CN114411414A - Palladium-free chemical copper plating method for surface of flexible nanofiber membrane - Google Patents
Palladium-free chemical copper plating method for surface of flexible nanofiber membrane Download PDFInfo
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- CN114411414A CN114411414A CN202210078721.9A CN202210078721A CN114411414A CN 114411414 A CN114411414 A CN 114411414A CN 202210078721 A CN202210078721 A CN 202210078721A CN 114411414 A CN114411414 A CN 114411414A
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- nanofiber membrane
- copper plating
- flexible
- palladium
- membrane
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 166
- 239000012528 membrane Substances 0.000 title claims abstract description 152
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 81
- 239000010949 copper Substances 0.000 title claims abstract description 81
- 238000007747 plating Methods 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000000126 substance Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 33
- 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
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000011282 treatment Methods 0.000 claims abstract description 21
- 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 19
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 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 5
- -1 potassium ferrocyanide dihydrate Chemical class 0.000 claims description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 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 15
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 238000009832 plasma treatment Methods 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 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
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 8
- 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
- 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 6
- 230000004913 activation Effects 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
- 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 5
- 239000003599 detergent Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 238000007772 electroless plating Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- PBKADZMAZVCJMR-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;dihydrate Chemical compound O.O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O PBKADZMAZVCJMR-UHFFFAOYSA-N 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 150000001879 copper Chemical class 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 description 13
- 239000004332 silver Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001994 activation Methods 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- ZNVNXKULFRSTGD-UHFFFAOYSA-N sulfuric acid pentahydrate Chemical compound S(=O)(=O)(O)O.O.O.O.O.O.S(=O)(=O)(O)O ZNVNXKULFRSTGD-UHFFFAOYSA-N 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
- 238000012369 In process control Methods 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- AWOPBNHMACSMTO-UHFFFAOYSA-N copper;sodium Chemical compound [Na+].[Cu+2] AWOPBNHMACSMTO-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 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
- 238000010965 in-process control Methods 0.000 description 1
- 239000003999 initiator Substances 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 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
- 229920000642 polymer 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
- 230000002035 prolonged effect Effects 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
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 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
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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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract
The invention provides a palladium-free chemical copper plating method for the surface of a flexible nanofiber membrane, which comprises the following steps: uniformly spraying polyvinyl alcohol-ethylene copolymer nanofiber suspension with the concentration of 0.5-3.0 wt% on the surface of a base material, and drying to obtain a nanofiber membrane; treating the obtained nanofiber membrane by plasma, immersing the nanofiber membrane into an acrylic acid aqueous solution with the concentration of 5-20 wt%, washing and drying to obtain a modified nanofiber membrane; placing the obtained modified nanofiber membrane in a silver nitrate solution for treatment for 20-50min, and washing and drying to obtain an activated nanofiber membrane; and (3) placing the activated nanofiber membrane in a chemical plating solution, treating for 1-3h at 60-80 ℃, washing and drying to obtain the flexible conductive membrane. According to the invention, the nanofiber membrane with a special structure is subjected to modification treatment, so that acrylic acid is uniformly combined on the surface of the nanofiber membrane, and the flexible conductive membrane obtained through activated copper plating treatment has excellent performance.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a palladium-free chemical copper plating method for the surface of a flexible nanofiber membrane.
Background
With the rapid development of electronic technology, copper clad laminate is used as the most basic material of PCB, and the demand of high performance flexible copper clad laminate is increased remarkably. The copper-clad plate is a composite material consisting of metal copper and high molecules and is mainly prepared by pressing, coating, vacuum sputtering, chemical copper plating and other modes.
The polymer is generally selected from polyester, polyimide, polyolefin, etc. The polyvinyl alcohol-ethylene copolymer (PVA-co-PE) film has excellent performances of large specific surface area, high porosity, tortuous pore structure, high filtering precision and the like, and the flexible nanofiber copper-coated 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, the 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 through the chemical modification of a conventional sodium-naphthalene tetrahydrofuran solution, substances damaging the environment are generated in the modification process, and the operation risk index is high; although the high-energy radiation grafting modification method has the advantages of easily controllable grafting rate, no need of an initiator and the like, the radiation amount is not easily controlled, and uncontrollable damage is easily caused to the physical and chemical properties of the material. In the electroless copper plating process, the traditional catalyst is a palladium catalyst, and the cost is high in practical application due to the high price of palladium, so that the current report that the palladium catalyst is replaced by a silver catalyst is provided.
The patent with the application number of CN201610899123.2 discloses a palladium-free electroless copper plating method for the surface of a polytetrafluoroethylene material, which introduces a large amount of carboxyl on the surface of the polytetrafluoroethylene material by means of low-temperature plasma grafting modification, and firmly bonds a plated copper layer with the surface of the material through chemical bonds. The polytetrafluoroethylene material used in the method has extremely low surface energy and single film structure, the modification effect is poor through low-temperature plasma modification treatment, and the problems of non-uniform carboxyl and low bonding strength of the activated polytetrafluoroethylene material when carboxyl is introduced again exist, so that the final product has non-uniform copper plating, poor conductivity and poor electromagnetic shielding property.
In view of the above, there is a need to design an improved method for electroless copper plating on the surface of flexible nanofiber membrane without palladium to solve the above problems.
Disclosure of Invention
The invention aims to provide a palladium-free chemical copper plating method for the surface of a flexible nanofiber membrane, which solves the problems of uneven copper plating, poor conductivity, poor electromagnetic shielding property, easy falling of a plating layer and the like in the existing chemical copper plating process.
In order to realize the aim, 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 polyvinyl alcohol-ethylene copolymer nanofiber suspension with the concentration of 0.5-3.0 wt% on the surface of a base material which is washed in advance, and drying to form a film to obtain a nanofiber film;
s2, modifying the nanofiber membrane: treating the nanofiber membrane prepared in the step S1 by using plasma, immersing the nanofiber membrane into an acrylic acid aqueous solution with the concentration of 5 wt% -20 wt% according to the bath ratio of 1:2-1:5 for treatment, and washing and drying to obtain a modified nanofiber membrane;
s3, activation of the nanofiber membrane: treating the modified nanofiber membrane prepared in the step S2 in a silver nitrate solution for 20-50min according to a bath ratio of 1:1-1:8, and washing and drying to obtain an activated nanofiber membrane;
s4, copper plating of the nanofiber membrane: and (3) placing the activated nanofiber membrane prepared in the step S3 in a chemical plating solution according to a bath ratio of 1:1-1:5, treating at 60-80 ℃ for 1-3h, washing and drying to obtain the flexible conductive membrane.
As a further improvement of the invention, the diameter of the polyvinyl alcohol-ethylene copolymer nano-fiber in the step S1 is 50nm-800 nm.
As a further improvement of the invention, the plasma treatment time in the step S2 is 2min-20 min.
As a further development of the invention, the treatment time in the aqueous acrylic acid solution is from 2 to 12 h.
As a further improvement of the invention, the pre-washing treatment of the substrate in the step S1 is that the substrate is put into a solution of detergent, sodium carbonate and deionized water with the mass ratio of 1:3:1000, treated in a water bath at 80 ℃ for 1h, taken out, washed to be neutral by deionized water, and dried at 60 ℃ for 1 h.
As a further improvement of the invention, the concentration of the silver nitrate solution in the step S3 is 1-2 g/L.
As a further improvement of the invention, the electroless plating solution in step S4 is a mixed solution of copper sulfate pentahydrate, disodium ethylene diamine tetraacetate dihydrate, sodium potassium tartrate, sodium hydroxide, potassium ferrocyanide dihydrate, 2' -bipyridine and 37 wt% of formaldehyde.
As a further improvement of the invention, the chemical plating solution has the concentrations of 16g/L of blue vitriol, 19.5g/L of disodium ethylene diamine tetraacetate dihydrate, 14g/L of sodium potassium 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 37 wt% formaldehyde.
As a further improvement of the invention, the conductivity of the flexible conductive film is as high as 4897.1s/cm, the electromagnetic shielding efficiency is as high as 58dB, and the absorption efficiency is more than 90%.
As a further improvement of the present invention, the base material in step S1 includes one or more of polyethylene nonwoven fabric and polypropylene nonwoven fabric.
The invention has the beneficial effects that:
(1) the invention provides a palladium-free chemical copper plating method for the surface of a flexible nanofiber membrane, which is characterized in that polyvinyl alcohol-ethylene copolymer nanofibers are prepared into a polyvinyl alcohol-ethylene copolymer nanofiber suspension and are uniformly sprayed on the surface of a base material, so that cross-linking of single fibers occurs in different degrees, and the nanofiber membrane with special pore diameter, pore and pore channel structures is formed; on the other hand, the PVA-co-PE nanofiber membrane contains abundant high-activity hydroxyl on the surface, and can effectively increase the surface polarity and the surface energy. 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 plasma modified PVA-co-PE nanofiber membrane can provide a rougher surface and more binding sites, so that high-activity carboxyl groups are uniformly grafted on the surface of the nanofiber membrane through chemical bonds. The existence of carboxyl enables silver ions to be uniformly grafted on the surface of the nanofiber membrane through coordination, so as to provide an active center for copper plating reaction, and the finally generated flexible conductive membrane is compact and uniform, has high conductivity and low surface resistance, reaches the conductor level, and has excellent conductivity and electromagnetic shielding performance.
(2) The invention provides a palladium-free chemical copper plating method for the surface of a flexible nanofiber membrane, wherein the nanofiber membrane is taken 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 the conventional electronic copper-clad plate is solved; the plasma induced grafting method is adopted, so that the pollution is avoided, the operation is easy, the cost is low, and the problem that the conductor film material for the electrons is difficult to popularize due to the cost is solved; the microporous structure of the nanofiber membrane and the copper-plated layer on the surface enable the material to have excellent electromagnetic shielding performance, and the problem of mutual interference among electronic elements is solved; because the surface of the flexible nanofiber membrane is plated with the copper conducting material, the hydrophobicity is improved, and the method has important significance for expanding the application range of electronic elements.
(3) The invention provides a palladium-free chemical copper plating method for the surface of a flexible nanofiber membrane, which does not use traditional palladium catalysis, adopts silver catalysis, and is simple in operation, easy in process control, economic, environment-friendly and easy for large-scale industrial production.
Drawings
FIG. 1 is a flow chart of the palladium-free electroless copper plating method on the surface of the flexible nanofiber membrane of the present invention.
Fig. 2 is a scanning electron microscope image of the flexible conductive film and the nanofiber film substrate prepared in example 1.
Fig. 3 is a graph of the conductivity of the flexible conductive film prepared in example 1.
Fig. 4 is a graph of electromagnetic shielding performance of the flexible conductive film prepared in example 1.
Fig. 5 is a water contact angle diagram 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 with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be 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 present invention provides a method for electroless copper plating on a surface of a flexible nanofiber membrane without palladium, comprising the following steps:
s1, preparing a nanofiber membrane:
placing the base material into a solution of a detergent, sodium carbonate and deionized water in a mass ratio of 1:3:1000, performing water bath treatment for 1h at 80 ℃, taking out the base material, cleaning the base material to be neutral by using the deionized water, and drying the base material for 1h at 60 ℃ to obtain the base material which is subjected to washing treatment in advance. 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 base material comprises one or more of polyethylene non-woven fabrics and polypropylene non-woven fabrics.
Preparing polyvinyl alcohol-ethylene copolymer nano-fibers with the diameter of 50nm-800nm into polyvinyl alcohol-ethylene copolymer nano-fiber suspension with the concentration of 0.5 wt% -3.0 wt%, uniformly spraying the suspension on the surface of a base material which is washed in advance, and forming a layer of PVA-co-PE film on the surface of the base material after drying to obtain the nano-fiber film.
S2, modifying the nanofiber membrane:
and (4) treating the nanofiber membrane prepared in the step S1 by using plasma for 2-20min, immersing the nanofiber membrane into an acrylic acid aqueous solution with the concentration of 5 wt% -20 wt% for treatment for 2-12h according to the bath ratio of 1:2-1:5, and washing and drying to obtain the modified nanofiber membrane.
The PVA-co-PE nanofiber membrane has a microporous structure, the specific surface area is large, the porosity is high, and the pore structure is tortuous; in addition, the PVA-co-PE nanofiber membrane contains abundant high-activity hydroxyl on the surface, and the polar group hydroxyl can effectively increase the surface polarity and the surface energy. 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. And in the plasma treatment process, the PVA-co-PE nanofiber membrane is etched, so that not only can the roughness of the surface be increased, the specific surface area of the PVA-co-PE nanofiber membrane be further increased, but also 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 treated by plasma 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 of the nanofiber membrane and the increase of the surface hydroxyl content, and abundant hydroxyl groups in PVA-co-PE molecules are bonded with carboxyl groups in acrylic acid molecules through hydrogen bonds, and finally a large amount of acrylic acid is firmly bonded on the surface of the nanofiber membrane to obtain the modified nanofiber membrane. A large number of polar groups of carboxyl can further improve the surface polarity and the surface energy of the nanofiber membrane, so that the chemical activity of the modified nanofiber membrane is greatly improved.
In addition, the PVA-co-PE molecules contain hydrophilic polyvinyl alcohol, and the acrylic acid liquid is a hydrophilic substance; and the PVA-co-PE membrane has a porous structure, so that a large amount of acrylic acid is further grafted on the surface of the nanofiber membrane.
S3, activation of the nanofiber membrane:
and (3) placing the modified nanofiber membrane prepared in the step S2 in a silver nitrate solution with the concentration of 1-2g/L for treatment for 20-50min according to the bath ratio of 1:1-1:8, and washing and drying to obtain the activated nanofiber membrane.
In the process, silver ions and carboxylate radicals in acrylic acid generate coordination (electrostatic) effect, so that the silver ions are firmly loaded 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 chemical plating.
S4, copper plating of the nanofiber membrane:
and (2) placing the activated nanofiber membrane prepared in the step S3 in a chemical plating solution according to a bath ratio of 1:1-1:5, treating for 1-3h at 60-80 ℃, performing chemical copper plating reaction on the activated nanofiber membrane adsorbing silver ions, depositing a copper layer on the surface of the PVA-co-PE nanofiber membrane, washing and drying to obtain the flexible conductive membrane.
Wherein, the chemical plating solution comprises the following components in percentage by concentration: 16g/L of copper sulfate pentahydrate, 19.5g/L of disodium ethylene diamine 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 37 wt% 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 ethylene diamine tetraacetate dihydrate can form a complex with copper ions, so that long-term stable conditions are provided for the copper ions; formaldehyde can reduce bivalent copper ions into metallic copper; sodium hydroxide provides a suitable pH for the reduction reaction; the potassium ferrocyanide dihydrate can properly control the reduction speed, and prevent the failure of the plating solution caused by the violent decomposition of the plating solution; 2,2' -bipyridine is used as a brightening agent to ensure that the surface of the finally obtained copper plating layer is bright.
In the presence of silver ion catalyst, copper ions are reduced into metallic copper by formaldehyde, and when the metallic copper begins to deposit on the surface, the copper layer can be used as catalyst for further reaction to play a catalytic role, so that the electroless copper plating can be continued.
The invention is described in detail below by means of a number of examples:
example 1
A palladium-free chemical copper plating method for the surface of a flexible nanofiber membrane comprises the following steps:
s1, preparing a nanofiber membrane:
placing the flexible polyethylene non-woven fabric substrate in a solution with the mass ratio of detergent to sodium carbonate to deionized water being 1:3:1000, carrying out water bath treatment for 1h at 80 ℃, taking out the polyethylene non-woven fabric, washing the polyethylene non-woven fabric with deionized water to be neutral, and drying the polyethylene non-woven fabric for 1h at 60 ℃ to obtain the pre-washed flexible polyethylene non-woven fabric.
Preparing PVA-co-PE nano-fibers with the diameter of 200nm into PVA-co-PE nano-fiber suspension with the concentration of 1 wt%, uniformly spraying the suspension on the surface of a flexible polyethylene non-woven fabric which is washed in advance, drying, and forming a layer of PVA-co-PE porous nano-fiber film on the surface of the polyethylene non-woven fabric to obtain a nano-fiber film, wherein the thickness of the obtained nano-fiber film is 50 mu m.
As shown in the left picture in FIG. 2, the scanning electron microscope picture of the original film appearance has a ruler of 5 μm, PVA-co-PE nano fibers are mutually crosslinked, and uniform pores exist, so that conditions are provided for subsequent plasma treatment and acrylic acid grafting.
Because similar polyethylene segments exist in the PVA-co-PE molecules and the polyolefin molecules, the PVA-co-PE molecules and the polyolefin molecules are arranged orderly, and the binding force of the PVA-co-PE molecules and the polyolefin molecules is strong, the PVA-co-PE nanofiber membrane is firmly coated on the surface of the polyolefin non-woven fabric.
S2, modifying the nanofiber membrane:
and (4) treating the nanofiber membrane prepared in the step S1 by using plasma for 5min, immersing the nanofiber membrane into 10 wt% acrylic acid aqueous solution according to the bath ratio of 1:2 for treatment for 10h, and washing and drying to obtain the modified nanofiber membrane.
S3, activation of the nanofiber membrane:
treating the modified nanofiber membrane (4cm multiplied by 3cm) prepared in the step S2 in silver nitrate solution with the concentration of 1.5g/L for 30min according to the bath ratio of 1:5, and washing the unadsorbed Ag by 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 determined to be 100mL for standby.
S4, copper plating of the nanofiber membrane:
and (3) placing the activated nanofiber membrane (4cm multiplied by 3cm) prepared in the step S3 in a chemical plating solution according to the bath ratio of 1:2, treating for 2h at 70 ℃, carrying out chemical copper plating reaction on the activated nanofiber membrane adsorbing silver ions, depositing a copper layer on the surface of the PVA-co-PE membrane, washing and drying to obtain the flexible conductive membrane.
The preparation method of the chemical plating solution comprises the following steps: 16.00g of sulfuric acid pentahydrate, 19.50g of disodium ethylene diamine tetraacetate dihydrate and 14.00g of potassium sodium tartrate are weighed and placed in a beaker, deionized water is added to dissolve the sulfuric acid pentahydrate, 14.50g of sodium hydroxide is added, 0.01g of potassium ferrocyanide dihydrate, 0.02g of 2,2' -bipyridine and 5mL of 37 wt% formaldehyde solution are added after the potassium ferrocyanide dihydrate is fully dissolved, and the mixture is prepared to 1000mL for later use.
As shown in the right picture in figure 2, the scanning electron microscope picture of the appearance of the copper-plated film has a ruler of 10 microns, and a compact copper film is formed on the nanofiber film to improve the electromagnetic shielding performance of the copper-plated film, which indicates that the flexible conductive film obtained by the process has better performance.
As shown in the conductivity chart of 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, which shows that the conductivity effect is good.
As shown in the electromagnetic shielding performance diagram (measured by a vector network analyzer) of fig. 4, EMI shielding refers to attenuation caused by absorption or reflection of energy of electromagnetic waves by a material, and the larger the attenuation value is, the better the shielding performance is; SE represents the shielding effectiveness of the shielding material; se (a) represents attenuation of electromagnetic wave energy by absorption by a material; se (r) represents attenuation of energy of the electromagnetic wave by reflection by the material; se (t) represents the total attenuation of the energy of the electromagnetic wave by absorption and reflection by the material, i.e. the electromagnetic shielding effectiveness of the material. As can be seen from the figure, the electromagnetic shielding effectiveness of the flexible conductive film is as high as 58dB, wherein the absorption efficiency is more than 90%, which shows that the obtained flexible conductive film has good absorption on electromagnetic waves; in addition, the 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 the electromagnetic shielding performance is improved from the two aspects of absorption and reflection.
As shown in the water contact angle diagram of the flexible conductive film shown in fig. 5, the original film is hydrophilic, water can wet the original film, and the prepared flexible conductive film is difficult to wet by water, so that the hydrophobicity is greatly improved, which is of great significance for expanding the application range of electronic devices.
Examples 2 to 6
Compared with the method in the embodiment 1, the difference of the electroless copper plating method without palladium on the surface of the flexible nanofiber membrane is that in the step S1, the concentration of the PVA-co-PE nanofiber suspension and the diameter of the PVA-co-PE nanofiber are different, and the rest is substantially the same as the embodiment 1, and the description is omitted.
The flexible conductive films prepared in examples 1 to 6 were subjected to performance tests, and the results are shown in table 1:
table 1 performance testing 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, both the conductivity and the electromagnetic shielding performance of the flexible conductive film tend to increase and then decrease; as the concentration of the nanofiber suspension is increased, the conductivity and the electromagnetic shielding performance of the flexible conductive film are increased.
When the diameter of the nanofiber is small (embodiment 4), a fiber film generated after intersection of different fibers is compact, and the number of holes on the surface of the nanofiber film is large, so that the roughness of the surface is large, after copper is deposited, a discontinuous copper layer is easily formed on the surface due to the existence of a large number of holes, so that the conductivity is reduced, and meanwhile, the electromagnetic shielding performance is poor.
With the increase of the diameter of the nano-fiber (examples 1 and 5), the pore density and the pore diameter of the fiber membrane are reduced after intersection of different fibers, and deposited copper easily covers the pores to form a flat copper layer, so that the copper membrane is compact, a rough fault cannot occur, and the conductivity of the flexible conductive membrane is better. Meanwhile, the flexible conductive film is compact, so that more electromagnetic waves are absorbed by the flexible conductive film, and the reflection of the flexible conductive film on the electromagnetic waves is increased due to the proper amount of holes in the nanofiber film and the copper-plated layer of the conductive film, so that the flexible conductive film has better electromagnetic shielding performance.
With the further increase of the diameter of the nanofiber (example 6), the depth of the hole of the nanofiber membrane is increased, the deposited copper is not enough to cover the hole, and the thicker fiber forms a bulge, so that a copper fault is caused, the copper distribution of the finally obtained flexible conductive membrane is not uniform, the conductivity is poor, and the electromagnetic shielding performance of the flexible conductive membrane is further weakened.
With the increase of the concentration of the nano-fiber, the surface structure of the nano-fiber film is affected, and further the conductivity and the electromagnetic shielding performance of the conductive film are affected. When the concentration is small, in order to reach the same thickness, multiple times of coating are needed, the intersection degree between fibers is increased, so that the nano fiber film has more holes and is difficult to form a continuous copper layer, and the performance of the flexible conductive film is deteriorated; when the concentration is high, the more flat the surface of the nanofiber membrane is, the more easily a continuous copper layer is formed, and the performance of the flexible conductive membrane becomes better.
Examples 7 to 11
Compared with the method in the embodiment 1, the difference of the electroless copper plating method without palladium on the surface of the flexible nanofiber membrane is that in the step S2, the plasma treatment time and the concentration of the acrylic acid solution are different, and the rest is substantially the same as the embodiment 1, and the description is omitted.
The flexible conductive films prepared in examples 7 to 11 were subjected to performance tests, and the results are shown in table 2:
table 2 performance testing 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, as the plasma treatment time is prolonged, the conductivity and the electromagnetic shielding performance of the flexible conductive film are increased first and then decreased. The etching degree and the roughness of the surface of the nanofiber membrane are increased along with the lengthening of the plasma treatment time, so that more attachment sites are provided for acrylic acid, the hydroxyl exposed on the surface is increased, more binding sites are further provided for the acrylic acid, the acrylic acid is uniformly bonded on the surface of the nanofiber membrane, conditions are provided for the subsequent grafting of silver ions, and the copper deposition of a conductive membrane is more uniform and compact, so that the conductivity performance of the conductive membrane is better; the plasma treatment changes the surface structure of the nanofiber membrane, and the special surface structure of the nanofiber membrane and the uniform and compact copper-plated layer of the conductive membrane ensure that the electromagnetic shielding performance of the nanofiber membrane is better. The plasma treatment time is too long, and the original structure of the nanofiber membrane can be damaged by long-time etching due to the fact that the nanofiber membrane has a special pore structure, so that the performance of the final flexible conductive membrane is poor.
Along with the increase of the concentration of the acrylic acid solution, the conductivity and the electromagnetic shielding performance of the flexible conductive film are firstly increased and then basically unchanged. As the concentration of the acrylic acid solution is increased, the number of acrylic acid grafted on the surface of the nanofiber membrane is increased, more binding sites are provided for silver ions, and further copper is uniformly and compactly deposited on the surface of the nanofiber membrane, so that 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, and on the other hand, silver ions are only used as a catalyst to promote copper plating reaction, and the process does not need to consume too many silver ions, so that 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
Compared with the method in the embodiment 1, the difference of the electroless palladium copper plating method on the surface of the flexible nanofiber membrane is that the copper plating time is different in the step S4, and the rest is substantially the same as that in the embodiment 1, and the description is omitted.
The flexible conductive films prepared in examples 12 to 14 were subjected to performance tests, and the results are shown in table 3:
table 3 performance testing 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 surface of the nanofiber continuously increases as the copper plating time increases; the increase of the electromagnetic shielding performance shows that the structure of the nanofiber membrane and the structure of the conductive membrane copper-plated layer achieve better synergistic effect.
However, after the copper plating time is increased to a certain degree, the conductivity and the electromagnetic shielding performance of the flexible conductive film basically tend to be stable along with the increase of the copper plating time.
Comparative example 1
Compared with the example 1, the difference of the electroless copper plating method without palladium on the surface of the PVA-co-PE film is that the PVA-co-PE film has a different structure, the film with the thickness same as that of the example 1 is prepared by a high-temperature mould pressing method, and then the film is pressed on the polyethylene non-woven fabric, and the rest is substantially the same as the example 1, and the details are not repeated.
The conductivity of the obtained flexible conductive film is 500s/cm, the electromagnetic shielding performance is 5.6dB, and the conductivity and the electromagnetic shielding performance are obviously poor, which shows that the PVA-co-PE film prepared in the comparative example 1 has no pore diameter and porosity of a special structure, and the surface structure of the film is single, so that the finally obtained flexible conductive film has poor performance.
In conclusion, the invention provides a palladium-free chemical 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 base material, so that cross-linking of single fibers occurs to different degrees, and the nanofiber membrane with a special structure is formed; and the PVA-co-PE nanofiber membrane has rich high-activity hydroxyl on the surface, and can effectively increase the surface polarity and the surface energy. 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 plasma modified PVA-co-PE nanofiber membrane can provide a rougher surface and more binding sites, so that high-activity carboxyl groups are uniformly grafted on the surface of the nanofiber membrane through chemical bonds. The existence of carboxyl enables silver ions to be uniformly grafted on the surface of the nanofiber membrane through coordination, so as to provide an active center for copper plating reaction, and the finally generated flexible conductive membrane is compact and uniform and has excellent performance. The method is simple to operate, the process is easy to control, the method is economic 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 level of a conductor is reached; the electromagnetic shielding performance is better; the hydrophobicity is strong.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A palladium-free chemical 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 polyvinyl alcohol-ethylene copolymer nanofiber suspension with the concentration of 0.5-3.0 wt% on the surface of a base material which is washed in advance, and drying to form a film to obtain a nanofiber film;
s2, modifying the nanofiber membrane: treating the nanofiber membrane prepared in the step S1 by using plasma, immersing the nanofiber membrane into an acrylic acid aqueous solution with the concentration of 5 wt% -20 wt% according to the bath ratio of 1:2-1:5 for treatment, and washing and drying to obtain a modified nanofiber membrane;
s3, activation of the nanofiber membrane: treating the modified nanofiber membrane prepared in the step S2 in a silver nitrate solution for 20-50min according to a bath ratio of 1:1-1:8, and washing and drying to obtain an activated nanofiber membrane;
s4, copper plating of the nanofiber membrane: and (3) placing the activated nanofiber membrane prepared in the step S3 in a chemical plating solution according to a bath ratio of 1:1-1:5, treating at 60-80 ℃ for 1-3h, washing and drying to obtain the flexible conductive membrane.
2. The method for palladium-free electroless copper plating on the surface of the flexible nanofiber membrane as claimed in claim 1, wherein the method comprises the following steps: the diameter of the polyvinyl alcohol-ethylene copolymer nanofiber in the step S1 is 50nm-800 nm.
3. The method for palladium-free electroless copper plating on the surface of the flexible nanofiber membrane as claimed in claim 1, wherein the method comprises the following steps: the duration of the plasma treatment in step S2 is 2-20 min.
4. The method for palladium-free electroless copper plating on the surface of the flexible nanofiber membrane as claimed in claim 1, wherein the method comprises the following steps: the time period for the treatment in the acrylic acid aqueous solution in step S2 is 2-12 h.
5. The method for palladium-free electroless copper plating on the surface of the flexible nanofiber membrane as claimed in claim 1, wherein the method comprises the following steps: the pre-washing treatment of the base material in the step S1 is to place the base material in a solution of detergent, sodium carbonate and deionized water in a mass ratio of 1:3:1000, perform water bath treatment for 1h at 80 ℃, take out the base material, wash the base material to be neutral with deionized water, and dry the base material for 1h at 60 ℃.
6. The method for palladium-free electroless copper plating on the surface of the flexible nanofiber membrane as claimed in claim 1, wherein the method comprises the following steps: the concentration of the silver nitrate solution in the step S3 is 1-2 g/L.
7. The method for palladium-free electroless copper plating on the surface of the flexible nanofiber membrane as claimed in claim 1, wherein the method comprises the following steps: in step S4, the electroless plating solution is a mixed solution of copper sulfate pentahydrate, disodium ethylenediaminetetraacetate dihydrate, sodium potassium tartrate, sodium hydroxide, potassium ferrocyanide dihydrate, 2' -bipyridine and 37 wt% of formaldehyde.
8. The method for electroless palladium copper plating on the surface of the flexible nanofiber membrane as claimed in claim 7, wherein the method comprises the following steps: in the chemical plating solution, the concentration of each substance is 16g/L of blue vitriol, 19.5g/L of ethylene diamine tetraacetic acid 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 37 wt% formaldehyde.
9. The method for palladium-free electroless copper plating on the surface of the flexible nanofiber membrane as claimed in claim 1, wherein the method comprises the following steps: 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%.
10. The method for palladium-free electroless copper plating on the surface of the flexible nanofiber membrane as claimed in claim 1, wherein the method comprises the following steps: the base material in the step S1 includes one or more of polyethylene non-woven fabric and polypropylene non-woven fabric.
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