Sol-gel method for producing an anti-corrosion coating on a metal substrate

Patent metadata

Field	Value
Publication number	US-11519072-B2
Application number	US-201716471966-A
Country	US
Kind code	B2
Filing date	Dec 20, 2017
Priority date	Dec 22, 2016
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

A sol-gel method for producing an anti-corrosion coating consisting of at least one layer of an oxide on a metal substrate. A non-aqueous solution of a precursor of the oxide is prepared and deposited on one surface at least of the metal substrate in order to cover said surface at least partially with a film comprising the precursor of the oxide. Hydrolysis-condensation of the precursor of the oxide is carried out by exposing the film to a humid atmosphere in order to form an oxide network in the film. Then, a treatment for stabilizing the film on the surface of the substrate is carried out, followed by a heat treatment of the surface of the metal substrate in order to crystallize the network of oxide and form the anti-corrosion coating.

First claim

The invention claimed is:

1. A sol-gel method for producing an anti-corrosion coating consisting of at least one layer of an oxide on a metal substrate, with the method successively comprising:
/a/ preparing a non-aqueous solution of a precursor of the oxide;
/b/ depositing the non-aqueous solution on one surface at least of the metal substrate in order to cover said surface of the metal substrate at least partially with a film comprising the precursor of the oxide; and
/c/ carrying out a hydrolysis-condensation of the precursor of the oxide by exposing the film to a humid atmosphere in order to form an oxide network in the film;
/d/ carrying out a treatment for stabilizing the film on the surface of the substrate;
/e/ carrying out a heat treatment of the surface of the metal substrate in order to crystallize the network of oxide and form the anti-corrosion coating;
wherein the step /b/ is carried out by putting the surface into contact with a predetermined volume of solution confined at least partially by a sealed membrane, the sealed membrane being able to slide via translation along the surface, with a controlled displacement of the sealed membrane allowing for the formation of a controlled thickness of film on the surface.

2. The method according to claim 1 , wherein the steps /b/ to /d/ are repeated in order to deposit more than one layer on the metal substrate.

3. The method according to claim 1 , wherein the treatment for stabilizing comprises exposing the film to a flow of gas brought to a temperature greater than an ambient temperature and less than 200° C.

4. The method according to claim 1 , wherein the treatment for stabilizing comprises exposing the film to ultraviolet radiation.

5. The method according to claim 1 , wherein the treatment for stabilizing is chosen from a treatment of the film assisted by microwaves and a treatment of the film by induction, at a temperature greater than an ambient temperature and less than 200° C.

6. The method according to claim 1 , wherein the precursor of the oxide is chosen from a precursor of titanium, a precursor of zirconium, a precursor of chromium, a precursor of yttrium, a precursor of cerium and a precursor of aluminum.

7. The method according to claim 1 , wherein the precursor of the oxide is chosen from: titanium ethoxide, titanium n-propoxide, titanium s-butoxide, titanium n-butoxide, titanium t-butoxide, titanium isobutoxide, titanium isopropoxide, tetrabutyl orthotitanate, tetra-tert-butyl orthotitanate, poly(dibutyltitanate), zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium ethoxide, zirconium 2-methoxymethyl-2-propoxide, zirconium 2-methyl-2-butoxide, zirconium isopropoxide, yttrium isopropoxide, yttrium n-butoxide, titanium methacrylate triisopropoxide, titanium diisopropoxide bis(tetramethylheptanedionate), titanium 2,4-pentanedionate, diisopropoxy-bis(ethylacetoacetato)titanate, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium 2-ethylhexoxide, titanium oxide bis(acetylacetonate), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)oxotitane, titanium bis(ammonium lactato)dihydroxide, zirconium bis(diethyl citrato)dipropoxide, zirconyl propionate, chromium acetate, cerium t-butoxide, cerium methoxyethoxide, aluminum s-butoxide, aluminum n-butoxide, aluminum t-butoxide, yttrium isopropoxide, yttrium butoxide, yttrium acetylacetonate, yttrium 2-methoxyethoxide, aluminum isopropoxide, aluminum ethoxide, aluminum tri-sec-butoxide, aluminum tert-butoxide, cerium isopropoxide.

8. The method according to claim 1 , wherein the solution of the precursor of the oxide comprises for one mole of the precursor of the oxide, 0 to 2 moles of complexing agent and 10 to 50 moles of ethanol.

9. The method according to claim 8 , wherein the solution of the precursor of the oxide further comprises for one mole of the precursor of the oxide up to 0.2 mole of a surfactant.

10. The method according to claim 1 , wherein the step /b/ is implemented by a technique chosen from: a dip-withdraw of the surface in the solution, the withdraw being carried out at a speed between 0.5 mm/s and 20 mm/s; a spraying of the solution onto the surface with a controlled spray flow rate and a controlled relative displacement speed of a sprayer with respect to the surface; an evaporation of the solution in an enclosure containing the surface and under controlled temperature and pressure.

11. The method according to claim 1 , wherein the step /b/ is carried out by putting the surface into contact with a spongy element impregnated with the solution and diffusing the solution via capillarity on the surface.

12. The method according to claim 1 , wherein the surface is an inside surface of a cylindrical substrate, with the sealed membrane being mobile in translation along an axis of the cylindrical substrate.

13. The method according to claim 1 , wherein the steps /b/ to /e/ are implemented on a production line carrying out a relative displacement of the metal substrate with respect to animated modules arranged to carry out the depositing of the solution on the surface, the exposing of the film to a humid atmosphere, the exposing of the film to a treatment for stabilizing and the exposing of the film to a heat treatment.

14. The method according to claim 1 , wherein the heat treatment is carried out at a temperature between 300° C. and 500° C.

Assignees

• Electricite De France
• Univ Sorbonne
• Centre Nat Rech Scient
• College France
• Centre National De La Rech Scientifique—Cnrs—

Inventors

• Astorg Adele
• Crozes Xavier
• Nicole Lionel
• Sanchez Clement

Classifications

• C23C18/1241

  Metallic substrates · CPC title

• C23C18/1254 Primary

  Sol or sol-gel processing · CPC title

• C23C18/1216 Primary

  Metal oxides (C23C18/1212 takes precedence) · CPC title

• C23C18/1279

  performed under reactive atmosphere, e.g. oxidising or reducing atmospheres · CPC title