EP0948670A2 - Electrolyte pour depot d'aluminium par galvanoplastie - Google Patents

Electrolyte pour depot d'aluminium par galvanoplastie

Info

Publication number: EP0948670A2
Authority: EP; European Patent Office
Prior art keywords: aluminum; electrolyte; complexes; lewis base; formula
Prior art date: 1996-11-27
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

Application number

EP97950148A

Other languages

German (de)

English (en)

Other versions

EP0948670B1 (fr

Inventor

Hans De Vries

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Rasant Alcotec Beschichtungstechnik GmbH

Original Assignee

Rasant Alcotec Beschichtungstechnik GmbH

Priority date (The priority date 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 date listed.)

1996-11-27

Filing date

1997-11-08

Publication date

1999-10-13

1997-11-08 Application filed by Rasant Alcotec Beschichtungstechnik GmbH filed Critical Rasant Alcotec Beschichtungstechnik GmbH

1999-10-13 Publication of EP0948670A2 publication Critical patent/EP0948670A2/fr

2002-10-09 Application granted granted Critical

2002-10-09 Publication of EP0948670B1 publication Critical patent/EP0948670B1/fr

2017-11-08 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

229910052782 aluminium Inorganic materials 0.000 title claims abstract description 59
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 40
239000003792 electrolyte Substances 0.000 title claims abstract description 37
238000009713 electroplating Methods 0.000 title abstract description 4
239000004411 aluminium Substances 0.000 title abstract 4
239000002879 Lewis base Substances 0.000 claims abstract description 19
150000007527 lewis bases Chemical class 0.000 claims abstract description 19
150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
229910052700 potassium Inorganic materials 0.000 claims abstract description 8
239000011877 solvent mixture Substances 0.000 claims abstract description 7
238000004519 manufacturing process Methods 0.000 claims abstract description 6
229910052792 caesium Inorganic materials 0.000 claims abstract description 5
229910052701 rubidium Inorganic materials 0.000 claims abstract description 5
238000005260 corrosion Methods 0.000 claims abstract description 4
230000007797 corrosion Effects 0.000 claims abstract description 4
150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 3
125000002524 organometallic group Chemical group 0.000 claims abstract description 3
229910052708 sodium Inorganic materials 0.000 claims abstract description 3
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
239000004215 Carbon black (E152) Substances 0.000 claims description 3
238000004070 electrodeposition Methods 0.000 claims description 3
229930195733 hydrocarbon Natural products 0.000 claims description 3
150000002430 hydrocarbons Chemical class 0.000 claims description 3
125000001931 aliphatic group Chemical group 0.000 claims description 2
150000001412 amines Chemical class 0.000 claims description 2
125000000217 alkyl group Chemical group 0.000 claims 1
150000008378 aryl ethers Chemical class 0.000 claims 1
238000000576 coating method Methods 0.000 abstract description 14
125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 2
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
239000000243 solution Substances 0.000 description 17
239000008151 electrolyte solution Substances 0.000 description 16
238000000151 deposition Methods 0.000 description 14
230000008021 deposition Effects 0.000 description 13
239000011248 coating agent Substances 0.000 description 12
150000001875 compounds Chemical class 0.000 description 10
229940021013 electrolyte solution Drugs 0.000 description 10
-1 aluminum halides Chemical class 0.000 description 8
239000000203 mixture Substances 0.000 description 8
239000002904 solvent Substances 0.000 description 7
XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
238000002844 melting Methods 0.000 description 4
230000008018 melting Effects 0.000 description 4
239000011591 potassium Substances 0.000 description 4
ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
229910001508 alkali metal halide Inorganic materials 0.000 description 3
150000008045 alkali metal halides Chemical class 0.000 description 3
229910052786 argon Inorganic materials 0.000 description 3
238000000034 method Methods 0.000 description 3
238000003860 storage Methods 0.000 description 3
SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
229910052783 alkali metal Inorganic materials 0.000 description 2
QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 2
239000007788 liquid Substances 0.000 description 2
NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
238000003756 stirring Methods 0.000 description 2
JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
239000008096 xylene Substances 0.000 description 2
DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
239000000654 additive Substances 0.000 description 1
230000000996 additive effect Effects 0.000 description 1
150000001340 alkali metals Chemical class 0.000 description 1
TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
150000001768 cations Chemical class 0.000 description 1
230000000052 comparative effect Effects 0.000 description 1
230000009918 complex formation Effects 0.000 description 1
238000002425 crystallisation Methods 0.000 description 1
230000008025 crystallization Effects 0.000 description 1
AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
238000007865 diluting Methods 0.000 description 1
238000009826 distribution Methods 0.000 description 1
230000000694 effects Effects 0.000 description 1
238000005868 electrolysis reaction Methods 0.000 description 1
230000008030 elimination Effects 0.000 description 1
238000003379 elimination reaction Methods 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
229910052736 halogen Inorganic materials 0.000 description 1
230000002401 inhibitory effect Effects 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
229910052751 metal Inorganic materials 0.000 description 1
239000002184 metal Substances 0.000 description 1
229910001512 metal fluoride Inorganic materials 0.000 description 1
238000002156 mixing Methods 0.000 description 1
239000011148 porous material Substances 0.000 description 1
235000003270 potassium fluoride Nutrition 0.000 description 1
239000011698 potassium fluoride Substances 0.000 description 1
238000002360 preparation method Methods 0.000 description 1
IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
239000000126 substance Substances 0.000 description 1
239000013589 supplement 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 an electrolyte for the electrodeposition of aluminum containing a metallorganis.chen 5 aluminum complex and the use of this electrolyte for the production of decorative corrosion-resistant aluminum layers.
Aluminum can be galvanically deposited from a large number of electrolytes. These electrolytes include e.g.
aluminum alkyl complexes were also used. This also includes, for example, electrolytes with aluminum complexes such as KF-2 AlEt or KF-2 AlMe 3 . Due to the changed alkali metal cation potassium, these complexes have a better electrical conductivity and a much better scatterability, which is similar to other metal deposits in aqueous electrolytes.
a major disadvantage of these compounds is that their melting points are around 127-129 ° C for KF-2 AlEt 3 and 151-152 ° C for KF-2 AlMe 3 .
the solubility of these complexes in aromatic hydrocarbons is also very low.
a -4 molar toluene solution of KF-2 AlEt 3 already crystallizes at approx. 60 - 65 ° C. This means that the storage of such solutions results in the active aluminum complex compound partially crystallizing out, so that such solutions are unusable after a short time.
EP-0 402 760 AI describes electrolytes for the deposition of aluminum which, in addition to compounds of the formula MF '2A1R 3, also contain non-complexed A1R 3 , an aromatic hydrocarbon and a glycol ether being used as solvents.
compounds of the composition KF-2 Al (i-Bu) 3 have a low melting point and are therefore useful as an additive for improving solubility, but larger concentrations of this compound in the electrolyte quickly cause gray deposits. Furthermore, the current density capacity of such complexes is low and this can quickly lead to the co-deposition of potassium, which is extremely undesirable for aluminum deposition.
composition of an electroplating bath in operation is constantly changing and the mixing ratio and concentration of the individual aluminum complexes must be kept constant.
Another disadvantage of these multi-component systems is therefore the complicated control and keeping the composition constant, as well as the more complex analysis.
Certain aluminum complexes, such as aluminum trimethyl, are still so expensive that it is desirable to avoid the use of such a complex compound for economic reasons alone.
aromatic hydrocarbons such as toluene or xylene are used almost exclusively as solvents. It has now surprisingly been found that when these aromatic hydrocarbons are partially replaced by organic Lewis bases, a considerable improvement in the solubility and also in other properties of the aluminum alkyl complexes is achieved which no longer require the use of multicomponent systems.
Lewis bases have a stronger affinity for aluminum alkyl compounds than some alkali metal halides.
the ratio of the solvent hydrocarbon to Lewis bases is 4: 1 to 1: 2.
M in formula (I) is potassium, rubidium or cesium.
Aluminum triethyl is preferably used as the aluminum compound A1R 3 .
An aliphatic, cycloaliphatic or aromatic ether compound or an amine is preferably used as the Lewis base.
an ether of the formula R1-O-R2, in which R 1 and R 2 are C1-C4 alkyl includes, for example, compounds such as methyl ether, ethyl ether, n-propyl ether, isopropyl ether, tert-butyl ether, n-butyl ether and isobutyl ether.
KF-2AlEt 3 is particularly preferred since this compound is generally one of the most easily accessible and inexpensive aluminum alkyl complexes.
the problems with the solubility of such complexes so far can be solved in a simple manner by adding a Lewis base, a diisopropyl ether or n-propyl ether in a very particularly preferred manner, to the toluene-containing solution.
a 4 molar solution of KF-2AlEt 3 in toluene usually already crystallizes out at room temperature. This is not observed in the electrolyte according to the invention in the solvent mixture with Lewis bases.
the electrical conductivity of the electrolytes according to the invention is somewhat lower than that of electrolytes in pure toluene and is far below the reduction in electrical conductivity to be expected from the person skilled in the art which would be expected if the complex were partially or completely destroyed.
the somewhat lower conductivity is also due to the higher solubility and compensated for a higher load capacity of such an electrolyte solution.
the coating in the case of parts of complicated shape scattered further into gaps and bores than in the case of the electrolytes without the addition of Lewis bases.
the tendency to dendritic growth or burns was also prevented by the inhibiting effect of the added Lewis base.
the layers obtained are matt to semi-glossy, smooth and low in pores and are produced at current densities of up to 2 A / dm 2 .
the electrolytes can be operated not only with direct current, but also with reverse polarity.
the electrolytic solution according to the invention is produced in a conventional manner by first adding the metal fluoride to the solvent mixture of hydrocarbon and a Lewis base. Then the amount of an aluminum alkyl compound calculated for complex formation is slowly added in small portions. After the addition, the mixture is warmed and stirred until all components have completely dissolved. The solution is then cooled to room temperature and can be stored for any length of time without the solution crystallizing.
the electrolyte solution according to the invention is preferably used for the production of decorative and corrosion-resistant aluminum layers.
Aluminum layers of high purity and quality can be applied in a simple and very economical manner with the electrolyte solution according to the invention.
the calculated amount of the solvent mixture was first placed in the stirred tank flooded with argon.
the potassium fluoride dried at 120 ° C. was then added with vigorous stirring.
the calculated amount of aluminum triethyl was then slowly added in small portions.
the solution heated up to approx. 80 ° C.
the solution was then heated to 100 ° C. and stirred for 2 hours.
the solution had a conductivity of 19 mS / cm.
the solution was then cooled to 18 ° C. without stirring.
the solution was still completely liquid afterwards. After decanting into a storage vessel, the solution was stored at 15-18 ° C. for 2 weeks without movement. Even after 2 weeks of storage, the solution was still completely liquid.
a coating was carried out with the electrolyte from Example 1.
a coating cell flooded with argon and provided with an entry lock system with approx. 6 1 contents
2 step angle plates with step depths of 20 mm and a current density of 1 A / dm 2 and 100 ° were placed in a frame frame of approx. 140 x 140 mm C coated using reverse polarity.
the anodes were arranged parallel to the frame and the deposition time was 60 min.
a fine-crystalline, smooth, silk-matt aluminum layer was created without burns or dendritic growth at the edges and tips.
the cathodic yield was 99.8%.
the spread was approximately 38%.
Example 2 The same experiment as in Example 2 was carried out with 1 A / dm 2 direct current instead of alternating current. A fine crystalline, smooth, matt aluminum layer was produced without burns or dendritic growth at the edges and tips. The cathodic yield was also almost 100%. The layer thickness distribution on the sheet was identical to that of Example 2.
a gap cathode (J-sheet) 50 mm wide and a gap of 2 mm was coated for 30 minutes in the electrolyte from Example 1 with a current density of 1 A / dm 2 , the anodes being parallel to the flat side of the cathode were arranged. After the sheet had been bent open, it was found that the coating had sprinkled in up to 7 mm from the edge, with a flowing runout of the coating up to about 16 mm from the edge. Approximately 18 mm in the middle of the sheet remained uncovered.
Example 4 As a comparison, an identical sheet was coated under the same conditions as in Example 4 in an electrolyte only with toluene without the addition of diisopropyl as a solvent (see EP 0 402 761 A1). The electrolyte scattered only approx. 4.5mm from the edge into the gap and the coating stopped abruptly. Around 41 mm in the middle of the sheet remained uncovered.

Landscapes

Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Electrochemistry (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Electroplating And Plating Baths Therefor (AREA)
Conductive Materials (AREA)
Electroplating Methods And Accessories (AREA)
Paints Or Removers (AREA)

EP97950148A 1996-11-27 1997-11-08 Electrolyte pour depot d'aluminium par galvanoplastie Expired - Lifetime EP0948670B1 (fr)

Applications Claiming Priority (3)

Application Number	Priority Date	Filing Date	Title
DE19649000A DE19649000C1 (de)	1996-11-27	1996-11-27	Elektrolyt zur galvanischen Abscheidung von Aluminium und dessen Verwendung
DE19649000		1996-11-27
PCT/EP1997/006218 WO1998023795A2 (fr)	1996-11-27	1997-11-08	Electrolyte pour depot d'aluminium par galvanoplastie

Publications (2)

Publication Number	Publication Date
EP0948670A2 true EP0948670A2 (fr)	1999-10-13
EP0948670B1 EP0948670B1 (fr)	2002-10-09

Family

ID=7812844

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP97950148A Expired - Lifetime EP0948670B1 (fr)	1996-11-27	1997-11-08	Electrolyte pour depot d'aluminium par galvanoplastie

Country Status (8)

Country	Link
EP (1)	EP0948670B1 (fr)
JP (1)	JP2001505253A (fr)
AT (1)	ATE225871T1 (fr)
AU (1)	AU5320098A (fr)
CA (1)	CA2272254A1 (fr)
DE (2)	DE19649000C1 (fr)
ES (1)	ES2186010T3 (fr)
WO (1)	WO1998023795A2 (fr)

Families Citing this family (3)

* 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
EP1647613A1 (fr) *	2004-10-15	2006-04-19	Aluminal Oberflächentechnik GmbH & Co. KG	Electrolyte pour la déposition galvanique d'aluminium

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
BE758730A (fr) *	1969-12-27	1971-04-16	Nisshin Steel Co Ltd	Procede de revetement d'aluminium
DE2453830C2 (de) *	1974-11-13	1986-07-31	Siemens AG, 1000 Berlin und 8000 München	Bad und Verfahren zur galvanischen Abscheidung von glänzenden Aluminiumüberzügen
DE3202265A1 (de) *	1982-01-25	1983-07-28	Siemens AG, 1000 Berlin und 8000 München	Elektrolyt zur galvanischen abscheidung von aluminium
DE3919069A1 (de) *	1989-06-10	1990-12-13	Studiengesellschaft Kohle Mbh	Aluminiumorganische elektrolyte und verfahren zur elektrolytischen abscheidung von aluminium
DE3919068A1 (de) *	1989-06-10	1990-12-13	Studiengesellschaft Kohle Mbh	Aluminiumorganische elektrolyte zur elektrolytischen abscheidung von hochreinem aluminium

1996
- 1996-11-27 DE DE19649000A patent/DE19649000C1/de not_active Expired - Fee Related
1997
- 1997-11-08 AU AU53200/98A patent/AU5320098A/en not_active Abandoned
- 1997-11-08 DE DE59708456T patent/DE59708456D1/de not_active Expired - Lifetime
- 1997-11-08 CA CA002272254A patent/CA2272254A1/fr not_active Abandoned
- 1997-11-08 AT AT97950148T patent/ATE225871T1/de not_active IP Right Cessation
- 1997-11-08 WO PCT/EP1997/006218 patent/WO1998023795A2/fr not_active Ceased
- 1997-11-08 ES ES97950148T patent/ES2186010T3/es not_active Expired - Lifetime
- 1997-11-08 JP JP52419998A patent/JP2001505253A/ja active Pending
- 1997-11-08 EP EP97950148A patent/EP0948670B1/fr not_active Expired - Lifetime

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9823795A2 *

Also Published As

Publication number	Publication date
CA2272254A1 (fr)	1998-06-04
ATE225871T1 (de)	2002-10-15
WO1998023795A3 (fr)	1998-07-09
JP2001505253A (ja)	2001-04-17
DE19649000C1 (de)	1998-08-13
DE59708456D1 (de)	2002-11-14
WO1998023795A2 (fr)	1998-06-04
EP0948670B1 (fr)	2002-10-09
ES2186010T3 (es)	2003-05-01
AU5320098A (en)	1998-06-22

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