[go: up one dir, main page]

EP1765522A2 - Method for depositing anti-corrosive coating onto metal surface - Google Patents

Method for depositing anti-corrosive coating onto metal surface

Info

Publication number
EP1765522A2
EP1765522A2 EP05749195A EP05749195A EP1765522A2 EP 1765522 A2 EP1765522 A2 EP 1765522A2 EP 05749195 A EP05749195 A EP 05749195A EP 05749195 A EP05749195 A EP 05749195A EP 1765522 A2 EP1765522 A2 EP 1765522A2
Authority
EP
European Patent Office
Prior art keywords
metal
metal oxide
layer
coating according
metal hydroxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05749195A
Other languages
German (de)
French (fr)
Other versions
EP1765522A4 (en
Inventor
Gregory Pipko
Asher Vitner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PIGMENTAN LTD
Original Assignee
Pigmentan Anticorrosive Pigments for Paints Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pigmentan Anticorrosive Pigments for Paints Ltd filed Critical Pigmentan Anticorrosive Pigments for Paints Ltd
Publication of EP1765522A2 publication Critical patent/EP1765522A2/en
Publication of EP1765522A4 publication Critical patent/EP1765522A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon

Definitions

  • the invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface.
  • the invention further provides a stable anti-corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide.
  • the corrosion protective element in paints is generally an anti-corrosive pigment (a corrosion inhibitor) based on cliromates. These pigments usually include heavy metals salts, which hinder the corrosion of the metal surface. Zinc compounds such as zinc phosphate and zinc chromate are currently widely used as anti-corrosive pigments. Zinc is a heavy metal element and is considered to be toxic at certain concentrations. Due to the growing awareness of the environmental damage associated with heavy metal products, there is an industrial need for effective anti-corrosive coating methods based on non heavy metals, non-toxic agents.
  • this invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface including the step of contacting the metal surface with a mixture including, inter alia, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide, thereby depositing the metal oxide and/or the metal hydroxide layer onto the metal surface.
  • this invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface including the step of contacting the metal surface with a mixture including, inter alia, an organic amine, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide, thereby depositing the metal oxide and/or the metal hydroxide layer onto the metal surface.
  • this invention provides a stable anti- corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby the layer is obtained by contacting the surface of the object with a mixture including, inter alia, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide.
  • this invention provides a stable anti-corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby the layer is obtained by contacting the surface of the object with a mixture including, inter alia, an organic amine, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide.
  • Figure 1 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe reference sample, according to embodiments of the invention
  • Figure 2 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%, according to embodiments of the invention
  • Figure 3 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%+ZnP 3%, according to embodiments of the invention
  • Figure 4 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%+ZnCr
  • Figure 5 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%+E 3%, according to embodiments of the invention
  • Figure 6 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%+M 3%, according to embodiments of the invention
  • Figure 7 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum reference sample, according to embodiments of the invention
  • Figure 8 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum sample after 14 days in NaCl
  • Figure 9 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum sample after 14 days in NaCl
  • Figure 10 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum sample after 14 days in NaCl
  • Figure 11 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum sample after 14 days in NaCl
  • this invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface including the step of contacting the metal surface with a mixture including, inter alia, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide, thereby depositing the metal oxide and/or the metal hydroxide layer onto the metal surface.
  • this invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface including the step of contacting the metal surface with a mixture including, inter alia, an organic amine, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide, thereby depositing the metal oxide and/or the metal hydroxide layer onto the metal surface.
  • this invention provides a stable anti- corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby the layer is obtained by contacting the surface of the object with a mixture including, inter alia, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide.
  • this invention provides a stable anti-corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby the layer is obtained by contacting the surface of the object with a mixture including, inter alia, an organic amine, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide.
  • the organic amine and the phosphoric acid and/or inorganic phosphate may react to form an organic phosphate.
  • the organic phosphate may react with the metal oxide and/or metal hydroxide to form oxiaminophosphate.
  • the oxiaminophosphate is an oxiaminophosphate of a metal.
  • the metal magnesium is another embodiment of the organic phosphate.
  • the mixture may include, inter alia, 1-5 % of oxiaminophosphate. In another embodiment, the mixture may include, inter alia, 1-3 % of oxiaminophosphate. In another embodiment, the mixture may include, inter alia, 3-5 % of oxiaminophosphate. In another embodiment, the mixture may include, inter alia, 3 % of oxiaminophosphate.
  • the oxiaminophosphate is obtained by adding phosphoric acid and/or inorganic phosphate (4-20%) to water (60-80%) containing an organic amine (2-10%) and then adding metal oxide and/or metal hydroxide (6-25%).
  • phosphoric acid and/or inorganic phosphate are added to water. In another embodiment, 5-15 % of phosphoric acid and/or inorganic phosphate are added to water. In another embodiment, the water contains 2-5% of organic amine. In another embodiment, the water contains 3-7 % of organic amine. In another embodiment, 6-10 % of metal oxide and/or metal hydroxide are added to the water. In another embodiment, 10-15 % of metal oxide and/or metal hydroxide are added to the water. In another embodiment, 15-25 % of metal oxide and/or metal hydroxide are added to the water.
  • the organic amine may be, inter alia, a quaternary amine.
  • the organic amine may be, inter alia, morpholine, dicyclohexylamine, ethanolamine, an aliphatic amine, an aromatic amine, melamine, hexamethylentetramine, pentamethylentetramine or any combination thereof.
  • the ethanolamine may be mono, di or tri ethanolamine, or any combination thereof.
  • the compound selected from the group consisting of a metal oxide and a metal hydroxide may be formed in solution by adding a base to a metal salt solution.
  • the metal of the metal oxide and/or metal hydroxide may be, inter alia, magnesium, calcium, iron, zinc, molybdenum, aluminum or any combination thereof.
  • the metal may be, inter alia, magnesium.
  • the metal oxide may be, inter alia, MgO.
  • the metal hydroxide may be, inter alia, Mg(OH) 2 .
  • the mixture may be, inter alia, a solution, emulsion suspension or slurry. In another embodiment, the mixture may be, inter alia, an aqueous mixture.
  • the thickness of the layer may be between 1-100 nm (nanometer). In another embodiment, the thickness of the layer may be between 5-60 nm. In another embodiment, the thickness of the layer may be between 10-50 nm. In another embodiment, the thickness of the layer may be between 10-20 nm.
  • the mixture may further include, inter alia, surface active agent, anti-corrosive agents, bactericides, colorants, or a combination thereof.
  • the metal surface may include, inter alia, iron, magnesium, aluminum or any combination thereof.
  • the metal object may include, inter alia, iron, magnesium, aluminum or any combination thereof.
  • the metal object may be, inter alia, a metal plate or a metal sheet.
  • the thickness of the oxide layer was approximately 7 nm (Fig. 1).
  • E represents an oxyaminophosphate of magnesium which was prepared by adding phosphoric acid (4-20%) to water (60-80%) containing monoethanol amine (2-10%) and then adding MgO (6-25 %).
  • Mg cone. 12.19%) having a thickness of approximately 12 nm and low amounts (relative to sample 2) of iron oxide layer having a thickness of approximately 7 nm.
  • phosphorous 7.99%
  • carbon 9.79%)
  • Na 2.30%)
  • Cl 1.37%
  • M represents an oxyaminophosphate of magnesium which was prepared by adding phosphoric acid (4-20%) to water (60-80%) containing melamine (2-10%) and then adding MgO (6-25%).
  • Example 2 Aluminum samples
  • the depth profile shows a layer of aluminum oxide and/or hydroxide on the surface area having a thickness of approximately 8 nm having a distinctive border with the aluminum (Fig. 7).
  • the depth profile shows a layer of aluminum oxide and/or hydroxide on the surface area having a thickness of approximately 12 nm having a distinctive border with the aluminum.
  • Zinc was found through a 2 nm depth from the surface area and phosphorous was found through a 5 nm depth from the surface area. Even though 13% of cliromium is present on the surface area, its concentration at a depth of 2 nm is about 1%. The results show that a 2 nm layer of chromate was formed (Fig. 9)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface. The invention further provides a stable anti-corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide.

Description

METHODS FOR ANTI-CORROSIVE COATING
FIELD OF THE INVENTION [001] The invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface. The invention further provides a stable anti-corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide.
BACKGROUND OF THE INVENTION [002] Every year about 5% of iron products worldwide are being replaced due to corrosion. Various coating methods are used to reduce the corrosion damage, most of which methods are based on applying paints. The corrosion protective element in paints is generally an anti-corrosive pigment (a corrosion inhibitor) based on cliromates. These pigments usually include heavy metals salts, which hinder the corrosion of the metal surface. Zinc compounds such as zinc phosphate and zinc chromate are currently widely used as anti-corrosive pigments. Zinc is a heavy metal element and is considered to be toxic at certain concentrations. Due to the growing awareness of the environmental damage associated with heavy metal products, there is an industrial need for effective anti-corrosive coating methods based on non heavy metals, non-toxic agents.
SUMMARY OF THE INVENTION [003] In one embodiment, this invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface including the step of contacting the metal surface with a mixture including, inter alia, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide, thereby depositing the metal oxide and/or the metal hydroxide layer onto the metal surface.
[004] In another embodiment, this invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface including the step of contacting the metal surface with a mixture including, inter alia, an organic amine, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide, thereby depositing the metal oxide and/or the metal hydroxide layer onto the metal surface.
[005] Furthermore, in another embodiment, this invention provides a stable anti- corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby the layer is obtained by contacting the surface of the object with a mixture including, inter alia, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide.
[006] In another embodiment, this invention provides a stable anti-corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby the layer is obtained by contacting the surface of the object with a mixture including, inter alia, an organic amine, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe reference sample, according to embodiments of the invention;
Figure 2 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%, according to embodiments of the invention; Figure 3 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%+ZnP 3%, according to embodiments of the invention;
Figure 4 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%+ZnCr
3%, according to embodiments of the invention;
Figure 5 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%+E 3%, according to embodiments of the invention;
Figure 6 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of a Fe sample after 14 days in NaCl 5%+M 3%, according to embodiments of the invention;
Figure 7 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum reference sample, according to embodiments of the invention;
Figure 8 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum sample after 14 days in NaCl
5%+ZnP 3%, according to embodiments of the invention;
Figure 9 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum sample after 14 days in NaCl
5%+ZnCr 3%, according to embodiments of the invention;
Figure 10 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum sample after 14 days in NaCl
5%+E 3%, according to embodiments of the invention;
Figure 11 shows an Auger spectrum (left); a depth profile chart (middle); and an element concentration table (right) of an aluminum sample after 14 days in NaCl
5%+M 3%, according to embodiments of the invention;
DETAILED DESCRIPTION OF THE INVENTION [007] In one embodiment, this invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface including the step of contacting the metal surface with a mixture including, inter alia, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide, thereby depositing the metal oxide and/or the metal hydroxide layer onto the metal surface.
[008] In another embodiment, this invention provides a method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface including the step of contacting the metal surface with a mixture including, inter alia, an organic amine, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide, thereby depositing the metal oxide and/or the metal hydroxide layer onto the metal surface.
[009] Furthermore, in another embodiment, this invention provides a stable anti- corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby the layer is obtained by contacting the surface of the object with a mixture including, inter alia, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide.
[0010] In another embodiment, this invention provides a stable anti-corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby the layer is obtained by contacting the surface of the object with a mixture including, inter alia, an organic amine, a phosphoric acid and/or an inorganic phosphate and a metal oxide and/or a metal hydroxide.
[0011] In one embodiment of the invention, the organic amine and the phosphoric acid and/or inorganic phosphate may react to form an organic phosphate.
[0012] In one embodiment of the invention, the organic phosphate may react with the metal oxide and/or metal hydroxide to form oxiaminophosphate. In another embodiment, the oxiaminophosphate is an oxiaminophosphate of a metal. In another embodiment, the metal magnesium.
[0013] In one embodiment of the invention, the mixture may include, inter alia, 1-5 % of oxiaminophosphate. In another embodiment, the mixture may include, inter alia, 1-3 % of oxiaminophosphate. In another embodiment, the mixture may include, inter alia, 3-5 % of oxiaminophosphate. In another embodiment, the mixture may include, inter alia, 3 % of oxiaminophosphate. [0014] In another embodiment of the invention, the oxiaminophosphate is obtained by adding phosphoric acid and/or inorganic phosphate (4-20%) to water (60-80%) containing an organic amine (2-10%) and then adding metal oxide and/or metal hydroxide (6-25%). In another embodiment, 4-10 % of phosphoric acid and/or inorganic phosphate are added to water. In another embodiment, 5-15 % of phosphoric acid and/or inorganic phosphate are added to water. In another embodiment, the water contains 2-5% of organic amine. In another embodiment, the water contains 3-7 % of organic amine. In another embodiment, 6-10 % of metal oxide and/or metal hydroxide are added to the water. In another embodiment, 10-15 % of metal oxide and/or metal hydroxide are added to the water. In another embodiment, 15-25 % of metal oxide and/or metal hydroxide are added to the water.
[0015] In one embodiment of the invention, the organic amine may be, inter alia, a quaternary amine. In another embodiment, the organic amine may be, inter alia, morpholine, dicyclohexylamine, ethanolamine, an aliphatic amine, an aromatic amine, melamine, hexamethylentetramine, pentamethylentetramine or any combination thereof. In another embodiment, the ethanolamine may be mono, di or tri ethanolamine, or any combination thereof.
[0016] In one embodiment of the invention, the compound selected from the group consisting of a metal oxide and a metal hydroxide may be formed in solution by adding a base to a metal salt solution.
[0017] In one embodiment of the invention, the metal of the metal oxide and/or metal hydroxide may be, inter alia, magnesium, calcium, iron, zinc, molybdenum, aluminum or any combination thereof. In another embodiment, the metal may be, inter alia, magnesium. In another embodiment, the metal oxide may be, inter alia, MgO. In another embodiment, the metal hydroxide may be, inter alia, Mg(OH)2.
[0018] In one embodiment of the invention, the mixture may be, inter alia, a solution, emulsion suspension or slurry. In another embodiment, the mixture may be, inter alia, an aqueous mixture.
[0019] In one embodiment of the invention, the thickness of the layer may be between 1-100 nm (nanometer). In another embodiment, the thickness of the layer may be between 5-60 nm. In another embodiment, the thickness of the layer may be between 10-50 nm. In another embodiment, the thickness of the layer may be between 10-20 nm.
[0020] In one embodiment of the invention, the mixture may further include, inter alia, surface active agent, anti-corrosive agents, bactericides, colorants, or a combination thereof.
[0021] In one embodiment of the invention, the metal surface may include, inter alia, iron, magnesium, aluminum or any combination thereof. In another embodiment, the metal object may include, inter alia, iron, magnesium, aluminum or any combination thereof. In another embodiment, the metal object may be, inter alia, a metal plate or a metal sheet.
EXPERIMENTAL SECTION
[0022] Surface analysis was performed using Auger Electron Spectroscopy (AES) on samples of steel and aluminum that were treated with solutions of 5% NaCl.
Example 1: Steel samples
[0023] Samples of steel were immersed in solutions of 5% NaCl with or without corrosion inhibitors for a period of two weeks and were then removed and washed with treated water. Surface analysis was performed using Auger electron spectroscopy.
Sample 1: Reference sample
No NaCl treatment was performed prior to analysis.
Iron oxide, silicon (2.65%), Na (7.56%) and carbon (9.76%), were detected on the surface area. The thickness of the oxide layer was approximately 7 nm (Fig. 1).
Sample 2:
NaCl treatment, no corrosion inhibitors were added to NaCl solution.
Iron oxide, Cl (0.71%), carbon (2.82%), were detected on the surface area. The thickness of the oxide layer was over 50 nm (Fig. 2). Sample 3:
NaCl treatment, ZnP 3% wt were added to NaCl solution.
Iron oxide, Cl (0.5%) and carbon (10.8%) and Na (5.96%), were detected on the surface area. No phosphorous and zinc were detected on the surface area. Oxygen were detected up to a depth of 90 nm, indicating corrosion (Fig. 3).
Sample 4:
NaCl treatment, ZnCr 3% wt were added to NaCl solution.
Chromium oxide, Zn (38.08%), carbon (3.54%) and Cl (9.86%), were detected on the surface area. The thickness of the chromium and zinc oxide layer was approximately 20 nm (Fig. 4).
Sample 5:
NaCl treatment, E 3% wt were added to NaCl solution.
Unexpected results showed a magnesium oxide layer (Mg cone. = 21.26%) having a thickness of approximately 15 nm and low amounts (relative to sample 2) of iron oxide layer having a thickness of approximately 8 nm. In addition, phosphorous (6.71%), carbon (7.57%) and Cl (2.17%), were detected on the surface area (Fig. 5).
"E", as referred to herein represents an oxyaminophosphate of magnesium which was prepared by adding phosphoric acid (4-20%) to water (60-80%) containing monoethanol amine (2-10%) and then adding MgO (6-25 %).
Sample 6:
NaCl treatment, M 3% wt were added to NaCl solution.
Unexpected results showed a magnesium oxide layer (Mg cone. = 12.19%) having a thickness of approximately 12 nm and low amounts (relative to sample 2) of iron oxide layer having a thickness of approximately 7 nm. In addition, phosphorous (7.99%), carbon (9.79%), Na (2.30%) and Cl (1.37%), were detected on the surface area (Fig. 6). "M", as referred to herein represents an oxyaminophosphate of magnesium which was prepared by adding phosphoric acid (4-20%) to water (60-80%) containing melamine (2-10%) and then adding MgO (6-25%).
Example 2: Aluminum samples
[0024] Samples of aluminum were immersed in solutions of 5% NaCl with or without corrosion inhibitors for a period of two weeks and were then removed and washed with treated water. Surface analysis was performed using Auger electron spectroscopy.
Sample 7: Reference sample
No NaCl treatment was performed prior to analysis.
Aluminum (29.5%), phosphorous (about 2%), carbon (about 14%) and oxygen (about 54%) were detected on the surface area. The depth profile shows a layer of aluminum oxide and/or hydroxide on the surface area having a thickness of approximately 8 nm having a distinctive border with the aluminum (Fig. 7).
Sample 8:
NaCl treatment, ZnP 3% wt were added to NaCl solution.
Aluminum (about 10%), silicon (about 7%), phosphorous (about 6%), Cl (about 0.7%), oxygen (about 66%) and zinc (about 3%) were detected on the surface area. The depth profile shows a layer of aluminum oxide and/or hydroxide on the surface area having a thickness of over 30 nm having no distinctive border with the aluminum. The results show that corrosion of the aluminum was formed. Zinc was found through a 2 nm depth from the surface area and phosphorous was found through a 6 nm depth from the surface area, showing that the ZnP does not provide a sufficient protection to the surface area. (Fig. 8) Sample 9:
NaCl treatment, ZnCr 3% wt were added to NaCl solution.
Aluminum (about 6.5%), phosphorous (about 4%), carbon (about 13%), Cl (about 2%), oxygen (about 56%), chromium (about 13%), and zinc (about 4%) were detected on the surface area. The depth profile shows a layer of aluminum oxide and/or hydroxide on the surface area having a thickness of approximately 12 nm having a distinctive border with the aluminum. Zinc was found through a 2 nm depth from the surface area and phosphorous was found through a 5 nm depth from the surface area. Even though 13% of cliromium is present on the surface area, its concentration at a depth of 2 nm is about 1%. The results show that a 2 nm layer of chromate was formed (Fig. 9)
Sample 10:
NaCl treatment, E 3% wt were added to NaCl solution.
Aluminum (about 0.7%), phosphorous (about 10%), carbon (about 2%), Cl (about 0.3%>), oxygen (about 49%) and magnesium (about 38%) were detected on the surface area. The depth profile and the surface analysis show that two layers were formed: one layer comprising oxidized aluminum, oxidized magnesium and phosphorous, the tliickness of which layer is approximately 15 nm; and a second layer comprised of aluminum oxide of about 15 micron depth from the surface area (Fig. 10). Sample 11 :
NaCl treatment, M 3% wt were added to NaCl solution.
Aluminum (about 24%), phosphorous (about 14%), carbon (about 10%), Cl (about 0.4%), oxygen (about 45%) and magnesium (about 5%>) were detected on the surface area. The depth profile that a layer of aluminum oxide, which comprises also magnesium and phosphorous is forrned on the surface area. Phosphorous was found through a 5 nm depth from the surface area. The overall thickness of the oxide layer is approximately 15 nm (Fig. 11).
[0025] It will be appreciated that the present invention is not limited by what has been described hereinabove and that numerous modifications, all of which fall within the scope of the present invention, exist. Rather the scope of the invention is defined by the claims that follow:

Claims

What we claim is: 1. A method for depositing a stable anti-corrosive metal oxide and/or metal hydroxide layer onto a metal surface comprising the step of: contacting said metal surface with a mixture comprising: an organic amine; a phosphoric acid and/or an inorganic phosphate; and a metal oxide and/or a metal hydroxide, thereby depositing said metal oxide and/or said metal hydroxide layer onto said metal surface.
2. The method according to claim 1, wherein said organic amine and said phosphoric acid and/or said inorganic phosphate react to form an organic phosphate.
3. The method according to claim 2, wherein said organic phosphate reacts with said metal oxide and/or said metal hydroxide to form oxiaminophosphate.
4. The method according to claim 1, wherein said organic amine is a quaternary amine.
5. The method according to claim 1, wherein said organic amine is morpholine, dicyclohexylamine, ethanolamine, an aliphatic amine, an aromatic amine, melamine, hexamethylentetramine, pentamethylentetramine or any combination thereof.
6. The method according to claim 5, wherein said ethanolamine is a mono, di or tri ethanolamine or any combination thereof.
7. The method according to claim 1, wherein said metal oxide and/or said metal hydroxide is formed in solution by adding a base to a metal salt solution.
8. The method according to claim 1, wherein said metal of said metal oxide and/or said metal hydroxide is magnesium, calcium, iron, zinc, molybdenum, aluminum or any combination thereof.
9. The method according to claim 8, wherein said metal is magnesium.
10. The method according to claim 1, wherein said metal oxide is MgO.
11. The method according to claim 1, wherein said metal hydroxide is Mg(OH)2.
12. The method according to claim 1, wherein said mixture is a solution, emulsion suspension or slurry.
13. The method according to claim 12, wherein said mixture is an aqueous mixture.
14. The method according to claim 1, wherein the thickness of said layer is between 1-100 nm.
15. The method according to claim 1, wherein the thickness of said layer is between 5-60 nm.
16. The method according to claim 1, wherein said metal surface comprises iron, magnesium, aluminum or any combination thereof.
17. The method according to claim 1, wherein said mixture further comprising surface active agent, anti-corrosive agents, bactericides, colorants, or a combination thereof.
18. A stable anti-corrosive coating layer on a metal object, which layer comprises metal oxide and/or metal hydroxide whereby said layer is obtained by contacting the surface of said object with a mixture comprising: an organic amine; a phosphoric acid and/or an inorganic phosphate; and a metal oxide and/or a metal hydroxide.
19. The coating according to claim 18, wherein said organic amine and said phosphoric acid and/or said inorganic phosphate react to form an organic phosphate.
20. The coating according to claim 19, wherein said organic phosphate reacts with said metal oxide and/or said metal hydroxide to form oxiaminophosphate.
21. The coating according to claim 18, wherein said organic amine is a quaternary amine.
22. The coating according to claim 18, wherein said organic amine is morpholine, dicyclohexylamine, ethanolamine, an aliphatic amine, an aromatic amine, melamine, hexamethylentetramine, pentamethylentetramine or any combination thereof.
23. The method according to claim 22, wherein said ethanolamine is a mono, di or tri ethanolamine or any combination thereof.
24. The coating according to claim 18, wherein said metal oxide and/or said metal hydroxide is formed in solution by adding a base to a metal salt solution.
25. The coating according to claim 18, wherein said metal of said metal oxide and/or said metal hydroxide is magnesium, calcium, iron, zinc, molybdenum, aluminum or any combination thereof.
26. The coating according to claim 25, wherein said metal is magnesium.
27. The coating according to claim 18, wherein said metal oxide is MgO.
28. The coating according to claim 18, wherein said metal hydroxide is Mg(OH)2.
29. The coating according to claim 18, wherein said mixture is a solution, emulsion suspension or slurry.
30. The coating according to claim 29, wherein said mixture is an aqueous mixture.
31. The coating according to claim 18, wherein the thickness of said layer is between 1-100 nm.
32. The coating according to claim 18, wherein the thickness of said layer is between 5-60 nm.
33. The coating according to claim 18, wherein said metal object comprises iron, magnesium, aluminum or any combination thereof.
34. The coating according to claim 18, wherein said mixture further comprising surface active agent, anti-corrosive agents, bactericides, colorants, or a combination thereof.
35. The coating according to claim 18, wherein said metal object is a metal plate or a metal sheet.
EP05749195A 2004-06-14 2005-06-14 Method for depositing anti-corrosive coating onto metal surface Withdrawn EP1765522A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US57885304P 2004-06-14 2004-06-14
PCT/IL2005/000623 WO2005120722A2 (en) 2004-06-14 2005-06-14 Method for depositing anti-corrosive coating onto metal surface

Publications (2)

Publication Number Publication Date
EP1765522A2 true EP1765522A2 (en) 2007-03-28
EP1765522A4 EP1765522A4 (en) 2011-01-26

Family

ID=35503687

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05749195A Withdrawn EP1765522A4 (en) 2004-06-14 2005-06-14 Method for depositing anti-corrosive coating onto metal surface

Country Status (4)

Country Link
US (1) US20080020145A1 (en)
EP (1) EP1765522A4 (en)
CN (1) CN101006142B (en)
WO (1) WO2005120722A2 (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1817441B1 (en) * 2004-11-29 2016-01-20 Pigmentan Ltd Methods of preventing corrosion
US20080302267A1 (en) * 2007-06-05 2008-12-11 Defalco Frank G Compositions and processes for deposition of metal ions onto surfaces of conductive substrates
WO2009152330A1 (en) 2008-06-12 2009-12-17 Latitude 18, Inc Inorganic phosphate resins and method for their manufacture
EP2510134B1 (en) * 2009-12-11 2018-09-19 Latitude 18, Inc. Inorganic phosphate corrosion resistant coatings
JP6134140B2 (en) 2009-12-11 2017-05-24 ラティテュード・１８，インコーポレイテッド Inorganic phosphate compositions and methods
US20130139930A1 (en) * 2009-12-18 2013-06-06 Latitude 18, Inc. Inorganic phosphate corrosion resistant coatings
WO2011075712A2 (en) * 2009-12-18 2011-06-23 Latitude 18, Inc. Inorganic phosphate corrosion resistant coatings
EP2519326A4 (en) * 2009-12-30 2016-08-24 3M Innovative Properties Co Filtering face-piece respirator having an auxetic mesh in the mask body
CA2789156A1 (en) 2010-02-09 2011-08-18 Latitude 18, Inc. Phosphate bonded composites and methods
CN102114463B (en) * 2011-03-02 2013-08-07 康海燕 Method for reducing tritium accumulation on oxide coating
CN105121381B (en) * 2013-02-15 2018-01-30 18纬度有限公司 Inorganic phosphate ceramics and coating
US20150120870A1 (en) * 2013-10-25 2015-04-30 Joseph Schuman Media distribution network, associated program products, and methods of using the same
CN107685008A (en) * 2017-09-26 2018-02-13 江苏固格澜栅防护设施有限公司 A kind of guardrail wires face coat means of defence
GB2572764B (en) * 2018-04-09 2023-06-07 Applied Graphene Mat Uk Ltd Corrosion protection for metallic substrates

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2564478A1 (en) * 1984-05-21 1985-11-22 Borsodi Vegyi Komb Aqueous corrosion inhibitor additives and process for their preparation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1109080A (en) * 1994-03-21 1995-09-27 金强 Water-soluble inorganic corrosionproof coating
CN1110699A (en) * 1995-01-16 1995-10-25 梅振祥 Rust-proof paint filler
IL120399A (en) * 1997-03-09 2003-07-31 Pigmentan Anticorrosive Pigmen Anticorrosive pigments
KR100567176B1 (en) * 1999-10-22 2006-04-03 제이에프이 스틸 가부시키가이샤 Metal surface treatment compositions and surface treatment metal materials
IL143551A0 (en) * 2001-06-04 2002-04-21 Pigmentan Ltd Paints and coatings composition useful for corrosion inhibition and a method for production therefor

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2564478A1 (en) * 1984-05-21 1985-11-22 Borsodi Vegyi Komb Aqueous corrosion inhibitor additives and process for their preparation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO2005120722A2 *

Also Published As

Publication number Publication date
US20080020145A1 (en) 2008-01-24
CN101006142A (en) 2007-07-25
WO2005120722A3 (en) 2006-01-26
CN101006142B (en) 2011-03-30
WO2005120722A2 (en) 2005-12-22
EP1765522A4 (en) 2011-01-26

Similar Documents

Publication Publication Date Title
US20080020145A1 (en) Method For Depositing Anti-Corrosive Coating Onto Metal Surface
Vukasovich et al. Molybdate in corrosion inhibition—A review
Guan et al. Corrosion protection of aluminum alloy 2024-T3 by vanadate conversion coatings
KR100531395B1 (en) Corrosion resistant trivalent chromium phosphated chemical conversion coatings
CA2074334A1 (en) Corrosion inhibition with water soluble rare earth chelates
Zehra et al. Chromates as corrosion inhibitors
BR102017019549A2 (en) METHOD OF ARRANGING A SUBSTRATE RESISTANT SYSTEM, CORROSION INHIBITOR SYSTEM DISPOSED IN A SUBSTRATE, AND CHEMICAL CONVERSION COATING SOLUTION
Ali Inhibition of mild steel corrosion in cooling systems by low-and non-toxic corrosion inhibitors
Heller et al. Chemical and structural analyses of subsurface crevices formed during spontaneous deposition of cerium-based conversion coatings
MXPA06004033A (en) Formulation for corrosion and scale inhibition.
CN104388942B (en) Steel rust inhibitor and preparation method thereof
US8845930B2 (en) Methods of preventing corrosion
IE49550B1 (en) Protective compositions for steel surfaces
Guo et al. Corrosion inhibition of magnesium (Mg) Alloys
IL180093A (en) Method for depositing anti-corrosive coating onto metal surface
US20090170817A1 (en) Corrosion inhibition
Amadeh et al. The use of rare earth cations as corrosion inhibitors for carbon steel in aerated NaCl solution
Markley et al. Multifunctional rare earth organic corrosion inhibitors
JP2004516387A (en) Corrosion inhibition methods suitable for use in drinking water
Kuznetsov Corrosion inhibitors in conversion coatings. III
JP4237853B2 (en) Corrosion inhibitor and corrosion prevention method for ferrous metals in cooling water system
EP1888815B1 (en) Organic compound and process for inhibiting corrosion on metallic surfaces
Raimbekova et al. Effect of various phosphate inhibitors on corrosion of low carbon steel in 3% sodium chloride solution
JPS59173277A (en) Method of controlling scale deposition on metal surface and/or corrosion of metal surface
JPS59193282A (en) Metal surface condition control

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20061220

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: VITNER, ASHER

Inventor name: PIPKO, GREGORY

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20101223

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 22/66 20060101ALI20101217BHEP

Ipc: B05D 5/00 20060101AFI20051229BHEP

Ipc: C23C 22/68 20060101ALI20101217BHEP

Ipc: C23F 11/167 20060101ALI20101217BHEP

Ipc: C09C 1/02 20060101ALI20101217BHEP

Ipc: C23C 22/62 20060101ALI20101217BHEP

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: PIGMENTAN LTD

17Q First examination report despatched

Effective date: 20110715

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120619