EP1141447B1 - Electrolyte organique d'aluminium et procede de revetement electrolytique avec de l'aluminium ou des alliages aluminium-magnesium - Google Patents

Electrolyte organique d'aluminium et procede de revetement electrolytique avec de l'aluminium ou des alliages aluminium-magnesium Download PDF

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Publication number
EP1141447B1
EP1141447B1 EP99962174A EP99962174A EP1141447B1 EP 1141447 B1 EP1141447 B1 EP 1141447B1 EP 99962174 A EP99962174 A EP 99962174A EP 99962174 A EP99962174 A EP 99962174A EP 1141447 B1 EP1141447 B1 EP 1141447B1
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Prior art keywords
magnesium
alet
aluminum
electrolyte
electrolyte according
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Expired - Lifetime
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EP99962174A
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German (de)
English (en)
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EP1141447A2 (fr
Inventor
Herbert Lehmkuhl
Klaus-Dieter Mehler
Bertram Reinhold
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Aluminal Oberflachentechnik GmbH
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Studiengesellschaft Kohle gGmbH
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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 used for electrolytic Deposition of aluminum-magnesium alloys electrically conductive materials are suitable, as well as a process for this Use of 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, R. Schfer, K. Ziegler Chem. Lng. 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 2 AlR 3 Complex compounds of the general type MX 2 AlR 3 , which are used either as molten salts or in the form of their solutions in liquid aromatic hydrocarbons, have been proposed as suitable electrolytes.
  • 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.
  • Gneupel obtained from a similar electrolyte from AlCl 3 , Li [AlH 4 ], MgBr 2 in a mixture of THF, diethyl ether and benzene (Mg / Al 0.6) metal deposits with up to 13% Mg (DDR patent 244573 A1).
  • the same authors describe an electrolyte solution consisting of ethyl magnesium bromide and triethyl aluminum in THF / toluene 1: 1, from which metal layers with a max. 10% Al were obtained.
  • R Et, iso-Bu
  • X F, Cl
  • M K, Cs, N
  • 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 (AlEt 3 ), alkali tetraalkyl aluminum is preferably a mixture of potassium and sodium tetraethyl aluminum.
  • the quantitative ratio of complex: AlEt 3 is 1: 0.5 to 1: 3, preferably 1: 2.
  • the proportion of Na [AlEt 4 ] is between 0 and 25 mol%, based on the total amount of K [AlEt 4 ] and Na [AlEt 4 ], but preferably between 5 and 20 mol%.
  • the addition of small amounts of Na [AlEt 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 [AlEt 4 ] / 0.2 mol Na [AlEt 4 ] / 2.0 mol AlEt 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-AlEt 3 ], Na [AlEt 4 ] and AlEt 3 .
  • AlEt 3 ensures that Na [AlEt 4 ] no sodium metal (W. Grimme, dissertation TH Aachen (1960); DBP 1114330 (1959); DBP 1146258 (1961)), but aluminum metal is electrolytically deposited.
  • 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-AlEt 3 ] to Na [AlEt 4 ] is preferably 2: 1 to ensure homogeneous solubility in 6 mol toluene per mol Na [AlEt 4 ] and the molar ratio Na [AlEt 4 ] to AlEt 3 is preferably 1: 2 in order to ensure perfect 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 prolonged period, there is no crystallization from this electrolyte solution, which would interfere with the technical usability of the electrolyte.
  • the specific conductivity at 95 ° C is 8.12 mS ⁇ cm -1 .
  • the electrolytic deposition leads from the electrolytes according to the invention to aluminum-magnesium alloy layers, which differ in their electrochemical Clearly differentiate properties from previously known layer systems.
  • the electrochemical behavior of the alloy layers corresponds in the cathodic partial reaction the magnesium type, in the anodic partial reaction the aluminum type combined with a pronounced passivity interval.
  • the alloy layers exhibit at room temperature in a 5% aqueous NaCl solution with a pH of 9.0 has a quiescent current potential of about -1380 to -1500 mV vs. S.C.E. at Mg incorporation rates of 5 to 50% by weight. Due to the layer passivity (formation of intermetallic phases) the partial cathodic reaction in contact with more electronegative metals, such as magnesium, additionally inhibited. The potential of the cathodic partial reaction is thereby compared to the rest potential to even more negative potential values postponed. As a result, 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 reduced.
  • the AlMg alloy layers therefore enable one extensive adaptation to the quiescent current potential of the magnesium alloy AZ91hp, which at around -1680 mV vs. S.C.E. contact corrosion on the magnesium is greatly reduced.
  • the alloy layers are therefore suitable for the Coating steel fasteners in contact with magnesium.
  • the Application potential here particularly affects applications in the automotive industry in the transmission, engine and body area.
  • the developed alloy layers which consist of non-aqueous electrolytes are also suitable as a high-quality surface coating for highly tempered steel parts with tensile strength> 1000 MPa lies and that not with conventional galvanic processes - due to the danger of hydrogen embrittlement - can be coated. Consequently there is a potential field of application for the coating of Quenched and tempered steels with alkali-resistant as well as aluminum or Magnesium compatible coatings.
  • 1 to 9 relate to electrolyte I
  • 10 to 14 relate to electrolyte II
  • an Rb [Al (Et) 4 ] electrolyte was used.
  • An electrolyte of the composition M [AlEt 4] / 3 AlEt 3/6 Toluene (M 20 mol% Na, 80 mol% K) was located between the anode and Al-Mg-Cu-anode rotating round cathode at 91-95 ° C electrolyzed.
  • the current densities were regulated to 0.4 A ⁇ dm -2 for the Al anode and to 0.2 A ⁇ dm -2 for the Mg anode, the amount of current was 3.5 mF.
  • the amount of toluene can gradually decrease due to evaporation, if it drops below 5 moles of toluene per mole of M [AlEt 4 ], the solution becomes inhomogeneous and some AlEt 3 separates in the form of an oil Droplets. In this case the amount of toluene must be increased to 6 mol toluene per mol M [AlEt 4 ].
  • Example 3 The electrolyte of Example 3 was again electrolyzed after replacing the cathode with a new copper sheet at 90-95 ° C.
  • the cathode current density was 0.9 A ⁇ dm -2 .
  • the cathode layer was even and shiny silver. It contained 54.9% by weight of Al and 45.1% by weight of Mg.
  • the electrolyte of Examples 3 and 4 was electrolyzed four times in a row 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.
  • Experiment No. Cathode layer appearance % By weight Electrolyte content in mAt / g al mg al mg 1 even, light gray 76.20 23.80 2 even, getting rougher on the edges 53.00 47.00 2.93 0040 3 gray, rough on the edges 29.95 70.05 2.80 0058 4 gray, rough dendritic on the edges 4.60 95.40 2.85 0070
  • An electrolyte with the composition 0.8 mol K [AlEt 4 ] /0.2 mol Na [AlEt 4 ] /2.0 AlEt 3 /3.3 mol toluene was between 2 anodes made of an aluminum-magnesium alloy with 25 wt .-% Mg and 75 wt .-% % Al and a rotating cylindrical screw M8 made of tempered steel (8.8) at 97-102 ° C with a cathodic current density of 0.8 A dm -2 and a current of 2.89 mF electrolyzed. Cathodic and anodic current yields were quantitative at 99.5%. The approximately 9 ⁇ m thick alloy layer was uniform, shiny silver and adhered well to the base material.
  • the anodic current efficiency was 98.8%.
  • the approximately 10 ⁇ m thick alloy layer was very even, matt silver and adhered well to the base material.
  • Example 7 was replaced ten times after each time the cathodes were replaced repeated an uncoated screw at 98 - 100 ° C.
  • the respective thicknesses the cathode layer was varied from 9 to 13 ⁇ m.
  • the anodic current efficiency was 99.5% over the ten trials.
  • 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 0.3 A ⁇ dm -2 at each anode.
  • the anodic current yield was quantitative, the cathodically deposited layer was uniform and matt silver.
  • Example 11 The electrolyte of Example 11 was electrolyzed after replacing the cathode with a new one, also made of tempering steel, at 95-104 ° C.
  • the anodic current densities were set to 0.45 ADm -2 for aluminum and 0.15 ADm -2 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 slowly rotated between the two anodes, the cathodic current density was 0.8 A ⁇ dm -2 . After passing through 3.5 mF, the cathode layer was 12 ⁇ m thick and was uniform and matt silver.
  • Example 13 was performed three times after replacing the cathode with an uncoated one repeated at 92 - 100 ° C.
  • the respective layer thicknesses were between 10 and 15 ⁇ m varies.
  • the anodic current yield was over the 4th Trials for the alloy anodes 98.9%.
  • the calculated layer thicknesses were between 12 and 20mm.
  • 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.

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  • 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)

Claims (19)

  1. Electrolyte exempt d'halogénure pour le dépôt électrolytique d'alliages aluminium-magnésium, caractérisé en ce qu'il contient un mélange alumino-organique, qui est constitué essentiellement
    soit par du tétraalkylaluminium alcalin M[AlR4],
    soit par du hexaalkylhydruroaluminium alcalin M[AlR3-H-AlR3] et du tétraalkylaluminium alcalin M[AlR4],
    et par du trialkylaluminium AlR3' ainsi que par un composé de magnésium, avec M = Li, Na, K, Rb ou Cs et,
    R, R' = CH3, C2H5, C3H7, n- ou iso-C4H9, R et R' étant identiques ou différents.
  2. Electrolyte selon la revendication 1, dans lequel le mélange alumino-organique est un mélange éthylalumino-organique, qui est constitué essentiellement soit par du K[AlEt4](A) et Na[AlEt4](B), avec un rapport molaire B:A dans la gamme 0 ≤ B:A < 1:3,
    soit par du Na[Et3Al-H-AIEt3](C) et Na[AlEt4](D), avec un rapport molaire D:C dans la gamme 1:4 ≤ D:C ≤ 1:1
    et par du trialkylaluminium(E).
  3. Electrolyte selon les revendications 1 et 2, dans lequel du triéthylaluminium AlEt3 est utilisé comme trialkylaluminium.
  4. Electrolyte selon les revendications 2 et 3, sans le constituant Na[Et3Al-H-AlEt3], le rapport molaire de A:B étant compris entre 9:1 et 3:1 et le rapport molaire de (A+B):E étant compris entre 1:0,5 et 1:3.
  5. Electrolyte selon la revendication 4, dans lequel le rapport molaire A:B est égal à 4:1.
  6. Electrolyte selon les revendications 2 et 3, sans le constituant K[AlEt4], dans lequel le rapport molaire de D:C est égal à 1:2 et le rapport molaire de D:E est de 1:2 à 1:1.
  7. Electrolyte selon les revendications 1 à 3, caractérisé en ce que le mélange alumino-organique est dissous dans un hydrocarbure aromatique liquide à 20°C.
  8. Electrolyte selon les revendications 4,5 et 7, caractérisé en ce que le mélange alumino-organique est dissous dans 2 à 6 moles de toluène, rapportées à la quantité totale utilisée de Na[AlEt4] et K[AlEt4].
  9. Electrolyte selon les revendications 2, 3,6 et 7, dans lequel le mélange alumino-organique est dissous dans 5 à 7 moles de toluène, rapportées au Na[AlEt4] utilisé.
  10. Electrolyte selon les revendications 1 à 3 et 7, caractérisé en ce que les constituants alumino-organiques sont dissous dans un mélange d'un hydrocarbure aromatique liquide avec un éther aliphatique monobasique, dibasique ou polybasique R"OR"'(R"=R"'=alkyle; ou R"=alkyle, R"'=CH2OR"), et le rapport molaire AlR3:R"OR"' est compris entre 0,5 et 1,0.
  11. Electrolyte selon la revendication 10, caractérisé en ce que l'éther aliphatique est du diméthoxyéthane CH3OCH2CH2OCH3, l'hydrocarbure aromatique est du toluène et le rapport molaire triéthylaluminium: diméthoxyéthane est de 0,8 à 0,9.
  12. Procédé de dépôt électrolytique d'alliages aluminium-magnésium sur des matériaux électriquement conducteurs, caractérisé en ce qu'on utilise un électrolyte selon les revendications 1 à 11 et, comme anodes, des anodes en aluminium et en magnésium ou des anodes en alliage d'aluminium-magnésium, la composition de l'alliage d'anode correspondant au revêtement d'alliage désiré.
  13. Procédé selon la revendication 12, caractérisé en ce que le procédé est mis en oeuvre sur une plage de températures de 80 à 105°C.
  14. Procédé selon les revendications 12 et 13, selon lequel on produit un revêtement d'alliage avec un rapport aluminium/magnésium compris entre 95:5 et 5:95.
  15. Procédé selon les revendications 12 à 14, selon lequel on règle la concentration de magnésium, nécessaire pour la teneur recherchée en magnésium du revêtement d'alliage, dans l'électrolyte, par préélectrolyse ou bien par addition, en une fois, de Mg[AlEt4]2 au début de l'électrolyse.
  16. Procédé selon la revendication 12, pour réduire ou éviter une corrosion par contact sur des pièces en magnésium, caractérisé en ce que des taux d'insertion de Mg de 5...50 % en poids à l'intérieur de la couche d'alliage conduisent à la formation des phases intermétalliques.
  17. Procédé selon la revendication 12, pour éviter une corrosion par criques de tension induite par le H2, selon lequel on utilise comme matériaux électriquement conducteurs, des éléments en acier très solides possédant une résistance à la traction > 1000 MPa
  18. Procédé selon la revendication 16, selon lequel en ce qui concerne les pièces en magnésium, il s'agit de pièces de l'industrie automobile dans le domaine des boítes de vitesses, des moteurs et des carrosseries.
  19. Electrolyte selon la revendication 1, dans lequel le constituant formé de magnésium est réglé, pour la concentration désirée de magnésium dans l'électrolyte, par préélectrolyse moyennant l'utilisation d'anodes en Al-Mg ou bien par addition, en une fois, de Mg[AlR4]2.
EP99962174A 1998-12-01 1999-11-27 Electrolyte organique d'aluminium et procede de revetement electrolytique avec de l'aluminium ou des alliages aluminium-magnesium Expired - Lifetime EP1141447B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19855666A DE19855666A1 (de) 1998-12-01 1998-12-01 Aluminiumorganische Elektrolyte und Verfahren zur elektrolytischen Beschichtung mit Aluminium oder Aluminium-Magnesium Legierungen
DE19855666 1998-12-01
PCT/EP1999/009236 WO2000032847A2 (fr) 1998-12-01 1999-11-27 Electrolyte organique d'aluminium et procede de revetement electrolytique avec de l'aluminium ou des alliages aluminium-magnesium

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EP1141447A2 EP1141447A2 (fr) 2001-10-10
EP1141447B1 true EP1141447B1 (fr) 2002-07-03

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US (1) US6652730B1 (fr)
EP (1) EP1141447B1 (fr)
JP (1) JP2002531698A (fr)
AT (1) ATE220129T1 (fr)
CA (1) CA2352800A1 (fr)
DE (2) DE19855666A1 (fr)
WO (1) WO2000032847A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008051883A1 (de) 2008-10-16 2010-04-22 Nano-X Gmbh Beschichtung zum kathodischen Korrosionsschutz von Metall, Verfahren zum Herstellen der Beschichtung und Verwendung der Beschichtung.

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088434A1 (fr) * 2001-04-30 2002-11-07 Alumiplate Incorporated Formulations d'electrodeposition d'aluminium
US7250102B2 (en) 2002-04-30 2007-07-31 Alumiplate Incorporated Aluminium electroplating formulations
DE10134559B4 (de) * 2001-07-16 2008-10-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Beschichtung von Bauteilen, mit dem Verfahren herstellbare Dispersionsschichten und Verwendung
DE10224089A1 (de) * 2002-05-31 2003-12-11 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von aluminiumorganischen Komplexen und deren Verwendung zur Herstellung von Elektrolytlösungen zur elektrochemischen Abscheidung von Aluminium-Magnesium-Legierungen
DE10226360A1 (de) * 2002-06-13 2003-12-24 Crompton Gmbh Verfahren zur Herstellung von Alkalitetraalkylaluminaten und deren Verwendung
EP1403402A1 (fr) 2002-09-25 2004-03-31 Aluminal Oberflächtentechnik GmbH & Co. KG Procédé pour la déposition electrolytique des materiaux avec aluminium, magnesium ou les alliages d'aluminium et magnesium
DE10257737B3 (de) * 2002-12-10 2004-02-26 Thyssenkrupp Stahl Ag Verfahren zur elektrolytischen Magnesium-Abscheidung auf verzinktem Blech
WO2004099218A1 (fr) * 2003-04-30 2004-11-18 Akzo Nobel N.V. Production de solutions de tetra-alkylaluminate de sodium et de potassium melangees
EP1518945A1 (fr) * 2003-09-27 2005-03-30 Aluminal Oberflächtentechnik GmbH & Co. KG Electrolyte pour la deposition galvanique d'alliages aluminium magnesium
EP1524336A1 (fr) * 2003-10-18 2005-04-20 Aluminal Oberflächtentechnik GmbH & Co. KG Pièces à usiner recouvertes d'un alliage aluminium-magnesium
EP1624091A1 (fr) * 2004-08-04 2006-02-08 Aluminal Oberflächentechnik GmbH & Co. KG Pièces revêtues d' un alliage aluminium/magnesium ou d'aluminium avec une couche intermédaire de zinc
CN103334132B (zh) * 2013-07-17 2016-05-25 沈阳大学 室温电沉积制备铝镁合金膜的方法
JP6572316B2 (ja) 2014-10-31 2019-09-04 べカルト ビンジャン スチール コード カンパニー．，リミテッドＢｅｋａｅｒｔ Ｂｉｎｊｉａｎｇ Ｓｔｅｅｌ Ｃｏｒｄ Ｃｏ．，Ｌｔｄ 曲げ部の曲率が制御される成形ソーワイヤ
CN104388998B (zh) * 2014-11-18 2016-08-24 沈阳大学 一种室温电沉积制备多孔纳米氧化铝的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE540052A (fr) * 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 (de) * 1973-07-26 1975-04-03 Siemens Ag Verfahren zum beschichten von hochfrequenz-heizspulen aus kupfer, messing, silber oder aluminium
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 (de) * 1989-06-10 1990-12-13 Studiengesellschaft Kohle Mbh Aluminiumorganische elektrolyte zur elektrolytischen abscheidung von hochreinem aluminium
US5015750A (en) * 1990-10-31 1991-05-14 Texas Alkyls, Inc. Preparation of trimethylaluminum

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008051883A1 (de) 2008-10-16 2010-04-22 Nano-X Gmbh Beschichtung zum kathodischen Korrosionsschutz von Metall, Verfahren zum Herstellen der Beschichtung und Verwendung der Beschichtung.

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ATE220129T1 (de) 2002-07-15
US6652730B1 (en) 2003-11-25
DE59901980D1 (de) 2002-08-08
WO2000032847A3 (fr) 2000-11-16
WO2000032847A2 (fr) 2000-06-08
DE19855666A1 (de) 2000-06-08
CA2352800A1 (fr) 2000-06-08
EP1141447A2 (fr) 2001-10-10
JP2002531698A (ja) 2002-09-24

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