CN114411414B - Palladium-free electroless copper plating method for surface of flexible nanofiber membrane - Google Patents
Palladium-free electroless copper plating method for surface of flexible nanofiber membrane Download PDFInfo
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- CN114411414B CN114411414B CN202210078721.9A CN202210078721A CN114411414B CN 114411414 B CN114411414 B CN 114411414B CN 202210078721 A CN202210078721 A CN 202210078721A CN 114411414 B CN114411414 B CN 114411414B
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- nanofiber membrane
- nanofiber
- membrane
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- palladium
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 167
- 239000012528 membrane Substances 0.000 title claims abstract description 148
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 74
- 239000010949 copper Substances 0.000 title claims abstract description 74
- 238000007747 plating Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000009832 plasma treatment Methods 0.000 claims abstract description 17
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- 238000007772 electroless plating Methods 0.000 claims abstract description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 4
- -1 polyethylene Polymers 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 239000004745 nonwoven fabric Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 claims description 7
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 7
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 7
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 13
- 239000004332 silver Substances 0.000 description 13
- 229910052763 palladium Inorganic materials 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KUNICNFETYAKKO-UHFFFAOYSA-N sulfuric acid;pentahydrate Chemical compound O.O.O.O.O.OS(O)(=O)=O KUNICNFETYAKKO-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- AWOPBNHMACSMTO-UHFFFAOYSA-N copper;sodium Chemical compound [Na+].[Cu+2] AWOPBNHMACSMTO-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- CBQKGISIWKPJMB-UHFFFAOYSA-N naphthalene;oxolane;sodium Chemical compound [Na].C1CCOC1.C1=CC=CC2=CC=CC=C21 CBQKGISIWKPJMB-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
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- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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Abstract
The invention provides a palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane, which comprises the following steps: uniformly spraying a polyvinyl alcohol-ethylene copolymer nanofiber suspension with the concentration of 0.5-3.0 wt% on the surface of a substrate, and drying to obtain a nanofiber membrane; the obtained nanofiber membrane is subjected to plasma treatment, immersed into an acrylic acid aqueous solution with the concentration of 5-20wt% for treatment, washed and dried to obtain a modified nanofiber membrane; placing the obtained modified nanofiber membrane into a silver nitrate solution for treatment for 20-50min, washing and drying to obtain an activated nanofiber membrane; and (3) placing the obtained activated nanofiber membrane in an electroless plating solution, treating for 1-3 hours at 60-80 ℃, and washing and drying to obtain the flexible conductive membrane. According to the invention, the nanofiber membrane with a special structure is modified, so that the acrylic acid is uniformly combined on the surface of the nanofiber membrane, and the flexible conductive membrane has excellent performance after copper plating treatment.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane.
Background
With the high-speed development of electronic technology, the copper-clad plate is used as the most basic material of the PCB, and the demand of the high-performance flexible copper-clad plate has a remarkable increasing trend. The copper-clad plate is a composite material composed of metallic copper and high polymer, and is mainly prepared by means of lamination, coating, vacuum sputtering, electroless copper plating and the like.
Wherein, the polymer is generally polyester, polyimide, polyolefin, etc. The polyvinyl alcohol-ethylene copolymer (PVA-co-PE) film has the excellent performances of large specific surface area, high porosity, tortuous pore canal structure, high filtering precision and the like, and the flexible nanofiber copper-clad film prepared by the surface chemical copper plating method has low dielectric constant and small dielectric loss factor, is an ideal high-frequency microwave dielectric material, and can be applied to electronic products such as navigation equipment, aircraft instruments, digital cameras, liquid crystal televisions, notebook computers and the like.
At present, a common preparation method for preparing the copper-clad plate is an electroless copper plating method. The electroless copper plating steps are typically degreasing, modification, activation and electroless plating. In the activation process, although the surface energy of the nanofiber film can be obviously improved by the chemical modification of the conventional sodium-naphthalene tetrahydrofuran solution, substances which damage the environment can be generated in the modification process, and the operation danger index is high; the high-energy radiation grafting modification method has the advantages of easily controlled grafting rate, no need of initiator and the like, but the radiation quantity is not easy to control, and uncontrollable damage to the physical and chemical properties of the material is easy to cause. In the electroless copper plating process, the traditional catalyst is a palladium catalyst, and the cost is high in practical application because palladium is expensive, and the silver catalyst is reported to replace the palladium catalyst at present.
Patent application number CN201610899123.2 discloses a palladium-free electroless copper plating method for polytetrafluoroethylene material surface, which adopts a low-temperature plasma grafting modification method to introduce a large number of carboxyl groups on polytetrafluoroethylene material surface, and enables the copper plating layer to be firmly combined with the material surface through chemical bonds. The polytetrafluoroethylene material used in the method has extremely low surface energy, a single film structure, poor modification effect through low-temperature plasma modification treatment, and the problems of uneven carboxyl and low bonding strength of the carboxyl when the activated polytetrafluoroethylene material is reintroduced into the carboxyl, which can lead to uneven copper plating, poor electrical conductivity and poor electromagnetic shielding performance of the final product.
In view of the foregoing, there is a need for an improved palladium-free electroless copper plating process on the surface of flexible nanofiber membranes to address the above-described problems.
Disclosure of Invention
The invention aims to provide a palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane, which solves the problems of uneven copper plating, poor conductivity, poor electromagnetic shielding performance, easy shedding of a plating layer and the like in the existing electroless copper plating process.
In order to achieve the aim of the invention, the invention provides a palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane, which comprises the following steps:
S1, preparing a nanofiber membrane: uniformly spraying a polyvinyl alcohol-ethylene copolymer nanofiber suspension with the concentration of 0.5-3.0 wt% on the surface of a substrate subjected to pre-washing treatment, and drying to form a film to obtain a nanofiber membrane;
S2, modifying a nanofiber membrane: the nanofiber membrane prepared in the step S1 is subjected to plasma treatment, immersed into an acrylic acid aqueous solution with the concentration of 5-20wt% according to the bath ratio of 1:2-1:5, washed and dried to obtain a modified nanofiber membrane;
S3, activating a nanofiber membrane: placing the modified nanofiber membrane prepared in the step S2 into a silver nitrate solution for treatment for 20-50min according to the bath ratio of 1:1-1:8, and washing and drying to obtain an activated nanofiber membrane;
s4, plating copper on the nanofiber membrane: and (3) placing the activated nanofiber membrane prepared in the step (S3) into an electroless plating solution according to a bath ratio of 1:1-1:5, treating for 1-3h at 60-80 ℃, and washing and drying to obtain the flexible conductive membrane.
As a further improvement of the present invention, the polyvinyl alcohol-ethylene copolymer nanofiber in step S1 has a diameter of 50nm to 800nm.
As a further improvement of the invention, the duration of the plasma treatment in the step S2 is 2min-20min.
As a further improvement of the present invention, the duration of the treatment in the aqueous acrylic acid solution is 2 to 12 hours.
As a further improvement of the invention, the pre-washing treatment of the substrate in the step S1 is that the substrate is placed in a solution of a detergent, sodium carbonate and deionized water in a mass ratio of 1:3:1000, treated in a water bath at 80 ℃ for 1h, taken out, washed to be neutral by the deionized water, and dried at 60 ℃ for 1h.
As a further improvement of the present invention, the concentration of the silver nitrate solution in the step S3 is 1-2g/L.
As a further improvement of the present invention, the electroless plating solution in step S4 is a mixed solution of copper sulfate pentahydrate, disodium ethylenediamine tetraacetate dihydrate, sodium potassium tartrate, sodium hydroxide, potassium ferrocyanide dihydrate, 2' -bipyridine and 37wt% formaldehyde.
As a further improvement of the invention, in the electroless plating solution, the concentrations of all substances are 16g/L of cupric sulfate pentahydrate, 19.5g/L of disodium ethylenediamine tetraacetate dihydrate, 14g/L of potassium sodium tartrate, 14.5g/L of sodium hydroxide, 0.01g/L of potassium ferrocyanide dihydrate, 0.02g/L of 2,2' -bipyridine and 5mL/L of 37wt% formaldehyde.
As a further improvement of the invention, the conductivity of the flexible conductive film is up to 4897.1s/cm, the electromagnetic shielding effectiveness is up to 58dB, and the absorption efficiency is up to more than 90%.
As a further improvement of the present invention, the substrate in step S1 includes one or more of polyethylene nonwoven fabric and polypropylene nonwoven fabric.
The beneficial effects of the invention are as follows:
(1) The invention provides a palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane, which is characterized in that polyvinyl alcohol-ethylene copolymer nanofiber is prepared into polyvinyl alcohol-ethylene copolymer nanofiber suspension, and the polyvinyl alcohol-ethylene copolymer nanofiber suspension is uniformly sprayed on the surface of a base material, so that different degrees of crosslinking occur between single fibers to form the nanofiber membrane with special pore diameter, pore and pore channel structures; on the other hand, the PVA-co-PE nanofiber membrane surface contains abundant high-activity hydroxyl groups, so that the surface polarity and the surface energy of the PVA-co-PE nanofiber membrane can be effectively increased. The special surface structure of the PVA-co-PE nanofiber membrane provides a larger specific surface and higher activity for plasma treatment, so that the plasma modification treatment is more sufficient. The PVA-co-PE nanofiber membrane modified by the plasma can provide a rougher surface and more binding sites, so that the surface of the nanofiber membrane is uniformly grafted with high-activity carboxyl through chemical bonds. The existence of carboxyl makes silver ions uniformly grafted on the surface of the nanofiber membrane through coordination, provides active centers for copper plating reaction, and makes the finally generated flexible conductive membrane compact and uniform, high in conductivity, low in surface resistance, reaching the conductor level and excellent in conductivity and electromagnetic shielding performance.
(2) The invention provides a palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane, which takes the nanofiber membrane as a base material, and the prepared flexible conductive membrane has excellent bending resistance, can be repeatedly used and is not easy to damage, so that the problem of poor bending resistance of a conventional electronic copper-clad plate is solved; the plasma induced grafting method is adopted, so that the method has no pollution, is easy to operate and low in cost, and solves the problem that the conductor film material for the electronic is difficult to popularize due to the cost; the microporous structure of the nanofiber membrane and the copper plating layer on the surface enable the material to have excellent electromagnetic shielding performance, so that the problem of mutual interference among electronic device elements is solved; based on the copper-plated conductive material on the surface of the flexible nanofiber membrane, the hydrophobicity is improved, and the method has important significance for expanding the application range of electronic device elements.
(3) The invention provides a palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane, which does not need traditional palladium catalysis and adopts silver catalysis, and the method is simple to operate, easy to control in process, economical and environment-friendly, and easy for large-scale industrial production.
Drawings
FIG. 1 is a flow chart of a palladium-free electroless copper plating process on the surface of a flexible nanofiber membrane of the present invention.
Fig. 2 is a scanning electron microscope image of the flexible conductive film and nanofiber film substrate prepared in example 1.
Fig. 3 is a conductivity chart of the flexible conductive film prepared in example 1.
Fig. 4 is an electromagnetic shielding property graph of the flexible conductive film prepared in example 1.
Fig. 5 is a water contact angle graph of the flexible conductive film prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the invention provides a palladium-free electroless copper plating method for a flexible nanofiber membrane surface, which comprises the following steps:
S1, preparing a nanofiber membrane:
And (3) placing the substrate in a solution of a detergent, sodium carbonate and deionized water in a mass ratio of 1:3:1000, carrying out water bath treatment at 80 ℃ for 1h, taking out the substrate, washing the substrate with deionized water to be neutral, and drying the substrate at 60 ℃ for 1h to obtain the substrate subjected to pre-washing treatment. The process can remove oil stains and other impurities on the surface of the substrate, and provides conditions for the subsequent firm coating of the polyvinyl alcohol-ethylene copolymer (PVA-co-PE) nanofiber suspension.
Wherein the substrate comprises one or more of polyethylene non-woven fabrics and polypropylene non-woven fabrics.
Preparing polyvinyl alcohol-ethylene copolymer nanofiber with the diameter of 50-800 nm into polyvinyl alcohol-ethylene copolymer nanofiber suspension with the concentration of 0.5-3.0 wt%, uniformly spraying the suspension on the surface of a pre-washed base material, and drying to form a layer of PVA-co-PE film on the surface of the base material to obtain the nanofiber film.
S2, modifying a nanofiber membrane:
and (3) treating the nanofiber membrane prepared in the step (S1) by plasma for 2-20min, immersing the nanofiber membrane into an acrylic acid aqueous solution with the concentration of 5-20wt% according to the bath ratio of 1:2-1:5, treating for 2-12h, and washing and drying to obtain the modified nanofiber membrane.
The PVA-co-PE nanofiber membrane has a microporous structure, and is large in specific surface area, high in porosity and tortuous in pore structure; in addition, the PVA-co-PE nanofiber membrane surface contains abundant high-activity hydroxyl groups, and the polar group hydroxyl groups can effectively increase the surface polarity and surface energy of the PVA-co-PE nanofiber membrane. Therefore, the special surface structure of the PVA-co-PE nanofiber membrane provides a larger specific surface for plasma treatment, so that the plasma modification treatment is more sufficient. In the plasma treatment process, the PVA-co-PE nanofiber membrane is etched, so that the surface roughness can be increased, the specific surface area of the PVA-co-PE nanofiber membrane is further increased, the hydroxyl content of the surface of the PVA-co-PE nanofiber membrane is higher, and the active sites of the surface are increased.
When the PVA-co-PE nanofiber membrane subjected to plasma treatment is further placed in an acrylic acid solution for treatment, more acrylic acid is adhered to the surface of the nanofiber membrane due to the increase of the surface roughness and the increase of the surface hydroxyl content of the nanofiber membrane, and abundant hydroxyl groups in PVA-co-PE molecules are bonded with carboxyl groups in acrylic acid molecules through hydrogen bonding, so that a large amount of acrylic acid is finally firmly bonded to the surface of the nanofiber membrane, and the modified nanofiber membrane is obtained. The surface polarity and surface energy of the nanofiber membrane can be further improved by a large amount of polar groups and carboxyl groups, so that the chemical activity of the modified nanofiber membrane is greatly improved.
In addition, because hydrophilic polyvinyl alcohol exists in PVA-co-PE molecules, acrylic acid liquid is hydrophilic substance; and the PVA-co-PE film has a porous structure, so that a large amount of acrylic acid is further grafted on the surface of the nanofiber film.
S3, activating a nanofiber membrane:
And (3) placing the modified nanofiber membrane prepared in the step (S2) into a silver nitrate solution with the concentration of 1-2g/L according to the bath ratio of 1:1-1:8, treating for 20-50min, and washing and drying to obtain the activated nanofiber membrane.
In the process, the silver ions and carboxylic acid radicals in the acrylic acid have coordination (electrostatic) effect, so that the silver ions are firmly supported on the surface of the modified nanofiber membrane. The silver ions not only provide an activation center for the modified nanofiber membrane, but also can be used as a catalyst for subsequent copper plating, and can accelerate the reaction of electroless plating.
S4, plating copper on the nanofiber membrane:
And (3) placing the activated nanofiber membrane prepared in the step (S3) into an electroless plating solution according to a bath ratio of 1:1-1:5, treating for 1-3h at 60-80 ℃, and carrying out electroless copper plating reaction on the activated nanofiber membrane adsorbed with silver ions, so that a copper layer is deposited on the surface of the PVA-co-PE nanofiber membrane, and washing and drying the surface of the PVA-co-PE nanofiber membrane to obtain the flexible conductive membrane.
Wherein, the chemical plating solution comprises the following components in percentage by weight: 16g/L of copper sulfate pentahydrate, 19.5g/L of disodium ethylenediamine tetraacetate dihydrate, 14g/L of potassium sodium tartrate, 14.5g/L of sodium hydroxide, 0.01g/L of potassium ferrocyanide dihydrate, 0.02g/L of 2,2' -bipyridine, 5mL/L of 37wt% formaldehyde and the balance of water.
Specifically, copper sulfate is the primary raw material for providing the desired plating metal; the potassium sodium tartrate and the disodium ethylenediamine tetraacetate dihydrate can form a complex with copper ions, so that long-term stable conditions are provided for the copper ions; formaldehyde can reduce cupric ions to metallic copper; sodium hydroxide provides a suitable pH for the reduction reaction; the potassium ferrocyanide dihydrate can properly control the reduction speed, so as to prevent the plating solution from being decomposed violently and leading to the failure of the plating solution; 2,2' -bipyridine is used as a brightening agent to enable the surface of the finally obtained copper plating layer to be bright.
In the presence of silver ion catalyst, copper ion is reduced to metallic copper by formaldehyde, when metallic copper begins to deposit on the surface, the copper layer acts as a catalyst for further reaction, so that electroless copper plating can be continued.
The invention is described in detail below by means of several examples:
Example 1
A palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane comprises the following steps:
S1, preparing a nanofiber membrane:
And (3) placing the flexible polyethylene non-woven fabric substrate in a solution of a detergent, sodium carbonate and deionized water in a mass ratio of 1:3:1000, performing water bath treatment at 80 ℃ for 1h, taking out the polyethylene non-woven fabric, washing the polyethylene non-woven fabric to be neutral by using the deionized water, and drying the polyethylene non-woven fabric at 60 ℃ for 1h to obtain the pre-washed flexible polyethylene non-woven fabric.
PVA-co-PE nanofiber with the diameter of 200nm is prepared into PVA-co-PE nanofiber suspension with the concentration of 1wt%, the suspension is uniformly sprayed on the surface of a flexible polyethylene non-woven fabric subjected to pre-washing treatment, and after drying, a layer of PVA-co-PE porous nanofiber membrane is formed on the surface of the polyethylene non-woven fabric, so that a nanofiber membrane is obtained, and the thickness of the nanofiber membrane is 50 mu m.
The original film morphology scanning electron microscope image shown in the left image of fig. 2 has a scale of 5 μm, and the PVA-co-PE nanofibers are crosslinked with each other and have uniform pores, so that conditions are provided for subsequent plasma treatment and acrylic acid grafting.
Because similar polyethylene fragments exist in PVA-co-PE molecules and polyolefin molecules, the molecules of the PVA-co-PE molecules and the polyolefin molecules are orderly arranged, and the binding force of the PVA-co-PE nano fiber film and the polyolefin non-woven fabric is strong, so that the PVA-co-PE nano fiber film is firmly coated on the surface of the polyolefin non-woven fabric.
S2, modifying a nanofiber membrane:
And (3) performing plasma treatment on the nanofiber membrane prepared in the step (S1) for 5min, immersing the nanofiber membrane into an acrylic acid aqueous solution with the concentration of 10wt% according to the bath ratio of 1:2, treating for 10h, and washing and drying to obtain the modified nanofiber membrane.
S3, activating a nanofiber membrane:
And (3) placing the modified nanofiber membrane (4 cm multiplied by 3 cm) prepared in the step (S2) into a silver nitrate solution with the concentration of 1.5g/L for treatment for 30min according to the bath ratio of 1:5, washing off the non-adsorbed Ag + by using deionized water, and drying to obtain the activated nanofiber membrane.
The preparation method of the silver nitrate solution comprises the following steps: 0.15g of silver nitrate is weighed, deionized water is added to dissolve the silver nitrate, and the volume is fixed to 100mL for standby.
S4, plating copper on the nanofiber membrane:
And (3) placing the activated nanofiber membrane (4 cm multiplied by 3 cm) prepared in the step (S3) into an electroless plating solution according to a bath ratio of 1:2, treating for 2 hours at 70 ℃, and carrying out electroless copper plating reaction on the activated nanofiber membrane adsorbed with silver ions, thereby depositing a copper layer on the surface of the PVA-co-PE membrane, and washing and drying to obtain the flexible conductive membrane.
The preparation method of the electroless plating solution comprises the following steps: 16.00g of pentahydrate sulfuric acid, 19.50g of disodium ethylenediamine tetraacetate dihydrate and 14.00g of potassium sodium tartrate are weighed and placed in a beaker, deionized water is added to dissolve the pentahydrate sulfuric acid, then 14.50g of sodium hydroxide is added, and after the pentahydrate sulfuric acid is fully dissolved, 5mL of formaldehyde solution with the concentration of 0.01g of ferrocyanide dihydrate, 0.02g of 2,2' -bipyridine and 37wt% is added to prepare 1000mL for standby.
As shown in the right graph of FIG. 2, the scale of the scanning electron microscope graph of the copper plating film morphology is 10 μm, a compact copper film is formed on the nanofiber film, the electromagnetic shielding performance of the nanofiber film is improved, and the flexible conductive film obtained by the process has good performance.
As shown in the conductivity chart shown in FIG. 3, after copper plating, the conductivity of the nanofiber membrane is improved from 386.3s/cm to 4897.1s/cm, and the conductivity is greatly improved, so that the conductivity effect is good.
As shown in an electromagnetic shielding performance chart (measured by a vector network analyzer) of fig. 4, EMI shielding refers to attenuation caused by absorption or reflection of electromagnetic wave energy by a material, and the larger the attenuation value is, the better the shielding performance is; SE denotes shielding effectiveness of the shielding material; SE (a) represents attenuation of electromagnetic wave energy by absorption of a material; SE (R) represents attenuation of energy of electromagnetic waves caused by reflection of materials; SE (T) represents the total attenuation of the energy of electromagnetic waves by absorption and reflection of the material, i.e. the electromagnetic shielding effectiveness of the material. The graph shows that the electromagnetic shielding effectiveness of the flexible conductive film is up to 58dB, wherein the absorption efficiency is more than 90%, which indicates that the flexible conductive film has good absorption to electromagnetic waves; in addition, it is also described that appropriate amount of holes on the surfaces of the nanofiber membrane and the conductive flexible membrane can increase the reflection process of electromagnetic waves, and simultaneously improve electromagnetic shielding performance from both absorption and reflection aspects.
As shown in the water contact angle diagram of the flexible conductive film shown in fig. 5, the as-received film exhibits hydrophilicity, water can wet the as-received film, and the prepared flexible conductive film is hardly wetted by water, and hydrophobicity is greatly improved, which is of great significance for expanding the application range of electronic components.
Examples 2 to 6
The palladium-free electroless copper plating method for the surface of the flexible nanofiber membrane is different from that of example 1 in that the concentration of the PVA-co-PE nanofiber suspension and the diameter of the PVA-co-PE nanofiber are different in step S1, and the other steps are substantially the same as those of example 1, and are not repeated herein.
The flexible conductive films prepared in examples 1 to 6 were subjected to performance test, and the results are shown in table 1:
TABLE 1 Performance test of Flexible conductive films prepared in examples 1-6
| Examples | Concentration (wt%) | Diameter (nm) | Conductivity (s/cm) | Electromagnetic shielding effectiveness (dB) |
| Example 1 | 1 | 200 | 4897.1 | 58.0 |
| Example 2 | 0.5 | 200 | 3508.7 | 35.6 |
| Example 3 | 3 | 200 | 5107.5 | 60.4 |
| Example 4 | 1 | 50 | 4386.8 | 55.2 |
| Example 5 | 1 | 400 | 5604.2 | 62.7 |
| Example 6 | 1 | 800 | 5237.1 | 61.2 |
As can be seen from table 1, as the diameter of the nanofiber increases, the conductivity and electromagnetic shielding properties of the flexible conductive film both tend to increase and then decrease; as the concentration of the nanofiber suspension increases, the conductivity and electromagnetic shielding of the flexible conductive film both increase.
When the diameter of the nanofiber is smaller (example 4), the fiber film generated after the intersection of different fibers is denser, the holes on the surface of the nanofiber film are more, the roughness of the surface is large, after copper is deposited, a discontinuous copper layer is easy to form on the surface due to the existence of a large number of holes, the conductivity is reduced, and meanwhile, the electromagnetic shielding performance is poor.
Along with the increase of the diameter of the nanofiber (examples 1 and 5), the hole density and the hole diameter of the fiber film are reduced after different fibers are intersected, and deposited copper is easy to cover the holes to form a smooth copper layer, so that the copper film is compact, no rough fault occurs, and the conductivity of the flexible conductive film is better. Meanwhile, the flexible conductive film is compact, so that more electromagnetic waves are absorbed by the flexible conductive film, and in addition, the proper amount of holes in the nanofiber film and the copper plating layer of the conductive film increase the reflection of the flexible conductive film on electromagnetic waves, so that the electromagnetic shielding performance of the flexible conductive film is good.
With further increase in nanofiber diameter (example 6), the pore depth of the nanofiber membrane increased, copper deposition was insufficient to cover the pores and coarser fibers formed ridges, resulting in copper faults, uneven copper distribution of the resulting flexible conductive film, poor conductivity, and further reduced electromagnetic shielding performance.
With the increase of the concentration of the nano fibers, the surface structure of the nano fiber film is influenced, and the conductivity and electromagnetic shielding performance of the conductive film are further influenced. When the concentration is small, the coating is needed for multiple times to achieve the same thickness, the degree of intersection between fibers is increased, so that the nanofiber membrane has multiple holes, a continuous copper layer is not easy to form, and the performance of the flexible conductive film is deteriorated; when the concentration is high, the surface of the nanofiber membrane is smoother, so that a continuous copper layer is easy to form, and the performance of the flexible conductive membrane is improved.
Examples 7 to 11
The difference between the electroless palladium plating method for the surface of the flexible nanofiber membrane and the method for electroless palladium plating in example 1 is that the plasma treatment time and the concentration of the acrylic acid solution in step S2 are different, and the other steps are substantially the same as those in example 1, and are not described in detail.
The flexible conductive films prepared in examples 7 to 11 were subjected to performance test, and the results are shown in table 2:
TABLE 2 Performance test of Flexible conductive films prepared in examples 7-11
| Examples | Time (min) | Concentration (wt%) | Conductivity (s/cm) | Electromagnetic shielding effectiveness (dB) |
| Example 1 | 5 | 10 | 4897.1 | 58.0 |
| Example 7 | 2 | 10 | 4302.4 | 52.6 |
| Example 8 | 10 | 10 | 4985.2 | 59.4 |
| Example 9 | 20 | 10 | 4632.7 | 55.8 |
| Example 10 | 5 | 5 | 4536.8 | 54.4 |
| Example 11 | 5 | 20 | 5243.7 | 60.4 |
As can be seen from table 2, the conductivity and electromagnetic shielding performance of the flexible conductive film increased and then decreased with the increase of the plasma treatment time. The method is mainly characterized in that along with the lengthening of the plasma treatment time, the etching degree of the surface of the nanofiber membrane is increased, the roughness is increased, more attachment sites are provided for acrylic acid, the hydroxyl exposed on the surface is increased, more binding sites are further provided for acrylic acid, so that the acrylic acid is uniformly bonded on the surface of the nanofiber membrane, conditions are provided for the subsequent grafting of silver ions, and further, the copper deposition of the conductive membrane is more uniform and compact, so that the conductivity performance of the conductive membrane is better; the surface structure of the nanofiber membrane is changed by plasma treatment, and the special surface structure of the nanofiber membrane and the uniform and compact copper plating layer of the conductive membrane lead the electromagnetic shielding performance of the nanofiber membrane to be better. The plasma treatment time is too long, and the nanofiber membrane has a special pore structure, so that the original structure of the nanofiber membrane can be damaged by long-time etching, and the performance of the final flexible conductive membrane is poor.
The conductivity and electromagnetic shielding performance of the flexible conductive film are increased with the increase of the concentration of the acrylic acid solution, and then are basically unchanged. Because, as the concentration of the acrylic acid solution increases, the amount of acrylic acid grafted on the surface of the nanofiber membrane increases, more binding sites are provided for silver ions, copper is uniformly and densely deposited on the surface of the nanofiber membrane, and the performance of the nanofiber membrane is better. However, as the concentration of the acrylic acid solution is further increased, on one hand, more acrylic acid cannot be grafted on the surface of the nanofiber membrane due to steric hindrance, on the other hand, silver ions are only used as a catalyst to promote the copper plating reaction, and the process does not need to consume too much silver ions, so that the copper finally deposited on the surface of the nanofiber membrane is basically unchanged, and the performance of the nanofiber membrane tends to be stable.
Examples 12 to 14
The difference between the electroless palladium plating method and the electroless palladium plating method of the flexible nanofiber membrane is that the electroless palladium plating time is different in step S4 compared with the electroless palladium plating method of the embodiment 1, and the other steps are substantially the same as those of the embodiment 1, and are not repeated here.
The flexible conductive films prepared in examples 12 to 14 were subjected to performance test, and the results are shown in table 3:
TABLE 3 Performance test of Flexible conductive films prepared in examples 12-14
| Examples | Time (h) | Conductivity (s/cm) | Electromagnetic shielding effectiveness (dB) |
| Example 1 | 2 | 4897.1 | 58.0 |
| Example 12 | 1 | 3824.1 | 43.7 |
| Example 13 | 3 | 5046.2 | 60.5 |
| Example 14 | 4 | 5085.7 | 60.6 |
As can be seen from table 3, as the copper plating time increases, both the conductivity and the electromagnetic shielding performance of the flexible conductive film increase, and the increase in conductivity indicates that the copper deposited on the nanofiber surface increases continuously as the copper plating time increases; the increased electromagnetic shielding performance indicates that the structure of the nanofiber membrane and the structure of the copper plating layer of the conductive membrane achieve better synergistic effect.
However, after the copper plating time is increased to a certain extent, the conductivity and electromagnetic shielding properties of the flexible conductive film tend to be substantially stable as the copper plating time is increased.
Comparative example 1
Compared with the embodiment 1, the PVA-co-PE film has a different structure, is prepared into a film with the same thickness as the embodiment 1 by a high-temperature die pressing method, and is pressed on a polyethylene non-woven fabric, and other materials are approximately the same as the embodiment 1, and are not repeated.
The conductivity of the obtained flexible conductive film is 500s/cm, the electromagnetic shielding performance is 5.6dB, the conductivity and the electromagnetic shielding performance are obviously poor, and the PVA-co-PE film prepared in comparative example 1 has no aperture and porosity with special structures, has a single film surface structure, and has poor performance.
In summary, the invention provides a palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane, which is characterized in that a polyvinyl alcohol-ethylene copolymer nanofiber suspension is uniformly sprayed on the surface of a substrate, so that different degrees of crosslinking between single fibers occur to form a nanofiber membrane with a special structure; the PVA-co-PE nanofiber membrane surface contains abundant high-activity hydroxyl groups, so that the surface polarity and the surface energy of the PVA-co-PE nanofiber membrane can be effectively increased. The special surface structure of the PVA-co-PE nanofiber membrane provides a larger specific surface and higher activity for plasma treatment, so that the plasma modification treatment is more sufficient. The PVA-co-PE nanofiber membrane modified by the plasma can provide a rougher surface and more binding sites, so that the surface of the nanofiber membrane is uniformly grafted with high-activity carboxyl through chemical bonds. The existence of carboxyl makes silver ions uniformly grafted on the surface of the nanofiber membrane through coordination, provides an active center for copper plating reaction, and makes the finally produced flexible conductive membrane compact and uniform and excellent in performance. The method is simple to operate, the process is easy to control, economical and environment-friendly, large-scale industrial production is easy to realize, and the obtained flexible conductive film has excellent bending resistance; the conductivity is high, the surface resistance is low, and the conductor level is reached; the electromagnetic shielding performance is better; the hydrophobicity is strong.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. A palladium-free electroless copper plating method for the surface of a flexible nanofiber membrane is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a nanofiber membrane: uniformly spraying a polyvinyl alcohol-ethylene copolymer nanofiber suspension with the concentration of 0.5-3.0 wt% on the surface of a substrate subjected to pre-washing treatment, and drying to form a film to obtain a nanofiber membrane; the substrate comprises one or more of polyethylene non-woven fabrics and polypropylene non-woven fabrics; the diameter of the polyvinyl alcohol-ethylene copolymer nanofiber is 50nm-800nm;
s2, modifying a nanofiber membrane: the nanofiber membrane prepared in the step S1 is subjected to plasma treatment, immersed into an acrylic acid aqueous solution with the concentration of 5-20wt% according to the bath ratio of 1:2-1:5, washed and dried to obtain a modified nanofiber membrane; the duration of the plasma treatment is 2-20min; the duration of the treatment in the acrylic acid aqueous solution is 2-12h; the surface of the nanofiber membrane contains high-activity hydroxyl, and the nanofiber membrane is uniformly grafted with high-activity carboxyl through chemical bonds;
S3, activating a nanofiber membrane: placing the modified nanofiber membrane prepared in the step S2 into a silver nitrate solution for treatment for 20-50min according to the bath ratio of 1:1-1:8, and washing and drying to obtain an activated nanofiber membrane;
S4, plating copper on the nanofiber membrane: placing the activated nanofiber membrane prepared in the step S3 into an electroless plating solution according to a bath ratio of 1:1-1:5, treating for 1-3h at 60-80 ℃, and washing and drying to obtain a flexible conductive membrane; the conductivity of the flexible conductive film is up to 4897.1s/cm, the electromagnetic shielding efficiency is up to 58dB, and the absorption efficiency is up to more than 90%.
2. The palladium-free electroless copper plating method for a flexible nanofiber membrane surface according to claim 1, wherein: the pre-washing treatment of the substrate in the step S1 is that the substrate is placed in a solution of a detergent, sodium carbonate and deionized water in a mass ratio of 1:3:1000, treated in a water bath at 80 ℃ for 1h, taken out, washed with deionized water to be neutral, and dried at 60 ℃ for 1h.
3. The palladium-free electroless copper plating method for a flexible nanofiber membrane surface according to claim 1, wherein: the concentration of the silver nitrate solution in the step S3 is 1-2g/L.
4. The palladium-free electroless copper plating method for a flexible nanofiber membrane surface according to claim 1, wherein: the chemical plating solution in the step S4 is a mixed solution composed of copper sulfate pentahydrate, disodium ethylenediamine tetraacetate dihydrate, sodium potassium tartrate, sodium hydroxide, potassium ferrocyanide dihydrate, 2' -bipyridine and 37wt% formaldehyde.
5. The palladium-free electroless copper plating method for a flexible nanofiber membrane surface according to claim 4, wherein: in the chemical plating solution, the concentration of each substance is 16g/L of copper sulfate pentahydrate, 19.5g/L of disodium ethylenediamine tetraacetate dihydrate, 14g/L of potassium sodium tartrate, 14.5g/L of sodium hydroxide, 0.01g/L of potassium ferrocyanide dihydrate, 0.02g/L of 2,2' -bipyridine and 5mL/L of 37wt% formaldehyde.
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