# US 10,309,025 B2 · Aluminum or aluminum alloy molten salt electroplating bath having good throwing power, electroplating method using the bath, and pretreatment method of the bath

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- Number: US 10,309,025 B2
- Document ID: US10309025B2
- Status: Granted
- Kind: B2
- Application number: 15/892,585
- Filed: 2018-02-09
- Published: 2018-06-14
- Granted: 2019-06-04
- Earliest claimed: 2011-01-05
- Assignees: Dipsol Chemicals Co., Ltd.
- Applicants: Dipsol Chemicals Co., Ltd.
- Inventors: Manabu Inoue; Akira Hashimoto; Tadahiro Onuma; Toshiki Inomata; Keisuke Nonomura; Naruaki Konno
- Web page: https://patentgrep.com/patent/US10309025B2

## CPC

- C25D 3/665: {from ionic liquids}
- C25D 3/44: Aluminium
- C25D 3/56: of alloys
- C25D 5/18: Electroplating using modulated, pulsed or reversing current
- C25D 5/611: {Smooth layers}
- C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR

## Abstract

The purpose of the present invention is to provide an electrical Al plating bath that poses little danger of exploding or igniting as a result of contacting air or water, and contains no benzene, toluene, xylene, naphthalene, or 1,3,5-trimethylbenzene, which have detrimental effects to humans. The present invention provides an electrical aluminum or aluminum alloy fused salt plating bath that is obtained by heat treatment of an electrical aluminum or aluminum alloy fused salt plating bath containing (A) a halogenated aluminum as the primary component and (B) at least one other type of halide after adding (C) one, two or more reducible compounds selected from the group consisting of hydrides of elements in Group 1 Periods 2 through 6 of the Periodic Table of Elements and/or hydrides of Group 13 Periods 2 through 6 of the Periodic Table of Elements and amine borane compounds.

## Claims

### Claim 1

A method for pretreating an aluminum or aluminum alloy molten salt plating bath which comprising:
(A) an aluminum halide as a main component,
(B) at least one further halide, wherein the further halide (B) is one or more compounds selected from the group consisting of N-alkylpyridinium halides, N-alkylimidazolium halides, N,N′-dialkylimidazolium halides, N-alkylpyrazolium halides, N,N′-dialkylpyrazolium halides, N-alkylpyrrolidinium halides, and N, N-dialkylpyrrolidinium halides, and
no organic solvent,
the method comprising:
adding (C) a reducing compound which is lithium aluminum hydride and/or dimethylamine borane to the plating bath, and
followed by a heat treatment, wherein the heat treatment includes decomposing the reducing compound (C) by heating the plating bath at a temperature of 50 to 100° C. for 0.5 to 8 hours,
wherein the plating bath is for electrolytic applications.

### Claim 2 (depends on 1)

The method according to claim 1, wherein
the aluminum halide (A) and the further halide (B) are contained at a molar ratio of from 1:1 to 3:1.

### Claim 3 (depends on 1)

The method according to claim 1, wherein
the heat treatment includes letting generated H2 gas out of the plating bath.

### Claim 4

A method for pretreating an aluminum or aluminum alloy molten salt plating bath which comprising:
(A) an aluminum halide as a main component,
(B) at least one further halide, wherein the further halide (B) is one or more compounds selected from the group consisting of N-alkylpyridinium halides, N-alkylimidazolium halides, N,N′-dialkylimidazolium halides, N-alkylpyrazolium halides, N,N′-dialkylpyrazolium halides, N-alkylpyrrolidinium halides, and N, N-dialkylpyrrolidinium halides, and
no organic solvent,
the method comprising:
adding (C) a reducing compound which is one or more compounds selected from the group consisting of lithium aluminum hydride, lithium hydride, lithium sodium hydride, sodium hydride, sodium borohydride, dimethylamine borane, diethylamine borane, and trimethylamine borane to the plating bath, and
followed by a heat treatment, wherein the heat treatment includes decomposing the reducing compound (C) by heating the plating bath at a temperature of 50 to 100° C. for 0.5 to 8 hours, and
removing an impurity metal originating from the aluminum halide (A) in the plating bath,
wherein the plating bath is for electrolytic applications.

### Claim 5 (depends on 4)

The method according to claim 4, wherein
said removing the impurity metal is a process in which the impurity metal is removed by immersing an Al wire or Al powder in the plating liquid, or a process in which the impurity metal is removed by placing a cathode aluminum plate or an anode aluminum plate in the plating liquid and applying a current therethrough.

### Claim 6 (depends on 4)

The method according to claim 4, wherein
the impurity metal is iron and/or copper.

### Claim 7

A method for pretreating an aluminum or aluminum alloy molten salt plating bath which comprising:
(A) an aluminum halide as a main component,
(B) at least one further halide, wherein the further halide (B) is one or more compounds selected from the group consisting of N-alkylpyridinium halides, N-alkylimidazolium halides, N,N′-dialkylimidazolium halides, N-alkylpyrazolium halides, N,N′-dialkylpyrazolium halides, N-alkylpyrrolidinium halides, and N, N-dialkylpyrrolidinium halides, and
no organic solvent,
the method comprising:
adding (C) a reducing compound which is one or more compounds selected from the group consisting of lithium aluminum hydride, lithium hydride, lithium sodium hydride, sodium hydride, sodium borohydride, dimethylamine borane, diethylamine borane, and trimethylamine borane to the plating bath, and
followed by a heat treatment, wherein the heat treatment includes decomposing the reducing compound (C) by heating the plating bath at a temperature of 50 to 100° C. for 0.5 to 8 hours,
wherein the plating bath is for electrolytic applications and the plating bath further comprises compounds (D) of one or more metals selected from the group consisting of Zr, Ti, Mo, W, Mn, Ni, Co, Sn, Zn, Si, Nd, and Dy in the amount of 0.1 to 100 g/l.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the plating bath further comprises 0.1 to 50 g/l of an organic polymer.

### Claim 9 (depends on 7)

The method according to claim 7, wherein the plating bath further comprises 0.001 to 0.1 mol/l of a brightening agent.
