US20220002877A1 - Method for aluminum electroless deposition - Google Patents
Method for aluminum electroless deposition Download PDFInfo
- Publication number
- US20220002877A1 US20220002877A1 US17/290,005 US201917290005A US2022002877A1 US 20220002877 A1 US20220002877 A1 US 20220002877A1 US 201917290005 A US201917290005 A US 201917290005A US 2022002877 A1 US2022002877 A1 US 2022002877A1
- Authority
- US
- United States
- Prior art keywords
- aluminum
- substrate
- solution
- electroless
- electroless deposition
- 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
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 101
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 77
- 230000008021 deposition Effects 0.000 title claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 107
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 97
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 47
- 239000011829 room temperature ionic liquid solvent Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 150000004678 hydrides Chemical class 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910002065 alloy metal Inorganic materials 0.000 claims abstract description 9
- 239000002841 Lewis acid Substances 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 56
- 239000002041 carbon nanotube Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910002677 Pd–Sn Inorganic materials 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000002048 multi walled nanotube Substances 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 6
- ZMLDXWLZKKZVSS-UHFFFAOYSA-N palladium tin Chemical compound [Pd].[Sn] ZMLDXWLZKKZVSS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- 239000002121 nanofiber Substances 0.000 claims description 4
- 239000002073 nanorod Substances 0.000 claims description 4
- 239000002071 nanotube Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002096 quantum dot Substances 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000271 Kevlar® Polymers 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910003090 WSe2 Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- ROUIDRHELGULJS-UHFFFAOYSA-N bis(selanylidene)tungsten Chemical compound [Se]=[W]=[Se] ROUIDRHELGULJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 239000004761 kevlar Substances 0.000 claims description 3
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 description 21
- 230000008569 process Effects 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 11
- 239000002608 ionic liquid Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229940063656 aluminum chloride Drugs 0.000 description 5
- 238000007772 electroless plating Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000002048 anodisation reaction Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- 229910009731 Li2FeSiO4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910017971 NH4BF4 Inorganic materials 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- VVIHROHFFISGNS-UHFFFAOYSA-K [Al+3].[Cl-].[Cl-].[Cl-].NC(N)=O Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].NC(N)=O VVIHROHFFISGNS-UHFFFAOYSA-K 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940055858 aluminum chloride anhydrous Drugs 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- ZTHNOZQGTXKVNZ-UHFFFAOYSA-L dichloroaluminum Chemical compound Cl[Al]Cl ZTHNOZQGTXKVNZ-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
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Images
Classifications
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- 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
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- 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
- C23C18/1635—Composition of the substrate
-
- 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
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
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- 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
- C23C18/1675—Process conditions
- C23C18/1687—Process conditions with ionic liquid
-
- 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
- C23C18/1689—After-treatment
-
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- 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
- C23C18/1889—Multistep pretreatment with use of metal 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
- C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/243—Chemical after-treatment using organic dyestuffs
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
Definitions
- the present invention relates to a method for electroless deposition of aluminum on a substrate which employs materials which are commercially available at a cost suitable for large scale production quantities.
- Aluminum coatings are applied to many substrates to impart strength, abrasion resistance corrosion resistance, barrier properties, thermal conductivity and electrical conductivity.
- the substrate may include, but is not limited to glass, metal, metal oxide, ceramic, organic materials, or polymer and may have any geometry varying from a simple geometry such as a flat sheet to a more complex geometry.
- Conventional methods for applying aluminum coatings or thin films include methods such as aluminum cladding wherein aluminum and another metal are bonded together by application of pressure at a suitable elevated pressure, thermal or slurry spray methods wherein molten or semi-molten aluminum or an aluminum containing slurry is sprayed onto a substrate, physical or chemical vapor deposition wherein thin aluminum film is produced through condensation of a vaporized form of aluminum under high vacuum or electrolytic deposition (also referred to as electrolytic plating) wherein electrical current is used to reduce dissolved aluminum cations to form an aluminum film on an electrode.
- electrolytic deposition also referred to as electrolytic plating
- aluminum cladding is generally limited to flat sheets and difficult to apply to complex geometries.
- Thermal or slurry spraying also has limitation to the geometry of the substrate and requires line of sight for the coating to be deposited.
- the spraying methods tend to have non-uniformity issue and the product may contain contaminants from the process and therefore limiting the application of this method.
- Physical or chemical vapor deposition requires expensive and specialized equipment, is conducted at a high temperature, and is only applicable to selected substrates with simple geometries.
- Aluminum electrodeposition in an aqueous medium is difficult because the standard reduction potential of aluminum is ⁇ 1.66E (V) and therefore, water is electrolyzed in favor of electrodeposition of aluminum.
- Electrolytic deposition of aluminum may be accomplished in a solvent system.
- this method is only applicable to the deposition of pure aluminum.
- ionic liquid based aluminum alloy deposition due to the low solution conductivity of aluminum or aluminum alloys, it is often difficult to plate alloy onto complex geometries, and also difficult to produce a coating of uniform thickness.
- this process requires very high power and is only applicable to conductive substrates. In the case of non-conductive substrates the surface has to be modified with a conductive or catalyst layer prior to the electrolytic deposition.
- Shitanda et al. (Electrochimica Acta, 54 (2009) 5889-5893) describes a method for electroless aluminum deposition on glass wherein the glass surface is first treated with a catalytic coating in a two stage process. The surface is initially treated with a tin chloride solution and then treated with a palladium chloride solution to prepare a Pd catalyst surface on the glass substrate. Next the part to be plated is dipped in 1-ethyl 3-methylImidazolium chloride (EMIC)—aluminum chloride Room Temperature Ionic liquid (RTIL) that has diisobutyl aluminum hydride in toluene as a liquid reducing agent.
- EMIC 1-ethyl 3-methylImidazolium chloride
- RTIL Room Temperature Ionic liquid
- the present inventors have studied this electroless plating process and determined that this method has two significant negative attributes which inhibit its use as an industrial scale process.
- the cost of the ionic liquid EMIC is extremely high and this material is not readily available as a commercial material. Additionally the method employs a two-step catalyzation process that must be optimized according to the type of surface to be plated.
- RTIL Lewis acid room temperature ionic liquid
- the AlCl 3 :NH 2 CONH 2 molar ratio of the AlCl 3 :NH 2 CONH 2 RTIL is from greater than 1:1 to 2:1 and in a special aspect the AlCl 3 :NH 2 CONH 2 molar ratio of the AlCl 3 :NH 2 CONH 2 RTIL is 2:1.
- the hydride reducing agent is selected from the group consisting of lithium hydride, lithium aluminum hydride, diisobutyl aluminum hydride and combinations thereof and in a special aspect the hydride reducing agent is lithium aluminum hydride.
- the aprotic anhydrous solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, dibutyl ether, dioxane, toluene and hexane.
- the alloy metal salt is dissolved in an aprotic solvent; and added to the RTIL prior to the addition of the hydride reducing agent; wherein the metal salt is selected from the group consisting of a halide salt of zinc, chromium, iron, nickel, tin, lead, copper, silver, gold and combinations thereof.
- the catalyst metal is selected from the group consisting of iron, palladium, silver, gold, platinum and combinations thereof and in a special aspect the catalyst metal in Pd.
- the activation of the surface of the substrate to be coated comprises: treating the surface with a colloidal solution of palladium-tin (Pd—Sn) nanoparticles in the presence of HCl and water to cover the surface of the substrate with a layer of adsorbed catalytic Pd—Sn nanoparticles comprising stannous hydroxide covered on their surface; cleaning the substrate surface from the residues of the colloidal solution; and placing the substrate in an acidic accelerator solution wherein the excess stannous hydroxide layer is removed from the surface of the substrate for an increased catalytic activity.
- Pd—Sn palladium-tin
- the substrate surface is non-reactive to Al deposition and/or is non-conductive.
- the substrate is a nanostructure and in a special aspect the nanostructure is selected from the group consisting of a nanofiber, a nanoparticle, a nanotube, a nano-rod and a quantum dot.
- the substrate is composed of a polymer selected from the group consisting of ABS, PLA, Nylon, Teflon and PMMA and the AlCl 3 :NH 2 CONH 2 molar ratio is from 1.3:1 to 1.5:1.
- the substrate is a metal coated polymer and the AlCl 3 :NH 2 CONH 2 molar ratio is 2:1.
- the substrate is selected from the group of fibers consisting of a glass fiber, an aramid fiber and a carbon fiber.
- the substrate is selected from the group of yarns consisting of a glass fiber yarn, a Kevlar fiber yarn and a carbon fiber yarn.
- the substrate is selected from the group consisting of a fullerene, a Bucky paper and a Bucky sheet.
- the substrate is selected from the group of 2-D materials consisting of graphene, molybdenum disulfide (MOS 2 ), tungsten disulfide (WS 2 ), tungsten diselenide (WSe 2 ), and zinc oxide (ZnO).
- MOS 2 molybdenum disulfide
- WS 2 tungsten disulfide
- WSe 2 tungsten diselenide
- ZnO zinc oxide
- the substrate is selected from the group consisting of graphene powder and graphene nanoparticles.
- the substrate is selected from the group consisting of a ZnO microtube and a ZnO nanowire.
- the substrate is selected from the group consisting of steel, a steel alloy, glass and a ceramic.
- the present invention includes a method for coating a substrate with an anodized aluminum oxide layer, comprising:
- RTIL Lewis acid room temperature ionic liquid
- the present invention includes aluminum or aluminum alloy coated carbon nanotubes and aluminum or aluminum alloy coated multi-wall carbon nanotubes.
- FIG. 1 is a schematic representation of the coating stages of the method according to one embodiment of the invention.
- FIG. 2 is a schematic representation of the experimental procedure of the example.
- FIG. 3 shows a chemical equation description of the Al deposition according to an embodiment of the invention.
- FIG. 4A shows a TEM image of CNTs coated with Al as prepared in the example.
- FIG. 4B shows a SEM image of CNTs coated with Al as prepared in the example.
- FIG. 5A shows a TEM image of the surface morphology of CNTs coated with Al as prepared in the example.
- FIG. 5B shows a SEM of the surface morphology of CNTs coated with Al as prepared in the example.
- FIG. 6 shows an EDX spectrum of CNTs coated with Al as prepared in the example.
- FIG. 7 shows and XRD diffraction pattern of CNTs coated with Al as prepared in the example.
- FIG. 8 shows a Raman analysis of CNTs coated with Al as prepared in the example.
- the inventors have discovered that when AlCl 3 —Urea at a molar ratio greater than 1:1 is employed as a RTIL in combination with specific hydride reducing agents in an anhydrous aprotic solvent an efficient and economical method for aluminum electroless plating was obtainable.
- the newly developed RTIL was found to generate the desired Al 2 Cl 7 ⁇ ions when used at a molar ratio of AlCl 3 to urea greater than 1:1.
- the inventors believe the Al plating process may be explained by the chemical processes shown in FIG. 3 . Interestingly and unexpectedly, as shown in FIG.
- Al deposition occurs not only by reduction of the Al 2 Cl 7 ⁇ ion but also via reduction of an ion derivative of the AlCl 3 .
- NH 2 CONH 2 RTIL shown as [AlCl 2 .(urea) n ] + and by catalyzed decomposition of the LiAlH 4 .
- the process could be scaled up to industrial levels in a cost effective manner without affecting the quality of aluminum coatings.
- a one-step colloidal palladium surface catalyzation process was adopted to render the surfaces to be electroless plated catalytic prior to the electroless plating process.
- the colloidal palladium resulted in a major cut in the optimization time for the catalyzation step of the entire electroless plating process compared to the conventional two-step system.
- the method may be universally applied to a wide variety of substrates of different chemical composition, size and geometries.
- a method for electroless deposition of aluminum or an aluminum alloy on a substrate surface comprises:
- RTIL Lewis acid room temperature ionic liquid
- the AlCl 3 :NH 2 CONH 2 ratio may vary from greater than 1:1 to 2:1. As the ratio increases toward 2:1 the Lewis acidity of the RTIL increases and the ratio may be adjusted within the described limits to provide a Lewis acidity compatible with the substrate to be plated.
- the AlCl 3 :NH 2 CONH 2 molar ratio may be 2:1.
- the hydride reducing agent may be selected from the group consisting of lithium hydride, lithium aluminum hydride, diisobutylaluminum hydride and combinations thereof.
- the hydride reducing agent may be lithium aluminum hydride (LiAlH 4 ).
- the hydride reducing agent may be dissolved in an aprotic anhydrous solvent to be added to the AlCl 3 :NH 2 CONH 2 RTIL.
- the aprotic anhydrous solvent may be one or more of tetrahydrofuran (THF), diethyl ether, dibutyl ether, dioxane, toluene and hexane.
- THF tetrahydrofuran
- the electroless mixture may be further diluted with one or more of these aprotic anhydrous solvents to lower the viscosity.
- An aluminum alloy plating may be obtained by dissolving an anhydrous alloy metal salt in the AlCl 3 :NH 2 CONH 2 RTIL prior to addition of the solution of the hydride reducing agent solution.
- the alloy metal salt may be first dissolved in one or more of the listed aprotic anhydrous solvents and the obtained solution added to the AlCl 3 :NH 2 CONH 2 RTIL.
- any solvent soluble salt may be useful, halide salts (F, Cl, Br and I) may be preferred and chloride salts may be most preferred.
- the alloy element may be any metal which alloys with aluminum and preferably may be one or more selected from zinc, chromium, iron, nickel, tin, lead, copper, silver and gold.
- the substrate When the substrate is a metal activation of the surface may not be necessary. However, when the substrate surface is not reactive to electroless Al deposition and/or not conductive, the surface may be activated with application of a metal catalyst.
- the catalyst metal may be selected from the group consisting of iron, palladium, silver, gold, platinum and combinations thereof. In one preferred aspect the catalyst may be palladium.
- the activation of the surface of the substrate to be coated comprises: treating the surface with a colloidal solution of palladium-tin (Pd—Sn) nanoparticles in the presence of HCl and water to cover the surface of the substrate with a layer of adsorbed catalytic Pd—Sn nanoparticles comprising stannous hydroxide covered on their surface; cleaning the substrate surface from the residues of the colloidal solution; and placing the substrate in an acidic accelerator solution wherein the excess stannous hydroxide layer is removed from the surface of the substrate for an increased catalytic activity.
- Pd—Sn nanoparticles and subsequent plating of aluminum is shown in FIG. 1 . This method is based upon the description of Cohen et al. (The Chemistry of Palladium-Tin Colloid Sensitizing Processes, J. Colloid Interface Sci. 1976, 55 (1), 156-162).
- the substrate surface need not be functionalized to promote application of the Pd—Sn nanoparticles.
- a layer of colloidal Pd—Sn nanoparticles is coated to the substrate surface (Carbon nanotubes in FIG. 1 ).
- the initial coating contains an excess amount of stannous hydroxide which is removed by treatment with an aqueous acid solution known as accelerator solution.
- the acid may be any inorganic acid capable of dissolving and removing stannous hydroxide and may be selected from H 2 SO 4 , HCl, HBF 4 and NH 4 BF 4 .
- the substrate may be a metal wherein application of a catalyst layer is not necessary or a non-reactive surface where catalytic activation is necessary.
- substrates where catalytic activation is necessary include non-metal nanostructures including nanofibers, nanoparticles, nanotubes, nano-rods and quantum dots.
- the Al coating of carbon nanotubes, including and multi-wall carbon nanotubes (MWCNT) is described in the Example and supporting analytical information shown in FIGS. 4-8 as described in the Example.
- the method may also be applied to single walled carbon nanotubes (SWCNT).
- the method for electroless deposition of Al or an Al alloy may be employed to coat polymers including ABS, PLA, polyamides, polyimides such as Kapton films, Teflon, fluorinated sulfones, polyethylene oxide and PMMA.
- Polyelectrolytes such as poly(ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS) may also be coated. Due to the potential for polymer degradation in a strong Lewis environment, the AlCl 3 :NH 2 CONH 2 molar ratio employed in the coating of these materials may be from 1.3:1 to 1.5:1.
- the AlCl 3 :NH 2 CONH 2 molar ratio employed in the coating may be 2:1.
- fibers such as glass fibers, aramid fibers and carbon fibers
- yarns such as glass fiber yarns, Kevlar fiber yarns and carbon fiber yarns
- allotropes of carbon such as fullerenes, Bucky paper and Bucky sheets
- graphene powder graphene nanoparticles, NMC532/graphite
- hollow carbon nanospheres Li 2 FeSiO 4 /C nanospheres.
- polystyrene nanospheres ZnO microtubes; ZnO nanowires; silver nanowires and 2-D materials such as graphene, molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ), tungsten diselenide (WSe 2 ), zinc phthalocyanine (ZnPc) and zinc oxide (ZnO).
- MoS 2 molybdenum disulfide
- WS 2 tungsten disulfide
- WSe 2 tungsten diselenide
- ZnPc zinc phthalocyanine
- ZnO zinc oxide
- LLZO Li conducting lanthanum zirconate ceramic structures
- substrates may include amorphous, polycrystalline, and single crystalline silicon, amorphous and polycrystalline silicon germanium (SiGe), silicon dioxide, silicon doped with any of antimony, phosphorous, arsenic, boron, gallium and indium as well as very large scale integration (VLSI) semi conducting surfaces, complimentary metal-oxide-semiconductors (CMOS), P-type semi conductor, N-type semi conductor, PN junctions, PNP junctions and NPN junctions.
- SiGe silicon germanium
- VLSI very large scale integration
- Additional substrates suitable for Al or Al coating according to the present invention may include microelectromechanical systems (MEMS), solar cells, and transparent electrodes for solar cells.
- MEMS microelectromechanical systems
- solar cells solar cells
- transparent electrodes for solar cells may include microelectromechanical systems (MEMS), solar cells, and transparent electrodes for solar cells.
- Metal salts may also be substrates which may be plated or coated according to the present invention.
- Examples of such metal salts may include LiS, MoO 3 , MnO 2 , LiNi 0.5 Mn 1.5 O 4 , indium tin oxide and MnCO 3 .
- the method for electroless deposition of aluminum or an aluminum alloy according to the present invention provides a low cost approach for aluminum or Al alloy electroless plating which is virtually universally applicable to a wide range of substrate materials.
- the materials employed are inexpensive and readily available in comparison to materials employed in previously described methods.
- the AlCl 3 :NH 2 CONH 2 RTIL has a wide electrochemical window and may be used to plate on non-conductive and non-reactive surfaces. Further, the method may be applied to coat or plate substrates of complex 3 dimensional structure.
- a further embodiment of the present invention includes a method to coat a substrate with an anodized aluminum oxide layer wherein an Al coated substrate obtained according to the first embodiment and the various aspects thereof may be submerged in an electrolytic solution and an anode current applied to the Al coating to obtain an aluminum oxide coating having an outer barrier layer.
- Anodization of aluminum is conventionally known and may be conducted in an electrolyte such as chromic acid, sulfuric acid, oxalic acid or phosphoric acid.
- an electrolyte such as chromic acid, sulfuric acid, oxalic acid or phosphoric acid.
- a thin aluminum oxide film is formed on the aluminum coating.
- the thickness of this barrier layer may be from 0.01-0.1 nm and may not change throughout the process as it dissolves at the outer side exposed to the electrolyte.
- the electrochemical field localizes on inhomogeneities of the surface of formed aluminum oxide and the oxide dissolves under the influence of the inhomogeneity of the field thus leading to the growth of pores.
- the alumina layer may then be dissolved, leaving a regular array of porous aluminum and when anodization is repeated a layer of porous aluminum oxide is obtained.
- organic or inorganic pigments may be inserted within the aluminum oxide pores to give the aluminum oxide an aesthetic look.
- the colored substrate may then be inserted in boiling water to seal the pores by forming a transparent outer aluminum hydroxide Al(OH) 3 layer via a method known in industry as “hydration pore closure”.
- Multi-wall carbon nanotubes were obtained from Thomas Swan Corporation (average diameter of 10-15 nm) were used in the present study.
- the colloidal palladium-tin solution and the accelerator acids were obtained from Macdermid Enthony USA.
- Aluminum chloride anhydrous was obtained from Alfa-Aeser.
- Urea 99.9% was obtained from Lobachemie India.
- the growth of aluminum on CNTs has taken place in 3 different steps.
- the first step is the catalytic activation of CNTs by palladium nanoparticles. Then, excess stannous hydroxide was removed from the surface via a group of accelerating acids.
- CNTs were catalyzed using a colloidal Pd—Sn solution based on the description of Cohen et al. (The Chemistry of Palladium-Tin Colloid Sensitizing Processes, J. Colloid Interface Sci. 1976, 55 (1), 156-162).
- the colloidal solution was prepared from 62.5 ml of commercial colloidal Pd—Sn concentrate, 50 ml of HCl (37%), and 137.5 ml of DI water.
- CNTs of 0.1 g were immersed in the prepared solution and left for 1-minute sonication agitation and extra 3 to 4 minutes of stir agitation. The CNTs were then filtered using a 0.22 m PTFE filter membrane on a microfiltration kit.
- the collected CNTs were then dispersed in what is known industrially as the accelerator solution.
- the acceleration step is composed of a group of acids beneficial for the removal of excess stannous hydroxide from the surface of palladium nanoparticles coated on CNTs.
- the concentration of the activator solution was 50 g/L.
- the CNTs were refiltered and collected using teasers.
- the entire experiment was carried out in a glove box filled with dry argon gas at ambient conditions.
- 50 grams of 2:1 molar ratio of anhydrous aluminum chloride were used to form an electrolyte that is rich with Al2Cl7 ⁇ ions.
- the aluminum chloride urea reaction is an exothermic reaction and excess heat may result in the decomposition of the entire electrolyte. Failure in controlling the exothermic heat of the reaction leads to a great failure in the electroless deposition. For this reason, strict procedures were carried out to prevent the thermal decomposition of the electrolyte by preparing the volume needed on 4 separate parts to reduce the heat created as a result of the exothermic reaction. The previous step was not sufficient in preventing the decomposition. Therefore, the volumetric flask was cooled with a sealed rubber ice bucket that preserved the dry environment of the chamber.
- An ideal electrolyte has a pale yellow color. If light brown color is observed, this will be a sign of the electrolyte decomposition.
- Lithium Aluminum Hydride (LiAlH 4 ) (LAH) was dissolved in Toluene, hexane, or diethyl ether and used as a reducing agent. 1.5, 1.9, 2.5, and 5 grams of LAH were tested. The activated CNTs were immersed in the electroless solution using sonication for 5 minutes and magnetic stirring for 10 minutes. The ionic liquid containing CNTs was viscous and could not be filtered without dilution using an organic solvent. This dilatant solvent had to be the same solvent used in diluting the LAH.
- FIG. 1 A schematic representation of the coating stages is shown in FIG. 1 and a schematic representation of the experimental procedures is shown in FIG. 2 .
- the Al coating was confirmed using SEM and TEM imaging. Chemical analysis was performed using EDX. Crystal structure of aluminum was confirmed using XRD. Raman analysis was carried out to confirm the existence of CNTs that are coated with aluminum.
- the aluminum coated MWCNTs were characterized by scanning electron microscopy (SEM) analysis using (LEO SUPRA 55VP FEG, Zeiss, equipped with Oxford EDS detector), transmission electron microscopy (TEM) using (JEM-2100 LaB6, JEOL, operating at 200 kV and equipped with Gatan SC200B CCD camera), energy dispersive X-ray (EDX) attached to the SEM, X-ray diffraction (XRD) using (Cu Ka, Panalytical Xpert Pro diffractometer).
- SEM scanning electron microscopy
- TEM transmission electron microscopy
- TEM transmission electron microscopy
- JEM-2100 LaB6, JEOL operating at 200 kV and equipped with Gatan SC200B CCD camera
- EDX energy dispersive X-ray
- XRD X-ray diffraction
- the aluminum coated on CNTs is nanostructured as shown in FIG. 5 -A.
- the aluminum coated CNTs were crushed with a mortar and pestle, it was possible to break some of the aluminum coated parts on the CNTs. Therefore, the difference of the coated and uncoated part of a CNT that has two branches could be shown in FIG. 5 -B.
- the aluminum coat is much thicker than the CNT itself which would be preferable when used in a composite material.
- FIG. 7 shows the XRD diffraction pattern of aluminum coated CNTs which confirmed the existence the aluminum coat in a crystalline form. As the diffraction depends on how heavy the atom is, it is difficult to observe the CNTs peak at 26° because of their low percentage in the sample as well as the large difference of atomic weight between aluminum and carbon.
Abstract
Description
- This application claims priority to U.S. Application No. 62/752,769, filed Oct. 30, 2018, the disclosure of which is incorporated herein by reference in its entirety.
- The present invention relates to a method for electroless deposition of aluminum on a substrate which employs materials which are commercially available at a cost suitable for large scale production quantities.
- Aluminum coatings are applied to many substrates to impart strength, abrasion resistance corrosion resistance, barrier properties, thermal conductivity and electrical conductivity. The substrate may include, but is not limited to glass, metal, metal oxide, ceramic, organic materials, or polymer and may have any geometry varying from a simple geometry such as a flat sheet to a more complex geometry.
- Conventional methods for applying aluminum coatings or thin films include methods such as aluminum cladding wherein aluminum and another metal are bonded together by application of pressure at a suitable elevated pressure, thermal or slurry spray methods wherein molten or semi-molten aluminum or an aluminum containing slurry is sprayed onto a substrate, physical or chemical vapor deposition wherein thin aluminum film is produced through condensation of a vaporized form of aluminum under high vacuum or electrolytic deposition (also referred to as electrolytic plating) wherein electrical current is used to reduce dissolved aluminum cations to form an aluminum film on an electrode. Each of these methods incurs energy, equipment and environmental requirements which may be problematic and is limited to a substrate of simple geometry. For example, aluminum cladding is generally limited to flat sheets and difficult to apply to complex geometries. Thermal or slurry spraying also has limitation to the geometry of the substrate and requires line of sight for the coating to be deposited. In addition, the spraying methods tend to have non-uniformity issue and the product may contain contaminants from the process and therefore limiting the application of this method. Physical or chemical vapor deposition, on the other hand, requires expensive and specialized equipment, is conducted at a high temperature, and is only applicable to selected substrates with simple geometries. Aluminum electrodeposition in an aqueous medium is difficult because the standard reduction potential of aluminum is −1.66E (V) and therefore, water is electrolyzed in favor of electrodeposition of aluminum.
- Electrolytic deposition of aluminum may be accomplished in a solvent system. However, in addition to the problem associated with the use of highly flammable solvents, this method is only applicable to the deposition of pure aluminum. When using ionic liquid based aluminum alloy deposition, due to the low solution conductivity of aluminum or aluminum alloys, it is often difficult to plate alloy onto complex geometries, and also difficult to produce a coating of uniform thickness. In addition, this process requires very high power and is only applicable to conductive substrates. In the case of non-conductive substrates the surface has to be modified with a conductive or catalyst layer prior to the electrolytic deposition.
- In view of the issues described regarding conventional aluminum application methods, electroless deposition of aluminum has become of increasing interest.
- Shitanda et al. (Electrochimica Acta, 54 (2009) 5889-5893) describes a method for electroless aluminum deposition on glass wherein the glass surface is first treated with a catalytic coating in a two stage process. The surface is initially treated with a tin chloride solution and then treated with a palladium chloride solution to prepare a Pd catalyst surface on the glass substrate. Next the part to be plated is dipped in 1-ethyl 3-methylImidazolium chloride (EMIC)—aluminum chloride Room Temperature Ionic liquid (RTIL) that has diisobutyl aluminum hydride in toluene as a liquid reducing agent. The main source of aluminum according to this method is attributed to reduction of Al2Cl7 − ions according to the equation:
-
4Al2Cl7 −+3e −→7AlCl4 −+Al - The present inventors have studied this electroless plating process and determined that this method has two significant negative attributes which inhibit its use as an industrial scale process. The cost of the ionic liquid EMIC is extremely high and this material is not readily available as a commercial material. Additionally the method employs a two-step catalyzation process that must be optimized according to the type of surface to be plated.
- Thus, there is a need for a method to apply aluminum coatings to various and multiple substrates that is economical on an industrial scale and is adaptable to a wide range of substrates and substrates of complex geometries and varying size including nanostructures such as nanofibers, nanoparticles, nanotubes, nano-rods and quantum dots.
- These and other objects are provided by the present invention, the first embodiment of which includes a method for electroless deposition of aluminum or an aluminum alloy on a substrate surface, comprising:
- activating the surface of the substrate to be coated by applying a coating of a catalyst metal;
- preparing a mixture of urea (NH2CONH2) and anhydrous aluminum chloride (AlCl3) wherein a molar ratio of AlCl3:NH2CONH2 is greater than 1:1 to obtain a Lewis acid room temperature ionic liquid (RTIL);
- dissolving a hydride reducing agent in an aprotic anhydrous solvent to obtain a hydride solution;
- optionally, when an Al alloy coating is to be deposited, adding an anhydrous alloy metal salt as a solution to the RTIL;
- mixing the hydride solution and the AlCl3:NH2CONH2 RTIL to obtain an electroless Al solution;
- exposing the activated surface of the substrate to the electroless Al solution; and
- removing the electroless Al solution from the substrate surface;
- wherein upon exposure of the activated substrate surface to the electroless Al solution, an Al or Al alloy coating is obtained on the activated substrate surface.
- In one aspect of the first embodiment the AlCl3:NH2CONH2 molar ratio of the AlCl3:NH2CONH2 RTIL is from greater than 1:1 to 2:1 and in a special aspect the AlCl3:NH2CONH2 molar ratio of the AlCl3:NH2CONH2 RTIL is 2:1.
- In one aspect of the first embodiment the hydride reducing agent is selected from the group consisting of lithium hydride, lithium aluminum hydride, diisobutyl aluminum hydride and combinations thereof and in a special aspect the hydride reducing agent is lithium aluminum hydride.
- In one aspect of the first embodiment, the aprotic anhydrous solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, dibutyl ether, dioxane, toluene and hexane.
- In one aspect of the first embodiment when an Al alloy coating is deposited, the alloy metal salt is dissolved in an aprotic solvent; and added to the RTIL prior to the addition of the hydride reducing agent; wherein the metal salt is selected from the group consisting of a halide salt of zinc, chromium, iron, nickel, tin, lead, copper, silver, gold and combinations thereof.
- In one aspect of the first embodiment the catalyst metal is selected from the group consisting of iron, palladium, silver, gold, platinum and combinations thereof and in a special aspect the catalyst metal in Pd.
- In another aspect of the first embodiment the activation of the surface of the substrate to be coated comprises: treating the surface with a colloidal solution of palladium-tin (Pd—Sn) nanoparticles in the presence of HCl and water to cover the surface of the substrate with a layer of adsorbed catalytic Pd—Sn nanoparticles comprising stannous hydroxide covered on their surface; cleaning the substrate surface from the residues of the colloidal solution; and placing the substrate in an acidic accelerator solution wherein the excess stannous hydroxide layer is removed from the surface of the substrate for an increased catalytic activity.
- In one aspect of the first embodiment the substrate surface is non-reactive to Al deposition and/or is non-conductive.
- In an aspect of the first embodiment the substrate is a nanostructure and in a special aspect the nanostructure is selected from the group consisting of a nanofiber, a nanoparticle, a nanotube, a nano-rod and a quantum dot.
- In one special aspect of the first embodiment the substrate is composed of a polymer selected from the group consisting of ABS, PLA, Nylon, Teflon and PMMA and the AlCl3:NH2CONH2 molar ratio is from 1.3:1 to 1.5:1.
- In another special aspect of the first embodiment, the substrate is a metal coated polymer and the AlCl3:NH2CONH2 molar ratio is 2:1.
- In another special aspect of the first embodiment the substrate is selected from the group of fibers consisting of a glass fiber, an aramid fiber and a carbon fiber.
- In a further special aspect of the first embodiment the substrate is selected from the group of yarns consisting of a glass fiber yarn, a Kevlar fiber yarn and a carbon fiber yarn.
- In a further special aspect of the first embodiment the substrate is selected from the group consisting of a fullerene, a Bucky paper and a Bucky sheet.
- In a further special aspect of the first embodiment the substrate is selected from the group of 2-D materials consisting of graphene, molybdenum disulfide (MOS2), tungsten disulfide (WS2), tungsten diselenide (WSe2), and zinc oxide (ZnO).
- In a further special aspect of the first embodiment the substrate is selected from the group consisting of graphene powder and graphene nanoparticles.
- In a further special aspect of the first embodiment the substrate is selected from the group consisting of a ZnO microtube and a ZnO nanowire.
- In an additional aspect of the first embodiment the substrate is selected from the group consisting of steel, a steel alloy, glass and a ceramic.
- In a second embodiment the present invention includes a method for coating a substrate with an anodized aluminum oxide layer, comprising:
- activating the surface of the substrate to be coated by applying a coating of a catalyst metal;
- preparing a mixture of urea (NH2CONH2) and anhydrous aluminum chloride (AlCl3) wherein a molar ratio of AlCl3:NH2CONH2 is greater than 1:1 to obtain a Lewis acid room temperature ionic liquid (RTIL);
- dissolving a hydride reducing agent in an aprotic anhydrous solvent to obtain a hydride solution;
- mixing the hydride solution and the AlCl3:NH2CONH2 RTIL to obtain an electroless Al solution;
- exposing the activated surface of the substrate to the electroless Al solution; and
- removing the electroless Al solution from the substrate surface to obtain an electroless aluminum plated substrate;
- submerging the electroless aluminum plated substrate in an electrolytic solution;
- applying an anode current to the aluminum coat to form an aluminum oxide coat comprising a barrier layer; and
- treating the aluminum oxide layer to form pores in the aluminum oxide structure.
- In a third embodiment, the present invention includes aluminum or aluminum alloy coated carbon nanotubes and aluminum or aluminum alloy coated multi-wall carbon nanotubes.
- The foregoing paragraphs have been provided by way of general introduction, and are not intended to limit the scope of the following claims.
- A more complete appreciation of the disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
-
FIG. 1 is a schematic representation of the coating stages of the method according to one embodiment of the invention. -
FIG. 2 is a schematic representation of the experimental procedure of the example. -
FIG. 3 shows a chemical equation description of the Al deposition according to an embodiment of the invention. -
FIG. 4A shows a TEM image of CNTs coated with Al as prepared in the example. -
FIG. 4B shows a SEM image of CNTs coated with Al as prepared in the example. -
FIG. 5A shows a TEM image of the surface morphology of CNTs coated with Al as prepared in the example. -
FIG. 5B shows a SEM of the surface morphology of CNTs coated with Al as prepared in the example. -
FIG. 6 shows an EDX spectrum of CNTs coated with Al as prepared in the example. -
FIG. 7 shows and XRD diffraction pattern of CNTs coated with Al as prepared in the example. -
FIG. 8 shows a Raman analysis of CNTs coated with Al as prepared in the example. - In the following description the words “a” and “an” and the like carry the meaning of “one or more.” The phrases “selected from the group consisting of,” “chosen from,” and the like include mixtures of the specified materials. Terms such as “contain(s)” and the like are open terms meaning ‘including at least’ unless otherwise specifically noted. All references, patents, applications, tests, standards, documents, publications, brochures, texts, articles, etc. mentioned herein are incorporated herein by reference. Where a numerical limit or range is stated, the endpoints are included. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out.
- In view of the above described disadvantages of conventionally known methods of Al electroless deposition, the inventors conducted research to find a low cost and readily available RTIL that would resolve the previously mentioned problems. Such an alternative ionic liquid would significantly lower the manufacturing cost of high surface area substrates such as Al-CNT powders and make it feasible to explore the wide variety of options in using such a composite with different Al-CNT percentages in industrial metallic parts. As described above the inventors recognized that Al2Cl7 − ions are the main ions that promote the electrodeposition of aluminum in any ionic liquid. Therefore, a search was conducted for a cost effective ionic liquid which supports the formation of Al2Cl7 − ions. It was discovered that an ionic liquid formed from AlCl3 and Urea results in the formation of Al2Cl7 − ions when used with 2:1 molar ratio or greater of AlCl3 and Urea respectively. This ionic compound was originally created as an electrolyte for batteries due to its high conductivity (Angell et al. Proc. Natl. Acad. Sci. 2017, 114 (5), 834-839). However, when used at higher molar ratios, aluminum undesirably deposited on battery electrodes which was problematic for battery function and performance,
- The inventors have discovered that when AlCl3—Urea at a molar ratio greater than 1:1 is employed as a RTIL in combination with specific hydride reducing agents in an anhydrous aprotic solvent an efficient and economical method for aluminum electroless plating was obtainable. The newly developed RTIL was found to generate the desired Al2Cl7 − ions when used at a molar ratio of AlCl3 to urea greater than 1:1. Although not wishing to be bound by theory the inventors believe the Al plating process may be explained by the chemical processes shown in
FIG. 3 . Interestingly and unexpectedly, as shown inFIG. 3 , Al deposition occurs not only by reduction of the Al2Cl7 − ion but also via reduction of an ion derivative of the AlCl3.NH2CONH2 RTIL shown as [AlCl2.(urea)n]+ and by catalyzed decomposition of the LiAlH4. - Due to the low cost of urea, the process could be scaled up to industrial levels in a cost effective manner without affecting the quality of aluminum coatings. In addition, a one-step colloidal palladium surface catalyzation process was adopted to render the surfaces to be electroless plated catalytic prior to the electroless plating process. The colloidal palladium resulted in a major cut in the optimization time for the catalyzation step of the entire electroless plating process compared to the conventional two-step system. Further the method may be universally applied to a wide variety of substrates of different chemical composition, size and geometries.
- Thus in a first general embodiment of the present disclosure a method for electroless deposition of aluminum or an aluminum alloy on a substrate surface is provided. The method comprises:
- activating the surface of the substrate to be coated by applying a coating of a catalyst metal;
- preparing a mixture of urea (NH2CONH2) and anhydrous aluminum chloride (AlCl3) wherein a molar ratio of AlCl3:NH2CONH2 is greater than 1:1 to obtain a Lewis acid room temperature ionic liquid (RTIL);
- dissolving a hydride reducing agent in an aprotic anhydrous solvent to obtain a hydride solution;
- optionally, when an Al alloy coating is to be deposited, adding an anhydrous alloy metal salt as a solution to the RTIL;
- mixing the hydride solution and the AlCl3:NH2CONH2 RTIL to obtain an electroless Al solution;
- exposing the activated surface of the substrate to the electroless Al solution; and
- removing the electroless Al solution from the substrate surface;
- wherein upon exposure of the activated substrate surface to the electroless Al solution, an Al or Al alloy coating is obtained on the activated substrate surface.
- The AlCl3:NH2CONH2 ratio may vary from greater than 1:1 to 2:1. As the ratio increases toward 2:1 the Lewis acidity of the RTIL increases and the ratio may be adjusted within the described limits to provide a Lewis acidity compatible with the substrate to be plated.
- In an aspect of the present method the AlCl3:NH2CONH2 molar ratio may be 2:1.
- The hydride reducing agent may be selected from the group consisting of lithium hydride, lithium aluminum hydride, diisobutylaluminum hydride and combinations thereof. In one preferred aspect the hydride reducing agent may be lithium aluminum hydride (LiAlH4).
- The hydride reducing agent may be dissolved in an aprotic anhydrous solvent to be added to the AlCl3:NH2CONH2 RTIL. The aprotic anhydrous solvent may be one or more of tetrahydrofuran (THF), diethyl ether, dibutyl ether, dioxane, toluene and hexane. In some RTIL compositions where viscosity is high, the electroless mixture may be further diluted with one or more of these aprotic anhydrous solvents to lower the viscosity.
- An aluminum alloy plating may be obtained by dissolving an anhydrous alloy metal salt in the AlCl3:NH2CONH2 RTIL prior to addition of the solution of the hydride reducing agent solution. The alloy metal salt may be first dissolved in one or more of the listed aprotic anhydrous solvents and the obtained solution added to the AlCl3:NH2CONH2 RTIL. Although any solvent soluble salt may be useful, halide salts (F, Cl, Br and I) may be preferred and chloride salts may be most preferred. The alloy element may be any metal which alloys with aluminum and preferably may be one or more selected from zinc, chromium, iron, nickel, tin, lead, copper, silver and gold.
- When the substrate is a metal activation of the surface may not be necessary. However, when the substrate surface is not reactive to electroless Al deposition and/or not conductive, the surface may be activated with application of a metal catalyst. The catalyst metal may be selected from the group consisting of iron, palladium, silver, gold, platinum and combinations thereof. In one preferred aspect the catalyst may be palladium.
- In one special aspect of the first embodiment the activation of the surface of the substrate to be coated comprises: treating the surface with a colloidal solution of palladium-tin (Pd—Sn) nanoparticles in the presence of HCl and water to cover the surface of the substrate with a layer of adsorbed catalytic Pd—Sn nanoparticles comprising stannous hydroxide covered on their surface; cleaning the substrate surface from the residues of the colloidal solution; and placing the substrate in an acidic accelerator solution wherein the excess stannous hydroxide layer is removed from the surface of the substrate for an increased catalytic activity. A schematic drawing of the application of the Pd—Sn nanoparticles and subsequent plating of aluminum is shown in
FIG. 1 . This method is based upon the description of Cohen et al. (The Chemistry of Palladium-Tin Colloid Sensitizing Processes, J. Colloid Interface Sci. 1976, 55 (1), 156-162). - As indicated in
FIG. 1 the substrate surface need not be functionalized to promote application of the Pd—Sn nanoparticles. According to the method a layer of colloidal Pd—Sn nanoparticles is coated to the substrate surface (Carbon nanotubes inFIG. 1 ). The initial coating contains an excess amount of stannous hydroxide which is removed by treatment with an aqueous acid solution known as accelerator solution. The acid may be any inorganic acid capable of dissolving and removing stannous hydroxide and may be selected from H2SO4, HCl, HBF4 and NH4BF4. - As indicated above the substrate may be a metal wherein application of a catalyst layer is not necessary or a non-reactive surface where catalytic activation is necessary.
- Examples of substrates where catalytic activation is necessary include non-metal nanostructures including nanofibers, nanoparticles, nanotubes, nano-rods and quantum dots. The Al coating of carbon nanotubes, including and multi-wall carbon nanotubes (MWCNT) is described in the Example and supporting analytical information shown in
FIGS. 4-8 as described in the Example. The method may also be applied to single walled carbon nanotubes (SWCNT). - The method for electroless deposition of Al or an Al alloy may be employed to coat polymers including ABS, PLA, polyamides, polyimides such as Kapton films, Teflon, fluorinated sulfones, polyethylene oxide and PMMA. Polyelectrolytes such as poly(ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS) may also be coated. Due to the potential for polymer degradation in a strong Lewis environment, the AlCl3:NH2CONH2 molar ratio employed in the coating of these materials may be from 1.3:1 to 1.5:1.
- However, if the polymer is already metal coated, thus protected from the AlCl3 Lewis acidity, the AlCl3:NH2CONH2 molar ratio employed in the coating may be 2:1.
- Other substrates that may be coated or plated according to the present invention include fibers, such as glass fibers, aramid fibers and carbon fibers; yarns, such as glass fiber yarns, Kevlar fiber yarns and carbon fiber yarns; allotropes of carbon such as fullerenes, Bucky paper and Bucky sheets; graphene powder; graphene nanoparticles, NMC532/graphite; hollow carbon nanospheres; Li2FeSiO4/C nanospheres. polystyrene nanospheres; ZnO microtubes; ZnO nanowires; silver nanowires and 2-D materials such as graphene, molybdenum disulfide (MoS2), tungsten disulfide (WS2), tungsten diselenide (WSe2), zinc phthalocyanine (ZnPc) and zinc oxide (ZnO).
- Other substrates which may be Al or Al alloy coated according to the present invention include all grades of steel and steel alloys, elemental and precious metals, metal alloys, glass including sulfide based glasses and ceramic materials including Li conducting lanthanum zirconate ceramic structures (LLZO). Included in this group of substrates may be copper, silver, gold, aluminum, zinc, nickel, platinum, iron, carbon steel, stainless steel, lead, bronze, brass, boron, gallium, indium, and lithium. Further possible substrates may include amorphous, polycrystalline, and single crystalline silicon, amorphous and polycrystalline silicon germanium (SiGe), silicon dioxide, silicon doped with any of antimony, phosphorous, arsenic, boron, gallium and indium as well as very large scale integration (VLSI) semi conducting surfaces, complimentary metal-oxide-semiconductors (CMOS), P-type semi conductor, N-type semi conductor, PN junctions, PNP junctions and NPN junctions.
- Additional substrates suitable for Al or Al coating according to the present invention may include microelectromechanical systems (MEMS), solar cells, and transparent electrodes for solar cells.
- Metal salts may also be substrates which may be plated or coated according to the present invention. Examples of such metal salts may include LiS, MoO3, MnO2, LiNi0.5Mn1.5O4, indium tin oxide and MnCO3.
- Advantageously, the method for electroless deposition of aluminum or an aluminum alloy according to the present invention provides a low cost approach for aluminum or Al alloy electroless plating which is virtually universally applicable to a wide range of substrate materials. The materials employed are inexpensive and readily available in comparison to materials employed in previously described methods. The AlCl3:NH2CONH2 RTIL has a wide electrochemical window and may be used to plate on non-conductive and non-reactive surfaces. Further, the method may be applied to coat or plate substrates of complex 3 dimensional structure.
- A further embodiment of the present invention includes a method to coat a substrate with an anodized aluminum oxide layer wherein an Al coated substrate obtained according to the first embodiment and the various aspects thereof may be submerged in an electrolytic solution and an anode current applied to the Al coating to obtain an aluminum oxide coating having an outer barrier layer. Anodization of aluminum is conventionally known and may be conducted in an electrolyte such as chromic acid, sulfuric acid, oxalic acid or phosphoric acid. According to known theory, during the anodization a thin aluminum oxide film is formed on the aluminum coating. As the electric current flows at the aluminum-electrolyte border there grows a thin dense electrolyte film as a barrier layer which forms due to the migration of aluminum ions towards oxygen ions. The thickness of this barrier layer may be from 0.01-0.1 nm and may not change throughout the process as it dissolves at the outer side exposed to the electrolyte.
- The electrochemical field localizes on inhomogeneities of the surface of formed aluminum oxide and the oxide dissolves under the influence of the inhomogeneity of the field thus leading to the growth of pores. The alumina layer may then be dissolved, leaving a regular array of porous aluminum and when anodization is repeated a layer of porous aluminum oxide is obtained.
- In an extended application of this process organic or inorganic pigments may be inserted within the aluminum oxide pores to give the aluminum oxide an aesthetic look. The colored substrate may then be inserted in boiling water to seal the pores by forming a transparent outer aluminum hydroxide Al(OH)3 layer via a method known in industry as “hydration pore closure”.
- The combination of the electroless deposition of aluminum according to the present invention and such methods to form an anodized aluminum oxide layer and porous alumina layer allows for application of these processes to a wide range of substrates as previously described and provides products and decorative structures not previously readily available.
- The above description is presented to enable a person skilled in the art to make and use the embodiments and aspects of the disclosure, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure. Thus, this disclosure is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. In this regard, certain embodiments within the disclosure may not show every benefit of the disclosure, considered broadly.
- Multi-wall carbon nanotubes were obtained from Thomas Swan Corporation (average diameter of 10-15 nm) were used in the present study. The colloidal palladium-tin solution and the accelerator acids were obtained from Macdermid Enthony USA. Aluminum chloride anhydrous was obtained from Alfa-Aeser. Urea (99.9%) was obtained from Lobachemie India.
- The growth of aluminum on CNTs has taken place in 3 different steps. The first step is the catalytic activation of CNTs by palladium nanoparticles. Then, excess stannous hydroxide was removed from the surface via a group of accelerating acids.
- CNTs were catalyzed using a colloidal Pd—Sn solution based on the description of Cohen et al. (The Chemistry of Palladium-Tin Colloid Sensitizing Processes, J. Colloid Interface Sci. 1976, 55 (1), 156-162). The colloidal solution was prepared from 62.5 ml of commercial colloidal Pd—Sn concentrate, 50 ml of HCl (37%), and 137.5 ml of DI water. CNTs of 0.1 g were immersed in the prepared solution and left for 1-minute sonication agitation and extra 3 to 4 minutes of stir agitation. The CNTs were then filtered using a 0.22 m PTFE filter membrane on a microfiltration kit. The collected CNTs were then dispersed in what is known industrially as the accelerator solution. The acceleration step is composed of a group of acids beneficial for the removal of excess stannous hydroxide from the surface of palladium nanoparticles coated on CNTs. The concentration of the activator solution was 50 g/L. The CNTs were refiltered and collected using teasers.
- For aluminum electroless deposition, the entire experiment was carried out in a glove box filled with dry argon gas at ambient conditions. To prepare the aluminum electroless deposition electrolyte, 50 grams of 2:1 molar ratio of anhydrous aluminum chloride were used to form an electrolyte that is rich with Al2Cl7− ions.
- The aluminum chloride urea reaction is an exothermic reaction and excess heat may result in the decomposition of the entire electrolyte. Failure in controlling the exothermic heat of the reaction leads to a great failure in the electroless deposition. For this reason, strict procedures were carried out to prevent the thermal decomposition of the electrolyte by preparing the volume needed on 4 separate parts to reduce the heat created as a result of the exothermic reaction. The previous step was not sufficient in preventing the decomposition. Therefore, the volumetric flask was cooled with a sealed rubber ice bucket that preserved the dry environment of the chamber.
- An ideal electrolyte has a pale yellow color. If light brown color is observed, this will be a sign of the electrolyte decomposition.
- After preparing the ionic liquid, Lithium Aluminum Hydride (LiAlH4) (LAH) was dissolved in Toluene, hexane, or diethyl ether and used as a reducing agent. 1.5, 1.9, 2.5, and 5 grams of LAH were tested. The activated CNTs were immersed in the electroless solution using sonication for 5 minutes and magnetic stirring for 10 minutes. The ionic liquid containing CNTs was viscous and could not be filtered without dilution using an organic solvent. This dilatant solvent had to be the same solvent used in diluting the LAH.
- After dilution, the CNTs were filtered and washed thoroughly with hexane.
- A schematic representation of the coating stages is shown in
FIG. 1 and a schematic representation of the experimental procedures is shown inFIG. 2 . - The Al coating was confirmed using SEM and TEM imaging. Chemical analysis was performed using EDX. Crystal structure of aluminum was confirmed using XRD. Raman analysis was carried out to confirm the existence of CNTs that are coated with aluminum.
- The aluminum coated MWCNTs were characterized by scanning electron microscopy (SEM) analysis using (LEO SUPRA 55VP FEG, Zeiss, equipped with Oxford EDS detector), transmission electron microscopy (TEM) using (JEM-2100 LaB6, JEOL, operating at 200 kV and equipped with Gatan SC200B CCD camera), energy dispersive X-ray (EDX) attached to the SEM, X-ray diffraction (XRD) using (Cu Ka, Panalytical Xpert Pro diffractometer).
- It was confirmed by TEM imaging shown in
FIG. 4 -A and SEM imaging shown inFIG. 4 -B that there is a considerable increase in the diameter of CNTs indicating that aluminum was coated successfully on the CNT's surface. - It was observed that the aluminum coated on CNTs is nanostructured as shown in
FIG. 5 -A. When the aluminum coated CNTs were crushed with a mortar and pestle, it was possible to break some of the aluminum coated parts on the CNTs. Therefore, the difference of the coated and uncoated part of a CNT that has two branches could be shown inFIG. 5 -B. The aluminum coat is much thicker than the CNT itself which would be preferable when used in a composite material. - Chemical analysis of the sample was conducted to confirm the existence of aluminum on the CNTs surface. The chemical analysis was conducted using an Energy Dispersive Xray (EDX). The EDX spectrum shown in
FIG. 6 indicates the presence of aluminum, carbon and some aluminum oxides in the tested sample as listed in Table 1. -
TABLE 1 ELEMENT WEIGHT % Aluminum 84.67 Oxygen 13.67 (due to Al activity) Carbon 1.67 TOTAL 100 - Aluminum in nature cannot be formed in an amorphous form. So, to confirm the FCC crystal structure of aluminum an XRD analysis was performed.
FIG. 7 shows the XRD diffraction pattern of aluminum coated CNTs which confirmed the existence the aluminum coat in a crystalline form. As the diffraction depends on how heavy the atom is, it is difficult to observe the CNTs peak at 26° because of their low percentage in the sample as well as the large difference of atomic weight between aluminum and carbon. - The presence of intact CNT inside the aluminum coat was confirmed via Raman analysis shown in
FIG. 8 which indicated the position of the Dband and the G-band of CNTs.
Claims (27)
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US20130243974A1 (en) * | 2012-03-15 | 2013-09-19 | Dh Holdings Co., Ltd. | Method of preparing nickel-coated nanocarbon |
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