US4405427A
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Electrodeposition of coatings on metals to enhance adhesive bonding
Assignee: McDonnell Douglas Corp
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Filing: 1981-11-02
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Granted: 1983-09-20
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Expires: 2001-11-02
Abstract
Abstract The invention is directed to the electrodeposition of a coating of a phosphorylated amide on a metal such as aluminum, and the formation of a chemical bond between the metal and the coating, such amide being in the form of (a) an organic polymer consisting of a poly (phosphinohydrazide), a poly (phosphinoguanide) or a poly (phosphinoureide), including homopolymers and copolymers thereof, and their thio analogs or (b) a 2:1 molar adduct of a nitrogen-containing compound such as hydrazine, guanidine or urea or its thio analog, and an organic phosphite or phosphonate. In the method of electrolytically depositing such coating on the metal substrate, e.g., aluminum, the substrate is employed as the anode in a non-aqueous or aqueous electrolyte containing a phosphorylated amide of the type noted above, e.g., poly (phosphinohydrazide), and electro-depositing a coating on the metal substrate, the organic coating formed being chemically bonded to the substrate, thereby enhancing adhesive bonding to the metal substrate, such coating being strongly bonded to the substrate and being corrosion resistant.
Inventors
- 👤 Norman R. Byrd
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 17:44
CPC Classifications
C; C09; C09D; C09D5/00; C09D5/44; C09D5/4484
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
162 words
A process for enhancing adhesive bonding of a metal substrate, which comprises passing an electric current through a non aqueous or aqueous electrolyte in which a metal substrate is the anode, the metal of said substrate being active and capable of forming an organometallic compound, said electrolyte containing a phosphorylated amide having a labile hydrogen, and capable of generating an anion during electrolysis, said phosphorylated amide being in the form of (a) an organic polymer consisting of a poly (phosphinohydrazide), a poly (phosphinoguanide) or a poly (phosphinoureide), including homopolymers and copolymers thereof, and their thio analogs, or (b) a 2:1 molar adduct of two moles of a nitrogen-containing compound of the group consisting of hydrazine, guanidine and urea, and its thio analog, to one mole of and organic phosphite or phosphonate, and their thio analogs, and electrodepositing a coating of said amide on said metal substrate wherein said anion is reacted with and is chemically bonded to the metal of said substrate.
Claim 2
Dependent Claim
162 words
A process for enhancing adhesive bonding of a metal substrate, which comprises passing an electric current through a non aqueous or aqueous electrolyte in which a metal substrate is the anode, the metal of said substrate being active and capable of forming an organometallic compound, said electrolyte containing a phosphorylated amide having a labile hydrogen, and capable of generating an anion during electrolysis, said phosphorylated amide being in the form of (a) an organic polymer consisting of a poly (phosphinohydrazide), a poly (phosphinoguanide) or a poly (phosphinoureide), including homopolymers and copolymers thereof, and their thio analogs, or (b) a 2:1 molar adduct of two moles of a nitrogen-containing compound of the group consisting of hydrazine, guanidine and urea, and its thio analog, to one mole of and organic phosphite or phosphonate, and their thio analogs, and electrodepositing a coating of said amide on said metal substrate wherein said anion is reacted with and is chemically bonded to the metal of said substrate.
Claim 3
Dependent Claim
22 words
The process as defined in claim 1, wherein said electrolyte is a non-aqueous electrolyte containing an inert organic solvent for said polymer.
Claim 4
Dependent Claim
27 words
The process as defined in claim 2, wherein said electrolyte contains a base capable of forming a salt with the P-H or N-H moiety of said polymer.
Claim 5
Dependent Claim
27 words
The process as defined in claim 2, wherein said organic solvent is selected from the group consisting of dimethylformamide, N-methyl pyrrolidone, tetrahydrofuran, ethylene glycol, and mixtures thereof.
Claim 6
Dependent Claim
45 words
The process as defined in claim 2, wherein said substrate is selected from the group consisting of aluminum, titanium, stainless steel, nickel, silver and copper, and said organic solvent is selected from the group consisting of dimethylformamide, N-methyl pyrrolidone, tetrahydrofuran, ethylene glycol, and mixtures thereof.
Claim 7
Dependent Claim
40 words
The process as defined in claim 5, wherein said current is direct current, said voltage ranging from about 15 to about 50 volts, and wherein said electrodeposition is carried out for a period up to more than about 5 minutes.
Claim 8
Dependent Claim
12 words
The process as defined in claim 6, wherein said substrate is aluminum.
Claim 9
Dependent Claim
14 words
The process as defined in claim 1, wherein said electrolyte is an aqueous electrolyte.
Claim 10
Dependent Claim
14 words
The process as defined in claim 8, wherein said base is an organic amine.
Claim 11
Dependent Claim
151 words
The process as defined in claim 1, wherein said organic polymer has a recurring structural unit having the formula (a), (b) or (c) below, and said adduct has the formula (d) noted below ##STR23## where X is O, S or NH; Y is O or S; and R is selected from the group consisting of H, alkyl containing from about 1 to about 6 carbon atoms, cycloalkyl containing from about 5 to about 7 carbon atoms, aryl containing from about 6 to about 14 carbon atoms, the corresponding halogenated alkyl and aryl groups, nitroaryl containing about 6 to about 14 carbon atoms, heterocyclic containing 5 to 6 members in the heterocyclic nucleus, and O, N or S as hetero atoms, amino, alkylamino containing from about 1 to about 8 carbon atoms in the alkyl group, arylamino containing from about 6 to about 14 carbon atoms, and n is 0 or 1.
Claim 12
Dependent Claim
58 words
The process as defined in claim 10, wherein said phosphorylated amide is a homopolymer or copolymer having the recurring structural unit (a), (b), or (c), and wherein the number of recurrent units in said homopolymers and copolymers can range from 3 to about 20, and the end groups of such homopolymers or copolymers are generally NH 2 groups.
Claim 13
Dependent Claim
20 words
The process as defined in claim 10, wherein said phosphorylated amide is a 2:1 molar adduct having the formula (d).
Claim 14
Dependent Claim
25 words
The process as defined in claim 10, wherein said phosphorylated amide is a poly (phosphinohydrazide) having the recurring structural unit (a), wherein Y is 0.
Claim 15
Dependent Claim
25 words
The process as defined in claim 10, wherein said phosphorylated amide is a poly (phosphinoguanide) having the recurring structural unit (b), wherein Y is 0.
Claim 16
Dependent Claim
25 words
The process as defined in claim 10, wherein said phosphorylated amide is a poly (phosphinoureide) having the recurring structural unit (c), wherein Y is 0.
Claim 17
Dependent Claim
14 words
The process as defined in claim 10, wherein said amide is poly (hydrazyl phosphinate).
Claim 18
Dependent Claim
26 words
A metal substrate containing an organic electrodeposited coating which is chemically bonded to said substrate to enhance adhesive bonding, produced by the process of claim 16.
Claim 19
Dependent Claim
13 words
The process as defined in claim 10, wherein said amide is dihydrazyl phosphinate.
Claim 20
Dependent Claim
15 words
The process as defined in claim 10, wherein said amide is poly (hydrazyl methyl phosphonate).
Claim 21
Dependent Claim
26 words
A metal substrate containing an organic electrodeposited coating which is chemically bonded to said substrate to enhance adhesive bonding, produced by the process of claim 19.
Claim 22
Dependent Claim
12 words
The process as defined in claim 10, wherein said amide is dihydrazylmethylphosphonate.
Claim 23
Dependent Claim
13 words
The process as defined in claim 10, wherein said amide is poly (co-hexamethylenediamine-hydrazylphosphinate).
Claim 24
Dependent Claim
14 words
The process as defined in claim 10, wherein said amide is poly (co-ethylenediamine hydrazylmethylphosphonate).
Claim 25
Dependent Claim
14 words
The process as defined in claim 10, wherein said amide is poly (urea phosphinate).
Claim 26
Dependent Claim
26 words
A metal substrate containing an organic electrodeposited coating which is chemically bonded to said substrate to enhance adhesive bonding, produced by the process of claim 10.
Claim 27
Dependent Claim
25 words
The process as defined in claim 1, wherein said substrate is selected from the group consisting of aluminum, titanium, stainless steel, nickel, silver and copper.
Claim 28
Dependent Claim
23 words
The process as defined in claim 26, wherein said electrodeposition is carried out at voltage ranging from about 1.5 to about 100 volts.
Claim 29
Dependent Claim
16 words
The process as defined in claim 1, wherein said current is direct current or alternating current.
Claim 30
Dependent Claim
23 words
The process as defined in claim 1, wherein said electrodeposition is carried out at voltage ranging from about 1 to about 300 volts.
Claim 31
Dependent Claim
32 words
The process as defined in claim 29, wherein said electrodeposition is carried out for a period up to not more than about 5 minutes, until the current drops to a minimal value.
Claim 32
Dependent Claim
19 words
The process as defined in claim 1, including applying an organic adhesive to said electrodeposited coating on said substrate.
Claim 33
Dependent Claim
14 words
The process as defined in claim 31, wherein said adhesive is an epoxy adhesive.
Claim 34
Dependent Claim
26 words
A metal substrate containing an organic electrodeposited coating which is chemically bonded to said substrate to enhance adhesive bonding, produced by the process of claim 1.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-09-19 | 1987-03-21 | 1987-09-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-09-19 | 1991-03-21 | 1991-09-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-09-19 | 1995-03-21 | 1995-09-20 | $7700.00 | Window Closed / Lapsed |