EP3243928A1 - Traitement de revêtement de conversion - Google Patents

Traitement de revêtement de conversion Download PDF

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Publication number
EP3243928A1
EP3243928A1 EP17170451.3A EP17170451A EP3243928A1 EP 3243928 A1 EP3243928 A1 EP 3243928A1 EP 17170451 A EP17170451 A EP 17170451A EP 3243928 A1 EP3243928 A1 EP 3243928A1
Authority
EP
European Patent Office
Prior art keywords
composition
substrate
container
chamber
kit
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Withdrawn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
EP17170451.3A
Other languages
German (de)
English (en)
Inventor
Blair Smith
Mark R. Jaworowski
Weilong Zhang
Michael A. Kryzman
Bart Antonie Van Hassel
Georgios S. Zafiris
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.)
Hamilton Sundstrand Corp
Original Assignee
Hamilton Sundstrand Corp
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 Hamilton Sundstrand Corp filed Critical Hamilton Sundstrand Corp
Publication of EP3243928A1 publication Critical patent/EP3243928A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K5/00—Pens with ink reservoirs in holders, e.g. fountain-pens
    • B43K5/18—Arrangements for feeding the ink to the nibs
    • B43K5/1818—Mechanical feeding means, e.g. valves; Pumps
    • B43K5/1827—Valves
    • B43K5/1836—Valves automatically closing
    • B43K5/1845—Valves automatically closing opened by actuation of the writing point
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43M—BUREAU ACCESSORIES NOT OTHERWISE PROVIDED FOR
    • B43M11/00—Hand or desk devices of the office or personal type for applying liquid, other than ink, by contact to surfaces, e.g. for applying adhesive
    • B43M11/06—Hand-held devices
    • B43M11/08—Hand-held devices of the fountain-pen type
    • 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
    • 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
    • C23C22/73—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 characterised by the process
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • This disclosure relates to coatings for corrosion protection, and more specifically to conversion coatings for corrosion protection of metal substrates.
  • conversion coatings have been used to protect metals such as aluminum, zinc, cadmium, tin, magnesium, iron, copper, silver, and their alloys such as zinc-nickel, tin-zinc, etc.
  • Conversion coating compositions have been commonly applied to large surface area substrates by immersion or spray application. Such techniques, however, can be cumbersome for touch-up application such as to repair abraded surfaces or at connection interfaces between assembled metal components.
  • Small scale handheld application of conversion coatings has been performed with felt pen-style applicators.
  • chromate conversion coatings utilizing hexavalent chromium have been effectively used to provide corrosion protection. However, the use of hexavalent chromium is largely in the process of being discontinued due to toxicity concerns.
  • Touch-up conversion coatings based on trivalent chromium have been applied with felt pen-style applicators; however, such trivalent conversion coatings have been found to be less effective at preventing corrosion than conversion coatings based on hexavalent chromium.
  • a kit for applying a coating comprises a first handheld container comprises a first liquid composition disposed therein that comprises a trivalent chromium salt.
  • a first applicator is disposed in fluid communication with the first container and is configured to dispense the first composition.
  • the kit also includes a second handheld container comprises a second liquid composition disposed therein comprising an oxidizing agent.
  • a second applicator is disposed in fluid communication with the second container and is configured to dispense the second composition.
  • a method of using the above-described kit comprises applying a coating of the first composition to a substrate, allowing a drying period of time to pass, applying the second composition to the coated substrate, and maintaining a wet layer of the second composition on the coated substrate for at least 0.5 minutes.
  • a method of protecting a trivalent chromium conversion-coated substrate from corrosion comprises contacting the substrate with a porous pad disposed on an end of an oblong handheld housing in fluid communication with a chamber disposed within the housing, and dispensing a liquid composition comprising an oxidizing agent disposed in the chamber onto the substrate through the porous pad.
  • FIG. 1 schematically depicts an example embodiment of a kit for applying a conversion coating.
  • a first container in the form of housing 10a has a liquid composition comprising a trivalent chromium salt disposed in chamber 11a formed by the housing 10a and barrier 12a.
  • a second container in the form of housing 10b has a liquid composition comprising an oxidizing agent disposed in chamber 11b formed by the housing 10b and barrier 12b.
  • the housings 10a and 10b can be configured in various shapes, sizes, and forms in order to facilitate being held by hand during use. In some embodiments, the housings are configured in an oblong configuration as depicted in FIG. 1 .
  • an oblong housing can have a maximum linear dimension in a cross-sectional plane perpendicular to the longest oblong axis in ranges having a lower endpoint of 5 mm, more specifically 10 mm, and even more specifically 15 mm, and an upper endpoint of 50 mm, more specifically 40 mm, more specifically 30 mm, and even more specifically 25 mm.
  • an oblong housing can be configured as a cylinder. Such embodiments can also be referred to as a "coating pen” or "coating pens”.
  • the cylinder can have a diameter in ranges having a lower endpoint of 5 mm, more specifically 10 mm, and even more specifically 15 mm, and an upper endpoint of 50 mm, more specifically of 40 mm, more specifically 30 mm, and even more specifically 25 mm.
  • the above upper and lower endpoints can be independently combined to disclose various different ranges.
  • the trivalent chromium salt composition can be an aqueous solution or a non-aqueous solution comprising trivalent chromium and various anions.
  • exemplary anions include nitrate, sulfate, phosphate, and/or acetate.
  • Specific exemplary trivalent chromium salts can include Cr 2 (SO 4 ) 3 , (NH) 4 Cr(SO 4 ) 2 , KCr(SO 4 ) 2 , CrF 3 Cr(NO3) 3 , and mixtures comprising any of the foregoing.
  • the concentration of the trivalent chromium salt in the composition, per liter of solution, can range from about 0.01 g to about 22 g, more specifically from about 3 g to about 12 g, and even more specifically from about 4 g to about 8.0 g.
  • concentration of the trivalent chromium salt in the composition can range from about 0.01 g to about 22 g, more specifically from about 3 g to about 12 g, and even more specifically from about 4 g to about 8.0 g.
  • Embodiments of compositions and the application thereof to substrates are described in US Patent Nos. 5,304,257 , 5,374,347 , 6,375,726 , 6,511,532 , 6,521,029 , and 6,511,532 .
  • Various additives and other materials can be included in the composition comprising trivalent chromium as disclosed in the patent literature, and the trivalent chromium salt composition can be selected from any of a number of known commercially-available compositions.
  • the oxidizing agent can be a peroxide or a permanganate salt.
  • the oxidizing agent is hydrogen peroxide (H 2 O 2 ).
  • peroxides other than hydrogen peroxide include inorganic peroxides (e.g. Li 2 O 2 , Na 2 O 2 , K 2 O 2 , BaO 2 ), and organic peroxides (e.g., R-OO-R', R-OO-H, or RCO-OO-R', where R, and R' are organic groups).
  • the oxidizing agent can be in aqueous or non-aqueous solutions at concentrations in ranges having a lower endpoint of 0.1 wt.%, more specifically 0.5 wt.%, more specifically 1.0 wt.%, more specifically 2.0 wt.%, more specifically 3.0 wt.%, and more specifically 4.0 wt.%, and an upper endpoint of 10.0 wt.%, more specifically 9.0 wt.%, more specifically 8 wt.%, more specifically 7 wt.%, more specifically 6 wt.%, more specifically 4 wt.%, and even more specifically 3.5 wt.%.
  • the above upper and lower endpoints can be independently combined to disclose various different ranges.
  • compositions in the chambers 11a, 11b can be dispensed by bringing the liquid compositions in the chambers 11a, 11b into contact with the dispensing applicators 14a, 14b, respectively.
  • Each dispensing applicator 14a, 14b can independently be selected as a porous material configured to transport the liquid composition from the respective chamber 11a, 11b to a substrate in contact with the outer surface of the applicator 14a, 14b.
  • the liquid composition can be brought into contact with the applicator 14a, 14b by bringing the dispensing applicator 14a, 14b into contact with a fixed-position surface (which can but does not have to be the substrate to be coated) and applying hand pressure on the housing 10a, 10b toward the surface to open the poppet valve 15a, 15b.
  • the dispensing applicators 14a, 14b are slideably mounted in the housing 10a, 10b. At rest, the dispensing applicators 14a, 14b are biased away from the main body of the housing 10a, 10b by applicator biasing members (not shown) to an at-rest position as shown in FIG. 1 .
  • This biasing force is transmitted through actuator 16a, 16b to apply an expansive force on the spring member 18a, 18b, which intern acts on the poppet valve 15a, 15b to keep it engaged on the barrier 12a, 12b and closed.
  • actuator 16a, 16b Upon the application of hand pressure urging housing 10a, 10b toward the surface, the counteracting force of the surface acting on the dispensing each applicator 14a, 14b compresses the spring member 18a, 18b until the fully compressed spring and actuator engage against the poppet valve 15a, 15b and displace it away from the barrier 12a, 12b to open the poppet valve 15a, 15b.
  • Hand pressure can be maintained to keep the poppet valve open for a period of time sufficient to charge a desired quantity of liquid into chamber 17a, 17b, at which point the hand pressure can be removed or relaxed so that the applicator biasing members again bias the applicators 14a, 14b to the at-rest position with the poppet valve 15a, 15b closed. Liquid in the chamber 17a, 17b can then continue to be delivered and spread on the substrate.
  • the applicators 14a, 14b are not limited to porous pads.
  • the applicators 14a, 14b could also be independently selected from brushes, rollers, nozzles, etc. When not in use, the applicators 14a, 14b can be covered with an air- and liquid-tight cap.
  • FIG. 2 Another example embodiment of a kit is schematically depicted in FIG. 2 , in which the first and second containers are configured as first and second chambers 11a, 11b formed by housing 10 and barrier 20, with applicators 14a, 14b disposed at opposing ends of the oblong or cylindrical housing 10.
  • the remaining components and features depicted in FIG. 2 and their operation are as in FIG. 1 , and do not require further explanation.
  • the embodiment depicted in FIG. 2 provides additional technical benefits of convenience and efficiency, while reducing the potential for cross-contamination between the compositions by delivering the two distinct chemical compositions through applicators disposed on opposite ends of a coating pen.
  • the applicator 14b can be formed from a material that is resistant to wicking of material from the coated substrate into the chamber 17b from which it could potentially infiltrate to the chamber 11b when the poppet valve 15b is open. Such materials can include surfaces that are resistant to wetting by the coated chromium salt composition.
  • the poppet valve 15b can include check-valve features (not shown, but known in the valve art) to prevent migration of fluid from chamber 17b into chamber 11b.
  • anti-contamination procedures can be followed such as draining or flushing the chamber 17b after application is complete, or using a surface other than the coated substrate for displacing the applicator 14b to charge the chamber 17b so that the poppet valve 15b is closed before the applicator 14b comes into contact with the coated substrate. Combinations of the above materials or procedures can be used as well.
  • the first liquid composition comprising the trivalent chromium salt can be allowed to contact the substrate for a period of time before applying the second composition comprising the oxidizing agent, and in some embodiments the kit can include instructions to that effect.
  • the amount of contact time can vary considerably depending on the ambient temperature and humidity, the specific properties of the applicator and the liquid composition, and the thickness with which it is applied. Any amount of contact time greater than zero can be used. In some embodiments, contact times can range from 1 minute to 5 minutes. In some embodiments, contact times can range from 1 minute to 3 minutes.
  • a wet layer of the second liquid composition comprising the oxidizing agent is maintained on the coated substrate for a minimum period of time.
  • minimum wet layer time limits can include 0.5 minutes, more specifically 1 minute, more specifically 1.5 minutes, more specifically 2 minutes, more specifically 3 minutes, more specifically 4 minutes, and even more specifically 5 minutes. Theoretically there is no maximum wet layer time; however, minimization of the opportunity costs of lost efficiency typically results in drying times that do not drastically exceed the specified minimum wet layer time.
  • a wet layer of the second liquid composition comprising the oxidizing agent is maintained by making a plurality of passes over the substrate with the applicator 14b, and in some embodiments the kit can include instructions to that effect.
  • the second liquid composition can be configured to maintain a wet layer for a target duration, e.g., through the inclusion of additives such as gel or thickening agents (e.g., fused silica, water soluble polymers) or lower volatility solvents.
  • Moisture can also be retained by film-forming agents in the first composition such as sodium or potassium salts of hexafluorotitanic acid or hexafluorozirconic acid, or the selection of a chromium salt with colligative properties such as high solubility that render it inherently slow-drying.
  • film-forming agents in the first composition such as sodium or potassium salts of hexafluorotitanic acid or hexafluorozirconic acid, or the selection of a chromium salt with colligative properties such as high solubility that render it inherently slow-drying.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Apparatus (AREA)
  • Chemical Treatment Of Metals (AREA)
EP17170451.3A 2016-05-10 2017-05-10 Traitement de revêtement de conversion Withdrawn EP3243928A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15/151,114 US20170327955A1 (en) 2016-05-10 2016-05-10 Conversion coating treatment

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EP3243928A1 true EP3243928A1 (fr) 2017-11-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119456345A (zh) * 2019-05-10 2025-02-18 汉高股份有限及两合公司 用于危险材料的施涂器

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11951506B2 (en) 2022-09-08 2024-04-09 Hamilton Sundstrand Corporation Two part applicator pen

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3063877A (en) * 1960-10-10 1962-11-13 Amchem Prod Method and solutions for treating metal surfaces
US4838957A (en) * 1982-08-24 1989-06-13 Amchem Products, Inc. Phosphate coatings for metal surfaces
US5304257A (en) 1993-09-27 1994-04-19 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium conversion coatings for aluminum
US5374347A (en) 1993-09-27 1994-12-20 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium solutions for sealing anodized aluminum
WO1999026794A1 (fr) * 1997-11-24 1999-06-03 Jacqueline Fulop Instrument marqueur et effaceur et son procede d'utilisation
US6048921A (en) * 1994-12-23 2000-04-11 Henkel Corporation Method for applying conversion coating with wick applicator
US6217935B1 (en) * 1991-11-22 2001-04-17 Henkel Corporation Method and hand held pen type applicator for applying hazardous chemicals
US6375726B1 (en) 2000-10-31 2002-04-23 The United States Of America As Represented By The Secretary Of The Navy Corrosion resistant coatings for aluminum and aluminum alloys
US6511532B2 (en) 2000-10-31 2003-01-28 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for anodized aluminum
US6521029B1 (en) 2000-10-31 2003-02-18 The United States Of America As Represented By The Secretary Of The Navy Pretreatment for aluminum and aluminum alloys
DE102009039887A1 (de) * 2009-09-03 2011-03-17 Innovent E.V. Verfahren zur Oberflächenbehandlung von magnesiumhaltigen Bauteilen

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3063877A (en) * 1960-10-10 1962-11-13 Amchem Prod Method and solutions for treating metal surfaces
US4838957A (en) * 1982-08-24 1989-06-13 Amchem Products, Inc. Phosphate coatings for metal surfaces
US6217935B1 (en) * 1991-11-22 2001-04-17 Henkel Corporation Method and hand held pen type applicator for applying hazardous chemicals
US5304257A (en) 1993-09-27 1994-04-19 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium conversion coatings for aluminum
US5374347A (en) 1993-09-27 1994-12-20 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium solutions for sealing anodized aluminum
US6048921A (en) * 1994-12-23 2000-04-11 Henkel Corporation Method for applying conversion coating with wick applicator
WO1999026794A1 (fr) * 1997-11-24 1999-06-03 Jacqueline Fulop Instrument marqueur et effaceur et son procede d'utilisation
US6375726B1 (en) 2000-10-31 2002-04-23 The United States Of America As Represented By The Secretary Of The Navy Corrosion resistant coatings for aluminum and aluminum alloys
US6511532B2 (en) 2000-10-31 2003-01-28 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for anodized aluminum
US6521029B1 (en) 2000-10-31 2003-02-18 The United States Of America As Represented By The Secretary Of The Navy Pretreatment for aluminum and aluminum alloys
DE102009039887A1 (de) * 2009-09-03 2011-03-17 Innovent E.V. Verfahren zur Oberflächenbehandlung von magnesiumhaltigen Bauteilen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119456345A (zh) * 2019-05-10 2025-02-18 汉高股份有限及两合公司 用于危险材料的施涂器

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US20170327955A1 (en) 2017-11-16

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