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US4452674A Expired / Lapsed US ⏱️ 0.0 years remaining

Electrolytes for electrochemically treated metal plates

Assignee: CNA Holdings LLC
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Filing: 1982-09-27
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Granted: 1984-06-05
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Expires: 2002-09-27
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Abstract

Abstract According to the invention there is provided an electrochemical process for applying a firmly bonded insoluble metal oxide-organic complex on a metal surface by employing the metal as anode and a water-soluble polybasic organic acid as electrolyte. The polybasic acid may be a polyphosphonic acid, polyphosphoric and polycarboxyl acid, or polysulfonic acid and is advantageously polymeric. Polyvinyl phosphonic acid (PVPA) is a preferred electrolyte. Direct current is used. The insoluble metal oxide-organic complex formed is composed of anodic oxide combined with polyacid, which forms a protective layer on the metal of improved corrosion resistance. The metal oxide-organic complex is well-suited to bond light sensitive coatings thereto. The metal may be steel, aluminum or magnesium. The process is economical and the product novel.

Inventors

  • 👤 Thomas N. Gillich
  • 👤 John E. Walls
  • 👤 Stanley F. Wanat
  • 👤 William J. Rozell

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-02 23:14
CPC Classifications
C; C25; C25D; C25D11/00; C25D11/02; C25D11/04; C25D11/06; B; B41; B41N; B41N3/00; B41N3/03; B41N3/034; C25D11/12

Claims Analysis

Total Claims: 62
Claim 1
Independent Claim 95 words
A process for preparing an element comprising; (a) cleaning a metal article, and (b) electrolyzing said metal article made anode using direct current in an aqueous organic electrolytic solution having dissolved therein an acid component, said acid component consisting essentially of a water-soluble polybasic organic acid or mixture of two or more water-soluble polybasic organic acids which, if carboxylic be at least tribasic, under electrolytic conditions sufficient to form a metal complex, including said organic acid, bonded to the surface of said metal article, wherein the surface of said element is substantially non-porous and hydrophilic.
Claim 2
Dependent Claim 95 words
A process for preparing an element comprising; (a) cleaning a metal article, and (b) electrolyzing said metal article made anode using direct current in an aqueous organic electrolytic solution having dissolved therein an acid component, said acid component consisting essentially of a water-soluble polybasic organic acid or mixture of two or more water-soluble polybasic organic acids which, if carboxylic be at least tribasic, under electrolytic conditions sufficient to form a metal complex, including said organic acid, bonded to the surface of said metal article, wherein the surface of said element is substantially non-porous and hydrophilic.
Claim 3
Dependent Claim 31 words
The process of claim 1, wherein said water-soluble organic acid is selected from the group consisting of sulfonic, phosphonic, phosphoric, and tribasic or higher functionality carboxylic acids and mixtures of these.
Claim 4
Dependent Claim 39 words
The process of claim 2, wherein said water-soluble organic acid is selected from the group consisting of the condensation product of benzene phosphonic acid and formaldehyde, phytic acid, polyvinyl phosphonic acid, 2-ethyl hexyl phosphonic acid, and mixtures of these.
Claim 5
Dependent Claim 18 words
The process of claim 2, wherein the metal article is composed of aluminum or one of its alloys.
Claim 6
Dependent Claim 13 words
The process of claim 2, wherein the metal article is composed of magnesium.
Claim 7
Dependent Claim 13 words
The process of claim 2, wherein the metal article is composed of steel.
Claim 8
Dependent Claim 14 words
The process of claim 4, wherein said water-soluble organic acid is nitrilo triacetic acid.
Claim 9
Dependent Claim 14 words
The process of claim 4, wherein said water-soluble organic acid is 1,2,4,5-benzene tetracarboxylic acid.
Claim 10
Dependent Claim 20 words
The process of claim 4, wherein said water-soluble organic acid is a condensation product of benzene phosphonic acid and formaldehyde.
Claim 11
Dependent Claim 19 words
The process of claim 4, wherein said water-soluble organic acid is a copolymer of methylvinyl ether and maleic anhydride.
Claim 12
Dependent Claim 14 words
The process of claim 4, wherein said water-soluble organic acid is polyvinyl sulfonic acid.
Claim 13
Dependent Claim 14 words
The process of claim 4, wherein said water-soluble organic acid is polystyrene sulfonic acid.
Claim 14
Dependent Claim 13 words
The process of claim 4, wherein said water-soluble organic acid is phytic acid.
Claim 15
Dependent Claim 13 words
The process of claim 4, wherein said water-soluble organic acid is alginic acid.
Claim 16
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is poly-n-butyl benzene sulfonic acid.
Claim 17
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is polydiisopropyl benzene sulfonic acid.
Claim 18
Dependent Claim 14 words
The process of claim 4, wherein said water-soluble organic acid is polyvinyl phosphonic acid.
Claim 19
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is dodecyl polyoxyethylene phosphonic acid.
Claim 20
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is dinonyl naphthalene disulfonic acid.
Claim 21
Dependent Claim 14 words
The process of claim 4, wherein said water-soluble organic acid is 2,2'-dinitro-4,4'-stilbene disulfonic acid.
Claim 22
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is diisopropyl polynaphthalene disulfonic acid.
Claim 23
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is 2-ethyl hexyl phosphonic acid.
Claim 24
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is dodecyl naphthalene disulfonic acid.
Claim 25
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is di-n-butyl naphthalene disulfonic acid.
Claim 26
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is polydecyl benzene sulfonic acid.
Claim 27
Dependent Claim 13 words
The process of claim 4, wherein said water-soluble organic acid is polyacrylic acid.
Claim 28
Dependent Claim 13 words
The process of claim 4, wherein said water-soluble organic acid is polymethacrylic acid.
Claim 29
Dependent Claim 15 words
The process of claim 4, wherein said water-soluble organic acid is diethylene diamine pentaacetic acid.
Claim 30
Dependent Claim 14 words
The process of claim 4, wherein said water-soluble organic acid is polynaphthalene sulfonic acid.
Claim 31
Dependent Claim 14 words
The process of claim 4, wherein said water-soluble organic acid is ethylenediamine tetraacetic acid.
Claim 32
Dependent Claim 16 words
The process of claim 4, wherein said water-soluble organic acid is hydroxyethyl ethylene diamine triacetic acid.
Claim 33
Dependent Claim 20 words
The process of claim 2, wherein said electrolyte solution has dissolved therein a mixture of two or more organic acids.
Claim 34
Dependent Claim 73 words
The process of claim 2, wherein said organic acid is present at a concentration of between about 0.05% and about 30% and said electrolysis is conducted at a voltage of at least about 5 volts, an average current density of between about 1.3 amps/dm 2 and about 4.3 amps/dm 2 , a time of between 0.08 minutes and about 5 minutes, and a temperature of between about -2° C. and about 60° C.
Claim 35
Dependent Claim 74 words
The process of claim 33, wherein said organic acid is present at a concentration of at least about 0.5%, said electrolysis is conducted at a voltage of between about 1.0 volts and about 30 volts, the average current density is between about 1.0 amperes/dm 2 and about 5 amperes/dm 2 , the time is between about 0.16 minutes and about 1 minute, and the temperature is between about 10° C. and about 35° C.
Claim 36
Dependent Claim 20 words
The process of claims 33 or 34, wherein said organic acid is the condensation product benzene phosphonic acid and formaldehyde.
Claim 37
Dependent Claim 15 words
The process of claims 33 or 34, wherein said organic acid is a phytic acid.
Claim 38
Dependent Claim 15 words
The process of claims 33 or 34, wherein said organic acid is polyvinyl phosphonic acid.
Claim 39
Dependent Claim 16 words
The process of claims 33 or 34, wherein said organic acid is 2-ethyl hexyl phosphonic acid.
Claim 40
Dependent Claim 33 words
The process of claim 3, wherein said metal article is lithographic aluminum sheet, and as an additional step, a light sensitive coating is applied to the surface of said insoluble metal oxide-organic complex.
Claim 41
Dependent Claim 32 words
The process of claim 39, wherein the light sensitive coating contains a sensitizer selected from the group consisting of o-quinone diazides, condensation products of the condensation of aromatic diazonium compounds, and photopolymers.
Claim 42
Dependent Claim 12 words
The process of claim 39, wherein said sensitizer is an o-quinone diazide.
Claim 43
Dependent Claim 18 words
The process of claim 39, wherein said sensitizer is a product of the condensation of a diazonium compound.
Claim 44
Dependent Claim 11 words
The process of claim 39, wherein said sensitizer is a photopolymer.
Claim 45
Dependent Claim 9 words
The product produced by the process of claim 2.
Claim 46
Dependent Claim 9 words
The product produced by the process of claim 3.
Claim 47
Dependent Claim 9 words
The product produced by the process of claim 17.
Claim 48
Dependent Claim 9 words
The product produced by the process of claim 33.
Claim 49
Dependent Claim 9 words
The product produced by the process of claim 34.
Claim 50
Dependent Claim 9 words
The product produced by the process of claim 39.
Claim 51
Dependent Claim 9 words
The product produced by the process of claim 40.
Claim 52
Dependent Claim 9 words
The product produced by the process of claim 41.
Claim 53
Dependent Claim 9 words
The product produced by the process of claim 42.
Claim 54
Dependent Claim 51 words
A metal article having a substantially nonporous, substantially insoluble hydrophilic metal complex layer thereon, said layer comprising an acid component, said acid component consisting essentially of an organic polybasic acid selected from the group consisting of sulfonic, phosphonic, phosphoric and tribasic or higher functionality carboxylic acids and mixtures of these acids.
Claim 55
Dependent Claim 51 words
A metal article having a substantially nonporous, substantially insoluble hydrophilic metal complex layer thereon, said layer comprising an acid component, said acid component consisting essentially of an organic polybasic acid selected from the group consisting of sulfonic, phosphonic, phosphoric and tribasic or higher functionality carboxylic acids and mixtures of these acids.
Claim 56
Dependent Claim 48 words
A metal article having a nonporous insoluble metal oxide-organic layer thereupon, said layer comprising anodic oxide combined with an organic acid selected from the group consisting of the condensation product of benzene phosphonic acid and formaldehyde, phytic acid, polyvinyl phosphonic acid, 2-ethyl polyphosphoric acid and mixtures of these.
Claim 57
Dependent Claim 48 words
A metal article having a nonporous insoluble metal oxide-organic layer thereupon, said layer comprising anodic oxide combined with an organic acid selected from the group consisting of the condensation product of benzene phosphonic acid and formaldehyde, phytic acid, polyvinyl phosphonic acid, 2-ethyl polyphosphoric acid and mixtures of these.
Claim 58
Dependent Claim 26 words
The product of claim 53, wherein said article is composed of a metal selected from the group consisting of aluminum and its alloys, steel and magnesium.
Claim 59
Dependent Claim 21 words
The product of claim 55, wherein said metal is aluminum and said metal oxide-organic layer has a light sensitive coating thereupon.
Claim 60
Dependent Claim 30 words
The product of claim 56, wherein said light sensitive coating contains a sensitizer selected from the group consisting of o-quinone diazides, condensation products of an aromatic diazonium compound and photopolymers.
Claim 61
Dependent Claim 9 words
The product produced by the method of claim 1.
Claim 62
Dependent Claim 9 words
The product produced by the method of claim 4.

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USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1987-06-05 1987-12-05 1988-06-05 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1991-06-05 1991-12-05 1992-06-05 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1995-06-05 1995-12-05 1996-06-05 $7700.00 Window Closed / Lapsed

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