EP1141447A2 - Aluminium organic electrolytes and method for electrolytic coating with aluminium or aluminium-magnesium-alloys - Google Patents
Aluminium organic electrolytes and method for electrolytic coating with aluminium or aluminium-magnesium-alloysInfo
- Publication number
- EP1141447A2 EP1141447A2 EP99962174A EP99962174A EP1141447A2 EP 1141447 A2 EP1141447 A2 EP 1141447A2 EP 99962174 A EP99962174 A EP 99962174A EP 99962174 A EP99962174 A EP 99962174A EP 1141447 A2 EP1141447 A2 EP 1141447A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminum
- aiet
- magnesium
- electrolyte
- toluene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 64
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 title claims abstract description 22
- 239000011248 coating agent Substances 0.000 title claims abstract description 18
- 239000005486 organic electrolyte Substances 0.000 title description 2
- 239000004411 aluminium Substances 0.000 title 2
- 239000011777 magnesium Substances 0.000 claims abstract description 72
- 239000003792 electrolyte Substances 0.000 claims abstract description 67
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 52
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 23
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004020 conductor Substances 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 132
- 238000005868 electrolysis reaction Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- 238000005336 cracking Methods 0.000 claims 1
- -1 dimethoxyethane Chemical class 0.000 abstract description 2
- 150000002170 ethers Chemical class 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 44
- 239000000243 solution Substances 0.000 description 17
- 238000000151 deposition Methods 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002370 organoaluminium group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910019086 Mg-Cu Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
Definitions
- the invention relates to organoaluminum electrolytes which are suitable for the electrolytic deposition of aluminum or aluminum-magnesium alloys on electrically conductive materials, and to a process for this purpose using soluble aluminum anodes or soluble aluminum and magnesium anodes or an anode made of aluminum-magnesium alloy .
- Organometallic complex compounds have been used for a long time for the electrolytic deposition of aluminum (dissertation H. Lehmkuhl, TH Aachen 1954, DE-PS 1047450; K. Ziegler, H. Lehmkuhl, Z. inorganic chemistry 283 (1956) 414; DE- PS 1056377; H. Lehmkuhl, Chem. Ing. Tech. 36 (1964) 616; EP-A 0084816; H. Lehmkuhl, K. Mehler and U. Landau in Adv. In electrochemical science and engineering (Ed. H. Gerischer , CW Tobias) Vol. 3, Weinheim 1994).
- MX can be either alkali metal (Na, K, Rb, Cs) or onium halides, preferably their fluorides.
- R are alkyl radicals with preferably one, two or four carbon atoms.
- the conductivity of the electrolyte was of the order of 1 * 10 to 7 • 10 '3 S • cm "1.
- the same authors described an electrolyte solution consisting of ethyl magnesium bromide and triethyl aluminum in THF / toluene 1: 1 the metal layers with a maximum of 10% Al were obtained.
- magnesium anodes cannot be dissolved with the proposed electrolytes during the coating process. Continuous addition of the Mg content is not possible by dissolving the magnesium anode when using fluoride or generally halide-containing organoaluminum complexes as electrolytes.
- dialkyl magnesium is used in ethereal solution to prepare the electrolyte. In a continuously operating coating process, the dialkyl magnesium would have to be supplied continuously in ethereal solution.
- diethyl ether that some complexes e.g. B. Na [Et 3 AI-F-AIEt 3 ] can be split into Na [Et 3 AIF] + Et g Al - OEt 2 (K. Ziegler, R. Köster, H. Lehmkuhl, K. Reinert, Liebigs Ann. Chem 629, 33-49 (1960)).
- dialkyl magnesium would first have to be made ether-free, which requires considerable effort and expense, or it would have to be prepared in ether-free form by reacting magnesium metal with dialkyl mercury, a very toxic compound.
- An electrolyte of type I according to the invention is dissolved in 2.5-6 mol per mol of complex compound of an aromatic hydrocarbon which is liquid at 20 ° C., preferably in toluene or a liquid xylene.
- the trialkyl aluminum is preferably triethyl aluminum (AIEt 3 ), alkali tetraalkyl aluminum is preferably a mixture of potassium and sodium tetraethyl aluminum.
- the quantitative ratio of complex: AIEt 3 is 1: 0.5 to 1: 3, preferably 1: 2.
- the proportion of Na [AIEt 4 ] is between 0 and 25 mol%, based on the total amount of K [AIEt 4 ] and NafAIEtJ, but is preferred between 5 and 20 mol%.
- the addition of small amounts of Na [AIEt 4 ] is preferred because, in the absence of this component, the aluminum anodes can only be dissolved with moderate to poor current yields, e.g. 3 AlEt 3 were as in K [AlEt 4] / / what if prolonged electrolysis lead 6 toluene only at about 22% to a loss of triethylaluminum.
- the electrolysis is carried out at temperatures between 80 and 105 ° C., preferably between 90 and 100 ° C.
- An exemplary electrolyte I is: 0.8 mol K [AIEt 4 ] / 0.2 mol Na [AIEt 4 ] / 2.0 mol AIEt 3 / 3.3 mol toluene. No crystallization takes place from this electrolyte solution even when standing at room temperature for a long time; the specific conductivity at 95 ° C. is 13.8 mS-cm "1 .
- Type II electrolytes preferably consist of mixtures of Na [Et 3 Al-H-AIEt 3 ], Na [AIEt 4 ] and AIEt 3 .
- AIEt 3 ensures that Na [AIEt 4 ] no sodium metal (W. Grimme, dissertation TH Aachen (1960); DBP 11 14330 (1959); DBP 1 146258 (1961)), but aluminum metal is electrolytically deposited.
- Na [Et 3 AI-H-AIEt 3 ] are very suitable as solutions in toluene for the electrolytic deposition and dissolution of aluminum at 90-105 ° C. In the electrolysis of this compound and in the absence of Na [AIEt 4 ] according to the invention, we have found that magnesium anodes are not dissolved.
- the electrolyte II according to the invention is dissolved in 5-7 mol per mol Na [AlEt 4 ] of an aromatic hydrocarbon liquid at 20 ° C., preferably in toluene or a liquid xylene.
- the quantitative ratio Na [Et 3 Al-H-AIEt 3 ] to Na [AIEt 4 ] is preferably 2: 1 to ensure homogeneous solubility in 6 mol toluene per mol Na [AIEt 4 ] and the molar ratio Na [AIEt 4 ] to AIEt 3 is preferably 1: 2 to ensure proper metal deposition by electrolysis.
- An exemplary electrolyte is II: 1 mol of Na [Et 3 Al-H-AlEt 3] / 0.5 mol of Na [AlEt 4] / 1 mol of AlEt 3/3 mol of toluene. Even when standing at room temperature for a long time, this electrolyte solution does not crystallize, which would interfere with the technical usability of the electrolyte.
- the specific conductivity at 95 ° C is 8.12 mS • cm " .
- the electrolytic deposition of aluminum-magnesium alloy layers from the electrolytes according to the invention is carried out using a soluble aluminum and a likewise soluble magnesium anode or using an anode made of aluminum-magnesium alloy. In the case of two anodes, these are switched separately to ensure a continuous procedure and to control a selectable and desired alloy composition.
- the electrolysis is expediently carried out in toluene solution at 90-100 ° C.
- the anodic (AI 95-100%; Mg 93-100%) and cathodic current yields are practically quantitative. Since a finite and therefore necessary concentration of magnesium only builds up in the course of an electrolysis, this state must first be established before using a freshly prepared electrolyte. This can be done 1 .
- the electrolytic deposition from the electrolytes according to the invention leads to aluminum-magnesium alloy layers which differ significantly in their electrochemical properties from previously known layer systems.
- the electrochemical behavior of the alloy layers corresponds to the magnesium type in the cathodic partial reaction, to the aluminum type in the anodic partial reaction, combined with a pronounced passivity interval.
- the alloy layers have a quiescent current potential of about -1380 to -1500 mV at room temperature in a 5% aqueous NaCl solution with a pH of 9.0. SCE at Mg incorporation rates of 5 to 50% by weight. Due to the layer passivity (formation of intermetallic phases), the cathodic partial reaction in contact with more electronegative metals, such as magnesium, is additionally inhibited. The potential of the cathodic partial reaction is thereby shifted from the resting potential to even more negative potential values. The result of this is that the remaining potential difference between the cathodic partial reaction of the alloy layer (at pH 9 oxygen reduction) and the anodic partial reaction of the magnesium is greatly reduced.
- the AlMg alloy layers therefore enable extensive adaptation to the quiescent current potential of the magnesium alloy AZ91 hp, which is approx. SCE is due to contact corrosion on magnesium is greatly reduced.
- the alloy layers are therefore suitable for coating steel fasteners in contact with magnesite ⁇ .
- the application potential here particularly concerns applications in the automotive industry in the transmission, engine and body area.
- the developed alloy layers which are deposited from non-aqueous electrolytes, are also suitable as a high-quality surface coating for highly tempered steel parts with a tensile strength of> 1000 MPa and which cannot be coated with conventional galvanic processes - due to the risk of hydrogen embrittlement. This results in a potential field of application for the coating of tempered and spring steels with alkali-resistant and aluminum or magnesium-compatible coatings.
- Example 17 an Rb [Al (Et) 4 ] electrolyte was used.
- the cathode layer was uniform, shiny silver and contained 72.4% Al and 27.6% Mg, the cathodic layer weighed 34.3 mg and was approx. 12 ⁇ m thick.
- the amount of toluene can gradually decrease due to evaporation, if it drops below 5 moles of toluene per mole of M [AIEt 4 ], the solution becomes inhomogeneous and a little AIEt 3 separates Form of oily droplets. In this case the amount of toluene must be increased to 6 mol toluene per mol M [AIEt 4 ].
- Example 3 The electrolyte of Example 3 was electrolyzed again at 90-95 ° C after replacing the cathode with a new copper sheet.
- the electrolyte of Examples 3 and 4 was electrolyzed four times in succession using only one magnesium anode.
- the nature of the cathode layer and the Al and Mg content of the electrolyte are shown in Table 1. Table 1
- An electrolyte with the composition K [AIEt 4 ] / AIEt 3/4 toluene with a specific conductivity of 17.3 mS • cm was between an anode consisting of aluminum sheet and magnesium sheet and a cathode made of TiAI 6 V 4 at 90- 95 ° C electrolyzed.
- An electrolyte with the composition 0.8 mol K [AIEt 4 ] /0.2 mol Na [AIEt 4 ] / 2.0 AIEt 3 /3.3 mol toluene was between 2 anodes made of an aluminum-magnesium alloy with 25 wt .-% Mg and 75 wt .-% % AI and a rotating cylindrical screw M8 made of tempered steel (8.8) at 97-102 ° C with -2 cathodic current density of 0.8 A • dm and a current of 2.89 mF electrolyzed. Cathodic and anodic current yields were mif'99.5% quantitative. The approx. 9 ⁇ m thick alloy layer was uniform, shiny silver and adhered well to the base material.
- Example 7 was repeated ten times after each time the cathodes were replaced by an uncoated screw at 98-100 ° C.
- the respective thicknesses of the cathode layer were varied from 9 to 13 ⁇ m.
- the anodic current yield over the ten tests was 99.5%.
- Example 10 The electrolyte obtained in the course of Example 10 was electrolyzed at 93-98 ° C. between the Al and Mg anode and a slowly rotating cylindrical cathode made from tempered steel (8.8).
- the anodic current density was on everyone
- Example 11 The electrolyte of Example 11 was electrolyzed after replacing the cathode with a new one, also made from tempering steel, at 95-104 ° C.
- the electrolyte of Example 11 was electrolyzed after replacing the cathode with a new one, also made from tempering steel, at 95-104 ° C.
- anodic current densities were set to 0.45 A • dm for aluminum and 0.15 A • dm for magnesium.
- the anodic current yields were 90%, the cathode layer was uniform and shiny silver; According to the analysis, the layer contained 71.8% Al and 28.2% Mg, the layer thickness was 13 ⁇ m.
- Example 12 The electrolyte of Example 12 was electrolyzed after replacing the anodes made of Al and Mg with two alloy anodes of the composition 75% by weight Al and 25% by weight Mg and after using a new cylindrical cathode made of tempering steel 8.8 at 93 ° C. During the electrolysis, the cathode rotated slowly between the two anodes, the cathodic current density was
- the cathode layer was 12 ⁇ m thick and was uniform and matt silver.
- Example 13 was repeated three times after replacing the cathode with an uncoated one at 92-100 ° C.
- the respective layer thicknesses were varied between 10 and 15 ⁇ m.
- the anodic current yield over the 4 tests for the alloy anodes was 98.9%.
- Example 15 Al deposition from Na [Et 3 Al-H-AIEt 3 ]
- Example 16 Al deposition from K [Et 3 AIH-AIEt 3 ]
- a test electrolysis was carried out at -2 -2 dm to 1.0 A dm. After passing through 7.73 mF, there was a uniform, silver-gray cathode layer. The current efficiency at the cathode was 100.0% and that at the anode was 99.6%.
- the specific conductivity at 95 ° C is 12.9mS cm "1 .
- the anodic current yield was 100% over 6 tests.
- the initial composition of the layer with a fresh electrolyte was 90.96% Al and 9.04% Mg.
- the system conditioned itself to a layer composition of 75.02% Al and 24.98% Mg.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19855666A DE19855666A1 (en) | 1998-12-01 | 1998-12-01 | Organoaluminum electrolytes and processes for electrolytic coating with aluminum or aluminum-magnesium alloys |
DE19855666 | 1998-12-01 | ||
PCT/EP1999/009236 WO2000032847A2 (en) | 1998-12-01 | 1999-11-27 | Aluminium organic electrolytes and method for electrolytic coating with aluminium or aluminium-magnesium-alloys |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1141447A2 true EP1141447A2 (en) | 2001-10-10 |
EP1141447B1 EP1141447B1 (en) | 2002-07-03 |
Family
ID=7889774
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99962174A Expired - Lifetime EP1141447B1 (en) | 1998-12-01 | 1999-11-27 | Aluminium organic electrolytes and method for electrolytic coating with aluminium or aluminium-magnesium-alloys |
Country Status (7)
Country | Link |
---|---|
US (1) | US6652730B1 (en) |
EP (1) | EP1141447B1 (en) |
JP (1) | JP2002531698A (en) |
AT (1) | ATE220129T1 (en) |
CA (1) | CA2352800A1 (en) |
DE (2) | DE19855666A1 (en) |
WO (1) | WO2000032847A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6734317B2 (en) | 2002-06-13 | 2004-05-11 | Crompton Gmbh | Process for the preparation of alkali metal tetraalkylaluminates and use thereof |
WO2005035835A3 (en) * | 2003-10-18 | 2005-06-23 | Aluminal Oberflaechentechnik | Workpieces coated with an aluminum/magnesium alloy |
US10835973B2 (en) | 2014-10-31 | 2020-11-17 | Bekaert Binjiang Steel Cord Co., Ltd. | Shaped saw wire with controlled curvature at bends |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002088434A1 (en) * | 2001-04-30 | 2002-11-07 | Alumiplate Incorporated | Aluminium electroplating formulations |
US7250102B2 (en) | 2002-04-30 | 2007-07-31 | Alumiplate Incorporated | Aluminium electroplating formulations |
DE10134559B4 (en) * | 2001-07-16 | 2008-10-30 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for coating components, processable dispersible coatings and use |
DE10224089A1 (en) * | 2002-05-31 | 2003-12-11 | Studiengesellschaft Kohle Mbh | Process for the preparation of organo-aluminum complexes and their use for the production of electrolyte solutions for the electrochemical deposition of aluminum-magnesium alloys |
EP1403402A1 (en) * | 2002-09-25 | 2004-03-31 | Aluminal Oberflächtentechnik GmbH & Co. KG | Process for the electrolytic deposition of materials with aluminium, magnesium or alloys of aluminium and magnesium |
DE10257737B3 (en) * | 2002-12-10 | 2004-02-26 | Thyssenkrupp Stahl Ag | Electrolytic magnesium deposition on a substrate made from sheet metal with a zinc (alloy) coating, used in the automobile industry, using a solvent for the deposition and heat treating the coated substrate |
WO2004099218A1 (en) * | 2003-04-30 | 2004-11-18 | Akzo Nobel N.V. | Production of mixed sodium and potassium tetraalkylaluminate solutions |
EP1518945A1 (en) * | 2003-09-27 | 2005-03-30 | Aluminal Oberflächtentechnik GmbH & Co. KG | Electrolyte for the galvanic deposition of aluminium magnesium alloys |
EP1624091A1 (en) * | 2004-08-04 | 2006-02-08 | Aluminal Oberflächentechnik GmbH & Co. KG | Workpieces coated with an aluminium/magnesium alloy or with aluminium having a zinc interlayer |
DE102008051883A1 (en) | 2008-10-16 | 2010-04-22 | Nano-X Gmbh | Coating for cathodic corrosion protection of metal, method for producing the coating and use of the coating. |
CN103334132B (en) * | 2013-07-17 | 2016-05-25 | 沈阳大学 | The method of almag film is prepared in room temperature electro-deposition |
CN104388998B (en) * | 2014-11-18 | 2016-08-24 | 沈阳大学 | A kind of method that porous nano aluminum oxide is prepared in room temperature electro-deposition |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE540052A (en) * | 1955-06-13 | |||
US3672965A (en) * | 1970-06-29 | 1972-06-27 | Continental Oil Co | Electroplating of aluminum |
US3672964A (en) * | 1971-03-17 | 1972-06-27 | Du Pont | Plating on aluminum,magnesium or zinc |
DE2338063A1 (en) * | 1973-07-26 | 1975-04-03 | Siemens Ag | PROCESS FOR COATING HIGH-FREQUENCY HEATING COILS MADE OF COPPER, BRASS, SILVER OR ALUMINUM |
US4778575A (en) * | 1988-01-21 | 1988-10-18 | The United States Of America As Represented By The United States Department Of Energy | Electrodeposition of magnesium and magnesium/aluminum alloys |
DE3919068A1 (en) * | 1989-06-10 | 1990-12-13 | Studiengesellschaft Kohle Mbh | ALUMINUM ORGANIC ELECTROLYTE FOR THE ELECTROLYTIC DEPOSITION OF HIGH-PURITY ALUMINUM |
US5015750A (en) * | 1990-10-31 | 1991-05-14 | Texas Alkyls, Inc. | Preparation of trimethylaluminum |
-
1998
- 1998-12-01 DE DE19855666A patent/DE19855666A1/en not_active Withdrawn
-
1999
- 1999-11-27 US US09/857,013 patent/US6652730B1/en not_active Expired - Lifetime
- 1999-11-27 CA CA002352800A patent/CA2352800A1/en not_active Abandoned
- 1999-11-27 DE DE59901980T patent/DE59901980D1/en not_active Expired - Lifetime
- 1999-11-27 JP JP2000585475A patent/JP2002531698A/en not_active Withdrawn
- 1999-11-27 EP EP99962174A patent/EP1141447B1/en not_active Expired - Lifetime
- 1999-11-27 AT AT99962174T patent/ATE220129T1/en not_active IP Right Cessation
- 1999-11-27 WO PCT/EP1999/009236 patent/WO2000032847A2/en active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO0032847A2 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6734317B2 (en) | 2002-06-13 | 2004-05-11 | Crompton Gmbh | Process for the preparation of alkali metal tetraalkylaluminates and use thereof |
WO2005035835A3 (en) * | 2003-10-18 | 2005-06-23 | Aluminal Oberflaechentechnik | Workpieces coated with an aluminum/magnesium alloy |
US10835973B2 (en) | 2014-10-31 | 2020-11-17 | Bekaert Binjiang Steel Cord Co., Ltd. | Shaped saw wire with controlled curvature at bends |
US11958122B2 (en) | 2014-10-31 | 2024-04-16 | Bekaert Binjiang Steel Cord Co., Ltd. | Shaped saw wire with controlled curvature at bends |
Also Published As
Publication number | Publication date |
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DE59901980D1 (en) | 2002-08-08 |
CA2352800A1 (en) | 2000-06-08 |
JP2002531698A (en) | 2002-09-24 |
US6652730B1 (en) | 2003-11-25 |
ATE220129T1 (en) | 2002-07-15 |
WO2000032847A2 (en) | 2000-06-08 |
WO2000032847A3 (en) | 2000-11-16 |
EP1141447B1 (en) | 2002-07-03 |
DE19855666A1 (en) | 2000-06-08 |
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