation method and application of multilayer ceramic film with oxide thin layer |
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| WO2015027769A1 (en) * | 2013-08-29 | 2015-03-05 | 天津工业大学 | Novel enhancing electrostatic spinning nanofiber membrane, producing method thereof, and device applied to method |
| AU2020103787A4 (en) * | 2020-11-30 | 2021-02-11 | Junada (qingdao) Technology Co., Ltd. | SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application |
| CN113149615A (en) * | 2021-01-16 | 2021-07-23 | 东南大学 | Super-elastic flexible three-dimensional composite ceramic nanofiber block and preparation method and application thereof |
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