US3372055A - Catalytic chromium plating process employing bis (arene) chromium - Google Patents
Catalytic chromium plating process employing bis (arene) chromium Download PDFInfo
- Publication number
- US3372055A US3372055A US456805A US45680565A US3372055A US 3372055 A US3372055 A US 3372055A US 456805 A US456805 A US 456805A US 45680565 A US45680565 A US 45680565A US 3372055 A US3372055 A US 3372055A
- Authority
- US
- United States
- Prior art keywords
- chromium
- arene
- bis
- substrate
- sulfur
- 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.)
- Expired - Lifetime
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 59
- 239000011651 chromium Substances 0.000 title claims description 53
- 229910052804 chromium Inorganic materials 0.000 title claims description 49
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 46
- 230000003197 catalytic effect Effects 0.000 title claims description 7
- 238000007747 plating Methods 0.000 title description 34
- 239000000758 substrate Substances 0.000 claims description 68
- 150000001845 chromium compounds Chemical class 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 150000001555 benzenes Chemical class 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 150000003464 sulfur compounds Chemical class 0.000 claims description 3
- AWNBGWWVMCBBST-UHFFFAOYSA-N chromium;cumene Chemical compound [Cr].CC(C)C1=CC=CC=C1.CC(C)C1=CC=CC=C1 AWNBGWWVMCBBST-UHFFFAOYSA-N 0.000 description 28
- -1 poly(vinyl chloride) Polymers 0.000 description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
- 150000003462 sulfoxides Chemical class 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 150000003573 thiols Chemical class 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 6
- 229930192474 thiophene Natural products 0.000 description 6
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 3
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical class [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical group CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CDKDZKXSXLNROY-UHFFFAOYSA-N octylbenzene Chemical compound CCCCCCCCC1=CC=CC=C1 CDKDZKXSXLNROY-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- JCIIKRHCWVHVFF-UHFFFAOYSA-N 1,2,4-thiadiazol-5-amine;hydrochloride Chemical compound Cl.NC1=NC=NS1 JCIIKRHCWVHVFF-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- KWSHGRJUSUJPQD-UHFFFAOYSA-N 1-phenyl-4-propan-2-ylbenzene Chemical group C1=CC(C(C)C)=CC=C1C1=CC=CC=C1 KWSHGRJUSUJPQD-UHFFFAOYSA-N 0.000 description 1
- BRSRUYVJULRMRQ-UHFFFAOYSA-N 1-phenylanthracene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 BRSRUYVJULRMRQ-UHFFFAOYSA-N 0.000 description 1
- RKLROMDZXDQSDF-UHFFFAOYSA-N 1-phenylphenanthrene Chemical compound C1=CC=CC=C1C1=CC=CC2=C1C=CC1=CC=CC=C21 RKLROMDZXDQSDF-UHFFFAOYSA-N 0.000 description 1
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 description 1
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 description 1
- CUUOZLVLTDWKJR-UHFFFAOYSA-N C=1C=CC=CC=1[Cr]C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1[Cr]C1=CC=CC=C1 CUUOZLVLTDWKJR-UHFFFAOYSA-N 0.000 description 1
- HPYIUKIBUJFXII-UHFFFAOYSA-N Cyclopentadienyl radical Chemical compound [CH]1C=CC=C1 HPYIUKIBUJFXII-UHFFFAOYSA-N 0.000 description 1
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PFUQSACCWFVIBW-UHFFFAOYSA-N [C].C1=CC=CC=C1 Chemical group [C].C1=CC=CC=C1 PFUQSACCWFVIBW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- YYUHNROGBMSKPM-UHFFFAOYSA-N benzene chromium 1,2,3,4-tetrahydronaphthalene Chemical compound [Cr].C1CCCC2=CC=CC=C12.C1=CC=CC=C1 YYUHNROGBMSKPM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HXNXAEYAXNPLHJ-UHFFFAOYSA-N butyl thiocyanate Chemical compound CCCCSC#N HXNXAEYAXNPLHJ-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- RMCQREAPGZPWGK-UHFFFAOYSA-N carbon subsulfide Chemical compound S=C=C=C=S RMCQREAPGZPWGK-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- UFYTZKOFKXUBQB-UHFFFAOYSA-N chromium 1,3-xylene Chemical compound [Cr].C1(=CC(=CC=C1)C)C.C1(=CC(=CC=C1)C)C UFYTZKOFKXUBQB-UHFFFAOYSA-N 0.000 description 1
- PLWCCMPAEIXBGQ-UHFFFAOYSA-N chromium;toluene Chemical compound [Cr].CC1=CC=CC=C1.CC1=CC=CC=C1 PLWCCMPAEIXBGQ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- BZRNNFDADQGMGA-UHFFFAOYSA-N ctk5d9411 Chemical compound Br[S] BZRNNFDADQGMGA-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WFCLYEAZTHWNEH-UHFFFAOYSA-N ethylthiocyanate Chemical compound CCSC#N WFCLYEAZTHWNEH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYHVQEYOFIYNJP-UHFFFAOYSA-N methyl thiocyanate Chemical compound CSC#N VYHVQEYOFIYNJP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000010658 organometallic substitution reaction Methods 0.000 description 1
- 229940096826 phenylmercuric acetate Drugs 0.000 description 1
- DCNLOVYDMCVNRZ-UHFFFAOYSA-N phenylmercury(.) Chemical class [Hg]C1=CC=CC=C1 DCNLOVYDMCVNRZ-UHFFFAOYSA-N 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- JMPVZWBJWHQJDD-UHFFFAOYSA-N sulfur tetrachloride Chemical compound ClS(Cl)(Cl)Cl JMPVZWBJWHQJDD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/263—Metals other than noble metals, Cu or Hg
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/17—Deposition methods from a solid phase
Definitions
- This invention relates to processes for producing a chromium plate on a solid platablesubstrate. More particularly, this invention relates to an improved catalytic chromium plating process wherein the chromium plate is formed by thermal decomposition of a bis(arene) chromium compound in the presence of a sulfur-containing catalyst.
- a chromium plate could be produced on a solid platable substrate by contacting the substrate with a bis(arene)chromium compound at a temperature at or above the thermal decomposition tem perature of the bis(arene)chromium compound. While various embodiments of this process are operable, they all have at least one important characteristic in common. Namely, they entail the use of a plating, i.e., contact, temperature of at least about 300 C., and preferably at least about 350 C., in order to effect the thermal decomposition of the bis(arene)chromium compound.
- Compounds serving as catalysts for the pur poses of thisinvention are elemental sulfur and sulfur compounds wherein the substituents attached to the sulfur atom are composed of atoms from the group consisting of carbon, hydrogen, oxygen, nitrogen, and halogen.
- Sulfur-containing compounds contemplated in this regard include hydrogen sulfide, sulfur. halides, carbon sulfides, vdialkyl sulfides, thiols, sulfoxides, alkyl thiocyanates, alkyl isothiocyanates, and thiophenes.
- sulfur-containing catalysts are sulfur; hydrogen sulfide; sulfur-halides such as sulfur monochloride (S 01 sulfur monobromide (S Br sulfur dichloride (S01 and sulfur tetrachloride (SCl carbon sulfides such as carbon subsulfide (C 5 and carbon disulfide (CS dialkyl sulfides of the formula:
- R and R are alkyl groups of 1 to 4 carbon atoms and may be the same or different, such as dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, di-n-butyl sulfide, and the like; thiols of the formula: R-S -H where R is "as defined above, such as. methyl mercaptan, ethyl mercaptan, n-butyl mercaptan, and thel-ike; sulfox ides of the formula:- Y
- R a'nd R are as'defined above, such as dimethyl sulfoxide, diet-hyl” sulfoxide, di-n-propyl sulfoxide, dimbutyl sulfoxide, and the like; alkyl thiocy'anatesof'the formula: I
- R is as defined above, such as methyl thiocyanate, ethyl thiocyanate, n-butyl thiocyanate, and the like; alkyl isothiocyanates of the formula:
- arene groups are uncharged aromatic hydrocarbons con taining either an isolated benzene ring or. an aryl-sub 3 stituted benzene structure.
- isolated benzene ring is intended to define a benzene ring as contained in benzene itself, or in a fused ring polycyclic aromatic hydrocarbon containing a benzene ring, wherein, by the Kekule formulation, any double bond in a ring fused to such benzene ring is removed from the benzene ring carbon atom nearest to it by at least two carbon atoms.
- isolated benzene ring is also intended to define a benzene ring as contained in a monocyclic aromatic hydrocarbon having one or more aliphatic su'bstitutents on a benzene ring, wherein any double bond external to the benzene carbon ring is removed from the benzene ring carbon atom nearest to it by at least two carbon atoms.
- benzene, indane, tetrahydronaphthalene
- naphthalene, indene, anthracene, phenanthrene, and styrene are examples of aromatic hydrocarbons which do not contain an isolated benzene ring.
- aryl-substituted benzenes also form bis(arene)- chromium compounds which are useful in the plating process of this invention.
- aryl-substituted benzenes are polyphenyls, alkyl-substituted polyphenyls, such as p-isopropyldiphenyl and p,p'-dimethyldiphenyl, phenylanthracene and phenylphenanthrene.
- the bis(arene)chromium compounds contemplated by this invention may, from the point of view of their organic moiety, be characterized as addition compounds in contrast to organometallic substitution compounds, wherein hydrogen or another substituent of the organic nucleus is substituted or removed in forming the organometallic compound.
- the bis(arene)chromium compounds are to be distinguished from the organornetallic compounds formed by the chemical bonding of a cyclopentadienyl radical with an element (Fischer and Pfab, Zeit. fiir Naturforschung, 7b, page 377 (1952)), and from phenyl mercury compounds, e.g., phenyl mercuric acetate (US. Patent 2,502,222).
- the bis(arene)chromium compounds contemplated by this invention can be represented more clearly by the formula (Ar) Cr, wherein Ar designates either an aromatic hydrocarbon containing an isolated benzene ring, or an aryl-substituted benzene, as hereinabove described.
- the bis(arene)chromium compounds can also have mixed Ar substituents, as more specifically represented by the formulai (Ar) (Ar')Cr wherein Ar and Ar independently designate members of the same class of aromatic hydrocarbons.
- Ar independently designate members of the same class of aromatic hydrocarbons.
- the exact nature of the bond between the aromatic hydrocarbon moiety and the metal is unknown. However, it is known that the isolatedbenzene ring or the benzene ring of the aryl-substituted benzene is complexed to the metal.
- the bis(arene)chromium compounds contemplated by this invention include, by way of illustration,.-bis (benzene) chromium, bis (tetrahydronaphth alene chromium, bis (toluene) chromium, bis(mesitylen'e) chromium, bis- (hexamethylbenzene)chromium, bis(ortho xylene)chromium, bis (meta-xylene) chromium, bis para-xylene) chrominum, bis(octylbenzene)chromium, (benzene) (tetrahydronaphthalene) chromium, bis (diphenyl)chromium, bis- (curnene)chromiurn, and the like.
- the preferred bis- (arene) chromium compounds are those in which the arene moiety is either benzene or a lower alkyl-substituted benzene in which the lower alkyl substituent(s) contain from 1 to about 8, and preferably from 1 to about 4 carbon atoms. 7
- anhydrous chromium salt such as a chromium halide
- aromatic hydrocarbon containing at least one isolated benzene ring or with an aryl-su'b stituted benzene
- the plating process of this invention entails contacting a suitable substrate over the area to be plated with the bis(arene)chromium compound in mutual contact with a catalytic amount of sulfur-containing catalyst, and heating the bis(arene)chromium compound and sulfur-containing catalyst in contact with the substrate at a temperature of a least the decomposition temperature of the bis(arene)chromium compound when in contact with the catalyst.
- a substantially pure, ordinarily uniform chromium plate is thereby produced on the substrate.
- the process of this invention be carried out in an inert atmosphere, i.e., in the absence of oxygen or oxygen-containing substances which react with the bis(arene)chromium compound, or with the resulting chromium plate itself, to form metal oxides which contaminate the plate.
- any amount thereof suflicient to catalyze the thermal decomposition of the bis(arene)chromium compound, resulting in the lowering of the decomposition temperature can be utilized with satisfactory effect.
- Such amounts will vary to a certain extent depending upon the particular catalyst employed and the plating rate desired, and can readily be determined by one skilled in the art in light of this disclosure.
- particularly good results can be obtained, for instance, employing the sulfur-containing catalyst in an amount varying in the range of from about 0.1 to about 5 weight percent, and preferably from about 0.2 to about 3 weight percent, based upon the amount of bis(arene)chromium compound employed. Within this range, an increase in the amount of catalyst ordinarily engenders a more rapid rate of plating. Greater amounts of catalyst can also be employed, although little additional advantage may accrue.
- the plating temperature to be employed will vary to a certain extent, depending upon the particular bis(arene) chromium compound and catalyst employed, as well as upon the desired rate of plating. In general, however, satisfactory results can be obtained at a plating temperature of atleast about C. and less than about 300 C., and preferably in the range of about 175 C. to about 250 C., with more rapid plating occurring as the plating temperature is increased. Plating temperatures above 300 C. can also be employed, although the use of such higher temperatures may limit the type of substrate which can be plated, for reasons such as those described above in connection with the prior art.
- the maximum plating temperature is, for practical purposes, determined by the decomposition (cracking) temperature of the arene moiety of the bis(arene)chromium compound.
- the heating period can also be varied broadly. Commercially acceptable plates can be obtained, for instance, by heating for a contact period of from about 10 minutes to about 3 hours, although somewhat shorter, as well as longer heating periods can also be employed. In general,
- any platable solid substrate which is thermally stable at the temperature encountered can be used in the plating process of this invention in a variety of shapes or forms.
- suitable substrates include glass, metals such as aluminum and iron, etc., thermoplastic and thermoset polymers such as poly(vinyl chloride), polyethylene, poly(ethylene terephthalate), the polyamide of isophthalic acid and metaphenylene diamine, polytetrafluoroethylene, polytrifiuorochloroethylene, acroleinpentaerythritol resins, etc., and the like.
- the substrate can be in the form of single sheets, laminates, fibers, films, molded or shaped articles, etc.
- the plating process of this invention can be carried out in various Ways and any of the conventional vaporphase plating techniques can be employed.
- the bis(arene)chromium compound is vaporized in a stream of inert gas and mixed, at a temperature below its decomposition temperature, with a second stream of inert gas containing the desired concentration of sulfur-containing catalyst.
- the mixture is then passed over the substrate, which is maintained at a temperature equal to or greater than the catalyzed decomposition temperature, whereby the bis(arene)chromium compound is decomposed on the surface of the substrate to produce a chromium plate.
- the plating process can be made continuous with respect to both substrate and plating gas.
- the substrate is initially contacted with the sulfur-containing catalyst by, for example, dipping the substrate into a solution of the catalyst in an inert solvent, such as ethanol, and subsequently evaporating the solvent, and then the bis(arene)chromium compound is vaporized in such manner that the resulting vapors are passed over and contacted with the substrate and catalyst at plating temperature.
- Example 1 A l-inch by 3-inch glass microscope slide was inserted into the large end of a 32 mm. diameter glass tube, 9 inches in length, necked down to 8 mm. diameter at one end. The large end of the tube was sealed with a gas flame, the tube was purged with nitrogen through the open end, and then 0.3 cc. of dicumenechromium was introduced into the tube. Three times in succession, the tube was evacuated to 15 mm. of Hg absolute pressure and then brought back to atmospheric pressure by addition of hydrogen sulfide. The tube was then again evacuated to 15 mm. of Hg absolute pressure, sealed with a gas flame, and placed in a resistance-heated, forcedconvection, thermostatically-controlled oven at 225 C. After 2 hours at this temperature, the tube was removed from the oven, cooled, and opened. Both the tube and the microscope slide were uniformly coated With .a shiny and adherent chromium plate.
- Example 2 A chromium plate was applied in an identical manner to that described in Example 1, except that the plating temperature was 200 C.
- Example 3 A chromium plate was applied in an identical manner to that described in Example 1, except that the plating temperature was C.
- Example 4 A l-inch by 3-inch glass microscope slide was inserted into a glass tube similar to that described in Example 1, the tube was purged with nitrogen, and then 0.3 cc. of dicumenechromium and 0.03 cc. of thiophene were added to the tube. The tube was then evacuated to 0.5 mm. Hg absolute pressure, sealed with a gas flame, and placed in a resistance-heated, forced-convection, thermostatically-controlled oven at 225. C. After 2 hours at this temperature, the tube was removed from the oven, cooled, and opened. Both the tube and the microscope slide were uniformly coated with a shiny and adherent chromium plate.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with (a) a bis(arene)chromium compound of the formula (Ar) Cr.
- Ar designates an organic hydrocarbon selected from the group consisting of aromatic hydrocarbons containing an isolated benzene ring and aryl-substituted benzenes, in mutual contact with (b) a catalytic amount of a sulfur-containing catalyst selected from the group consisting, of elemental sulfur and sulfur compounds wherein the substituents attached to the sulfur atom are composed of atoms selected from the group consisting of carbon, hydrogen, oxygen, nitrogen and halogen, said catalyst being present in an amount sufficient to catalyze the thermal decomposition of said bis(arene)chromium compound, and heating said his (arene)chromium compound and said catalyst in contact with said substrate at a temperature-of at least the decomposition temperature of said bis-(arene)chromium compound in contact with said catalyst and below about 330 C., therebyv producing a chromium plate on said substrate.
- a sulfur-containing catalyst selected from the group consisting, of elemental sulfur and sulfur compounds wherein the substituents attached to the sulfur
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with (a) a bis(arene)chromium compound of the formula (Ar) Cr wherein Ar designates an organic hydrocarbon selected from the group consisting of aromatic hydrocarbons containing an isolated benzene ring and aryl-substituted benzenes, in mutual contact with (b) a catalytic amount of a sulfur-containing catalyst selected from the group consisting of elemental sulfur, hydrogen sulfide, the sulfur halides, the carbon sulfides, the dialkyl sulfides of the formula:
- R and R are alkyl groups of l to 4 carbon atoms, the thiols of the formula:
- each R is independently selected from the group consisting of a hydrogen atom and a methyl group
- said catalyst being present in an amount sufiicient to catalyze the thermal decomposition of said bis(arene)chromium compound, and heating said bis(arene)chromium compound and said catalyst in contact with said substrate at a temperature of at least the decomposition temperature of said bis(arene)chromium compound in contact with said catalyst and below about 300 C., thereby producing a chromium plate on said substrate.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with hydrogen sulfide, said hydrogen sulfide being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said hydrogen sulfide in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with sulfur monochloride, said sulfur monochloride being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said sulfur monochloride in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with carbon disulfide, said carbon disulfide being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said carbon disulfide in contact with said substrate at a temperature of from about 175 6.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with a dialkyl sulfide of the formula:
- R and R are alkyl groups of l to 4 carbon atoms, said dialkyl sulfide being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said dialkyl sulfide in contact with said substrate at a temperature of from about C. to about 250 C., thereby producing a chromium plate on said substrate.
- dialkyl sulfide is dimethyl sulfide.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with a thiol of the formula:
- R is an alkyl group of 1 to 4 carbon atoms, said thiol being present in an amount sufiicient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said thiol in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with a sulfoxide of the formula:
- R and R are alkyl groups of l to 4 carbon atoms, said sulfoxide being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said sulfoxide in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with an alkyl thiocyanate of the formula:
- R is an alkyl group of 1 to 4 carbon atoms, said alkyl thiocyanate being present in an amount sufiicient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said alkyl thiocyanate in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
- a process for producing a chromium plate on a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with an alkyl isothiocyanate of the formula:
- R is an alkyl group of l to 4 carbon atoms, said alkyl isothiocyanate being present in an amount sufiicient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said alkyl isothiocyanate in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
- a process for producing a chromium plateon a platable solid substrate in an inert atmosphere comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with thiophene, said thiophene being present in an amount sufiicient to catalyze the thermal decomposition of said dicumenechrornium, and heating said dicumenechromium and said thiophene in contact with said substrate at a 10 temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
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Description
3 372 055 CATALYTIC CHROliIIUlVI PLATING PROCESS EMPLOYING BIS(ARENE)CHROMIUM Frank P. Maclarlane, Jr., St. Albans, and Bernard I.
Pesetsky, outh Charleston, W. Va., assiguors to Union Carbide Corporation, a corporation of New York No Drawing. Filed May 18, 1965, Ser. No. 456,805 Claims. (Cl. 117-1072) This invention relates to processes for producing a chromium plate on a solid platablesubstrate. More particularly, this invention relates to an improved catalytic chromium plating process wherein the chromium plate is formed by thermal decomposition of a bis(arene) chromium compound in the presence of a sulfur-containing catalyst.
Heretofore, it was known that a chromium plate could be produced on a solid platable substrate by contacting the substrate with a bis(arene)chromium compound at a temperature at or above the thermal decomposition tem perature of the bis(arene)chromium compound. While various embodiments of this process are operable, they all have at least one important characteristic in common. Namely, they entail the use of a plating, i.e., contact, temperature of at least about 300 C., and preferably at least about 350 C., in order to effect the thermal decomposition of the bis(arene)chromium compound.
Unfortunately, however, the necessity for utilizing such elevated plating temperatures limits the selection of substrates which canbe plated in accordance with the process. Thus, for instance, the use of many synthetic resins, such as polyethylene and poly(vinyl chloride), etc., which decompose when heated to temperatures of a'bout30() C. and higher, is precluded in this regard. In addition, the use of such elevated temperatures may damage the temper of many steel products, particularly temperedspring steel, on which a chromium plate is often desirable. Further, the use of such elevated temperatures may be a hazard in plating large glass objects which are ordinarily subject to strain unless heating and cooling operations are slow, the latter, in turn, being an undesirable feature from a commercial point of view. Finally such elevated temperatures are often above the stability range of common 7 Advantageously, it has now been found that upon contacting a platable solid substrate in an inert atmosphere with a bis(arene)chromium compound in mutual contact with a sulfur-containing catalyst, the thermal decomposition of the bis(arene)chromium compound,'producing a substantially pure chromium plate 'on the substrate, can be carried out at a temperature materially lower than that necessary in the uncatalyzed plating processes of the prior art, i.e., at temperatures as low as about 175 C., or lower. In this manner, substrates such as large glass objects, many synthetic resins, and tempered steels, etc., which are not thermally stable'at the elevated temperatures employed in accordance with prior art plating techniques as indicated above, can now be plated satisfactorily through the practice of the improved process of this'invention. At the same time, through the use of lower I Patented Mar. 5, 1968 "ice plating temperatures, a more convenient and economical plating process is made possible, The present invention is based upon the discovery that the thermal decomposition of bis(arene)chromium com pounds is catalyzed by sulfur-containing compounds which substantially lower the thermal decomposition temperature of the bis(arene)chromium compound when in contact therewith. Compounds serving as catalysts for the pur poses of thisinvention are elemental sulfur and sulfur compounds wherein the substituents attached to the sulfur atom are composed of atoms from the group consisting of carbon, hydrogen, oxygen, nitrogen, and halogen. Sulfur-containing compounds contemplated in this regard include hydrogen sulfide, sulfur. halides, carbon sulfides, vdialkyl sulfides, thiols, sulfoxides, alkyl thiocyanates, alkyl isothiocyanates, and thiophenes.
Specifically illustrative of the sulfur-containing catalysts are sulfur; hydrogen sulfide; sulfur-halides such as sulfur monochloride (S 01 sulfur monobromide (S Br sulfur dichloride (S01 and sulfur tetrachloride (SCl carbon sulfides such as carbon subsulfide (C 5 and carbon disulfide (CS dialkyl sulfides of the formula:
RS-R' where R and R are alkyl groups of 1 to 4 carbon atoms and may be the same or different, such as dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, di-n-butyl sulfide, and the like; thiols of the formula: R-S -H where R is "as defined above, such as. methyl mercaptan, ethyl mercaptan, n-butyl mercaptan, and thel-ike; sulfox ides of the formula:- Y
where R a'nd R are as'defined above, such as dimethyl sulfoxide, diet-hyl" sulfoxide, di-n-propyl sulfoxide, dimbutyl sulfoxide, and the like; alkyl thiocy'anatesof'the formula: I
where R is as defined above, such as methyl thiocyanate, ethyl thiocyanate, n-butyl thiocyanate, and the like; alkyl isothiocyanates of the formula:
arene groups are uncharged aromatic hydrocarbons con taining either an isolated benzene ring or. an aryl-sub 3 stituted benzene structure. As employed herein, the term isolated benzene ring is intended to define a benzene ring as contained in benzene itself, or in a fused ring polycyclic aromatic hydrocarbon containing a benzene ring, wherein, by the Kekule formulation, any double bond in a ring fused to such benzene ring is removed from the benzene ring carbon atom nearest to it by at least two carbon atoms. The term isolated benzene ring is also intended to define a benzene ring as contained in a monocyclic aromatic hydrocarbon having one or more aliphatic su'bstitutents on a benzene ring, wherein any double bond external to the benzene carbon ring is removed from the benzene ring carbon atom nearest to it by at least two carbon atoms. Thus, benzene, indane, tetrahydronaphthalene,
9,10-dihydroanthracene, 9,IO-dihydroplrenanthrene, alkylsubstituted benzenes such as toluene, ethylbenzene, buytlbenzene, octyl benzene, etc., and alkenyl-substituted benzenes in which double bonds external to the benzene ring are separated therefrom by at least two carbon atoms, such as allylbenzene, etc., are examples of aromatic hydrocarbons containing an isolated benzene ring. By contrast, naphthalene, indene, anthracene, phenanthrene, and styrene are examples of aromatic hydrocarbons which do not contain an isolated benzene ring.
As also mentioned above, a class of aromatic hydrocarbons which do not contain an isolated benzene ring, namely aryl-substituted benzenes, also form bis(arene)- chromium compounds which are useful in the plating process of this invention. Examples of such aryl-substituted benzenes are polyphenyls, alkyl-substituted polyphenyls, such as p-isopropyldiphenyl and p,p'-dimethyldiphenyl, phenylanthracene and phenylphenanthrene.
The bis(arene)chromium compounds contemplated by this invention may, from the point of view of their organic moiety, be characterized as addition compounds in contrast to organometallic substitution compounds, wherein hydrogen or another substituent of the organic nucleus is substituted or removed in forming the organometallic compound. Thus, the bis(arene)chromium compounds are to be distinguished from the organornetallic compounds formed by the chemical bonding of a cyclopentadienyl radical with an element (Fischer and Pfab, Zeit. fiir Naturforschung, 7b, page 377 (1952)), and from phenyl mercury compounds, e.g., phenyl mercuric acetate (US. Patent 2,502,222). Formation of such substitution compounds, it is to be noted, involves elimination of hydrogen from the cyclopentadiene or benzene nucleus. In the case of the bis(arene)chromium compounds of the present invention, the chemical union of the metal with the aromatic hydrocarbon does not involve the elimination of hydrogen or any other substituent of the organic nucleus. The bis- (arene)chromium compounds may, therefore, be regarded as the addition products of chromium with aromatic hydrocarbons.
The bis(arene)chromium compounds contemplated by this invention can be represented more clearly by the formula (Ar) Cr, wherein Ar designates either an aromatic hydrocarbon containing an isolated benzene ring, or an aryl-substituted benzene, as hereinabove described. The bis(arene)chromium compounds can also have mixed Ar substituents, as more specifically represented by the formulai (Ar) (Ar')Cr wherein Ar and Ar independently designate members of the same class of aromatic hydrocarbons. The exact nature of the bond between the aromatic hydrocarbon moiety and the metal is unknown. However, it is known that the isolatedbenzene ring or the benzene ring of the aryl-substituted benzene is complexed to the metal.
The bis(arene)chromium compounds contemplated by this invention include, by way of illustration,.-bis (benzene) chromium, bis (tetrahydronaphth alene chromium, bis (toluene) chromium, bis(mesitylen'e) chromium, bis- (hexamethylbenzene)chromium, bis(ortho xylene)chromium, bis (meta-xylene) chromium, bis para-xylene) chrominum, bis(octylbenzene)chromium, (benzene) (tetrahydronaphthalene) chromium, bis (diphenyl)chromium, bis- (curnene)chromiurn, and the like. The preferred bis- (arene) chromium compounds are those in which the arene moiety is either benzene or a lower alkyl-substituted benzene in which the lower alkyl substituent(s) contain from 1 to about 8, and preferably from 1 to about 4 carbon atoms. 7
The bis(arene)chromium compounds can be prepared by reacting an anhydrous chromium salt, such as a chromium halide, with an aromatic hydrocarbon containing at least one isolated benzene ring, or with an aryl-su'b stituted benzene, in the presence of an anhydrous alu= minum halide and a reducing agent. The bis(arene)chromium compounds and methods for their production are described more fully in United States Patent 2,953,586 and such description is incorporated herein by reference.
The plating process of this invention, as hereinabove described, entails contacting a suitable substrate over the area to be plated with the bis(arene)chromium compound in mutual contact with a catalytic amount of sulfur-containing catalyst, and heating the bis(arene)chromium compound and sulfur-containing catalyst in contact with the substrate at a temperature of a least the decomposition temperature of the bis(arene)chromium compound when in contact with the catalyst. A substantially pure, ordinarily uniform chromium plate is thereby produced on the substrate. In addition, it is essential that the process of this invention be carried out in an inert atmosphere, i.e., in the absence of oxygen or oxygen-containing substances which react with the bis(arene)chromium compound, or with the resulting chromium plate itself, to form metal oxides which contaminate the plate.
The function of the sulfur-containing material employed in accordance with this invention being that of a catalyst, any amount thereof suflicient to catalyze the thermal decomposition of the bis(arene)chromium compound, resulting in the lowering of the decomposition temperature, can be utilized with satisfactory effect. Such amounts will vary to a certain extent depending upon the particular catalyst employed and the plating rate desired, and can readily be determined by one skilled in the art in light of this disclosure. Moreover, particularly good results can be obtained, for instance, employing the sulfur-containing catalyst in an amount varying in the range of from about 0.1 to about 5 weight percent, and preferably from about 0.2 to about 3 weight percent, based upon the amount of bis(arene)chromium compound employed. Within this range, an increase in the amount of catalyst ordinarily engenders a more rapid rate of plating. Greater amounts of catalyst can also be employed, although little additional advantage may accrue.
The plating temperature to be employed will vary to a certain extent, depending upon the particular bis(arene) chromium compound and catalyst employed, as well as upon the desired rate of plating. In general, however, satisfactory results can be obtained at a plating temperature of atleast about C. and less than about 300 C., and preferably in the range of about 175 C. to about 250 C., with more rapid plating occurring as the plating temperature is increased. Plating temperatures above 300 C. can also be employed, although the use of such higher temperatures may limit the type of substrate which can be plated, for reasons such as those described above in connection with the prior art. The maximum plating temperature is, for practical purposes, determined by the decomposition (cracking) temperature of the arene moiety of the bis(arene)chromium compound.
The heating period can also be varied broadly. Commercially acceptable plates can be obtained, for instance, by heating for a contact period of from about 10 minutes to about 3 hours, although somewhat shorter, as well as longer heating periods can also be employed. In general,
thicker plates are ordinarily produced as the heating period is extended.
Any platable solid substrate which is thermally stable at the temperature encountered can be used in the plating process of this invention in a variety of shapes or forms. By way of illustration, suitable substrates include glass, metals such as aluminum and iron, etc., thermoplastic and thermoset polymers such as poly(vinyl chloride), polyethylene, poly(ethylene terephthalate), the polyamide of isophthalic acid and metaphenylene diamine, polytetrafluoroethylene, polytrifiuorochloroethylene, acroleinpentaerythritol resins, etc., and the like. Moreover, the substrate can be in the form of single sheets, laminates, fibers, films, molded or shaped articles, etc.
The plating process of this invention can be carried out in various Ways and any of the conventional vaporphase plating techniques can be employed. In a preferred embodiment of the invention, the bis(arene)chromium compound is vaporized in a stream of inert gas and mixed, at a temperature below its decomposition temperature, with a second stream of inert gas containing the desired concentration of sulfur-containing catalyst. The mixture is then passed over the substrate, which is maintained at a temperature equal to or greater than the catalyzed decomposition temperature, whereby the bis(arene)chromium compound is decomposed on the surface of the substrate to produce a chromium plate. As will be apparent to one skilled in the plating art, the plating process can be made continuous with respect to both substrate and plating gas. In another embodiment of the invention, the substrate is initially contacted with the sulfur-containing catalyst by, for example, dipping the substrate into a solution of the catalyst in an inert solvent, such as ethanol, and subsequently evaporating the solvent, and then the bis(arene)chromium compound is vaporized in such manner that the resulting vapors are passed over and contacted with the substrate and catalyst at plating temperature.
Other means for bringing the substrate, bis(arene) chromium compound and sulfur-containing catalyst into mutual contact at a plating temperature so as to produce or deposit a chromium plate on the substrate will occur to those skilled in the art in light of this disclosure and can be employed within the contemplation of this inventlon.
The invention can be illustrated further by the following specific examples of its practice.
Example 1 A l-inch by 3-inch glass microscope slide was inserted into the large end of a 32 mm. diameter glass tube, 9 inches in length, necked down to 8 mm. diameter at one end. The large end of the tube was sealed with a gas flame, the tube was purged with nitrogen through the open end, and then 0.3 cc. of dicumenechromium was introduced into the tube. Three times in succession, the tube was evacuated to 15 mm. of Hg absolute pressure and then brought back to atmospheric pressure by addition of hydrogen sulfide. The tube was then again evacuated to 15 mm. of Hg absolute pressure, sealed with a gas flame, and placed in a resistance-heated, forcedconvection, thermostatically-controlled oven at 225 C. After 2 hours at this temperature, the tube was removed from the oven, cooled, and opened. Both the tube and the microscope slide were uniformly coated With .a shiny and adherent chromium plate.
Example 2 A chromium plate was applied in an identical manner to that described in Example 1, except that the plating temperature was 200 C.
Example 3 A chromium plate was applied in an identical manner to that described in Example 1, except that the plating temperature was C.
Example 4 A l-inch by 3-inch glass microscope slide was inserted into a glass tube similar to that described in Example 1, the tube was purged with nitrogen, and then 0.3 cc. of dicumenechromium and 0.03 cc. of thiophene were added to the tube. The tube was then evacuated to 0.5 mm. Hg absolute pressure, sealed with a gas flame, and placed in a resistance-heated, forced-convection, thermostatically-controlled oven at 225. C. After 2 hours at this temperature, the tube was removed from the oven, cooled, and opened. Both the tube and the microscope slide were uniformly coated with a shiny and adherent chromium plate.
Examples 5 to 10 Example Number Catalyst Plating T emperature C.)
Ethyl mercaptan 10 Sulfur monochloride In each case, an adherent chromium coating was applied to the slide.
Eiforts to chromium plate glass slides in an identical manner to that described in the above examples, but omitting the use of a sulfur-containing catalyst, were unsuccessful at temperatures of about 250 C. and evidence of plating Was not observed under such conditions'until the plating temperature reached 300 C., and then only after heating periods of several hours.
Although the invention has been illustrated by themeceding examples, it is not to be construed as limited to the materials employed therein, but rather the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments of this invention can be made without departing from the spirit and scope thereof.
What is claimed is:
1. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with (a) a bis(arene)chromium compound of the formula (Ar) Cr. wherein Ar designates an organic hydrocarbon selected from the group consisting of aromatic hydrocarbons containing an isolated benzene ring and aryl-substituted benzenes, in mutual contact with (b) a catalytic amount of a sulfur-containing catalyst selected from the group consisting, of elemental sulfur and sulfur compounds wherein the substituents attached to the sulfur atom are composed of atoms selected from the group consisting of carbon, hydrogen, oxygen, nitrogen and halogen, said catalyst being present in an amount sufficient to catalyze the thermal decomposition of said bis(arene)chromium compound, and heating said his (arene)chromium compound and said catalyst in contact with said substrate at a temperature-of at least the decomposition temperature of said bis-(arene)chromium compound in contact with said catalyst and below about 330 C., therebyv producing a chromium plate on said substrate.
2. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with (a) a bis(arene)chromium compound of the formula (Ar) Cr wherein Ar designates an organic hydrocarbon selected from the group consisting of aromatic hydrocarbons containing an isolated benzene ring and aryl-substituted benzenes, in mutual contact with (b) a catalytic amount of a sulfur-containing catalyst selected from the group consisting of elemental sulfur, hydrogen sulfide, the sulfur halides, the carbon sulfides, the dialkyl sulfides of the formula:
'RS--R where R and R are alkyl groups of l to 4 carbon atoms, the thiols of the formula:
RS-I-I where R is as defined above, the sulfoxides of the formula:
T RSR where R and R are as defined above, the alkyl thiocyanates of the formula:
R-SCEN where R is as defined above, the alkyl isothiocyanates of the formula:
R-N=C=S where R is as defined above, and the thiophenes of the formula:
R1-o-oRr Elk-( i R1 S where each R is independently selected from the group consisting of a hydrogen atom and a methyl group, said catalyst being present in an amount sufiicient to catalyze the thermal decomposition of said bis(arene)chromium compound, and heating said bis(arene)chromium compound and said catalyst in contact with said substrate at a temperature of at least the decomposition temperature of said bis(arene)chromium compound in contact with said catalyst and below about 300 C., thereby producing a chromium plate on said substrate.
3. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with hydrogen sulfide, said hydrogen sulfide being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said hydrogen sulfide in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
4. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with sulfur monochloride, said sulfur monochloride being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said sulfur monochloride in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
5. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with carbon disulfide, said carbon disulfide being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said carbon disulfide in contact with said substrate at a temperature of from about 175 6. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with a dialkyl sulfide of the formula:
where R and R are alkyl groups of l to 4 carbon atoms, said dialkyl sulfide being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said dialkyl sulfide in contact with said substrate at a temperature of from about C. to about 250 C., thereby producing a chromium plate on said substrate.
7. The process according to claim 6 wherein the dialkyl sulfide is dimethyl sulfide.
8. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with a thiol of the formula:
where R is an alkyl group of 1 to 4 carbon atoms, said thiol being present in an amount sufiicient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said thiol in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
9. The process according to claim 8 wherein the thiol is ethyl mercaptan.
10. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with a sulfoxide of the formula:
0 Rates where R and R are alkyl groups of l to 4 carbon atoms, said sulfoxide being present in an amount sufficient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said sulfoxide in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
11. The process according to claim 10 wherein the sulfoxide is dimethyl sulfoxide.
12. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with an alkyl thiocyanate of the formula:
where R is an alkyl group of 1 to 4 carbon atoms, said alkyl thiocyanate being present in an amount sufiicient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said alkyl thiocyanate in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
13. A process for producing a chromium plate on a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with an alkyl isothiocyanate of the formula:
where R is an alkyl group of l to 4 carbon atoms, said alkyl isothiocyanate being present in an amount sufiicient to catalyze the thermal decomposition of said dicumenechromium, and heating said dicumenechromium and said alkyl isothiocyanate in contact with said substrate at a temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
14. The process according to claim 13 wherein the alkyl isothiocyanate is methyl isothiocyanate.
15. A process for producing a chromium plateon a platable solid substrate in an inert atmosphere, which process comprises contacting said substrate over the area to be plated with dicumenechromium in mutual contact with thiophene, said thiophene being present in an amount sufiicient to catalyze the thermal decomposition of said dicumenechrornium, and heating said dicumenechromium and said thiophene in contact with said substrate at a 10 temperature of from about 175 C. to about 250 C., thereby producing a chromium plate on said substrate.
References Cited UNITED STATES PATENTS 2,886,468 5/1959 Hoover et al 117107.2 2,892,857 6/1959 Ecke et al. 117-107.2 2,953,586 9/1960 Hafner et al. 117--107.2 3,203,827 8/1965 Hill 117107.2
10 ALFRED L. LEAVITT, Primary Examiner.
A. GOLIAN, Assistant Examiner.
Claims (1)
1. A PROCESS FOR PRODUCING A CHROMIUM PLATE ON A PLATABLE SOLID SUBSTRATE IN AN INERT ATMOSPHERE, WHICH PROCESS COMPRISES CONTACTING SAID SUBSTRATE OVER THE AREA TO BE PLATED WITH (A) A BIS(ARENE)CHROMIUM COMPOUND OF THE FORMULA (AR)2CR WHEREIN AR DESIGNATES AN ORGANIC HYDROCARBON SELECTED FROM THE GROUP CONSISTING OF AROMATIC HYDROCARBONS CONTAINING AN ISOLATED BENZENE RING AND ARYL-SUBSTITUTED BENZENES, IN MUTUAL CONTACT WITH (B) A CATALYTIC AMOUNT OF A SULFUR-CONTAINING CATALYST SELECTED FROM THE GROUP CONSISTING OF ELEMENTAL SULFUR AND SULFUR COMPOUNDS WHEREIN THE SUBSTITUENTS ATTACHED TO THE SULFUR ATOM ARE COMPOSED OF ATOMS SELECTED FROM THE GROUP CONSISTING OF CARBON, HYDROGEN, OXYGEN, NITROGEN AND HALOGEN, SAID CATALYST BEING PRESENT IN AN AMOUNT SUFFICIENT TO CATALYZE THE THERMAL DECOMPOSITION OF SAID BIS(ARENE)CHROMIUM COMPOUND, AND HEATING SAID BIS (ARENE)CHROMIUM COMPOUND AND SAID CATALYST IN CONTACT WITH SAID SUBSTRATE AT A TEMPERATURE OF AT LEAST THE DECOMPOSITION TEMPERATURE OF SAID BIS(ARENE) CHROMIUM COMPOUND IN CONTACT WITH SAID CATALYST AND BELOW ABOUT 330*C., THEREBY PRODUCING A CHROMIUM PLATE ON SAID SUBSTRATE.
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US456805A US3372055A (en) | 1965-05-18 | 1965-05-18 | Catalytic chromium plating process employing bis (arene) chromium |
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US456805A US3372055A (en) | 1965-05-18 | 1965-05-18 | Catalytic chromium plating process employing bis (arene) chromium |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997037057A1 (en) * | 1996-03-29 | 1997-10-09 | International Business Machines Corporation | Deposition method and precursor therefor |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2886468A (en) * | 1953-07-16 | 1959-05-12 | Thomas B Hoover | Nickel plating process |
US2892857A (en) * | 1956-09-06 | 1959-06-30 | Ethyl Corp | Chemical process |
US2953586A (en) * | 1955-10-05 | 1960-09-20 | Union Carbide Corp | Method for preparing organo-metallic compounds |
US3203827A (en) * | 1962-06-26 | 1965-08-31 | Union Carbide Corp | Chromium plating process |
-
1965
- 1965-05-18 US US456805A patent/US3372055A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2886468A (en) * | 1953-07-16 | 1959-05-12 | Thomas B Hoover | Nickel plating process |
US2953586A (en) * | 1955-10-05 | 1960-09-20 | Union Carbide Corp | Method for preparing organo-metallic compounds |
US2892857A (en) * | 1956-09-06 | 1959-06-30 | Ethyl Corp | Chemical process |
US3203827A (en) * | 1962-06-26 | 1965-08-31 | Union Carbide Corp | Chromium plating process |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997037057A1 (en) * | 1996-03-29 | 1997-10-09 | International Business Machines Corporation | Deposition method and precursor therefor |
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