CN115305598A - Core-shell structure shielding material and preparation method thereof - Google Patents

Core-shell structure shielding material and preparation method thereof Download PDF

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CN115305598A
CN115305598A CN202211017241.8A CN202211017241A CN115305598A CN 115305598 A CN115305598 A CN 115305598A CN 202211017241 A CN202211017241 A CN 202211017241A CN 115305598 A CN115305598 A CN 115305598A
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shell
spinning
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CN115305598B (en
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高心蕊
何宗倍
李书良
宋鹏程
吴莹
杨静
喻冲
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Nuclear Power Institute of China
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention discloses a core-shell structure shielding material and a preparation method thereof, wherein the core-shell structure shielding material comprises a core layer and a shell layer, and the shell layer is coaxially arranged at the outer side of the core layer; the nuclear layer takes polyvinyl alcohol as a matrix and carbon fillers as electromagnetic shielding fillers; the shell layer takes polyacrylonitrile as a matrix and adopts heavy metal as an ionization shielding functional filler; the core-shell structure shielding material is prepared by adopting coaxial spinning for electrostatic spinning. Because the shielding material with the core-shell structure is prepared by adopting the coaxial spinning technology, the coaxial spinning can ensure that the internal fibers of the shielding material are uniformly distributed, and the reduction of the shielding performance caused by the nonuniform distribution of the internal fibers of the shielding material is avoided, namely the shielding material with the core-shell structure has higher electromagnetic shielding function and ionization shielding function.

Description

Core-shell structure shielding material and preparation method thereof
Technical Field
The invention relates to the technical field of functional materials, in particular to a core-shell structure shielding material and a preparation method thereof.
Background
The electrostatic spinning method is a simple and efficient nano-fiber preparation technology, mainly utilizes a polymer solution or a melt to form a jet flow under the action of a strong electric field, and the solvent is continuously volatilized through stretching and bending movement, so that the nano-scale continuous fiber can be finally obtained on a receiving device. Different from the traditional spinning method, the electrostatic spinning is a method for preparing superfine fibers under the action of a high-voltage electrostatic field, and continuous nano-scale fibers can be prepared.
Due to the structural limitation of the spinning nozzle, the traditional electrostatic spinning can only carry out the spinning of a single spinning solution. The main drawbacks include (1) the limited variety of spinnable materials. Many poorly spinnable polymers cannot be electrospun alone due to limitations such as poor solubility or molecular chain compactness. (2) multicomponent spinning is not easy. If the multi-component material preparation is carried out based on the traditional electrostatic spinning, a plurality of raw materials can only be prepared into the same spinning solution for spinning. And therefore, is limited by the compatibility of the components. Meanwhile, the phenomenon of uneven distribution inside the fiber is very easy to occur due to different interfacial tensions of different components.
The coaxial electrostatic spinning can make 2 or more different spinning solutions pass through the outlet of the coaxial spinneret under the driving of the electric field force to prepare the continuous composite nanofiber. The spinnability requirement for the core layer material in the coaxial spinning is not high, and the multi-component material can be conveniently prepared, so that the defects of the traditional electrostatic spinning can be overcome.
The core-shell structure fiber is a composite fiber with a double-layer or even multi-layer structure, and the inner core and the outer shell of the core-shell structure fiber are respectively composed of components with different structures and physical properties. The core-shell structure fiber prepared by utilizing the coaxial electrostatic spinning technology can fully exert the characteristics of small diameter, large specific surface area, high porosity and the like of the electrospun fiber. By changing the core/shell component of the fiber and controlling the proportion of the core/shell, the nano-fiber with various components and different functions can be prepared. The core/shell structure fiber has the advantages of both core and shell components, is a novel functional fiber with performance superior to that of a core or shell material, shows wide application prospect in multiple aspects, and has the following main application fields: the tissue engineering aspect can be used as a degradable bracket, can promote wound healing, drug delivery and the like; the filtration aspect can be used as a filtration membrane; available for ion batteries in terms of energy storage and generation; can be used for manufacturing optical or chemical sensors; it can also be used in enzyme and catalyst.
Disclosure of Invention
The invention aims to provide a core-shell structure shielding material, which has uniform internal fiber distribution and higher electromagnetic shielding function and ionization shielding function.
In addition, the invention also provides a preparation method for preparing the core-shell structure shielding material.
The invention is realized by the following technical scheme:
a core-shell structure shielding material comprises a core layer and a shell layer, wherein the shell layer is coaxially arranged on the outer side of the core layer;
the nuclear layer takes polyvinyl alcohol as a matrix and carbon fillers as electromagnetic shielding fillers; the shell layer takes polyacrylonitrile as a matrix and adopts heavy metal as an ionization shielding functional filler;
the core-shell structure shielding material is prepared by adopting coaxial spinning for electrostatic spinning.
The shell layer and the core layer of the shielding material with the core-shell structure respectively have the ionization shielding function and the electromagnetic shielding function, so that the shielding material with the core-shell structure has the electromagnetic shielding function and the ionization shielding function.
The core-shell structure shielding material is prepared by adopting a coaxial spinning technology, so that the internal fibers of the shielding material can be uniformly distributed by the coaxial spinning, and the reduction of the shielding performance caused by the nonuniform distribution of the internal fibers of the shielding material is avoided, namely, the core-shell structure shielding material has higher electromagnetic shielding function and ionization shielding function.
Further, heavy metals include W and WO 3 、Bi 2 O 3 Or Gd 2 O 3 。
The heavy metals have ionization shielding function.
Further, the carbon-based filler includes multi-walled carbon nanotubes (MWNTs) or Graphene Oxide (GO).
The carbon-based filler has an electromagnetic shielding function.
Furthermore, the mass ratio of the ionization shielding functional filler in the shell layer is 5-15wt%.
Furthermore, the mass of the electromagnetic shielding functional filler in the core layer accounts for 1-5wt%.
Too much filler addition results in failure to spin, and therefore, it is necessary to control the amount of filler added reasonably.
The preparation method of the core-shell structure shielding material comprises the following steps:
s1, preparing a nuclear layer spinning solution from polyvinyl alcohol and a carbon-based filler;
s2, preparing polyacrylonitrile and heavy metal into a shell spinning solution;
s3, carrying out electrostatic spinning on the core-layer spinning solution and the shell-layer spinning solution by adopting coaxial spinning to obtain the core-shell structure shielding material: specifically, the method comprises the following steps: and respectively adding the prepared core layer spinning solution and shell layer spinning solution into an injector, connecting a coaxial spinning special needle, and carrying out electrostatic spinning. Aiming at the material system, a coaxial spinning needle head is customized, the inner diameter is 0.35mm, and the outer diameter is 1.22mm.
The spinning parameters were set as: the core layer injection rate is 0.55mL/h, and the shell layer injection rate is 1.15mL/h; the spinning voltage is 20kV; the receiving distance is 15cm; ambient relative humidity 60%. And after spinning is finished, taking down the aluminum foil for receiving the fibers on the collector, and performing vacuum drying for 24 hours to remove the solvent which is not volatilized in the spinning process.
The formula composition of the core layer spinning solution and the shell layer spinning solution of the invention is shown in table 1:
TABLE 1
Figure BDA0003810987450000021
Figure BDA0003810987450000031
Further, in step S1, the viscosity of the core layer spinning solution is controlled to be 100-190 mPa.S, and the content of the carbon-based filler is controlled to be 1-5wt%.
Further, in step S1, the preparation process of the core layer spinning solution is as follows:
respectively preparing dispersion liquid of polyvinyl alcohol and carbon series filling material, then mixing the two dispersion liquids, then carrying out ultrasonic treatment, when the carbon series filling material is multi-wall carbon nano tube, firstly carrying out acid treatment on the multi-wall carbon nano tube, and then preparing the dispersion liquid of the multi-wall carbon nano tube.
Specifically, in order to improve the dispersibility of MWNTs in polyvinyl alcohol (PVA), it is necessary to subject them to acid treatment. The acid treatment conditions were: MWNT are subjected to ultrasonication in a mixed solution of hydrochloric acid and nitric acid at 55 ℃ for 3 hours and then allowed to stand for one day. Washing with deionized water for 4-5 times until the pH value reaches neutral, and oven drying at 60 deg.C for 8 hr. And adding the MWNT subjected to acid treatment into deionized water, and carrying out ultrasonic treatment for 5 hours to obtain MWNT dispersion liquid. Dissolving a certain amount of polyvinyl alcohol (PVA) particles in deionized water to obtain PVA dispersion liquid with a certain concentration, and controlling the concentration of the PVA dispersion liquid to be 8.5wt%. And mixing the PVA dispersion liquid with the MWNT subjected to acid treatment, and then carrying out ultrasonic treatment to obtain the MWNT/PVA solution. For GO filler, GO does not need to be pretreated, is added into deionized water for ultrasonic dispersion for 5 hours, is poured into a pre-prepared PVA dispersion liquid with the concentration of 8.5wt%, and is continuously subjected to ultrasonic treatment for 3 hours to obtain a GO/PVA solution.
Further, in the step S2, the viscosity of the shell spinning solution is controlled to be 200-300 mPa.S, and the mass fraction of the heavy metal in the shell spinning solution is 5-15wt%.
In order to ensure that the viscous stress of the shell solution on the core solution in the coaxial spinning process is enough to overcome the internal tension between the two solutions and ensure that the shell has enough surface tension to balance with the electric field force, the shell solution must have a larger viscosity and be within a certain range to guide the core solution to better form fibers. Therefore, the mass fraction of the heavy metal filler in the shell spinning solution needs to be controlled to be 5-15wt%.
Further, in step S2, the preparation process of the shell spinning solution is as follows:
weighing a certain amount of Polyacrylonitrile (PAN) powder, adding the Polyacrylonitrile (PAN) powder into a N, N-Dimethylformamide (DMF) solution, and controlling the concentration of the PAN/DMF solution to be 15wt%. Then adding heavy metal fillers with different masses, stirring for 36 hours at a constant temperature of 65 ℃ on a magnetic stirrer, standing for a period of time to eliminate bubbles, and preparing the shell spinning solution.
The viscosity is determined by the type of filler and the amount of filler added; viscosity directly affects spinnability and spinning effect; either too high or too low of a viscosity, uniform fibers cannot be spun. In addition, the material type and the filler addition amount can also influence the electromagnetic and ionization shielding effects. Therefore, the type and the addition amount of the filler need to be reasonably controlled, so that the prepared core-shell structure shielding material not only can be used for spinning uniform fibers, but also has electromagnetic and ionization shielding effects.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the core-shell structure shielding material provided by the invention uses the fillers with electromagnetic shielding effect and ionization shielding effect in the core layer and the shell layer respectively, so that the core-shell structure shielding material has the electromagnetic ionization composite shielding function.
2. The core-shell structure shielding material adopts a coaxial spinning technology, reasonably designs the shell spinning solution and the core spinning solution for being suitable for coaxial spinning, matches the parameters of the coaxial spinning, realizes uniform distribution of internal fibers of the prepared core-shell structure shielding material, and has a higher electromagnetic shielding function and an ionization shielding function.
3. The core-shell structure shielding material has strong designability and wearing comfort, and is suitable for being used as protective clothing and protective fabric.
4. The invention adopts a coaxial electrostatic spinning technology, and prepares the shielding material with the core-shell composite structure by regulating and controlling solution parameters such as shielding components, viscosity, electro-spinning property and the like, process parameters such as flow speed, voltage and the like in the spinning process, so that the shielding material has the electromagnetic shielding function and the ionization shielding function at the same time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1:
a core-shell structure shielding material comprises a core layer and a shell layer, wherein the shell layer is coaxially arranged on the outer side of the core layer;
the core layer takes polyvinyl alcohol as a matrix and multi-walled carbon nanotubes (MWNT) as an electromagnetic shielding functional filler; the shell layer takes polyacrylonitrile as a matrix and adopts WO 3 As ionization shielding functional filler;
the core-shell structure shielding material is prepared by adopting coaxial spinning to carry out electrostatic spinning.
The preparation method of the core-shell structure shielding material of the embodiment comprises the following steps:
s1, preparing a core layer spinning solution (MWNT/PVA solution):
the MWNT concentration in the MWNT/PVA solution is 1wt%, the viscosity of the spinning solution is 105 mPa.S, and the preparation process comprises the following steps:
subjecting MWNT to ultrasonic treatment in a mixed solution of hydrochloric acid and nitric acid (the volume ratio of hydrochloric acid to nitric acid is 1; washing with deionized water for 4-5 times until pH reaches neutral, and oven drying at 60 deg.C for 8 hr. And adding the MWNT subjected to acid treatment into deionized water, and carrying out ultrasonic treatment for 5 hours to obtain MWNT dispersion liquid. Mixing the PVA dispersion liquid with the concentration of 8.5wt% with the MWNT treated by the acid, and then carrying out ultrasonic treatment to obtain MWNT/PVA solution.
S2, preparing shell spinning solution (WO) 3 PAN solution):
WO 3 WO in PAN solution 3 The concentration is 10wt%, the viscosity of the spinning solution is 245 mPa.S, and the preparation process comprises the following steps:
polyacrylonitrile (PAN) was dissolved in N, N-Dimethylformamide (DMF) to control the concentration of the PAN/DMF solution to 15wt%. Then adding a certain amount of WO 3 To a concentration of 10wt% in the PAN/DMF solution; then stirring the mixture on a magnetic stirrer at a constant temperature of 65 ℃ and standing the mixture to prepare the shell spinning solution.
S3, carrying out electrostatic spinning on the core-shell spinning solution and the shell spinning solution by adopting coaxial spinning to obtain the core-shell structure shielding material, specifically:
and (3) carrying out electrostatic spinning on the prepared core layer spinning solution and shell layer spinning solution by using a special coaxial spinning special needle. The spinning parameters were set as: the core layer injection rate is 0.55mL/h, and the shell layer injection rate is 1.15mL/h; the spinning voltage is 20kV; the receiving distance is 15cm; ambient relative humidity 60%. And after spinning is finished, vacuum drying is carried out for 24 hours, and the core-shell structure shielding material is obtained.
Example 2:
the preparation method of the core-shell structure shielding material of the embodiment comprises the following steps:
s1, preparing a core layer spinning solution (MWNT/PVA solution):
the MWNT concentration in the MWNT/PVA solution is 2.5wt%, the viscosity of the spinning solution is 135mPa & S, and the preparation process comprises the following steps:
subjecting MWNT to ultrasonic treatment in a mixed solution of hydrochloric acid and nitric acid (the volume ratio of hydrochloric acid to nitric acid is 1; washing with deionized water for 4-5 times until pH reaches neutral, and oven drying at 60 deg.C for 8 hr. And adding the MWNT subjected to acid treatment into deionized water, and carrying out ultrasonic treatment for 5 hours to obtain MWNT dispersion liquid. Mixing the PVA dispersion liquid with the concentration of 8.5wt% with the MWNT treated by the acid, and then carrying out ultrasonic treatment to obtain MWNT/PVA solution.
S2, preparing a shell spinning solution (W/PAN solution):
the W concentration in the W/PAN solution is 15wt%, the viscosity of the spinning solution is 294 mPa.S, and the preparation process comprises the following steps:
polyacrylonitrile (PAN) was dissolved in N, N-Dimethylformamide (DMF) to control the concentration of the PAN/DMF solution to 15wt%. Then adding a certain mass of W to ensure that the W concentration in the W/PAN solution is 15wt%, stirring at a constant temperature of 65 ℃ on a magnetic stirrer, and standing to prepare the shell spinning solution.
S3, carrying out electrostatic spinning on the core-shell spinning solution and the shell spinning solution by adopting coaxial spinning to obtain the core-shell structure shielding material, specifically:
and (3) performing electrostatic spinning on the prepared core-layer spinning solution and shell-layer spinning solution by using a special coaxial spinning needle. The spinning parameters were set as: the core layer injection rate is 0.55mL/h, and the shell layer injection rate is 1.15mL/h; the spinning voltage is 20kV; the receiving distance is 15cm; ambient relative humidity 60%. And after spinning is finished, vacuum drying is carried out for 24 hours, and the core-shell structure shielding material is obtained.
Example 3:
the electromagnetic shielding filler of the embodiment adopts Graphene Oxide (GO) and Bi 2 O 3 As ionization shielding functional filler.
The preparation method of the core-shell structure shielding material of the embodiment comprises the following steps:
s1, preparing a core layer spinning solution (GO/PVA solution):
the GO concentration in the GO/PVA solution is 5wt%, the viscosity of the spinning solution is 187mPa & S, and the preparation process comprises the following steps:
adding a certain amount of GO into deionized water for ultrasonic dispersion for 5 hours, pouring into a pre-prepared PVA dispersion liquid with the concentration of 8.5wt%, and continuing to perform ultrasonic dispersion for 3 hours to obtain a GO/PVA solution.
S2, preparing shell spinning solution (Bi) 2 O 3 PAN solution):
Bi 2 O 3 bi in PAN solution 2 O 3 The concentration is 5wt%, the viscosity of the spinning solution is 201mPa & S, and the preparation process comprises the following steps:
PAN was dissolved in DMF and the concentration of the PAN/DMF solution was controlled to 15wt%. Then adding a certain mass of Bi 2 O 3 Making Bi into 2 O 3 PAN solutionBi in liquid 2 O 3 The concentration is 5wt%, and then stirring and standing are carried out on a magnetic stirrer at the constant temperature of 65 ℃ to prepare the shell spinning solution.
S3, carrying out electrostatic spinning on the core-shell spinning solution and the shell spinning solution by adopting coaxial spinning to obtain the core-shell structure shielding material, specifically:
and (3) performing electrostatic spinning on the prepared core-layer spinning solution and shell-layer spinning solution by using a special coaxial spinning needle. The spinning parameters were set as: the core layer injection rate is 0.55mL/h, and the shell layer injection rate is 1.15mL/h; the spinning voltage is 20kV; the receiving distance is 15cm; ambient relative humidity 60%. And after spinning is finished, vacuum drying is carried out for 24 hours, and the core-shell structure shielding material is obtained.
Example 4:
the electromagnetic shielding filler of the embodiment adopts Graphene Oxide (GO) and Gd 2 O 3 As ionization shielding functional filler.
The preparation method of the core-shell structure shielding material of the embodiment comprises the following steps:
s1, preparing a core layer spinning solution (GO/PVA solution):
the GO concentration in the GO/PVA solution is 1.25wt%, the viscosity of the spinning solution is 122mPa & S, and the preparation process is as follows:
adding a certain amount of GO into deionized water for ultrasonic dispersion for 5 hours, pouring into a pre-prepared PVA dispersion liquid with the concentration of 8.5wt%, and continuing to perform ultrasonic dispersion for 3 hours to obtain a GO/PVA solution.
S2, preparing shell spinning solution (Gd) 2 O 3 PAN solution):
Gd 2 O 3 gd in PAN solution 2 O 3 The concentration is 7.5wt%, the viscosity of the spinning solution is 219 mPa.S, and the preparation process comprises the following steps:
PAN was dissolved in DMF and the concentration of the PAN/DMF solution was controlled to 15wt%. Then adding a certain mass of Gd 2 O 3 Stirring the mixture on a magnetic stirrer at a constant temperature of 65 ℃ and standing the mixture to prepare the shell spinning solution.
S3, carrying out electrostatic spinning on the core-shell spinning solution and the shell spinning solution by adopting coaxial spinning to obtain the core-shell structure shielding material, specifically:
and (3) carrying out electrostatic spinning on the prepared core layer spinning solution and shell layer spinning solution by using a special coaxial spinning special needle. The spinning parameters were set as: the core layer injection rate is 0.55mL/h, and the shell layer injection rate is 1.15mL/h; the spinning voltage is 20kV; the receiving distance is 15cm; ambient relative humidity 60%. And after spinning is finished, vacuum drying is carried out for 24 hours, and the core-shell structure shielding material is obtained.
Comparative example 1:
the electromagnetic shielding filler of the comparative example adopts MWNT and Bi 2 O 3 As ionization shielding functional filler.
The preparation method of the comparative example comprises the following steps:
s1, preparing a core layer spinning solution (MWNT/PVA solution):
the MWNT concentration in the MWNT/PVA solution is 8wt%, the viscosity of the spinning solution is 288 mPa.S, and the preparation process is as follows:
subjecting MWNT to ultrasonic treatment in a mixed solution of hydrochloric acid and nitric acid (the volume ratio of hydrochloric acid to nitric acid is 1; washing with deionized water for 4-5 times until pH reaches neutral, and oven drying at 60 deg.C for 8 hr. And adding the MWNT subjected to acid treatment into deionized water, and carrying out ultrasonic treatment for 5 hours to obtain MWNT dispersion liquid. Mixing the PVA dispersion liquid with the concentration of 8.5wt% with the MWNT treated by the acid, and then carrying out ultrasonic treatment to obtain MWNT/PVA solution.
S2, preparing shell spinning solution (Bi) 2 O 3 PAN solution):
Bi 2 O 3 bi in PAN solution 2 O 3 The concentration is 5wt%, the viscosity of the spinning solution is 201mPa & S, and the preparation process comprises the following steps:
PAN was dissolved in DMF and the concentration of the PAN/DMF solution was controlled to 15wt%. Then adding a certain mass of Bi 2 O 3 Stirring the mixture on a magnetic stirrer at a constant temperature of 65 ℃ and standing the mixture to prepare the shell spinning solution.
S3, carrying out electrostatic spinning on the core-layer spinning solution and the shell-layer spinning solution by adopting coaxial spinning, and specifically:
and (3) carrying out electrostatic spinning on the prepared core layer spinning solution and shell layer spinning solution by using a special coaxial spinning special needle. The spinning parameters were set as: the core layer injection rate is 0.55mL/h, and the shell layer injection rate is 1.15mL/h; the spinning voltage is 20kV; the receiving distance is 15cm; ambient relative humidity 60%. And after spinning is finished, vacuum drying is carried out for 24 hours.
The cross section of the fiber is observed by a scanning electron microscope, and a complete core-shell structure is not formed. The shell layer does not completely wrap the core layer, but rather a mixture of core layer and shell layer material occurs. The main reason is that the viscosity of the core layer is high, the viscosity of the shell layer is low, a composite taylor cone cannot be formed at the spray head, and then the complete core-shell structure fiber cannot be stretched out from the taylor cone under the action of an electric field.
Comparative example 2:
the electromagnetic shielding functional filler of the comparative example adopts GO and uses W as an ionization shielding functional filler.
The preparation method of the comparative example comprises the following steps:
s1, preparing a core layer spinning solution (GO/PVA solution):
the GO concentration in the GO/PVA solution is 3wt%, the viscosity of the spinning solution is 151mPa & S, and the preparation process comprises the following steps:
adding a certain amount of GO into deionized water for ultrasonic dispersion for 5 hours, pouring into a pre-prepared PVA dispersion liquid with the concentration of 8.5wt%, and continuing to perform ultrasonic treatment for 3 hours to obtain a GO/PVA solution.
S2, preparing a shell spinning solution (W/PAN solution):
the W/PAN solution has the W concentration of 19wt% and the spinning solution viscosity of 345mPa & S, and the preparation process comprises the following steps:
PAN was dissolved in DMF and the concentration of the PAN/DMF solution was controlled to 15wt%. Then adding a certain mass of W, stirring at a constant temperature of 65 ℃ on a magnetic stirrer, and standing to prepare the shell spinning solution.
S3, carrying out electrostatic spinning on the core-layer spinning solution and the shell-layer spinning solution by adopting coaxial spinning to obtain the core-shell structure shielding material, and specifically:
and (3) carrying out electrostatic spinning on the prepared core layer spinning solution and shell layer spinning solution by using a special coaxial spinning special needle. The spinning parameters were set as: the core layer injection rate is 0.55mL/h, and the shell layer injection rate is 1.15mL/h; the spinning voltage is 20kV; the receiving distance is 15cm; ambient relative humidity 60%.
In the comparative example, the amount of charge of the shell solution is small due to the excessively high content of the shell filler, and the charges cannot be accumulated under the action of an electrostatic field, so that fibers with complete shapes cannot be obtained, and performance tests cannot be performed.
Comparative example 3:
the electromagnetic shielding functional filler of the comparative example adopts GO and uses WO 3 As a filler with ionization shielding function.
The preparation method of the comparative example comprises the following steps:
s1, preparing a core layer spinning solution (GO/PVA solution):
the GO concentration in the GO/PVA solution is 0.5wt%, the viscosity of the spinning solution is 48mPa & S, and the preparation process comprises the following steps:
adding a certain amount of GO into deionized water for ultrasonic dispersion for 5 hours, pouring into a pre-prepared PVA dispersion liquid with the concentration of 8.5wt%, and continuing to perform ultrasonic dispersion for 3 hours to obtain a GO/PVA solution.
S2, preparing shell spinning solution (WO) 3 PAN solution):
WO 3 WO in PAN solution 3 The concentration is 2.5wt%, the viscosity of the spinning solution is 117 mPa.S, and the preparation process comprises the following steps:
polyacrylonitrile (PAN) was dissolved in N, N-Dimethylformamide (DMF) to control the concentration of the PAN/DMF solution to 15wt%. Then adding a certain amount of WO 3 To a concentration of 10wt% in the PAN/DMF solution; then stirring the mixture on a magnetic stirrer at a constant temperature of 65 ℃ and standing the mixture to prepare the shell spinning solution.
S3, carrying out electrostatic spinning on the core-shell spinning solution and the shell spinning solution by adopting coaxial spinning to obtain the core-shell structure shielding material, specifically:
and (3) carrying out electrostatic spinning on the prepared core layer spinning solution and shell layer spinning solution by using a special coaxial spinning special needle. The spinning parameters were set as: the core layer injection rate is 0.55mL/h, and the shell layer injection rate is 1.15mL/h; the spinning voltage is 20kV; the receiving distance is 15cm; ambient relative humidity 60%. And after spinning is finished, vacuum drying is carried out for 24 hours.
The X-ray shielding properties of the core-shell structure shielding materials prepared in examples 1 to 4, comparative examples 1 and 3 are shown in table 2:
the test conditions were:
1) Experimental apparatus: a Si (Li) detector, a spectrometer, an X-ray machine and an excitation sample (an iron sheet, a copper sheet, a lead sheet and a molybdenum sheet);
2) The experimental conditions are as follows: high pressure: 25KV, current: 50 μ a, probe high pressure: 1000V, detector gain: 0.7505X 32.
TABLE 2
Figure BDA0003810987450000091
From the data in table 2, it can be seen that:
1) The invention not only can spin uniform fiber, but also has ionization shielding effect.
2) Comparison of the data of comparative example 1 and example 3 shows that: bi of both 2 O 3 The contents were the same, but the comparative example 1 did not form a complete core-shell structure, i.e., the ionization shielding material Bi in the shell layer of the outer layer 2 O 3 And is not distributed completely over the fibers, so that the ionization shielding performance is inferior to that of the examples.
3) Comparative example 1 and comparative example 3, although WO was selected for each 3 As ionization shielding filler, but WO in comparative example 3 3 The content is low, so that the ionization shielding performance is poor, and the material cannot be used as an ionization shielding material.
Electromagnetic shielding properties of the core-shell structure shielding materials prepared in examples 1 to 4 and comparative example 1 are shown in table 3:
TABLE 3
Serial number Type of facing SE(dB)
1 Example 1 25
2 Example 2 43
3 Example 3 64
4 Example 4 33
5 Comparative example 1 40
6 Comparative example 3 11
From the data in table 3, it can be seen that:
1) And the electromagnetic shielding fillers are added less in the embodiment 1, the embodiment 2 and the embodiment 4, so the electromagnetic shielding performance is more general.
2) Although the electromagnetic shielding filler is added in a large amount in comparative example 1, the electromagnetic shielding performance is more general because the complete conductive path cannot be formed due to discontinuous filler distribution.
3) Comparative example 4 and comparative example 3, although GO was selected as the electromagnetic shielding filler, the content of GO in comparative example 3 was low, and thus the electromagnetic shielding performance was poor, and it could not be used as the electromagnetic shielding material. (generally, it is considered that the electromagnetic shielding effectiveness exceeds 20dB to be used as the electromagnetic shielding material)
The comprehensive analysis on the electromagnetic and ionization shielding properties shows that the core-shell structure shielding fiber prepared by the invention has better electromagnetic ionization comprehensive shielding properties.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The shielding material with the core-shell structure is characterized by comprising a core layer and a shell layer, wherein the shell layer is coaxially arranged on the outer side of the core layer;
the nuclear layer takes polyvinyl alcohol as a matrix and carbon fillers as electromagnetic shielding fillers; the shell layer takes polyacrylonitrile as a matrix and adopts heavy metal as an ionization shielding functional filler;
the core-shell structure shielding material is prepared by adopting coaxial spinning for electrostatic spinning.
2. The core-shell structure shielding material of claim 1, wherein the heavy metal comprises W and WO 3 、Bi 2 O 3 Or Gd 2 O 3 。
3. The core-shell structure shielding material of claim 1, wherein the carbon-based filler comprises multi-walled carbon nanotubes or graphene oxide.
4. The core-shell structure shielding material of claim 1, wherein the mass ratio of the ionization shielding functional filler in the shell layer is 5-15wt%.
5. The core-shell structure shielding material according to claim 1, wherein the mass ratio of the electromagnetic shielding functional filler in the core layer is 1-5wt%.
6. The preparation method of the core-shell structure shielding material according to any one of claims 1 to 5, comprising the following steps:
s1, preparing core-layer spinning solution from polyvinyl alcohol and carbon fillers;
s2, preparing polyacrylonitrile and heavy metal into a shell spinning solution;
and S3, carrying out electrostatic spinning on the core-shell spinning solution and the shell spinning solution by adopting coaxial spinning to obtain the core-shell structure shielding material.
7. The preparation method according to claim 6, wherein the viscosity of the core layer spinning solution is controlled to 100 to 190 mPa-S and the content of the carbon-based filler is controlled to 1 to 5wt% in step S1.
8. The preparation method according to claim 6, wherein the core layer spinning solution is prepared by:
respectively preparing dispersion liquid of polyvinyl alcohol and carbon series filler, then mixing the two dispersion liquids, carrying out ultrasonic treatment, when the carbon series filler is a multi-wall carbon nano tube, firstly carrying out acid treatment on the multi-wall carbon nano tube, and then preparing the dispersion liquid of the multi-wall carbon nano tube.
9. The preparation method according to claim 6, wherein in the step S2, the viscosity of the shell spinning solution is controlled to be 200 to 300 mPa.S, and the mass fraction of the heavy metal in the shell spinning solution is 5 to 15wt%.
10. The preparation method of claim 6, wherein the shell spinning solution is prepared by the following steps in step S2:
adding polyacrylonitrile powder into N, N-dimethylformamide solution to obtain PAN/DMF solution, adding heavy metal into the PAN/DMF solution, and stirring at constant temperature to obtain shell layer spinning solution.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010229560A (en) * 2009-03-25 2010-10-14 Teijin Ltd Inorganic nanoparticle-matrix material fibrous composite and method for producing the same
CN102021670A (en) * 2010-12-31 2011-04-20 中国纺织科学研究院 Conductive core-sheath compound fibre and preparation method thereof
CN103147165A (en) * 2013-01-25 2013-06-12 四川大学 Double-wall structured hollow ultrafine polymer fiber and preparation method thereof
US20140103583A1 (en) * 2012-10-15 2014-04-17 Quynh Pham Systems and methods for facilitating the generation of core-sheath taylor cones in electrospinning
CN107523939A (en) * 2016-06-21 2017-12-29 刘向文 A kind of ultrathin flexible electromagnetic shielding film and preparation method thereof
CN108411492A (en) * 2018-03-08 2018-08-17 南通大学 A kind of preparation method of X, gamma-rays protection non-woven fabrics
CN109518454A (en) * 2018-12-04 2019-03-26 浪莎针织有限公司 A kind of conductive hollow Bicomponent side-by-side composite fibre and preparation method thereof
CN112342693A (en) * 2020-10-30 2021-02-09 西安交通大学苏州研究院 Synthesis method of metal organic framework compound flexible film with limited growth

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010229560A (en) * 2009-03-25 2010-10-14 Teijin Ltd Inorganic nanoparticle-matrix material fibrous composite and method for producing the same
CN102021670A (en) * 2010-12-31 2011-04-20 中国纺织科学研究院 Conductive core-sheath compound fibre and preparation method thereof
US20140103583A1 (en) * 2012-10-15 2014-04-17 Quynh Pham Systems and methods for facilitating the generation of core-sheath taylor cones in electrospinning
CN103147165A (en) * 2013-01-25 2013-06-12 四川大学 Double-wall structured hollow ultrafine polymer fiber and preparation method thereof
CN107523939A (en) * 2016-06-21 2017-12-29 刘向文 A kind of ultrathin flexible electromagnetic shielding film and preparation method thereof
CN108411492A (en) * 2018-03-08 2018-08-17 南通大学 A kind of preparation method of X, gamma-rays protection non-woven fabrics
CN109518454A (en) * 2018-12-04 2019-03-26 浪莎针织有限公司 A kind of conductive hollow Bicomponent side-by-side composite fibre and preparation method thereof
CN112342693A (en) * 2020-10-30 2021-02-09 西安交通大学苏州研究院 Synthesis method of metal organic framework compound flexible film with limited growth

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