CN114525677A - Preparation of Cu-PPy electromagnetic shielding fabric - Google Patents
Preparation of Cu-PPy electromagnetic shielding fabric Download PDFInfo
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- CN114525677A CN114525677A CN202210270301.0A CN202210270301A CN114525677A CN 114525677 A CN114525677 A CN 114525677A CN 202210270301 A CN202210270301 A CN 202210270301A CN 114525677 A CN114525677 A CN 114525677A
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- 239000004744 fabric Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000007747 plating Methods 0.000 claims abstract description 45
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000009713 electroplating Methods 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 87
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 229920000128 polypyrrole Polymers 0.000 description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 19
- 239000010949 copper Substances 0.000 description 19
- 239000010410 layer Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 230000005670 electromagnetic radiation Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920006052 Chinlon® Polymers 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/20—Halides of elements of Groups 4 or 14 of the Periodic Table, e.g. zirconyl chloride
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Chemically Coating (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention discloses a preparation method of a Cu-PPy electromagnetic shielding fabric, and belongs to the technical field of electromagnetic shielding fabrics. The method comprises the steps of immersing a fabric into absolute ethyl alcohol and acetone solutions, and then sequentially immersing the fabric into a coarsening solution, a sensitizing solution and an activating solution for reaction respectively; then putting the fabric into a plating solution for reaction to obtain a copper-plated fabric; preparing a pyrrole monomer sulfuric acid solution, selecting a saturated dry mercury electrode as a reference electrode, a platinum sheet electrode as an auxiliary electrode and a copper-plated fabric as a working electrode, electroplating, and drying to obtain the Cu-PPy electromagnetic shielding fabric. The coated fabric prepared by the method is light and thin, has good flexibility and simple experimental condition requirements. The electromagnetic shielding fabric is provided with two shielding layers, electromagnetic waves can be reflected for multiple times in the shielding layers, so that the emission quantity of the electromagnetic waves is reduced, the secondary pollution of the electromagnetic waves to the environment is avoided, and a good shielding effect is achieved within a wide shielding range (8-12 GHz).
Description
Technical Field
The invention relates to the technical field of electromagnetic shielding fabrics, in particular to a preparation method of a Cu-PPy electromagnetic shielding fabric.
Background
In recent years, the problem of electromagnetic radiation has become more prominent with the development of electronic technology. Through research, excessive electromagnetic radiation can not only cause great harm to human bodies, such as leukemia, cardiovascular diseases and the like; it also affects the normal use of peripheral equipment, causing control failure of the equipment and resulting in irreparable loss. Therefore, the research on the material with the electromagnetic shielding effect for resisting the harm brought by the electromagnetic radiation has important significance. How to enable the fabric to have the electromagnetic shielding effect is a great research hotspot, and the electromagnetic shielding fabric not only needs to have the electromagnetic shielding function, but also needs to have the characteristics of good air permeability, good wear resistance, comfortable wearing and the like.
At present, the method for preparing the electromagnetic shielding fabric mainly comprises a metal blending method, a chemical plating method, an electroplating method, a magnetron sputtering plating method and the like. Among them, the electroless plating method can realize continuous production, and the plating layer is uniform and is not limited by the size and shape of the plated article, so that it is receiving much attention. The fabric needs to be modified before chemical plating, so that the plating layer is firmly attached to the surface of the fabric, and the chinese patent CN101876145A prepares the electromagnetic shielding fabric by modifying the surface of the polyester fabric, but the palladium activator used for modifying the polyester fabric is expensive, and the palladium-containing waste liquid after reaction has a certain influence on the environment. Chinese patent CN110172824A researches a chinlon silver plating process, which takes chinlon fabric as a flexible substrate to realize chinlon by a silver chemical liquid phase deposition methodSilver metallization of nylon surface, which is a silver chemical solution composed of silver salt solution in oxidizing solution, complexing agent and formaldehyde in reducing solution for reducing Ag in deposition solution+The silver-plated fabric is deposited on the surface of the substrate continuously, but the electromagnetic shielding effect of the silver-plated fabric is not studied, and the scarcity of the metal limits the development of the silver-plated fabric. Therefore, the electromagnetic shielding fabric which has good electromagnetic radiation shielding performance, corrosion resistance, compact and uniform plating layer and low cost has important research significance.
Disclosure of Invention
The invention aims to provide a preparation method of a Cu-PPy electromagnetic shielding fabric, which aims to overcome the defects of infirm adhesion, low electromagnetic shielding efficiency and the like of a single metal coating prepared by the existing method and does not change the characteristics of wearability and light weight of the fabric. The electromagnetic shielding fabric has an obvious effect on the absorption function of electromagnetic waves, and the electromagnetic waves are reflected and absorbed on the copper plating layer and the polypyrrole layer for multiple times, so that the electromagnetic shielding effect is improved, the reflected electromagnetic waves are reduced, and the secondary pollution of the reflected electromagnetic waves to the environment is avoided. After the fabric is plated with copper, polypyrrole is continuously coated on the surface of the fabric, and the electromagnetic shielding effectiveness of the Cu-PPy fabric can reach 34.93dB and is 25.4dB higher than that of the copper-plated fabric.
In order to achieve the purpose, the invention provides the following scheme:
one of the purposes of the invention is to provide a preparation method of a Cu-PPy electromagnetic shielding fabric, which comprises the following steps:
(1) immersing the fabric into a mixed solution of absolute ethyl alcohol and acetone, and then sequentially immersing the fabric into a roughening solution, a sensitizing solution and an activating solution for reaction respectively;
the coarsening liquid is NaOH solution, and the sensitizing liquid is SnCl2Placing the solution in HCl solution to obtain the activated solution, wherein the activated solution is AgNO3A solution;
(2) preparing a plating solution comprising CuSO4·5H2O, sodium potassium tartrate tetrahydrate and formaldehyde, and then placing the fabric obtained in the step (1) in a prepared plating solution for reaction to obtain a copper-plated fabric;
(3) preparing a pyrrole monomer sulfuric acid solution, electroplating polypyrrole, selecting a saturated dry mercury electrode (SCE) as a reference electrode, a platinum sheet electrode as an auxiliary electrode, using the copper-plated fabric obtained in the step (2) as a working electrode, electroplating, and drying to obtain the Cu-PPy electromagnetic shielding fabric.
Further, the volume ratio of the absolute ethyl alcohol and the acetone solution in the step (1) is 1: 3; the coarsening liquid is NaOH solution, and the concentration of the NaOH solution is 180-220 g/L; the sensitizing solution is 15g/L SnCl2Placing in 30mL/L HCl solution (here, 15g SnCl/L solution)2And 30mL of HCl solution), the concentration of HCl solution is 37 wt%; the activating solution is AgNO3The concentration of the solution is 10 g/L.
Further, after the fabric in the step (1) is immersed in a solution of absolute ethyl alcohol and acetone to remove oil stains and impurities, washing the fabric for 2-3 times by using deionized water; after the fabric is immersed in the coarsening solution, magnetically stirring for 20min, and then washing for 2-3 times by using deionized water; after the fabric is immersed in the sensitizing solution, magnetically stirring for 20min, and then washing for 2-3 times by using deionized water; after the fabric is immersed in the activating solution, magnetically stirring for 30min, then washing for 2-3 times by using deionized water, and drying; the reaction temperature is 50-80 ℃.
Further, the CuSO of step (2)4·5H2The mass concentration of O is 20-40 g/L, and the potassium sodium tartrate tetrahydrate and CuSO4·5H2The mass ratio of O is 2: 1-5: 1, and the concentration of formaldehyde is 30-50 mL/L; the plating solution was adjusted to pH 12 with NaOH.
Further, the fabric in the step (2) is placed in a plating solution, stands for 16-24 hours at room temperature, is taken out, is washed for 3-5 times by deionized water, and is dried.
Further, the preparation process of the pyrrole monomer sulfuric acid acidic solution in the step (3) is as follows: pyrrole is dropped into H with the concentration of 0.05mol/L2SO4In solution, pyrrole and H2SO4The molar mass ratio of 0.1-2 mol: 0.01-0.05 mol, and ultrasonically stirring for 10min to disperse pyrrole monomers.
Further, the pH value of the pyrrole monomer sulfuric acid solution electroplated in the step (3) is kept at 1, the electroplating potential is 0.65V, and the electroplating time is 5-20 min.
The invention also aims to provide the Cu-PPy electromagnetic shielding fabric prepared by the preparation method.
Because the noble metal has higher cost, the invention replaces the noble metal with the base metal copper, so that the electroplated fiber has the function of shielding electromagnetic radiation, has the excellent characteristics of corrosion resistance and compact and uniform plating layer, reduces the cost and has good market prospect. Because copper attached to the surface of the fabric is easy to oxidize, polypyrrole (PPy) is a conductive high polymer, is insoluble in water, is stable in chemical substances, and is generated by oxidizing a pyrrole monomer, wherein the pyrrole monomer is a five-membered heterocyclic compound formed by C, N elements, is colorless and transparent, and is easy to oxidize. The preparation method of PPy comprises chemical oxidation polymerization and electrochemical oxidation polymerization, and because the electrochemical oxidation reduction method needs to use oxidants such as ferric trichloride and the like, and the oxidants react with copper simple substances, so that the copper simple substances on the surface of the fabric are greatly reduced, and the expected effect cannot be achieved, the polypyrrole coating is coated on the surface of the copper-plated fabric by adopting an electroplating method.
The method comprises the steps of firstly pretreating the fabric to modify the fabric, then carrying out chemical copper plating on the surface of the fabric, and then coating polypyrrole on the surface of the fabric in an electroplating mode. The fabric electromagnetic shielding effectiveness can be improved by changing the experimental parameters of each step, and the polypyrrole is coated on the surface of the copper-plated fabric again, so that a coating layer can be formed on the surface of the copper-plated fabric, the problem that a copper-plated layer of the fabric is easy to oxidize is effectively solved, and the fabric electromagnetic shielding effectiveness is also improved. After the copper plating finishing is carried out on the surface of the fabric, the highest electromagnetic shielding effectiveness can reach 25.4dB, and after the polypyrrole is continuously coated on the surface of the fabric, the highest electromagnetic shielding effectiveness of the fabric can reach 34.93dB (the test frequency is 8-12 GHz).
The invention has the beneficial effects that: the electromagnetic shielding fabric with relatively good shielding effectiveness is prepared, and the prepared coating fabric is light and thin, has good flexibility and simple experimental condition requirements. The electromagnetic shielding fabric is provided with two shielding layers, electromagnetic waves can be reflected in the shielding layers for multiple times, so that the emission quantity of the electromagnetic waves is reduced, the secondary pollution of the electromagnetic waves to the environment is avoided, and a good shielding effect is achieved within a wide shielding range (8-12 GHz).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is an electromagnetic shielding mechanism of the present invention, wherein 1 is a fabric, 2 is a copper-plated layer, and 3 is a polypyrrole layer;
FIG. 2 is an electron microscope image of a fabric subjected to electroless copper plating finishing in example 3 of the present invention;
FIG. 3 is an electron microscope image of a fabric subjected to electroless copper plating finishing in example 4 of the present invention;
FIG. 4 is an electron microscope image of a fabric subjected to electroless copper plating finishing in example 5 of the present invention;
FIG. 5 is a graph showing the shielding effectiveness of the copper-coated fabric of example 5 before and after polypyrrole was electroplated;
FIG. 6 is a graph showing the change of the relationship among the absorption rate, the reflection rate and the transmittance of the electromagnetic wave in example 5 of the present invention;
FIG. 7 is a graph showing the shielding effectiveness of the copper-coated fabric of example 6 of the present invention before and after different plating times for plating polypyrrole.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the present invention, all solutions are aqueous solutions unless otherwise specified.
Example 1
Selecting common pure cotton fabric (Ctn) with the size of 8 multiplied by 8cm2The thickness is about 0.3mm, the warp and weft density is 106 multiplied by 100, and the good Cu-PPy electromagnetic shielding fabric can be prepared according to the following steps.
(1) Soaking the cotton fabric into an absolute ethyl alcohol and acetone solution (the volume ratio of the absolute ethyl alcohol to the acetone solution is 1:3), removing oil stains and impurities, taking out, and washing with deionized water for 3 times;
preparing a roughening solution with NaOH solution concentration of 180g/L, immersing the fabric into the roughening solution, magnetically stirring at 70 ℃ for 20min, taking out and washing with deionized water for 3 times;
15g/L SnCl2Placing the fabric in 30mL/L HCl solution to prepare sensitizing solution, and placing the fabricMagnetically stirring in sensitizing solution at 70 deg.C for 20min, taking out, and washing with deionized water for 3 times;
AgNO with solution concentration of 10g/L3And (3) immersing the fabric into the activating solution at 70 ℃, magnetically stirring for 30min, taking out, washing for 3 times by using deionized water, and drying.
(2) Using beaker as plating bath to prepare plating solution, main agent CuSO4·5H2The concentration of O is 25g/L, the mass ratio of the complexing agent potassium sodium tartrate tetrahydrate to the main agent is 2:1, the concentration of the reducing agent formaldehyde is 30mL/L, and NaOH is added to control the pH value of the solution to be 12. And (2) placing the fabric obtained in the step (1) in a plating solution, standing for 20h at room temperature, taking out, washing for 5 times by using deionized water, and drying to obtain the copper-plated fabric.
(3) Preparing pyrrole monomer sulfuric acid solution, dripping pyrrole into H with the concentration of 0.05mol/L2SO4In solution, pyrrole and H2SO4The molar mass ratio of 0.3mol to 0.05mol, and stirring for 10min by ultrasonic.
And (3) electroplating polypyrrole, selecting a saturated dry mercury electrode as a reference electrode, a platinum sheet electrode as an auxiliary electrode, using the copper-plated fabric obtained in the step (2) as a working electrode, keeping the pH value of the solution at 1, and electroplating potential at 0.65V for 10min, and drying to obtain the Cu-PPy electromagnetic shielding fabric.
Measuring the surface resistance of the fabric subjected to electroless copper plating finishing to be 126.72 omega/sq, and the electromagnetic shielding effectiveness to be 15.73dB (the test frequency is 8-12 GHz); the electromagnetic shielding effectiveness of the fabric after the polypyrrole coating is electroplated and finished is 23.34dB, compared with the fabric before the polypyrrole coating is coated, the electromagnetic shielding effectiveness of the fabric is obviously improved, and the shielding effectiveness is increased by 48%.
Example 2
This example was similar to example 1, except that the concentration of the roughening solution was varied and the concentration of the NaOH solution was 200 g/L.
Measuring the surface resistance of the fabric after chemical plating finishing to be 95.85 omega/sq and the electromagnetic shielding effectiveness to be 19.76 dB; the electromagnetic shielding effectiveness of the fabric after the polypyrrole is electroplated is 28.59dB, and the shielding effectiveness is increased by 45%.
Example 3
This example and implementationExample 2 the same, except that the parameters of the main agent of the electroless plating were different, the main agent CuSO4·5H2The O concentration was 35 g/L.
An electron microscope image of the fabric after only the electroless plating finish is shown in fig. 2. Measuring the surface resistance of the fabric after chemical plating finishing to be 82.83 omega/sq and the electromagnetic shielding effectiveness to be 21.96 dB; the electromagnetic shielding effectiveness of the fabric after polypyrrole electroplating is 30.19dB, and the shielding effectiveness is increased by 37%.
Example 4
This example is the same as example 3, except that the concentration of the reducing agent formaldehyde was varied and the concentration of the reducing agent formaldehyde was 50 mL/L.
An electron microscope image of the fabric after only the electroless plating finish is shown in fig. 3. The surface resistance of the fabric after the chemical plating finishing is measured to be 70.85 omega/sq, and the electromagnetic shielding effectiveness is 21.76 dB; the electromagnetic shielding effectiveness of the fabric after the polypyrrole is electroplated is 30.59dB, and the shielding effectiveness is increased by 40%.
Example 5
This example is the same as example 4, except that the concentration parameters of the complexing agent potassium sodium tartrate tetrahydrate are different, and the mass ratio of the complexing agent potassium sodium tartrate tetrahydrate to the main agent is 5: 1.
An electron microscope image of the fabric after only the chemical plating finishing and the electroplating polypyrrole finishing is shown in fig. 4. The surface resistance of the fabric after chemical plating finishing is measured to be 62.85 omega/sq, and the electromagnetic shielding effectiveness is 25.4 dB; the electromagnetic shielding effectiveness of the fabric after polypyrrole electroplating is 34.59dB (the test frequency is 8-12 GHz), and the shielding effectiveness of the fabric before and after polypyrrole electroplating is shown in FIG. 5, which is increased by 36%.
To further investigate the absorption of electromagnetic waves by the electromagnetic shielding fabric, the relationship among the absorption rate, reflectance and transmittance of electromagnetic waves is calculated as shown in fig. 6, from which it can be seen that: the sum of the absorptivity and the reflectivity is gradually increased along with the increase of the concentration of the complexing agent potassium sodium tartrate tetrahydrate, the transmittance is gradually reduced, which shows that the electromagnetic shielding effectiveness is increased, and when the mass ratio of the complexing agent to the main agent is 5:1, more than 99% of electromagnetic waves can be shielded; and it can be found from the figure that the absorptivity far exceeds the reflectivity, which shows that the electromagnetic shielding mechanism of the present invention mainly absorbs the electromagnetic wave.
Example 6
This example is the same as example 5, except that the plating time parameters were different, and the plating time was 15 min. The shielding effectiveness of the fabric before and after different times of polypyrrole plating is shown in figure 7.
As can be seen from fig. 7, after 15min of plating PPy, the electromagnetic shielding performance was reduced compared to 5min of plating, which indicates that the longer the plating time, the better the electromagnetic shielding performance of the plated fabric. This is probably because the thickness of the copper plating layer increases with the increase of the plating time, the plating film formed on the surface becomes smoother, and PPy gradually deposits on the copper plated fabric, and as the copper plating layer becomes smoother, the anchoring effect of PPy with the copper layer is weakened, so that PPy on the surface of the fabric cannot be firmly deposited on the surface of the copper film, PPy starts to agglomerate, loose particles are formed on the surface of PPy plating layer, and are removed in the subsequent washing process, thereby causing the decrease of the electromagnetic shielding effectiveness.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (8)
1. A preparation method of a Cu-PPy electromagnetic shielding fabric is characterized by comprising the following steps:
(1) immersing the fabric into a mixed solution of absolute ethyl alcohol and acetone, and then sequentially immersing the fabric into a roughening solution, a sensitizing solution and an activating solution for reaction respectively;
the coarsening solution is NaOH solution, and the sensitizing solution is SnCl2Placing the solution in HCl solution to obtain the activated solution, wherein the activated solution is AgNO3A solution;
(2) preparing a plating solution comprising CuSO4·5H2O, sodium potassium tartrate tetrahydrate and formaldehyde, and then placing the fabric obtained in the step (1) in a plating solution for reaction to obtain a copper-plated fabric;
(3) and (3) preparing a pyrrole monomer sulfuric acid solution, selecting a saturated dry mercury electrode as a reference electrode, a platinum sheet electrode as an auxiliary electrode, the copper-plated fabric obtained in the step (2) as a working electrode, electroplating, and drying to obtain the Cu-PPy electromagnetic shielding fabric.
2. The method for preparing a Cu-PPy electromagnetic shielding fabric according to claim 1, wherein the volume ratio of the absolute ethanol solution to the acetone solution in step (1) is 1: 3; the coarsening liquid is NaOH solution, and the concentration of the NaOH solution is 180-220 g/L; the sensitizing solution is 15g/L SnCl2Placing the mixture in 30mL/L HCl solution, wherein the concentration of the HCl solution is 37 wt%; the activating solution is AgNO3The concentration of the solution is 10 g/L.
3. The method for preparing a Cu-PPy electromagnetic shielding fabric according to claim 1, wherein the fabric of step (1) is immersed in a solution of absolute ethanol and acetone to remove oil stains and impurities, and then washed with deionized water for 2-3 times; after the fabric is immersed in the coarsening solution, magnetically stirring for 20min, and then washing for 2-3 times by using deionized water; after the fabric is immersed in the sensitizing solution, magnetically stirring for 20min, and then washing for 2-3 times by using deionized water; after the fabric is immersed in the activation solution, magnetically stirring for 30min, then washing with deionized water for 2-3 times, and drying; the reaction temperature is 50-80 ℃.
4. The method for preparing a Cu-PPy EMI shielding fabric as claimed in claim 1, wherein said CuSO of step (2)4·5H2The mass concentration of O is 20-40 g/L, and the potassium sodium tartrate tetrahydrate and CuSO4·5H2The mass ratio of O is 2: 1-5: 1, and the concentration of formaldehyde is 30-50 mL/L; the plating solution was adjusted to pH 12 with NaOH.
5. The method for preparing a Cu-PPy electromagnetic shielding fabric according to claim 1, wherein the fabric obtained in step (2) is placed in a plating solution, left to stand at room temperature for 16-24 hours, taken out, washed with deionized water for 3-5 times, and dried.
6. The method for preparing a Cu-PPy electromagnetic shielding fabric according to claim 1, wherein the step (3) of preparing the pyrrole monomer sulfuric acid acidic solution comprises: pyrrole is dropped into H with the concentration of 0.05mol/L2SO4In solution, pyrrole and H2SO4The molar mass ratio of (b) is 0.1-2 mol: 0.01-0.05 mol, and ultrasonic stirring is carried out for 10 min.
7. The method for preparing a Cu-PPy electromagnetic shielding fabric according to claim 1, wherein the pH value of the electroplating solution in the step (3) is kept at 1, the electroplating potential is 0.65V, and the electroplating time is 5-20 min.
8. A Cu-PPy electromagnetic shielding fabric prepared by the preparation method of any one of claims 1-7.
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CN1236839A (en) * | 1998-05-21 | 1999-12-01 | 刘绍之 | Electromagnetically shielding fabrics and production method thereof |
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CN202163064U (en) * | 2011-07-19 | 2012-03-14 | 上海工程技术大学 | Electromagnetic shielding fabric |
CN105506991A (en) * | 2016-01-14 | 2016-04-20 | 复旦大学 | Preparing method for copper ammonia fiber conductive textile |
CN109130383A (en) * | 2018-07-25 | 2019-01-04 | 深圳市弘海电子材料技术有限公司 | A kind of bilayer electromagnetic shielding film and preparation method thereof |
CN109487542A (en) * | 2018-11-19 | 2019-03-19 | 吉林省泰华电子股份有限公司 | A kind of electromagnetic shielding preparation process of copper facing nickel fibre |
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CN1236839A (en) * | 1998-05-21 | 1999-12-01 | 刘绍之 | Electromagnetically shielding fabrics and production method thereof |
CN102154832A (en) * | 2010-12-31 | 2011-08-17 | 泉州红瑞兴纺织有限公司 | Fabric coating finishing agent with electromagnetic shielding function and preparation method thereof |
CN202163064U (en) * | 2011-07-19 | 2012-03-14 | 上海工程技术大学 | Electromagnetic shielding fabric |
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