CN111139595B - MTES/graphene composite fiber membrane preparation device and method - Google Patents
MTES/graphene composite fiber membrane preparation device and method Download PDFInfo
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Abstract
The invention belongs to the technical field of functional composite fiber membrane preparation, and particularly relates to a device and a method for preparing an MTES/graphene composite fiber membrane, wherein the main structure of the device for preparing the MTES/graphene composite fiber membrane comprises a receiving roller and two electrostatic spinning machines, the two electrostatic spinning machines are respectively connected to the receiving roller, the receiving roller is connected with a negative voltage, the electrostatic spinning machines are connected with a positive voltage, and the electrostatic spinning machines can be independently adjusted according to spinning requirements in the spinning process; the specific technological process comprises the steps of respectively preparing a trimethoxy silane ethanol solution and a graphene dispersion liquid, simultaneously spinning through two electrostatic spinning machines to prepare a composite fiber membrane, and sintering the composite fiber membrane at a high temperature to obtain the MTES/graphene composite fiber membrane which takes trimethoxy silane as a hydrophobic material, graphene as a conductive material, polyvinylpyrrolidone as a graphene carrier and has good uniformity, large water contact angle, adjustable hydrophobicity and conductivity and stable performance.
Description
The technical field is as follows:
the invention belongs to the technical field of functional composite fiber membrane preparation, and particularly relates to a device and a method for preparing an MTES/graphene composite fiber membrane, which can be used for preparing a composite fiber membrane with hydrophobicity and conductivity in a micro-nano size.
Background art:
electrostatic spinning is a special form of electrostatic atomization of high-molecular fluid, and substances split by atomization are not micro droplets but polymer micro jet flows, can travel for a considerable distance and are finally solidified into fibers. Electrospinning is a special fiber manufacturing process, where polymer solutions or melts are jet spun in a strong electric field. Under the action of the electric field, the liquid drop at the needle head changes from a spherical shape to a conical shape (i.e. a Taylor cone), and fiber filaments are obtained by extending from the tip of the cone, so that polymer filaments with nanometer-scale diameters can be produced. Electrostatic spinning is used as a new technology for preparing nano-fibers, and equipment mainly comprises a high-voltage power supply, an injection pump and a receiving plate, wherein the injection pump drives a solution to a nozzle, a high-voltage electric field is applied between the nozzle and the receiving plate, when the voltage reaches a critical value, solution droplets form a Taylor cone under the action of electric field force and surface tension, and then a solute is deposited on the collecting plate in a fiber form along with volatilization of a solvent. The spinning voltage, the receiving distance and the emitting speed have important influence on the performance of the fiber membrane, and along with the continuous development of the electrostatic spinning technology, the application of the electrostatic spinning technology in the aspects of preparing multifunctional composite fiber membranes, spinning, energy equipment, medical treatment and the like is gradually expanded.
Currently, Polytetrafluoroethylene (PTFE) is commonly used as a hydrophobic material in the preparation of composite fibrous membranes having hydrophobic properties. Journal literature: the electrostatic spinning method disclosed in Kang W, ZHao HH, Ju JG, Shi ZJ, QiaoCM, ChengBW (2016) Electrospun poly (tetrafluoroethylene) nanofiber membranes from PTFE-PVA-BA-H2O gel-spinning solutions. fibers Polymer 17(9): 1403-1413 has the problems of complicated process and difficulty in obtaining hydrophobic fiber membranes. The electrostatic spinning is mainly carried out by mixing, spinning and spinningThe composite fiber membrane is prepared by two methods of axial spinning, but the two methods are difficult to ensure the uniformity of the composite fiber membrane, and the composite fiber membrane generally has two or more than two properties. Journal literature: jia GB, PlentzJ, Delith J, Delith A, Wahyono RA, Andra G (2019) Large area graphene displacement on hydrophilic surfaces, flexible textures, glass fibers and 3D structures coatings 9(3): 1-10 disclose that in the preparation of hydrophobic and conductive composite fiber membranes, the conductivity and hydrophobicity of the fiber membranes need to be adjusted. The preparation method of the aminated nano titanium dioxide/silicon dioxide composite fiber membrane disclosed by Chinese patent 201710976856.6 comprises the following steps: by using electrostatic spinning technology, aminated TiO is taken2/SiO2The precursor solution is put in an injector, the spinning speed and voltage are controlled, and after a period of time, compact aminated nano TiO is obtained on a collecting plate2/SiO2The precursor fiber film of the composite material is dried in vacuum to obtain the aminated nanometer TiO2/SiO2Composite fiber film, aminated nano TiO2/SiO2The preparation method of the composite fiber film precursor solution comprises the following steps: under the magnetic stirring, tetrabutyl titanate and tetraethoxysilane are dissolved in a mixed solvent of ethanol and acetic acid, a silane coupling agent is added into the mixed solution under the alkalescent condition after uniform mixing, and the mixture reacts for 6 to 12 hours at the temperature of 150 ℃ to obtain a uniform precursor solution, wherein the molar ratio of tetrabutyl titanate to tetraethoxysilane is 1: (0.5-2), the volume ratio of tetrabutyl titanate to ethanol to acetic acid is 1:2 (0.5-1), the flow rate of spinning is 1.5mL/h, the spinning voltage is 10kV, the silane coupling agent is one of 3-aminopropyltriethoxysilane and aminopropyltrimethoxysilane, the pH is 8-10, and the mass ratio of the silane coupling agent to ethyl orthosilicate is (0.005-0.008): 1. the above-mentioned patent methods and the methods described in the prior art have hardly achieved the intended objects. Therefore, it is urgently needed to develop and design a composite fiber membrane preparation device and method with good uniformity.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and seeks to design a preparation device and a preparation method of an MTES/graphene composite fiber membrane with hydrophobicity and conductivity in a micro-nano size.
In order to achieve the purpose, the main structure of the MTES/graphene composite fiber membrane preparation device comprises a receiving roller, a left spinning machine, a left injection pump, a right spinning machine and a right injection pump; the left side of the receiving roller is provided with a left spinning machine, the left spinning machine is connected with a left injection pump, the right side of the receiving roller is provided with a right spinning machine, and the right spinning machine is connected with a right injection pump; the receiving roller is connected with the negative voltage, and the left spinning machine and the right spinning machine are respectively connected with the positive voltage.
The left spinning machine and the right spinning machine related by the invention are both electrostatic spinning machines; the left injection pump and the right injection pump are both micro-injection pumps.
The preparation method of the MTES/graphene composite fiber membrane is realized based on an MTES/graphene composite fiber membrane preparation device, and the technical process comprises the following steps:
(1) preparing a trimethoxy silane (MTES) ethanol solution;
(2) preparing a graphene dispersion liquid;
(3) preparing a composite fiber membrane by an electrostatic spinning method;
(4) and sintering the composite fiber membrane at a high temperature.
The specific process of the step (1) comprises the following steps: firstly, pouring trimethoxy silane (MTES) and absolute ethyl alcohol into a beaker, putting the beaker on a magnetic stirrer, stirring while dropwise adding an acetic acid aqueous solution to form a mixed solution, stirring at room temperature, and performing rotary evaporation to evaporate the volume of the mixed solution to 1/3 of the original volume to form a fiber gel; then, adding anhydrous ethanol and a silane coupling agent into the fiber gel to form a mixture; finally, magnetically stirring the mixture at room temperature to ensure that the viscosity of the mixture meets the spinning requirement; wherein the mass of the silane coupling agent is 3% of the mass of the fiber gel; trimethoxysilane (MTES) was purchased from Nanjing Kun chemical industries, Ltd as a finished product in a colorless transparent liquid in physical state.
The specific process of the step (2) comprises the following steps: putting polyvinylpyrrolidone and absolute ethyl alcohol into a beaker, putting the beaker on a magnetic stirrer, stirring at room temperature, adding graphene after PVP is completely dissolved, and continuing stirring and performing ultrasonic treatment to obtain uniformly dispersed graphene dispersion liquid; the graphene is a conductive material, and the polyvinylpyrrolidone is a carrier of the graphene.
The specific process of the step (3) related by the invention comprises the following steps: loading the mixture prepared in the step (1) into a left injection pump, loading the graphene dispersion liquid prepared in the step (2) into a right injection pump, and simultaneously performing electrostatic spinning on a left spinning machine and a right spinning machine to obtain a composite fiber membrane; the positive voltage of electrostatic spinning is 20kV, the negative voltage is 2.0kV, the receiving distance is 15-20cm, and the extrusion speed of the left injection pump and the right injection pump is 0.1-0.3 ml/h.
The specific process of the step (4) related by the invention comprises the following steps: sintering the composite fiber membrane prepared in the step (3) for 2-3h at 500 ℃ to obtain an MTES/graphene composite fiber membrane; wherein MTES has hydrophobicity, and graphene has conductivity.
Compared with the prior art, the main structure of the MTES/graphene composite fiber membrane preparation device comprises a receiving roller and two electrostatic spinning machines, wherein the two electrostatic spinning machines are respectively connected to the receiving roller, the receiving roller is connected with a negative voltage, the electrostatic spinning machines are connected with a positive voltage, and the electrostatic spinning machines can be independently adjusted according to spinning requirements in the spinning process; the specific technological process of the preparation method of the MTES/graphene composite fiber membrane comprises the steps of respectively preparing a trimethoxy silane (MTES) ethanol solution and a graphene dispersion liquid, simultaneously spinning through two electrostatic spinning machines to prepare the composite fiber membrane, and sintering the composite fiber membrane at a high temperature to prepare the MTES/graphene composite fiber membrane which takes trimethoxy silane (MTES) as a hydrophobic material, takes graphene as a conductive material, takes polyvinylpyrrolidone as a graphene carrier and has good uniformity, large water contact angle, adjustable hydrophobicity and electrical conductivity and stable performance.
Description of the drawings:
fig. 1 is a schematic diagram of a main structure principle of an MTES/graphene composite fiber membrane preparation apparatus according to the present invention.
Fig. 2 is an electron microscope scanning image of the MTES/graphene composite fiber film prepared in example 1 of the present invention.
The specific implementation mode is as follows:
the invention is further described below by way of an embodiment example in conjunction with the accompanying drawings.
Example 1:
the main structure of the MTES/graphene composite fiber membrane preparation device related to this embodiment includes a receiving roller 1, a left spinning machine 2, a left injection pump 3, a right spinning machine 4, and a right injection pump 5; a left spinning machine 2 is arranged on the left side of the receiving roller 1, the left spinning machine 2 is connected with a left injection pump 3, a right spinning machine 4 is arranged on the right side of the receiving roller 1, and the right spinning machine 4 is connected with a right injection pump 5; the receiving roller 1 is connected with a negative voltage, and the left spinning machine 2 and the right spinning machine 4 are respectively connected with a positive voltage; the left spinning machine 2 and the right spinning machine 4 are both electrostatic spinning machines; the left injection pump 3 and the right injection pump 5 are both micro-injection pumps.
The preparation method of the MTES/graphene composite fibrous membrane related to the embodiment is realized based on an MTES/graphene composite fibrous membrane preparation device, and the specific process comprises the following steps:
(1) firstly, pouring 42.5ml of trimethoxy silane (MTES) with the density of 0.96g/ml and 80ml of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent into a beaker, putting the beaker on a magnetic stirrer, dropwise adding 20ml of acetic acid aqueous solution with the density of 2.5mol/L while stirring to form a mixed solution, stirring for 12 hours at room temperature, and then rotationally evaporating under the conditions of the temperature of 30 ℃ and the rotating speed of 40r/min to evaporate the volume of the mixed solution to 1/3 of the original volume to form a fiber gel; then, absolute ethyl alcohol with the purity of more than or equal to 99.7 percent and 0.46g of silane coupling agent are added into the fiber gel to form a mixture, and the volume of the mixture is 140 ml; finally, magnetically stirring the mixture for 200 hours at room temperature to ensure that the viscosity of the mixture meets the spinning requirement;
(2) putting 1g of polyvinylpyrrolidone (PVP) and 11.5g of absolute ethyl alcohol with the purity of more than or equal to 99.7% in a beaker, putting the beaker on a magnetic stirrer, stirring for 2-3h at room temperature, adding 0.05g of graphene after the PVP is completely dissolved, continuing stirring and carrying out ultrasonic treatment for 2-3h to obtain uniformly dispersed graphene dispersion liquid;
(3) loading the mixture prepared in the step (1) into a left injection pump 3, loading the graphene dispersion liquid prepared in the step (2) into a right injection pump 5, and simultaneously performing electrostatic spinning on a left spinning machine 2 and a right spinning machine 4 to obtain a composite fiber membrane; the positive voltage of electrostatic spinning is 20kV, the negative voltage is 2.0kV, the receiving distance is 15-20cm, and the extrusion speed of the left injection pump and the right injection pump is 0.1-0.3 ml/h;
(4) sintering the composite fiber membrane prepared in the step (3) for 2-3h at 500 ℃ to obtain an MTES/graphene composite fiber membrane; wherein MTES has hydrophobicity, and graphene has conductivity.
The scanning result of the electron microscope of the MTES/graphene composite fiber film prepared in this example is shown in fig. 2: the fiber shape is uniform.
Example 2:
the preparation method of the MTES/graphene composite fibrous membrane related to the embodiment is realized based on an MTES/graphene composite fibrous membrane preparation device, and the specific process comprises the following steps:
(1) firstly, pouring 42.5ml of trimethoxy silane (MTES) with the density of 0.96g/ml and 80ml of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent into a beaker, putting the beaker on a magnetic stirrer, dropwise adding 20ml of acetic acid aqueous solution with the density of 2.5mol/L while stirring to form a mixed solution, stirring for 12 hours at room temperature, and then rotationally evaporating under the conditions of the temperature of 30 ℃ and the rotating speed of 40r/min to evaporate the volume of the mixed solution to 1/3 of the original volume to form a fiber gel; then, absolute ethyl alcohol and 0.46g of silane coupling agent are added into the fiber gel to form a mixture, and the volume of the mixture is 140 ml; finally, magnetically stirring the mixture for 200 hours at room temperature to ensure that the viscosity of the mixture meets the spinning requirement;
(2) putting 1g of polyvinylpyrrolidone (PVP) and 11.5g of absolute ethyl alcohol with the purity of more than or equal to 99.7% in a beaker, putting the beaker on a magnetic stirrer, stirring for 2-3h at room temperature, adding 0.1g of graphene after the PVP is completely dissolved, continuing stirring and carrying out ultrasonic treatment for 2-3h to obtain uniformly dispersed graphene dispersion liquid;
(3) loading the mixture prepared in the step (1) into a left injection pump 3, loading the graphene dispersion liquid prepared in the step (2) into a right injection pump 5, and simultaneously performing electrostatic spinning on a left spinning machine 2 and a right spinning machine 4 to obtain a composite fiber membrane; the positive voltage of electrostatic spinning is 20kV, the negative voltage is 2.0kV, the receiving distance is 15-20cm, and the extrusion speed of the left injection pump and the right injection pump is 0.1-0.3 ml/h;
(4) sintering the composite fiber membrane prepared in the step (3) for 2-3h at 500 ℃ to obtain an MTES/graphene composite fiber membrane; wherein MTES has hydrophobicity, and graphene has conductivity.
Example 3:
the preparation method of the MTES/graphene composite fibrous membrane related to the embodiment is realized based on an MTES/graphene composite fibrous membrane preparation device, and the specific process comprises the following steps:
(1) firstly, pouring 42.5ml of trimethoxy silane (MTES) with the density of 0.96g/ml and 80ml of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent into a beaker, putting the beaker on a magnetic stirrer, dropwise adding 20ml of acetic acid aqueous solution with the density of 2.5mol/L while stirring to form a mixed solution, stirring for 12 hours at room temperature, and then rotationally evaporating under the conditions of the temperature of 30 ℃ and the rotating speed of 40r/min to evaporate the volume of the mixed solution to 1/3 of the original volume to form a fiber gel; then, absolute ethyl alcohol and 0.46g of silane coupling agent are added into the fiber gel to form a mixture, and the volume of the mixture is 140 ml; finally, magnetically stirring the mixture for 200 hours at room temperature to ensure that the viscosity of the mixture meets the spinning requirement;
(2) putting 1g of polyvinylpyrrolidone (PVP) and 11.5g of absolute ethyl alcohol with the purity of more than or equal to 99.7% in a beaker, putting the beaker on a magnetic stirrer, stirring for 2-3h at room temperature, adding 0.15g of graphene after the PVP is completely dissolved, continuing stirring and carrying out ultrasonic treatment for 2-3h to obtain uniformly dispersed graphene dispersion liquid;
(3) loading the mixture prepared in the step (1) into a left injection pump 3, loading the graphene dispersion liquid prepared in the step (2) into a right injection pump 5, and simultaneously performing electrostatic spinning on a left spinning machine 2 and a right spinning machine 4 to obtain a composite fiber membrane; the positive voltage of electrostatic spinning is 20kV, the negative voltage is 2.0kV, the receiving distance is 15-20cm, and the extrusion speed of the left injection pump and the right injection pump is 0.1-0.3 ml/h;
(4) sintering the composite fiber membrane prepared in the step (3) for 2-3h at 500 ℃ to obtain an MTES/graphene composite fiber membrane; wherein MTES has hydrophobicity, and graphene has conductivity.
Example 4:
the preparation method of the MTES/graphene composite fibrous membrane related to the embodiment is realized based on an MTES/graphene composite fibrous membrane preparation device, and the specific process comprises the following steps:
(1) firstly, pouring 42.5ml of trimethoxy silane (MTES) with the density of 0.96g/ml and 80ml of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent into a beaker, putting the beaker on a magnetic stirrer, dropwise adding 20ml of acetic acid aqueous solution with the density of 2.5mol/L while stirring to form a mixed solution, stirring for 12 hours at room temperature, and then rotationally evaporating under the conditions of the temperature of 30 ℃ and the rotating speed of 40r/min to evaporate the volume of the mixed solution to 1/3 of the original volume to form a fiber gel; then, absolute ethyl alcohol and 0.46g of silane coupling agent are added into the fiber gel to form a mixture, and the volume of the mixture is 140 ml; finally, magnetically stirring the mixture for 200 hours at room temperature to ensure that the viscosity of the mixture meets the spinning requirement;
(2) putting 1g of polyvinylpyrrolidone (PVP) and 11.5g of absolute ethyl alcohol with the purity of more than or equal to 99.7% in a beaker, putting the beaker on a magnetic stirrer, stirring for 2-3h at room temperature, adding 0.2g of graphene after the PVP is completely dissolved, continuing stirring and carrying out ultrasonic treatment for 2-3h to obtain uniformly dispersed graphene dispersion liquid;
(3) loading the mixture prepared in the step (1) into a left injection pump 3, loading the graphene dispersion liquid prepared in the step (2) into a right injection pump 5, and simultaneously performing electrostatic spinning on a left spinning machine 2 and a right spinning machine 4 to obtain a composite fiber membrane; the positive voltage of electrostatic spinning is 20kV, the negative voltage is 2.0kV, the receiving distance is 15-20cm, and the extrusion speed of the left injection pump and the right injection pump is 0.1-0.3 ml/h;
(4) sintering the composite fiber membrane prepared in the step (3) for 2-3h at 500 ℃ to obtain an MTES/graphene composite fiber membrane; wherein MTES has hydrophobicity, and graphene has conductivity.
Example 5:
this example relates to the test of the conductivity and hydrophilicity and hydrophobicity of the MTES/graphene composite fiber membranes prepared in examples 1 to 4, and the results are shown in table 1:
the absolute ethyl alcohol in the step (1) is subjected to rotary evaporation, and the table shows that the conductivity of the MTES/graphene composite fiber membrane is adjusted by the content of graphene, and the higher the content of graphene is, the higher the conductivity of the MTES/graphene composite fiber membrane is; and the MTES/graphene composite fiber membrane has a larger water contact angle and stable hydrophobicity.
Claims (1)
1. A preparation method of an MTES/graphene composite fiber membrane is characterized by being realized based on an MTES/graphene composite fiber membrane preparation device, wherein the main structure of the MTES/graphene composite fiber membrane preparation device comprises a receiving roller, a left spinning machine, a left injection pump, a right spinning machine and a right injection pump; the left side of the receiving roller is provided with a left spinning machine, the left spinning machine is connected with a left injection pump, the right side of the receiving roller is provided with a right spinning machine, and the right spinning machine is connected with a right injection pump; the receiving roller is connected with the negative voltage, and the left spinning machine and the right spinning machine are respectively connected with the positive voltage; the left spinning machine and the right spinning machine are both electrostatic spinning machines; the left injection pump and the right injection pump are both micro injection pumps; the technological process of the preparation method of the MTES/graphene composite fiber membrane comprises the following steps:
(1) preparing a trimethoxy silane ethanol solution;
(2) preparing a graphene dispersion liquid;
(3) preparing a composite fiber membrane by an electrostatic spinning method;
(4) sintering the composite fiber membrane at high temperature; the specific process of the step (1) comprises the following steps: firstly, pouring trimethoxy silane and absolute ethyl alcohol into a beaker, putting the beaker on a magnetic stirrer, stirring while dropwise adding an acetic acid aqueous solution to form a mixed solution, stirring at room temperature, and performing rotary evaporation to evaporate the volume of the mixed solution to 1/3 of the original volume to form fiber gel; then, adding anhydrous ethanol and a silane coupling agent into the fiber gel to form a mixture; finally, magnetically stirring the mixture at room temperature to ensure that the viscosity of the mixture meets the spinning requirement; wherein the mass of the silane coupling agent is 3% of the mass of the fiber gel; trimethoxy silane is a finished product which is purchased from Nanjing Kun chemical industry Co., Ltd and is colorless and transparent liquid in a physical state; the specific process of the step (2) comprises the following steps: putting polyvinylpyrrolidone and absolute ethyl alcohol into a beaker, putting the beaker on a magnetic stirrer, stirring at room temperature, adding graphene after PVP is completely dissolved, and continuing stirring and performing ultrasonic treatment to obtain uniformly dispersed graphene dispersion liquid; the graphene is a conductive material, and the polyvinylpyrrolidone is a carrier of the graphene; the specific process of the step (3) is as follows: loading the mixture prepared in the step (1) into a left injection pump, loading the graphene dispersion liquid prepared in the step (2) into a right injection pump, and simultaneously performing electrostatic spinning on a left spinning machine and a right spinning machine to obtain a composite fiber membrane; the positive voltage of electrostatic spinning is 20kV, the negative voltage is 2.0kV, the receiving distance is 15-20cm, and the extrusion speed of the left injection pump and the right injection pump is 0.1-0.3 ml/h; the specific process of the step (4) is as follows: sintering the composite fiber membrane prepared in the step (3) for 2-3h at 500 ℃ to obtain an MTES/graphene composite fiber membrane; wherein MTES has hydrophobicity, and graphene has conductivity.
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| KR20100019172A (en) * | 2008-08-08 | 2010-02-18 | 코오롱패션머티리얼 (주) | Method of manufacturing nanofiber web |
| CN102652903A (en) * | 2012-05-03 | 2012-09-05 | 东华大学 | Preparation method of high temperature resistant silicon dioxide nanometer fiber filtering membrane |
| CN106637502A (en) * | 2016-12-21 | 2017-05-10 | 北京化工大学 | Method for preparing graphene/silica nanocomposite fiber through coaxial electrostatic spinning |
| CN110172784A (en) * | 2019-05-21 | 2019-08-27 | 浙江理工大学 | A kind of preparation method of gradient-structure multilayer micro nanometer fiber combine dressing |
| CN211814725U (en) * | 2020-01-06 | 2020-10-30 | 青岛科技大学 | MTES/graphene composite fiber membrane preparation facilities |
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| KR20100019172A (en) * | 2008-08-08 | 2010-02-18 | 코오롱패션머티리얼 (주) | Method of manufacturing nanofiber web |
| CN102652903A (en) * | 2012-05-03 | 2012-09-05 | 东华大学 | Preparation method of high temperature resistant silicon dioxide nanometer fiber filtering membrane |
| CN106637502A (en) * | 2016-12-21 | 2017-05-10 | 北京化工大学 | Method for preparing graphene/silica nanocomposite fiber through coaxial electrostatic spinning |
| CN110172784A (en) * | 2019-05-21 | 2019-08-27 | 浙江理工大学 | A kind of preparation method of gradient-structure multilayer micro nanometer fiber combine dressing |
| CN211814725U (en) * | 2020-01-06 | 2020-10-30 | 青岛科技大学 | MTES/graphene composite fiber membrane preparation facilities |
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