CN110983764A - Conductive aromatic polyamide fiber with composite metal coating structure - Google Patents
Conductive aromatic polyamide fiber with composite metal coating structure Download PDFInfo
- Publication number
- CN110983764A CN110983764A CN201911326096.XA CN201911326096A CN110983764A CN 110983764 A CN110983764 A CN 110983764A CN 201911326096 A CN201911326096 A CN 201911326096A CN 110983764 A CN110983764 A CN 110983764A
- Authority
- CN
- China
- Prior art keywords
- fiber
- nickel
- plating
- solution
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 221
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 76
- 239000002184 metal Substances 0.000 title claims abstract description 76
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 57
- 239000004760 aramid Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 261
- 238000007747 plating Methods 0.000 claims abstract description 181
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 128
- 238000009713 electroplating Methods 0.000 claims abstract description 110
- 239000000126 substance Substances 0.000 claims abstract description 74
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010949 copper Substances 0.000 claims abstract description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 claims abstract description 52
- 229910052709 silver Inorganic materials 0.000 claims abstract description 52
- 239000004332 silver Substances 0.000 claims abstract description 51
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 239000004020 conductor Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 3
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 129
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 33
- 229920006231 aramid fiber Polymers 0.000 claims description 28
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000001110 calcium chloride Substances 0.000 claims description 20
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 20
- 229910000510 noble metal Inorganic materials 0.000 claims description 19
- 239000003381 stabilizer Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000006172 buffering agent Substances 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 229910000521 B alloy Inorganic materials 0.000 claims description 11
- VFYPSWGDJSPEQI-UHFFFAOYSA-N [B].[P].[Ni] Chemical compound [B].[P].[Ni] VFYPSWGDJSPEQI-UHFFFAOYSA-N 0.000 claims description 11
- 230000003213 activating effect Effects 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007772 electroless plating Methods 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 238000004873 anchoring Methods 0.000 claims description 4
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 229910001096 P alloy Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005238 degreasing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 107
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 10
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 239000001509 sodium citrate Substances 0.000 description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 8
- 206010042674 Swelling Diseases 0.000 description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 7
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 5
- 229940081974 saccharin Drugs 0.000 description 5
- 235000019204 saccharin Nutrition 0.000 description 5
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229940116318 copper carbonate Drugs 0.000 description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229960002885 histidine Drugs 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- -1 yarns Substances 0.000 description 3
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 2
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 2
- 229940043349 potassium metabisulfite Drugs 0.000 description 2
- 235000010263 potassium metabisulphite Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 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
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- IFGCUJZIWBUILZ-UHFFFAOYSA-N sodium 2-[[2-[[hydroxy-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyphosphoryl]amino]-4-methylpentanoyl]amino]-3-(1H-indol-3-yl)propanoic acid Chemical compound [Na+].C=1NC2=CC=CC=C2C=1CC(C(O)=O)NC(=O)C(CC(C)C)NP(O)(=O)OC1OC(C)C(O)C(O)C1O IFGCUJZIWBUILZ-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/20—Halides of elements of Groups 4 or 14 of the Periodic Table, e.g. zirconyl chloride
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/28—Halides of elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- 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
- D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
-
- 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
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
-
- 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
- D06M11/80—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 boron or compounds thereof, e.g. borides
-
- 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
- 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
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Chemically Coating (AREA)
Abstract
The invention belongs to the technical field of electromagnetic shielding materials and conductive materials, and discloses a conductive aromatic polyamide fiber with a composite metal coating structure, wherein a chemical nickel plating or nickel alloy layer is deposited on a substrate of an aromatic polyamide synthetic fiber; depositing an electroplated copper metal layer on the substrate of the chemical nickel plating or nickel alloy layer; depositing a nickel-electroplating metal layer on the substrate of the copper-electroplating metal layer; selectively depositing or not depositing a silver electroplating metal layer on the substrate of the nickel electroplating metal layer; the preparation method comprises the steps of washing, degreasing, pretreatment, activation, reduction, chemical plating and electroplating. The chemical plating can endow the fiber with continuous conductivity, and the subsequent electroplating can effectively avoid the defects of the chemical plating and improve the production efficiency. The conductive aromatic polyamide fiber prepared by the method has the advantages of conductivity, light weight, high strength and flame retardance, and has wide application prospect in the field of electromagnetic shielding.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding materials and conductive materials, and particularly relates to a conductive aromatic polyamide fiber with a composite metal coating structure.
Background
Currently, the closest prior art: the electromagnetic environment of modern instruments and equipment is increasingly complex, and research and development of efficient wide-frequency electromagnetic shielding materials have great practical significance to national defense construction and social life. Aromatic polyamide fiber, abbreviated as aramid fiber, has at least 85% of amido bonds in the molecular structure directly connected with 2 aromatic rings, is mainly divided into poly-p-phenylene terephthalamide (PPTA, aramid 1414) and poly-m-phenylene isophthalamide (PMIA, aramid 1313), and also comprises aramid fiber 14, poly-copolymerized aramid fiber, heterocyclic aramid fiber and other various types. The conductive aramid fiber has the advantages of conductivity, light weight, high strength, flame retardance, flexibility, good durability, high compatibility, processability and the like, can reduce the weight by 50-90% compared with copper fiber and stainless steel fiber, and is a light electromagnetic shielding material and a conductive material which are preferred by special departments such as aerospace, electronic communication and the like.
The patent CN102421277A and CN104831527A have used a vacuum coating method to prepare conductive aramid fiber material, but the method mainly aims at the flat samples such as paper, fabric, and film, and the samples in fiber state have uneven sputtering phenomenon, and the equipment is expensive.
At present, the research on the conductive aramid fiber is mainly focused on the chemical plating field, such as patent CN104179004A of the university of the great industry, patent CN107326657A of sengilo, patent CN105133301A of the university of shanghai, patent CN107164951A of the science and technology of seville metal material, patent CN105839402A of the university of wuhan and han theory, and other research papers, such as: "Surface dispersed metal-attached fiber prepared by two-inserted poly (dopamine) fusion," ACS application. Mater. Interface, 2013,5, 2062-. The key points of the researches are mainly focused on the research and development of chemical plating pretreatment and a plating solution formula, wherein the strength of the fiber is often damaged and the catalytic effect is not ideal by a classic 'etching-sensitizing-activating' pretreatment method, while a newly developed pretreatment method has the disadvantages of complex process, higher cost and unclear prospect of large-scale industrial application and basically stays in a laboratory stage. Chemical plating can endow aramid fiber with the conductive characteristic, but basically only can plate single-layer metal, and has certain limitation in the field of electromagnetic shielding; the existence of a reducing agent in the plating solution influences the long-term stability of the plating solution; for silver with the best conductivity, the standard electrode potential is positive, and the silver has an autocatalytic deposition effect, so that the chemical plating solution is very easy to decompose and turbid, poor plating and waste are easily caused, and the electromagnetic shielding efficiency of the silver is further influenced. At present, the technology of chemical nickel plating is relatively stable and mature, the cost is lower, the reaction is controllable, the plating solution can be kept in a clear state all the time in the plating process, but the electromagnetic shielding efficiency of the plating layer is general.
In summary, the problems of the prior art are as follows: in the prior art, the vacuum coating technology is mainly used for two-dimensional plane samples, is not suitable for fibrous samples and is expensive in equipment.
In the prior art, the high strength of aramid fiber is often damaged by common etching treatment, and noble metal catalytic points and anchor points obtained by a most classical etching-sensitizing-activating pretreatment method of chemical plating are often insufficient to support a subsequent plating layer; the industrial application of in-situ deposition of a polymeric tie layer between fibers and plating is not obvious in view of cost considerations.
In the prior art, the plating solution of the chemical plating technology is unstable, poor plating and waste are easily caused, and a high-quality and large-thickness plating layer is difficult to obtain, so that the electromagnetic shielding efficiency is influenced; meanwhile, the plating solution can not be recycled for a long time, and the production cost is increased.
In the prior art, the chemical nickel plating technology is the most widely applied chemical plating technology, the plating solution can be kept in a clear state all the time, the reaction and the cost are controllable, but the electric conductivity and the electromagnetic shielding efficiency of the obtained plating layer are general.
In the prior art, the influence of the structural design of the coating on the shielding effectiveness is not considered, and the conductivity, the magnetic conductivity, the corrosion resistance, the durability, the economy and the light weight of the coating are not considered, so that the fiber cannot be endowed with good metal texture, and more effective electromagnetic shielding cannot be performed, so that the advantages of the metalized aramid fiber cannot be exerted.
There is a certain difficulty in solving the above problems. The aramid fiber has high crystallinity, particularly para-aramid fiber, the crystallinity is over 80 percent, the surface is smooth and compact, the reaction energy is low, compared with fibers such as terylene and cotton, a metal coating is difficult to deposit on the surface of the aramid fiber, and a process method needs to be carefully considered; meanwhile, the strength of the aramid fiber cannot be reduced too much by all treatment modes. In view of the sensitive use of conductive aramid, there are fewer related references, adding to the corresponding difficulties. However, the strategic value and significance of the metallized conductive aramid fiber are determined in the application field, and the prior art needs to be improved so as to improve the broadband electromagnetic shielding efficiency and obtain the ideal performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a conductive aromatic polyamide fiber with a composite metal coating structure. The invention selects the mode of multilayer combination of the high-permeability plating layer and the high-conductivity plating layer, and has the advantages of conductivity, magnetism conductivity, corrosion resistance, durability, economy and light weight of the plating layer, the total plating thickness can reach more than 1 micron, the fiber has good metal texture, and the intrinsic characteristics of light weight, high strength, heat resistance, flexibility, strong processability and the like of the fiber. The conductive aromatic polyamide fiber provided by the invention has flexible designability, can perform more effective electromagnetic shielding, and has wide application prospect in the fields of aviation, aerospace, deep sea, satellite, communication, electronics, medical treatment and the like.
The invention is realized by the following steps, and the conductive aromatic polyamide fiber with the composite metal coating structure comprises:
(1) an aromatic polyamide synthetic fiber substrate;
(2) depositing a layer of chemical nickel plating or nickel alloy layer on the substrate (1);
(3) depositing a layer of electroplated copper metal layer on the substrate in the step (2);
(4) depositing a nickel electroplating metal layer on the substrate in the step (3);
(5) and (4) optionally depositing a silver electroplating metal layer on the substrate.
Further, the chemical structural formula of the aromatic polyamide fiber is shown in the specification
Wherein Ar is1Is composed of
Ar2、Ar3Is composed of
One of them, Ar2And Ar3May be the same chemical structure segment.
Further, the fibers are present in the form of fibers, yarns, and fabrics.
Further, the nickel alloy component is a nickel-phosphorus, nickel-boron, or nickel-phosphorus-boron alloy plating layer.
Another object of the present invention is to provide a method for preparing an electrically conductive aromatic polyamide fiber having a composite metal plating structure, comprising the steps of:
(a) washing and removing oil, and removing dirt, oil agent and impurities on the surface of the fiber;
(b) pretreating, swelling the fiber, improving the wettability and the surface area of the fiber surface, and improving the bonding fastness of the fiber matrix and a subsequent plating layer;
(c) activating, namely soaking the fiber by using a noble metal salt solution to form a thin noble metal ion active layer on the surface of the fiber;
(d) reducing, namely soaking the fibers by using a reducing solution to form a noble metal simple substance particle layer on the surfaces of the fibers, wherein the noble metal simple substance particle layer can be used as an anchoring point between the fibers and a subsequent plating layer and also has a catalytic function;
(e) chemical plating, namely depositing a layer of metal nickel or nickel alloy on the surface of the fiber;
(f) electroplating copper, namely depositing a metal copper layer on the surface of the fiber treated in the step (e);
(g) electroplating nickel, and depositing a metal nickel layer on the surface of the fiber treated in the step (f);
(h) optionally, depositing a metallic silver layer on the surface of the fiber treated in (g).
Further, the chemical structural formula of the aromatic polyamide fiber is shown in the specification
Wherein Ar is1Is composed of
Ar2、Ar3Is composed of
One of them, Ar2And Ar3May be the same chemical structure segment.
The fibers are present in the form of fibers, yarns or fabrics.
The washing and oil removing process in the step (a) comprises the following steps: putting the aromatic polyamide fiber into 0.01-20 wt% of sodium hydroxide (NaOH) or potassium hydroxide (KOH) solution, ultrasonically cleaning for 5-60 min, taking out, and rinsing with deionized water.
The pretreatment process of the step (b) is as follows: and (3) putting the deoiled fiber into a pretreatment solution, dipping for 5-60 min at 25-150 ℃, taking out, and rinsing with deionized water.
Further, the pretreatment solution is sulfuric acid (H)2SO4) Solution, calcium chloride (CaCl)2) In dimethyl sulfoxide (DMSO), CaCl2N-methylpyrrolidone (NMP) solution of (5), CaCl2Dimethylacetamide (DMAc) solution, or CaCl2Of Dimethylformamide (DMF), in particular calcium chloride (CaCl)2) In Dimethylsulfoxide (DMSO). The concentration of the sulfuric acid solution is 10-98 wt%, and the concentration of the calcium chloride solution is 3-5 wt%. These solvents are used in the polymerization or spinning of aromatic polyamide fibres and have the function of swelling the fibresThe wettability and the surface area of the fiber can be improved, the adsorbability of the fiber to ions is increased, and the chemical structure and the strength of the fiber are not damaged; the calcium chloride has the function of dissolving aid; the heating may further promote swelling of the fibers
The activation process of the step (c) is as follows: and (3) putting the pretreated fiber into a noble metal salt solution with the concentration of 0.1-100 g/L, soaking at 25-120 ℃ for 5-90 min, taking out, and slowly rinsing with deionized water.
The noble metal salt is silver nitrate (AgNO)3) Or palladium chloride (PdCl)2) Especially silver nitrate, since Ag+The ions can be adsorbed with Cl on the surface of the fiber after swelling treatment-An AgCl layer (insoluble in water) is formed, which is reduced to an Ag interfacial layer with catalysis and riveting after reduction treatment.
The solvent is NMP, DMSO, DMAc, DMF or water, and particularly DMSO can further swell the fiber to allow noble metal ions to better permeate into the fiber. Appropriate heating further promotes swelling of the fibers and diffusion of metal ions.
After activation treatment, an AgCl interface layer or a Pd layer is absorbed on the surface of the swelled fiber2+The ionic layer has a thickness of about 100 to 1000 nm.
The reduction process in the step (d) is as follows: and (3) putting the activated fiber into a reducing solution for reduction treatment, wherein the concentration of the reducing solution is 1-10 g/L, soaking for 5-30 min at 25-35 ℃, taking out, and rinsing with deionized water.
Further, the reducing agent comprises stannous chloride, sodium borohydride, dimethylamino borane or hydrazine hydrate, especially sodium borohydride.
The solvent is NMP, DMSO, DMAc, DMF or water, especially water.
The aqueous solution of sodium borohydride in the step can achieve good reduction effect at very dilute concentration and normal temperature (1 g/L).
After reduction treatment, the noble metal ion layer on the surface of the fiber is reduced into a noble metal single layer, the thickness of the layer is about 100-1000 nm, the noble metal single layer is formed by noble metal nano particles, deposition of subsequent chemical plating metal can be catalyzed, the riveting effect is achieved, and the bonding fastness of the subsequent plating layer and the fiber substrate is improved.
The chemical plating process in the step (e) comprises the following steps: preparing a chemical nickel plating solution by using nickel salt, a complexing agent, a reducing agent, a buffering agent, a stabilizing agent and the like, and depositing a nickel-based metal plating layer on the surface of the fiber at the temperature of 30-90 ℃, wherein the content of nickel is 85-100 wt%, and the thickness of the plating layer is 100-500 nm. As the underlying nickel-based metal layer, the plating layer needs to ensure certain thickness (>100nm) and continuity so as to withstand the impact of subsequent current and ensure the effective performance of subsequent electroplating. The defects (cracks, poor plating and the like) of the chemical plating layer have inheritance, and the quality of the chemical plating layer has great influence on the quality of the whole composite plating layer, so the plating speed and the internal stress of the plating layer need to be controlled to ensure the quality of the plating layer.
The reducing agent used in this step is generally sodium hypophosphite, dimethylamino borane, hydrazine hydrate.
Further, by adjusting the pH value of the solution and the concentration of each component, phosphorus and boron elements in the reducing agent can be co-deposited with nickel, so that nickel-phosphorus, nickel-boron or nickel-phosphorus-boron alloy is obtained.
The chemical nickel plating is the most stable one of all chemical plating, is low in price, has high plating quality, and can endow the fiber with initial conductivity.
The process of electroplating copper in the step (f) comprises the following steps: preparing an electroplating copper solution by using copper salt, a complexing agent, a stabilizing agent, a buffering agent and the like, depositing for 15-120 min at 25-60 ℃ under a certain current or voltage, and depositing a metal copper coating with the thickness of 250-1000 nm, preferably 500-800 nm, on the surface of the fiber treated by the step (e). The electroplated copper layer is used as the second layer of the composite coating, has the conductivity and electromagnetic shielding effectiveness which are second only to that of silver, and has the price and the relative atomic mass which are lower than those of silver, so that the cost performance is high. The copper plating layer is the main body of the composite plating layer, which ensures that the composite plating layer has good conductivity and electromagnetic shielding effectiveness, so that the composite plating layer has certain thickness (larger than the nickel plating layer and the silver plating layer);
the process of electroplating nickel in the step (g) is as follows: preparing an electroplating nickel solution by using nickel salt, a complexing agent, a stabilizing agent, a buffering agent, a brightening agent and the like, depositing for 15-60 min at 40-70 ℃ under a certain current or voltage, and depositing a metal nickel coating with the thickness of 200-500 nm, preferably 200-300 nm on the surface of the fiber treated by the step (f). The nickel electroplated layer can solve the problems of poor corrosion resistance and durability of the copper electroplated layer, prevent copper atoms from diffusing outwards, and simultaneously has better magnetic conductivity and electrical conductivity.
The optional silver electroplating process of step (f) is as follows: silver salt, complexing agent, stabilizer, buffering agent, brightener and the like are used to prepare an electrosilvering solution, the solution is deposited for 15-60 min at 25-45 ℃ under a certain current or voltage, and a metal silver coating with the thickness of 200-500 nm, especially 200-300 nm, is deposited on the surface of the fiber treated by the step (g). The silver layer can further improve the conductivity, electromagnetic shielding efficiency and corrosion resistance of the fiber, and improve the welding performance of the fiber, thereby meeting the requirements of more severe application environments.
Another object of the present invention is to provide an aerospace electromagnetic shielding material and conductor prepared using the conductive aramid fiber having a composite metal plating structure.
Another object of the present invention is to provide a marine and satellite electromagnetic shielding material and a conductor prepared using the conductive aramid fiber having a composite metal plating structure.
The invention also aims to provide an electromagnetic shielding material and a conductor prepared by using the conductive aromatic polyamide fiber with the composite metal coating structure in the communication and medical fields.
In summary, the advantages and positive effects of the invention are: according to the invention, the surface of the aromatic polyamide fiber is plated with the multiple metal conductive layers, so that the aromatic polyamide fiber has good conductivity and metal texture, and has the performances of light weight, high strength, flame retardance, heat resistance, strong processability and the like. The material can be widely applied to special fields of aviation, aerospace, navigation, satellites, communication, medical treatment and the like, and can be used as an electromagnetic shielding material, a conductor and the like.
The chemical plating can endow the fiber with continuous conductivity, the subsequent electroplating can effectively avoid the defects of the chemical plating, improve the utilization rate and the production efficiency of the plating solution, reduce the cost, obtain the required weight gain/thickening rate according to the design and endow the fiber with better metal texture. The electroplating is carried out on the surface of a good conductor, so the method firstly uses an electroless plating method to plate a nickel-based metal on the surface of the aramid fiber, and then designs and electroplates a multi-layer metal electroplated layer structure on the aramid fiber.
In the composition of the composite plating layer, the nickel-based chemical plating layer is mainly used for endowing the fiber with primary conductivity, so that the subsequent electroplating process becomes feasible; compared with other chemical plating layers, the nickel-based metal plating solution is stable, the quality of the plating layer is high, and the bonding firmness with the aramid fiber substrate is the best. The electroplated copper layer is used as a second layer and a main body structure of the composite coating, has the conductivity and electromagnetic shielding efficiency second only to silver, and has higher cost performance and relative atomic mass lower than that of silver; the next third nickel electroplated layer solves the problem of poor corrosion resistance and durability of the copper electroplated layer, can prevent copper atoms from diffusing outwards, and has better magnetic permeability and electrical conductivity; the outermost silver plating layer (which can be selectively plated) can further improve the conductivity, electromagnetic shielding performance and corrosion resistance of the fiber, and simultaneously endow the fiber with good welding performance.
The structural design of the composite coating refers to the design concept of a macroscopic layered electromagnetic shielding structure, integrates the characteristics of various single-layer shielding materials, combines the intrinsic performance and the structural effect of the materials together to play a role, selects a mode of multilayer combination of a high-permeability material and a high-permeability material, considers the durability, the economy and the light weight of the coating, can carry out more effective shielding, and meets more complex and severe use requirements.
The electroless nickel and nickel alloys of the present invention impart primary conductivity to the fibers and provide for electroplating, as opposed to the prior art of simple electroless plating.
Compared with products such as conductive terylene, conductive cotton and the like, the conductive aramid product has very high value and wide application in special fields due to incomparable advantages, but the plating difficulty of the aramid fiber is different from that of common fiber in the same day due to the characteristics of high crystallinity and high inertia of the aramid fiber. The invention provides a new idea for solving the problem of preparation of the conductive aramid fiber.
Drawings
Fig. 1 is a flow chart of a method for preparing an electrically conductive aromatic polyamide fiber with a composite metal plating structure according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a conductive aramid fiber composite metal plating layer according to an embodiment of the present invention.
FIG. 3 is a scanning electron microscope photograph of an all para-aramid fiber provided in an embodiment of the present invention.
FIG. 4 is a (a) SEM and cross-sectional (b) TEM image of an aramid fiber after swelling-activation-reduction as described in example 1, provided in accordance with an embodiment of the present invention.
FIG. 5 is a scanning electron microscope photograph of para-aramid fiber after electroless nickel plating according to the method described in example 1, in accordance with an embodiment of the present invention.
FIG. 6 is a scanning electron microscope photograph of para-aramid fiber provided in accordance with an embodiment of the present invention after electro-coppering as described in example 1.
FIG. 7 is a scanning electron microscope photomicrograph of para-aramid fiber after being electroplated with nickel as described in example 1, in accordance with an embodiment of the present invention.
FIG. 8 is a scanning electron microscope photograph of para-aramid fiber after electro-silvering as described in example 1, in accordance with an embodiment of the present invention.
Fig. 9 is a photograph of electromagnetic shielding effectiveness data of the conductive aramid fabric according to the present invention prepared in the methods of examples 1 and 2, which includes six sets of data plated with: Ni-P-B, Ni, Ni-P-B/Cu/Ni, Ni/Cu/Ni, Ni-P-B/Cu/Ni/Ag, Ni/Cu/Ni/Ag. Of these, the former two are obtained by electroless plating, and the latter four are obtained by combining electroless plating (first layer) with electroplating (second to fourth layers).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The prior art does not select a mode of combining a high-permeability coating and a high-permeability coating in a multilayer manner, does not give consideration to the conductivity, the permeability, the corrosion resistance, the economy and the light weight of the coatings, cannot endow the fiber with good metal texture, and cannot carry out more effective electromagnetic shielding. In the prior art, the vacuum deposition method has high cost and is not suitable for fiber samples. In the prior art, the chemical plating solution is easy to decompose and turbid, poor plating and waste are easy to cause, and a high-quality plating layer is difficult to obtain.
In view of the problems of the prior art, the present invention provides a conductive aromatic polyamide fiber with a composite metal plating structure, and the present invention is described in detail below with reference to the accompanying drawings.
The conductive aromatic polyamide fiber with the composite metal coating structure provided by the embodiment of the invention is short for aramid fiber, and the structural formula is as follows:
wherein Ar is1Is composed of
Ar2、Ar3Is composed of
One of them, Ar2And Ar3May be the same chemical structure segment.
The method comprises the steps of firstly, cleaning and deoiling aromatic polyamide fiber to remove oil agent and dirt on the surface of the fiber; then, pretreating the fiber to increase the wettability and the surface area of the fiber surface so as to improve the bonding fastness between a subsequent plating layer and a base material; the activation is to adsorb a layer of noble metal ions on the surface of the pretreated fiber; forming a noble metal anchor point and a catalytic point which are firmly combined with the substrate on the surface of the fiber after reduction treatment; then chemically plating nickel on the surface of the fiber; and then sequentially carrying out an electro-coppering process, an electro-nickelling process and an electro-silvering process (optional), and finally obtaining the conductive aromatic polyamide fiber with the composite metal coating structure.
The plated aramid fibers of the present invention may be present in the form of fibers, yarns, fabrics, and the like.
As shown in fig. 1, a method for preparing an electrically conductive aromatic polyamide fiber with a composite metal plating structure provided in an embodiment of the present invention specifically includes:
s101, washing and removing oil. Putting the aromatic polyamide fiber into 0.01-20 wt% of sodium hydroxide (NaOH) or potassium hydroxide (KOH) solution, ultrasonically cleaning for 5-60 min, taking out, and rinsing with deionized water to remove dirt, oil and impurities on the surface of the fiber.
And S102, preprocessing. And (3) putting the washed fiber into a pretreatment solution, dipping for 5-60 min at 25-150 ℃, taking out, and rinsing with deionized water. The pretreatment solution is sulfuric acid (H)2SO4) Solution, calcium chloride (CaCl)2) In dimethyl sulfoxide (DMSO), CaCl2N-methylpyrrolidone (NMP) solution of (5), CaCl2Dimethylacetamide (DMAc) solution, or CaCl2Of Dimethylformamide (DMF), in particular calcium chloride (CaCl)2) In Dimethylsulfoxide (DMSO). The concentration of the sulfuric acid solution is 10-98 wt%, and the concentration of the calcium chloride solution is 3-5 wt%. The step is used for increasing the wettability and the surface area of the fiber surface and improving the bonding firmness of the fiber and a subsequent metal coating.
And S103, activating. And (3) putting the pretreated fiber into a silver nitrate or palladium chloride solution with the concentration of 0.1-100 g/L, particularly a silver nitrate solution, soaking for 5-90 min at 25-120 ℃, taking out, and slowly rinsing with deionized water. The solvent of the activating solution may be NMP, DMSO, DMAc, DMF or water, especially DMSO. The activation treatment can form a thin active layer of noble metal ions on the surface of the fiber.
And S104, reducing. And (3) putting the activated fiber into a stannous chloride, sodium borohydride, dimethylamine borane or hydrazine hydrate solution with the concentration of 1-10 g/L, soaking for 5-30 min at 25-35 ℃, taking out, and rinsing with deionized water. The solvent of the reducing solution may be NMP, DMSO, DMAc, DMF or water, especially water. After reduction, noble metal target points which are firmly combined with the substrate are formed on the surface of the fiber, and the target points can be used as anchoring points and catalytic points of a subsequent chemical plating layer.
And S105, chemically plating nickel. Nickel salt, complexing agent, reducing agent, buffering agent, stabilizer, etc. are compounded into chemical nickel plating solution, and one layer of nickel-base metal is deposited homogeneously on the surface of fiber. The chemical nickel plating generally uses sodium hypophosphite, dimethylamino borane, hydrazine hydrate and the like as reducing agents, and the codeposition of phosphorus, boron and nickel in the reducing agents can be controlled by adjusting the pH value of the plating solution and the concentration of each component, so that pure nickel or alloy plating layers of nickel-phosphorus, nickel-boron, nickel-phosphorus-boron and the like can be respectively obtained. The nickel and nickel alloy coatings differ in structure and performance, and the composition can be designed according to specific application scenarios.
S106, electroplating copper, preparing an electroplating copper solution by using copper salt, a complexing agent, a stabilizing agent, a buffering agent and the like, immersing the fiber with the surface coated with nickel or nickel alloy into the electroplating copper solution, and depositing a layer of metallic copper on the chemical coating of the nickel or nickel alloy under a certain current or voltage. The copper plating layer can enable the fiber to have good conductivity and good electromagnetic shielding efficiency (second to silver), and meanwhile, the fiber is light in weight and high in cost performance.
S107, electroplating nickel, preparing nickel salt, a complexing agent, a stabilizing agent, a buffering agent, a brightening agent and the like into an electroplating nickel solution, immersing the fibers with copper plated on the surfaces into the electroplating nickel solution, and depositing a layer of metal nickel on the copper electroplating layer under a certain current or voltage. When the fiber is in service in the air, the nickel coating is more stable than the copper coating, the attenuation of the conductivity is relatively slow, the fiber has better corrosion resistance and durability, and the good magnetic conductivity also has a certain magnetic shielding effect.
And S108, optionally, after the seventh step of nickel electroplating, preparing silver electroplating solution by using silver salt, complexing agent, stabilizer, buffering agent, brightener and the like, and depositing a layer of metal silver on the fiber nickel electroplating layer under a certain current or voltage, wherein the nickel electroplating layer also plays a role in separation, so that copper atoms are prevented from directly diffusing to the silver layer. The silver plating layer can further improve the conductivity, durability and electromagnetic shielding effectiveness of the fiber and improve the weldability of the fiber.
The structure of the conductive aromatic polyamide fiber prepared by the process is shown in figure 2, wherein the optimal thickness of the electroless nickel plating layer or the nickel alloy layer is 100-500 nm, the optimal thickness of the electroplated copper layer is 500-800 nm, the optimal thickness of the electroplated nickel layer is 200-300 nm, and the optimal thickness of the electroplated silver layer is 200-300 nm.
The invention is further described with reference to specific embodiments and the accompanying drawings.
Example 1:
the preparation method of the conductive aromatic polyamide fiber with the composite metal coating structure provided by the embodiment of the invention comprises the following steps:
the first step is as follows: deoiling, namely putting the poly-p-phenylene terephthamide (PPTA) fiber into 0.01 wt% of sodium hydroxide solution, ultrasonically cleaning for 30min at normal temperature, taking out, and rinsing with deionized water.
The second step is that: pretreating by immersing the fibres in CaCl2DMSO solution (CaCl)2Content of 5 wt%), soaked at 60 deg.C for 30min, and rinsed with deionized water.
The third step: activating, putting the pretreated fiber into AgNO3DMSO solution (AgNO)3The concentration of (1) is 10g/L), the temperature is 80 ℃, and the solution is taken out and rinsed slowly after 60 min.
The fourth step: and (3) reducing, namely putting the activated fiber into 1g/L sodium borohydride aqueous solution, carrying out reduction treatment at normal temperature, taking out after 10min, and rinsing the fiber by using deionized water.
The fifth step: chemical nickel plating, the reduced fiber is put into a chemical nickel plating solution, and the formula of the chemical nickel plating solution is as follows: 10-20 g/L of nickel sulfate, 25-35 g/L of sodium citrate, 5-10 g/L of sodium hypophosphite, 0.1-0.5 g/L of dimethylamino borane and 10mg/L of sodium dodecyl sulfate. Adjusting the pH value to 9.5-10.5 by using ammonia water, plating for 30min at 50 ℃, and rinsing by using deionized water.
And a sixth step: and (2) copper electroplating, namely placing the fibers subjected to chemical nickel plating into copper electroplating solution, wherein the formula of the copper electroplating solution is as follows: 5-10 g/L of basic copper carbonate, 80-100 g/L of hydroxyethylidene diphosphonic acid, 40-50 g/L of potassium carbonate and 0.1-0.3 g/L of selenium dioxide. Adjusting the pH value to 9.0-10.0 by using potassium hydroxide. And taking the fiber as a cathode and the electrolytic copper foil as an anode, plating for 60min at the temperature of 30-40 ℃, and rinsing with deionized water.
The seventh step: and (2) electroplating nickel, namely putting the fibers after copper electroplating into a nickel electroplating solution, wherein the formula of the nickel electroplating solution is as follows: 100-150 g/L of nickel sulfate, 10-20 g/L of nickel chloride, 100-150 g/L of sodium citrate, 30-50 g/L of boric acid, 0.5-0.8 g/L of saccharin, 0.05-0.08 g/L of sodium dodecyl sulfate and pH value of 6.0-7.0. And taking the fiber as a cathode and the electrolytic nickel foil as an anode, plating for 30min at 40-50 ℃, and rinsing with deionized water.
Eighth step: and (3) silver electroplating, namely putting the fibers subjected to nickel electroplating into a silver electroplating solution, wherein the formula of the silver electroplating solution is as follows: 30-40 g/L of silver nitrate, 100-120 g/L of 5, 5-dimethyl hydantoin, 50-70 g/L of potassium carbonate, 40-50 g/L of sodium pyrophosphate, 0.5-1 g/L of L-histidine and 10mL/L of a stabilizer, and the pH value is adjusted to 10.0-11.0 by using potassium hydroxide. The stabilizer is a solution prepared from 4-8 g/L of 1, 4-butynediol, 2-4 g/L of triethanolamine and 2-4 g/L of vanillin. And taking the fiber as a cathode and the electrolytic silver foil as an anode, plating for 30min at 25-30 ℃, and rinsing with deionized water.
The scanning electron microscope picture of the PPTA fiber used in this example is shown in FIG. 3, and the fiber is rigid and has a very dense surface.
After the swelling-activating-reducing treatment is performed according to the process of the embodiment 1, the topography of the surface and the cross section of the fiber is shown in fig. 4, and it can be seen that after the pretreatment process, an Ag nanoparticle catalyst layer with a thickness of about 1 μm is formed on the surface of the fiber, the enrichment of Ag nanoparticles can catalyze the subsequent electroless nickel plating reaction, which is beneficial to the formation of a continuous nickel plating layer, and meanwhile, the Ag nanoparticle layer also plays a role in riveting, so that the bonding fastness of the electroless nickel plating layer and the fiber substrate is increased.
FIG. 5 is a scanning electron microscope topography of the fiber surface after electroless nickel plating according to the process of example 1. In addition, the composition of the nickel can be determined by combining energy spectrum (EDS) and X-ray photoelectron spectroscopy (XPS) analysis.
FIG. 6 is a scanning electron microscope topographical view of the fiber surface after copper electroplating according to the process of example 1.
FIG. 7 is a scanning electron microscope topography of the fiber surface after nickel electroplating according to the process of example 1.
FIG. 8 is a scanning electron microscope topographical view of the fiber surface after silver electroplating according to the process of example 1.
As can be seen from fig. 5 to 8, a flat, dense, continuous metal coating is formed on the surface of the fiber after each step of coating.
Example 2:
the preparation method of the conductive aromatic polyamide fiber with the composite metal coating structure provided by the embodiment of the invention comprises the following fifth step of chemical plating:
the fifth step: chemical nickel plating, the reduced fiber is put into a chemical nickel plating solution, and the formula of the chemical nickel plating solution is as follows: 10-20 g/L of nickel sulfate, 25-35 g/L of sodium citrate, 10-15 g/L of sodium hypophosphite, 2.5-5.0 g/L of dimethylamino borane and 10mg/L of sodium dodecyl sulfate. Adjusting the pH value to 8.0-9.0 by using ammonia water, plating for 30min at 50 ℃, and rinsing by using deionized water.
Except for this step, the other process steps were identical to example 1.
The analysis of energy spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) can determine that the plating component obtained by the fifth electroless nickel plating process of example 2 is a nickel-phosphorus-boron alloy, and is a high-phosphorus alloy, and the phosphorus content is greater than 10 wt%.
The flat electrical resistance of the PPTA plain weave fabrics after each of the electroless, electrolytic copper and electrolytic nickel and silver plating steps were tested using the processes of example 1 and example 2, respectively, and the data is shown in table 1. As can be seen from Table 1, as the plating process gradually progresses, the plane resistance of the PPTA fabric rapidly decreases, and the conductivity of the sample after electroplating is greatly improved. The electroless nickel-phosphorus-boron alloy layer is less conductive than the electroless nickel layer; but the difference of the electrical conductivity of the two samples becomes smaller through the subsequent copper electroplating and nickel electroplating processes; after the final silver electroplating process, the conductivity of the electroless nickel-phosphorus-boron alloy layer substrate is slightly higher than that of the electroless nickel substrate. In the early-stage experiment, after the PPTA fabric is subjected to chemical silvering, the optimal plane resistance value is 20-30 m omega/□; after silver plating according to examples 1 and 2, the sheet resistance was about 5.5 m.OMEGA./□, and the conductivity was greatly improved.
The nickel-phosphorus-boron alloy plating layer and the nickel plating layer have different electrical conductivity, magnetism and acid and alkali corrosion resistance, after electroplating is carried out on the nickel-phosphorus-boron alloy plating layer and the nickel plating layer, the electrical conductivity of the obtained composite plating layer is slightly different, and the required plating layer structure and the corresponding process conditions can be selected according to different application scenes.
TABLE 1 plane resistance of the samples of example 1 and example 2
The PPTA plain weave fabrics were plated by the processes of example 1 and example 2, respectively, and the electromagnetic shielding effectiveness of the fabrics in the frequency range of 30 kHz-1.5 GHz after each step of electroless plating, electro-coppering, electro-nickel plating and electro-silver plating was tested, and the related data are shown in FIG. 9. It can be seen from the figure that compared with a pure chemical nickel plating process, the electromagnetic shielding performance of the electroplated sample is greatly improved, especially after the final silver electroplating process, the electromagnetic shielding performance is stabilized at about 90db, and the method can be applied to application scenes with more strict requirements on the electromagnetic shielding performance. In the early experiment, after the PPTA fabric is subjected to chemical silver plating, the optimal shielding value in the frequency range of 30 kHz-1.5 GHz is 70-75 db, which is basically equal to the electromagnetic shielding performance of the Ni/Cu/Ni sample in the embodiment 1, and is far inferior to the electromagnetic shielding performance of the samples after the silver plating in the embodiments 1 and 2. The chemical silver plating solution can not be recycled, and the electroplating solution can be recycled, so that the economy is higher.
The nickel-phosphorus-boron alloy plating layer and the nickel plating layer have different electrical conductivity, magnetism and acid and alkali corrosion resistance, after electroplating is carried out on the nickel-phosphorus-boron alloy plating layer and the nickel plating layer, the electromagnetic shielding performance of the obtained composite plating layer is slightly different, and the required plating layer structure and the corresponding process conditions can be selected according to different application scenes.
The advantages and value of the process of the invention can be demonstrated by the above comparison.
Example 3:
the preparation method of the conductive aromatic polyamide fiber with the composite metal coating structure provided by the embodiment of the invention comprises the following steps:
the first step is as follows: deoiling, namely putting the poly-p-phenylene terephthamide (PPTA) fiber into 0.1 wt% of sodium hydroxide solution, ultrasonically cleaning for 10min at normal temperature, taking out, and rinsing with deionized water.
The second step is that: pretreating by immersing the fibres in CaCl2DMF solution (CaCl) of2Content of 5 wt%), soaked at 100 deg.C for 20min, and rinsed with deionized water.
The third step: activating, putting the pretreated fiber into AgNO3NMP solution (AgNO)330g/L) at 85 deg.C for 30min, and slowly rinsing.
The fourth step: and (3) reducing, namely putting the activated fiber into a 2g/L sodium borohydride aqueous solution, carrying out reduction treatment at normal temperature, taking out after 10min, and rinsing the fiber by using deionized water.
The fifth step: chemical nickel plating, the reduced fiber is put into a chemical nickel plating solution, and the formula of the chemical nickel plating solution is as follows: 10-20 g/L of nickel sulfate, 20-35 g/L of sodium citrate, 5-10 g/L of ammonium chloride, 10-15 g/L of sodium hypophosphite, 2.5-5.0 g/L of dimethylamino borane and 20mg/L of sodium dodecyl sulfate. Adjusting the pH value to 8.0-9.0 by using KOH, plating for 45min at 45 ℃, and rinsing by using deionized water.
And a sixth step: and (2) copper electroplating, namely placing the fibers subjected to chemical nickel plating into copper electroplating solution, wherein the formula of the copper electroplating solution is as follows: 5-10 g/L of basic copper carbonate, 80-100 g/L of hydroxyethylidene diphosphonic acid, 40-50 g/L of potassium carbonate and 0.1-0.3 g/L of selenium dioxide. Adjusting the pH value to 9.0-10.0 by using potassium hydroxide. And taking the fiber as a cathode and the electrolytic copper foil as an anode, plating for 90min at the temperature of 30-40 ℃, and rinsing with deionized water.
The seventh step: and (2) electroplating nickel, namely putting the fibers after copper electroplating into a nickel electroplating solution, wherein the formula of the nickel electroplating solution is as follows: 300-350 g/L of nickel sulfate, 12-15 g/L of sodium chloride, 30-40 g/L of boric acid, 0.2-0.4 g/L of coumarin, 0.5-0.8 g/L of saccharin, 0.8-1.0g/L of 1, 4-butynediol, 0.05-0.08 g/L of sodium dodecyl sulfate and pH value of 3-4. And taking the fiber as a cathode and electrolytic nickel foil as an anode, plating for 45min at 50-60 ℃, and rinsing with deionized water.
Optionally, the eighth step: and (3) silver electroplating, namely putting the fibers subjected to nickel electroplating into a silver electroplating solution, wherein the formula of the silver electroplating solution is as follows: 30-40 g/L of silver nitrate, 100-120 g/L of 5, 5-dimethyl hydantoin, 50-70 g/L of potassium carbonate, 40-50 g/L of sodium pyrophosphate, 0.5-1 g/L of L-histidine and 10mL/L of a stabilizer, and the pH value is adjusted to 10.0-11.0 by using potassium hydroxide. The stabilizer is a solution prepared from 4-8 g/L of 1, 4-butynediol, 2-4 g/L of triethanolamine and 2-4 g/L of vanillin. And taking the fiber as a cathode and the electrolytic silver foil as an anode, plating for 45min at 25-30 ℃, and rinsing with deionized water.
Example 4:
the preparation method of the conductive aromatic polyamide fiber with the composite metal coating structure provided by the embodiment of the invention comprises the following steps:
the first step is as follows: deoiling, namely putting the poly-p-phenylene terephthamide (PPTA) fiber into 0.02 wt% of sodium hydroxide solution, ultrasonically cleaning for 20min at normal temperature, taking out, and rinsing with deionized water.
The second step is that: pretreating, namely soaking the fiber into a sulfuric acid solution containing 50 wt%, soaking for 15min at 60 ℃, taking out, and rinsing with deionized water.
The third step: activating, putting the pretreated fiber into 0.1g/L PdCl2Solution (solution additionally contains 3.5mL/LHydrochloric acid) at 30 deg.C for 25min, and slowly rinsing.
The fourth step: reducing, putting the activated fiber into 20g/L SnCl2The solution (the solution additionally contains 15mL/L hydrochloric acid) is subjected to reduction treatment at normal temperature, and is taken out after 10min and rinsed by deionized water.
The fifth step: chemical nickel plating, the reduced fiber is put into a chemical nickel plating solution, and the formula of the chemical nickel plating solution is as follows: 10-20 g/L of nickel sulfate, 20-35 g/L of sodium citrate, 3-8 g/L of sodium hypophosphite, 1-5 g/L of dimethylamino borane and 15mg/L of sodium dodecyl sulfate. Adjusting the pH value to 9.0-10.0 by using ammonia water, plating for 30min at 55 ℃, and rinsing by using deionized water.
And a sixth step: and (2) copper electroplating, namely placing the fibers subjected to chemical nickel plating into copper electroplating solution, wherein the formula of the copper electroplating solution is as follows: 35-45 g/L of copper sulfate, 250-300 g/L of citric acid, 1-5 g/L of triethanolamine, 15-20 g/L of sodium bicarbonate and 0.01-0.05 g/L of selenium dioxide, and adjusting the pH value to 9.0-10.0 by using potassium hydroxide. And (3) plating the fiber as a cathode and the electrolytic copper foil as an anode for 100min at the temperature of 30-40 ℃, and rinsing with deionized water.
The seventh step: and (2) electroplating nickel, namely putting the fibers after copper electroplating into a nickel electroplating solution, wherein the formula of the nickel electroplating solution is as follows: 300-350 g/L of nickel sulfate, 12-15 g/L of sodium chloride, 30-40 g/L of boric acid, 0.2-0.4 g/L of coumarin, 0.5-0.8 g/L of saccharin, 0.8-1.0g/L of 1, 4-butynediol, 0.05-0.08 g/L of sodium dodecyl sulfate and pH value of 3-4. And taking the fiber as a cathode and electrolytic nickel foil as an anode, plating for 30min at 50-60 ℃, and rinsing with deionized water.
Eighth step: and (3) silver electroplating, namely putting the fibers subjected to nickel electroplating into a silver electroplating solution, wherein the formula of the silver electroplating solution is as follows: 30-40 g/L silver nitrate, 100-120 g/L5, 5-dimethyl hydantoin, 50-70 g/L potassium carbonate, 40-50 g/L sodium pyrophosphate, 0.5-1 g/L tryptophan, 0.1g/L polyethylene glycol (molecular weight 1000), 10mL/L stabilizer, and the pH value is adjusted to 10.0-11.0 by using potassium hydroxide. The stabilizer is a solution prepared from 4-8 g/L1, 4-butynediol and 2-4 g/L triethanolamine. And (3) taking the fiber as a cathode and the electrolytic silver foil as an anode, plating for 60min at 25-30 ℃, and rinsing with deionized water.
Example 5:
the preparation method of the conductive aromatic polyamide fiber with the composite metal coating structure provided by the embodiment of the invention comprises the following steps:
the first step is as follows: deoiling, namely putting the poly-p-phenylene terephthamide (PPTA) fiber into 0.05 wt% of sodium hydroxide solution, ultrasonically cleaning for 15min at normal temperature, taking out, and rinsing with deionized water.
The second step is that: pretreating by immersing the fibres in CaCl2NMP solution (CaCl)2Content of 3 wt%), soaked at 60 deg.C for 45min, and rinsed with deionized water.
The third step: activating, putting the pretreated fiber into AgNO3DMAc solution (AgNO)350g/L) at a temperature of 75 ℃ for 10min, and then taking out and slowly rinsing.
The fourth step: and (3) reducing, namely putting the activated fiber into a 2g/L sodium borohydride aqueous solution, carrying out reduction treatment at normal temperature, taking out the fiber after 5min, and rinsing the fiber with deionized water.
The fifth step: chemical nickel plating, the reduced fiber is put into a chemical nickel plating solution, and the formula of the chemical nickel plating solution is as follows: 10-20 g/L of nickel acetate, 15-25 g/L of sodium citrate, 1-5 g/L of ammonium chloride, 5-10 g/L of sodium hypophosphite, 0.1-0.5 g/L of dimethylamino borane and 10mg/L of sodium dodecyl sulfate. Adjusting the pH value to 9.5-10.5 by using KOH, plating for 30min at 55 ℃, and rinsing by using deionized water.
And a sixth step: and (2) copper electroplating, namely placing the fibers subjected to chemical nickel plating into copper electroplating solution, wherein the formula of the copper electroplating solution is as follows: 15-25 g/L of basic copper carbonate, 100-150 g/L of triethanolamine, 20-30 g/L of ammonium citrate, 5-10 g/L of potassium nitrate and 0.1-0.3 g/L of selenium dioxide. Adjusting the pH value to 9.0-10.0 by using potassium hydroxide. And taking the fiber as a cathode and the electrolytic copper foil as an anode, plating for 45min at 30-40 ℃, and rinsing with deionized water.
The seventh step: and (2) electroplating nickel, namely putting the fibers after copper electroplating into a nickel electroplating solution, wherein the formula of the nickel electroplating solution is as follows: 280-320 g/L of nickel sulfate, 50-100 g/L of nickel chloride, 40-60 g/L of boric acid, 0.5-0.8 g/L of saccharin, 0.8-1.0g/L of 1, 4-butynediol, 0.05-0.08 g/L of sodium dodecyl sulfonate and pH value of 3-4. And (3) taking the fiber as a cathode and the electrolytic nickel foil as an anode, plating for 30min at 55-60 ℃, and rinsing with deionized water.
Eighth step: and (3) silver electroplating, namely putting the fibers subjected to nickel electroplating into a silver electroplating solution, wherein the formula of the silver electroplating solution is as follows: 30-40 g/L of silver nitrate, 200-250 g/L of sodium thiosulfate, 40-60 g/L of potassium carbonate, 40-60 g/L of potassium metabisulfite, 0.3-0.6 g/L of thiosemicarbazide, 0.5-1 g/L of tryptophan and 0.1-0.5 g/L of triethanolamine, and the pH value is adjusted to 9.0-10.0 by using potassium hydroxide. And taking the fiber as a cathode and the electrolytic silver foil as an anode, plating for 30min at 25-30 ℃, and rinsing with deionized water.
Example 6:
the preparation method of the conductive aromatic polyamide fiber with the composite metal coating structure provided by the embodiment of the invention comprises the following steps:
the first step is as follows: deoiling, namely putting the poly-p-phenylene terephthamide (PPTA) fiber into 0.01 wt% potassium hydroxide solution, ultrasonically cleaning for 40min at normal temperature, taking out, and rinsing with deionized water.
The second step is that: pretreating by immersing the fibres in CaCl2DMAc solution (CaCl) of2Content of 5 wt%), soaked at 90 deg.C for 25min, and then rinsed with deionized water.
The third step: activating, putting the pretreated fiber into AgNO3DMF solution (AgNO)360g/L) at 100 deg.C for 5min, and slowly rinsing.
The fourth step: and (3) reducing, namely putting the activated fiber into a 2g/L sodium borohydride aqueous solution, carrying out reduction treatment at normal temperature, taking out the fiber after 5min, and rinsing the fiber with deionized water.
The fifth step: chemical nickel plating, the reduced fiber is put into a chemical nickel plating solution, and the formula of the chemical nickel plating solution is as follows: 20-25 g/L of nickel sulfate, 5-10 g/L of sodium citrate, 40-45 g/L of sodium pyrophosphate, 1-1.5 g/L of dimethylamino borane and 10mg/L of sodium dodecyl sulfate. Adjusting the pH value to 10.0-10.5 by using ammonia water, plating for 30min at 30 ℃, and rinsing by using deionized water.
And a sixth step: and (2) copper electroplating, namely placing the fibers subjected to chemical nickel plating into copper electroplating solution, wherein the formula of the copper electroplating solution is as follows: 5-10 g/L of basic copper carbonate, 80-100 g/L of hydroxyethylidene diphosphonic acid, 40-50 g/L of potassium carbonate and 0.1-0.3 g/L of selenium dioxide. Adjusting the pH value to 9.0-10.0 by using potassium hydroxide. And taking the fiber as a cathode and the electrolytic copper foil as an anode, plating for 90min at the temperature of 30-40 ℃, and rinsing with deionized water.
The seventh step: and (2) electroplating nickel, namely putting the fibers after copper electroplating into a nickel electroplating solution, wherein the formula of the nickel electroplating solution is as follows: 100-150 g/L of nickel sulfate, 10-20 g/L of nickel chloride, 100-150 g/L of sodium citrate, 30-50 g/L of boric acid, 0.5-0.8 g/L of saccharin, 0.05-0.08 g/L of sodium dodecyl sulfate and pH value of 6.0-7.0. And taking the fiber as a cathode and the electrolytic nickel foil as an anode, plating for 30min at 40-50 ℃, and rinsing with deionized water. .
Eighth step: and (3) silver electroplating, namely putting the fibers subjected to nickel electroplating into a silver electroplating solution, wherein the formula of the silver electroplating solution is as follows: putting the fibers after nickel electroplating into an electroplating silver solution, wherein the formula of the electroplating silver is as follows: 30-40 g/L of silver nitrate, 200-250 g/L of sodium thiosulfate, 40-60 g/L of potassium carbonate, 40-60 g/L of potassium metabisulfite, 0.3-0.6 g/L of thiosemicarbazide, 0.5-1 g/L of L-histidine and 0.1-0.5 g/L of triethanolamine, and the pH value is adjusted to 9.0-10.0 by using potassium hydroxide. And taking the fiber as a cathode and the electrolytic silver foil as an anode, plating for 30min at 25-30 ℃, and rinsing with deionized water.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The conductive aromatic polyamide fiber with the composite metal coating structure is characterized in that a chemical nickel plating or nickel alloy layer is deposited on a substrate of an aromatic polyamide synthetic fiber;
depositing an electroplated copper metal layer on the substrate of the electroless nickel or nickel alloy plating layer;
depositing a nickel electroplating metal layer on the substrate of the copper electroplating metal layer;
and selectively depositing or not depositing an electroplated silver metal layer on the substrate of the electroplated nickel metal layer.
2. The conductive aromatic polyamide fiber having a composite metal plating structure of claim 1, wherein the aromatic polyamide fiber has a chemical formula of:
wherein Ar is1、Ar2、Ar3Is composed of
One of them.
3. The electrically conductive aramid fiber having a composite metal plating structure of claim 1, wherein the aramid fiber is present in the form of a fiber, a yarn, and a fabric;
the chemical nickel-plating alloy layer comprises nickel and phosphorus, nickel and boron or nickel, phosphorus and boron alloy plating layers.
4. The method for preparing the conductive aromatic polyamide fiber having a composite metal plating layer structure according to claim 1, wherein the method for preparing the conductive aromatic polyamide fiber having a composite metal plating layer structure comprises the steps of:
firstly, washing and removing oil to remove dirt, oil agent and impurities on the surface of the fiber;
secondly, pretreating and swelling the fibers;
thirdly, activating, namely soaking the fiber by using a noble metal salt solution to form a thin noble metal ion active layer on the surface of the fiber;
fourthly, reducing, namely soaking the fibers by using a reducing solution to form a precious metal particle layer on the surfaces of the fibers to be used as an anchoring point and a catalytic point between the fibers and a subsequent plating layer;
fifthly, chemical plating is carried out, and a layer of metal nickel or nickel alloy is deposited on the surface of the fiber;
sixthly, electroplating copper, and depositing a metal copper layer on the surface of the fiber treated in the fifth step;
step seven, electroplating nickel, and depositing a metal nickel layer on the surface of the fiber treated in the step six;
and step eight, selectively depositing a layer of metal silver on the surface of the fiber treated by the step seven.
5. The method for preparing the conductive aromatic polyamide fiber with the composite metal coating structure according to claim 4, wherein the first step specifically comprises: and (5) washing and removing oil. Putting the aromatic polyamide fiber into 0.01-20 wt% of sodium hydroxide or potassium hydroxide solution, ultrasonically cleaning for 5-60 min, taking out, and rinsing with deionized water to remove dirt, oil and impurities on the surface of the fiber;
the second step specifically comprises: and (3) pretreatment, namely putting the cleaned fiber into a pretreatment solution, dipping for 5-60 min at 25-150 ℃, taking out, and rinsing with deionized water. The pretreatment solution is sulfuric acid (H)2SO4) Solution, calcium chloride (CaCl)2) In dimethyl sulfoxide (DMSO), CaCl2N-methylpyrrolidone (NMP) solution of (5), CaCl2Dimethylacetamide (DMAc) solution, or CaCl2Of Dimethylformamide (DMF), in particular calcium chloride (CaCl)2) In Dimethylsulfoxide (DMSO). The concentration of the sulfuric acid solution is 10-98 wt%, and the concentration of the calcium chloride solution is 3-5 wt%;
the third step specifically comprises: activating, namely putting the pretreated fiber into silver nitrate or palladium chloride solution with the concentration of 0.1-100 g/L, soaking at 25-120 ℃ for 5-90 min, taking out, and slowly rinsing with deionized water; the solvent of the activating solution is NMP, DMSO, DMAc, DMF or water;
the fourth step specifically includes: reducing, namely putting the activated fiber into a stannous chloride, sodium borohydride, dimethylamine borane or hydrazine hydrate solution with the concentration of 1-10 g/L, soaking for 5-30 min at 25-35 ℃, taking out, and rinsing with deionized water; the solvent of the reducing solution is NMP, DMSO, DMAc, DMF or water; after reduction, a noble metal target point firmly combined with the substrate is formed on the surface of the fiber, and the target point is used as an anchoring point and a catalytic point of a subsequent chemical plating layer.
6. The method for preparing conductive aromatic polyamide fiber with composite metal coating structure as claimed in claim 4, wherein the fifth step of electroless plating comprises: preparing a chemical nickel plating solution by using nickel salt, a complexing agent, a reducing agent, a buffering agent, a stabilizing agent and the like, and depositing a layer of metal nickel or nickel alloy on the surface of the fiber;
the reducing agent is sodium hypophosphite, dimethylamino borane and hydrazine hydrate;
by adjusting the pH value of the solution and the concentration of each component, phosphorus and boron elements in the reducing agent can be co-deposited with nickel to obtain nickel-phosphorus, nickel-boron or nickel-phosphorus-boron alloy.
7. The method for preparing conductive aromatic polyamide fiber with composite metal coating structure as claimed in claim 4, wherein the sixth step of copper electroplating comprises: preparing an electrolytic copper plating solution by using copper salt, a complexing agent, a stabilizing agent, a buffering agent and the like, and depositing a metal copper plating layer on the fiber surface treated by the fifth step under a certain current or voltage;
the process of the seventh step of nickel electroplating comprises the following steps: preparing nickel salt, complexing agent, stabilizer, buffering agent, brightener and the like into nickel electroplating solution, and depositing a metal nickel coating on the fiber surface treated in the sixth step under a certain current or voltage;
the eighth step of the optional silver electroplating process comprises the following steps: silver salt, complexing agent, stabilizer, buffering agent, brightener and the like are used to prepare silver electroplating solution, and a layer of metallic silver coating is deposited on the fiber surface treated by the seventh step under certain current or voltage.
8. An aerospace electromagnetic shielding material and conductor prepared by using the conductive aromatic polyamide fiber with a composite metal plating layer structure of claim 1.
9. A marine, satellite electromagnetic shielding material and conductor prepared by using the conductive aromatic polyamide fiber with a composite metal plating layer structure of claim 1.
10. An electromagnetic shielding material and a conductor in the communication and medical fields, which are prepared by using the conductive aromatic polyamide fiber with the composite metal coating structure of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911326096.XA CN110983764B (en) | 2019-12-20 | 2019-12-20 | Conductive aromatic polyamide fiber with composite metal coating structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911326096.XA CN110983764B (en) | 2019-12-20 | 2019-12-20 | Conductive aromatic polyamide fiber with composite metal coating structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110983764A true CN110983764A (en) | 2020-04-10 |
| CN110983764B CN110983764B (en) | 2022-04-05 |
Family
ID=70073601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911326096.XA Active CN110983764B (en) | 2019-12-20 | 2019-12-20 | Conductive aromatic polyamide fiber with composite metal coating structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110983764B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112267116A (en) * | 2020-10-28 | 2021-01-26 | 深圳亚太航空技术有限公司 | Light aramid fiber wave-proof sleeve |
| CN112680959A (en) * | 2020-12-16 | 2021-04-20 | 深圳大学 | Metallized stretchable elastic fabric and preparation method thereof |
| CN113512877A (en) * | 2021-07-30 | 2021-10-19 | 铜陵蔚屹新材料有限公司 | Continuous production process for silver metal firmly attached aromatic special fiber filament |
| CN114687205A (en) * | 2022-04-19 | 2022-07-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Multi-metal compounding method of high polymer fiber material and multi-metal composite fiber |
| CN115074998A (en) * | 2022-07-21 | 2022-09-20 | 武汉汉烯科技有限公司 | High-conductivity electroplated metal fiber pretreated by graphene and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0284328A (en) * | 1988-03-18 | 1990-03-26 | Asahi Chem Ind Co Ltd | Metallized film |
| US5302415A (en) * | 1992-12-08 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Electroless plated aramid surfaces and a process for making such surfaces |
| CN1345383A (en) * | 1999-02-03 | 2002-04-17 | 拜尔公司 | Metallizable moulded part |
| CN102071421A (en) * | 2010-01-15 | 2011-05-25 | 比亚迪股份有限公司 | Plastic product and preparation method thereof |
| CN103221577A (en) * | 2010-07-23 | 2013-07-24 | 希斯康先进材料股份有限公司 | Electrically conductive metal-oated fibers, continuous process for preparation thereof, and use thereof |
| CN104452272A (en) * | 2014-11-18 | 2015-03-25 | 上海大学 | Preparation method of silver-plated aromatic polysulphonamide fiber |
| CN104894846A (en) * | 2015-06-26 | 2015-09-09 | 上海大学 | Preparation method of nickel-plated aromatic polyamide fiber |
| CN109487542A (en) * | 2018-11-19 | 2019-03-19 | 吉林省泰华电子股份有限公司 | A kind of electromagnetic shielding preparation process of copper facing nickel fibre |
-
2019
- 2019-12-20 CN CN201911326096.XA patent/CN110983764B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0284328A (en) * | 1988-03-18 | 1990-03-26 | Asahi Chem Ind Co Ltd | Metallized film |
| US5302415A (en) * | 1992-12-08 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Electroless plated aramid surfaces and a process for making such surfaces |
| CN1345383A (en) * | 1999-02-03 | 2002-04-17 | 拜尔公司 | Metallizable moulded part |
| CN102071421A (en) * | 2010-01-15 | 2011-05-25 | 比亚迪股份有限公司 | Plastic product and preparation method thereof |
| CN103221577A (en) * | 2010-07-23 | 2013-07-24 | 希斯康先进材料股份有限公司 | Electrically conductive metal-oated fibers, continuous process for preparation thereof, and use thereof |
| CN104452272A (en) * | 2014-11-18 | 2015-03-25 | 上海大学 | Preparation method of silver-plated aromatic polysulphonamide fiber |
| CN104894846A (en) * | 2015-06-26 | 2015-09-09 | 上海大学 | Preparation method of nickel-plated aromatic polyamide fiber |
| CN109487542A (en) * | 2018-11-19 | 2019-03-19 | 吉林省泰华电子股份有限公司 | A kind of electromagnetic shielding preparation process of copper facing nickel fibre |
Non-Patent Citations (5)
| Title |
|---|
| HONGWEI PANG等: "A novel Ag catalyzation process using swelling impregnation method for electroless Ni deposition on Kevlar® fiber", 《APPLIED SURFACE SCIENCE》 * |
| 凌新龙 等: "芳纶纤维的改性研究新进展", 《天津工业大学学报》 * |
| 朱大勇 等: "CaCl2和多巴胺处理对芳纶纤维表面结构与性能的影响", 《高分子材料科学与工程》 * |
| 梁晶晶 等: "镀银导电芳纶纤维的制备及其性能研究", 《功能材料》 * |
| 邵勤思: "导电芳香族聚砜酰胺纤维的制备与性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112267116A (en) * | 2020-10-28 | 2021-01-26 | 深圳亚太航空技术有限公司 | Light aramid fiber wave-proof sleeve |
| CN112680959A (en) * | 2020-12-16 | 2021-04-20 | 深圳大学 | Metallized stretchable elastic fabric and preparation method thereof |
| CN113512877A (en) * | 2021-07-30 | 2021-10-19 | 铜陵蔚屹新材料有限公司 | Continuous production process for silver metal firmly attached aromatic special fiber filament |
| CN113512877B (en) * | 2021-07-30 | 2022-05-03 | 铜陵蔚屹新材料有限公司 | Continuous production process for silver metal firmly attached aromatic special fiber filament |
| CN114687205A (en) * | 2022-04-19 | 2022-07-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Multi-metal compounding method of high polymer fiber material and multi-metal composite fiber |
| CN115074998A (en) * | 2022-07-21 | 2022-09-20 | 武汉汉烯科技有限公司 | High-conductivity electroplated metal fiber pretreated by graphene and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110983764B (en) | 2022-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110983764B (en) | Conductive aromatic polyamide fiber with composite metal coating structure | |
| Lee et al. | Ultrahigh electromagnetic interference shielding performance of lightweight, flexible, and highly conductive copper-clad carbon fiber nonwoven fabrics | |
| CN111254423B (en) | Method for electroplating silver on aromatic polyamide fiber and application | |
| JP5461988B2 (en) | Metal laminated polyimide substrate and manufacturing method thereof | |
| CN102701603B (en) | Preparation method for copper/zinc coating on surface of glass fiber | |
| KR101365457B1 (en) | Method of Manufacturing Ni-coated Nano- carbons | |
| US9595719B2 (en) | Composite metal foil and production method therefor | |
| US20130323527A1 (en) | Porous metal foil and production method therefor | |
| CN107354752B (en) | Surface-coated silver F-12 conductive fiber and preparation method thereof | |
| JP5255015B2 (en) | Electroless copper plating method for polymer fiber | |
| CN107541953A (en) | A kind of composite conducting fiber and preparation method thereof | |
| KR101423169B1 (en) | A Method for Manufacturing of Shield Sheet for Preventing Electromagnetic Wave | |
| JP2011153372A (en) | Metal multilayer laminated electrical insulator, and method for producing the same | |
| CN102747394B (en) | Activating solution, its preparation method, and direct electroplating method of polar plastic surface | |
| KR101664857B1 (en) | Conductive yarn and method for preparing the same | |
| Fatema et al. | Iodine-aided palladium-free catalyzation process for durable electroless nickel plating on Kevlar® fiber | |
| JP4060363B2 (en) | Production of polymer monofilaments or yarns coated with heat stable metals | |
| JP2004502055A (en) | Fabric having gold layer formed thereon and method for producing same | |
| CN116083890A (en) | Substrate surface treatment method and application thereof | |
| JP4298946B2 (en) | Electromagnetic shielding material | |
| CN115216755A (en) | Method for activating electroless copper plating by copper salt on surface of non-woven fabric through two-step method | |
| Bai et al. | Highly conducting surface-silverized aromatic polysulfonamide (PSA) fibers with excellent performance prepared by nano-electroplating | |
| CN114032675A (en) | Conductive fiber and preparation method thereof | |
| CN112813675A (en) | Metallized polyimide fiber and preparation method thereof | |
| JP5039638B2 (en) | Metal-plated fiber structure and metal structure obtained by firing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Shao Qinsi Inventor after: Zhang Leilei Inventor after: Li Xiaolin Inventor after: Fu Qianru Inventor after: Li Minna Inventor after: Wang Shasha Inventor after: Rong Zhongyan Inventor after: Zhang Jiujun Inventor after: Bai Ruicheng Inventor before: Shao Qinsi Inventor before: Fu Qianru Inventor before: Li Minna Inventor before: Wang Shasha Inventor before: Rong Zhongyan Inventor before: Zhang Jiujun Inventor before: Bai Ruicheng |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |