US3418216A - Organometallic electrolyte for galvanic deposition of zinc, aluminum, gallium and indium - Google Patents
Organometallic electrolyte for galvanic deposition of zinc, aluminum, gallium and indium Download PDFInfo
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- US3418216A US3418216A US515804A US51580465A US3418216A US 3418216 A US3418216 A US 3418216A US 515804 A US515804 A US 515804A US 51580465 A US51580465 A US 51580465A US 3418216 A US3418216 A US 3418216A
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- Prior art keywords
- aluminum
- electrolyte
- complex
- zinc
- indium
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- 239000003792 electrolyte Substances 0.000 title description 74
- 229910052782 aluminium Inorganic materials 0.000 title description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title description 36
- 229910052725 zinc Inorganic materials 0.000 title description 23
- 239000011701 zinc Substances 0.000 title description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 22
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title description 19
- 229910052733 gallium Inorganic materials 0.000 title description 19
- 229910052738 indium Inorganic materials 0.000 title description 19
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title description 17
- 125000002524 organometallic group Chemical group 0.000 title description 10
- 230000008021 deposition Effects 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 description 52
- 150000003839 salts Chemical class 0.000 description 27
- -1 sulphate radical Chemical class 0.000 description 26
- 238000000151 deposition Methods 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 229930195733 hydrocarbon Natural products 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 150000004010 onium ions Chemical class 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 238000009713 electroplating Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 150000002902 organometallic compounds Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 229910052714 tellurium Inorganic materials 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229940052303 ethers for general anesthesia Drugs 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- SOMSXRFNBORXAU-UHFFFAOYSA-N benzene toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1 SOMSXRFNBORXAU-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- LBKYCOGBBDATCR-UHFFFAOYSA-N benzyl(diethyl)alumane Chemical compound CC[Al](CC)CC1=CC=CC=C1 LBKYCOGBBDATCR-UHFFFAOYSA-N 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- ILXWFJOFKUNZJA-UHFFFAOYSA-N ethyltellanylethane Chemical compound CC[Te]CC ILXWFJOFKUNZJA-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- MCWWHQMTJNSXPX-UHFFFAOYSA-N tribenzylalumane Chemical compound C=1C=CC=CC=1C[Al](CC=1C=CC=CC=1)CC1=CC=CC=C1 MCWWHQMTJNSXPX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/42—Electroplating: Baths therefor from solutions of light metals
- C25D3/44—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
Definitions
- Organometallic electrolytes for galvanic deposition of aluminum are already known. These are complex compounds of aluminum alkyls and alkali halogenides as well as homogeneous liquid phase aluminum alkyls and their complex combinations with quaternary ammonia compounds.
- the invention concerns an organometallic electrolyte for galvanic depositing of one of the elements zinc, aluminum, gallium or indium, consisting of a complex compound between a metal compound of the formula MeX R and a quaternary onium salt of the formula [R R R R Y]X whereby:
- Me is an atom of zinc, aluminum, gallium or indium
- R is an alkyl radical with C to C Y is a nitrogen, phosphorus, arsenic or tellurium atom,
- R R R R means hydrocarbon radicals and m are values 0, 1 or 2,
- n are values 1, 2 or 3 and m-l-n is equal to the capacity of the element to combine with hydrogen.
- the electrolyte is characterized by the fact that at least one of the hydrotarbor radicals R to R is a benzyl, phenyl, cyclohexyl or a strongly branched hydrocarbon radical with C to C while the remaining radicals of the onium salt are alkyl radicals with C to C
- the molar ratio between onium salt and the metal alkyl in the complex compound amounts, in the electrolyte according to the invention, is 1:1 or preferably, 1:2.
- the effective organic groups i.e. the benzyl, phenyl, cyclohexyl or branched hydrocarbon radicals are inserted into the onium ion and not into the metal alkyl molecule of the electrolyte.
- the variably large organic groups are tightly bound to the central atom of the onium ions, i.e. to the nitrogen, phosphorus, arsenic or tellurium atom and do not undergo any exchange or disproportioning process, the mixed organometals of zinc, aluminum, gallium and indium are not stable, but disproportionate into the pure orgauometals.
- the self-ignition danger and hydrolysis tendency is especially sharply reduced in electrolytes according to the invention, which consist of a complex compound of a mole of an onium salt and one or two moles of a metal alkyl, and whose onium salt contains the benzyl group C H CH
- electrolytes consist of a complex compound of a mole of an onium salt and one or two moles of a metal alkyl, and whose onium salt contains the benzyl group C H CH
- trimethylbenzylammoniumhexethylfluorodialanate 3) 3 e s z z s) 3 2 a] respectively s) 3( e 5 2) 2 5) s is reduced so much that the compound which is liquid at room temperature does not even emit smoke when contacting air and no longer burns the skin.
- a dangerfree handling of this electrolyte for the purpose of galvanic depositing, is therefore quite possible.
- the zinc alkyls which are even more inflammable by air than the aluminum alkyls, become, in complexes with onium salts containing benzyl groups, readily manageable electrolyte liquids, which may be used for depositing zinc.
- the 1:1 complex compound and the corresponding 1:2 complex compound are also liquid and not self-igniting at room temperature. They emit only a slight smoke in the air and their reaction with water has only slight vehemence. They are good organometallic electrolytes for depositing zinc, having specific conductances of 2.4 resp. 2.1- ohm -cm. at 100 C.
- the phenyl and cyclohexyl groups reduce the melting point of the complex compound to a lesser degree, however they are also liquid at room temperature.
- a phenyl containing electrolyte is the complex compound trimethylphenylammonium-tricthylchloroalanate,
- the melting range of this compound is 2022 C.
- the compound has an electric conductance of 149-10 ohm cm.-
- the 1:2 complex correspond thereto has a melting scope of 97 to --l00 C. and a specific conductance of 1.81-10 ohm cm.- and is therefore a very suitable electrolyte for depositing aluminum.
- Both compounds may be very favorably produced according to the method disclosed in application Ser. No. 355,222 by reaction of readily produced components dimethylaniline, chloromethane and aluminumtriethyl.
- the quaternary phosphonium salt complex compound may be obtained This electrolyte complex first solidifies below 33 C., and at 100 C. has a specific conductance capacity of 2410* ohmcm. In this compound, a hydrogen atom of the ethyl radical in the phosphonium ion is substituted by a chlorine atom, which reduces flammability even further.
- organic groups which also reduce the autooxidation and the hydrolysis rate of the complex compounds, are the strongly branched, and therefore space filling, hydrocarbon radicals with C to C for example, the tertiarybutyl radical-C(CH and the isopropyl radi- Cai'CH(cH3)2.
- solubility of the complexes containing an inserted radical is increased in aromatic hydrocarbons. This is very important for the washing processes which, for galvanotechnical reasons, follow electroplating of objects.
- the following table illustrates how the insertion of a phenyl, respectively, a benzyl radical, in place of a methyl radical in the onium ion of an aluminum complex compound efiects a reduction in the melting range and the specific conductance.
- the aluminum compound whose onium ion contains four methyl groups, autooxidizes and has a strong tendency toward hydrolysis, the two other compounds named in the table, are favorable electrolytes, according to the invention.
- the loss of conductance capacity may be partially compensated by thinning the complex compound with 2-4 mols of aromatic hydrocarbon, for example, benzene, toluene or xylene, or higher aliphatic or cyclic ethers, for example, di-n-butylether, isopropylether, tetrahydrofuran or dioxane.
- aromatic hydrocarbon for example, benzene, toluene or xylene, or higher aliphatic or cyclic ethers, for example, di-n-butylether, isopropylether, tetrahydrofuran or dioxane.
- the electrolyte complex compounds strongly dissociate into onium and metalalkylhalogenide complexes. This increases somewhat the conductance capacity of the electrolyte liquid.
- electrolytes with little flammability are obtained through a combination of onium ions, which contain benzyl, phenyl, cyclohexyl or strongly branched hydrocarbon radicals, with higher halogen-substituted organometal ions, into a complex compound.
- the electrolytes which are comprised of a complex compound of an onium salt containing the above mentioned hydrocarbon radicals and a metal alkyl containing one or two halogen substituents, are distinguished by low flammability, poor self-ignition, slight tendency toward autooxidation and hydrolysis, a relatively low melting temperature and a good electrical conductance. These electrolytes are therefore extraordinarily suitable for galvanic depositing of the metals zinc, aluminum, gallium and indium.
- electrolytes are the complex compounds which are derived from the trimethylbenzylammonium-fluoride-aluminum-triethyl complex by substituting fluorine for one or two ethyl radicals.
- Table III the melting range and the electric conductivity of these compounds are compared to the triethyl aluminum complex compound.
- the acid salts of the quaternary onium salts which are used as the starting materials for producing the electrolytes according to the present invention, may be produced according to a process which is closely disclosed in 11.8. patent application Ser. No. 367,578.
- the acid salt trimethylbenzylammoniuzmhydrogendifluoride is produced by reacting trimethylbenzylammoniumchloride with an excess of hydrogen fluoride.
- the acid salt resulting from this reaction is then ether extracted whereby trimethylbenzylammoniumtrihydrogentetrafiuoride occurs.
- This compound is reacted with sodium alcoholate to yield the colorless, crystalline and hygroscopic compound trimethylbenzylammoniumhydrogendifluoride.
- the equations for the above described process are:
- the acid salt trimethylbenzylammonium-hydrogendifluoride is reacted with triethyl aluminum.
- the electrolyte which solidifies at 15 to -17 C., is thermically stable up to C. and shows no development of smoke or heat in the air.
- the reaction with water is also slow and without danger. Due to the low autooxidation :and rate of hydrolysis there is no danger of self-ignition.
- the electrolyte is harmless and easy to handle.
- the acid onium chlorides and onium bromides may be reacted in the same manner as the acid oniumfluorides, with the metal alkylys of zinc, aluminum, gallium or indium.
- the method, according to the invention, of producing electrolyte complex compounds with higher halogenide substituted metal alkyls of acid onium salts has many advantages.
- the reactants are easily available.
- the acid halogenides are even more readily obtainable as solvent free quaternary onium compounds, than the neutral onium salts.
- Trialkyl-aluminum may be purchased.
- Trialkylgallium and-indium may be produced according to the methods disclosed in co-assigned applications Ser. Nos. 162,212 and 108,996 now respectively Patent Nos. 3,310,574 and 3,318,931.
- a method of producing dialkyl zinc is found in the Hiither thesis (Technische Hoch Anlagen Aachen, 1957).
- the rapid and complete conversion of the solid salts is expedited by the gas development, in the present method, i.e. through the escape of alkanes.
- the strongly exothermic reactions are preferably performed in ethers, aliphatic or aromatic hydrocarbons, for example, in diethylether, hexane, benzene or toluene.
- the most favorable reaction mediums were in the aromatic hydrocarbons, since they dissolve the developing complex salts.
- the solutions of the onium salt complex compound may find use as electrolytes. If the complex compounds are to be obtained per se, then aliphatic ethers or hydrocarbons are recommended as a solvent for removing the considerable heat of reaction.
- a second combination utilized an electrolyte, thinned with an equimolar amount of toluene.
- the bath temperature was C.
- the electrical data was 0.5 a./dm. cathode current density at 1.3 to 1.5 v. cell voltage.
- An aluminum layer of approximately 80a thickness grew in 16 hours and had a fine crystalline, brightly polished (shining)appearance.
- R an alkyl radical with C to C Y a nitrogen, phosphorus, arsenic or tellurium atom
- R R R R represent hydrocarbons and m the values n the values 1, 2 or 3 and m+n is equal to the capacity of the element to combine with hydrogen wherein at least one of the hydrocarbon radicals R to R is selected from the group of benzyl, phenyl, cyclohexyl and strongly branched hydrocarbon radical with C to C and the remaining radicals of the oniurn salt are C to C alkyls.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DES0094664 | 1964-12-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3418216A true US3418216A (en) | 1968-12-24 |
Family
ID=7518840
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US515804A Expired - Lifetime US3418216A (en) | 1964-12-17 | 1965-12-16 | Organometallic electrolyte for galvanic deposition of zinc, aluminum, gallium and indium |
Country Status (8)
Country | Link |
---|---|
US (1) | US3418216A (de) |
AT (2) | AT266861B (de) |
BE (1) | BE673423A (de) |
CH (1) | CH484195A (de) |
DE (1) | DE1496993B1 (de) |
FR (1) | FR1461819A (de) |
GB (1) | GB1104930A (de) |
SE (1) | SE344216B (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USB535813I5 (de) * | 1974-12-23 | 1976-01-27 | ||
US4032413A (en) * | 1974-11-13 | 1977-06-28 | Siemens Aktiengesellschaft | Electroplating bath and method for the electrodeposition of bright aluminum coatings |
US5104840A (en) * | 1990-03-20 | 1992-04-14 | Institut Francais Du Petrole | Non-aqueous liquid composition with an ionic character and its use as a solvent |
WO2004016571A2 (en) * | 2002-08-16 | 2004-02-26 | Sachem, Inc. | Lewis acid ionic liquids |
US20050131118A1 (en) * | 2002-08-16 | 2005-06-16 | Roger Moulton | Ionic liquids containing a sulfonate anion |
WO2015069871A1 (en) * | 2013-11-06 | 2015-05-14 | Research Foundation Of The City University Of New York | Ionic liquid comprising alkaline earth metal |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4076600A (en) * | 1976-12-20 | 1978-02-28 | R. O. Hull & Company, Inc. | Leveling agent for acid zinc electroplating baths and method |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268421A (en) * | 1961-12-04 | 1966-08-23 | Nat Steel Corp | Electrodeposition of metals from a fused bath of aluminum halohydride organic complex and composition therefor |
US3308143A (en) * | 1962-11-14 | 1967-03-07 | Continental Oil Co | Process for decomposing trialkylaluminum complex |
-
1964
- 1964-12-17 DE DE19641496993 patent/DE1496993B1/de not_active Withdrawn
-
1965
- 1965-11-26 AT AT823467A patent/AT266861B/de active
- 1965-11-26 AT AT1065265A patent/AT264945B/de active
- 1965-12-08 BE BE673423D patent/BE673423A/xx unknown
- 1965-12-15 CH CH1733865A patent/CH484195A/de not_active IP Right Cessation
- 1965-12-15 SE SE16247/65A patent/SE344216B/xx unknown
- 1965-12-15 FR FR42409A patent/FR1461819A/fr not_active Expired
- 1965-12-16 US US515804A patent/US3418216A/en not_active Expired - Lifetime
- 1965-12-17 GB GB53724/65A patent/GB1104930A/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268421A (en) * | 1961-12-04 | 1966-08-23 | Nat Steel Corp | Electrodeposition of metals from a fused bath of aluminum halohydride organic complex and composition therefor |
US3308143A (en) * | 1962-11-14 | 1967-03-07 | Continental Oil Co | Process for decomposing trialkylaluminum complex |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4032413A (en) * | 1974-11-13 | 1977-06-28 | Siemens Aktiengesellschaft | Electroplating bath and method for the electrodeposition of bright aluminum coatings |
USB535813I5 (de) * | 1974-12-23 | 1976-01-27 | ||
US3981819A (en) * | 1974-12-23 | 1976-09-21 | Rca Corporation | Luminescent sulfides of monovalent and trivalent cations |
US5104840A (en) * | 1990-03-20 | 1992-04-14 | Institut Francais Du Petrole | Non-aqueous liquid composition with an ionic character and its use as a solvent |
WO2004016571A3 (en) * | 2002-08-16 | 2005-02-24 | Sachem Inc | Lewis acid ionic liquids |
US20040122229A1 (en) * | 2002-08-16 | 2004-06-24 | Roger Moulton | Lewis acid ionic liquids |
WO2004016571A2 (en) * | 2002-08-16 | 2004-02-26 | Sachem, Inc. | Lewis acid ionic liquids |
US20050131118A1 (en) * | 2002-08-16 | 2005-06-16 | Roger Moulton | Ionic liquids containing a sulfonate anion |
US7053232B2 (en) * | 2002-08-16 | 2006-05-30 | Sachem, Inc. | Lewis acid ionic liquids |
US20090200513A1 (en) * | 2002-08-16 | 2009-08-13 | University Of South Alabama | Ionic Liquids Containing a Sulfonate Anion |
US7750166B2 (en) | 2002-08-16 | 2010-07-06 | University Of South Alabama | Ionic liquids containing a sulfonate anion |
WO2015069871A1 (en) * | 2013-11-06 | 2015-05-14 | Research Foundation Of The City University Of New York | Ionic liquid comprising alkaline earth metal |
CN106463769A (zh) * | 2013-11-06 | 2017-02-22 | 纽约城市大学研究基金会 | 包含碱土金属的离子液体 |
Also Published As
Publication number | Publication date |
---|---|
GB1104930A (en) | 1968-03-06 |
CH484195A (de) | 1970-01-15 |
DE1496993B1 (de) | 1972-05-04 |
SE344216B (de) | 1972-04-04 |
AT266861B (de) | 1968-12-10 |
BE673423A (de) | 1966-04-01 |
AT264945B (de) | 1968-09-25 |
FR1461819A (fr) | 1966-12-09 |
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