US20210262095A1 - Electroless nickel plating of silicone rubber - Google Patents
Electroless nickel plating of silicone rubber Download PDFInfo
- Publication number
- US20210262095A1 US20210262095A1 US17/314,705 US202117314705A US2021262095A1 US 20210262095 A1 US20210262095 A1 US 20210262095A1 US 202117314705 A US202117314705 A US 202117314705A US 2021262095 A1 US2021262095 A1 US 2021262095A1
- Authority
- US
- United States
- Prior art keywords
- nickel
- organosiloxane polymer
- silicone rubber
- solution
- positively charged
- 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.)
- Abandoned
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 93
- 229920002379 silicone rubber Polymers 0.000 title claims description 132
- 239000004945 silicone rubber Substances 0.000 title claims description 130
- 238000007747 plating Methods 0.000 title description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 105
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 74
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 63
- -1 polydimethylsiloxane Polymers 0.000 claims description 61
- 239000003054 catalyst Substances 0.000 claims description 58
- 229920001296 polysiloxane Polymers 0.000 claims description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 38
- 229920002873 Polyethylenimine Polymers 0.000 claims description 25
- 239000000412 dendrimer Substances 0.000 claims description 22
- 229920000736 dendritic polymer Polymers 0.000 claims description 22
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 4
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 150000003335 secondary amines Chemical class 0.000 claims description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 229920000209 Hexadimethrine bromide Polymers 0.000 claims description 3
- 229920000707 Poly(2-dimethylamino)ethyl methacrylate) methyl chloride Polymers 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 3
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 3
- 239000002096 quantum dot Substances 0.000 claims description 3
- 229940063673 spermidine Drugs 0.000 claims description 3
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims description 3
- 229910002855 Sn-Pd Inorganic materials 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 62
- 239000011248 coating agent Substances 0.000 abstract description 30
- 238000000576 coating method Methods 0.000 abstract description 30
- 239000000243 solution Substances 0.000 description 103
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 91
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 18
- 238000000151 deposition Methods 0.000 description 18
- 239000012702 metal oxide precursor Substances 0.000 description 18
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 238000005530 etching Methods 0.000 description 14
- 230000008961 swelling Effects 0.000 description 14
- 230000008021 deposition Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 229910002666 PdCl2 Inorganic materials 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- 229910019430 NaSnO3 Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000003637 basic solution Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 150000002815 nickel Chemical class 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 239000012080 ambient air Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 description 2
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 description 2
- BSGHSLDKEDDYHI-UHFFFAOYSA-N 3-(2-ethylhexoxymethyl)heptane;titanium Chemical compound [Ti].CCCCC(CC)COCC(CC)CCCC BSGHSLDKEDDYHI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GGBZETYPUORFEI-UHFFFAOYSA-N [V+5].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] Chemical compound [V+5].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] GGBZETYPUORFEI-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000004703 alkoxides Chemical group 0.000 description 2
- UCRXQUVKDMVBBM-UHFFFAOYSA-N benzyl 2-amino-3-(4-phenylmethoxyphenyl)propanoate Chemical compound C=1C=CC=CC=1COC(=O)C(N)CC(C=C1)=CC=C1OCC1=CC=CC=C1 UCRXQUVKDMVBBM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CKEGKURXFKLBDX-UHFFFAOYSA-N butan-1-ol;hafnium Chemical compound [Hf].CCCCO.CCCCO.CCCCO.CCCCO CKEGKURXFKLBDX-UHFFFAOYSA-N 0.000 description 2
- PVZMSIQWTGPSHJ-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO PVZMSIQWTGPSHJ-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920005560 fluorosilicone rubber Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- LVNAMAOHFNPWJB-UHFFFAOYSA-N methanol;tantalum Chemical compound [Ta].OC.OC.OC.OC.OC LVNAMAOHFNPWJB-UHFFFAOYSA-N 0.000 description 2
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- MMXXQALNTZVDLM-UHFFFAOYSA-N CC(C)[O-].[Ti+4] Chemical compound CC(C)[O-].[Ti+4] MMXXQALNTZVDLM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910020264 Na2TiO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 238000007792 addition Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/208—Multistep pretreatment with use of metal first
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1565—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C23C18/02—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 thermal decomposition
- C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- 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
- C23C18/285—Sensitising or activating with tin based compound or composition
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Definitions
- the present disclosure relates to a method for coating nickel on an organosiloxane polymer.
- the present disclosure also relates to a nickel organosiloxane polymer composite.
- Silicone rubber is an elastomer composed of organosiloxane polymers such that they contain organic and inorganic moieties. Due to the Si—O bond and inorganic properties, silicone rubber tends to be superior over ordinary organic rubbers in terms of flexibility, heat resistance and chemical stability. Consequently, silicone rubber has been used widely in many areas including electronic, automotive and biomedical industries.
- metalized silicone rubber is a very useful material because it combines merits of the metallic surface with those of silicone rubber, such as softness, flexibility, stretchability, moldability, chemical and heat resistance. Potential applications may therefore include those that require electrical or thermal conductivity, electromagnetic interference (EMI) shielding, actuation, sensing or even corrosion protection.
- EMI electromagnetic interference
- metalized silicone rubbers may be used in interconnectors of flexible electronics, in smart sealing components and/or functionalized microfluidic devices.
- silicone rubber has very low surface energy and lacks reactive sites.
- the physical method relies on metal vapour deposition and may include e-beam assisted deposition, plasma assisted deposition, chemical and physical vapour deposition etc. Such physical methods, however, likely require high vacuum and tend to be difficult for industry adoption due to expensive equipments needed. Meanwhile, chemical methods may exploit reduction of metal ions to deposit metal on the polymer, e.g. in aqueous solution. Such chemical methods may be known as “electroless metal plating”. Examples so far include coating silicone rubber with noble metals such as platinum (Pt) and gold (Au) via electroless plating, and in such examples, the silicone rubber surface is first activated by ultraviolet (UV) laser and H 2 PtCl 6 solution, followed by coating with the noble metal salt solution that may be highly reactive. Although such chemical methods have been extensively utilized due to their energy efficiency, expensive specialized equipments and rare materials render such chemical methods economically unfeasible.
- UV ultraviolet
- a nickel organosiloxane polymer composite comprising:
- FIG. 1 shows a schematic illustration of an embodiment of the present method.
- FIG. 2 shows the contact angle (CA) of water droplet on various silicone rubber surfaces.
- FIG. 3 shows photos of untreated silicone rubber and silicone rubber that has undergone electroless nickel plating according to embodiments of the present method.
- FIG. 4 shows scanning electron microscopy (SEM) images of a nickel plated silicone rubber derived from an embodiment of the present method.
- the scale bar in both images represent 10 ⁇ m.
- the difference between the left and right SEM images lies in their magnification.
- the left SEM image has a magnification of ⁇ 300 while the right SEM image has a magnification of ⁇ 2500.
- FIG. 5 shows a schematic diagram of coating silicone with TiO 2 using titanium isopropoxide (TIP) and isopropyl alcohol (IPA) according to an embodiment disclosed herein.
- TIP titanium isopropoxide
- IPA isopropyl alcohol
- FIG. 6 shows the negatively charged structure of a tin-palladium (Sn—Pd) colloidal catalyst.
- FIG. 7 shows a typical setup of electroless nickel plating (ENP) bath.
- the present disclosure relates to a method that enables the coating of nickel onto an organosiloxane polymer (e.g. silicone rubber) by using electroless nickel plating (ENP).
- ENP electroless nickel plating
- the present disclosure also relates to a nickel organosiloxane polymer composite derived from the present method.
- the nickel organosiloxane polymer composite has improved adhesion strength of nickel plated on the organosiloxane polymer with improved plating quality.
- Electroless plating is a process in which a metal layer is deposited on a substrate by chemical reduction in the absence of an external electric current. This process is advantageously energy efficient.
- platinum plating on silicone rubber and nickel plating on silicone-rich polyester have been attempted.
- these require specialized equipments, such as ultraviolet laser or argon plasma to treat the silicone rubber surface, which render such techniques economically unviable.
- the present method uses a solution based method to modify an organosiloxane polymer (e.g. silicone rubber) surface for deposition of a catalyst for subsequent electroless nickel plating.
- the advantages of the present method are therefore, an easy to apply method, improved electroless nickel plating efficiency with reduced processing time of less than 30 mins, cost effectiveness, and the resultant nickel being plated in high quality.
- the articles “a”, “an” and “the” as used with regard to a feature or element include a reference to one or more of the features or elements.
- the term “about” or “approximately” as applied to a numeric value encompasses the exact value and a reasonable variance.
- phrase of the form of “at least one of A and B” may include A or B or both A and B.
- phrase of the form of “at least one of A and B and C”, or including further listed items may include any and all combinations of one or more of the associated listed items.
- a method for coating nickel on an organosiloxane polymer comprising: forming a transition metal oxide on the organosiloxane polymer, etching the transition metal oxide with a basic solution, contacting the organosiloxane polymer comprising the etched transition metal oxide with an aqueous solution comprising a positively charged species to attach the positively charged species on the etched transition metal oxide, depositing a metal catalyst on the positively charged species, and treating the metal catalyst with an acidic solution to develop an activated organosiloxane polymer before transferring the activated organosiloxane polymer to a solution comprising nickel and/or nickel derivatives.
- the organosiloxane polymer may be selected from the group consisting of polydimethylsiloxane, vinyl methyl polysiloxane (VMQ), phenyl methyl polysiloxane (PMQ), phenyl vinyl methyl polysiloxane (PVMQ), fluoro vinyl methyl polysiloxane (FVMQ) and derivatives of silicone rubber, wherein Q represents a quaternary silicon.
- VMQ vinyl methyl polysiloxane
- PMQ phenyl methyl polysiloxane
- PVMQ phenyl vinyl methyl polysiloxane
- FVMQ fluoro vinyl methyl polysiloxane
- the organosiloxane polymer may be selected from the group consisting of polydimethylsiloxane, vinyl methyl polysiloxane, phenyl methyl polysiloxane, phenyl vinyl methyl polysiloxane, fluoro vinyl methyl polysiloxane and derivatives of silicone rubber, wherein the polysiloxane may comprise at least one quaternary silicon.
- the silicon atoms in vinyl methyl polysiloxane may be quaternary silicon atoms.
- the transition metal oxide may comprise titanium oxide.
- the transition metal oxide may be selected from the group consisting of titanium oxide, zirconium oxide, vanadium oxide, hafnium oxide, niobium oxide and tantalum oxide.
- the forming may comprise contacting the organosiloxane polymer with a solution comprising a swelling agent and a transition metal oxide precursor for up to 30 minutes, and drying the organosiloxane polymer in ambient conditions comprising a temperature from 15° C. to 30° C. and a relative humidity from 30% to 70% to form the transition metal oxide on the organosiloxane polymer.
- the transition metal oxide precursor may be used to form an intermediate layer linking the organosiloxane polymer (e.g. silicone rubber) with the subsequent transition metal oxide layer that may be formed on surface of the organosiloxane polymer.
- the transition metal oxide precursor may have one or more alkoxide groups that can be hydrolyzed to form a three-dimensional (3D) network. In some embodiments, the transition metal oxide precursor may have four alkoxide groups.
- the organosiloxane polymer may expand to allow diffusion of the swelling agent as well as transition metal oxide precursor into the matrix of the organosiloxane polymer.
- the hydrolyzation and/or gelation of the transition metal oxide precursor embedded into and/or on the organosiloxane polymer may form a transition metal oxide network that mixes or merges (interpenetrating) with matrix of the organosiloxane polymer.
- the existence of such an intermediate layer in a transition metal oxide-polysiloxane interpenetrating structure advantageously enhances adhesion between the transition metal oxide layer and organosiloxane polymer.
- the thickness and structure of this intermediate layer may depend on time, temperature, humidity etc.
- the intermediate layer developed may be too thin to promote adhesion.
- Intermediate layer with high thickness undesirably reduces flexibility of the organosiloxane polymer.
- the advantage to the duration, temperature and/or humidity range lies in the ability to form an intermediate layer with a thickness sufficient to enhance adhesion between the transition metal oxide layer and organosiloxane polymer.
- the organosiloxane polymer may be contacted with the solution comprising the swelling agent and the transition metal oxide precursor for up to 30 mins, up to 20 mins, up to 10 mins, up to 5 minutes etc.
- the longer the duration the higher the amount of transition metal oxide that may be eventually formed on the organosiloxane polymer.
- the humidity i.e. moisture in air
- the swelling agent may be selected from the group consisting of isopropyl alcohol, methanol, 2-methoxyethanol, ethanol, 1-propanol, tert-butanol and their mixtures thereof.
- the swelling agent may penetrate the matrix of the organosiloxane polymer so that the transition metal oxide precursor may be able to diffuse into the matrix. If the transition metal oxide precursor only absorbs on the surface of the organosiloxane polymer, poor adhesion between the subsequently formed transition metal oxide and the organosiloxane polymer may develop.
- the swelling agent helps in formation of an intermediate layer to enhance such an adhesion.
- the organosiloxane polymer may not be swellable when the solution only contains transition metal oxide precursor.
- the swelling agent may comprise or consist of an alcohol.
- the use of alcohol as the swelling agent is advantageous because it is compatible with the transition metal oxide precursor and does not compromise hydrolysis rate of the transition metal oxide precursor.
- the alcohol may be isopropyl alcohol.
- the swelling agent may comprise or consist of isopropyl alcohol. Isopropyl alcohol may be preferred as it provides adequate swelling of the organosiloxane polymer and easily removed due to its low boiling point.
- the transition metal oxide precursor may comprise or consist of titanium isopropoxide.
- the transition metal oxide precursor may be selected from the group consisting of titanium isopropoxide, titanium propoxide, titanium methoxide, titanium ethoxide, titanium butoxide, titanium tert-butoxide, titanium 2-ethylhexyloxide, zirconium tert-butoxide, zirconium isopropoxide, vanadium isobutoxide, vanadium oxytriethoxide, vanadium oxytriisopropoxide, vanadium oxytripropoxide, hafnium n-butoxide, hafnium tert-butoxide, niobium ethoxide, tantalum methoxide, tantalum ethoxide and tantalum butoxide.
- the transition metal oxide prescursor and the swelling agent may comprise a volume ratio of 1:1 to 1:99.
- the volume ratio may be 1:9 (e.g. a TIP/IPA volume ratio of 10:90).
- the volume ratio may be 1:3 (e.g. a TIP/IPA volume ratio of 25:75).
- the transition metal oxide may be etched to modify hydrophilicity of the transition metal oxide coated organosiloxane polymer (e.g. silicone rubber) such that there is an increase in surface energy.
- Etching at this stage of the present method advantageously removes contaminants that may be present on surface of the modified organosiloxane polymer. This also advantageously increases surface energy of the modified organosiloxane polymer and may lead to stronger absorption and/or adsorption of positively charges species that may be subsequently coated thereon.
- the etching may occur for up to 1 min. In some embodiments, the etching may occur for at least 30 seconds or less than 30 seconds.
- a basic solution may be used.
- the basic solution may comprise or consist of NaOH according to various embodiments.
- the basic solution may comprise a concentration of 0.1 to 10 M in various embodiments.
- the basic solution may be selected from the group consisting of NaOH, KOH, LiOH and ammonia. Where NaOH is used, the NaOH may comprise or consist of a concentration of 3 M.
- the organosilioxane polymer e.g. silicone rubber
- the organosilioxane polymer may be coated with a positively charged species such that the positively charged species attached on the etched transition metal oxide changes polarity of charges present on the etched transition metal oxide.
- a positively charged species By using a positively charged species, the negatively charged surface of the organosiloxane polymer coated with the etched transition metal oxide may be tuned to become positively charged. This advantageously improves deposition of catalyst for subsequent electroless metal plating.
- the positively charged species is not a surfactant.
- the positively charged species may carry multiple charges on each molecule of the species. When they are absorbed and/or adsorbed on the negatively charged transition metal oxide, some of the charges may be neutralized while the rest remain charged. Therefore, the charging state of the surface may be inverted from negative to positive. In comparison, a surfactant molecule tends to carry only one charge and is unable to invert the charge of the transition metal oxide layer.
- the positively charged species may be coated on the etched transition metal oxide by contacting the organosiloxane polymer with an aqueous solution comprising the positively charged species.
- the aqueous solution may comprise or consist of 0.01 weight percent (wt %) to 1 wt % of the positively charged species.
- the positively charged species may be selected from the group consisting of positively charged nanoparticles or nanocolloids, and dendrimers comprising nitrogen.
- the positively charged species may also be selected from the group consisting of polymers having at least one primary amine, secondary amine, tertiary amine, pyridinyl, quaternized amine and/or quaternized pyridinyl, and their mixtures thereof.
- the positively charged nanoparticles or nanocolloids may comprise or consist of cetyltrimethylammonium bromide (CTAB) stabilized gold nanoparticles, spermidine stabilized silver nanoparticles, 2-(dimethylamino)ethanethiol-capped CdTe quantum dots and/or their mixtures thereof.
- CTAB cetyltrimethylammonium bromide
- the dendrimers may comprise or consist of polyamidoamine dendrimers, polyethylenimine dendrimers, polypropylenimine hexadecaamine dendrimers, ammonium-capped thiophosphoryl chloride dendrimers, ammonium-capped cyclotriphosphazene dendrimers and/or their mixtures thereof.
- the polymers may comprise or consist of polyamine, polyallylamine, polyetheramine, polyethylenimine, polyvinylpyridine, polybrene, chitosan, poly(2-(trimethylamino)ethyl methacrylate), poly(diallyldimethylammonium chloride), poly(N,N-dimethyl-3,5-dimethylene-piperidinium chloride), poly(2-vinyl-1-methylpyridinium bromide) and/or their mixtures thereof.
- the positively charged species may be polyethylenimine.
- the organosiloxane polymer of the contacting step may be contacted with the aqueous solution (comprising the positively charged species) for at least 5 minutes. In other embodiments, the contacting may be 5 mins or less.
- the catalyst for ENP may be deposited thereon.
- the depositing may comprise or consist contacting the positively charged species with a solution comprising the metal catalyst for at least 5 minutes to deposit the metal catalyst on the positively charged species. In other embodiments, the duration may be 5 mins or less.
- the metal catalyst may comprise or consist of, without being limited to, tin-palladium (Sn—Pd) colloidal metal catalyst.
- Other catalyst may be used depending on the metal to be deposited.
- Pd based catalyst may be used for plating other metals.
- Other catalysts, such as those that are copper based, may be used for plating other metals like gold, platinum etc.
- the metal catalyst (e.g. the tin-palladium colloidal metal catalyst) may be prepared by: dissolving PdCl 2 in an amount of 0.05 gram to 0.15 gram in 30 ml to 50 ml of HCl to form a first solution, dissolving SnCl 2 in 10 ml to 30 ml of HCl and subsequently adding 10 ml to 30 ml of water to form a second solution, mixing the first and second solutions, and continuously stirring the mixture (of the first and second solutions) for 10 minutes to 30 minutes, dissolving 4 gram to 5 gram of NaCl, 0.4 gram to 1.2 gram of NaSnO 3 and 5 gram to 15 gram of SnCl 2 in 40 ml to 60 ml of water to form a third solution, adding the third solution to the mixture over a duration of 20 minutes to 40 minutes, and incubating the mixture under continuous stirring for 3 hours to 5 hours at 60° C.
- PdCl 2 in an amount of 0.05
- the amount of each reagents used and the timing affect the quality of the Sn—Pd catalyst formed.
- the Sn—Pd catalyst formed under such conditions is advantageously stable with high catalytic activity, uniform in size and in the nano-scale. Otherwise, the Sn—Pd colloidal catalyst tends to aggregate during or after its formation, and/or catalytic activity may be reduced.
- the SnCl 2 for forming the second solution may be dissolved in an amount that may be at least three times the amount of PdCl 2 dissolved for forming the first solution. In some embodiments, the SnCl 2 may be dissolved in an amount of 0.5 gram to 1.5 gram.
- the concentration of HCl for forming the first solution and second solution may be 4 to 8 M and 9 to 12 M, respectively. In some embodiments, the concentration of HCl for forming the first solution and second solution may be 6 M and 12 M, respectively. These concentrations of HCl is advantageously useful for controlling size of the Sn—Pd nanocolloidal catalysts. Otherwise, the catalyst particle size may become undesirably large until it adversely affects their deposition on the modified organosiloxane polymer and also the catalytic activity.
- the metal catalyst may be treated with an acidic solution as mentioned above. This may activate the metal catalyst, so that the metal (e.g. nickel) can be electrolessly plated on. This treatment may be for at least 1 min or even less than 1 min. In some embodiments, the treatment with the acidic solution may be 3 mins.
- the acidic solution may comprise or consist of HCl. Since the outer layer of a Sn—Pd colloidal catalyst may contain Sn 2+ and/or Cl ⁇ , activation using an acidic solution may be required to remove such ions to have the active Pd site(s) exposed.
- the activated organosiloxane polymer may be transferred to a solution bath for electroless metal plating, particularly electroless nickel plating (ENP).
- the solution may comprise nickel and/or nickel derivatives.
- Such a solution may be an electroless nickel plating (ENP) solution.
- the activated organosiloxane polymer may be contacted with the ENP solution for at least 2 minutes. In other embodiments, the contact may be 2 mins or less.
- the ENP solution of the present method may be prepared by mixing 4 to 6 g/l (gram/litre) of NiSO 4 , 0.5 to 1.5 g/l of NaH 2 PO 4 , 0.5 to 1.5 g/l of oxycarboxylic acid and an amount of ammonia sufficient to maintain pH of the ENP solution between 4.5 and 5.5.
- the amounts for the various reagents may be determined to provide a preferred plating speed of the metal, in this instance, nickel. If concentrations happen to be too high, plating may be too fast and quality of the metal (e.g. nickel) coating may be adversely affected.
- the pH may be critical in the redox-reduction reaction between Ni 2+ and H 2 PO 4 ⁇ . Otherwise, the reaction for electroless plating would not occur.
- the ENP solution may be prepared by mixing 4.7 g/l of NiSO 4 , 1 g/l of NaH 2 PO 4 , 1 g/l of oxycarboxylic acid and an amount of ammonia sufficient to maintain pH of ENP solution at 4.9.
- the nickel derivatives may comprise or consist of nickel sulphate.
- the nickel derivatives may be selected from the group consisting of nickel sulphate, nickel chloride, nickel acetate, nickel nitrate and any acceptable nickel salts thereof.
- a 1-part silicone rubber or a 2-part silicone rubber may be used as the organosiloxane polymer.
- the forming step of the present method may further comprise preparation of the organosiloxane polymer, the preparation comprising the steps of: blending an organosiloxane polymer precursor with a cross-linking agent to form a blended mixture and curing the blended mixture at 170° C. to 180° C. under 8 MPa to 12 MPa for at least 5 minutes, or mixing two organosiloxane polymer precursors with a curing agent and curing at 25° C. to 35° C. for 48 hours.
- the cross-linking agent may be dicumyl peroxide.
- the curing agent may comprise or consist of platinum.
- the method may further comprise rinsing the organosiloxane polymer with isopropyl alcohol before the etching and rinsing with water after each of the etching, the contacting, the depositing and the treating.
- the present disclosure also provides for a nickel organosiloxane polymer composite comprising: a transition metal oxide layer formed on the organosiloxane polymer, and a positively charged species attached on the transition metal oxide layer with nickel coated on the positively charged species.
- the nickel organosiloxane polymer composite derived from the present method, has a high quality of nickel plated on the organosiloxane polymer with improved adhesion of nickel to the organosiloxane polymer.
- Embodiments and advantages described above in relation to the present method may be applicable and/or valid to embodiments of the nickel organosiloxane polymer composite, and vice versa.
- the nickel organosiloxane polymer may further comprise a trace amount of Sn—Pd catalyst under the nickel coated on the positively charged species. This may help to improve adhesion of nickel to the organosiloxane polymer.
- the organosiloxane polymer may be selected from the group consisting of polydimethylsiloxane, vinyl methyl polysiloxane, phenyl methyl polysiloxane, phenyl vinyl methyl polysiloxane, fluoro vinyl methyl polysiloxane and derivatives of silicone rubber, wherein the polysiloxane comprises a quaternary silicon.
- the transition metal oxide layer may comprise or consist of titanium oxide.
- the transition metal oxide layer may be selected from the group consisting of titanium oxide, zirconium oxide, vanadium oxide, hafnium oxide, niobium oxide and tantalum oxide.
- the positively charged species may be selected from the group consisting of positively charged nanoparticles or nanocolloids, and dendrimers comprising nitrogen.
- the positively charged species may also be selected from the group consisting of polymers having at least one primary amine, secondary amine, tertiary amine, pyridinyl, quaternized amine and/or quaternized pyridinyl, and their mixtures thereof.
- the positively charged nanoparticles or nanocolloids may comprise or consist of cetyltrimethylammonium bromide (CTAB) stabilized gold nanoparticles, spermidine stabilized silver nanoparticles, 2-(dimethylamino)ethanethiol-capped CdTe quantum dots and/or their mixtures thereof.
- CTAB cetyltrimethylammonium bromide
- the dendrimers may comprise or consist of polyamidoamine dendrimers, polyethylenimine dendrimers, polypropylenimine hexadecaamine dendrimers, ammonium-capped thiophosphoryl chloride dendrimers, ammonium-capped cyclotriphosphazene dendrimers and/or their mixtures thereof.
- the polymers may comprise or consist of polyamine, polyallylamine, polyetheramine, polyethylenimine, polyvinylpyridine, polybrene, chitosan, poly(2-(trimethylamino)ethyl methacrylate), poly(diallyldimethylammonium chloride), poly(N,N-dimethyl-3,5-dimethylene-piperidinium chloride), poly(2-vinyl-1-methylpyridinium bromide) and/or their mixtures thereof.
- the positively charged species may be polyethylenimine.
- the nickel, the Sn—Pd catalyst, the positively charged species and the transition metal oxide layer may form or may comprise a thickness of 2.52 to 3 ⁇ m.
- the overall thickness of these layers may also depend on the various agents used and duration of each of the steps of the present method.
- the present disclosure relates to an electroless plating method to coat nickel on an organosiloxane polymer e.g. silicone rubber, polydimethylsiloxane (PDMS), vinyl methyl polysiloxane (VMQ), phenyl methyl polysiloxane (PMQ), phenyl vinyl methyl polysiloxane (PVMQ), fluoro vinyl methyl polysiloxane (FVMQ) and derivatives of silicone rubber, wherein Q represents a quaternary silicon.
- PDMS polydimethylsiloxane
- VMQ vinyl methyl polysiloxane
- PMQ phenyl methyl polysiloxane
- PVMQ phenyl vinyl methyl polysiloxane
- FVMQ fluoro vinyl methyl polysiloxane
- derivatives of silicone rubber wherein Q represents a quaternary silicon.
- Q represents a quaternary silicon.
- the present method may include, as a non-limiting example, the following steps: sol-gel coating of titanium oxide (TiO 2 ) on silicone surface, etching of TiO 2 layer to increase the hydrophilicity and/or surface energy, coating of positively charged polyethylenimine, deposition of tin-palladium (Sn—Pd) colloidal catalyst, activation and electroless nickel plating (ENP).
- TiO 2 coating and then treatment with polyethylenimine (PEI) the silicone surface may be tuned from being inert and hydrophobic to hydrophilic and positively charged. The latter allows for deposition of Pd catalyst, which aids in electroless plating of nickel.
- the nickel film obtained via such steps advantageously has good continuity, high electrical conductivity and strong adhesion with the silicone.
- the present method involves plating metal on silicone.
- the present method also involves modifying silicone surface to be hydrophilic and charged.
- the present method further involves depositing catalyst on silicone surface for electroless plating.
- a metalized coating on silicone rubber that may provide high electrical conductivity and good durability may be produced.
- the present method and nickel coated organosiloxane polymer composite are described below by way of non-limiting examples.
- the present method of ENP is schematically illustrated in FIG. 1 , which includes the following steps.
- silicone rubber 1 was dipped into titanium isopropoxide-isopropyl alcohol (TIP/IPA) mixture (1-75 vol %) for about 5 minutes (mins) to coat or anchor a thin TiO 2 film 3 on the silicone rubber surface. This may be called a sol-gel procedure.
- TIP/IPA titanium isopropoxide-isopropyl alcohol
- step 200 the TiO 2 modified silicone rubber from step 100 was dipped into aqueous NaOH (0.1-10 M) for about 1 min so as to enhance hydrophilicity or increase surface energy of the TiO 2 film 3 by chemically etching it, and to increase its electrical potential. A negatively charged surface 5 was obtained.
- aqueous NaOH 0.1-10 M
- step 300 the negatively charged silicone rubber from step 200 was dipped into aqueous PEI (0.01-1 wt %) for about 10 mins to invert the sign of charge of the surface 5 by adsorption of positively charged PEI 7. A positively charged surface 9 was then obtained.
- step 400 the positively charged silicone rubber from step 300 was dipped into a Sn—Pd colloidal suspension solution for about 5 mins to deposit Pd catalyst 11.
- step 500 the catalyzed silicone rubber from step 400 was dipped into HCl solution for about 3 mins to activate the Pd catalyst 11 and nickel 13 was subsequently coated on the silicone rubber surface via ENP for about 5 mins.
- durations exemplified for each step disclosed in this example are non-limiting and may be shorter.
- Example 1b Nickel Plated Silicone Rubber with Shore a Hardness of 30
- Silicone rubber with Shore A hardness of 30 was prepared by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under a pressure of 10 MPa for 6 mins. The coating was performed through the following steps:
- the modified silicone rubber from (4) was immersed in 1 M HCl for 3 mins and rinsed with water, then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l (gram/litre) of NiSO 4 , 1 g/l of NaH 2 PO 2 , 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- the Sn—Pd catalyst of step (4) was prepared through the following steps:
- Example 1c Nickel Plated Silicone Rubber with Shore A Hardness of 70
- Silicone rubber with Shore A hardness of 70 was prepared by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under 10 MPa for 6 mins. The coating was performed through the following steps:
- the modified silicone rubber from (4) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO 4 , 1 g/l of NaH 2 PO 2 , 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- the Sn—Pd catalyst of step (4) was prepared through the following steps:
- Example 1d Nickel Plated Silicone Rubber with Shore a Hardness of 43
- Silicone rubber with Shore A hardness of 43 was prepared from 2-parts silicone (Sylgard 184).
- the 2-parts silicones comprise platinum (Pt) curing agent which was first blended and then cured at room temperature for 48 hours. The coating was performed through the following steps:
- the modified silicone rubber from (4) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO 4 , 1 g/l of NaH 2 PO 2 , 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- the Sn—Pd catalyst of step (4) was prepared through the following steps:
- Silicone rubber with Shore A hardness of 30 was prepared by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under 10 MPa for 6 mins. The coating was performed through the following steps:
- the modified silicone rubber from (3) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO 4 ; 1 g/l of NaH 2 PO 2 , 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- the Sn—Pd catalyst of step (3) was prepared through the following steps:
- Silicone rubber with Shore A hardness of 30 was prepared from by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under 10 MPa for 6 mins. The coating is performed through the following steps:
- the modified silicone rubber from (3) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO 4 , 1 g/l of NaH 2 PO 2 , 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- the Sn—Pd catalyst of step (3) was prepared through the following steps:
- Silicone rubber with Shore A hardness of 30 was prepared by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under 10 MPa for 6 mins. The coating was performed through the following steps:
- the modified silicone rubber from (3) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO 4 , 1 g/l of NaH 2 PO 2 , 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- the Sn—Pd catalyst of step (3) was prepared through the following steps:
- FIG. 2 shows the water contact angles of neat and TiO 2 coated silicone rubber at 120° and 76°, respectively. With TiO 2 coating and subsequent NaOH etching, the silicone rubber becomes even more hydrophilic with higher surface energy, having a water contact angle of 28°.
- FIG. 3 shows a photo of nickel plated silicone rubber from example 1b where the metallic coating is uniform and fully covers the silicone rubber surface.
- FIG. 4 shows the scanning electron microscopy (SEM) images of the nickel plated silicone rubber from example 1b.
- SEM scanning electron microscopy
- the surface conductivity of the nickel plated samples was measured by 4-probe resistivity meter (Mitsubishi Chemical Analytech MCP-T370). The thickness was estimated by the weight of the deposited nickel layer. Adhesion strength between the coating and substrate was determined by using the pull out adhesion test (DeFelsko PosiTest AT-A) in accordance with ASTM D 4541. All the data are listed in table 1 below.
- TIP The structure of TIP is shown below.
- TIP is prepared in the form of TIP/IPA solution before used. Silicone rubber is then immersed into the TIP/IPA solution. The silicone rubber will be swelled by the IPA and this allows the TIP molecules to enter the silicone rubber matrix. Subsequently, the silicone rubber is removed from the solution and rinsed with IPA. The TIP inside the silicone rubber matrix then diffuses to the surface and may be hydrolyzed by moisture in the air to form crosslinked TiO 2 on the surface of the silicone rubber. This process is shown in FIG. 5 .
- IPA IPA
- other feasible swelling agents may include methanol, 2-methoxyethanol, ethanol, 1-propanol, tert-butanol and/or their mixtures thereof.
- other transition metal oxide such as zirconium oxide, vanadium oxide, hafnium oxide, niobium oxide or tantalum oxide may be used.
- transition metal oxide precursor other transition metal oxide precursor such as titanium propoxide, titanium methoxide, titanium ethoxide, titanium butoxide, titanium tert-butoxide, titanium 2-ethylhexyloxide, zirconium tert-butoxide, zirconium isopropoxide, vanadium isobutoxide, vanadium oxytriethoxide, vanadium oxytriisopropoxide, vanadium oxytripropoxide, hafnium n-butoxide, hafnium tert-butoxide, niobium ethoxide, tantalum methoxide, tantalum ethoxide or tantalum butoxide may be used.
- transition metal oxide precursor such as titanium propoxide, titanium methoxide, titanium ethoxide, titanium butoxide, titanium tert-butoxide, titanium 2-ethylhexyloxide, zirconium tert-butoxide, zirconium isopropoxid
- Table 2 below shows how some properties of TiO 2 coated silicone rubber may be affected by duration of immersion in TIP/IPA.
- the hardness of silicone rubber increased with more TiO 2 coating.
- the duration of immersion in TIP/IPA becomes longer, the amount of TiO 2 hydrolyzed or coated on the silicone surface increases and the hardness of the modified silicone becomes higher. Based on this, the duration of immersion may be considered for limiting to 5 mins or less to minimize or avoid too high a hardness while yielding a silicone fully coated with TiO 2 .
- the effect of TIP concentration was also studied, using a silicone rubber with Shore A hardness of 30. The results are shown in table 3 below.
- TIP Concentration TIP IPA Water Contact Time Concentration Shore A Thickness Angle (mins) Ratio Hardness ( ⁇ m) (°) 5 25:75 35 5.1 82 10:90 32 2.6 85
- TIP IPA Water Contact Concentration Shore A Thickness Angle Ratio Time Hardness ( ⁇ m) (°) 25:75 30 seconds 31 0.9 88 1 min 33 1.6 78 2 mins 34 3.7 77 10:90 30 seconds 30 0.7 95 1 min 30-31 1.3 84 2 mins 30-31 1.5 81
- Neat silicone rubber has a water contact angle of 120° while TiO 2 modified silicone rubber may have a water contact angle in the range of about 75° to 85°.
- the decrease in water contact angle signifies that coating of silicone rubber with the transition metal oxide, TiO 2 , is successful.
- the water contact angle of TiO 2 coated silicone rubber is still considered high and not very hydrophilic. It is postulated that this may be because of adsorption of organic molecules on TiO 2 . While the hydrophilicity of TiO 2 can be tuned using ultraviolet radiation, a chemical method is used in the present disclosure instead.
- This chemical method relies on using a basic solution to etch the transition metal oxide, e.g. TiO 2 .
- the basic solution may include NaOH, KOH, LiOH, ammonia etc.
- An example of using NaOH is represented in the equation below.
- the resultant Sn—Pd colloidal catalyst (in solution) has a darker colour with no precipitate at bottom.
- the composition of an ENP solution was prepared as follows: 4.7 g/l of NiSO 4 , 1 g/l of NaH 2 PO 2 , 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- the ENP solution was green in colour.
- the etched TiO 2 silicone rubber was then immersed in the Sn—Pd catalyst solution for 5 mins. It was then removed and rinsed with water, followed by contacting with 1 M HCl for 3 mins to activate the catalyst. Subsequently, the catalyst coated silicone rubber was immersed in the ENP solution for nickel electroless plating.
- the ENP bath was at 88° C. to 90° C. However, few bubbles were observed on the silicone rubber surface and no reaction occurred. Even after some time, the silicone rubber floated to the surface, signifying that it has turned hydrophobic, losing its earlier hydrophilicity. This showed that ENP was unsuccessful. It was then concluded that it was the Sn—Pd catalyst deposition that was not successful because bubbles were actually generated from the metal pin used to load the samples into the ENP bath (see setup in FIG. 7 ). It was then attributed that both TiO 2 and Sn—Pd colloidal catalyst being negatively charged (even though both are hydrophilic and possess polar groups), resulted in electrostatic repulsion leading to unsuccessful deposition of catalyst. A negatively charged Sn—Pd catalyst is shown in FIG. 6 .
- the etched TiO 2 silicone rubber surface has to be modified to be positively charged and branched PEI (from Sigma 408727, Mw about 25,000, Mn about 10,000) was used.
- PEI positive charged species such as positively charged nanoparticles or nanocolloids, dendrimers comprising nitrogen and/or their mixtures thereof may be used.
- Polymers having at least one primary amine, secondary amine, tertiary amine, pyridinyl, quaternized amine and/or quaternized pyridinyl and/or their mixtures thereof may also be used.
- the procedure was therefore changed to immersing the etched TiO 2 silicone rubber in 1 wt % PEI solution for 10 mins before contacting the PEI coated silicone rubber with Sn—Pd colloidal catalyst solution, HCl activation solution and the ENP bath which have been described above.
- the setup of FIG. 7 was used and successful ENP was observed.
- the Sn—Pd deposition can be observed by the naked eye as a film red in colour on the silicone rubber was deposited and this red film was not removed when rinsed with water.
- the ENP stage after immersing the sample into the ENP bath, vigorous bubbling from the sample surface was observed which turned darker promptly first and then became white grey due to colour of nickel deposited.
- a summary of the characterized nickel plated silicone rubber are tabulated in table 5 below. These samples were derived with immersion duration of 5 mins in TIP/IPA (50:50 volume ratio).
- the electrical conductivity of the present nickel plated silicone rubber may be further improved by, for example, incorporating metal coated glass beads (about up to 80 wt %), Cu or Ag nanowires, or carbon nanoparticles, into a 2-parts silicone rubber. It can also be improved with metallic coating (conductive silicone oil with peroxide, further electroplating etc.) of a 2-parts silicone rubber.
- the thermal conductivity of the present nickel plated silicone rubber may be further improved by, for example, incorporating silicon carbide or boron nitride, into a 2-parts silicone rubber.
- Nickel plated organosiloxane polymers derived through the present method can include EMI shielding/gasket, flexible electrodes, soft actuators, microfluidic devices etc.
- table 6 demonstrates that the present nickel plated silicone rubber, and the present method, are advantageous over current industrial products. It should be noted that lower hardness yields better sealing performance when the silicone rubber is used for gasket applications while conductive silicone rubber with Shore A hardness below 40 is in higher demand by the industry.
- the present nickel plated silicone rubber can also be developed into a conductive foam.
- the present method can be used to plate nickel on other organosiloxane polymers.
- PDMS is a type of soft mold used in nanoimprinting. Its advantages include easy to replicate surface structures, low cost and ease of demolding. Accordingly, one potential application of the present method is to imprint metal coated nanostructures using nickel plated PDMS mold.
- the PDMS mold may be first plated with nickel and then used to imprint patterns (e.g. photoresist). This is because PDMS has a relatively lower surface energy than the pattern-imprinted material, after demolding, the metal (e.g. nickel) may be transferred to the material, resulting in a metallized pattern.
- the metallized pattern made via the present method can be in any shape and has a continuous metallic surface.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemically Coating (AREA)
Abstract
According to the present disclosure, a method for coating nickel on an organosiloxane polymer is provided. A nickel organosiloxane polymer composite is also provided.
Description
- The present disclosure relates to a method for coating nickel on an organosiloxane polymer. The present disclosure also relates to a nickel organosiloxane polymer composite.
- Silicone rubber is an elastomer composed of organosiloxane polymers such that they contain organic and inorganic moieties. Due to the Si—O bond and inorganic properties, silicone rubber tends to be superior over ordinary organic rubbers in terms of flexibility, heat resistance and chemical stability. Consequently, silicone rubber has been used widely in many areas including electronic, automotive and biomedical industries.
- The metallization of silicone rubber, i.e. the deposition of thin metallic film on its surface, is of great interest in the industries. Metalized silicone rubber is a very useful material because it combines merits of the metallic surface with those of silicone rubber, such as softness, flexibility, stretchability, moldability, chemical and heat resistance. Potential applications may therefore include those that require electrical or thermal conductivity, electromagnetic interference (EMI) shielding, actuation, sensing or even corrosion protection. For example, metalized silicone rubbers may be used in interconnectors of flexible electronics, in smart sealing components and/or functionalized microfluidic devices.
- The metallization of silicone rubber, however, is extremely difficult because silicone rubber has very low surface energy and lacks reactive sites.
- Conventionally, two types of methods have been reported for metallizing silicone rubber. One is physical in nature while the other is chemical in nature.
- The physical method relies on metal vapour deposition and may include e-beam assisted deposition, plasma assisted deposition, chemical and physical vapour deposition etc. Such physical methods, however, likely require high vacuum and tend to be difficult for industry adoption due to expensive equipments needed. Meanwhile, chemical methods may exploit reduction of metal ions to deposit metal on the polymer, e.g. in aqueous solution. Such chemical methods may be known as “electroless metal plating”. Examples so far include coating silicone rubber with noble metals such as platinum (Pt) and gold (Au) via electroless plating, and in such examples, the silicone rubber surface is first activated by ultraviolet (UV) laser and H2PtCl6 solution, followed by coating with the noble metal salt solution that may be highly reactive. Although such chemical methods have been extensively utilized due to their energy efficiency, expensive specialized equipments and rare materials render such chemical methods economically unfeasible.
- Conventionally, electroless nickel plating has been specifically applied on silicone-rich polyester surface but not on neat organosiloxane polymers (e.g. neat silicone rubber surface) due to inertness and low surface energy of the latter. The term “neat” means that a material is solely made of a single material. For example, a neat silicone rubber is composed only of silicone rubber.
- There is thus a need to provide for a method of electroless nickel plating on organsiloxane polymers, including silicone rubber, which resolves and/or ameliorates the issues mentioned above. The method provided should serve as an improved way to coat nickel and/or nickel derivatives onto neat organosiloxane polymers, including silicone rubber.
- There is also a need to provide for an organosiloxane polymer composite with nickel and/or nickel derivatives coated thereon. The nickel coated organosiloxane polymer composite should at least circumvent or ameliorate one or more of the issues as mentioned above.
- In one aspect, there is provided for a method for coating nickel on an organosiloxane polymer comprising:
- forming a transition metal oxide on the organosiloxane polymer;
- etching the transition metal oxide with a basic solution;
- contacting the organosiloxane polymer comprising the etched transition metal oxide with an aqueous solution comprising a positively charged species to attach the positively charged species on the etched transition metal oxide;
- depositing a metal catalyst on the positively charged species; and
- treating the metal catalyst with an acidic solution to develop an activated organosiloxane polymer before transferring the activated organosiloxane polymer to a solution comprising nickel and/or nickel derivatives.
- In another aspect, there is provided for a nickel organosiloxane polymer composite comprising:
- a transition metal oxide layer formed on the organosiloxane polymer; and
- a positively charged species attached on the transition metal oxide layer with nickel coated on the positively charged species.
- The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention. In the following description, various embodiments of the present disclosure are described with reference to the following drawings, in which:
-
FIG. 1 shows a schematic illustration of an embodiment of the present method. -
FIG. 2 shows the contact angle (CA) of water droplet on various silicone rubber surfaces. -
FIG. 3 shows photos of untreated silicone rubber and silicone rubber that has undergone electroless nickel plating according to embodiments of the present method. -
FIG. 4 shows scanning electron microscopy (SEM) images of a nickel plated silicone rubber derived from an embodiment of the present method. The scale bar in both images represent 10 μm. The difference between the left and right SEM images lies in their magnification. The left SEM image has a magnification of ×300 while the right SEM image has a magnification of ×2500. -
FIG. 5 shows a schematic diagram of coating silicone with TiO2 using titanium isopropoxide (TIP) and isopropyl alcohol (IPA) according to an embodiment disclosed herein. -
FIG. 6 shows the negatively charged structure of a tin-palladium (Sn—Pd) colloidal catalyst. -
FIG. 7 shows a typical setup of electroless nickel plating (ENP) bath. - The following detailed description refers to the accompanying drawings that show, by way of illustration, specific details and embodiments in which the invention may be practised.
- Features that are described in the context of an embodiment may correspondingly be applicable to the same or similar features in the other embodiments. Features that are described in the context of an embodiment may correspondingly be applicable to the other embodiments, even if not explicitly described in these other embodiments. Furthermore, additions and/or combinations and/or alternatives as described for a feature in the context of an embodiment may correspondingly be applicable to the same or similar feature in the other embodiments.
- The present disclosure relates to a method that enables the coating of nickel onto an organosiloxane polymer (e.g. silicone rubber) by using electroless nickel plating (ENP). This generally involves modifying the organosiloxane polymer's surface so that it becomes hydrophilic and positively charged. On this modified surface, palladium (Pd) catalyst is then deposited with subsequent ENP achieved. The present disclosure also relates to a nickel organosiloxane polymer composite derived from the present method. Advantageously, the nickel organosiloxane polymer composite has improved adhesion strength of nickel plated on the organosiloxane polymer with improved plating quality.
- Electroless plating is a process in which a metal layer is deposited on a substrate by chemical reduction in the absence of an external electric current. This process is advantageously energy efficient. Conventionally, platinum plating on silicone rubber and nickel plating on silicone-rich polyester have been attempted. However, these require specialized equipments, such as ultraviolet laser or argon plasma to treat the silicone rubber surface, which render such techniques economically unviable. The present method, however, uses a solution based method to modify an organosiloxane polymer (e.g. silicone rubber) surface for deposition of a catalyst for subsequent electroless nickel plating. The advantages of the present method are therefore, an easy to apply method, improved electroless nickel plating efficiency with reduced processing time of less than 30 mins, cost effectiveness, and the resultant nickel being plated in high quality.
- Having outlined various advantages of the present method and the nickel organosiloxane polymer composite, definitions of certain terms are first discussed before going into details of the various embodiments.
- The word “substantially” does not exclude “completely” e.g. a composition which is “substantially free” from Y may be completely free from Y. Where necessary, the word “substantially” may be omitted from the definition of the invention.
- In the context of various embodiments, the articles “a”, “an” and “the” as used with regard to a feature or element include a reference to one or more of the features or elements.
- In the context of various embodiments, the term “about” or “approximately” as applied to a numeric value encompasses the exact value and a reasonable variance.
- As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
- As used herein, the phrase of the form of “at least one of A and B” may include A or B or both A and B. Correspondingly, the phrase of the form of “at least one of A and B and C”, or including further listed items, may include any and all combinations of one or more of the associated listed items.
- Unless specified otherwise, the terms “comprising” and “comprise”, and grammatical variants thereof, are intended to represent “open” or “inclusive” language such that they include recited elements but also permit inclusion of additional, unrecited elements.
- Having defined the various terms as mentioned above, details of the various embodiments are now described below.
- In the present disclosure, there is provided for a method for coating nickel on an organosiloxane polymer comprising: forming a transition metal oxide on the organosiloxane polymer, etching the transition metal oxide with a basic solution, contacting the organosiloxane polymer comprising the etched transition metal oxide with an aqueous solution comprising a positively charged species to attach the positively charged species on the etched transition metal oxide, depositing a metal catalyst on the positively charged species, and treating the metal catalyst with an acidic solution to develop an activated organosiloxane polymer before transferring the activated organosiloxane polymer to a solution comprising nickel and/or nickel derivatives.
- In various embodiments, the organosiloxane polymer may be selected from the group consisting of polydimethylsiloxane, vinyl methyl polysiloxane (VMQ), phenyl methyl polysiloxane (PMQ), phenyl vinyl methyl polysiloxane (PVMQ), fluoro vinyl methyl polysiloxane (FVMQ) and derivatives of silicone rubber, wherein Q represents a quaternary silicon. In other words, the organosiloxane polymer may be selected from the group consisting of polydimethylsiloxane, vinyl methyl polysiloxane, phenyl methyl polysiloxane, phenyl vinyl methyl polysiloxane, fluoro vinyl methyl polysiloxane and derivatives of silicone rubber, wherein the polysiloxane may comprise at least one quaternary silicon. To illustrate, the silicon atoms in vinyl methyl polysiloxane may be quaternary silicon atoms.
- In various embodiments, the transition metal oxide may comprise titanium oxide. In various embodiments, the transition metal oxide may be selected from the group consisting of titanium oxide, zirconium oxide, vanadium oxide, hafnium oxide, niobium oxide and tantalum oxide.
- According to the present method, the forming may comprise contacting the organosiloxane polymer with a solution comprising a swelling agent and a transition metal oxide precursor for up to 30 minutes, and drying the organosiloxane polymer in ambient conditions comprising a temperature from 15° C. to 30° C. and a relative humidity from 30% to 70% to form the transition metal oxide on the organosiloxane polymer.
- The transition metal oxide precursor may be used to form an intermediate layer linking the organosiloxane polymer (e.g. silicone rubber) with the subsequent transition metal oxide layer that may be formed on surface of the organosiloxane polymer. The transition metal oxide precursor may have one or more alkoxide groups that can be hydrolyzed to form a three-dimensional (3D) network. In some embodiments, the transition metal oxide precursor may have four alkoxide groups. When the organosiloxane polymer (e.g. silicone rubber) is contacted with the solution comprising the swelling agent and transition metal oxide precursor, the organosiloxane polymer may swell, i.e. the organosiloxane polymer may expand to allow diffusion of the swelling agent as well as transition metal oxide precursor into the matrix of the organosiloxane polymer. The hydrolyzation and/or gelation of the transition metal oxide precursor embedded into and/or on the organosiloxane polymer may form a transition metal oxide network that mixes or merges (interpenetrating) with matrix of the organosiloxane polymer. The existence of such an intermediate layer in a transition metal oxide-polysiloxane interpenetrating structure advantageously enhances adhesion between the transition metal oxide layer and organosiloxane polymer. The thickness and structure of this intermediate layer may depend on time, temperature, humidity etc. For example, if the time of contact is short and humidity is low, the intermediate layer developed may be too thin to promote adhesion. Intermediate layer with high thickness, however, undesirably reduces flexibility of the organosiloxane polymer. The advantage to the duration, temperature and/or humidity range lies in the ability to form an intermediate layer with a thickness sufficient to enhance adhesion between the transition metal oxide layer and organosiloxane polymer.
- In some embodiments, the organosiloxane polymer may be contacted with the solution comprising the swelling agent and the transition metal oxide precursor for up to 30 mins, up to 20 mins, up to 10 mins, up to 5 minutes etc. The longer the duration, the higher the amount of transition metal oxide that may be eventually formed on the organosiloxane polymer. The humidity (i.e. moisture in air) allows hydrolysis of the transition metal oxide precursor to form transition metal oxide on the organosiloxane polymer.
- In various embodiments, the swelling agent may be selected from the group consisting of isopropyl alcohol, methanol, 2-methoxyethanol, ethanol, 1-propanol, tert-butanol and their mixtures thereof. The swelling agent may penetrate the matrix of the organosiloxane polymer so that the transition metal oxide precursor may be able to diffuse into the matrix. If the transition metal oxide precursor only absorbs on the surface of the organosiloxane polymer, poor adhesion between the subsequently formed transition metal oxide and the organosiloxane polymer may develop. The swelling agent helps in formation of an intermediate layer to enhance such an adhesion. The organosiloxane polymer may not be swellable when the solution only contains transition metal oxide precursor.
- In various embodiments, the swelling agent may comprise or consist of an alcohol. The use of alcohol as the swelling agent is advantageous because it is compatible with the transition metal oxide precursor and does not compromise hydrolysis rate of the transition metal oxide precursor. The alcohol may be isopropyl alcohol. In some embodiments, the swelling agent may comprise or consist of isopropyl alcohol. Isopropyl alcohol may be preferred as it provides adequate swelling of the organosiloxane polymer and easily removed due to its low boiling point.
- In various embodiments, the transition metal oxide precursor may comprise or consist of titanium isopropoxide. In some embodiments, the transition metal oxide precursor may be selected from the group consisting of titanium isopropoxide, titanium propoxide, titanium methoxide, titanium ethoxide, titanium butoxide, titanium tert-butoxide, titanium 2-ethylhexyloxide, zirconium tert-butoxide, zirconium isopropoxide, vanadium isobutoxide, vanadium oxytriethoxide, vanadium oxytriisopropoxide, vanadium oxytripropoxide, hafnium n-butoxide, hafnium tert-butoxide, niobium ethoxide, tantalum methoxide, tantalum ethoxide and tantalum butoxide.
- In various embodiments, the transition metal oxide prescursor and the swelling agent may comprise a volume ratio of 1:1 to 1:99. In some instances, the volume ratio may be 1:9 (e.g. a TIP/IPA volume ratio of 10:90). In other instances, the volume ratio may be 1:3 (e.g. a TIP/IPA volume ratio of 25:75).
- After forming the transition metal oxide on the organosiloxane polymer, the transition metal oxide may be etched to modify hydrophilicity of the transition metal oxide coated organosiloxane polymer (e.g. silicone rubber) such that there is an increase in surface energy. Etching at this stage of the present method advantageously removes contaminants that may be present on surface of the modified organosiloxane polymer. This also advantageously increases surface energy of the modified organosiloxane polymer and may lead to stronger absorption and/or adsorption of positively charges species that may be subsequently coated thereon. In various embodiments, the etching may occur for up to 1 min. In some embodiments, the etching may occur for at least 30 seconds or less than 30 seconds.
- To carry out the etching, a basic solution may be used. The basic solution may comprise or consist of NaOH according to various embodiments. The basic solution may comprise a concentration of 0.1 to 10 M in various embodiments. In some embodiments, the basic solution may be selected from the group consisting of NaOH, KOH, LiOH and ammonia. Where NaOH is used, the NaOH may comprise or consist of a concentration of 3 M.
- After etching the transition metal oxide, the organosilioxane polymer (e.g. silicone rubber) may be coated with a positively charged species such that the positively charged species attached on the etched transition metal oxide changes polarity of charges present on the etched transition metal oxide. By using a positively charged species, the negatively charged surface of the organosiloxane polymer coated with the etched transition metal oxide may be tuned to become positively charged. This advantageously improves deposition of catalyst for subsequent electroless metal plating. The positively charged species is not a surfactant. The positively charged species may carry multiple charges on each molecule of the species. When they are absorbed and/or adsorbed on the negatively charged transition metal oxide, some of the charges may be neutralized while the rest remain charged. Therefore, the charging state of the surface may be inverted from negative to positive. In comparison, a surfactant molecule tends to carry only one charge and is unable to invert the charge of the transition metal oxide layer.
- In various embodiments, the positively charged species may be coated on the etched transition metal oxide by contacting the organosiloxane polymer with an aqueous solution comprising the positively charged species. In various embodiments, the aqueous solution may comprise or consist of 0.01 weight percent (wt %) to 1 wt % of the positively charged species.
- In various embodiments, the positively charged species may be selected from the group consisting of positively charged nanoparticles or nanocolloids, and dendrimers comprising nitrogen. The positively charged species may also be selected from the group consisting of polymers having at least one primary amine, secondary amine, tertiary amine, pyridinyl, quaternized amine and/or quaternized pyridinyl, and their mixtures thereof. The positively charged nanoparticles or nanocolloids may comprise or consist of cetyltrimethylammonium bromide (CTAB) stabilized gold nanoparticles, spermidine stabilized silver nanoparticles, 2-(dimethylamino)ethanethiol-capped CdTe quantum dots and/or their mixtures thereof.
- The dendrimers may comprise or consist of polyamidoamine dendrimers, polyethylenimine dendrimers, polypropylenimine hexadecaamine dendrimers, ammonium-capped thiophosphoryl chloride dendrimers, ammonium-capped cyclotriphosphazene dendrimers and/or their mixtures thereof. The polymers may comprise or consist of polyamine, polyallylamine, polyetheramine, polyethylenimine, polyvinylpyridine, polybrene, chitosan, poly(2-(trimethylamino)ethyl methacrylate), poly(diallyldimethylammonium chloride), poly(N,N-dimethyl-3,5-dimethylene-piperidinium chloride), poly(2-vinyl-1-methylpyridinium bromide) and/or their mixtures thereof. In some embodiments, the positively charged species may be polyethylenimine.
- In various embodiments, the organosiloxane polymer of the contacting step may be contacted with the aqueous solution (comprising the positively charged species) for at least 5 minutes. In other embodiments, the contacting may be 5 mins or less.
- Once the positively charged species are attached on the etched transition metal oxide of the organosiloxane polymer, the catalyst for ENP may be deposited thereon. In the present method, the depositing may comprise or consist contacting the positively charged species with a solution comprising the metal catalyst for at least 5 minutes to deposit the metal catalyst on the positively charged species. In other embodiments, the duration may be 5 mins or less.
- According to various embodiments, the metal catalyst may comprise or consist of, without being limited to, tin-palladium (Sn—Pd) colloidal metal catalyst. Other catalyst may be used depending on the metal to be deposited. Pd based catalyst may be used for plating other metals. Other catalysts, such as those that are copper based, may be used for plating other metals like gold, platinum etc.
- In the present method, the metal catalyst (e.g. the tin-palladium colloidal metal catalyst) may be prepared by: dissolving PdCl2 in an amount of 0.05 gram to 0.15 gram in 30 ml to 50 ml of HCl to form a first solution, dissolving SnCl2 in 10 ml to 30 ml of HCl and subsequently adding 10 ml to 30 ml of water to form a second solution, mixing the first and second solutions, and continuously stirring the mixture (of the first and second solutions) for 10 minutes to 30 minutes, dissolving 4 gram to 5 gram of NaCl, 0.4 gram to 1.2 gram of NaSnO3 and 5 gram to 15 gram of SnCl2 in 40 ml to 60 ml of water to form a third solution, adding the third solution to the mixture over a duration of 20 minutes to 40 minutes, and incubating the mixture under continuous stirring for 3 hours to 5 hours at 60° C. to 70° C. The amount of each reagents used and the timing affect the quality of the Sn—Pd catalyst formed. The Sn—Pd catalyst formed under such conditions is advantageously stable with high catalytic activity, uniform in size and in the nano-scale. Otherwise, the Sn—Pd colloidal catalyst tends to aggregate during or after its formation, and/or catalytic activity may be reduced.
- In some embodiments, the SnCl2 for forming the second solution may be dissolved in an amount that may be at least three times the amount of PdCl2 dissolved for forming the first solution. In some embodiments, the SnCl2 may be dissolved in an amount of 0.5 gram to 1.5 gram.
- In various embodiments, the concentration of HCl for forming the first solution and second solution may be 4 to 8 M and 9 to 12 M, respectively. In some embodiments, the concentration of HCl for forming the first solution and second solution may be 6 M and 12 M, respectively. These concentrations of HCl is advantageously useful for controlling size of the Sn—Pd nanocolloidal catalysts. Otherwise, the catalyst particle size may become undesirably large until it adversely affects their deposition on the modified organosiloxane polymer and also the catalytic activity.
- Once the metal catalyst has been prepared and deposited on the positively charged species of the organosiloxane polymer, the metal catalyst may be treated with an acidic solution as mentioned above. This may activate the metal catalyst, so that the metal (e.g. nickel) can be electrolessly plated on. This treatment may be for at least 1 min or even less than 1 min. In some embodiments, the treatment with the acidic solution may be 3 mins. The acidic solution may comprise or consist of HCl. Since the outer layer of a Sn—Pd colloidal catalyst may contain Sn2+ and/or Cl−, activation using an acidic solution may be required to remove such ions to have the active Pd site(s) exposed.
- Once the metal catalyst has been deposited and activated, the activated organosiloxane polymer may be transferred to a solution bath for electroless metal plating, particularly electroless nickel plating (ENP). In various embodiments, the solution may comprise nickel and/or nickel derivatives. Such a solution may be an electroless nickel plating (ENP) solution. The activated organosiloxane polymer may be contacted with the ENP solution for at least 2 minutes. In other embodiments, the contact may be 2 mins or less.
- In various embodiments, the ENP solution of the present method may be prepared by mixing 4 to 6 g/l (gram/litre) of NiSO4, 0.5 to 1.5 g/l of NaH2PO4, 0.5 to 1.5 g/l of oxycarboxylic acid and an amount of ammonia sufficient to maintain pH of the ENP solution between 4.5 and 5.5. The amounts for the various reagents may be determined to provide a preferred plating speed of the metal, in this instance, nickel. If concentrations happen to be too high, plating may be too fast and quality of the metal (e.g. nickel) coating may be adversely affected. The pH may be critical in the redox-reduction reaction between Ni2+ and H2PO4 −. Otherwise, the reaction for electroless plating would not occur.
- In some embodiments, the ENP solution may be prepared by mixing 4.7 g/l of NiSO4, 1 g/l of NaH2PO4, 1 g/l of oxycarboxylic acid and an amount of ammonia sufficient to maintain pH of ENP solution at 4.9.
- In various embodiments, the nickel derivatives may comprise or consist of nickel sulphate. The nickel derivatives may be selected from the group consisting of nickel sulphate, nickel chloride, nickel acetate, nickel nitrate and any acceptable nickel salts thereof.
- In the present method, a 1-part silicone rubber or a 2-part silicone rubber may be used as the organosiloxane polymer. To prepare such silicone rubbers, the forming step of the present method may further comprise preparation of the organosiloxane polymer, the preparation comprising the steps of: blending an organosiloxane polymer precursor with a cross-linking agent to form a blended mixture and curing the blended mixture at 170° C. to 180° C. under 8 MPa to 12 MPa for at least 5 minutes, or mixing two organosiloxane polymer precursors with a curing agent and curing at 25° C. to 35° C. for 48 hours. In various embodiments, the cross-linking agent may be dicumyl peroxide. The curing agent may comprise or consist of platinum.
- Between various steps of the present method, washing off residual chemicals may be required. In various embodiments, the method may further comprise rinsing the organosiloxane polymer with isopropyl alcohol before the etching and rinsing with water after each of the etching, the contacting, the depositing and the treating.
- The present disclosure also provides for a nickel organosiloxane polymer composite comprising: a transition metal oxide layer formed on the organosiloxane polymer, and a positively charged species attached on the transition metal oxide layer with nickel coated on the positively charged species. The nickel organosiloxane polymer composite, derived from the present method, has a high quality of nickel plated on the organosiloxane polymer with improved adhesion of nickel to the organosiloxane polymer. Embodiments and advantages described above in relation to the present method may be applicable and/or valid to embodiments of the nickel organosiloxane polymer composite, and vice versa.
- In various embodiments, the nickel organosiloxane polymer may further comprise a trace amount of Sn—Pd catalyst under the nickel coated on the positively charged species. This may help to improve adhesion of nickel to the organosiloxane polymer.
- The organosiloxane polymer may be selected from the group consisting of polydimethylsiloxane, vinyl methyl polysiloxane, phenyl methyl polysiloxane, phenyl vinyl methyl polysiloxane, fluoro vinyl methyl polysiloxane and derivatives of silicone rubber, wherein the polysiloxane comprises a quaternary silicon.
- In various embodiments, the transition metal oxide layer may comprise or consist of titanium oxide. In various embodiments, the transition metal oxide layer may be selected from the group consisting of titanium oxide, zirconium oxide, vanadium oxide, hafnium oxide, niobium oxide and tantalum oxide.
- The positively charged species may be selected from the group consisting of positively charged nanoparticles or nanocolloids, and dendrimers comprising nitrogen. The positively charged species may also be selected from the group consisting of polymers having at least one primary amine, secondary amine, tertiary amine, pyridinyl, quaternized amine and/or quaternized pyridinyl, and their mixtures thereof. The positively charged nanoparticles or nanocolloids may comprise or consist of cetyltrimethylammonium bromide (CTAB) stabilized gold nanoparticles, spermidine stabilized silver nanoparticles, 2-(dimethylamino)ethanethiol-capped CdTe quantum dots and/or their mixtures thereof. The dendrimers may comprise or consist of polyamidoamine dendrimers, polyethylenimine dendrimers, polypropylenimine hexadecaamine dendrimers, ammonium-capped thiophosphoryl chloride dendrimers, ammonium-capped cyclotriphosphazene dendrimers and/or their mixtures thereof. The polymers may comprise or consist of polyamine, polyallylamine, polyetheramine, polyethylenimine, polyvinylpyridine, polybrene, chitosan, poly(2-(trimethylamino)ethyl methacrylate), poly(diallyldimethylammonium chloride), poly(N,N-dimethyl-3,5-dimethylene-piperidinium chloride), poly(2-vinyl-1-methylpyridinium bromide) and/or their mixtures thereof. In some embodiments, the positively charged species may be polyethylenimine.
- In various embodiments, the nickel, the Sn—Pd catalyst, the positively charged species and the transition metal oxide layer may form or may comprise a thickness of 2.52 to 3 μm. The overall thickness of these layers may also depend on the various agents used and duration of each of the steps of the present method.
- While the methods described above are illustrated and described as a series of steps or events, it will be appreciated that any ordering of such steps or events are not to be interpreted in a limiting sense. For example, some steps may occur in different orders and/or concurrently with other steps or events apart from those illustrated and/or described herein. In addition, not all illustrated steps may be required to implement one or more aspects or embodiments described herein. Also, one or more of the steps depicted herein may be carried out in one or more separate acts and/or phases.
- The present disclosure relates to an electroless plating method to coat nickel on an organosiloxane polymer e.g. silicone rubber, polydimethylsiloxane (PDMS), vinyl methyl polysiloxane (VMQ), phenyl methyl polysiloxane (PMQ), phenyl vinyl methyl polysiloxane (PVMQ), fluoro vinyl methyl polysiloxane (FVMQ) and derivatives of silicone rubber, wherein Q represents a quaternary silicon. The latter means that the silicon atom(s) in the polysiloxane (with Q in its abbreviation) is a quaternary silicon atom(s).
- The present method may include, as a non-limiting example, the following steps: sol-gel coating of titanium oxide (TiO2) on silicone surface, etching of TiO2 layer to increase the hydrophilicity and/or surface energy, coating of positively charged polyethylenimine, deposition of tin-palladium (Sn—Pd) colloidal catalyst, activation and electroless nickel plating (ENP). By using TiO2 coating and then treatment with polyethylenimine (PEI), the silicone surface may be tuned from being inert and hydrophobic to hydrophilic and positively charged. The latter allows for deposition of Pd catalyst, which aids in electroless plating of nickel. The nickel film obtained via such steps advantageously has good continuity, high electrical conductivity and strong adhesion with the silicone.
- The present method involves plating metal on silicone. The present method also involves modifying silicone surface to be hydrophilic and charged. The present method further involves depositing catalyst on silicone surface for electroless plating.
- According to various non-limiting embodiments of the present method, a metalized coating on silicone rubber that may provide high electrical conductivity and good durability may be produced. The present method and nickel coated organosiloxane polymer composite are described below by way of non-limiting examples.
- The present method of ENP is schematically illustrated in
FIG. 1 , which includes the following steps. - In
step 100,silicone rubber 1 was dipped into titanium isopropoxide-isopropyl alcohol (TIP/IPA) mixture (1-75 vol %) for about 5 minutes (mins) to coat or anchor a thin TiO2 film 3 on the silicone rubber surface. This may be called a sol-gel procedure. - In step 200, the TiO2 modified silicone rubber from
step 100 was dipped into aqueous NaOH (0.1-10 M) for about 1 min so as to enhance hydrophilicity or increase surface energy of the TiO2 film 3 by chemically etching it, and to increase its electrical potential. A negatively chargedsurface 5 was obtained. - In step 300, the negatively charged silicone rubber from step 200 was dipped into aqueous PEI (0.01-1 wt %) for about 10 mins to invert the sign of charge of the
surface 5 by adsorption of positively chargedPEI 7. A positively chargedsurface 9 was then obtained. - In
step 400, the positively charged silicone rubber from step 300 was dipped into a Sn—Pd colloidal suspension solution for about 5 mins to depositPd catalyst 11. - In
step 500, the catalyzed silicone rubber fromstep 400 was dipped into HCl solution for about 3 mins to activate thePd catalyst 11 andnickel 13 was subsequently coated on the silicone rubber surface via ENP for about 5 mins. - The durations exemplified for each step disclosed in this example are non-limiting and may be shorter.
- Silicone rubber with Shore A hardness of 30 was prepared by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under a pressure of 10 MPa for 6 mins. The coating was performed through the following steps:
- (1) The silicone rubber was immersed in TIP/IPA solution (50:50 volume ratio) for 5 mins and then rinsed with IPA and dried in ambient air.
- (2) The modified silicone rubber from (1) was immersed in 3 M NaOH solution for 1 min and then rinsed with water.
- (3) The modified silicone rubber from (2) was immersed in 1 weight percent (wt %) branched PEI solution for 10 mins and then rinsed with water.
- (4) The modified silicone rubber from (3) was immersed in Sn—Pd colloidal catalyst solution for 5 mins. This was followed by rinsing with water.
- (5) The modified silicone rubber from (4) was immersed in 1 M HCl for 3 mins and rinsed with water, then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l (gram/litre) of NiSO4, 1 g/l of NaH2PO2, 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- The Sn—Pd catalyst of step (4) was prepared through the following steps:
- (a) Dissolving 0.1 g PdCl2 in 40 ml of 6 M HCl under magnetic stirring.
- (b) Adding 1 g SnCl2 into 20 ml of 12 M HCl. After complete dissolution, 20 ml of water was added to the solution of (b) to become more diluted.
- (c) Solution of (b) was then added to solution of (a) under continuous stirring for 20 mins.
- (d) 4.4 g of NaCl, 0.8 g of NaSnO3 and 10 g of SnCl2 were dissolved in 50 ml water. Subsequently, solution of (d) was added slowly to solution of (c) for 30 mins.
- (e) The mixture from (d) was kept in a water bath at 65° C. for 4 hours under stirring.
- Silicone rubber with Shore A hardness of 70 was prepared by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under 10 MPa for 6 mins. The coating was performed through the following steps:
- (1) The silicone rubber was immersed in TIP/IPA solution (50:50) for 5 mins and then rinsed with IPA and dried in ambient air.
- (2) The modified silicone rubber from (1) was immersed in 3 M NaOH solution for 1 min and then rinsed with water.
- (3) The modified silicone rubber from (2) was immersed in 1 wt % branched PEI solution for 10 mins and then rinsed with water.
- (4) The modified silicone rubber from (3) was immersed in Sn—Pd colloidal catalyst solution for 5 mins, followed by rinsing with water.
- (5) The modified silicone rubber from (4) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO4, 1 g/l of NaH2PO2, 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- The Sn—Pd catalyst of step (4) was prepared through the following steps:
- (a) 0.1 g PdCl2 was dissolved in 40 ml of 6 M HCl under magnetic stirring.
- (b) 1.0 g SnCl2 was added into 20 ml of 12 M HCl. After complete dissolution, 20 ml water was added to the solution.
- (c) Solution of (b) was added into solution of (a) under continuous stirring for 20 mins.
- (d) 4.4 g of NaCl, 0.8 g of NaSnO3 and 10 g of SnCl2 were dissolved in 50 ml water. Subsequently, solution of (d) was added slowly into solution of (c) for 30 mins.
- (e) The mixture from (d) was kept in a water bath at 65° C. for 4 hours under stirring.
- Silicone rubber with Shore A hardness of 43 was prepared from 2-parts silicone (Sylgard 184). The 2-parts silicones comprise platinum (Pt) curing agent which was first blended and then cured at room temperature for 48 hours. The coating was performed through the following steps:
- (1) The 2-parts silicone rubber was immersed in TIP/IPA (50:50) solution for 5 mins and then rinsed with IPA and dried in ambient air.
- (2) The modified silicone rubber from (1) was immersed in 3 M NaOH solution for 1 min and then rinsed with water.
- (3) The modified silicone rubber from (2) was immersed in 1 wt % branched PEI solution for 10 mins and then rinsed with water.
- (4) The modified silicone rubber from (3) was immersed in Sn—Pd colloidal catalyst for 5 mins, followed by rinsing with water.
- (5) The modified silicone rubber from (4) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO4, 1 g/l of NaH2PO2, 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- The Sn—Pd catalyst of step (4) was prepared through the following steps:
- (a) 0.1 g PdCl2 was dissolved in 40 ml of 6 M HCl under magnetic stirring.
- (b) 1.0 g SnCl2 was added into 20 ml of 12 M HCl. After complete dissolution, 20 mL water was added to the solution.
- (c) Solution of (b) was added into solution of (a) under continuous stirring for 20 mins
- (d) 4.4 g of NaCl, 0.8 g of NaSnO3 and 10 g of SnCl2 were dissolved in 50 ml water. Subsequently, solution of (d) was added slowly into solution of (c) for 30 mins.
- (e) The mixture from (d) was kept in a water bath at 65° C. for 4 hours under stirring.
- Silicone rubber with Shore A hardness of 30 was prepared by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under 10 MPa for 6 mins. The coating was performed through the following steps:
- (1) The silicone rubber was immersed in 3 M NaOH solution for 1 min and then rinsed with water.
- (2) The modified silicone rubber from (1) was immersed in 1 wt % branched PEI solution for 10 mins and then rinsed with water.
- (3) The modified silicone rubber from (2) was immersed in Sn—Pd colloidal catalyst for 5 mins, followed by rinsing with water.
- (4) The modified silicone rubber from (3) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO4; 1 g/l of NaH2PO2, 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- The Sn—Pd catalyst of step (3) was prepared through the following steps:
- (a) 0.1 g PdCl2 was dissolved in 40 ml of 6 M HCl under magnetic stirring.
- (b) 1.0 g SnCl2 was added into 20 ml of 12 M HCl. After complete dissolution, 20 ml water was added to the solution.
- (c) Solution of (b) was added into solution of (a) under continuous stirring for 20 mins.
- (d) 4.4 g of NaCl, 0.8 g of NaSnO3 and 10 g of SnCl2 were dissolved in 50 ml water. Subsequently, solution of (d) was added slowly into solution of (c) for 30 mins.
- (e) The mixture from (d) was kept in a water bath at 65° C. for 4 hours under stirring.
- Silicone rubber with Shore A hardness of 30 was prepared from by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under 10 MPa for 6 mins. The coating is performed through the following steps:
- (1) The silicone rubber was immersed in TIP/IPA solution (50:50) for 5 mins and then rinsed with IPA and dried in ambient air.
- (2) The modified silicone rubber from (1) was immersed in 1 wt % branched polyethylenimine (PEI) solution for 10 min, then rinsed with water.
- (3) The modified silicone rubber from (2) was immersed in Sn—Pd colloidal catalyst for 5 mins, followed by rinsing with water.
- (4) The modified silicone rubber from (3) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO4, 1 g/l of NaH2PO2, 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- The Sn—Pd catalyst of step (3) was prepared through the following steps:
- (a) 0.1 g PdCl2 was dissolved in 40 ml of 6 M HCl under magnetic stirring.
- (b) 1.0 g SnCl2 was added into 20 ml of 12 M HCl. After complete dissolution, 20 ml water was added to the solution.
- (c) Solution of (b) was added into solution of (a) under continuous stirring for 20 mins.
- (d) 4.4 g of NaCl, 0.8 g of NaSnO3 and 10 g of SnCl2 were dissolved in 50 ml water. Subsequently, solution of (d) was added slowly into solution of (c) for 30 mins.
- (e) The mixture from (d) was kept in a water bath at 65° C. for 4 hours under stirring.
- Silicone rubber with Shore A hardness of 30 was prepared by blending 1-part silicone (from Momentive) with dicumyl peroxide and cured at 175° C. under 10 MPa for 6 mins. The coating was performed through the following steps:
- (1) The silicone rubber was immersed in TIP/IPA solution (50:50) for 5 mins and then rinsed by IPA and dried in ambient air.
- (2) The modified silicone rubber from (1) was immersed in 3 M NaOH solution for 1 min and then rinsed with water.
- (3) The modified silicone rubber from (2) was immersed in Sn—Pd colloidal catalyst for 5 mins, followed by rinsing with water.
- (4) The modified silicone rubber from (3) was immersed in 1 M HCl for 3 mins and rinsed with water, and then immersed in an ENP solution at 89° C. for 5 mins with the following composition: 4.7 g/l of NiSO4, 1 g/l of NaH2PO2, 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9.
- The Sn—Pd catalyst of step (3) was prepared through the following steps:
- (a) 0.1 g PdCl2 was dissolved in 40 ml of 6 M HCl under magnetic stirring.
- (b) 1.0 g SnCl2 was added into 20 ml of 12 M HCl. After complete dissolution, 20 ml water was added to the solution.
- (c) Solution of (b) was added into solution of (a) under continuous stirring for 20 mins.
- (d) 4.4 g of NaCl, 0.8 g of NaSnO3 and 10 g of SnCl2 were dissolved in 50 ml water. Subsequently, solution of (d) was added slowly into solution of (c) for 30 mins.
- (e) The mixture from (d) was kept in a water bath at 65° C. for 4 hours under stirring.
- The resultant nickel plated silicone rubber derived from the present method was characterized and the results are discussed as follow.
-
FIG. 2 shows the water contact angles of neat and TiO2 coated silicone rubber at 120° and 76°, respectively. With TiO2 coating and subsequent NaOH etching, the silicone rubber becomes even more hydrophilic with higher surface energy, having a water contact angle of 28°. -
FIG. 3 shows a photo of nickel plated silicone rubber from example 1b where the metallic coating is uniform and fully covers the silicone rubber surface. -
FIG. 4 shows the scanning electron microscopy (SEM) images of the nickel plated silicone rubber from example 1b. The difference between the left and right SEM images lies in their magnification, the left image having a magnification of ×300 while the right image has a magnification of ×2500. The plated nickel layer has high continuity, conductivity, smoothness and adhesion to silicone rubber. - The surface conductivity of the nickel plated samples was measured by 4-probe resistivity meter (Mitsubishi Chemical Analytech MCP-T370). The thickness was estimated by the weight of the deposited nickel layer. Adhesion strength between the coating and substrate was determined by using the pull out adhesion test (DeFelsko PosiTest AT-A) in accordance with ASTM D 4541. All the data are listed in table 1 below.
-
TABLE 1 Properties of Nickel Plated Silicone Rubber. Nickel Coating Surface Adhesion Nickel Thickness Resistivity Strength Deposition (μm) (Ω/sq) (MPa) Example 1b Yes 2.5 1.3 0.48 Example 1c Yes 2.8 0.8 0.79 Example 1d Yes 3.0 1.2 0.90 Comparative No — — — Example 1a Comparative Yes 1.4 26.3 0.31 Example 1b Comparative No — — — Example 1c - The structure of TIP is shown below.
- TIP can be hydrolyzed by water and this is depicted by the equation below.
-
Ti{OCH(CH3)2}4+2H2O→TiO2+4(CH3)2CHOH - As the hydrolysis of TIP is fast, TIP is prepared in the form of TIP/IPA solution before used. Silicone rubber is then immersed into the TIP/IPA solution. The silicone rubber will be swelled by the IPA and this allows the TIP molecules to enter the silicone rubber matrix. Subsequently, the silicone rubber is removed from the solution and rinsed with IPA. The TIP inside the silicone rubber matrix then diffuses to the surface and may be hydrolyzed by moisture in the air to form crosslinked TiO2 on the surface of the silicone rubber. This process is shown in
FIG. 5 . - Apart from using IPA as the swelling agent, other feasible swelling agents may include methanol, 2-methoxyethanol, ethanol, 1-propanol, tert-butanol and/or their mixtures thereof. Apart from coating TiO2, other transition metal oxide such as zirconium oxide, vanadium oxide, hafnium oxide, niobium oxide or tantalum oxide may be used. This implies other than TIP as the transition metal oxide precursor, other transition metal oxide precursor such as titanium propoxide, titanium methoxide, titanium ethoxide, titanium butoxide, titanium tert-butoxide, titanium 2-ethylhexyloxide, zirconium tert-butoxide, zirconium isopropoxide, vanadium isobutoxide, vanadium oxytriethoxide, vanadium oxytriisopropoxide, vanadium oxytripropoxide, hafnium n-butoxide, hafnium tert-butoxide, niobium ethoxide, tantalum methoxide, tantalum ethoxide or tantalum butoxide may be used.
- Table 2 below shows how some properties of TiO2 coated silicone rubber may be affected by duration of immersion in TIP/IPA.
-
TABLE 2 Immersion of Silicone Rubber in TIP/IPA Solution (50/50) for Various Duration before Rinsing with IPA and Drying in Air Time TiO2 Thickness Water Contact Angle (mins) Shore A Hardness (μm) (°) 0 38 0 120 1 43 12 85 2 45 19 81 5 49 22 76 10 52 28 74 20 54 33 80 - As observed from table 2, the hardness of silicone rubber increased with more TiO2 coating. In other words, when the duration of immersion in TIP/IPA becomes longer, the amount of TiO2 hydrolyzed or coated on the silicone surface increases and the hardness of the modified silicone becomes higher. Based on this, the duration of immersion may be considered for limiting to 5 mins or less to minimize or avoid too high a hardness while yielding a silicone fully coated with TiO2. The effect of TIP concentration was also studied, using a silicone rubber with Shore A hardness of 30. The results are shown in table 3 below.
-
TABLE 3 Comparison of TIP Concentration TIP:IPA Water Contact Time Concentration Shore A Thickness Angle (mins) Ratio Hardness (μm) (°) 5 25:75 35 5.1 82 10:90 32 2.6 85 - As seen from table 3, thickness of TiO2 decreased when concentration of TIP was lowered. This also resulted in lowering of hardness. Meanwhile, table 4 below demonstrates the effect of duration of immersion at different concentration of TIP. The concentration ratio is based on volume of the reagents and hence may be referred to as a volume ratio as well.
-
TABLE 4 Effect of Immersion Duration at Different TIP Concentration TIP:IPA Water Contact Concentration Shore A Thickness Angle Ratio Time Hardness (μm) (°) 25:75 30 seconds 31 0.9 88 1 min 33 1.6 78 2 mins 34 3.7 77 10:90 30 seconds 30 0.7 95 1 min 30-31 1.3 84 2 mins 30-31 1.5 81 - Neat silicone rubber has a water contact angle of 120° while TiO2 modified silicone rubber may have a water contact angle in the range of about 75° to 85°. The decrease in water contact angle signifies that coating of silicone rubber with the transition metal oxide, TiO2, is successful. However, the water contact angle of TiO2 coated silicone rubber is still considered high and not very hydrophilic. It is postulated that this may be because of adsorption of organic molecules on TiO2. While the hydrophilicity of TiO2 can be tuned using ultraviolet radiation, a chemical method is used in the present disclosure instead.
- This chemical method relies on using a basic solution to etch the transition metal oxide, e.g. TiO2. The basic solution may include NaOH, KOH, LiOH, ammonia etc. An example of using NaOH is represented in the equation below.
-
TiO2+2NaOH→Na2TiO3+H2O - As a non-limiting example, this is carried out by immersing the TiO2 coated silicone rubber into 3 M NaOH. After 1 min, the water contact angle was measured, dropping from 74° to 28°. This demonstrates such a chemical method is advantageous for enhancing hydrophilicity of the silicone rubber such that the surface energy of the silicone rubber is increased.
- It was presumed that after etching the TiO2 silicone rubber, the latter would have been ready for ENP. To this end, the preparation of a Sn—Pd colloidal solution was carried out as follows.
- (1) Dissolution of 0.1 PdCl2 in 40 ml 50% HCl (HCl:water in 50:50 ratio). The 50% HCl and HCl:water ratio are derived on a volume basis.
- (2) 1.0 g of SnCl2 was added into 20 ml concentrated HCl (37%). After complete dissolution, 20 ml water was added.
- (3) Solution of (2) was added to solution of (1) under stirring. The mixture turned from red to a darker colour under continuous stirring for 20 mins.
- (4) 4.4 g of NaCl, 0.8 g of NaSnO3 and 10 g of SnCl2 were dissolved in 50 ml water. Subsequently, solution of (4) was added slowly into solution of (3) for 30 mins.
- (e) The mixture from (4) was kept in a water bath at 65° C. for 4 hours under stirring.
- It was observed that the resultant Sn—Pd colloidal catalyst (in solution) has a darker colour with no precipitate at bottom. Meanwhile, the composition of an ENP solution was prepared as follows: 4.7 g/l of NiSO4, 1 g/l of NaH2PO2, 1 g/l of oxycarboxylic acid and a certain amount of ammonia to adjust the pH to 4.9. The ENP solution was green in colour. The etched TiO2 silicone rubber was then immersed in the Sn—Pd catalyst solution for 5 mins. It was then removed and rinsed with water, followed by contacting with 1 M HCl for 3 mins to activate the catalyst. Subsequently, the catalyst coated silicone rubber was immersed in the ENP solution for nickel electroless plating. The ENP bath was at 88° C. to 90° C. However, few bubbles were observed on the silicone rubber surface and no reaction occurred. Even after some time, the silicone rubber floated to the surface, signifying that it has turned hydrophobic, losing its earlier hydrophilicity. This showed that ENP was unsuccessful. It was then concluded that it was the Sn—Pd catalyst deposition that was not successful because bubbles were actually generated from the metal pin used to load the samples into the ENP bath (see setup in
FIG. 7 ). It was then attributed that both TiO2 and Sn—Pd colloidal catalyst being negatively charged (even though both are hydrophilic and possess polar groups), resulted in electrostatic repulsion leading to unsuccessful deposition of catalyst. A negatively charged Sn—Pd catalyst is shown inFIG. 6 . To resolve this, the etched TiO2 silicone rubber surface has to be modified to be positively charged and branched PEI (from Sigma 408727, Mw about 25,000, Mn about 10,000) was used. Other than PEI, positively charged species such as positively charged nanoparticles or nanocolloids, dendrimers comprising nitrogen and/or their mixtures thereof may be used. Polymers having at least one primary amine, secondary amine, tertiary amine, pyridinyl, quaternized amine and/or quaternized pyridinyl and/or their mixtures thereof may also be used. - The procedure was therefore changed to immersing the etched TiO2 silicone rubber in 1 wt % PEI solution for 10 mins before contacting the PEI coated silicone rubber with Sn—Pd colloidal catalyst solution, HCl activation solution and the ENP bath which have been described above. The setup of
FIG. 7 was used and successful ENP was observed. After PEI treatment and dipping in the Sn—Pd solution, the Sn—Pd deposition can be observed by the naked eye as a film red in colour on the silicone rubber was deposited and this red film was not removed when rinsed with water. As for the ENP stage, after immersing the sample into the ENP bath, vigorous bubbling from the sample surface was observed which turned darker promptly first and then became white grey due to colour of nickel deposited. A summary of the characterized nickel plated silicone rubber are tabulated in table 5 below. These samples were derived with immersion duration of 5 mins in TIP/IPA (50:50 volume ratio). -
TABLE 5 Characterized Results Summary of Various Samples Conduc- Adhesion Coating Shore A tivity Strength Thickness Hardness Silicone Sample (Ω/sq) (MPa) (μm) 30 From Momentive 26030 1.3 0.48 2.5 70 From Momentive 22870 0.8 0.79 2.8 43 Dow Corning Slygard 1.2 0.9 3 184 - The electrical conductivity of the present nickel plated silicone rubber may be further improved by, for example, incorporating metal coated glass beads (about up to 80 wt %), Cu or Ag nanowires, or carbon nanoparticles, into a 2-parts silicone rubber. It can also be improved with metallic coating (conductive silicone oil with peroxide, further electroplating etc.) of a 2-parts silicone rubber.
- The thermal conductivity of the present nickel plated silicone rubber may be further improved by, for example, incorporating silicon carbide or boron nitride, into a 2-parts silicone rubber.
- Application of nickel plated organosiloxane polymers derived through the present method can include EMI shielding/gasket, flexible electrodes, soft actuators, microfluidic devices etc.
- A comparison of a nickel plated silicone rubber derived via the present method with current industrial products is shown in table 6 below.
-
TABLE 6 Comparison of Present Sample with Current Industrial Products Nickel Holland EMI Plated Shielding Conductive Holland Silicone Systems Rubber Shielding Rubber of 5750 ECR-213 Systems 5770 Present (Industrial (Industrial (Industrial Method Product) Product) Product) Material Nickel Conductive Conductive Nickel plated plated silicone silicone polyurethane silicone filled with filled with foam rubber Ag/Cu nickel/graphite Shore 32 78 60 Less than 10 A Hardness Density 1.1 3.5 1.9 Less than 0.1 (g/cm3) Resistivity 0.0003 0.002 0.1 0.02 (Ω cm) Working −60 to 220 −60 to 220 −60 to 220 −45 to 85 Temperature (° C.) - Clearly, table 6 demonstrates that the present nickel plated silicone rubber, and the present method, are advantageous over current industrial products. It should be noted that lower hardness yields better sealing performance when the silicone rubber is used for gasket applications while conductive silicone rubber with Shore A hardness below 40 is in higher demand by the industry. The present nickel plated silicone rubber can also be developed into a conductive foam.
- Apart from using silicone rubber as an example, the present method can be used to plate nickel on other organosiloxane polymers. One such example is PDMS. PDMS is a type of soft mold used in nanoimprinting. Its advantages include easy to replicate surface structures, low cost and ease of demolding. Accordingly, one potential application of the present method is to imprint metal coated nanostructures using nickel plated PDMS mold. For implantation, the PDMS mold may be first plated with nickel and then used to imprint patterns (e.g. photoresist). This is because PDMS has a relatively lower surface energy than the pattern-imprinted material, after demolding, the metal (e.g. nickel) may be transferred to the material, resulting in a metallized pattern. Unlike e-beam evaporation, the metallized pattern made via the present method can be in any shape and has a continuous metallic surface.
- While the invention has been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is thus indicated by the appended claims and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced.
Claims (10)
1. A nickel organosiloxane polymer composite comprising:
a transition metal oxide layer formed on the organosiloxane polymer; and
a positively charged species attached on the transition metal oxide layer with nickel coated on the positively charged species.
2. The nickel organosiloxane polymer composite according to claim 1 , wherein the nickel organosiloxane polymer further comprises a trace amount of Sn—Pd catalyst under the nickel coated on the positively charged species.
3. The nickel organosiloxane polymer composite according to claim 1 , wherein the organosiloxane polymer is selected from the group consisting of polydimethylsiloxane, vinyl methyl polysiloxane, phenyl methyl polysiloxane, phenyl vinyl methyl polysiloxane, fluoro vinyl methyl polysiloxane and derivatives of silicone rubber, wherein the polysiloxane comprises a quaternary silicon.
4. The nickel organosiloxane polymer composite according to claim 1 , wherein the transition metal oxide layer comprises titanium oxide.
5. The nickel organosiloxane polymer composite according to claim 4 , wherein the transition metal oxide layer is selected from the group consisting of titanium oxide, zirconium oxide, vanadium oxide, hafnium oxide, niobium oxide and tantalum oxide.
6. The nickel organosiloxane polymer composite according to claim 1 , wherein the positively charged species is selected from the group consisting of positively charged nanoparticles or nanocolloids, dendrimers comprising nitrogen, polymers having at least one primary amine, secondary amine, tertiary amine, pyridinyl, quaternized amine and/or quaternized pyridinyl and their mixtures thereof.
7. The nickel organosiloxane polymer composite according to claim 6 , wherein the positively charged nanoparticles or nanocolloids comprise cetyltrimethylammonium bromide (CTAB) stabilized gold nanoparticles, spermidine stabilized silver nanoparticles, 2-(dimethylamino)ethanethiol-capped CdTe quantum dots and/or their mixtures thereof.
8. The nickel organosiloxane polymer composite according to claim 6 , wherein the dendrimers comprise polyamidoamine dendrimers, polyethylenimine dendrimers, polypropylenimine hexadecaamine dendrimers, ammonium-capped thiophosphoryl chloride dendrimers, ammonium-capped cyclotriphosphazene dendrimers and/or their mixtures thereof.
9. The nickel organosiloxane polymer composite according to claim 6 , wherein the polymers comprise polyamine, polyallylamine, polyetheramine, polyethylenimine, polyvinylpyridine, polybrene, chitosan, poly(2-(trimethylamino)ethyl methacrylate), poly(diallyldimethylammonium chloride), poly(N,N-dimethyl-3,5-dimethylene-piperidinium chloride), poly(2-vinyl-1-methylpyridinium bromide) and/or their mixtures thereof.
10. The nickel organosiloxane polymer composite according to claim 2 , wherein the nickel, the Sn—Pd catalyst, the positively charged species and the transition metal oxide layer comprise a thickness of 2.52 to 3 μm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/314,705 US20210262095A1 (en) | 2016-11-03 | 2021-05-07 | Electroless nickel plating of silicone rubber |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SG10201609215P | 2016-11-03 | ||
SG10201609215P | 2016-11-03 | ||
PCT/SG2017/050543 WO2018084804A1 (en) | 2016-11-03 | 2017-10-30 | Electroless nickel plating of silicone rubber |
US201916345684A | 2019-04-26 | 2019-04-26 | |
US17/314,705 US20210262095A1 (en) | 2016-11-03 | 2021-05-07 | Electroless nickel plating of silicone rubber |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/345,684 Division US11028484B2 (en) | 2016-11-03 | 2017-10-30 | Electroless nickel plating of silicone rubber |
PCT/SG2017/050543 Division WO2018084804A1 (en) | 2016-11-03 | 2017-10-30 | Electroless nickel plating of silicone rubber |
Publications (1)
Publication Number | Publication Date |
---|---|
US20210262095A1 true US20210262095A1 (en) | 2021-08-26 |
Family
ID=62076969
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/345,684 Active 2038-03-08 US11028484B2 (en) | 2016-11-03 | 2017-10-30 | Electroless nickel plating of silicone rubber |
US17/314,705 Abandoned US20210262095A1 (en) | 2016-11-03 | 2021-05-07 | Electroless nickel plating of silicone rubber |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/345,684 Active 2038-03-08 US11028484B2 (en) | 2016-11-03 | 2017-10-30 | Electroless nickel plating of silicone rubber |
Country Status (2)
Country | Link |
---|---|
US (2) | US11028484B2 (en) |
WO (1) | WO2018084804A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11355614B2 (en) * | 2018-02-01 | 2022-06-07 | Hefei Boe Display Technology Co., Ltd. | Thin film transistor, method for preparing the same, display substrate and display device |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110306174A (en) * | 2019-07-29 | 2019-10-08 | 深圳市飞荣达科技股份有限公司 | Colloid nickel composition and its application |
KR20240036699A (en) * | 2021-09-30 | 2024-03-20 | 미쓰이 가가쿠 가부시키가이샤 | Manufacturing method of composite material to be plated and manufacturing method of anisotropic conductive sheet |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0134825A1 (en) | 1983-08-22 | 1985-03-27 | Allied Corporation | Pretreatment of plastic materials for metal plating |
GB9722028D0 (en) | 1997-10-17 | 1997-12-17 | Shipley Company Ll C | Plating of polymers |
JP3705344B2 (en) * | 2000-08-17 | 2005-10-12 | 信越化学工業株式会社 | Conductive silicone rubber composition |
CN101122016B (en) | 2007-09-07 | 2010-09-01 | 中国矿业大学 | Silicon rubber chemical copper-plating technique |
JP5518998B2 (en) | 2010-03-23 | 2014-06-11 | Jx日鉱日石金属株式会社 | Electroless plating pretreatment agent, electroless plating method and electroless plated product using the same |
US20120094035A1 (en) | 2010-10-18 | 2012-04-19 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D. | Method for preparing plastic particles coated with metal |
US9617643B2 (en) * | 2012-10-26 | 2017-04-11 | Board Of Trustees Of Michigan State University | Methods for coating metals on hydrophobic surfaces |
-
2017
- 2017-10-30 WO PCT/SG2017/050543 patent/WO2018084804A1/en active Application Filing
- 2017-10-30 US US16/345,684 patent/US11028484B2/en active Active
-
2021
- 2021-05-07 US US17/314,705 patent/US20210262095A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11355614B2 (en) * | 2018-02-01 | 2022-06-07 | Hefei Boe Display Technology Co., Ltd. | Thin film transistor, method for preparing the same, display substrate and display device |
Also Published As
Publication number | Publication date |
---|---|
US20190352779A1 (en) | 2019-11-21 |
WO2018084804A1 (en) | 2018-05-11 |
US11028484B2 (en) | 2021-06-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20210262095A1 (en) | Electroless nickel plating of silicone rubber | |
CA2426648C (en) | Plating method of metal film on the surface of polymer | |
CA1087599A (en) | Method of depositing a metal on a surface | |
US7892596B2 (en) | Nanoparticle coating process for fuel cell components | |
TW593743B (en) | Method for plating metal | |
CN102933745A (en) | Process for coating a surface of a substrate made of nonmetallic material with a metal layer | |
KR100367164B1 (en) | Metal plating pretreatment agent and metal plating method using the same | |
CA1233158A (en) | Catalytic process and system | |
JP4891919B2 (en) | Improved stabilization and performance of autocatalytic electroless process | |
CN105330821B (en) | The copolymer of 2-glycidyl ether capped polysiloxane compound and non-aromatic polyamines | |
JP6024044B2 (en) | Conductive film forming bath | |
TWI540222B (en) | Method of metallization for surface of substrate and substrate manufactured by the same | |
CN111511962B (en) | Surface-activated polymers | |
US8814997B2 (en) | Electroless plating pretreatment agent, electroless plating method using same, and electroless plated object | |
Wang et al. | A novel process of electroless nickel plating on PVC with semi-IPN hydrogel pretreatment | |
WO2010047330A1 (en) | Resin complex and laminate | |
US20070202247A1 (en) | Method of depositing a nanoparticle coating on a bipolar plate and removing the nanoparticle coating from the lands of the bipolar plate | |
JP2010047828A (en) | Pretreatment method for electroless plating and electroless plating method of substrate | |
CN104204294B (en) | Promote the method for sticky limit between dielectric substrate and metal layer | |
WO2017199833A1 (en) | Electroless nickel plating method | |
KR20170040125A (en) | Catalyst-containing metal silicon oligomer, method for manufacturing same, and applicaiton for catalyst-containing metal silicon oligomer | |
CN106282979A (en) | Chemical plating front surface modifies system and the surface modification method of organic polymer base material | |
JP6040516B2 (en) | Method for forming zinc oxide film and zinc oxide film forming body | |
US20100040773A1 (en) | Method and Composition to Repair Pinholes and Microvoids in Immersion Silver Plated PWB's Thereby Relieving Creep Corrosion | |
JP2020084220A (en) | Plated molding of polyolefin, method for manufacturing the same, method for plating polyolefin molding containing recycled polyolefin and method for applying electrical conductivity or antibacterial to polyolefin molding containing recycled polyolefin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |