US4448647A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Electrochemically treated metal plates
Assignee: CNA Holdings LLC
•
Filing: 1982-09-27
•
Granted: 1984-05-15
•
Expires: 2002-09-27
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 poly basic organic acid as electrolyte together with a strong inorganic acid such as phosphoric acid or further admixed with another strong inorganic acid such as sulfuric. 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 or aluminum. 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
2026-11-01 19:24
CPC Classifications
B; B41; B41N; B41N3/00; B41N3/03; B41N3/034; C; C25; C25D; C25D11/00; C25D11/02; C25D11/04; C25D11/06; C25D11/12
Claims Analysis
Total Claims: 61
Claim 1
Independent Claim
127 words
A process for preparing an element comprising (a) cleaning a metal article, (b) electrolyzing said metal article made anodic using direct current in an aqueous electrolytic solution having dissolved therein a mixture of electrolytes comprising: i. a water-soluble organic acid or mixture of two or more water-soluble organic acids selected from the group consisting of organic phosphoric acids, sulfonic acids, phosphonic acids, diethylene diamine penta acetic acid, ethylene diamine tetra acetic acid, hydroxyethyl ethylene diamine triacetic acid, and nitrilo triacetic acid; and ii. a strong inorganic acid comprising a phosphorus oxo acid having POH groups in which the hydrogen atom is ionizable under electrolytic conditions sufficient to form an insoluble substantially non-porous metal oxide-organic complex, including said organic acid, bonded to the surface of said metal article.
Claim 2
Dependent Claim
127 words
A process for preparing an element comprising (a) cleaning a metal article, (b) electrolyzing said metal article made anodic using direct current in an aqueous electrolytic solution having dissolved therein a mixture of electrolytes comprising: i. a water-soluble organic acid or mixture of two or more water-soluble organic acids selected from the group consisting of organic phosphoric acids, sulfonic acids, phosphonic acids, diethylene diamine penta acetic acid, ethylene diamine tetra acetic acid, hydroxyethyl ethylene diamine triacetic acid, and nitrilo triacetic acid; and ii. a strong inorganic acid comprising a phosphorus oxo acid having POH groups in which the hydrogen atom is ionizable under electrolytic conditions sufficient to form an insoluble substantially non-porous metal oxide-organic complex, including said organic acid, bonded to the surface of said metal article.
Claim 3
Dependent Claim
13 words
The process of claim 1, wherein said phosphorus oxo acid is phosphoric acid.
Claim 4
Dependent Claim
13 words
The process of claim 2, wherein said phosphorus oxo acid is phosphorous acid.
Claim 5
Dependent Claim
33 words
The process of claim 1, wherein said water-soluble organic acid is selected from the group consisting of the condensation product of benzene phosphonic acid, 2-ethyl hexyl phosphonic acid, and mixtures of these acids.
Claim 6
Dependent Claim
18 words
The process of claim 1 wherein the metal article is composed of aluminum or one of its alloys.
Claim 7
Dependent Claim
13 words
The process of claim 1, wherein the metal article is composed of steel.
Claim 8
Dependent Claim
14 words
The process of claim 5, wherein said water-soluble organic acid is nitrilo triacetic acid.
Claim 9
Dependent Claim
20 words
The process of claim 5, wherein said water-soluble organic acid is a condensation product of benzene phosphonic acid and formaldehyde.
Claim 10
Dependent Claim
19 words
The process of claim 5, wherein said water-soluble organic acid is a copolymer of methylvinyl ether and maleic acid.
Claim 11
Dependent Claim
14 words
The process of claim 5, wherein said water-soluble organic acid is polyvinyl sulfonic acid.
Claim 12
Dependent Claim
14 words
The process of claim 5, wherein said water-soluble organic acid is polystyrene sulfonic acid.
Claim 13
Dependent Claim
13 words
The process of claim 5, wherein said water-soluble organic acid is phytic acid.
Claim 14
Dependent Claim
13 words
The process of claim 5, wherein said water-soluble organic acid is alginic acid.
Claim 15
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is poly-n-butyl benzene sulfonic acid.
Claim 16
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is polydiisopropyl benzene sulfonic acid.
Claim 17
Dependent Claim
14 words
The process of claim 5, wherein said water-soluble organic acid is polyvinyl phosphonic acid.
Claim 18
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is dodecyl polyoxyethylene phosphonic acid.
Claim 19
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is dinonyl naphthalene disulfonic acid.
Claim 20
Dependent Claim
14 words
The process of claim 5, wherein said water-soluble organic acid is 2,2'-dinitro-4,4'-stilbene disulfonic acid.
Claim 21
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is diisopropyl polynaphthalene disulfonic acid.
Claim 22
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is 2-ethyl hexyl phosphonic acid.
Claim 23
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is dodecyl naphthalene disulfonic acid.
Claim 24
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is di-n-butyl naphthalene disulfonic acid.
Claim 25
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is polydecyl benzene sulfonic acid.
Claim 26
Dependent Claim
13 words
The process of claim 5, wherein said water-soluble organic acid is polyacrylic acid.
Claim 27
Dependent Claim
13 words
The process of claim 5, wherein said water-soluble organic acid is polymethacrylic acid.
Claim 28
Dependent Claim
15 words
The process of claim 5, wherein said water-soluble organic acid is diethylene diamine pentaacetic acid.
Claim 29
Dependent Claim
14 words
The process of claim 5, wherein said water-soluble organic acid is polynaphthalene sulfonic acid.
Claim 30
Dependent Claim
14 words
The process of claim 5, wherein said water-soluble organic acid is ethylenediamine tetraacetic acid.
Claim 31
Dependent Claim
16 words
The process of claim 5, wherein said water-soluble organic acid is hydroxyethyl ethylene diamine triacetic acid.
Claim 32
Dependent Claim
21 words
The process of claim 1, wherein said electrolyte solution has dissolved therein a mixture of two or more said organic acids.
Claim 33
Dependent Claim
19 words
The process of claim 1, wherein said inorganic acid is phosphoric acid and said electrolyte further comprises sulfuric acid.
Claim 34
Dependent Claim
73 words
The process of claim 30, wherein said organic acid is present at a concentration of between about 0.5% and about 30% and said electrolysis is conducted at a voltage of at least about 5 volts, an average current density of between about 0.2 amperes/dm 2 and about 6 amperes/dm 2 , a time of between 0.8 minutes and about 5 minutes, and a temperature of between about -2° C. and about 60° C.
Claim 35
Dependent Claim
73 words
The process of claim 30, wherein said organic acid is present at a concentration of at least about 0.5%, said eiectrolysis is conducted at a voltage of between about 10 volts and about 30 volts, the average current density is between about 0.2 amperes/dm and about 6 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
19 words
The process of claims 32, wherein said organic acid is the condensation product of benzene phosphonic acid and formaldehyde.
Claim 37
Dependent Claim
13 words
The process of claims 32, wherein said organic acid is a phytic acid.
Claim 38
Dependent Claim
13 words
The process of claims 32, wherein said organic acid is polyvinyl phosphonic acid.
Claim 39
Dependent Claim
14 words
The process of claims 32, 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
20 words
The process of claim 39, wherein said sensitizer is a product of the condensation of aromatic 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
13 words
The process of claim 40, wherein said organic acid is polyvinyl phosphonic acid.
Claim 46
Dependent Claim
9 words
The product produced by the process of claim 5.
Claim 47
Dependent Claim
9 words
The product produced by the process of claim 4.
Claim 48
Dependent Claim
9 words
The product produced by the process of claim 16.
Claim 49
Dependent Claim
9 words
The product produced by the process of claim 33.
Claim 50
Dependent Claim
9 words
The product produced by the process of claim 34.
Claim 51
Dependent Claim
9 words
The product produced by the process of claim 39.
Claim 52
Dependent Claim
9 words
The product produced by the process of claim 40.
Claim 53
Dependent Claim
9 words
The product produced by the process of claim 41.
Claim 54
Dependent Claim
9 words
The product produced by the process of claim 42.
Claim 55
Dependent Claim
53 words
A metal article having a substantially nonporous, insoluble metal oxide-organic layer comprising anodic oxide combined with one or more organic acids selected from the group consisting of sulfonic acid, phosphonic acid, organic phosphoric acids; diethylene diamine penta acetic acid, ethylene diamine tetra acetic acid, hydroxyethyl ethylene diamine triacetic acid, and nitrilo triacetic acid.
Claim 56
Dependent Claim
53 words
A metal article having a substantially nonporous, insoluble metal oxide-organic layer comprising anodic oxide combined with one or more organic acids selected from the group consisting of sulfonic acid, phosphonic acid, organic phosphoric acids; diethylene diamine penta acetic acid, ethylene diamine tetra acetic acid, hydroxyethyl ethylene diamine triacetic acid, and nitrilo triacetic acid.
Claim 57
Dependent Claim
51 words
A metal article having a substantially 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 hexyl phosphonic acid and mixtures of these acids.
Claim 58
Dependent Claim
51 words
A metal article having a substantially 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 hexyl phosphonic acid and mixtures of these acids.
Claim 59
Dependent Claim
25 words
The product of claim 54, wherein said article is composed of a metal selected from the group consisting of aluminum and its alloys, and steel.
Claim 60
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 61
Dependent Claim
30 words
The product of claim 57, 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.
References Cited (Backward Citations)
US2578400A
Cited
US2918416A
Cited
US3275537A
Cited
US3307951A
Cited
DE1251616B
Cited
US4153461A
Cited
US3620939A
Cited
US3756826A
Cited
US3844908A
Cited
US3857766A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-05-15 | 1987-11-14 | 1988-05-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-05-15 | 1991-11-14 | 1992-05-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-05-15 | 1995-11-14 | 1996-05-15 | $7700.00 | Window Closed / Lapsed |